scientific highlights - Liten

Transcription

RAPP O R T S C I E N TI F I Q U E
SC I ENTI FI C H I G H LI G HTS
2 0 1 4/ 2 0 1 5
Éditorial
Foreword
LES ACTIVITÉS DE RECHERCHE ET
DÉVELOPPEMENT DU LITEN AU SERVICE DE LA
TRANSITION ENERGÉTIQUE
Le Liten a l’ambition de constituer un pont entre la
recherche amont et l’industrie en développant la base
technologique de nouvelles filières industrielles dans le
domaine des énergies renouvelables à faible empreinte
carbone et de l’efficacité énergétique. Le développement
de compétences scientifiques et de briques technologiques
constitue le fondement de cette stratégie et positionne le
Liten au cœur de la transition énergétique.
Avec 43 thèses soutenues, 275 publications de rang A et 320 brevets déposés
en 2014 et au cours des 6 premiers mois de 2015, nous cultivons l’excellence
scientifique et technologique sur toute la chaine de maturité technologique,
depuis les matériaux et composants jusqu’à leur intégration et leur contrôle dans
des systèmes prototypes de démonstration.
Dans ce rapport scientifique 2014-2015 un florilège des meilleurs résultats obtenus,
pour la plupart avec nos partenaires académiques et industriels, vous est présenté
qui je l’espère vous donnera l’envie de collaborer ou de venir travailler avec nous.
LITEN RESEARCH AND DEVELOPMENT ACTIVITIES
IN SUPPORT TO ENERGY TRANSITION
Liten aims to build a bridge between discovery research and business by developing the
technological foundation for new commercial enterprises in the areas of renewable energy
with low carbon footprint and of energy efficiency. This strategy, based on developing new
scientific expertise and technological advances, places Liten firmly at the heart of energy
transition.
With 43 theses presented, 275 A-ranked publications and 320 patents posted in 2014 and
in the first half of 2015, we nurture scientific and technological excellence along all stages
of technological readiness, from materials and components all the way to their integration
and control in prototype systems for demonstration purposes.
In this scientific report for 2014/2015 we present a selection of the best results obtained,
most of them with our academic and business partners, which we hope will inspire you to
work with us or for us
Florence Lambert
Directrice du Liten
Head of Liten
Sommaire
Contents
L’INSTITUT LITEN : DE LA RECHERCHE AU TRANSFERT TECHNOLOGIQUE
POUR LES ÉNERGIES RENOUVELABLES ET L’EFFICACITÉ ÉNERGÉTIQUE
THE LITEN INSTITUTE: FROM RESEARCH TO TECHNOLOGICAL TRANSFER FOR
RENEWABLE ENERGIES AND ENERGY EFFICIENCY .......................................................... 4
MATÉRIAUX ET PROCÉDÉS
MATERIALS AND PROCESSES ............................................................................................. 7
EXTENDED CONTRIBUTION ON THERMOELECTRICITY:
FROM THEORY TO NANOSTRUCTURED MATERIALS AND THERMO-ELECTRIC GENERATORS..................... 8
HIGHLIGHTS:
NANOMATÉRIAUX / NANOMATERIALS........................................................................................12
MICROSOURCES D’ÉNERGIE / MICRO ENERGY SOURCES.................................................................15
ÉLECTRONIQUE ORGANIQUE / ORGANIC ELECTRONICS...................................................................16
MISE EN ŒUVRE DES MATÉRIAUX / MATERIALS PROCESSING........................................................19
ÉNERGIES RENOUVELABLES
RENEWABLE ENERGIES........................................................................................................ 23
EXTENDED CONTRIBUTION ON HIGH TEMPERATURE STEAM ELECTROLYSIS TO PRODUCE HYDROGEN..... 24
HIGHLIGHTS:
HYDROGÈNE / HYDROGEN........................................................................................................ 28
BIOMASSE ET GAZ DE SYNTHÈSE / BIOMASS AND SYNGAS.......................................................... 32
ÉNERGIE SOLAIRE / SOLAR ENERGY.......................................................................................... 35
ÉFFICACITÉ ÉNERGÉTIQUE
ENERGY EFFICIENCY............................................................................................................ 41
EXTENDED CONTRIBUTION ON LI ION BATTERIES: FROM INNOVATIVE MATERIALS TO INTEGRATED SYSTEMS.. 42
HIGHLIGHTS:
BATTERIES / BATTERIES.......................................................................................................... 46
PILES À COMBUSTIBLE / FUEL CELLS......................................................................................... 50
RÉSEAUX ÉLECTRIQUES ET STOCKAGE / POWER GRIDS AND STORAGE........................................... 54
EFFICACITÉ THERMIQUE : PROCÉDÉS ET BÂTIMENTS /
ENERGY EFFICIENCY: PROCESSES AND BUILDINGS....................................................................... 56
LISTE DES PUBLICATIONS DE 01/2014 À 09/2015
PUBLICATIONS FROM JANUARY 2014 TO SEPTEMBER 2015.......................................... 60
L’institut Liten : de la recherche au transfert technologique
pour les énergies renouvelables et l’efficacité énergétique
The Liten Institute: from research to technological transfer
for renewable energies and energy efficiency
Le Laboratoire d’Innovations pour les Technologies des Energies Nouvelles et les Nanomatériaux (Liten), créé en
2004, a pour mission de réaliser des recherches appliquées, orientées vers le transfert industriel, dans le domaine
des nouvelles technologies de l’énergie et des matériaux avancés. Centré sur un des piliers de la stratégie CEA
« les énergies non émettrices de gaz à effet de serre » et répondant à une des priorités gouvernementales « le
développement de la base technologique de filières industrielles performantes dans les énergies nouvelles »,
le Liten construit sa feuille de route dans un contexte politique national de transition énergétique. Fort de
1100 collaborateurs dont 750 permanents le Liten a un budget de R&D de plus de 140 M€ dont plus de 70%
proviennent de ressources externes au CEA.
The purpose of Liten, the Laboratory for Innovation in New Energy Technologies and Nanomaterials, created in
2004, is to conduct applied research, turned towards industrial transfer, in the field of new energy technologies and
advanced nanomaterials. Based on one of the core strategies of CEA, i.e. “energies producing no greenhouse gases”
and in response to one of the government priorities, i.e. “the development of a technological ground for efficient
industry sectors in the field of new energies”, Liten builds its strategic roadmap in the national political context of
the energy transition. With a staff of 1100, 750 of whom in permanent roles, Liten has a R&D budget of over 140 M€,
over 70% of which comes from sources external to CEA.
Les activités de R&D du Liten s’articulent autour de trois axes thématiques :
The R&D activities of Liten are organized around three thematic axes:
4
Les énergies renouvelables
Renewable energies
Le Liten axe son activité de recherche d’une part sur
l’énergie solaire comme source d’énergie renouvelable au
fort potentiel de croissance, et d’autre part sur les vecteurs
énergétiques renouvelables que sont l’hydrogène et les
gaz de synthèse dans l’optique d’une substitution des
ressources fossiles. La production d’électricité solaire
photovoltaïque classique ou à concentration est étudiée
sur toute l’échelle de la valeur depuis les matériaux et leur
mise en œuvre jusqu’à l’intégration de cellules innovantes
en module et en système. La production de chaleur
puis d’électricité solaire thermodynamique est abordée
essentiellement sous l’angle système. L’hydrogène comme
vecteur énergétique n’est pertinent que si son empreinte
carbone est faible et sa sureté d’usage démontrée. C’est
dans cette optique que le Liten travaille d’une part sur la
production d’hydrogène par électrolyse de l’eau (voir article
de synthèse pages 24-27) et sur son stockage, et d’autre
part sur la production de gaz de synthèse par conversion
thermochimique de la biomasse ou par méthanation du
CO2.
Liten orientates its research activity on both solar energy, a
renewable energy source with high growth potential, and
on renewable energy carriers like hydrogen or syngas, as
potential substitutes for fossil fuels. The production of solar
photovoltaic electricity, either classical or concentrated,
is studied across its entire value chain from material and
processing to integration of innovating cells into modules
and systems. Research on production of heat and electricity
from solar thermal is mainly related to the system analysis.
Hydrogen can only be considered a relevant energy carrier
if its carbon footprint is low and it is demonstrably safe to
use. It is why Liten conducts researches both on hydrogen
production by water electrolysis (see extended contribution
pages 24-27) and its storage, and on syngas production using
biomass thermochemical conversion or CO2 methanisation.
Les usages à haute efficacité énergétique High energy efficiency usages
L’intégration d’énergies renouvelables, de nature
intermittente, nécessite une adaptation des réseaux
électriques et le développement de capacités de
stockage et de gestion de l’énergie auxquels s’intéresse
Le Liten. L’augmentation des rendements de conversion
entre les différents vecteurs énergétiques que sont
l’électricité, l’hydrogène, le gaz naturel ou la chaleur
et leur usage constitue un gisement d’économies
d’énergie et d’innovations technologiques susceptibles
d’irriguer le tissu industriel. Il convient de lui adjoindre
la recherche de flexibilité et d’agilité pour passer d’un
vecteur énergétique à l’autre dans une approche tournée
vers les réseaux d’énergies électrique, gaz et chaleur.
Si l’optimisation des échanges thermiques dans les
procédés industriels continue d’être un axe fort au Liten,
deux domaines d’application sont ciblés en priorité, le
secteur des transports et celui du bâtiment, tous deux
forts consommateurs d’énergies fossiles en France. Dans
le contexte de développement des véhicules électriques
et hybrides, le Liten dédie une part importante de son
activité de recherche aux batteries (voir article de synthèse
pages 42-45) et aux piles à combustible, deux générateurs
électrochimiques à haut rendement, et à leur intégration
et hybridation. L’optimisation énergétique des bâtiments,
individuels ou industriels, définit également un axe de
recherche allant du monitoring au développement et à
l’intégration en vraie grandeur de solutions innovantes
d’isolation ou de ventilation.
integrating renewable energies, which are intermittent by
nature, requires adapting electrical grids and developing
energy storage and management capacities, which is of
particular interest for Liten. Increasing conversion ratios
between energy carriers such as electricity, hydrogen, syngas
or heat may generate a huge potential for energy savings
and technological innovations which should benefit industry.
In addition, research on flexibility and speed to convert from
one energy carrier to another also needs to be considered
through a system analysis approach focused on energy grids
coupling electrical, gas and heat grids. If the optimisation
of thermal exchanges in industrial processes is still a major
R&D axis of Liten, two application areas have also become
of major priority, namely transportation and buildings, both
major consumers of fossil fuel in France. Accompanying the
current development of electro-mobility , Liten dedicates a
large part of its research activity to batteries (see extended
contribution pages 42-45) and fuel cells, two high yield
electrochemical generators, and to their integration
and hybridization. Making buildings (whether homes or
businesses) energy efficient is also another research area,
that goes from monitoring to development and integration
of full sized innovative solutions for thermal insulation or air
conditioning.
Les matériaux
Materials
Socle de compétence historique du Liten, l’activité de
recherche dans les matériaux s’organise en soutien aux
thématiques précédentes avec un focus particulier
sur la synthèse et l’ingénierie des nano matériaux
ou des matériaux nano-structurés et des procédés
associés dans une logique d’économie de la matière.
Leur intégration dans des micro-sources d’énergie ou
dans des dispositifs de récupération d’énergie définit
un des axes de recherche du Liten (voir article de
synthèse pages 8-11). Pour accompagner la démarche
de passage à l’échelle, le Liten s’investit également
dans le développement de procédés de mise en
œuvre associant complexité des formes fabriquées,
sobriété en matière et en énergie et innocuité
pour l’environnement. Dans la même logique, des
recherches se concentrent sur la substitution de
matériaux critiques et le recyclage.
Research in the field of materials, historically a key
specialisation at Liten, is run to support the abovementioned activities, with particular emphasis on synthesis
and engineering of nanomaterials or nanostructured
materials and on associated processes with an approach
of matter economy. Integrating nanomaterials into energy
micro-sources or energy harvesting devices is one of the core
area of material R&D at Liten (see extended contribution
pages 8-11). In line with the scaling up approach at Liten,
developments are also made on processing tools allowing
the manufacture of complex shapes which require limited
matter or energy, and are environment friendly. Research
also focuses on replacing rare or critical materials and on
recycling.
L’ensemble de ces activités est illustré dans les 37 «highlights» qui composent ce rapport scientifique 2014-2015.
All these research activities are illustrated in the 37 highlights gathered in this scientific report 2014-2015.
5
La stratégie de recherche du Liten sur l’ensemble de la chaîne de la valeur
Liten research strategy over the whole value chain
Le Liten conduisant des recherches destinées aux transferts technologiques vers le tissu industriel, il s’attache à couvrir une
large gamme de TRL pour passer graduellement de la preuve de concept à l’échelle du laboratoire à la démonstration, ceci
sur tous les éléments de la chaine de la valeur du matériau au système et au prototype préindustriel (Figure 1).
With research activities turned towards technological transfer to industry, Liten is particularly keen to cover a large range of TRL
in order to shift gradually from laboratory proof of concept to full scale demonstration, for all the components of the value chain
from material to systems and pre-industrial prototype (Figure 1).
Fig. 1 - Illustration de la stratégie de recherche Liten
sur l’ensemble de la chaine de la valeur en montant
en niveau de maturité (TRL) pour chaque élément et
exemples de réalisations.
Illustration of Liten’s research strategy over the whole
value chain, increasing at each step the technology
readiness level (TRL) and examples of achievements.
La réussite de cette stratégie de recherches est conditionnée par le bon équilibre entre les collaborations académiques,
plutôt dans le cadre de projets de ressourcement, et les partenariats industriels généralement pour les projets dits de
maturation et pour l’accompagnement des transferts de technologies (Figure 2).
The success of this strategy relies on finding the right balance between academic collaborations, preferably within basic research
projects, and industrial partnerships, generally for so called ‘maturation’ projects and to support technology transfers (Figure 2).
L’accroissement de la maturité technologique se déroule suivant un processus itératif. Ainsi, le retour d’expérience issu
du passage à l’échelle supérieure fait l’objet d’une analyse approfondie. Ce processus permet d’identifier les mécanismes
limitant les performances ou la durée de vie, d’améliorer le concept à sa base et, pour les conditions d’usage, de définir les
essais accélérés pertinents ou de cibler le paramètre à mesurer et contrôler durant le fonctionnement pour l’optimisation
au niveau du système.
Cette stratégie de recherche itérative s’appuie sur un couplage étroit entre i) élaboration et conception, ii) test et
caractérisation iii) modélisation et simulation. Elle associe également étroitement le processus d’innovation, aboutissant
à des dépôts de brevets, et l’analyse scientifique approfondie des mécanismes impliqués au cœur des publications. Cette
association entre innovation et compréhension et la recherche d’un bon équilibre entre les deux sont illustrées en Figure 2
par le nombre annuel de publications et de brevets du Liten au cours des 5 dernières années.
Increasing the TRL is an iterative process: experimental
feedback gained from scaling up is analysed in-depth,
which allows identifying the mechanisms limiting either
performance or lifetime, and improving the concept
itself upon. At the stage of running systems under
targeted usage conditions, it also allows defining relevant
accelerated testing or pinpointing which parameter needs
to be monitored upon operation in order to optimise the
system. This iterative research strategy is based on a close
interaction between i) design and manufacture, ii) tests
and characterisation, iii) modelling and simulation. It also
creates a close link between the innovation process, which
results in patent applications, and in-depth scientific analysis
of mechanisms, which results in scientific publications. The
link between innovation and understanding and the need
to balance both are illustrated in Figure 2 which shows the
annual numbers of publications and patent applications of
Liten for the last five years.
6
Fig. 2 - Nombre annuel de publications et facteurs d’impacts moyens associés comparé
au nombre de brevets sur les 5 dernières années.
Annual number of publications and related impact factors compared to number of patent
applications for the last five years.
Matériaux et Procédés
Materials and processes
SOMMAIRE / CONTENTS
Extended contribution on thermoelectricity:
from theory to nanostructured materials and thermoelectric generators......................................................................................... 8
HIGHLIGHTS
q Synthesis and purification of copper nanowires for flexible transparent electrodes ...........................................................12
q Doping efficiency of single and randomly stacked bilayer graphene by iodine adsorption..............................................13
q Photonic Nanojet: a promising fabrication tool for producing functionalized surfaces .....................................................14
q Twisting Phonons in Complex Crystals with Quasi-One-Dimensional Substructures ..........................................................15
q Integration of a graphene ink as gate electrode for printed organic thin-film transistors .................................................16
q EQE asymmetry and capacitance depletion in semi-transparent organic photodetector:
characterization and modeling ......................................................................................................................................................................17
q Printed microsensors arrays for monitoring of batteries and fuel cells.......................................................................................18
q Toward high performance sintered magnets ......................................................................................................................................19
q Fabrication of components: progress in diffusion welding of heat exchangers......................................................................20
q Recycling of new technologies for green energy: critical & strategic metals recovery.........................................................21
THÈSES / PHD
2014
• BOUQUET Nicolas (DTBH): Optimisation des propriétés
de surface pour la réalisation de joints soudés par diffusion :
application aux échangeurs de chaleur compacts
• MAYOUSSE Céline (DTNM): Electrodes transparentes souples
à nanomatériaux
07/11/14
• BOUTHINON Benjamin (DTNM): Physique des photodiodes
organiques : Modélisation et caractérisation • SILVEIRA STEIN Sergio (DTNM): Etude et développement
de nouveaux matériaux nanostructurés pour les systèmes de
récupération d’énergie thermoélectrique
30/09/14
18/12/14
• MASSONET Nicolas (DTNM): Matériaux hybrides imprimables
pour des applications thermoélectriques
• VRACAR Radivoje (DTNM): Développement de matériaux
thermoélectriques Mg2Si1-xSnx de type n et p pour applications
thermoélectriques à moyennes températures
12/09/14
19/09/14
22/10/14
2015
• JARAMILLO Juliana (DTNM): Simulation et réalisation de
dispositifs nano-thermiques à base de nano-gaps et de surfaces
nano-structurées
13/05/15
7
THERMOELECTRICITY
FROM THEORY TO NANOSTRUCTURED MATERIALS AND
THERMO-ELECTRIC GENERATORS
THE PROJECT TEAM
Lux Aixala, Violaine Salvador, Julia Simon, Gilles Gaillard, Guillaume Savelli, Mathieu Boidot, Christelle Navone, Valérian Cinçon, Alizee Visconti,
Jean Leforestier, Magatte Gueye, Jesus Carrete Montana, Alexandre Carella, Thierry Baffie, Etienne Yvenou, Sébastien Vesin.
Thermoactive materials appear as a new class of materials in the field of new technologies for energy mainly addressing
the domain of energy harvesting. Thermoelectric generators (TEG) are designed for benefiting from waste heat to produce
electricity often with a limited power output. Nevertheless, it permits to increase the overall efficiency of systems where
the competing technologies cannot be used.
Combining N-type and P-type thermoelectric (TE) materials, TEG directly convert temperature differences to electric
voltage with an efficiency related to the dimensionless figure of merit ZT, which is defined by:
(Eq.1)
ZT=(σ×S²)/λ T
where σ, S, λ and T are the electrical conductivity, the Seebeck coefficient, the thermal conductivity and the temperature,
respectively. The higher the ZT value, the better the thermoelectric behavior. ZT values are spread around 1 depending on
the nature of the materials and the temperature range. Moreover, as shown in Equation 1, performances of TE materials
strongly depend on the temperature range of desired applications.
1 - THEORETICAL APPROACH: FROM VALIDATION TO PREDICTION
Thanks to our development of a novel method to predict materials thermal conductivity from first principles1, we have
been able to perform the first high throughput investigations of thermoelectric materials. So far we have investigated the
wide class of materials known as half Heuslers. From 79,057 theoretical compound entries, we found 75 stable compounds
(figure 1).
Our team is also recognized for pioneering and advancing the field of thermal conductivity calculations from first principles.
We have recently demonstrated that it is possible to achieve crystalline SiGe nanostructures with thermal conductivities
much lower than the so called “alloy limit”.
We are also the creators of computer program “ShengBTE” www.shengBTE.org published in 2014. This is the first publicly
available software capable of predicting thermal conductivity of crystalline materials from first principles, and it has a
growing community of users.
8
Fig. 1 - Number of
compounds during the
screening (left) and
evolution of the valence
per unit cell distribution
(center). All the final
75 compounds follow
the 8/18 octet rule.
Distribution of nanograined ZT at different
temperatures for the
stable half-Heuslers,
compared to standard
semiconductors2 (right).
2 - NANOSTRUCTURATION OF MATERIALS
2.1 - NANOSTRUCTURATION WITHIN BULK MATERIALS
As compared to a monolithic material, theoretical calculations have shown that a small volume fraction of a nanometersize second phase, homogeneously dispersed in the microstructure of a sintered polycrystalline material, leads to a
drastic reduction of the lattice thermal conductivity without affecting the power factor3. Then a strong increase of the ZT
parameter is predicted. Dense n type Mg2Si0.5875Sn0.4Sb0.01254 and p type MnSi1.775 polycrystalline alloys (grain size of 7 and
10 μm, respectively) have been prepared by gas-phase atomization followed by spark plasma sintering. Both materials,
devoted to applications in the range 200-500 °C, have been nanostructured by tailoring an intensive in-situ precipitation
during the sintering step (no second phase added). The formed precipitates have a nanometer-size character (average
diameter ranging from 7 to 20 nm and concentrations around 5.1x10-3 and 8.9x10-4 /nm2 for the Mg2Si0.5875Sn0.4Sb0.0125 and
MnSi1.77 alloys, respectively) (Figure 2).
Fig. 2 - left a) N-type Mg2Si0.5875Sn0.4Sb0.0125, b center) P-type MnSi1.77, c right) ZT parameter as function of temperature compared to the State-of-art (SOA).
As shown in Figure 2, high ZT values are obtained that are among the best reported for this kind of materials. Similar
trends have been observed on N and P-type Si92Ge086 alloys that have been nanostructured ex-situ (a second phase is
incorporated).
2.2 - NANOSTRUCTURATION WITHIN THIN FILMS
The research on thermoelectric systems based on thin films is mainly driven by applications in the microelectronic field
where the energy consumption due to heat losses in large computers becomes a crucial problem. For ten years we have
developed materials compatible with microelectronic applications. Silicon- and germanium-based materials have been
chosen as TE active materials. Thus Si/SiGe superlattices, then SiGe/Ge quantum dots superlattices (n- and p-doped, monoand polycrystalline, for both cases) have been grown by using an industrial Reduced Pressure CVD tool, highlighting a
decrease of the thermal conductivity compared to bulk materials7-8.
