3D Imaging of Catalyst Support Corrosion in Polymer Electrolyte Fuel Cells

During the lifetime of a polymer electrolyte fuel cell, the pore structure of the Pt/C catalyst layer may change as a result of carbon corrosion. Three-dimensional visualization of porosity changes is important to understand the origin of fuel cell performance deterioration. A focused ion beam/scanning electron microscopy (FIB/SEM) approach was adopted together with electron tomographic studies to visualize the three-dimensional pore structure of a Pt/C catalyst. In the case of pristine catalyst layers, the pores form an interconnected network. After 1000 start-up/shut-down cycles, severe carbon corrosion leads to a collapse of the support structure. The porosity of the degraded catalyst layer shrinks drastically, resulting in a structure of predominantly isolated pores. These porosity changes hinder the mass transport in the catalyst layer, consequently leading to a substantial loss of fuel cell performance. FIB/SEM serial sectioning and electron tomography allows three-dimensional imaging of the catalys...

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

[2]  David A. Muller,et al.  Characterization of Carbon Corrosion-Induced Structural Damage of PEM Fuel Cell Cathode Electrodes Caused by Local Fuel Starvation , 2008 .

[3]  Jenn-Jiang Hwang,et al.  Electrochemical performance of PEM fuel cell with Pt–Ru electro-catalyst layers deposited by sputtering , 2006 .

[4]  Marcio Gameiro,et al.  Quantitative three-dimensional microstructure of a solid oxide fuel cell cathode , 2009 .

[5]  Hansung Kim,et al.  Effect of water electrolysis catalysts on carbon corrosion in polymer electrolyte membrane fuel cells. , 2010, Journal of the American Chemical Society.

[6]  Konstantin Mischaikow,et al.  Three-Dimensional Analysis of Solid Oxide Fuel Cell Ni-YSZ Anode Interconnectivity , 2009, Microscopy and Microanalysis.

[7]  Hansung Kim,et al.  Effect of operating conditions on carbon corrosion in polymer electrolyte membrane fuel cells , 2009 .

[8]  Junliang Zhang,et al.  Transmission Electron Microscopy Observation of Corrosion Behaviors of Platinized Carbon Blacks under Thermal and Electrochemical Conditions , 2010 .

[9]  Jon M. Hiller,et al.  Three-dimensional reconstruction of a solid-oxide fuel-cell anode , 2006, Nature materials.

[10]  Direct imaging of coal pore space accessible to liquid metal , 1991 .

[11]  I. Manke,et al.  3D Visualisation of PEMFC Electrode Structures Using FIB Nanotomography , 2010 .

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

[13]  Brian Theobald,et al.  An investigation into factors affecting the stability of carbons and carbon supported platinum and platinum/cobalt alloy catalysts during 1.2 V potentiostatic hold regimes at a range of temperatures , 2007 .

[14]  F. de Bruijn,et al.  Review: Durability and Degradation Issues of PEM Fuel Cell Components , 2008 .

[15]  P. Munroe,et al.  FIB‐induced damage in silicon , 2004, Journal of microscopy.

[16]  Wei Li,et al.  Investigation of Pt catalytic effects on carbon support corrosion of the cathode catalyst in PEM fuel cells using DEMS spectra , 2009 .

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

[18]  Sean James Ashton,et al.  Non-destructive transmission electron microscopy study of catalyst degradation under electrochemical treatment , 2008 .

[19]  J. McCaffrey,et al.  Surface damage formation during ion-beam thinning of samples for transmission electron microscopy. , 2001, Ultramicroscopy.

[20]  Thomas F. Fuller,et al.  Modeling and Investigation of Design Factors and Their Impact on Carbon Corrosion of PEMFC Electrodes , 2008 .

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

[22]  James A. Gilbert,et al.  In situ small-angle X-ray scattering observation of Pt catalyst particle growth during potential cycling. , 2008, Journal of the American Chemical Society.

[23]  Stephen J. Harris,et al.  Measurement of three-dimensional microstructure in a LiCoO2 positive electrode , 2011 .

[24]  A. Verkleij,et al.  Electron tomography for heterogeneous catalysts and related nanostructured materials. , 2009, Chemical reviews.

[25]  Hartmut Fuess,et al.  Spatially resolved degradation effects in membrane-electrode-assemblies of vehicle aged polymer electrolyte membrane fuel cell stacks , 2009 .

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

[27]  Sean James Ashton,et al.  Fuel cell catalyst degradation on the nanoscale , 2008 .

[28]  J R Kremer,et al.  Computer visualization of three-dimensional image data using IMOD. , 1996, Journal of structural biology.

[29]  Ampere A. Tseng,et al.  Nanofabrication: Fundamentals and Applications , 2008 .

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

[31]  R. Zengerle,et al.  Direct three-dimensional reconstruction of a nanoporous catalyst layer for a polymer electrolyte fuel cell , 2011 .

[32]  J. Frank Electron tomography : methods for three-dimensional visualization of structures in the cell , 2005 .

[33]  E. Gyenge,et al.  Characterizing the Structural Degradation in a PEMFC Cathode Catalyst Layer: Carbon Corrosion , 2009 .

[34]  P. Haldar,et al.  Surface oxidation of carbon supports due to potential cycling under PEM fuel cell conditions , 2010 .

[35]  J. Xie,et al.  Investigation of the Carbon Corrosion Process for Polymer Electrolyte Fuel Cells Using a Rotating Disk Electrode Technique , 2010, ECS Transactions.

[36]  K. D. van der Mast,et al.  Autotuning of a TEM using minimum electron dose , 1989 .

[37]  Ned Djilali,et al.  Modelling and simulations of carbon corrosion during operation of a Polymer Electrolyte Membrane fuel cell , 2009 .

[38]  P. Rüegsegger,et al.  A new method for the model‐independent assessment of thickness in three‐dimensional images , 1997 .

[39]  J. Willsau,et al.  The influence of Pt-activation on the corrosion of carbon in gas diffusion electrodes. A DEMS study , 1984 .

[40]  Q. Tao,et al.  Oxidation of Carbon Supports at Fuel Cell Cathodes: Differential Electrochemical Mass Spectrometric Study , 2010 .

[41]  Moses Ender,et al.  Three-dimensional reconstruction of a composite cathode for lithium-ion cells , 2011 .