Issue

Vol. 19 (2027)

Atomic and Molecular Structure Regulated In Situ Cross-Linked Polyurethane Gel Electrolyte for High-Performance Lithium Metal Batteries

https://doi.org/10.1007/s40820-026-02307-4
Jialun Ni
Institute for Clean Energy Technology, North China Electric Power University, Beijing 102206, People’s Republic of China
Yong Zeng
School of Innovation and Entrepreneurship, Southern University of Science and Technology, Shenzhen 518055, People’s Republic of China
De Ning
Centre for Photonics Information and Energy Materials, Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, People’s Republic of China
Xuan He
Sunwoda Mobility Energy Technology Co., Ltd, Shenzhen 518107, People’s Republic of China
Xiaokang Ju
Sunwoda Mobility Energy Technology Co., Ltd, Shenzhen 518107, People’s Republic of China
Xueling Liu
Institute for Clean Energy Technology, North China Electric Power University, Beijing 102206, People’s Republic of China
Rui Gao
Institute for Clean Energy Technology, North China Electric Power University, Beijing 102206, People’s Republic of China
Yingchun Xu
School of Innovation and Entrepreneurship, Southern University of Science and Technology, Shenzhen 518055, People’s Republic of China
Ruijie Du
Institute for Clean Energy Technology, North China Electric Power University, Beijing 102206, People’s Republic of China
Dong Zhou
School of Advanced Energy, Sun Yat-Sen University Shenzhen Campus, Shenzhen 518107, People’s Republic of China
Jun Wang
School of Innovation and Entrepreneurship, Southern University of Science and Technology, Shenzhen 518055, People’s Republic of China
Yongli Li
Institute for Clean Energy Technology, North China Electric Power University, Beijing 102206, People’s Republic of China

Corresponding Author: Yongli Li

yongli.li@ncepu.edu.cn

Nano-Micro Letters, Vol. 19 (2027), Article Number: 18

Abstract

The incompatibility of conventional electrolytes with high-voltage cathodes and lithium metal anodes limits the performance of lithium metal batteries (LMBs). Here, an in situ cross-linked polyurethane gel electrolyte (G-P3 AR) is designed through atomic and molecular structure regulation. The polyester segments widen the highest occupied molecular orbital–lowest unoccupied molecular orbital gap, extending the electrochemical stability window to 4.97 V for compatibility with NCM811 cathodes. Polyether segments exhibit a lower Li+ binding energy, reducing the desolvation barrier and enhancing anode stability. At the atomic level, sp2-hybridized boron in the chain extender immobilizes anions (TFSI− and DFOB−) through Lewis acid–base interactions, raising the Li+ transference number to 0.78 and enabling exceptional rate capability (157.7 mAh g−1 at 2 C in the Li||NCM811 cell). Hydrogen bonding between the polymer and solvent restructures the solvation sheath, promoting inorganic-rich interphases. The Li|G-P3 AR|NCM811 cell retains 81.7% capacity after 500 cycles at 0.5 C charge/1 C discharge, demonstrating a rational electrolyte design strategy for high-performance LMBs.


Highlights:
1 Hybrid polyester/polyether segments simultaneously enable high-voltage stability (4.97 V) and fast Li+ desolvation in Li||NCM811 batteries for both cathode and anode compatibility.
2 The sp2-hybridized boron Lewis acid centers anchor anions via acid-base interactions, boosting Li+ transference number to 0.78 and enhancing rate capability (157.7 mAh g−1 at 2 C).
3 Hydrogen bonding restructures solvation sheath, promoting anion-derived inorganic-rich solid electrolyte interphase/cathode electrolyte interphase that delivers 81.7% capacity retention after 500 cycles.

