http://www.fch-ju.eu/ Programme Review Day 2012 Brussels, 28 & 29 November
Fuel Cells and ydrogen Joint Undertaking DEMMEA (245156) Understanding the Degradation Mechanisms of Membrane Electrode Assembly for igh Temperature PEMFCs and ptimization of the Individual Components Aikaterini Andreopoulou ICET/FRT Coordinator: Advent Technologies S.A.
0. Project & Partnership description Start and end dates: 01 January 2010 to 31 December 2012 ICET/FRT Four (4) EU members (France, Germany, Greece, Czech Republic) and Switzerland Five (5) Research organizations (FRT, TUD, ICTP, CNRS, PSI) Two (2) SME (ADVENT, NEXT) ne (1) Industrial partner (FUMATEC)
1. Project description Aims of DEMMEA The ultimate goal is to understand the degradation phenomena of a high temperature PEM fuel cell and make targeted modifications on the MEA system in order to increase performance and life time. Main bjectives Understand the functional operation as well as the degradation phenomena of high temperature 3 P 4 imbibed PEM. Understand the degradation mechanisms of Pt based electrocatalysts and of the electrochemical interface. Modeling in correlation with experimental observations. Combined use of advanced experimental techniques. Design and development of accelerated tests and prediction tools for the MEA s performance.
1. Strategy Polymer electrolytes of different chemical structures. Influence of the chemical structure on the oxidative stability and proton conductivity. New catalytic structures depicting lower corrosion and/or higher utilization of the catalyst. Use and development of in situ spectroscopic techniques for the study of the catalytic layer under fuel cell operation. SoA and new selected MEAs will be fully characterized by means of in situ measurements in respect to their degradation mechanisms. Development of a mathematical model describing platinum catalyst dissolution, movement and redistribution inside the cell. WP1: Management WP2 Polymer Electrolytes WP4 In-situ Spectroscopic study of MEAs WP6 Mathematical modeling of the catalyst degradation WP7 Dissemination and Public Awareness WP3 Catalysts and Catalytic Layers WP5 MEAs Testing and Degradation
Polymer electrolytes Synthesis of alternative chemical structures in order to get a deeper inside on its effect on their properties DEMMEA 245156 1. Project achievements N S C 3 S x 1-x 3 C 0.10 Conductivity vs side groups Pyridine content x~60 @ r.t. N S N N S S x S x 1-x C S 3 Na S S Na 3 S 0.6-x S 3 Na z S 3 Na 1-y 0.4-z y σ (S/cm) 0.08 0.06 0.04 0.02 Terpolymer with carboxyl side groups TPS 0.00 100 200 300 400 500 600 Doping Level (%wt)
82 80 78 76 74 72 70 68 Binding Energy (ev) In situ spectroscopic measurements &high pressure XPS studies of the electrochemical interface DEMMEA 245156 1. Project achievements < 200mV adsorption 200mV 300mV 300mV 600mV no P 3 4 & P 3 4 adsorption adsorption detectable 600mV 800mV () & P 3 4 adsorption > 800mV () adsorption 0.05 mbar 2 120 o C +1.5 V x 10-1 +1.0 V 0.45 V
New electrocatalysts DEMMEA 245156 1. Project achievements Cell voltage, Volt 0,65 0,64 0,63 0,62 0,61 Pt/C conventional catalyst 25% 2 in e Stability test under lean 2 reformate gas 100% 2 λ=1.3 at anode λ=1.6 at cathode T=180 o C Cell voltage, V 0,630 0,625 0,620 0,615 0,610 0,605 0,600 0,595 0,590 0,585 0,580 T=175 o C deg, rate= 10μV/h 0.2 A/cm 2 Synthetic reformate: 25% 2, 1 %C, 12% 2, 62 % e Pt/modified MWCNTs 0,575 0,60 0 100 200 300 400 time, hours 0,570 0 30 60 90 120 150 time, h
In situ diagnostic tools for MEA degradation DEMMEA 245156 1. Project achievements AC impedance spectroscopy Electrochemically active surface area Locally resolved measurements Long term operation Accelerated tests Channel 9 (utlet) Channel 8 Channel 7 Channel 6 Channel 5 (Mid) Channel 4 Channel 3 Channel 2 Channel 1 (Inlet) 2.0 Current (A) 1.5 1.0 0 200 400 600 Time (h)
1. Project achievements R Potential / V 1,1 1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 Air 2 Air start stop Air Air 30 seconds 30 seconds Air 0,1 0,0-0,1 Time Current / A 4 3 2 1 0-1 1 2 3 4 5 6 7 8 9 Cathodic currents on the Air side + - -2 residence time: 1.9 seconds 50 cc/min -3 599 600 601 602 603 604 605 Anodic currents on the Air side
1. Project achievements Mathematical model describing platinum catalyst dissolution, movement and redistribution inside the cell
1. Project achievements Schematic representation of the degradation mechanism 3 P 4 Pt C support Pt C support Pt + PEM 2 depletion area experiencing high positive polarization Pt Dissolution/Deposition migration Less positive polarization area
2. Alignment to MAIP/AIP Principal output of DEMMEA Development of characterization and control methodologies for PEM fuel cells, Understanding degradation and proton conductivity. Improvement of the novel state of the art polymeric 3 P 4 doped membranes based on aromatic polyethers with pyridine polar groups, Diminishing the degradation of the catalytic layer. Advanced design and synthesis of electrocatalysts and catalytic layer based on new structural architecture, MEAs manufacture, electrochemical characterization and long term testing of single cells.
2. Alignment to MAIP/AIP Standardization and harmonization of PEM fuel cells production and safety procedures. Production of reliable robust and less expensive high temperature polymer electrolytes. Low cost and highly efficient production of new advanced high temperature PEM fuel cell electrodes Low cost, robust and highly efficient MEAs as the key component for igh Temperature PEM fuel cell applications. Validation of high performance for power densities exceeding 0.17 W/cm 2 at a cell potential of 700 mv (single cells).
DEMMEA 2451 3. Cross cutting issues dissemination The established contact between academia and high technology industry is capable to stimulate high level of scientific career opportunities. DEMMEA has already attracted the participation of young scientists whose advanced knowledge will benefit Europe. ADVENT (SME), NEXT (SME) and FUMATEC (Industry) ensure fast dissemination of the results that have already come out of the project through technology improvement that broadens their cooperation with industrial end users. ther dissemination activities & public awareness: ne session devoted to the DEMMEA project during the ELMEMPR conference, August 2012, Czech Republic (http://www.elmempro.com) 10 publications in peer reviewed journals Participation in more than 30 conferences and events 1 patent application Website dedicated to DEMMEA project (http://demmea.iceht.forth.gr)
4. Enhancing cooperation Technology transfer: ighly interdisciplinary approach since the consortium consists of companies and academic institutes whose expertise cover a broad range of activities. Interface with international and national research projects, e.g.: IRAFC 245202 09 ΣΥΝ 51 453 Eurostars E!5094
4. Future perspectives Exploitation of the system application in: AUX power units CP units Battery chargers with LPG (300 W) Power supply in remote/off grid areas (2kW) Telecommunications (5kW) Regenerative fuel cells for space (3kW satellites) Portable applications (70 W) Stationary back up power systems
Thank you for your attention! DEMMEA 245156