Chemical Stability via Radical Decomposition Using Silicotungstic Acid Moieties for Polymer Electrolyte Fuel Cells
Abstract
Chemical degradation of perfluorinated sulfonic acid membranes, such as Nafion, via radical attack, represents one of the current challenges of fuel cell durability. Here we report on a recent breakthrough in chemical durability that has been achieved through using covalently attached heteropoly acid (HPA) moieties as both the proton conducting acid and the radical decomposition catalyst. Exceptional chemical durability is reported for a thin (25 um) film in an accelerated stress test that eventually had an open circuit voltage decay rate of 520 uV h-1, which was shown to be a result of the formation of an electrical short after thinning due to mechanical stresses. A mechanism is proposed using density functional theory in which the W atoms in the HPA reversibly change oxidation state from W(VI) to W(V) while decomposing radical species. Using rate constants found in the literature and realistic concentrations of scavenging species, it is hypothesized that the rate of radical decomposition can be >35x faster for HPA containing membranes than it is for Ce doped films. Furthermore, it is concluded that covalently tethered HPA should be considered as a next generation chemical stabilization strategy for polymer electrolyte fuel cells.
- Publication Date:
- Research Org.:
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office
- OSTI Identifier:
- 1482850
- Alternate Identifier(s):
- OSTI ID: 1492509
- Report Number(s):
- NREL/JA-5900-73180
Journal ID: ISSN 0013-4651; /jes/165/14/F1264.atom
- Grant/Contract Number:
- EE0006363; AC36-08GO28308
- 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: 14; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 30 DIRECT ENERGY CONVERSION; fuel cells; PEM; fuel cell electrolyte membrane; radical deposition mechanism
Citation Formats
Motz, Andrew R., Kuo, Mei-Chen, Bender, Guido, Pivovar, Bryan S., and Herring, Andrew M. Chemical Stability via Radical Decomposition Using Silicotungstic Acid Moieties for Polymer Electrolyte Fuel Cells. United States: N. p., 2018.
Web. doi:10.1149/2.1361814jes.
Motz, Andrew R., Kuo, Mei-Chen, Bender, Guido, Pivovar, Bryan S., & Herring, Andrew M. Chemical Stability via Radical Decomposition Using Silicotungstic Acid Moieties for Polymer Electrolyte Fuel Cells. United States. https://doi.org/10.1149/2.1361814jes
Motz, Andrew R., Kuo, Mei-Chen, Bender, Guido, Pivovar, Bryan S., and Herring, Andrew M. Tue .
"Chemical Stability via Radical Decomposition Using Silicotungstic Acid Moieties for Polymer Electrolyte Fuel Cells". United States. https://doi.org/10.1149/2.1361814jes.
@article{osti_1482850,
title = {Chemical Stability via Radical Decomposition Using Silicotungstic Acid Moieties for Polymer Electrolyte Fuel Cells},
author = {Motz, Andrew R. and Kuo, Mei-Chen and Bender, Guido and Pivovar, Bryan S. and Herring, Andrew M.},
abstractNote = {Chemical degradation of perfluorinated sulfonic acid membranes, such as Nafion, via radical attack, represents one of the current challenges of fuel cell durability. Here we report on a recent breakthrough in chemical durability that has been achieved through using covalently attached heteropoly acid (HPA) moieties as both the proton conducting acid and the radical decomposition catalyst. Exceptional chemical durability is reported for a thin (25 um) film in an accelerated stress test that eventually had an open circuit voltage decay rate of 520 uV h-1, which was shown to be a result of the formation of an electrical short after thinning due to mechanical stresses. A mechanism is proposed using density functional theory in which the W atoms in the HPA reversibly change oxidation state from W(VI) to W(V) while decomposing radical species. Using rate constants found in the literature and realistic concentrations of scavenging species, it is hypothesized that the rate of radical decomposition can be >35x faster for HPA containing membranes than it is for Ce doped films. Furthermore, it is concluded that covalently tethered HPA should be considered as a next generation chemical stabilization strategy for polymer electrolyte fuel cells.},
doi = {10.1149/2.1361814jes},
journal = {Journal of the Electrochemical Society},
number = 14,
volume = 165,
place = {United States},
year = {Tue Nov 20 00:00:00 EST 2018},
month = {Tue Nov 20 00:00:00 EST 2018}
}
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Cited by: 5 works
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Figures / Tables:
Figure 1: Structure of silicotungstic acid functionalized poly(vinylidene fluoride-co-hexafluoropropylene) (PolyHPA) reproduced with permission from the Royal Society of Chemistry from Ref. 26.
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