程红伟， 段彤， 李佳敏， 李兰林， 孙强超

上海大学 材料科学与工程学院，中国，上海 200444

引用格式：

程红伟， 段彤， 李佳敏， 等. 复合固态电解质中微纳粉体填料的研究进展［J］. 中国粉体技术， 2025， 31（4）： 1-13.

CHENG Hongwei， DUAN Tong， LI Jiamin， et al. Research progress of micro- and nano-powder fillers in composite solid electrolytes［J］. China Powder Science and Technology， 2025， 31（4）： 1-13.

收稿日期： 2024-10-18，修回日期： 2024-11-20，上线日期： 2025-03-31。

基金项目： 国家自然科学基金项目，编号 ：52404423，51874196；上海市自然科学基金，编号：23ZR1421600。

第一作者简介： 程红伟（1980—），男，教授，博士，博士生导师，上海市东方学者，研究方向为资源综合利用与电化学储能。E-mail：hwcheng@shu.edu.cn。

摘要： 【目的】 梳理复合固态电解质中微纳粉体填料的研究进展，为开发具有离子电导率高、机械性能出色和化学稳定性良好的新型填料材料提供参考。【研究现状】 复合固态电解质具有离子导电率高、加工易、电化学窗口宽等优势，综述近年来国内外粉体填料的研究成果，粉体填料分为惰性、活性和功能性填料；概述氧化物型、矿物质型、其他非金属型、铁电性质类等惰性填料；钠超离子导体型、钙钛矿型、石榴石型、硫化物型等活性填料；金属有机框架型、共价有机框架型等功能型填料；综述填料在降低聚合物链的结晶度、促进锂盐的解离以及固定阴离子等提升电解质电化学性能的作用机制；揭示不同填料的设计原理。【结论与展望】认为填料在改善复合固态电解质物化性质方面发挥关键作用，复合固态电解质填料的研究和应用前景十分广阔，为固态锂金属电池技术的进步提供强有力的支持；未来的发展方向包括材料创新、填料设计优化、先进表征技术应用及应用领域的拓展。

关键词： 粉体填料； 颗粒尺度； 复合固态电解质； 固态锂金属电池

Abstract

Significance This study aims to conduct a comprehensive review of the latest research advancements in micro- and nano-powder fillers for composite solid electrolytes （CSEs）， offering valuable insights for the development of novel filler materials with superior ionic conductivity， exceptional mechanical properties， and excellent chemical stability. CSEs exhibit remarkable attributes， including high ionic conductivity， easy processing， and a broad electrochemical window. Fillers play a crucial role in enhancing the physical and chemical properties of CSEs. This review encompasses recent research achievements in fillers， elucidating their mechanisms for improving the electrochemical performance of CSEs by reducing polymer chain crystallinity， facilitating lithium salt dissociation， and stabilizing anionic species. Furthermore， it outlines the strengths and limitations of fillers while emphasizing the design principles for different types of fillers. The prospects for research and application of CSE fillers are promising， with future directions focusing on material innovation， optimization of filler design， utilization of advanced characterization techniques， and expansion into new application areas. These efforts are expected to significantly advance solid-state lithium metal battery technology.

Progress The polymers commonly utilized in this process， such as polyethylene oxide （PEO）， polyethylene glycol diacrylate （PEGDA）， and polyvinylidene fluoride （PVDF）， typically demonstrate relatively high crystallinity at room temperature. The incorporation of fillers， including inert materials like Al₂O₃， BaTiO₃， as well as fast ion conductors such as LLZTO， effectively reduces polymer crystallinity and improves the mobility of polymer chains. Early research primarily concentrated on exploring Lewis acid-base interactions between fillers and polymers， proposing that rapid ion conduction channels could be established on filler surfaces. Subsequent studies have focused on constructing these swift ion conduction channels， which are closely linked to the orientation and morphology of fillers within the polymer matrix. Recent advancements have discovered complex interactions among polymers， fillers， and lithium salts within CSEs. These interactions manifest primarily in two aspects： （1） the interplay between fillers and lithium salts， which involves changes in chemical environment of lithium ions， chiefly reflected in variations of ionic conductivity and lithium ion transference numbers （t_Li⁺）； （2） the interplay between fillers and polymers， involving modifications in polymer's structural composition， reflected in changes of crystallinity （X_c）， glass transition temperature （T_g）， and spherulite formation. Despite this progress， interface stability remains the fundamental challenge for solid-state lithium batteries （SSLBs）. These challenges are influenced by interactions at both CSEs/cathode and CSEs/anode surfaces， including issues such as inadequate electrolyte/electrode contact， lithium dendrite growth， and high-voltage decomposition.

Conclusions and Prospects CSEs exhibit tremendous potential in advancing solid-state battery technology through the incorporation of fillers to enhance their performance. This review presents a comprehensive review of various types of fillers， including inert， active， and functional fillers， as well as their characteristics and impact mechanisms on CSE performance. It illuminates the synergistic effects of fillers in enhancing electrochemical performance by reducing polymer chain crystallinity， facilitating lithium salt dissociation， and stabilizing anions. Notably， the interface interactions between fillers and the polymer matrix are pivotal for establishing rapid Li⁺ transport pathways. By optimizing filler dispersion and improving interface compatibility， the migration rate of lithium ions can be significantly enhanced， thereby improving the conductive properties of electrolytes. Despite significant progress in optimizing filler properties through various strategies， challenges such as the impact of fillers on ion transport dynamics， non-uniform lithium deposition， and dendrite formation still exist. Future research should focus on the following directions： 1） Material innovation. Leveraging artificial intelligence models to identify and design new fillers； 2） Filler optimization. Investigating microstructural features of fillers and their effects on performance； 3） Advanced characterization techniques. Utilizing cutting-edge characterization methods to explore the dynamic changes of fillers throughout the process of charging and discharging； 4） High-pressure compatibility. Developing composite fillers integrated with small molecule plasticizers to improve interfacial stability.

Keywords： powder filler； particle scale； composite solid electrolyte； solid-state lithium metal battery

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