English

Uniform Garnet Nanoparticle Dispersion in Composite Polymer Electrolytes

• Hanmei Lü ,
• Xin Chen ,
• Qifu Sun ,
• Ning Zhao ^, ,
• Xiangxin Guo ^,

• College of Physics, Qingdao University, Qingdao 266071, Shandong Province, China

Corresponding author: Email: n.zhao@qdu.edu.cn (N.Z.); Email: xxguo@qdu.edu.cn (X.G.)

• Received Date: 08 May 2023
  Accepted Date: 06 June 2023
  Revised Date: 06 June 2023
  Available Online: 15 March 2024
• Fund Project:

  the Key R&D Program of Shandong Province 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

Abstract: Solid-state lithium batteries (SSLBs) have the potential to further boost the energy density of Li-ion batteries and improve their safety by facilitating the use of Li-metal anodes and limiting flammability, respectively. Solid electrolytes, as key SSLB materials, significantly impact battery performance, among which composite polymer/garnet electrolytes are promising materials for manufacturing SSLBs on a large scale, owing to polymer electrolyte processing ease in combination with the thermal stabilities and high ionic conductivities of garnet electrolytes, both of which are beneficial. Uniformly dispersing garnet particles in the polymer matrix is important for ensuring a highly ionically conductive composite polymer electrolyte. However, high nanoparticle surface energies and incompatible organic–inorganic interfaces lead to garnet particle agglomeration in the polymer matrix and a poorly ionically conductive composite electrolyte. With the aim of promoting Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) particle dispersion in both solvents and polymer matrices, in this study, we introduced the 3-glycidyloxypropyl trimethoxy silane (GPTMS) coupling agent onto the LLZTO surface. A 5-nm-thick GPTMS shell was constructed on each LLZTO nanoparticle by covalently bonding GPTMS molecules on the surface of the nanoparticle. The lipophilic epoxy group in GPTMS enables the uniform dispersion of GPTMS-modified LLZTO nanoparticles (LLZTO@GPTMS) in organic solvents, such as acetonitrile, N-methylpyrrolidone, and N, N-dimethylformamide. Particle-size-distribution experiments reveal that LLZTO-nanoparticle dispersity is positively correlated with solvent polarity. Well-dispersed LLZTO suspensions led to superior polyethylene-oxide-based (PEO-based) composite polymer electrolyte ionic conductivities of 2.31 × 10⁻⁴ S∙cm⁻¹ at 30 ℃. Both symmetric lithium batteries and SSLBs that use LiFePO₄ (LFP) cathodes, lithium-metal anodes, and the optimal PEO: LLZTO@GPTMS electrolyte exhibited prolonged cycling lives. Moreover, the polyethylene separator was homogeneously coated with LLZTO nanoparticles following GPTMS modification. LFP|Li batteries with LLZTO@GPTMS-coated PE separators exhibited better cycling stabilities than those of batteries with unmodified LLZTO/PE. This study demonstrated that GPTMS effectively improves LLZTO-nanoparticle dispersibility in both organic solvents and polymer matrices, which is also instructive for other organic–inorganic composite systems.

Key words:
• Solid-state Li battery
•  /  Garnet electrolyte
•  /  Composite solid electrolyte
•  /  Silane coupling agent
•  /  Nanoparticle dispersion

• 1. [1]

     Zhao, N.; Khokhar, W.; Bi, Z. J.; Shi, C.; Guo, X. X.; Fan, L. Z.; Nan, C. W. Joule 2019, 3 (5), 1190. doi: 10.1016/j.joule.2019.03.019

  2. [2]

     Bi, Z. J.; Mu, S.; Zhao, N.; Sun, W. H.; Huang, W. L.; Guo, X. X. Energy Storage Mater. 2021, 35, 512. doi: 10.1016/j.ensm.2020.11.038

  3. [3]

     金锋, 李静, 胡晨吉, 董厚才, 陈鹏, 沈炎宾, 陈立桅. 物理化学学报, 2019, 35 (12), 1399. doi: 10.3866/PKU.WHXB201904085Jin, F.; Li, J.; Hu, C. J.; Dong, H. C.; Chen, P.; Shen, Y. B.; Chen, L. W. Acta Phys. -Chim. Sin. 2019, 35 (12), 1399. doi: 10.3866/PKU.WHXB201904085

  4. [4]

     Hu, X.; Zuo, D.; Cheng, S.; Chen, S.; Liu, Y.; Bao, W.; Deng, S.; Harris, S. J.; Wan, J. Chem. Soc. Rev. 2023, 52 (3), 1103. doi: 10.1039/D2CS00322H

  5. [5]

     Mi, J.; Ma, J.; Chen, L.; Lai, C.; Yang, K.; Biao, J.; Xia, H.; Song, X.; Lv, W.; Zhong, G.; et al. Energy Storage Mater. 2022, 48, 375. doi: 10.1016/j.ensm.2022.02.048

