IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-024-55244-4.html
   My bibliography  Save this article

Adjusting Hirshfeld charge of TEMPO catholytes for stable all-organic aqueous redox flow batteries

Author

Listed:
  • Gonggen Tang

    (University of Science and Technology of China)

  • Wenyi Wu

    (University of Science and Technology of China)

  • Yahua Liu

    (Hefei University of Technology)

  • Kang Peng

    (University of Science and Technology of China)

  • Peipei Zuo

    (University of Science and Technology of China)

  • Zhengjin Yang

    (University of Science and Technology of China)

  • Tongwen Xu

    (University of Science and Technology of China)

Abstract

2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivatives are typical catholytes in aqueous organic redox flow batteries (AORFBs), but reported lifetime of them is limited. We find that the increase of Hirshfeld charge decreases the Gibbs free energy change (ΔG) values of side reactions of TEMPO, a near-linear relationship, and then exacerbates their degradation. Here we predict and synthesize a TEMPO derivative, namely TPP-TEMPO, by analyzing the Hirshfeld charge. TPP-TEMPO, with the smallest Hirshfeld charge and highest ΔG, is an order of magnitude more stable than TMA-TEMPO (N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride, a control with the largest Hirshfeld charge and lowest ΔG). We further elaborate on their decomposition pathways, identify byproducts, and mitigate degradation by supporting electrolyte engineering. Finally, a TPP-TEMPO/BTMAP-Vi (1,1′-bis[3-(trimethylammonio)propyl]-4,4′-bipyridinium tetrachloride) cell achieves a capacity density of ~12 Ah L−1 and a low capacity fade rate of 0.0018% per cycle (or 0.0067% per hour).

Suggested Citation

  • Gonggen Tang & Wenyi Wu & Yahua Liu & Kang Peng & Peipei Zuo & Zhengjin Yang & Tongwen Xu, 2025. "Adjusting Hirshfeld charge of TEMPO catholytes for stable all-organic aqueous redox flow batteries," Nature Communications, Nature, vol. 16(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-024-55244-4
    DOI: 10.1038/s41467-024-55244-4
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-024-55244-4
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-024-55244-4?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. Yanxin Yao & Jiafeng Lei & Yang Shi & Fei Ai & Yi-Chun Lu, 2021. "Assessment methods and performance metrics for redox flow batteries," Nature Energy, Nature, vol. 6(6), pages 582-588, June.
    2. Aaron Hollas & Xiaoliang Wei & Vijayakumar Murugesan & Zimin Nie & Bin Li & David Reed & Jun Liu & Vincent Sprenkle & Wei Wang, 2018. "A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries," Nature Energy, Nature, vol. 3(6), pages 508-514, June.
    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. Dominik Emmel & Simon Kunz & Nick Blume & Yongchai Kwon & Thomas Turek & Christine Minke & Daniel Schröder, 2023. "Benchmarking organic active materials for aqueous redox flow batteries in terms of lifetime and cost," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    2. Xie, Heping & Wu, Yifan & Liu, Tao & Wang, Fuhuan & Chen, Bin & Liang, Bin, 2020. "Low-energy-consumption electrochemical CO2 capture driven by biomimetic phenazine derivatives redox medium," Applied Energy, Elsevier, vol. 259(C).
    3. Zou, Wen-Jiang & Kim, Young-Bae & Jung, Seunghun, 2024. "Capacity fade prediction for vanadium redox flow batteries during long-term operations," Applied Energy, Elsevier, vol. 356(C).
    4. Zhiquan Wei & Zhaodong Huang & Guojin Liang & Yiqiao Wang & Shixun Wang & Yihan Yang & Tao Hu & Chunyi Zhi, 2024. "Starch-mediated colloidal chemistry for highly reversible zinc-based polyiodide redox flow batteries," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    5. Jiashen Meng & Xuhui Yao & Xufeng Hong & Lujun Zhu & Zhitong Xiao & Yongfeng Jia & Fang Liu & Huimin Song & Yunlong Zhao & Quanquan Pang, 2023. "A solution-to-solid conversion chemistry enables ultrafast-charging and long-lived molten salt aluminium batteries," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    6. Dominic Hey & Rajesh B. Jethwa & Nadia L. Farag & Bernardine L. D. Rinkel & Evan Wenbo Zhao & Clare P. Grey, 2023. "Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    7. Liang, Mengjun & Karthick, Ramalingam & Wei, Qiang & Dai, Jinhong & Jiang, Zhuosheng & Chen, Xuncai & Oo, Than Zaw & Aung, Su Htike & Chen, Fuming, 2022. "The progress and prospect of the solar-driven photoelectrochemical desalination," Renewable and Sustainable Energy Reviews, Elsevier, vol. 155(C).
    8. Leung, P. & Martin, T. & Xu, Q. & Flox, C. & Mohamad, M.R. & Palma, J. & Rodchanarowan, A. & Zhu, X. & Xing, W.W. & Shah, A.A., 2021. "A new aqueous all-organic flow battery with high cell voltage in acidic electrolytes," Applied Energy, Elsevier, vol. 282(PA).
    9. Gabriel S. Nambafu & Aaron M. Hollas & Shuyuan Zhang & Peter S. Rice & Daria Boglaienko & John L. Fulton & Miller Li & Qian Huang & Yu Zhu & David M. Reed & Vincent L. Sprenkle & Guosheng Li, 2024. "Phosphonate-based iron complex for a cost-effective and long cycling aqueous iron redox flow battery," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    10. Rémy Richard Jacquemond & Maxime van der Heijden & Emre Burak Boz & Eric Ricardo Carreón Ruiz & Katharine Virginia Greco & Jeffrey Adam Kowalski & Vanesa Muñoz Perales & Fikile Richard Brushett & Kitt, 2024. "Quantifying concentration distributions in redox flow batteries with neutron radiography," Nature Communications, Nature, vol. 15(1), pages 1-16, December.
    11. Chunchun Ye & Anqi Wang & Charlotte Breakwell & Rui Tan & C. Grazia Bezzu & Elwin Hunter-Sellars & Daryl R. Williams & Nigel P. Brandon & Peter A. A. Klusener & Anthony R. Kucernak & Kim E. Jelfs & Ne, 2022. "Development of efficient aqueous organic redox flow batteries using ion-sieving sulfonated polymer membranes," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    12. Igor Iwakiri & Tiago Antunes & Helena Almeida & João P. Sousa & Rita Bacelar Figueira & Adélio Mendes, 2021. "Redox Flow Batteries: Materials, Design and Prospects," Energies, MDPI, vol. 14(18), pages 1-45, September.
    13. Park, Gyunho & Jeong, Hayoung & Lee, Wonmi & Han, Jeong Woo & Chang, Duck Rye & Kwon, Yongchai, 2024. "Scaled-up aqueous redox flow battery using anthraquinone negalyte and vanadium posilyte with inorganic additive," Applied Energy, Elsevier, vol. 353(PB).

    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:16:y:2025:i:1:d:10.1038_s41467-024-55244-4. 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.