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Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte


By increasing the charging voltage, a cell specific energy of >400 W h kg−1 is achievable with LiNi0.8Mn0.1Co0.1O2 in Li metal batteries. However, stable cycling of high-nickel cathodes at ultra-high voltages is extremely challenging. Here we report that a rationally designed sulfonamide-based electrolyte enables stable cycling of commercial LiNi0.8Co0.1Mn0.1O2 with a cut-off voltage up to 4.7 V in Li metal batteries. In contrast to commercial carbonate electrolytes, the electrolyte not only suppresses side reactions, stress-corrosion cracking, transition-metal dissolution and impedance growth on the cathode side, but also enables highly reversible Li metal stripping and plating leading to a compact morphology and low pulverization. Our lithium-metal battery delivers a specific capacity >230 mA h g−1 and an average Coulombic efficiency >99.65% over 100 cycles. Even under harsh testing conditions, the 4.7 V lithium-metal battery can retain >88% capacity for 90 cycles, advancing practical lithium-metal batteries.

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Fig. 1: Challenges for durable high-voltage Li || NMC811 cells.
Fig. 2: Electrochemical performances of Li || NMC811 cells using different electrolytes.
Fig. 3: Characterizations of cathode–electrolyte side reactions and CEIs at 4.7 V cut-off voltage.
Fig. 4: Structural characterizations of the cycled NMC811 cathodes with different electrolytes.
Fig. 5: Proposed stress-corrosion cracking (SCC) mechanism for polycrystalline cathodes and its suppression by limiting reaction-product solubilities in the liquid electrolyte.
Fig. 6: Electrochemical performance and characterizations of the LMA in different electrolytes.
Fig. 7: Electrochemical performance of Li || NMC811 cells under practical conditions.

Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information.


  1. 1.

    Li, W., Erickson, E. M. & Manthiram, A. High-nickel layered oxide cathodes for lithium-based automotive batteries. Nat. Energy 5, 26–34 (2020).

    Google Scholar 

  2. 2.

    Xue, W. et al. Intercalation-conversion hybrid cathodes enabling Li–S full-cell architectures with jointly superior gravimetric and volumetric energy densities. Nat. Energy 4, 374–382 (2019).

    Google Scholar 

  3. 3.

    Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).

    Google Scholar 

  4. 4.

    Xue, W. et al. Gravimetric and volumetric energy densities of lithium-sulfur batteries. Curr. Opin. Electrochem. 6, 92–99 (2017).

    Google Scholar 

  5. 5.

    Manthiram, A., Song, B. & Li, W. A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries. Energy Storage Mater. 6, 125–139 (2017).

    Google Scholar 

  6. 6.

    Noh, H.-J., Youn, S., Yoon, C. S. & Sun, Y.-K. Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x=1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries. J. Power Sources 233, 121–130 (2013).

    Google Scholar 

  7. 7.

    Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).

    Google Scholar 

  8. 8.

    Niu, C. et al. Self-smoothing anode for achieving high-energy lithium metal batteries under realistic conditions. Nat. Nanotechnol. 14, 594–601 (2019).

    Google Scholar 

  9. 9.

    Li, W., Song, B. & Manthiram, A. High-voltage positive electrode materials for lithium-ion batteries. Chem. Soc. Rev. 46, 3006–3059 (2017).

    Google Scholar 

  10. 10.

    Ahmed, S. et al. Cost of automotive lithium-ion batteries operating at high upper cutoff voltages. J. Power Sources 403, 56–65 (2018).

    Google Scholar 

  11. 11.

    Jung, R., Metzger, M., Maglia, F., Stinner, C. & Gasteiger, H. A. Chemical versus electrochemical electrolyte oxidation on NMC111, NMC622, NMC811, LNMO, and conductive carbon. J. Phys. Chem. Lett. 8, 4820–4825 (2017).

    Google Scholar 

  12. 12.

