铟锡双金属修饰层协同抑制锌枝晶生长

doi:10.6023/A24120389

摘要/Abstract

水系锌离子电池因其低成本、高安全性和环境友好等优点, 在规模化储能领域展现出巨大的应用潜力. 然而, 枝晶生长、表面钝化以及析氢等副反应导致的锌电极稳定性差和寿命短的问题, 限制了水系锌离子电池在大规模应用中的推广. 本研究通过气相沉积工艺, 在锌电极表面依次沉积了铟锡双金属修饰层, 综合利用铟金属层的高析氢过电位及其较强的锌原子吸附能, 锡金属层较低的锌离子迁移能垒, 协同抑制锌电极枝晶生长、腐蚀和析氢等副反应, 同时加速界面处锌离子的传输动力学. 结果显示, Zn@In@Sn电极在电流密度为1 mA•cm⁻², 面积容量为0.5 mAh•cm⁻²条件下能保持40 mV的低沉积/剥离电位差, 并实现超过3000 h的稳定循环, 远优于纯铟修饰层(64 mV, 1500 h)和纯锡修饰层(85 mV, 1600 h). 与MnO₂正极材料匹配组装的全电池, 在1 A•g⁻¹的电流密度下, 经过1000个稳定循环后, 容量保持127.9 mAh•g⁻¹, 显示出优异的电化学性能和循环稳定性.

关键词: 锌离子电池, 锌电极, 铟锡双金属修饰层, 无枝晶, 高传输动力学

Aqueous zinc-ion batteries are considered as a promising candidate for future grid energy storage due to their cost-effectiveness, safety, and environmental compatibility, however their large scale application is impeded by the stability and longevity issues stemming from dendrite growth, and side reactions such as passivation and hydrogen evolution. Herein, an indium-tin bimetallic layer is introduced onto the Zn electrode surface via sequential vapor deposition of indium and tin, comprehensively utilizing the indium layer with higher hydrogen evolution overpotential and greater adsorption energy for Zn atoms, the Sn layer with lower Zn²⁺ migration barrier to synergistically inhibit Zn dendrites, corrosion and hydrogen evolution, and simultaneously facilitate rapid transport of Zn²⁺ at the interface. The thickness of In-Sn layer is determined to be only two hundred nanometers, which can not only efficiently protect Zn electrode but also avoid the energy loss due to the increase of Zn electrode resistance. Both the X-ray diffraction (XRD) peaks of In and Sn are detected, assuring the synergistical effect of In and Sn layer. The contact angle of 2.0 mol•L⁻¹ ZnSO₄ on Zn electrode decreases from 102.31° to 54.35° after coating In-Sn layer, decreasing the contact impedance between Zn electrode and electrolyte. The linear sweep voltammetry (LSV) results demonstrate the hydrogen evolution potential decreases from －1.776 V (pure Zn) to －1.979 V after coating In-Sn layer, indicating less hydrogen evolution and side reactions. The corrosion current density of Zn@In@Sn displays the smallest value of 0.868 mA•cm⁻², compared with those of Zn (4.017 mA•cm⁻²) and Zn@In (3.515 mA•cm⁻²), demonstrating less corrosion. Consequently, the Zn@In@Sn electrode demonstrates an extended lifespan of up to 3000 h under low polarization of 40 mV at a current density of 1 mA•cm⁻² and an areal capacity of 0.5 mAh•cm⁻², obviously better than those of Zn@In (64 mV, 1500 h) and Zn@Sn (85 mV, 1600 h). The full cell using manganese dioxide as the cathode and Zn@In@Sn as the anode maintains approximately 127.9 mAh•g⁻¹ after 1000 stable cycles at a current density of 1 A•g⁻¹.

Key words: Zn-ion battery, Zn electrode, indium-tin bimetallic layer, dendrite-free, high transferring kinetics

引用此文

李奔, 赵宇, 高欣, 孙雨涵, 赵宝雁, 罗巧梅, 鲍晓冰, 苟蕾, 崔艳华, 樊小勇. 铟锡双金属修饰层协同抑制锌枝晶生长[J]. 化学学报, 2025, 83(3): 237-301.

Ben Li, Yu Zhao, Xin Gao, Yuhan Sun, Baoyan Zhao, Qiaomei Luo, Xiaobing Bao, Lei Gou, Yanhua Cui, Xiaoyong Fan. The Indium-tin Bimetallic Modification Layer Synergistically Inhibited Zinc Dendrite Growth[J]. Acta Chimica Sinica, 2025, 83(3): 237-301.

