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A quasi-solid-state electrolyte with high ionic conductivity for stable lithium-ion batteries

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Abstract

The practical applications of solid-state electrolytes in lithium-ion batteries (LIBs) are hindered by their low ionic conductivity and high interfacial resistance. Herein, an ethoxylated trimethylolpropane triacrylate based quasi-solid-state electrolyte (ETPTA-QSSE) with a three-dimensional (3D) network is prepared by a one-step in-situ photopolymerization method. The 3D network is designed to overcome the contradiction between the plasticizer-related ionic conductivity and the thickness-dependent mechanical property of quasi-solid-state electrolytes. The ETPTA-QSSE achieves superb room-temperature ionic conductivity up to 4.55×10−3 S cm−1, a high lithium ion transference number of 0.57, along with a wide electrochemical window of 5.3 V (vs. Li+/Li), which outperforms most ever of the reported solid-state electrolytes. Owing to the robust network structure and the cathode-electrolyte integrated electrode design, Li metal symmetrical cells show reduced interface resistance and reinforced electrode/ electrolyte interface stability. When applying the ETPTA-QSSE in LiFePO4∥Li cells, the quasi-solid-state cell demonstrates an enhanced initial discharge capacity (155.5 mAh g−1 at 0.2 C) accompanied by a high average Coulombic efficiency of greater than 99.3%, offering capacity retention of 92% after 200 cycles. Accordingly, this work sheds light on the strategy of enhancing ionic conductivity and reducing interfacial resistance of quasi-solid-state electrolytes, which is promising for high-voltage LIBs.

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References

  1. Goodenough J B, Kim Y. Challenges for rechargeable Li batteries. Chem Mater, 2009, 22: 587–603

    Article  Google Scholar 

  2. Goodenough J B, Park K S. The Li-ion rechargeable battery: A perspective. J Am Chem Soc, 2013, 135: 1167–1176

    Article  Google Scholar 

  3. Zhou D, Shanmukaraj D, Tkacheva A, et al. Polymer electrolytes for lithium-based batteries: Advances and prospects. Chem, 2019, 5: 2326–2352

    Article  Google Scholar 

  4. Wan J, Xie 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  Google Scholar 

  5. Hatzell K B, Chen X C, Cobb C L, et al. Challenges in lithium metal anodes for solid-state batteries. ACS Energy Lett, 2020, 5: 922–934

    Article  Google Scholar 

  6. Ge J, Fan L, Rao A M, et al. Surface-substituted prussian blue analogue cathode for sustainable potassium-ion batteries. Nat Sustain, 2022, 5: 225–234

    Article  Google Scholar 

  7. Zhang Q, Liu K, Ding F, et al. Recent advances in solid polymer electrolytes for lithium batteries. Nano Res, 2017, 10: 4139–4174

    Article  Google Scholar 

  8. Manthiram A, Yu X, Wang S. Lithium battery chemistries enabled by solid-state electrolytes. Nat Rev Mater, 2017, 2: 16103

    Article  Google Scholar 

  9. Zhang J, Zhao N, Zhang M, et al. Flexible and ion-conducting membrane electrolytes for solid-state lithium batteries: Dispersion of garnet nanoparticles in insulating polyethylene oxide. Nano Energy, 2016, 28: 447–454

    Article  Google Scholar 

  10. Shi Y, Liu G X, Wan J, et al. In-situ nanoscale insights into the evolution of solid electrolyte interphase shells: Revealing interfacial degradation in lithium metal batteries. Sci China Chem, 2021, 64: 734–738

    Article  Google Scholar 

  11. Jiang T, He P, Wang G, et al. Solvent-free synthesis of thin, flexible, nonflammable garnet-based composite solid electrolyte for all-solidstate lithium batteries. Adv Energy Mater, 2020, 10: 1903376

    Article  Google Scholar 

  12. Zhao Y, Wang L, Zhou Y, et al. Solid polymer electrolytes with high conductivity and transference number of Li ions for Li-based rechargeable batteries. Adv Sci, 2021, 8: 2003675

