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Aqueous electrolyte design for super-stable 2.5 V LiMn2O4 || Li4Ti5O12 pouch cells

Nature Energy volume 7, pages 186–193 (2022)Cite this article

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Abstract

To compete with commercial organic electrolytes, aqueous electrolytes beyond water-in-salt electrolytes with a lower salt concentration of <5.0 m (mol kgsolvent–1) and wider electrochemical stability window of >3.0 V are urgently needed. Here we report a 4.5 m lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)–KOH–CO(NH2)2–H2O non-flammable ternary eutectic electrolyte that expands the electrochemical stability window to >3.3 V by forming a robust solid–electrolyte interphase. The ternary eutectic electrolyte enables Li1.5Mn2O4 || Li4Ti5O12 pouch cells to achieve a high average Coulombic efficiency of 99.96% and capacity retention of 92% after 470 cycles at an areal capacity of 2.5 mAh cm–2, a low positive/negative capacity ratio of 1.14 and a lean electrolyte (3 g Ah–1). The Li loss due to the solid–electrolyte interphase formation in the initial charge/discharge cycles is compensated by an excess 0.5 Li in the Li1.5Mn2O4 cathode, which converts the Li1.5Mn2O4 || Li4Ti5O12 cell into LiMn2O4 || Li4Ti5O12 after solid–electrolyte interphase formation. The 2.5 V aqueous Li1.5Mn2O4 || Li4Ti5O12 pouch cells with practical settings demonstrate a promising approach towards safe, low-cost and high-energy aqueous Li-ion batteries.

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Fig. 1: Spectrum analysis of intermolecular interaction.
Fig. 2: The electrochemical stability window of aqueous electrolytes.
Fig. 3: Structural and chemical analysis of SEI layer.
Fig. 4: Electrochemical performances of 2.5 V LiMn2O4 || Li4Ti5O12 and 2.6 V LiVPO4F || Li4Ti5O12 full cells at an areal capacity of 1.5 mAh cm–2.
Fig. 5: Electrochemical performances of 2.5 V LiMn2O4 || Li4Ti5O12 pouch cells.

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The data supporting the findings of this study are available within the article and its Supplementary Information files.

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Acknowledgements

This work was financially supported by the US Department of Energy ARPA-E grant DEAR0000389.

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Author notes

  1. These authors contributed equally: Jijian Xu, Xiao Ji.

Authors and Affiliations

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

    Jijian Xu, Xiao Ji, Jiaxun Zhang, Chongyin Yang, Pengfei Wang, Sufu Liu, Kyle Ludwig, Fu Chen, Peter Kofinas & Chunsheng Wang

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Contributions

J.X. and C.W. conceived the idea for the project. J.X., J.Z. and C.Y. prepared the materials and performed the electrochemical experiments. X.J. conducted the quantum chemistry calculations and molecular dynamics simulations. J.X., P.W. and S.L. conducted the characterizations. K.L. and P.K. completed the differential scanning calorimetry tests. F.C. performed the NMR measurements. All the authors discussed the results, analysed the data and draughted the manuscript.

Corresponding author

Correspondence to Chunsheng Wang.

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Competing interests

J.X., X.J. and C.H. are inventors on the US patent application (application number 2021-158-1) filed by the University of Maryland regarding the electrolytes described in this Article.

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Nature Energy thanks Maria Lukatskaya and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Notes 1–7, Tables 1–6 and Figs. 1–33.

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Xu, J., Ji, X., Zhang, J. et al. Aqueous electrolyte design for super-stable 2.5 V LiMn2O4 || Li4Ti5O12 pouch cells. Nat Energy 7, 186–193 (2022). https://doi.org/10.1038/s41560-021-00977-5

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