Keywords

In situ polymerization Lithium metal batteries Polyurethane electrolytes Solvation structure
Ni, Jialun, Yong Zeng, De Ning, Xuan He, Xiaokang Ju, Xueling Liu, Rui Gao, Yingchun Xu, Ruijie Du, Dong Zhou, Jun Wang, and Yongli Li. 2026. “Atomic and Molecular Structure Regulated In Situ Cross-Linked Polyurethane Gel Electrolyte for High-Performance Lithium Metal Batteries”. Nano-Micro Letters 19 (August):18. https://doi.org/10.1007/s40820-026-02307-4.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. H. Yang, L. Wang, Y. Li, Z. Zhuo, T. Wu et al., Co-free gradient lithium-rich cathode for high-energy batteries with optimized cyclability. Proc. Natl. Acad. Sci. USA. 121(50), e2412460121 (2024). https://doi.org/10.1073/pnas.2412460121
  2. T. Wu, X. Zhang, Y. Li, H. Du, T. Liu et al., Quantitative identification of dopant occupation in Li-rich cathodes. Adv. Mater. 37(3), 2408543 (2025). https://doi.org/10.1002/adma.202408543
  3. M. Bai, X. Tang, M. Zhang, H. Wang, Z. Wang et al., An in-situ polymerization strategy for gel polymer electrolyte Si||Ni-rich lithium-ion batteries. Nat. Commun. 15, 5375 (2024). https://doi.org/10.1038/s41467-024-49713-z
  4. T. Wu, X. Liu, X. Zhang, Y. Lu, B. Wang et al., Full concentration gradient-tailored Li-rich layered oxides for high-energy lithium-ion batteries. Adv. Mater. 33(2), 2001358 (2021). https://doi.org/10.1002/adma.202001358
  5. F. Makhlooghiazad, L.A. O’Dell, L. Porcarelli, C. Forsyth, N. Quazi et al., Zwitterionic materials with disorder and plasticity and their application as non-volatile solid or liquid electrolytes. Nat. Mater. 21(2), 228–236 (2022). https://doi.org/10.1038/s41563-021-01130-z
  6. F. Yu, Y. Mu, M. Han, J. Liu, K. Zheng et al., Electrochemically stable and ultrathin polymer-based solid electrolytes for dendrite-free all-solid-state lithium-metal batteries. Mater. Futur. 4(1), 015101 (2025). https://doi.org/10.1088/2752-5724/ada0cc
  7. H. Zhang, L. Huang, H. Xu, X. Zhang, Z. Chen et al., A polymer electrolyte with a thermally induced interfacial ion-blocking function enables safety-enhanced lithium metal batteries. eScience 2(2), 201–208 (2022). https://doi.org/10.1016/j.esci.2022.03.001
  8. L. Ye, X. Li, A dynamic stability design strategy for lithium metal solid state batteries. Nature 593(7858), 218–222 (2021). https://doi.org/10.1038/s41586-021-03486-3
  9. F. Pei, Y. Huang, L. Wu, S. Zhou, Q. Kang et al., Multisite crosslinked poly(ether-urethane)-based polymer electrolytes for high-voltage solid-state lithium metal batteries. Adv. Mater. 36(49), 2409269 (2024). https://doi.org/10.1002/adma.202409269
  10. X. Miao, J. Hong, S. Huang, C. Huang, Y. Liu et al., In situ gel polymer electrolyte with rapid Li+ transport channels and anchored anion sites for high-current-density lithium-ion batteries. Adv. Funct. Mater. 35(1), 2411751 (2025). https://doi.org/10.1002/adfm.202411751
  11. S. Yuan, K. Ding, X. Zeng, D. Bin, Y. Zhang et al., Advanced nonflammable organic electrolyte promises safer Li-metal batteries: from solvation structure perspectives. Adv. Mater. 35(13), 2206228 (2023). https://doi.org/10.1002/adma.202206228
  12. C.V. Amanchukwu, Z. Yu, X. Kong, J. Qin, Y. Cui et al., A new class of ionically conducting fluorinated ether electrolytes with high electrochemical stability. J. Am. Chem. Soc. 142(16), 7393–7403 (2020). https://doi.org/10.1021/jacs.9b11056
