Real-space measurement of orbital electron populations for Li1-xCoO2

Shang, Tongtong; Xiao, Dongdong; Meng, Fanqi; Rong, Xiaohui; Gao, Ang; Lin, Ting; Tang, Zhexin; Liu, Xiaozhi; Li, Xinyan; Zhang, Qinghua; Wen, Yuren; Xiao, Ruijuan; Wang, Xuefeng; Su, Dong; Hu, Yong-Sheng; Li, Hong; Yu, Qian; Zhang, Ze; Petricek, Vaclav; Wu, Lijun; Gu, Lin; Zuo, Jian-Min; Zhu, Yimei; Nan, Ce-Wen; Zhu, Jing

doi:10.1038/s41467-022-33595-0

Title: Real-space measurement of orbital electron populations for Li_1-xCoO₂

Journal Article · Mon Oct 03 00:00:00 EDT 2022 · Nature Communications

DOI:https://doi.org/10.1038/s41467-022-33595-0· OSTI ID:1897503

Shang, Tongtong ^[1]; Xiao, Dongdong ^[2]; Meng, Fanqi ^[3];

^[4]; Gao, Ang ^[1]; Lin, Ting ^[1]; Tang, Zhexin ^[1];

^[4];

^[1]; Zhang, Qinghua ^[4]; Wen, Yuren ^[5]; Xiao, Ruijuan ^[4];

^[4];

^[6]; Zhang, Ze ^[6];

^[7];

^[8] more »

Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China)
Chinese Academy of Sciences (CAS), Beijing (China); Songshan Lake Materials Laboratory, Guangdong (China)
Tsinghua Univ., Beijing (China)
Chinese Academy of Sciences (CAS), Beijing (China)
Univ. of Science and Technology, Beijing (China)
Zhejiang Univ., Hangzhou (China)
Czech Academy of Sciences (CAS), Prague (Czech Republic)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Songshan Lake Materials Laboratory, Guangdong (China)
Univ. of Illinois at Urbana-Champaign, IL (United States)

The operation of lithium-ion batteries involves electron removal from and filling into the redox orbitals of cathode materials, experimentally probing the orbital electron population thus is highly desirable to resolve the redox processes and charge compensation mechanism. Here, we combine quantitative convergent-beam electron diffraction with high-energy synchrotron powder X-ray diffraction to quantify the orbital populations of Co and O in the archetypal cathode material LiCoO₂. The results indicate that removing Li ions from LiCoO₂ decreases Co t_2g orbital population, and the intensified covalency of Co–O bond upon delithiation enables charge transfer from O 2p orbital to Co e_g orbital, leading to increased Co e_g orbital population and oxygen oxidation. Theoretical calculations verify these experimental findings, which not only provide an intuitive picture of the redox reaction process in real space, but also offer a guidance for designing high-capacity electrodes by mediating the covalency of the TM–O interactions.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Beijing Natural Science Foundation; National Key Research and Development Program of China; Chinese Academy of Sciences; National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: SC0012704; Z190010; 2019YFA0308500; XDB07030200; 51421002; 51672307; 51991344; 52025025; 51788104

OSTI ID:: 1897503

Report Number(s):: BNL-223678-2022-JAAM

Journal Information:: Nature Communications, Vol. 13, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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