English

Porous Copper Foam Co-operation with Thiourea for Dendrite-free Lithium Metal Anode

• Qin Jinli ^1, ,
• Ren Longtao ^1, ,
• Cao Xin ^1, ,
• Zhao Yajun ^1, ,
• Xu Haijun ^{3, ,} ,
• Liu Wen ^{1, ,} ,
• Sun Xiaoming ^1,2,

• 1.

  State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China

• 2.

  Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

• 3.

  College of Mathematics and Physics, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Xu Haijun. E-mail:hjxu@buct.edu.cn; Liu Wen. E-mail:wenliu@mail.buct.edu.cn

• Received Date: 04 September 2020
  Accepted Date: 30 September 2020
  Revised Date: 29 September 2020
  Available Online: 15 January 2021
• Fund Project:

  The project was supported by the National Natural Science Foundation of China (21771018, 21875004), the Beijing University of Chemical Technology (buctrc201901), the National Natural Science Foundation of China and Ministry of Foreign Affairs and International Cooperation, Italy (NSFC-MAECI 51861135202), the Natural Science Foundation of Beijing (2192037), the National Key Research and Development Project (2018YFB1502401, 2018YFA0702002), the Royal Society and the Newton Fund through the Newton Advanced Fellowship Award (NAF\R1\191294), the Program for Changjiang Scholars and Innovation Research Team in the University (IRT1205), the Fundamental Research Funds for the Central Universities, and the Long-term Subsidy mechanism from the Ministry of Finance and the Ministry of Education of China

Abstract: With the rapid development of electric vehicles and portable electronic devices, traditional lithium-ion batteries with graphite anodes cannot satisfy demands for increased energy density. Lithium metal, with a high theoretical specific capacity (3860 mAh·g^-1), low density (0.534 g·cm^-3), and the lowest potential (-3.040 V vs. standard hydrogen electrode), has received much attention as an ideal anode material for next-generation energy storage devices. However, the uncontrolled growth of lithium dendrites and low Coulombic efficiency caused by negative side reactions have severely hindered the development of lithium metal batteries. Here, we propose a strategy based on the synergistic effect between a porous copper foam and thiourea, which uses the "super-filling" effect of thiourea molecules to achieve the uniform deposition of lithium metal on the surface of the porous copper foam. The unique curvature enhance coverage mechanism of thiourea molecules can accelerate Li deposition rate in grooves and achieve "super-filling" growth. The porous copper foam was obtained through simple multi-step processing. Scanning electron microscopy images showed many small pores evenly distributed on the surface; these pores acted as nucleation sites for lithium deposition. With the effect of thiourea, lithium was preferentially deposited in the small pores and then filled to the top, and finally deposited uniformly on the surface of the porous copper foam. The morphologies of the different electrodes deposited with capacities of 1, 3, and 10 mAh·cm^-2 demonstrated the synergistic effect between the porous copper foam and thiourea, which can inhibit the growth of lithium dendrites. Through this strategy, stable lithium plating/stripping over 500 h was achieved at a current density of 1 mA·cm^-2 with a fixed capacity of 1 mAh·cm^-2 while maintaining a voltage hysteresis below 20 mV. Meanwhile, greatly enhanced Coulombic efficiency and longer cycle life times were achieved: the Li||LiFePO₄ full cell maintained 94% capacity after 300 cycles at 5C. Exploiting the synergy between the electrolyte and framework provides a novel approach for fabricating advanced lithium metal batteries. This work thus details a novel strategy for lithium anode protection that may also be extended to other metal anodes, thereby facilitating the development of next-generation energy storage devices.

Key words:
• Lithium metal anode
•  /  Thiourea
•  /  Lithium dendrite
•  /  3D framework
•  /  Porous copper foam

• 1. [1]

     Yang, J.; Hu, C.; Jia, Y.; Pang, Y.; Wang, L.; Liu, W.; Sun, X. ACS Appl. Mater. Interfaces 2019, 11 (9), 8717. doi: 10.1021/acsami.9b00507

  2. [2]

     Fan, L.; Li, S.; Liu, L.; Zhang, W.; Gao, L.; Fu, Y.; Chen, F.; Li, J.; Zhuang, H. L.; Lu, Y. Adv. Energy Mater. 2018, 8 (33), 1802350. doi: 10.1002/aenm.201802350

  3. [3]

     Yue, X. Y.; Li, X. L.; Bao, J.; Qiu, Q. Q.; Liu, T.; Chen, D.; Yuan, S. S.; Wu, X. J.; Lu, J.; Zhou, Y. N. Adv. Energy Mater. 2019, 9 (35), 1901491. doi: 10.1002/aenm.201901491

  4. [4]

     Wang, H.; Wang, Q.; Cao, X.; He, Y.; Wu, K.; Yang, J.; Zhou, H.; Liu, W.; Sun, X. Adv. Mater. 2020, 32 (37), 2001259. doi: 10.1002/adma.202001259

  5. [5]

     Wang, Q.; Yang, C.; Yang, J.; Wu, K.; Hu, C.; Lu, J.; Liu, W.; Sun, X.; Qiu, J.; Zhou, H. Adv. Mater. 2019, 31 (41), 1903248. doi: 10.1002/adma.201903248

  6. [6]

     Niu, C.; Pan, H.; Xu, W.; Xiao, J.; Zhang, J. G.; Luo, L.; Wang, C.; Mei, D.; Meng, J.; Wang, X.; et al. Nat. Nanotechnol. 2019, 14 (6), 594. doi: 10.1038/s41565-019-0427-9