  6. [6]

     Li, W. K.; Zhao, N.; Bi, Z. J.; Guo, X. X. Appl. Phys. Lett. 2022, 121 (3), 7. doi: 10.1063/5.0098255

  7. [7]

     Chen, X.; Jia, Z. Q.; Lv, H. M.; Wang, C. G.; Zhao, N.; Guo, X. X. J. Power Sources 2022, 545, 6. doi: 10.1016/j.jpowsour.2022.231939

  8. [8]

     Li, W. K.; Zhao, N.; Bi, Z. J.; Guo, X. X. J. Inorg. Mater. 2022, 37 (2), 189. doi: 10.15541/jim20210486

  9. [9]

     王晗, 安汉文, 单红梅, 赵雷, 王家钧. 物理化学学报, 2021, 37 (11), 2007070. doi: 10.3866/PKU.WHXB202007070Wang, H.; An, H. W.; Shan, H. M.; Zhao, L.; Wang, J. J. Acta Phys. -Chim. Sin. 2021, 37 (11), 2007070. doi: 10.3866/PKU.WHXB202007070

  10. [10]

      Tufail, M. K.; Zhai, P.; Jia, M.; Zhao, N.; Guo, X. Energy Mater. Adv. 2023, 4, 0015. doi: 10.34133/energymatadv.0015

  11. [11]

      Zhai, P. B.; Yang, Z. L.; Wei, Y.; Guo, X. X.; Gong, Y. J. Adv. Energy Mater. 2022, 12 (42), 13. doi: 10.1002/aenm.202200967

  12. [12]

      Chen, L. K.; Gu, T.; Ma, J. B.; Yang, K.; Shi, P. R.; Biao, J.; Mi, J. S.; Liu, M.; Lv, W.; He, Y. B. Nano Energy 2022, 100, 10. doi: 10.1016/j.nanoen.2022.107470

  13. [13]

      Huo, H. Y.; Chen, Y.; Luo, J.; Yang, X. F.; Guo, X. X.; Sun, X. L. Adv. Energy Mater. 2019, 9 (17), 8. doi: 10.1002/aenm.201804004

  14. [14]

      Mu, S.; Bi, Z. J.; Gao, S. H.; Guo, X. X. Chem. Res. Chin. Univ. 2021, 37 (2), 246. doi: 10.1007/s40242-021-1054-1

  15. [15]

      Zhang, J. X.; Zhao, N.; Zhang, M.; Li, Y. Q.; Chu, P. K.; Guo, X. X.; Di, Z. F.; Wang, X.; Li, H. Nano Energy 2016, 28, 447. doi: 10.1016/j.nanoen.2016.09.002

  16. [16]

      虞鑫润, 马君, 牟春博, 崔光磊. 物理化学学报, 2022, 38 (3), 1912061. doi: 10.3866/PKU.WHXB201912061Yu, X. R.; Ma, J.; Mou, C. B.; Cui, G. L. Acta Phys. -Chim. Sin. 2022, 38 (3), 1912061. doi: 10.3866/PKU.WHXB201912061

  17. [17]

      Zhai, P. B.; Chang, D. M.; Bi, Z. J.; Zhao, N.; Guo, X. X. Energy Storage Sci. Technol. 2022, 11 (9), 2847. doi: 10.19799/j.cnki.2095-4239.2022.0097

  18. [18]

      Chen, L.; Li, Y. T.; Li, S. P.; Fan, L. Z.; Nan, C. W.; Goodenough, J. B. Nano Energy 2018, 46, 176. doi: 10.1016/j.nanoen.2017.12.037

  19. [19]

      Huang, Z. Y.; Pang, W. Y.; Liang, P.; Jin, Z. H.; Grundish, N.; Li, Y. T.; Wang, C. A. J. Mater. Chem. A 2019, 7 (27), 16425. doi: 10.1039/c9ta03395e

  20. [20]

      Li, L. S.; Deng, Y. F.; Chen, G. H. J. Energy Chem. 2020, 50, 154. doi: 10.1016/j.jechem.2020.03.017

  21. [21]

      Zagorski, J.; del Amo, J. M. L.; Cordill, M. J.; Aguesse, F.; Buannic, L.; Llordes, A. ACS Appl. Energ. Mater. 2019, 2 (3), 1734. doi: 10.1021/acsaem.8b01850

  22. [22]

      Althues, H.; Henle, J.; Kaskel, S. Chem. Soc. Rev. 2007, 36 (9), 1454. doi: 10.1039/b608177k

  23. [23]

      Shrestha, S.; Wang, B.; Dutta, P. Adv. Colloid Interface Sci. 2020, 279, 16. doi: 10.1016/j.cis.2020.102162

