Clarification of underneath capacity loss for O3-type Ni, co free layered cathodes at high voltage for sodium ion batteries

Zhou, Dong1,2; Ning, De3; Wang, Jun2; Liu, Jiahua4; Zhang, Gaoyuan5; Xiao, Yinguo4; Zheng, Jiaxin4; Li, Yongli5; Li, Jie6; Liu, Xinzhi1,7

2023-02-01

10.1016/j.jechem.2022.11.031

Journal of Energy Chemistry   影响因子和分区

2095-4956

Earth abundant O3-type NaFe0.5Mn0.5O2 layered oxide is regarded as one of the most promising cathodes for sodium ion batteries due to its low cost and high energy density. However, its poor structural stability and cycle life strongly impede the practical application. Herein, the dynamic phase evolution as well as charge compensation mechanism of O3-type NaFe0.5Mn0.5O2 cathode during sodiation/desodiation are revealed by a systemic study with operando X-ray diffraction and X-ray absorption spectroscopy, high resolution neutron powder diffraction and neutron pair distribution functions. The layered structure experiences a phase transition of O3 -. P3 -. OP2 -. ramsdellite during the desodiation, and a new O30 phase is observed at the end of the discharge state (1.5 V). The density functional theory (DFT) calculations and nPDF results suggest that depletion of Na+ ions induces the movement of Fe into Na layer resulting the formation of an inert ramsdellite phase thus causing the loss of capacity and structural integrity. Meanwhile, the operando XAS clarified the voltage regions for active Mn3+/Mn4+ and Fe3+/ Fe4+ redox couples. This work points out the universal underneath problem for Fe-based layered oxide cathodes when cycled at high voltage and highlights the importance to suppress Fe migration regarding the design of high energy O3-type cathodes for sodium ion batteries.(c) 2022 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

Sodium ion batteries Layered oxide cathode Iron migration Operando X-ray absorption spectroscopy Neutron measurements

SCI ; EI

英语

其他

Guangdong Basic and Applied Basic Research Foundation["2019A1515110897","2019B1515120028"]

Chemistry ; Energy & Fuels ; Engineering

Chemistry, Applied ; Chemistry, Physical ; Energy & Fuels ; Engineering, Chemical

WOS:000917718800001

ELSEVIER

20230213350881

Cathodes ; Density functional theory ; Design for testability ; Distribution functions ; Iron oxides ; Manganese compounds ; Metal ions ; Nickel compounds ; Sodium compounds ; Stability

Metallurgy:531.1 ; Secondary Batteries:702.1.2 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Sun Yat Sen Univ, Sch Phys, Guangdong Prov Key Lab Magnetoelectr Phys & Device, Guangzhou 510275, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Sch Innovat & Entrepreneurship, Shenzhen 518055, Guangdong, Peoples R China
3.Chinese Acad Sci, Shenzhen Inst Adv Technol, Ctr Photon Informat & Energy Mat, Shenzhen 518055, Guangdong, Peoples R China
4.Peking Univ, Sch Adv Mat, Shenzhen Grad Sch, Shenzhen 518055, Guangdong, Peoples R China
5.North China Elect Power Univ, Inst Clean Energy Technol, Beijing 102206, Peoples R China
6.Politecn Milan, Dept Energy, Via Lambruschini 4, I-20156 Milan, Italy
7.Sun Yat Sen Univ, Ctr Phys Mech & Biophys, Sch Phys, Guangzhou 510275, Guangdong, Peoples R China

Zhou, Dong,Ning, De,Wang, Jun,et al. Clarification of underneath capacity loss for O3-type Ni, co free layered cathodes at high voltage for sodium ion batteries[J]. Journal of Energy Chemistry,2023,77:479-486.

Zhou, Dong.,Ning, De.,Wang, Jun.,Liu, Jiahua.,Zhang, Gaoyuan.,...&Liu, Xinzhi.(2023).Clarification of underneath capacity loss for O3-type Ni, co free layered cathodes at high voltage for sodium ion batteries.Journal of Energy Chemistry,77,479-486.

Zhou, Dong,et al."Clarification of underneath capacity loss for O3-type Ni, co free layered cathodes at high voltage for sodium ion batteries".Journal of Energy Chemistry 77(2023):479-486.