IDEAS home Printed from https://ideas.repec.org/a/nat/natene/v3y2018i8d10.1038_s41560-018-0207-z.html
   My bibliography  Save this article

Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release

Author

Listed:
  • Enyuan Hu

    (Brookhaven National Laboratory)

  • Xiqian Yu

    (Brookhaven National Laboratory
    Chinese Academy of Sciences)

  • Ruoqian Lin

    (Brookhaven National Laboratory
    Brookhaven National Laboratory)

  • Xuanxuan Bi

    (Argonne National Laboratory)

  • Jun Lu

    (Argonne National Laboratory)

  • Seongmin Bak

    (Brookhaven National Laboratory)

  • Kyung-Wan Nam

    (Dongguk University-Seoul)

  • Huolin L. Xin

    (Brookhaven National Laboratory)

  • Cherno Jaye

    (National Institute of Standards and Technology)

  • Daniel A. Fischer

    (National Institute of Standards and Technology)

  • Kahlil Amine

    (Argonne National Laboratory)

  • Xiao-Qing Yang

    (Brookhaven National Laboratory)

Abstract

Voltage fade is a major problem in battery applications for high-energy lithium- and manganese-rich (LMR) layered materials. As a result of the complexity of the LMR structure, the voltage fade mechanism is not well understood. Here we conduct both in situ and ex situ studies on a typical LMR material (Li1.2Ni0.15Co0.1Mn0.55O2) during charge–discharge cycling, using multi-length-scale X-ray spectroscopic and three-dimensional electron microscopic imaging techniques. Through probing from the surface to the bulk, and from individual to whole ensembles of particles, we show that the average valence state of each type of transition metal cation is continuously reduced, which is attributed to oxygen release from the LMR material. Such reductions activate the lower-voltage Mn3+/Mn4+ and Co2+/Co3+ redox couples in addition to the original redox couples including Ni2+/Ni3+, Ni3+/Ni4+ and O2−/O−, directly leading to the voltage fade. We also show that the oxygen release causes microstructural defects such as the formation of large pores within particles, which also contributes to the voltage fade. Surface coating and modification methods are suggested to be effective in suppressing the voltage fade through reducing the oxygen release.

Suggested Citation

  • Enyuan Hu & Xiqian Yu & Ruoqian Lin & Xuanxuan Bi & Jun Lu & Seongmin Bak & Kyung-Wan Nam & Huolin L. Xin & Cherno Jaye & Daniel A. Fischer & Kahlil Amine & Xiao-Qing Yang, 2018. "Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release," Nature Energy, Nature, vol. 3(8), pages 690-698, August.
    • Handle: RePEc:nat:natene:v:3:y:2018:i:8:d:10.1038_s41560-018-0207-z
    DOI: 10.1038/s41560-018-0207-z
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41560-018-0207-z
    File Function: Abstract
    Download Restriction: Access to the full text of the articles in this series is restricted.
    File URL: https://libkey.io/10.1038/s41560-018-0207-z?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
    ---><---

    As the access to this document is restricted, you may want to search for a different version of it.

    Citations

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


    Cited by:

    1. Xiao, Hanxu & E, Jiaqiang & Tian, Sicheng & Huang, Yuxin & Song, Xinyu, 2024. "Effect of composite cooling strategy including phase change material and liquid cooling on the thermal safety performance of a lithium-ion battery pack under thermal runaway propagation," Energy, Elsevier, vol. 295(C).
    2. Fang Fu & Xiang Liu & Xiaoguang Fu & Hongwei Chen & Ling Huang & Jingjing Fan & Jiabo Le & Qiuxiang Wang & Weihua Yang & Yang Ren & Khalil Amine & Shi-Gang Sun & Gui-Liang Xu, 2022. "Entropy and crystal-facet modulation of P2-type layered cathodes for long-lasting sodium-based batteries," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    3. Kit McColl & Robert A. House & Gregory J. Rees & Alexander G. Squires & Samuel W. Coles & Peter G. Bruce & Benjamin J. Morgan & M. Saiful Islam, 2022. "Transition metal migration and O2 formation underpin voltage hysteresis in oxygen-redox disordered rocksalt cathodes," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    4. Xuelong Wang & Liang Yin & Arthur Ronne & Yiman Zhang & Zilin Hu & Sha Tan & Qinchao Wang & Bohang Song & Mengya Li & Xiaohui Rong & Saul Lapidus & Shize Yang & Enyuan Hu & Jue Liu, 2023. "Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    5. Linze Li & Bin Ouyang & Zhengyan Lun & Haoyan Huo & Dongchang Chen & Yuan Yue & Colin Ophus & Wei Tong & Guoying Chen & Gerbrand Ceder & Chongmin Wang, 2023. "Atomic-scale probing of short-range order and its impact on electrochemical properties in cation-disordered oxide cathodes," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    6. Qingyuan Li & De Ning & Deniz Wong & Ke An & Yuxin Tang & Dong Zhou & Götz Schuck & Zhenhua Chen & Nian Zhang & Xiangfeng Liu, 2022. "Improving the oxygen redox reversibility of Li-rich battery cathode materials via Coulombic repulsive interactions strategy," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    7. Zhichen Xue & Nikhil Sharma & Feixiang Wu & Piero Pianetta & Feng Lin & Luxi Li & Kejie Zhao & Yijin Liu, 2023. "Asynchronous domain dynamics and equilibration in layered oxide battery cathode," Nature Communications, Nature, vol. 14(1), pages 1-8, December.
    8. Ho-Young Jang & Donggun Eum & Jiung Cho & Jun Lim & Yeji Lee & Jun-Hyuk Song & Hyeokjun Park & Byunghoon Kim & Do-Hoon Kim & Sung-Pyo Cho & Sugeun Jo & Jae Hoon Heo & Sunyoung Lee & Jongwoo Lim & Kisu, 2024. "Structurally robust lithium-rich layered oxides for high-energy and long-lasting cathodes," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    9. Sunyoung Lee & Hayoung Park & Jae Young Kim & Jihoon Kim & Min-Ju Choi & Sangwook Han & Sewon Kim & Wonju Kim & Ho Won Jang & Jungwon Park & Kisuk Kang, 2024. "Unveiling crystal orientation-dependent interface property in composite cathodes for solid-state batteries by in situ microscopic probe," Nature Communications, Nature, vol. 15(1), pages 1-11, 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:natene:v:3:y:2018:i:8:d:10.1038_s41560-018-0207-z. 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.