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Ultrathin thiol-ene crosslinked polymeric electrolyte for solid-state and high-performance lithium metal batteries

超薄烯-巯交联聚合物电解质及其固态高性能锂金属 电池

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Abstract

Solid polymer electrolyte (SPE) is a potential material for the next-generation safe battery system. However, the inability of SPEs to maintain mechanical strength and ionic conductivity is a bottleneck in further research. Here, a poly(ether-thioether) electrolyte with a thiol-ene crosslinked network was prepared by in situ click polymerization and supported on an electro-spun polyimide (PI) mat to provide an ultrathin membrane (19 µm in thickness). Combining a thiol-ene crosslinked network and the reinforcement of the electro-spun PI mat, this SPE membrane obtains high storage modulus (135 MPa), high ionic conductivity (2.24 × 10−4 S cm−1), and wide electrochemical window (up to 4.0 V) at 60°C. In addition, the Li-Li symmetrical cell based on the as-prepared electrolyte demonstrates stable cycling performance during Li plating/strip**, lasting more than 800 h at 0.1 mA cm−2. Such LiFePO4/Li cells with an ultrathin thiol-ene network SPE membrane achieve over 250-cycle stability at 0.5 C and 60°C. This work develops a new ultrathin polymer electrolyte for stable solid-state and high-performance lithium metal batteries.

摘要

固态聚合物电解质(SPE)是下一代安全电池系统的潜在材料, 但 SPE不能同时保持较高的机械**度和离子传导率, 使下一步研究进入瓶 颈. 在此, 我们通过原位点击反应在静电纺丝聚酰亚胺(PI)膜上制备了 一种具有交联结构的聚醚硫醚电解质, 厚度仅为19 μm. 由于烯-巯网络 的交联结构和静电纺丝PI膜的增**作用, 该SPE膜在60°C下具有 135 MPa的储能模量, 2.24 × 10−4 S cm−1的离子传导率和4.0 V的电化学 稳定窗口, 并且锂-锂对称电池在0.1 mA cm−2下循环超过800 h, 展现出 了优异的循环稳定性. 用该超薄聚合物电解质膜组装的LiFePO4/Li电池 在60°C, 0.5 C下能够循环超过250圈. 这项工作开发了一种用于固态高 性能锂金属电池的新型聚合物电解质.

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References

  1. Zhou Q, Ma J, Dong S, et al. Intermolecular chemistry in solid polymer electrolytes for high-energy-density lithium batteries. Adv Mater, 2019, 31: 1902029

    Article  CAS  Google Scholar 

  2. Cui Y, Wan J, Ye Y, et al. A fireproof, lightweight, polymer-polymer solid-state electrolyte for safe lithium batteries. Nano Lett, 2020, 20: 1686–1692

    Article  CAS  Google Scholar 

  3. Zhou B, Yang M, Zuo C, et al. Flexible, self-healing, and fire-resistant polymer electrolytes fabricated via photopolymerization for all-solid-state lithium metal batteries. ACS Macro Lett, 2020, 9: 525–532

    Article  CAS  Google Scholar 

  4. Song Y, Liu X, Ren D, et al. Simultaneously blocking chemical crosstalk and internal short circuit via gel-stretching derived nanoporous non-shrinkage separator for safe lithium-ion batteries. Adv Mater, 2022, 34: 2106335

    Article  CAS  Google Scholar 

  5. Vishnugopi BS, Kazyak E, Lewis JA, et al. Challenges and opportunities for fast charging of solid-state lithium metal batteries. ACS Energy Lett, 2021, 6: 3734–3749

    Article  CAS  Google Scholar 

  6. ** G, **ao M, Wang S, et al. Polymer-based solid electrolytes: Material selection, design, and application. Adv Funct Mater, 2021, 31: 2007598

    Article  CAS  Google Scholar 

  7. Tan DHS, Banerjee A, Chen Z, et al. From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat Nanotechnol, 2020, 15: 170–180

    Article  CAS  Google Scholar 

  8. Liu H, Cheng XB, Huang JQ, et al. Controlling dendrite growth in solid-state electrolytes. ACS Energy Lett, 2020, 5: 833–843

