Programme Review Day 2011 Brussels, 22 November

Transcription

1 Programme Review Day 2011 Brussels, 22 November

2 ROBANODE (245355) Dr. Dimitrios K. Niakolas 1 1 Foundation for Research and Technology Hellas, Institute of Chemical Engineering and High Temperature Chemical Processes, GR-26500, Patras, Greece (FORTH/ICE-HT) FCH-JU, Programme Review, 22 November 2011, Brussels-Belgium

3 No Partner Short Name & Logo FORTH/ ICE-HT TUC NTUA EPFL CSIC CNRS CERECO S.A. Saint Gobain CREE Country Greece Germany Greece Switzerland Spain France Greece France Four (4) EU members (France, Germany, Greece, Spain) and Switzerland Six (6) Research organizations (FORTH/ICE-HT, TUC, NTUA, EPFL, CSIC, CNRS) One (1) SME (CERECO S.A.) One (1) Industrial partner (Saint Gobain CREE)

4 ROBANODE Timeline Start date 01/01/2010 P1 P2 End date 31/12/ st Reporting Period 2 nd Reporting period Final Report Month: Midterm review 31/10/2011

5 Aims of ROBANODE A deeper insight with regards to the interference and the concerted action of the various factors that contribute to degradation of Ni - based cermet anodes in SOFCs. Agglomeration of Ni particles due either to thermal or electrochemical sintering. Degradation due to carbon deposition and improvement of tolerance under CH 4 Internal Steam Reforming (ISR) (S/C = 0.5 or less). Degradation due to sulfur contamination and tolerance improvement under CH 4 ISR conditions in the presence of H 2 S (5 30ppm). RedOx tolerance of the cermet anodes.

6 Main Objectives Understanding the interrelations between the aforementioned degradation factors so that targeted modifications in the structure and morphology of the Ni-based anodes can be made. Modeling of the degradation processes in correlation with experimental observations. Simulation of the chemical and physicochemical processes under SOFC operation.

7 Strategy State-of-the-art Ni-based cermet anodes (e.g. NiO/GDC) will be modified with a second metal (e.g. Au, Mo and other) and their performance concerning carbon and sulfur tolerance will be studied. The degradation processes in the modified anodes will be investigated using various techniques (including XPS, UPS, SEM, TEM, XRD, TPR impedance spectroscopy and other ) The outcome of the aforementioned studies will be used as feedback to a mathematical model for prediction of the anode behavior.

8 Strategy Mathematical modeling will be also used to simulate the thermal and electrochemical sintering of Ni particles in the modified anodes. The kinetics of Ni oxidation during redox cycles. Half-cells, full cells and stacks will be fabricated for electrochemical testing of the modified anodes and for investigation of the long-term performance.

9 Milestones Implementation of management Model describing the degradation processes Preparation of modified anode powders Research Activities WP0: Management WP1: Mathematical Modeling of anode performance and degradation WP2: Materials Preparation Preparation of cells Comparison of the model predictions with the observed electrochemical behavior of the anode. WP4: Electrochemical testing WP3: Characterization of the prepared materials Establishment of communication with scientific community, other projects and wide public. WP5: Dissemination and public awareness

10 Alignment to MAIP/AIP & Innovation According to MAIP/AIP: Fuel cell stacks for stationary power applications require an operational lifetime up to 40,000 hours This target has not been achieved yet and anode degradation is one of the main reasons. The ultimate goal of ROBANODE is the study, understanding and modeling of the degradation mechanisms of state-of-the-art (SoA) Ni based cermet anodes. Thus ROBANODE fits exactly to the objectives of: Degradation and lifetime fundamentals of SOFCs.

11 Alignment to MAIP/AIP & Innovation Principal output of ROBANODE Development of a model for prediction of the (SoA) Ni-based anode performance and degradation. Development and improvement/optimization of (SoA) Ni-based anodes, easily commercialized, for CH 4 fuelled SOFCs (under Internal Reforming or Direct Oxidation conditions). Study of degradation mechanism due to thermal and electrochemical sintering. Study of degradation mechanism due to carbon deposition and sulfur poisoning.

