English

Percolation Structure Design of Organic-inorganic Composite Electrolyte with High Lithium-Ion Conductivity

• Xinrun Yu ^{1, 2,} ,
• Jun Ma ^{2, ,} ,
• Chunbo Mou ^1, ,
• Guanglei Cui ^{2, ,}

• 1.

  College of Materials Science and Engineering, Qingdao University, Qingdao 266071, Shandong Province, China

• 2.

  Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao Industrial Energy Storage Technology Institute, Qingdao 266101, Shandong Province, China

Corresponding author: Email: majun@qibebt.ac.cn (J.M.); Email: cuigl@qibebt.ac.cn (G.C.)

• Received Date: 25 December 2019
  Accepted Date: 15 January 2020
  Revised Date: 14 January 2020
  Available Online: 15 March 2022
• Fund Project:

  the National Natural Science Foundation of China 

Abstract: With the increasing demand for safe high energy density energy storage systems, solid-state lithium metal batteries have attracted extensive attention. The solid electrolyte, which is expected to replace the traditional liquid organic electrolyte core in solid-state lithium metal batteries because of its excellent mechanical properties and non-flammability. Lithium-ion solid-state electrolytes can be categorized into two broad types: inorganic electrolytes and polymer electrolytes. Inorganic solid electrolytes have the advantages of high room-temperature ionic conductivity, wide electrochemical window, and high mechanical strength. However, their high brittleness, high solid-solid interface contact resistance, complex preparation process, and high cost make future development and practical applications challenging. In contrast to inorganic electrolytes, polymer electrolytes are easy to process and exhibit better flexibility and easy formation of a good, stable interface with lithium metal. However, solid polymer electrolytes still exhibit insufficient ionic conductivity at room temperatures compared with polymer solid electrolytes. Therefore, neither the inorganic electrolytes nor the polymer electrolytes alone can meet the requirements of high-performance solid-state lithium metal batteries. Recently, dispersing ceramic fillers (especially fast lithium-ion conductors) in a polymer matrix to integrate with composite polymer electrolytes has been developed as an effective strategy for enhancing room-temperature ionic conductivity, mechanical properties, and thermal stability of solid polymer electrolytes. Inorganic fillers do not only reduce the polymer matrix crystallization but also improve the lithium-ion conductivity by promoting the dissociation of lithium salts. The Lewis acid-base groups and oxygen vacancy at the surface of inorganic fillers can increase the migration number of lithium ions. Nevertheless, the effect of the percolation structure of inorganic fillers on the conductivity of organic-inorganic composite electrolytes should be discussed. It is believed that the organic-inorganic interface is the main reason for the significantly enhanced lithium-ion conductivity of composite electrolytes based on the percolation theory. In this paper, from the perspective of percolation structure design, we summarize the progress on high lithium-ion conductive organic-inorganic composite electrolytes with different dimensional-structured inorganic fillers. From one-dimensional filler to three-dimensional filler, the ionic conductivity of a composite electrolyte can be significantly influenced by the rational design and optimization of the percolation structure and orientation of the inorganic filler. Vertically aligned inorganic fillers provide optimal ion transport pathways in the polymer matrix, significantly improving the lithium-ion conductivity of the composite electrolytes. Furthermore, the advantages and disadvantages of the different percolation structures are compared and discussed objectively. Finally, future development trends of organic-inorganic composite electrolytes are discussed.