9
More recently, new kind of SiGe-based nanostructures have been grown based on our theoretical works that suggested
the use of silicides as competitive TE9. For the first time, n- and p-doped, mono and-polycrystalline, silicide quantum dots
superlattices have been grown. These new nanostructures integrate TiSi2 or MoSi2 dots in a SiGe matrix, as illustrated in
figure 3. The TE characterization of these nanostructures has shown a simultaneous increase of the in-plane power factor
by a factor 3.5 thanks to the modulation of the doping effect and a decrease of the cross-plane thermal conductivity down
to 20 %, by adding phonon diffusion by the dispersion of nanoparticles at 300 K10-11-12.
The perspectives consist in integrating our new nanostructured materials in thermoelectric generators. To reach this goal,
a thesis has started at the beginning of 2015 on this topic, in partnership with the Université de Sherbrooke, Canada, and
an ICT25 European project (STREAMS) will start at the beginning of 2016.
(a)
(b)
Fig. 3 - Cross section TEM images ofn-SiGe/TiSi2 mono- (a) and polycrystalline (b) quantum dots superlattices.
3 - FROM MATERIALS TO ASSEMBLY AND SYSTEMS
The applications require the assembly of many TE legs together within a TE module, which can stand long time in harsh
operating conditions. For energy saving applications, a high cadency production of TE modules is needed, since every
module is only delivering few watts. Current approach is a planar assembly of legs between electrodes. The challenge at
this step is to deliver a strong and reliable assembly technology which offers a minimum electrical resistance. Moreover,
it is important to reduce chemical diffusion between TE material and surrounding elements. The thermal coefficient
mismatch should be minimized13. A novel assembly technology based on nano-silver soldering has been investigated,
with promising results. More than 1000 cycles (150 °C-400 °C) and 500 h durability testing (550 °C) have been successfully
achieved with minor power output reduction14 . Technological solutions are under investigation to prevent the oxidation
which was identified as the main failure mode of our devices.
Thermoelectric modules are further integrated in thermoelectric generators (TEG) which may comprise single module or
multiple modules. Maximum output power of such system is today limited to tens of kW15-16 and requires a huge number
of TE modules since overall efficiency remains limited, below 10 %. TEG prototypes using Bi2Te3 and Si80Ge20 thermoelectric
modules were simulated (under Matlab®), prototyped, assembled, and tested at CEA17. Output power reached from 30 W
to 100 W as a function of inlet gas temperature varying from 450 °C to 750 °C (figure 4). Further improvement potentials
were identified. A 1 kW prototype of TEG based on Bi2Te3 dedicated to marine engines has been built by HotBlock OnBoard,
our industrial partner, with the support of CEA, and will be used as a communication product during 2015.
Further research activities are ongoing with Valeo and HotBlock OnBoard through the “RENOTER2” funded project. CEA
is manufacturing “net shape” sustainable and low cost TE materials Mg2Si0,4Sn0,6 and MnSi1,77 for automotive applications
(figure 5). Such exhaust heat exchanger for hybrid gasoline vehicles may be able to reach a maximum power output of 240
W leading to 4 g/km of CO2 emission reduction.
10
Fig. 4 - 45W thermoelectric generator using 30 Si80Ge20 TE modules.
Fig. 5 - TE ring manufactured by CEA and their assembly in a
TE tube generator by Valeo
ORGANIC THERMOELECTRICITY
ORGANIC THERMOELECTRICITY
For low temperature thermoelectric materials (T < 200 °C),
the record is still being ZT=1.2 at room temperature
(ZT=1.5 at T=100 °C) for bismuth telluride alloys. But the
mass implementation of TEG based on bismuth telluride
is prevented by a high production cost. Since 2011, we
have been exploring the use of polymers and composites
for low temperature TE applications. These materials
exhibit a very low thermal conductivity (typically 0.2
– 0.4 W/K) hence our efforts are mainly focused on the
increase of both the Seebeck coefficient and the
electrical conductivity. Highly conductive polyaniline
and poly(3,4-ethylenedioxythiophene (PEDOT) are
prepared thanks to patented CEA procedures18. PEDOT
stabilized with trifluoromethane sulfonate exhibits a
very high conductivity above 1200 S/cm. Treatment
with sulfuric acid improves electrical conductivity above
2200 S/cm thanks to a better crystallinity and the highest
reported oxidation state for PEDOT materials19. The
Seebeck coefficient of PEDOT can be increased from 18
μV/K up to 160 μV/K thanks to the fine redox control of
the charge carrier concentration. This treatment leads to
PEDOT materials with ZT above 0.1 which is among the
best reported values20. Innovative processing methods
have been developed to obtain free standing films of
PEDOT and their easy transfer on various substrates
without affecting their thermoelectric properties, even
for thick layers. n-type TE materials based on coordination
polymers (poly[Kx(Ni-1,1,2,2-ethenetetrathiolate)]) have
been formulated and processed in combination with
PEDOT materials in TE devices such as efficient flexible
heat flux sensors.
2D heat flux sensors producing 5mV from the body heat
1 - W. Li, J. Carrete, N. A. Katcho, N. Mingo, Computer Physics Communications 185 (6), 1747-1758 (2014)
2 - J. Carrete, Wu Li, N. Mingo, S. Wang, S. Curtarolo, Physical Review X, 4, 011019 (2014)
3 - N. Mingo et al. : Nano Lett, 9, 711, (2009)
4 - G. Bernard-Granger et al. : submitted to Acta Materialia, (2014)
5 - G. Bernard-Granger et al. : J Alloys Comp, 618, 403, (2015)
6 - K. Favier et al. : Acta Materiala, 64, 429, (2014)
7 - G. Savelli & al., J. Micromech. Microeng. 18, (2008)
8 - D. Hauser & al., Thin solid Films 520, (2012)
9 - N. Mingo & al., Nano Lett. 9, (2009)
10 - S. Silveira Stein & al., Proc. IEEE Nano Conf., Toronto, Canada, (2014)
11 - G. Savelli et al., Nanotechnology 26, (2015)
12 - G. Savelli et al., Thin Solid Films, accepted, (2015)
13 - M. Schwartz : Brazing – 2nd edition – ASM International (2003)
14 - L. Aixala et al. : presentation at IAV 4th thermoelectric congress, Berlin, Germany, (2014)
15 - Alphabet Energy : http://www.prweb.com/releases/2014/10/prweb12229734.htm
16 - H. Kaibe et al. : http://www.komatsu.com.sg/CompanyInfo/profile/report/pdf/164-E-05.pdf (2011)
17 - K. Romanjek et al. : submitted to Journal of Electronic Materials (2014)
18 - A. Carella & al, Patent pending, (2014)
19 - N. Massonnet & al, Chem. Sci., (2015)
20 - Q. Zhang & al, Adv. Mater., (2014)
11
Synthesis and purification of copper nanowires
for flexible transparent electrodes
CONTEXT
Transparent conductive thin films are essential components for
touch screens, solar cells and many other optoelectronic devices.
The fabrication of transparent electrodes is commonly realized
with indium tin oxide (ITO). However, ITO is not able to meet the
future demands for flexible transparent conductive films in particular because of its intrinsic brittleness.
APPROACH
Great efforts have been devoted to develop new materials produced at low cost, and processable at low temperature. Among
them metallic nanowires used in the form of random networks
appear as a very promising alternative to ITO. Though mainly silver
has been used so far [1,2], the use of less expensive metals such as
copper would certainly be of interest [3].
to tackle potential issues such as stability and scale-up of the chemical synthesis of the nanowires. Studies are ongoing.
PARTNERS, FUNDINGS, ACKNOWLEDGMENTS
This work benefited from a grant by the DGA (Direction Générale
de l’Armement).
References
[1] Langley D., Giusti G. Mayousse C., Celle C., Bellet D., Simonato J.P.,
Nanotechnology, 2013, 24, 452001
[2] Mayousse C., Celle C., Fraczkiewicz A., Simonato J.P., Nanoscale,
2015, 7, 2107-2115
[3] Mayousse C., Celle C., Carella A., Simonato J.P., Nano Research,
2014, 7(3), 315-324
RESULTS
The hydrothermal synthesis of long copper nanowires (up to hundreds of microns) has been demonstrated. It is based on a simple
protocol using only water, copper chloride and octadecylamine
which play both the roles of reducing and capping agents (the latter is necessary to promote a one-dimensional growth). We have
also shown that the purification of the nanowires is very important and can be easily achieved by wet treatment with glacial acetic acid. The process is carried out at room temperature and no
post-treatment is necessary.
Fabrication of random networks of purified copper nanowires
leads to highly flexible transparent electrodes with excellent
optoelectronic performances (e.g., 55 Ω/ at 94% transparency,
Figure 1). Like for silver nanowires based electrodes a high transparency in the mid-infrared region was measured.
Both transparent conductive materials were successfully integrated in capacitive touch sensors to demonstrate a potential
application of these nanowires based flexible transparent electrodes. Briefly, when a conductive object such as a finger is approaching or touching the electrode through the protective coating,
the local electric field is modified and induces a capacitance
change, which can be monitored and used to modulate for instance the lighting power of a LED (Figure 2). The touch sensors
were functional for at least several months.
In addition, hybrid materials with the conductive polymer PEDOT:
PSS show similar properties (e.g., 46 Ω/ at 93% transparency),
with improved mechanical properties.
Fig. 1:Transmittance as a function of the sheet resistance for Cu
nanowire based electrodes
Inset: Cu nanowires deposited on a flexible PEN substrate
No contact
Contact
Fig. 2: Use of Cu NW based electrodes on a capacitive touch sensor. The capacitance change is operated by approaching a finger
close to the surface, which modifies oscillation values (top 362;
down: 273)
CONCLUSIONS AND PERSPECTIVES
The performances obtained with these copper nanowires are very
good and meet the requirements of many applications, in particular for optoelectronics. Further studies are nonetheless expected
TEAM
Céline Mayousse, Caroline Celle, Alexandre Carella,
Jean-Pierre Simonato .
CONTACT
[email protected] , [email protected]
12
Doping efficiency of single and randomly stacked
bilayer graphene by iodine adsorption
CONTEXT
To produce large scale transparent conductive electrodes based
on bi dimensional graphene material, conductivity enhancement
through efficient doping is needed. Indeed while graphene exhibits a very high carrier mobility in theory, it suffers from a rather
low carrier density. Thus the carrier density has to be enhanced
by doping to produce transparent conducting film and fulfill the
specifications requested by the applications (Transmission >90%
with square resistance below 100 Ohm). Unlike dopant chemisorption, dopant physisorption appears especially promising as it
can increase the charge carrier concentration and maintain a high
level of carrier mobility.
APPROACH
Among the wide variety of dopants that can be physisorbed on
graphene one of the most promising is iodine. The graphene
doping of type p (holes) by iodine vapor at relatively low temperature (100 °C) is suitable for significantly improving the conductivity of graphene and carbon nanotubes. CVD grown graphene
samples have been prepared on platinum at rather low temperature (700°C) and transferred on Si/SiO2 substrate by electrochemistry using bubbling of hydrogen at the interface between
Pt and graphene. These samples where used to make electrical
characterization and X-ray photoelectron emission microscopy
(XPEEM) to assess the doping efficiency and stability on single
layer or folded double layer graphene (figure 1).
RESULTS
Polyiodide complexes (I3- and I5-) have been identified by XPS and
Raman spectroscopy as the doping species. The graphene work
function increases from 4.3eV to 4.7 eV after iodine treatment
(figure 2). More efficient doping has been observed on the bilayer
thanks to iodine complexe intercalation. The amount of iodine on
the surface is close to 1% and very interestingly the doping efficiency is maintained up to 300°C but with a slight decrease for
temperature larger than 200°C (figure 2). These results have been
confirmed by electrical measurements on devices revealing a
resistivity decrease from 2 kOhm square down to 670 Ohm square
after iodine doping.
This work was carried out in the frame of the GraphEN collaborative project between Liten, Leti, Inac and Neel Institute.
References
[1] Kim, H., Renault, O., Tyurnina, A., Simonato, J.P., Rouchon, D.,
Mariolle, D., Chevalier, N., Dijon, J.
Doping efficiency of single and randomly stacked bilayer graphene
by iodine adsorption
(2014) APPLIED PHYSICS LETTERS Volume: 105 Published: JUL 7 2014
Fig. 1 - left: energy filtered secondary electron PEEM image and
work function map (right) of 1L and 2L doped graphene layer
The efficiency of iodine as a p type dopant up to 300°C on CVD
graphene has been demonstrated. Bilayer graphene was found to
contain a higher amount of dopant than single layer graphene,
suggesting that iodine can intercalate between the layers of the
non-Bernal stacked graphene which is not the case for graphite.
These preliminary results open new perspectives for stable TCF
based on doped stacked graphene layers.
Fig. 2: Work function and iodine concentration evolution versus
annealing temperature.
TEAM
Anastasia Tiurnina, Jean Dijon, Jean-Pierre Simonato,
Olivier Renault, Hokwon Kim
CONTACT
[email protected] , [email protected];
[email protected]
13
Photonic Nanojet: a promising fabrication tool
for producing functionalized surfaces
CONTEXT
High density periodic nanostructures over very large surfaces (>>
cm²) are very promising in the domain of energy for example to
optimize solar cells efficiency, reduce engine friction, minimize
aircraft drag, enhance electrical systems lifetime by improving
polymer surface hydrophobicity. However, very few lithography
techniques fulfill all the required criteria: spatial resolution, low
writing time, low cost, compatibility with a wide range of materials
or non-planar surfaces.
Laboratoire Hubert Curien, Prof. Yves Jourlin, St Etienne.
References
[1] O. Delléa et al., IPAS 2014, Springer, Berlin Heidelberg, 107–117.
[2] O. Delléa, O. Shavdina et al., submitted patent, n°15 52837.
[3] O. Shavdina, O. Delléa et al., Langmuir 2015, 31, 7877−7884.
APPROACH
Nanosphere lithography, also called colloidal lithography, based
on the assembly of size-monodisperse nanospheres is an easy,
inexpensive, efficient, and flexible manufacturing approach[1].
Usually, the 2D hexagonal closed packed nanoparticle array is
used as mask. Our approach consists in using the focalizing properties of the spheres to pattern the substrate. Indeed, being irradiated by an optical beam, each sphere is acting as a near-field
microlens generating a field enhancement underneath, called
“photonic nanojet”.
Fig. 1: Electric field
in symmetry plane
of the spheres of
1µm.
RESULTS
We first applied the rigorous coupled wave analysis (RCWA) theory
to calculate the electric field distribution during the illumination
of a microsphere hexagonal 2D array with a plane wave (fig. 1).
We observed that nanojets can be generated for a wide range of
microsphere diameters (from 2λ to more than 40λ) and investigated key parameters to optimize the energy, focus, diameter and
length of the nanojets (fig. 2) [2]. We demonstrated for example the
possibility to increase both the energy and the focus of the nanojet by a factor greater than 2.
Depending on the operating conditions and the nature of the
substrate on which the particles are deposited, the photonic
nanojet can achieve the following physical operations: ablation,
crosslinking, photolysis, growth of metallic nanoparticles, fusion.
Experimentally, an enhanced Langmuir Blodgett technique
called Boostream® compatible with 2D or 3D large surfaces [3] was
employed to transfer 1 µm silica sphere arrays on photosensitive
TiO2 xerogel previously deposited on glass. The insolation and
development condition has lead to a large area hexagonal array
of periodically organized nanopillars (fig. 3) in accordance with
theory.
Fig. 2: Optimized
calculation of
nanojet parameters
in comparison with
conventional nanosphere assembly.
Fig. 3: Large area
hexagonal array of
periodically organized TiO2 nanopillars
Photonic nanojet is a maskless subwavelength-resolution direct
write nanopatterning tool combining several physical phenomena at subwavelength scale. Our future work will focus on the
fabrication and characterization of smart surfaces associating
periodic structures and nanoparticles growth for catalysis.
TEAM
Olivier Delléa, Olga Shavdina, Pascal Fugier.
CONTACT
[email protected]
14
Twisting phonons in complex crystals with
quasi-one-dimensional substructures
CONTEXT
A variety of crystals contain quasi-one-dimensional (1D) substructures, which yield distinctive electronic, spintronic, optical, and
thermoelectric properties. There is a lack of understanding of the
lattice dynamics that influences the properties of such complex
crystals.
APPROACH
Here we employ inelastic neutron scatting measurements and
density functional theory calculations to show that numerous
low-energy optical vibration modes are present in higher manganese silicides (HMS), an example of such crystals. Including unusually low-frequency twisting motions of the Si ladders inside the
Mn chimneys, these optical modes provide a large phase space
for scattering acoustic phonons. A hybrid phonon and diffusion
model is proposed to explain the low and anisotropic thermal
conductivity of HMS and evaluate nanostructuring as an approach
to further suppressing the thermal conductivity and enhancing
the thermoelectric energy conversion efficiency.
This work has emerged from a consortium including the theory
team at Liten/DTNM and several other world-leading theoretical
and experimental groups at Oak Ridge National Lab, Cornell University and the University of Texas, among others. The full list of
participants and further details can be found in[1]. This work was
partly carried out in the frame of two projects : PHIMS (ANR) and
SIEVE (CARNOT).
References
[1] Chen et al.,
Nature Communications, 6 :6723 (2015)
RESULTS
These experiments and calculations clearly reveal that the complex
Nowotny chimney ladder structure of HMS gives rise to numerous
low-lying optical vibration modes, including a peculiar twisting
polarization that undergoes avoided crossings with the acoustic
branches near the Brillouin zone center. In addition, the calculation reveals a reversal of the group velocity anisotropy at energies
above and below about 10 meV. These observations help explain
the considerable anisotropy in the thermal conductivity of HMS.
According to a combined low-frequency phonon and high-frequency diffusion model, our calculation suggests that glass-like
thermal conductivity is achievable by introducing grain boundary
scattering with a length scale of about 10 nm. Therefore, a ZT larger than 1 is possible by nanostructuring HMS, as a ZT of 0.6-0.7
has been achieved in doped samples with grain size of several
micrometers. More broadly, the twisting polarization discovered
in HMS gives the first glimpse of the elusive and important lattice
dynamics in a wide range of complex crystals with promising functionalities as a result of internal quasi-1D substructures.
Fig. 1: Measured INS (ARCS) signal and simulated dynamical
structure factor for the HMS crystal at 300 K. S(Q,E) data obtained
by ARCS (top) for the HMS crystal and simulated dynamical structure factor (bottom) for Mn4Si7, a, along [H00] in the (4,0,0) Brillouin zone, showing the LA and LO modes
This discovery offers new insights into the structure-property relationships of a broad class of materials with quasi-1D substructures
for various applications.
TEAM
Natalio Mingo, Jesus Carrete Montana.
CONTACT
15
Integration of a graphene ink as gate electrode for
printed organic thin-film transistors
CONTEXT
Great progress has been made in the development of organic
electronic materials since the discovery of conducting and semiconducting polymers. These materials can be processed in solution, as inks. Traditional high-volume printing techniques can be
used for manufacturing of organic electronic devices on various
flexible substrates at low cost. The development of solution of
organic semiconductors has allowed the emergence of a new
generation of air-stable P- and N-type materials for Organic ThinFilm Transistors (OTFTs).
References
[1] M. Benwadih et al. / Organic Electronics 15 (2014) 614–621
APPROACH
CEA Liten proposed to integrate a graphene ink as gate electrode
in a printed complementary organic technology, which exhibits
performance and process compatibility that complies with low
cost objectives.
RESULTS
Complementary printed OTFTs have been manufactured with
graphene ink as a gate electrode allowing obtaining higher semiconductor mobilities : 3 cm2V-1s-1 for the P-type and 0.9 cm2V-1s1
for the N-type have been achieved (figure 1). The seven-stage
ring oscillator has reached high oscillation frequencies of 2.1 kHz
at 40 V, corresponding to a delay/gate value of 34 µs (figure 2).
The use of 1% wgt adhesive in the silver paste is mandatory to
have a good adhesion on the CYTOP dielectric layer. However it
decreases the gate dielectric capacitance and consequently the
electrical performance of the transistors. The use of graphene ink
as a gate in the organic complementary technology has enabled
a lower cost and a higher electrical mobility than the silver paste
(figure 3). Different morphological and electrical characterizations
have been conducted on the graphene ink to optimize its integration in organic devices. A value of 37 Ω/sq was measured for the
sheet resistance of the printed graphene ink, the roughness of the
layer characterized by AFM was 78 nm. Besides, the decrease of
dielectric thickness has lowered the threshold voltage around 10
V, which was the goal to reach in order to use lower supply voltages (15 V).
Fig. 1: Comparison of transfer characteristics of P-type (left) and N-type (right)
OTFTs with a 500 nm- and 750 nm-thick dielectric
Fig. 2: Output characteristics of an organic
seven-stage ring
oscillator (L =20 µm
W =1000 µm) with
Vdd = 20 V
This process may give rise to other kinds of new and highly relevant techniques combining altogether very high performances,
reliability and low fabrication costs.
Fig. 3: Picture of an
organic circuit on
flexible substrate
This work was funded in the frame of the European FP7 project
COSMIC. The authors want to thank Polyera Corp. for supplying
N-type semiconductor ActivInk® material.
TEAM
Mohammed Benwadih, Abdelkader Aliane,
Jacqueline Bablet
CONTACT
[email protected]
16
EQE asymmetry and capacitance depletion in semi-transparent
organic photodetector: characterization and modeling
CONTEXT
Semi-transparent bulk heterojunction organic photodiodes processed in air present singular features. Depending on the characteristics of the active layer (polymer energy level, active layer
thickness …), the External Quantum Efficiency (EQE) can show
significant differences when the device is illuminated either from
the substrate side or from the top side [1]. These differences are
independent of the optical absorption of the stack. This work aims
at understanding the causes of this unknown internal dissymmetry.
References
[1] B. Bouthinon, R. Clerc, J.M Verilhac, S. Jacob, A. Gras, J. Joimel, O.
Dhez, A. Revaux,
ICOE 2014
Fig. 1: Schematic of organic photodetector investigated in this work.
APPROACH
To investigate this issue, photodiodes presenting the typical
inverted architecture shown in Fig. 1 are processed and investigated for different blend thicknesses. EQE from both sides (fig.2)
and Capacitance versus Voltage characteristics (fig.3) have been
measured and compared to TCAD (Technology Computer Aided
Design) simulation.
RESULTS
Results shown in Fig. 2 indicate a large discrepancy between
back and front EQE, the back side being 3 times more efficient
than the front side at 0V and 620 nm. This discrepancy is reduced
when increasing the reverse polarization. When such a difference appears, a depletion zone of about 200 nm (thinner than
the active layer in the case of photodiodes) is extracted from the
complementary capacitance versus voltage measurement in the
dark (Fig. 3). These two features (EQE asymmetry and capacitance
depletion) are the signature of charged species present in the
active layer gap. These charges lead to potential bending (Fig.
4) and apparition of a low electric field zone close to PEDOT: PSS
electrode. TCAD simulation allows reproduction of all photodiode
experimental characteristics either using p-type doping (which
would be unintentional in our case) or by including acceptor
states. The amount of species increases after ageing and leads to
higher depletion (Fig.3) and EQE dissymmetry.
