Toluene Tolerated Li9.88GeP1.96Sb0.04S11.88Cl0.12 Solid Electrolyte toward Ultrathin Membranes for All-Solid-State Lithium Batteries

Xiaolei Zhao; Pan Xiang; Jinghua Wu; Ziqiang Liu; Lin Shen; Gaozhan Liu; Ziqi Tian; Liang Chen; Xiayin Yao

doi:10.1021/acs.nanolett.2c04140

Toluene Tolerated Li_9.88GeP_1.96Sb_0.04S_11.88Cl_0.12 Solid Electrolyte toward Ultrathin Membranes for All-Solid-State Lithium Batteries

Nano Lett. 2023 Jan 11;23(1):227-234. doi: 10.1021/acs.nanolett.2c04140. Epub 2022 Dec 19.

Authors

Xiaolei Zhao^{1

2}, Pan Xiang¹, Jinghua Wu¹, Ziqiang Liu^{1

2}, Lin Shen¹, Gaozhan Liu¹, Ziqi Tian^{1

2}, Liang Chen^{1

2}, Xiayin Yao^{1

2}

Affiliations

¹ Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo315201, P.R. China.
² Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing100049, P.R. China.

PMID: 36535024
DOI: 10.1021/acs.nanolett.2c04140

Abstract

Sulfide solid electrolyte membranes employed in all-solid-state lithium batteries generally show high thickness and poor chemical stability, which limit the cell-level energy density and cycle life. In this work, Li_9.88GeP_1.96Sb_0.04S_11.88Cl_0.12 solid electrolyte is synthesized with Sb, Cl partial substitution of P, S, possessing excellent toluene tolerance and stability to lithium. The formed SbS₄^3- group in Li_9.88GeP_1.96Sb_0.04S_11.88Cl_0.12 exhibits low adsorption energy and reactivity for toluene molecules, confirmed by first-principles density functional theory calculation. Using toluene as the solvent, ultrathin Li_9.88GeP_1.96Sb_0.04S_11.88Cl_0.12 membranes with adjustable thicknesses can be well prepared by the wet coating method, and an 8 μm thick membrane exhibits an ionic conductivity of 1.9 mS cm^-1 with ultrahigh ionic conductance of 1860 mS and ultralow areal resistance of 0.68 Ω cm^-2 at 25 °C. The obtained LiCoO₂|Li_9.88GeP_1.96Sb_0.04S_11.88Cl_0.12 membrane|Li all-solid-state lithium battery shows an initial reversible capacity of 125.6 mAh g^-1 with a capacity retention of 86.3% after 250 cycles at 0.1 C under 60 °C.

Keywords: all-solid-state lithium batteries; solvent stability; sulfide solid electrolytes; ultrathin membranes; wet coating.