Key words:
• Inorganic nano-filler
•  /  Polymer electrolyte
•  /  Composite electrolyte
•  /  High lithium-ion conductivity

• 1. [1]

     Cheng, F.; Liang, J.; Tao, Z.; Chen, J. Adv. Mater. 2011, 23, 1695. doi: 10.1002/adma.201003587

  2. [2]

     Tarascon, J. M.; Armand, M. Nature 2001, 414, 359. doi: 10.1038/35104644

  3. [3]

     Lin, D.; Liu, Y.; Cui, Y. Nat. Nanotechnol. 2017, 12, 194. doi: 10.1038/nnano.2017.16

  4. [4]

     Liu, B.; Zhang, J. G.; Xu, W. Joule 2018, 2, 833. doi: 10.1016/j.joule.2018.03.008

  5. [5]

     Fan, L.; Wei, S.; Li, S.; Li, Q.; Lu, Y. Adv. Energy Mater. 2018, 8, 1702657. doi: 10.1002/aenm.201702657

  6. [6]

     Chen, S.; Wen, K.; Fan, J.; Bando, Y.; Golberg, D. J. Mater. Chem. A 2018, 6, 11631. doi: 10.1039/c8ta03358g

  7. [7]

     Nowak, S.; Winter, M. J. Electrochem. Soc. 2015, 162 (14), A2500. doi: 10.1149/2.0121514jes

  8. [8]

     Schroeder, D. J.; Hubaud, A. A.; Vaughey, J. T. Mater. Res. Bull. 2014, 49, 614. doi: 10.1016/j.materresbull.2013.10.006

  9. [9]

     崔闻宇, 安茂忠, 杨培霞. 物理化学学报, 2010, 26 (5), 1233. doi: 10.3866/PKU.WHXB20100530Cui, W. Y.; An, M. Z.; Yang, P. X. Acta Phys. -Chim. Sin. 2010, 26 (5), 1233. doi: 10.3866/PKU.WHXB20100530

  10. [10]

      Chen, R.; Qu, W.; Guo, X.; Li, L.; Wu, F. Mater. Horiz. 2016, 3, 487. doi: 10.1039/c6mh00218h

  11. [11]

      Hu, Y. S. Nat. Energy 2016, 1, 16042. doi: 10.1038/nenergy.2016.42

  12. [12]

      Janek, J.; Zeier, W. G. Nat. Energy 2016, 1, 16141. doi: 10.1038/nenergy.2016.141

  13. [13]

      Zhou, D.; Shanmukaraj, D.; Tkacheva, A.; Armand, M.; Wang, G. Chemistry 2019, 5, 2326. doi: 10.1016/j.chempr.2019.05.009

  14. [14]

      Cheng, X. B.; Zhao, C. Z.; Yao, Y. X.; Liu, H.; Zhang, Q. Chemistry 2019, 5, 74. doi: 10.1016/j.chempr.2018.12.002

  15. [15]

      Zhu, Y.; He, X.; Mo, Y. ACS Appl. Mater. Interfaces 2015, 7, 23685. doi: 10.1021/acsami.5b07517

  16. [16]

      Bachman, J. C.; Muy, S.; Grimaud, A.; Chang, H. H.; Pour, N.; Lux, S. F.; Paschos, O.; Maglia, F.; Lupart, S.; Lamp, P.; et al. Chem. Rev. 2016, 116, 140. doi: 10.1021/acs.chemrev.5b00563

  17. [17]

      Chinnam, P. R.; Wunder, S. L. ACS Energy Lett. 2016, 2, 134. doi: 10.1021/acsenergylett.6b00609

  18. [18]

      Han, F.; Zhu, Y.; He, X.; Mo, Y.; Wang, C. Adv. Energy Mater. 2016, 6(8), 1501590. doi: 10.1002/aenm.201501590

  19. [19]

      Yao, X.; Huang, B.; Yin, J.; Peng, G.; Huang, Z.; Gao, C.; Liu, D.; Xu, X. Chin. Phys. B 2016, 25, 018802. doi: 10.1088/1674-1056/25/1/018802

  20. [20]

      Hu, P.; Chai, J.; Duan, Y.; Liu, Z.; Cui, G.; Chen, L. J. Mater. Chem. A 2016, 4, 10070. doi: 10.1039/c6ta02907h

  21. [21]

      Zhang, X.; Wang, S.; Xue, C.; Xin, C.; Lin, Y.; Shen, Y.; Li, L.; Nan, C. W. Adv. Mater. 2019, 31, e1806082. doi: 10.1002/adma.201806082