Fig. 2: Experimental back and front side External
Quantum Efficiency (EQE) measured at 0V.
Fig. 3: Capacitance – voltage
characteristics measured
(dots) and simulated (lines) in
dark condition at a frequency
response of 100Hz before and
after ageing.
The presence of charge species in the gap of organic photodiode
active layer layer leads to high. It leads to high dissymmetry
between front and back performance of the device. This phenomenon is amplified after ageing of the device. Next step will be to
determine the origin of these gap states.
Fig.4: Simulated potential in
the active layer at 0V under
illumination showing the
impact of the acceptor like
trap state on the potential
distribution.
PARTNERSHIP
This work was performed in partnership with the start-up ISORG.
CONTACT
[email protected]
17
Printed microsensors arrays for monitoring of batteries and
fuel cells
CONTEXT
Accurate monitoring of electrochemical generators such as batteries and fuel cells is necessary to optimize performance and durability in addition to increase safety. For that purpose, more and
more information from the individual cells under operation are
required (temperature and cell voltage distribution, mechanical
stress, deformation…). Operando monitoring of the cells thanks
to low cost and minimally invasive sensors is thus necessary.
APPROACH
Arrays of micro-sensors were produced using printing as low cost
process of fabrication. For battery monitoring, arrays of sensors
composed of three types of sensors were developed: temperature
sensors (Wheatstone bridges, using positive temperature coefficient and negative temperature coefficient materials inks), polyvinylidene difluoride (PVDF) piezoelectric sensors for acoustic emission [1,2], and strain gauges [3].
For fuel cell (PEMFC) application, the objectives were notably to
produce arrays of sensors for the mapping of local voltages. These
sensors had to be directly placed in the cell, either between the
gas diffusion layer (GDL) and the bipolar plate (BP) or integrated
inside a Membrane/ Electrode Assembly (MEA).
The micro-sensors arrays were printed on flexible support such as
a polymer or a paper sheet or directly on the sample to monitor.
Printing technology demonstrated the capability to produce
non-intrusive arrays of micro sensors that could be placed directly
on batteries or in fuel cell to record numerous different relevant
parameters for in-operando monitoring. This low cost process can
be used to drastically reduce the cost of the instrumented cells.
It remains, however, to develop the tools that could analyse and
integrate all these information into the generator’s management
system.
This work was partly carried out in the frame of a national program
Institut Carnot Energy for Future (MICROCAPT).
References
[1] N. Kircheva, PhD thesis, INPG, Grenoble, 2013
[2] S. Genies et al. Patent EP2702632 A1, 2011
[3] STALLION Project ref: 308800,FP7-ENERGY-2012
[4] A.G. Hsieh et al Energy Environ. Sci., 2015,8, 1569-1577
RESULTS
Arrays of sensors used for battery application demonstrated the
possibility to record the temperature variation and the gradient of
temperature that appears on a cylindrical 18650 battery between
the ends of the cylinder (connectors) and the middle (Fig. 1)
during cycling. PVDF piezoelectric sensors were used to detect the
acoustic signals emitted by Li-ion batteries during operation. In
particular, it was possible to detect the early signs of the thermal
runaway and prevent fire or explosion of the battery issued from
over-heating (Fig. 2). Piezo sensors were also used for preliminary
tests of ultrasound characterization as initiated by [4].
Preliminary tests were also conducted on strain gauges directly
printed on pouch cells package.
For PEMFC, arrays of microsensors were printed on Polyethylene
terephthalate (PET) and Polyether ether ketone (PEEK). The thermomechanical behaviour of the PET (Tg≈100°C) has allowed a
successful integration of a first one inside a MEA (Cf. top figure at
the middle) while a second one has been cut in order to design an
open instrumented grid to probe local voltages between bipolar
plates and MEA into stacks. Both are currently being validated in
fuel cells.
Fig. 1: Evolution of
the temperature
recorded by six
printed sensors
(Wheatstone bridge)
placed on a 18650
battery during
discharge (1C rate).
Fig. 2: Principle of
ultrasonic acoustic
characterization
using printed PVDF
piezoelectric sensors
for batteries study.
Example of use of
piezo sensors for the
detection of early
signs of the thermal
runaway of a battery
TEAM
Nicolas Guillet, Romain Gwoziecki, Jean Francois Blachot
CONTACT
[email protected]
18
Toward high performance sintered magnets
CONTEXT
The ability of hard magnet to keep their magnetization under a
demagnetizing field is called coercivity. The coercivity of NdFeB
magnets used in motors and generators is currently tuned by
using heavy rare earth (HRE) in substitution of Nd. Another way,
allowing low and sustainable HRE addition, lies on a better control
of the microstructure. Basically, finer grain boundaries, homogeneous and low grain size are targeted to avoid nucleation of
demagnetizing process. In the framework of the PhD Thesis of
Brice Hugonnet [1], close investigation of the powder arrangement during sintering has highlighted the role of mechanisms
acting at the granular scale.
References
[1] B. Hugonnet et al., NdFeB sintering analysis, International
Conference on Magnetism, Barcelona (2015)
APPROACH
Micron sized NdFeB powder beds, obtained by jet milling have
been aligned under high magnetic field (7T). Equipment of the
Liten magnet platform has been used. This sample preparation
leads to a very specific monocrystalline grain arrangement featuring pillars of grains connected along their c axis. Anisotropic
grain contact distribution is particularly exacerbated. After isostatic compaction, the evolution of the anisotropic grain packing
has been analyzed. Sintering treatment has been interrupted at
different stages allowing partially consolidated microstructure
to be observed by SEM. Quantitative image analysis has been
developed in order to follow the distribution of contacts between
grains.
Fig. 1: Microstructure at 975°C
showing the remaining pillars
RESULTS
Fig. 2: Shrinkage curves during
sintering along 2 directions:
parallel (blue) and perpendicular (red) to magnetic alignment
It has been found that the initial pillar structure remains stable and
effective until the beginning of the final stage of sintering (Fig.1).
The link with the macroscopic anisotropic shrinkage of the sample,
recorded by dilatometry experiment (Fig.2), has been established.
This is highlighted by the grain boundaries orientation distribution (Fig.3).
The histogram in Fig.3 clearly shows a larger amount of grain
boundaries with a normal vector oriented along the alignment
direction. The following shrinkage mechanism of powder beds
is proposed. It is assumed that the local shrinkage between two
particles occurs in the direction of the contact normal vector. As
the macroscopic shrinkage is the sum of all the local shrinkages, a
non-isotropic contact orientation distribution implies a non-isotropic shrinkage.
Fig. 3: Grain boundaries orientation distribution obtained
by image analysis on a sample
quenched at 975°C during the
densification
The work has established that powder grains arrangement and
contact distributions have a strong impact on the shrinkage rate
of NdFeB. These parameters depend on powder alignment and
compaction stages, currently performed in the process route. As
a result, process can be improved for instance by enhancing grain
contacts. Lowering sintering temperature can be induced. Such
effect would be beneficial for microstructure homogeneity and
coercivity.
TEAM
Brice Hugonnet, Michel Bailleux, Stéphane Genevrier,
Olivier Tosoni, Cyril Rado, Florence Servant
CONTACT
[email protected]
19
Fabrication of components: progress in diffusion welding of
heat exchangers
CONTEXT
Diffusion welding (DW) is a high temperature joining process
that allows to achieve complex parts, i.e components with intricate geometry or made of a combination of different materials.
In diffusion welding a force is applied on the parts to be welded,
at high temperature, which results in solid state bonding. A deep
understanding of the mechanisms responsible for the formation
of interfaces is required in order to optimise the process parameters with regard to the required properties (strength, tightness,
dimensional accuracy…).
AN INVESTIGATION OF DIFFUSION WELDING
MECHANISMS
“How surfaces become interfaces” has been a subject of deep
investigations. Several mechanisms take place during DW: porosity removal, transformation of surface layers and grain boundary
motion. These mechanisms operate simultaneously and may
interfere in a complex way.
Detailed studies and models exist in the literature, they mostly
address porosity removal in which both material plasticity,
visco-plasticity and diffusion play a role (A. Hill, E.R. Wallach,
Modelling solid state diffusion bonding, Acta Metall. 37 (1989)
2425-2437). No description of how grain boundary (GB) motion
proceeds in the vicinity of the interface has been reported. GB
motion away from the bond line is considered as the ultimate step
of DW, because it leads to the disappearance of the interface. In [1],
an original approach, based on the use of interrupted DW tests,
allowed to highlight this phenomenon. Given a set of DW parameters, several DWed samples were fabricated at different times. The
mean grain size and the crossing ratio, i.e. the fraction of GBs that
moved more than 2 µm away from the bond line, were measured.
Figure 1 shows that GB crossing is almost fully achieved at the
beginning of the temperature plateau. Detailed microstructural
analysis (Figure 2) shows that GBs may be temporarily pinned at
the interface by pores or impurities such as oxides, but once they
are free of moving, they rapidly leave the interface plane. Triple
points act as initiation sites because of their tendency to rapidly
equilibrate, forming 120° angles (Y shape). Then, GBs move away
from the interface in the same way as they move inside the material [2].
Other applications (e.g. reactor-exchangers for processing of chemical products) should also benefit from these results and gain
acceptance in the industry.
Future studies shall address the effect of surface topology on porosity removal and the effect of pinning on grain boundary motion.
PARTNERS, FUNDINGS, ACKOWLEDGEMENTS
This work has been made in the frame of the ASTRID fast breeder
reactor project leaded by the CEA Nuclear Energy Division (DEN).
References
[1] N. Bouquet, Université de Bourgogne, PhD thesis, 2014.
[2] N. Bouquet, E. Rigal, S. Chomette, F. Bernard and O. Heintz
«Interface formation during HIP-bonding of austenitic stainless steel»,
10th Int. Conf. on brazing, high temperature, brazing and diffusion
welding, Aachen, Germany, 18-20 june 2013.
the mean grain size
D and the extent
of grain boundary
crossing (normalised
to the final condition)
during diffusion welding of 316L steel.
Fig. 2: Top/ microstrucrure at 220min,
showing pores
(yellow lines) and
triple point motion
(purple lines).
Bottom/ microstructure at 300min
showing interface
The results show that fully homogeneous microstructures can be
achieved, which means that a DWed component can be considered as a monolithic material. This is of paramount importance for
an application such as the sodium gas compact heat exchanger of
the ASTRID nuclear power plant, because it opens the possibility
for a codification of the process without considering weld coefficients.
TEAM
Emmanuel Rigal, Nicolas Bouquet, Sébastien Chomette,
Isabelle Chu
CONTACT
[email protected]
20
Recycling of new technologies for green energy:
Critical and strategic metals recovery
CONTEXT
Due to the rapid growth in demand for some metals, a shortage
or an unexpected higher cost of these metals could be a potential
bottleneck to the deployment of new technologies, mostly for low
carbon energy technologies which use large amounts of critical
and strategic metals (rare earths, Li, Pt, Co, Ag…). In this perspective, CEA TECH Liten leads several projects aiming at the recovery
of these metals by recycling end of life technologies which are
developed internally such as permanent magnets, Li-ion batteries,
photovoltaic cells, fuel cells etc…
APPROACH
The selected processes for recycling technologies are based on:
• Dry treatment of system/component/material to concentrate
critical metals in a low fraction of materials by dismantling, shredding, sieving…
• Hydrometallurgical process to extract critical metals,
• Valorization of recovered metals in a closed loop as new materials
for remanufacturing.
on the decrease of environmental impact by substituting mineral
acids by ionic liquids and on the other hand on the technological
transfer to industry.
These works are partly supported by ANR (RECVAL-HPM project),
CARNOT Institute (RECYPAC projects), DGA (TERRAMAG project).
References
[1] PhD thesis, Marion Joulié, 2015
[2] FR2997095, Procédé pour isoler les terres rares et/ou élément(s)
métallique(s) annexe(s) contenus dans la phase magnétique
d’aimants permanents, R. Laucournet, C. Lecorre
RESULTS
Several experiments dealing with the recovery of critical metals
from used components were achieved thanks to green technologies for energy.
The recovery of high value metallic elements in used Li-ion batteries was investigated. The approach consists in the understanding of leaching mechanism. For instance, the figure 1 shows that
the leaching step of Li-ion battery based on NMC materials can
contribute to the chemical separation of metal elements. Mn precipitates and can be recovered with very high purity whereas the
other elements (Ni, Co Li) are released in the solution from material.
The permanent magnets can contain up to 30 wt% of rare earths
(Nd, Pr, Dy, Sm…). The recovery of rare earths elements (REEs) was
studied from used magnets collected from waste of electrical and
electronic equipment. Amongst investigated routes, a patented
multistep process (fig.2) was developed allowing to recover
>85wt% of REEs. This process [2] consists in a demagnetization, a
chemical treatment under H2 in order to separate metal coating
from magnet bulk and a hydrometallurgical step to recover REEs
as metallic salt. Currently, this process is adapted for the extraction
of REEs from used Ni-MH batteries.
Most of works carried out have shown the efficiency of developed
processes to recover critical metals by hydrometallurgical routes.
The economic balance of global developed process is strongly linked to the efficiency of the upstream steps which consist in a dry
sorting process. The objective is to concentrate in a small fraction
the targeted elements. The next steps will focus on the one hand
Fig. 1: Dissolution kinetic of NMC material (H2SO4 1M, 30°C, S/L
= 4%)
Fig. 2: Multistep process for the REEs recovery from used
magnets collected in WEEE
TEAM
Richard Laucournet, Emmanuel Billy, Denis Vincent .
CONTACT
[email protected]
21
Des matériaux innovants au service des nouvelles énergies
Innovative materials for new energy
Nanoparticules de platine supportées
sur du carbone utilisées comme
catalyseurs pour les piles à combustible
de type PEMFC (image de microscopie
électronique à balayage).
Platinium nanoparticles on carbon
support used as catalysts in PEMFC
fuel cell (scanning electron microscopy
image).
Image du signal photoluminescent
d’une plaquette silicium (156x156
mm2) issue d’un tirage Czochralski.
L’échantillon a subi une étape de
traitement thermique, au cours de
laquelle l’oxygène contenu dans le
matériau a précipité. Les zones pour
lesquelles le signal photoluminescent
est faible correspondent aux régions
les plus riches en précipités d’oxygène.
Photoluminescence image of a
Czochralski-grown
silicon
wafer
(156x156 mm2) which experienced a
high temperature annealing step. The
low photoluminescence regions are
associated with oxygen precipitate-rich
regions.
Image MEB montrant la microstructure
d’un matériau de stockage d’hydrogène
SEM image showing the microstructure
of a hydrogen storage material
22
Énergies renouvelables
Renewable energies
SOMMAIRE / CONTENTS
Extended contribution on high temperature steam electrolysis to produce hydrogen................................................24
HIGHLIGHTS
q Solid–liquid equilibria in the quaternary system NaBH4-NaBO2–NaOH–H2O during hydrogen generation from
sodium borohydride hydrolysis......................................................................................................................................................................28
q Elaboration and characterization of anode catalysts in a PEM water electrolyzer..................................................................29
q Accurate predictions of H2O and CO2 co electrolysis outlet gas composition in solid oxide cells operated at high
temperatures ........................................................................................................................................................................................................30
q Improvement of the hydrogen storage capacity by mixing hydride and pressure storage ...............................................31
q Development of heat-exchanger reactors for CO2 methanation..................................................................................................32
q Volatile species release during torrefaction of biomass and its macromolecular constituents.........................................33
q On-line method of tar quantification by mass spectrometry during steam gasification of biomass..............................34
q Investigating the spatial distribution of Oxygen-related defects in Czochralski silicon ingots.........................................35
q In-situ quantitative chemical analysis of molten photovoltaic silicon for refining process monitoring.........................36
q Laser processed Interdigitated Back Contact Heterojunction solar cells...................................................................................37
q Highly-integrated, receiverless medium CPV module above 30% efficiency at a competitive cost................................38
q Laser-Patterned Organic PV Modules: High Geometric Fill Factor and Freedom of Design................................................39
q Ultra High Gas Barrier encapsulation films: low cost wet process and characterization......................................................40
«HABILITATIONS À DIRIGER DES RECHERCHES»
• Sébastien DUBOIS (DTS): On the effect of impurities on the
photovoltaic performances of crystalline silicon solar cells
• Capucine DUPONT (DTBH): Etude de la conversion thermochimique
des biomasses en vue d’améliorer l’adéquation ressources/procédé
(02/07/2014)
(20/03/2015)
THÈSES / PHD
2014
2015
• AICART Jérôme (DTBH): Modélisation et validation expérimentale d’un
co-électrolyseur de la vapeur d’eau et du dioxyde de carbone à haute température
(03/06/14)
• BOLDRIGHINI Patrick (DTS): Adhésifs améliorés pour l’encapsulation des modules
organiques photovoltaïques flexibles (30/06/15)
• ALTAMURA Giovanni (DTNM): Développement de cellules solaires à base de films
minces CZTSSe (01/09/14)
• BOUNAAS Lofti (DTS): Etude et intégration de matériaux avancés pour la
passivation face arrière de cellules photovoltaïques minces (30/06/14)
• De SAINT JEAN Myriam (DTBH): Étude énergétique et évaluation économique
d’une boucle de stockage - déstockage d’énergie électrique d’origine renouvelable
sur méthane de synthèse à l’aide d’un convertisseur électrochimique réversible SOEC
- SOFC (16/10/14)
• GALLIEN Benjamin (DTS): Contraintes thermomécaniques et dislocations dans les
lingots de silicium pour applications photovoltaïques (10/04/14)
• GIRAUD Stephen (DTS): Croissance de couches minces de Si pour applications
photovoltaïques par une technique d’épitaxie en phase liquide (01/12/14)
• LANTERNE Adeline (DTS): Etude, réalisation et caractérisation de dopages
phosphore et bore par implantation ionique pour une application aux cellules solaires
(04/11/14)
• LAURENT Julien (DTS): Amélioration du rendement matière lors de la cristallisation
de lingots de silicium photovoltaïque multi-cristallin (02/12/14)
• MABILLE Loic (DTS): Vers la compréhension des mécanismes de dégradation et de
vieillissement des assemblages photovoltaïques pour des applications sous haute
concentration (13/03/14)
• BOTTOIS Clément (DTS): Nanoparticules pour la réalisation de couches de transport de
trous appliquées au photovoltaïque organique (22/04/15)
• DINSENMEYER Rémi (DTBH): Étude des écoulements avec changement de phase :
application à l’évaporation directe dans les centrales solaires à concentration (09/01/15)
• JIMENEZ Lucia (DTBH): Comportement et stratégies de gestion des espèces inorganiques
dans une installation de gazéification de la biomasse (27/01/15)
• MARTINI Thibaut (DTNM): Etude de la formulation d’encre à base de précurseurs Cu,
Zn, Sn, S et du recuit de cristallisation pour le dépot hors vide de couches photovoltaïques
(31/03/15)
• PEDUZZI Emmanuela (DTBH): Biomass To Liquids: Thermo-Economic Analysis and MultiObjective Optimisation (29/01/2015)
• QUINCI Thomas (DTS): Étude d’un nouveau concept de cellule photovoltaïque simple
jonction à base d’hétérojonction de phosphure de gallium déposé en couche mince sur
substrat de silicium cristallin (02/07/2015)
• TIMERKAEVA Dilyara (DTS): Ingénierie des éléments légers dans le silicium pour
applications photovoltaïques (10/04/15)
• TURMAGAMBETOV Tleuzhan (DTS): De l’influence de contaminations par le cuivre et
le titane sur les performances photovoltaïques de cellules solaires au silicium cristallin
(29/05/15)
• SORIA Bruno (DTS): Etude des performances électriques annuelles de modules
photovoltaïques bifaces. Cas particulier modules bifaces intégrés en façade verticale
(21/10/14)
23
HIGH TEMPERATURE STEAM ELECTROLYSIS
TO PRODUCE HYDROGEN
THE PROJECT TEAM
Stephane Di Iorio, Denis Reynaud, Patrick Mayoussier, Bruno Oresic, Charlotte Bernard,
Lucile Bernadet, Philippe Szynal, Florence Lefebvre-Joud, Julie Mougin, Michel Planque,
Magali Reytier, Lionel Tallobre, Sarah Loraux, Guilhem Roux, Thomas Donnier-Marechal
Bertrand Morel, Marie Petitjean, Jerome Laurencin, Pascal Giroud,
Missing André Chatroux.
Different technologies of water electrolysis are being developed worldwide to produce hydrogen. Alkaline electrolysis is
the most mature, already commercialized and used historically to produce deuterium. It suffers of little flexibility contrarily
to PEM electrolysis which is also commercialized, offers rapid transient capabilities when coupled with renewable energies
but suffers on its side of a high cost due to the electrolyte membrane, the titanium micro-porous and the catalysts. Solid
Oxide electrolysis is less mature but offers potentially the highest efficiency thanks to the possibility to recover waste heat
and to the capability of operating reversibly, in fuel cell mode (SOFC) and in electrolysis mode (SOEC). For these reasons,
Liten has decided to develop this technology.
Solid oxide Fuel cells (SOFC) and Solid Oxide Electrolysis cells (SOEC) are electrochemical converters operating at “high
temperature” (700°C-900°C). They offer very attractive efficiencies without the use of noble-metal catalysts. Their main
bottleneck is the durability of cell and stack materials due to the fact that ceramics, glasses and metals are stacked for
being run at high temperatures despite very different expansion coefficients and under harsh conditions. Consequently,
the optimization of the ceramic cells and the careful design of SOEC stacks are critical issues for producing SOEC systems
with long lifetime, high performances and reasonable cost. A second key point is the scaling-up of SOEC system from
current few kW stacks to future MW production plants maintaining similar level of performances and durability in order to
reach competitive hydrogen production cost.
1 - LITEN APPROACH
Liten research on SOEC covers different scales from material to system with both experimental and modelling approach.
The first step consists in linking electrodes microstructure with electrochemical cell performances. This is done thanks to
a coupled characterisation approach based on electrochemical tests and advanced microstructure characterisation using
large experiments (ESRF). Quantified microstructure parameters (porosity, specific area, mean pore diameter…) are then
used as inputs in multi-physic models for analysing and understanding the cell electrochemical behaviour. Thermal, fluidic
electrochemical and mechanical behaviour of single repeat unit (SRU: cell and interconnects) can similarly be characterised
and simulated for being analysed and optimised (figure 1).
24
Fig. 1 Liten approach from material to electrochemical performance
In a second step, thermal and electrochemical behaviour of a full stack is evaluated thanks to previous SRU data. The heat
source and temperature maps are then simulated to achieve different working parameters allowing the optimisation of
the process and operating conditions.
