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Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization

Abstract

Lithium (Li) pulverization and associated large volume expansion during cycling is one of the most critical barriers for the safe operation of Li-metal batteries. Here, we report an approach to minimize the Li pulverization using an electrolyte based on a fluorinated orthoformate solvent. The solid–electrolyte interphase (SEI) formed in this electrolyte clearly exhibits a monolithic feature, which is in sharp contrast with the widely reported mosaic- or multilayer-type SEIs that are not homogeneous and could lead to uneven Li stripping/plating and fast Li and electrolyte depletion over cycling. The highly homogeneous and amorphous SEI not only prevents dendritic Li formation, but also minimizes Li loss and volumetric expansion. Furthermore, this new electrolyte strongly suppresses the phase transformation of the LiNi0.8Co0.1Mn0.1O2 cathode (from layered structure to rock salt) and stabilizes its structure. Tests of high-voltage Li||NMC811 cells show long-term cycling stability and high rate capability, as well as reduced safety concerns.

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Fig. 1: SEI on the Li anode.
Fig. 2: Electrochemical performances of different electrolytes.
Fig. 3: Li consumption and volumetric expansion after 100 cycles in Li||NMC811 cells.
Fig. 4: SEI information obtained by XPS measurement on Li electrodes after 100 cycles in Li||NMC811 cells with electrolytes.
Fig. 5: Structural and CEI/SEI properties of the electrodes.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

This work has been supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, of the US Department of Energy (DOE), through the Advanced Battery Materials Research program (Battery500 Consortium) under contract number DE-AC02-05CH11231. The SEM, TEM and XPS were conducted in the William R. Wiley Environmental Molecular Sciences Laboratory—a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory. The Pacific Northwest National Laboratory is operated by Battelle for the DOE under the contract DE-AC05-76RL01830. The LiFSI salt was provided by K. Murata of Nippon Shokubai.

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J.-G.Z., W.X. and X.C. proposed the research and designed the experiments. X.C. performed the electrochemical measurements and conducted the SEM observations, with help from X.R. L.Z., B.E.M., B.W.A. and C.W. performed the focused-ion-beam SEM and TEM. M.H.E. performed the XPS measurements. H.W., W.H. and Y.C. carried out the cryo-EM. C.N. and H.L. prepared the NMC811 electrodes. X.C., W.X. and J.-G.Z. prepared the manuscript, with input from all other co-authors.

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Correspondence to Wu Xu or Ji-Guang Zhang.

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Cao, X., Ren, X., Zou, L. et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat Energy 4, 796–805 (2019). https://doi.org/10.1038/s41560-019-0464-5

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