Battery - FIST SA

Transcription

Battery - FIST SA

Technology
offers portfolio
CNRS
BATTERY
19/08/2014
Frédéric Mougel
V1
83 Bd Exelmans, 75016 PARIS
Tel + 33 (0) 1 40 51 00 90
Fax + 33 (0) 1 40 51 78 58
Email : [email protected] – web : www.fist.fr
S.A. au capital de 1 128 122€ R.C.S B 388 461 154
SIREN 388 461 154 00030
Code APE 6630Z TVA CEE FR 60 388 461 154
Table of contents
Global patent portfolio quick overview .................................................................................................................. 4
Temporal Evolution ............................................................................................................................. 4
Status breakdown................................................................................................................................ 4
Part 1: Cathode Material ......................................................................................................................................... 5
Part 1.1: Brief market overview ............................................................................................................................. 6
Part 1.2: Available Technologies ........................................................................................................................... 10
New process for synthesis of inorganic materials ................................................................................................. 11
New fluorosulfate useful as cathodic material in LIB ............................................................................................ 12
New synthesis of fluorosulfate useful as cathodic material in LIB ........................................................................ 14
New fluorosulfate useful as cathodic material in LIB ............................................................................................ 15
New sulfate useful as cathodic material in LIB ..................................................................................................... 16
New hydroxysulfate useful as cathodic material in LIB......................................................................................... 17
UPCOMING OPPORTUNITIES ................................................................................................................................ 18
Part 2: Anode Materials ........................................................................................................................................ 19
Method for production of an anode for lithium ion battery ................................................................................ 20
Porous carbon materials from squaric acid .......................................................................................................... 21
OTHER OPPORTUNITIES ........................................................................................................................................ 22
Part 3: Electrolyte.................................................................................................................................................. 23
Boron or aluminum complexes ............................................................................................................................. 24
Ionic conducting gels ............................................................................................................................................. 25
A new additive to enhance power for batteries or enhance energy for supercapacities ..................................... 26
High energy non aqueous batteries containing ion conducting gels, and method for preparing and using the
same ...................................................................................................................................................................... 27
Hybrid composite electrode for energy storage ................................................................................................... 28
Process to reduce capacity loss during first cycle ................................................................................................. 29
Solid polymeric electrolyte for LIB ........................................................................................................................ 30
Part 4: Measurement Devices ............................................................................................................................... 32
In-operando measurement device for LIB ............................................................................................................ 33
Part 5: Solid State batteries .................................................................................................................................. 35
Iron-doped V2O5 thin layers ................................................................................................................................. 36
Lithium ion conducting lithium sulphur oxynitride thin film................................................................................. 37
All solid-state electrochemical systems – one step assembly ............................................................................... 38
Part 6: Miscellaneous ............................................................................................................................................ 39
Table of content
2
Method for the electrolytic production of self-supporting conductive nanocomposite elements ...................... 40
Welding process for Al/Cu electrodes ................................................................................................................... 41
CNRS Key figures ................................................................................................................................................... 43
Budget forecast for 2013................................................................................................................... 43
Personnel ........................................................................................................................................... 43
Organization ...................................................................................................................................... 43
International relations ....................................................................................................................... 43
Industrial relations ............................................................................................................................ 43
Awards ............................................................................................................................................... 43
Table of content
3
Global patent portfolio quick overview
Temporal Evolution
16
Number of patents family
14
12
10
8
Abandonned
6
Valid
4
2
0
Year of priority filing
Status breakdown
Part 1:
Cathode Material
Table of content
5
Part
Brief
Table of content
market
1.1:
overview
6
According to market study made by AVICENNE, cathode material’s market is a 1.85 B$
business in 2012 (representing 75 000T).
This market has a CAGR of 16% between 2002-2012.
Main compounds are:
LCO (LiCoO2)
NMC (Li (NiMnCo)O2)
NCA (Li(NiCoAl)O2)
LMO (LiMn2O4)
LFP (LiFePO4)
Table of content
7
Polyanionic Portfolio.
CNRS proposes a patent portfolio related to polyanionic materials by replacing phosphate
groups by sulfate one’s.
Fluoro sulfates/ phosphates exhibit higher operating voltages vs Li than isostructural
hydroxysulfate/ phosphate material.
Figure: Courtesy of ALISTORE (LRCS)
This is due to Due to an increased ionicity of the M–F bonds
Figure: Courtesy of ALISTORE (LRCS)
With the same redox couple involved, LiVPO4F presents a potential higher than Li3V2(PO4)3
(~ 0.54 V of difference !!!).
Table of content
8
Performances of this different materials are given hereunder:
4.0
400 Wh/Kg
600 Wh/Kg
T- LiFeSO4F
Li2Fe(SO4)2
3.5
Voltage ( V)
800 Wh/Kg
LiCoO2
LiFePO4
3.0
FePO4.nH2O
LiFeP2O7
Li2FeSiO4F
2.5
2.0
50
100
150
200
250
Capacity (mAh/g)
Figure: Courtesy of Laboratoire de Réactivité de Chimie du Solide (Amiens)
Table of content
9
Part 1.2:
Available Technologies
Table of content
10
New process for synthesis of inorganic
materials
CONTEXT
Synthesis of inorganic compounds usually imply process at high
temperature (ceramic, sintering) or solvothermal processes (precipitation
in liquid medium at room temperature).
Ceramic processes allow to obtain polydispersed powders and are costly
due to high temperature. On the contrary solvothermal process gives a
better control on particle size if the steps of nuclear growth are well
controlled. Yet, existence of soluble precursors can limit the range of
inorganic compound available and by-products are often obtain. A
supplementary step of purification is needed and these by- products must
be retreated.
