可控刻蚀原位构筑Zn-Sn-Bi修饰层及其抑制锌负极枝晶性能

doi:10.6023/A26020056

摘要/Abstract

水系锌离子电池凭借其固有的安全性、成本效益及环境相容性, 已成为电网规模储能领域极具应用前景的候选体系. 然而, 锌金属负极在实际应用中面临严峻挑战: 锌离子的不规则电镀/剥离过程易诱发锌枝晶的不可控生长, 同时伴随析氢反应、界面钝化等副反应的发生. 这些问题不仅导致电池库仑效率降低、锌利用率下降, 还会显著缩短电池循环寿命, 严重制约了水系锌离子电池的产业化应用进程. 本研究采用可控蚀刻技术, 在锌箔表面原位构筑了具有三维分层结构的Zn-Sn-Bi三元合金修饰层(Zn-Sn-Bi@Zn). 其中, 引入的亲锌性Sn和Bi金属位点可显著降低锌的形核过电位, 引导Zn²⁺实现均匀成核; 独特的三维分层骨架结构具备丰富的活性位点与较大的比表面积, 能有效局域化电流密度, 促进锌的均匀沉积, 从物理层面抑制枝晶的生长; 此外, 该合金修饰层良好的亲水性与优异的导电性, 可显著加速界面电荷转移效率, 提升电池反应动力学性能. 得益于合金修饰层的多重保护作用, Zn-Sn-Bi@Zn对称电池在0.2 mA•cm⁻²电流密度、0.2 mAh•cm⁻²面积容量条件下, 实现了超过2800 h的超长稳定循环, Zn-Sn-Bi@Zn半电池循环450周后, 平均库仑效率高达99.7%, 展现出优异的镀锌/剥离可逆性及耐腐蚀性能. 将其与δ-MnO₂正极组装成全电池后, 在1 A•g⁻¹电流密度下循环1600次, 仍可保持156.6 mAh•g⁻¹的高可逆比容量, 其循环稳定性与倍率性能均显著优于基于裸锌负极的对照电池. 该项工作为高性能水系锌离子电池的开发提供了一种有效的技术理念.

关键词: 水系锌离子电池, 锌金属负极, 三元合金, 刻蚀, 抑制枝晶

Aqueous zinc-ion batteries (AZIBs) have emerged as promising candidates for grid-scale energy storage due to their inherent safety, cost-effectiveness, and environmental friendliness. However, the practical application of zinc metal anodes faces significant challenges. The irregular plating/stripping processes readily trigger uncontrollable growth of zinc dendrites, accompanied by side reactions such as the hydrogen evolution reaction and interfacial passivation. These issues lead to reduced Coulombic efficiency, diminished zinc utilization, and shortened cycle life, severely hindering the further development of AZIBs. To address these critical drawbacks, this study reports an in-situ construction of a three-dimensional hierarchical Zn-Sn-Bi ternary alloy protective layer (denoted as Zn-Sn-Bi@Zn) on commercial zinc foil via a controllable chemical etching strategy. The fabrication process involves pre-treatment of the zinc foil, followed by immersion in a specifically formulated chemical etching solution to build a three-dimensional porous scaffold. Subsequently, hydrophilic and zincophilic Sn and Bi metal components are uniformly introduced onto and within the scaffold, forming a robust and conductive composite interface. The incorporated zincophilic Sn and Bi sites can significantly reduce the nucleation overpotential for zinc deposition, guiding the uniform nucleation of Zn²⁺. Furthermore, the unique three-dimensional hierarchical architecture provides abundant active sites and a substantially increased specific surface area. This structure effectively localizes and homogenizes the current density, promoting the even deposition of zinc and thereby physically suppressing dendrite formation. Moreover, the engineered alloy layer exhibits enhanced hydrophilicity and high electrical conductivity, which markedly accelerate interfacial charge transfer kinetics and improve overall reaction dynamics. Comprehensive electrochemical evaluations demon-strate that, benefiting from the multifunctional protection offered by this alloy layer, the Zn-Sn-Bi@Zn symmetric cell achieves an exceptionally stable cycling lifespan exceeding 2800 h under a current density of 0.2 mA•cm⁻² and an areal capacity of 0.2 mAh•cm⁻². After 450 cycles, the Zn-Sn-Bi@Zn half-cell achieves an average Coulombic efficiency as high as 99.7%, showing excellent reversibility of Zn plating/stripping and good corrosion resistance. When paired with a δ-MnO₂ cathode to assemble a full cell, the device delivers a high reversible specific capacity of 156.6 mAh•g⁻¹ after 1600 cycles at a current density of 1 A•g⁻¹. Both the cycling stability and rate capability of this full cell are substantially superior to those of counterparts employing bare zinc anodes.