    Article  Google Scholar 

  13. Oh D Y, Nam Y J, Park K H, et al. Excellent compatibility of solvate ionic liquids with sulfide solid electrolytes: Toward favorable ionic contacts in bulk-type all-solid-state lithium-ion batteries. Adv Energy Mater, 2015, 5: 1500865

    Article  Google Scholar 

  14. Cheng E J, Kimura T, Shoji M, et al. Ceramic-based flexible sheet electrolyte for Li batteries. ACS Appl Mater Interfaces, 2020, 12: 10382–10388

    Article  Google Scholar 

  15. Fan W, Li N W, Zhang X, et al. A dual-salt gel polymer electrolyte with 3D cross-linked polymer network for dendrite-free lithium metal batteries. Adv Sci, 2018, 5: 1800559

    Article  Google Scholar 

  16. Ding C, Huang L, Guo Y, et al. An ultra-durable gel electrolyte stabilizing ion deposition and trapping polysulfides for lithium-sulfur batteries. Energy Storage Mater, 2020, 27: 25–34

    Article  Google Scholar 

  17. Al-Masri D, Yunis R, Zhu H, et al. A new approach to very high lithium salt content quasi-solid state electrolytes for lithium metal batteries using plastic crystals. J Mater Chem A, 2019, 7: 25389–25398

    Article  Google Scholar 

  18. Tan R, Gao R, Zhao Y, et al. Novel organic-inorganic hybrid electrolyte to enable LiFePO4 quasi-solid-state Li-ion batteries performed highly around room temperature. ACS Appl Mater Interfaces, 2016, 8: 31273–31280

    Article  Google Scholar 

  19. Jiang G, Qu C, Xu F, et al. Glassy metal-organic-framework-based quasi-solid-state electrolyte for high-performance lithium-metal batteries. Adv Funct Mater, 2021, 31: 2104300

    Article  Google Scholar 

  20. Zhou J, Ji H, Liu J, et al. A new high ionic conductive gel polymer electrolyte enables highly stable quasi-solid-state lithium sulfur battery. Energy Storage Mater, 2019, 22: 256–264

    Article  Google Scholar 

  21. Zhou M, Liu R, Jia D, et al. Ultrathin yet robust single lithium-ion conducting quasi-solid-state polymer-brush electrolytes enable ultra-long-life and dendrite-free lithium-metal batteries. Adv Mater, 2021, 33: 2100943

    Article  Google Scholar 

  22. Li Z, Zhou X Y, Guo X. High-performance lithium metal batteries with ultraconformal interfacial contacts of quasi-solid electrolyte to electrodes. Energy Storage Mater, 2020, 29: 149–155

    Article  Google Scholar 

  23. Choudhury S, Mangal R, Agrawal A, et al. A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles. Nat Commun, 2015, 6: 10101

    Article  Google Scholar 

  24. Tu Z, Kambe Y, Lu Y, et al. Nanoporous polymer-ceramic composite electrolytes for lithium metal batteries. Adv Energy Mater, 2014, 4: 1300654

    Article  Google Scholar 

  25. Byrne N, Efthimiadis J, MacFarlane D R, et al. The enhancement of lithium ion dissociation in polyelectrolyte gels on the addition of ceramic nano-fillers. J Mater Chem, 2004, 14: 127–133

    Article  Google Scholar 

  26. Zou X, Lu Q, Zhong Y, et al. Flexible, flame-resistant, and dendrite-impermeable gel-polymer electrolyte for Li-O2/air batteries workable under hurdle conditions. Small, 2018, 14: 1801798

    Article  Google Scholar 

  27. Choi C S, Lau J, Hur J, et al. Synthesis and properties of a photopatternable lithium-ion conducting solid electrolyte. Adv Mater, 2018, 30: 1703772

    Article  Google Scholar 

  28. Zardalidis G, Pipertzis A, Mountrichas G, et al. Effect of polymer architecture on the ionic conductivity. Densely grafted poly(ethylene oxide) brushes doped with LiTF. Macromolecules, 2016, 49: 2679–2687

