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A cyclic phosphate-based battery electrolyte for high voltage and safe operation

Abstract

The traditional electrolyte for lithium-ion batteries is a combination of 1 M LiPF6 with a cyclic carbonate-based solvent (for example, ethylene carbonate). The lack of a suitable alternative solvent has hindered further exploration of new functional electrolytes. Here we design and synthesize a fluorinated cyclic phosphate solvent, 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxaphospholane 2-oxide (TFEP), for use in lithium-ion batteries. Our design rationale is that this solvent molecule has a fused chemical structure of cyclic carbonates that can form a stable solid electrolyte interphase and organic phosphates that can trap hydrogen radicals and prevent combustion. An electrolyte formula composed of 0.95 M LiN(SO2F)2 in TFEP/2,2,2-trifluoroethyl methyl carbonate shows excellent non-flammability with zero self-extinguishing time and enables the highly stable operation of graphite anodes (~0.1 V versus lithium) and high-voltage LiNi0.5Mn1.5O4 cathodes (~4.7 V versus lithium), and thereby outperforms traditional electrolytes. This work opens up new frontiers in electrolyte developments towards safe lithium-ion batteries with higher energy densities.

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Fig. 1: Design of the fluorinated cyclic phosphate solvent (TFEP).
Fig. 2: Physical properties of the various electrolytes.
Fig. 3: Electrochemical performance of the graphite electrode in a half-cell.
Fig. 4: Graphite surface passivation in the 0.95 M LiFSI in TFEP/FEMC electrolyte.
Fig. 5: Al passivation in the 0.95 M LiFSI in the TFEP/FEMC electrolyte.
Fig. 6: Electrochemical performances of the high-voltage cathodes.
Fig. 7: Comparison of the properties and performances of the 0.95 M LiFSI in TFEP/FEMC and the conventional 1 M LiPF6 in EC/DMC electrolytes.

Data availability

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

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Acknowledgements

This work was supported by JSPS KAKENHI Specially Promoted Research (no. 15H05701 to A.Y. and no. 19H05459 to E.N.). Q.Z. is grateful to the Japan Society for the Promotion of Sciences (JSPS) for a JSPS Fellowship at The University of Tokyo (no. P18332) and the Grant-in-Aid for JSPS Fellows (no. 18F18332).

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Contributions

A.Y. and E.N. conceived and directed the project. Q.Z., Y.Y. and R.S. proposed the concept and designed the experiments. Q.Z. performed the experiments and analysed the data. S.K. performed the XPS measurements. Y.L. conducted the DFT calculations. K.K. performed the electrochemical impedance measurements. All the authors contributed to the discussion. Q.Z., Y.Y. and A.Y. wrote the manuscript, and all the authors contributed to editing the manuscript.

Corresponding authors

Correspondence to Eiichi Nakamura or Atsuo Yamada.

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The authors have submitted a patent on this work with JP application No. 2020-24251.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–20 and Table 1.

Supplementary Video 1

Flammable test for the electrolyte of 1 M LiPF6 in EC/DMC.

Supplementary Video 2

Flammable test for the electrolyte of 0.98 M LiFSI in FEMC.

Supplementary Video 3

Flammable test for the electrolyte of 0.95 M LiFSI in TFEP/FEMC.

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Zheng, Q., Yamada, Y., Shang, R. et al. A cyclic phosphate-based battery electrolyte for high voltage and safe operation. Nat Energy 5, 291–298 (2020). https://doi.org/10.1038/s41560-020-0567-z

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