TECHNICAL DESCRIPTION
The invention described a new process of inorganic compound’s
synthesis in ionic liquid and at low temperature.
DEVELOPMENT STAGE
Reference
02508-01
Keywords
Li-ion battery,
cathode materials,
fluorosulfate.
Status of Patent
French Priority patent
application
n°
FR0805875 filed on
October 23rd , 2008
N°FR 0953529 filed
on May 28th, 2009
N° FR0955233 filed
on July 27th, 2009
entitled
Synthesis were made at a laboratory scale and electrochemical tests were
done on the obtained powders.
BENEFITS
- Cost effective (from energetic and raw material point of view)
- Homogeneous particle size
- No oxidation parasitic reaction
INDUSTRIAL APPLICATIONS
Inventors
Nadir RECHAM
Michel ARMAND
Jean-Marie
TARASCON
Exemples of possible synthesis :
LiFePO4, Na2FePO4F, Na2MnPO4F, Na2(FexMn1-x)PO4F, LiFePO4F, NaFeSO4F,
LiTiPO4F, LiFeSO4F, LiCoSO4F, LiNiSO4F, LiFe1-yMnySO4F, FeSO4F, …
Commercial Status
Exclusive or nonexclusive license
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
Table of content
11
New fluorosulfate
material in LIB
useful
as
cathodic
CONTEXT
Since the introduction of the first Li-ion battery by Sony in the nineties,
demand for batteries with enhanced performances is increasing. LIB are
widely used in laptop, cellular phones, electronic products (cameras, mp3
readers,…). They also penetrating the market of power tools and are
studied also as candidates in hybrid/electric vehicles.
Conventional materials for cathodes are oxides such as LCO, NMC or NCA,
spinelles phases or olivine structures (LFP).
Sulfate-based materials are interesting as they should theoritically have
higher potential than phosphate-based materials.
The invention described a new family of fluoro sulfate materials having a
distorded tavorite structure and corresponding to Li/NaMSO4F. In
addition their synthesis without ionic liquids is also described and
claimed.
Members of this family: LiFeSO4F, LiCoSO4F, LiNiSO4F, LiFe1-yMnySO4F,
NaFeSO4F, NaCoSO4F,…
Reference
02508 -03
Keywords
Fuel cells;
membranes;
PEMFC; precursor
Li-ion battery,
cathode materials,
fluorosulfates.
Status of Patent
Priority patent
application n°
FR0805875 filed on
October 23rd ,
2008
N°FR 0953529 filed
on May 28th, 2009
N° FR0955233 filed
on July 27th, 2009
entitled
DEVELOPMENT STAGE
Table of content
12
Inventors
Nadir RECHAM
Michel ARMAND
Jean-Marie
TARASCON
BENEFITS
- Easy synthesis (fast and economic)
- Good electrochemical performances
fluorinated oxyanion unit)
(one
inserted
lithium
by
Exemples of possible synthesis :
LiFePO4, Na2FePO4F, Na2MnPO4F, Na2(FexMn1-x)PO4F, LiFePO4F, NaFeSO4F,
LiTiPO4F, LiFeSO4F, LiCoSO4F, LiNiSO4F, LiFe1-yMnySO4F, FeSO4F, …
Table of content
Commercial Status
Laboratory
Laboratoire
de
Réactivité
et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
13
New synthesis of fluorosulfate useful as
cathodic material in LIB
CONTEXT
Since the introduction of the first Li-ion battery by Sony in the nineties, demand
for batteries with enhanced performances is increasing. LIB are widely used in
laptop, cellular phones, electronic products (cameras, mp3 readers,…). They also
penetrating the market of power tools and are studied also as candidates in
hybrid/electric vehicles.
Sulfate-based materials are interesting as they should theoritically have higher
potential than phosphate-based materials.
The invention described a new way to synthetize the fluorosulfate (cf DI
2508-03) material using a polymer as a support for the reaction.
Members of this family are LiFeSO4F,
LiFe1-yMnySO4F, NaFeSO4F, NaCoSO4F,…
LiCoSO4F,
LiNiSO4F,
Reference
03700-01
Keywords
Li-ion battery,
cathode materials,
fluorosulfate
Status of Patent
Priority
patent
application
n°
FR1053788 entitled
“Procédé
de
préparation
de
fluorosulfates
de
métal alcalin et de
métal de transition”
filed on May 17th ,
2010
DEVELOPMENT STAGE
Synthesis were made at a laboratory scale and electrochemical tests were done
on the obtained powders.
BENEFITS
Easy synthesis (fast and economic)
Good electrochemical performances (one inserted lithium by fluorinated
oxyanion unit)
Cathode material in LIB.
Inventors
Nadir RECHAM
Michel ARMAND
Jean-Marie
TARASCON
Mohamed ATI
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
Table of content
14
New fluorosulfate
material in LIB
useful
as
cathodic
CONTEXT
Reference
04328-01
Keywords
Li-ion battery,
cathode materials,
fluorosulfate
Status of Patent
The invention described a new family of fluorosulfate material having a
triplite structure with its synthesis via dry process
Priority
patent
application
n°
FR1151864 entitled
“Nouveau matériau
fluoré
utilisable
comme
matière
active
d’électrode”
filed on March 8th ,
2011
Members of this family are the Fe/Mn solid solution LiFe1-xMnxSO4F.
DEVELOPMENT STAGE
Synthesis were made at a laboratory scale and electrochemical tests were done
on the obtained powders.
