卤化物固态电解质制备工艺研究进展：从实验室合成到规模化制造

Preparation Strategies of Halide Solid-State Electrolytes: From Laboratory Synthesis to Scalable Manufacturing

摘要

卤化物固态电解质因具有较好的氧化稳定性、较高的离子电导率和良好的机械可加工性，近年来成为全固态电池领域的重要研究方向. 随着氯化物以及氧氯化物、氮氯化物等体系的发展，卤化物固态电解质在离子传输性能和结构调控方面取得了显著进展. 然而，此类材料目前仍主要停留在实验室小批量制备和电池验证阶段，其规模化应用仍面临诸多问题. 本文综合评述了机械球磨法、固相反应法、溶液法、气相沉积法及相关复合工艺等主要制备方法，比较了不同工艺在结构调控和规模化制备潜力等方面的特点，并进一步分析了卤化物固态电解质由实验室制备走向规模化制造过程中待解决的问题，包括批次一致性控制、制造成本降低、环境稳定性提升、工艺过程可控性以及与实际电池制造的适配，以期为卤化物固态电解质的工艺优化、规模化制备及其在全固态电池中的应用研究提供参考.

Abstract

Owing to their favorable oxidative stability, high ionic conductivity, and good mechanical processability, halide solid-state electrolytes have emerged as promising electrolyte candidates for all-solid-state batteries. With the development of systems such as chlorides, oxychlorides, and nitride-chlorides, halide solid-state electrolytes have made significant progress in ionic transport performance and structural regulation. However, these materials are still mainly at the stage of laboratory-scale preparation and cell validation, and their scalable application still faces several issues. This review summarizes the major preparation methods, including ball milling, solid-state reaction, solution-based synthesis, vapor-phase deposition, and related hybrid processing strategies. The characteristics of different processes in terms of structural regulation and scalable preparation potential are compared, and the key issues that need to be addressed during the transition from laboratory preparation to scalable manufacturing are further analyzed, including batch-to-batch consistency control, manufacturing-cost reduction, environmental-stability improvement, process controllability, and compatibility with practical battery-manufacturing workflows, thereby providing a reference for process optimization, scalable preparation, and application research of halide solid-state electrolytes in all-solid-state batteries.

关键词

卤化物固态电解质 / 全固态电池 / 制备工艺 / 规模化制备

Key words

Halide solid-state electrolyte / All-solid-state battery / Preparation strategy / Scalable preparation

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基金资助

吉林省科技发展计划项目(YDZJ202501ZYTS291, 20260602013RC)

长春市科技发展计划项目(2024GZZ02)

广东省资助项目(2021ZT09C064)

国家自然科学基金(12275119, 52227802, 12426301, 525B2028)

广东省基础与应用基础研究基金(2024B1515120042)

深圳市科技计划项目(KQTD20200820113047086)

深圳市固态电池研发重点实验室(SYSPG20241211173726011)

粤港澳光热电能源材料与器件联合实验室(2019B121205001)

广东省电驱动力能源材料重点实验室(2018B030322001)