  13. X. Hou, T. Li, Y. Qiu, M. Jiang, H. Lin et al., Interfacial chemistry of perfluorinated-anion additives deciphering ether-based electrolytes for sodium-ion batteries. ACS Energy Lett. 9(2), 461–467 (2024). https://doi.org/10.1021/acsenergylett.3c02811
  14. X. Yi, X. Li, J. Zhong, S. Wang, Z. Wang et al., Unraveling the mechanism of different kinetics performance between ether and carbonate ester electrolytes in hard carbon electrode. Adv. Funct. Mater. 32(48), 2209523 (2022). https://doi.org/10.1002/adfm.202209523
  15. Z. Wang, A. Hu, Y. Yin, W. Xu, Y. Wang et al., Ionization-targeted modulation enables fast-charging and high-temperature lithium-metal batteries. Adv. Funct. Mater. 36(7), e13437 (2026). https://doi.org/10.1002/adfm.202513437
  16. G. Liu, Z. Cao, P. Wang, Z. Ma, Y. Zou et al., Switching electrolyte interfacial model to engineer solid electrolyte interface for fast charging and wide-temperature lithium-ion batteries. Adv. Sci. 9(26), 2201893 (2022). https://doi.org/10.1002/advs.202201893
  17. Y. Zhao, T. Zhou, D. Baster, M. El Kazzi, J.W. Choi et al., Targeted functionalization of cyclic ether solvents for controlled reactivity in high-voltage lithium metal batteries. ACS Energy Lett. 8(7), 3180–3187 (2023). https://doi.org/10.1021/acsenergylett.3c01004
  18. D. Ruan, L. Tan, S. Chen, J. Fan, Q. Nian et al., Solvent versus anion chemistry: unveiling the structure-dependent reactivity in tailoring electrochemical interphases for lithium-metal batteries. JACS Au 3(3), 953–963 (2023). https://doi.org/10.1021/jacsau.3c00035
  19. Y. Chen, M. Li, Y. Liu, Y. Jie, W. Li et al., Origin of dendrite-free lithium deposition in concentrated electrolytes. Nat. Commun. 14, 2655 (2023). https://doi.org/10.1038/s41467-023-38387-8
  20. Z. Lu, H. Yang, J. Sun, J. Okagaki, Y. Choe et al., Conformational isomerism breaks the electrolyte solubility limit and stabilizes 4.9 V Ni-rich layered cathodes. Nat. Commun. 15, 9108 (2024). https://doi.org/10.1038/s41467-024-53570-1
  21. Y. Wang, Z. Li, Y. Hou, Z. Hao, Q. Zhang et al., Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries. Chem. Soc. Rev. 52(8), 2713–2763 (2023). https://doi.org/10.1039/d2cs00873d
  22. H.K. Bergstrom, B.D. McCloskey, Ion transport in (localized) high concentration electrolytes for Li-based batteries. ACS Energy Lett. 9(2), 373–380 (2024). https://doi.org/10.1021/acsenergylett.3c01662
  23. C. Gao, Y. Zhou, Y. Huang, S. Wang, X. Ma, Bioinspired vascular bundle structured nanocellulose/PVDF-HFP composite membranes for efficient ion transport and stable all-solid-state lithium batteries. Nano-Micro Lett. 18(1), 254 (2026). https://doi.org/10.1007/s40820-026-02092-0
  24. Y. Wang, P. Li, B. Liu, X. Wei, W. Fu et al., Solid polymer electrolytes: ion conduction enhancement and comprehensive frontiers. Mater. Futures 4(4), 042103 (2025). https://doi.org/10.1088/2752-5724/ae0ce3
  25. H. Yang, L. Zhu, W. Li, Y. Tang, X. Li et al., Lignocellulose-mediated gel polymer electrolytes toward next-generation energy storage. Nano-Micro Lett. 18(1), 84 (2025). https://doi.org/10.1007/s40820-025-01927-6
  26. J. Li, X. Zhu, Z. Xu, H. Ren, S. Muhammad et al., Dynamic metal-ligand coordinated self-healing polymer electrolytes for lithium-ion batteries: correlating coordination mechanisms with electrochemical properties. Adv. Funct. Mater. 35(49), e10177 (2025). https://doi.org/10.1002/adfm.202510177
