Ice-Crystallization Kinetics in the Catalyst Layer of a Proton-Exchange-Membrane Fuel Cell

Dursch, T. J.; Trigub, G. J.; Lujan, R.; Liu, J. F.; Mukundan, R.; Radke, C. J.; Weber, A. Z.

doi:10.1149/2.004403jes

Ice-Crystallization Kinetics in the Catalyst Layer of a Proton-Exchange-Membrane Fuel Cell

Journal Article · Tue Dec 17 04:00:00 EST 2013 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.004403jes· OSTI ID:1571001

Dursch, T. J. ^[1]; Trigub, G. J. ^[2]; Lujan, R. ^[3]; Liu, J. F. ^[2]; Mukundan, R. ^[3]; Radke, C. J. ^[4]; Weber, A. Z. ^[5]

Univ. of California, Berkeley, CA (United States). Chemical and Biomolecular Engineering Dept.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technology Division
Univ. of California, Berkeley, CA (United States). Chemical and Biomolecular Engineering Dept.
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of California, Berkeley, CA (United States). Chemical and Biomolecular Engineering Dept.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technology Division

Nucleation and growth of ice in the catalyst layer of a proton-exchange-membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry and isothermal galvanostatic cold-starts. Isothermal ice-crystallization rates and ice-nucleation rates are obtained from heat-flow and induction-time measurements at temperatures between 240 and 273 K for four commercial carbon-support materials with varying ionomer fraction and platinum loading. Measured induction times follow expected trends from classical nucleation theory and reveal that the carbon-support material and ionomer fraction strongly impact the onset of ice crystallization. Conversely, dispersed platinum particles play little role in ice crystallization. Following our previous approach, a nonlinear ice-crystallization rate expression is obtained from Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory. A validated rate expression is now available for predicting ice crystallization within water-saturated catalyst layers. Using a simplified PEMFC isothermal cold-start continuum model, we compare cell-failure time predicted using the newly obtained rate expression to that predicted using a traditional thermodynamic-based approach. From this comparison, we identify conditions under which including ice-crystallization kinetics is critical and elucidate the impact of freezing kinetics on low-temperature PEMFC operation. The numerical model illustrates that cell-failure time increases with increasing temperature due to a longer required time for ice nucleation. Hence, ice-crystallization kinetics is critical when induction times are long (i.e., in the "nucleation-limited" regime for T > 263 K). Cell-failure times predicted using ice-freezing kinetics are in good agreement with the isothermal cold-starts, which also exhibit long and distributed cell-failure times for T > 263 K. These findings demonstrate a significant departure from cell-failure times predicted using the thermodynamic-based approach.

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1571001

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 3 Vol. 161; ISSN 0013-4651

Publisher:: IOP Publishing

Country of Publication:: United States

Language:: English

References (34)

