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Article(id=1195431906377511434, tenantId=1146029695717560320, journalId=1189645257101713411, issueId=1195431904737542161, articleNumber=null, orderNo=null, doi=10.19822/j.cnki.1671-6329.20230218, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=null, receivedDateStr=null, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1762942776531, onlineDateStr=2025-11-12, pubDate=1741104000000, pubDateStr=2025-03-05, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762942776531, onlineIssueDateStr=2025-11-12, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762942776531, creator=13701087609, updateTime=1762942776531, updator=13701087609, issue=Issue{id=1195431904737542161, tenantId=1146029695717560320, journalId=1189645257101713411, year='2025', volume='', issue='3', pageStart='1', pageEnd='62', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762942776138, creator=13701087609, updateTime=1762945355266, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1195442722434757298, tenantId=1146029695717560320, journalId=1189645257101713411, issueId=1195431904737542161, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1195442722434757299, tenantId=1146029695717560320, journalId=1189645257101713411, issueId=1195431904737542161, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=24, endPage=31, ext={EN=ArticleExt(id=1195431906612392460, articleId=1195431906377511434, tenantId=1146029695717560320, journalId=1189645257101713411, language=EN, title=Analysis of the Application Prospects of Solid State Lithium Battery, columnId=null, journalTitle=Automotive Digest, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Safety reliability, and driving range are critical considerations that impact consumer decisions in the electric vehicle market. Battery capacity and safety serve as principal metrics for evaluating the dependability of electirc vehicles. In order to enhance the battery capacity and safety reliability of electric vehicles and consolidate China’s leading advantage in new energy vehicles, this paper conducts a comparative analysis of the features of liquid and solid-state batteries of electirc vehicles, delineates the benefits and technical pathways of solid-state batteries, and identifies the challenges and strategic solutions in the advancement of solid-state battery technology. The paper concludes with an analysis of the capacity planning for the commercial deployment of solid-state batteries, offering insights for further research in the field.

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电动汽车的安全可靠性和续驶里程是影响消费者购车决策的重要因素，而电池容量和安全性是衡量电动车可靠性的重要指标。为了提高电动汽车的电池容量和安全可靠性，巩固中国新能源汽车的领先优势，对比了电动汽车液态电池和固态电池的特点，阐述了固态电池优势和技术路线，总结了固态电池技术发展的难点及解决策略，最后分析了固态电池商业化应用产能规划，旨在对相关研究提供参考。

