Article(id=1320090006836850905, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320089968630944199, articleNumber=null, orderNo=null, doi=10.14062/j.issn.0454-5648.20250066, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1738598400000, receivedDateStr=2025-02-04, revisedDate=1742227200000, revisedDateStr=2025-03-18, acceptedDate=null, acceptedDateStr=null, onlineDate=1792663583715, onlineDateStr=2026-10-22, pubDate=1750348800000, pubDateStr=2025-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792663583715, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792663583715, creator=13701087609, updateTime=1792663583715, updator=13701087609, issue=Issue{id=1320089968630944199, tenantId=1146029695717560320, journalId=1263187385517883426, year='2025', volume='53', issue='6', pageStart='1403', pageEnd='1776', issueExtLink='null', onlineDate='null', pubDate='1750348800000', pubDateStr='2025-06-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792663574607, creator='13701087609', updateTime=1792663739055, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320090658786881616, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320089968630944199, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320090658786881617, tenantId=1146029695717560320, journalId=1263187385517883426, issueId=1320089968630944199, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1561, endPage=1576, ext={EN=ArticleExt(id=1320090007042371802, articleId=1320090006836850905, tenantId=1146029695717560320, journalId=1263187385517883426, language=EN, title=Progress on Halide Solid Electrolytes in All-Solid-State Sodium Batteries, columnId=1321945714683392392, journalTitle=Journal of the Chinese Ceramic Society, columnName=Special Issue on Development of All-Solid-State Batteries—Review, runingTitle=null, highlight=null, articleAbstract=

All-solid-state sodium batteries (ASSSBs) emerge as a highly promising next-generation energy storage technology due to their inherent high safety, abundant sodium resources, and potential for cost-effective production. A central to the performance of these batteries is solid electrolyte (SSE) that has a pivotal role in determining the overall electrochemical performance. Among various SSE candidates, halide solid electrolytes (HSSEs) have attracted much attention due to their high ionic conductivity, wide electrochemical window and good deformability. These characteristics make HSSEs particularly suitable for high-energy-density applications, where conventional liquid electrolytes often fall short due to safety concerns and limited voltage windows.

The crystal structures of halide SSEs are intricately linked to their ion transport mechanisms and electrochemical performance. These structures can be broadly classified based on the metal elements incorporated and the arrangement of halide ions. For instance, sodium-based halide SSEs can be categorized into three main types, i.e., those with subgroup 3 and 4 elements (i.e., Sc, Y, La-Lu, Zr, Hf), subgroup 5 elements (i.e., Nb, Ta), and subgroup 3 main group elements (i.e., Al, Ga, In). Each category exhibits distinct structural characteristics and corresponding ionic conductivities. For instance, Na3YCl6, which belongs to the subgroup 3 and 4 elements category, is reported to have an ionic conductivity of 1.4×10−7 S/cm at room temperature and a monoclinic crystal structure. In contrast, NaTaCl6 as a member of the subgroup 5 elements category has an ionic conductivity of 6.2×10−5 S/cm and a monoclinic structure. These structural differences can affect the ion transport mechanisms and overall electrochemical performance of SSEs.

The synthesis methods of halide SSEs play a crucial role in determining their structural and electrochemical properties. Common synthesis methods include mechanical milling, solid-state annealing, and wet chemical synthesis. Mechanical milling, especially high-energy ball milling, can introduce structural disorder and defects, which enhance the ionic conductivity of SSEs. For instance, ball-milled NaTaCl6 (NTC) exhibits a higher ionic conductivity of 4×10−3 S/m, compared to its as-synthesized form. Solid-state annealing can improve the crystallinity and phase purity of SSEs, but it may also lead to a decrease in ionic conductivity due to the reduction of structural defects. Wet chemical synthesis offers a more scalable and energy-efficient approach, but it requires careful control of the synthesis parameters to achieve the desired crystal structure and ionic conductivity.

Interface stability between SSEs and the electrodes is another critical issue that needs to be addressed for the practical application of ASSSBs. Halide SSEs generally exhibit good chemical stability and compatibility with cathode materials due to their wide electrochemical window and high oxidation resistance. However, the interface between SSEs and sodium metal anode remains a challenge. The poor electrochemical reduction stability of halide SSEs can lead to severe interfacial reactions and degradation when in direct contact with sodium metal. To mitigate this issue, various strategies are proposed, such as alloying sodium with other metals (i.e., Sn) to form a more stable interface, using protective coatings to prevent direct contact between SSEs and sodium, and employing composite electrolytes to enhance the overall stability of the interface.