  22. [22]

      Zhang, W.; Nie, J.; Li, F.; Wang, Z. L.; Sun, C. Nano Energy 2018, 45, 413. doi: 10.1016/j.nanoen.2018.01.028

  23. [23]

      费慧芳, 刘永鹏, 魏传亮, 张煜婵, 冯金奎, 陈传忠, 于慧君. 物理化学学报, 2020, 36 (5), 1905015. doi: 10.3866/PKU.WHXB201905015Fei, H. F.; Liu, Y. P.; Wei, C. L.; Zhang, Y. C.; Feng, J. K.; Chen, C. Z.; Yu, H. J. Acta Phys. -Chim. Sin. 2020, 36 (5), 1905015. doi: 10.3866/PKU.WHXB201905015

  24. [24]

      Quartarone, E.; Mustarelli, P. Chem. Soc. Rev. 2011, 40, 2525. doi: 10.1039/c0cs00081g

  25. [25]

      Zhou, Q.; Ma, J.; Dong, S.; Li, X.; Cui, G. Adv. Mater. 2019, 31(50), 1902029. doi: 10.1002/adma.201902029

  26. [26]

      Hu, T. S.; Hong, P. K.; Saikia, D.; Kao, H. M.; Chen, M. C. Ionics 2014, 20, 1561. doi: 10.1007/s11581-014-1107-2

  27. [27]

      Masoud, E. M.; El-Bellihi, A. A.; Bayoumy, W. A.; Mousa, M. A. J. Alloy. Compd. 2013, 575, 223. doi: 10.1016/j.jallcom.2013.04.054

  28. [28]

      Zhang, X.; Liu, T.; Zhang, S.; Huang, X.; Xu, B.; Lin, Y.; Xu, B.; Li, L.; Nan, C. W.; Shen, Y. J. Am. Chem. Soc. 2017, 139, 13779. doi: 10.1021/jacs.7b06364

  29. [29]

      Zheng, J.; Tang, M.; Hu, Y. Y. Angew. Chem. Int. Ed. 2016, 55, 12538. doi: 10.1002/anie.201607539

  30. [30]

      Zhao, Y.; Wu, C.; Peng, G.; Chen, X.; Yao, X.; Bai, Y.; Wu, F.; Chen, S.; Xu, X. J. Power Sources 2016, 301, 47. doi: 10.1016/j.jpowsour.2015.09.111

  31. [31]

      Dieterich, W.; Dürr, O.; Pendzig, P.; Bunde, A.; Nitzan, A. Phys. A 1999, 266, 229. doi: 10.1016/S0378-4371(98)00597-4

  32. [32]

      Li, Z.; Huang, H.; Zhu, J.; Wu, J.; Yang, H.; Wei, L.; Guo, X. ACS Appl. Mater. Interfaces 2018, 11 (1), 784. doi: 10.1021/acsami.8b17279

  33. [33]

      Kitajima, S.; Kitaura, H.; Im, D.; Hwang, Y.; Ishida, M.; Zhou, H. Solid State Ionics 2018, 316, 29. doi: 10.1016/j.ssi.2017.12.018

  34. [34]

      Chen, L.; Li, Y.; 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

  35. [35]

      Liu, X.; Peng, S.; Gao, S.; Cao, Y.; You, Q.; Zhou, L.; Jin, Y.; Liu, Z.; Liu, J. ACS Appl. Mater. Interfaces 2018, 10, 15691. doi: 10.1021/acsami.8b01631

  36. [36]

      Zhai, H.; Xu, P.; Ning, M.; Cheng, Q.; Mandal, J.; Yang, Y. Nano Lett. 2017, 17, 3182. doi: 10.1021/acs.nanolett.7b00715

  37. [37]

      Liu, W.; Liu, N.; Sun, J.; Hsu, P. C.; Li, Y.; Lee, H. W.; Cui, Y. Nano Lett. 2015, 15, 2740. doi: 10.1021/acs.nanolett.5b00600