BENEFITS
Easy synthesis (fast and economic)
Good electrochemical performances
Operating voltage of 3.9V (to be compared with 3.6 V of LiFeSO4F or
3.45 V of LFP)
Inventors
Prabeer BARPANDA
Michel ARMAND
Jean-Marie
TARASCON
Mohamed ATI
Jean Noël CHOTARD
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
Table of content
15
New sulfate useful as cathodic material in
LIB
CONTEXT
Reference
05158-01
Keywords
Li-ion battery,
cathode materials,
fluorosulfate
Status of Patent
Priority
patent
application
n°
FR1251854 entitled
“Sulfates
utiles
comme
matériaux
d’électrodes” filed on
Fébruary 29th , 2012
The invention described a new family of sulfate material with chemical
formula (Na,Li)xFey(SO4)z. Li2Fe2(SO4)3 is excluded.
DEVELOPMENT STAGE
BENEFITS
Classical synthesis (ionothermal route or solid state route)
Operating voltage of 3.8V
No fluor
Table of content
Inventors
Jean-Marie
TARASCON
Mohamed ATI
Jean Noël CHOTARD
Marine REYNAUD
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
16
New hydroxysulfate useful as cathodic
material in LIB
CONTEXT
Reference
05158-02
Keywords
Li-ion battery,
cathode materials,
fluorosulfate
Status of Patent
Priority
patent
application
n°
FR1251854 entitled
“Sulfates
utiles
comme
matériaux
d’électrodes” filed on
February 29th , 2012
The invention described a new family of hydroxysulfate material with
chemical formula LixFeSO4OH with x<=1.
DEVELOPMENT STAGE
BENEFITS
Classical synthesis (ionothermal route or solid state route) with low cost
precursors
Operating voltage of 3.6V.
No fluor
Table of content
Inventors
Jean-Marie
TARASCON
Mohamed ATI
Jean Noël CHOTARD
Marine REYNAUD
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
17
UPCOMING OPPORTUNITIES
(Further information upon request)
- Dr DOLLE’s invention, Ref. 03228-02/FM, entitled “Synthèse d’un
fluorophosphate métallique et utilisation comme matériau actif d’électrode pour
accumulateur »
Patent: Patent application N° FR 09 05405 filed on November 10, 2009. PCT extension
filed. National phases in Europe and USA. CNRS coowner but not patent manager, further
information upon request.
Table of content
18
Part 2:
Anode Materials
According to market study made by AVICENNE, anode material’s market weight 0.6
B$ in 2012 (representing 38 000T).
Main compounds are:
Graphite in its natural form or artificial
Mesocarbon microbeads
Some new materials enter into market such as amorphous phase, titanate (Li4Ti5O12)
or Si or Sn phases.
Table of content
19
Method for production of an anode for
lithium ion battery
CONTEXT
In LIB development during past years, efforts were mainly done in
cathode materials. However, in recent years, research were also made to
replace the traditional graphite anode by other materials allowing better
electrochemical performances.
The invention relates to a method for production of an anode for a lithium
ion battery, said annode comprising a current collector made from a
transition metal in a sponge form and an active material made from a
binary phosphide. The method involves subjecting a transition metal
sponge to the effect of phosphorous vapors at a temperature of 300-600
degree Celsius. The phosphorous is present in a stoichiometric amount
with respect to the transition metal. An active material is made from a
binary phosphide of the metal. The reaction between the metal sponge
and the phosphorous is implemented during a time of 6-120 hours.
BENEFITS
The method allows an anode to be obtained which has a continuity
solution between active material and a current collector in order to
optimize the active material/current collector interface with better
electronic conductivity so providing anode with improved cycling behavior.
The method therefore eliminates the need to mix carbon with the active
material to improve its electroconductivity. The method allows the
synthesis of the active material and the production of the anode to be
carried out in a single step so simplifying the production of the battery.
The anode formed and its compounds are non-toxic, and are stable to the
air and the water. The use of the sponge permits rapid reaction between
the transition metal and phosphorus, and leads to a uniform deposit of the
metal phosphide layer.
This invention could be used to develop the anode of rechargeable
lithium-ion batteries. The anode and its components are not toxic and are
stable in presence of water or air.
Table of content
Reference
00177-01
Keywords
Battery; Collector;
Foam; Anode;
Phosphide lithium.
Status of Patent
Priority patent of
invention n°
FR0504961 filed in
May 18, 2005
entitled: "Procédé
de préparation
d'une anode pour
batterie à ionlithium »
Inventors
Laure
MONCONDUITJEGOU, Frédéric
GILLOT, JeanMarie TARASCON
Commercial Status
Laboratory
Institut Charles
GERHARDT (ICG,
UMR5253),
Montpellier,
France
20
Porous carbon materials from squaric acid
CONTEXT
There are currently a high number of porous carbon materials and a high
number of associated processes. Nevertheless, there is a demand for easy
one-step process leading to such material.
In the present work, the inventors have developped an easy one-step
process to prepare a porous carbon material mixing Pyrolysis and
Boudouard equilibrium from oxocarbones (squaric acid).
Material’s characteristics:
Sp2 carbon configuration ;
Interconected pores (size 40A) ;
Specific surface (BET) 750 m²/g ;
Expanded foam ;
BENEFITS
Apart from the material’s own benefits such as a high porosity and the
fact it is a conductor, the process offers numerous advantages:
One-step;
Low temperature;
DEVELOMENT STAGE
Suitable process for multi-gram scale synthesis;
Scale-up being assessed;
Porous carbon materials can be used in numerous applications :
Electrodes, electrochemical storage ;
Light wave detection device ;
Separation chemistry (chromatography, …) ;
Heterogeneous catalysts,
Absorbant materials
Table of content
Reference
03757-01
Keywords
Porous, carbon, foam,
squaric acid, electrode,
separation, catalysis,
absorption, detection.