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

分享此文

图/表 6

图1. 锌在纯锌电极表面(左侧)和铟锡双金属层修饰的锌电极表面(右侧)的沉积过程

Figure 1. The scheme of zinc deposition process on the bare zinc electrode surface (left) and indium-tin bimetallic modified zinc electrode surface (right)

图2. 纯锌电极的SEM图(a); Zn@In@Sn电极的SEM (b)及其元素分布(c)图; Zn@In@Sn电极的In3d (d)、Sn3d (e)和Zn2p (f)的高分辨率X射线光电子能谱(XPS); Zn@In@Sn (g)和纯锌(h)电极的3D表面轮廓图; 修饰层厚度(i)

Figure 2. SEM image of bare Zn (a); SEM image (b) and corresponding element distribution spectra (EDS, c) of Zn@In@Sn; high-resolution XPS spectra of In 3d (d), Sn 3d (e), and Zn 2p (f) of Zn@In@Sn electrode; 3D surface profile of Zn@In@Sn (g) and Zn (h); modification layer thickness profile (i)

图3. 纯Zn和Zn@In@Sn电极在2.0 mol?L?1 ZnSO4电解液中浸泡7 d后的表征: 纯Zn (a)和Zn@In@Sn (c)的扫描电子显微镜(SEM)图(比例尺: 10 μm), 纯Zn (b)和Zn@In@Sn (d)的3D表面轮廓图, 纯Zn和Zn@In@Sn的X射线衍射(XRD)图(e). 2.0 mol?L?1 ZnSO4电解液在纯Zn和Zn@In@Sn上的接触角(f)

Figure 3. The characterization of pure Zn and Zn@In@Sn electrodes after immersion in 2.0 mol?L?1 ZnSO4 electrolyte for 7 d: SEM images of pure Zn (a) and Zn@In@Sn (c) (Scale bar: 10 μm), 3D mapping of pure Zn (b) and Zn@In@Sn (d), XRD patterns (e) of pure Zn and Zn@In@Sn. Contact angles (f) of 2.0 mol?L?1 ZnSO4 electrolyte on pure Zn and Zn@In@Sn electrodes

图4. 在2.0 mol?L?1 ZnSO4溶液中, 纯Zn (a)和Zn@In@Sn (b)电极在5.0 mA?cm?2电流密度下的原位光学显微镜图(比例尺: 200 μm). 纯锌和Zn@In@Sn电极的CV (c), LSV (d), CA (e)和Tafel (f)曲线

Figure 4. In situ optical microscope images of pure Zn (a) and Zn@In@Sn (b) electrodes in 2.0 mol?L?1 ZnSO4 at a current density of 5.0 mA?cm?2 (Scale bar: 200 μm). CV (c), LSV (d), CA (e), and Tafel (f) curves of bare Zn and Zn@In@Sn

图5. 在2.0 mA?cm?2 (面容量: 0.5 mAh?cm?2)条件下, Zn//Cu和Zn@In@Sn//Cu半电池的库仑效率(a), Zn@In@Sn//Cu (b)和Zn//Cu (c)半电池充/放电曲线图; (d) Zn//Zn, Zn@In//Zn@In, Zn@Sn//Zn@Sn和Zn@In@Sn//Zn@In@Sn电池在电流密度1 mA?cm?2 (面积容量: 0.5 mAh?cm?2)下的长循环性能; 纯锌, Zn@In和Zn@In@Sn的电化学阻抗谱(e); 对称Zn//Zn和Zn@In@Sn//Zn@In@Sn电池在1.0至5.0 mA?cm?2不同电流密度下, 固定容量为1 mAh?cm?2的倍率性能(f); 经过200 h后Zn@In@Sn电极的扫描电子显微镜(SEM)图(g)

Figure 5. CE (a) of Zn plating/stripping in the Zn//Cu and Zn@In@Sn//Cu half-cells at 2.0 mA?cm?2 (area capacity: 0.5 mAh?cm?2) and corresponding charge/discharge profiles of Zn@In@Sn//Cu (b) and Zn//Cu (c) half-cells. (d) Long-term galvanostatic cycling performance of symmetric cells Zn//Zn, Zn@In//Zn@In, Zn@Sn//Zn@Sn and Zn@In@Sn//Zn@In@Sn at current density 1 mA?cm?2 (area capacity: 0.5 mAh?cm?2). The electrochemical impedance spectra (e) of bare Zn, Zn@In and Zn@In@Sn. The rate capability (f) of symmetric Zn//Zn and Zn@In@Sn//Zn@In@Sn cells under different current densities from 1.0 to 5.0 mA?cm?2 with an area capacity of 1 mAh?cm?2. SEM and EDS images (g) of Zn@In@Sn electrodes after 200 h

