Enhanced Bulk and Interfacial Conductivity in All-Solid-State Lithium Metal Batteries via Garnet Surface Phosphorylation

作者：Lin Yang, Yongbiao Mu, Lingfeng Zou, Chao Li, Xin Wang, Yitian Feng, Youqi Chu, Chaozhu Huang, Qing Zhang, Lin Zeng · 发表于：Nano Letters · 年份：2025 · DOI：10.1021/acs.nanolett.4c05334 · 被引用次数：15 · 研究领域：Advanced Battery Materials and Technologies、Advancements in Battery Materials、Polyoxometalates: Synthesis and Applications

The composite electrolyte of polyvinylidene fluoride (PVDF) and Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZO) is considered one of the most promising electrolytes for next-generation lithium batteries. However, the presence of Li 2 CO 3 on the LLZO surface reduces conductivity and leads to PVDF chain cross-linking. In this study, H 3 PO 4 is used to remove the alkaline Li 2 CO 3 layer, and the effect of residual Li 3 PO 4 on bulk conductivity and lithium metal interface conduction is investigated. The phosphorylation of the LLZO surface enhances ion transport channels, increasing ionic conductivity to 5.06 × 10 –4 S cm –1 . Notably, Li 3 PO 4 catalyzes the decomposition of LiFSI, facilitating the formation of abundant inorganic compounds with rapid lithium-ion diffusion capability such as Li 3 N, LiF and Li 2 S 2 O 7, which increases the interfacial exchange current density of lithium symmetric batteries by approximately 3.5 times. Additionally, a Li||LFP battery achieved 89% capacity retention after 400 cycles at 1C. These results demonstrate a promising strategy for developing commercial solid-state electrolytes for all-solid-state lithium metal batteries.