Tendinte in fizica aplicata: specificitate si

Tendinte in fizica aplicata:
specificitate si diversitate
Eugen Stamate
Reactive Plasma Processing
Technical University of Denmark
Outline
- DTU Energy
- Procese cu plasma pentru conversia si stocatea energiei
- Civism universitar
- Diversitate si specificitate in cercetarea de fizica aplicata
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DTU Energy, Technical University of Denmark
DTU Energy
• Sustainable technologies for energy conversion and storage
• 230 staff (over 100 PhDs)
• Research spans from fundamental investigations to component
manufacture
• Focus on industrial collaboration and industrially relevant processes
• Created in 2012 including parts of:
– Risø DTU National Laboratory
for Sustainable Energy
– DTU Chemistry
• Located on two campuses: Risø and Lyngby
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DTU Energy, Technical University of Denmark
Technologies
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Fuel cells
Electrolysis
Solar cells
Batteries
Synthetic fuels
Membranes for oxygen or hydrogen separation
Magnetic refrigeration
Thermoelectric components
Flue gas purification using electrochemical cells
• FCH Test Center for
fuel cell and hydrogen
technologies
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DTU Energy, Technical University of Denmark
Activitate stiintifica
Domenii de interes
- fizica plasmei (aspecte fundamentale, diagnoza, surse de plasma pentru
presiuni joase si presiune atmosferica)
- procesare cu plasma (corodare, implantare ionica, procese de suprafata,
reducerea de noxe)
- straturi subtiri si nanostructuri (pulverizare prin magnetron, producerea de
nanoparticule cu plasme termice, oxizi conductori si transparenti)
- materiale pentru conversia si stocarea energiei (celule electrochimice,
generatori termoelectrici, baterii)
Curs academic
- Advanced plasma processes for tailoring materials and nanostructures
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DTU Energy, Technical University of Denmark
Li thin film batteries
high power density
Small volume and
Energy storage – essential for an information based society
Targeted applications:
- MEMS
- Smart cards
- Micro-cameras
- Microelectronics
Thin-film battery
Koo et al., Nanoletters (2012)
DTU Energy, Technical University of Denmark
Lithium Ion Batteries
Conventional Lithium ion battery
Less compatible with micro and
nanoelectronic devices, safety issues
All-solid-state thin film Lithium
ion battery
Both electrodes are capable of reverse lithium
insertion. Because of difference in chemical
potential the transport delivers (discharge) or
consumes (charge) energy.
Requirements:
- High ionic conductivity
- Stability with anode and cathode
- Large potential window
DTU Energy, Technical University of Denmark
Needs to be compatible with soldering
– stand more than 220°C
Main requirements:
Anode and cathode:
- high ionic conductivity as to provide high charge/discharge rates
- high electronic conductivity
- low volume expansion during lithium intercalation
- high compatible with volume variation during charge/discharge
- high mechanical and thermal stability
Electrolyte:
- high ionic conductivity
- electrochemical and thermal stability
- performance in a wide temperature range
- compact structure
- without voids or cracks
- good adhesion with electrode materials
- blocking for electron transport
DTU Energy, Technical University of Denmark
Introduction - Lipon
Material: Li3PO4 (Developed in ’90s at Oak Ridge laboratories
by Bates and coworkers)
• Deposited film: Lithium phosporus oxinitride (LiPON): Li3.3PO3.9N0.17 (glassy)
• Moderate conductivity, compensated with a film thickness of about 1 µm
• Deposition methods in N2-atmosphere
Main: RF magnetron sputtering (2-4 nm/min sintered, 30 nm/min powder)
Alternative: Ion beam assisted deposition, Pulsed laser deposition, E-beam evaporation,
Plasma assisted direct vapor deposition, Plasma enhanced metalorganic CVD
Challenges
• Moderate Li+ ion conductivity
• Reacts with air
How to increase the
conductivity?
DTU Energy, Technical University of Denmark
Conductivity mechanism
The Li+ conductivity is highly dependent on the LiPON structure. Incorporation of
nitrogen into the Li3PO4 network looks to be the issue.
Triply coordinated nitrogen atoms
induce a larger structural disorder
and gives a higher conductivity!
Francisco Munoz: Journal of Power Sources 198 (2012) 432– 433: “however, no
unique set of optimized parameters has been found that can best fulfill the
requirements for the material performance. Furthermore, no concluding
interpretation has been given to the effect of nitrogen on the electrical conductivity
improvement through nitrogen incorporation.”
DTU Energy, Technical University of Denmark
Mass spectrometry
ions
radicals
DTU Energy, Technical University of Denmark
N1s (a) and P2p (b) peaks by XPS for 5 and
50 mTorr deposited for 100 W in 150 min.
DTU Energy, Technical University of Denmark
SOFC Working Principle
SOFC: Converts chemical energy from fuels into electrical energy
Overall electrochemical reaction:
(anode)
Fuels:
850-1000 ⁰C
(air)
hydrogen
natural gas
methane
methanol
Porous electrodes
LSM-YSZ
DTU Energy, Technical University of Denmark
Compact
electrolyte
LSM: LaSrMnO
(cathode)
Challenge: Low Temperature SOFCs (LT-SOFCs)
• Conventional SOFCs, 850-1000⁰C
• Current research trend:
Reduction in operating temperature 600-800⁰C leads to:
- Diverse materials selection
- Increase in life time
- Cost benefits (non expensive catalysts)
- Verstaile design options
Applications:
Sectors requring 100 W-10 kW of power
e.g., portable domestic devices, power generation
DTU Energy, Technical University of Denmark
Challenges of Low Temperature-SOFCs
Breakdown of losses in SOFC
measured in H2 /25%H2O at 700 ˚C
Electrode related
Electrolyte related
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High electrode polarization resistance
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High ohmic resistance of electrolyte
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Need of nanostructured
electrocatalysts/electrodes
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Requirement of thin electrolyte
*A.