  38. [38]

      Zhu, P.; Yan, C.; Dirican, M.; Zhu, J.; Zang, J.; Selvan, R. K.; Chung, C. C.; Jia, H.; Li, Y.; Kiyak, Y.; et al. J. Mater. Chem. A 2018, 6, 4279. doi: 10.1039/c7ta10517g

  39. [39]

      Liu, W.; Lee, S. W.; Lin, D.; Shi, F.; Wang, S.; Sendek, A. D.; Cui, Y. Nat. Energy 2017, 2, 17035. doi: 10.1038/nenergy.2017.35

  40. [40]

      Tang, W.; Tang, S.; Zhang, C.; Ma, Q.; Xiang, Q.; Yang, Y. W.; Luo, J. Adv. Energy Mater. 2018, 8, 1800866. doi: 10.1002/aenm.201800866

  41. [41]

      Tang, W.; Tang, S.; Guan, X.; Zhang, X.; Xiang, Q.; Luo, J. Adv. Funct. Mater. 2019, 29, 1900648. doi: 10.1002/adfm.201900648

  42. [42]

      Jia, W.; Li, Z.; Wu, Z.; Wang, L.; Wu, B.; Wang, Y.; Cao, Y.; Li, J. Solid State Ionics 2018, 315, 7. doi: 10.1016/j.ssi.2017.11.026

  43. [43]

      Kammoun, M.; Berg, S.; Ardebili, H. Nanoscale 2015, 7, 17516. doi: 10.1039/c5nr04339e

  44. [44]

      Cheng, S.; Smith, D. M.; Li, C. Y. Macromolecule 2015, 48, 4503. doi: 10.1021/acs.macromol.5b00972

  45. [45]

      Yuan, M.; Erdman, J.; Tang, C.; Ardebili, H. RSC Adv. 2014, 4, 59637. doi: 10.1039/c4ra07919a

  46. [46]

      Li, A.; Liao, X.; Zhang, H.; Shi, L.; Wang, P.; Cheng, Q.; Borovilas, J.; Li, Z.; Huang, W.; Fu, Z.; et al. Adv. Mater. 2019, 32, 1905517. doi: 10.1002/adma.201905517

  47. [47]

      Zekoll, S.; Marriner-Edwards, C.; Hekselman, A. K. O.; Kasemchainan, J.; Kuss, C.; Armstrong, D. E. J.; Cai, D.; Wallace, R. J.; Richter, F. H.; Thijssen, J. H. J.; et al. Energy Environ. Sci. 2018, 11, 185. doi: 10.1039/c7ee02723k

  48. [48]

      Xie, H.; Yang, C.; Fu, K.; Yao, Y.; Jiang, F.; Hitz, E.; Liu, B.; Wang, S.; Hu, L. Adv. Energy Mater. 2018, 8, 1703474. doi: 10.1002/aenm.201703474

  49. [49]

      Bae, J.; Li, Y.; Zhang, J.; Zhou, X.; Zhao, F.; Shi, Y.; Goodenough, J. B.; Yu, G. Angew. Chem. Int. Ed. 2018, 57, 2096. doi: 10.1002/anie.201710841

  50. [50]

      Zhou, Q.; Zhang, J.; Cui, G. Macromol. Mater. Eng. 2018, 303, 1800337. doi: 10.1002/mame.201800337

  51. [51]

      Duan, H.; Fan, M.; Chen, W. P.; Li, J. Y.; Wang, P. F.; Wang, W. P.; Shi, J. L.; Yin, Y. X.; Wan, L. J.; Guo, Y. G. Adv. Mater. 2019, 31, e1807789. doi: 10.1002/adma.201807789

  52. [52]

      Zhou, W.; Wang, Z.; Pu, Y.; Li, Y.; Xin, S.; Li, X.; Chen, J.; Goodenough, J. B. Adv. Mater. 2018, 31, 1805574. doi: 10.1002/adma.201805574

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