A Theoretical Model for Computing Freezing Point Depression of Lithium-Ion Battery Electrolytes

Self, Julian; Bergstrom, Helen K.; Fong, Kara D.; McCloskey, Bryan D.; Persson, Kristin A.

doi:10.1149/1945-7111/ac3e47

Title: A Theoretical Model for Computing Freezing Point Depression of Lithium-Ion Battery Electrolytes

Journal Article · 21 December 2021 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/1945-7111/ac3e47 · OSTI ID:1863776

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Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry

Reliable prediction of freezing point depression in liquid electrolytes will accelerate the development of improved Li-ion batteries which can operate in low temperature environments. In this work we establish a computational methodology to calculate activity coefficients and liquidus lines for battery-relevant liquid electrolytes. Electronic structure methods are used in conjuction with classical molecular dynamics simulations and theoretical expressions for Born solvation energy, ion-atmosphere effects from Debye-Hückel theory and solvent entropic effects. The framework uses no a priori knowledge beyond neat solvent properties and the concentration of salt. LiPF₆ in propylene carbonate (PC), LiPF₆ in dimethyl carbonate (DMC) and LiClO₄ in DMC are investigated up to 1 molal with accuracy better than 3 °C when compared to experimental freezing point measurements. Finally, we find that the difference in freezing point depression between the propylene carbonate-based electrolyte and the dimethyl carbonate electrolytes originates from the difference in the solvent dielectric constant.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Institutes of Health (NIH); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1863776

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 12 Vol. 168; ISSN 0013-4651

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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