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However, their poor humid-air stability demands ultra-dry processing environments, severely limiting industrial scalability. Here, we report a water-assisted synthesis strategy to construct a zirconium-based core-shell structured HSSE, Li2Zr1.5OCl6@Li2CO3 (LZOC-H), under industrially viable dry-room conditions (dew point &amp;lt;\u221240\u202f\u00b0C). By exploiting trace ambient H2O and CO2 during synthesis, a self-derived Li2CO3-rich layer is formed in situ, significantly enhancing air stability. The resulting LZOC-H electrolyte achieves a relatively high room-temperature ionic conductivity of 1.12\u202fmS\u202fcm\u22121 and excellent moisture resistance. Full cell (Ni89|LZOC-H|LPSC|Li\u2013In) shows an initial capacity of 200.4\u202fmAh\u202fg\u22121 and retains 93.5% capacity over 1000 cycles at 1\u202fC. Moreover, a pouch cell with a silicon anode fabricated in a dry room demonstrates stable cycling (85.1% retention over 300 cycles). This work offers a scalable and rare-earth-metal-free pathway for producing moisture-resistant HSSEs, addressing key challenges in ASSLBs\u2019 commercialization.<\/jats:p>","DOI":"10.1093\/nsr\/nwag209","type":"journal-article","created":{"date-parts":[[2026,4,21]],"date-time":"2026-04-21T11:26:12Z","timestamp":1776770772000},"source":"Crossref","is-referenced-by-count":3,"title":["Hydrate\/moisture co-assisted synthesis enables humid-air stability of halide solid-state electrolytes"],"prefix":"10.1093","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4899-9987","authenticated-orcid":false,"given":"Xiangzhen","family":"Zhu","sequence":"first","affiliation":[{"name":"Eastern Institute for Advanced Study, Zhejiang Key Laboratory of All-Solid-State Battery, Ningbo Key Laboratory of All-Solid-State Battery, Eastern Institute of Technology, Ningbo Institute of Digital Twin , Ningbo 315200 ,","place":["China"]},{"name":"Solid State Batteries Research Center, GRINM (Guangdong) Institute for Advanced Materials and Technology, Foshan Key Laboratory of Advanced Electrochemical Functional Materials and Technology , Foshan 528051 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chao","family":"Liu","sequence":"additional","affiliation":[{"name":"Solid State Batteries Research Center, GRINM (Guangdong) Institute for Advanced Materials and Technology, Foshan Key Laboratory of Advanced Electrochemical Functional Materials and Technology , Foshan 528051 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaolong","family":"Yan","sequence":"additional","affiliation":[{"name":"Solid State Batteries Research Center, GRINM (Guangdong) Institute for Advanced Materials and Technology, Foshan Key Laboratory of Advanced Electrochemical Functional Materials and Technology , Foshan 528051 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Battery, Ningbo Key Laboratory of All-Solid-State Battery, Eastern Institute of Technology, Ningbo Institute of Digital Twin , Ningbo 315200 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yueyue","family":"Wang","sequence":"additional","affiliation":[{"name":"Solid State Batteries Research Center, GRINM (Guangdong) Institute for Advanced Materials and Technology, Foshan Key Laboratory of Advanced Electrochemical Functional Materials and Technology , Foshan 528051 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Han","family":"Wu","sequence":"additional","affiliation":[{"name":"Eastern Institute for Advanced Study, Zhejiang Key Laboratory of All-Solid-State Battery, Ningbo Key Laboratory of All-Solid-State Battery, Eastern Institute of Technology, Ningbo Institute of Digital Twin , Ningbo 315200 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yue","family":"Gong","sequence":"additional","affiliation":[{"name":"Solid State Batteries Research Center, GRINM (Guangdong) Institute for Advanced Materials and Technology, Foshan Key Laboratory of Advanced Electrochemical Functional Materials and Technology , Foshan 528051 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanlong","family":"Wu","sequence":"additional","affiliation":[{"name":"Solid State Batteries Research Center, GRINM (Guangdong) Institute for Advanced Materials and Technology, Foshan Key Laboratory of Advanced Electrochemical Functional Materials and Technology , Foshan 528051 ,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xinmiao","family":"Wang","sequence":"additional","affiliation":[{"name":"Eastern Institute for Advanced Study, Zhejiang Key Laboratory of All-Solid-State Battery, Ningbo Key Laboratory of 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