IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v14y2023i1d10.1038_s41467-023-43031-6.html
   My bibliography  Save this article

Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state

Author

Listed:
  • Xuelong Wang

    (Brookhaven National Laboratory
    Chinese Academy of Sciences)

  • Liang Yin

    (Chinese Academy of Sciences
    Argonne National Laboratory)

  • Arthur Ronne

    (Brookhaven National Laboratory
    Stony Brook University)

  • Yiman Zhang

    (Oak Ridge National Laboratory)

  • Zilin Hu

    (Chinese Academy of Sciences)

  • Sha Tan

    (Brookhaven National Laboratory)

  • Qinchao Wang

    (Brookhaven National Laboratory)

  • Bohang Song

    (Oak Ridge National Laboratory)

  • Mengya Li

    (Oak Ridge National Laboratory)

  • Xiaohui Rong

    (Chinese Academy of Sciences)

  • Saul Lapidus

    (Argonne National Laboratory)

  • Shize Yang

    (Yale University)

  • Enyuan Hu

    (Brookhaven National Laboratory)

  • Jue Liu

    (Oak Ridge National Laboratory)

Abstract

Reversible lattice oxygen redox reactions offer the potential to enhance energy density and lower battery cathode costs. However, their widespread adoption faces obstacles like substantial voltage hysteresis and poor stability. The current research addresses these challenges by achieving a non-hysteresis, long-term stable oxygen redox reaction in the P3-type Na2/3Cu1/3Mn2/3O2. Here we show this is accomplished by forming spin singlet states during charge and discharge. Detailed analysis, including in-situ X-ray diffraction, shows highly reversible structural changes during cycling. In addition, local CuO6 Jahn-Teller distortions persist throughout, with dynamic Cu-O bond length variations. In-situ hard X-ray absorption and ex-situ soft X-ray absorption study, along with density function theory calculations, reveal two distinct charge compensation mechanisms at approximately 3.66 V and 3.99 V plateaus. Notably, we observe a Zhang-Rice-like singlet state during 3.99 V charging, offering an alternative charge compensation mechanism to stabilize the active oxygen redox reaction.

Suggested Citation

  • 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.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-43031-6
    DOI: 10.1038/s41467-023-43031-6
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-023-43031-6
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-023-43031-6?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
    ---><---