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Ltd., Guangzhou 511434, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1195656827804365312, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, authorId=1195656827686924797, language=CN, stringName=李先洲, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=null, address=广汽传祺汽车有限公司， 广州 511434, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1195656827607233017, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, xref=null, ext=[AuthorCompanyExt(id=1195656827615621626, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, companyId=1195656827607233017, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Guang Zhou Automobile Group Motor Co. Ltd., Guangzhou 511434), AuthorCompanyExt(id=1195656827619815931, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, companyId=1195656827607233017, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=广汽传祺汽车有限公司， 广州 511434)])])], keywords=[Keyword(id=1195656827921805825, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=EN, orderNo=1, keyword=Solid state lithium battery), Keyword(id=1195656827997303298, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=EN, orderNo=2, keyword=Commercial application), Keyword(id=1195656828131521027, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=EN, orderNo=3, keyword=New energy vehicle), Keyword(id=1195656828223795716, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=CN, orderNo=1, keyword=固态锂电池), Keyword(id=1195656828295098885, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=CN, orderNo=2, keyword=商业化应用), Keyword(id=1195656828370596358, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=CN, orderNo=3, keyword=新能源汽车)], refs=[Reference(id=1195656829092016653, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, doi=null, pmid=null, pmcid=null, year=2017, volume=35, issue=8, pageStart=26, pageEnd=36, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=任耀宇, journalName=科技导报, refType=null, unstructuredReference=任耀宇. 全固态锂电池研究进展[J]. 科技导报, 2017, 35(8): 26-36., articleTitle=全固态锂电池研究进展, refAbstract=null), Reference(id=1195656829175902734, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, doi=null, pmid=null, pmcid=null, year=2016, volume=138, issue=47, pageStart=15443, pageEnd=15450, url=null, language=null, rfNumber=[2], rfOrder=1, authorNames=LIU W, LIN D, PEI A, journalName=JAM Chen Soc, refType=null, unstructuredReference=LIU W, LIN D, PEI A, et al. 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电池类型 液态 半固态 全固态
液态含量/wt% 25 5~10 0
电解质 有机溶剂、LiPF6、添加剂 复合电解质（聚合物、氧化物、
溶剂、LiTFSI、添加剂）		 聚合物或氧化物或硫化物
隔膜 传统隔膜 隔膜、氧化物涂覆 无隔膜
负极 石墨 硅、石墨 硅、石墨或锂
正极 三元或铁锂 高镍三元或铁锂 高镍三元或铁锂或镍锰氧或富锂锰基
封装方式 卷绕或叠片、方形或圆柱或软包 卷绕/叠片、方形或软包 叠片、软包
能量密度/Wh·kg-1 250 350 500
), ArticleFig(id=1195656828722917898, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=CN, label=表1, caption=

液态电池、半固态和全固态电池对比

, figureFileSmall=null, figureFileBig=null, tableContent=
电池类型 液态 半固态 全固态
液态含量/wt% 25 5~10 0
电解质 有机溶剂、LiPF6、添加剂 复合电解质（聚合物、氧化物、
溶剂、LiTFSI、添加剂）		 聚合物或氧化物或硫化物
隔膜 传统隔膜 隔膜、氧化物涂覆 无隔膜
负极 石墨 硅、石墨 硅、石墨或锂
正极 三元或铁锂 高镍三元或铁锂 高镍三元或铁锂或镍锰氧或富锂锰基
封装方式 卷绕或叠片、方形或圆柱或软包 卷绕/叠片、方形或软包 叠片、软包
能量密度/Wh·kg-1 250 350 500
), ArticleFig(id=1195656828785832459, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
企业 动态
赣锋锂业 新余基地具备2 GWh固态电池产能，重庆赣锋20 GWh正在建设中，为东风E79和赛力斯供应固态电池
辉能科技 2021年半固态电池产能已达1 GWh，2022年投资80亿美元，建成半固态锂电池生产基地，2024年量产全固态电池，为奔驰和越南Vinfast供应固态电池
