Mo， Al掺杂的Li7La3Zr2O12 基复合固态电解质的制备及全固态电池性能研究

doi:10.19799/j.cnki.2095-4239.2023.0197

储能科学与技术 ›› 2023, Vol. 12 ›› Issue (5): 1490-1499.doi: 10.19799/j.cnki.2095-4239.2023.0197

• 喜迎东北大学建校百年-储能电池关键材料与循环技术专刊 • 上一篇下一篇

Mo， Al掺杂的Li₇La₃Zr₂O₁₂ 基复合固态电解质的制备及全固态电池性能研究

易永利¹(), 于冉²(), 李武¹, 金翼², 戴哲仁³

^1.国网浙江省电力有限公司温州供电公司，浙江温州 325000
^2.中国电力科学研究院有限公司，北京 100192
^3.国网浙江省电力有限公司，浙江杭州 310063

收稿日期:2023-03-31 修回日期:2023-04-30 出版日期:2023-05-05 发布日期:2023-05-29
通讯作者: 于冉 E-mail:yiyongli8@qq.com;yr0306@qq.com
作者简介:易永利（1983—），男，硕士，高级工程师，从事电网设备开发及运检。E-mail：yiyongli8@qq.com；
基金资助:
浙江省电力有限公司科技项目（5211WZ2000X5,适用于电力系统的高安全固态化直流电源系统开发与应用）

Preparation of Mo， Al-doped Li₇La₃Zr₂O₁₂-based composite solid electrolyte and performance of all-solid-state batterys

Yongli YI¹(), Ran YU²(), Wu LI¹, Yi JIN², Zheren DAI³

^1.State Grid Zhejiang Wenzhou Power Supply Company, Wenzhou 325000, Zhejiang, China
^2.China Electric Power Research Institute, Beijing 100192, China
^3.State Grid Zhejiang Electric Power Co. , Ltd. , Hangzhou 310063, Zhejiang, China

Received:2023-03-31 Revised:2023-04-30 Online:2023-05-05 Published:2023-05-29
Contact: Ran YU E-mail:yiyongli8@qq.com;yr0306@qq.com

摘要/Abstract

摘要：

通过固态电解质构建的全固态锂离子电池具有极高的安全性及可靠性，是目前锂离子电池领域的研究热点。其中复合固态电解质既改善了聚合物电解质力学性能差、离子电导率低等缺点又解决了无机固态电解质的界面接触等问题。本文通过溶胶-凝胶法制备了掺杂了Al、Mo的Li₇La₃Zr₂O₁₂粉体，并将其与PEO（聚环氧乙烷）复合，利用溶液浇筑法制备了不同比例的复合固态电解质，考察其在全固态电池中的性能。通过X射线衍射（XRD）、扫描电子显微镜（SEM）、差示扫描量热仪（DSC)等测试手段对Li_6.65Al_0.05La₃Zr_1.9Mo_0.1O₁₂粉体以及复合固态电解质进行了材料表征。同时利用电化学工作站、电池充放电测试系统测试了复合固态电解质在全固态电池中的应用性能。与纯PEO电解质相比，复合15% Li_6.65Al_0.05La₃Zr_1.9Mo_0.1O₁₂的电解质电化学窗口为4.79 V，可以在0.2 mA/cm²下稳定循环500 h，在0.1 C倍率下，循环100圈容量保持率为89.9%。

关键词: 复合固态电解质, 聚环氧乙烷, Li₇La₃Zr₂O₁₂, 掺杂, 全固态锂电池

Abstract:

All-solid-state lithium-ion batteries constructed with solid-state electrolytes have extremely high safety and reliability and are currently a research hotspot. Composite solid-state electrolytes not only improve the mechanical properties and low ionic conductivity of polymer electrolytes but can also solve the issue of interfacial contact with inorganic solid-state electrolytes. Herein, Li₇La₃Zr₂2O₁₂ powder doped with Al and_{Mo was prepared using the sol-gel method. Furthermore, PEO compounds with different proportions of the Li_6.65Al_0.05La₃Zr_1.9Mo_0.1O₁₂ powder were prepared using the solution casting method, and their performances in solid-state batteries were investigated. The Li_6.65Al_0.05La₃Zr_1.9Mo_0.1O₁₂ powder and its composite solid-state electrolytes were characterized using various analytical methods, such as X-ray diffraction, scanning electron microscopy, and differential thermal analysis. The performance of the composite solid-state electrolytes in all-solid-state batteries was evaluated using an electrochemical workstation and a battery charging and discharging test system. Compared with pure PEO electrolyte, the 15%-Li_6.65Al_0.05La₃Zr_1.9Mo_0.1O₁₂ composite electrolyte exhibited an electrochemical window of up to 4.79 V and a stable circulation at 0.2 mA/cm² and 0.1 C ratio for about 500 h. Furthermore, it exhibited a capacity retention of 89.9% after 100 cycles.}

Key words: solid-state composite electrolyte, PEO, LLZO, doping, all-solid-state lithium-ion battery

中图分类号:

TQ 152

易永利, 于冉, 李武, 金翼, 戴哲仁. Mo， Al掺杂的Li₇La₃Zr₂O₁₂ 基复合固态电解质的制备及全固态电池性能研究[J]. 储能科学与技术, 2023, 12(5): 1490-1499.

Yongli YI, Ran YU, Wu LI, Yi JIN, Zheren DAI. Preparation of Mo， Al-doped Li₇La₃Zr₂O₁₂-based composite solid electrolyte and performance of all-solid-state batterys[J]. Energy Storage Science and Technology, 2023, 12(5): 1490-1499.

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LALZMO复合量	电子电导率(10^-6, 25℃)/(S/cm)	厚度L	拟合X2	电化学窗口
0%	4.78	0.15 mm	0.00778	4.10 V
5%	9.43	0.17 mm	0.00980	4.42 V
10%	31.45	0.17 mm	0.00748	4.67 V
15%	51.77	0.18 mm	0.00769	4.79 V
20%	6.84	0.18 mm	0.00889	4.74 V

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Mo， Al掺杂的Li₇La₃Zr₂O₁₂ 基复合固态电解质的制备及全固态电池性能研究

Preparation of Mo， Al-doped Li₇La₃Zr₂O₁₂-based composite solid electrolyte and performance of all-solid-state batterys

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