Transition-Metal Vacancy Manufacturing and Sodium-Site Doping Enable a High-Performance Layered Oxide Cathode through Cationic and Anionic Redox Chemistry

被引:109
作者
Shen, Qiuyu [1 ]
Liu, Yongchang [1 ,2 ]
Zhao, Xudong [1 ]
Jin, Junteng [1 ]
Wang, Yao [1 ]
Li, Shengwei [1 ]
Li, Ping [1 ]
Qu, Xuanhui [1 ]
Jiao, Lifang [2 ]
机构
[1] Univ Sci & Technol Beijing, Beijing Adv Innovat Ctr Mat Genome Engn, Inst Adv Mat & Technol, State Key Lab Adv Met & Mat, Beijing 100083, Peoples R China
[2] Nankai Univ, Key Lab Adv Energy Mat Chem, Minist Educ, Tianjin 300071, Peoples R China
基金
中国国家自然科学基金;
关键词
anionic redox chemistry; density functional theory calculations; layered oxide cathodes; reaction mechanisms; sodium-ion batteries; OXYGEN-REDOX; ELECTRON HOLES; HIGH-ENERGY; P2-TYPE; NA2/3NI1/3MN2/3O2;
D O I
10.1002/adfm.202106923
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Triggering the anionic redox chemistry in layered oxide cathodes has emerged as a paradigmatic approach to efficaciously boost the energy density of sodium-ion batteries. However, their practical applications are still plagued by irreversible lattice oxygen release and deleterious structure distortion. Herein, a novel P2-Na0.76Ca0.05[Ni0.230.08Mn0.69]O-2 cathode material featuring joint cationic and anionic redox activities, where native vacancies are produced in the transition-metal (TM) layers and Ca ions are riveted in the Na layers, is developed. Random vacancies in the TM sites induce the emergence of nonbonding O 2p orbitals to activate anionic redox, which is confirmed by systematic electrochemical measurements, ex situ X-ray photoelectron spectroscopy, in situ X-ray diffraction, and density functional theory computations. Benefiting from the pinned Ca ions in the Na sites, a robust layered structure with the suppressed P2-O2 phase transition and enhanced anionic redox reversibility upon charge/discharge is achieved. Therefore, the electrode displays exceptional rate capability (153.9 mA h g(-1) at 0.1 C with 74.6 mA h g(-1) at 20 C) and improved cycling life (87.1% capacity retention at 0.1 C after 50 cycles). This study provides new opportunities for designing high-energy-density and high-stability layered sodium oxide cathodes by tuning local chemical environments.
引用
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页数:11
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