2 - LITEN RESULTS
2.1 - MULTI-SCALE AND MULTI-PHYSIC MODELLING OF SOLID OXIDE ELECTROLYSIS CELL: FROM ELECTRODES MICROSTRUCTURE
CHARACTERISATION TO CELL PERFORMANCE AND DURABILITY PREDICTIONS
To improve the durability, significant attention is given to understanding and modelling of the global response of the
ceramic cell. A multi-scale and multi-physic modelling approach has been developed at Liten which originality lies in the
encompassing of coupled electrochemical, thermal and mechanical phenomena1. It also describes the basic relationships
between the electrodes operating mechanisms2 and the global efficiency of the system. Since key parameters of the
model can only be determined via three dimensional reconstructions, microstructures of the porous electrodes have been
investigated by X-ray nano-tomography experiments performed at the European Synchrotron radiation Facilities (ESRF,
beamline ID22)3.
Active functional layers as well as porous cell supports have been characterised with a high spatial resolution and a large
field of view obtained for the very first time (figure 2). Thanks to the numerical analysis of the 3D reconstructions, some
electrochemical and mechanical properties, which cannot be directly measured by other classical techniques, have been
determined. These properties, introduced in the model as input data, have allowed us to highlight the major role of the
electrode microstructure in the cell performances4. Similar approach on aged cells has allowed better understanding of
degradation mechanisms5. In the case of Ni-YSZ cermet electrodes, Ni coarsening can explain in a large extent the loss in
cell performances (figure 3). Similar work is being done on oxygen electrodes.
Fig. 2: Three dimensional
reconstruction of a ceramic
cell obtained by X-ray nanotomography at ESRF.
1 - Laurencin J. et al., J. Power Sources, 2008 ; Laurencin J. et al., J. Power Sources, 2011 ;
Aicart J. et al., Fuel Cells, 2014 ; Laurencin J. et al., J. Euro. Ceram. Soc., 2008 ; Laurencin J. et
al., J. Euro. Ceram. Soc., 2008 ; Delette G. et al., Eur. J. Mech. A, 2012.
2 - Lay-Grindler E. et al., Int. J. Hydrogen - Energy, 2013 ; Usseglio-Viretta F. et al., J. Power
Sources, 2014.
3 - Laurencin J. et al., J. Power Sources, 2012 ; Quey R. et al., Materials Characterization,
2013 ; Villanova J. et al., J. Power Sources, 2013 ; Villanova J. et al., J. Mater. Science, 2014.
4 - Delette G. et al., Inter. J. Hydrogen Energy, 2013.
25
Fig. 3: Simulated polarization curve
of a classical Ni-YSZ electrode
before and after operation. The
inserts (2D micrographs extracted
from the whole 3D reconstruction)
show extensive Ni agglomeration.
In addition to ceramic cell improvement, another way to increase the performance of SOEC is to increase the operating
pressure. Despite a negative thermodynamic effect of the pressure on the Open Circuit Voltage (OCV), original tests (figure
4 and figure 5) and simulation models on single cells have highlighted that the limiting current density can be shifted
towards higher steam conversion rates by increasing the operating pressure6. The hydrogen production can be improved
under pressure at the thermoneutral voltage 1.3 V and at high steam conversion rate, which is a target for the application.
The model describes accurately the experimentally observed pressure phenomena. It appears that the improvement of
the limiting current seems due to a decrease of the concentration overpotential at the cathode. This could be explained
by a better diffusion in the porous cermet under pressure. At 1.3 V and above 5 bar, the performances are sufficiently
improved by pressure to allow working with stronger and finer microstructure with cheaper manufacturing processes.
Fig. 4: experimental device dedicated to
SOEC tests at 800 °C – 30 bar
Fig. 5: pressure effect on single cell electrolysis performances with innovative
sealing solutions (T=800°C, 35/58.5/6.5 vol.% of N2/H2O/H2 at the cathode side,
air at the anode side
Experimental studies are being run under pressure with lower temperature to determine the impact on the activation
overpotentials, as well as the performances of co-electrolysis of steam and CO2 for power to gas applications.
2.2 - FROM CELL TO STACK: SEALING IS ONE OF THE TOUGHEST CHALLENGE FOR HIGH TEMPERATURE ELECTROLYSIS AND FUEL CELL
TECHNOLOGY
A SOEC stack is composed of alternating ceramic based electrochemical cells and metallic interconnects. Due to thermal
cycling between room temperature and high operating temperature, complete sealing is tricky but essential to avoid
potential dangerous hydrogen and oxygen leaks at high pressure and high temperature. So sealing solutions are still
one of the toughest challenges for SOEC and SOFC planar stacks. This is mainly due to the use of brittle ceramic cells
as electrochemical converters surrounded by stiff metallic materials as interconnects for ensuring electrical contact and
gas management around the cells. Even with appropriate stack design, the unavoidable thermal expansion mismatch
(TEC) between cell, interconnect and sealing associated with the required high operation temperature (700 – 800°C)
leads to tightness loss, efficiency decrease, hot spots and breakage. Glass seals constitute a reference solution for this
technology even if they have to be protected from pressure differentials above few hundreds millibars. On the other hand,
high temperature metallic seals can withstand high levels of pressure but they have to be specifically designed to be soft
enough to run with low load level and thermal expansion mismatch. Moreover, they should present electrical insulation
solutions to avoid any cell short-circuit.
Specific sealing solutions have been developed in CEA-Liten using iterative design, modelling and dedicated testing
approach. First a secure glass based solution integrating a mica foil was successfully introduced in the stack design for
atmospheric pressure running7 allowing reaching one of the best high temperature electrolysis performances in the world,
fulfilling targeted cost11. It is also important to validate the previous solutions on real size stack (geometry and number of
26
cell) to evaluate the behaviour discrepancy between central and external cells due to thermal gradient witch could lower
performances and durability with respect single cell.
Secondly, in order to design new well-adapted metallic seals dedicated to pressurized operation, an original computational
model has been developed in collaboration with ENSMP that links the local mechanical fields, easily reached by finite
element calculations, to the leakage rate by taking into account the strain rate dependence of the metallic seal materials8.
This innovative approach on metallic seals has led to a new patented seal design in collaboration with the Technetics
Company and opens new possibilities for pressurized electrolysis operation9. In particular, high efficiency gains are
expected at the system level for hydrogen production (figures 4 and 5).
Performances achieved at stack level (25 cells of 100 cm2) are the first goal reached by Liten at the best level of the State
of the art (figure 6)10 11 12 13.
(1) Eifer + Topsoe (2012) 25 cells
A. Brisse et al, Energy Procedia, 29,53 (2012)
(2) DTU + Topsoe (2013) 10 cells
M. Chen et al, Fuel Cells, 13 (4) 638-645 (2013)
(3) SofcPower (2013) 6 cells
S. Diethelm et al, Fuel Cells, 13 (4) 631-638 (2013)
Fig. 6: Liten SOEC stack performances at 800 °C
and comparison with other results
2.3 - SYSTEM INTEGRATION
The last level of integration has been the design and operation of a complete SOEC system called SYDNEY (figure 7).
The purpose of this system is to optimise the use of the heat available upon operation in order to lower the electricity
consumption of the stack and BOP. An optimised thermal insulation and dedicated heat exchangers allow the recuperation
of the exhaust heat for preheating of the input gases (figure 8). By assuming a heat source at 150°C to produce the steam
from liquid water, the SYDNEY system has a hydrogen production rate of 1.2 Nm3/h with an electric yield of 3.5 kWh/Nm14.
The demonstration has been done that there is no need of high temperature heat source to reach high level of efficiencies.
3 - CONCLUSION AND PERSPECTIVES
Fig. 7: 25 cell stack in the SYDNEY system
Fig. 8: Evolution of the electric consumption of the heating system during hydrogen
production
This technology also allows the use of carbon
species. Therefore, it offers the possibility of
producing electricity in a fuel cell mode fed
by hydrogen or directly by methane (natural
gas) or biogas. It also allows electrolyzing a
mixture of steam and CO2 to obtain a syngas
(H2 + CO), first elements for other synthetic fuels
production (methane, methanol, DME, diesel ...).
Moreover, these downstream catalytic reactions
also provide heat, which can be used to produce
the steam for the SOEC, leading to a very high
efficiency process.
The flexibility of this technology can then provide
useful connections between electrical, natural
gas and heat grids. It gives a perspective of low
carbon footprint electricity storage associated
with a way of CO2 reuse. Such operation
conditions are being studied at Liten.
5 - Lay-Grindler E. et al., J. Power Sources, 2014.
6 - L. Bernadet et al, Inter. J. Hydrogen Energy, 40 (38), 2015, 12918-12928
7 - Mougin J. et al., Fuel Cells, 2013 ; Mougin J. et al., Energy Procedia, 2012.
8 - Peigat L., PhD thesis, 2012 ; Peigat L. et al., Int. J. Hydrogen Energy, 2014 ; Berard P.
et al., Mat. Sci. Eng. A, 2011.
9 - Reytier M. et al., ECS Transactions, 2011. 35 (3) 2617-2624
10 - M. Reytier et al, ECS trans, 57(1) 3151-3160 (2013)
11 - M. Reytier et al, awarded in WHEC conference (2014), Int. J. Hydrogen Energy 40
(35), 2015, 11370-11377
12 - J. Mougin et al, Fuel Cells, 13 (4) 623-630 (2013)
13 - J. Mougin et al, Energy Procedia, 29, 445 (2012)
14 - A. Chatroux et al ECS Transactions, 2015, 68 (1) 3519-3526
27
Solid–liquid equilibria in the quaternary system NaBH4NaBO2-NaOH-H2O during hydrogen generation from sodium
borohydride hydrolysis
CONTEXT
Hydrogen generation by hydrolysis of borohydrides is a promising
technology for portable fuel cells. Particularly, sodium borohydride (NaBH4) presents many advantages for that purpose. For
example, NaBH4 solutions are non–flammable thus yielding safe
processes; the rate of H2 generation is easily controlled by a catalyst; reaction products are environmentally friendly and finally the
reaction by–product (NaBO2.yH2O, hydrated sodium borate) can
be recycled.
APPROACH
To increase the energy density of a hydrogen generator system,
the NaBH4 concentration has to be maximized; nevertheless,
NaBO2 crystallization must be avoided. Sodium borohydride
decomposes spontaneously in water to produce hydrogen and
hydrated sodium borate compounds according to the reaction :
NaBH4+(2+y)H2O => 4H2+NaBO2·yH2O
Sodium hydroxide is added to the solution to limit this self-decomposition, thus stabilizing the system. Therefore, the delimitation of
the homogeneous liquid domain in the quaternary phase diagram
system NaBH4–NaBO2–NaOH–H2O is a crucial isssue. Indeed, such
a diagram is the main basis for the understanding of the evolution
of the solution during the hydrolysis reaction in the H2 generator.
CONCLUSIONS
This work contributed to a better understanding of the solubility
limit of the quaternary system NaBH4–NaBO2–NaOH–H2O during
the lifetime of the Hydrogen generator.
This work was carried out in collaboration with Christelle Goutaudier, Richard Tenu and Jean Jacques Counioux from Claude Bernard Lyon 1 University.
References
[1] Lifetime analysis of a hydrogen generator by hydrolysis of sodium
borohydride
T. Vilarinho-Franco et al Energy Procedia, 2013
[2] Solid–Liquid Equilibria in the ternary system NaBO2–NaOH–H2O
T. Vilarinho-Franco et al Fluid Phase Equilibria (2013)
RESULTS
A substantial literature review and critical analysis of three
aqueous boundary binary systems (NaBO2–H2O, NaBH4–H2O and
NaOH–H2O), and two aqueous boundary ternary systems (NaBH4–
NaOH–H2O : 0% of hydrolysis conversion and NaBO2–NaOH–H2O:
100% of conversion) was necessary and mandatory to establish
the solid–liquid equilibria in the quaternary system.
The experimental techniques used concerned solubility measurements and solid phase characterization by powder X-ray crystallography.
Thus, the isothermal for the NaBO2–NaOH–H2O ternary system at
50, 25 and 10 °C have been redetermined experimentally under
atmospheric pressure. Numerous inconsistencies about the solid
phases have been evidenced and two different double salts have
been highlighted. The determination of solid phases by XRD and
XR crystallography, specifically the ones of the triphasic regions,
has given confirmation that both double salts present a narrow
two-phase region. The Na2BO2(OH) has been observed only at
50 °C. After a systematic investigation about the solid phases of
this ternary system, the double salt Na3[(B(OH)4)2OH] has been discovered at 10 °C. All crystallographic data were communicated to
the Cambridge Crystallographic Data Center (CCDC 924935).
Fig. 1: Isotherm at 50 °C
of the ternary system
NaBO2–NaOH–H2O
Fig. 2: Isoplethic section
for a constant NaOH
composition of the quaternary system at atm
pressure and 20°C.
TEAM
Tatiana Vilarinho-Franco, Jérome Delmas, Isabelle Rougeaux, Philippe Capron
CONTACT
[email protected]
28
Elaboration and characterization of anode catalysts
in a PEM water electrolyzer
CONTEXT
The world energy demand has been continuously increasing since
years 1850. Fossil energy sources are not sustainable anymore.
One of the green solutions is the use of hydrogen as fuel in energy
conversion systems like fuel cells. Water electrolysis represents
one of the best means for the sustainable hydrogen production.
But global costs and performances have to be optimized.
APPROACH
It is well known that the cathodic reaction in water electrolyzer,
catalyzed by platinum nanoparticles, occurs easily with low over
potential, while the anodic reaction so called oxygen evolution
reaction (OER) requires largest overpotential. Several studies have
shown that the most efficient electro catalysts are noble metal
oxides electrodes. Ruthenium oxide (RuO2) is the most active catalyst but its activity is not sufficient for long term utilization due
to the increase of ruthenium oxidation state. Hydrolysis method
of synthesis was tested [1] at the University of Poitiers (IC2MP) and
characterized in complete cell at Liten. Iridium oxide is stable and
has also interesting catalytic properties. It may be inserted in the
RuO2 oxide to stabilize it. Consequently RuO2-IrO2 mixed nanocatalysts were synthesized and characterized [2]. In order to reduce
costs and stabilize RuO2, other elements like tin or titanium could
also be inserted [3]. Main results of results achieved with the University of Poitiers are reported here.
This work was partly carried out in the frame of national ANR programs (AIRELLES and AITOILES) and acknowledgments are due for
additional industrial support.
References
[1] Audichon, T., Mayousse, E., Napporn, T.W., Morais, C., Comminges,
C., Kokoh, K.B. (2014) ELECTROCHIMICA ACTA - Volume: 132 - Pages:
284-291
[2] Audichon, T., Mayousse, E., Morisset, S., Morais, C., Comminges,
C., Napporn, T.W., Kokoh, K.B. - (2015) INTERNATIONAL JOURNAL OF
HYDROGEN ENERGY Volume: 39 Issue: 30 Pages: 16785-16796
[3] Kokoh, K.B., Mayousse, E., Napporn, T.W. , Servat, K., Guillet, N.,
Soyez, E., Grosjean, A., Rakotondrainibé, A., Paul-Joseph, J. (2014)
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY Volume: 39 - Issue:
5 - Pages: 1924-1931
Fig. 1: Polarization curves
obtained in a 25 cm2
single electrolyzer cell
at 60 °C and 80 °C and
atmospheric pressure
without ohmic resistance
correction for the RuO2
anode catalyst [1] (1 mg
cm-2).
RESULTS
Ruthenium oxide electrocatalysts were synthesized using hydrolysis in ethanol medium (co-precipitation).
Physical, physicochemical and electrochemical characterizations
of the materials were performed. MEA were prepared and tested
at CEA. Polarization curves obtained with a RuO2 anode (1 mg cm-2)
in a 25 cm² single electrolyzer cell at 60 °C and 80 °C under atmospheric pressure are reported in Fig.1. Performances are very interesting with 1.682 V at 1 A cm-2 at 80 °C (around 4 kWh Nm-3(H2)).
However, as shown in Fig.2, the degradation of the performance
is important with an increase of the cell voltage of 330 µV h-1 at 1
A cm-2. Addition of a small amount of iridium in RuO2 (10 wt. % of
iridium) increased significantly both performance and stability of
the catalyst[2] . Indeed, as plotted in Fig.2, the degradation rate at 1
A cm-2 for Ru0.9Ir0.1O2 is reduced to 90 µV h-1.
Fig. 2: Durability test at
1 A cm-2 and 2 A cm-2
for the Ru0.9Ir0.1O2
and RuO2 catalyst at
80 °C and atmospheric
pressure [2].
The synthesis method was efficient to provide large amount of
pure RuO2 or mixed RuO2-IrO2 oxides with high surface area. The
Ru0.9Ir0.1O2 catalyst is a promising material as it shows a satisfactory performance profile under realistic operating conditions and
is more stable than pure RuO2 reported in previous work[1]. Further
improvement can be still efficient by adding a third “diluting” metal
for decreasing the cost of the electrolyzer as previously tested [3].
TEAM
Frédéric Fouda-Onana, Nicolas Guillet, Eric Mayousse
CONTACT
[email protected]
29
Accurate predictions of H2O and CO2 co‑electrolysis
outlet gas composition in solid oxide cells operated at
high temperatures
CONTEXT
Thanks to a highly efficient production of cost effective hydrogen,
high temperature steam electrolysis has gained more and more
interest in recent years. An originality of the technology is that it
offers the possibility to co-electrolyze steam and carbon dioxide,
allowing the conversion of CO2 into syngas composed primarily
of H2 and CO. This mixture can be further transformed by chemical processes into methane or liquid fuels for both stationary and
transport applications. By an adjustment of the H2O/CO2 ratio at
the inlet, the H2/CO ratio at the outlet can be fine-tuned to fit with
the downstream process. However, the operating mechanisms of
co-electrolysis are still unclear and have to be identified to ensure
a better understanding and prediction of the process.
APPROACH
In the frame of a multi-scale and multi-physic approach developed at the laboratory, a former steam electrolysis model [1] has
been adapted for co-electrolysis. The model has been modified by
introducing a “surface ratio” that takes into account the competition between the direct reduction of steam and carbon dioxide in
the cathode [2]. Once validated on dedicated experiments [3], simulations have been carried out to investigate the main limitations
and possibilities of co-electrolysis [4].
The experimental and modelling approach has to be extended to
investigate the cell durability in co-electrolysis mode. For this purpose, the elemental phenomena in terms of reactive and transport
mechanisms have to be introduced in the modelling framework.
Work in collaboration with Pr. L. Dessemond (LEPMI). Partially supported by EIT through KIC InnoEnergy (Minerve project), and the
European Union’s FCH-JU Programme (Sophia project).
References
[1] J. Laurencin, D. Kane, G. Delette, J. Deseure, F. Lefebvre-Joud, J.
Power Sources, 196 (2011) 2080–2093.
[2] J. Aicart, J. Laurencin, M. Petitjean, L. Dessemond, Fuel Cells, 14
(2014) 430-447.
[3] J. Aicart, M. Petitjean, J. Laurencin, L. Tallobre, L. Dessemond, Int. J.
Hydrogen Energy, 40 (2015) 3134-3148.
[4] J. Aicart, PhD thesis, University of Grenoble, 2014.
RESULTS
Cell voltages and outlet gas compositions have been measured at
different cell current densities. Highly accurate correlations have
been found between the model outputs and the experimental
gas measurements in terms of performances and outlet gas compositions (Fig. 1). These results have allowed validating the model
assumption stipulating that H2O and CO2 co-electrolysis can be
described through the “surface ratio” parameter depending on
the local partial pressures calculated in the vicinity of the electro-catalyst particles. Once the model validated, a set of simulation has been carried out to investigate the co-electrolysis operating mechanisms in terms of local current densities, gas molar
fractions, etc…. The analysis has revealed that CO is mainly produced by the direct CO2 reduction whereas the role of the reverse
water gas shift reaction in the electrode remains negligible under
high polarisation. Operating maps have also been computed
to identify the influence of the main parameters on cell performances, temperatures, gas outlet composition, etc… (Fig. 2). Such
approach has allowed demonstrating the technological relevance
of co-electrolysis.
Fig. 1: Gas chromatography analyses and
simulated outlet compositions at T=800°C (after
condensation of H2O).
Fig. 2: Ratio H2/CO at
the cell outlet plotted
as function of the
cell voltage and the
inlet cathodic gas flux
(T=800°C)
TEAM
Jérôme Aicart, Marie Petitjean, Jérôme Laurencin
CONTACT
30
Improvement of the hydrogen storage capacity by
mixing hydride and pressure storage
CONTEXT
Higher volume and mass capacities have to be reached for
hydrogen storage systems for mobile applications. Prototypes
from Japan or US used a type III composite high pressure vessel
(metallic liner) filled with metal hydride powder that can store
hydrogen reversibly in order to increase the storage capacity.
This type of hybrid system showed promising capacity for heavy
mobile application (truck, tractors…). But the metal hydrides and
the heat exchanger needed to perform fast absorption are still too
expensive
APPROACH
Acknowledgments are due to DMAT at CEA Ripault. This work is
supported by a Carnot project (RESHYD).
References
[1] Patent : E.N.1462908, Réservoir de stockage d’hydrogène à
hydrures métalliques offrant un chargement en hydrogène amélioré
[2] Oral communication: GdR HYSPàC Corsica, Oct 2015
[3] Oral communication : Development of a type IV hybrid tank based
on compressed hydrogen and metal hydride for heavy vehicles
application, E MRS 2015 Fall, Poland, Sept 2015
A 37l type IV composite vessel (polymer liner) developed by CEA Le
Ripault has been combined with the hydride technology of CEA/
Liten in Grenoble. A new lighter heat management system with
metal hydrides has been developed to be inserted in the polymer
liner during the manufacturing process. A numerical model of the
H2 tank filling process has been implemented to validate the efficiency of the new heat exchanger. Then a research on a more efficient and low cost hydride material has been conducted.
RESULTS
A model based on the data from CEA Le Ripault showed that
the mass of hydride has to be maximized to reach the maximum
volume storage capacity whereas a pressure between 200 and 350
bars depending on the properties of the hydrides – seems to be
optimal for hybridization.
Another original idea was to use Hydrogen itself as thermal fluid:
the hydrogen circulates in a loop comprising the tank, a circulator and a 2nd heat exchanger water/H2. The H2 flowing through
the tank [1] is partly absorbed and stored, and the rest takes the
heat of exothermic reaction of absorption away to the 2ndary heat
exchanger (fig.1). The numerical simulation of such a cooling loop
has shown that 90% of the full capacity can be reached in 5 min [2].
A new hydride container adapted to the cooling system has been
designed and successfully implemented in the rotomolding and
winding process of the tank. Concerning the hydride material,
the synthesis of new alloys based on body centred cubic (BCC)
structure has been carried out by substituting vanadium (expensive) with molybdenum (Ti5V70M05Cr20) or iron. If Mo increases the
pressure of absorption, iron substitution needs to be combined
with activation to compensate the decrease in absorption kinetics.