卫蓝新能源 在北京、江苏、浙江以及山东建设生产基地，2022年投入400亿元于山东淄博建设100 GWh固态锂电池生产基地；
签约湖州，投入139亿元年产20 GWh，为蔚来和吉利供应固态电池
清陶能源 2022年在成都建设了10 GWh固态电池产线，2023年2月，投资100亿元建设15 GWh固态电池产线，为上汽、北汽供应固态电池
孚能科技 分4代研发，半固态电池供应东风岚图
QuantumScape 2024年大规模生产全固态电池，首批24层锂固态电池已交付测试，将为大众、丰田供应固态电池
太蓝新能源 2022年已启动重庆基地1.2 GWh半固态锂电池产线建设
2022年9月，年产10 GWh生产基地签约安徽淮南，总投资70亿元
麻省固能 2023年产能1 GWh上海嘉定超级工厂竣工，将为通用、现代、本田供应固态电池
国轩高科 2023年半固态电池已批量交付
2025年后生产能量密度800 Wh/L、超过400 Wh/kg、循环寿命800次全固态电池
Solid Power 2022年6月，已完成固态电池产线安装，将为宝马、福特供应固态电池
), ArticleFig(id=1195656828894884364, tenantId=1146029695717560320, journalId=1189645257101713411, articleId=1195431906377511434, language=CN, label=表2, caption=

电池产能规划

, figureFileSmall=null, figureFileBig=null, tableContent=
企业 动态
赣锋锂业 新余基地具备2 GWh固态电池产能，重庆赣锋20 GWh正在建设中，为东风E79和赛力斯供应固态电池
辉能科技 2021年半固态电池产能已达1 GWh，2022年投资80亿美元，建成半固态锂电池生产基地，2024年量产全固态电池，为奔驰和越南Vinfast供应固态电池
卫蓝新能源 在北京、江苏、浙江以及山东建设生产基地，2022年投入400亿元于山东淄博建设100 GWh固态锂电池生产基地；
签约湖州，投入139亿元年产20 GWh，为蔚来和吉利供应固态电池
清陶能源 2022年在成都建设了10 GWh固态电池产线，2023年2月，投资100亿元建设15 GWh固态电池产线，为上汽、北汽供应固态电池
孚能科技 分4代研发，半固态电池供应东风岚图
QuantumScape 2024年大规模生产全固态电池，首批24层锂固态电池已交付测试，将为大众、丰田供应固态电池
太蓝新能源 2022年已启动重庆基地1.2 GWh半固态锂电池产线建设
2022年9月，年产10 GWh生产基地签约安徽淮南，总投资70亿元
麻省固能 2023年产能1 GWh上海嘉定超级工厂竣工，将为通用、现代、本田供应固态电池
国轩高科 2023年半固态电池已批量交付
2025年后生产能量密度800 Wh/L、超过400 Wh/kg、循环寿命800次全固态电池
Solid Power 2022年6月，已完成固态电池产线安装，将为宝马、福特供应固态电池
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固态锂电池应用前景分析
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李先洲
汽车文摘 | 2025,(3): 24-31
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汽车文摘 | 2025, (3): 24-31
固态锂电池应用前景分析
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李先洲
作者信息
  • 广汽传祺汽车有限公司， 广州 511434
Analysis of the Application Prospects of Solid State Lithium Battery
Xianzhou Li
Affiliations
  • Guang Zhou Automobile Group Motor Co. Ltd., Guangzhou 511434
出版时间: 2025-03-05 doi: 10.19822/j.cnki.1671-6329.20230218
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摘要
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电动汽车的安全可靠性和续驶里程是影响消费者购车决策的重要因素，而电池容量和安全性是衡量电动车可靠性的重要指标。为了提高电动汽车的电池容量和安全可靠性，巩固中国新能源汽车的领先优势，对比了电动汽车液态电池和固态电池的特点，阐述了固态电池优势和技术路线，总结了固态电池技术发展的难点及解决策略，最后分析了固态电池商业化应用产能规划，旨在对相关研究提供参考。

固态锂电池  /  商业化应用  /  新能源汽车

Safety reliability, and driving range are critical considerations that impact consumer decisions in the electric vehicle market. Battery capacity and safety serve as principal metrics for evaluating the dependability of electirc vehicles. In order to enhance the battery capacity and safety reliability of electric vehicles and consolidate China’s leading advantage in new energy vehicles, this paper conducts a comparative analysis of the features of liquid and solid-state batteries of electirc vehicles, delineates the benefits and technical pathways of solid-state batteries, and identifies the challenges and strategic solutions in the advancement of solid-state battery technology. The paper concludes with an analysis of the capacity planning for the commercial deployment of solid-state batteries, offering insights for further research in the field.

