EFFECT OF STRUCTURE AND IMPURITIES ON CHARGE TRANSFER REACTIONS IN SOLID STATE ELECTROCHEMICAL DEVICES
EMSL Project ID
30429
Abstract
Interfaces between solid state electrodes, electrolytes, and the gas phase play an important role in the functioning of many solid state electrolyte devices. In actual devices, porous electrodes are employed both as the mechanical support and as a means to increase the geometrical dimensions over which electrochemical reactions actually occur. However, porous electrodes are unsuitable to obtain specific electrode kinetics information in a systematic way because of the inherent conflation of the effect of geometry and microstructure and the specific electrode kinetics. To circumvent this conflation, we propose to employ patterned electrode structures and heteroepitaxial thin films of electrode materials on single crystal solid electrolytes to investigate specific electrode kinetics and impurity effects on the stability of solid state electrochemical devices. To this end, we propose to use the unique materials deposition and characterization facilities available at EMSL. Thus, the goals of the proposed work are to obtain quantitative information on cathode electrode kinetics as a function of temperature, oxygen partial pressure, and impurities such as Cr, using phenomenological models that relate electrode geometry and specific reaction kinetics to the overall measured rates of the charge-transfer reactions. The quantitative information so obtained will help to distinguish between the relative importance of electrode pore surface areas and TPBs in the charge transfer process. Other important goals are to understand the structural rearrangements (vacancy formation and ordering, surface segregation, surface reconstruction, etc) that affect the oxygen reduction process at the two phase and the three phase interfaces.Project Details
Project type
Large-Scale EMSL Research
Start Date
2008-08-22
End Date
2009-08-23
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Archival Journal Papers:
1) L.Miara, S.N.Basu, U.B.Pal, and S.Gopalan, "2D Numerical Model for Identification of Oxygen Reduction Reaction Mechanisms in Patterned Cathodes of La0.6Sr0.4Co0.2Fe0.8O3-δ", J.Electrochem.Soc., 159 (8) F419-F425 (2012)
2) L.Miara, J.N.Davis, S.Basu, U.B.Pal, and S.Gopalan, "Application of a State-Space Model to Patterned Cathodes of (La0.87Ca0.13)0.95MnO3", J.Electrochem.Soc, 158 B1523 (2011)
3) L.F.J.Piper, A.R.H.Preston, S.-W.Cho, A.DeMasi, B.Chen, J.Laverock, K.E.Smith, L.J.Miara, J.N.Davis, S.N.Basu, U.Pal, S.Gopalan, L.Saraf, T.Kaspar, A.Y.Matsuura, P.-A.Glans, and J.-H.Guo, "Soft X-Ray Spectroscopic Study of Dense Strontium-Doped Lanthanum Manganite Cathodes for Solid Oxide Fuel Cell Applications", J.Electrochem.Soc, 158 (2) B99-B105 (2011)
Refereed Conference Proceedings, Extended Abstracts, and Presentations:
1) L.Miara, U. Pal, and S.Gopalan, "Mechanistic Interpretation of the Oxygen Reduction Kinetics of La0.85Ca0.15MnO3 Cathode", ECS Trans. 35 (1), 2119 (2011)
2) L.J.Miara, K.J.Yoon, S.G.Topping, L.Saraf, U.B.Pal, and S.Gopalan, "Polarization Resistance of La0.85Ca0.15MnO3 Cathodes for Solid Oxide Fuel Cells (SOFCs) Measured Using Patterned Electrodes", ECS Transactions, 28 (23) 137-146, (2010)
3) J. N. Davis, L. Miara , L. Saraf, T. C. Kaspar, S. Gopalan, U. B. Pal, J. C. Woicik, K. F. Ludwig, and S.N. Basu, ?Hard X-Ray Fluorescence Measurements of Heteroepitaxial Solid Oxide Fuel Cell Cathode Material?, ECS Transactions, 41 (11) 19-24 (2012)
