Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application

doi:10.1021/acsami.9b17614

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Title: Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application

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Abstract

In this study, in situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O ₂ transport resistance for low-loaded (0.05 mg _Pt cm ^-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reducedmore »« less

Authors:

^[1];

^[1]; Chowdhury, Anamika ^[2]; Medina, Samantha ^[3];

^[4];

^[1]; More, Karren L. ^[5]; Kariuki, Nancy ^[6]; Myers, Deborah J. ^[6];

^[7];

^[1];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Colorado School of Mines, Golden, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: 2019-11-19

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Science (SC)

OSTI Identifier:: 1580098

Report Number(s):: NREL/JA-5900-74854
Journal ID: ISSN 1944-8244

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 11; Journal Issue: 50; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 30 DIRECT ENERGY CONVERSION; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Pt/C catalyst inks; ionomer coverage; ink formulation and processing; in situ electrochemical diagnostics; oxygen transport resistance

Citation Formats


                    Van Cleve, Tim, Khandavalli, Sunilkumar, Chowdhury, Anamika, Medina, Samantha, Pylypenko, Svitlana, Wang, Min, More, Karren L., Kariuki, Nancy, Myers, Deborah J., Weber, Adam Z., Mauger, Scott A., Ulsh, Michael J., and Neyerlin, Kenneth C. Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.  United States: N. p., 2019. 
        Web.  doi:10.1021/acsami.9b17614.

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                    Van Cleve, Tim, Khandavalli, Sunilkumar, Chowdhury, Anamika, Medina, Samantha, Pylypenko, Svitlana, Wang, Min, More, Karren L., Kariuki, Nancy, Myers, Deborah J., Weber, Adam Z., Mauger, Scott A., Ulsh, Michael J., & Neyerlin, Kenneth C. Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application.  United States.  doi:10.1021/acsami.9b17614.

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                    Van Cleve, Tim, Khandavalli, Sunilkumar, Chowdhury, Anamika, Medina, Samantha, Pylypenko, Svitlana, Wang, Min, More, Karren L., Kariuki, Nancy, Myers, Deborah J., Weber, Adam Z., Mauger, Scott A., Ulsh, Michael J., and Neyerlin, Kenneth C. Tue .  
        "Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application".  United States.  doi:10.1021/acsami.9b17614.

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@article{osti_1580098,

  title        = {Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application},

  author       = {Van Cleve, Tim and Khandavalli, Sunilkumar and Chowdhury, Anamika and Medina, Samantha and Pylypenko, Svitlana and Wang, Min and More, Karren L. and Kariuki, Nancy and Myers, Deborah J. and Weber, Adam Z. and Mauger, Scott A. and Ulsh, Michael J. and Neyerlin, Kenneth C.},

  abstractNote = {In this study, in situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O2 transport resistance for low-loaded (0.05 mgPt cm-2) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H2, O2) transport resistance resulting from pore, thin film, and interfacial phenomena.},

  doi          = {10.1021/acsami.9b17614},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 50,

  volume       = 11,

  place        = {United States},

  year         = {2019},

  month        = {11}

}

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