具有优异热稳定性和溶剂稳定性的快锂离子导体—锆基氧氯化物固态电解质  

Fast Li+-conducting Zr^(4+)-based oxychloride electrolyte with good thermal and solvent stability

作　　者：李冰 李玉涛 张洪申 仵亭亭 郭思杰 曹安民 Bing Li;Yutao Li;Hong-Shen Zhang;Ting-Ting Wu;Sijie Guo;An-Min Cao(CAS Key Laboratory of Molecular Nanostructure and Nanotechnology,and Beijing National Laboratory for Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;University of Chinese Academy of Sciences,Beijing 100049,China;Beijing Frontier Research Center on Clean Energy,Huairou Division,Institute of Physics,Chinese Academy of Sciences,Beijing 101400,China;National Engineering Research Center for Advanced Polymer Processing Technology,Key Laboratory of Advanced Material Processing&Mold(Ministry of Education),Zhengzhou University,Zhengzhou 450002,China)

机构地区：[1]CAS Key Laboratory of Molecular Nanostructure and Nanotechnology,and Beijing National Laboratory for Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]Beijing Frontier Research Center on Clean Energy,Huairou Division,Institute of Physics,Chinese Academy of Sciences,Beijing 101400,China [4]National Engineering Research Center for Advanced Polymer Processing Technology,Key Laboratory of Advanced Material Processing&Mold(Ministry of Education),Zhengzhou University,Zhengzhou 450002,China

出　　处：《Science China Materials》2023年第8期3123-3128,共6页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22025507 and 21931012);the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(ZDBSLYSLH020);Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202010).

摘　　要：成本低廉的锂离子导体氯化物固态电解质Li_(2)ZrCl_(6),属于三方晶系,可在4.2 V下保持稳定,与高压正极材料具有良好的兼容性.然而,相对较低的室温离子电导率、较差的化学稳定性和热稳定性等缺点阻碍了它在全固态电池中的进一步发展.基于此,我们利用Li_(2)O,ZrCl_(4)和LiCl合成了新型氧氯化物固态电解质,并通过O^(2−)对Cl^(−)的取代来优化固态电解质的性能.结果表明增加Li_(2)O的含量会降低三方相Li_(2)ZrCl_(6)的结晶度,且诱导单斜结构的产生.新合成的Li_(2.22)Zr_(1.11)Cl_(5.33)O_(0.67)室温电导率可到10^(−3)S cm^(−1).此外,Li_(2)O的加入能够提高固态电解质的热稳定性和溶剂稳定性.固态电解质Li_(2.22)Zr_(1.11)Cl_(5.33)O_(0.67)良好的离子电导率及稳定性使得Li–In/LiCoO_(2)全固态电池具有稳定的循环性能.Li_(2)ZrCl_(6)with a trigonal structure is a low-cost Li+-conducting chloride electrolyte,which is stable at high voltages up to 4.2 V and is compatible with high-voltage cathodes.However,its relatively low room-temperature ionic conductivity,poor stability in different solvents and at high temperatures limit its application for next-generation allsolid-state batteries.Herein,we prepared new oxychloride electrolytes with different molar ratios of Li_(2)O,ZrCl_(4),and LiCl,replacing Cl^(−)with O^(2−)anion to optimize the electrolyte performance.The results showed that increasing the Li_(2)O content reduced the crystallization degree of trigonal Li_(2)ZrCl_(6)and induced a monoclinic structure in the prepared oxychloride electrolyte.The oxychloride with the general formula Li_(2.22)Zr_(1.11)Cl_(5.33)O_(0.67)had a high room-temperature ionic conductivity above 10^(−3)S cm^(−1).Moreover,introducing Li_(2)O considerably increased the thermal and solvent stability of the electrolyte.Good ionic conductivity and stability of the electrolyte enable the stable cycling of all-solid-state Li–In/LiCoO_(2)batteries.

关 键 词：固态电解质 锂离子导体 全固态电池 室温电导率 正极材料 离子电导率 三方晶系 化学稳定性 

分 类 号：TQ131.11[化学工程—无机化工] TM912[电气工程—电力电子与电力传动]