English

Three-Dimensional Macro-/Mesoporous C-TiC Nanocomposites for Dendrite-Free Lithium Metal Anode

• Wei Zhang ^{1, 2,} ,
• Haichen Liang ^1, ,
• Kerun Zhu ^1, ,
• Yong Tian ^1, ,
• Yao Liu ^1, ,
• Jiayin Chen ^1, ,
• Wei Li ^{1, ,}

• 1.

  Department of Chemistry, Fudan University, Shanghai 200433, China.

• 2.

  Zhuhai-Fudan Innovation Institute, Hengqin New District, Zhuhai 519000, Guangdong Province, China

Corresponding author: Wei Li, Email: weilichem@fudan.edu.cn; Tel.: +86-21-31249998

• Received Date: 13 May 2021
  Accepted Date: 22 June 2021
  Revised Date: 06 June 2021
  Available Online: 15 June 2022
• Fund Project:

  the National Key R & D Program of China 

  the National Key R & D Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the China Postdoctoral Science Foundation 

  the China Postdoctoral Science Foundation 

  the Science and Technology Commission of Shanghai Municipality 

  the Guangdong Basic and Applied Basic Research Foundation 

Abstract: In previous decades, lithium-ion batteries (LIBs) were the most commonly used energy storage systems for powering portable electronic devices because LIBs exhibit reliable cyclability. However, owing to the low specific capacity of graphite used in the anode, further increase in the energy density of LIBs was limited. The Li metal anode is promising for the construction of next-generation high-energy-density batteries because of its ultrahigh theoretical capacity (3860 mAh·g^-1) and low redox potential (-3.04 V vs. standard hydrogen electrode). However, the high activity of Li causes dendritic growth during cycling, which leads to cracking of the solid-electrolyte interphase (SEI), increase in side reactions, and formation of dead Li. Several strategies have been proposed to address these issues, including use of electrolyte additives, high-concentration electrolytes, protection of the Li metal surface with various coatings, use of solid-state electrolytes, and design of a three-dimensional (3D) "Li host" for regulating the nucleation and deposition of Li metal. Among them, the design of a 3D "Li host" has proven to be a simple and effective strategy. However, the commonly used 3D "Li hosts" include nanostructured carbons, which are lithiophobic and, thus, provide limited interaction sites with Li⁺ ions, leading to the deposition of Li metal on the "Li host" surface. Therefore, it is necessary to design a 3D "Li host" with enhanced interaction with Li⁺ ions to achieve uniform deposition. Herein, we develop a soft-hard templating route to synthesize 3D macro-/mesoporous C-TiC (denoted as 3DMM C-TiC) nanocomposites, which has been used in Li metal batteries. The as-synthesized materials possess high surface areas (~510 m²·g^-1), ordered structures, large pore volumes, and excellent conductivity. The continuous plating and stripping of Li metal and the formation of the hierarchically porous structure with sufficient volume to allow uniform Li deposition result in the alleviation of the volume change. The high specific surface area significantly decreases the local current density and suppresses dendrite growth. Consequently, ultrasmall TiC nanoparticles are uniformly distributed in the 3D macro-/mesoporous framework, which improves conductivity, enhances their interaction with Li⁺ ions, and promotes the uniform deposition of Li metal. Therefore, the fabricated 3DMM C-TiC||Li battery displays stable cycling performance with improved Coulombic efficiency (98%) over 300 cycles. Moreover, when the 3DMM C-TiC based Li metal anode is assembled with a LiFePO₄ (LFP) cathode, the resultant full cells exhibit high specific capacity and excellent cycling stability. This study provides insight for the effective design of a 3D "Li host" for dendrite-free Li metal anodes.

Key words:
• Lithium metal anode
•  /  Macro-/mesoporous structure
•  /  TiC
•  /  Lithium dendrites

• 1. [1]

     Manthiram, A. ACS Cent. Sci. 2011, 3, 1063. doi: 10.1021/acscentsci.7b00288

  2. [2]

     Zubi, G.; Dufo-López, R.; Carvalho, M.; Pasaoglu, G. Renew. Sustain. Energy Rev. 2018, 89, 292. doi: 10.1016/j.rser.2018.03.002

  3. [3]

     Wang, Q.; Jiang, L.; Yu, Y.; Sun, J. Nano Energy 2019, 55, 93. doi: 10.1016/j.nanoen.2018.10.035

  4. [4]

     Blomgren, G. E. J. Electrochem. Soc. 2016, 164, A5019. doi: 10.1149/2.0251701jes

  5. [5]

     Goodenough, J. B. Energy Storage Mater. 2015, 1, 158. doi: 10.1016/j.ensm.2015.07.001

