IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v8y2017i1d10.1038_s41467-017-02041-x.html
   My bibliography  Save this article

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

Author

Listed:
  • William E. Gent

    (Stanford University
    Lawrence Berkeley National Laboratory)

  • Kipil Lim

    (Stanford University
    SLAC National Accelerator Laboratory)

  • Yufeng Liang

    (Lawrence Berkeley National Laboratory)

  • Qinghao Li

    (Lawrence Berkeley National Laboratory
    National Key Laboratory of Crystal Materials, Shandong University)

  • Taylor Barnes

    (Lawrence Berkeley National Laboratory)

  • Sung-Jin Ahn

    (Samsung Advanced Institute of Technology, 130, Samsung-ro)

  • Kevin H. Stone

    (SLAC National Accelerator Laboratory)

  • Mitchell McIntire

    (Stanford University)

  • Jihyun Hong

    (Stanford University
    SLAC National Accelerator Laboratory)

  • Jay Hyok Song

    (Samsung SDI, 130, Samsung-ro)

  • Yiyang Li

    (Stanford University)

  • Apurva Mehta

    (SLAC National Accelerator Laboratory)

  • Stefano Ermon

    (Stanford University)

  • Tolek Tyliszczak

    (Lawrence Berkeley National Laboratory)

  • David Kilcoyne

    (Lawrence Berkeley National Laboratory)

  • David Vine

    (Lawrence Berkeley National Laboratory)

  • Jin-Hwan Park

    (Samsung Advanced Institute of Technology, 130, Samsung-ro)

  • Seok-Kwang Doo

    (Samsung Advanced Institute of Technology, 130, Samsung-ro)

  • Michael F. Toney

    (SLAC National Accelerator Laboratory
    SLAC National Accelerator Laboratory)

  • Wanli Yang

    (Lawrence Berkeley National Laboratory)

  • David Prendergast

    (Lawrence Berkeley National Laboratory)

  • William C. Chueh

    (Stanford University
    SLAC National Accelerator Laboratory)

Abstract

Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li1.17–x Ni0.21Co0.08Mn0.54O2, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.

Suggested Citation

  • William E. Gent & Kipil Lim & Yufeng Liang & Qinghao Li & Taylor Barnes & Sung-Jin Ahn & Kevin H. Stone & Mitchell McIntire & Jihyun Hong & Jay Hyok Song & Yiyang Li & Apurva Mehta & Stefano Ermon & T, 2017. "Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides," Nature Communications, Nature, vol. 8(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_s41467-017-02041-x
    DOI: 10.1038/s41467-017-02041-x
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-017-02041-x
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-017-02041-x?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    Citations

    Citations are extracted by the CitEc Project, subscribe to its RSS feed for this item.
    as


    Cited by:

    1. Jun-Hyuk Song & Seungju Yu & Byunghoon Kim & Donggun Eum & Jiung Cho & Ho-Young Jang & Sung-O Park & Jaekyun Yoo & Youngmin Ko & Kyeongsu Lee & Myeong Hwan Lee & Byungwook Kang & Kisuk Kang, 2023. "Slab gliding, a hidden factor that induces irreversibility and redox asymmetry of lithium-rich layered oxide cathodes," Nature Communications, Nature, vol. 14(1), pages 1-10, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_s41467-017-02041-x. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    We have no bibliographic references for this item. You can help adding them by using this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.