    Article  Google Scholar 

  29. Chen G, Zhang F, Zhou Z, et al. A flexible dual-ion battery based on PVDF-HFP-modified gel polymer electrolyte with excellent cycling performance and superior rate capability. Adv Energy Mater, 2018, 8: 1801219

    Article  Google Scholar 

  30. Duan J, Huang L, Wang T, et al. Shaping the contact between Li metal anode and solid-state electrolytes. Adv Funct Mater, 2020, 30: 1908701

    Article  Google Scholar 

  31. Duan H, Yin Y X, Zeng X X, et al. In-situ plasticized polymer electrolyte with double-network for flexible solid-state lithium-metal batteries. Energy Storage Mater, 2018, 10: 85–91

    Article  Google Scholar 

  32. Lin D, Liu W, Liu Y, et al. High ionic conductivity of composite solid polymer electrolyte via in situ synthesis of monodispersed SiO2 nanospheres in poly(ethylene oxide). Nano Lett, 2016, 16: 459–465

    Article  Google Scholar 

  33. Cao J, Xie Y, Yang Y, et al. Achieving uniform Li plating/stripping at ultrahigh currents and capacities by optimizing 3D nucleation sites and Li2Se-enriched SEI. Adv Sci, 2022, 9: 2104689

    Article  Google Scholar 

  34. Li Z, Xie H X, Zhang X Y, et al. In situ thermally polymerized solid composite electrolytes with a broad electrochemical window for all-solid-state lithium metal batteries. J Mater Chem A, 2020, 8: 3892–3900

    Article  Google Scholar 

  35. Cho S J, Jung G Y, Kim S H, et al. Monolithic heterojunction quasi-solid-state battery electrolytes based on thermodynamically immiscible dual phases. Energy Environ Sci, 2019, 12: 559–565

    Article  Google Scholar 

  36. Kim S H, Choi K H, Cho S J, et al. Printable solid-state lithium-ion batteries: A new route toward shape-conformable power sources with aesthetic versatility for flexible electronics. Nano Lett, 2015, 15: 5168–5177

    Article  Google Scholar 

  37. Si Z, Li J, Ma L, et al. The ultrafast and continuous fabrication of a polydimethylsiloxane membrane by ultraviolet-induced polymerization. Angew Chem Int Ed, 2019, 58: 17175–17179

    Article  Google Scholar 

  38. Jeon Y M, Kim S, Lee M, et al. Polymer-clay nanocomposite solidstate electrolyte with selective cation transport boosting and retarded lithium dendrite formation. Adv Energy Mater, 2020, 10: 2003114

    Article  Google Scholar 

  39. Wen P, Lu P, Shi X, et al. Photopolymerized gel electrolyte with unprecedented room-temperature ionic conductivity for high-energy-density solid-state sodium metal batteries. Adv Energy Mater, 2021, 11: 2002930

    Article  Google Scholar 

  40. Bruce P G, Vincent C A. Steady state current flow in solid binary electrolyte cells. J Electroanal Chem Interfacial Electrochem, 1987, 225: 1–17

    Article  Google Scholar 

  41. Xu H, Wang A, Liu X, et al. A new fluorine-containing star-branched polymer as electrolyte for all-solid-state lithium-ion batteries. Polymer, 2018, 146: 249–255

    Article  Google Scholar 

  42. Liu W, Lin D, Sun J, et al. Improved lithium ionic conductivity in composite polymer electrolytes with oxide-ion conducting nanowires. ACS Nano, 2016, 10: 11407–11413

    Article  Google Scholar 

  43. He X, Ni Y, Hou Y, et al. A new insight into the ionic conduction mechanism of quasi-solid polymer electrolyte through multispectral characterizations. Angew Chem Int Ed, 2021, 60: 22672–22677

    Article  Google Scholar 

  44. Nag A, Ali M A, Singh A, et al. N-Boronated polybenzimidazole for composite electrolyte design of highly ion conducting pseudo solidstate ion gel electrolytes with a high Li-transference number. J Mater Chem A, 2019, 7: 4459–4468

