钠氯化物固态电解质研究进展

doi:10.15541/jim20250307

无机材料学报 ›› 2026, Vol. 41 ›› Issue (4): 409-420.DOI: 10.15541/jim20250307 CSTR: 32189.14.10.15541/jim20250307

• 综述 • 下一篇

钠氯化物固态电解质研究进展

彭德招¹^,²(), 李瑞¹^,², 王文鸿¹^,², 王梓瑞¹^,², 章志珍¹^,²()

¹ 中山大学·深圳材料学院, 深圳 518107
² 中山大学材料学院, 广州 510006

收稿日期:2025-07-19 修回日期:2025-09-17 出版日期:2026-04-20 网络出版日期:2025-10-17
通讯作者: 章志珍, 副教授. E-mail: zhangzhzh28@mail.sysu.edu.cn
作者简介:彭德招(1999-), 男, 博士研究生. E-mail: pengdzh5@mail2.sysu.edu.cn
基金资助:
深圳市优秀科技创新人才培养项目(RCYX20221008092929074);广东省科技计划项目(2023B0909060004);深圳市面上项目(JCYJ20220530150200001);广东省“珠江人才计划”青年拔尖人才项目(2021QN02L210);国家自然科学基金区域创新发展联合项目(U22A20439)

Research Progress on Sodium Chloride Solid Electrolytes

PENG Dezhao¹^,²(), LI Rui¹^,², WANG Wenhong¹^,², WANG Zirui¹^,², ZHANG Zhizhen¹^,²()

¹ School of Materials, Shenzhen Campus of Sun Yat-sen University, Shenzhen 518107, China
² School of Materials, Sun Yat-sen University, Guangzhou 510006, China

Received:2025-07-19 Revised:2025-09-17 Published:2026-04-20 Online:2025-10-17
Contact: ZHANG Zhizhen, associate professor. E-mail: zhangzhzh28@mail.sysu.edu.cn
About author:PENG Dezhao (1999-), male, PhD candidate. E-mail: pengdzh5@mail2.sysu.edu.cn
Supported by:
Shenzhen Science and Technology Program(RCYX20221008092929074);Guangdong S&T Program(2023B0909060004);Shenzhen Fundamental Research Program(JCYJ20220530150200001);Guangdong Pearl River Talent Program(2021QN02L210);National Natural Science Foundation of China(U22A20439)

摘要/Abstract

摘要：

钠离子电池具有成本低廉、钠资源丰富等优势, 是锂离子电池的潜在替代技术。开发兼具高离子电导率与宽电化学窗口的钠离子固态电解质对推动钠离子固态电池的发展与应用具有重要意义。在诸多固态电解质中, 氯化物电解质因具有高离子电导率、高氧化电位以及良好的塑性, 近年来受到广泛关注。本文系统梳理了钠氯化物固态电解质的发展脉络, 重点总结了固态电解质元素组成、晶体结构与离子电导率之间的内在关联, 并阐述了通过阳/阴离子掺杂、非晶化及异质结构复合等策略调控电解质离子输运性质的作用机制。此外, 本文讨论了钠氯化物固态电解质的电化学稳定性及其与正极材料的化学/电化学兼容性, 总结了其与钠金属负极的界面失效机制, 并简要概述了钠氯化物全固态电池的研究进展。最后, 本文凝练了氯化物全固态钠离子电池在实际应用中面临的关键挑战, 并对未来研究方向进行展望, 为该类材料在能源转换与储存领域中的实际应用提供指导。

关键词: 固态电解质, 离子电导率, 氯化物, 离子迁移, 固态电池, 综述

Abstract:

Sodium-ion batteries are widely considered a promising alternative to lithium-ion batteries owing to their low cost and the abundance of sodium resources. Advances in development and application of all-solid-state sodium-ion batteries (ASSBs) critically depend on the availability of solid electrolytes that combine high ionic conductivity with wide electrochemical stability window. Among various solid electrolytes, chloride solid electrolytes have attracted considerable attention in recent years due to their high ionic conductivity, high oxidation potential and favorable deformability. This review provides a comprehensive overview of development of sodium chloride solid electrolytes, emphasizing interplay of chemical composition, crystal structure and ionic conductivity, and further examining how modification approaches, including cation/anion doping, amorphization and heterostructure engineering, govern their ionic transport behavior. In addition, this review also evaluates the electrochemical stability of sodium chloride solid electrolytes, and their chemical and electrochemical compatibility with common cathode materials, which are crucial for enabling practical cell configurations. The interfacial degradation mechanisms that arise at the interface with sodium metal anode are also analyzed, and recent advances in chloride-based ASSBs are concisely reviewed. Finally, key challenges that hinder practical deployment of chloride-based ASSBs are highlighted, and prospective research directions are proposed, which are expected to provide valuable insights to guide future application of chloride solid electrolytes in energy conversion and storage technologies.

Key words: solid electrolyte, ionic conductivity, chloride, ion transport, solid-state battery, review

中图分类号:

TM911

彭德招, 李瑞, 王文鸿, 王梓瑞, 章志珍. 钠氯化物固态电解质研究进展[J]. 无机材料学报, 2026, 41(4): 409-420.

