Jin Yingmin, Lin Ruifan, Li Yumeng, Zhang Xuebai, Tan Siping, Shuai Yong, Xiong Yueping
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, China.
State Key Laboratory of Advanced Chemical Power Sources, Guizhou Meiling Power Sources Co. Ltd., Zunyi, Guizhou, 563003, China.
Angew Chem Int Ed Engl. 2024 Jun 10;63(24):e202403661. doi: 10.1002/anie.202403661. Epub 2024 May 7.
The development of highly producible and interfacial compatible in situ polymerized electrolytes for solid-state lithium metal batteries (SSLMBs) have been plagued by insufficient transport kinetics and uncontrollable dendrite propagation. Herein, we seek to explore a rationally designed nanofiber architecture to balance all the criteria of SSLMBs, in which LaSrCoO (LSC) enriched with high valence-state Co species and oxygen vacancies is developed as electronically conductive nanofillers embedded within ZnO/ZnN-functionalized polyimide (Zn-PI) nanofiber framework for the first time, to establish Li transport highways for poly vinylene carbonate (PVC) electrolyte and eliminate nonuniform Li deposits. Revealed by characterization and theoretical calculation under electric field, the positive-negative electrical dipole layer in LSC derived from electron migration between Co and O atoms aids in accelerating Li diffusion kinetics through densified electric field around filler particle, featuring a remarkable ionic conductivity of 1.50 mS cm at 25 °C and a high Li transference number of 0.91 without the risk of electron leakage. Integrating with the preferential sacrifice of ZnO/ZnN on PI nanofiber upon immediate detection of dendritic Li, which takes part in reconfiguring hierarchical SEI chemistry dominated by LiN/Li-Zn alloy inner layer and LiF outer layer, SSLMBs are further endowed with prolonged cycling lifespan and exceptional rate capability.
用于固态锂金属电池（SSLMBs）的高产量且界面兼容的原位聚合电解质的开发一直受到传输动力学不足和枝晶生长不可控的困扰。在此，我们试图探索一种合理设计的纳米纤维结构，以平衡SSLMBs的所有标准，其中首次开发了富含高价态钴物种和氧空位的LaSrCoO（LSC）作为嵌入ZnO/ZnN功能化聚酰亚胺（Zn-PI）纳米纤维框架内的电子导电纳米填料，为聚碳酸亚乙烯酯（PVC）电解质建立锂传输通道并消除不均匀的锂沉积。通过电场下的表征和理论计算表明，LSC中由Co和O原子之间的电子迁移产生的正负电偶极层有助于通过填料颗粒周围致密的电场加速锂扩散动力学，在25℃时具有1.50 mS cm的显著离子电导率和0.91的高锂迁移数，且没有电子泄漏的风险。在立即检测到枝晶锂时，ZnO/ZnN在PI纳米纤维上优先牺牲，参与重新配置以LiN/Li-Zn合金内层和LiF外层为主的分级SEI化学，SSLMBs进一步具有延长的循环寿命和出色的倍率性能。