CEA developed and tested Zr based catalysts [3] but reducing the
absorption pressure (fig.2). These catalysts are nevertheless a promising way to be further explored.
The hydrogen thermal loop is a promising technology even if high
pressure circulators have to be developed. Further researches
have to focus on cheaper and lighter hydrides which are necessary
to take more advantage of pressure-hydride systems.
Fig. 1: Scheme of the thermal loop to cool the hydride absorbing the
H2. The thermal fluid is H2 itself.
Fig. 2: Effect of the substitution of V by Mo and Fe with a catalyst on
the H2 absorption pressure plateau
TEAM
Albin Chaise, Vasile Iosub, Olivier Gillia
CONTACT
[email protected], [email protected],
[email protected]
31
Development of heat-exchanger reactors for CO2
methanation
CONTEXT
While the Renewable Energy share is increasing in Europe inducing surplus assessed in France beyond 10 TWh by 2030 and
50 TWh by 2050 [1], its intermittency and uneven distribution
requires efficient conversion system and large storage capacity.
The Power-to-Gas concept, where H2 produced by electrolysis is
combined in catalytic reactors with captured CO2 to produce synthetic methane (SNG) is gaining interest. The use of the huge storage capacity of natural gas grids offers nearly 130TWh per year of
storage capacity. The catalytic methanation reactor at the core of
a Power to Gas system has to ensure high CO2 conversion, selectivity, flexibility and durability at a competitive cost [2], [3].
APPROACH
The main challenges arising in the CO2 methanation are related to
the high exothermicity of the balanced reaction (169 kJ/mol). An
uncontrolled temperature of the reaction leads to a fast catalyst
deactivation and a reduced CO2 conversion. An innovative compact heat-exchanger reactor for CO2 conversion into methane has
been designed, manufactured and tested.
This work was carried out in the frame of the CARNOT Energie du
futur program (SYDGAHR). Part of this work was performed in the
frame of the PhD of Julien Ducamp in collaboration with Strasbourg University.
References
[1] ADEME/GRDF/GRTgaz report (2014) Etude portant sur l’hydrogène
et la méthanation comme procédé de valorisation de l’électricité
excédentaire.
[2] Pierre Baurens, et al. (2015). Le stockage d’énergie, Conversion
d’énergie en gaz combustible. Paris: Presse des Mines. Chapitre 2 : La
filière Power to SNG
[3] Alain Bengaouer, et al. (2015). Le stockage d’énergie, Conversion
d’énergie en gaz combustible. Paris: Presse des Mines. Chapitre 6 :
Méthanation de CO2
RESULTS
The reactor architecture is based on layers of millistructured fixedbed channels. Layers of cooling channels are inserted between
each reactive layer. Reactor plates of SS-316L are assembled
by diffusion bonding by Hot Isostatic Pressing allowing a high
mechanical strength and low channel deformations (Fig. 1). Reactor performances have been evaluated with an industrial catalyst in stoichiometric conditions. CO2 conversion up to 95% was
obtained at the pressure of 2.5 bar and the impact of GHSV (reactant flow rate divided by the reactor volume) variations from 4000
to 10000 h-1 is limited (Fig. 2). Both analytic (100 hours) and reactor
(700 hours) ageing tests followed by post-mortem catalyst characterization confirmed the influence of maximum temperature on
the deactivation kinetics of the catalyst.
The design and upscaling to larger scale, although favoured by
the modular structure of the reactor, requires the understanding
and modelling of reaction kinetics, heat transfer and mass transfer
within the channels. This has been done by identifying individual
contributions (intrinsic kinetics, thermal conductivity of the bed)
with analytical experiments, derivation of correlations, implementation in a multi-dimensional heterogeneous model and adjustment with experimental results. In-situ sampling of the product
gas in reactive channel allows the identification of the axial evolution of gas composition, conversion, selectivity and comparison
with the model (Fig. 3).
Fig. 1: Core of the reactor-exchanger
Fig. 2: Impact of GSHV on
CO2 conversion at 2.5 bar
and 290°C (blue curve)
compared to thermodynamic equilibrium (red
curve)
Fig. 3: Conversion and
selectivity, comparison of
model and experiment at
4 bar and 265°C
Industrialization and upscaling of this reactor-exchanger technology is underway in the frame of the common laboratory “LACRE”
established with ATMOSTAT. It will be validated in two Power-toSNG demonstration projects: CO2-SNG in Poland at the scale of
5Nm3/h of SNG (eq. 100kWe) (Kic-InnoEnergy, led by TAURON)
and Jupiter 1000 at the scale of 25Nm3/h of SNG (eq. 500kWe) in
France, led by GRTgaz.
TEAM
Laurent Bedel, Pierre Baurens, Alain Bengaouer, Julien
Cigna, Julien Ducamp, Isabelle Moro
CONTACT
[email protected], alain.bengaouer @cea.fr
32
Volatile species release during torrefaction of
biomass and its macromolecular constituents
CONTEXT
Torrefaction is a mild pyrolysis of biomass (typically between 250°C
and 300°C during a few tens of minutes). It mainly produces a solid
energy carrier suitable for use as fuel in gasification or combustion.
Condensable species such as acids and phenols are co-products
seen as problematic compounds and are usually burnt. However,
they could also be a source of “green” chemicals. This requires
being able to predict the condensable species released versus
operating conditions and feedstock. At the moment, torrefaction
mechanisms are poorly known and the few existing models are
feedstock-specific. Moreover, they are only focused on solid mass
loss and no information is available on the kinetics of volatile – gas
and condensable species release.
This work was carried out in the frame of Timothée Nocquet’s PhD
thesis, in partnership with CIRAD and Ecole des Mines d’Albi.
References
[1] Nocquet, T., Dupont, C., Commandre, JM., Grateau, M., Thiéry, S.,
Nguyen, MH., Salvador, S. 2014 Energy, 72, 180-187.
[2] Nocquet, T., Dupont, C., Commandre, JM., Grateau, M., Thiéry, S.,
Nguyen, MH., Salvador, S. 2014 Energy, 72, 188-194.
APPROACH
The objective of this study is to develop a modelling approach of
biomass torrefaction able to predict both solid and volatile yields
versus operating conditions and feedstock. For this purpose experiments have been carried out on beechwood and its macromolecular constituents – cellulose, lignin and hemicelluloses.
RESULTS
Data were obtained through torrefaction tests in a thermobalance
and in the lab-scale device TORNADE (Fig. 1). The mass balance
was very satisfactory with values between 99 and 104%. The main
volatile species measured were water, formaldehyde, acetic acid
and CO2. Smaller amounts of methanol, CO, formic acid and furfural were also quantified. Each constituent did not produce all
species. Beech torrefaction could be described by the summative
contribution of its constituents up to 250°C (Fig. 2). At higher temperatures, tests on mixtures of the constituents showed interactions between cellulose and the two other constituents.
On the basis of these results, a torrefaction model was developed
and validated on tests with beech at various temperatures. This
model consists in the superposition of “sub-models” describing
the torrefaction of each constituent. The interactions between
constituents are described through an empirical factor related to
cellulose rate decomposition.
Fig. 1: Scheme of the TORNADE device
This study was the first attempt of prediction of both solid and
volatile yields during torrefaction versus operating conditions and
feedstock. Work is planned to understand interactions origin, to
validate the model on other biomasses and to extend its predictability to species of interest for chemical industry.
Fig. 2: Comparison of solid mass loss versus time between beech and
prediction from the summative contribution of each constituent
TEAM
Capucine Dupont, Timothée Nocquet, Elvira Rodriguez,
Maria Gonzalez-Martinez, Maguelone Grateau, Sébastien Thiéry
CONTACT
[email protected]
33
On-line method of tar quantification by mass spectrometry
during steam gasification of biomass
CONTEXT
Contaminants as tar like BTX (Benzene, Toluene, Xylene) and PAH
(Polycyclic Aromatic Hydrocarbons), which are present in the gas
obtained from biomass gasification, may induce saturation of the
gas cleaning systems or degradation of the catalysts used for further fuel synthesis. They are important to be measured on-line in
order to detect rapidly their variations for process control. Furthermore, after gas cleaning systems, they are at a trace level, i.e. ppbv
level, and difficult to measure.
References
Defoort F., Thiery S., Ravel S. “A promising new on-line method of tar
quantification by mass spectrometry during steam gasification of
biomass”
(2014) BIOMASS AND BIOENERGY 65, pp. 64-71
APPROACH
Soft ionization mass spectrometry based on the Ion Molecule
Reaction Mass Spectrometry (IMR-MS) principle (Figure1) is a
very sensitive on-line method. Almost no overlapping spectra can
damage the interpretation of the detected results due to the low
energy of ionization induced by Hg, Xe or Kr. IMR-MS has been
used to measure concentrated (> 1 ppmv) and trace (< 1 ppmv)
tars at the exhaust of the CEA-Grenoble high temperature bubbling fluidized bed (LFHT) and tar cracker (PEGASE) respectively.
To give confidence in the measurements, the approach was to
compare IMR-MS results with other measurements methods such
as microgas-chromatography (µGC-TCD) for benzene and toluene,
Tar Protocol (TP) or Solid Phase Adsorption (SPA) technique, both
technics used for BTX and PAH.
Fig. 1: IMR-MS principle
RESULTS
A very good agreement is observed for benzene and toluene
between the four analytical methods (IMR-MS, µGC-TCD, TP and
SPA). Results for benzene at the exhaust of the Fluidized bed for
high concentration (>1 ppmv) and tar cracker for low concentration (<1 ppmv) are shown in Figure 2a and 2b respectively. Results
are in the 15% relative uncertainties range.
Other results with Naphthalene, PAH and thiophene (C4H4S) are
also comparable to TP and SPA results.
a- exhaust Fluidized bed (>1 ppmv)
With the IMR-MS method, it is possible to measure on-line and
successfully, concentrated or very low tar amounts, in a real syngas at the output of two pilot scale facilities.
The comparison with other tar measurement methods such as
µGC-TCD, the Tar Protocol and SPA allows a good confidence in
this new promising method.
Some improvements should be made, such as the calibration of
the IMR-MS apparatus with PAHs and thiophene to have a better
precision in the measurement.
Work was partially funded by the French National Research Agency
(ANR) thanks to AMAZON project.
b- exhaust tar cracker (<1 ppmv)
Fig. 2: Benzene measured by IMR-MS, µGC-TCD, TP and SPA in
wet and dry gas sampling
TEAM
Françoise Defoort, Sébastien Thiery, Serge Ravel
CONTACT
[email protected]
34
Investigating the spatial distribution of Oxygenrelated defects in Czochralski silicon ingots
CONTEXT
Oxygen (O)-related defects such as precipitates, thermal donors
(TD) or boron-oxygen (B-O) complexes can strongly limit the
conversion efficiencies (η) of monocrystalline Czochralski (Cz)
silicon (Si) solar cells. The foundations of a new technique (the
so-called Oxymap technique actually developed with AET TECHNOLOGIES) to map the interstitial O concentration ([Oi]), which
is the common brick to the formation of all these defects, were
laid in previous contributions from the authors [1]. This technique
relies on resistivity measurements before and after the thermal
activation of O clusters which modify the charge carrier density.
Recently this technique was extended to high resolution mappings of the as-grown TD concentration and the prediction of the
relative η losses (Δη) under illumination due to the B-O complexes
activation [2]. These recent improvements were used in order to
investigate the distribution of [Oi] and to assess the impact of its
related defects on the quality of industrial-like Cz ingots.
PARTNERSHIP
Acknowledgments are due to DMAT at CEA Ripault. This work is
supported by a Carnot project (RESHYD).
References
[1] J. Veirman, S. Dubois, N. Enjalbert, J-P. Garandet and M. Lemiti,
Energy Procedia. 8, 41 (2011).
[2]B. Martel et al, 42nd IEEE PVSC, New Orleans, USA (2015)
APPROACH
A Cz ingot was grown from a 90 kg Si feedstock using standard pulling conditions and cut into wafers. The particularity of this ingot is
that most of the Si could be crystallized. This offered the opportunity to study the defects distribution over an exceptionally broad
solidified fraction (up to 99%). Twenty five wafers were regularly
sampled along the ingot’s height and tested with Oxymap. From
these data the distribution of the O-related defects over the height
and the diameter of the ingot could be reconstructed.
Fig. 1: Longitudinal (top), radial (right) and 2D [Oi] variations at ingot
level. The radial profiles are shown for solidified fractions of 11 and
94.3 %.
RESULTS
Figure 1 shows the [Oi] distribution in the Cz ingot. This graph
reflects the defect distributions in a longitudinal slice going
through the ingot rotation axis which, owing to the axisymmetric
configuration of a Cz puller, provides information throughout the
entire ingot. Note that such a mapping is hardly achievable with
other existing techniques. The [Oi] radial distribution features a
bell-like shape. Furthermore the higher the solidified fraction, the
larger the [Oi] drop at the perimeter of the ingot. This observation
a priori unrelated to O out-diffusion from solid Si, could be due to
a changing configuration of the convection patterns during the
growth of the ingot and therefore brings new insights into the
mechanisms behind the O incorporation from the Si melt. Figure
2 presents the predicted Δη values. Even if they are rather tight,
these η losses are significant and can dramatically alter the quality
of the cell matching before the module fabrication, when carried
out only on the basis of initial (before light soaking) η.
CONCLUSIONS
The newly developed Oxymap technique was successfully applied
for mapping the distribution of the main O-related defects over
the height of a Cz ingot.
Fig. 2: Variation along the ingot’s height of the predicted relative
efficiency losses due to the B-O complexes activation. The line is only a
guide to the eyes.
TEAM
Benoit Martel, Jordi Veirman, Miguel Cascant, Mathieu
Tomassini, Nicolas Enjalbert, Jacky Stadler, Emmanuelle
Fayard, Mickael Albaric, Sébastien Dubois
CONTACT
[email protected]
35
In-situ quantitative chemical analysis of molten photovoltaic
silicon for refining process monitoring
CONTEXT
In recent PV Si material developments, the borrowing from metallurgical purification processes opened the route of the upgraded
metallurgical grade silicon (UMG-Si): a silicon material with a purity
level consistent with photovoltaic applications. The efficiency of
such purification treatments is determined from the evolution
of the impurities concentration in the melt during the process.
Usually, standard analytical techniques such as Glow Discharge
Mass Spectrometry (GDMS) or Inductive Coupled Plasma Optical
Emission Spectroscopy or Mass Spectrometry (ICP-OES/MS), are
performed on samples taken from the melt during the treatment
process. However, this off-line analysis is time consuming. Thus for
a significantly better responsiveness on the processes, there is a
strong industrial demand for the in-line monitoring of these process kinetics.
The LIBS based analytical method is now available to be used for
in-line monitoring of silicon purification processes such as plasma
treatment or directional solidification.
The LIBS equipment used in this work was developed in
partnership with the Canadian National Research Council.
References
[1] L. Patatut et al., Proceedings 42th IEEE-PVSC, 2015.
[2] L. Patatut et al., Best poster award, 8th CSSC, 2015.
APPROACH
The Laser Induced Breakdown Spectroscopy (LIBS) is ultimately
the most likely technique satisfying such application as it allows
fast and remote quantifying of a wide variety of elements without sampling. This chemical analysis consists in performing
in-situ laser ablation of the melt followed by the ionization of the
vaporized material generating a micro-plasma. The optical analysis of the emission due to the plasma de-excitation after the laser
pulse affords an emission spectrum with spectral lines characteristic of the impurities nature (wavelength) and of their concentration (intensity) in the melt. The CEA-Liten developed a technique
based on inert gas bubbling through a pipe inserted in the melt
to ensure a fresh sampling and renewed surface for each analysis
with a composition truly melt representative regardless of possible surface oxidation and composition inhomogeneity.
Fig. 1: Calibration
graphs for B and Al
(ppmw: weight ppm)
RESULTS
First, the signal acquisition has been optimized to overcome
experimental fluctuations due to bubbles movement in the melt.
Second, experimental parameters affecting plasma physics such
as laser energy and bubbling gas have been chosen to maximize
signal sensitivity and instrumental limits. Third, B and Al calibration curves have been established (Fig. 1). The selected conditions
allow a reliable measurement over time (Relative Standard Deviation < 10 %), with a ppm level of detection limit.
Finally various amounts of impurities have been blindly added to
a silicon melt. Figure 2 shows the results of LIBS measurements
and sampling for ex-situ ICP-OES analyses. The relative uncertainty
level that is below 15 % for LIBS is equivalent to the ICP-OES one.
These blind measurements have demonstrated the quantitative
capabilities of the methodology.
Fig. 2: Validation on
unknown samples
TEAM
Loïc Patatut, Marion Sérasset, Malek Benmansour,
David Pelletier, Hélène Lignier
CONTACT
[email protected]; [email protected]
36
Laser processed Interdigitated Back Contact
Heterojunction solar cells
CONTEXT
Interdigitated back contact heterojunction (IBC-HET) solar cells
technology is one of the most promising technologies for the
upcoming generations of high efficiency c-Si PV modules (Fig.1).
In the last years, IBC-HET technology has attracted the interest of
many institutes and companies worldwide. With its IBC-HET solar
cell process, Panasonic currently holds the world record efficiency
for a single junction c-Si solar cell (IEEE J. Photovoltaics, 4, 6, pp.
1433–1435, 2014). However, the industrialization of the IBC-HET
technology is actually constrained by the complexity of the solar
cells back side processing (Fig.2), which usually involves costly and
time consuming photolithography steps.
production with a laser based process. The first batch of fully processed (metallized) IBC-HET cells with the optimized process is
currently in progress.
PARTNERSHIP
This work was partly carried out in the frame of a national ANR
program (SMASH-IBC2) and European projects (CHEETAH, HERCULES).
References
[1] T.Desrues, Proc. 40thIEEE PVSC, Denver, CO., June 8-13, 2014
APPROACH
To define the back surface field (BSF) and emitter regions of the
IBC-HET solar cells, CEA-Liten is currently developing a novel
method based on laser ablation for the back side processing of
the cell [1]. Laser ablation is a fast and low cost technique that
allows patterning the back side layers stack of large area IBC-HET
solar cells. However a laser ablation process might induce some
damage at the c-Si/a-Si:H interface thus limiting the final performance of the devices. The challenge is then to develop a low-cost
and robust laser process that allows obtaining high efficiency IBCHET solar cells.
Fig. 1: Future market shares of c-Si PV. Source: IRTPV 2014
RESULTS
The best IBC-HET cell efficiency achieved so far at CEA-Liten using
the laser ablation approach is 20% on (18cm2). This efficiency has
been independently certified at CalLab. For larger area solar cells
(100cm2) an efficiency of 19.3% has been demonstrated. The final
efficiency of laser processed IBC-HET cells is constrained by the
compromise between the c-Si/a-Si:H interface quality preservation and keeping an optimal patterning on the back side of the
a-Si:H layers (no residues). This compromise leads to moderate fill
factor and open circuit voltages (Voc) of the processed cells (74.9%
and 689mV respectively for our best cell). In order to overcome
this bottleneck, the solar cells back side layer stack and the laser
ablation process are currently being optimized. Initial results are
very promising, showing an optimal patterning of the cells back
side, without any residues as shown in figure 3, while preserving
a high c-Si/a-Si:H interface quality. Preliminary cell precursors (not
metallized) show carrier lifetimes and implied Voc values up to 2ms
and 730mV respectively after the back side a-Si:H patterning process.
Fig. 2: Schematic view
of an IBC-HET solar cell
structure. n+ and p+
doped a-Si:H (BSF and
emitter) regions are
depicted in yellow and
red colours.
Fig. 3: Detail of residues left in a laser ablation process for the BSF
patterning of IBC-HET cells (top). Successful patterning of emitter and
BSF region with an optimized laser process (bottom)
An industrial large-scale laser based process for the back side
patterning of large area IBC-HET solar cells is under development.
Preliminary results show that it is possible to successfully pattern
the a-Si:H layers stack while keeping high interface quality thus
opening the door for future high efficiency IBC-HET solar cells
TEAM
Samuel Harrison, Oriol Nos Aguila, Guillaume d’Alonzo,
Christine Denis, Delfina Muñoz
CONTACT
[email protected], [email protected]
37
Highly-integrated, receiverless medium CPV module above
30% efficiency at a competitive cost
CONTEXT
Concentrator photovoltaics (CPV) technology requires reducing
costs in the competitive world of electricity production. Medium
concentrator photovoltaics (MCPV) generally employs mirrors as
primary optics, Si cells and a heat sink based on metallic fins integrated in a classical one-axis CPV tracker. CEA-Liten proposes a
highly integrated receiverless (HIRL) MCPV concept.
This work was partly carried out in the frame of a national ANR
program (CARNOT PV HIPE) and in collaboration with Fraunhofer-ISE within the Virtual Lab program.
APPROACH
The HIRL-MCPV concept (Fig. 1) uses III-V multijunction solar cells
(MJSC). They are integrated on the rear of a linear parabolic mirror
by means of a straightforward lamination process, allowing the
mirror to act as optical concentrator, mechanical substrate and
heat sink. The HIRL-MCPV concept development is based on electrical, thermal and mechanical modeling as well as design of the
modules. First proof of concept prototypes have been fabricated
and characterized, showing technological feasibility.
Fig. 1: Sketch of one of the
prototypes of HIRL-MCPV
module fabricated and characterized at CEA-Liten
RESULTS
Research on suitable encapsulating materials for lamination has
been carried out with regard to their transparency and resistance
to concentrated doses of ultraviolet light. The lamination process
has been optimized, characterizing it through visual and electrical inspection (electroluminescence and dark I-V) accelerated
ageing and isolation dielectric tests (up to 2,500 V). An array of 4
series-connected MJSC has been designed and fabricated, including cell mounting and interconnection with micrometric tolerance thanks to wire-bonding and dedicated pick and place tools.
A scaled array prototype has been designed taking into account
the thermal behaviour under solar illumination (Fig. 2). The cell
array has then been laminated into the mirror-based module prototype and the whole has been characterized in a CPV module
solar simulator, i.e. with collimated rays. An efficiency of 30.8% has
been obtained (Fig. 3).
A cost analysis model has also been carried out (Fig. 4), considering the cost of cells, materials, machines, utilities, labour, tracker,
inverter and balance of system. It showed a CPV module cost of
0.59 €/Wp, far below current industrial equivalent.
Fig. 2: Thermal simulation
of the receiverless MCPV
system
Fig. 3: I-V curve of the HIRL
MCPV module prototype
measured with the Helios
3189 CPV module simulator
Fig. 4: Pie-chart with a
detailed breakdown of the
costs of the HIRL MCPV system based on high-efficiency
III-V solar cells and an overall
efficiency of 30%
These encourageing results show a great potential for the HIRLMCPV system, both from a technical and an economical point of
view.
