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

Abstract

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 coadditivesmore » and paves a way to refine (ultra)high‐voltage LiCoO 2 cathode for high‐energy‐density energy storages.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [1];  [3];  [1];  [1];  [2];  [2];  [4]; ORCiD logo [5]
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  1. School of Energy Xiamen University Xiamen 361102 China
  2. State Key Laboratory for Physical Chemistry of Solid Surface Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China
  3. Engineering Research Center of MTEES (Ministry of Education) School of Chemistry South China Normal University Guangzhou 510006 China
  4. Advanced Light Source Lawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA
  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
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1804203
Grant/Contract Number:  
DE‐AC02‐05CH11231
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Name: Advanced Functional Materials Journal Volume: 30 Journal Issue: 43; Journal ID: ISSN 1616-301X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Yang, Xuerui, Lin, Min, Zheng, Guorui, Wu, Jue, Wang, Xianshu, Ren, Fucheng, Zhang, Wenguang, Liao, Ying, Zhao, Weimin, Zhang, Zhongru, Xu, Ningbo, Yang, Wanli, and Yang, Yong. Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy. Germany: N. p., 2020. Web. doi:10.1002/adfm.202004664.
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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. Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy. Germany. https://doi.org/10.1002/adfm.202004664
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Yang, Xuerui, Lin, Min, Zheng, Guorui, Wu, Jue, Wang, Xianshu, Ren, Fucheng, Zhang, Wenguang, Liao, Ying, Zhao, Weimin, Zhang, Zhongru, Xu, Ningbo, Yang, Wanli, and Yang, Yong. Thu . "Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy". Germany. https://doi.org/10.1002/adfm.202004664.
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@article{osti_1804203,
title = {Enabling Stable High‐Voltage LiCoO 2 Operation by Using Synergetic Interfacial Modification Strategy},
author = {Yang, Xuerui and Lin, Min and Zheng, Guorui and Wu, Jue and Wang, Xianshu and Ren, Fucheng and Zhang, Wenguang and Liao, Ying and Zhao, Weimin and Zhang, Zhongru and Xu, Ningbo and Yang, Wanli and Yang, Yong},
abstractNote = {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.},
doi = {10.1002/adfm.202004664},
journal = {Advanced Functional Materials},
number = 43,
volume = 30,
place = {Germany},
year = {Thu Sep 03 00:00:00 EDT 2020},
month = {Thu Sep 03 00:00:00 EDT 2020}
}
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