  24. [24]

      Jia, M. Y.; Zhao, N.; Bi, Z. J.; Fu, Z. Q.; Xu, F. F.; Shi, C.; Guo, X. X. ACS Appl. Mater. Interfaces 2020, 12 (41), 46162. doi: 10.1021/acsami.0c13434

  25. [25]

      Kango, S.; Kalia, S.; Celli, A.; Njuguna, J.; Habibi, Y.; Kumar, R. Prog. Polym. Sci. 2013, 38 (8), 1232. doi: 10.1016/j.progpolymsci.2013.02.003

  26. [26]

      Xie, Y. J.; Hill, C. A. S.; Xiao, Z. F.; Militz, H.; Mai, C. Compos. Pt. A-Appl. Sci. Manuf. 2010, 41 (7), 806. doi: 10.1016/j.compositesa.2010.03.005

  27. [27]

      Li, C.; Liang, Z.; Li, Z.; Cao, D.; Zuo, D.; Chang, J.; Wang, J.; Deng, Y.; Liu, K.; Kong, X.; et al. Nano Lett. 2023, 23 (9), 4014. doi: 10.1021/acs.nanolett.3c00783

  28. [28]

      Yan, C. Y.; Zhu, P.; Jia, H.; Du, Z.; Zhu, J. D.; Orenstein, R.; Cheng, H.; Wu, N. Q.; Dirican, M.; Zhang, X. W. Energy Storage Mater. 2020, 26, 448. doi: 10.1016/j.ensm.2019.11.018

  29. [29]

      Zhang, Z. Y.; Zhang, S.; Geng, S. X.; Zhou, S. B.; Hu, Z. L.; Luo, J. Y. Energy Storage Mater. 2022, 51, 19. doi: 10.1016/j.ensm.2022.06.025

  30. [30]

      Li, X. X.; Zheng, B. Y.; Xu, L. M.; Wu, D. D.; Liu, Z. L.; Zhang, H. C. Rare Metal Mat. Eng. 2012, 41 (1), 24. doi: 10.1016/s1875-5372(12)60024-1

  31. [31]

      Li, H.; Wang, C. A.; Guo, Z. H.; Wang, H. R.; Zhang, Y. X.; Hong, R.; Peng, Z. R. Effects of Silane Coupling Agents on the Electrical Properties of Silica/Epoxy Nanocomposites, In IEEE International Conference on Dielectrics (ICD), Montpellier, France July 03–07; IEEE: Montpellier, France, 2016; pp. 1036.

  32. [32]

      Jia, M. Y.; Bi, Z. J.; Shi, C.; Zhao, N.; Guo, X. X. J. Power Sources 2021, 486, 7. doi: 10.1016/j.jpowsour.2020.229363

  33. [33]

      Gu, J.; Zhang, Q.; Dang, J.; Zhang, J.; Chen, S. Polym. Bull. 2009, 62 (5), 689. doi: 10.1007/s00289-009-0045-z

  34. [34]

      Yan, B.; Kotobuki, M.; Liu, J. Mater. Technol. 2016, 31 (11), 623. doi: 10.1080/10667857.2016.1196033

  35. [35]

      Song, S. D.; Chen, B. T.; Ruan, Y. L.; Sun, J.; Yu, L. M.; Wang, Y.; Thokchom, J. Electrochim. Acta 2018, 270, 501. doi: 10.1016/j.electacta.2018.03.101

  36. [36]

      Ghadimi, A.; Metselaar, I. H. Exp. Therm. Fluid Sci. 2013, 51, 1. doi: 10.1016/j.expthermflusci.2013.06.001

  37. [37]

      Jiang, L. Q.; Gao, L.; Sun, J. J. Colloid Interface Sci. 2003, 260 (1), 89. doi: 10.1016/s0021-9797(02)00176-5

  38. [38]

      Sadeghi, R.; Etemad, S. G.; Keshavarzi, E.; Haghshenasfard, M. Microfluid. Nanofluid. 2015, 18 (5–6), 1023. doi: 10.1007/s10404-014-1491-y

  39. [39]

      Isaac, J. A.; Devaux, D.; Bouchet, R. Nat. Mater. 2022, 21(12), 1412. doi: 10.1038/s41563-022-01343-w

  40. [40]

      Huang, W. L.; Zhao, N.; Bi, Z. J.; Shi, C.; Guo, X. X.; Fan, L. Z.; Nan, C. W. Mater. Today Nano 2020, 10, 100075. doi: 10.1016/j.mtnano.2020.100075

  41. [41]

      Pan, K. C.; Zhang, L.; Qian, W. W.; Wu, X. K.; Dong, K.; Zhang, H. T.; Zhang, S. J. Adv. Mater. 2020, 32 (17), 8. doi: 10.1002/adma.202000399

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