    Xue, W. et al. FSI-inspired solvent and ‘full fluorosulfonyl’ electrolyte for 4 V class lithium-metal batteries. Energy Environ. Sci. 13, 212–220 (2020).

    Google Scholar 

  13. 13.

    Suo, L. et al. Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proc. Natl Acad. Sci. USA 115, 1156–1161 (2018).

    Google Scholar 

  14. 14.

    Ma, L., Nie, M., Xia, J. & Dahn, J. R. A systematic study on the reactivity of different grades of charged Li[NixMnyCoz]O2 with electrolyte at elevated temperatures using accelerating rate calorimetry. J. Power Sources 327, 145–150 (2016).

    Google Scholar 

  15. 15.

    Jung, R., Metzger, M., Maglia, F., Stinner, C. & Gasteiger, H. A. Oxygen release and its effect on the cycling stability of LiNixMnyCozO2(NMC) cathode materials for Li-ion batteries. J. Electrochem. Soc. 164, A1361–A1377 (2017).

    Google Scholar 

  16. 16.

    Laszczynski, N., Solchenbach, S., Gasteiger, H. A. & Lucht, B. L. Understanding electrolyte decomposition of graphite/NCM811 cells at elevated operating voltage. J. Electrochem. Soc. 166, A1853–A1859 (2019).

    Google Scholar 

  17. 17.

    Ryu, H.-H., Park, K.-J., Yoon, C. S. & Sun, Y.-K. Capacity fading of Ni-rich Li[NixCoyMn1–xy]O2 (0.6 ≤ x ≤ 0.95) cathodes for high-energy-density lithium-ion batteries: bulk or surface degradation? Chem. Mater. 30, 1155–1163 (2018).

    Google Scholar 

  18. 18.

    Xu, G.-L. et al. Building ultraconformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes. Nat. Energy 4, 484–494 (2019).

    Google Scholar 

  19. 19.

    Li, W., Kim, U. H., Dolocan, A., Sun, Y. K. & Manthiram, A. Formation and inhibition of metallic lithium microstructures in lithium batteries driven by chemical crossover. ACS Nano 11, 5853–5863 (2017).

    Google Scholar 

  20. 20.

    Xue, W. et al. Manipulating sulfur mobility enables advanced Li-S batteries. Matter 1, 1047–1060 (2019).

    Google Scholar 

  21. 21.

    Xue, W. et al. Double-oxide sulfur host for advanced lithium-sulfur batteries. Nano Energy 38, 12–18 (2017).

    Google Scholar 

  22. 22.

    Li, S. et al. Developing high‐performance lithium metal anode in liquid electrolytes: challenges and progress. Adv. Mater. 30, 1706375 (2018).

    Google Scholar 

  23. 23.

    Kushima, A. et al. Liquid cell transmission electron microscopy observation of lithium metal growth and dissolution: root growth, dead lithium and lithium flotsams. Nano Energy 32, 271–279 (2017).

    Google Scholar 

  24. 24.

    Xu, H. et al. Surpassing lithium metal rechargeable batteries with self-supporting Li–Sn–Sb foil anode. Nano Energy 74, 104815 (2020).

    Google Scholar 

  25. 25.

    Tatara, R. et al. Enhanced cycling performance of Ni-rich positive electrodes (NMC) in Li-ion batteries by reducing electrolyte free-solvent activity. ACS Appl. Mater. Interfaces 11, 34973–34988 (2019).

    Google Scholar 

  26. 26.

    Fan, X. et al. Highly fluorinated interphases enable high-voltage Li-metal batteries. Chem 4, 174–185 (2018).

    Google Scholar 

  27. 27.

    Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018).

    Google Scholar 

  28. 28.

    Fan, X. et al. All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents. Nat. Energy 4, 882–890 (2019).

    Google Scholar 

  29. 29.

    Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).

    Google Scholar 

  30. 30.

    Cao, X. et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat. Energy 4, 796–805 (2019).

    Google Scholar 

  31. 31.

    Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).

    Google Scholar 

  32. 32.

