Anion competition for Li^(+)solvated coordination environments in poly(1,3 dioxolane)electrolyte to enable high-voltage lithium metal solid-state batteries  

作　　者：Qiujun Wang Yanqiang Ma Xiaomeng Jia Di Zhang Zhaojin Li Huilan Sun Qujiang Sun Bo Wang Li-Zhen Fan 

机构地区：[1]Hebei Key Laboratory of Flexible Functional Materials,School of Materials Science and Engineering,Hebei University of Science and Technology,Shijiazhuang 050000,Hebei,China [2]Beijing Advanced Innovation Center for Materials Genome Engineering,Institute of Advanced Materials and Technology,University of Science and Technology Beijing,Beijing 100083,China

出　　处：《Journal of Energy Chemistry》2024年第9期633-641,共9页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22008053,52002111);the Natural Science Foundation of Hebei Province(B2021208061,B2022208006,B2023208014);the Beijing Natural Science Foundation(Z200011).

摘　　要：Gel-based polymer electrolytes are limited by the polarity of the residual solvent,which restricts the coupling-breaking behaviour during Li^(+)conduction,resulting in the Li^(+)transport kinetics being greatly affected.Here,we designed anion competitive gel polymer electrolyte(ACPE)by introducing lithium difluoro(oxalato)borate(LiDFOB)anion into the 1,3-dioxolane(DOL)in situ polymerisation system.ACPE enhances the ionic dipole interaction between Li^(+)and the solvent molecules and synergizes with Li^(+)across the solvation site of the polymer ethylene oxide(EO)unit,combination that greatly improves the Li^(+)transport efficiency.As a result,ACPE exhibits 1.12 mS cm^(−1)ionic conductivity and 0.75 Li^(+)transfer number at room temperature.Additionally,this intra-polymer solvation sheath allows preferential desolvation of DFOB−,which contributes to the formation of kinetically stable anion-derived interphase and effectively mitigates side reactions.Our results demonstrate that the assembled Li||NCM622 solid-state battery exhibits lifespan of over 300 cycles with average Coulombic efficiency of 98.8%and capacity retention of 80.3%.This study introduces a novel approach for ion migration and interface design,paving the way for high-safety and high-energy-density batteries.

关 键 词：Li-metal batteries Poly(1 3-dioxolane) In situ polymerization Solid-state polymer electrolytes Anion competition 

分 类 号：TM912[电气工程—电力电子与电力传动] O646[理学—物理化学]