  6. [6]

     Scrosati, B.; Hassoun, J.; Sun, Y. K. Energy Environ. Sci. 2011, 4, 3287. doi: 10.1039/c1ee01388b

  7. [7]

     Liu, T.; Ren, Y.; Shen, Y.; Zhao, S. X.; Lin, Y.; Nan, C. W. J. Power Sources 2016, 324, 349. doi: 10.1016/j.jpowsour.2016.05.111

  8. [8]

     Liu, K.; Liu, Y.; Lin, D.; Pei, A.; Cui, Y. Sci. Adv. 2018, 4, eaas9820. doi: 10.1126/sciadv.aas9820

  9. [9]

     An, W.; Gao, B.; Mei, S.; Xiang, B.; Fu, J.; Wang, L.; Zhang, Q.; Chu, P.; Huo, K. Nat. Commun. 2019, 10, 1447. doi: 10.1038/s41467-019-09510-5

  10. [10]

      王木钦, 彭哲, 林欢, 李振东, 刘健, 任重民, 何海勇, 王德宇. 物理化学学报, 2021, 37, 2007016. doi: 10.3866/PKU.WHXB202007016Wang, M. Q.; Peng, Z.; Lin, H.; Li, Z. D.; Liu, J.; Ren, Z. M.; He, H. Y.; Wang, D. Y. Acta Phys. -Chim. Sin. 2021, 37, 2007016. doi: 10.3866/PKU.WHXB202007016

  11. [11]

      刘凡凡, 张志文, 叶淑芬, 姚雨, 余彦. 物理化学学报, 2021, 37, 2006021. doi: 10.3866/PKU.WHXB202006021Liu, F. F.; Zhang, Z. W.; Ye, S. F.; Yao, Y.; Yu, Y. Acta Phys. -Chim. Sin. 2021, 37, 2006021. doi: 10.3866/PKU.WHXB202006021

  12. [12]

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

  13. [13]

      Liu, Y.; Zhai, Y.; Xia, Y.; Li, W; Zhao, D. Small Struct. 2021, 2000118. doi: 10.1002/sstr.202000118

  14. [14]

      Li, C.; Wei, J.; Li, P.; Tang, W.; Feng, W.; Liu, J.; Wang, Y; Xia, Y. Sci. Bull. 2019, 64, 478. doi: 10.1016/j.scib.2019.03.004

  15. [15]

      Guo, Y; Li, H; Zhai, T. Adv. Mater. 2017, 29, 1700007. doi: 10.1002/adma.201700007

  16. [16]

      岳昕阳, 马萃, 包戬, 杨思宇, 陈东, 吴晓京, 周永宁. 物理化学学报, 2021, 37, 2005012. doi: 10.3866/PKU.WHXB202005012Yue, X. Y.; Ma, C.; Bao, J.; Yang, S. Y.; Chen, D.; Wu, X. J.; Zhou, Y. N. Acta Phys. -Chim. Sin. 2021, 37, 2005012. doi: 10.3866/PKU.WHXB202005012

  17. [17]

      Liu, S.; Xia, X.; Zhong, Y.; Deng, S.; Yao, Z.; Zhang, L.; Chen, X; Wang, X; Zhang, Q.; Tu, J. Adv. Energy Mater. 2018, 8, 1702322. doi: 10.1002/aenm.201702322

  18. [18]

      Yuan, S.; Bao, L. J.; Wei, J.; Xia, Y.; Truhlar, D. G.; Wang, Y. Energy Environ. Sci. 2019, 12 2047. doi: 10.1039/c9ee01473j

  19. [19]

      Qian, J.; Henderson, W. A.; Xu, W.; Bhattacharya, P.; Engelhard, M.; Borodin, O.; Zhang, J. Nat. Commun. 2015, 6, 6362. doi: 10.1038/ncomms7362

  20. [20]

      秦金利, 任龙涛, 曹欣, 赵亚军, 许海军, 刘文, 孙晓明. 物理化学学报, 2021, 37, 2009020. doi: 10.3866/PKU.WHXB202009020Qin, J. L.; Ren, L. T.; Cao, X.; Zhao, Y. J.; Xu, H. J.; Liu, W.; Sun, X. M. Acta Phys. -Chim. Sin. 2021, 37, 2009020. doi: 10.3866/PKU.WHXB202009020

  21. [21]

      Xia, S.; Lopez, J.; Liang, C.; Zhang, Z.; Bao, Z.; Cui, Y.; Liu, W. Adv. Sci. 2019, 6, 1802353. doi: 10.1002/advs.201802353

  22. [22]

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

  23. [23]