4) L.Miara, K.J.Yoon, S.G.Topping, L.Saraf, U.Pal, and S.Gopalan, " Polarization Resistance of La0.85Ca0.15MnO3 Cathodes for Solid Oxide Fuel Cells (SOFCs) Measured Using Patterned Electrodes ", ECS Trans. 28 (23), 137 (2010)
5) J. N. Davis, L. Miara , L. Saraf, T. C. Kaspar, S. Gopalan, U. B. Pal, J. C. Woicik, K. F. Ludwig, and S.N. Basu, ?Hard X-Ray Fluorescence Measurements of Heteroepitaxial Solid Oxide Fuel Cell Cathode Material?, Presented at PRiME 2012, The Electrochemical Society, Honolulu, HI, October 9-14 (2012)
6) L.Miara, L.Piper, J.N.Davis, L.Saraf, T.Kaspar, S.Basu, K.E.Smith, U.B.Pal, and S.Gopalan, "Surface Segregation Studies of SOFC Cathodes: Combining Soft X-Rays and Electrochemical Impedance Spectroscopy", MRS Proceedings (2009), 1217 : 1217-Y07-04
7) J.N. Davis, L. Saraf, T.C. Kaspar, S. Gopalan, U.B. Pal, J.C. Woicik, K.F. Ludwig and S.N. Basu, ?Electronic Structure Surface Evolution of Heteroepitaxial Solid Oxide Fuel Cell Cathode Material?, Presented at MRS Fall Meeting, Boston, MA, November 25-30 (2012)
8) Oxygen Reduction Reaction in SOFC Cathodes: An Investigation Using Thin Films L. Miara (Boston University), K. Yoon, L. Saraf (Pacific Northwest National Laboratory), U. Pal, and S. Gopalan (Boston University), Symposium on Solid State Ionics Devices, Las Vegas, NV 2010.
9) J. N. Davis, L. Miara , L. Saraf, T. C. Kaspar, S. Gopalan, U. B. Pal, K. F. Ludwig, and S.N. Basu, ?Direct Measurement of Oxygen Tracer Diffusion of Heteroepitaxial La0.8Sr0.2MnO3 Cathode Material.? Extended Abstract, Proceedings of The Electrochemical Society, Montreal, Canada (2011).
SECA Workshop Posters:
1 ) http://www.netl.doe.gov/publications/proceedings/12/seca/pdf/poster/Gopalan.pdf (2008 SECA meeting)
2) Epitaxial Cathode Thin-films to explore the fundamental science of Cathode interfaces in SOFCs (2009 SECA meeting)
3) Solid Oxide Fuel Cell Cathodes: Unraveling the Relationship between Structure, Surface Chemistry and Oxygen Reduction (2010 SECA meeting)
4) Application of a State-Space Model to Patterned Cathodes of (La0.87Ca0.13)0.95MnO3, L. J. Miara, J. N. Davis, S. N. Basu, U. B. Pal and S.Gopalan (2011 SECA meeting)
5) Unraveling Oxygen Reduction Mechanisms in Solid Oxide Fuel Cell Cathodes, L. J. Miara, J. N. Davis, S. N. Basu, U. B. Pal and S.Gopalan (2012 SECA meeting)
SECA Workshop Presentations:
1) Solid Oxide Fuel Cell Cathodes: Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction, Srikanth Gopalan, Kevin E. Smith,
Soumendra N. Basu, Karl F. Ludwig, Uday B. Pal (2010)
2) Oxygen Reduction Kinetics in LSM and LSCF, Kinetics of Oxygen Reduction in
LSM and LSCF, Linc Miara, Jacob Davis, U.B.Pal, S.N.Basu, K.Ludwig, and S.Gopalan (2011)
3) A Two Dimension Numerical Model for Identification of Surface Diffusion in Patterned Cathodes of La0.6Sr0.4Co0.2Fe0.8O3-δ, L.Miara, J.N.Davis, U.B.Pal, S.N.Basu, K.Ludwig, and S.Gopalan (2011)
4) Unraveling Oxygen Reduction Mechanisms in Solid Oxide Fuel Cell Cathodes, , L.Miara, J.N.Davis, U.B.Pal, S.N.Basu, K.Ludwig, and S.Gopalan (2012)
5) Yang Yu, Deniz Cetin, Heng Luo, Xi Lin, Karl Ludwig, Uday Pal, Srikanth Gopalan, and Soumendra Basu, ?Surface Segregation and Phase Formation In SOFC Cathode Thin Films?, Jacob Davis, Presented at the 14th Annual SECA Workshop, Pittsburgh, PA, July 23-24 (2013).