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Title: Actualizing In Situ X-ray Absorption Spectroscopy Characterization of PEMFC-Cycled Pt-Electrodes

Abstract

The family of the PtM (M represents transition metals such as Co, Ni, Pd, etc.) alloys is the most promising cathode electrocatalysts for proton exchange membrane fuel cells (PEMFCs) owing to their superior oxygen reduction reaction (ORR) activity to pure Pt. However, the activity gain fades with long-term PEMFC operation, and the degradation mechanism is not yet fully understood. To truly understand the degradation mechanism of the carbon supported PtM nanoparticles (PtM/C) in the cathode of a membrane electrode assembly (MEA) upon long-term PEMFC operation, it is essential to characterize the PEMFC-cycled electrode under working conditions. Herein, we showed that operando X-ray absorption spectroscopy (XAS) characterization of PtM/C electrocatalysts cycled in a PEMFC has inherent difficulties since Pt and especially M dissolve during PEMFC operation and migrate into the membrane; the bulk XAS spectrum is an average of the signals from the electrode and the membrane. Alternatively, we developed a method that allows for in situ XAS characterization on PEMFC-cycled PtM/C electrocatalysts. As a result, we justified the method by showing that the dissolved species in the membrane were separated from the PtM/C electrocatalyst in the cathode, and the in situ XAS signals arose exclusively from the electrocatalyst.

Authors:
ORCiD logo; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1439253
Alternate Identifier(s):
OSTI ID: 1475163
Report Number(s):
BNL-209094-2018-JAAM
Journal ID: ISSN 0013-4651; /jes/165/9/F597.atom
Grant/Contract Number:  
EE0000458; SC0012704
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 9; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; PEMFC; PtM electrocatalyst; XAS

Citation Formats

Miller, Todd E., Davies, Veronica, Li, Jingkun, Ghoshal, Shraboni, Stavitski, Eli, Attenkofer, Klaus, Mukerjee, Sanjeev, and Jia, Qingying. Actualizing In Situ X-ray Absorption Spectroscopy Characterization of PEMFC-Cycled Pt-Electrodes. United States: N. p., 2018. Web. doi:10.1149/2.0151809jes.
Miller, Todd E., Davies, Veronica, Li, Jingkun, Ghoshal, Shraboni, Stavitski, Eli, Attenkofer, Klaus, Mukerjee, Sanjeev, & Jia, Qingying. Actualizing In Situ X-ray Absorption Spectroscopy Characterization of PEMFC-Cycled Pt-Electrodes. United States. doi:10.1149/2.0151809jes.
Miller, Todd E., Davies, Veronica, Li, Jingkun, Ghoshal, Shraboni, Stavitski, Eli, Attenkofer, Klaus, Mukerjee, Sanjeev, and Jia, Qingying. Sat . "Actualizing In Situ X-ray Absorption Spectroscopy Characterization of PEMFC-Cycled Pt-Electrodes". United States. doi:10.1149/2.0151809jes.
@article{osti_1439253,
title = {Actualizing In Situ X-ray Absorption Spectroscopy Characterization of PEMFC-Cycled Pt-Electrodes},
author = {Miller, Todd E. and Davies, Veronica and Li, Jingkun and Ghoshal, Shraboni and Stavitski, Eli and Attenkofer, Klaus and Mukerjee, Sanjeev and Jia, Qingying},
abstractNote = {The family of the PtM (M represents transition metals such as Co, Ni, Pd, etc.) alloys is the most promising cathode electrocatalysts for proton exchange membrane fuel cells (PEMFCs) owing to their superior oxygen reduction reaction (ORR) activity to pure Pt. However, the activity gain fades with long-term PEMFC operation, and the degradation mechanism is not yet fully understood. To truly understand the degradation mechanism of the carbon supported PtM nanoparticles (PtM/C) in the cathode of a membrane electrode assembly (MEA) upon long-term PEMFC operation, it is essential to characterize the PEMFC-cycled electrode under working conditions. Herein, we showed that operando X-ray absorption spectroscopy (XAS) characterization of PtM/C electrocatalysts cycled in a PEMFC has inherent difficulties since Pt and especially M dissolve during PEMFC operation and migrate into the membrane; the bulk XAS spectrum is an average of the signals from the electrode and the membrane. Alternatively, we developed a method that allows for in situ XAS characterization on PEMFC-cycled PtM/C electrocatalysts. As a result, we justified the method by showing that the dissolved species in the membrane were separated from the PtM/C electrocatalyst in the cathode, and the in situ XAS signals arose exclusively from the electrocatalyst.},
doi = {10.1149/2.0151809jes},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 165,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1149/2.0151809jes

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