  27. S. Zhang, W. Chen, W. Hao, D. Li, C. Zhang et al., A composite gel polymer electrolyte by incorporating modified POSS endowing inorganic-rich SEI formation and stable cycle life for lithium metal batteries. Chem. Eng. J. 484, 149499 (2024). https://doi.org/10.1016/j.cej.2024.149499
  28. J. Zhu, J. Zhang, R. Zhao, Y. Zhao, J. Liu et al., In situ 3D crosslinked gel polymer electrolyte for ultra-long cycling, high-voltage, and high-safety lithium metal batteries. Energy Storage Mater. 57, 92–101 (2023). https://doi.org/10.1016/j.ensm.2023.02.012
  29. T. Li, X.-Q. Zhang, N. Yao, Y.-X. Yao, L.-P. Hou et al., Stable anion-derived solid electrolyte interphase in lithium metal batteries. Angew. Chem. Int. Ed. 60(42), 22683–22687 (2021). https://doi.org/10.1002/anie.202107732
  30. Y. Li, S. Ma, Y. Zhao, S. Chen, T. Xiao et al., Synergetic control of Li+ transport ability and solid electrolyte interphase by boron-rich hexagonal skeleton structured all-solid-state polymer electrolyte. Energy Environ. Mater. 7(3), e12648 (2024). https://doi.org/10.1002/eem2.12648
  31. S. Zhang, F. Sun, X. Du, X. Zhang, L. Huang et al., In situ-polymerized lithium salt as a polymer electrolyte for high-safety lithium metal batteries. Energy Environ. Sci. 16(6), 2591–2602 (2023). https://doi.org/10.1039/D3EE00558E
  32. X.-Y. Huang, C.-Z. Zhao, W.-J. Kong, N. Yao, Z.-Y. Shuang et al., Tailoring polymer electrolyte solvation for 600 Wh kg−1 lithium batteries. Nature 646(8084), 343–350 (2025). https://doi.org/10.1038/s41586-025-09565-z
  33. L. Wu, F. Pei, D. Cheng, Y. Zhang, H. Cheng et al., Flame-retardant polyurethane-based solid-state polymer electrolytes enabled by covalent bonding for lithium metal batteries. Adv. Funct. Mater. 34(16), 2310084 (2024). https://doi.org/10.1002/adfm.202310084
  34. F. Pei, L. Wu, Y. Zhang, Y. Liao, Q. Kang et al., Interfacial self-healing polymer electrolytes for long-cycle solid-state lithium-sulfur batteries. Nat. Commun. 15(1), 351 (2024). https://doi.org/10.1038/s41467-023-43467-w
  35. Y. Chai, J. Gao, L. Yang, W. Wu, D. Ning et al., In situ coordinated MOF-polymer composite electrolyte for solid-state lithium metal batteries with exceptional high-rate performance. Small 22(12), 2412494 (2026). https://doi.org/10.1002/smll.202412494
  36. J. Chen, D. Zhang, L. Zhu, M. Liu, T. Zheng et al., Hybridizing carbonate and ether at molecular scales for high-energy and high-safety lithium metal batteries. Nat. Commun. 15, 3217 (2024). https://doi.org/10.1038/s41467-024-47448-5
  37. L. Yang, Y. Chu, Y. Feng, Y. Mu, L. Zou et al., Breaking voltage limitations: triethyl phosphate-engineered PVDF-based electrolytes with dual-interphase stabilization for 4.7 V-class quasi-solid-state lithium metal batteries. J. Am. Chem. Soc. 147(29), 25940–25949 (2025). https://doi.org/10.1021/jacs.5c08493
  38. S. Huo, L. Sheng, W. Xue, L. Wang, H. Xu et al., Challenges of polymer electrolyte with wide electrochemical window for high energy solid-state lithium batteries. InfoMat 5(3), e12394 (2023). https://doi.org/10.1002/inf2.12394
  39. Z. Zhu, Y. Li, J. Ji, X. Qi, J. Pan et al., Taming the ion-dipole interaction via rational diluent selection for low-temperature Li-metal batteries. Angew. Chem. Int. Ed. 64(15), e202423940 (2025). https://doi.org/10.1002/anie.202423940
  40. D. Hu, H. Huang, C. Wang, Q. Hong, H. Wang et al., Tailoring multiple interactions in poly (urethane-urea)-based solid-state polymer electrolytes for long-term cycling lithium metal batteries. Adv. Energy Mater. 15(26), 2406176 (2025). https://doi.org/10.1002/aenm.202406176