Status of Patent
French patent
application FR1156870
filed on July 27th, 2011
and entitled « Procédé
de préparation d'une
mousse de carbone,
matériau obtenu et
applications »
Inventors
Philippe Poizot
Franck Dolhem
Jean-Noël Chotard
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
and Laboratoire de
glycochimie, des
antimicrobiens et
des agroressources
(LG2A FRE3517)
Amiens, France
21
OTHER OPPORTUNITIES
- Dr ROSSO’s invention, Ref. 04312-01/FM, entitled “Anodes de batteries Liion »
Patent: Patent application N° FR1154525 filed on May 24 2011.
CNRS coowner but not patent manager, further information upon request.
- Dr JUMAS’s invention, Ref. 00272-01/FM, entitled “Matériau composite
d’électrode négative, procédé de fabrication, électrode négative et accumulateru
lithium-ion »
Patent: Patent application N° FR0451742 filed on July 30 2004.
CNRS coowner but not patent manager; further information upon request.
Table of content
22
Part 3:
Electrolyte
According to market study made by AVICENNE, electrolyte’s market weight 0.46 B$
in 2012 (representing 26 000T).
Usually electrolyte are made from a lithium salt (mainly LiPF6) dissolved in a mix of
organic solvent such as ethylene carbonate with ethyl methyl carbonate, dimethyl
carbonate, diethyl carbonate, propylene carbonate.
However in Lithium polymere technology, electrolyte is made of solid polymer
sometimes wetted with lithium salt and solvent
Table of content
23
Boron or aluminum complexes
The aim of this invention is to provide a complex able to form an adduit with a
salt, the aforementioned adduit having a nucleophilic anion part and being
soluble in polar solvents aprotic.
Reference
02090-01
The invention rests primarily on the fact that, in an unexpected way, complexes
formed by Lewis acid derived from boron or aluminum are able to form
complexes with an anion Z chosen among F ('), OCN ('), O (2 '), O [2] (2 '), O [2] ('
'), OH ('), RO ('), RN (2') 'R [2] NR (') and CN ('), HNCN ('1) NCN (2') and NR (3') of a
salt whose cation can be an alkaline cation.
Keywords
Boron, Aluminum,
solvents, lithium
battery
It relates to boron or aluminum complexes, to the preparation thereof, and to
the use thereof for solubilizing ion components. The complexes have one of the
following formulas: (I, II, III, IV, V, and VI) wherein D is B or Al; R1 is R, RF, NO2,
CN, C(=O)OR, RSO2, or RFSO2; X1, X2, X3, and X4 each is a divalent group >C=O,
>C=NC N, >C=C(C N)2, >CR2R3, or >SO2; Y1, Y2, and Y3, each is a divalent group O-, >N(C N), >N(CORF), >N(SO2R4), >NR4, >N(COR4), or >N(SO2RF); R1, R2, and
R3, each is H, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group,
an oxaalkyl group, or an alkenyl group; R4 is an alkyl group, an aryl group, an
alkylaryl group, a heteroaryl group, an arylalkyl group, an oxaalkyl group, an
alkenyl group, or an RFCH2 group; RF is a perfluoroalkyl group, partially
fluoridated alkyl group, or a partially or totally fluoridated phenyl group; each of
groups R'2 and R'3 is R or F.
French patent
application N° 08
01506 filed in March
19, 2008, entitled
“Nouveaux
complexes du bore
et de l'aluminium
BENEFITS AND INDUSTRIAL APPLICATIONS
These boron/aluminum complexes allow the solubilization of ion components
which could have various uses, particularly as additives of lithium battery
electrolytes to increase their solubility.
Status of Patent
Inventors
ARMAND Michel
TARASCON JeanMarie
RECHAM Nadir
GRUGEON Sylvie
LARUELLE
Stéphane
DEVARAJ
Shanmukaraj
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
Table of content
24
Ionic conducting gels
CONTEXT
The sol-gel process is well known in the prior art, simple to implement, takes
place under mild conditions and facilitates the shaping of materials.
In a standard fashion, the sol-gel process consists of a hydrolysis and
condensation process which, starting with a molecular precursor (true solution)
leads to the formation of a colloidal solution (or sol) then, by connection of the
colloidal particles, to the formation of a continuous solid skeleton named a gel.
The non-hydrolytic sol-gel process is a particular case of a sol-gel process, taking
place in the absence of water. Another notable particular case consists of a solgel process for obtaining silica gels by using formic acid (formation of water in
situ) (Sharp, 1994; Dai, 2000).
Ionic Liquids have remarkable properties such as zero volatility, a high ionic
conductivity as well as catalytic properties. They are currently used in numerous
fields, in particular as electrolytes.
Inventors have decided to combine properties of silica gels and ionic liquids.
The invention describes a one-step process consisting in preparing a new ionic
conductive gel in solid form known as ionogel. The method consist in a step of
mixing an ionic liquid with at least one molecular precursor containing at least
one hydrolysable group, if necessary in the presence of an acid such as
carboxylic acid. The mixture is subsequently left to stand for one or more days
until a gel is formed by polycondensation of the molecular precursor(s). The gel
contains the aforementioned ionic liquid and can be set in particular in
transparent monolithic solid form.
