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

Nature Catalysis volume 7, pages 776–784 (2024)Cite this article

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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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References

  1. Jiang, L. et al. Building aqueous K-ion batteries for energy storage. Nat. Energy 4, 495–503 (2019).

    Article  CAS  Google Scholar 

  2. Kundu, D., Adams, B. D., Duffort, V., Vajargah, S. H. & Nazar, L. F. A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode. Nat. Energy 1, 16119 (2016).

    Article  CAS  Google Scholar 

  3. Xu, C., Li, B., Du, H. & Kang, F. Energetic zinc ion chemistry: the rechargeable zinc ion battery. Angew. Chem. Int. Ed. 51, 933–935 (2012).

    Article  CAS  Google Scholar 

  4. Li, C., Jin, S., Archer, L. A. & Nazar, L. F. Toward practical aqueous zinc-ion batteries for electrochemical energy storage. Joule 6, 1733–1738 (2022).

    Article  Google Scholar 

  5. Liu, Y., Zhu, Y. & Cui, Y. Challenges and opportunities towards fast-charging battery materials. Nat. Energy 4, 540–550 (2019).

    Article  Google Scholar 

  6. Choi, C. et al. Achieving high energy density and high power density with pseudocapacitive materials. Nat. Rev. Mater. 5, 5–19 (2019).

    Article  Google Scholar 

  7. Michelbacher, C. J. et al. Enabling Fast Charging: a Technology Gap Assessment No. INL/EXT-17-41638 (US Department of Energy, 2017).

  8. Tsiropoulos, I., Siskos, P. & Capros, P. The cost of recharging infrastructure for electric vehicles in the EU in a climate neutrality context: factors influencing investments in 2030 and 2050. Appl. Energy 322, 119446 (2022).

    Article  Google Scholar 

  9. Li, W., Dahn, J. R. & Wainwright, D. S. Rechargeable lithium batteries with aqueous electrolytes. Science 264, 1115–1118 (1994).

    Article  CAS  PubMed  Google Scholar 

  10. Zhang, N. et al. Materials chemistry for rechargeable zinc-ion batteries. Chem. Soc. Rev. 49, 4203–4219 (2020).

    Article  CAS  PubMed  Google Scholar 

  11. Jia, X., Liu, C., Neale, Z. G., Yang, J. & Cao, G. Active materials for aqueous zinc ion batteries: synthesis, crystal structure, morphology and electrochemistry. Chem. Rev. 120, 7795–7866 (2020).

    Article  CAS  PubMed  Google Scholar 

  12. Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

    Article  CAS  PubMed  Google Scholar 

  13. Simon, P., Gogotsi, Y. & Dunn, B. Where do batteries end and supercapacitors begin? Science 343, 1210–1211 (2014).

    Article  CAS  PubMed  Google Scholar 

  14. Yuan, Y. et al. Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries. Nat. Sustain. 5, 890–898 (2022).

    Article  Google Scholar 

  15. Wu, X. et al. Diffusion-free Grotthuss topochemistry for high-rate and long-life proton batteries. Nat. Energy 4, 123–130 (2019).

    Article  CAS  Google Scholar 

  16. Fang, G. et al. Simultaneous cationic and anionic redox reactions mechanism enabling high‐rate long‐life aqueous zinc‐ion battery. Adv. Funct. Mater. 29, 1905267 (2019).

    Article  CAS  Google Scholar 

  17. Wang, L., Huang, K. W., Chen, J. & Zheng, J. Ultralong cycle stability of aqueous zinc-ion batteries with zinc vanadium oxide cathodes. Sci. Adv. 5, eaax4279 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  18. Park, M. J., Yaghoobnejad Asl, H. & Manthiram, A. Multivalent-ion versus proton insertion into battery electrodes. ACS Energy Lett. 5, 2367–2375 (2020).

    Article  CAS  Google Scholar 

  19. Wan, F. et al. Aqueous rechargeable zinc/sodium vanadate batteries with enhanced performance from simultaneous insertion of dual carriers. Nat. Commun. 9, 1656 (2018).

    Article  PubMed  PubMed Central  Google Scholar 

  20. Chao, D. et al. Roadmap for advanced aqueous batteries: from design of materials to applications. Sci. Adv. 6, eaba4098 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  21. Choi, D., Blomgren, G. E. & Kumta, P. N. Fast and reversible surface redox reaction in nanocrystalline vanadium nitride supercapacitors. Adv. Mater. 18, 1178–1182 (2006).

    Article  CAS  Google Scholar 

  22. Ge, J., Fan, L., Rao, A. M., Zhou, J. & Lu, B. Surface-substituted Prussian blue analogue cathode for sustainable potassium-ion batteries. Nat. Sustain. 5, 225–234 (2021).

    Article  Google Scholar 

  23. Luo, J. Y., Cui, W. J., He, P. & Xia, Y. Y. Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. Nat. Chem. 2, 760–765 (2010).

    Article  PubMed  Google Scholar 

  24. Pastel, G. R. et al. A sobering examination of the feasibility of aqueous aluminum batteries. Energy Environ. Sci. 15, 2460–2469 (2022).