Solid state lithium battery  /  Commercial application  /  New energy vehicle
李先洲. 固态锂电池应用前景分析. 汽车文摘, 2025 , (3) : 24 -31 . DOI: 10.19822/j.cnki.1671-6329.20230218
Xianzhou Li. Analysis of the Application Prospects of Solid State Lithium Battery[J]. Automotive Digest, 2025 , (3) : 24 -31 . DOI: 10.19822/j.cnki.1671-6329.20230218
正文
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0 引言
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全固态电池是动力电池的重要发展方向。全固态电池性能具有颠覆目前液态锂电池的潜力，其具有更高安全性、更高能量密度、更长低温续驶里程以及更长寿命。
目前，国外研究机构与企业将主要精力集中于全固态电池领域，其中硫化物电解质技术路线在全固态电池研究中占据主导地位，成为重点研究方向。半固态电池固液混合的电化学原理与液态锂离子电池相同，不属于完全意义上的颠覆性技术，而是作为提升电池安全性的有效技术手段。目前，半固态电池虽已进入量产装车阶段，但仍需解决良品率、电池成本、充电倍率以及循环寿命问题。从全行业看，现阶段产业界整体倾向于遵循固液混合的技术路径进行研发。当前，外资车企已经敏锐捕捉到固态电池技术的发展机遇，积极投入资源推进固态电池装车应用，其战略意图明确指向被中国自主品牌占领的市场份额。为了巩固中国自主品牌技术领先优势，中国车企应开展固态电池产业链的研究和布局。
本文探索了提高液态锂电池的容量及安全性的技术发展方向。通过分析固态电池技术及商业化应用的瓶颈，分析了固态电池取代液态锂电池的技术路径。全固态锂电池在商业化推广应用方面仍有些课题待解决，目前采用半固态锂电池将是液态电池与全固态电池之间的最佳过渡方案。2025—2027年，硫化物电解质的固态锂电池将率先应用于高端新能源车，车企为掌握主动权，应尽早谋划和布局固态锂电池，避免因产品力不足而导致产品高端化失败。
1 锂电池分类
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根据电解质的不同，锂电池可分为液态电池和固态电池2大类。液态电池以石墨为负极，正极采用锂离子氧化物材料，电解质采用含有锂盐的有机溶剂。液态电池中有机溶剂存在易燃、高腐蚀性的问题，同时抗氧化性较差，存在热失控风险，具有一定安全隐患[1-2]。为了解决上述问题，研究人员提出将电解液部分或全部替换为固态电解质。根据电解液固态程度，固态电池可分为半固态电池、准固态电池和全固态电池3种类型[3]。根据电解质种类不同，固态电池可分为聚合物固态电池和无机固态电池。聚合物固态电池的代表性体系是聚环氧乙烷，无机固态电池主要包括氧化物、硫化物和卤化物体系[4]。图1为液态电池与全固态电池结构对比。表1为固态电池、半固态电池和全固态电池对比。
目前，在电池技术领域，主流的液态锂电池的能量密度上限普遍被认为约300 Wh/kg，但实际上，由于技术限制和安全性考虑，目前市场上液态电池的能量密度仅能实现约230 Wh/kg。相比之下，固态电池的能量密度在理论上可以达到700 Wh/kg，几乎是液态电池的2倍。特别是以锂作为负极的固态电池，因其更高的能量密度、更好的安全性能和更长的使用寿命，被视为锂电池发展的关键方向。专家指出，固态电池的部分核心材料已经实现了批量生产，并且在技术上也取得了突破，已经有适用于无人机的固态电池问世[5]。这标志着固态电池在商业化道路上迈出了重要一步，未来有望在更多领域实现广泛应用。
2 固态电池优点
