Influence of the Distribution of Platinum Deposits on the Properties and Degradation of Platinum-Impregnated Nafion Membranes

In proton exchange membrane fuel cells (PEMFCs), platinum (Pt) from the electrodes can be deposited in the electrolyte membrane, altering its properties and causing degradation. To investigate these impacts, in some studies, membranes with artificially deposited Pt were used, however, with contradictory results. In this study, we compared membranes impregnated with 0 to 4.4 wt% Pt. Specifically, the Pt particle distribution and mass transport in the membrane as well as the membrane decomposition is investigated after performing open circuit durability tests for∼140 h. The properties of the membrane electrode assemblies (MEAs) are studied by electrochemical characterization. The changes upon degradation are investigated by thickness determination, infrared spectroscopy, fluoride emission, hydrogen permeability, and electrical conductivity. Our investigation confirmed that the particle density, not the Pt amount, is the determining factor in the extent of membrane decomposition: fluoride emission decreased exponentially with particle density. We further found a considerable difference in the particle distribution between artificial and in-situ Pt deposits. Moreover, properties of both membrane types changed contrary to each other during the durability test. In conclusion, Pt-impregnated membranes do not reflect the state of degraded membranes with in-situ formed deposits but are suitable to investigate the influence of particle distributions.

[1]  Frédéric Maillard,et al.  Membrane and Active Layer Degradation upon PEMFC Steady-State Operation I. Platinum Dissolution and Redistribution within the MEA , 2007 .

[2]  M. Watanabe,et al.  Preparation of highly dispersed SiO2 and Pt particles in Nafion®112 for self-humidifying electrolyte membranes in fuel cells , 2006 .

[3]  K. Andreas Friedrich,et al.  Influence of Platinum Precipitation On Properties and Degradation of Nafion® Membranes , 2013 .

[4]  Xiao-Zi Yuan,et al.  Electrochemical Impedance Spectroscopy in PEM Fuel Cells , 2010 .

[5]  Jong-Hyun Lee,et al.  Degradation of proton exchange membrane by Pt dissolved/deposited in fuel cells , 2009 .

[6]  T. Murahashi,et al.  Change of Pt Distribution in the Active Components of Phosphoric Acid Fuel Cell , 1988 .

[7]  K. I. Grais,et al.  A study of secondary electron emission in insulators and semiconductors , 1982 .

[8]  Kazuhiko Shinohara,et al.  Membrane degradation mechanism during open-circuit voltage hold test , 2008 .

[9]  F. Coms The Chemistry of Fuel Cell Membrane Chemical Degradation , 2008, ECS Transactions.

[10]  J. Anzai,et al.  Degradation Mechanism of the PFSA Membrane and Influence of Deposited Pt in the Membrane , 2007 .

[11]  Ernest Yeager,et al.  Platinum Dissolution in Concentrated Phosphoric Acid , 1979 .

[12]  W. Yoon,et al.  Study of Polymer Electrolyte Membrane Degradation under OCV Hold Using Bilayer MEAs , 2010 .

[13]  Kazuhiko Shinohara,et al.  Membrane Degradation Behavior during Open-Circuit Voltage Hold Test , 2007 .

[14]  Atsuko Y. Nosaka,et al.  Detection of OH radicals as the effect of Pt particles in the membrane of polymer electrolyte fuel cells , 2010 .

[15]  Hubert A. Gasteiger,et al.  Handbook of fuel cells : fundamentals technology and applications , 2003 .

[16]  J. Lindgren,et al.  FTIR study of water in cast Nafion films , 2000 .

[17]  Jae-Il Kim,et al.  A study on self-humidifying PEMFC using Pt–ZrP–Nafion composite membrane , 2004 .

[18]  Hiroyuki Uchida,et al.  Self‐Humidifying Polymer Electrolyte Membranes for Fuel Cells , 1996 .