    Zheng, Q. et al. A cyclic phosphate-based battery electrolyte for high voltage and safe operation. Nat. Energy 5, 291–298 (2020).

    Google Scholar 

  33. 33.

    Shyamsunder, A. et al. Inhibiting polysulfide shuttle in lithium–sulfur batteries through low-ion-pairing salts and a triflamide solvent. Angew. Chem. Int. Ed. 56, 6192–6197 (2017).

    Google Scholar 

  34. 34.

    Feng, S. et al. Molecular design of stable sulfamide- and sulfonamide-based electrolytes for aprotic Li-O2 batteries. Chem 5, 2630–2641 (2019).

    Google Scholar 

  35. 35.

    Kim, U. H. et al. Microstructure‐controlled Ni‐rich cathode material by microscale compositional partition for next‐generation electric vehicles. Adv. Energy Mater. 9, 1803902 (2019).

    Google Scholar 

  36. 36.

    Park, G.-T., Ryu, H.-H., Park, N.-Y., Yoon, C. S. & Sun, Y.-K. Tungsten doping for stabilization of Li[Ni0.90Co0.05Mn0.05]O2 cathode for Li-ion battery at high voltage. J. Power Sources 442, 227242 (2019).

    Google Scholar 

  37. 37.

    Eftekhari, A. Energy efficiency: a critically important but neglected factor in battery research. Sustain. Energy Fuels 1, 2053–2060 (2017).

    Google Scholar 

  38. 38.

    Pritzl, D., Solchenbach, S., Wetjen, M. & Gasteiger, H. A. Analysis of vinylene carbonate (VC) as additive in graphite/LiNi0.5Mn1.5O4 cells. J. Electrochem. Soc. 164, A2625–A2635 (2017).

    Google Scholar 

  39. 39.

    Ma, T. et al. Revisiting the corrosion of the aluminum current collector in lithium-ion batteries. J. Phys. Chem. Lett. 8, 1072–1077 (2017).

    Google Scholar 

  40. 40.

    Sun, H.-H. & Manthiram, A. Impact of microcrack generation and surface degradation on a nickel-rich layered Li[Ni0.9Co0.05Mn0.05]O2 cathode for lithium-ion batteries. Chem. Mater. 29, 8486–8493 (2017).

    Google Scholar 

  41. 41.

    Liu, H. et al. Intergranular cracking as a major cause of long-term capacity fading of layered cathodes. Nano Lett. 17, 3452–3457 (2017).

    Google Scholar 

  42. 42.

    Li, W., Dolocan, A., Li, J., Xie, Q. & Manthiram, A. Ethylene carbonate-free electrolytes for high-nickel layered oxide cathodes in lithium-ion batteries. Adv. Energy Mater. 9, 1901152 (2019).

    Google Scholar 

  43. 43.

    Yan, P. et al. Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries. Nat. Energy 3, 600–605 (2018).

    Google Scholar 

  44. 44.

    Kim, J. et al. Controllable solid electrolyte interphase in nickel-rich cathodes by an electrochemical rearrangement for stable lithium-ion batteries. Adv. Mater. 30, 1704309 (2018).

    Google Scholar 

  45. 45.

    Cha, H. et al. Boosting reaction homogeneity in high‐energy lithium‐ion battery cathode materials. Adv. Mater. 32, 2003040 (2020).

    Google Scholar 

  46. 46.

    Zhang, F. et al. Surface regulation enables high stability of single-crystal lithium-ion cathodes at high voltage. Nat. Commun. 11, 3050 (2020).

    Google Scholar 

  47. 47.

    Friedrich, F. et al. Capacity fading mechanisms of NCM-811 cathodes in lithium-ion batteries studied by X-ray diffraction and other diagnostics. J. Electrochem. Soc. 166, A3760–A3774 (2019).

    Google Scholar 

  48. 48.

