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Zn2+-mediated catalysis for fast-charging aqueous Zn-ion batteries

Abstract

Rechargeable aqueous zinc-ion batteries (AZIBs), renowned for their safety, high energy density and rapid charging, are prime choices for grid-scale energy storage. Historically, ion-shuttling models centring on ion-migration behaviour have dominated explanations for charge/discharge processes in aqueous batteries, like classical ion insertion/extraction and pseudocapacitance mechanisms. However, these models struggle to account for the exceptional performance of AZIBs compared to other aqueous metal-ion batteries. Here we present a catalysis model elucidating the Zn2+ anomaly in aqueous batteries, explaining it through the concept of adsorption in catalysis. Such behaviour can serve the charge/discharge role, predominantly dictated by solvated metal cations and cathode materials. First-principles calculations suggest optimal adsorption/desorption behaviour (water dissociation process) with the Zn2+–vanadium nitride (VN) combination. Experimentally, AZIBs implementing VN cathodes demonstrate fast-charging kinetics, showing a capacity of 577.1 mAh g−1 at a current density of 300,000 mA g−1. The grasp of catalysis steps within AZIBs can drive solutions beyond state-of-the-art fast-charging batteries.

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Fig. 1: The ion-shuttling and catalysis models used to describe AZIBs.
Fig. 2: Mechanistic investigation of the water dissociation model.
Fig. 3: Design of pure VN and morphology of VN@rGO.
Fig. 4: Structural information and evolution of VN@rGO and VNxOy@rGO.
Fig. 5: Electrochemical behaviours of VN@rGO and VNxOy@rGO in 2 M aqueous ZnSO4 solutions.

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Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (52172233, 51832004, 21905218, 51872218 and 52072285; L.M.), the Natural Science Foundation of Guangdong Province (no. 2021A1515010144; L.M.), the National Key Research and Development Program of China (2020YFA0715000; L.M.), the Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory (XHT2020-003; L.M.) and the Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City (520LH055; L.M.). The computational study was supported by the Marsden Fund Council from Government funding (21-UOA-237; Z.W.) and Catalyst: Seeding General Grant (22-UOA-031-CGS; Z.W.), managed by Royal Society Te Apārangi. All DFT calculations were carried out on the New Zealand eScience Infrastructure (NeSI) high-performance computing facilities. G.I.N.W. is supported by a James Cook Research Fellowship from New Zealand Government funding, administered by the Royal Society Te Apārangi. This research also used resources of the Advanced Photon Source, a US DOE Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02- 06CH11357.

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Authors

Contributions

J. Lu, K.A., Z.W. and L.M. supervised this project. Y.D., R.L., C.Z. and Jiantao Li conceived the ideas. Y.D. designed the materials and experiments. R.L., C.Z. and Y.M. carried out theoretical calculations. Jiantao Li and Y.R. conducted XAS and high-energy XRD characterizations. Y.Y. and C.Y. designed the figures and participated in the draft writing. Z.C. performed materials synthesis and tested the electrochemical performance. J.Z. carried out SEM and EIS measurements. Jinghao Li carried out basic characterizations such as XRD and XPS. R.Y. performed the STEM characterization. L.C. carried out UPS tests. S.Z., G.H. and P.R.S. carried out the X-ray micro-CT characterizations. Q.A. provided help with SEM, XRD and UPS tests. Y.D., R.L., C.Z., G.I.N.W. and Jiantao Li wrote the manuscript. All authors discussed the results and assisted with manuscript preparation.

Corresponding authors

Correspondence to Jun Lu, Khalil Amine, Ziyun Wang or Liqiang Mai.

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Nature Catalysis thanks Stefan Freunberger, Yan Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work

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Supplementary methods, Figs. 1–35, Tables 1–4, notes 1–7 and references 1–170.

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Atomic Coordinates

Atomic coordinates of the optimized computational models.

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Dai, Y., Lu, R., Zhang, C. et al. Zn2+-mediated catalysis for fast-charging aqueous Zn-ion batteries. Nat Catal 7, 776–784 (2024). https://doi.org/10.1038/s41929-024-01169-6

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