TEAM
Pablo Garcia-Linares, Clément Weick, Mathieu Baudrit
CONTACT
[email protected],[email protected],
[email protected]
38
Laser-patterned organic PV modules:
high Geometric Fill Factor and freedom of design
CONTEXT
Over the last decade, the whole field of Organic Solar Cells (OSCs)
has turned from a lab curiosity into an emerging technology. Yet,
various challenges are still to be faced to ensure a bright industrial future for OSCs. Among them, the modules Geometrical Fill
Factor (GFF, typically in the range 40–60%) has to be considerably
increased to compete with existing technologies where standard
GFF exceeds 90%.
This GFF is limited first by the relatively high sheet resistance of
the transparent front electrode that limits the OPV cells width.
Secondly the rather low resolution of the used coating technologies is mainly responsible for the large interconnection areas
between the cells. As these areas do not contribute to power
conversion, they severely decrease the GFF and ultimately the
modules power output.
A high precision and versatile production process of flexible OPV
modules exhibiting a GFF greater than 90% and with identical performances as hand-made lab devices has been demonstrated. This
process will be extended to the processing of larger modules (up
to 15 x 15 cm²) to achieve higher efficiency.
This work was funded via the CARNOT program (LASPV project).
References
[1] A. Barbot et al ; Oral Comm ; Plastic Electronics - 2015 (Dresden)
[2] S. Berson et al ; Oral Comm ; ICFPE 2015 (Taïwan)
APPROACH
At CEA-Liten, high-resolution laser patterning has been employed
to overcome this issue and achieve high GFF modules. The
approach relies on the alternation of simple plain coatings followed by subsequent patterning of the various layers.
RESULTS
To enable OPV modules processing via laser ablation, three distinct scribing steps are required, hereafter referred to as P1, P2 and
P3 (Fig. 1).
P1 first achieves structuring of the transparent conducting oxide
(TCO) bottom electrode. Then P2 simultaneously ablates the hole
transport layer (HTL), the active layer (CA) and the electron transport layer (ETL). Here, the main challenge is the selective and total
ablation of this three-layer stack without altering the TCO underneath. Modules are then completed via the P3 scribe that results
in isolation of the top silver electrode to enable the connection of
the single cells.
Each scribing step was first individually optimized adapting the
laser power output, its scanning speed and the laser spots overlaps.
Once done, fully laser-patterned flexible 5 x 5 cm² OPV modules
showing GFF in excess of 90% were then produced (Table 1 & Fig.
2). These results represent more than a two-fold increase with respect to the reference chemically etched modules. In addition, this
was done without significant losses in terms of device efficiency
PCE (Table 1). Laser patterning being a fully numeric method,
modules design can be swiftly changed via a drawing software
without any hardware modification. In that way, the number of
stripes was easily tuned from 3 to 8 and round-shaped modules
were also processed. Here again, GFF as high as 90% were achieved.
Fig. 1: The 3 scribing steps
of a serially connected
OPV Module
Table 1. Results achieved with laser processing
Fig. 2: Fully laser
patterned OPV modules
with GFF > 90%
TEAM
Didier Gallaire, Jean-Yves Laurent, Anthony Barbot,
Matthieu Manceau, Solenn Berson
CONTACT
[email protected]
39
Ultra High Gas Barrier encapsulation films: low cost wet
process and characterization
CONTEXT
Organic electronic devices need to be protected from oxygen
and moisture thanks to a careful encapsulation using ultra-high
gas barrier materials (UHB). The UHB use for organic photovoltaics
should combine very low costs while remaining transparent and
flexible.
Adding a thin dense inorganic layer on a polymer substrate is one
of the ways to obtain such gas barrier materials. Usually, thin silica
and silicon nitride layers are used for this purpose, as they are
easily deposited by plasma enhanced chemical vapor deposition.
Nevertheless, vacuum deposition techniques are considered to be
expensive especially when several layers are deposited as required
for UHB. In addition, the control of the UHB materials remains
challenging due to the lack of sensitivity of the commonly used
instruments and the time of measurement.
red to a roll to roll pilot line and the characterization technique has
become an automated instrument already commercialized.
This work was funded via the Joint Research laboratory Sollia with
Arkema and a FP7 European funding (X10D project)
References
[1] A. Morlier et al ; Thin Solid Films 550 (2014) 85–89
[2] S. Cros et al. Organic Electronics 15 (2014) 3746–3755
APPROACH
Fig. 1: Investigation (IR,
TOF-SIMS) of the multilayer structure of the
converted precursor:
local concentrations of
SiH ( - ), SiN (•), O2 (line),
H (dashed line) and Si
(dotted line)
CEA-Liten produced UHB flexible encapsulation films using the
wet deposition of inorganic precursors on low cost polymeric
substrates (PET), which are in turn cured into a thin inorganic
gas barrier structure. The development of the process has been
monitored thanks to a home-made characterization technique
allowing the rapid screening of the gas barrier properties and the
measurement of ultra-low water and oxygen transmission rates.
RESULTS
We investigated the structural properties of the gas barrier layer
after UV curing of the precursor (Fig. 1). We have shown that the
conversion occurred only on the surface and could not be totally
achieved for thick layers. Indeed, it has been shown that the principal limitation of this curing process may not come from the
irradiation dose but mainly from the hindered oxygen diffusion.
Thanks to the use of the home-made permeation techniques (Fig.
2), the relation between the multilayer structure of the converted
precursor and the gas barrier properties of the coated encapsulation films has been demonstrated (patent pendind). The achieved
oxygen and water transmission rates (respectively OTR and WVTR)
are similar to those obtained using vacuum techniques (Fig. 3) and
can be obtained using low cost wet techniques and low cost substrates.
Fig. 2: Scheme of the
permeation measurement technique
developed at CEA-Liten
to measure gas barrier
properties
Fig. 3: OTR (solid line)
and WVTR (dashed line)
of PHPS single layers
deposited on a PET
substrate
We demonstrated a low cost production process of flexible UHB
encapsulation films able to protect OPV modules and other
flexible organic electronic devices. The performances have been
optimized thanks to the understanding of the multilayer structure
of the converted precursor and the use of home-made gas barrier
characterization techniques. The process has now been transfer-
40
TEAM
Arnaud Morlier, Fabien Jaubert, Clément Soumaire,
Stéphane Cros, Manuel Hidalgo, Dominique Thil, Solenn
Berson
CONTACT
[email protected]
Efficacité énergétique
Energy efficiency
SOMMAIRE / CONTENTS
Extended contribution on Li Ion batteries: from innovative materials to integrated systems.................................42
HIGHLIGHTS
q Development of silicon electrodes for high energy density Li-ion battery...............................................................................46
q Ageing study of LiFePO4 based Li-ion batteries...................................................................................................................................47
q Statistical Method Tools to Predict Li-ion battery lifetime in automotive environment ......................................................48
q Honeycomb grids for advanced lead-acid batteries .........................................................................................................................49
q Three-dimensional analysis of Nafion layers in PEM Fuel Cell electrodes..................................................................................50
q High Resolution Raman microspectroscopy for quantification of water content in polymer electrolyte during
PEMFC operation..................................................................................................................................................................................................51
q Towards higher PEMFC performances: a coupled “bipolar plate|MEA” design approach....................................................52
q An algorithm for diagnosis of proton exchange membrane fuel cells by electrochemical impedance spectroscopy....... 53
q Electric Vehicle Integration into Distribution Network: Challenges and Opportunities.......................................................54
q Development of a modeling and simulation platform: a common environment for the evaluation
of energy systems................................................................................................................................................................................................55
q Supercritical organic Rankine cycle..........................................................................................................................................................56
q Advanced aerogel-based insulating materials for building applications ..................................................................................57
q Residential seasonal heat storage demonstrator ...............................................................................................................................58
q International conference on solar energy and buildings: Eurosun ..............................................................................................59
«HABILITATIONS À DIRIGER DES RECHERCHES»
• Philippe Azais (DEHT): De la recherche à l’industrialisation des supercondensateurs - (02/07/2014)
THÈSES / PHD
2014
• ABBEZZOT Cédric (DTS): Gestion et évaluation technique des systèmes de stockage
dans les centrales PV de grande puissance (15/12/14)
• BRIAULT Pauline (DEHT): Développement d’une cellule SOFC de type monochambre pour la production d’électricité à partir de gaz d’échappement d’un moteur
thermique (16/01/14)
• CHANCELIER LEA (DEHT): Développement de solutions innovantes d’électrolytes
pour sécuriser les accumulateurs Li-ion (24/10/2014)
• CHHOR Sarine (DEHT): Etude in-situ par méthodes couplées de la formation de
l’interface Electrolyte solide(SEI) dans les accumulateurs Li-ion (négative C)
(19/12/14)
• DABONOT Aurore (DEHT): Développement de supercondensateurs pour
l’application au véhicule hybride électrique (29/09/14)
• MONGKOLTANATAS Jiravan (DTS): Participation d’un système de stockage à la stabilité
d’un réseau insulaire (03/12/14)
• PUSCASU Onoriu (DTNM): Développement de systèmes de récupération d’énergie au
sein des puces électroniques (22/01/2014)
• RADVANYI Etienne (DEHT): Formulation d’électrodes Négatives Composites Si-C pour
accumulateurs Li-Ion (06/02/14)
2015
• DONVAL Gael (DEHT): Modélisations par calculs DFT de spectres EELS obtenus sur le
silicium comme matériaux de batterie au lithium (20/03/2015)
• FAGGIANELLI Ghuvan-Antone (DTS): Approche Energétique et économique de la
réhabilitation par la simulation et le retour d’expérience (14/11/14)
• GUIMET Adrien (DEHT): Membrane conductrice protonique à base de réseaux
interpénétrés de polymères pour applications pile à combustible et électrolyse
(02/04/15)
• JOUSSE Jérémie (DTS): Intégration de la technologie lithium-ion dans un système
PV autonome (16/10/14)
• MARIAS Foivos (DTBH): Compréhension des mécanismes physiques présents dans des
systèmes G/S ou L/S par réaction thermochimique (29/01/15)
• LEPESANT Mathieu (DEHT): Etude et réalisation de catalyseurs multimétalliques
nano-organisés pour pile à combustible PEM (09/10/14)
• VEERAPANDIAN Ponnuchamy (DEHT): Dynamique des ions lithium dans les batteries
Li-ion (23/01/15)
• LUU Ngoc An (DTS): Développement de stratégies innovantes de gestion et
de contrôle d’un réseau insulaire comportant des sources photovoltaïques et du
stockage (18/12/14)
• WALUS Sylvia (DEHT): Etude et développement d’un système électrochimique basé sur
le soufre et le lithium pour le stockage de l’énergie (15/01/15)
41
THE LI ION BATTERIES: FROM INNOVATIVE MATERIALS TO
INTEGRATED SYSTEMS
THE PROJECT TEAM
Frédéric Fabre, Cédric Haon, Matthieu Desbois Renaudin, Thibaut Gutel, Daniel Chatroux, Carole Bourbon, Jean Francois Colin, Willy Porcher, Agnès Brun,
Lionel Picard, Laurent Garnier, Laura Boutafa, Daniel Tomasi.
1 - CONTEXT AND MOTIVATIONS
Among all rechargeable portable energy storage systems, Li-ion batteries offer today the highest energy density levels
(400–700 Wh.L-1, and 150–270 Wh.kg-1), for a nominal voltage of 3 to 4 V, low self-discharge characteristics (5–10% per
month), and a broad range of operating temperatures (from –20 C to +65 C). The principle underpinning this technology
involves triggering the reversible electrochemical intercalation of lithium ions into two distinct materials, the electrodes,
for different potential values. Li ions move from one electrode to the other through the electrolyte, a liquid carbonates
mixture with dissolved Li salt. As there is no generic solution, battery chemistry is designed according to the investigated
application.
2 - LITEN APPROACH AND RESULTS ON LI ION BATTERIES
A specific attention has been given to increasing the energy density of Li ion batteries for fulfilling transportation
application specifications while keeping cost acceptable and reenforcing safety. In that respect, two electrode materials
already extensively studied worldwide have been selected for being further optimized and their production scaled up
simultaneously. Real size batteries could be produced and their energy density increase demonstrated.
2.1 - POSITIVE ELECTRODE MATERIAL FOR HIGH ENERGY: LI-RICH LAYERED OXIDES
Materials of generic composition Li1+xM1-xO2 (M=Ni, Mn…), also called “Li-rich layered oxides”, in comparison to classic
LiMO2 cathode materials, stand as one of the most promising materials due to a very high practical capacity that can reach
up to 250 - mAh.g-1 (150 to 200 mAh.g-1 for classic LiMO2). At cell level, 300 Wh.kg-1 can be expected (with carbon negative
electrode), and even 350 Wh.kg-1 when combined with improved negative electrode (Si or Li). However, despite these high
expected performances, several drawbacks such as a high first irreversible capacity loss, degasing, or voltage decay upon
cycling constitute key issues towards the commercialization of Li-rich oxides.
Unusual and complex charge/discharge mechanisms such as the participation of oxygen to the electrochemistry and the
cationic migration have been studied thanks to synchrotron diffraction at the ESRF, electronic microscopy at the NanoCharacterization Platform, and electrochemical tests. In situ X-Ray diffraction study combined with a transmission electronic
microscopy study have led to the identification of an irreversible structural change during first charge, accompanied with
the formation of a secondary spinel structured phase at the surface of the particle, which could create the first irreversible
capacity loss1. A coupled EELS/TEM study allowed the observation of a continuous cationic migration during cycling that
42
is part of the voltage decay mechanism2 (Figure 1). Finally an in situ XAS study at ESRF coupled with fine electrochemical
analyses gave the identification of the different electrochemical processes and of the link between high and low potential
processes in the material. Based on these results, a voltage window could be determined for cycling this material without
operating voltage decay.
structure and chemical
composition of the
Li-Rich material during
cycling. A spinel
phase appears at the
surface and the bulk is
enriching in Mn.
In parallel the development of synthesis processes has been carried out for these materials. First developments were
done on solid state synthesis, with an optimization of the particle size leading to reaching stable 230 mAh.g-1 capacity.
Coprecipitation synthesis via a specific design of experiment was then carried out. The goal was not only to increase
the performances of the material, but also to optimize its morphology as co-precipitation allows obtaining spherical
aggregates with high tapped density which are both desirable for the production of high energy density electrodes. A
material with a stable capacity of 250 mAh.g-1 could be achieved with an increase of tapped density from 1.2 to 1.6.
This synthesis process has been scaled up with success at kg scale on a pilot reactor with electrochemical performance
maintained (cf CEA patent WO2015/014807). The 40 first cycles of the upscaled material are presented on figure 2
Fig. 2: Discharge
capacity vs cycle number
for the CEA Li-Rich
material after scaling-up
the synthesis process.
This material when compared to materials currently produced
appears to be cost and energy competitive. Ongoing
synthesis efforts are now turned towards doping and coating
of this optimized material in order to reduce degassing and
further stabilize the structure formed during first charge in
order to avoid the continuous cationic migration and the
voltage decay.
2.2 - NEGATIVE ELECTRODE MATERIAL FOR HIGH ENERGY: SILICON-BASED COMPOSITES
Silicon, with its high theoretical specific capacity (3579 mAh.g-1 vs 372 mAh.g-1 for graphite), appears today as a very
promising negative electrode material for high energy density Li-ion batteries. However, silicon suffers major electrochemical
performances fading upon charge and discharge cycles due to huge volume changes leading to mechanical pulverization
of particles, loss of electronic contacts and instability of the solid electrolyte interphase.
Several research approaches have been initiated in the last 5 years dealing either with material stabilisation or with cell
designs aiming fundamental understanding of lithiation and degradation mechanisms and solution strategy identification.
One of them, rather exploratory, concerns the integration of core-shell silicon carbon nanoparticles and is done in
collaboration with CEA-IRAMIS (Figure 3). Their diameter in the range of 20 to 200 nm, the core organization (amorphous
or polycrystalline), the shell thickness and its organization (turbostratic or graphitic) can be controlled thanks to the
synthesis process in one step using laser pyrolysis technique on an original reactor with two successive reaction zones to
avoid silicon carbide formation. The positive impact of the size reduction towards 30 nm diameters core shell Si-C particles
allows achieving a really high coulombic efficiency upon cycling [3], even if, due to a specific surface superior to 150 m².g-1,
the initial irreversible capacity is too high. In addition, it has been demonstrated that the carbon shell allows protecting
the silicon form oxidation with better lithiation kinetics and higher SEI stability [4].
Fig. 3: 4 materials
synthesis using the
laser pyrolysis set up
of CEA-IRAMIS: at left
part) Crystallized silicon
particles of 30 nm, at the
right part) Amorphous
silicon particles of 20 nm,
without carbon shell and
with a carbon shell.
1 - Simonin L. et al., J. Mater. Chem., 2012; Boulineau A. et al., Chem. Mater., 2012.
2 - Boulineau A. et al., Nano Letters, 2013.
3 - J. Sourice, A. Quinsac, Y. Leconte, O. Sublemontier, W. Porcher, C. Haon, A. Bordes, E. De Vito, A.
Boulineau, S. Jouanneau, N. Herlin-Boime ,C. Reynaud, One-Step Synthesis of Si@C Nanoparticles by
Laser Pyrolysis: High-Capacity Anode Material for Lithium-Ion Batteries, ACS Appl. Mater. Interfaces,
2015, 7 (12), pp 6637
4 - J. Sourice, thesis, Université Parsi-Sud, 2015
43
Interesting progresses have also been obtained in the understanding of (de)lithiation and degradation mechanisms of
silicon-carbon composites electrodes by using powerful (nano)characterization tools. The instability of the passivating
layer formed on silicon surface was confirmed as the primary cause of cycle life limitation and the use of prelithiation of
the electrode (Figure 4), to cycle on highly lithiated silicon domain, has been shown to stabilize fully the SEI with 75% of
the capacity recovers after 300 cycles for a Li-ion prototype with a specific capacity of 1200 mAh/g on the silicon [5]. Work
is ongoing to develop a scalable solution for lithium pre-loading.
Fig. 4: Potential
evolution of a Li-ion
prototype integrating
NMC at the positive
electrode, silicon at
the negative electrode
prelithiated at Li2.1Si
with a capacity cycled of
1200 mAh.g-1, and a Li
reference electrode.
Using more mature solutions, a technology transfer
could be successfully achieved towards the start-up
Prollion leading to the commercialization in 2013 of a 1Ah
accumulator with an energy density of 250 Wh.kg-1 for
luxury watches that include a battery powered beacon.
This high specific energy density is reached thanks to a
silicon based electrochemistry giving high power-rate,
long autonomy and no compromise on safety (www.
prollion.com/fr/produits/batteries).
Further improvement of the energy density was achieved in a prototype integrating high capacity silicon-graphite
cathodes that exhibit more than 300 Wh.kg-1(CEA internal Mmilestone). Even if some improvements are still needed on
cycle life to meet specifications of portable applications and HEV or EV market, this level of energy density stands among
the best current performances worldwide.
2.3 - ELECTROLYTE: HIGH VOLTAGE ISSUE
Designing high energy density or high power systems, generally leads in increasing positive electrode voltage. Active
materials already exist (Ni-Mn spinels, Co based phosphates…) that exhibit working potentials around 4.8V vs Li compared
to around 4V for conventional systems. At these elevated working voltages, new issues appear for the batteries. Indeed,
efficiencies and capacities are observed to collapse while cells begin to inflate due to the degradation of the mixture of
solvents and salt constituting the electrolyte. Commonly composed of alkyl carbonates and LiPF6, this ionic conductive
solution cannot withstand the contact with high voltage surfaces and oxidizes to form oligomers, radicals and gases,
mainly CO2 generating a safety issue as well.
Different approaches are being studied worldwide such as organic additives to passivate high voltage surfaces, inorganic
coatings on the active materials, stable solvents, new salts, ionic liquids (which should be oxidation proof ), etc. Liten
contributed to these efforts, mainly in testing and in post-mortem analyses (gases, liquids and surfaces) for understanding
the impact of each solution. Collaborations with INSA (Institut National des Sciences Appliquée de Lyon) and CPE (Ecole
Supérieure de Chimie Physique Electronique de Lyon), have also been initiated on solid polymer electrolyte and ionic
liquid electrolyte respectively[6], [7], [8], [9], [10], [11].
With this organization and methodology, a recent electrolyte composition (insourced solvents and formulation), based
on ester solvents and additives, led to a drastic decreasing of gas generation during cycling (divided by 10 compared to
optimized carbonate solution at high temperature). This confidential work has been achieved within the framework of
CEA-Renault collaboration.
2.4 - THE DESIGN OF BATTERY SYSTEMS
To be used in the targeted application, the battery pack has to be equipped with different subsystems, like sensors,
electrical protection devices, thermal management system, mechanical casing and control unit, commonly named Battery
Management System (BMS). The BMS is the intelligence of the battery system and its main functions can be classified in
the following priority order: 1) ensure the safety of the pack, 2) calculate the state of charge, 3) balance the pack, and 4)
communicate with the application.
To generate breakthrough innovations in battery systems three different CEA teams have joined forces:
• A common Leti - Liten laboratory, is in charge of BMS electronic parts: sensors, balancing system, microcontroller
electronic board with embedded software;
• A second team is in charge of the implementation of algorithms SOC, SOE, SOH (states of charge, energy and health). For
example, auto-adaptive algorithms, are developed based on electrical and ageing models adjusted with tests, performed
both in laboratory but also in real conditions;
• A third group is in charge of the electrical, mechanical and thermal designs, the integration and the final tests of the
battery system.
This organisation allows innovative architectures and power electronics solutions to be developed fulfilling customer
requirements such as safety aspects, fast charging capabilities, weight, volume but also durability. The first example (Fig 5
and Fig 6) presents the hardware electronic architecture and the curves resulting of the balancing algorithm at the end of
the charge. The second example deals with an innovative Smart Battery Module which integrates not only power energy
but also auxiliary DC/DC converter allowing removing, the auxiliary battery in EV, thanks to redundancy (figure 7) [12].
44
5 - WO 2014/041076: Method for operating a lithium battery involving an active material of a specific
electrode
6 - E. Bolimowska, F. Castiglione, D. Stošić, H. Rouault, A Mele, C. Santini, ECS 227th Meeting, Chicago
(USA) 24-28 May, 2015
7 - E. Bolimowska, H. Srour, L. Chancelier, H. Rouault, T. Gutel, C. Santini and S. Mailley, ECS 227th
Meeting, Chicago (USA) 24-28 May, 2015
8- H. Rouault, C. Santini, J. Santos Pena, E. Bolimowska, 6th International Congress on Ionic Liquids,
Jeju (Korea), June 16-20, 2015
9 - Srour, H. , Traïkia, M. , Fenet, B., Rouault, H., Costa Gomes, M.F , Santini, C., Husson, P., Journal of
Solution Chemistry, (2015) 44 (3-4),. 495-510
10 - Srour, H., Rouault, H., Santini, C., Journal of the Electrochemical Society, (2013) 160 (1), A66-A69
Fig.6: Balancing sequence at the end of charge
Fig.5: Battery pack and BMS architecture
Fig.7: Smart module with redundant DC/DC converter
During the last five years, tens of demonstrators from less than 1kWh up to more than 100kWh have been delivered mainly
in industrial programs and always adapted to specific applications (figure 8).
