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Simultaneously Enhance Humidity Tolerance and Ionic Conductivity of Halide Electrolytes by Cation–Anion Co‐Doping
Author(s) -
Wang Weizong,
Jing Kexuan,
Ma He,
Liang Kang,
Wei Peng,
Liu Jiangchuan,
Ren Yurong,
Zhao Qian,
Ding Zhengping
Publication year - 2025
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.202500943
Subject(s) - ionic conductivity , conductivity , electrolyte , halide , doping , materials science , ionic bonding , ion , humidity , inorganic chemistry , analytical chemistry (journal) , chemical engineering , chemistry , electrode , thermodynamics , organic chemistry , optoelectronics , physics , engineering
Abstract Halide solid‐state electrolytes (SSEs) with high ionic conductivity and oxidation stability show significant potentials for the commercialization of all‐solid‐state batteries (ASSBs). However, their practical applications are limited by poor humidity tolerance and decreased ionic conductivity. Herein, the Li 3/3‐ x In 1‐ x M x Cl 5.6 F 0.4 ( M = Hf, Zr, Fe, and Y; x = 0.015, 0.02, 0.025, 0.075, 0.1, 0.125, and 0.15) are synthesized by co‐doping Li 3 InCl 6 with M and F ions for high‐performance ASSBs. Li 2.98 In 0.98 Hf 0.02 Cl 5.6 F 0.4 achieves the highest ionic conductivity of 1.04 mS cm −1 at room temperature and good humidity tolerance of 87.96% conductivity retention after 24 h exposure. The analysis of experiments combining BVSE and AIMD simulations indicates that it benefits from the enhanced rigid structure that is thermodynamically stable to water caused by Cl − doping with F − and higher Li + vacancies concentration that facilitates Li + conduction generated by In 3+ doping with Hf 4+ . Moreover, an all‐solid‐state battery ensembled with Li 2.98 In 0.98 Hf 0.02 Cl 5.6 F 0.4 , LiCoO 2 and Li–In alloy, exhibits a high discharge capacity of 83.6 mAh g −1 and 78.6% capacity retention after 100 cycles under 0.5 C at 25 °C. This work provides a reliable strategy for designing advanced halide SSEs for commercial applications in ASSBs by cation–anion co‐doping.