In addition, the scalability and reproducibility of halide SSEs are also critical factors for their practical application. The existing synthesis methods often involve complex procedures and high-energy inputs, which limit the large-scale production of these materials. It is essential for the commercialization of halide SSEs to develop cost-effective and scalable synthesis routes. Moreover, the long-term stability and reliability of ASSSBs incorporating halide SSEs need to be thoroughly evaluated under various operating conditions (i.e., temperature, cycling rate and environmental factor).

Summary and Prospects

Halide solid-state electrolytes (HSSEs) are poised to revolutionize all-solid-state sodium batteries (ASSSBs) due to their exceptional ionic conductivity (i.e., often surpassing 10-3 S/cm), broad electrochemical stability windows (i.e., up to 6 V vs. Na+/Na), and mechanical flexibility, which enable dense electrode-electrolyte integration and mitigate dendrite growth. However, their practical implementation faces multifaceted challenges. Crystal structure optimization is required to balance ionic transport and thermodynamic stability, particularly in systems like Na3YCl6 or Na2ZrCl6, where lattice defects and anion/cation disorder impede performance. Synthesis methods such as mechanochemical milling or solvent-based routes need refinement to reduce impurities and ensure reproducibility. Electrode-electrolyte interface instability, driven by chemical incompatibility or volumetric changes during cycling, remains a critical bottleneck for long-term cycling. Scalable production techniques should bridge a gap between lab-scale innovations and industrial manufacturing. Future research should prioritize structure-property relationship studies using computational tools like density functional theory (DFT) to design HSSEs with tailored ion migration pathways, coupled with advanced in-situ characterization (i.e., synchrotron X-ray tomography or cryo-electron microscopy) to probe dynamic interfacial degradation mechanisms. Simultaneously, innovative material engineering strategies, such as inorganic-polymer composites (i.e., HSSE-PEO hybrids) to enhance interfacial adhesion or novel dual-phase electrolytes to suppress side reactions can address stability and conductivity trade-offs. The development of low-cost synthesis routes (i.e., aqueous precursor processing or scalable sintering) and rigorous evaluation of HSSEs under extreme temperatures, high current densities, and a prolonged cycling will be pivotal for commercialization. In addition, interface optimization via atomic-layer-deposited protective coatings or 3D nanostructured electrodes can also minimize interfacial resistance and improve charge transfer kinetics. With rapid advancements in material discovery, machine learning-driven design, and interdisciplinary collaboration, HSSEs become a threshold of practical application, having ASSSBs with unparalleled energy density (i.e., >400 Wh/kg), inherent safety, and cycle lifetimes exceeding 5000 cycles. The field trajectory indicates that resolving these challenges could have sodium-based solid-state batteries as mainstream solutions for grid storage and electric vehicles, marking a paradigm shift in sustainable energy storage.

, authors=Huijuan HUANG, Hai YANG, Yu YAO, Yan YU, authorsList=Huijuan HUANG, Hai YANG, Yu YAO, Yan YU, authorCompany=null, correspAuthors=Yan YU, authorNote=

HUANG Huijuan (1996-), female, Ph.D. E-mail:

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YU Yan (1979-), female, Ph.D., Professor. E-mail:
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固态钠电池具有高安全性和丰富的钠资源优势,已成为下一代储能技术的研究热点。其中,固态电解质是固态钠电池的核心材料之一,对电池的综合性能具有决定性作用。在各类固态电解质中,卤化物固态电解质(因其高离子电导率、宽电化学窗口和良好的可变形性等优势,被认为是最具前景的电解质材料之一。然而,其在材料制备、界面稳定性等方面仍面临诸多挑战。本文聚焦卤化物电解质,系统综述了其在固态钠电池中的最新研究进展,重点探讨了其晶体结构、离子传输机制、合成方法以及界面稳定性策略。同时,对卤化物电解质在固态钠电池中的未来应用前景进行了展望。

, authors=黄慧娟, 杨海, 姚雨, 余彦, authorsList=黄慧娟, 杨海, 姚雨, 余彦, authorCompany=null, correspAuthors=余彦, authorNote=

黄慧娟(1996—),女,博士

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余彦(1979—),女,博士,教授
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固态钠电池卤化物电解质研究进展
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黄慧娟 , 杨海 , 姚雨 , 余彦
硅酸盐学报 | 全固态电池发展专刊—综合评述 2025,53(6): 1561-1576
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硅酸盐学报 |全固态电池发展专刊—综合评述 2025 , 53 (6) : 1561 -1576
固态钠电池卤化物电解质研究进展
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黄慧娟 , 杨海, 姚雨, 余彦
作者信息
  • 中国科学技术大学材料科学与工程系,合肥 230026
通讯作者:
余彦(1979—),女,博士,教授
作者简介:

黄慧娟(1996—),女,博士

Progress on Halide Solid Electrolytes in All-Solid-State Sodium Batteries
Huijuan HUANG , Hai YANG, Yu YAO, Yan YU
Affiliations
  • Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China
  • Corresponding Author:
    YU Yan (1979-), female, Ph.D., Professor. E-mail:

    HUANG Huijuan (1996-), female, Ph.D. E-mail:

出版时间: 2025-06-20 doi: 10.14062/j.issn.0454-5648.20250066
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固态钠电池具有高安全性和丰富的钠资源优势,已成为下一代储能技术的研究热点。其中,固态电解质是固态钠电池的核心材料之一,对电池的综合性能具有决定性作用。在各类固态电解质中,卤化物固态电解质(因其高离子电导率、宽电化学窗口和良好的可变形性等优势,被认为是最具前景的电解质材料之一。然而,其在材料制备、界面稳定性等方面仍面临诸多挑战。本文聚焦卤化物电解质,系统综述了其在固态钠电池中的最新研究进展,重点探讨了其晶体结构、离子传输机制、合成方法以及界面稳定性策略。同时,对卤化物电解质在固态钠电池中的未来应用前景进行了展望。

固态钠电池  /  卤化物电解质  /  离子电导率  /  界面改性  /  电化学稳定性

All-solid-state sodium batteries (ASSSBs) emerge as a highly promising next-generation energy storage technology due to their inherent high safety, abundant sodium resources, and potential for cost-effective production. A central to the performance of these batteries is solid electrolyte (SSE) that has a pivotal role in determining the overall electrochemical performance. Among various SSE candidates, halide solid electrolytes (HSSEs) have attracted much attention due to their high ionic conductivity, wide electrochemical window and good deformability. These characteristics make HSSEs particularly suitable for high-energy-density applications, where conventional liquid electrolytes often fall short due to safety concerns and limited voltage windows.

The crystal structures of halide SSEs are intricately linked to their ion transport mechanisms and electrochemical performance. These structures can be broadly classified based on the metal elements incorporated and the arrangement of halide ions. For instance, sodium-based halide SSEs can be categorized into three main types, i.e., those with subgroup 3 and 4 elements (i.e., Sc, Y, La-Lu, Zr, Hf), subgroup 5 elements (i.e., Nb, Ta), and subgroup 3 main group elements (i.e., Al, Ga, In). Each category exhibits distinct structural characteristics and corresponding ionic conductivities. For instance, Na3YCl6, which belongs to the subgroup 3 and 4 elements category, is reported to have an ionic conductivity of 1.4×10−7 S/cm at room temperature and a monoclinic crystal structure. In contrast, NaTaCl6 as a member of the subgroup 5 elements category has an ionic conductivity of 6.2×10−5 S/cm and a monoclinic structure. These structural differences can affect the ion transport mechanisms and overall electrochemical performance of SSEs.

The synthesis methods of halide SSEs play a crucial role in determining their structural and electrochemical properties. Common synthesis methods include mechanical milling, solid-state annealing, and wet chemical synthesis. Mechanical milling, especially high-energy ball milling, can introduce structural disorder and defects, which enhance the ionic conductivity of SSEs. For instance, ball-milled NaTaCl6 (NTC) exhibits a higher ionic conductivity of 4×10−3 S/m, compared to its as-synthesized form. Solid-state annealing can improve the crystallinity and phase purity of SSEs, but it may also lead to a decrease in ionic conductivity due to the reduction of structural defects. Wet chemical synthesis offers a more scalable and energy-efficient approach, but it requires careful control of the synthesis parameters to achieve the desired crystal structure and ionic conductivity.

Interface stability between SSEs and the electrodes is another critical issue that needs to be addressed for the practical application of ASSSBs. Halide SSEs generally exhibit good chemical stability and compatibility with cathode materials due to their wide electrochemical window and high oxidation resistance. However, the interface between SSEs and sodium metal anode remains a challenge. The poor electrochemical reduction stability of halide SSEs can lead to severe interfacial reactions and degradation when in direct contact with sodium metal. To mitigate this issue, various strategies are proposed, such as alloying sodium with other metals (i.e., Sn) to form a more stable interface, using protective coatings to prevent direct contact between SSEs and sodium, and employing composite electrolytes to enhance the overall stability of the interface.

