Issue

Vol. 17 (2025)

Molecule-Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

https://doi.org/10.1007/s40820-024-01508-z
Qiqi Sun
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Zelong Gong
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Tao Zhang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Jiafeng Li
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Xianli Zhu
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Ruixiao Zhu
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Lingxu Wang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Leyuan Ma
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Xuehui Li
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Miaofa Yuan
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Zhiwei Zhang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Luyuan Zhang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Zhao Qian
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Longwei Yin
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China
Rajeev Ahuja
Condensed Matter Theory, Department of Physics and Astronomy, Uppsala University, Uppsala 75120, Sweden
Chengxiang Wang
Key Laboratory for Liquid‑Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, People’s Republic of China

Corresponding Author: Chengxiang Wang

wcxmat@sdu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 18

Abstract

The risk of flammability is an unavoidable issue for gel polymer electrolytes (GPEs). Usually, flame-retardant solvents are necessary to be used, but most of them would react with anode/cathode easily and cause serious interfacial instability, which is a big challenge for design and application of nonflammable GPEs. Here, a nonflammable GPE (SGPE) is developed by in situ polymerizing trifluoroethyl methacrylate (TFMA) monomers with flame-retardant triethyl phosphate (TEP) solvents and LiTFSI–LiDFOB dual lithium salts. TEP is strongly anchored to PTFMA matrix via polarity interaction between -P = O and -CH2CF3. It reduces free TEP molecules, which obviously mitigates interfacial reactions, and enhances flame-retardant performance of TEP surprisingly. Anchored TEP molecules are also inhibited in solvation of Li+, leading to anion-dominated solvation sheath, which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers. Such coordination structure changes Li+ transport from sluggish vehicular to fast structural transport, raising ionic conductivity to 1.03 mS cm−1 and transfer number to 0.41 at 30 °C. The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm−2, and 4.2 V LiCoO2|SGPE|Li battery delivers high average specific capacity > 120 mAh g−1 over 200 cycles. This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.


Highlights:
1 Nonflammable gel polymer electrolyte (SGPE) is developed by in situ polymerizing trifluoroethyl methacrylate (TFMA) monomers with flame-retardant triethyl phosphate (TEP) solvents and LiTFSI–LiDFOB dual lithium salts.
2 Molecular polarity interaction between TEP and PTFMA mitigates interfacial reactions and changes the solvation of Li+.
3 SGPE forms stable inorganic-rich solid electrolyte interface/cathode electrolyte interface layer, exhibiting well compatibility with Li anode and LiCoO2-type high-voltage cathode.

