Interfacial solvation-structure regulation for stable Li metal anode by a desolvation coating technique

Li, Guo-Xing; Lennartz, Peter; Koverga, Volodymyr; Kou, Rong; Nguyen, Au; Jiang, Heng; Liao, Meng; Wang, Daiwei; Dandu, Naveen; Zepeda, Michael; Wang, Haiying; Wang, Ke; Ngo, Anh T.; Brunklaus, Gunther; Wang, Donghai

doi:10.1073/pnas.2311732121

Title: Interfacial solvation-structure regulation for stable Li metal anode by a desolvation coating technique

Journal Article · 17 January 2024 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2311732121 · OSTI ID:2469994

^[1];

^[2]; Koverga, Volodymyr ^[3]; Kou, Rong ^[1]; Nguyen, Au ^[1]; Jiang, Heng ^[1];

^[1]; Wang, Daiwei ^[1]; Dandu, Naveen ^[3];

^[4]; Wang, Haiying ^[1]; Wang, Ke ^[1]; Ngo, Anh T. ^[3];

^[2];

^[1]

Pennsylvania State Univ., University Park, PA (United States)
Helmholtz Institute Münster (Germany)
Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Illinois, Chicago, IL (United States)

Rechargeable lithium (Li) metal batteries face challenges in achieving stable cycling due to the instability of the solid electrolyte interphase (SEI). The Li-ion solvation structure and its desolvation process are crucial for the formation of a stable SEI on Li metal anodes and improving Li plating/stripping kinetics. This research introduces an interfacial desolvation coating technique to actively modulate the Li-ion solvation structure at the Li metal interface and regulate the participation of the electrolyte solvent in SEI formation. Through experimental investigations conducted using a carbonate electrolyte with limited compatibility to Li metal, the optimized desolvation coating layer, composed of 12-crown-4 ether-modified silica materials, selectively displaces strongly coordinating solvents while simultaneously enriching weakly coordinating fluorinated solvents at the Li metal/electrolyte interface. This selective desolvation and enrichment effect reduce solvent participation to SEI and thus facilitate the formation of a LiF-dominant SEI with greatly reduced organic species on the Li metal surface, as conclusively verified through various characterization techniques including XPS, quantitative NMR, operando NMR, cryo-TEM, EELS, and EDS. The interfacial desolvation coating technique enables excellent rate cycling stability (i.e., 1C) of the Li metal anode and prolonged cycling life of the Li||LiCoO₂ pouch cell in the conventional carbonate electrolyte (E/C 2.6 g/Ah), with 80% capacity retention after 333 cycles.

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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)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2469994

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 4 Vol. 121; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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