欢迎访问《电化学(中英文)》期刊官方网站,今天是

电化学(中英文) ›› 2023, Vol. 29 ›› Issue (11): 2204071.  doi: 10.13208/j.electrochem.2204071

所属专题: “下一代二次电池”专题文章

• 论文 • 上一篇    

LiF-Sn复合修饰层改性石榴石/锂金属界面

杨武, 郑雪凡, 武玉琪, 汤士军, 龚正良()   

  1. 厦门大学能源学院,福建 厦门 361005
  • 收稿日期:2022-04-07 修回日期:2022-05-19 接受日期:2022-05-25 出版日期:2023-11-28 发布日期:2022-06-06
  • 通讯作者: *龚正良,Tel: (86-592)2880703,E-mail: zlgong@xmu.edu.cn
  • 基金资助:
    国家自然科学基金项目(21875196);国家自然科学基金项目(21935009);福建省引导性计划项目(2019H0003);厦门大学大学生创新创业训练计划项目(202110384606)

LiF-Sn Composite Modification Layer to Modify Garnet/Lithium Metal Interface

Wu Yang, Xue-Fan Zheng, Yu-Qi Wu, Shi-Jun Tang, Zheng-Liang Gong()   

  1. College of Energy, Xiamen University, Xiamen 361005, Fujian, China
  • Received:2022-04-07 Revised:2022-05-19 Accepted:2022-05-25 Published:2023-11-28 Online:2022-06-06

摘要:

锂金属和固态电解质在能量密度和安全性能上有巨大的提升潜力,被视为全固态电池的重要组成部分。具有高锂离子电导率(约10-3 S·cm-1)和高剪切模量(55 GPa)的无机石榴石型固态电解质被认为是理想的固态电解质之一,然而锂枝晶生长的问题依旧难以解决。在本文中,通过在石榴石表面蒸镀一层LiF-Sn复合修饰层,增加石榴石与锂金属的界面浸润性的同时构建了离子快速传输通道,阻挡了电子向石榴石体相的注入,有效地抑制了锂枝晶的生长。界面修饰层的存在使得界面阻抗由969 Ω·cm2降低至3.5 Ω·cm2,对称电池的临界电流密度提升至1.3 mA·cm-2,对称电池在0.4 mA·cm-2的电流密度下稳定循环200 h。

关键词: LiF, Sn, 真空热蒸镀, 临界电流密度, 长循环性能

Abstract:

The growing demands for electric vehicles and consumer electronics,as well as the expanding renewable energy storage market,have promoted extensive research on energy storage technologies with low cost,high energy density and safety. Lithium (Li) metal and solid-state electrolytes are considered as important components for next-generation batteries because of their great potential for improvements in energy density and safety performance. Inorganic garnet-type solid electrolytes with high Li-ion conductivity (about 10-3 S·cm-1) and high shear modulus (55 GPa) are considered to be ideal solid-state electrolytes,however,the issue of Li dendrite growth still obstructs their practical application. Herein,a simple and efficient strategy was developed to suppress the Li dendrite formation in the garnet solid electrolytes. A composite modification layer made of 2 nm LiF and 2 nm Sn thin layers was prepared on the surface of the Li6.5La3Zr1.4Ta0.6O12 (LLZTO) solid electrolyte by the high vacuum evaporation. The composite modification layer combined the advantages of LiF and Sn,which effectively improves the interfacial contact between the Li metal and LLZTO electrolyte,and promotes the uniform Li plating/stripping. The LiF-Sn composite modification layer was deposited on the surface of garnet electrolyte to increase the interfacial wettability between the garnet electrolyte and Li metal,which blocks the injection of electrons into the bulk phase of garnet. The LiF-Sn modification layer effectively enhanced the interfacial contact and inhibited the growth of lithium dendrites. Benefiting from the LiF-Sn interfacial modification,the cross-sectional SEM image shows the intimate contact between the LLZTO-LiF-Sn and the Li metal without any voids. In addition,the interfacial impedance of Li/garnet electrolyte interface decreased from 969 Ω·cm2 to 3.5 Ω·cm2. Meanwhile, the critical current density of the Li symmetric cell increased to 1.3 mA·cm-2, and the Li symmetric cell could be cycled stably for 200 h at a current density of 0.4 mA·cm-2. After disassembling the short-circuited Li/LLZTO/Li cell and reacting the Li metal with alcohol solution,it was found that Li dendrites had grown into the LLZTO pellet. However,the surface of the LiF-Sn-protected LLZTO remained smooth without dark spots from dendrites. The excellent electrochemical performance clearly shows that the LiF-Sn composite modification can effectively inhibit the formation of Li dendrite inside the garnet SSE, proving that this interfacial engineering provides a practical solution for addressing the key challenge of Li/LLZTO interface. At the same time,high vacuum evaporation is a matured industrial technology with large-scale application prospects and can be widely used to solve solid-state interface problems.

Key words: LiF, Sn, Vacuum thermal evaporation, Critical current density, Long cycle performance