    Article  Google Scholar 

  45. Han F, Zhu Y, He X, et al. Electrochemical stability of Li10GeP2S12 and Li7La3Zr2O12 solid electrolytes. Adv Energy Mater, 2016, 6: 1501590

    Article  Google Scholar 

  46. Lee M, Hong J, Lee B, et al. Multi-electron redox phenazine for ready-to-charge organic batteries. Green Chem, 2017, 19: 2980–2985

    Article  Google Scholar 

  47. Xie Y, Cao J, Wang X, et al. MOF-derived bifunctional Co0.85Se nanoparticles embedded in N-doped carbon nanosheet arrays as efficient sulfur hosts for lithium-sulfur batteries. Nano Lett, 2021, 21: 8579–8586

    Article  Google Scholar 

  48. Li S, Zhang W, Liu J, et al. Maximizing catalytically active surface gallium for electrocatalysis of lithium polysulfides in lithium-sulfur batteries by silica@gallium core-shell particles. Appl Surf Sci, 2021, 563: 150381

    Article  Google Scholar 

  49. Li Y, Xu B, Xu H, et al. Hybrid polymer/garnet electrolyte with a small interfacial resistance for lithium-ion batteries. Angew Chem Int Ed, 2017, 56: 753–756

    Article  Google Scholar 

  50. Ye F, Zhang X, Liao K, et al. A smart lithiophilic polymer filler in gel polymer electrolyte enables stable and dendrite-free Li metal anode. J Mater Chem A, 2020, 8: 9733–9742

    Article  Google Scholar 

  51. Chen S, Wen K, Fan J, et al. Progress and future prospects of highvoltage and high-safety electrolytes in advanced lithium batteries: From liquid to solid electrolytes. J Mater Chem A, 2018, 6: 11631–11663

    Article  Google Scholar 

  52. Zhang Y, Sun X, Cao D, et al. Self-stabilized LiNi0.8Mn0.1Co0.1O2 in thiophosphate-based all-solid-state batteries through extra LiOH. Energy Storage Mater, 2021, 41: 505–514

    Article  Google Scholar 

  53. Lee S, Lee K, Ku K, et al. Utilizing latent multi-redox activity of p-type organic cathode materials toward high energy density lithium-organic batteries. Adv Energy Mater, 2020, 10: 2001635

    Article  Google Scholar 

  54. Liu W, Li J, Li W, et al. Inhibition of transition metals dissolution in cobalt-free cathode with ultrathin robust interphase in concentrated electrolyte. Nat Commun, 2020, 11: 3629

    Article  Google Scholar 

  55. Gu M, Fan L, Zhou J, et al. Regulating solvent molecule coordination with KPF6 for superstable graphite potassium anodes. ACS Nano, 2021, 15: 9167–9175

    Article  Google Scholar 

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Authors and Affiliations

  1. College of Chemistry, Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated Materials, Fuzhou University, Fuzhou, 350108, China

    WenJing Zhang, SenLin Li, YuRong Zhang, JingDong Liu & YuanHui Zheng

  2. College of Physics and Information Engineering, Fuzhou University, Fuzhou, 350108, China

    XingHui Wang

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  1. WenJing Zhang
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  2. SenLin Li
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  5. JingDong Liu
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  6. YuanHui Zheng
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Correspondence to XingHui Wang or YuanHui Zheng.

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This work was supported by the Recruitment Program of Global Experts, the Hundred-Talent Project of Fujian, and Fuzhou University.

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The supporting information is available online at https://tech.scichina.com and https://link.springer.com. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Zhang, W., Li, S., Zhang, Y. et al. A quasi-solid-state electrolyte with high ionic conductivity for stable lithium-ion batteries. Sci. China Technol. Sci. 65, 2369–2379 (2022). https://doi.org/10.1007/s11431-022-2075-8

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  • DOI: https://doi.org/10.1007/s11431-022-2075-8

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