English

Research Progress of Functional Binders in Silicon-Based Anodes for Lithium-Ion Batteries

• Jingshuo Zhang ^1, ,
• Yue Zhai ^1, ,
• Ziyun Zhao ^1, ,
• Jiaxing He ^1, ,
• Wei Wei ^3, ,
• Jing Xiao ^{1, 3, 4,} ,
• Shichao Wu ^{1, 2, ,} ,
• Quan-Hong Yang ^{1, 2, 3, 4, ,}

• 1.

  Nanoyang Group, Tianjin Key Laboratory of Advanced Carbon and Electrochemical Energy Storage, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), and National Industry-Education Integration Platform of Energy Storage, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

• 2.

  Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China

• 3.

  Tianmu Lake Institute of Advanced Energy Storage Technologies, Liyang 213300, Jiangsu Province, China

• 4.

  Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou 350207, China

Corresponding author: Email: wushichao@tju.edu.cn (S.W.); Email: qhyangcn@tju.edu.cn (Q.Y.)

• Received Date: 02 June 2023
  Accepted Date: 20 July 2023
  Revised Date: 05 July 2023
  Available Online: 15 June 2024
• Fund Project:

  the National Key Research and Development Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

Abstract: Silicon (Si) has a high theoretical gravimetric capacity (3579 mAh∙g⁻¹ for Li₁₅Si₄), which is almost ten times higher than that of graphite (372 mAh∙g⁻¹) anode. Besides, it has low electrochemical potentials (0.4 V vs. Li⁺/Li), and abundant reserves. Thus, Si becomes a key anode material for the development of high-energy lithium-ion batteries. Nano-Si, typically compounded with graphite, has opened its commercialization. But the specific capacity of commercial Si/graphite composites is generally below 600 mAh∙g⁻¹, which is far below the theoretical specific capacity of Si. In the meanwhile, the high cost, high specific surface area and low tap density of nano-Si limit its volumetric energy density and large-scale production further. Compared to the above materials, micro-Si (1–10 μm) is gaining industry attention for its low cost, as it does not require high-energy ball milling to reduce the particle size. Also, low specific surface area and high tap density conduce to reducing interfacial side reactions and increasing volumetric energy density. Therefore, micro-Si has a particular advantage over application in high volumetric energy density storage devices. However, due to the huge stress caused by significant volume change (300%), there are more severe problems such as particle pulverization, electrode disintegration, conductive network failure and uncontrolled growth of solid electrolyte interphases, which greatly hinder its commercialization. Binders are essential in adapting to Si volume changes to ensure the integrity of the electrode and keeping the tight contact among the active material, conductive additive and current collector to provide a stable conductive network. The development of high-capacity and high-stability micro-Si-based anodes poses greater challenges to the design of binders. In this review, we first clarify the binding mechanism of binders, factors that influence the bonding forces, and design strategies of binders for relieving the volume change of Si electrodes. As a major part, we systematically discuss the strategies and corresponding mechanisms of functional binders for silicon-based anodes from aspects of self-healing binders, conductive binders, ion-conductive binders, and the facilitating effect of functional binders on the stable SEI (Solid Electrolyte Interphase) formation. Finally, the existing problems and challenges are pointed out in terms of long-cycle stability, initial Coulombic efficiency (ICE) and binder ratio under commercial loading. We put forward the promising directions for developing functional binders towards the practical use of micro-Si anode: an ideal binder should be multifunctional and helpful to robust electron/ion conductive networks and stable SEI throughout the long cycling life of micro-Si, where the polymer molecular structure of functional binders can be systematically designed by artificial intelligence and machine learning technologies.

Key words:
• Lithium-ion battery
•  /  Silicon-based anode
•  /  Functional binder
•  /  Self-healing polymer
•  /  Conductive polymer

• 1. [1]

     殷鸿尧, 于跃, 李宗诚, 张港鸿, 冯玉军. 物理化学学报, 2019, 35, 1341. doi: 10.3866/PKU.WHXB201904042Yin, H. Y.; Yu, Y.; Li, Z. C, ; Zhang, G. H.; Feng, Y. J. Acta Phys. -Chim. Sin. 2019, 35, 1341. doi: 10.3866/PKU.WHXB201904042

  2. [2]

     Kwon, T. W.; Choi, J. W.; Coskun, A. Chem. Soc. Rev. 2018, 47, 2145. doi: 10.1039/c7cs00858a

  3. [3]