Keywords

Anchoring effect Nonflammable gel electrolyte In situ cross-linked Electrode–electrolyte interface Li metal battery
Sun, Qiqi, Zelong Gong, Tao Zhang, Jiafeng Li, Xianli Zhu, Ruixiao Zhu, Lingxu Wang, Leyuan Ma, Xuehui Li, Miaofa Yuan, Zhiwei Zhang, Luyuan Zhang, Zhao Qian, Longwei Yin, Rajeev Ahuja, and Chengxiang Wang. 2024. “Molecule-Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery”. Nano-Micro Letters 17 (September):18. https://doi.org/10.1007/s40820-024-01508-z.
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References
  1. C.M. Thomas, W.J. Hyun, H.C. Huang, D. Zeng, M.C. Hersam, Blade-coatable hexagonal boron nitride ionogel electrolytes for scalable production of lithium metal batteries. ACS Energy Lett. 7(4), 1558–1565 (2022). https://doi.org/10.1021/acsenergylett.2c00535
  2. H. Li, Y. Kang, W. Wei, C. Yan, X. Ma et al., Branch-chain-rich diisopropyl ether with steric hindrance facilitates stable cycling of lithium batteries at − 20 °C. Nano-Micro Lett. 16, 197 (2024). https://doi.org/10.1007/s40820-024-01419-z
  3. E. Park, J. Park, K. Lee, Y. Zhao, T. Zhou et al., Exploiting the steric effect and low dielectric constant of 1,2-dimethoxypropane for 4.3 V lithium metal batteries. ACS Energy Lett. 8(1), 179–188 (2023). https://doi.org/10.1021/acsenergylett.2c02003
  4. Z. Zhang, J. Gou, K. Cui, X. Zhang, Y. Yao et al., 12.6 μm-thick asymmetric composite electrolyte with superior interfacial stability for solid-state lithium-metal batteries. Nano-Micro Lett. 16, 181 (2024). https://doi.org/10.1007/s40820-024-01389-2
  5. W. Cai, Y. Deng, Z. Deng, Y. Jia, Z. Li et al., Quasi-localized high-concentration electrolytes for high-voltage lithium metal batteries. Adv. Energy Mater. 13(31), 2301396 (2023). https://doi.org/10.1002/aenm.202301396
  6. Y. Mu, S. Yu, Y. Chen, Y. Chu, B. Wu et al., Highly efficient aligned ion-conducting network and interface chemistries for depolarized all-solid-state lithium metal batteries. Nano-Micro Lett. 16, 86 (2024). https://doi.org/10.1007/s40820-023-01301-4
  7. H. Wang, J. Song, K. Zhang, Q. Fang, Y. Zuo et al., A strongly complexed solid polymer electrolyte enables a stable solid state high-voltage lithium metal battery. Energy Environ. Sci. 15(12), 5149–5158 (2022). https://doi.org/10.1039/D2EE02904A
  8. H. Wan, Z. Wang, S. Liu, B. Zhang, X. He et al., Critical interphase overpotential as a lithium dendrite-suppression criterion for all-solid-state lithium battery design. Nat. Energy 8(5), 473–481 (2023). https://doi.org/10.1038/s41560-023-01231-w
  9. L. Lin, F. Liu, Y. Zhang, C. Ke, H. Zheng et al., Adjustable mixed conductive interphase for dendrite-free lithium metal batteries. ACS Nano 16(8), 13101–13110 (2022). https://doi.org/10.1021/acsnano.2c05832
  10. S. Huang, K. Long, Y. Chen, T. Naren, P. Qing et al., In situ formed tribofilms as efficient organic/inorganic hybrid interlayers for stabilizing lithium metal anodes. Nano-Micro Lett. 15, 235 (2023). https://doi.org/10.1007/s40820-023-01210-6
  11. M. Mao, X. Ji, Q. Wang, Z. Lin, M. Li et al., Anion-enrichment interface enables high-voltage anode-free lithium metal batteries. Nat. Commun. 14(1), 1082 (2023). https://doi.org/10.1038/s41467-023-36853-x
  12. Z. Jiang, T. Yang, C. Li, J. Zou, H. Yang et al., Synergistic additives enabling stable cycling of ether electrolyte in 4.4 V Ni-Rich/Li metal batteries. Adv. Funct. Mater. 33(51), 2306868 (2023). https://doi.org/10.1002/adfm.202306868
  13. Z. Bi, Q. Sun, M. Jia, M. Zuo, N. Zhao et al., Molten salt driven conversion reaction enabling lithiophilic and air-stable garnet surface for solid-state lithium batteries. Adv. Funct. Mater. 32(52), 2208751 (2022). https://doi.org/10.1002/adfm.202208751
  14. L. Huang, H. Fu, J. Duan, T. Wang, X. Zheng et al., Negating Li+ transfer barrier at solid-liquid electrolyte interface in hybrid batteries. Chem 8(7), 1928–1943 (2022). https://doi.org/10.1016/j.chempr.2022.03.002