    Article  CAS  Google Scholar 

  9. Cui G, Tominaga Y. Polymer electrolytes toward next-generation batteries. Macro Chem Phys, 2022, 223: 2200013

    Article  CAS  Google Scholar 

  10. Zhao Q, Stalin S, Zhao CZ, et al. Designing solid-state electrolytes for safe, energy-dense batteries. Nat Rev Mater, 2020, 5: 229–252

    Article  CAS  Google Scholar 

  11. Famprikis T, Canepa P, Dawson JA, et al. Fundamentals of inorganic solid-state electrolytes for batteries. Nat Mater, 2019, 18: 1278–1291

    Article  CAS  Google Scholar 

  12. Balaish M, Gonzalez-Rosillo JC, Kim KJ, et al. Processing thin but robust electrolytes for solid-state batteries. Nat Energy, 2021, 6: 227–239

    Article  CAS  Google Scholar 

  13. Fan L, Wei S, Li S, et al. Recent progress of the solid-state electrolytes for high-energy metal-based batteries. Adv Energy Mater, 2018, 8: 1702657

    Article  Google Scholar 

  14. Li S, Zhang S, Shen L, et al. Progress and perspective of ceramic/polymer composite solid electrolytes for lithium batteries. Adv Sci, 2020, 7: 1903088

    Article  CAS  Google Scholar 

  15. Xue Z, He D, **e X. Poly(ethylene oxide)-based electrolytes for lithium-ion batteries. J Mater Chem A, 2015, 3: 19218–19253

    Article  CAS  Google Scholar 

  16. **ao Y, Wang Y, Bo SH, et al. Understanding interface stability in solid-state batteries. Nat Rev Mater, 2019, 5: 105–126

    Article  Google Scholar 

  17. Cheng J, Hou G, Sun Q, et al. A novel coral-like garnet for high-performance PEO-based all solid-state batteries. Sci China Mater, 2022, 65: 364–372

    Article  CAS  Google Scholar 

  18. Sarapas JM, Tew GN. Poly(ether-thioethers) by thiol-ene click and their oxidized analogues as lithium polymer electrolytes. Macromolecules, 2016, 49: 1154–1162

    Article  CAS  Google Scholar 

  19. Yue L, Ma J, Zhang J, et al. All solid-state polymer electrolytes for high-performance lithium ion batteries. Energy Storage Mater, 2016, 5: 139–164

    Article  Google Scholar 

  20. Zhong L, Wang S, **ao M, et al. Addressing interface elimination: Boosting comprehensive performance of all-solid-state Li-S battery. Energy Storage Mater, 2021, 41: 563–570

    Article  Google Scholar 

  21. Lv Z, Zhou Q, Zhang S, et al. Cyano-reinforced in-situ polymer electrolyte enabling long-life cycling for high-voltage lithium metal batteries. Energy Storage Mater, 2021, 37: 215–223

    Article  Google Scholar 

  22. Xu R, **ao B, Xuan C, et al. Facile and powerful in situ polymerization strategy for sulfur-based all-solid polymer electrolytes in lithium batteries. ACS Appl Mater Interfaces, 2021, 13: 34274–34281

    Article  CAS  Google Scholar 

  23. Liu Y, Zhao Y, Lu W, et al. PEO based polymer in plastic crystal electrolytes for room temperature high-voltage lithium metal batteries. Nano Energy, 2021, 88: 106205

    Article  CAS  Google Scholar 

  24. Fan LZ, He H, Nan CW. Tailoring inorganic-polymer composites for the mass production of solid-state batteries. Nat Rev Mater, 2021, 6: 1003–1019

    Article  CAS  Google Scholar 

  25. Zhang B, Zhang Y, Zhang N, et al. Synthesis and interface stability of polystyrene-poly(ethylene glycol)-polystyrene triblock copolymer as solid-state electrolyte for lithium-metal batteries. J Power Sources, 2019, 428: 93–104

    Article  CAS  Google Scholar 

  26. Meabe L, Huynh TV, Mantione D, et al. UV-cross-linked poly(ethylene oxide carbonate) as free standing solid polymer electrolyte for lithium batteries. Electrochim Acta, 2019, 302: 414–421

