Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy

Yang, Xuerui; Lin, Min; Zheng, Guorui; Wu, Jue; Wang, Xianshu; Ren, Fucheng; Zhang, Wenguang; Liao, Ying; Zhao, Weimin; Zhang, Zhongru; Xu, Ningbo; Yang, Wanli; Yang, Yong

doi:10.1002/adfm.202004664

Enabling Stable High‐Voltage LiCoO ₂ Operation by Using Synergetic Interfacial Modification Strategy

Journal Article · Thu Sep 03 00:00:00 EDT 2020 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202004664· OSTI ID:1804203

Yang, Xuerui ^[1]; Lin, Min ^[2]; Zheng, Guorui ^[2]; Wu, Jue ^[2]; Wang, Xianshu ^[3]; Ren, Fucheng ^[1]; Zhang, Wenguang ^[3]; Liao, Ying ^[1]; Zhao, Weimin ^[1]; Zhang, Zhongru ^[2]; Xu, Ningbo ^[2]; Yang, Wanli ^[4]; ^[5]

School of Energy Xiamen University Xiamen 361102 China
State Key Laboratory for Physical Chemistry of Solid Surface Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China
Engineering Research Center of MTEES (Ministry of Education) School of Chemistry South China Normal University Guangzhou 510006 China
Advanced Light Source Lawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA
School of Energy Xiamen University Xiamen 361102 China, State Key Laboratory for Physical Chemistry of Solid Surface Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China

Abstract

Structural and interfacial instability of the LiCoO ₂ cathode under a voltage exceeding 4.5 V (vs Li/Li ⁺ ) severely hinders its practical applications for high‐energy‐density lithium batteries. Herein, a modified electrolyte with nitriles (suberonitrile or 1,3,6‐hexanetricarbonitrile) and fluoroethylene carbonate (FEC) coadditives is demonstrated to form an ultrathin and uniform interface layer on LiCoO ₂ cathode under a synergetic effect. As such, LiCoO ₂ /Li cells display excellent cyclability at a cutoff voltage of 4.6 V with a capacity retention over 72% after 300 cycles and 60% after 200 cycles at 30 and 55 °C, respectively, even achieving operation at a high current rate (10 C) upon 500 cycles as compared to the controls with fast‐falling capacity to zero. Furthermore, an adsorption‐coordination mechanism between nitriles and cobalt and synergetic effect of coadditives are explored by the alliance of spectroscopic analysis and theoretical calculations. The contributed lone‐pairs on the N 2p orbital of nitriles in coordination lowers the real oxidation state of Co ^3+/4+ so that it decreases its catalysis on electrolytes, and the synergy from nitrile‐derived species regulates FEC to form an LiF‐containing electron‐insulated interface layer. This work shares a new insight to nitriles with the synergy of coadditives and paves a way to refine (ultra)high‐voltage LiCoO ₂ cathode for high‐energy‐density energy storages.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1804203

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 43 Vol. 30; ISSN 1616-301X

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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