Barfod, A. Hagen, S. Ramousse, P. Hendriksen, and M. Mogensen, Fuel Cells, vol. 6, no.2 pp 141-145, 2006
DTU Energy, Technical University of Denmark
Existing Ni-YSZ composite ceramic-metal (cermet)
anodes
Advantages
Disadvantages
• Catalytically active
• Densification during operation
• High electronic conduction
• Sensitivity to oxygen
• Compatible with electrolytes
YSZ
e.g.,
• Poisoning by sulfur
• Not suitable for low temperature
Objective
Demonstration of suitable SOFC anodes having low polarization
resistance operable in the range of 400 to 600˚C
DTU Energy, Technical University of Denmark
Incorporation of Catalytic Activity by Infiltration
o Nanostructured electrodes prepared by infiltration results in considerable improvement
of ceramic electrodes;
o Noble metals Pt, Ru and Pd are widely used for heterogeneous catalysis;
o The catalyst can accommodate a large number of H2 in the crystal structure making
it ideal for H2 oxidation
DTU Energy, Technical University of Denmark
Catalytic Modification at the Interface Using a
Pd Thin Film: Metal Functional Layer
ScYSZ – Zirconia stabilized with Scandia and Yttria
What is the effect of this modification in STN and Pd-CGO
infiltrated STN?
DTU Energy, Technical University of Denmark
GRC, 27 July - 2 August 2014, Bryant University, USA
Rp with/without the MFL
DTU Energy, Technical University of Denmark
Distribution of Pd on STN backbone
TEM and EDX analyses on CGO modified STN backbone.
TEM of STN with
nanostructured Pd-CGO
a) STN/ScYSZ interface with distributed
Pd nanoparticles, (b) high magnification
showing the presence of Pd.
DTU Energy, Technical University of Denmark
Plasma physics: past and present
Chemistry
Plasma
Repertoire:
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Basics of gas discharges (’60s)
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Waves and instabilities (’70s)
- Thin films (’80s-)
- Etching, implantation (’80s -)
- Plasma chemistry (’90s -)
- Plasma bio, (’00s -)
- Plasma nano (’05s -)
- Plasma medicine (’10s -)
- ???
DTU Energy, Technical University of Denmark
Plasma processing: present and future
DTU Energy, Technical University of Denmark
Actvitate profesionala
Romania
Japonia
Denmark
1986-1996
1996-2006
2006-2016
86-91: Student
1996-2006
2006-2016
Facultatea de Fizica
Nagoya Institute of Technology
2006 - Risø National Laboratory
Universitatea Al. I. Cuza, Iasi
PhD student, Lecturer (96-01)
91-96 Asistent cercetare,
doctorand
Doctorat inginerie 2001
2007 - Technical University of
Denmark, Department of Energy
Conversion and Storage (2012)
Facultatea de Fizica
Doctorat fizica 1998
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Nagoya University (01-06)
JSPS Fellow
Senior Scientist/Associate
Professor
Associate Professor
Reactive Plasma Processing
DTU Energy, Technical University of Denmark
Recunoastere profesionala
”Plasma Physics Innovation Prize
2012” awarded by the
European Physical Society
DTU Energy, Technical University of Denmark
Activitate civica
- Februarie 2003 – initiator al demersului anti-nepotism universitar
(www.nepotism.org)
- Octombrie 2003 - membru fondator al Forumului Academic Roman
(www.forumul-academic-roman.org)
- Noiembrie 2003 - coautor al Studiului FAR (23 de pagini de reforma
publicate integral in Observator Cultural 2003-2004 si transmis catre
organizatiile UE). Studiul a influentat programul de reforma promovat
intre anii 2004-2009.
- Mai 2005: membru fondator al Societatii Romano-Japoneze pentru
Stiinta si Tehnologie
- Septembrie 2007-2008 - membru al comisiei prezidentiale pentru
educatie (demisie, martie 2008 ca urmare a alegerii EBA ca secretar
general al T-PDL)
- Martie 2016 - Initiator al Asociatiei Academice Romano-Daneze
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DTU Energy, Technical University of Denmark
Specificity and diversity
Denmark
Japan
Romania
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Population 5.7 mil
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Population 126 mil
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Population 20 mil
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DTU Energy 46% frg.
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Nagoya University 5% frg.
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X % frg.
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Master project: 6 months
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Master project: 2 years
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Master project: 2 years
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Cost PhD student
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Cost PhD student
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Cost PhD student
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(3y) 200 000 Euro +44%
0 Yen (travel, publications)
Mass education system (80%) Brain drain: positive
Elite education system
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Elite education system
Brain drain: negligible
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Brain drain: negative
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DTU Energy, Technical University of Denmark
15000 Euro +Y%
Specificity and diversity
Denmark
Japan
Romania
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Subjective network
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Strong companies
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Weak companies
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Industrial collaboration
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Intellectual training
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Intellectual training
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Strong international partners Added value for Denmark
Weak international ability
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Lack of strategy
National pride
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Poor branding
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H2020 approach
High cost
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competitor
DTU Energy, Technical University of Denmark
Less performing
Va multumesc pentru atentie!
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DTU Energy, Technical University of Denmark