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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The datasets generated and/or analysed during the current study are available from the corresponding authors on reasonable request.
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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.
The authors declare no competing interests.
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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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