12 Alignment to MAIP/AIP & Innovation Modified (SoA) anodes and cells preparation/characterization Au-NiO/GDC, Mo-NiO/GDC and Au-Mo-NiO/GDC Degradation studies due to carbon deposition and sulphur poisoning. Electrolyte-Supported Cells Anode-Supported Cells

13 Intensity /a.u. d(δwt.%)/dtemp Alignment to MAIP/AIP & Innovation Modified (SoA) anodes and cells preparation/characterization 510 K, 0.2 mbar H K,0.2 mbar H K,0.2 mbar CH 4 Ce 4+ Ce 4+ NiO Several ex-situ techniques In Situ XPS, NEXAFS XRD, e.t.c. Ce 3+ Ce 3+ Ni 0,3 0,2 Ramp from room temp up to C with 5 0 C/min and 10% H 2 /Ar Ni/GDC 3wt% Au-Ni/GDC 10wt% Mo-Ni/GDC 3wt% Au-10wt% Mo-Ni/GDC 3wt% Au-30wt% Mo-Ni/GDC 0, Binding Energy /ev 0, Temp, 0 C

14 V (mv) Alignment to MAIP/AIP & Innovation ESC and ASC performance and stability/stability testing g carbon /g cat. Catalytic-Kinetic experiments T = C 20% CH 4, 10% H 2 O Ni/GDC 10wt.% Mo-Ni/GDC 3wt.% Au-Ni/GDC 3wt.% Au - 10wt.% Mo-Ni/GDC Time, min r (μmole/sec cm 2 ) 9,0 8,0 7,0 6,0 5,0 4,0 3,0 2,0 rh 2 rco rco 2 T=850 0 C, S/C=0,5 5%H2O - 10%CH4 1, , I (ma cm -2 ) Electrocatalytic experiments

15 U (V) Alignment to MAIP/AIP & Innovation ESC and ASC performance and stability/stability testing Cell & Stack testing RedOx stability 1.2 All tests provide feedback data for the Model Development i (A/cm2) H2_initial CH4_initial CH4_final H2_final 2D model for description of fuel cell performance (power) under CH 4 steam reforming conditions and concomitant production of H 2

16 Alignment to MAIP/AIP & Innovation Medium and long-term impact of ROBANODE Improvement and optimization of the properties and design of (SoA) Nibased anodes. Minimization of degradation due to carbon deposition and sulfur poisoning in CH 4 fuelled SOFCs operating at o C under H 2 O / CH 4 < 1 in the presence of H 2 S (up to 30ppm). Long-term stability and reliability (degradation rate less than 0.5% /1000 h and operational lifetime of h) of natural gas fuelled SOFCs operating at o C.

17 Cross-cutting issues-dissemination-cooperation Proper dissemination activities through Peer Reviewed Publications, Participation in Conferences and several events. The established contact between academia and high technology industry through ROBANODE is capable to stimulate scientific career opportunities. Results coming out of the project are being shared not only among the project partners but also with all SOFC stakeholders, coming both from the scientific community and the related industry, as well as with the wider public. ROBANODE web site:

18 Cross-cutting issues-dissemination-cooperation ROBANODE has the potentiality to contribute to the rapid penetration of the (SoA) Ni-based SOFCs into market. ROBANODE partners have high experience in the exploitation of the research results. CERECO S.A. and Saint Gobain CREE can ensure fast dissemination of the expected ROBANODE technology improvement, to more industrial end-users. The up to now results have triggered the interest of other organizations.

19 Thank you all for your Attention!

20 Cell Voltage (mv) Time (hrs) Long term stability test of 3wt.% Au-Ni/GDC vs. Ni/GDC OCP T = C I = 500 macm -2 OCP (S/C=3/2) (Ref) (S/C=1/2) (Dry CH 4 ) 800 (H 2 -H 2 O) 700 (S/C=3/2) (S/C=1/2) 600 (H 2 -H 2 O)