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Designing phosphazene-derivative electrolyte matrices to enable high-voltage lithium metal batteries for extreme working conditions

Nature Energy volumeΒ 8,Β pages 1023–1033 (2023)Cite this article

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Abstract

The current high-energy lithium metal batteries are limited by their safety and lifespan owing to the lack of suitable electrolyte solutions. Here we report a synergy of fluorinated co-solvent and gelation treatment by a butenoxycyclotriphosphazene (BCPN) monomer, which facilitates the use of ether-based electrolyte solutions for high-energy lithium metal batteries. We show that the safety risks of fire and electrolyte leakage are eliminated by the fluorinated co-solvent and fireproof polymeric matrices. The compatibility with high-energy cathodes is realized by a well-tailored Li+ solvation sheath, along with BCPN-derived protective surface films developed on the cathodes. Our Li | |LiNi0.8Co0.1Mn0.1O2 cells reach high-capacity retention, superior low-temperature performance, good cyclability under high pressure and steady power supply under abusive conditions. Our electrolyte design concept provides a promising path for high energetic, durable and safe rechargeable Li batteries.

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Fig. 1: Design of NGPE and investigation on the solvation structures.
Fig. 2: Safety of the NGPE.
Fig. 3: Interfacial compatibility between NGPE and electrodes.
Fig. 4: Li | NGPE | NCM811 coin cell performance under extreme operating environments.
Fig. 5: Li | NGPE | NCM811 pouch cells performance under abuse conditions.
Fig. 6: 500 mAh pouch cell performance under abuse conditions.

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References

  1. Dunn, B. et al. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).

    ArticleΒ  Google ScholarΒ 

  2. Cui, C. et al. A highly reversible, dendrite-free lithium metal anode enabled by a lithium–fluoride-enriched interphase. Adv. Mater. 32, 1906427 (2020).

    ArticleΒ  Google ScholarΒ 

  3. Liu, B. et al. Advancing lithium metal batteries. Joule 2, 833–845 (2018).

    ArticleΒ  Google ScholarΒ 

  4. Makhlooghiazad, F. et al. Zwitterionic materials with disorder and plasticity and their application as non-volatile solid or liquid electrolytes. Nat. Mater. 21, 228–236 (2022).

    ArticleΒ  Google ScholarΒ 

  5. Xiao, J. How lithium dendrites form in liquid batteries. Science 366, 426–427 (2019).

    ArticleΒ  Google ScholarΒ 

  6. Koch, V. R. et al. The stability of the secondary lithium electrode in tetrahydrofuran-based electrolytes. J. Electrochem. Soc. 125, 1371–1377 (1978).

    ArticleΒ  Google ScholarΒ 

  7. Holoubek, J. et al. Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature. Nat. Energy 6, 303–313 (2021).

    ArticleΒ  Google ScholarΒ 

  8. Park, M. S. et al. A highly reversible lithium metal anode. Sci. Rep. 4, 3815 (2014).

    ArticleΒ  Google ScholarΒ 

  9. Zhou, D. et al. Polymer electrolytes for lithium-based batteries: advances and prospects. Chem 5, 2326–2352 (2019).

    ArticleΒ  Google ScholarΒ 

  10. Zhang, Z. et al. Fluorinated electrolytes for 5 V lithium-ion battery chemistry. Energy Environ. Sci. 6, 1806–1810 (2013).

    ArticleΒ  Google ScholarΒ 

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

    ArticleΒ  Google ScholarΒ 

  12. Jaumaux, P. et al. Non-flammable liquid and quasi-solid electrolytes toward highly-safe alkali metal-based batteries. Adv. Funct. Mater. 31, 2008644 (2021).

    ArticleΒ  Google ScholarΒ 

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

    ArticleΒ  Google ScholarΒ 

  14. Tan, L. et al. Intrinsic nonflammable ether electrolytes for ultrahigh-voltage lithium metal batteries enabled by chlorine functionality. Angew. Chem. Int. Ed. 61, e202203693 (2022).

    ArticleΒ  Google ScholarΒ 

  15. Wang, X. et al. Nonflammable trimethyl phosphate solvent-containing electrolytes for lithium-ion batteries: I. fundamental properties. J. Electrochem. Soc. 148, A1058 (2001).

    ArticleΒ  Google ScholarΒ 

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

    ArticleΒ  Google ScholarΒ 

  17. Guan, X. et al. In-situ crosslinked single ion gel polymer electrolyte with superior performances for lithium metal batteries. Chem. Eng. J. 382, 122935 (2020).

