Strategic Electrochemistry Research Center Introduction to SERC Project status Some highlights Outlook Mogens Mogensen
Introduction SERC is about:
8 Active Industry Participants Participants with a contributing budget Dinex A/S Henrik Christensen DME Danish Micro Engineering A/S - Curt Sander DONG Energy A/S - Martin Wittrup Hansen Haldor Topsøe A/S - John Bøgild Hansen IRD Fuel Cells A/S - Laila Grahl-Madsen PBI-Dansensor A/S - Peter Nyfelt Franklen Topsoe Fuel Cell A/S - Niels Christiansen Videometer A/S - Niels Christian Krieger Lassen
2 Passive (Interested) Industry Companies Danfoss - Per Balslev American Power Corporation?
6 Scandinavian University Institutes 3 Universities Participants with a contributing budget Department of Chemistry, DTU - Torben Jacobsen and Claus Hviid Christensen Department of Physics, DTU - Ib Chorkendorff and Jan Rossmeisl Department of Informatics and Mathematical Modeling, DTU - Rasmus Larsen Institute of Chemical Engineering, Biotechnology and Environmental Technology, SDU - Eivind Skou Polymer and Materials Chemistry, Lund University - Reine Wallenberg Risø DTU - Kent Kammer, Johan Hjelm, Jacob Bowen, Karin Vels, Mogens Mogensen
3 European Supporting Institutes University of St. Andrews, Scotland John Irvine Max Planck Institute, Stuttgart, DE Joachim Maier University of Twente, NL Henny Bouwmeester
Purpose of the Center 1. To carry out industrially relevant research on electrochemistry on a high international level 2. To educate PhD-students and train postdocs 3. To exchange knowledge between Risø DTU, the other university institutes and the industry partners
Status of 12 Projects 1. Postdoc project: Construction and implementation of experimental set-ups for high pressure electrolysis. Participants: HTAS, DONG, Risø DTU. Postdoc Søren Højgaard Jensen: Started in SERC, July 2007 2. Ph.D. project: Stability of the LSM-SZ-interface at realistic operation conditions. Participants: TOFC, Risø DTU. Ph.D.-student Iris Maura Breel: February 1, 2008 3. Ph.D. project: Inexpensive electrocatalysts for O 2 reduction. Participants: IRD A/S, DTU Phys, Risø DTU. Ph.D.-student Federico Calle Vallejo: November 1, 2007 4. Ph.D. project: In-situ characterization of SOC electrodes using CAHT-SPM. Participants: DME - Danish Micro Engineering A/S, DTU-Chem, Risø DTU. Ph.D.- student Anne-Mette Nørgaard, April 2008. 5. Ph.D. project: Automatic quantitative image analysis (QIA) of 3D FEGSEM micrographs. Participants: Videometer A/S, DTU IMM, Lund University, Risø DTU. Ph.D.-student Peter Stanley Jørgensen: March 1, 2007 6. Ph.D. project: Selective NO conversion electrocatalysts. Participants: Dinex A/S, DTU-Phys, SDU-Chem, Risø DTU. Ph.D.-student Rebecka Werchmeister, March 1, 2007
Projects cont. 7. Ph.D. project: New inexpensive materials for robust oxygen sensor electrodes. Participants: PBI-Dansensor A/S, DTU-Chem, Risø. Ph.D.-student Anders Lund: February 1, 2008 8. Ph.D. project: Surface compositions and structures of clean SOC materials. Participants: DTU-Phys, Risø. PhD-student Thomas Andersen: November 1, 2007 9. Postdoc project: Durability of solid oxide cells at increased pressure. Participants: HTAS, DONG, Risø and possibly Topsoe Fuel Cell. 10. Ph.D.-project: Improved low-temperature oxygen sensors. Participants: PBI- Dansensor A/S, DTU-Chem, Risø. 11. Ph.D.-project: Detailed in-situ investigation of SOC electrodes using CAHT-SPM. Participants: DME Danish Micro Engineering A/S, DTU-Chem, Risø. (We hope that Nils Ohmer will apply for this by mid 2009). 12. Ph.D.-project: Cheap electrocatalysts for H 2 oxidation. Participants: DTU-Phys, IRD A/S, DTU-Chem, Risø.