     Tan, D. H. S.; Chen, Y. -T.; Yang, H.; Bao, W.; Sreenarayanan, B.; Doux, J. -M.; Li, W.; Lu, B.; Ham, S. -Y.; Sayahpour, B.; et al. Science 2021, 373, 1494. doi: 10.1126/science.abg7217

  4. [4]

     Kovalenko, I.; Zdyrko, B.; Magasinski, A.; Hertzberg, B.; Milicev, Z.; Burtovyy, R.; Luzinov, I.; Yushin, G. Science 2011, 334, 75. doi: 10.1126/science.1209150

  5. [5]

     Choi, S.; Kwon, T. -W.; Coskun, A.; Choi, J. W. Science 2017, 357, 279. doi: 10.1126/science.aal4373

  6. [6]

     Xiao, J.; Han, J.; Kong, D.; Shi, H.; Du, X.; Zhao, Z.; Chen, F.; Lan, P.; Wu, S.; Zhang, Y.; et al. Energy Storage Mater. 2022, 50, 554. doi: 10.1016/j.ensm.2022.05.034

  7. [7]

     Ren, Y.; Xiang, L.; Yin, X.; Xiao, R.; Zuo, P.; Gao, Y.; Yin, G.; Du, C. Adv. Funct. Mater. 2022, 32, 2110046. doi: 10.1002/adfm.202110046

  8. [8]

     Pan, S.; Han, J.; Wang, Y.; Li, Z.; Chen, F.; Guo, Y.; Han, Z.; Xiao, K.; Yu, Z.; Yu, M.; et al. Adv. Mater. 2022, 34, 2203617. doi: 10.1002/adma.202203617

  9. [9]

     Mu, T.; Sun, Y.; Wang, C.; Zhao, Y.; Doyle-Davis, K.; Liang, J.; Sui, X.; Li, R.; Du, C.; Zuo, P.; et al. Nano Energy 2022, 103, 107829. doi: 10.1016/j.nanoen.2022.107829

  10. [10]

      Han, J.; Tang, D. M.; Kong, D.; Chen, F.; Xiao, J.; Zhao, Z.; Pan, S.; Wu, S.; Yang, Q. H. Sci. Bull. 2020, 65, 1563. doi: 10.1016/j.scib.2020.05.018

  11. [11]

      Wu, H.; Chan, G.; Choi, J. W.; Ryu, I.; Yao, Y.; McDowell, M. T.; Lee, S. W.; Jackson, A.; Yang, Y.; Hu, L.; et al. Nat. Nanotechnol. 2012, 7, 310. doi: 10.1038/nnano.2012.35

  12. [12]

      Yu, Y.; Gu, L.; Zhu, C.; Tsukimoto, S.; van Aken, P. A.; Maier, J. Adv. Mater. 2010, 22, 2247. doi: 10.1002/adma.200903755

  13. [13]

      Hu, Y. S.; Demir-Cakan, R.; Titirici, M. M.; Muller, J. O.; Schlogl, R.; Antonietti, M.; Maier, J. Angew. Chem. Int. Ed. 2008, 47, 1645. doi: 10.1002/anie.200704287

  14. [14]

      Magasinski, A.; Dixon, P.; Hertzberg, B.; Kvit, A.; Ayala, J.; Yushin, G. Nat. Mater. 2010, 9, 353. doi: 10.1038/nmat2725

  15. [15]

      Zhao, Z.; Han, J.; Chen, F.; Xiao, J.; Zhao, Y.; Zhang, Y.; Kong, D.; Weng, Z.; Wu, S.; Yang, Q. H. Adv. Energy Mater. 2022, 12, 2103565. doi: 10.1002/aenm.202103565

  16. [16]

      Chen, F.; Han, J.; Kong, D.; Yuan, Y.; Xiao, J.; Wu, S.; Tang, D. M.; Deng, Y.; Lv, W.; Lu, J.; et al. Natl. Sci. Rev. 2021, 8, 12. doi: 10.1093/nsr/nwab012

  17. [17]

      Chen, J.; Fan, X.; Li, Q.; Yang, H.; Khoshi, M. R.; Xu, Y.; Hwang, S.; Chen, L.; Ji, X.; Yang, C.; et al. Nat. Energy 2020, 5, 386. doi: 10.1038/s41560-020-0601-1

  18. [18]

      Zhu, T.; Sternlicht, H.; Ha, Y.; Fang, C.; Liu, D.; Savitzky, B. H.; Zhao, X.; Lu, Y.; Fu, Y.; Ophus, C.; et al. Nat. Energy 2023, 8, 129. doi: 10.1038/s41560-022-01176-6

  19. [19]