Key words: aqueous zinc-ion battery, zinc metal anode, ternary alloy, etching, dendrite suppression

引用此文

胡雨青, 关志强, 朱从乐, 李晨, 赵含玥, 李俊哲, 伊廷锋. 可控刻蚀原位构筑Zn-Sn-Bi修饰层及其抑制锌负极枝晶性能[J]. 化学学报, 2026, 84(6): 859-870.

Yuqing Hu, Zhiqiang Guan, Congle Zhu, Chen Li, Hanyue Zhao, Junzhe Li, Tingfeng Yi. In-Situ Construction of Zn-Sn-Bi Modification Layer by Controlled Etching and Its Performance in Inhibiting Zinc Dendrites[J]. Acta Chimica Sinica, 2026, 84(6): 859-870.

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图/表 7

图1. Zn-Sn-Bi@Zn电极的制备流程示意图

Figure 1. Schematic diagram of the preparation process of Zn-Sn-Bi@Zn electrode

图2. (a) Zn-Sn@Zn, (b) Zn-Bi@Zn, (c) Zn-Sn-Bi@Zn的SEM图, (d) Zn-Sn-Bi@Zn电极截面Zn, Sn和Bi元素的EDS能谱图, (e) Zn-Sn@Zn、Zn-Bi@Zn和Zn-Sn-Bi@Zn的XRD谱图, (f) Zn-Sn-Bi@Zn的XPS全谱图, (g) Zn, (h) Sn和(i) Bi元素的XPS高分辨谱图

Figure 2. SEM images of (a) Zn-Sn@Zn, (b) Zn-Bi@Zn and (c) Zn-Sn-Bi@Zn, (d) EDS elemental mapping images of Zn, Sn, and Bi elements in the cross-section of the Zn-Sn-Bi@Zn electrode, (e) XRD patterns of Zn-Sn@Zn, Zn-Bi@Zn and Zn-Sn-Bi@Zn, XPS spectra of the Zn-Sn-Bi@Zn electrode: (f) survey spectrum, high-resolution XPS spectrum of (g) Zn, (h) Sn and (i) Bi

图3. (a)裸锌循环100周过程的SEM和EDS, (b) Zn-Sn-Bi@Zn循环100周过程的SEM和EDS, (c~f) 2 mol•L−1 ZnSO4电解液在Zn-Sn-Bi@Zn、Zn-Sn@Zn、Zn-Bi@Zn和裸锌上的接触角

Figure 3. (a) SEM and EDS of bare zinc during 100 cycles, (b) SEM and EDS of Zn-Sn-Bi@Zn during 100 cycles, (c~f) Contact angles of 2 mol•L−1 ZnSO4 electrolyte on Zn-Sn-Bi@Zn, Zn-Sn@Zn, Zn-Bi@Zn, and bare Zn electrodes

图4. (a) 2 mol•L−1的ZnSO4溶液中裸锌和(b) Zn-Sn-Bi@Zn电极在5 mA•cm−2电流密度下的原位光学显微图, 裸锌、Zn-Sn@Zn、Zn-Bi@Zn和Zn-Sn-Bi@Zn的(c)对称电池LSV曲线, (d) Tafel曲线和(e) EIS曲线

Figure 4. (a) In-situ optical microscopy images of the bare Zn electrode and (b) Zn-Sn-Bi@Zn electrode in 2 mol•L−1 ZnSO4 electrolyte solution at a current density of 5 mA•cm−2, (c) LSV curves of symmetric cells based on bare Zn, Zn-Sn@Zn, Zn-Bi@Zn and Zn-Sn-Bi@Zn electrodes, (d) Tafel plots of bare Zn, Zn-Sn@Zn, Zn-Bi@Zn, and Zn-Sn-Bi@Zn electrodes, (e) EIS curves of symmetric cells based on bare Zn, Zn-Sn@Zn, Zn-Bi@Zn, and Zn-Sn-Bi@Zn electrodes

图5. (a) －150 mV下的CA曲线, (b) 1 mV•s−1下的CV曲线, (c) 1 mA•cm−2, 1 mAh•cm−2下Bare Zn//Cu和Zn-Sn-Bi@Zn//Cu半电池的库仑效率, (d) Zn-Sn-Bi@Zn, (e) Zn-Sn@Zn和(f) Zn-Bi@Zn电极的锌离子迁移数, (g)裸锌和Zn-Sn-Bi@Zn沉积过程示意图

