Tuning Interphasial Chemistry with Titanium–Oxo Clusters for High-Energy-Density Lithium Metal Batteries

作者：Wenjie Lin, Qiang Gao, Yi Hang Zhang, Fenghua Zhang, Zhenyu Huang, Qi Kang, Yaqi Liao, Lin Wu, Shuaipeng Hao, Yang Ren, Fei Pei, Yunhui Huang · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c13474 · 被引用次数：26 · 研究领域：Advanced Battery Materials and Technologies、Fiber-reinforced polymer composites、Advancements in Battery Materials

Trace amounts of water in commercial carbonate-based electrolytes produce hydrogen fluoride (HF), accelerating the corrosion of high-nickel cathodes and the dissolution of transition metal ions. This severely damages electrode–electrolyte interphase stability and intensifies electrolyte decomposition, causing rapid capacity degradation and failure of high-voltage lithium metal batteries (HVLMBs). Herein, we propose polycaprolactone diol-modified titanium–oxo clusters (TOC–PCL) as a multifunctional electrolyte additive to tune interphasial chemistry on high-nickel cathodes and Li anodes. Trace H 2 O and HF are effectively eliminated via TOC–PCL hydrolysis in the electrolyte, followed by in situ construction of stable electrode–electrolyte interphase enriched with inorganic components (TiO 2, Li 2 TiF 6, and LiF) during cycling, substantially inhibiting interphase chemical corrosion. As a result, the LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li cell (NCM811:12 mg cm –2 ) with the TOC–PCL additive delivered over 1000 cycles at 1 C with 80.4% capacity retention, as well as even under ultrahigh cathode loading (41 mg cm –2 ) and nickel content (96 wt %). The 1.6-Ah NCM811 pouch cell with a 50 μm Li thickness exhibited a high energy density (401.6 Wh kg –1 ) over 150 cycles. This universal strategy of TOC–PCL multifunctional additives was extended to 3-Ah NCM811||silicon–carbon pouch cells, resulting in considerably prolonged cycling life of 500 cycles at 0.5 C. This study highlights the broad ...