BENEFITS
Reference
63426
Keywords
Sol-gel, ionic
conductor.
Status of Patent
French patent
application Fr 03
08190
filed on 4 July 2003
Entitled “Ionic
conducting gels,
preparation method
and use of the
same”
Inventors
André VIOUX,
Jean LE BIDEAU,
Marie-Alexandra
NEOUZE,
Fabrice LEROUX
The invention relates to ionogels, having the following characteristics and
advantages:
They are monolithic solids ;
They are stable to temperature of approximately 350°C;
They are transparent;
They are ionic conductors their ionic conductivity being in particular comprised
between approximately 10-4 and 10-3 S.cm-1 at ambient temperature and
between 10-2 and 10-1 S.cm-1 at 230 °C.
Commercial
Status
UMR6502), Nantes,
France
Applications for this invention are manifold. This new gel can be used as
electrolyte in fuel cells and batteries as it has a very good ionic conductivity and
it is stable at high temperature.
It also can be used in optical display thanks to its transparence.
Table of content
Laboratory
Institut des
Matériaux Jean
Rouxel (IMN,
25
A new additive to enhance power for
batteries
or
enhance
energy
for
supercapacities
CONTEXT
Batteries as Lithium Ion Batteries (LIB) usually have good performance in terms
of energy density. On the contrary, supercapacity are known to exhibit good
performance in terms of power density as could be seen in typical Ragonne plot
hereunder.
Reference
04216-01
Keywords
Additives, battery,
supercapacity.
Status of Patent
This invention describes compound that could be used as additives in LIB
electrolyte. These compounds fill the gap between battery and supercapacitor.
BENEFITS
Enhancement of power for batteries
Enhancement of energy for supercapacitor
“Hybride” electrode between battery and supercapacitor could be used and
their performances are enhanced (power and energy)
Low cost manufacturing of electrode
Could be used with organic materials.
Priority patent
application n° FR 11
54137 filed on May 12,
2011 entitled "
Composés à
groupement Redox,
leur utilisation comme
additif d’électrolyte,
composition
d’électrolyte et
systèmes
électrochimiques les
contenant
Inventors
GAUBICHER Joël
MADEC Lénaïc
BOUVREE Audrey
BLANCHARD Philippe
LESTRIEZ Bernard
BROUSSE Thierry
GUYOMARD
Dominique
The main application of this invention are batteries and supercapcitors.
Commercial
Status
DEVELOPMENT STAGE
Tests done demonstrate that energy and power delivered are multiply by 1.5 –
2.5 compared to the same system without the additives.
Laboratory
Institut des
Matériaux Jean
Rouxel (IMN,
UMR6502), Nantes,
France
Table of content
26
High energy non aqueous batteries
containing ion conducting gels, and method
for preparing and using the same
This invention describes a process to modify electrodes (anodes or cathodes) in
order to improve the junction between the electrode and the solid electrolyte
(ionogel).
The preparation of the composite electrode includes a step of pouring a
medium comprising at least one ionic liquid and a lithium, sodium or
magnesium salt with at least one inorganic molecular precursor or a
polymerisable monomer, said medium being in excess, and a step of in situ
polycondensation or polymerisation
Reference
02537-01
Keywords
Electrolyte; lithium
battery; composite
electrode.
Status of Patent
This invention describes compound that could be used as additives in LIB
electrolyte. These compounds fill the gap between battery and supercapacitor.
BENEFITS
The process allows to avoid the following drawbacks:
Security due to a lack of liquid electrolyte and explosion or fire.
Multistep fabrication including hot lamination, Bellcore technology (gel
electrolyte) or sintering for ceramic electrolyte.
A low quantity of active material in the electrode.
The patented process is fully compatible with state of the art electrode
preparation process with no need of high temperature or additional chemical
treatment.
As all solid electrolyte is obtained, there is no problem of security as fire,
explosion...
Thick electrode can be obtained without a diminution of active material.
The presence of active material is increased. For example for LiCoO2 electrode
or LiNi1/3Mn1/3Co1/3O2 electrode with the patented process we can obtain a 8590 wt% of active material compared to 40-45 wt% usually observed.
This process could be used obviously in lithium accumulator. However it is not
limited to this application.
For example we can underline other applications such as:
Micro batteries: as there is no treatment needed more than 100°C, the
process could be implemented directely on a printed circuit.
Non rechargeable lithium batteries
NiCd, NiMH accumulators
Alcaline cells
Fuel cells
Supercapacitors or electrochromic systems
Table of content
French patent
application FR 09
50936 filed in February
13, 2009
Entitled: "Gels
conducteurs ioniques,
leur procédé de
préparation et leur
utilisation comme
électrolyte”
Inventors
LE BIDEAU Jean,
GUYOMARD
Dominique, DUCROS
Jean-Baptiste,
SOUDAN Patrick
Commercial
Status
Laboratory
Institut des
Matériaux Jean
Rouxel (IMN,
UMR6502), Nantes,
France
27
Hybrid composite electrode for energy
storage
CONTEXT
The aim of this invention is to improve the performances of electrodes, by
improving the contact first between the particles of active material, and on the
other hand between the particles and the current collector.
The invention relates to a composite electrode which includes a mixture of
active material particles (AM) and particles constituted with a material
generating an electronic conductivity (EC). This mixture is supported by an
electrical lead forming a DC current collector.
The electrode can be made by a method which consists of modifying the AM
particles and the EC particles that must react together and with the material of
the collector in order to form covalent and electrostatic bonds between said
particles, as well as between said particles and the current collector, and then
placing the different constituents in contact.