  15. Y. Zhai, W. Hou, M. Tao, Z. Wang, Z. Chen et al., Enabling high-voltage “superconcentrated ionogel-in-ceramic” hybrid electrolyte with ultrahigh ionic conductivity and single Li+-ion transference number. Adv. Mater. 34(39), 2205560 (2022). https://doi.org/10.1002/adma.202205560
  16. X. Li, Y. Wang, K. Xi, W. Yu, J. Feng et al., Quasi-solid-state ion-conducting arrays composite electrolytes with fast ion transport vertical-aligned interfaces for all-weather practical lithium-metal batteries. Nano-Micro Lett. 14, 210 (2022). https://doi.org/10.1007/s40820-022-00952-z
  17. M. Yang, F. Feng, Y. Ren, S. Chen, F. Chen et al., Coupling anion-capturer with polymer chains in fireproof gel polymer electrolyte enables dendrite-free sodium metal batteries. Adv. Funct. Mater. 33(46), 2305383 (2023). https://doi.org/10.1002/adfm.202305383
  18. Z. Lu, J. Yu, J. Wu, M.B. Effat, S.C.T. Kwok et al., Enabling room-temperature solid-state lithium-metal batteries with fluoroethylene carbonate-modified plastic crystal interlayers. Energy Storage Mater. 18, 311–319 (2019). https://doi.org/10.1016/j.ensm.2018.08.021
  19. T. Deng, L. Cao, X. He, A.-M. Li, D. Li et al., In situ formation of polymer-inorganic solid-electrolyte interphase for stable polymeric solid-state lithium-metal batteries. Chem 7(11), 3052–3068 (2021). https://doi.org/10.1016/j.chempr.2021.06.019
  20. K. Yang, L. Chen, J. Ma, C. Lai, Y. Huang et al., Stable interface chemistry and multiple ion transport of composite electrolyte contribute to ultra-long cycling solid-state LiNi0.8Co0.1Mn0.1O2/lithium metal batteries. Angew. Chem. Int. Ed. 60(46), 24668–24675 (2021). https://doi.org/10.1002/anie.202110917
  21. Y. Nie, T. Yang, D. Luo, Y. Liu, Q. Ma et al., Tailoring vertically aligned inorganic-polymer nanocomposites with abundant lewis acid sites for ultra-stable solid-state lithium metal batteries. Adv. Energy Mater. 13(13), 2204218 (2023). https://doi.org/10.1002/aenm.202204218
  22. X. Wang, X. Shen, P. Zhang, A. Zhou, J. Zhao et al., Promoted Li+ conduction in PEO-based all-solid-state electrolyte by hydroxyl-modified glass fiber fillers. Rare Met. 42, 875–884 (2023). https://doi.org/10.1007/s12598-022-02218-4
  23. Y. Shan, L. Li, X. Chen, S. Fan, H. Yang et al., Gentle haulers of lithium-ion–nanomolybdenum carbide fillers in solid polymer electrolyte. ACS Energy Lett. 7(7), 2289–2296 (2022). https://doi.org/10.1021/acsenergylett.2c00849
  24. Z. Zhang, W.-Q. Han, From liquid to solid-state lithium metal batteries: fundamental issues and recent developments. Nano-Micro Lett. 16, 24 (2024). https://doi.org/10.1007/s40820-023-01234-y
  25. L. Wang, S. Xu, Z. Wang, E. Yang, W. Jiang et al., A nano fiber–gel composite electrolyte with high Li+ transference number for application in quasi-solid batteries. eScience 3(2), 100090 (2023). https://doi.org/10.1016/j.esci.2022.100090
  26. Z. Shen, J. Zhong, J. Chen, W. Xie, K. Yang et al., SiO2 nanofiber composite gel polymer electrolyte by in-situ polymerization for stable Li metal batteries. Chin. Chem. Lett. 34(3), 107370 (2023). https://doi.org/10.1016/j.cclet.2022.03.093
  27. B. Qiu, F. Xu, J. Qiu, M. Yang, G. Zhang et al., Electrode-electrolyte interface mediation via molecular anchoring for 4.7 V quasi-solid-state lithium metal batteries. Energy Storage Mater. 60, 102832 (2023). https://doi.org/10.1016/j.ensm.2023.102832
  28. H.X. Yang, Z.K. Liu, Y. Wang, N.W. Li, L. Yu, Multiscale structural gel polymer electrolytes with fast Li+ transport for long-life Li metal batteries. Adv. Funct. Mater. 33(1), 2209837 (2023). https://doi.org/10.1002/adfm.202209837
  29. B. Qiu, K. Liang, W. Huang, G. Zhang, C. He et al., Crystal-facet manipulation and interface regulation via TMP-modulated solid polymer electrolytes toward high-performance Zn metal batteries. Adv. Energy Mater. 13(32), 2301193 (2023). https://doi.org/10.1002/aenm.202301193
