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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
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    References listed on IDEAS

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    1. 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.
    2. 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.
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