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及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小时的超长稳定循环,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 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 demonstrate 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 hours 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 batteries, 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, doi: 10.6023/A26020056.

Hu Yuqing, Guan Zhiqiang, Zhu Congle, Li Chen, Zhao Hanyue, Li Junzhe, Yi Tingfeng. In-Situ Construction of Zn-Sn-Bi Modification Layer by Controlled Etching and Its Performance in Inhibiting Zinc Dendrites[J]. Acta Chimica Sinica, doi: 10.6023/A26020056.

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

分享此文

参考文献

[1] Yang M.; Bi S.; Wang X.; Zhang Y.; Hu Y.; Tian J.; Liu L.; Niu, Z. J. Am. Chem. Soc.2025, 147, 9294.
[2] Tang M.; Liu Q.; Zou X.; Zhang B.; An L. Adv. Mater.2025, 37, 2501361.
[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.
[4] Wei Z.-B.; Bao M.-F.; Xu S.-B.; Cheng Y.; Chen S.-J.; Lin N.; Mao, A.-Q. Acta Chim. Sinica2025, 83, 868
(in Chinese). (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 )
[5] Zhu J.; Tie Z.; Bi S.; Niu, Z. Angew. Chem. Int. Ed.2024, 136, e202403712.
[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.
[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.
[11] Wang Z.; Hu S.; Wang D.; Huang J.; Qi J.; Liu H.; Li X.; Han C.; Cheng H. M.Adv. Funct. Mater. 2025, 2502186.
[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.
[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. Sinica2025, 83, 237
(in Chinese). (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.)
[15] Wu J.; Li M.; Li H.; Wang Z.; Chen T.; Wang, Y. Coordin Chem Rev2025, 531, 216478.
[16] Kim A.; Kim H.; Nam, K. W. J. Mater. Chem. A2025, 13, 29109.
[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.
[18] Huang C.; Zhao M.; Xu C.; Lv Y.; Fang M.; Dong Q.; Xu Y.; Bo Z.; Lu, J. Angew. Chem. Int. Ed.2025, 137, e202511410.
[19] Zhao H.; Chen M.; Yu J.; Sheng B.; Han X.; Tian Q.; Xu J.; Chen, J. J Colloid Interf Sci2025, 678, 441.
[20] Yan Z.; Cheng Q.; Sun M.; Wu B.; Zhu Y.; Tong Z.; Li M.; Jia C.; Zhao P. SmartMat2025, 6, e1323.
[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.
[23] Zhang Q.; Wan L.; Cheng S.; Wang J.; Dai Y.; Gao X.; He G.; Li H. SmartMat2025, 6, e70034.
[24] Shi Y.; Liu Y.; Chang R.; Zhang G.; Rang Y.; Xu Z.-L.; Meng Q.; Cao P.; Zhou X.; Tang J. Nano-Micro Lett2025, 17, 254.
[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 Compd2025, 1013, 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 J2025, 504, 159115.
[28] Guo W.; Chen J.; Wang X.; Su Y.; Sun J.; Zheng G. Small Sci.2026, 6, e202500466.
[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.
[30] Tian Y.; Liang C.; Liang Y.; Jiang, H. J. Mater. Chem. A2025, 13, 35184.
[31] Hu Y.; Li F.; Jiang F.; Li J.; Ma Y.; Qin Q.; Yan S.; Luo, S.-h. J. Energy Storage2025, 132, 117769.
[32] Hu X.; Lai G.; Liu Y.; Zhou P.; Lu B.; El-Bahy Z. M.; Ebaid M. S.; Chen L.; Zhou, J., Design of dual-electrode interfacial kinetics regulator for long-lasting Ah-level zinc-iodine batteries. eScience2025, 5, 100455.
[33] Deng Z.; Zhang W.; Gao Q.; Yang L.; Wu Y.; Zhu, M. ACS Appl. Mater. Interfaces2025, 17, 16942.
[34] Zhao Z.; Liao Y.; Li S.; Xu B.; Liu Q.; Zhang Y.; Huang Y.; Wang,J. Adv. Funct. Mater. 2025, e20763.
[35] Li M.; Li Y.; Cui C.; Tian S. Mater. Lett.2025, 384, 138099.
[36] Qi B.; Huang M.; Song M.; Zhou W.; Tan H. Mater.2025, 18, 2997.
[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.
[38] Zhang P.; Wang T.; Ding P.; Hu F.; Zou Z.; He W.; Borra V.; Gao Q.; Zhang H.; Tang, J. J. Energy Storage2026, 143, 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.
[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.
[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.
[42] Bi Y.; Jiang F.; Liu P.; Wan Y.; Sun L.; Liu, W. J. Alloy. Compd.2026, 1052, 186158.
[43] Hao Z.-T.; Zhao J.-F.; Li H.-T.; Li Z.; Pan L.; Li, J. Acta Chim. Sinica2024, 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.)
[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. Sinica2024, 82, 426
(in Chinese). (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.)
[45] Huang J.; Zhong Y.; AlMasoud N.; Alomar T. S.; Xie Y.; Lu B.; Liang S.; El-Bahy Z. M.; Tian S.; Zhou, J., Tailored fluoroborate-based electrolyte with fast interphase formation kinetics toward stable Ah-level zinc batteries. Adv. Powder Mater.2025, 4, 100306.