Effects of Cathode Corrosion on Through-Plane Water Transport in Proton Exchange Membrane Fuel Cells.

The corrosion of carbon in the cathodes of proton-exchange-membrane fuel cells leads to electrode collapse, reduced active catalyst area, and increased surface hydrophilicity. While these effects have been linked to performance degradation over cell lifetime, the role of corrosion in the evolving water balance has not been clear. In this study, neutron imaging was used to evaluate the through-plane water distribution within several cells over the course of accelerated stress testing using potential holds and square-wave cycling. A dramatic decrease in water retention was observed in each cell after the cathode was severely corroded. The increasing hydrophilic effect of carbon surface oxidation (quantified by ex situ X-ray photoelectron spectroscopy) was overwhelmed by the drying effect of increased internal heat generation. To evaluate this mechanism, the various observed electrode changes are included in a multiphase, non-isothermal one-dimensional cell model, and the simulated alterations to cell performance and water content are compared with those observed experimentally. Simulation results are consistent with the idea that collapse and compaction of the catalyst layer is the dominant limitation to cell performance and not the lower amounts of active Pt surface area, and that higher temperature gradients result in drying out of the cell.

[1]  Jiujun Zhang,et al.  A review of accelerated stress tests of MEA durability in PEM fuel cells , 2009 .

[2]  L. J. Bregoli,et al.  A Reverse-Current Decay Mechanism for Fuel Cells , 2005 .

[3]  S. Maaß,et al.  Carbon support oxidation in PEM fuel cell cathodes , 2008 .

[4]  T. Springer,et al.  Characterization of polymer electrolyte fuel cells using ac impedance spectroscopy , 1996 .

[5]  M. Fowler,et al.  Wettability and capillary behavior of fibrous gas diffusion media for polymer electrolyte membrane fuel cells , 2009 .

[6]  T. Jarvi,et al.  Characterization of Vulcan Electrochemically Oxidized under Simulated PEM Fuel Cell Conditions , 2004 .

[7]  D. Wood,et al.  Durability Aspects of Gas-Diffusion and Microporous Layers , 2009 .

[8]  Thomas W. Tighe,et al.  Water Transport Mechanisms in PEMFC Gas Diffusion Layers , 2010 .

[9]  R. Borup,et al.  Influence of the microporous layer on carbon corrosion in the catalyst layer of a polymer electrolyte membrane fuel cell , 2012 .

[10]  A. Taniguchi,et al.  Analysis of electrocatalyst degradation in PEMFC caused by cell reversal during fuel starvation , 2004 .

[11]  A. Weber,et al.  Effective-Diffusivity Measurement of Partially-Saturated Fuel-Cell Gas-Diffusion Layers , 2012 .

[12]  Adam Z. Weber,et al.  Coupled Thermal and Water Management in Polymer Electrolyte Fuel Cells , 2006 .

[13]  D. Jacobson,et al.  Accurate measurement of the through-plane water content of proton-exchange membranes using neutron radiography. , 2012, Journal of applied physics.

[14]  Yun Wang,et al.  Through-Plane Water Distribution in a Polymer Electrolyte Fuel Cell: Comparison of Numerical Prediction with Neutron Radiography Data , 2010 .

[15]  Thomas F. Fuller,et al.  XPS investigation of Nafion® membrane degradation , 2007 .

[16]  D. Candusso,et al.  A review on polymer electrolyte membrane fuel cell catalyst degradation and starvation issues: Causes, consequences and diagnostic for mitigation , 2009 .

[17]  D. Schiraldi Polymer Electrolyte Fuel Cell Durability , 2009 .

[18]  Y. Sakiyama,et al.  Influence of humidification on deterioration of gas diffusivity in catalyst layer on polymer electrolyte fuel cell , 2010 .

[19]  Hardcover,et al.  Carbon: Electrochemical and Physicochemical Properties , 1988 .

[20]  Adam Z. Weber,et al.  Modeling and High-Resolution-Imaging Studies of Water-Content Profiles in a Polymer-Electrolyte-Fuel-Cell Membrane-Electrode Assembly , 2008 .

[21]  Suresh G. Advani,et al.  In situ comparison of water content and dynamics in parallel, single-serpentine, and interdigitated flow fields of polymer electrolyte membrane fuel cells , 2010 .

[22]  F. Büchi,et al.  Polymer electrolyte fuel cell durability , 2009 .

[23]  A. Weber,et al.  Modeling Low-Platinum-Loading Effects in Fuel-Cell Catalyst Layers , 2011 .

[24]  Matthew M. Mench,et al.  Investigation of Temperature-Driven Water Transport in Polymer Electrolyte Fuel Cell: Phase-Change-Induced Flow , 2009 .

[25]  K. Yager,et al.  Effect of Confinement on Structure, Water Solubility, and Water Transport in Nafion Thin Films , 2012 .

[26]  J. Jorné,et al.  Study of the Exchange Current Density for the Hydrogen Oxidation and Evolution Reactions , 2007 .