    Article  CAS  Google Scholar 

  27. Zhou B, Jiang J, Zhang F, et al. Crosslinked poly(ethylene oxide)-based membrane electrolyte consisting of polyhedral oligomeric silsesquioxane nanocages for all-solid-state lithium ion batteries. J Power Sources, 2020, 449: 227541

    Article  CAS  Google Scholar 

  28. Wang Q, Dong T, Zhou Q, et al. An in-situ generated composite solid-state electrolyte towards high-voltage lithium metal batteries. Sci China Chem, 2022, 65: 934–942

    Article  CAS  Google Scholar 

  29. Wen P, Zhao Y, Wang Z, et al. Solvent-free synthesis of the polymer electrolyte via photo-controlled radical polymerization: Toward ultra-fast in-built fabrication of solid-state batteries under visible light. ACS Appl Mater Interfaces, 2021, 13: 8426–8434

    Article  CAS  Google Scholar 

  30. Zhang Y, Lu W, Cong L, et al. Cross-linking network based on poly (ethylene oxide): Solid polymer electrolyte for room temperature lithium battery. J Power Sources, 2019, 420: 63–72

    Article  CAS  Google Scholar 

  31. He F, Tang W, Zhang X, et al. High energy density solid state lithium metal batteries enabled by sub-5 µm solid polymer electrolytes. Adv Mater, 2021, 33: 2105329

    Article  CAS  Google Scholar 

  32. Wu J, Rao Z, Cheng Z, et al. Ultrathin, flexible polymer electrolyte for cost-effective fabrication of all-solid-state lithium metal batteries. Adv Energy Mater, 2019, 9: 1902767

    Article  CAS  Google Scholar 

  33. Wu J, Yuan L, Zhang W, et al. Reducing the thickness of solid-state electrolyte membranes for high-energy lithium batteries. Energy Environ Sci, 2021, 14: 12–36

    Article  CAS  Google Scholar 

  34. Wang Z, Shen L, Deng S, et al. 10 µm-thick high-strength solid polymer electrolytes with excellent interface compatibility for flexible all-solid-state lithium-metal batteries. Adv Mater, 2021, 33: 2100353

    Article  CAS  Google Scholar 

  35. Wan J, **e J, Kong X, et al. Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries. Nat Nanotechnol, 2019, 14: 705–711

    Article  CAS  Google Scholar 

  36. Xu Y, Zhang S, Liang T, et al. Porous polyamide skeleton-reinforced solid-state electrolyte: Enhanced flexibility, safety, and electrochemical performance. ACS Appl Mater Interfaces, 2021, 13: 11018–11025

    Article  CAS  Google Scholar 

  37. Lu J, Zhou J, Chen R, et al. 4.2 V poly(ethylene oxide)-based all-solid-state lithium batteries with superior cycle and safety performance. Energy Storage Mater, 2020, 32: 191–198

    Article  Google Scholar 

  38. Mindemark J, Lacey MJ, Bowden T, et al. Beyond PEO—Alternative host materials for Li+-conducting solid polymer electrolytes. Prog Polym Sci, 2018, 81: 114–143

    Article  CAS  Google Scholar 

  39. Wang H, Sheng L, Yasin G, et al. Reviewing the current status and development of polymer electrolytes for solid-state lithium batteries. Energy Storage Mater, 2020, 33: 188–215

    Article  Google Scholar 

  40. Evans J, Vincent CA, Bruce PG. Electrochemical measurement of transference numbers in polymer electrolytes. Polymer, 1987, 28: 2324–2328

    Article  CAS  Google Scholar 

  41. Xuan C, Gao S, Wang Y, et al. In-situ generation of high performance thiol-conjugated solid polymer electrolytes via reliable thiol-acrylate click chemistry. J Power Sources, 2020, 456: 228024

    Article  CAS  Google Scholar 

  42. Wang H, Wang Q, Cao X, et al. Thiol-branched solid polymer electrolyte featuring high strength, toughness, and lithium ionic conductivity for lithium-metal batteries. Adv Mater, 2020, 32: 2001259

