Tendinte in fizica aplicata: specificitate si diversitate · Tendinte in fizica aplicata: specificitate si diversitate Eugen Stamate Reactive Plasma Processing . Technical University

Tendinte in fizica aplicata: specificitate si diversitate

Eugen Stamate Reactive Plasma Processing Technical University of Denmark

DTU Energy, Technical University of Denmark

Outline

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- DTU Energy

- Procese cu plasma pentru conversia si stocatea energiei

- Civism universitar

- Diversitate si specificitate in cercetarea de fizica aplicata


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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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

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Presenter

Presentation Notes

Clockwise from the top: solid oxide fuel cell, polymer solar cell, magnetic refrigeration device, lithium-nickel-cobalt battery


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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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


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


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


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?


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


Mass spectrometry

ions

radicals


N1s (a) and P2p (b) peaks by XPS for 5 and 50 mTorr deposited for 100 W in 150 min.


(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


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


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


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


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


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


Rp with/without the MFL


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.


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


Plasma processing: present and future


Actvitate profesionala

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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


Recunoastere profesionala ”Plasma Physics Innovation Prize 2012” awarded by the

European Physical Society


Activitate civica

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- 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


Specificity and diversity

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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


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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


Va multumesc pentru atentie!

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Documents

Tendinte in fizica aplicata: specificitate si diversitate · Tendinte in fizica aplicata: specificitate si diversitate Eugen Stamate Reactive Plasma Processing . Technical University