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Chemical Reaction Networks Explain Gas Evolution Mechanisms in Mg-Ion Batteries
[Image: see text] Out-of-equilibrium electrochemical reaction mechanisms are notoriously difficult to characterize. However, such reactions are critical for a range of technological applications. For instance, in metal-ion batteries, spontaneous electrolyte degradation controls electrode passivation...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10251523/ https://www.ncbi.nlm.nih.gov/pubmed/37235548 http://dx.doi.org/10.1021/jacs.3c02222 |
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author | Spotte-Smith, Evan Walter Clark Blau, Samuel M. Barter, Daniel Leon, Noel J. Hahn, Nathan T. Redkar, Nikita S. Zavadil, Kevin R. Liao, Chen Persson, Kristin A. |
author_facet | Spotte-Smith, Evan Walter Clark Blau, Samuel M. Barter, Daniel Leon, Noel J. Hahn, Nathan T. Redkar, Nikita S. Zavadil, Kevin R. Liao, Chen Persson, Kristin A. |
author_sort | Spotte-Smith, Evan Walter Clark |
collection | PubMed |
description | [Image: see text] Out-of-equilibrium electrochemical reaction mechanisms are notoriously difficult to characterize. However, such reactions are critical for a range of technological applications. For instance, in metal-ion batteries, spontaneous electrolyte degradation controls electrode passivation and battery cycle life. Here, to improve our ability to elucidate electrochemical reactivity, we for the first time combine computational chemical reaction network (CRN) analysis based on density functional theory (DFT) and differential electrochemical mass spectroscopy (DEMS) to study gas evolution from a model Mg-ion battery electrolyte—magnesium bistriflimide (Mg(TFSI)(2)) dissolved in diglyme (G2). Automated CRN analysis allows for the facile interpretation of DEMS data, revealing H(2)O, C(2)H(4), and CH(3)OH as major products of G2 decomposition. These findings are further explained by identifying elementary mechanisms using DFT. While TFSI(–) is reactive at Mg electrodes, we find that it does not meaningfully contribute to gas evolution. The combined theoretical–experimental approach developed here provides a means to effectively predict electrolyte decomposition products and pathways when initially unknown. |
format | Online Article Text |
id | pubmed-10251523 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-102515232023-06-10 Chemical Reaction Networks Explain Gas Evolution Mechanisms in Mg-Ion Batteries Spotte-Smith, Evan Walter Clark Blau, Samuel M. Barter, Daniel Leon, Noel J. Hahn, Nathan T. Redkar, Nikita S. Zavadil, Kevin R. Liao, Chen Persson, Kristin A. J Am Chem Soc [Image: see text] Out-of-equilibrium electrochemical reaction mechanisms are notoriously difficult to characterize. However, such reactions are critical for a range of technological applications. For instance, in metal-ion batteries, spontaneous electrolyte degradation controls electrode passivation and battery cycle life. Here, to improve our ability to elucidate electrochemical reactivity, we for the first time combine computational chemical reaction network (CRN) analysis based on density functional theory (DFT) and differential electrochemical mass spectroscopy (DEMS) to study gas evolution from a model Mg-ion battery electrolyte—magnesium bistriflimide (Mg(TFSI)(2)) dissolved in diglyme (G2). Automated CRN analysis allows for the facile interpretation of DEMS data, revealing H(2)O, C(2)H(4), and CH(3)OH as major products of G2 decomposition. These findings are further explained by identifying elementary mechanisms using DFT. While TFSI(–) is reactive at Mg electrodes, we find that it does not meaningfully contribute to gas evolution. The combined theoretical–experimental approach developed here provides a means to effectively predict electrolyte decomposition products and pathways when initially unknown. American Chemical Society 2023-05-26 /pmc/articles/PMC10251523/ /pubmed/37235548 http://dx.doi.org/10.1021/jacs.3c02222 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Spotte-Smith, Evan Walter Clark Blau, Samuel M. Barter, Daniel Leon, Noel J. Hahn, Nathan T. Redkar, Nikita S. Zavadil, Kevin R. Liao, Chen Persson, Kristin A. Chemical Reaction Networks Explain Gas Evolution Mechanisms in Mg-Ion Batteries |
title | Chemical Reaction Networks
Explain Gas Evolution Mechanisms
in Mg-Ion Batteries |
title_full | Chemical Reaction Networks
Explain Gas Evolution Mechanisms
in Mg-Ion Batteries |
title_fullStr | Chemical Reaction Networks
Explain Gas Evolution Mechanisms
in Mg-Ion Batteries |
title_full_unstemmed | Chemical Reaction Networks
Explain Gas Evolution Mechanisms
in Mg-Ion Batteries |
title_short | Chemical Reaction Networks
Explain Gas Evolution Mechanisms
in Mg-Ion Batteries |
title_sort | chemical reaction networks
explain gas evolution mechanisms
in mg-ion batteries |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10251523/ https://www.ncbi.nlm.nih.gov/pubmed/37235548 http://dx.doi.org/10.1021/jacs.3c02222 |
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