三维多孔铜和锌镀层协同构筑无枝晶锂金属电极

doi:10.6023/A21110529

摘要/Abstract

金属锂具有高理论比容量和低氧化还原电位, 被认为是高能量密度二次电池最理想的负极材料之一, 但其在循环过程中的枝晶生长和体积变化易造成电池失效和安全隐患. 以孔径为5 μm左右的自制三维多孔铜为基底, 在其表面电沉积锌层(3D Cu@Zn), 作为金属锂沉积的集流体, 构筑无枝晶锂金属电极. 三维多孔铜的孔结构稳定, 孔径大小适宜, 可有效降低局部电流密度和缓解体积变化. 锌镀层可降低锂金属的形核过电位, 诱导锂的均匀沉积, 有效抑制锂枝晶生长. 以3D Cu@Zn为集流体, 锂沉积面积容量为4 mAh•cm^–2, 电极表面仍无枝晶出现, 经过锂剥离后表面仍然光滑; 而铜箔上沉积的锂显示明显的枝晶和不均匀性, 3D Cu上沉积的锂显示局部不均匀性和一定量枝晶. 在电流密度为0.5和 1 mA•cm^–2, 面积容量为1 mAh•cm^–2条件下, Li||3D Cu@Zn半电池获得了稳定的库伦效率; 在2 mA•cm^–2的高电流密度和1 mAh•cm^–2的面积容量条件下, Li||3D Cu@Zn@Li对称电池可稳定循环700 h以上; 以3D Cu@Zn@Li为负极, LiFePO₄为正极的全电池, 在1 C倍率下, 经过150次循环后仍保持88 mAh•g^–1的容量, 均明显优于Cu片和3D Cu作为集流体的锂金属电极.

关键词: 锂金属, 三维多孔铜, 锌, 电沉积, 锂枝晶

Metal Li has been considered as one promising anode due to its high theoretical capacity and the lowest redox potential, however its dendrites growth and volumetric changes during cycling easily cause battery failure and safety hazards. Here a three dimensional (3D) porous Cu with pore size of about 5 μm coated with Zn layer is used as current collector for Li deposition to construct dendrite-free metal Li electrode. The suitable pore size and high stability of 3D Cu is beneficial to decrease local current density and buffer volumetric changes, and the Zn layer can decrease the nucleation overpotential of Li, synergistically induce uniform deposition of Li and effectively suppress the growth of Li dendrites. There is no dendrite appears when the 3D Cu@Zn is used as the current collector even the depositing capacity increases to 4 mAh•cm^–2, and displays smooth surface after Li stripping, however, the Li on Cu appears obvious dendrites and non-uniformity, Li on 3D Cu appears local non-uniformity and some dendrites. The semi-cell Li||3D Cu@Zn demonstrates stable coulombic efficiency at 0.5 and 1 mA•cm^–2 with a capacity of 1 mAh•cm^–2, the symmetrical cell Li||3D Cu@Zn@Li stably cycle for above 700 h at high current density of 2 mA•cm^–2 with a capacity of 1 mAh•cm^–2. The full cell with 3D Cu@Zn@Li as anode and LiFePO₄ as cathode remains 88 mAh•g^–1 after 150 cycles, which is much better than those using Cu@Li plate and 3D Cu@Li as the anodes.

Key words: lithium metal, three-dimensional porous copper, zinc, electrodeposition, lithium dendrite

引用此文

樊小勇, 张帅, 朱永强, 敬茂森, 王凯鑫, 张露露, 李巨龙, 许磊, 苟蕾, 李东林. 三维多孔铜和锌镀层协同构筑无枝晶锂金属电极[J]. 化学学报, 2022, 80(4): 517-525.