In addition, the scalability and reproducibility of halide SSEs are also critical factors for their practical application. The existing synthesis methods often involve complex procedures and high-energy inputs, which limit the large-scale production of these materials. It is essential for the commercialization of halide SSEs to develop cost-effective and scalable synthesis routes. Moreover, the long-term stability and reliability of ASSSBs incorporating halide SSEs need to be thoroughly evaluated under various operating conditions (i.e., temperature, cycling rate and environmental factor).

Summary and Prospects

Halide solid-state electrolytes (HSSEs) are poised to revolutionize all-solid-state sodium batteries (ASSSBs) due to their exceptional ionic conductivity (i.e., often surpassing 10-3 S/cm), broad electrochemical stability windows (i.e., up to 6 V vs. Na+/Na), and mechanical flexibility, which enable dense electrode-electrolyte integration and mitigate dendrite growth. However, their practical implementation faces multifaceted challenges. Crystal structure optimization is required to balance ionic transport and thermodynamic stability, particularly in systems like Na3YCl6 or Na2ZrCl6, where lattice defects and anion/cation disorder impede performance. Synthesis methods such as mechanochemical milling or solvent-based routes need refinement to reduce impurities and ensure reproducibility. Electrode-electrolyte interface instability, driven by chemical incompatibility or volumetric changes during cycling, remains a critical bottleneck for long-term cycling. Scalable production techniques should bridge a gap between lab-scale innovations and industrial manufacturing. Future research should prioritize structure-property relationship studies using computational tools like density functional theory (DFT) to design HSSEs with tailored ion migration pathways, coupled with advanced in-situ characterization (i.e., synchrotron X-ray tomography or cryo-electron microscopy) to probe dynamic interfacial degradation mechanisms. Simultaneously, innovative material engineering strategies, such as inorganic-polymer composites (i.e., HSSE-PEO hybrids) to enhance interfacial adhesion or novel dual-phase electrolytes to suppress side reactions can address stability and conductivity trade-offs. The development of low-cost synthesis routes (i.e., aqueous precursor processing or scalable sintering) and rigorous evaluation of HSSEs under extreme temperatures, high current densities, and a prolonged cycling will be pivotal for commercialization. In addition, interface optimization via atomic-layer-deposited protective coatings or 3D nanostructured electrodes can also minimize interfacial resistance and improve charge transfer kinetics. With rapid advancements in material discovery, machine learning-driven design, and interdisciplinary collaboration, HSSEs become a threshold of practical application, having ASSSBs with unparalleled energy density (i.e., >400 Wh/kg), inherent safety, and cycle lifetimes exceeding 5000 cycles. The field trajectory indicates that resolving these challenges could have sodium-based solid-state batteries as mainstream solutions for grid storage and electric vehicles, marking a paradigm shift in sustainable energy storage.

sodium ion batteries  /  halide solid electrolytes  /  ion conductivity  /  interfacial modification  /  electrochemical stability
黄慧娟, 杨海, 姚雨, 余彦. 固态钠电池卤化物电解质研究进展. 硅酸盐学报, 2025 , 53 (6) : 1561 -1576 . DOI: 10.14062/j.issn.0454-5648.20250066
Huijuan HUANG, Hai YANG, Yu YAO, Yan YU. Progress on Halide Solid Electrolytes in All-Solid-State Sodium Batteries[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (6) : 1561 -1576 . DOI: 10.14062/j.issn.0454-5648.20250066
  • 国家自然科学基金(51925207; 52394170; 52394171; U24A2067; 52472261; U23A20579; 52402322; 52102321)
  • 中国博士后科学基金(GZB20230697)
  • 中国科学技术大学青年基金(WK2060000065)
  • 辽宁滨海实验室(LBLF-2023-03)
  • 中国科学院“变革性洁净能源技术与示范”战略性先导科技专项(XDA0400202)
  • 中央高校基本科研业务费专项资金(20720220010)
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doi: 10.14062/j.issn.0454-5648.20250066
  • 接收时间:2025-02-04
  • 首发时间:2026-10-22
  • 出版时间:2025-06-20
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  • 收稿日期:2025-02-04
  • 修回日期:2025-03-18
基金
国家自然科学基金(51925207; 52394170; 52394171; U24A2067; 52472261; U23A20579; 52402322; 52102321)
中国博士后科学基金(GZB20230697)
中国科学技术大学青年基金(WK2060000065)
辽宁滨海实验室(LBLF-2023-03)
中国科学院“变革性洁净能源技术与示范”战略性先导科技专项(XDA0400202)
中央高校基本科研业务费专项资金(20720220010)
作者信息
    中国科学技术大学材料科学与工程系,合肥 230026

通讯作者:

余彦(1979—),女,博士,教授
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
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