    ArticleΒ  Google ScholarΒ 

  18. Miao, R. et al. PVDF-HFP-based porous polymer electrolyte membranes for lithium-ion batteries. J. Power Sources 184, 420–426 (2008).

    ArticleΒ  Google ScholarΒ 

  19. VondrΓ‘k, J. et al. Gel polymer electrolytes based on PMMA. Electrochim. Acta 46, 2047–2048 (2001).

    ArticleΒ  Google ScholarΒ 

  20. Xu, G. et al. Prescribing functional additives for treating the poor performances of high-voltage (5 V-class) LiNi0.5Mn1.5O4/MCMB Li-ion batteries. Adv. Energy Mater. 8, 1701398 (2018).

    ArticleΒ  Google ScholarΒ 

  21. He, M. et al. High voltage LiNi0.5Mn0.3Co0.2O2/graphite cell cycled at 4.6 V with a FEC/HFDEC-based electrolyte. Adv. Energy Mater. 7, 1700109 (2017).

    ArticleΒ  Google ScholarΒ 

  22. von Aspern, N. et al. Fluorine and lithium: ideal partners for high-performance rechargeable battery electrolytes. Angew. Chem. Int. Ed. 58, 15978–16000 (2019).

    ArticleΒ  Google ScholarΒ 

  23. Yamada, Y. et al. Advances and issues in developing salt-concentrated battery electrolytes. Nat. Energy 4, 269–280 (2019).

    ArticleΒ  Google ScholarΒ 

  24. Chen, X. et al. Atomic insights into the fundamental interactions in lithium battery electrolytes. Acc. Chem. Res. 53, 1992–2002 (2020).

    ArticleΒ  Google ScholarΒ 

  25. Kim, S. C. et al. Potentiometric measurement to probe solvation energy and its correlation to lithium battery cyclability. J. Am. Chem. Soc. 143, 10301–10308 (2021).

    ArticleΒ  Google ScholarΒ 

  26. Abraham, K. M. et al. Highly conductive PEO-like polymer electrolytes. Chem. Mater. 9, 1978–1988 (1997).

    ArticleΒ  Google ScholarΒ 

  27. Zhou, D. et al. Stable conversion chemistry-cased lithium metal batteries enabled by hierarchical multifunctional polymer electrolytes with near-single ion conduction. Angew. Chem. Int. Ed. 58, 6001–6006 (2019).

    ArticleΒ  Google ScholarΒ 

  28. Chao, P. et al. Novel phosphorus–nitrogen–silicon flame retardants and their application in cycloaliphatic epoxy systems. Polym. Chem. 6, 2977–2985 (2015).

    ArticleΒ  Google ScholarΒ 

  29. Chen, S. et al. Progress and future prospects of high-voltage and high-safety electrolytes in advanced lithium batteries: from liquid to solid electrolytes. J. Mater. Chem. A 6, 11631–11663 (2018).

    ArticleΒ  Google ScholarΒ 

  30. Adams, B. D. et al. Accurate determination of coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8, 1702097 (2018).

    ArticleΒ  Google ScholarΒ 

  31. Jiang, L. et al. Inhibiting solvent co-intercalation in a graphite anode by a localized high-concentration electrolyte in fast-charging batteries. Angew. Chem. Int. Ed. 60, 3402–3406 (2021).

    ArticleΒ  Google ScholarΒ 

  32. Li, Y. et al. High-safety and high-voltage lithium metal batteries enabled by a nonflammable ether-based electrolyte with phosphazene as a cosolvent. ACS Appl. Mater. Interfaces 13, 10141–10148 (2021).

    ArticleΒ  Google ScholarΒ 

  33. Boukamp, B. A. et al. Fast ionic conductivity in lithium nitride. Mater. Res. Bull. 13, 23–32 (1978).

    ArticleΒ  Google ScholarΒ 

  34. Feng, Z. et al. In-situ formation of hybrid Li3PO4–AlPO4–Al(PO3)3 coating layer on LiNi0.8Co0.1Mn0.1O2 cathode with enhanced electrochemical properties for lithium-ion battery. Chem. Eng. J. 382, 122959 (2020).

    ArticleΒ  Google ScholarΒ 

  35. McBrayer, J. D. et al. Mechanical studies of the solid electrolyte interphase on anodes in lithium and lithium ion batteries. Nanotechnology 32, 502005 (2021).

    ArticleΒ  Google ScholarΒ 

  36. Chen, C. et al. Impact of dual-layer solid-electrolyte interphase inhomogeneities on early-stage defect formation in Si electrodes. Nat. Commun. 11, 3283 (2020).

