A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K - And L -edge XANES spectral simulations and resonance photoelectron spectroscopy

Kei Kubobuchi, Masato Mogi, Masashi Matsumoto, Teruhisa Baba, Chihiro Yogi, Chikai Sato, Tomoyuki Yamamoto, Teruyasu Mizoguchi, Hideto Imai

    Research output: Contribution to journalArticle

    7 Citations (Scopus)

    Abstract

    X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

    Original languageEnglish
    Article number142125
    JournalJournal of Applied Physics
    Volume120
    Issue number14
    DOIs
    Publication statusPublished - 2016 Oct 14

    Fingerprint

    electrode materials
    electric batteries
    photoelectron spectroscopy
    valence
    evaluation
    ions
    x rays
    simulation
    fine structure
    diffraction
    spectroscopy
    catalysis
    wave functions
    orbitals
    physics
    estimates
    electronics

    ASJC Scopus subject areas

    • Physics and Astronomy(all)

    Cite this

    A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K - And L -edge XANES spectral simulations and resonance photoelectron spectroscopy. / Kubobuchi, Kei; Mogi, Masato; Matsumoto, Masashi; Baba, Teruhisa; Yogi, Chihiro; Sato, Chikai; Yamamoto, Tomoyuki; Mizoguchi, Teruyasu; Imai, Hideto.

    In: Journal of Applied Physics, Vol. 120, No. 14, 142125, 14.10.2016.

    Research output: Contribution to journalArticle

    Kubobuchi, Kei ; Mogi, Masato ; Matsumoto, Masashi ; Baba, Teruhisa ; Yogi, Chihiro ; Sato, Chikai ; Yamamoto, Tomoyuki ; Mizoguchi, Teruyasu ; Imai, Hideto. / A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K - And L -edge XANES spectral simulations and resonance photoelectron spectroscopy. In: Journal of Applied Physics. 2016 ; Vol. 120, No. 14.
    @article{95374a6780954d18ad029dd08b744a5c,
    title = "A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K - And L -edge XANES spectral simulations and resonance photoelectron spectroscopy",
    abstract = "X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.",
    author = "Kei Kubobuchi and Masato Mogi and Masashi Matsumoto and Teruhisa Baba and Chihiro Yogi and Chikai Sato and Tomoyuki Yamamoto and Teruyasu Mizoguchi and Hideto Imai",
    year = "2016",
    month = "10",
    day = "14",
    doi = "10.1063/1.4963379",
    language = "English",
    volume = "120",
    journal = "Journal of Applied Physics",
    issn = "0021-8979",
    publisher = "American Institute of Physics Publising LLC",
    number = "14",

    }

    TY - JOUR

    T1 - A valence state evaluation of a positive electrode material in an Li-ion battery with first-principles K - And L -edge XANES spectral simulations and resonance photoelectron spectroscopy

    AU - Kubobuchi, Kei

    AU - Mogi, Masato

    AU - Matsumoto, Masashi

    AU - Baba, Teruhisa

    AU - Yogi, Chihiro

    AU - Sato, Chikai

    AU - Yamamoto, Tomoyuki

    AU - Mizoguchi, Teruyasu

    AU - Imai, Hideto

    PY - 2016/10/14

    Y1 - 2016/10/14

    N2 - X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

    AB - X-ray absorption near edge structure (XANES) analysis is an element-specific method for proving electronic state mostly in the field of applied physics, such as battery and catalysis reactions, where the valence change plays an important role. In particular, many results have been reported for the analysis of positive electrode materials of Li-ion batteries, where multiple transition materials contribute to the reactions. However, XANES analysis has been limited to identifying the valence state simply in comparison with reference materials. When the shape of XANES spectra shows complicated changes, we were not able to identify the valence states or estimate the valence quantitatively, resulting in insufficient reaction analysis. To overcome such issues, we propose a valence state evaluation method using K- and L-edge XANES analysis with first-principles simulations. By using this method, we demonstrated that the complicated reaction mechanism of Li(Ni1/3Co1/3Mn1/3)O2 can be successfully analyzed for distinguishing each contribution of Ni, Co, Mn, and O to the redox reactions during charge operation. In addition to the XANES analysis, we applied resonant photoelectron spectroscopy (RPES) and diffraction anomalous fine structure spectroscopy (DAFS) with first-principles calculations to the reaction analysis of Co and Mn, which shows no or very little contribution to the redox. The combination of RPES and first-principles calculations successfully enables us to confirm the contribution of Co at high potential regions by electively observing Co 3d orbitals. Through the DAFS analysis, we deeply analyzed the spectral features of Mn K-edges and concluded that the observed spectral shape change for Mn does not originate from the valence change but from the change in distribution of wave functions around Mn upon Li extraction.

    UR - http://www.scopus.com/inward/record.url?scp=84991704922&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=84991704922&partnerID=8YFLogxK

    U2 - 10.1063/1.4963379

    DO - 10.1063/1.4963379

    M3 - Article

    AN - SCOPUS:84991704922

    VL - 120

    JO - Journal of Applied Physics

    JF - Journal of Applied Physics

    SN - 0021-8979

    IS - 14

    M1 - 142125

    ER -