  41. Z. Wei, Z. Liu, X. Fu, Y. Wang, A. Yuan et al., Effect of crystalline structure on water resistance of waterborne polyurethane. Eur. Polym. J. 157, 110647 (2021). https://doi.org/10.1016/j.eurpolymj.2021.110647
  42. J. Petry, M. Dietel, M. Thelakkat, Semi-interpenetrating network electrolytes utilizing ester-functionalized low tg polysiloxanes in lithium-metal batteries. Adv. Energy Mater. 15(12), 2403531 (2025). https://doi.org/10.1002/aenm.202403531
  43. H. Hu, J. Li, F. Lin, J. Huang, H. Zheng et al., Induction effect of fluorine-grafted polymer-based electrolytes for high-performance lithium metal batteries. Nano-Micro Lett. 17(1), 256 (2025). https://doi.org/10.1007/s40820-025-01738-9
  44. X. Xie, P. Zhang, X. Li, Z. Wang, X. Qin et al., Rational design of F-modified polyester electrolytes for sustainable all-solid-state lithium metal batteries. J. Am. Chem. Soc. 146(9), 5940–5951 (2024). https://doi.org/10.1021/jacs.3c12094
  45. K. Liu, S. Jiang, T.L. Dzwiniel, H.-K. Kim, Z. Yu et al., Molecular design of a highly stable single-ion conducting polymer gel electrolyte. ACS Appl. Mater. Interfaces 12(26), 29162–29172 (2020). https://doi.org/10.1021/acsami.0c03363
  46. Y. Wang, S. Zhang, Z. Chen, H. Zhang, F. Tian et al., Long-life lithium metal batteries enabled by in situ solidified polyphosphoester-based electrolyte. Adv. Mater. 38(3), e14210 (2026). https://doi.org/10.1002/adma.202514210
  47. M. Li, D.A. Rakov, Y. Fan, C. Wang, C. Wang et al., Balancing solvation ability of polymer and solvent in gel polymer electrolytes for efficient lithium metal batteries. Angew. Chem. Int. Ed. 64(41), e202513450 (2025). https://doi.org/10.1002/anie.202513450
  48. K. Wang, V. Koverga, N. Maslekar, F. Wu, R. Kuphl et al., Novel zwitterionic polyurethane-in-salt electrolytes with high ion conductivity, elasticity, and adhesion for high-performance solid-state lithium metal batteries. Adv. Energy Mater. 15(30), 2405676 (2025). https://doi.org/10.1002/aenm.202405676
  49. Y. Mo, Y. Gao, M. Li, S. Qi, W. Zhang et al., Fluorinated deep eutectic polymer electrolytes with hydrogen bonds-rich networks: realizing targeted management of primary solvation sheath migration. Small 21(13), 2501741 (2025). https://doi.org/10.1002/smll.202501741
  50. S. Wang, W. Sun, B. Zhang, J. Guan, T. Wu et al., Elastic bridging design of a fluorine-free electrolyte enables high-performance lithium batteries. Adv. Mater. 38(25), e72977 (2026). https://doi.org/10.1002/adma.72977
  51. X. Chen, W. Li, C. Luo, H. Zhang, C. Gao et al., A bioinspired piezoelectric stress buffer layer for SiOx-based electrodes toward high-energy lithium batteries. Adv. Mater. 37(45), e04360 (2025). https://doi.org/10.1002/adma.202504360
  52. X. Wu, H. Zeng, S. He, R. He, Z. Zhang et al., Intermolecular hydrogen bonding tailors solvation structures for low-temperature and long-cycling lithium-ion batteries. Adv. Funct. Mater. 36(13), e19001 (2026). https://doi.org/10.1002/adfm.202519001
  53. X. Zhang, X. Dong, X. Yue, J. Gao, Z. Shi et al., Solvation regulation via hydrogen bonding to mitigate Al current collector corrosion for high-voltage Li-ion batteries. Adv. Energy Mater. 15(10), 2403588 (2025). https://doi.org/10.1002/aenm.202403588