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液态电池、半固态电池以及固态电池的结构均相同，一般两端分别为正、负极，中间为电解液或电解质，以完成负离子的输运，实现能量的存储和转换。电芯可分为圆柱、软包和方壳3种类型，其通过串、并联的方式组合成一个模组或电池包以满足汽车或者其他应用需求。相对液态或半固态电池，固态电池具有可燃性低、电压高的优点，其在电动汽车中的应用有助于提升车辆安全性和续驶里程。
固态电池具备以下优势：使用全固态电解质后，锂离子电池的材料体系发生改变，无需使用嵌锂的石墨负极，直接使用锂作为负极，明显减少负极材料的用量，电池的能量密度明显提高[7]。液态锂离子电池中隔膜和电解液占据了电池约40%的体积和25%的质量。若采用固态电解质，正负极之间的距离可以缩短至几到十几微米，能大幅度降低电池厚度[8]。全固态电池轻薄化后，柔性程度明显提高，通过使用适当的封装材料（非刚性外壳），电池可以承受几百到几千次的弯曲且保证性能基本不衰减[9]。传统锂电池电解液为有机液体，在高温下发生氧化分解产生气体以及发生燃烧的可能性增加[10-12]。采用全固态电池，可解决上述问题。固态电池电芯可以先串联后并联一次组装成型，减少系统热管理需求，成组效率大幅提升，更有效利用空间。固态电池不存在或仅存在少量液体，便于回收。
3 固态电池技术路线
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在固态锂电池产业化进程中，日企较为积极。2023年6月，丰田宣布固态电池商业化的最新规划，预计最早于2027年推出搭载固态电池的电动汽车，该车型充电时间缩短至10 min，续驶里程可达1 200 km[13]。为解决短路起火问题，理想的固态电解质应具备以下特征：材料需具备液体电解质的电导率；对锂金属具有化学和电化学稳定性；尽可能地少产生锂枝晶；制造成本低，适合商业推广。目前，固态电池主流的技术路径包括聚合物、硫化物、氧化物和卤化物[14-15]。
上述路径各有其优势和局限性。例如，韩国主攻硫化物技术体系，同时在氧化物和聚合物方面也积累了技术储备，可能是基于不单一依赖某一技术路径，也可能是考虑到电池体系在技术过渡阶段的需求适配。尽管韩企在电芯开发方面速度落后于日企，但其在正负极材料方面具有技术和研发优势，特别是高能量密度的高镍三元等材料，有望较快搭建固态电池材料供应链。
日本致力于发展硫化物体系，欧洲倾向于聚合物技术，美国则并行推进多条路线，我国则主要以氧化物路线为主。有机聚合物基锂离子导体发现于20世纪70年代[16]，锂离子以锂盐的形式溶于聚合物基体。常用的聚合物基体为聚环氧乙烷，加入各种锂盐后，其室温电导率一般为10-5 S/cm。早期将有机溶液作为液态塑化剂加入聚合物基体，形成凝胶聚合物，主要包括聚丙烯腈、聚甲基丙烯酸甲酯、聚氯乙烯以及聚偏氟乙烯[17-18]。凝胶聚合物电解质材料的室温电导率可达10-3 S/cm以上，但其力学性能显著下降，且对锂金属不稳定，通过实现聚合物基体的交联有助于缓解力学性能的降低，但与锂金属间较低的稳定性仍限制了在高能量密度锂电池中的应用[19]。通过加入固体塑化剂、陶瓷颗粒等填料或与其他聚合物单体共聚合等方式，可有效地将电导率提高至10-4 S/cm[20]。目前，大部分经改造的电解质材料在不含有机溶液情况下的室温电导率仍较低[21]。最近研究报道含有锂盐的全氟聚醚本身的锂离子迁移数可达0.91，通过加入硫化物锂离子导体作为填料，形成的复合物的锂离子迁移数可达0.99，室温电导率可达10-4 S/cm[22]。基于聚合物良好的柔性和可加工性，聚合物电解质特别适用于为可穿戴设备供电。但由于锂盐对湿度敏感，合成过程需在干燥条件下进行，增加了生产成本。此外，聚合物的热稳定性对电池工作温度的变化范围有严格要求。若采用锂金属作为电池负极时，一些聚合物电解质的机械强度通常难以阻止锂枝晶的生长[23]。上述问题限制了聚合物电解质的广泛应用。聚合物电解质优点为易加工，与现有的液态电解液的生产设备、工艺均兼容，机械性能好且比较柔软。缺点为性能上限较低且热稳定性普遍在200 ℃以下，在高温下易发生起火燃烧，安全性较差。聚合物虽最早开始投入商业化应用，但未得到大面积推广。
