Tailoring Cathode Interphase Chemistry for High‐Voltage Li‐ion Batteries

作者：Di Lu, Ruhong Li, Ling Lv, Baochen Ma, Shuo‐Qing Zhang, Haikuo Zhang, Yiqiang Huang, Menglu Li, Xiaolong Fu, Lixin Chen, Tao Deng, Xiulin Fan · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202518546 · 被引用次数：7 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Advanced Battery Technologies Research

Abstract To unlock the potential of cyclability and energy density of Lithium‐ion batteries (LIBs), cathode interphase engineering is pivotal. However, a comprehensive methodology for rational cathode interphase design remains elusive. In this study, we propose a unified framework for designing robust cathode interphases by elucidating the role of heavy transition metal (TM)‐oxygen (O) hybridization [quantified by the energy gap between TM 3d and O 2p orbitals (Δ δ )] and the chemical bonding strength [measured by the integrals of crystal orbital Hamilton population (ICOHP)] at the cathode surface. A large Δ δ , coupled with a low ICOHP value, is identified as critical for forming an effective and stable cathode interphase. Guided by this principle, N ‐fluorobis(phenylsulfonyl)amine (NFA) additive with high Δ δ [0.432 eV for LiCoO 2 (LCO) and 0.350 eV for LiNiO 2 ] and low ICOHP values (−1.461 eV for Co‐N and −0.377 eV for O‐Li) is stood out, which effectively passivates aggressive high‐voltage cathodes. This strategy enables superior battery cyclic performance, with 4.55 V graphite||LCO pouch cells achieving over 357 cycles and 4.6 V graphite||LiNi 0.8 Mn 0.1 Co 0.1 O 2 pouch cells exceeding 400 cycles in carbonate electrolytes with simple formulations. The proposed cathode interphase design framework offers a promising pathway toward high‐voltage LIBs with ultralong lifespans.