Time Schedules Original Project type Main host Other participants Postdoc Risø HTAS, DONG Ph.D. Risø Topsoe Fuel Cell, DTU-Chem Ph.D. DTU-Phys (CAMd) IRD, DTU-Chem (CSG), Risø Ph.D. Risø DME, DTU-Chem Ph.D. Risø Videometer, Lund, DTU-IMM Ph.D. Risø Dinex, DTU-Phys (CAMd), SDU-Chem Ph.D. DTU-Chem (CSG) PBI-Dansensor, Risø Ph.D. DTU-Phys (CINF) Risø Postdoc Risø HTAS, DONG Ph.D. Risø PBI-Dansensor, DTU-Chem (CSG) Ph.D. Risø DME, DTU-Chem Ph.D. DTU-Phys (CAMd) IRD, DTU-Chem (CSG), Risø 2007 2008 2009 2010 2011 2012 Now o. Project type Main host Other participants Postdoc DTU-Risø HTAS, Elsam Ph.D. DTU-Risø Topsoe Fuel Cell, DTU-Chem Ph.D. DTU-Phys (CAMP) IRD, DTU-Chem (CSG), Risø Ph.D. DTU-Risø DME, DTU-Chem Ph.D. DTU-Risø Videometer, Lund, DTU-IMM Ph.D. DTU-Risø Dinex, DTU-Phys (CAMP), SDU-Chem Ph.D. DTU-Chem (CSG) PBI-Dansensor, Risø Ph.D. DTU-Phys (CINF) Risø Postdoc DTU-Risø HTAS, Elsam Ph.D. DTU-Risø PBI-Dansensor, DTU-Chem (CSG) Ph.D. DTU-Risø DME, DTU-Chem Ph.D. DTU-Phys (CAMP) IRD, DTU-Chem (CSG), Risø 2007 2008 2009 2010 2011 2012
Some highlights Project 1: Electrolysis (Søren H.J) Analysis of Differences in Impedance Spectra (ADIS) High pressure solid oxide electrolysis cells (HP-SOEC) Project 4: Characterization of electrodes - CAHT-SPM (Work of Nils Ohmer, Master student) CAHT-SPM of ScYSZ Grain boundaries Project 5: Automatic quantitative image analysis (Peter Stanley J.) QIA of 3D FIB-FEGSEM micrographs Project 6: Selective NO conversion electrocatalysts (Rebecka) 5 cell stack test
Analysis of Differences in Impedance Spectra - ADIS Impedance of a Ni/ZrO 2 YSZ LSM/YSZ solid oxide cell
Definition of ΔZ Z is the slope ΔZ is the difference in slope
ADIS on the LSM/YSZ electrode Equivalent circuit model:(rq) Operating condition f sav [Hz] n av 762 C, 63% O 2 /37% N 2 318±36 1.01±0.03 737 C, 63% O 2 /37% N 2 202±18 0.93±0.01 To be published in Handbook of Fuel Cells V
ADIS on the LSM/YSZ electrode
HP-SOC test stand, Strategy 1 Safety report is being prepared + similar test system as we use today - 20 bar max
CAHT-SPM Principle
SEM CAHT-SPM: ScYSZ Grain boundaries Sample annealed at 1700 C for 10 h. Measured using CAHT-SPM at 650 C. Topography Surface resistivity
QIA of 3D micrographs 3D segmentation Predict cell performance parameters. Model Feature extraction Quantitative values - TPB lengths - Path widths - Phase shape descriptors - Phase volume fractions -etc.
NO Conversion - Porous cell NO + C Polluted exhaust Porous electrode Anode Soot particle e - Porosity in electrolyte O 2 - e - Electrolyte particle Porous electrode Cathode Purified exhaust
5 cell stack Stack with 11 layer (= 5 cells) Composite electrode of LSM15 and CGO, and electrolyte of CGO Gold current collector Gas flows through porous cell 25 ml/min Glass sealings for sides Area: 0.38 cm 2 Height: app. 500 μm
Cyclic voltammetry on stack
Polarization 0.7 V at 400 C in Ar with 1000 ppm NO
Conversion of NO in Ar with 1000 ppm NO - without O 2 No visible conversion at 300 C Visible conversion at 350 C to 450 C Best results at 400 C Inhibition at 450 C 350 C 400 C 450 C % Conversion 33 % 100 % 44 %
Conversion of NO in Ar with 1000 ppm NO + 4% O 2 Conversion is visible in outlet concentrations Lower conversion than without O 2 Best result at 350 C Inhibition at 450 C Not possible to reach 100 % conversion 350 C 400 C 450 C % Conversion 34 % 29 % 12 %
Main finding with 5 cell stack It was possible to measure gas conversion in porous cell stack The materials LSM15 and CGO have catalytic activity towards conversion of NO without polarization The mixed electrodes of LSM15 and CGO can convert NO when polarized 350-400 C seems to be the most optimal temperature range
Outlook The first 8 projects are running now as planned. They have built-in synergy in the sense that they can help each other. Søren HJ s ADIS may be very helpful for e.g. Rebecka s and Iris electrode measurements. If Iris find out how to make the LSM/YSZ interface stable, this will be helpful for Rebecka s project. Peter SJ s QIA will be of great help to all etc. It is even more important that all the SERC projects are well integrated with all other Risø activities in this are. The projects are not only of help for each other, but for most Danish projects related to electrochemistry of fuel cells, electrolysis cell ++, if we will be successful in our communications. Open SERC semi-annual meetings.