Xiaoyong Fan, Shuai Zhang, Yongqiang Zhu, Maosen Jing, Kaixin Wang, Lulu Zhang, Julong Li, Lei Xu, Lei Gou, Donglin Li. Construction of Dendrite-free Lithium Metal Electrode Using Three-Dimensional Porous Copper and Zinc Coatings[J]. Acta Chimica Sinica, 2022, 80(4): 517-525.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 11

图1. 金属锂在铜箔(a), 3D Cu (b)和3D Cu@Zn (c)上的沉积/剥离行为示意图

Figure 1. Schematic of Li plating/stripping behavior on Cu foil (a), 3D Cu (b) and 3D Cu@Zn (c)

图2. 3D Cu (a, c), 3D Cu@Zn (b, d)的扫描电子显微镜(SEM)图和3D Cu(图a插图)和3D Cu@Zn(图b插图)的宏观数码照片

Figure 2. Scanning electron microscope (SEM) images of 3D Cu (a, c), 3D Cu@Zn (b, d) and digital photos of 3D Cu (inset in a) and 3D Cu@Zn (inset in b)

图3. 3D Cu@Zn中Cu和Zn的SEM图以及相应的X射线能谱分析图(EDS) (a)及3D Cu@Zn的X射线衍射分析(XRD)图(b)

Figure 3. SEM and corresponding energy dispersive spectrometer (EDS) mapping images of Cu and Zn of 3D Cu@Zn (a) and X-ray diffraction (XRD) patterns of 3D Cu@Zn (b)

图4. Li||3D Cu@Zn、Li||3D Cu和Li||Cu半电池在电流密度为0.5 mA•cm–2 (a)和1 mA•cm–2 (b), 容量为1 mAh•cm–2条件下的库仑效率(CE)、在电流密度为1 mA•cm–2, 容量为1 mAh•cm–2条件下的初始放电曲线(插图为锂在不同集流体上的形核过电位)(c)以及3D Cu@Zn 在电流密度为1 mA•cm–2, 容量为 1 mAh•cm–2条件下, 在第1、5、10、30、50、60次循环的充放电曲线(d)

Figure 4. Coulombic efficiency (CE) of Li||3D Cu@Zn, Li||3D Cu and Li||Cu cells at 0.5 mA•cm–2 (a) and 1 mA•cm–2 (b), (c) their voltage profiles of Li plating at 1 mA•cm–2 with a capacity of 1 mAh•cm–2 (inset is nucleation overpotential of lithium on different current collectors) and charge/discharge profiles of the 3D Cu@Zn in the 1st, 5th, 10th, 30th, 50th, 60th cycle at 1 mA•cm–2 with a capacity of 1 mAh•cm–2 (d)

图5. 电流密度为0.5 mA•cm–2 (a)和2.0 mA•cm–2 (d), 容量为1 mAh•cm–2条件下, 对称电池的时间-电压曲线、在0.5 mA•cm–2的电流密度下, 250~260 h (b), 500~510 h (c)以及2.0 mA•cm–2的电流密度下, 80~90 h (e), 290~300 h (f)的局部放大时间-电压曲线

Figure 5. Voltage-time profiles of the Li electrochemical plating/stripping process in symmetric cells at 0.5 mA•cm–2 (a) and 2.0 mA•cm–2 (d) with a capacity of 1 mAh•cm–2, and the magnified voltage-time profiles in the ranges 250~260 h (b) and 500~510 h (c) at 0.5 mA•cm–2, 80~90 h (e) and 290~300 h (f) at 2.0 mA•cm–2

图6. 3D Cu@Zn、3D Cu和Cu在0.5 mA•cm–2的电流密度下, 容量从1 mAh•cm–2增加到4 mAh•cm–2并剥离3 mAh•cm–2的SEM图 3D Cu@Zn (a~c), 3D Cu (e~g)和Cu (i~k)上沉积1, 2和4 mAh•cm–2的SEM照片. 在3D Cu@Zn (d), 3D Cu (h)和Cu (l)上剥离3 mAh•cm–2容量锂的SEM图

Figure 6. SEM image of the Li plating and stripping behavior on 3D Cu@Zn, 3D Cu and Cu with the capacity increasing from 1 to 4 mAh•cm–2 and stripping 3 mAh•cm–2 at a current density of 0.5 mA•cm–2 SEM images of the Li plating with the capacities of 1, 2 and 4 mAh•cm–2 on 3D Cu@Zn (a~c), 3D Cu (e~g) and Cu (i~k). SEM images of Li stripping with a capacity of 3 mAh•cm–2 on 3D Cu@Zn (d), 3D Cu (h) and Cu (l)

图7. 在电流密度0.5 mA•cm–2, 容量1 mAh•cm–2下, 循环50圈后, Cu (a, d), 3D Cu (b, e)和3D Cu@Zn (c, f)的SEM图

