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Title: Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes

Abstract

The emergence of magnesium and calcium batteries as potential beyond Li ion energy storage technologies has generated significant interest into the fundamental aspects of alkaline earth metal cation coordination in multivalent electrolytes and the impact of coordination on application-critical electrolyte properties such as solubility, transport, and electrochemical stability. Understanding these details in calcium electrolytes is of immediate importance due to recent, unprecedented demonstrations of reversible calcium metal electrodeposition in a limited number of ethereal solvent-based systems. In this work, we provide insight connecting Ca2+ coordination tendencies to important calcium battery electrolyte properties. Our results demonstrate a clear solvent:Ca2+ coordination strength trend across a series of cyclic ether and linear glyme solvents that controls the extent of ion association in solutions of "weakly" coordinating salts. We apply understanding gained from these results to rationalize relative anion:Ca2+ coordination tendencies and attendant Ca2+ coordination structures using two oxidatively stable anions of particular interest for current battery electrolytes. Armed with this understanding of solvent and anion interactions with Ca2+, we demonstrate and interpret differences in electrochemical calcium deposition behavior across several electrolyte exemplars with varying solvent and anion coordination strengths. Our findings demonstrate that solvents exhibiting especially strong coordination to Ca2+, such as triglyme,more » can inhibit reversible calcium deposition despite effective elimination of anion:Ca2+ coordination while solvents exhibiting more modest coordination strength, such as 1,2-dimethoxyethane, may enable deposition provided anion:Ca2+ coordination is substantially limited. These results reveal that the strength of coordination of both anion and solvent should be considered in the design of electrolytes for calcium batteries.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Joint Center for Energy Storage Research, Lemont, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Joint Center for Energy Storage Research, Lemont, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Advanced Photon Source, Argonne National Laboratory, Lemont, Illinois 60439, United States
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1644403
Alternate Identifier(s):
OSTI ID: 1756838
Report Number(s):
SAND2020-7560J
Journal ID: ISSN 2574-0962; 687570
Grant/Contract Number:  
AC04-94AL85000; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 9; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Raman; X-ray; electrochemistry; electrodeposition; energy storage; simulation; spectroscopy

Citation Formats

Hahn, Nathan T., Driscoll, Darren M., Yu, Zhou, Sterbinsky, George E., Cheng, Lei, Balasubramanian, Mahalingam, and Zavadil, Kevin R. Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes. United States: N. p., 2020. Web. doi:10.1021/acsaem.0c01070.
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Hahn, Nathan T., Driscoll, Darren M., Yu, Zhou, Sterbinsky, George E., Cheng, Lei, Balasubramanian, Mahalingam, & Zavadil, Kevin R. Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes. United States. https://doi.org/10.1021/acsaem.0c01070
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Hahn, Nathan T., Driscoll, Darren M., Yu, Zhou, Sterbinsky, George E., Cheng, Lei, Balasubramanian, Mahalingam, and Zavadil, Kevin R. Thu . "Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes". United States. https://doi.org/10.1021/acsaem.0c01070. https://www.osti.gov/servlets/purl/1644403.
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@article{osti_1644403,
title = {Influence of Ether Solvent and Anion Coordination on Electrochemical Behavior in Calcium Battery Electrolytes},
author = {Hahn, Nathan T. and Driscoll, Darren M. and Yu, Zhou and Sterbinsky, George E. and Cheng, Lei and Balasubramanian, Mahalingam and Zavadil, Kevin R.},
abstractNote = {The emergence of magnesium and calcium batteries as potential beyond Li ion energy storage technologies has generated significant interest into the fundamental aspects of alkaline earth metal cation coordination in multivalent electrolytes and the impact of coordination on application-critical electrolyte properties such as solubility, transport, and electrochemical stability. Understanding these details in calcium electrolytes is of immediate importance due to recent, unprecedented demonstrations of reversible calcium metal electrodeposition in a limited number of ethereal solvent-based systems. In this work, we provide insight connecting Ca2+ coordination tendencies to important calcium battery electrolyte properties. Our results demonstrate a clear solvent:Ca2+ coordination strength trend across a series of cyclic ether and linear glyme solvents that controls the extent of ion association in solutions of "weakly" coordinating salts. We apply understanding gained from these results to rationalize relative anion:Ca2+ coordination tendencies and attendant Ca2+ coordination structures using two oxidatively stable anions of particular interest for current battery electrolytes. Armed with this understanding of solvent and anion interactions with Ca2+, we demonstrate and interpret differences in electrochemical calcium deposition behavior across several electrolyte exemplars with varying solvent and anion coordination strengths. Our findings demonstrate that solvents exhibiting especially strong coordination to Ca2+, such as triglyme, can inhibit reversible calcium deposition despite effective elimination of anion:Ca2+ coordination while solvents exhibiting more modest coordination strength, such as 1,2-dimethoxyethane, may enable deposition provided anion:Ca2+ coordination is substantially limited. These results reveal that the strength of coordination of both anion and solvent should be considered in the design of electrolytes for calcium batteries.},
doi = {10.1021/acsaem.0c01070},
journal = {ACS Applied Energy Materials},
number = 9,
volume = 3,
place = {United States},
year = {Thu Jul 23 00:00:00 EDT 2020},
month = {Thu Jul 23 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acsaem.0c01070
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