Improved modeling and understanding of diffusion-media wettability on polymer-electrolyte-fuel-cell performance Weber, Adam Z. Journal of Power Sources, Vol. 195, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.03.011	journal	August 2010
Non-isothermal melting of ice in the gas-diffusion layer of a proton-exchange-membrane fuel cell Dursch, T. J.; Trigub, G. J.; Liu, J. F. International Journal of Heat and Mass Transfer, Vol. 67 https://doi.org/10.1016/j.ijheatmasstransfer.2013.08.067	journal	December 2013
Characteristics of subzero startup and water/ice formation on the catalyst layer in a polymer electrolyte fuel cell Ge, Shanhai; Wang, Chao-Yang Electrochimica Acta, Vol. 52, Issue 14 https://doi.org/10.1016/j.electacta.2007.01.038	journal	April 2007
Effective-Diffusivity Measurement of Partially-Saturated Fuel-Cell Gas-Diffusion Layers Hwang, G. S.; Weber, A. Z. Journal of The Electrochemical Society, Vol. 159, Issue 11 https://doi.org/10.1149/2.024211jes	journal	January 2012
Behavior of water below the freezing point in PEFCs Ishikawa, Y.; Morita, T.; Nakata, K. Journal of Power Sources, Vol. 163, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.08.026	journal	January 2007
Isothermal Ice Crystallization Kinetics in the Gas-Diffusion Layer of a Proton-Exchange-Membrane Fuel Cell Dursch, T. J.; Ciontea, M. A.; Radke, C. J. Langmuir, Vol. 28, Issue 2 https://doi.org/10.1021/la2033737	journal	December 2011
Cold Start of a Polymer-Electrolyte Fuel Cell I. Development of a Two-Dimensional Model Balliet, Ryan J.; Newman, John Journal of The Electrochemical Society, Vol. 158, Issue 8 https://doi.org/10.1149/1.3592430	journal	January 2011
Water Movement During Freezing in a Polymer-Electrolyte-Membrane Fuel Cell Balliet, Ryan J.; Thomas-Alyea, Karen E.; Newman, John 214th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2981863	conference	January 2008
Modeling Transport in Polymer-Electrolyte Fuel Cells Weber, Adam Z.; Newman, John Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020729l	journal	October 2004
Crystal Nucleation Rates from Probability Distributions of Induction Times Jiang, Shanfeng; ter Horst, Joop H. Crystal Growth & Design, Vol. 11, Issue 1 https://doi.org/10.1021/cg101213q	journal	January 2011
Induction time and metastability limit in new phase formation Kashchiev, D.; Verdoes, D.; van Rosmalen, G. M. Journal of Crystal Growth, Vol. 110, Issue 3 https://doi.org/10.1016/0022-0248(91)90273-8	journal	March 1991
Saturation Dependent Effective Transport Properties of PEFC Gas Diffusion Layers Rosén, Tomas; Eller, Jens; Kang, Jinfen Journal of The Electrochemical Society, Vol. 159, Issue 9 https://doi.org/10.1149/2.005209jes	journal	January 2012
A Multiphase Model for Cold Start of Polymer Electrolyte Fuel Cells Mao, Leng; Wang, Chao-Yang; Tabuchi, Yuichiro Journal of The Electrochemical Society, Vol. 154, Issue 3 https://doi.org/10.1149/1.2430651	journal	January 2007
Effects of ionomer content and oxygen permeation of the catalyst layer on proton exchange membrane fuel cell cold start-up Hiramitsu, Y.; Mitsuzawa, N.; Okada, K. Journal of Power Sources, Vol. 195, Issue 4 https://doi.org/10.1016/j.jpowsour.2009.08.016	journal	February 2010
Cold start characteristics and freezing mechanism dependence on start-up temperature in a polymer electrolyte membrane fuel cell Tabe, Yutaka; Saito, Masataka; Fukui, Kaoru Journal of Power Sources, Vol. 208 https://doi.org/10.1016/j.jpowsour.2012.02.052	journal	June 2012
In situ neutron imaging technique for evaluation of water management systems in operating PEM fuel cells Satija, R.; Jacobson, D. L.; Arif, M. Journal of Power Sources, Vol. 129, Issue 2 https://doi.org/10.1016/j.jpowsour.2003.11.068	journal	April 2004
Characteristics of the PEMFC Repetitively Brought to Temperatures below 0°C Cho, EunAe; Ko, Jae-Joon; Ha, Heung Yong Journal of The Electrochemical Society, Vol. 150, Issue 12 https://doi.org/10.1149/1.1621877	journal	January 2003