      McBrayer, J. D.; Rodrigues, M. -T. F.; Schulze, M. C.; Abraham, D. P.; Apblett, C. A.; Bloom, I.; Carroll, G. M.; Colclasure, A. M.; Fang, C.; Harrison, K. L.; et al. Nat. Energy 2021, 6, 866. doi: 10.1038/s41560-021-00883-w

  20. [20]

      Wang, Q.; Zhu, M.; Chen, G.; Dudko, N.; Li, Y.; Liu, H.; Shi, L.; Wu, G.; Zhang, D. Adv. Mater. 2022, 34, 2109658. doi: 10.1002/adma.202109658

  21. [21]

      Lopez, J.; Mackanic, D. G.; Cui, Y.; Bao, Z. Nat. Rev. Mater. 2019, 4, 312. doi: 10.1038/s41578-019-0103-6

  22. [22]

      Li, P.; Kim, H.; Myung, S. -T.; Sun, Y. -K. Energy Storage Mater. 2021, 35, 550. doi: 10.1016/j.ensm.2020.11.028

  23. [23]

      Zhao, Y. M.; Yue, F. S.; Li, S. C.; Zhang, Y.; Tian, Z. R.; Xu, Q.; Xin, S.; Guo, Y. G. InfoMat 2021, 3, 460. doi: 10.1002/inf2.12185

  24. [24]

      Kwon, T. -W.; Choi, J. W.; Coskun, A. Joule 2019, 3, 662. doi: 10.1016/j.joule.2019.01.006

  25. [25]

      安惠芳, 姜莉, 李峰, 吴平, 朱晓舒, 魏少华, 周益明. 物理化学学报, 2020, 36, 1905034. doi: 10.3866/PKU.WHXB201905034An, H.; Jiang, L.; Li, F.; Wu, P.; Zhu, X.; Wei, S.; Zhou, Y. Acta Phys. -Chim. Sin. 2020, 36, 1905034. doi: 10.3866/PKU.WHXB201905034

  26. [26]

      Zhao, Z.; Chen, F.; Han, J.; Kong, D.; Pan, S.; Xiao, J.; Wu, S.; Yang, Q. H. Adv. Energy Mater. 2023, 13, 2300367. doi: 10.1002/aenm.202300367

  27. [27]

      Chen, H.; Ling, M.; Hencz, L.; Ling, H. Y.; Li, G.; Lin, Z.; Liu, G.; Zhang, S. Chem. Rev. 2018, 118, 8936. doi: 10.1021/acs.chemrev.8b00241

  28. [28]

      Liu, G.; Zheng, H.; Song, X.; Battaglia, V. S. J. Electrochem. Soc. 2012, 159, A214. doi: 10.1149/2.024203jes

  29. [29]

      Hernandez, C. R.; Etiemble, A.; Douillard, T.; Mazouzi, D.; Karkar, Z.; Maire, E.; Guyomard, D.; Lestriez, B.; Roué, L. Adv. Energy Mater. 2018, 8, 1701787. doi: 10.1002/aenm.201701787

  30. [30]

      朱思颖, 李辉阳, 胡忠利, 张桥保, 赵金保, 张力. 物理化学学报, 2022, 38, 2103052. doi: 10.3866/PKU.WHXB202103052Zhu, S.; Li, H.; Hu, Z.; Zhang, Q.; Zhao, J.; Zhang, L. Acta Phys. -Chim. Sin. 2022, 38, 2103052. doi: 10.3866/PKU.WHXB202103052

  31. [31]

      Wu, S.; Yang, Y.; Liu, C.; Liu, T.; Zhang, Y.; Zhang, B.; Luo, D.; Pan, F.; Lin, Z. ACS Energy Lett. 2020, 6, 290. doi: 10.1021/acsenergylett.0c02342

  32. [32]

      Lee, H. A.; Shin, M.; Kim, J.; Choi, J. W.; Lee, H. Adv. Mater. 2021, 33, 2007460. doi: 10.1002/adma.202007460

  33. [33]

      Han, D. Y.; Han, I. K.; Son, H. B.; Kim, Y. S.; Ryu, J.; Park, S. Adv. Funct. Mater. 2023, 33, 2213458. doi: 10.1002/adfm.202213458

  34. [34]

      Xu, Z.; Yang, J.; Zhang, T.; Nuli, Y.; Wang, J.; Hirano, S. -I. Joule 2018, 2, 950. doi: 10.1016/j.joule.2018.02.012

  35. [35]

