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Title: Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode

Abstract

Increasing interest in high-energy lithium-ion batteries has triggered the demand to clarify the reaction mechanism in battery cathodes during high-potential operation. However, the reaction mechanism often involves both transition-metal and oxygen activities that remain elusive. Here we report a comprehensive study of both cationic and anionic redox mechanisms of LiNiO 2 nearly full delithiation. Selection of pure LiNiO 2 removes the complication of multiple transition metals. Using combined X-ray absorption spectroscopy, resonant inelastic X-ray scattering, and operando differential electrochemical mass spectrometry, we are able to clarify the redox reactions of transition metals in the bulk and at the surface, reversible lattice oxygen redox, and irreversible oxygen release associated with surface reactions. Many findings presented here bring attention to different types of oxygen activities and metal-oxygen interactions in layered oxides, which are of crucial importance to the advancement of a Ni-rich layered oxide cathode for high capacity and long cycling performance.

Authors:
 [1];  [2]; ORCiD logo [3];  [4]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [1]
  1. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  2. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  3. Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
  4. Shell International Exploration & Production, Houston, Texas 77082, United States
  5. Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1594940
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Volume: 4; Journal Issue: 12; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
Redox reactions; Oxides; Lattices; Oxygen Oxidation

Citation Formats

Li, Ning, Sallis, Shawn, Papp, Joseph K., Wei, James, McCloskey, Bryan D., Yang, Wanli, and Tong, Wei. Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode. United States: N. p., 2019. Web. doi:10.1021/acsenergylett.9b02147.
Li, Ning, Sallis, Shawn, Papp, Joseph K., Wei, James, McCloskey, Bryan D., Yang, Wanli, & Tong, Wei. Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode. United States. doi:10.1021/acsenergylett.9b02147.
Li, Ning, Sallis, Shawn, Papp, Joseph K., Wei, James, McCloskey, Bryan D., Yang, Wanli, and Tong, Wei. Wed . "Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode". United States. doi:10.1021/acsenergylett.9b02147.
@article{osti_1594940,
title = {Unraveling the Cationic and Anionic Redox Reactions in a Conventional Layered Oxide Cathode},
author = {Li, Ning and Sallis, Shawn and Papp, Joseph K. and Wei, James and McCloskey, Bryan D. and Yang, Wanli and Tong, Wei},
abstractNote = {Increasing interest in high-energy lithium-ion batteries has triggered the demand to clarify the reaction mechanism in battery cathodes during high-potential operation. However, the reaction mechanism often involves both transition-metal and oxygen activities that remain elusive. Here we report a comprehensive study of both cationic and anionic redox mechanisms of LiNiO2 nearly full delithiation. Selection of pure LiNiO2 removes the complication of multiple transition metals. Using combined X-ray absorption spectroscopy, resonant inelastic X-ray scattering, and operando differential electrochemical mass spectrometry, we are able to clarify the redox reactions of transition metals in the bulk and at the surface, reversible lattice oxygen redox, and irreversible oxygen release associated with surface reactions. Many findings presented here bring attention to different types of oxygen activities and metal-oxygen interactions in layered oxides, which are of crucial importance to the advancement of a Ni-rich layered oxide cathode for high capacity and long cycling performance.},
doi = {10.1021/acsenergylett.9b02147},
journal = {ACS Energy Letters},
number = 12,
volume = 4,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
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This content will become publicly available on October 30, 2020
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