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All-temperature zinc batteries with high-entropy aqueous electrolyte

Nature Sustainability volume 6, pages 325–335 (2023)Cite this article

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Abstract

Electrification of transportation and rising demand for grid energy storage continue to build momentum around batteries across the globe. However, the supply chain of Li-ion batteries is exposed to the increasing challenges of resourcing essential and scarce materials. Therefore, incentives to develop more sustainable battery chemistries are growing. Here we show an aqueous ZnCl2 electrolyte with introduced LiCl as supporting salt. Once the electrolyte is optimized to Li2ZnCl4⋅9H2O, the assembled Zn–air battery can sustain stable cycling over the course of 800 hours at a current density of 0.4 mA cm−2 between −60 °C and +80 °C, with 100% Coulombic efficiency for Zn stripping/plating. Even at −60 °C, >80% of room-temperature power density can be retained. Advanced characterization and theoretical calculations reveal a high-entropy solvation structure that is responsible for the excellent performance. The strong acidity allows ZnCl2 to accept donated Cl− ions to form ZnCl42− anions, while water molecules remain within the free solvent network at low salt concentration or coordinate with Li ions. Our work suggests an effective strategy for the rational design of electrolytes that could enable next-generation Zn batteries.

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Fig. 1: Transport properties over wide temperature window.
Fig. 2: Solvation structure.
Fig. 3: Zn metal anode performances.
Fig. 4: Zn–air cell performances.

Data availability

The datasets generated and/or analysed during the current study are available from the corresponding authors on reasonable request.

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Acknowledgements

We thank A. Angell at Arizona State University for invaluable advice. We also thank K. Gaskell from Department of Chemistry and Biochemistry at University of Maryland and I. Hill from Department of Physics and Atmospheric Science at Dalhousie University for the guidance of XPS analysis. The principal investigator (C.W.) received financial support from the US Department of Energy (DOE) through ARPA-E grant DEAR0000389. O.B., J.V. and T.P.P. acknowledge support from the US Army, DEVCOM Army Research Laboratory and the Joint Center for Energy Storage Research (JCESR) funded by the Department of Energy, through IAA SN2020957. C.Y. acknowledges the support of the Natural Sciences and Engineering Research Council of Canada (NSERC) through Discovery Grant RGPIN-2021-02426. J.-P. Piquemal and L. Lagardere (Sorbonne Université) helped with Tinker-HP installation and modification. E.T. and A.K. acknowledge financial support from the National Science Foundation through grant CBET 1847469. E.H. and X.-Q.Y. are supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US DOE through the Advanced Battery Materials Research (BMR) Program. Access to the vSANS instrument was provided by the Center for High Resolution Neutron Scattering, a partnership between the National Science Foundation and the National Institute of Standards and Technology under agreement DMR-1508249. This research used resources 7-BM (QAS) of the National Synchrotron Light Source II, a US DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. Certain commercial equipment, instruments, materials, suppliers or software are identified in this paper to foster understanding. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the materials or equipment identified is necessarily the best available for the purpose.

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Author notes

  1. These authors contributed equally: Chongyin Yang, Jiale Xia, Chunyu Cui.

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Chongyin Yang, Jiale Xia, Chunyu Cui, Jijian Xu, Xiao Ji, Singyuk Hou, Xiyue Zhang & Chunsheng Wang

  2. Department of Physics and Atmospheric Science, Dalhousie University, Halifax, NS, Canada

    Chongyin Yang & Wentao Song

  3. Battery Science Branch, DEVCOM Army Research Laboratory, Adelphi, MD, USA

    Travis P. Pollard, Jenel Vatamanu, Michael S. Ding & Oleg Borodin

  4. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD, USA

    Antonio Faraone, Joseph A. Dura & Madhusudan Tyagi

  5. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Madhusudan Tyagi & Howard Wang

  6. Department of Energy, Environmental and Chemical Engineering, Washington University, St Louis, MO, USA

    Alex Kattan & Elijah Thimsen

  7. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Enyuan Hu & Xiao-Qing Yang

  8. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

    Sooyeon Hwang & Dong Su

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

    Yang Ren

  10. Department of Physics, City University of Hong Kong, Kowloon, Hong Kong, China

    Yang Ren

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  1. Chongyin Yang
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Contributions

C.Y., O.B. and C.W. conceived the idea of the study. C.Y., C.C., J. Xia, X.J., J. Xu, X.Z. and S. Hou prepared the materials and performed electrochemical experiments. T.P.P, J.V. and O.B. conducted DFT and MD simulations. C.Y., A.F., J.A.D., M.T. and H.W. performed neutron scattering measurements. C.Y., A.K. and E.T. conducted activity coefficient measurements. C.Y., E.H., S. Hwang, D.S., Y.R. and X.-Q.Y. performed X-ray diffraction and scattering measurements. C.Y., C.C. and M.S.D. performed DSC measurements. C.Y. and W.S. performed XPS analysis. C.Y., O.B. and C.W. wrote the paper, and all authors contributed to editing the manuscript.

Corresponding authors

Correspondence to Oleg Borodin or Chunsheng Wang.

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Nature Sustainability thanks Andrzej Eilmes, Katja Kretschmer, Guanjie He and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Figs. 1–17, Table 1 and Discussion.

Supplementary Video 1

Demonstration of Zn-ion battery performance at −70 °C.

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Yang, C., Xia, J., Cui, C. et al. All-temperature zinc batteries with high-entropy aqueous electrolyte. Nat Sustain 6, 325–335 (2023). https://doi.org/10.1038/s41893-022-01028-x

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