UCl3型卤化物电解质中离子传输与氧化稳定性的协同调控

doi:10.15541/jim20260213

无机材料学报

UCl₃型卤化物电解质中离子传输与氧化稳定性的协同调控

鲍茂浩¹, 窦树明^1,2, 刘斌辉^3,4, 崔忠慧⁵, 赵宁¹, 郭向欣¹

1.青岛大学物理科学学院,青岛 266071;
2.青岛大学材料科学与工程学院,青岛 266071;
3.中国电子产品可靠性与环境试验研究所,广州 511370;
4.智能产品质量评价与可靠性技术工业和信息化部重点实验室,广州 511370;
5.融固新材料科技(绍兴)有限公司,绍兴 312065

收稿日期:2026-05-15 修回日期:2026-07-26
通讯作者: 窦树明, 副教授. E-mail: dousm2022@163.com, 郭向欣, 教授. E-mail: xxguo@qud.edu.cn
作者简介:鲍茂浩(1998–), 男, 硕士研究生. E-mail: baomaohao@qdu.edu.cn

Balancing Ionic Conductivity and Oxidative Stability in UCl₃-Type Halide Solid Electrolytes

BAO Maohao¹, DOU Shuming^1,2, LIU Binhui^3,4, CUI Zhonghui⁵, ZHAO Ning¹, GUO Xiangxin¹

1. College of Physics, Qingdao University, Qingdao 266071, China;
2. College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China;
3. China Electronic Product Reliability and Environmental Testing Research Institute, Guangzhou 511370, China;
4. Key Laboratory of Quality Evaluation and Reliability Technology for Intelligent Product, Ministry of Industry and Information Technology, Guangzhou 511370, China;
5. Ronggu New Materials Technology (Shaoxing) Co., Ltd., Shaoxing 312065, China

Received:2026-05-15 Revised:2026-07-26
Contact: DOU Shuming, associate professor. E-mail: dousm2022@163.com; GUO Xiangxin, professor. E-mail: xxguo@qud.edu.cn
About author:BAO Maohao (1998–), male, Master candidate. E-mail: baomaohao@qdu.edu.cn
Supported by:
National Key R&D Program of China (2023YFB2503900); National Natural Science Foundation of China (12474171, 52372203); Natural Science Foundation of Shandong Province (ZR2025QC1340)

摘要/Abstract

摘要： 兼具高离子电导率和宽电化学窗口的卤化物固体电解质是实现高电压全固态锂电池的关键,然而这两种性能往往难以兼顾。本研究提出了一种阴阳离子共掺杂策略,用以调控UCl₃型Li_0.388Ta_0.238La_0.475Cl₃(LTLC)卤化物电解质的微观结构和电化学性能。在阴离子位点进行氟取代,可有效拓宽电解质的电化学窗口。在此基础上,进一步引入Zr⁴⁺,不仅有效拓展了锂离子输运通道,还削弱了锂离子与氟离子之间的相互作用力。双掺杂电解质Li_0.447Ta_0.179Zr_0.059La_0.475Cl_2.6F_0.4(LTZ_0.059LCF_0.4)优化后在30 ℃下离子电导率可达0.87 mS·cm^-1,电化学窗口为4.52 V。采用该电解质与钴酸锂正极组装的全固态锂电池在0.1C(1C=180 mA·g^-1)的初始比容量高达182.3 mAh·g^-1,循环300圈后容量保持率为81.2%。此外,该电解质与LiNi_0.9Co_0.05Mn_0.05O₂(NCM9055)正极具有良好的兼容性,电池在240圈循环后仍能保持109.8 mAh·g^-1的可逆比容量。研究表明循环后正极表面形成一层薄而均匀的正极/电解质界面层,有效保护正极,抑制严重的界面副反应。本工作为面向高能量密度全固态锂电池的先进卤化物电解质提供了一种可行的协同共掺杂策略。

关键词: 卤化物固体电解质, 阴阳离子共掺杂, 离子电导率, 电化学窗口, 全固态锂电池

Abstract: Halide solid electrolytes that exhibit both high ionic conductivity and good oxidative stability are critical for high-energy-density all-solid-state lithium batteries (ASSLBs), yet these two properties usually are rarely achieved simultaneously. Herein, synergistic co-doping of cation and anion is developed to tailor the structural and electrochemical properties of UCl₃-type Li_0.388Ta_0.238La_0.475Cl₃ (LTLC) electrolytes. Fluorine substitution at anion sites extends the electrochemical window, while subsequent Zr⁴⁺ incorporation increases the ionic conductivity through expanding Li⁺ transport channels and weakening Li-F interactions. The optimized co-doped Li_0.447Ta_0.179Zr_0.059La_0.475Cl_2.6F_0.4 (LTZ_0.059LCF_0.4) electrolytes achieve the ionic conductivity of 0.87 mS·cm^-1 at 30 ℃, and the upper electrochemical window above 4.52 V. ASSLBs using these electrolytes and LiCoO₂ cathodes deliver the initial specific capacity of 182.3 mAh·g^-1 at 0.1C (1C=180 mA·g^-1) and capacity retention of 81.2% after 300 cycles. Furthermore, these electrolytes demonstrate excellent compatibility with LiNi_0.9Co_0.05Mn_0.05O₂ (NCM9055) cathodes, maintaining the reversible capacity of 109.8 mAh·g^-1 at 0.1C after 240 cycles. Thin and homogeneous CEI layers are uniformly formed on the cathode surfaces, effectively protecting the cathodes from severe interfacial side reactions. This work establishes a feasible co-doping strategy for advanced halide electrolytes toward high-energy-density ASSLBs.

Key words: halide solid electrolyte, cation-anion co-doping, ionic conductivity, electrochemical window, all-solid-state lithium battery

中图分类号:

TM911

鲍茂浩, 窦树明, 刘斌辉, 崔忠慧, 赵宁, 郭向欣. UCl₃型卤化物电解质中离子传输与氧化稳定性的协同调控[J]. 无机材料学报, DOI: 10.15541/jim20260213.

BAO Maohao, DOU Shuming, LIU Binhui, CUI Zhonghui, ZHAO Ning, GUO Xiangxin. Balancing Ionic Conductivity and Oxidative Stability in UCl₃-Type Halide Solid Electrolytes[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260213.

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UCl₃型卤化物电解质中离子传输与氧化稳定性的协同调控

Balancing Ionic Conductivity and Oxidative Stability in UCl₃-Type Halide Solid Electrolytes

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