      Han, X.; Gong, Y.; Fu, K.; He, X.; Hitz, G. T.; Dai, J.; Pearse, A.; Liu, B.; Wang, H.; Rubloff, G.; et al. Nat. Mater. 2016, 16, 572. doi: 10.1038/nmat4821

  24. [24]

      Gu, Y.; Wang, W. W.; Li, Y. J.; Wu, Q. H.; Tang, S.; Yan, J. W.; Zheng, M. S.; Wu, D. Y.; Fan, C. H.; Hu, W. Q.; et al. Nat. Commun. 2018, 9, 1339. doi: 10.1038/s41467-018-03466-8

  25. [25]

      Li, Y.; Sun, Y.; Pei, A.; Chen, K.; Vailionis, A.; Li, Y.; Zheng, G.; Sun, J.; Cui, Y. ACS Cent. Sci. 2018, 4, 97. doi: 10.1021/acscentsci.7b00480

  26. [26]

      Liang, X.; Pang, Q.; Kochetkov, I. R.; Sempere, M. S.; Huang, H.; Sun, X.; Nazar, L. F. Nat. Energy 2017, 2, 17119. doi: 10.1038/nenergy.2017.119

  27. [27]

      张云博, 林乔伟, 韩俊伟, 韩志远, 李曈, 康飞宇, 杨全红, 吕伟. 物理化学学报, 2021, 37, 2008088. doi: 10.3866/PKU.WHXB202008088Zhang, Y. B.; Lin, Q. W.; Han, J. W.; Han, Z. Y.; Li, T.; Kang, F. Y.; Yang, Q. H.; Lü, W. Acta Phys. -Chim. Sin. 2021, 37, 2008088. doi: 10.3866/PKU.WHXB202008088

  28. [28]

      Yun, Q.; He, Y. B.; Lv, W.; Zhao, Y.; Li, B.; Kang, F.; Yang, Q. H. Adv. Mater. 2016, 28, 6932. doi: 10.1002/adma.201601409

  29. [29]

      Zhai, P. B.; Wang, T. S.; Yang, W. W.; Cui, S. Q.; Zhang, P.; Nie, A.; Zhang, Q.; Gong, Y. J. Adv. Energy Mater. 2019, 9, 1804019. doi: 10.1002/aenm.201804019

  30. [30]

      王骞, 吴恺, 王航超, 刘文, 周恒辉. 物理化学学报, 2021, 37, 2007092. doi: 10.3866/PKU.WHXB202007092.Wang, Q.; Wu, K.; Wang, H. C.; Liu, W.; Zhou, H. H. Acta Phys. -Chim. Sin. 2021, 37, 2007092. doi: 10.3866/PKU.WHXB202007092

  31. [31]

      Liu, L.; Yin, Y. X.; Li, J. Y.; Wang, S. H.; Guo, Y. G.; Wan, L. J. Adv. Mater. 2018, 30, 1706216. doi: 10.1002/adma.201706216

  32. [32]

      Zhang, R.; Chen, X.; Shen, X.; Zhang, X. Q.; Chen, X. R.; Cheng, X. B.; Yan, C.; Zhao, C. Z.; Zhang, Q. Joule 2018, 2, 764. doi: 10.1016/j.joule.2018.02.001

  33. [33]

      Adams, B. D.; Zheng, J.; Ren, X.; Xu, W.; Zhang, J. G. Adv. Energy Mater. 2018, 8, 1702097. doi: 10.1002/aenm.201702097

  34. [34]

      Zhang, W.; Zu, L.; Kong, B.; Chen, B.; He, H.; Lan, K.; Liu, Y.; Yang, J.; Zhao, D. iScience 2018, 3, 149. doi: 10.1016/j.isci.2018.04.009

  35. [35]

      Peng, H. J.; Zhang, G.; Chen, X.; Zhang, Z. W.; Xu, W. T.; Huang, J. Q.; Zhang, Q. Angew. Chem. Int. Ed. 2016, 55, 12990. doi: 10.1002/anie.201605676

  36. [36]

      Liu, Y.; Lan, K.; Li, S.; Liu, Y.; Kong, B.; Wang, G.; Zhang, P.; Wang, R.; He, H.; Ling, Y.; et al. J. Am. Chem. Soc. 2017, 139, 517. doi: 10.1021/jacs.6b11641

  37. [37]

      Liu, Y.; Lan, K.; Bagabas, A. A.; Zhang, P.; Gao, W.; Wang, J.; Sun, Z.; Fan, J.; Elzatahry, A. A.; Zhao, D. Small 2016, 12, 860. doi: 10.1002/smll.201503420

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