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

doi:10.1021/acsami.9b17614

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

Full Record
Other Related Research

Abstract

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. Inmore »« 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); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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

OSTI Identifier:: 1580098

Alternate Identifier(s):: OSTI ID: 1601817

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.

Copy to clipboard


                    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.

Copy to clipboard


                    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.  https://www.osti.gov/servlets/purl/1580098.

Copy to clipboard


                    
@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 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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acsami.9b17614

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 8 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Tailoring Electrode Microstructure via Ink Content to Enable Improved Rated Power Performance for Platinum Cobalt/High Surface Area Carbon Based Polymer Electrolyte Fuel Cells

Journal Article Van Cleve, Timothy ; Wang, Guanxiong ; Mooney, Mason ; ... - Journal of Power Sources

Improvements in polymer electrolyte fuel cell (PEFC) electrode performance have primarily focused on catalyst and ionomer developments, marginalizing the importance of catalyst ink formulation. Herein, the effect of ink formulation is examined across a series of cathodes comprised of PtCo supported on high surface area carbon (PtCo/HSC) and Nafion ionomer using an array of in situ electrochemical and ex situ characterization techniques. In contrast to prior work on Pt/Vu systems, ink water content had little effect on the electrochemically determined ionomer coverage for the PtCo/HSC electrocatalyst examined here. Characterization using nano-scale resolution X-ray computed tomography (nano-CT) demonstrated that water-rich inkmore »« less
DOI: 10.1016/j.jpowsour.2020.228889
Synthesis and Characterization of Mixed-Conducting Corrosion Resistant Oxide Supports

Technical Report Ramani, Vijay K.

An extensive search and evaluation of electrochemically stable catalyst supports (including metal oxides like RuO2-SiO2, RuO2-TiO2, and ITO was perfomed during the 4 years of the project. The suports were also catalyzed by deposition of Pt and tested for its performance and electrochemical stability in RDE and fuel cell experiments. For testing the electrochemical stability and fuel cell performance of the catalysts and supports, we have employed the protocols in use at the Department of Energy and Nissan Technological Center North America (NTCNA). The use of such procedures allows a precise and reproducible estimation of the performance and stability ofmore »« less
DOI: 10.2172/1326167

Full Text Available
Utilizing ink composition to tune bulk-electrode gas transport, performance, and operational robustness for a Fe–N–C catalyst in polymer electrolyte fuel cell

Journal Article Osmieri, Luigi ; Wang, Guanxiong ; Cetinbas, Firat C. ; ... - Nano Energy

With lower site density and turnover frequency, platinum group metal (PGM)-free catalysts based electrodes are often greater than 50 mu m thick in order to increase performance across the fuel cell operating range. Consequently, PGM-free electrodes have an additional bulk electrode transport resistance beyond the local or aggregate level transport in thin platinum-based electrodes. In parallel to the development of more active and durable PGM-free catalysts, advancements in understanding the interplay between PGM-free electrode fabrication, bulk-electrode transport, proton conductivity and performance are needed. Here, the relationship between ionic and gas phase transport through the electrode thickness is modified by adjustingmore »« less
DOI: 10.1016/j.nanoen.2020.104943
Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique: II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness

Journal Article Shinozaki, Kazuma ; Zack, Jason W. ; Pylypenko, Svitlana ; ... - Journal of the Electrochemical Society

Platinum electrocatalysts supported on high surface area and Vulcan carbon blacks (Pt/HSC, Pt/V) were characterized in rotating disk electrode (RDE) setups for electrochemical area (ECA) and oxygen reduction reaction (ORR) area specific activity (SA) and mass specific activity (MA) at 0.9 V. Films fabricated using several ink formulations and film-drying techniques were characterized for a statistically significant number of independent samples. The highest quality Pt/HSC films exhibited MA 870 ± 91 mA/mgPt and SA 864 ± 56 μA/cm² Pt while Pt/V had MA 706 ± 42 mA/mgPt and SA 1120 ± 70 μA/cm² Pt when measured in 0.1 M HClO₄,more »« less
Cited by 28
DOI: 10.1149/2.0551512jes

Full Text Available
Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study

Journal Article Kabir, Sadia ; Myers, Deborah J. ; Kariuki, Nancy ; ... - ACS Applied Materials and Interfaces

To increase the commercialization of fuel cell electric vehicles, it is imperative to improve the activity and performance of electrocatalysts through combined efforts focused on material characterization and device-level integration. Obtaining fundamental insights into the ongoing structural and compositional changes of electrocatalysts is crucial for not only transitioning an electrode from its as-prepared to functional state, also known as 'conditioning', but also for establishing intrinsic electrochemical performances. Here, we investigated several oxygen reduction reaction (ORR) electrocatalysts via in situ and ex situ characterization techniques to provide fundamental insights into the interfacial phenomena that enable peak ORR mass activity and highmore »« less
Cited by 11
DOI: 10.1021/acsami.9b11365

Full Text Available

Similar Records