固态锂金属电池中不均匀离子通量介导的正负极耦合失效机制  

Codependent failure mechanisms between cathode and anode in solid state lithium metal batteries:mediated by uneven ion flux

作　　者：郑越 张舒 马君 孙富 Markus Osenberg AndréHilger Henning Markötter Fabian Wilde Ingo Manke 胡中波 崔光磊 Yue Zheng;Shu Zhang;Jun Ma;Fu Sun;Markus Osenberg;AndréHilger;Henning Markötter;Fabian Wilde;Ingo Manke;Zhongbo Hu;Guanglei Cui(Qingdao Industrial Energy Storage Research Institute,Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266101,China;College of Materials Science and Opto-Electronic Technology,University of Chinese Academy of Sciences,Beijing 100049,China;Shandong Energy Institute,Qingdao 266101,China;Institute of Applied Materials,Helmholtz-Zentrum Berlin für Materialien und Energie,Berlin 14109,Germany;Department of Non-Destructive Testing,Bundesanstalt für Materialforschung und-Prüfung,Berlin 12205,Germany;Institute of Materials Physics,Helmholtz-Zentrum Hereon,Geesthacht 21502,Germany)

机构地区：[1]Qingdao Industrial Energy Storage Research Institute,Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266101,China [2]College of Materials Science and Opto-Electronic Technology,University of Chinese Academy of Sciences,Beijing 100049,China [3]Shandong Energy Institute,Qingdao 266101,China [4]Institute of Applied Materials,Helmholtz-Zentrum Berlin für Materialien und Energie,Berlin 14109,Germany [5]Department of Non-Destructive Testing,Bundesanstalt für Materialforschung und-Prüfung,Berlin 12205,Germany [6]Institute of Materials Physics,Helmholtz-Zentrum Hereon,Geesthacht 21502,Germany

出　　处：《Science Bulletin》2023年第8期813-825,M0004,共14页科学通报（英文版）

基　　金：supported by the Key-Area Research and Development Program of Guangdong Province(2020B090919005);the National Natural Science Foundation of China(21975274 and 52101276);the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA22010600);Shandong Provincial Natural Science Foundation(ZR2020KE032 and ZR2022QB160);the Youth Innovation Promotion Association of CAS(2021210);the Shandong Energy Institute(SEI)(SEI I202117);Parts of the work were also supported by the BMWi/BMWK project HiBrain(03ET039G)。

摘　　要：本文通过联用无损三维同步辐射X射线断层扫描成像技术(SXCT)和其他非原位测试技术及有限元模拟,深入研究了LiNi0.8Co0.1Mn0.1O2|Li6PS5Cl|Li全固态电池的衰退机制.研究发现正极电化学-机械力学耦合失效诱导的反应异质性产生不均匀的锂离子通量并传输到负极,进而导致不均匀的锂沉积、溶解行为及死锂的产生等.锂负极不均匀的电化学反应行为又反作用于正极并强化其反应异质性,形成一种正负极衰退互相促进的正强化机制.随着电池继续循环,正负极的不均匀反应加剧造成其结构破坏,同时正负极体积缩胀引起电解质巨大塑性变形,最终致使电池失效.对比实验表明采用LiZr_(2)(PO_(4))_(3)(LZP)对正极进行改性,不仅有效抑制了正极的电化学-机械力学耦合失效,而且显著提高了负极锂沉积-溶解均匀性和电解质的结构完整性.该研究首次提出了全固态金属锂电池正负极相互依赖、相互关联的失效机制,为提升全固态金属锂电池性能提供了新思路.An in-depth understanding of the degradation mechanisms is a prerequisite for developing the nextgeneration all solid-state lithium metal battery(ASSLMB)technology.Herein,synchrotron X-ray computed tomography(SXCT)together with other probing tools and simulation method were employed to rediscover the decaying mechanisms of LiNi0.8Co0.1Mn0.1O2(NCM)|Li6PS5Cl(LPSCl)|Li ASSLMB.It reveals that the detachment and isolation of NCM particles cause the current focusing on the remaining active regions of cathode.The extent of Li stripping and the likelihood of Li+plating into LPSCl facing the active NCM particles becomes higher.Besides,the homogeneity of Li stripping/plating is improved by homogenizing the electrochemical reactions at the cathode side by LiZr_(2)(PO_(4))_(3)(LZP)coating.These results suggest a codependent failure mechanism between cathode and anode that is mediated by uneven Li ion flux.This work contributes to a holistic understanding of the degradation mechanisms in ASSLMBs and opens new opportunities for their further optimization and development.

关 键 词：Current density distribution Lithium ion flux Solid-state lithium metal batteries Codependent failure mechanism Cathode deactivation 

分 类 号：TM912[电气工程—电力电子与电力传动]