图6. 在1 A?g?1条件下, Zn@In@Sn//MnO2, Zn@In//MnO2和Zn//MnO2电池的长循环性能(a)和相应的充放电曲线(b, c); Zn@In@Sn//MnO?电池点亮小灯泡的照片(d); Zn@In@Sn//MnO2的CV曲线(e); 循环前(f)和200个循环后(g), Zn//MnO2, Zn@In//MnO2和Zn@In@Sn//MnO2电池的电化学阻抗谱(EIS); Zn//MnO2, Zn@In//MnO2和Zn@In@Sn//MnO2电池的倍率性能(h)

Figure 6. Long-term cycling performance (a) and corresponding charging/discharging (b, c) curves of Zn@In@Sn//MnO2, Zn@In//MnO2 and Zn//MnO2 batteries at 1 A?g?1. The photo (d) of the Zn@In@Sn//MnO? battery lighting up a small bulb. CV curves (e) of Zn@In@Sn//MnO?. EIS of Zn//MnO2, Zn@In//MnO2 and Zn@In@Sn//MnO2 batteries before cycling (f) and after 200 cycles (g); Rate performance (h) of bare Zn//MnO2, Zn@In//MnO2 and Zn@In@Sn//MnO2 full cells

参考文献 45

[1]	Lee, J. H.; Kim, R.; Kim, S.; Heo, J.; Kwon, H.; Yang, J. H.; Kim, H. T. Energ. Environ. Sci. 2020, 13, 2839.
	Hao, J. N.; Yuan, L. B.; Johannessen, B.; Zhu, Y. L.; Jiao, Y.; Ye, C.; Xie, F. X.; Qiao, S. Z. Angew. Chem., Int. Ed. 2021, 60, 25114.
[2]	Ruan, P. C.; Liang, S. Q.; Lu, B. G.; Fan, H. J.; Zhou, J. Angew. Chem., Int. Ed. 2022, 61, e202200598.
[3]	Hu, X.; Zhao, Z.; Yang, Y.; Zhang, H.; Lai, G.; Lu, B.; Zhou, P.; Chen, L.; Zhou, J. InfoMat. 2024, 6, e12620.
[4]	Ming, J.; Guo, J.; Xia, C.; Wang, W.; Alshareef, H. N. Mater. Sci. Eng. R-Rep. 2019, 135, 58.
[5]	Xie, X. S.; Liang, S. Q.; Gao, J. W.; Guo, S.; Guo, J. B.; Wang, C.; Xu, G. Y.; Wu, X. W.; Chen, G.; Zhou, J. Energ. Environ. Sci. 2020, 13, 503.
[6]	Chen, A. S.; Zhao, C. Y.; Guo, Z. K.; Lu, X. Y.; Liu, N. N.; Zhang, Y.; Fan, L. S.; Zhang, N. Q. Energy Storage Mater. 2022, 44, 353.
[7]	Zuo, Y.; Wang, K.; Pei, P.; Wei, M.; Liu, X.; Xiao, Y.; Zhang, P. Mater. Today Energy 2021, 20, 100692.
[8]	Ji, H. M.; Xie, C. L.; Zhang, Q.; Li, Y. X.; Li, H. H.; Wang, H. Y. Acta Chim. Sinica 2023, 81, 29 (in Chinese).
	(姬慧敏, 谢春霖, 张旗, 李熠鑫, 李欢欢, 王海燕, 化学学报, 2023, 81, 29.) doi: 10.6023/A22100413
[9]	Huang, S.; Yuan, Z.; Salla, M.; Wang, X.; Zhang, H.; Huang, S.; Lek, D. G.; Li, X.; Wang, Q. Energ. Environ. Sci. 2023, 16, 438.
[10]	Zhang, X.; Li, J.; Liu, Y.; Lu, B.; Liang, S.; Zhou, J. Nat. Commun. 2024, 15, 2735.
[11]	Liang, Y. L.; Dong, H.; Aurbach, D.; Yao, Y. Nat. Energy 2020, 5, 646.
[12]	Zhou, Y.; Yuan, C.; Wang, S. J.; Zhu, Y. J.; Cheng, S.; Yang, X.; Yang, Y.; Hu, J.; He, J. L.; Li, Q. Energy Storage Mater. 2020, 28, 255.
