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

doi:10.1021/acsenergylett.9b02147

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

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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:

Li, Ning ^[1]; Sallis, Shawn ^[2];

^[3]; Wei, James ^[4];

^[5];

^[2];

^[1]

Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
Shell International Exploration & Production, Houston, Texas 77082, United States
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:: 2019-10-30

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.

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                    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.

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                    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.

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@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}

}

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