    Article  CAS  Google Scholar 

  25. Cao, L. et al. Fluorinated interphase enables reversible aqueous zinc battery chemistries. Nat. Nanotechnol. 16, 902–910 (2021).

    Article  CAS  PubMed  Google Scholar 

  26. Li, K. & Xue, D. Estimation of electronegativity values of elements in different valence states. J. Phys. Chem. A 110, 11332–11337 (2006).

    Article  CAS  PubMed  Google Scholar 

  27. Sproul, G. Electronegativity and bond type: predicting bond type. J. Chem. Educ. 78, 387 (2001).

    Article  CAS  Google Scholar 

  28. Kinraide, T. B. & Yermiyahu, U. A scale of metal ion binding strengths correlating with ionic charge, Pauling electronegativity, toxicity and other physiological effects. J. Inorg. Biochem. 101, 1201–1213 (2007).

    Article  CAS  PubMed  Google Scholar 

  29. Miranda-Quintana, R. A., Martinez Gonzalez, M. & Ayers, P. W. Electronegativity and redox reactions. Phys. Chem. Chem. Phys. 18, 22235–22243 (2016).

    Article  CAS  PubMed  Google Scholar 

  30. Tan, S. et al. Revealing the origin of highly efficient polysulfide anchoring and transformation on anion‐substituted vanadium nitride host. Adv. Funct. Mater. 31, 2008034 (2020).

    Article  Google Scholar 

  31. Li, J. et al. Multi‐scale investigations of δ‐Ni0.25V2O5·nH2O cathode materials in aqueous zinc‐ion batteries. Adv. Energy Mater. 10, 2000058 (2020).

    Article  CAS  Google Scholar 

  32. Chen, W. et al. Two-dimensional quantum-sheet films with sub-1.2-nm channels for ultrahigh-rate electrochemical capacitance. Nat. Nanotechnol. 17, 153–158 (2022).

    Article  CAS  PubMed  Google Scholar 

  33. Rudolph, W. W., Brooker, M. H. & Tremaine, P. R. Raman spectroscopy of aqueous ZnSO4 solutions under hydrothermal conditions: solubility, hydrolysis and sulfate ion pairing. J. Solution Chem. 28, 621–630 (1999).

    Article  CAS  Google Scholar 

  34. Zhao, H. et al. In operando synchrotron studies of NH4+ preintercalated V2O5·nH2O nanobelts as the cathode material for aqueous rechargeable zinc batteries. ACS Nano 14, 11809–11820 (2020).

    Article  CAS  PubMed  Google Scholar 

  35. Zuo, S. et al. Direct detection and visualization of the H+ reaction process in a VO2 cathode for aqueous zinc-ion batteries. J. Phys. Chem. Lett. 12, 7076–7084 (2021).

    Article  CAS  PubMed  Google Scholar 

  36. Dai, Y. et al. Quicker and more Zn2+ storage predominantly from the interface. Adv. Mater. 33, 2100359 (2021).

    Article  CAS  Google Scholar 

  37. Liu, Y. et al. In-situ electrochemically activated surface vanadium valence in V2C MXene to achieve high capacity and superior rate performance for Zn-ion batteries. Adv. Funct. Mater. 31, 2008033 (2020).

    Article  Google Scholar 

  38. Deng, S. et al. Electrochemically induced metal-organic-framework-derived amorphous V2O5 for superior rate aqueous zinc-ion batteries. Angew. Chem. Int. Ed. 59, 22002–22006 (2020).

    Article  CAS  Google Scholar 

  39. Wang, L. et al. Ultrahigh-rate and ultralong-life aqueous batteries enabled by special pair-dancing proton transfer. Sci. Adv. 9, eadf4589 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. Li, M. et al. Universal multifunctional hydrogen bond network construction strategy for enhanced aqueous Zn2+/proton hybrid batteries. Nano Energy 100, 107539 (2022).

    Article  CAS  Google Scholar 

Download references

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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Author notes

  1. These authors contributed equally: Yuhang Dai, Ruihu Lu, Chengyi Zhang, Jiantao Li.

Authors and Affiliations

  1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, P. R. China

    Yuhang Dai, Jiexin Zhu, Jinghao Li, Ruohan Yu, Lianmeng Cui, Qinyou An & Liqiang Mai

  2. Electrochemical Innovation Lab, Department of Chemical Engineering, University College London, London, UK

    Yuhang Dai, Jiexin Zhu, Siyu Zhao, Guanjie He & Paul R. Shearing

  3. Department of Engineering Science, University of Oxford, Oxford, UK

    Yuhang Dai & Paul R. Shearing

  4. School of Chemical Sciences, University of Auckland, Auckland, New Zealand

    Ruihu Lu, Chengyi Zhang, Yu Mao, Geoffrey I. N. Waterhouse & Ziyun Wang

  5. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    Jiantao Li, Yifei Yuan & Khalil Amine

  6. Department of Materials Science and Metallurgy, University of Cambridge, Cambridge, UK

    Chumei Ye

  7. Department of Physics, The Chinese University of Hong Kong, New Territories, Hong Kong, P. R. China

    Zhijun Cai

  8. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, USA

    Yang Ren

  9. College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, P. R. China

    Jun Lu

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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.

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

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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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