PENG Dezhao, LI Rui, WANG Wenhong, WANG Zirui, ZHANG Zhizhen. Research Progress on Sodium Chloride Solid Electrolytes[J]. Journal of Inorganic Materials, 2026, 41(4): 409-420.

图/表 8

图1 钠氯化物固态电解质材料的发展历程

Fig. 1 Development timeline of sodium chloride solid electrolytes

图2 不同类型钠氯化物固态电解质的晶体结构

Fig. 2 Crystal structures of different sodium chloride solid electrolytes (a) NaMCl4; (b) Na2MCl4; (c) NaMCl6; (d) Na2MCl6; (e) Na3MCl6 (P21/n); (f) Na3MCl6 ($\text{R}\overline{3}$); (g) Na3MCl6 ($\text{P}\overline{3}1\text{c}$); (h) UCl3

图3 NaMCl6型固态电解质的离子输运性质[52]

Fig. 3 Ion transport properties of NaMCl6 solid electrolytes[52] (a) Arrhenius plots of NaTaCl6 and NaNbCl6; (b, c) Atomic trajectories of Na and Cl atoms from ab initio molecular dynamics (AIMD) simulations for (b) NaTaCl6 and (c) NaNbCl6

图4 Na3-xMCl6-x/Na2-xMCl6-x型固态电解质的相图、离子输运性质及结构[36,59]

Fig. 4 Phase diagram, ion transport properties and structures of Na3-xMCl6-x/Na2-xMCl6-x solid electrolytes[36,59] (a) Phase diagram of NaCl-YCl3-ZrCl4[59]; (b) Transmission electron microscope image of Na0.625Y0.25Zr0.75Cl4.375[59]; (c) Selected area electron diffraction pattern of Na0.625Y0.25Zr0.75Cl4.375[59]; (d) Ionic conductivity and activation energy of NaxZrCl4+x at 25 ℃[36]; (e, f) Na+ and vacancy contents in (e) Na2ZrCl6 and (f) Na0.5ZrCl4.5[36]; (g) Energy profiles along the Na+ transport pathways in Na0.5ZrCl4.5[36]; (h) Crystal structure of Na0.5ZrCl4.5[36]

图5 xNa2O2-HfCl4型固态电解质的离子输运性质及结构[39]

Fig. 5 Ion transport property and structure of xNa2O2-HfCl4 solid electrolytes[39] (a) Arrhenius plots of xNa2O2-HfCl4; (b) Wavelet-transformed EXAFS contour plots of Na2O2-HfCl4 at Hf L3-edge[39];(c) AIMD-generated structure of amorphous Na2O2-HfCl4 at 500 K[39]

图6 xUCl3-(1-x)NaTaCl6型固态电解质的离子输运性质及结构[69]

Fig. 6 Ion transport property and structure of xUCl3-(1-x)NaTaCl6 solid electrolytes[69] (a) Arrhenius plots of 0.62Na0.75Sm1.75Cl6-0.38NaTaCl6 and 0.57Na0.75La1.75Cl6-0.43NaTaCl6; (b, c) Transmission electron microscope images of 0.62Na0.75Sm1.75Cl6-0.38NaTaCl6

图7 钠氯化物固态电解质的电化学稳定性及其与电极材料的兼容性[36,71,74]

Fig. 7 Electrochemical stability of sodium chloride solid electrolytes and their compatibilities with electrode materials[36,71,74] (a) Calculated electrochemical stability windows of Na-M-X ternary compounds, including fluorides, chlorides, bromides, iodides, oxides, and sulfides[71]; (b) Calculated reaction energies between different cathodes and solid electrolytes for Na3YCl6 (NYC), Na3YBr6 (NYB), Na3PS4 (NPS), and Na10GeP2S12 (NGPS)[71]; (c) Calculated reaction energies between Na0.5ZrCl4.5, Na0.5ZrCl4F0.5 solid electrolytes and Na3V2(PO4)3 (NVP) cathode, Na anode and Na15Sn4 anode[36]; (d) Impedance evolution of Na9Sn4|Na2.25Y0.25Zr0.75Cl6|Na cells with the time increasing[74]; (e) Zr3d and Y3d XPS spectra of Na2.25Y0.25Zr0.75Cl6 obtained from Na9Sn4|Na2.25Y0.25Zr0.75Cl6|Na cells after charging and discharging[74]

图8 氯化物全固态钠离子电池的电化学性能[36-37,39,59]

Fig. 8 Electrochemical performance of chloride all-solid-state sodium-ion batteries[36-37,39,59] (a) Schematic illustration of halide-based all-solid-state battery[36]; (b) Long cycling profiles of NaCrO2|Na2.25Y0.25Zr0.75Cl6|Na2(B10H10)0.5(B12H12)0.5|Na9Sn4 cells[59]; (c) Charge-discharge curves of Na3V2(PO4)3|NaTaCl6|Na3PS4|Na15Sn4 cells during cycling[37];(d) Long cycling profiles of Na3V2(PO4)3|NaTaCl6|Na3PS4|Na15Sn4 cells[37]; (e) Charge-discharge curves of Na0.85Mn0.5Ni0.4Fe0.1O2|Na2O2-HfCl4|Na3PS4|Na15Sn4 cells with different rate currents[39] and corresponding (f) long cycling profiles[39]

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钠氯化物固态电解质研究进展

Research Progress on Sodium Chloride Solid Electrolytes

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