    ArticleΒ  Google ScholarΒ 

  37. Yoon, I. et al. Measurement of mechanical and fracture properties of solid electrolyte interphase on lithium metal anodes in lithium ion batteries. Energy Stor. Mater. 25, 296–304 (2020).

    Google ScholarΒ 

  38. Verma, A. et al. Mechanistic analysis of mechano-electrochemical interaction in silicon electrodes with surface film. J. Electrochem. Soc. 164, A3570 (2017).

    ArticleΒ  Google ScholarΒ 

  39. Zheng, J. et al. 3D visualization of inhomogeneous multi-layered structure and Young’s modulus of the solid electrolyte interphase (SEI) on silicon anodes for lithium ion batteries. Phys. Chem. Chem. Phys. 16, 13229–13238 (2014).

    ArticleΒ  Google ScholarΒ 

  40. Zou, L. et al. Solid–liquid interfacial reaction trigged propagation of phase transition from surface into bulk lattice of Ni-rich layered cathode. Chem. Mater. 30, 7016–7026 (2018).

    ArticleΒ  Google ScholarΒ 

  41. Li, Y. et al. High-safety and high-voltage lithium metal batteries enabled by a nonflammable ether-based electrolyte with phosphazene as a cosolvent. ACS Appl. Mater. Inter. 13, 10141–10148 (2021).

    ArticleΒ  Google ScholarΒ 

  42. Morita, M. et al. Anodic behavior of aluminum current collector in LiTFSI solutions with different solvent compositions. J. Power Sources 119–121, 784–788 (2003).

    ArticleΒ  Google ScholarΒ 

  43. von Wald Cresce, A. et al. Anion solvation in carbonate-based electrolytes. J. Phys. Chem. C. 119, 27255–27264 (2015).

    ArticleΒ  Google ScholarΒ 

  44. Liu, X. et al. Conformal prelithiation nanoshell on LiCoO2 enabling high-energy lithium-ion batteries. Nano Lett. 20, 4558–4565 (2020).

    ArticleΒ  Google ScholarΒ 

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

    ArticleΒ  Google ScholarΒ 

  46. Chen, S. et al. Strongly solvating ether electrolytes for high-voltage lithium metal batteries. ACS Appl. Mater. Interfaces 15, 13155–13164 (2023).

    ArticleΒ  Google ScholarΒ 

  47. Gwon, H. et al. Recent progress on flexible lithium rechargeable batteries. Energy Environ. Sci. 7, 538–551 (2014).

    ArticleΒ  Google ScholarΒ 

  48. Li, W. et al. High-voltage positive electrode materials for lithium-ion batteries. Chem. Soc. Rev. 46, 3006–3059 (2017).

    ArticleΒ  Google ScholarΒ 

  49. Liu, X. et al. Thermal runaway of lithium-ion batteries without internal short circuit. Joule 2, 2047–2064 (2018).

    ArticleΒ  Google ScholarΒ 

  50. Feng, X. et al. Mitigating thermal runaway of lithium-ion batteries. Joule 4, 743–770 (2020).

    ArticleΒ  Google ScholarΒ 

  51. Wu, J. et al. A synergistic exploitation to produce high-voltage quasi-solid-state lithium metal batteries. Nat. Commun. 12, 5746 (2021).

    ArticleΒ  Google ScholarΒ 

  52. Xu, K. β€œCharge-transfer” process at graphite/electrolyte interface and the solvation sheath structure of Li+ in nonaqueous electrolytes. J. Electrochem. Soc. 154, A162 (2007).

    ArticleΒ  Google ScholarΒ 

  53. Xu, K. et al. Solvation sheath of Li+ in nonaqueous electrolytes and its implication of graphite/electrolyte interface chemistry. J. Phys. Chem. C. 111, 7411–7421 (2007).

    ArticleΒ  Google ScholarΒ 

  54. Zhang, L. et al. Synthesis design of interfacial nanostructure for nickel–rich layered cathodes. Nano Energy 97, 107119 (2022).

    ArticleΒ  Google ScholarΒ 

  55. Wu, Y. et al. High-voltage and high-safety practical lithium batteries with ethylene carbonate-free electrolyte. Adv. Energy Mater. 11, 2102299 (2021).

    ArticleΒ  Google ScholarΒ 

  56. Ji, Y. et al. Toward a stable electrochemical interphase with enhanced safety on high-voltage LiCoO2 cathode: a case of phosphazene additives. J. Power Sources 359, 391–399 (2017).