    Article  CAS  Google Scholar 

  43. Homann G, Stolz L, Nair J, et al. Poly(ethylene oxide)-based electrolyte for solid-state-lithium-batteries with high voltage positive electrodes: Evaluating the role of electrolyte oxidation in rapid cell failure. Sci Rep, 2020, 10: 4390

    Article  Google Scholar 

  44. Yang X, Jiang M, Gao X, et al. Determining the limiting factor of the electrochemical stability window for PEO-based solid polymer electrolytes: Main chain or terminal −OH group? Energy Environ Sci, 2020, 13: 1318–1325

    Article  CAS  Google Scholar 

  45. Deng K, Guan T, Liang F, et al. Flame-retardant single-ion conducting polymer electrolytes based on anion acceptors for high-safety lithium metal batteries. J Mater Chem A, 2021, 9: 7692–7702

    Article  CAS  Google Scholar 

  46. Deng K, Zhou S, Xu Z, et al. A high ion-conducting, self-healing and nonflammable polymer electrolyte with dynamic imine bonds for dendrite-free lithium metal batteries. Chem Eng J, 2022, 428: 131224

    Article  CAS  Google Scholar 

  47. Lu Y, Tu Z, Archer LA. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat Mater, 2014, 13: 961–969

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Key Research and Development Program (2019YFA0705701), the National Natural Science Foundation of China (22179149, 22075329, 22008267, 51573215 and 21978332), the Basic and Applied Basic Research Foundation of Guangdong province (2021A0505030022, 2019A1515010803 and 2020A1515011445), and Guangzhou Scientific and Technological Planning Project (201804020025 and 201904010271).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. The Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province/State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou, 510275, China

    Zhifeng Li  (**志峰), Tianyi Wang  (王天羿), Lei Zhong  (钟雷), Min **ao  (肖敏), Shuan** Wang  (王拴紧), Sheng Huang  (黄盛) & Yuezhong Meng  (孟跃中)

  2. School of Chemical Engineering and Technology, Sun Yat-Sen University, Zhuhai, 519082, China

    Dongmei Han  (**东梅)

  3. School of Materials Science and Engineering, Beihang University, Bei**g, 100083, China

    Shichao Zhang  (张世超)

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  1. Zhifeng Li  (**志峰)
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Contributions

Li Z and Wang T carried out the project and wrote the original draft; Zhong L and Meng Y refined the draft and supervised the project; **ao M, Han D, Wang S, Zhang S, and Huang S contributed to the data analysis and discussion. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Lei Zhong  (钟雷) or Yuezhong Meng  (孟跃中).

Additional information

Zhifeng Li is currently a ME candidate at the School of Material Science and Engineering, Sun Yat-sen University. He received his BE degree from Sun Yat-sen University in 2020. His research interest is solid polymer electrolytes and their applications in LIBs.

Tianyi Wang received his BE degree from the School of Materials Science and Engineering, Sun Yat-sen University in 2016. He is studying for a doctorate degree under the supervision of Prof. Yuezhong Meng at Sun Yat-sen University.

Lei Zhong received her PhD degree from the School of Material Science and Engineering, Sun Yat-sen University in 2018. She became a postdoctoral and associate research fellow at the School of Materials Science and Engineering, Sun Yat-sen university in 2018 and 2020, respectively. Her research interest includes solid electrolytes and their applications in energy devices, such as lithium sulfur batteries.

Yuezhong Meng received his BSc, MSc, and PhD degrees from Dalian University of Technology. He worked at the City University of Hong Kong, McGill University, Nanyang Technological University and the National University of Singapore for more than 8 years. He became a “Hundred Talents” member of Chinese Academy of Sciences in 1998. Now he is a Pearl-River professor at Sun Yat-sen University and the director of the Key Laboratory of Low-carbon Chemistry and Energy Conservation of Guangdong Province.

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The authors declare that they have no conflict of interest.

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Li, Z., Wang, T., Zhong, L. et al. Ultrathin thiol-ene crosslinked polymeric electrolyte for solid-state and high-performance lithium metal batteries. Sci. China Mater. 66, 1332–1340 (2023). https://doi.org/10.1007/s40843-022-2259-3

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