Abstract
The solid–electrolyte interphase (SEI) in lithium (Li) metal batteries is often heterogeneous, containing a diverse range of species and has poor mechanical stability. The SEI undergoes constant cracking and reconstruction during electrochemical cycling, which is accompanied by the exhaustion of active Li and electrolytes, hindering practical applications of the batteries. Here we propose an in situ structural design of SEI to promote its homogeneity and improve its mechanical stability. A bilayer structure of SEI is tailored through trioxane-modulated electrolytes: the inner layer is dominated by LiF to improve homogeneity while the outer layer contains Li polyoxymethylene to improve mechanical stability, synergistically leading to mitigated reconstruction of SEI and reversible Li plating/stripping. The coin cell consisting of an ultrathin Li metal anode (50 μm) and a high-loading cathode (3.0 mAh cm−2)—with the tailored bilayer SEI—achieves 430 cycles tested at 1.2 mA cm−2, while the cell with an anion-derived SEI undergoes only 200 cycles under same conditions. A prototype 440 Wh kg−1 pouch cell (5.3 Ah), with a low negative/positive capacity ratio of 1.8 and lean electrolytes of 2.1 g Ah−1, achieves 130 cycles.
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Acknowledgements
J.-Q.H. acknowledges support by the National Key Research and Development Program (2021YFB2400300 and 2021YFB2500300) and Beijing Natural Science Foundation (JQ20004). X.-Q.Z. acknowledges support by the National Natural Science Foundation of China (22209010), China Postdoctoral Science Foundation (2021M700404) and Beijing Institute of Technology Research Fund Program for Young Scholars. X.C. acknowledges support by National Natural Science Foundation of China (22109086). We also acknowledge the support from Tsinghua National Laboratory for Information Science and Technology for theoretical simulations. We thank G.-X. Liu, J.-X. Tian, S.-Y. Sun, X.-Q. Ding and Y.-Q. Li for their helpful discussions.
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J.-Q.H. and X.-Q.Z. conceived and designed the experiments. Q.-K.Z. assembled the coin cells and pouch cells. Q.-K.Z., X.-Q.Z., J.X., L.-P.H. and B.-Q.L. carried out material characterizations and electrochemical measurements. J.W. and R.W. performed in situ AFM characterization. T.-L.S carried out the ToF-SIMS tests. N.Y. and X.C. performed the MD simulations. J.-Q.H. supervised this project. All authors engaged in result discussions. X.-Q.Z, M.-Y.Z, H.-J.P., Q.Z. and J.-Q.H. co-wrote the paper with input from all authors.
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A patent related to the work has been submitted (application number CN202210942310.X) by Beijing Institute of Technology. The inventors are Jia-Qi Huang, Qian-Kui Zhang and Xue-Qiang Zhang. The patent refers to the methodology in this paper but provides more analogous additives than this work. The other authors declare no competing interests.
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Zhang, QK., Zhang, XQ., Wan, J. et al. Homogeneous and mechanically stable solid–electrolyte interphase enabled by trioxane-modulated electrolytes for lithium metal batteries. Nat Energy 8, 725–735 (2023). https://doi.org/10.1038/s41560-023-01275-y
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DOI: https://doi.org/10.1038/s41560-023-01275-y
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