    References listed on IDEAS

    as
    1. Robert A. House & Gregory J. Rees & Miguel A. Pérez-Osorio & John-Joseph Marie & Edouard Boivin & Alex W. Robertson & Abhishek Nag & Mirian Garcia-Fernandez & Ke-Jin Zhou & Peter G. Bruce, 2020. "First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk," Nature Energy, Nature, vol. 5(10), pages 777-785, October.
    2. Gaurav Assat & Jean-Marie Tarascon, 2018. "Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries," Nature Energy, Nature, vol. 3(5), pages 373-386, May.
    3. Jie-Nan Zhang & Qinghao Li & Chuying Ouyang & Xiqian Yu & Mingyuan Ge & Xiaojing Huang & Enyuan Hu & Chao Ma & Shaofeng Li & Ruijuan Xiao & Wanli Yang & Yong Chu & Yijin Liu & Huigen Yu & Xiao-Qing Ya, 2019. "Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V," Nature Energy, Nature, vol. 4(7), pages 594-603, July.
    4. Arnaud J. Perez & Quentin Jacquet & Dmitry Batuk & Antonella Iadecola & Matthieu Saubanère & Gwenaëlle Rousse & Dominique Larcher & Hervé Vezin & Marie-Liesse Doublet & Jean-Marie Tarascon, 2017. "Approaching the limits of cationic and anionic electrochemical activity with the Li-rich layered rocksalt Li3IrO4," Nature Energy, Nature, vol. 2(12), pages 954-962, December.
    5. 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.
    6. Akihisa Tsuchimoto & Xiang-Mei Shi & Kosuke Kawai & Benoit Mortemard de Boisse & Jun Kikkawa & Daisuke Asakura & Masashi Okubo & Atsuo Yamada, 2021. "Nonpolarizing oxygen-redox capacity without O-O dimerization in Na2Mn3O7," Nature Communications, Nature, vol. 12(1), pages 1-7, December.
    7. Feng Lin & Isaac M. Markus & Dennis Nordlund & Tsu-Chien Weng & Mark D. Asta & Huolin L. Xin & Marca M. Doeff, 2014. "Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries," Nature Communications, Nature, vol. 5(1), pages 1-9, May.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. 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.
    2. 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.
    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. 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.
    5. 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.
    6. Junbo Zhang & Haikuo Zhang & Suting Weng & Ruhong Li & Di Lu & Tao Deng & Shuoqing Zhang & Ling Lv & Jiacheng Qi & Xuezhang Xiao & Liwu Fan & Shujiang Geng & Fuhui Wang & Lixin Chen & Malachi Noked & , 2023. "Multifunctional solvent molecule design enables high-voltage Li-ion batteries," Nature Communications, Nature, vol. 14(1), pages 1-14, December.
    7. Yi Pei & Qing Chen & Meiyu Wang & Pengjun Zhang & Qingyong Ren & Jingkai Qin & Penghao Xiao & Li Song & Yu Chen & Wen Yin & Xin Tong & Liang Zhen & Peng Wang & Cheng-Yan Xu, 2022. "A medium-entropy transition metal oxide cathode for high-capacity lithium metal batteries," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    8. Qi Liang & Peirong Li & Yue Zhao & Supeng Chen & Jixiang Yin & Yingchun Lyu & Qiang Li & Qinghao Li, 2023. "Investigation on the Origin of Sluggish Anionic Redox Kinetics in Cation-Disordered Cathode," Energies, MDPI, vol. 16(18), pages 1-12, September.
    9. 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.
    10. Xinlei Shi & Xiangqian Fan & Yinbo Zhu & Yang Liu & Peiqi Wu & Renhui Jiang & Bao Wu & Heng-An Wu & He Zheng & Jianbo Wang & Xinyi Ji & Yongsheng Chen & Jiajie Liang, 2022. "Pushing detectability and sensitivity for subtle force to new limits with shrinkable nanochannel structured aerogel," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    11. 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.
    12. Xiyang Wang & Qilei Yang & Xinbo Li & Zhen Li & Chuan Gao & Hui Zhang & Xuefeng Chu & Carl Redshaw & Shucheng Shi & Yimin A. Wu & Yongliang Ma & Yue Peng & Junhua Li & Shouhua Feng, 2024. "Exploring the dynamic evolution of lattice oxygen on exsolved-Mn2O3@SmMn2O5 interfaces for NO Oxidation," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    13. Zijian Cai & Bin Ouyang & Han-Ming Hau & Tina Chen & Raynald Giovine & Krishna Prasad Koirala & Linze Li & Huiwen Ji & Yang Ha & Yingzhi Sun & Jianping Huang & Yu Chen & Vincent Wu & Wanli Yang & Chon, 2024. "In situ formed partially disordered phases as earth-abundant Mn-rich cathode materials," Nature Energy, Nature, vol. 9(1), pages 27-36, January.
    14. Xu Luo & Hongyu Zhao & Xin Tan & Sheng Lin & Kesong Yu & Xueqin Mu & Zhenhua Tao & Pengxia Ji & Shichun Mu, 2024. "Fe-S dually modulated adsorbate evolution and lattice oxygen compatible mechanism for water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    15. Nian Zhang & Guoxi Ren & Lili Li & Zhi Wang & Pengfei Yu & Xiaobao Li & Jing Zhou & Hui Zhang & Linjuan Zhang & Zhi Liu & Xiaosong Liu, 2024. "Dynamical evolution of CO2 and H2O on garnet electrolyte elucidated by ambient pressure X-ray spectroscopies," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    16. Ke Chen & Pallab Barai & Ozgenur Kahvecioglu & Lijun Wu & Krzysztof Z. Pupek & Mingyuan Ge & Lu Ma & Steven N. Ehrlich & Hui Zhong & Yimei Zhu & Venkat Srinivasan & Jianming Bai & Feng Wang, 2024. "Cobalt-free composite-structured cathodes with lithium-stoichiometry control for sustainable lithium-ion batteries," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    17. Hongnan Jia & Na Yao & Yiming Jin & Liqing Wu & Juan Zhu & Wei Luo, 2024. "Stabilizing atomic Ru species in conjugated sp2 carbon-linked covalent organic framework for acidic water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    18. Ziyao Gao & Chenglong Zhao & Kai Zhou & Junru Wu & Yao Tian & Xianming Deng & Lihan Zhang & Kui Lin & Feiyu Kang & Lele Peng & Marnix Wagemaker & Baohua Li, 2024. "Kirkendall effect-induced uniform stress distribution stabilizes nickel-rich layered oxide cathodes," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    19. Ermanno Miele & Wesley M. Dose & Ilya Manyakin & Michael H. Frosz & Zachary Ruff & Michael F. L. Volder & Clare P. Grey & Jeremy J. Baumberg & Tijmen G. Euser, 2022. "Hollow-core optical fibre sensors for operando Raman spectroscopy investigation of Li-ion battery liquid electrolytes," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    20. Dong Hou & Zhengrui Xu & Zhijie Yang & Chunguang Kuai & Zhijia Du & Cheng-Jun Sun & Yang Ren & Jue Liu & Xianghui Xiao & Feng Lin, 2022. "Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes," Nature Communications, Nature, vol. 13(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:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-43031-6. 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.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with 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.