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Title: Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack

Abstract

Electrochemistry is necessarily a science of interfacial processes, and understanding electrode/electrolyte interfaces is essential to controlling electrochemical performance and stability. Undesirable interfacial interactions hinder discovery and development of rational materials combinations. By example, we examine an electrolyte, magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2) dissolved in diglyme, next to the Mg metal anode, which is purported to have a wide window of electrochemical stability. However, even in the absence of any bias, using in situ tender X-ray photoelectron spectroscopy, we discovered an intrinsic interfacial chemical instability of both the solvent and salt, further explained using first-principles calculations as driven by Mg 2+ dication chelation and nucleophilic attack by hydroxide ions. The proposed mechanism appears general to the chemistry near or on metal surfaces in hygroscopic environments with chelation of hard cations and indicates possible synthetic strategies to overcome chemical instability within this class of electrolytes.

Authors:
 [1];  [2];  [2];  [3];  [4];  [3];  [2];  [2]; ORCiD logo [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Maryland, College Park, MD (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chinese Academy of Sciences (CAS), Shanghai (China)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1473937
Alternate Identifier(s):
OSTI ID: 1480074
Report Number(s):
[SAND-2018-9890J]
[Journal ID: ISSN 0897-4756; 667716]
Grant/Contract Number:  
[AC04-94AL85000; AC02-05CH11231; SC0001160]
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
[ Journal Volume: 29; Journal Issue: 19]; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yu, Yi, Baskin, Artem, Valero-Vidal, Carlos, Hahn, Nathan T., Liu, Qiang, Zavadil, Kevin R., Eichhorn, Bryan W., Prendergast, David, and Crumlin, Ethan J. Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b03404.
Yu, Yi, Baskin, Artem, Valero-Vidal, Carlos, Hahn, Nathan T., Liu, Qiang, Zavadil, Kevin R., Eichhorn, Bryan W., Prendergast, David, & Crumlin, Ethan J. Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack. United States. doi:10.1021/acs.chemmater.7b03404.
Yu, Yi, Baskin, Artem, Valero-Vidal, Carlos, Hahn, Nathan T., Liu, Qiang, Zavadil, Kevin R., Eichhorn, Bryan W., Prendergast, David, and Crumlin, Ethan J. Thu . "Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack". United States. doi:10.1021/acs.chemmater.7b03404. https://www.osti.gov/servlets/purl/1473937.
@article{osti_1473937,
title = {Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack},
author = {Yu, Yi and Baskin, Artem and Valero-Vidal, Carlos and Hahn, Nathan T. and Liu, Qiang and Zavadil, Kevin R. and Eichhorn, Bryan W. and Prendergast, David and Crumlin, Ethan J.},
abstractNote = {Electrochemistry is necessarily a science of interfacial processes, and understanding electrode/electrolyte interfaces is essential to controlling electrochemical performance and stability. Undesirable interfacial interactions hinder discovery and development of rational materials combinations. By example, we examine an electrolyte, magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) dissolved in diglyme, next to the Mg metal anode, which is purported to have a wide window of electrochemical stability. However, even in the absence of any bias, using in situ tender X-ray photoelectron spectroscopy, we discovered an intrinsic interfacial chemical instability of both the solvent and salt, further explained using first-principles calculations as driven by Mg2+ dication chelation and nucleophilic attack by hydroxide ions. The proposed mechanism appears general to the chemistry near or on metal surfaces in hygroscopic environments with chelation of hard cations and indicates possible synthetic strategies to overcome chemical instability within this class of electrolytes.},
doi = {10.1021/acs.chemmater.7b03404},
journal = {Chemistry of Materials},
number = [19],
volume = [29],
place = {United States},
year = {2017},
month = {9}
}

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