In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Fu, Jinzhao; Jin, Wenting; Yang, Songge; Hou, Jiahui; Meng, Zifei; Liu, Guangchen; Yao, Zeyi; Wang, Zexin; Yang, Zhenzhen; Zhong, Yu; Wang, Yan

doi:10.1016/j.mattod.2025.08.038

Title: In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Journal Article · Thu Sep 11 20:00:00 EDT 2025 · Materials Today

DOI: https://doi.org/10.1016/j.mattod.2025.08.038 · OSTI ID:3018344

^[1]; Jin, Wenting ^[1]; Yang, Songge ^[1]; Hou, Jiahui ^[1];

^[1];

^[1]; Wang, Zexin ^[1]; Yang, Zhenzhen ^[2];

^[1];

^[1]

Worcester Polytechnic Institute, MA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Halide-based solid-state electrolytes (SSEs) are promising candidates for next-generation all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and chemical stability. However, their poor interfacial compatibility with lithium metal anode and Li-In alloy significantly hinder practical application due to the requirement for a protective interlayer. In this study, a novel approach to overcome this limitation is presented by introducing iron (Fe) doping into Li₃InCl₆ (LIC), which enables direct and stable contact with lithium-indium (Li-In) metal without a protective interlayer. Thermodynamic and computational analyses identified Fe³⁺ as a suitable dopant based on its similar reduction potential to In³⁺ and structural compatibility within the halide lattice. The synthesized 10 at. % Fe-doped LIC exhibits high phase purity, retained ionic conductivity, and notably improved interfacial stability. Full-cell tests using Fe-LIC achieve over 300 cycles with 80 % capacity retention. At the same time, symmetric Li-In/ Fe-LIC/ Li-In cells sustain over 500 h of operation, representing the first reported long-term cycling of LIC-based ASSLB without a protective interlayer. In conclusion, this work establishes Fe doping as an effective strategy to stabilize halide SSEs of In system against Li-In alloy, thereby simplifying cell architecture and advancing the development of safer, high-performance halide-based solid-state electrolytes.

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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:: 3018344

Journal Information:: Materials Today, Journal Name: Materials Today Vol. 90; ISSN 1369-7021

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

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