[13]	Yuan, L. B.; Hao, J. N.; Kao, C. C.; Wu, C.; Liu, H. K.; Dou, S. X.; Qiao, S. Z. Energ. Environ. Sci. 2021, 14, 5669.
[14]	Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T. Nano-Micro Lett. 2022, 14, 42.
[15]	Guo, X.; He, G. J. Mater. Chem. A 2023, 11, 11987.
[16]	Zhou, J.; Shan, L. T.; Tang, B. Y.; Liang, S. Q. Chin. Sci. Bull. 2020, 65, 3562 (in Chinese).
	(周江, 单路通, 唐博雅, 梁叔全, 科学通报, 2020, 65, 3562.)
[17]	Liang, G. J.; Zhu, J. X.; Yan, B. X.; Li, Q.; Chen, A.; Chen, Z.; Wang, X. Q.; Xiong, B.; Fan, J.; Xu, J.; Zhi, C. Y. Energ. Environ. Sci. 2022, 15, 1086.
[18]	Long, X. T.; Liu, Y. Z.; Wang, D. X.; Nie, Y. H.; Lai, X. Y.; Luo, D.; Wang, X. J. Mater. Chem. A 2024, 12, 13181.
[19]	Wang, M.; Wang, Q.; Yao, H.; Su, F.; Shan, Z.; Shen, H.; Liu, T.; Zhao, J.; Ding, C. J. Alloy. Compd. 2023, 947, 169678.
[20]	Lu, K.; Jing, H.; Guo, Q.; Liu, C.; Liu, B.; Xia, X.; Wang, F.; Lei, W.; Xia, M.; Hao, Q. J. Energy Chem. 2024, 102, 37.
[21]	Yang, Q.; Bang, G. J.; Guo, Y.; Liu, Z. X.; Yon, B. X.; Wang, D. H.; Huang, Z. D.; Li, X. L.; Fan, J.; Zhi, C. Y. Adv. Mater. 2019, 31, 1903778.
[22]	Wang, A. R.; Zhou, W. J.; Huang, A. X.; Chen, M. F.; Tian, Q. H.; Chen, J. Z. J. Colloid Interf. Sci. 2021, 586, 362.
[23]	Mao, C.; Chang, Y.; Zhao, X.; Dong, X.; Geng, Y.; Zhang, N.; Dai, L.; Wu, X.; Wang, L.; He, Z. J. Energy Chem. 2022, 75, 135.
[24]	Kang, L. T.; Cui, M. W.; Jiang, F. Y.; Gao, Y. F.; Luo, H. J.; Liu, J. J.; Liang, W.; Zhi, C. Y. Adv. Energy Mater. 2018, 8, 1801090.
[25]	Deng, C. B.; Xie, X. S.; Han, J. W.; Tang, Y.; Gao, J. W.; Liu, C. X.; Shi, X. D.; Zhou, J.; Liang, S. Q. Adv. Funct. Mater. 2020, 30, 2000599.
[26]	Zhang, H.; Li, F.; Li, Z.; Gao, L.; Xu, B.; Wang, C. Batteries 2024, 10, 178.
[27]	Hao, Z. T.; Zhao, J. F.; Li, H. T.; Li, Z.; Pan, L.; Li, J. Acta Chim. Sinica 2024, 82, 416 (in Chinese).
	(郝再涛, 赵健飞, 李慧同, 李展, 潘朗, 李江, 化学学报, 2024, 82, 416.) doi: 10.6023/A24010006
[28]	Hao, J. N.; Li, X. L.; Zhang, S. L.; Yang, F. H.; Zeng, X. H.; Zhang, S.; Bo, G. Y.; Wang, C. S.; Guo, Z. P. Adv. Funct. Mater. 2020, 30, 2001263.
[29]	Khamsanga, S.; Uyama, H.; Nuanwat, W.; Pattananuwat, P. Sci. Rep. 2022, 12, 8689. doi: 10.1038/s41598-022-12657-9 pmid: 35606404
[30]	Cui, M. W.; Xiao, Y.; Kang, L. T.; Du, W.; Gao, Y. F.; Sun, X. Q.; Zhou, Y. L.; Li, X. M.; Li, H. F.; Jiang, F. Y.; Zhi, C. Y. ACS Appl. Energy Mater. 2019, 2, 6490.