      Li, Z.; Wu, G.; Yang, Y.; Wan, Z.; Zeng, X.; Yan, L.; Wu, S.; Ling, M.; Liang, C.; Hui, K. N.; et al. Adv. Energy Mater. 2022, 12, 2201197. doi: 10.1002/aenm.202201197

  36. [36]

      Li, B.; Cao, P. F.; Saito, T.; Sokolov, A. P. Chem. Rev. 2023, 123, 701. doi: 10.1021/acs.chemrev.2c00575

  37. [37]

      Wang, C.; Wu, H.; Chen, Z.; McDowell, M. T.; Cui, Y.; Bao, Z. Nat. Chem. 2013, 5, 1042. doi: 10.1038/nchem.1802

  38. [38]

      Li, C. H.; Zuo, J. L. Adv. Mater. 2020, 32, 1903762. doi: 10.1002/adma.201903762

  39. [39]

      Kim, J.; Park, K.; Cho, Y.; Shin, H.; Kim, S.; Char, K.; Choi, J. W. Adv. Sci. 2021, 8, 2004290. doi: 10.1002/advs.202004290

  40. [40]

      Zhang, L.; Zhang, L.; Chai, L.; Xue, P.; Hao, W.; Zheng, H. J. Mater. Chem. A 2014, 2, 19036. doi: 10.1039/c4ta04320k

  41. [41]

      Ying, H.; Zhang, Y.; Cheng, J. Nat. Commun. 2014, 5, 3218. doi: 10.1038/ncomms4218

  42. [42]

      Chen, Z.; Wang, C.; Lopez, J.; Lu, Z.; Cui, Y.; Bao, Z. Adv. Energy Mater. 2015, 5, 1401826. doi: 10.1002/aenm.201401826

  43. [43]

      Jiao, X.; Yin, J.; Xu, X.; Wang, J.; Liu, Y.; Xiong, S.; Zhang, Q.; Song, J. Adv. Funct. Mater. 2020, 31, 2005699. doi: 10.1002/adfm.202005699

  44. [44]

      Kim, S. -M.; Kim, M. H.; Choi, S. Y.; Lee, J. G.; Jang, J.; Lee, J. B.; Ryu, J. H.; Hwang, S. S.; Park, J. -H.; Shin, K.; et al. Energy Environ. Sci. 2015, 8, 1538. doi: 10.1039/c5ee00472a

  45. [45]

      Zhao, H.; Wei, Y.; Qiao, R.; Zhu, C.; Zheng, Z.; Ling, M.; Jia, Z.; Bai, Y.; Fu, Y.; Lei, J.; et al. Nano Lett. 2015, 15, 7927. doi: 10.1021/acs.nanolett.5b03003

  46. [46]

      Liu, X.; Xu, Z.; Iqbal, A.; Chen, M.; Ali, N.; Low, C.; Qi, R.; Zai, J.; Qian, X. Nano-Micro Lett. 2021, 13, 54. doi: 10.1007/s40820-020-00564-5

  47. [47]

      Chiang, C. K.; Fincher, C. R.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis, E. J.; Gau, S. C.; MacDiarmid, A. G. Phys. Rev. Lett. 1977, 39, 1098. doi: 10.1103/PhysRevLett.39.1098

  48. [48]

      Chen, S.; Song, Z.; Wang, L.; Chen, H.; Zhang, S.; Pan, F.; Yang, L. Accounts Chem. Res. 2022, 55, 2088. doi: 10.1021/acs.accounts.2c00259

  49. [49]

      Liu, G.; Xun, S.; Vukmirovic, N.; Song, X.; Olalde-Velasco, P.; Zheng, H.; Battaglia, V. S.; Wang, L.; Yang, W. Adv. Mater. 2011, 23, 4679. doi: 10.1002/adma.201102421

  50. [50]

      Zhao, H.; Wang, Z.; Lu, P.; Jiang, M.; Shi, F.; Song, X.; Zheng, Z.; Zhou, X.; Fu, Y.; Abdelbast, G.; et al. Nano Lett. 2014, 14, 6704. doi: 10.1021/nl503490h

  51. [51]

      Wu, M.; Xiao, X.; Vukmirovic, N.; Xun, S.; Das, P. K.; Song, X.; Olalde-Velasco, P.; Wang, D.; Weber, A. Z.; Wang, L. W.; et al. J. Am. Chem. Soc. 2013, 135, 12048. doi: 10.1021/ja4054465

  52. [52]

      Zhu, T.; Liu, G. J. Electrochem. Soc. 2021, 168, 050533. doi: 10.1149/1945-7111/abff01

  53. [53]