BENEFITS
Benefits of the batteries using these composite electrodes:
•
Better performances under high voltage
•
Lifetime increased
These composite electrodes can be used in secondary lithium batteries and
especially in a range of temperature from -40°C to 110°C.
These batteries can be Lithium polymer or Li-ion batteries with liquid or solid
electrolytes
We can underline other applications such as:
NiMH accumulators
Supercapacitors
Fuel cells
Table of content
Reference
02722-01
Keywords
Composite electrode.
Status of Patent
Priority patent of
invention n° FR09
01664 filed in april 06,
2009, entitled "
Electrode composite”
Inventors
LESTRIEZ Bernard,
GUYOMARD
Dominique,
GAUBICHER Joël.
Commercial
Status
Laboratory
Institut des
Matériaux Jean
Rouxel (IMN,
UMR6502), Nantes,
France
28
Process to reduce capacity loss during first
cycle
CONTEXT
During the first cycling of a lithium-ion batterie, a solid electrolyte interface
(SEI) is formed on the negative anode (graphite is the most used anode
material).
The SEI formation protect the anode but one drawback is that lithium ion are
used to form this SEI resulting in a loss of capacity for the battery.
The invention relates to a composite electrode which includes a mixture of
active material particles (AM) and particles constituted with a material
generating an electronic co The invention proposes to use sacrificial salt that
during the first cycle will be oxidized producing by this way alkali ion such as
lithium. This lithium will then be used to form the SEI, avoiding or reducing the
loss of capacity.
Reference
03402-01
Keywords
SEI formation.
Status of Patent
Priority patent of
invention n°
FR1054804 filed in
June 6th, 2010,
entitled " Procédé
pour l’élaboration
d’une batterie au
lithium ou sodium”
Salts are chosen in order to produce only gases as byproduct of oxidation.
These gases will then be eliminated of the system. LIB are generally sealed after
the first cycle to allow gases formed by the electrolyte reduction due to the
formation of the SEI to be evacuated.
BENEFITS
-
Reduced loss due to SEI formation during first cycle.
Production of porosity in the cathode which favors fast cinetic.
Inventors
ARMAND Michel,
TARASCON Jean-Marie
LARUELLE Stéphane,
GRUGEON Sylvie,
DEVARAJ
Shanmukaraj.
Formation of LIB
Commercial
Status
Laboratory
Laboratoire de
Réactivité et
Chimie des
Solides, (LRCS
UMR6007)
Amiens, France.
Table of content
29
Solid polymeric electrolyte for LIB
CONTEXT
Electrolyte is an important component of lithium-ion batteries. For a large part,
electrolyte is made of a dissolved lithium salts in a mix of organic solvents.
However, gel polymers are also used as electrolyte due to their facility to adopt
different forms.
Gel polymers are generally made of linear polymers (such as PEO or
PVDF/hexafluoropropylene copolymer), lithium salt and organic solvants. Key
criteria is the ionic conductivity at RT which is close to that of liquid electrolytes.
It also exists all solid state LIB in which there is no organic solvent in the polymer.
Main advantage is that there is no evaporation of solvents.
The present invention is a new solid polymeric electrolyte which comprises a
polymeric matrix in the form of a semi-interpenetrating polymer network
consisting of a linear elastomer, ie NBR (8.8 14.5 parts by weight) and a crosslinked ionic copolymer (35.0-58.1 parts by weight). This matrix includes a lithium
salt solution (12.4 parts by weight) in an ionic liquid (15.0-43.8 parts by weight).
Thin films can be made.
Reference
06306-01
Keywords
Solid electrolyte;
ionic liquid; NBR.
Status of Patent
Russian priority
patent application
filed on July 3rd,
2012 and entitled
“Solid state
polymer
electrolyte for
lithium batteries”
DEVELOPMENT STAGE
Different compositions were made and tests with a lithium metal as anode was
made. Cathode was LFP. Electrochemical measurements were made at 40°C.
BENEFITS
Thin films are obtained without the need of a substrate and present good
mechanical properties
Better ionic conductivity at similar ionic liquid content
Enhanced lifetime and security
Table of content
Inventors
Sergeevich
Alexander
SHAPLOV
Elena Iosifovna
LOZINSKAYA
Yakov Semenovich
VYGODSKII
Petr Sergeevich
VLASOV
Frédéric VIDAL
Michel ARMAND
Christine SURCIN
Commercial Status
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
30
Separator in all solid state batteries
Electrolyte
Table of content
(LRCS UMR6007)
Amiens, France.
A.N.Nesmeyanov
Institute of
Organoelement
Compounds of
Russian Academy
of Sciences
(INEOS RAS)
Moscow, Russia
31
Part 4:
Measurement
Devices
Table of content
32
In-operando measurement device
for LIB
Reference
05157-01
Keywords
Battery, In
operando
Mössbauer, XRD.
The invention is related to characterization of Lithium-ion battery during cycling.
In particular it allows recording Mössbauer spectra with X-Ray Diffraction.
BENEFITS AND INDUSTRIAL APPLICATIONS
This device allows a better understanding of lithium ion batteries during cycling.
Thanks to these measurements, electrode materials can be optimized.
Failure mechanisms could be explained.