[19]  N. Bunce,et al.  STRUCTURE AND CHEMISTRY OF NAFION-H: A FLUORINATED SULFONIC ACID POLYMER , 1986 .

[20]  D. Curtin,et al.  Advanced materials for improved PEMFC performance and life , 2004 .

[21]  Min-Soo Kim,et al.  Effects of operating parameters on hydrogen crossover rate through Nafion® membranes in polymer electrolyte membrane fuel cells , 2013 .

[22]  Deborah J. Jones,et al.  The effect of dissolution, migration and precipitation of platinum in Nafion ® -based membrane electrode assemblies during fuel cell operation at high potential , 2008 .

[23]  Hubert A. Gasteiger,et al.  Impact of Gas Partial Pressure on PEMFC Chemical Degradation , 2006 .

[24]  Minoru Inaba,et al.  Gas crossover and membrane degradation in polymer electrolyte fuel cells , 2006 .

[25]  Erik Kjeang,et al.  Pt Band Formation Enhances the Stability of Fuel Cell Membranes , 2013 .

[26]  Mathias Schulze,et al.  Dry layer preparation and characterisation of polymer electrolyte fuel cell components , 2000 .

[27]  Amit Chakma,et al.  Gas permeation through water-swollen hydrogel membranes , 2008 .

[28]  Hubert A. Gasteiger,et al.  Aspects of the Chemical Degradation of PFSA Ionomers used in PEM Fuel Cells , 2005 .

[29]  Meilin Liu,et al.  The effect of platinum in a Nafion membrane on the durability of the membrane under fuel cell conditions , 2010 .

[30]  Deborah J. Myers,et al.  Effect of voltage on platinum dissolution : Relevance to polymer electrolyte fuel cells , 2006 .

[31]  G. C. Sarti,et al.  FTIR-ATR Study of Water Distribution in a Short-Side-Chain PFSI Membrane , 2012 .

[32]  Peter S. Fedkiw,et al.  An Impregnation‐Reduction Method to Prepare Electrodes on Nafion SPE , 1989 .

[33]  H. Uchida,et al.  New Evaluation Method for Degradation Rate of Polymer Electrolytes , 2006 .

[34]  Hubert A. Gasteiger,et al.  Instability of Pt ∕ C Electrocatalysts in Proton Exchange Membrane Fuel Cells A Mechanistic Investigation , 2005 .

[35]  James M. Fenton,et al.  Membrane Degradation Mechanisms in PEMFCs , 2006, ECS Transactions.

[36]  Srikanth Arisetty,et al.  Thermodynamics and Kinetics of Platinum Dissolution from Carbon-Supported Electrocatalysts in Aqueous Media under Potentiostatic and Potentiodynamic Conditions , 2013 .

[37]  Hubert A. Gasteiger,et al.  Effect of hydrogen and oxygen partial pressure on Pt precipitation within the membrane of PEMFCs , 2007 .

[38]  Gerald F. Dionne,et al.  Effects of secondary electron scattering on secondary emission yield curves , 1973 .

[39]  H. Urushibata,et al.  Effect of operational potential on performance decay rate in a phosphoric acid fuel cell , 1996 .

[40]  Su-Moon Park,et al.  Electrochemical impedance spectroscopy. , 2010, Annual review of analytical chemistry.

[41]  S. Hamrock,et al.  In-Depth Profiling of Degradation Processes in a Fuel Cell: 2D Spectral-Spatial FTIR Spectra of Nafion Membranes. , 2012, ACS macro letters.

[42]  Mallika Gummalla,et al.  Degradation of Polymer-Electrolyte Membranes in Fuel Cells II. Theoretical model , 2010 .

[43]  Nahid Mohajeri,et al.  Evaluation of the Effect of Impregnated Platinum on PFSA Degradation for PEM Fuel Cells , 2013 .

[44]  Robert M. Darling,et al.  Kinetic Model of Platinum Dissolution in PEMFCs , 2003 .