      Liu, D.; Zhao, Y.; Tan, R.; Tian, L. -L.; Liu, Y.; Chen, H.; Pan, F. Nano Energy 2017, 36, 206. doi: 10.1016/j.nanoen.2017.04.043

  54. [54]

      Higgins, T. M.; Park, S. H.; King, P. J.; Zhang, C. J.; McEvoy, N.; Berner, N. C.; Daly, D.; Shmeliov, A.; Khan, U.; Duesberg, G.; et al. ACS Nano 2016, 10, 3702. doi: 10.1021/acsnano.6b00218

  55. [55]

      Tsai, C. -Y.; Liu, Y. -L. Electrochim. Acta 2021, 379, 138180. doi: 10.1016/j.electacta.2021.138180

  56. [56]

      Munaoka, T.; Yan, X.; Lopez, J.; To, J. W. F.; Park, J.; Tok, J. B. H.; Cui, Y.; Bao, Z. Adv. Energy Mater. 2018, 8, 1703138. doi: 10.1002/aenm.201703138

  57. [57]

      Hu, Y.; Shao, D.; Chen, Y.; Peng, J.; Dai, S.; Huang, M.; Guo, Z. -H.; Luo, X.; Yue, K. ACS Appl. Energy Mater. 2021, 4, 10886. doi: 10.1021/acsaem.1c01849

  58. [58]

      Cai, Y.; Liu, C.; Yu, Z.; Ma, W.; Jin, Q.; Du, R.; Qian, B.; Jin, X.; Wu, H.; Zhang, Q.; et al. Adv. Sci. 2023, 10, 2205590. doi: 10.1002/advs.202205590

  59. [59]

      Liu, H.; Wu, Q.; Guan, X.; Liu, M.; Wang, F.; Li, R.; Xu, J. ACS Appl. Energy Mater. 2022, 5, 4934. doi: 10.1021/acsaem.2c00329

  60. [60]

      Garsuch, R. R.; Le, D. -B.; Garsuch, A.; Li, J.; Wang, S.; Farooq, A.; Dahn, J. R. J. Electrochem. Soc. 2008, 155, A721. doi: 10.1149/1.2956964

  61. [61]

      Li, Z.; Zhang, Y.; Liu, T.; Gao, X.; Li, S.; Ling, M.; Liang, C.; Zheng, J.; Lin, Z. Adv. Energy Mater. 2020, 10, 1903110. doi: 10.1002/aenm.201903110

  62. [62]

      Liu, J.; Zhang, Q.; Zhang, T.; Li, J. -T.; Huang, L.; Sun, S. -G. Adv. Funct. Mater. 2015, 25, 3599. doi: 10.1002/adfm.201500589

  63. [63]

      Zeng, W.; Wang, L.; Peng, X.; Liu, T.; Jiang, Y.; Qin, F.; Hu, L.; Chu, P. K.; Huo, K.; Zhou, Y. Adv. Energy Mater. 2018, 8, 1702314. doi: 10.1002/aenm.201702314

  64. [64]

      Oh, D. Y.; Nam, Y. J.; Park, K. H.; Jung, S. H.; Kim, K. T.; Ha, A. R.; Jung, Y. S. Adv. Energy Mater. 2019, 9, 1802927. doi: 10.1002/aenm.201802927

  65. [65]

      Zhu, J.; Zhang, Z.; Zhao, S.; Westover, A. S.; Belharouak, I.; Cao, P. F. Adv. Energy Mater. 2021, 11, 2003836. doi: 10.1002/aenm.202003836

  66. [66]

      Nguyen, C. C.; Yoon, T.; Seo, D. M.; Guduru, P.; Lucht, B. L. ACS Appl. Mater. Inter. 2016, 8, 12211. doi: 10.1021/acsami.6b03357

  67. [67]

      Parikh, P.; Sina, M.; Banerjee, A.; Wang, X.; D'Souza, M. S.; Doux, J. -M.; Wu, E. A.; Trieu, O. Y.; Gong, Y.; Zhou, Q.; et al. Chem. Mater. 2019, 31, 2535. doi: 10.1021/acs.chemmater.8b05020

  68. [68]

      Browning, K. L.; Browning, J. F.; Doucet, M.; Yamada, N. L.; Liu, G.; Veith, G. M. Phys. Chem. Chem. Phys. 2019, 21, 17356. doi: 10.1039/c9cp02610j

  69. [69]

      Browning, K. L.; Sacci, R. L.; Doucet, M.; Browning, J. F.; Kim, J. R.; Veith, G. M. ACS Appl. Mater. Inter. 2020, 12, 10018. doi: 10.1021/acsami.9b22382

•