Fig.8: autobus with fast charge capability (4 min) at the end of the line13
3 - CONCLUSION AND FURTHER STEPS
Cells used for pack integration were either
commercial or CEA made. In the same time, about
100 patents have been published, representing
approximately 40% of the CEA battery portfolio.
Battery Systems are not the only solutions to answer
to the different electrical energy storage needs.
Hybrid solutions with super capacitors or fuel
cells e.g. PEMFC are also considered as they allow
cumulating the advantages of each solution. Liten
is now considering PEMFC/batteries hybridisation
through the three following questions:
• Is hybrid interesting or not regarding targeted
mission profile, environmental conditions, and
constraints of cost, durability, weight and what
is the best hybridization ratio (peak power ratio
between the two electrochemical generators)?
• What is the best electrical architecture?
• What is the best algorithm for exploiting energy
from the right source at the right moment during
the mission profile?
In order to increase performances and durability of battery electric vehicles, Liten started exploring new ways to improve
battery components and system. On one hand, Liten is investigating “Post Li-ion” electrochemical systems such as Li-S or
Na-ion promising innovative solutions. On the other hand, in a global system approach Liten is also developing experience
in hybridization of battery and fuel cell systems for automotive applications. At each step of this innovative process, from
material, components, cells and systems, Liten is developing multi-scale and multi-physic modelling tools coupled with
phenomenological observation of degradation and ageing mechanisms in order to understand the different phenomenon
occurring at different level of integration.
11 - Srour, H., Rouault, H., Santini, C., Journal of the Electrochemical Society, (2013) 160 (6), A781-A785
12 - L. Garnier, contribution to a book (2015, IEA request), Advanced Hybrid and Electric Vehicles, Task
17 Methods for System Optimization and Vehicle Integration, contribution 6.6.3 Benefits through
optimized power electronics and drive train technologies
13 - D Chatroux, conference PCIM 2012, Autobus with four minutes charge at the end of the line
14 - Ramon Naiff da Fonseca et al., 2013, “Optimization of the Sizing and Energy Management Strategy
for an Hybrid Fuel Cell Vehicle Including Fuel Cell Dynamics and Durability constraints”
45
Development of silicon electrodes for high energy density
Li-ion battery
CONTEXT
With a capacity of 3600 mAh.g-1, 10 times higher than the commercial material, silicon is a promising anode active material for
Li-ion batteries. However, because of the huge volume changes
undergone by Si particles when (de)alloying with lithium, Si electrodes suffer from rapid capacity fading.
References
[1] E. Radvanyi, W. Porcher, E. De Vito, A. Montani, S.Franger and S.
Jouanneau Si Larbi, Phys. Chem. Chem. Phys., 2014, 16, 17142
[2] E. Radvanyi, K. Van Havenbergh, W. Porcher, S. Jouanneau , J.-S.
bridel, S. Put and S.Franger, Electrochimica Acta 137 (2014) 751–757
APPROACH
A strong understanding of the associated failure mechanisms is
necessary to improve the electrochemical performances. To reach
this goal, CEA-Liten has investigated nano-Si based electrodes by
several characterization techniques:
• conventional techniques: Scanning Electron Microscopy (SEM),
X-ray photoelectron spectrometry (XPS), Focused Ion Beam (FIB),
Electrochemical Impedance Spectroscopy (EIS),
• non-conventional techniques in the Li-ion battery research field:
Auger Electron Spectroscopy and Hg porosimetry.
RESULTS
A clear picture of the failure mechanisms of nano-Si based electrodes is provided in figure 2. The porosity evolution within the
electrode has been followed combining Hg analyses, SEM observations of electrode cross-sections, and EIS measurements, For
the first time, a real dynamic of the pore size distribution has been
evidenced: the first cycles lead to the formation of a micrometric
porosity which is not initially present. During the following cycles,
these large pores are progressively filled up with electrolyte
decomposition products appearing continuously at the Si particle
surface. Thus, from the 50th cycle, Li+ ion diffusion is dramatically
hindered leading to a strongly heterogeneous lithiation of the
electrode and a rapid capacity fading.
Fig. 1: Schematic representation of the reaction mechanism of the Solid
Electrolyte Interface increasing at the silicon surface upon cycling.
Thanks to a better understanding of the silicon fading mechanisms, optimisations of the formulation, the electrolyte and the
prelithiation have been proposed or confirmed.
We acknowledge CEA-INSTN for supporting part of this study.
EIS experiments were tailored thanks to the expertise of Sylvain
Franger (CNRS – Univ. Paris-Sud) and a collaborative approach
with Umicore. Umicore and CEA also work together in a collaborative project: Active NAnoSilicon Technology in Advanced battery
System for Li-Ion battery Application (ANASTASIA).
Fig. 2: Schematic view of
the failure mechanisms
of nano-Si based electrodes upon cycling.
TEAM
Etienne Radvanyi, Willy Porcher, Christophe Vincens, Eric
De Vito, Cédric Haon, Séverine Jouanneau
CONTACT
[email protected]
46
Ageing study of LiFePO4 based Li-ion batteries
CONTEXT
Among Li-ion battery technologies, cells containing a LiFePO4
(LFP) positive electrode present long cycle life, low cost and high
safety. Those advantages make it as a good candidate for electric
mobility. For this purpose CEA developed and transferred a proprietary version of this material to Belife (Prayon/Umicore).
APPROACH
LFP based Li-ion cells were studied: on one hand, coupled with a
Li4Ti5O12 (LTO) negative electrode, cycling tests were carried out.
On the other hand calendar ageing on commercial LFP-graphite
cells was conducted: 3 references of commercial C/LFP cells have
been deeply characterized in the collaborative project SIMCAL, at
3 storage temperatures for 3 state-of-charges (SOC), equivalent to
9 calendar ageing conditions. From these measurements, CEA has
developed a predictive ageing model used to predict the calendar
ageing according to some dynamic and real usage profiles, and
consequently to define the best strategies to prolong the batteries
lifetime.
This work was partly carried out in collaboration with IMN Nantes
(R. Castaing PhD thesis). Besides, results have been obtained on
commercial cells in the project SIMCAL, with the financial support
of the French National Research Agency (ANR).
References
[1]Castaing, R., Reynier, Y., Dupre, N., Schleich, D., Jouanneau Si Larbi,
S., Guyomard, D., Moreau, P.
Degradation diagnosis of aged Li4Ti5O12/LiFePO4 batteries
(2014) JOURNAL OF POWER SOURCES - Volume 267 - Pages: 744-752
[2] Grolleau, S., Delaille, A., Gualous, H., Gyan, P., Revel, R., Bernard, J.,
Redondo-Iglesias, E., Peter, J.
Calendar ageing of commercial graphite/LiFePO4 cell Predicting
capacity fade under time dependent storage conditions
(2014) JOURNAL OF POWER SOURCES Volume 255 Pages 450-458
RESULTS
It was found that structural stability for both LFP and LTO electrodes was excellent with no intrinsic capacity loss after 6 months
ageing [1]. The root cause for capacity fade of full cell was attributed
to internal capacity imbalance coming from parasitic side reaction on the electrode surface (electrolyte decomposition, impurities resulting in surface layers building up). By using appropriate
electrolyte and clean assembly process, outstanding cycle life
can be obtained with more than 15000 full cycles at a 3C charge/
discharge rate and nearly no capacity loss (fig. 1).
Considering calendar ageing results obtained on 3 commercial
cells references, they confirm a similar trend for the C/LFP chemistry, with a quite good stability but with a degradation accelerated with the level of temperature, and in a less extent with the
level of SOC (fig. 2). Moreover, as for some other Li-ion technologies with a negative electrode based on graphite, the Solid Electrolyte Interphase (SEI) growth is the only origin of the degradation observed.
Fig. 1: Ageing at room temperature of LiFePO4-Li4Ti5O12 cells cycled at
1C and 3C rates (1h or 20 min discharge)
These new insights pave the way to more widespread use of these
new technologies for electric mobility.
Nevertheless, it has to be expressed here that the quite low energy
density values of the C/LFP technology (average value around 100
Wh/kg), and even lower for the LTO/LFP technology, leads to select
this technology for energy requirements rather low, as for e-bike
or e-scooters for examples, much more than for e-cars.
Fig. 2: Calendar ageing results obtained on a commercial C/LFP
reference according to 9 storage conditions
TEAM
Yvan Reynier, Rémi Castaing, Arnaud Delaille
CONTACT
47
Statistical method tools to predict Li-ion battery lifetime in
automotive environment
CONTEXT
The lifetime of Li-ion battery for automotive application is one of
the major challenges to decrease the cost of BEV (Battery Electric
Vehicle). Online SoH (State of Health) estimation and prediction
are necessary to optimize the BEV use and the confidence of the
users.
References
[1] A. Barre, F Suard, M. Gerard, M. Montaru, Statistical analysis for
understanding and predicting battery degradations in real life
electric vehicle use, JPS, 245:846-856 (2014)
[2] A. Barre, F. Suard, M. Gérard and D. Riu, Electric vehicles
performance estimation through a patterns extraction and
classification methodology, JPS, 273, 670-679, (2015)
APPROACH
The proposed approach is a new methodology to estimate the global battery performances under real-life electric vehicle use. The
performances, here the ageing parameters, are estimated through
a continuous extraction of battery signal patterns (vehicle speed,
temperature, battery voltage and current). The signal patterns are
used to identify the physical degradation behavior of batteries.
The analysis framework (Fig. 1) is decomposed into the data collection, the patterns extraction, and SoH estimation using a non-linear regression model.
The approach has been applied on real data collected on BEV
ageing tests performed at CEA under uncontrolled conditions. First
the patterns are extracted using a vehicle acceleration criterion.
The patterns are then compared by a distance metric classification
(Dynamic Time Warping (DTW) metric). Third, a classification algorithm (like Support Vector Machine (SVM) or K-Means) is applied
to learn a model based on a training set from the data. Different
combinations of metric and features (current, power, temperature,
state of charge (SOC) have been evaluated to identify the optimal
set of parameters corresponding to the best accuracy.
Fig. 1: methodology of
the analysis framework
RESULTS
The classification has been tested for an online analysis. Fig. 2
shows the results of the SoH estimation, compared to the real SoH.
The SoH prediction is good so such method is able to predict the
battery lifetime using simply a global measurement. Moreover,
the SVM classification is more reliable than a linear model, to predict the end of life of the battery.
The presented results demonstrated the relevance of a mathematical analysis to predict online vehicle lifetime. The next steps are
to demonstrate the prediction algorithm for a real vehicle and to
use this classification to optimize a vehicle fleet use.
ACKNOWLEDGMENTS
This work has been carried out within a LIST-Liten energy transversal program.
Fig. 2: estimating SoH (red bullet) compared to the real SoH (blue line).
Bottom figure compared the linear model estimation and RVM estimation accuracy.
TEAM
Frédéric Suard, Mathias Gerard, Maxime Montaru
CONTACT
[email protected]
48
Honeycomb grids for advanced lead-acid batteries
CONTEXT
The lead acid batteries represent more than 85% of the battery
market (in terms of storage capacity). This leading position is the
result of global, highly efficient collection and recycling infrastructure, high safety in operation and low investment costs (CAPEX).
However, the life-time of most of the lead battery types is rather
short, with consequently high operational expenses (OPEX). Another important drawback of this technology is its low energy density, which is the result of inefficient use of the lead, the latter also
being a limited natural resource.
APPROACH
The improvement of the lead-acid battery parameters can be
done by replacing the classical current collectors (grids) by honeycomb structures based on carbon/carbon composites coated with
thin layers of lead and lead alloys [1]. The new honeycomb grids are
lighter than the classical current collectors, and their “smart” structure allows better active material utilisation and longer cycle life.
CAPEX and OPEX thanks to lead loading reduction, longer cycle
life of the negative plates and improved energy density of the battery.
This work was partly funded by ANR within the project CARBOLEAD 2010 (program Stock-E 2010). The project was carried
out in collaboration with the University of Lorraine (IJL), Material
Mates and Steco Power.
References
[1] A. Kirchev, N. Kircheva, US Patent 8173300 (B2), 2012-05-08
[2] A. Kirchev, S. Dumenil, M. Alias, R. Christin, A. de Mascarel, M.
Perrin, J Power Sources 279 (2015) 809-824
RESULTS
Carbon/carbon composite current collectors have been developed using two different types of composite honeycomb precursors –recycled cellulose paper and m-aramid (Nomex®) fibre
paper, both impregnated with thermosetting resins. After a rapid
pyrolysis, the organic structures are converted into carbonaceous
materials with electric conductivity allowing the application of
metallic lead coating by electrodeposition. The resulting carbon
honeycomb grid can replace readily the actual current collectors,
keeping the same battery cells design.
During the initial phases of the development, the technology was
validated on small-scale battery cells [2]. The results showed that
the honeycomb grids are particularly useful as negative plate current collectors, delivering active material utilisation in the range
of 65-69% vs. the traditional 45-50%. The demonstrated cycle life
of the negative plates exceeded 1000 deep cycles and 2000 equivalent cycles in partial state of charge without any indications of
significant electrode deterioration. During the final stages of the
development, the technology was scaled up to grids suitable for
the mainstream lead-acid battery types. 160 positive plates and
140 negative plates have been manufactured at lab-scale by
CEA-Liten and further used to assemble 8 battery monoblocks
(12V/ 20Ah). Four of these prototypes were used for technology
demonstration as the power source of an electric scooter E-Max
110s. Figure 1 presents the battery pack integration and its performance during a test driving at the site of INES in Savoie Technolac.
The scooter achieved distances longer than 20km with nearly 3
times reduced storage capacity proving the electrical performance of the new current collector technology.
The results show that the new current collectors decrease both
(a)
(b)
(c)
Fig. 1: Battery pack integration (a) and its performance in terms of
voltage (b) and current (c) during a test driving at the site of INES in
Savoie Technolac.
TEAM
Angel Kirchev, Lionel Serra, Gilles Brichard, Sebastien
Dumenil, Laurent Vinit, Baptiste Jammet
Contact
[email protected]
49
Three-dimensional analysis of Nafion layers in PEM Fuel
Cell electrodes
CONTEXT
To reach market competitiveness, fuel cell vehicles still require
reductions in costs and improvements in durability. Consequently, several research programs were devoted to optimize
the membrane/electrode assembly (MEA) components and to
increase the understanding of the degradation mechanisms. In
these research domains, investigation of the MEA microstructure
has become an essential step. Transmission electron microscopy
(TEM) is a powerful tool for analyzing carbon support and catalyst nanoparticle structures and their distribution, as well as their
chemical composition. However, the ionomer network inside the
electrode has never been imaged even though it plays a crucial
role in ionic conduction through the electrode. The main difficulty
for ionomer imageing is that the ionomer mainly forms an ultrathin layer surrounding the carbon support. Moreover these two
components present an insufficient difference in contrast.
study the degradation of the ionomer within the active layer after
fuel cell operation.
This work was carried out in the frame of a CEA-Nanoscience program (project TOMOENER) in collaboration with CEA/DSM/INAC.
References
[1] M. Lopez-Haro, L. Guetaz, T. Printemps, A. Morin, S. Escribano, P.H.
Jouneau, P. Bayle-Guillemaud, F. Chandezon, and G. Gebel, Nature
Commun., 5, 5229 (2014).
APPROACH
In this study, electron tomography in HAADF-STEM (high annular
dark field – scanning transmission electron microscopy) mode was
successfully used to image for the first time the 3D morphology of
the ultrathin ionomer layer surrounding the carbon particles [1].
For this experiment, the ionomer contrast was enhanced by selectively staining the ionic domains with Cs+ ions. In order to avoid
high contrast of the Pt nanoparticles (compared to the ionomer
contrast), a model active layer consisting of ionomer and carbon
black without Pt nanoparticles was prepared using usual electrode manufacturing processes.
(a)
RESULTS
The influence of the ionomer/carbon black ratio introduced in the
catalytic ink was studied by preparing two samples with two different ionomer/carbon black ratios equal to 0.5 and 0.2 w/w. Figure
1 shows the 3D-rendered volume extracted from the reconstructed tomogram for both samples. The 3D repartition of the ultrathin ionomer layer (in blue) surrounding the carbon black (in grey)
is clearly revealed. The quantitative tomogram data analyses have
shown that doubling the amount of ionomer in the catalyst layer
does not change the mean thickness of the ionomer layer, measured around 7 nm, but leads to a twofold increase in its degree of
carbon particle coverage.
(b)
Fig. 1: 3D-rendered volume extracted from the
reconstructed electron tomogram showing the
ionomer ultrathin layer (in blue) surrounding
black carbon particles (in grey) for the sample a)
with the ionomer/carbon black = 0.5 w/w and b)
with the ionomer/carbon black = 0.2 w/w
These electron tomography analyses are of great interest for finding the optimum manufacturing process that will lead to the
maximum carbon coverage without increasing the ionomer layer
thickness. In addition, the developed protocol will be adapted to
TEAM
L. Guétaz, S. Escribano, A. Morin, G. Gebel, M. Lopez
(INAC), P.H. Jouneau (INAC), P. Bayle-Guillemaud (INAC),
F. Chandezon (INAC), T.Printemps (LETI)
50
CONTACT
[email protected]
High Resolution Raman microspectroscopy for
quantification of water content in polymer electrolyte
during PEMFC operation
CONTEXT
Because of its strong coupling with all the physical, chemical and
electrochemical phenomena governing the operation and the
degradation mechanisms, the water content within the polymer
electrolyte membrane is a crucial parameter for the understanding and the modelling of performance and durability of Proton
Exchange Membrane Fuel Cells (PEMFC). Unfortunately, it is also
very difficult to measure it operando.
APPROACH
Liten developed, in collaboration with the European Institute on
Membrane (Montpellier – France), an original method to measure
directly and accurately the water content in membrane in operating PEMFC using confocal Raman microscopy. [1] We designed a
dedicated single cell and the protocols for data acquisition and
treatment. The area of the Raman bands, associated to the vibrational modes of the polymer backbone on one hand and to water
on the other hand, are directly used to quantify the volume fraction of water within the membrane. The spatial resolution can
reach the µm scale thanks to confocal microscopy.
FUNDINGS
National ANR program (INEXTREMIS) Interdisciplinary Research
Program from CNRS (GesteauPAC).
References
[1] S. Deabate, P. Huguet, A. Morin et al., Fuel Cells (2014), DOI:
10.1002/fuce.201300236.
[2] Peng, A.Z., Morin, A., Huguet, P., Lanteri, Y., Deabate, S.
Asymmetric bi-layer PFSA membranes as model systems for the study
of water management in the PEMFC. (2014) PHYSICAL CHEMISTRY
CHEMICAL PHYSICS, Vol 16
Fig. 1: Inner water concentration (vol. fraction) profiles
across the thickness of a
bi-layer membrane during
PEMFC operation
RESULTS
Thanks to this technique we directly measured with a very high
accuracy the concentration profiles through the membrane
thickness during PEMFC operating up to 50°C (Figure 1). The impact
of the current density on the evolution of the water concentration
profile has been studied. We have demonstrated that the water
content within the membrane can decrease although the current density, and hence the amount of water produced in the cell,
increases[2] (figure2). This has been related to the local increase
of temperature which leads to a dehydration of the membrane.
This result is consistent with the value of the ohmic resistance of
the membrane, which was simultaneously measured, (figure 3)
as well as with the simulations, demonstrating the reliability of
the method. We have also shown that the water profile through
the membrane thickness can be modified by using asymmetric
membrane allowing changing the water distribution within the
cell.
Fig. 2: Evolution of the
average volume fraction of water within the
different layers of bi-layers
membranes as a function of
the current density
With Raman microscopy, we have designed an original tool able to
measure accurately the local content of water within a membrane
during PEMFC operation. This will bring invaluable information to
understand fuel cell performance and degradation. Future work
is planned to perform measurements at higher temperature (up
to 100°C).
PARTNERSHIP
This work was achieved in collaboration with Dr Stefano Deabate
and Pr Patrice Huguet from European Institute on Membrane
(Montpellier – France)
Fig. 3: Evolution of the
average ohmic resistance
of bi-layers membranes as
a function of the current
density
TEAM
Arnaud Morin, Gérard Gebel
CONTACT
51
Towards higher PEMFC performances: a coupled “bipolar
plate|MEA” design approach
Reactant concentrations in the MEA
Single cell set-up on test bench
CONTEXT
Membrane Electrode Assembly (MEA) developments for Proton
Exchange Membrane Fuel Cell (PEMFC) are usually performed at
small single cell scale. However, this approach may over-estimate
the final results and invalidate previous work in real stack operation. Indeed, heterogeneities arising from the effective bipolar
plate design and/or unappropriated MEA composition in large cell
can decrease significantly the performances when compared to
smaller scale evaluation.
Coolant flow modelling
This work was partly carried out in the frame of a “Carnot Energies
du Futur” program (OSCAR project) and acknowledgments are
due for additional industrial support.
References
[1] M. Lopez-Haro, L. Guetaz, T. Printemps, A. Morin, S. Escribano, P.H.
Jouneau, P. Bayle-Guillemaud, F. Chandezon, and G. Gebel, Nature
Commun., 5, 5229 (2014).
APPROACH
Work has been carried out to test different MEA formulation in
both small and large single cells with representative stack flowfield designs. This database was then used to model the electrochemical and fluidic behavior depending on the flow-field pattern
and the MEA properties. These simulations make it then possible
to propose an optimal “flow field|MEA” couple to maximize the
performances.
RESULTS
Several potential flow-field designs have been studied using reference MEA design. Electrochemical performances in various operating conditions as well as fluidic properties of the plate design
enable to select the most promising design for the transportation
applications. Meanwhile, continuous development on MEA at
small scale in 2014 led to a huge increase of the performances by
optimizing the composition (catalyst nature, membrane, ionomer
ratio, and gas diffusion layers). However, dedicated attention has
been paid to check each MEA evolution in large scale cell to avoid
any misleading development step (figure 1). These iterations
between small and large cell enabled to obtain almost the same
performance levels in both laboratory 25 cm² single cell and large
single cell representative for real bipolar plate. These results led
to the selection of an optimized “flow field|MEA” couple with high
performances level (figure 2). This enhancement implies that both
optimized designs manage to reduce heterogeneities along the
active area and thus maximize the overall performances. Electrochemical and fluidic modelling have also been helpful to understand this increase in performances in order to finally conceive a
new PEMFC design with high performances.
