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Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides
Author(s) -
Han Miao,
Jiao Junyu,
Liu Zepeng,
Shen Xi,
Zhang Qinghua,
Lin HongJi,
Chen ChienTe,
Kong Qingyu,
Pang Wei Kong,
Guo Zaiping,
Yu Richeng,
Gu Lin,
Hu Zhiwei,
Wang Zhaoxiang,
Chen Liquan
Publication year - 2020
Publication title -
advanced energy materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.08
H-Index - 220
eISSN - 1614-6840
pISSN - 1614-6832
DOI - 10.1002/aenm.201903634
Subject(s) - materials science , lithium (medication) , redox , hysteresis , transition metal , x ray absorption spectroscopy , neutron diffraction , chemical physics , absorption spectroscopy , crystallography , condensed matter physics , crystal structure , chemistry , metallurgy , medicine , biochemistry , physics , quantum mechanics , endocrinology , catalysis
Lithium‐rich layered oxides are promising candidate cathode materials for the Li‐ion batteries with energy densities above 300 Wh kg −1 . However, issues such as the voltage hysteresis and decay hinder their commercial applications. Due to the entanglement of the transition metal (TM) migration and the anionic redox upon lithium extraction at high potentials, it is difficult to recognize the origin of these issues in conventional Li‐rich layered oxides. Herein, Li 2 MoO 3 is chosen since prototype material to uncover the reason for the voltage hysteresis as the TM migration and anionic redox can be eliminated below 3.6 V versus Li + /Li in this material. On the basis of comprehensive investigations by neutron powder diffraction, scanning transmission electron microscopy, synchrotron X‐ray absorption spectroscopy, and density functional theory calculations, it is clarified that the ordering–disordering transformation of the Mo 3 O 13 clusters induced by the intralayer Mo migration is responsible for the voltage hysteresis in the first cycle; the hysteresis can take place even without the anionic redox or the interlayer Mo migration. A similar suggestion is drawn for its iso‐structured Li 2 RuO 3 ( C 2/ c ). These findings are useful for understanding of the voltage hysteresis in other complicated Li‐rich layered oxides.