Effect of the Solvate Environment of Lithium Cations on the Resistance of the Polymer Electrolyte/Electrode Interface in a Solid-State Lithium Battery

Alexander V Chernyak; Nikita A Slesarenko; Anna A Slesarenko; Guzaliya R Baymuratova; Galiya Z Tulibaeva; Alena V Yudina; Vitaly I Volkov; Alexander F Shestakov; Olga V Yarmolenko

doi:10.3390/membranes12111111

Effect of the Solvate Environment of Lithium Cations on the Resistance of the Polymer Electrolyte/Electrode Interface in a Solid-State Lithium Battery

Membranes (Basel). 2022 Nov 8;12(11):1111. doi: 10.3390/membranes12111111.

Authors

Affiliations

¹ Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS, 142432 Chernogolovka, Russia.
² Scientific Center in Chernogolovka RAS, 142432 Chernogolovka, Russia.
³ Faculty of Fundamental Physical and Chemical Engineering, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia.

Abstract

The effect of the composition of liquid electrolytes in the bulk and at the interface with the LiFePO₄ cathode on the operation of a solid-state lithium battery with a nanocomposite polymer gel electrolyte based on polyethylene glycol diacrylate and SiO₂ was studied. The self-diffusion coefficients on the 7Li, 1H, and 19F nuclei in electrolytes based on LiBF₄ and LiTFSI salts in solvents (gamma-butyrolactone, dioxolane, dimethoxyethane) were measured by nuclear magnetic resonance (NMR) with a magnetic field gradient. Four compositions of the complex electrolyte system were studied by high-resolution NMR. The experimentally obtained ¹H chemical shifts are compared with those theoretically calculated by quantum chemical modeling. This made it possible to suggest the solvate shell compositions that facilitate the rapid transfer of the Li⁺ cation at the nanocomposite electrolyte/LiFePO₄ interface and ensure the stable operation of a solid-state lithium battery.

Keywords: NMR; chemical shifts; nanocomposite; organic electrolyte; polymer electrolyte; quantum chemical modeling; self-diffusion coefficients; solid-state lithium battery; solvate shell.

Grants and funding

This research was supported by the Ministry of Education and Science of the Russian Federation, project no. AAAA-A19-119071190044-3 (Experiment) and project no. AAAA-A19-119111390022-2 (Quantum chemical modeling).