Status of Patent
French patent
application n° 12
58086 filed in
August 30, 2012,
entitled “Analyse
des
caractéristiques
d’un matériau
d’électrode d’une
cellule
électrochimique”
Inventors
JUMAS Jean-Claude
STIEVANO Lorenzo
SOUGRATI Moulay
Tahar
FULLENWARTH
Julien
FRAISSE Bernard
Commercial Status
Laboratory
Institut Charles
GERHARDT (ICG,
UMR5253),
Montpellier,
France
Table of content
33
- Dr BATISSE’s invention, Ref. 05940-01/FM, entitled « Cellule
électrochimique » related to an electrochemical cell design to allow in operando
supercapacitor or LIB electrochemical testing with simultaneous analysis of emitting
gas (through MS or GC coupling) and transmission spectroscopy measurement.
Patent: Patent application N° FR1360441 filed on October 25 2013.
Table of content
34
Part 5:
Solid State
batteries
Table of content
35
Iron-doped V2O5 thin layers
CONTEXT
In order to be able to feed micro-electronics circuits for long periods, it is
necessary to increase the density of energy of the microbatteries and
consequently their capacity.
Many studies are therefore currently carried out on thin layer positive electrode
materials.
Vanadium(V) oxide (V2O5), and more generally oxides of transition metals having
a lamellar structure, arouse intensive research works, since they are more
promising than the sulphides because of their greater chemical stability, higher
potentials as compared to the Li/Li+ redox cell and larger discharge capacities.
There is still a need for thin layers positive electrodes for use in microbatteries
presenting an improved behaviour in cycling.
The invention relates to an iron-doped vanadium oxide (FeyV2O5), the process of
preparation thereof and to thin layers of positive electrode comprising irondoped vanadium oxide having a strong capacity and potentially usable in allsolid-state lithium microbatteries. The invention also relates to the preparation
process of said thin layers by cathode pulverization method.
In the present invention, the known cathode pulverization method has been
improved and comprises the step of carrying out a simultaneous pulverization
starting from two different targets in one pulverisation chamber ( a first
Vanadium-containing-target (the V-target) and a second Iron-containing target
(the Fe-target).
This invention could be used to develop all solid state lithium microbatteries.
This invention opens up the possibility to improve behavior in cycling as
compared to vanadium oxide
Reference
00728-01
Keywords
Thin layer, iron,
microbattery
Status of Patent
Priority patent of
invention n°
US61/012942 filed in
December 12, 2007
entitled "Couches
minces de V2O5
dopé au fer
présentant une forte
capacité"
Inventors
PECQUENARD
Brigitte,
LEVASSEUR Alain,
FUESS Astrid
Commercial Status
Laboratory
Institut de Chimie
de la Matière
Condensée
(ICMCB UPR9048),
Bordeaux, France
Table of content
36
Lithium ion conducting lithium
sulphur oxynitride thin film
The object of the present invention is to provide an electrolytic material that has
an improved ionic conductivity compared with materials of the prior art, and/or
that can be prepared from stable targets suitable for industrial scale
manufacture.
Accordingly, this invention relates to a material (lithium ion conducting) for uses
as electrolyte in microbatteries. Electrolytic material comprises an amorphous
compound having the atomic composition LixSMwOyNz with x= 0.5-3 y= 1-6;
z=0.1-1; w less or equal to 0.3; and M= B, Ge, Si, P, As, Cl, Br, and/or I.
This material can be prepared in the form of a thin film deposited on a substrate,
by radiofrequency magnetron sputtering, deposition being carried out under the
following conditions:
- Specific nature of the plasma used for cathode sputtering
- Nature of the target used for cathode sputtering
- Nature of the substrate used for deposition.
Reference
63853
Keywords
Conduction,
lithium, thin film
Status of Patent
Priority patent of
invention N°
US11/339607 filed in
January 26, 2006,
entitled: "Lithium ion
conducting lithium
sulphur oxynitride
thin film, and a
process for the
preparation thereof"
This invention could be used to develop electrochemical generators in the form
of micro-batteries.
Inventors
VINATIER Philippe,
LEVASSEUR Alain,
PECQUENARD
Brigitte, JOO
Kyong-Hee.
Commercial Status
Laboratory
Institut de Chimie
de la Matière
Condensée
(ICMCB UPR9048),
Bordeaux, France
Table of content
37
All solid-state electrochemical
systems – one step assembly
CONTEXT
The aim of this invention is to replace usual liquid electrolytes (organic solvent
and lithium salts) by solid electrolytes and to produce an all solid state battery.
The difficuly in manufacturing all-solid state batteries consists in sintering
together ceramic electrodes and electrolyte materials without generating
reaction between these materials.
This invention relates to a one-step assembly of an all solid state battery by a
Spark Plasma Sintering process.
Two different mixtures are prepared:
•
Mixture 1: anode active material powder, electrolyte solid powder and
an element improving the electronic conductivity
•
Mixture 2: lithium based cathode active material powder, electrolyte
solid powder and an element improving the electronic conductivity
The assembly of the battery is made by superposition of a layer of mixture 1 and
a layer of mixture 2 which are separated by an electrolyte powder layer. The
three layers are sintered together in appropriate conditions.
Reference
02987-01
Keywords
Solid state battery,
Sinteringl.
Status of Patent
Priority patent of
invention n° FR10
51149 filed in February
18, 2010, entitled "
Procédé de
préparation d'une
batterie monolithique
par frittage sous
courant pulsé”
BENEFITS
Advantage of the process used in this invention:
quick and easy to implement
no secondary reaction between the elements of the different layers
One step process
Benefits of the battery obtained with this process
Self-supported
Electrode layers are thicker than in all-solid state batteries available so
far
Good electronic conductivity properties
Good thermal stability (up to 350°C)
Inventors
DOLLE Mickael, ROZIER
Patrick, DELAIZIR
Gaëlle, TARASCON
Jean-Marie, VIALLET
Virginie, MORCRETTE
Mathieu, SEZNEC
Vincent, BOUCHET
Renaud, ABOULAICH
Abdelmaula, TORTET
Laurence
Commercial Status
This invention can be used to the manufacturing of “voluminous” all solid-state
electrochemical generators (contrary to microbatteries).
