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Title: Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF 6 in Propylene Carbonate Solutions

Abstract

Highly concentrated electrolytes (HCEs) based on LiPF 6 in propylene carbonate (PC) have been examined as lithium-ion battery electrolytes. These HCEs have lower ionic conductivities and higher viscosities than ethylene carbonate (EC) electrolytes with 1.2 M LiPF 6 , but they have higher Li + ion transference numbers. Electrochemical cycling behaviour of LiNi 0.8 Co 0.015 Al 0.05 O 2 //graphite cells with 3.2 M LiPF 6 in PC resembles that of cells with EC-based electrolytes; the HCE cells have higher impedance, which can be lowered by increasing test temperature. By employing Raman and infrared spectroscopy, combined with density functional theory and ab initio molecular dynamics simulations, we reveal that the Li + solvation structure and speciation are key factors that determine cell performance. Two distinct regimes are observed as a function of salt concentration—in the conventional regime, the solvation number (SN) is mostly constant, while in the HCE regime it decreases linearly. Graphite exfoliation is suppressed only at very high salt concentrations ( > 2.4 M), where [ PC ] free /[Li + ] < 1 and P F 6 − f r e e > P C f r e e . Results from the Advanced Electrolyte Model indicate that Li + desolvation improves at higher LiPF 6 concentrations, thereby mitigating PC co-intercalation into the graphite. However, Li + ion transport is hindered in the HCEs, which increases impedance at both the oxide-positive and graphite-negative electrodes.

Authors:
ORCiD logo; ; ; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
OSTI Identifier:
1835347
Alternate Identifier(s):
OSTI ID: 1798189
Grant/Contract Number:  
AC02-06CH11357; AC07-05ID14517
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 168 Journal Issue: 5; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Advanced electrolyte model; graphite anode; ion solvation; ion transport; lithium-ion battery; vibrational spectroscopy

Citation Formats

Åvall, Gustav, Wallenstein, Joachim, Cheng, Gang, Gering, Kevin L., Johansson, Patrik, and Abraham, Daniel P. Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF 6 in Propylene Carbonate Solutions. United States: N. p., 2021. Web. doi:10.1149/1945-7111/abfdc3.
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Åvall, Gustav, Wallenstein, Joachim, Cheng, Gang, Gering, Kevin L., Johansson, Patrik, & Abraham, Daniel P. Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF 6 in Propylene Carbonate Solutions. United States. https://doi.org/10.1149/1945-7111/abfdc3
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Åvall, Gustav, Wallenstein, Joachim, Cheng, Gang, Gering, Kevin L., Johansson, Patrik, and Abraham, Daniel P. Thu . "Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF 6 in Propylene Carbonate Solutions". United States. https://doi.org/10.1149/1945-7111/abfdc3.
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@article{osti_1835347,
title = {Highly Concentrated Electrolytes: Electrochemical and Physicochemical Characteristics of LiPF 6 in Propylene Carbonate Solutions},
author = {Åvall, Gustav and Wallenstein, Joachim and Cheng, Gang and Gering, Kevin L. and Johansson, Patrik and Abraham, Daniel P.},
abstractNote = {Highly concentrated electrolytes (HCEs) based on LiPF 6 in propylene carbonate (PC) have been examined as lithium-ion battery electrolytes. These HCEs have lower ionic conductivities and higher viscosities than ethylene carbonate (EC) electrolytes with 1.2 M LiPF 6 , but they have higher Li + ion transference numbers. Electrochemical cycling behaviour of LiNi 0.8 Co 0.015 Al 0.05 O 2 //graphite cells with 3.2 M LiPF 6 in PC resembles that of cells with EC-based electrolytes; the HCE cells have higher impedance, which can be lowered by increasing test temperature. By employing Raman and infrared spectroscopy, combined with density functional theory and ab initio molecular dynamics simulations, we reveal that the Li + solvation structure and speciation are key factors that determine cell performance. Two distinct regimes are observed as a function of salt concentration—in the conventional regime, the solvation number (SN) is mostly constant, while in the HCE regime it decreases linearly. Graphite exfoliation is suppressed only at very high salt concentrations ( > 2.4 M), where [ PC ] free /[Li + ] < 1 and P F 6 − f r e e > P C f r e e . Results from the Advanced Electrolyte Model indicate that Li + desolvation improves at higher LiPF 6 concentrations, thereby mitigating PC co-intercalation into the graphite. However, Li + ion transport is hindered in the HCEs, which increases impedance at both the oxide-positive and graphite-negative electrodes.},
doi = {10.1149/1945-7111/abfdc3},
journal = {Journal of the Electrochemical Society},
number = 5,
volume = 168,
place = {United States},
year = {Thu May 13 00:00:00 EDT 2021},
month = {Thu May 13 00:00:00 EDT 2021}
}
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