Citation: Qin Jinli, Ren Longtao, Cao Xin, Zhao Yajun, Xu Haijun, Liu Wen, Sun Xiaoming. Porous Copper Foam Co-operation with Thiourea for Dendrite-free Lithium Metal Anode[J]. Acta Physico-Chimica Sinica, ;2021, 37(1): 200902. doi: 10.3866/PKU.WHXB202009020 shu

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, hjxu@buct.edu.cn Liu Wen, wenliu@mail.buct.edu.cn
Received Date: 4 September 2020
Revised Date: 29 September 2020
Accepted Date: 30 September 2020
Available Online: 21 October 2020
Fund Project: the Beijing University of Chemical Technology buctrc201901The 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 Chinathe Royal Society and the Newton Fund through the Newton Advanced Fellowship Award NAF\R1\191294the National Natural Science Foundation of China 21771018the National Key Research and Development Project 2018YFB1502401the National Natural Science Foundation of China and Ministry of Foreign Affairs and International Cooperation, Italy NSFC-MAECI 51861135202the National Natural Science Foundation of China 21875004the National Key Research and Development Project 2018YFA0702002the Natural Science Foundation of Beijing 2192037the Program for Changjiang Scholars and Innovation Research Team in the University IRT1205

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.
- 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 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 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 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 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 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 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 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 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 doi: 10.1002/anie.201912217
10. [10]
  Guo, 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]
  Liu, 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 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 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 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 doi: 10.1016/j.ensm.2018.04.030
16. [16]
  Liu, 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 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 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 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 doi: 10.1021/acs.nanolett.9b01567
21. [21]
  Wang, 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 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 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 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 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 doi: 10.1016/j.ensm.2019.04.003
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