[31]	Song, R.; Zhao, M. Q.; Wang, S.; Lu, Y; Bao, X. B.; Luo, Q. M.; Gou, L.; Fan, X. Y.; Li, D. L. Acta Chim. Sinica 2024, 82, 426 (in Chinese). doi: 10.6023/A24010019
	(宋瑞, 赵铭钦, 王帅, 卢垚, 鲍晓冰, 罗巧梅, 苟蕾, 樊小勇, 李东林, 化学学报, 2024, 82, 426.) doi: 10.6023/A24010019
[32]	Liang, P. C.; Yi, J.; Liu, X. Y.; Wu, K.; Wang, Z.; Cui, J.; Liu, Y. Y.; Wang, Y. G.; Xia, Y. Y.; Zhang, J. J. Adv. Funct. Mater. 2020, 30, 528.
[33]	Du, W. C.; Ang, E. H. X.; Yang, Y.; Zhang, Y. F.; Ye, M. H.; Li, C. C. Energ. Environ. Sci. 2020, 13, 3330.
[34]	Wang, Y. Y.; Chen, Y. J.; Liu, W.; Ni, X. Y.; Qing, P.; Zhao, Q. W.; Wei, W. F.; Ji, X. B.; Ma, J. M.; Chen, L. B. J. Mater. Chem. A 2021, 9, 8452.
[35]	Wu, P.; Xu, L. Y.; Xiao, X. M.; Ye, X. M.; Meng, Y. Z.; Liu, S. Adv. Mater. 2024, 36, 2306601.
[36]	Wang, S.; Sun, Y. H.; Gao, X.; Song, R.; Zhao, M. Q.; Lu, Y.; Bao, X. B.; Luo, Q. M.; Gou, L.; Fan, X. Y. Chem. J. Chin. Univ. 2024, 45, 67 (in Chinese).
	(王帅, 孙雨涵, 高欣, 宋瑞, 赵铭钦, 卢垚, 鲍晓冰, 罗巧梅, 苟蕾, 樊小勇, 高等学校化学学报, 2024, 45, 67.)
[37]	Li, B. Y.; Yang, K.; Ma, J. B.; Shi, P. R.; Chen, L. K.; Chen, C. M.; Hong, X.; Cheng, X.; Tang, M. C.; He, Y. B.; Kang, F. Y. Angew. Chem., Int. Ed. 2022, 61, e202212587.
[38]	Han, W.; Zheng, X. D.; Yang, K.; Tsang, C. S.; Zheng, F. Y.; Wong, L. W.; Lai, K. H.; Yang, T. F.; Wei, Q.; Li, M. J.; Io, W. F.; Guo, F.; Cai, Y.; Wang, N.; Hao, J. H.; Lau, S. P.; Lee, C. S.; Ly, T. H.; Yang, M.; Zhao, J. Nat. Nanotechnol. 2023, 18, 55.
[39]	Fan, X. Y.; Zhu, Y. Q.; Wu, Y.; Zhang, S.; Xu, L.; Gou, L.; Li, D. L. Chem. J. Chin. Univ. 2022, 43, 65 (in Chinese).
	(樊小勇, 朱永强, 毋妍, 张帅, 许磊, 苟蕾, 李东林, 高等学校化学学报, 2022, 43, 65.)
[40]	Chen, M.; Gong, Y.; Zhao, Y.; Song, Y.; Tang, Y.; Zeng, Z.; Liang, S.; Zhou, P.; Lu, B.; Zhang, X.; Zhou, J. Natl. Sci. Rev. 2024, 11, nwae205.
[41]	Meng, Y.; Wang, M.; Xu, J.; Xu, K.; Zhang, K.; Xie, Z.; Zhu, Z.; Wang, W.; Gao, P.; Li, X.; Chen, W. Angew. Chem. Int. Ed. 2023, 62, e202308454.
[42]	Liu, W.; Zhao, Q. W.; Yu, H. M.; Wang, H.; Huang, S. Z.; Zhou, L. J.; Wei, W. F.; Zhang, Q. C.; Ji, X. B.; Chen, Y. J.; Chen, L. B. Adv. Funct. Mater. 2023, 33, 2302661.
[43]	Xin, Y.; Qi, J.; Xie, H.; Ge, Y.; Wang, Z.; Zhang, F.; He, B.; Wang, S.; Tian, H. Adv. Funct. Mater. 2024, 34, 2403222.
[44]	Luo, W.; Wang, Y.; Chou, S.; Xu, Y.; Li, W.; Kong, B.; Dou, S. X.; Liu, H. K.; Yang, J. Nano Energy 2016, 27, 255.
[45]	Lin, J. H.; Chen, C.-Y. Surf. Coat. Tech. 2022, 436, 128270.