Figure 5. (a) CA curves at －150 mV, (b) CV curves at a scan rate of 1 mV•s−1, (c) Coulombic efficiency of bare Zn//Cu and Zn-Sn-Bi@Zn//Cu half-cells under the condition of 1 mA•cm−2 (areal capacity: 1 mAh•cm−2), Zinc ion transference numbers of (d) Zn-Sn-Bi@Zn, (e) Zn-Sn@Zn, and (f) Zn-Bi@Zn electrodes, (g) Schematic illustrations of the Zn deposition process on the bare Zn and Zn-Sn-Bi@Zn electrodes

图6. 对称电池Bare Zn, Zn-Sn@Zn, Zn-Bi@Zn和Zn-Sn-Bi@Zn (a)在电流密度0.2 mA•cm−2 (面积容量: 0.2 mAh•cm−2)下的长循环性能, (b)在电流密度5 mA•cm−2 (面积容量: 1 mAh•cm−2)下的长循环性能, (c)在0.5至15 mA•cm−2不同电流密度下, 固定容量为1 mAh•cm−2的倍率性能, (d)经过100周循环后Zn-Sn-Bi@Zn电极的SEM图

Figure 6. (a) Long-cycle performance of symmetric cells based on bare Zn, Zn-Sn@Zn, Zn-Bi@Zn, and Zn-Sn-Bi@Zn electrodes at a current density of 0.2 mA•cm−2 (areal capacity: 0.2 mAh•cm−2) and (b) 5 mA•cm−2 (areal capacity: 1 mAh•cm−2), (c) Rate performance of the symmetric cells with a fixed capacity of 1 mAh•cm−2 under different current densities from 0.5 to 15 mA•cm−2, (d) SEM images of the Zn-Sn-Bi@Zn electrode after 100 cycles

图7. Bare Zn//δ-MnO2和Zn-Sn-Bi@Zn//δ-MnO2全电池的(a) CV曲线, (b)在1 A•g−1下的容量曲线, (c) EIS图, (d)倍率性能, (e)在1 A•g−1条件下的长循环性能

Figure 7. (a) CV curves, (b) capacity-voltage profile at a current density of 1 A•g−1, (c) EIS spectra, (d) rate capabilities, and (e) long-cycle performance at a current density of 1 A•g−1 of bare Zn//δ-MnO2 and Zn-Sn-Bi@Zn//δ-MnO2 cells