    Xu, R., Sun, H., de Vasconcelos, L. S. & Zhao, K. Mechanical and structural degradation of LiNixMnyCozO2 cathode in Li-ion batteries: an experimental study. J. Electrochem. Soc. 164, A3333–A3341 (2017).

    Google Scholar 

  49. 49.

    Yao, Y.-X. et al. Regulating interfacial chemistry in lithium-ion batteries by a weakly-solvating electrolyte. Angew. Chem. Int. Ed. 60, 4090–4097 (2020).

    Google Scholar 

  50. 50.

    Yu, Y. et al. Coupled LiPF6 decomposition and carbonate dehydrogenation enhanced by highly covalent metal oxides in high-energy Li-ion batteries. J. Phys. Chem. C 122, 27368–27382 (2018).

    Google Scholar 

  51. 51.

    Wolf, M., May, B. M. & Cabana, J. Visualization of electrochemical reactions in battery materials with X-ray microscopy and mapping. Chem. Mater. 29, 3347–3362 (2017).

    Google Scholar 

  52. 52.

    Yu, Y. et al. Revealing electronic signatures of lattice oxygen redox in lithium ruthenates and implications for high-energy Li-ion battery material designs. Chem. Mater. 31, 7864–7876 (2019).

    Google Scholar 

  53. 53.

    Evans, J., Vincent, C. A. & Bruce, P. G. Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 28, 2324–2328 (1987).

    Google Scholar 

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We acknowledge support by the Department of Energy, Basic Energy Sciences, under award number DE-SC0002633 (Chemomechanics of Far-From-Equilibrium Interfaces). We acknowledge the cathodes provided by the US Department of Energy CAMP Facility, Argonne National Laboratory, and the LiFSI salt by KISCO. This work made use of the Material Research Science and Engineering Center Shared Experimental Facilities supported by the National Science Foundation under award number DMR-1419807. Z.S. acknowledges the research grant at the Department of Materials Science and Engineering at the Massachusetts Institute of Technology. This work used resources of the beamline FXI/18ID of the National Synchrotron Light Source II, a US Department of Energy Office of Science User Facility operated for the Department of Energy Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. This work used resources of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy Office of Science by Argonne National Laboratory, and was supported by the US Department of Energy under contract no. DE-AC02-06CH11357 and the Canadian Light Source and its funding partners. J. Lopez acknowledges support by an appointment to the Intelligence Community Postdoctoral Research Fellowship Program at the Massachusetts Institute of Technology, administered by Oak Ridge Institute for Science and Education through an interagency agreement between the US Department of Energy and the Office of the Director of National Intelligence. We also thank C. Mao at Zhu Hai Smooth Way Company for valuable suggestions and G. Leverick from Y. Shao-Horn’s group at the Massachusetts Institute of Technology for the support in measuring the water content by Karl Fisher titration.

Author information




W.X., Y.D., J.A.J., Y.S.-H. and J. Li conceived the concept and the project. M.H., W.Z. and S.L. synthesized the solvent. W.X. designed the electrolyte and conducted electrochemical measurements. Y.L. conducted TOF-SIMS measurements and analysed the results. Y.G.Z. conducted in situ DEMS measurements. R.G. conducted focused ion beam and TEM analysis. W.X., X.X., D.Y., Z.S., C-J.S., I.H. and W.-K.L. conducted in situ synchrotron-based FXI measurements and analysed the results. P.L. conducted ICP-MS measurements. W.X., G.X., J. Lopez, W.F. and R.X. conducted other characterizations. W.X., Y.D., Y.Y., Y.S.-H, J.A.J. and J. Li wrote and revised the manuscript. All authors discussed the results and reviewed the manuscript.

Corresponding authors

Correspondence to Yanhao Dong or Yang Shao-Horn or Jeremiah A. Johnson or Ju Li.

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The authors declare no competing interests.

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Peer review information Nature Energy thanks Corsin Battaglia and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–23, Tables 1–6, note and references.

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Xue, W., Huang, M., Li, Y. et al. Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte. Nat Energy 6, 495–505 (2021).

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