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Electrolyte design for Li-ion batteries under extreme operating conditions

Nature volume 614, pages 694–700 (2023)Cite this article

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Abstract

The ideal electrolyte for the widely used LiNi0.8Mn0.1Co0.1O2 (NMC811)||graphite lithium-ion batteries is expected to have the capability of supporting higher voltages (≥4.5 volts), fast charging (≤15 minutes), charging/discharging over a wide temperature range (±60 degrees Celsius) without lithium plating, and non-flammability1,2,3,4. No existing electrolyte simultaneously meets all these requirements and electrolyte design is hindered by the absence of an effective guiding principle that addresses the relationships between battery performance, solvation structure and solid-electrolyte-interphase chemistry5. Here we report and validate an electrolyte design strategy based on a group of soft solvents that strikes a balance between weak Li+–solvent interactions, sufficient salt dissociation and desired electrochemistry to fulfil all the aforementioned requirements. Remarkably, the 4.5-volt NMC811||graphite coin cells with areal capacities of more than 2.5 milliampere hours per square centimetre retain 75 per cent (54 per cent) of their room-temperature capacity when these cells are charged and discharged at −50 degrees Celsius (−60 degrees Celsius) at a C rate of 0.1C, and the NMC811||graphite pouch cells with lean electrolyte (2.5 grams per ampere hour) achieve stable cycling with an average Coulombic efficiency of more than 99.9 per cent at −30 degrees Celsius. The comprehensive analysis further reveals an impedance matching between the NMC811 cathode and the graphite anode owing to the formation of similar lithium-fluoride-rich interphases, thus effectively avoiding lithium plating at low temperatures. This electrolyte design principle can be extended to other alkali-metal-ion batteries operating under extreme conditions.

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Fig. 1: Electrolyte design strategies.
Fig. 2: Physical properties of the electrolytes.
Fig. 3: Electrochemical performance of NMC811||graphite full cells.
Fig. 4: Characterization of SEI layers on graphite anode after cycling at −30 °C.

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The data that support the findings of this study are available within this article and its Supplementary information. Additional data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US DOE through the Applied Battery Research for Transportation (ABRT) programme under contract number DE-SC0012704. Research was sponsored by the Army Research Laboratory and was accomplished under cooperative agreement number W911NF-20-2-0284. This research used beamline 28-ID-2 of the National Synchrotron Light Source II, a US DOE Office of Science user facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704.

Author information

Authors and Affiliations

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

    Jijian Xu, Jiaxun Zhang, Singyuk Hou, Hongli Wan & Chunsheng Wang

  2. Battery Science Branch, Army Research Directorate, US DEVCOM Army Research Laboratory, Adelphi, MA, USA

    Travis P. Pollard, Kang Xu & Oleg Borodin

  3. Department of Chemistry, Rutgers, The State University of New Jersey, Newark, NJ, USA

    Qingdong Li & Huixin He

  4. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Sha Tan, Enyuan Hu & Xiao-Qing Yang

  5. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, USA

    Fu Chen

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Contributions

J.X. and C.W. conceived the idea for the project. J.X., J.Z., H.W. and S.H. prepared the materials and performed electrochemical experiments. T.P.P., K.X. and O.B. conducted the quantum chemistry calculations and MD simulations. F.C. carried out the NMR analysis. J.L. and H.H. performed the AFM measurements. S.T., E.H. and X.-Q.Y. conducted the PDF experiments. All the authors discussed the results, analysed the data and drafted the manuscript.

Corresponding authors

Correspondence to Oleg Borodin or Chunsheng Wang.

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Extended data figures and tables

Extended Data Fig. 1 Illustration of the capacity matching and kinetic matching.

a, Thick interface between the commercial carbonate-based electrolyte and lithiated graphite anodes. b, Self-limiting interface between the designed electrolyte and lithiated graphite anodes. c-e, Schematic illustration of (c) capacity mismatching and (d) capacity matching as a function of charge rate or charge temperature, as well as (e) resistance matching between anode and cathode.

Extended Data Fig. 2 X-ray measurements and MD simulation results.

a, b, A structure factor S(Q) from X-ray measurements (solid black line) and MD simulations (blue dash) for 1M LiTFSI in MDFA/MDFSA–TTE electrolyte and two dominating solvents MDFA and TTE. S(Q) for MDFA and TTE were shifted by −1.5 and 3.0.

Extended Data Fig. 3 MD simulation results.

a, b, A snapshot of MD simulation box of LiTFSI in MDFA (a) and 1M LiTFSI in MDFA/MDFSA–TTE (b) from MD simulations at 25 °C. Solvent is shown as wireframe. c, Li+(MDFA)4 free Li+ (solvent separated from TFSI−) from MD simulation of 1M LiTFSI in MDFA/MDFSA–TTE (b, c) at 25 °C. Jmol colour scheme are used: Li – purple, N – blue, F – green, S – yellow, C – grey, O –red, H – white. d, Ion and solvent self-diffusion coefficients from MD simulations of 1M LiTFSI in MDFA/MDFSA–TTE electrolyte. e, Conductivity of 1M LiTFSI in MDFA-MDFSA–TTE electrolyte from MD simulations and experiments.

Extended Data Fig. 4 Rate performance of polycrystalline NMC811||graphite pouch cells at 25 °C.

a-f, Pouch cells with different amount of 1M LiTFSI MDFA/MDFSA–TTE electrolyte under 3C (a, c, e), and 4C (b, d, f).

Extended Data Fig. 5 Cycling performance at ultralow temperature.

Cycling performance of NMC811||graphite full cells at 0.1C under −50/60 °C.

Extended Data Fig. 6 Kinetic analysis of the low-temperature process.

a, Cell illustration of three-electrode set up for kinetic analysis. b, Cell voltage and electrode potential of NMC811||graphite pouch cells in 0.2C under −30 °C. c, d, Nyquist impedance plots and fitted lines using the equivalent circuit of the three-electrode cells containing 1M LiTFSI MDFA/MDFSA–TTE electrolyte at (c) 25 °C and (d) −30 °C. Impedance spectra were obtained at 50% SOC.

Extended Data Fig. 7 DFT calculations of reaction energies.

a-c, Reaction energies from PBE+U (red) and SCAN (blue) (units: eV) for dehydrogenation of MDFA on Li0.5NiO2 (a), TTE on Li0.5NiO2 (b), and Li+-MDFSA on Li1.0NiO2 – a single F− ion is present on the surface as well to neutralize the cell (c). Refer to text for explanation of the large energy difference in (c).

Extended Data Table 1 Physical properties of organic solvents used for low-temperature batteries
Full size table
Extended Data Table 2 Summary of MD simulation equilibration and production runs
Full size table

Supplementary information

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Xu, J., Zhang, J., Pollard, T.P. et al. Electrolyte design for Li-ion batteries under extreme operating conditions. Nature 614, 694–700 (2023). https://doi.org/10.1038/s41586-022-05627-8

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