  54. S. Wang, L. Zhang, Z. Hu, B. Zhang, N. Li et al., Intrinsic structural and coordination chemistry insights of Li salts in rechargeable lithium batteries. Adv. Mater. 37(11), 2420428 (2025). https://doi.org/10.1002/adma.202420428
  55. M. Qin, Z. Zeng, F. Ma, C. Gu, X. Chen et al., Doping in solvation structure: enabling fluorinated carbonate electrolyte for high-voltage and high-safety lithium-ion batteries. ACS Energy Lett. 9(6), 2536–2544 (2024). https://doi.org/10.1021/acsenergylett.4c00790
  56. N. Yao, X. Chen, S.-Y. Sun, Y.-C. Gao, L. Yu et al., Identifying the lithium bond and lithium ionic bond in electrolytes. Chem 11(1), 102254 (2025). https://doi.org/10.1016/j.chempr.2024.07.016
  57. B.D. Adams, J. Zheng, X. Ren, W. Xu, J.-G. Zhang, Accurate determination of coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8(7), 1702097 (2018). https://doi.org/10.1002/aenm.201702097
  58. N. Meng, Y. Ye, Z. Yang, H. Li, F. Lian, Developing single-ion conductive polymer electrolytes for high-energy-density solid state batteries. Adv. Funct. Mater. 33(43), 2305072 (2023). https://doi.org/10.1002/adfm.202305072
  59. J. Li, X. Chen, S. Muhammad, S. Roy, H. Huang et al., Development of solid polymer electrolytes for solid-state lithium battery applications. Mater. Today Energy 43, 101574 (2024). https://doi.org/10.1016/j.mtener.2024.101574
  60. Z. Zheng, X. Liu, X.-Q. Zhang, S.-Y. Sun, J.-L. Li et al., Deciphering coulombic efficiency of lithium metal anodes by screening electrolyte properties. Angew. Chem. Int. Ed. 64(30), e202507387 (2025). https://doi.org/10.1002/anie.202507387
  61. Z. Hao, Y. Wu, Q. Zhao, J. Tang, Q. Zhang et al., Functional separators regulating ion transport enabled by metal-organic frameworks for dendrite-free lithium metal anodes. Adv. Funct. Mater. 31(33), 2102938 (2021). https://doi.org/10.1002/adfm.202102938
  62. Q. Liu, A. Cresce, M. Schroeder, K. Xu, D. Mu et al., Insight on lithium metal anode interphasial chemistry: reduction mechanism of cyclic ether solvent and SEI film formation. Energy Storage Mater. 17, 366–373 (2019). https://doi.org/10.1016/j.ensm.2018.09.024
  63. Y. Chai, D. Ning, D. Zhou, J. Gao, J. Ni et al., Construction of flexible asymmetric composite polymer electrolytes for high-voltage lithium metal batteries with superior performance. Nano Energy 130, 110160 (2024). https://doi.org/10.1016/j.nanoen.2024.110160
  64. J. Chen, X. Deng, X. Jia, Y. Gao, H. Chen et al., Li+ ion-dipole interaction-enabled a dynamic supramolecular elastomer interface layer for dendrite-free lithium metal anodes. J. Am. Chem. Soc. 146(45), 30836–30847 (2024). https://doi.org/10.1021/jacs.4c08766
  65. H. Peng, T. Long, J. Peng, H. Chen, L. Ji et al., Molecular design for in-situ polymerized solid polymer electrolytes enabling stable cycling of lithium metal batteries. Adv. Energy Mater. 14(22), 2400428 (2024). https://doi.org/10.1002/aenm.202400428
  66. Y. Zeng, F. Liu, Q. Zhang, D. Cheng, Y. Xu et al., A thermoresponsive electrolyte additive for high-energy, long-cycling, and safe lithium batteries. Joule 9(9), 102100 (2025). https://doi.org/10.1016/j.joule.2025.102100
  67. J. Wu, Z. You, M. Li, H. Chen, S. Feng et al., Synergistic reduction and oxidation resistant interface modifier for high-voltage and high-loading solid-state lithium batteries. Adv. Energy Mater. 15(9), 2403585 (2025). https://doi.org/10.1002/aenm.202403585
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE

Most read articles by the same author(s)