    ArticleΒ  Google ScholarΒ 

  57. Wan, T. H. et al. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim. Acta 184, 483–499 (2015).

    ArticleΒ  Google ScholarΒ 

  58. Lu, Y. et al. The timescale identification decoupling complicated kinetic processes in lithium batteries. Joule 6, 1172–1198 (2022).

    ArticleΒ  Google ScholarΒ 

  59. Thompson, A. P. et al. LAMMPSβ€”a flexible simulation tool for particle-based materials modeling at the atomic, meso, and continuum scales. Comput. Phys. Commun. 271, 108171 (2022).

    ArticleΒ  MATHΒ  Google ScholarΒ 

  60. Jorgensen, W. L. et al. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).

    ArticleΒ  Google ScholarΒ 

  61. Bayly, C. I. et al. A well-behaved electrostatic potential based method using charge restraints for deriving atomic chargesβ€”the RESP model. J. Phys. Chem. 97, 10269–10280 (1993).

    ArticleΒ  Google ScholarΒ 

  62. Park, C. et al. Molecular simulations of electrolyte structure and dynamics in lithium–sulfur battery solvents. J. Power Sources 373, 70–78 (2018).

    ArticleΒ  Google ScholarΒ 

  63. MartΓ­nez, L. et al. PACKMOL: a package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157–2164 (2009).

    ArticleΒ  Google ScholarΒ 

  64. Stukowski, A. Visualization and analysis of atomistic simulation data with OVITO–the Open Visualization Tool. Model. Simul. Mat. Sci. Eng. 18, 015012 (2009).

    ArticleΒ  Google ScholarΒ 

  65. Holoubek, J. et al. Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature. Nat. Energy 6, 303–313 (2021).

    ArticleΒ  Google ScholarΒ 

  66. Hockney, R. W. et al. Computer Simulation Using Particles (CRC Press, 1988).

  67. Gaussian 16 rev. C.01 (Gaussian Inc., 2016).

  68. Lu, T. et al. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).

    ArticleΒ  Google ScholarΒ 

Download references

Acknowledgements

B.L. acknowledges support by the National Natural Science Foundation of China (number 52072208 and number 52261160384), Shenzhen Science and Technology Program (KCXFZ20211020163810015), the Fundamental Research Project of Shenzhen (number JCYJ20220818101004009), Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N111) and Shenzhen Outstanding Talents Training Fund. G.W. acknowledges the support from Australian Research Council (ARC) Discovery Projects (DP200101249 and DP210101389) and the ARC Research Hub for Integrated Energy Storage Solutions (IH180100020). B.S. acknowledges the financial support from the Australian Research Council (ARC) through the ARC Future Fellowship (FT220100561).

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Author notes

  1. These authors contributed equally: Yuefeng Meng, Dong Zhou.

Authors and Affiliations

  1. Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, China

    Yuefeng Meng,Β Dong Zhou,Β Yao Tian,Β Yifu Gao,Β Yao Wang,Β Feiyu KangΒ &Β Baohua Li

  2. School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yuefeng Meng,Β Yifu GaoΒ &Β Feiyu Kang

  3. School of Chemistry and Materials Science, Guangdong University of Education, Guangzhou, China

    Ruliang Liu

  4. Centre for Clean Energy Technology, School of Mathematical and Physical Sciences, Faculty of Science, University of Technology Sydney, Sydney, New South Wales, Australia

    Bing SunΒ &Β Guoxiu Wang

  5. Centre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Vitoria-Gasteiz, Spain

    Michel Armand

  6. Department of Chemistry and Institute of Nanotechnology & Advanced Materials (BINA), Bar-Ilan University, Ramat Gan, Israel

    Doron Aurbach

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Contributions

D.Z., M.A., B.L. and G.W. conceived and designed this work. Y.M. performed the experiments and wrote the manuscript. Y.G. and Y.T. carried out the computations. R.L., Y.W., B.S., F.K. and D.A. discussed the results and participated in the preparation of the paper.

Corresponding authors

Correspondence to Dong Zhou, Michel Armand, Baohua Li, Guoxiu Wang or Doron Aurbach.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–48, Tables 1–9 and Notes 1–4.

Supplementary Video 1

Combustion test of pure ether electrolyte.

Supplementary Video 2

Combustion test of ether–SFE electrolyte.

Supplementary Video 3

Combustion test of NGPE.

Supplementary Video 4

Leakage test of liquid electrolyte and NGPE.

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Meng, Y., Zhou, D., Liu, R. et al. Designing phosphazene-derivative electrolyte matrices to enable high-voltage lithium metal batteries for extreme working conditions. Nat Energy 8, 1023–1033 (2023). https://doi.org/10.1038/s41560-023-01339-z

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