[27]  A. Wokaun,et al.  The effect of platinum on carbon corrosion behavior in polymer electrolyte fuel cells , 2011 .

[28]  Mahlon Wilson,et al.  Scientific aspects of polymer electrolyte fuel cell durability and degradation. , 2007, Chemical reviews.

[29]  M. Hickner,et al.  Antiplasticization and Water Uptake of Nafion Thin Films. , 2012, ACS macro letters.

[30]  M. L. Studebaker,et al.  The Influence of Ultimate Composition upon the Wettability of Carbon Blacks , 1955 .

[31]  Don W. Green,et al.  Perry's Chemical Engineers' Handbook , 2007 .

[32]  A. Weber Improved modeling and understanding of diffusion-media wettability on polymer-electrolyte-fuel-cell performance , 2010 .

[33]  J. Fierro,et al.  Electrochemical stability of carbon nanofibers in proton exchange membrane fuel cells , 2011 .

[34]  J. Yi,et al.  Temperature-Driven Water Transport Through Membrane Electrode Assembly of Proton Exchange Membrane Fuel Cells , 2006 .

[35]  Alexander Wokaun,et al.  Simultaneous neutron imaging of six operating PEFCs: Experimental set-up and study of the MPL effect , 2012 .

[36]  S. Kjelstrup,et al.  Ex situ measurements of through-plane thermal conductivities in a polymer electrolyte fuel cell , 2010 .

[37]  Hubert A. Gasteiger,et al.  Determination of Catalyst Unique Parameters for the Oxygen Reduction Reaction in a PEMFC , 2006 .

[38]  A. Weber,et al.  Liquid-Water-Droplet Adhesion-Force Measurements on Fresh and Aged Fuel-Cell Gas-Diffusion Layers , 2012 .

[39]  Adam Z. Weber,et al.  Effects of Microporous Layers in Polymer Electrolyte Fuel Cells , 2005 .

[40]  Hubert A. Gasteiger,et al.  Carbon-Support Requirements for Highly Durable Fuel Cell Operation , 2009 .

[41]  T. Jarvi,et al.  Electrocatalytic corrosion of carbon support in PEMFC cathodes , 2004 .

[42]  Nathan P. Siegel,et al.  In Situ High-Resolution Neutron Radiography of Cross-Sectional Liquid Water Profiles in Proton Exchange Membrane Fuel Cells , 2008 .

[43]  A. Hexemer,et al.  Controlling Nafion Structure and Properties via Wetting Interactions , 2012 .

[44]  Matthew M. Mench,et al.  Investigation of temperature-driven water transport in polymer electrolyte fuel cell: Thermo-osmosis in membranes , 2009 .

[45]  M. Pourbaix Atlas of Electrochemical Equilibria in Aqueous Solutions , 1974 .

[46]  K. Kinoshita,et al.  Influence of electrochemical treatment in phosphoric acid on the wettability of carbons , 1975 .

[47]  Chaoyang Wang,et al.  Modeling and diagnostics of polymer electrolyte fuel cells , 2010 .

[48]  C. Hebling,et al.  Hydrophilicity and hydrophobicity study of catalyst layers in proton exchange membrane fuel cells , 2006 .

[49]  Paul Taichiang Yu,et al.  Mitigation of Carbon Corrosion in Microporous Layers in PEM Fuel Cells , 2007 .

[50]  Adam Z. Weber,et al.  Effective Diffusion-Medium Thickness for Simplified Polymer-Electrolyte-Fuel-Cell Modeling , 2008 .

[51]  G. Maranzana,et al.  Thermal Effect on Water Transport in Proton Exchange Membrane Fuel Cell , 2012 .

[52]  Nathan P. Siegel,et al.  Understanding Liquid Water Distribution and Removal Phenomena in an Operating PEMFC via Neutron Radiography , 2008 .

[53]  Mike L. Perry,et al.  Systems Strategies to Mitigate Carbon Corrosion in Fuel Cells , 2006 .

[54]  P. Mukherjee,et al.  Measurement of Water Content in Polymer Electrolyte Membranes Using High Resolution Neutron Imaging , 2010 .

[55]  Chao-Yang Wang,et al.  A Nonisothermal, Two-Phase Model for Polymer Electrolyte Fuel Cells , 2006 .

[56]  Mark Pritzker,et al.  On the role of the microporous layer in PEMFC operation , 2009 .

[57]  Hubert A. Gasteiger,et al.  The Impact of Carbon Stability on PEM Fuel Cell Startup and Shutdown Voltage Degradation , 2006 .

[58]  Svein Sunde,et al.  Carbon Corrosion of a PEMFC During Shut-down/Start-up when Using an Air Purge Procedure , 2008 .

[59]  W. Gu,et al.  Durable PEM Fuel Cell Electrode Materials: Requirements and Benchmarking Methodologies , 2006 .

[60]  H. Tang,et al.  PEM fuel cell cathode carbon corrosion due to the formation of air/fuel boundary at the anode , 2006 .