Figure 7. SEM images of Li plating on Cu (a, d), 3D Cu (b, e) and 3D Cu@Zn (c, f) at 0.5 mA•cm–2 with a capacity of 1 mAh•cm–2 after 50 cycles

图8. 3D Cu@Zn@Li, 3D Cu@Li和Cu@Li作为负极, 正极的面载量约为1 mg•cm–2的全电池在1 C下的循环性能曲线(a)及其充电/放电曲线(b~d)

Figure 8. Cyclability profiles of the full cells using 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes, cathode capacity of about 1 mg•cm–2 at 1 C (a) and their charge/discharge profiles (b~d)

图9. 3D Cu@Zn@Li, 3D Cu@Li和Cu@Li作为负极, 正极的面载量约为1 mg•cm–2的全电池在不同电流密度下的循环性能曲线(a)及其充电/放电曲线(b~d)

Figure 9. Cyclability profiles (a) of the full cells using 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes, cathode capacity of about 1 mg•cm–2 at different current densities and their charge/discharge profiles (b~d)

图10. 3D Cu@Zn@Li, 3D Cu@Li和Cu@Li作为负极, 正极容量约为3 mg•cm–2的全电池在2 C下的循环性能曲线(a)及其充电/放电曲线(b~d)

Figure 10. Cyclability profiles of the full cells using 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes, cathode capacity of about 3 mg•cm–2 at 2 C (a) and their charge/discharge profiles (b~d)

图11. 3D Cu@Zn@Li、3D Cu@Li和Cu@Li作为负极, 正极容量约为10 mg•cm–2的NCM全电池在1 C下的循环性能曲线(a)及其充电/放电曲线(b~d)

Figure 11. Cyclability profiles of the full cells using NCM cathode with a capacity of about 10 mg•cm–2, 3D Cu@Zn@Li, 3D Cu@Li and Cu@Li as the anodes (a) and their charge/discharge profiles (b~d) at 1 C

