The Effect of Key Electronic States on Excess Lithium Intercalation in Li2RuyMn1- yO3

Shun Zheng; Ji Li; Pengfei Yu; Yande Li; Yujian Xia; XiaoBao Li; Guoxi Ren; Nian Zhang; Zheng Jiang; Xiaosong Liu

doi:10.1021/acs.jpclett.3c00340

The Effect of Key Electronic States on Excess Lithium Intercalation in Li₂Ru_yMn_{1- y}O₃

J Phys Chem Lett. 2023 Apr 6;14(13):3296-3306. doi: 10.1021/acs.jpclett.3c00340. Epub 2023 Mar 29.

Authors

Shun Zheng^{1

2}, Ji Li³, Pengfei Yu¹, Yande Li^{1

2}, Yujian Xia⁴, XiaoBao Li^{1

2}, Guoxi Ren¹, Nian Zhang¹, Zheng Jiang³, Xiaosong Liu^{4

5

6}

Affiliations

¹ State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China.
² University of the Chinese Academy of Sciences, Beijing 100049, China.
³ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China.
⁴ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230029, China.
⁵ Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang, Jiangsu 213300, China.
⁶ School of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China.

PMID: 36988183
DOI: 10.1021/acs.jpclett.3c00340

Abstract

Excess reversible lithium storage is an alternative crucial strategy besides the expansion of redox centers to boost the capacity of layered cathodes. However, the mechanism of excess Li⁺ intercalation is far from being comprehended, indisputably hindering the development of layered cathodes. Herein, the comparative study of Li₂Ru_yMn_1-yO₃ and Li₂Ru_yTi_1-yO₃ by X-ray absorption and photoemission spectroscopies attempts to illustrate the origin. The charge transfer from Ru to Mn through TM-O π bonding interaction with the formation of O holes has been revealed in Li₂Ru_yMn_1-yO₃, which originates from the inductive effect and the approaching energy level of Mn and Ru bands. The electronic state is thought to reduce the Coulomb repulsion of Li⁺ with the matrix, promoting excess Li⁺ intercalation. The results are instructive to the rational design of layered cathodes to achieve a larger reversible capacity in a wide voltage window.