Boosting the Reversibility and Kinetics of Anionic Redox Chemistry in Sodium-Ion Oxide Cathodes via Reductive Coupling Mechanism

Yao Wang; Xudong Zhao; Junteng Jin; Qiuyu Shen; Yang Hu; Xiaobai Song; Han Li; Xuanhui Qu; Lifang Jiao; Yongchang Liu

doi:10.1021/jacs.3c08070

Boosting the Reversibility and Kinetics of Anionic Redox Chemistry in Sodium-Ion Oxide Cathodes via Reductive Coupling Mechanism

J Am Chem Soc. 2023 Oct 18;145(41):22708-22719. doi: 10.1021/jacs.3c08070. Epub 2023 Oct 9.

Authors

Yao Wang¹, Xudong Zhao², Junteng Jin¹, Qiuyu Shen¹, Yang Hu³, Xiaobai Song¹, Han Li¹, Xuanhui Qu¹, Lifang Jiao⁴, Yongchang Liu^{1

4}

Affiliations

¹ Beijing Advanced Innovation Center for Materials Genome Engineering, Institute for Advanced Materials and Technology, State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China.
² Tianjin Key Laboratory for Photoelectric Materials and Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China.
³ Helmholtz Institute Ulm (HIU), Helmholtzstraße 11, Ulm 89081, Germany.
⁴ Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China.

PMID: 37813829
DOI: 10.1021/jacs.3c08070

Abstract

Activating anionic redox chemistry in layered oxide cathodes is a paradigmatic approach to devise high-energy sodium-ion batteries. Unfortunately, excessive oxygen redox usually induces irreversible lattice oxygen loss and cation migration, resulting in rapid capacity and voltage fading and sluggish reaction kinetics. Herein, the reductive coupling mechanism (RCM) of uncommon electron transfer from oxygen to copper ions is unraveled in a novel P2-Na_0.8Cu_0.22Li_0.08Mn_0.67O₂ cathode for boosting the reversibility and kinetics of anionic redox reactions. The resultant strong covalent Cu-(O-O) bonding can efficaciously suppress excessive oxygen oxidation and irreversible cation migration. Consequently, the P2-Na_0.8Cu_0.22Li_0.08Mn_0.67O₂ cathode delivers a marvelous rate capability (134.1 and 63.2 mAh g^-1 at 0.1C and 100C, respectively) and outstanding long-term cycling stability (82% capacity retention after 500 cycles at 10C). The intrinsic functioning mechanisms of RCM are fully understood through systematic in situ/ex situ characterizations and theoretical computations. This study opens a new avenue toward enhancing the stability and dynamics of oxygen redox chemistry.