Theory of Cation Solvation in the Helmholtz Layer of Li-Ion Battery Electrolytes

Goodwin, Zachary A. H.; Markiewitz, Daniel M.; Wu, Qisheng; Qi, Yue; Bazant, Martin Z.

doi:10.1021/acsaem.5c00883

Theory of Cation Solvation in the Helmholtz Layer of Li-Ion Battery Electrolytes

Journal Article · Mon Jun 02 00:00:00 EDT 2025 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.5c00883· OSTI ID:2570530

^[1]; ^[2]; Wu, Qisheng ^[3]; Qi, Yue ^[3]; ^[2]

Univ. of Oxford (United Kingdom); Harvard Univ., Cambridge, MA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Brown Univ., Providence, RI (United States)

The solvation environments of Li⁺ in conventional nonaqueous battery electrolytes, such as LiPF₆ in mixtures of ethylene carbaronate (EC) and ethyl methyl carbonate (EMC), are often used to rationalize transport properties and solid electrolyte interphase (SEI) formation. Solvation environments in the compact electrical double layer (EDL) next to the electrode, also known as the Helmholtz layer, determine (partially) what species can react to form the SEI, with bulk solvation environments often being used as a proxy. Here, we develop and test a theory of cation solvation in the Helmholtz layer of nonaqueous Li-ion battery electrolytes. First, we validate the theory against bulk and diffuse EDL atomistic molecular dynamics (MD) simulations of LiPF₆ EC/EMC mixtures as a function of surface charge, where we find the theory can qualitatively capture the solvation environments. Next, we turn to the Helmholtz layer, where we find the main effect of the solvation structures next to the electrode is an apparent reduction in the number of binding sites between Li⁺ and the solvents, again where we find reasonable agreement with our developed theory. Finally, by solving a simplified version of the theory, we find that the probability of Li⁺ binding to each solvent remains equal to the bulk probability, suggesting that the bulk solvation environments are a reasonable place to start when understanding battery electrolytes. Our developed formalism can be parametrized from bulk MD simulations and used to predict the solvation environments in the Helmholtz layer through reducing the number of available coordination sites, which can be used to determine what could react and form the SEI.

View Accepted Manuscript (DOE)

Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019112; SC0019112

OSTI ID:: 2570530

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 12 Vol. 8; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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