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

Åvall, Gustav; Wallenstein, Joachim; Cheng, Gang; Gering, Kevin L.; Johansson, Patrik; Abraham, Daniel P.

doi:10.1149/1945-7111/abfdc3

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

Journal Article · Thu May 13 00:00:00 EDT 2021 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/abfdc3· OSTI ID:1835347

; Wallenstein, Joachim; Cheng, Gang;

;

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: 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

Grant/Contract Number:: AC02-06CH11357; AC07-05ID14517

OSTI ID:: 1835347

Alternate ID(s):: OSTI ID: 1798189

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Vol. 168 Journal Issue: 5; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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

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