  7. [7]

     Zhang, W.; Fan, L.; Tong, Z.; Miao, J.; Shen, Z.; Li, S.; Chen, F.; Qiu, Y.; Lu, Y. Small Methods 2019, 3 (11), 1900325. doi: 10.1002/smtd.201900325

  8. [8]

     Xue, P.; Sun, C.; Li, H.; Liang, J.; Lai, C. Adv. Sci. 2019, 6 (18), 1900943. doi: 10.1002/advs.201900943

  9. [9]

     Sun, X.; Zhang, X.; Ma, Q.; Guan, X.; Wang, W.; Luo, J. Angew. Chem. Int. Ed. 2020, 59 (17), 6665. doi: 10.1002/anie.201912217

  10. [10]

      郭峰, 陈鹏, 康拓, 王亚龙, 刘承浩, 沈炎宾, 卢威, 陈立桅.物理化学学报, 2019, 35 (12), 1365. doi: 10.3866/PKU.WHXB201903008Guo, F.; Chen, P.; Kang, T.; Wang, Y. L.; Liu, C. H.; Shen, Y. B.; Lu, W.; Chen, L. W. Acta Phys. -Chim. Sin. 2019, 35 (12), 1365. doi: 10.3866/PKU.WHXB201903008

  11. [11]

      刘亚, 郑磊, 谷巍, 沈炎宾, 陈立桅.物理化学学报, 2021, 37, 2004058. doi: 10.3866/PKU.WHXB202004058Liu, Y.; Zheng, L.; Gu, W.; Shen, Y. B.; Chen, L. W. Acta Phys. -Chim. Sin. 2021, 37, 2004058. doi: 10.3866/PKU.WHXB202004058

  12. [12]

      Cha, E.; Patel, M. D.; Park, J.; Hwang, J.; Prasad, V.; Cho, K.; Choi, W. Nat. Nanotechnol. 2018, 13 (4), 337. doi: 10.1038/s41565-018-0061-y

  13. [13]

      Liang, Z.; Yan, K.; Zhou, G.; Pei, A.; Zhao, J.; Sun, Y.; Xie, J.; Li, Y.; Shi, F.; Liu, Y.; et al. Sci. Adv. 2019, 5 (3), eaau5655. doi: 10.1126/sciadv.aau5655

  14. [14]

      Li, J.; Zou, P.; Chiang, S. W.; Yao, W.; Wang, Y.; Liu, P.; Liang, C.; Kang, F.; Yang, C. Energy Storage Mater. 2020, 24, 700. doi: 10.1016/j.ensm.2019.06.019

  15. [15]

      Wang, Q.; Yang, C.; Yang, J.; Wu, K.; Qi, L.; Tang, H.; Zhang, Z.; Liu, W.; Zhou, H. Energy Storage Mater. 2018, 15, 249. doi: 10.1016/j.ensm.2018.04.030

  16. [16]

      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

  17. [17]

      Zhang, R.; Shen, X.; Cheng, X. B.; Zhang, Q. Energy Storage Mater. 2019, 23, 556. doi: 10.1016/j.ensm.2019.03.029

  18. [18]

      Cheng, Y.; Ke, X.; Chen, Y.; Huang, X.; Shi, Z.; Guo, Z. Nano Energy 2019, 63, 103854. doi: 10.1016/j.nanoen.2019.103854

  19. [19]

      Pu, K. C.; Zhang, X.; Qu, X. L.; Hu, J. J.; Li, H. W.; Gao, M. X.; Pan, H. G.; Liu, Y. F. Rare Metals 2020, 39 (6), 616. doi: 10.1007/s12598-020-01432-2

  20. [20]

      Liu, Y.; Zhang, S.; Qin, X.; Kang, F.; Chen, G.; Li, B. Nano Lett. 2019, 19 (7), 4601. doi: 10.1021/acs.nanolett.9b01567

  21. [21]

      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.; Peng, Z.; Lin, H.; Li, Z.; Liu, J.; Ren, Z.; He, H.; Wang, D. Acta Phys. -Chim. Sin. 2021, 37, 2007016. doi: 10.3866/PKU.WHXB202007016

  22. [22]

      Zuo, T. T.; Yin, Y. X.; Wang, S. H.; Wang, P. F.; Yang, X.; Liu, J.; Yang, C. P.; Guo, Y. G. Nano Lett. 2018, 18 (1), 297. doi: 10.1021/acs.nanolett.7b04136

  23. [23]

      Zachman, M. J.; Tu, Z.; Choudhury, S.; Archer, L. A.; Kourkoutis, L. F. Nature 2018, 560 (7718), 345. doi: 10.1038/s41586-018-0397-3

  24. [24]

      Li, K.; Hu, Z.; Ma, J.; Chen, S.; Mu, D.; Zhang, J. Adv. Mater. 2019, 31 (33), 1902399. doi: 10.1002/adma.201902399

  25. [25]

      Zhu, J.; Chen, J.; Luo, Y.; Sun, S.; Qin, L.; Xu, H.; Zhang, P.; Zhang, W.; Tian, W.; Sun, Z. Energy Storage Mater. 2019, 23, 539. doi: 10.1016/j.ensm.2019.04.005

  26. [26]

      Ke, X.; Liang, Y.; Ou, L.; Liu, H.; Chen, Y.; Wu, W.; Cheng, Y.; Guo, Z.; Lai, Y.; Liu, P.; Shi, Z. Energy Storage Mater. 2019, 23, 547. doi: 10.1016/j.ensm.2019.04.003

•