参考文献 45

[1]	Yang, M.; Bi, S.; Wang, X.; Zhang, Y.; Hu, Y.; Tian, J.; Liu, L.; Niu, Z. J. Am. Chem. Soc. 2025, 147, 9294. doi: 10.1021/jacs.4c15126 pmid: 40059326
[2]	Tang, M.; Liu, Q.; Zou, X.; Zhang, B.; An, L. Adv. Mater. 2025, 37, 2501361. doi: 10.1002/adma.v37.48
[3]	Xin, Y.; Qi, J.; Xie, H.; Ge, Y.; Wang, Z.; Zhang, F.; He, B.; Wang, S.; Tian, H. Adv. Funct. Mater. 2024, 34, 2403222. doi: 10.1002/adfm.v34.39
[4]	Wei, Z.-B.; Bao, M.-F.; Xu, S.-B.; Cheng, Y.; Chen, S.-J.; Lin, N.; Mao, A.-Q. Acta Chim. Sinica 2025, 83, 868 (in Chinese). doi: 10.6023/A25040107
	(韦正兵, 鲍梦凡, 徐世彪, 程怡, 陈诗洁, 林娜, 冒爱琴, 化学学报, 2025, 83, 868.) doi: 10.6023/A25040107
[5]	Zhu, J.; Tie, Z.; Bi, S.; Niu, Z. Angew. Chem. Int. Ed. 2024, 63, e202403712. doi: 10.1002/anie.v63.22
[6]	Wang, P.; Tong, Y.; Wang, J.; Bai, R.; Xiao, Z.; Zhang, H.; An, Q.; Wang, K. Small 2025, e14368.
[7]	Luo, Y.; Hu, J.; Luo, J.; Cai, S.; He, L.; Wei, C.; Zou, G.; Hou, H.; Ji, X. Energy Storage Mater. 2025, 104656.
[8]	Zhang, Z.; Liu, T.; She, F.; Jiao, Y.; Wang, Y.; Yuan, G. J. Colloid Interface Sci. 2025, 690, 137338. doi: 10.1016/j.jcis.2025.137338
[9]	Jia, T.; Wei, L.; Zhu, Z.; Guo, X. J. Colloid Interface Sci. 2025, 138469.
[10]	Jeon, H. G.; Heo, S. W.; Song, J.; Kim, C. Adv. Energy Mater. 2025, 15, 2500155. doi: 10.1002/aenm.v15.21
[11]	Wang, Z.; Hu, S.; Wang, D.; Huang, J.; Qi, J.; Liu, H.; Li, X.; Han, C.; Cheng, H. M. Adv. Funct. Mater. 2025, 35, 2502186. doi: 10.1002/adfm.v35.34
[12]	Li, Y.; Liu, X.; Zhang, M.; Sheng, D.; Ren, P.; Che, L.; Wang, X.; Shen, Z. X. ACS Mater. Lett. 2024, 6, 1938.
[13]	Zhu, J.; Yang, M.; Hu, Y.; Yao, M.; Chen, J.; Niu, Z. Adv. Mater. 2024, 36, 2304426. doi: 10.1002/adma.v36.3
[14]	Li, B.; Zhao, Y.; Gao, X.; Sun, Y.-H.; Zhao, B.-Y.; Luo, Q.-M.; Bao, X.-B.; Gou, L.; Cui, Y.-H.; Fan, X.-Y. Acta Chim. Sinica 2025, 83, 237 (in Chinese). doi: 10.6023/A24120389
	(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, 化学学报, 2025, 83, 237.) doi: 10.6023/A24120389
[15]	Wu, J.; Li, M.; Li, H.; Wang, Z.; Chen, T.; Wang, Y. Coordin. Chem. Rev. 2025, 531, 216478. doi: 10.1016/j.ccr.2025.216478
[16]	Kim, A.; Kim, H.; Nam, K. W. J. Mater. Chem. A 2025, 13, 29109. doi: 10.1039/D5TA03948G
[17]	Xu, G.; Li, Y.; Li, J.; Li, J.; Liu, X.; Wang, C.; Mai, W.; Yang, G.; Pan, L. Angew. Chem. Int. Ed. 2025, 64, e202511389. doi: 10.1002/anie.v64.39
[18]	Huang, C.; Zhao, M.; Xu, C.; Lv, Y.; Fang, M.; Dong, Q.; Xu, Y.; Bo, Z.; Lu, J. Angew. Chem. Int. Ed. 2025, 64, e202511410. doi: 10.1002/anie.v64.40
[19]	Zhao, H.; Chen, M.; Yu, J.; Sheng, B.; Han, X.; Tian, Q.; Xu, J.; Chen, J. J. Colloid Interf. Sci. 2025, 678, 441. doi: 10.1016/j.jcis.2024.09.150
[20]	Yan, Z.; Cheng, Q.; Sun, M.; Wu, B.; Zhu, Y.; Tong, Z.; Li, M.; Jia, C.; Zhao, P. SmartMat 2025, 6, e1323. doi: 10.1002/smm2.v6.1
[21]	Xie, W.; Lv, D.; Cai, D.; Liu, C.; Zhou, J.; Chen, Q.; Zhang, C.; Li, C. C.; Zhan, H. Small 2025, e12450.
[22]	Mamat, M.; Wu, J.; Yang, L.; Abliz, A.; Wang, S.; Li, H. ACS Sustainable Chem. Eng. 2025, 13, 12553. doi: 10.1021/acssuschemeng.5c04021
[23]	Zhang, Q.; Wan, L.; Cheng, S.; Wang, J.; Dai, Y.; Gao, X.; He, G.; Li, H. SmartMat 2025, 6, e70034. doi: 10.1002/smm2.v6.4
