Hybrid ion/electron interfacial regulation stabilizes the cobalt/oxygen redox of ultrahigh-voltage lithium cobalt oxide for fast-charging cyclability

Zhihong Bi; Anping Zhang; Gongrui Wang; Cong Dong; Pratteek Das; Xiaoyu Shi; Zhong-Shuai Wu

doi:10.1016/j.scib.2024.04.015

Hybrid ion/electron interfacial regulation stabilizes the cobalt/oxygen redox of ultrahigh-voltage lithium cobalt oxide for fast-charging cyclability

Sci Bull (Beijing). 2024 Apr 6:S2095-9273(24)00249-4. doi: 10.1016/j.scib.2024.04.015. Online ahead of print.

Authors

Zhihong Bi¹, Anping Zhang¹, Gongrui Wang², Cong Dong¹, Pratteek Das², Xiaoyu Shi², Zhong-Shuai Wu³

Affiliations

¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; University of Chinese Academy of Sciences, Beijing 100049, China.
² State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; Dalian National Laboratory of Clean Energy, Chinese Academy of Sciences, Dalian 116023, China.
³ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China; Dalian National Laboratory of Clean Energy, Chinese Academy of Sciences, Dalian 116023, China. Electronic address: wuzs@dicp.ac.cn.

PMID: 38734585
DOI: 10.1016/j.scib.2024.04.015

Abstract

High-voltage and fast-charging LiCoO₂ (LCO) is key to high-energy/power-density Li-ion batteries. However, unstable surface structure and unfavorable electronic/ionic conductivity severely hinder its high-voltage fast-charging cyclability. Here, we construct a Li/Na-B-Mg-Si-O-F-rich mixed ion/electron interface network on the 4.65 V LCO electrode to enhance its rate capability and long-term cycling stability. Specifically, the resulting artificial hybrid conductive network enhances the reversible conversion of Co^3+/4+/O^2-/ⁿ^- redox by the interfacial ion-electron cooperation and suppresses interface side reactions, inducing an ultrathin yet compact cathode electrolyte interphase. Simultaneously, the derived near-surface Na⁺/Mg²⁺/Si⁴⁺-pillared local intercalation structure greatly promotes the Li⁺ diffusion around the 4.55 V phase transition and stabilizes the cathode interface. Finally, excellent 3 C (1 C = 274 mA g^-1) fast charging performance is demonstrated with 73.8% capacity retention over 1000 cycles. Our findings shed new insights to the fundamental mechanism of interfacial ion/electron synergy in stabilizing and enhancing fast-charging cathode materials.

Keywords: Fast-charging; High-voltage; Interfacial ion–electron cooperation; LiCoO(2); Local intercalation.