  30. X. Fan, R. Zhang, S. Sui, X. Liu, J. Liu et al., Starch-based superabsorbent hydrogel with high electrolyte retention capability and synergistic interface engineering for long-lifespan flexible zinc−air batteries. Angew. Chem. Int. Ed. 62(22), e202302640 (2023). https://doi.org/10.1002/anie.202302640
  31. A. Wang, S. Geng, Z. Zhao, Z. Hu, J. Luo, In situ cross-linked plastic crystal electrolytes for wide-temperature and high-energy-density lithium metal batteries. Adv. Funct. Mater. 32(28), 2201861 (2022). https://doi.org/10.1002/adfm.202201861
  32. S. Li, S. Zhang, S. Chai, X. Zang, C. Cheng et al., Structured solid electrolyte interphase enable reversible Li electrodeposition in flame-retardant phosphate-based electrolyte. Energy Storage Mater. 42, 628–635 (2021). https://doi.org/10.1016/j.ensm.2021.08.015
  33. Z. Li, S. Weng, J. Fu, X. Wang, X. Zhou et al., Nonflammable quasi-solid electrolyte for energy-dense and long-cycling lithium metal batteries with high-voltage Ni-rich layered cathodes. Energy Storage Mater. 47, 542–550 (2022). https://doi.org/10.1016/j.ensm.2022.02.045
  34. H. Yang, Y. Qiao, Z. Chang, P. He, H. Zhou, Designing cation–solvent fully coordinated electrolyte for high-energy-density lithium–sulfur full cell based on solid–solid conversion. Angew. Chem. Int. Ed. 60(32), 17726–17734 (2021). https://doi.org/10.1002/anie.202106788
  35. G. Chen, K. Zhang, Y. Liu, L. Ye, Y. Gao et al., Flame-retardant gel polymer electrolyte and interface for quasi-solid-state sodium ion batteries. Chem. Eng. J. 401, 126065 (2020). https://doi.org/10.1016/j.cej.2020.126065
  36. Q. Sun, Z. Cao, Z. Ma, J. Zhang, H. Cheng et al., Dipole–dipole interaction induced electrolyte interfacial model to stabilize antimony anode for high-safety lithium-ion batteries. ACS Energy Lett. 7(10), 3545–3556 (2022). https://doi.org/10.1021/acsenergylett.2c01408
  37. S.-J. Tan, J. Yue, Y.-F. Tian, Q. Ma, J. Wan et al., In-situ encapsulating flame-retardant phosphate into robust polymer matrix for safe and stable quasi-solid-state lithium metal batteries. Energy Storage Mater. 39, 186–193 (2021). https://doi.org/10.1016/j.ensm.2021.04.020
  38. H. Sun, J. Liu, J. He, H. Wang, G. Jiang et al., Stabilizing the cycling stability of rechargeable lithium metal batteries with tris(hexafluoroisopropyl)phosphate additive. Sci. Bull. 67(7), 725–732 (2022). https://doi.org/10.1016/j.scib.2022.01.012
  39. Q. Wang, X. Xu, B. Hong, M. Bai, J. Li et al., Molecular reactivity and interface stability modification in in-situ gel electrolyte for high performance quasi-solid-state lithium metal batteries. Energy Environ. Mater. 6(3), e12351 (2023). https://doi.org/10.1002/eem2.12351
  40. J. Wu, Z. Gao, Y. Wang, X. Yang, Q. Liu et al., Electrostatic interaction tailored anion-rich solvation sheath stabilizing high-voltage lithium metal batteries. Nano-Micro Lett. 14, 147 (2022). https://doi.org/10.1007/s40820-022-00896-4
  41. S. Lin, H. Hua, P. Lai, J. Zhao, A multifunctional dual-salt localized high-concentration electrolyte for fast dynamic high-voltage lithium battery in wide temperature range. Adv. Energy Mater. 11(36), 2101775 (2021). https://doi.org/10.1002/aenm.202101775
  42. X. Mu, X. Li, C. Liao, H. Yu, Y. Jin et al., Phosphorus-fixed stable interfacial nonflammable gel polymer electrolyte for safe flexible lithium-ion batteries. Adv. Funct. Mater. 32(35), 2203006 (2022). https://doi.org/10.1002/adfm.202203006
  43. D. Seng, M. Georges, Living radical emulsion polymerization using the nanoprecipitation technique: an extension to atom transfer radical polymerization. J. Polym. Sci. A Polym. Chem. 44(13), 4027–4038 (2006). https://doi.org/10.1002/pola.21506