[24]	Shi, Y.; Liu, Y.; Chang, R.; Zhang, G.; Rang, Y.; Xu, Z.-L.; Meng, Q.; Cao, P.; Zhou, X.; Tang, J. Nano-Micro Lett. 2025, 17, 254. doi: 10.1007/s40820-025-01765-6
[25]	Gopalakrishnan, M.; Hlaing, M. T.; Kulandaivel, T.; Kao-ian, W.; Etesami, M.; Liu, W.-R.; Nguyen, M. T.; Yonezawa, T.; Limphirat, W.; Kheawhom, S. J. Alloy. Compd. 2025, 1013, 178521. doi: 10.1016/j.jallcom.2025.178521
[26]	Zhong, L.; Yan, Y.; Ye, Z.; Zhang, X.; Yang, W.; Zheng, J.; Lin, X.; Zhang, L.; Zhou, G.; Lin, H. Chem. Eng. J. 2025, 172018.
[27]	Ao, H.; Ma, T.; Wang, R.; Zhang, S. Chem. Eng. J. 2025, 504, 159115. doi: 10.1016/j.cej.2024.159115
[28]	Guo, W.; Chen, J.; Wang, X.; Su, Y.; Sun, J.; Zheng, G. Small Sci. 2026, 6, e202500466. doi: 10.1002/smsc.v6.1
[29]	Li, R.; Du, Y.; Li, Y.; He, Z.; Dai, L.; Wang, L.; Wu, X.; Zhang, J.; Yi, J. ACS Energy Lett. 2022, 8, 457. doi: 10.1021/acsenergylett.2c01960
[30]	Tian, Y.; Liang, C.; Liang, Y.; Jiang, H. J. Mater. Chem. A 2025, 13, 35184. doi: 10.1039/D5TA05002B
[31]	Hu, Y.; Li, F.; Jiang, F.; Li, J.; Ma, Y.; Qin, Q.; Yan, S.; Luo, S.-H. J. Energy Storage 2025, 132, 117769. doi: 10.1016/j.est.2025.117769
[32]	Hu, X.; Lai, G.; Liu, Y.; Zhou, P.; Lu, B.; El-Bahy, Z. M.; Ebaid, M. S.; Chen, L.; Zhou, J. eScience 2025, 5, 100455. doi: 10.1016/j.esci.2025.100455
[33]	Deng, Z.; Zhang, W.; Gao, Q.; Yang, L.; Wu, Y.; Zhu, M. ACS Appl. Mater. Interfaces 2025, 17, 16942. doi: 10.1021/acsami.5c00853
[34]	Zhao, Z.; Liao, Y.; Li, S.; Xu, B.; Liu, Q.; Zhang, Y.; Huang, Y.; Wang, J. Adv. Funct. Mater. 2026, 36, e20763. doi: 10.1002/adfm.v36.16
[35]	Li, M.; Li, Y.; Cui, C.; Tian, S. Mater. Lett. 2025, 384, 138099. doi: 10.1016/j.matlet.2025.138099
[36]	Qi, B.; Huang, M.; Song, M.; Zhou, W.; Tan, H. Materials 2025, 18, 2997. doi: 10.3390/ma18132997
[37]	Cai, H.-J.; Gao, M.-Y.; Guo, M.-W.; Deng, R.-R.; Li, Y.; Ru, J.-J.; Hua, Y.-X.; Zhang, Q.-B.; Xu, C.-Y. Electrochim. Acta 2025, 543, 147610. doi: 10.1016/j.electacta.2025.147610
[38]	Zhang, P.; Wang, T.; Ding, P.; Hu, F.; Zou, Z.; He, W.; Borra, V.; Gao, Q.; Zhang, H.; Tang, J. J. Energy Storage 2026, 143, 119578. doi: 10.1016/j.est.2025.119578
[39]	Bi, Y.-Y.; Tian, S.-L.; Yu, Y.; Zhang, Y.; Sun, L.-S.; Li, J.; Liu, W.-Q.; Li, K.; Huang, G. Green Chem. 2025, 27, 13413. doi: 10.1039/D5GC03908H
[40]	Li, Z.; Su, M.; Chen, X.; Chao, F.; Lu, R.; Zhang, C.; Mao, Y.; Cao, D.; Zhu, K.; Wang, Z. Adv. Energy Mater. 2025, 15, e03597. doi: 10.1002/aenm.v15.43
[41]	Tao, J.; Chen, Q.; Chen, Z.; Cui, B.; Xu, X.; Han, J.; Yuan, R.; Xu, Q.; Peng, Y.; Liu, H. ACS Appl. Energy Mater. 2025, 8, 6829. doi: 10.1021/acsaem.5c00620
[42]	Bi, Y.; Jiang, F.; Liu, P.; Wan, Y.; Sun, L.; Liu, W. J. Alloy. Compd. 2026, 1052, 186158. doi: 10.1016/j.jallcom.2026.186158
[43]	Hao, Z.-T.; Zhao, J.-F.; Li, H.-T.; Li, Z.; Pan, L.; Li, J. Acta Chim. Sinica 2024, 82, 416 (in Chinese). doi: 10.6023/A24010006
	(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
[44]	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
[45]	Huang, J.; Zhong, Y.; AlMasoud, N.; Alomar, T. S.; Xie, Y.; Lu, B.; Liang, S.; El-Bahy, Z. M.; Tian, S.; Zhou, J. Adv. Powder Mater. 2025, 4, 100306.