硫化物电解质属于无机固态电解质，由氧化物固体电解质衍生而来，电解质中的氧元素被硫元素取代。极大地提高了电解质的室温离子电导率[24]。硫化物电解质按结晶形态分为晶态、玻璃态及玻璃陶瓷电解质。晶态固体电解质的典型代表为Thio-LISICON和Li2SiP2S12体系[25]。Thio-LISICON化学通式为Li4-xA1-γBγS4（A=Ge、Si等，B=P、Al、Zn等），室温离子电导率最高达2.2×10-3 S/cm。Li2SiP2S12体系对金属Li和高电压正极都具有良好的兼容性[26]。玻璃态及玻璃陶瓷电解质以Li2S-P2S5体系为主要代表，离子电导率可达10-4~10-2 S/cm[27]。但是硫化物遇空气会迅速水解生成H2S气体，电解质合成需在惰性气氛环境下进行，增加了研发、制造、运输及储存成本。由于S2-比O2-容易氧化，硫化物电解质在高电压下更易氧化分解，电化学窗口更窄。硫化物在3种材料体系中电导率最高，并且电化学稳定窗口较宽，但其热动力稳定性较差[28]。硫化物是硬度较高的无机粉末，与电极的界面相容性较差，使得电池界面传导电阻较大，对电池的倍率性能影响较大。同时，电极材料的粉末间隙需通过电解质填充以加快锂离子的传导，硫化物难以达到此效果。电池充放电过程中电极材料体积将产生变化，可能破坏无机电解质的结构[29]。硫化物电解质对电池的制备技术要求较高成为硫化物电池难以商业化应用的主要原因。日本东京工业大学在2011年将硫化物电解质的导电率提高到了1.2×10-2 S/cm，可以与电解液的导锂性相媲美，该电解质通过高温真空烧结法制得，相比于2001年的同类型电解质导电率提高了近10倍，Li10GeP2S12具有新型的三维晶格结构，其内部锂原子呈链状排列，晶格中具有允许锂离子通过的位置空隙，在外电场作用下锂离子发生热震动，从而达到较高传导性。2010年丰田公司披露了一款10 cm×10 cm的全固态电池产品原型，电池同样采用层叠串联结构，平均电压为14.4 V，正极采用LiCoO2，负极采用石墨，电解质采用硫化物材料。2012年，该公司利用室温导电率为1.2×10-2 S/cm的电解质材料Li10GeP2S12，采用层叠串联结构，以Ni-Co-Mn三元材料为正极，石墨为负极，制作了单体电压达28 V的电池原型，其能量密度相对于液态电解液电池提高5倍。目前，此款电池已应用于电动滑板车。另外，硫化物仍无法避免锂枝晶的产生，且生产工艺复杂，硫化物易与空气中的水、氧气反应产生硫化氢剧毒气体，有毒气体可以通过工艺处理，但将增加了成本[30]。
卤化物电解质的化学通式为Lia-M-Xb，源于在卤化锂LiX（X=Br、Cl、F）中引入高价态的过渡金属元素M阳离子，调节Li+及空位浓度进而形成类似Lia-M-Xb类化合物[31]。相较于氧化物及硫化物，一价卤素阴离子与Li+的相互作用比与S2-或O2-的相互作用更弱且半径更大，极大地提高了电解质的室温离子电导率，电解质理论离子电导率可达10-2 S/cm量级[32]。同时，卤化物一般具有较高的氧化还原电位，与高压正极材料具有更好的兼容性，可以实现在高电压窗口下的稳定循环，被认为是全固态锂离子电池中非常有发展潜力的材料[33]。目前常见卤化物电解质有Lia-M-Cl6、Lia-M-Cl4及Lia-M-Cl8类卤化物，其中前2类离子电导率可达10-3 S/cm[34]。但卤化物电解质在不同温度下易发生相转变从而影响电导率，且在空气中易水解，合成成本高昂[35]。
综合来看，硫化物全固态电池潜力最大，多家动力电池巨头以其为主要技术路径。其中丰田拥有全世界最多的固态电池专利。氧化物具有较好的导电性和稳定性，并且离子电导率比聚合物更高，热稳定性高达1 000 ℃，同时机械稳定性和电化学稳定性均较高。但相对于硫化物，其电导率偏低，容量、倍率性能受限。国内的研发目前主要集中在固液混合方向，结合了固态电解质层和电解液的优点。氧化物固态电解质由氧化物类无机盐组成，可分为晶态电解质和非晶态电解质。当前商用化主要聚焦在晶态电解质材料的研究，主流的晶态电解质材料体系有石榴石（Li7La3Zr2O12，LLZO）结构固态电解质、钙钛矿（Li3xLa2/3-xTiO3，LLTO）结构固态电解质、NASICON钠超离子导体型固态电解质和LISICON锂离子导体型固体电解质等[36]。NASICON型电解质利用NASICON骨架结构通过锂钠替换可以制备高性能Li+固态电解质，目前主流材料为磷酸钛铝锂体系[37]。上述材料中，LLZO对于锂负极具有较高的兼容性，NaSiCON型和钙钛矿型电解质对金属Li的电化学稳定性较差。整体上，氧化物固态电解质室温离子导电率较高，达到10-5~10-3 S/cm，并且电化学窗口宽、化学稳定性高、机械强度较大，是理想的固态电解质材料体系，但其存在烧结温度较高和机械加工容易脆裂风险[38]。