  44. Y. Wang, S. Chen, Z. Li, C. Peng, Y. Li et al., In-situ generation of fluorinated polycarbonate copolymer solid electrolytes for high-voltage Li-metal batteries. Energy Storage Mater. 45, 474–483 (2022). https://doi.org/10.1016/j.ensm.2021.12.004
  45. Q. Sun, S. Wang, Y. Ma, D. Song, H. Zhang et al., Li-ion transfer mechanism of gel polymer electrolyte with sole fluoroethylene carbonate solvent. Adv. Mater. 35(28), 2300998 (2023). https://doi.org/10.1002/adma.202300998
  46. Y. Su, X. Rong, A. Gao, Y. Liu, J. Li et al., Rational design of a topological polymeric solid electrolyte for high-performance all-solid-state alkali metal batteries. Nat. Commun. 13(1), 4181 (2022). https://doi.org/10.1038/s41467-022-31792-5
  47. L. Qiao, S. Rodriguez Peña, M. Martínez-Ibañez, A. Santiago, I. Aldalur et al., Anion π–π stacking for improved lithium transport in polymer electrolytes. J. Am. Chem. Soc. 144(22), 9806–9816 (2022). https://doi.org/10.1021/jacs.2c02260
  48. F. Chen, X. Wang, M. Armand, M. Forsyth, Cationic polymer-in-salt electrolytes for fast metal ion conduction and solid-state battery applications. Nat. Mater. 21(10), 1175–1182 (2022). https://doi.org/10.1038/s41563-022-01319-w
  49. M. Arrese-Igor, M. Martinez-Ibañez, E. Pavlenko, M. Forsyth, H. Zhu et al., Toward high-voltage solid-state Li-metal batteries with double-layer polymer electrolytes. ACS Energy Lett. 7(4), 1473–1480 (2022). https://doi.org/10.1021/acsenergylett.2c00488
  50. J. Hu, C. Lai, K. Chen, Q. Wu, Y. Gu et al., Dual fluorination of polymer electrolyte and conversion-type cathode for high-capacity all-solid-state lithium metal batteries. Nat. Commun. 13(1), 7914 (2022). https://doi.org/10.1038/s41467-022-35636-0
  51. J. Ma, G. Zhong, P. Shi, Y. Wei, K. Li et al., Constructing a highly efficient “solid–polymer–solid” elastic ion transport network in cathodes activates the room temperature performance of all-solid-state lithium batteries. Energy Environ. Sci. 15(4), 1503–1511 (2022). https://doi.org/10.1039/D1EE03345J
  52. H. Wu, B. Tang, X. Du, J. Zhang, X. Yu et al., LiDFOB initiated in situ polymerization of novel eutectic solution enables room-temperature solid lithium metal batteries. Adv. Sci. 7(23), 2003370 (2020). https://doi.org/10.1002/advs.202003370
  53. S. Liu, X. Ji, N. Piao, J. Chen, N. Eidson et al., An inorganic-rich solid electrolyte interphase for advanced lithium-metal batteries in carbonate electrolytes. Angew. Chem. Int. Ed. 60(7), 3661–3671 (2021). https://doi.org/10.1002/anie.202012005
  54. J. He, A. Bhargav, A. Manthiram, Covalent organic framework as an efficient protection layer for a stable lithium-metal anode. Angew. Chem. Int. Ed. 61(18), e202116586 (2022). https://doi.org/10.1002/anie.202116586
  55. C. Cui, X. Fan, X. Zhou, J. Chen, Q. Wang et al., Structure and interface design enable stable Li-rich cathode. J. Am. Chem. Soc. 142(19), 8918–8927 (2020). https://doi.org/10.1021/jacs.0c02302
  56. X. Yu, L. Wang, J. Ma, X. Sun, X. Zhou et al., Selectively wetted rigid–flexible coupling polymer electrolyte enabling superior stability and compatibility of high-voltage lithium metal batteries. Adv. Energy Mater. 10(18), 1903939 (2020). https://doi.org/10.1002/aenm.201903939
  57. Q. Zhou, S. Dong, Z. Lv, G. Xu, L. Huang et al., A temperature-responsive electrolyte endowing superior safety characteristic of lithium metal batteries. Adv. Energy Mater. 10(6), 1903441 (2020). https://doi.org/10.1002/aenm.201903441
  58. W. Liu, C. Yi, L. Li, S. Liu, Q. Gui et al., Designing polymer-in-salt electrolyte and fully infiltrated 3D electrode for integrated solid-state lithium batteries. Angew. Chem. Int. Ed. 60(23), 12931–12940 (2021). https://doi.org/10.1002/anie.202101537
  59. Z. Chang, Y. Qiao, H. Deng, H. Yang, P. He et al., A liquid electrolyte with de-solvated lithium ions for lithium-metal battery. Joule 4(8), 1776–1789 (2020). https://doi.org/10.1016/j.joule.2020.06.011
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