参考文献 45

[1]	Balogun, M.-S.; Qiu, W.; Luo, Y.; Meng, H.; Mai, W.; Onasanya, A.; Olaniyi, T. K.; Tong, Y. Nano Res. 2016, 9, 2823. doi: 10.1007/s12274-016-1171-1
[2]	Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Chem. Rev. 2017, 117, 10403. doi: 10.1021/acs.chemrev.7b00115
[3]	Winter, M.; Barnett, B.; Xu, K. Chem. Rev. 2018, 118, 11433. doi: 10.1021/acs.chemrev.8b00422
[4]	Jin, L.; Shen, C.; Shellikeri, A.; Wu, Q.; Zheng, J.; Andrei, P.; Zhang, J.-G.; Zheng, J. P. Energy Environ. Sci. 2020, 13, 2341. doi: 10.1039/D0EE00807A
[5]	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
[6]	Xu, F.; Wang, H.; Yu, T.; Xu, S.; Qu, C.; Xu, X.; Zhuang, R. Acta Chim. Sinica 2021, 79, 378. (in Chinese) doi: 10.6023/A20100462
	(徐飞, 王洪强, 于涛, 徐顺奇, 曲昌镇, 许潇洒, 庄容, 化学学报, 2021, 79, 378.) doi: 10.6023/A20100462
[7]	Wang, Z.; Wang, J.; Mao, Q.; Yang, S.; Cheng, D.; Zhang, Z.; He, H.; Zhou, K. Chem. Eng. J. 2021, 407, 126861. doi: 10.1016/j.cej.2020.126861
[8]	Chen, K.-H.; Wood, K. N.; Kazyak, E.; LePage, W. S.; Davis, A. L.; Sanchez, A. J.; Dasgupta, N. P. J. Mater. Chem. A 2017, 5, 11671. doi: 10.1039/C7TA00371D
[9]	Louli, A. J.; Eldesoky, A.; Weber, R.; Genovese, M.; Coon, M.; deGooyer, J.; Deng, Z.; White, R. T.; Lee, J.; Rodgers, T.; Petibon, R.; Hy, S.; Cheng, S. J. H.; Dahn, J. R. Nat. Energy 2020, 5, 693. doi: 10.1038/s41560-020-0668-8
[10]	Wood, K. N.; Kazyak, E.; Chadwick, A. F.; Chen, K. H.; Zhang, J. G.; Thornton, K.; Dasgupta, N. P. ACS Cent. Sci. 2016, 2, 790. doi: 10.1021/acscentsci.6b00260
[11]	Wang, Z.; Sun, Y.; Qian, Z.; Wang, R. Chem. J. Chin. Univ. 2020, 42, 1017. (in Chinese)
	(王增强, 孙一翎, 钱正芳, 王任衡, 高等化学学报, 2020, 42, 1017.)
[12]	Zhou, H.; He, P.; Zhu, X.; Deng, H.; Yang, H.; Qiao, Y.; Chang, Z. Acta Chim. Sinica 2021, 79, 139. (in Chinese) doi: 10.6023/A20090442
	(周豪慎, 何平, 朱星宇, 邓瀚, 杨慧军, 乔羽, 常智, 化学学报, 2021, 79, 139.) doi: 10.6023/A20090442
[13]	Chi, S. S.; Wang, Q.; Han, B.; Luo, C.; Jiang, Y.; Wang, J.; Wang, C.; Yu, Y.; Deng, Y. Nano Lett. 2020, 20, 2724. doi: 10.1021/acs.nanolett.0c00352
[14]	Zhan, Y.; Shi, P.; Zhang, X.; Wei, J.; Zhang, Q.; Huang, J. Chem. J. Chin. Univ. 2021, 42, 1569. (in Chinese)
	(詹迎新, 石鹏, 张学强, 魏俊宇, 张乾魁, 黄佳琦, 高等学校化学学报, 2021, 42, 1569.)
[15]	Zhang, D.; Dai, A.; Fan, B.; Li, Y.; Shen, K.; Xiao, T.; Hou, G.; Cao, H.; Tao, X.; Tang, Y. ACS Appl. Mater. Interfaces 2020, 12, 31542. doi: 10.1021/acsami.0c09503
[16]	Liu, H.; Wang, E.; Zhang, Q.; Ren, Y.; Guo, X.; Wang, L.; Li, G.; Yu, H. Energy Storage Mater. 2019, 17, 253.
[17]	Lin, K.; Xu, X.; Qin, X.; Zhang, G.; Liu, M.; Lv, F.; Xia, Y.; Kang, F.; Chen, G.; Li, B. Energy Storage Mater. 2020, 26, 250.
[18]	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.
[19]	Chi, S.-S.; Liu, Y.; Song, W.-L.; Fan, L.-Z.; Zhang, Q. Adv. Funct. Mater. 2017, 27, 1700348. doi: 10.1002/adfm.201700348
[20]	Ke, X.; Cheng, Y.; Liu, J.; Liu, L.; Wang, N.; Liu, J.; Zhi, C.; Shi, Z.; Guo, Z. ACS Appl. Mater. Interfaces 2018, 10, 13552. doi: 10.1021/acsami.8b01978
[21]	Medvedev, A. Z.; Zherebilov, A. F.; Masliiy, A. I.; Poddubnyi, N. P. Russ. J. Electrochem. 2008, 44, 761. doi: 10.1134/S1023193508060189
[22]	Meng, X.; Song, Y.; Shu, T. J. Power Sources 2020, 27, 1069.
