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Cation replacement method enables high-performance electrolytes for multivalent metal batteries

Nature Energy volume 9, pages 285–297 (2024)Cite this article

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Abstract

High-performance, cost-efficient electrolyte systems are sought after for high-energy-density multivalent metal batteries. However, the expensive precursor and complex synthesis process hinders exploration of cathode electrode/electrolyte interfaces and solvation structures. Here we developed a universal cation replacement method to prepare low-cost, high-reversibility magnesium and calcium electrolytes derived from a zinc organoborate solvation structure. By rationally adjusting the precursor chain length and F-substitution degree, we can fine tune anion participation in the primary solvation shell. A completely dissociated Mg organoborate electrolyte enables high current endurance and enhanced electrochemical kinetics, whereas the Ca organoborate electrolyte with strong coordination/B–H inclusion offers a stable solid–electrolyte interphase with high coulombic efficiency. A rechargeable 53.4 Wh kg−1 Mg metal prototype is achieved with a 30 μm Mg anode, a low electrolyte/sulfur ratio (E/S = 5.58 μl mg−1) and a modified separator/interlayer. This work provides innovative strategies for reversible electrolyte systems and high-energy-density multivalent metal batteries.

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Fig. 1: Synthesis route and characterization of different Ca/Mg solvates.
Fig. 2: Simulation of the solvation shell.
Fig. 3: Electrochemical performance of Ca/Mg solvates and passivation layer analysis.
Fig. 4: Characterizations of the passivation layer on the Mg/Ca anode.
Fig. 5: Correlation between the molecular structure and properties and performance.
Fig. 6: Deposition morphology and behaviour.
Fig. 7: Electrochemical performance of Mg metal full cells and the pathway towards high energy density.

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Data availability

All data that support the main findings are available in the main text and the Supplementary Information.

Code availability

The Python codes for Mg2+/Ca2+ solvation analysis are available at https://github.com/liuqilei/zhejiang_university.

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Acknowledgements

We owe our gratitude to Y. Yao and H. Dong for their help on this work. S.L. thanks his colleagues who still helped him complete this article after graduation. We thank L. Wu and S. Chang at the Center of Cryo-Electron Microscopy (CCEM), Zhejiang University, for the technical assistance on Cryo-EM. We thank N. Zheng at State Key Laboratory of Chemical Engineering in Zhejiang University for performing SEM and Raman. We thank Y. Lu at the school of Materials Science and Engineering in Zhejiang University for performing XPS. We thank D. Chen from Shiyanjia Lab (www.shiyanjia.com) for providing invaluable assistance with the X-ray single-crystal analysis. We acknowledge financial support from the Natural Science Foundation of China (22022813, 21878268), the National Key R&D Program of China (2018YFA0209600), the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang (2019R01006), the Key R&D Program of Zhejiang Province (2019C01155) and the Fundamental Research Funds for China Central Universities (DUT22LAB608).

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Author notes

  1. These authors contributed equally to this work: Siyuan Li, Jiahui Zhang, Shichao Zhang.

Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, Institute of Pharmaceutical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China

    Siyuan Li, Jiahui Zhang, Shichao Zhang, Hao Cheng, Lei Fan, Weidong Zhang, Xinyang Wang, Qian Wu & Yingying Lu

  2. ZJU-Hangzhou Global Scientific and Technological Innovation Center, Hangzhou, China

    Jiahui Zhang, Hao Cheng, Qian Wu & Yingying Lu

  3. State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Institute of Chemical Process Systems Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, China

    Qilei Liu

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Contributions

S.L. conceived the idea and designed the experiments. S.L. and J.Z. synthesized the electrolytes. Q.L. and H.C. performed the DFT/MD calculation. S.Z. provided the PVA separator. H.C. and X.W. synthesized and fabricated sulfur electrodes. L.F., W.Z. and Q.W. prepared GO/Cu membranes. All authors participated in writing the manuscript. Y.L. supervised the project.

Corresponding author

Correspondence to Yingying Lu.

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Competing interests

S.L., H.C., J.Z., S.Z. and Y.L. declare that this work has been filed as Chinese Patent Application number 2023102361925. All other authors declare no competing interests.

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Li, S., Zhang, J., Zhang, S. et al. Cation replacement method enables high-performance electrolytes for multivalent metal batteries. Nat Energy 9, 285–297 (2024). https://doi.org/10.1038/s41560-023-01439-w

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