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Two-electron redox chemistry via single-atom catalyst for reversible zinc–air batteries

Nature Sustainability volume 7, pages 463–473 (2024)Cite this article

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Abstract

Rechargeable zinc–air batteries (ZABs) are considered to be one of the most sustainable alternative systems in a post-lithium-ion future owing to their lowest possible dependency on critical raw materials and high theoretical energy densities. However, their performance is still not up to par with their potential because of the sluggish kinetics of the oxygen reduction reaction. Here we report a single-atom catalyst design that transforms the sluggish four-electron oxygen reduction reaction into a fast two-electron pathway and enables a zinc peroxide (ZnO2) chemistry in ZABs. With accessible FeN2S2 active sites on mesoporous graphene, the catalyst serves to promote transport of electrolyte, oxygen and electron and confines the growth of ZnO2, which would otherwise form dead products. As a result, as-fabricated ZAB in a neutral electrolyte shows a voltage as high as 1.2 V at 0.2 mA cm−2, a high round-trip efficiency of 61% and an excellent operation stability beyond ∼400 h. This work provides guidelines for the rational design of multifunctional cathodes and would accelerate the adoption of sustainable batteries in the metal–air category.

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Fig. 1: Catalyst synthesis and characterization.
Fig. 2: The electrocatalytic ORR performance in neutral solution and corresponding DFT simulations.
Fig. 3: Performance of 2e− neutral ZABs.
Fig. 4: The dynamic structure evolution.
Fig. 5: Ex situ TEM and the reaction process.

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All data in this work are available in the text and Supplementary Information. The relevant raw data for each figure or table (in the text and Supplementary Information) are listed in Excel documents and provided as source or supplementary data files. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2022YFA1503501 to W.L. and 2021YFA1201900 to Fei W.), the National Nature Science Foundation of China (grant nos. 22088101 to D.Z., U21A20329 to W.L., 52261135631 to Fei W. and 22105041 to W.Z.), the Science and Technology Commission of Shanghai Municipality (21TQ1400100 to W.L. and 21511103300 to Fei W.), the Program of Shanghai Academic Research Leader (21XD1420800 to W.L.) and the Shanghai Pilot Program for Basic Research–FuDan University 21TQ1400100 (21TQ008 to W.L.). We acknowledge Y. Kong and M. Gao from University of Science and Technology of China and Dalian Institute of Chemical Physics, Chinese Academy of Sciences, respectively, for their valuable help and suggestions regarding theoretical simulations.

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Author notes

  1. These authors contributed equally: Wei Zhang, Jiangwei Zhang, Nan Wang.

Authors and Affiliations

  1. Laboratory of Advanced Materials, Department of Chemistry, Department of Materials Science, State Key Laboratory of Molecular Engineering of Polymers and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, China

    Wei Zhang, Nan Wang, Kerun Zhu, Chaochao Yang, Yan Ai, Fengmei Wang, Yong Tian, Yuzhu Ma, Yao Ma, Xingmiao Zhang, Linlin Duan, Dongliang Chao, Fei Wang, Dongyuan Zhao & Wei Li

  2. College of Energy Material and Chemistry, Inner Mongolia University, Hohhot, China

    Jiangwei Zhang, Yuzhu Ma & Dongyuan Zhao

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Contributions

W.L. and Fei W. conceived and designed the experiments and calculations. W.Z., N.W., K.Z., C.Y., Y.A., Fengmei W., Y.T., Yuzhu M., Yao M. X. Z., L.D. and D.C. fabricated the samples and conducted the structure characterization and electrochemical experiments. J.Z. and K.Z. performed the synchrotron-based characterizations. W.Z., J. Z., N.W., W.L., Fei W. and D.Z. wrote the paper. All authors discussed the results and commented on the paper.

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Correspondence to Fei Wang or Wei Li.

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Nature Sustainability thanks Minghao Yu, Xinbo Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary experimental section, Figs. 1–56 and Tables 1–7.

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Supplementary Data 1

All source data for supplementary figures.

Source data

Source Data Fig. 1

Corresponding height profiles of the meso-FeNSC. XANES, FT-EXAFS and WT contour plot spectra at the Fe K edge of Fe foil, FePc, FeS, Fe2O3 and the meso-FeNSC. The corresponding EXAFS fitting curves of the meso-FeNSC in R space.

Source Data Fig. 2

Voltammograms in O2-saturated 0.1 M PBS at 10 mV s−1. LSV curves together with the corresponding H2O2 currents on the ring electrode recorded at 1,600 rpm in O2-saturated 0.1 M PBS. The calculated electron transfer number (n) and H2O2 selectivity (H2O2%) in O2-saturated 0.1 M PBS. The stability at a fixed disk potential of the meso-FeNSC at 0.35 V versus RHE in O2-saturated 0.1 M PBS. The free energy diagram of ORR processes on the meso-FeNSC and meso-FeNC catalysts.

Source Data Fig. 3

Galvanostatic charge–discharge profiles of neutral ZABs fabricated with SP, meso-C, meso-FeNC and meso-FeNSC. Galvanostatic voltage profiles of the neutral ZABs fabricated with meso-FeNSC in capacity fixed mode (fixed capacity 1 mAh cm−2) at current density of 0.2, 0.5, 1.0, 2.0 and 4.0 mA cm−2. The long-term cycling performance of neutral ZABs fabricated with meso-FeNSC at current density of 0.2 mA cm−2. A comparison of the discharge voltage of the 2e− ZABs in this work and other ZABs.

Source Data Fig. 4

The XANES spectra of meso-FeNSC discharged to different potentials. The fitted average oxidation states of Fe from XANES spectra. FT-EXAFS spectra and corresponding contour plots at the Fe K edge of the meso-FeNSC discharged to different potentials. EXAFS fitting curves for R space of the meso-FeNSC discharged to different potentials.

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Zhang, W., Zhang, J., Wang, N. et al. Two-electron redox chemistry via single-atom catalyst for reversible zinc–air batteries. Nat Sustain 7, 463–473 (2024). https://doi.org/10.1038/s41893-024-01300-2

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