Table of content
Laboratory
Laboratoire de
Réactivité et
Chimie des Solides,
(LRCS UMR6007)
Amiens, France.
38
Part 6:
Miscellaneous
Table of content
39
Method for the electrolytic production of selfsupporting conductive nanocomposite elements
CONTEXT
In the field of energy storage using batteries, the properties of the electrodes,
and especially of the current collectors that the electrodes include, are an
important element as regards the overall performance of the batteries. In order
for a material to be able to be used as a collector, it is desirable for it to have a
high electronic conductivity, good electrochemical stability and a large area of
contact with the active material. Nanomaterials have a high area/volume ratio
thereby increasing the reaction rates, by reducing the diffusional limitations, and
the use of nanomaterials for production of current collectors is under
development.
The invention relates to a self-supporting composite element and to a method of
producing such element. The composite element comprises a substrate of
electronic conductive material which is covered with metal nanowires that are
essentially oriented along a plane that is perpendicular to the substrate.
The element is produced in a cell comprising a cathode which is formed by the
substrate to be covered, one or more anodes and an electrolyte which is formed
by a solution of a precursor of the metal material and optionally containing a
conductive ionic salt, a flat porous membrane which is placed between the
cathode and each of the anodes and a spacer element between each membrane
and the anode adjacent thereto, the different constituent parts of the cell being
maintained in contact
INDUSTRIAL APPLICATIONS.
The current collectors and the electrodes according to the invention may be
used in many electrochemical devices, such as lithium-ion rechargeable
batteries, lithium/polymer rechargeable batteries, non-rechargeable generators,
supercapacitors and electrochromic devices
Reference
00178-01
Keywords
Current collector
Status of Patent
Priority patent of
invention n° FR
0504960 filed in May
18, 2005, entitled "
Elément composite
comprenant un
substrat conducteur
et un revêtement
métallique
nanostructuré »
Inventors
SIMON Patrice,
TABERNA PierreLouis,
CAMBRONNE JeanPascal, LEBEY
Thierry ,
TARASCON JeanMarie
Commercial Status
Laboratory
Laboratoire
réactivité et chimie
des solides (LRCS,
UMR7314)
Table of content
40
Welding process for Al/Cu electrodes
CONTEXT
When realizing battery pack, it is important to have mechanical contacts
between current collectors. Welding of thin copper and aluminum electrode isn’t
possible due to the large difference between their respective melting point
(around 600°C).
The invention relates to a specific welding process (called MIG CMT) allowing the
welding between two thin (less than 1 mm) plates of copper and aluminum.
In the above figure, we can see the welding with (from left to right), aluminum
electrode, welding zone and copper electrode
Development stage
Over 30 tests were done with good reproductibility without specific optimization
of the process. Analysis demonstrates the welding between Al/Cu.
In addition, preliminary tests demonstrate a good resistance to vibrations and a
normal use of the welded cells.
Future developments are ongoing for welding the electrode in end to end
relation.
INDUSTRIAL APPLICATIONS.
Pack manufacturing
Table of content
Reference
05200-01
Keywords
Current collector
Status of Patent
Priority patent of
invention n° FR
1260984 filed in
November 19, 2012,
entitled " Soudage
hétérogène
Aluminium Cuivre »
Inventors
Alexandre BENOIT
Donald SCHLEICH
Pascal PAILLARD
Thierry BAUDIN
Commercial Status
Laboratory
Institut des
Matériaux Jean
Rouxel (IMN,
UMR6502), Nantes,
France
Institut de Chimie
Moléculaire et des
Matériaux (ICMMO
UMR 8182), Orsay,
France
41
- Dr VINASSA’s invention, Ref. 06203-01/FM, related to Battery Management System
Patent: Patent application N° FR1359508 filed on October 1, 2013. Not published yet, further
information upon request.
Table of content
42
CNRS Key figures
Source: CNRS internet website
Budget forecast for 2013

3.4 billion Euros
Personnel

Over 32,000 employees of which 24,955 are CNRS tenured employees:
o 11,204 researchers
o 13,751 engineers and support staff
Organization



10 institutes (3 of which have the status of national institutes)
19 regional offices, ensuring decentralized direct management of laboratories
1,028 research units (95 % are joint research laboratories with universities and industry)
International relations









50 exchange agreements (with over 40 countries)
4,600 foreign visiting scientists (PhD students, post-docs and visiting researchers)
1,690 permanent foreign researchers
420 permanent foreign engineers and technicians
331 International Programs for Scientific Cooperation (PICS)
127 International Associated Laboratories (LEA/LIA)
112 International Research Groups (GDRE/GDRI)
30 International Joint Units (UMI)
10 CNRS offices abroad (Beijing, Brussels, Hanoï, Malta, Moscow, New Dehli, Pretoria, Rio de
Janeiro, Tokyo, Washington)
Industrial relations




25 framework agreements with major international industrial groups
4,521 main patents (is in the Top 100 Global Innovators, and 7th applicant in France)
959 licenses and other financially remunerating active acts
704 companies created with CNRS since 2000
Awards


19 Nobel Prizes
12 Fields Medals
Table of content
43
www.fist.fr
Table of content
44

Battery - FIST SA

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