Water Uptake of Fuel-Cell Catalyst Layers Kusoglu, Ahmet; Kwong, Anthony; Clark, Kyle T. Journal of The Electrochemical Society, Vol. 159, Issue 9 https://doi.org/10.1149/2.031209jes	journal	January 2012
The Energetics of Nucleation Uhlmann, D. R.; Chalmers, B. Industrial & Engineering Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/ie50669a006	journal	September 1965
Three-dimensional multiphase modeling of cold start processes in polymer electrolyte membrane fuel cells Jiao, Kui; Li, Xianguo Electrochimica Acta, Vol. 54, Issue 27 https://doi.org/10.1016/j.electacta.2009.06.072	journal	November 2009
Low temperature thermal properties of Nafion 117 membranes in water and methanol-water mixtures Corti, Horacio R.; Nores-Pondal, Federico; Pilar Buera, M. Journal of Power Sources, Vol. 161, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.06.005	journal	October 2006
Isothermal Cold Start of Polymer Electrolyte Fuel Cells Tajiri, Kazuya; Tabuchi, Yuichiro; Wang, Chao-Yang Journal of The Electrochemical Society, Vol. 154, Issue 2 https://doi.org/10.1149/1.2402124	journal	January 2007
Pseudo-isothermal ice-crystallization kinetics in the gas-diffusion layer of a fuel cell from differential scanning calorimetry Dursch, T. J.; Ciontea, M. A.; Trigub, G. J. International Journal of Heat and Mass Transfer, Vol. 60 https://doi.org/10.1016/j.ijheatmasstransfer.2012.12.048	journal	May 2013
Kinetics of Phase Change. I General Theory Avrami, Melvin The Journal of Chemical Physics, Vol. 7, Issue 12, p. 1103-1112 https://doi.org/10.1063/1.1750380	journal	December 1939
Effects of operating and design parameters on PEFC cold start Tajiri, Kazuya; Tabuchi, Yuichiro; Kagami, Fumio Journal of Power Sources, Vol. 165, Issue 1 https://doi.org/10.1016/j.jpowsour.2006.12.017	journal	February 2007
Super-cooled water behavior inside polymer electrolyte fuel cell cross-section below freezing temperature Ishikawa, Y.; Hamada, H.; Uehara, M. Journal of Power Sources, Vol. 179, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.01.031	journal	May 2008
In Situ Imaging of Liquid Water and Ice Formation in an Operating PEFC during Cold Start Ge, Shanhai; Wang, Chao-Yang Electrochemical and Solid-State Letters, Vol. 9, Issue 11 https://doi.org/10.1149/1.2337860	journal	January 2006
Analysis of Cold Start in Polymer Electrolyte Fuel Cells Mao, Leng; Wang, Chao-Yang Journal of The Electrochemical Society, Vol. 154, Issue 2 https://doi.org/10.1149/1.2402123	journal	January 2007
Phase-change-related degradation of catalyst layers in proton-exchange-membrane fuel cells Hwang, Gi Suk; Kim, Hyoungchul; Lujan, Roger Electrochimica Acta, Vol. 95 https://doi.org/10.1016/j.electacta.2013.02.017	journal	April 2013
Cyclic Voltammetry Study of Ice Formation in the PEFC Catalyst Layer during Cold Start Ge, Shanhai; Wang, Chao-Yang Journal of The Electrochemical Society, Vol. 154, Issue 12 https://doi.org/10.1149/1.2784166	journal	January 2007
Cold-Start of a PEFC Visualized with High Resolution Dynamic In-Plane Neutron Imaging Oberholzer, P.; Boillat, P.; Siegrist, R. Journal of The Electrochemical Society, Vol. 159, Issue 2 https://doi.org/10.1149/2.085202jes	journal	January 2011
Wettability of Nafion and Nafion/Vulcan Carbon Composite Films Li, Xiaoan; Feng, Fangxia; Zhang, Ke Langmuir, Vol. 28, Issue 16 https://doi.org/10.1021/la300388x	journal	April 2012
Kinetics of Phase Change. II Transformation‐Time Relations for Random Distribution of Nuclei Avrami, Melvin The Journal of Chemical Physics, Vol. 8, Issue 2 https://doi.org/10.1063/1.1750631	journal	February 1940
A PEM fuel cell model for cold-start simulations Meng, Hua Journal of Power Sources, Vol. 178, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.12.035	journal	March 2008

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