The performances levels obtained in 2014 are very promising and
beyond state-of-art references. Bipolar plate manufacturing and
further research on MEA are on-going to validate these latest CEA
developments at the full stack scale.
Fig. 1: MEA performances evolution in 2014 in large single cell (H2/
air, 80°C, 1.5 bar, HR 50%/50%, stoichiometry 1.5/2)
Fig. 2: Performances evolution coupling “plate flow-field & MEA”
designs optimization (see Fig. 1 for operating conditions)
TEAM
Fabrice Micoud, Jean-Phillipe Poirot, Jérémy Allix, Rémi
Vincent, Pascal Schott, Sébastien Rosini and Eric Pinton.
CONTACT
[email protected]; [email protected]
52
An algorithm for diagnosis of proton exchange membrane
fuel cells by electrochemical impedance spectroscopy
CONTEXT
The Proton Exchange Membrane Fuel Cell (PEMFC) is one of the
most attractive energy conversion devices, to be used as a power
source for portable, stationary and mobile applications. However
water management is a key issue to obtain satisfactory and stable
PEMFC performances and durability.
APPROACH
The Electrochemical Impedance Spectroscopy (EIS) has been
demonstrated to be a powerful non-invasive in situ experimental technique for investigating the complex processes occurring
within a PEMFC. The aim of the present study is to identify and
characterise PEMFC flooding by using EIS and to diagnose the
flooding for a stack through a simplified physic-based model associated to impedance spectroscopy measurements.
This work was carried out in the frame of a national ANR program
(OMNISCIENT) in close collaboration with LEPMI (Laboratory of
Electrochemistry and Physico-chemistry of Materials and Interfaces).
References
[1] S. Tant et al., “An algorithm for diagnosis of proton exchange
membrane fuel cells by electrochemical impedance spectroscopy,”
Electrochimica Acta, vol. 135, pp. 368–379, Jul. 2014.
RESULTS
During this study, made in close collaboration with the Laboratory of Electrochemistry and Physico-chemistry of Materials and
Interfaces) (LEPMI) an electrochemical parameter fitting algorithm
was proposed [1]. A careful study of the electrochemical kinetics
laws allowed us to demonstrate that, as long as both electrodes
follow a Tafel behavior, the cathode and anode active layer resistances are strongly correlated. This correlation obviously removes
a liberty degree in the model and allows an accurate fitting of the
utilized model’s electrochemical parameters of our PEMFC stack
EIS. The reduced number of liberty degrees eases the convergence
of the solution of the model. This algorithm was successfully
tested on data recorded for three different PEMFC stacks, based
on metallic or composite bipolar plates, to investigate the impact
of water flooding at different operating points. As shown in figure
1, the impedance diagrams are recorded on a H2/Air PEMFC stack,
for 4 operating points (current densities and cell voltages) along
the polarisation curves at high, moderate and low cell potentials.
On each impedance diagram are also plotted the different contributions identified using the model. Good correlation obtained
between experimental results and the simplified model makes
then possible to identify the signature of water flooding in real
time and so to optimise water management within a stack in operation (figure 2).
EIS stands for a relevant tool of monitoring the state-of-health of
a PEMFC stack with respect of the water content in the membrane
electrode assembly. The model developed here to match experimental impedance diagrams gives useful information to monitor
a fuel cell stack with a minimum of fitting parameters. This type of
model can be easily embedded in hardware dedicated to fuel cell
system diagnosis in order to optimise water management at stack
level and so to increase system efficiency and durability.
Fig.1: Evolution of the electrochemical impedance spectroscopy with the current
and identification of the different contribution using a physical model
Fig. 2: Evolution of stack electrical parameters identified
according to the smart model as a function of gases relative
humidity.
TEAM
Sylvain Tant, Sébastien Rosini, Hortense Lafôret,
Fabrice Micoud
CONTACT
[email protected]
53
Electric vehicle integration into distribution network:
challenges and opportunities
CONTEXT
With the rapid growth of electric vehicles (EV) connected to the
distribution network (energy transition law with 7 million of EV
charging points in France), this EV integration presents challenges
and can have several impacts on grid such as increasing the peak
load and the risk of congestion (overload), the voltage variation
and voltage unbalance, losses and harmonics …
The EV integration into grid also presents opportunities such as
the contribution to ancillary services. Therefore it is necessary to
estimate technical and economic impacts and to propose solutions for EV control and management.
FUNDINGS
This work was partly carried out in the frame of Ademe Greenlys
project (greenlys.fr).
References
[1] T. Tran-Quoc, X. Le Pivert, Mehdi, “Stochastic Approach to Assess
Impacts of Electric Vehicles on the Distribution Network”, IEEE-ISGT,
Oct 2012, Berlin
APPROACH
In order to study EV integration into grid, a stochastic approach
using probabilistic three Phase Load Flow (PLF) program is developed by using Monte Carlo techniques with random variables of
EV charging such as the battery state of charge (SOC), the starting time and the departure time of charging and the location of
EV. Different indicators are proposed such as indicators related
to: power flow in lines, voltages, unbalance voltage rate, losses,
to economic criteria (charging cost). Different control and management strategies for EVs are proposed to reduce charging costs,
facilitate EV integration, maximize usage of PV energy to charge
EVs, reduce negative impacts, and maximize the EV participation
to ancillary services. For optimal management strategies, the
constraints are respected such as power exchange with the grid,
power limited by distribution system operator (DSO), initial SOC,
comfort conditions and priority of EV. A bisection method coupled
with linear programming is proposed. For a real time control, fuzzy
logic is also proposed.
Fig. 1: Power flows of
transformer
Fig. 2: Total EV charging
power without
RESULTS
To assess impacts of EV on the distribution network several scenarios have been simulated (For each scenario, 1 000 simulations
have been carried out with the Monte-Carlo technique). The
results show that an EV penetration rate superior to 20% leads to
overloads of transformer (fig 1). The proposed control and management strategies for EVs are validated by simulations for different
objectives, different scenarios and on different grids. Fig. 2 shows
the total charging power of parking with 50 EVs in two cases:
without management and with management (with or without
demand of DSO). Fig. 3 shows a real time control of 20 EVs in order
to maximize the usage of PV energy.
Fig. 3: Maximize usage of
PV energy: without (top)
and with (bottom) the
proposed solution
Thus impacts of EV on grid can be fully evaluated. The proposed
solutions for EV control and management permit to increase the
EV penetration into grid. A real demonstration is underway.
TEAM
Quoc Tuan Tran, Van Lin Nguyen, Hervé Buttin, Olivier
Wiss
CONTACT
[email protected]
54
Development of a modeling and simulation tool: a common
environment for the evaluation of energy systems
CONTEXT
Along with the increasing penetration of renewable energies,
energetic systems become more and more complex due to the
multiplicity of technologies (different energy sources, storage and
information technologies), actors and business models. To cope
with this complexity, modeling and simulation are required to
design energetic systems, optimize components, sizing and operating strategies according to technical and economic criteria.
This work was carried out in the frame of the ULISSE project funded by the Carnot Institute “énergies du futur”.a
References
[1] Guinot B., PhD thesis, Université de Grenoble, 2013.
[2] F.Bourry, D.L. Ha “Advanced Simulation Tool for the Optimal
Management of Photovoltaic Generation in Combined Systems.” In
2013 IEEE PowerTech Conference
APPROACH
An unification of simulation approaches was initiated starting from
a comprehensive analysis of existing in-house developed tools
(ODYSSEY [1] and M2C [2]) and a review of simulation requirements,.
The objective was to improve capitalization on components and
control models and to favour coherence between studies by building common methods and investigating the development of a
common simulation tool.
RESULTS
The analysis performed by research teams on modelling and simulation requirements and approaches led to a joint specification
document for a simulation tool (architecture, functionalities, etc.).
The identified objectives for this tool were:
• to integrate all Liten technologies and adapt to any anticipated
case studies (self-consumption, micro-grid, power-to-gas,...);
• to support multi energetic vectors (electrical, hydrogen, thermal,
gas), and their associated network;
• to achieve every required type of study (techno-economic optimization, control design,...).
From these specifications, a first version of SPIDER (Simulation
Platform for the Integration of Distributed Energy Resources)
was developed (fig.1: the SPIDER user interface). The inventory
and analysis work also showed an important variety of tools and
approaches suggesting a strong added-value in sharing methods
and models. Although a common tool facilitates inter-laboratory
work, it may also impose some trade-off between simplicity, flexibility, control design approaches and calculation performances. To
face these limitations, SPIDER is fully integrated into a common
Liten tool, designed to share models, analysis modules and simulation applications (as illustrated in Fig. 2).
The project allowed the development of a common tool based on
the analysis of modelling and simulation requirements at Liten. It
also initiated the implementation of a framework to share models,
methods and applications. This will undoubtedly favour capitalization between research teams and ensure higher efficiency on each
envisioned simulation study.
Fig.1: SPIDER user interface (self-consumption case study)
Fig. 2: Illustration of the simulation framework for energy systems evaluation
TEAM
Cyil Bourasseau, Franck Bourry, Benjamin Guinot, Liem
Than Phan
CONTACT
55
Supercritical Organic Rankine Cycle
CONTEXT
Recovery of waste heat in industrial processes is an important
contribution to energy saving worldwide. The valorization of
this waste heat can be done by different methods. One of these
solutions is to convert heat to electricity through thermodynamic
cycles. This technical and technological challenge is also a key
point to renewable natural resources use (solar, geothermal, biomass).
APPROACH
Numerous thermodynamic cycles and technological solutions
have been proposed. Among them, Rankine Cycle system is the
most widely used for medium temperature whereas Brayton or
Stirling cycles seem the most interesting processes at high temperature. First of all, CEA established a new database of existing
systems based on quantitative elements, such as system working temperature, system power, system efficiency (Fig. 1, [1]).
The database containing more than 1100 references have been
analyzed through thermodynamic models [2]. It appears that at
low temperature, solutions have to be developed and optimized.
An innovative solution for this temperature range (80-150°C) is a
supercritical organic Rankine cycle (ORC) machine.
FUNDINGS
This work was partly carried out as part of a CARNOT program
(SSORC project). Part of this work is done as part of the PhD thesis
of Arnaud Landelle, co-funded by ADEME and CEA.
References
[1] N. Tauveron, S. Colasson, J.-A. Gruss, 2014, Available systems for
the Conversion of Waste Heat To Electricity, IMECE2014 Conf.
[2] N. Tauveron, S. Colasson, J.-A. Gruss, 2015, Conversion of waste
heat to electricity: cartography of possible cycles due to hot source
characteristics. ECOS Conf.
[3] A. Landelle, N. Tauveron, P. Haberschill, N. Tauveron, S. Colasson,
2015, Experimental and analytical study of transcritical organic
Rankine cycles at low temperature, ASME ORC Conf.
RESULTS
This cycle is not really new in the scientific community but rarely
experimentally studied. The purpose of the experimental study is
to develop a few kWe prototype (photographs above) of a supercritical ORC, able to be adjusted to a variable heat source (such
as industrial waste or renewable source which are often irregular).
The complete system has been defined and designed by the laboratory.
A first task was to characterize various component behavior in
supercritical regimes. In such cycles, the pump plays a strategic
role. A comprehension study has been performed to quantify
thermal and power exchanges [3]. Expander is also a key component. Various technologies were possible, but in the range of “low
power (i.e. under 50 kWe)” a scroll compressor used in the refrigeration industry, modified to work as an expander, was selected as
an attractive, efficient and low cost alternative to turbomachines
(photo). Secondly the complete cycle has been built and tested in
the subcritical regime and compared to simulation results (Fig. 2).
In the next months, dynamic behavior in supercritical regime will
be investigated.
Fig. 1: Map of Maximum temperature versus Power for various thermodynamic cycles and technologies
Fig. 2: ORC performance: comparison of experimental data and simulation results
TEAM
Stéphane Colasson, Nicolas Tauveron, Jérôme Bentivoglio, Arnaud Landelle, Tommy Aime
CONTACT
[email protected]
56
Advanced aerogel-based insulating materials for building
applications
CONTEXT
The recent 2012/27/EU Directive has underlined the importance of
the renovation of the existing building stock. The share of the building sector is about 43% of the total energy consumption. In this
sector, space heating remains the largest energy end-use. Nowadays, to meet the energy efficiency standards and regulations, the
insulation thickness could reach more than 30 cm. Therefore, there
is a growing interest in the so-called super-insulating materials
such as Aerogels. In this context, a new insulating rendering based
on silica-aerogels has been developed for building applications.
CHARACTERISTICS
The rendering has a very good thermal insulation performance. It
is prepared on-site through mixing with water and it is then projected onto the façade through a classical plastering machine (see
middle image on top). Its projection application facilitates building rehabilitation [1].
APPROACH
To test the hygro-thermal performance of buildings having the
aerogel-based rendering, a full-scale experimental house with the
rendering applied to its exterior facades (see left image on top)
was built at INES experimental field in Chambéry. In addition,
numerical models have been developed and their results have
been compared to on-site measurements. The energy demand
of an old house under rehabilitation located in different climates
has been calculated, firstly without the aerogel rendering and
secondly with a thickness of 4 cm aerogel rendering (Fig. 1). The
results show that the reduction in energy consumption is around
45% for all climates. For instance the annual energy demand
decreases from 244 kWh/m² to 141 kWh/m² in Lyon (Semi-continental climate). Moreover, adding the aerogel-based rendering
on the exterior surface of non-insulated or already internally insulated walls reduces significantly the moisture and mold risks (Fig.
2) [2, 3].
The aerogel-based rendering external insulation system is coupled
to an active closed-loop water based system embedded in the
rendering for the aim of decreasing the space heating demands
and/or producing domestic hot water [4, 5, 6].
PARTNERS
Parex group, PCAS, CSTB, LOCIE, ARMINES, CEA, and Wienerberger
ACKNOWLEDGMENTS
This work was funded via the “FUI Parex.IT project” and “PAREX
group” financial supports.
This work was part of Mohamad IIBRAHIM PhD thesis
References
Peer-reviewed journal articles
[1] Ibrahim et al. Limiting windows offset thermal bridge losses using
a new insulating coating. Applied Energy 123 (2014) 220-231
[2] Ibrahim et al. A study on the thermal performance of exterior
walls covered with a recently patented silica-aerogel-based insulating
coating. Building and Environment 81 (2014), 112-122
[3] Ibrahim et al. Hygrothermal Performance of Exterior Walls Covered
with Aerogel-Based Insulating Rendering. Energy and Buildings 84
(2014) 241–251
[4] Ibrahim et al. Transferring the South Solar Energy to the North
Facade through Embedded Water Pipes. Energy 78 (2014) 834-845
Patents
[5] Wurtz E. and Ibrahim M. Bâtiment intégrant un dispositif de
régulation thermique, dispositif et procédé de régulation associés.
Patent WO2015044111 A1
[6] Achard P., Ibrahim M., Wurtz E. Procédé de pose d’un parement
extérieur sur une façade d’un bâtiment et bâtiment correspondant.
French Patent application N° E.N. 15 55759
Fig. 1: Annual energy
demand for an
old house located
in different cities
without and with
4cm of the aerogel
render
CONCLUSION
Fig. 2: Exterior wall’s
total water content
for different insulation configurations
The aerogel-based rendering has a significant impact on decreasing the house energy consumption and improving thermal
comfort. It is ideal for old building retrofit cases.
PERSPECTIVES
New silica Advanced Aerogel-Based Composite Panels (see right
image on top) with extremely low thermal conductivity are being
developed for building thermal insulation applications within an
EU H2020 funded project (HOMESKIN).
TEAM
Mohamad Ibrahim, Etienne Wurtz
CONTACT
57
Residential seasonal heat storage demonstrator
CONTEXT
Household demand represents almost 40% of European final
energy consumption. Most of this energy is dedicated to house
heating and domestic hot water production.
Solar thermal collector presents a very interesting energy conversion ratio, but the time gap between heating demand and solar
resource availability leads to a limited energy saving fraction. Therefore, seasonal storage is a key solution since it allows collecting
heat in summer and discharging it in winter.
A first full scale thermochemical seasonal storage demonstrator
was built and connected to an experimental house. First results
show that the system works and that both energy density and
solar fraction can reach record levels.
This works was carried out as part of a CARNOT program
(StockHiDens project).
APPROACH
Among several available technologies, thermochemical storage
was selected for its record density and absence of systematic long
term losses. Indeed, the heat is stored in salt hydrates through
reversible exothermic hydration and endothermic dehydration
reactions[1]. In order to improve the maturity of this promising
technology as seasonal heat storage, a real scale demonstrator
was designed, built and commissioned as a stand-alone heating
system of an experimental house located at INES platform, which
is a world premiere.
References
[1] Marias et al.; Thermodynamic analysis and experimental study
of solid/gas reactor operating in open mode ; Energy ; Volume 66, 1
March 2014, Pages 757-765
[2] Wyttenbach et al. Thermochemical seasonal storage demonstrator
for a single-family house: design, Eurosun 2014
DESIGN
Detailed dynamic thermal simulations were performed to design
and size the system. With 1580 kWh of storage capacity (6000 kg of
strontium bromide) and a solar panel surface of 18.5 m², our single
family house aims to reach a record 84% house heating solar fraction.
The fixed bed reactor technology under atmospheric pressure
was selected for its minimal amount of moving parts and its overall lower technological level. Experimental data, thermodynamic
calculations and CFD results (Fig. 2) led to divide the stock in five
units and to optimize internal design regarding heat transfer and
pressure drop.
An innovative air flow allocation system (Fig. 1) was designed to
handle variable output power and multiple modes: space heating from stock or solar, regeneration and ventilation. A control
strategy algorithm analyses the house demand, the environmental conditions and the reactor state of charge in order to select
the appropriate fluid circuit with the right temperatures and flow
rates [2].
Fig. 1: Innovative flow allocation system
Fig. 3: Space heating energy [kWh]
RESULTS
First winter field test were performed in February. During one
month, 194 renewable kWh were used for space heating, including 142 kWh from the storage and 51 kWh from direct solar (Fig. 3).
The state of charge curve shows that one unit was used from less
than 30% to almost 70%. Though it was a cold period, significant
partial regeneration occurred during sunny days (Fig. 4).
These good results validate the system principle. Experimental
data are being analysed in order to improve performances for next
cold season.
Fig. 2: CFD simulation of a reactor unit,
partial section
Fig. 4: State of charge of a 316 kWh unit
TEAM
Joël Wyttenbach, Louis Stephan
CONTACT
58
International conference on solar energy and buildings:
Eurosun
CONTEXT
In September 2014 INES and CEA have hosted the 10th International Congress Eurosun dedicated to solar thermal and building,
the first international conference on solar thermal in France after
more than 40 years.
RESULTS
From September 16th to 19th, 2014, INES and CEA have been the
guests of the 10th International Congress Eurosun worn by ISES
(International Solar Energy Society). During three days, more than
300 scientists, engineers have exchanged on the latest scientific
developments. Significant trends have been observed:
• R & D increase in the field of PVT collectors with still major questions on product types (covered, uncovered, air or liquid …) and
associated systems;
• Thermal storage (sensible, latent, thermochemical ...) becomes
an essential component for energy management and savings, and
is no longer dedicated to solar thermal energy;
• Development of solar thermal applications in district heating
networks, in European countries outside Denmark, pioneer in the
development of this technology;
• The significant emergence of the use of solar heat for industrial
processes.
Eurosun in figures
• More than 300 participants
• More than 200 papers presented orally or as posters
• 21 parallel sessions
• 49 countries represented
Eurosun Proceedings are freely available for download at
http://proceedings.ises.org/
This work was carried out with the strong support of INES General Secretary in collaboration with ISES (International Solar Energy
Society).
A retrospective between the 1st and the 10th edition of this conference has highlighted the major influence of political decisions
(including regulations) on the dissemination of technological
innovations to the mass market.
In parallel to Eurosun, INES and CEA have organised the “États
Généraux de la Chaleur Solaire”. Managed by Enerplan and ADEME,
this new annual event brings together all the French solar thermal
sector: over 120 people have been given the opportunity to discuss the recovery plan carried out by Enerplan Uniclima.
References
[1] www.eurosun2014.org
[2] www.ines-solaire.org
[3] www.ises.org
Finally, a workshop dedicated to PVT collectors co-organized by
CETHIL, INES, CEA, Fraunhofer ISE and SPF allowed to review this
technology and to define a roadmap for the coming years.
TEAM
Philippe Papillon, Estelle Bonhomme
CONTACT
[email protected],
[email protected]
59
Publications 2014/2015
MATÉRIAUX ET PROCÉDÉS
MATERIALS AND PROCESSES
2014
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2014
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Matter and Materials Physics Volume 89, Issue 3, 21
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60
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MATERIALS - Volume 456 - January 2015 - Pages 449-454
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Number: 155426 - Published: APR 24 2014
q L indsay, L., Broido, D.A., Carrete, J., Mingo, N., Reinecke,
T.L. - Anomalous pressure dependence of thermal
conductivities of large mass ratio compounds - (2015)
PHYSICAL REVIEW B 91 (12), 121202
qC
hen, Xi, Weathers, A., Carrete, J., Mukhopadhyay, S.,
Delaire, O., Stewart, D.A., Mingo, N., Girard, S.N., Ma, J.,
Abernathy, D.L., Yan, J.Q., Sheshka, R., Sellan, D.P., Meng,
F., Jin, S., Zhou, J.S., Shi, L. - Twisting phonons in complex crystals with quasi-one-dimensional substructures
- (2015) NATURE COMMUNICATIONS - Volume: 6 - Article
Number: 6723 - Published: APR 2015
q L i, Wu, Mingo, N. - Ultralow lattice thermal conductivity of the fully filled skutterudite YbFe4Sb12 due to
the flat avoided-crossing filler modes - (2015) PHYSICAL
REVIEW B - Volume: 91 - Issue: 14 - Article Number:
144304 - Published: APR 15 2015
qV
ermeersch, B., Carrete, J., Mingo, N., Shakouri, A. Superdiffusive heat conduction in semiconductor alloys.
I. Theoretical foundations - (2015) PHYSICAL REVIEW
B (Condensed Matter and Materials Physics) - Volume:
91 - Issue: 8 - Pages: 085202 (9 pp.) - DOI: 10.1103/
PhysRevB.91.085202
q S avelli, G., Silveira Stein, S., Bernard-Granger, G.,
Faucherand, P., Montes, L., Dilhaire, S., Pernot,
G. - Titanium-based silicide quantum dot superlattices for thermoelectrics applications - (2015)
NANOTECHNOLOGY - Volume:26 - Issue:27 Pages:275605 - DOI:10.1088/0957-4484/26/27/275605
qB
errichon, J.D., - Louahlia-Gualous, H. , - Bandelier, P.,
- Clement, P., - Bariteau, N. - Experimental study of flooding phenomenon in a power plant reflux air-cooled
condenser - (2015) APPLIED THERMAL ENGINEERING Volume 79 - 25 March 2015 - Pages 214-224
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