4 固态电池技术瓶颈及攻克方向
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固体电池技术发展受电解质材料的研发进展的影响。目前主要技术难点在于离子电导率偏低、固体电解质或电极间界面阻抗大、界面相容性较差以及充放电过程中的材料体积膨胀收缩导致界面容易分离，直接影响电池的低温性能、快充性能、能量密度与功率密度。
（1）传统液态电解质的分子结构较为松散，离子可以更自由地运动，而固态电解质的晶体结构比较稳定，离子的运动需克服晶格的位移和能垒，导致离子电导率受限。因此液态电解质室温离子电导率约为10-2 S/cm，但固态电解质离子电导率通常比电解液低10倍以上。低离子电导率将限制电池的充放电速率，导致电池的功率输出受限，降低电池在高功率需求下的能量密度。因此固态电池在商业化之前需突破离子电导率的瓶颈。
（2）在全固态锂电池中，电极与电解质之间的界面接触由固液面变为固固点，由于固相无润湿性，因此固固界面将形成更高的电阻，不利于锂离子在正负极之间传输，导致电池的功率输出能力减弱、充放电效率降低。
（3）固态电解质材料与正负极极片之间的阻抗增大，电池在充放电过程中正负极不断膨胀和收缩，产生大量的内部微裂纹，导致固态锂金属电池快速失效、寿命减少。
针对以上3项问题，主要的改善方向集中在元素掺杂、界面层修饰以及电极柔性复合。
（1）在固态电解质掺杂其他物质，如将锆酸锂（LiZrO2）等含锆成分添加至固态电解质中，以改善其离子电导率和界面稳定性[39]。锆酸锂作为一种具有高离子迁移率的材料，可以提供更多的离子传输通道，促进离子在电池中的快速传输。除此之外，锆掺杂工艺还可以改善固态电解质与电极之间的接触界面，减少界面阻抗和界面反应，提高电池的循环稳定性。
（2）引入界面修饰层，增加接触、降低阻抗、减少副反应、提升稳定性[40]。常用的界面修饰材料主要包括LiNbO3、LiPO3和Al2O3。界面修饰层能提高界面的粘附性和相容性，增加有效的接触面积，有助于提高离子在界面处的传输效率。界面修饰层还可以起到物理和化学屏障的作用，减少界面反应发生，提高界面稳定性。
（3）采用复合电极、柔性、无定形以及凝胶态界面，如目前已有的液态锂电池方案与固态电解质进行混合[41]。
当前固态锂电池的应用大体还处于实验室阶段。聚合物固态电解质和传统液态锂电池接近，可利用现有设备改造生产，并且工艺简单、成本较低，较容易达到量产。目前聚合物薄膜电池已经小批量生产，但只适用于微型器件，难以制造大容量的电芯。氧化物电解质接近量产条件，目前常用氧化物体系与电解液或聚合物复合制成固液混合电池，产业链基本成熟，是国内混合固液类型的固态锂电池逐渐趋同的路线。硫化物电解质的高成本问题短期较难改善，据赣锋锂业估算，350 Wh/kg体系硫化物全固态电池成本约为40 元/Wh，距离量产还尚为遥远。目前卤化物电解质的研究进展较快，虽然其离子电导率、正极材料兼容性、环境稳定性等问题有待进一步改善，但其成本低、环境友好、相比其他电解质具有更为优异的高电压正极稳定性、相对较高的锂离子电导率等特性使其适合作为正极侧的电解质推动全固态电池走向实用化。
5 固态电池商业化应用产能规划
