Post on 03-Nov-2019
Tendinte in fizica aplicata: specificitate si diversitate
Eugen Stamate Reactive Plasma Processing Technical University of Denmark
DTU Energy, Technical University of Denmark
Outline
2
- DTU Energy
- Procese cu plasma pentru conversia si stocatea energiei
- Civism universitar
- Diversitate si specificitate in cercetarea de fizica aplicata
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
3
DTU Energy, Technical University of Denmark
Technologies • 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
4
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
5
DTU Energy, Technical University of Denmark
Li thin film batteries
Sm
all v
olum
e an
d
high
pow
er d
ensi
ty Targeted applications:
- MEMS
- Smart cards
- Micro-cameras
- Microelectronics
Koo et al., Nanoletters (2012)
Thin-film battery
Energy storage – essential for an information based society
DTU Energy, Technical University of Denmark
Lithium Ion Batteries
All-solid-state thin film Lithium ion battery
Needs to be compatible with soldering
– stand more than 220°C
Both electrodes are capable of reverse lithium insertion. Because of difference in chemical
potential the transport delivers (discharge) or consumes (charge) energy.
Conventional Lithium ion battery
Less compatible with micro and
nanoelectronic devices, safety issues
Requirements:
- High ionic conductivity
- Stability with anode and cathode
- Large potential window
DTU Energy, Technical University of Denmark
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
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
Introduction - Lipon
• Moderate Li+ ion conductivity
• Reacts with air
Challenges
How to increase the conductivity?
DTU Energy, Technical University of Denmark
Triply coordinated nitrogen atoms induce a larger structural disorder
and gives a higher conductivity!
The Li+ conductivity is highly dependent on the LiPON structure. Incorporation of nitrogen into the Li3PO4 network looks to be the issue.
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.”
Conductivity mechanism
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
(anode)
(cathode)
LSM-YSZ
SOFC Working Principle
850-1000 ⁰C
Fuels:
hydrogen
natural gas
methane
methanol
Overall electrochemical reaction:
(air)
SOFC: Converts chemical energy from fuels into electrical energy
Porous electrodes
Compact electrolyte
LSM: LaSrMnO
DTU Energy, Technical University of Denmark
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
Electrode related • High electrode polarization resistance
• Need of nanostructured electrocatalysts/electrodes
Electrolyte related • High ohmic resistance of electrolyte
• Requirement of thin electrolyte
Breakdown of losses in SOFC
measured in H2 /25%H2O at 700 ˚C
*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
Objective
Demonstration of suitable SOFC anodes having low polarization
resistance operable in the range of 400 to 600˚C
Existing Ni-YSZ composite ceramic-metal (cermet) anodes
Advantages Disadvantages
• Catalytically active
• High electronic conduction
• Compatible with electrolytes e.g., YSZ
• Densification during operation
• Sensitivity to oxygen
• Poisoning by sulfur
• Not suitable for low temperature
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
What is the effect of this modification in STN and Pd-CGO infiltrated STN?
ScYSZ – Zirconia stabilized with Scandia and Yttria
GRC, 27 July - 2 August 2014, Bryant University, USA
DTU Energy, Technical University of Denmark
Rp with/without the MFL
DTU Energy, Technical University of Denmark
a) STN/ScYSZ interface with distributed Pd nanoparticles, (b) high magnification
showing the presence of Pd.
TEM of STN with
nanostructured Pd-CGO
Distribution of Pd on STN backbone TEM and EDX analyses on CGO modified STN backbone.
DTU Energy, Technical University of Denmark
Plasma physics: past and present
- Basics of gas discharges (’60s)
- Waves and instabilities (’70s)
- Thin films (’80s-)
- Etching, implantation (’80s -)
- Plasma chemistry (’90s -)
- Plasma bio, (’00s -)
- Plasma nano (’05s -)
- Plasma medicine (’10s -)
- ???
Repertoire:
Plasma
Chemistry
DTU Energy, Technical University of Denmark
Plasma processing: present and future
DTU Energy, Technical University of Denmark
Actvitate profesionala
23
86-91: Student
Facultatea de Fizica
Universitatea Al. I. Cuza, Iasi
91-96 Asistent cercetare, doctorand
Facultatea de Fizica
Doctorat fizica 1998
1996-2006
Nagoya Institute of Technology
PhD student, Lecturer (96-01)
Doctorat inginerie 2001
Nagoya University (01-06)
JSPS Fellow
Associate Professor
2006-2016
2006 - Risø National Laboratory
2007 - Technical University of Denmark, Department of Energy Conversion and Storage (2012)
Senior Scientist/Associate Professor
Reactive Plasma Processing
Romania
1986-1996
Japonia
1996-2006
Denmark
2006-2016
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
25
- 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
DTU Energy, Technical University of Denmark
Specificity and diversity
26
Denmark
- Population 5.7 mil
- DTU Energy 46% frg.
- Master project: 6 months
- Cost PhD student
(3y) 200 000 Euro +44%
- Mass education system (80%)
- Brain drain: positive
Japan
- Population 126 mil
- Nagoya University 5% frg.
- Master project: 2 years
- Cost PhD student
0 Yen (travel, publications)
- Elite education system
- Brain drain: negligible
Romania
- Population 20 mil
- X % frg.
- Master project: 2 years
- Cost PhD student
15000 Euro +Y%
- Elite education system
- Brain drain: negative
DTU Energy, Technical University of Denmark
27
Denmark
- Subjective network
- Industrial collaboration
- Strong international partners
- Added value for Denmark
Japan
- Strong companies
- Intellectual training
- Weak international ability
- National pride
Romania
- Weak companies
- Intellectual training
- Lack of strategy
- Poor branding
Specificity and diversity
High cost competitor Less performing
H2020 approach
DTU Energy, Technical University of Denmark
Va multumesc pentru atentie!
28