[23]	Singh, H.; Dheeraj, P. B.; Singh, Y. P.; Rathore, G.; Bhardwaj, M. J. Electroanal. Chem. 2017, 785, 1. doi: 10.1016/j.jelechem.2016.12.013
[24]	Wang, N.; Hu, W. C.; Lu, Y. H.; Deng, Y. F.; Wan, X. B.; Zhang, Y. W.; Du, K.; Zhang, L. Trans. IMF 2013, 89, 261. doi: 10.1179/174591911X13119320025636
[25]	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
[26]	Zhang, D.; Dai, A.; Wu, M.; Shen, K.; Xiao, T.; Hou, G.; Lu, J.; Tang, Y. ACS Energy. Lett. 2019, 5, 180. doi: 10.1021/acsenergylett.9b01987
[27]	Zhao, H.; Lei, D.; He, Y.-B.; Yuan, Y.; Yun, Q.; Ni, B.; Lv, W.; Li, B.; Yang, Q.-H.; Kang, F.; Lu, J. Adv. Energy Mater. 2018, 8, 1800266. doi: 10.1002/aenm.201800266
[28]	Qiu, H.; Tang, T.; Asif, M.; Huang, X.; Hou, Y. Adv. Funct. Mater. 2019, 29, 1808468. doi: 10.1002/adfm.201808468
[29]	Fan, X.; Sun, R.; Zhu, Y.; Zhang, S.; Gou, L.; Lu, L.; Li, D. Small 2021, 18, e2106161.
[30]	Fan, X.-Y.; Jiang, Z.; Huang, L.; Wang, X.; Han, J.; Sun, R.; Gou, L.; Li, D.-L.; Ding, Y.-L. ACS Appl. Mater. Interfaces 2020, 12, 20344. doi: 10.1021/acsami.9b23501
[31]	Fan, X.-Y.; Han, J.; Ding, Y.-L.; Deng, Y.-P.; Luo, D.; Zeng, X.; Jiang, Z.; Gou, L.; Li, D.-L.; Chen, Z. Adv. Energy Mater. 2019, 9, 1900673. doi: 10.1002/aenm.201900673
[32]	Chi, S.-S.; Wang, Q.; Han, B.; Luo, C.; Jiang, Y.; Wang, J.; Wang, C.; Yu, Y.; Deng, Y. Nano Lett. 2020, 20, 2724. doi: 10.1021/acs.nanolett.0c00352
[33]	Ye, Y.; Liu, Y.; Wu, J.; Yang, Y. J. Power Sources 2020, 472, 228520. doi: 10.1016/j.jpowsour.2020.228520
[34]	Zhao, F.; Zhou, X.; Deng, W.; Liu, Z. Nano Energy 2019, 62, 55. doi: 10.1016/j.nanoen.2019.04.087
[35]	Wang, G.; Xiong, X.; Zou, P.; Fu, X.; Lin, Z.; Li, Y.; Liu, Y.; Yang, C.; Liu, M. Chem. Eng. J. 2019, 378, 122243. doi: 10.1016/j.cej.2019.122243
[36]	Fan, X.-Y.; Cui, Y.; Liu, P.; Gou, L.; Xu, L.; Li, D.-L. Phys. Chem. Chem. Phys. 2016, 18, 22224. doi: 10.1039/C6CP03374A
[37]	Zhang, Q.; Luan, J.; Tang, Y.; Ji, X.; Wang, S.; Wang, H. J. Mater. Chem. A 2018, 6, 18444. doi: 10.1039/C8TA07612J
[38]	Liu, J.; Ma, H.; Wen, Z.; Li, H.; Yang, J.; Pei, N.; Zhang, P.; Zhao, J. J. Energy. Chem. 2022, 64, 354. doi: 10.1016/j.jechem.2021.04.044
[39]	Yang, T.; Qian, T.; Shen, X.; Wang, M.; Liu, S.; Zhong, J.; Yan, C.; Rosei, F. J. Mater. Chem. A 2019, 7, 14496. doi: 10.1039/C9TA02640A
[40]	Luo, N.; Ji, G.-J.; Wang, H.-F.; Li, F.; Liu, Q.-C.; Xu, J.-J. ACS Nano 2020, 14, 3281. doi: 10.1021/acsnano.9b08844 pmid: 32119516
[41]	Huang, G.; Han, J.; Zhang, F.; Wang, Z.; Kashani, H.; Watanabe, K.; Chen, M. Adv. Mater. 2019, 31, e1805334.
[42]	Zhang, C.; Lyu, R.; Lv, W.; Li, H.; Jiang, W.; Li, J.; Gu, S.; Zhou, G.; Huang, Z.; Zhang, Y.; Wu, J.; Yang, Q. H.; Kang, F. Adv. Mater. 2019, 31, e1904991.
[43]	Domínguez-Ríos, C.; Moreno, M. V.; Torres-Sánchez, R.; Antúnez, W.; Aguilar-Elguézabal, A.; González-Hernández, J. Surf. Coat. Technol. 2008, 202, 4848. doi: 10.1016/j.surfcoat.2008.04.069
[44]	Wang, R.; Shi, F.; He, X.; Shi, J.; Ma, T.; Jin, S.; Tao, Z. Sci. China Mater. 2020, 64, 1087. doi: 10.1007/s40843-020-1528-5
[45]	Vinokurov, E. G.; Kandyrin, K. L.; Bondar', V. V. Russ. J. Appl. Chem. 2010, 83, 659. doi: 10.1134/S1070427210040166