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液态锂电池经历了几十年的发展已经形成了三元锂或磷酸铁锂构成的正极材料体系，负极正在向硅基迭代。上述革新虽然可以增加能量密度，但均为渐进式创新，而且理论存在天花板，现有锂电池的能量密度已接近理论极限，未来固态电池才是发展的主流方向。固态电池除了技术的更新迭代外，成本过高也将影响到商业化推广。在实验室可以通过制造芯片的纳米级精度设备与工艺制备电池样品，但对于大规模生产而言该方法成本较高。若改用低成本工艺则合格率无法保证。随着全固态锂离子电池研究的推进，新型的电池生产技术及试制生产线不断面世。由于全固态锂离子电池无需注入电解液，且单体内可以采取层叠串联技术，可采用印刷、涂布、卷对卷等新型技术进行大面积生产。2023年以来，国内多家新能源车企宣布了固态电池装车规划。据报道，比亚迪全固态锂电池在重庆生产即将装车试验，该项目属于国家级重点项目。该固态电池使用硅基材料作为固态电池负极，比刀片电池的能量密度提升了2倍。比亚迪在2016年之前就开始研发固态锂电池，目前在国内的相关专利数量位列第一。氧化物以及硫化物固态锂电池2种技术路线均可装车试验，仰望车型已配备固态电池。除了自用，比亚迪还将其外供奔驰、宝马、奥迪和红旗等品牌。长安深蓝、智己、埃安等车企普遍规划2025年前装车半固态电池。大众、宝马、丰田、奔驰以及日产等也计划于2025—2030年推出搭载全固态电池的汽车。目前主要电池厂商电池产能规划如表2所示。
安全可控、能量密度、快速充电能力、长循环稳定性、寿命和价格是市场对动力电池产品应用的6大需求。平衡上述属性是固态电池企业研发和生产能力面临的重大考验。据报道，日本东京工业大学利用高熵材料设计开发了一种高离子导电性的固体电解质，通过增加已知锂快离子导体的成分复杂性，使得锂离子电导率较传统材料提高了约2.3~3.8倍，从而能缩短电池充电时间[42]，是目前全球最高水平。此外，研究团队改良了制造工艺，负极采用锂金属代替传统的石墨，使得正极容量提高了1.8倍。试制的全固态电池每平方厘米电极的电池容量超过20 mA，是目前全球公布的最高水平。
6 结束语
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固态电池将迎来快速发展期，目前具有潜力的固态电解质为聚合物、硫化物、氧化物和卤化物。其中聚合物、硫化物材料的电池及氧化物的薄膜电池已进入商业化应用。目前国内固态电解质侧重于氧化物，日韩侧重于聚合物（过渡方案）和硫化物。考虑到全固态电池研发和加工门槛较高，固液混合电池作为中间方案有望率先大规模生产，成为液态锂离子电池的有效补充。混合固液锂电池中同时含有液体和固体电解质，相较全固态锂电池，固液混合锂电池虽然在安全性、能量密度和电位上限方面不太完美，但工艺门槛更容易突破，因此混合固态电池被视为液态电池向全固态电池迭代的一种重要方案，短期内有望成为国内企业主要路线。
全固态锂电池在高能量密度、高功率、宽工作温度范围和高安全性方面的应用，仍有些问题待解决。全固态电池的发展主要依赖于固态电解质材料的发展，在各种固态电解质中，硫化物具有与液体电解质相当的高离子导电率，是短期内的开发方向，硫化物电解质技术成熟度最高，有望率先实现产业化。今后将由单一电解质向复合电解质的方向发展，复合电解质技术潜力巨大。全固态电池具有较大发展前景，未来替代现有锂离子电池成为主流储能电源。在2025—2030年期间，主要是小批量测试和迭代，2027年固态电池需求将不足2.5 GWh，配置固态电池的汽车预计2030年开始规模化量产，传统动力锂电池迭代到先进电池，并不会大批量转换阶跃到固态电池。预计2030年上市的新车型将大面积搭载固态电池。尚未规划固态电池的车企，为掌握主动和制高点，应提前谋划和布局，可以与专业电池厂商采用合资合作方式掌控核心技术。
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doi: 10.19822/j.cnki.1671-6329.20230218
  • 首发时间：2025-11-12
  • 出版时间：2025-03-05
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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
光柄菇属 Pluteus 5 2.39
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