Wang Chao, Li Wenxin, Li Dabing, Zhao Xiaoxue, Li Yang, Zhang Yanling, Qi Xiang, Wu Meng, Fan Li-Zhen
Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China.
School of Future Technologies, Beijing Institute of Technology, Beijing 100081, China.
ACS Nano. 2024 Nov 19;18(46):32175-32185. doi: 10.1021/acsnano.4c11205. Epub 2024 Nov 7.
The integrated approach of interfacial engineering and composite electrolytes is crucial for the market application of Li metal batteries (LMBs). A 22 μm thin-film type polymer/LiLaZrTaO (LLZTO) composite solid-state electrolyte (LPCE) was designed that combines fast ion conduction and stable interfacial evolution, enhancing lithium metal interface stability and cycling performance. The ether-based molecular coordination groups/clusters formed by triethylene glycol dimethyl ether (TGDE) and anions facilitated the movement of Li between the polymer chain segments. These specific coordination clusters significantly "constrained" the interaction between anions and Li, inducing the anions to follow the clusters to the Li metal and preferentially participate in solid electrolyte interface (SEI) derivatization. The inorganic salt-rich gradient SEI modulates Li deposition and inhibits uncontrolled dendrite growth, achieving stable cycling of Li symmetric cell at 0.2 mA cm for over 2000 h. Furthermore, the Li||NCM811 cell at a rate of 0.1 C exhibits an initial discharge capacity of 194.5 mAh g, maintaining a capacity retention rate of over 90% after 500 cycles. This work demonstrates the importance of domain-limited ion clusters in ion transport and interfacial evolution, providing a perspective for solid-state LMBs.
界面工程与复合电解质的集成方法对于锂金属电池（LMBs）的市场应用至关重要。设计了一种22μm薄膜型聚合物/LiLaZrTaO（LLZTO）复合固态电解质（LPCE），它结合了快速离子传导和稳定的界面演化，增强了锂金属界面稳定性和循环性能。由三甘醇二甲醚（TGDE）和阴离子形成的醚基分子配位基团/簇促进了锂在聚合物链段之间的移动。这些特定的配位簇显著“限制”了阴离子与锂之间的相互作用，促使阴离子跟随簇迁移到锂金属上，并优先参与固体电解质界面（SEI）衍生化。富含无机盐的梯度SEI调节锂沉积并抑制不受控制的枝晶生长，实现了锂对称电池在0.2 mA cm下超过2000 h的稳定循环。此外，Li||NCM811电池在0.1 C的倍率下初始放电容量为194.5 mAh g，在500次循环后容量保持率超过90%。这项工作证明了域限离子簇在离子传输和界面演化中的重要性，为固态LMBs提供了一个视角。
