铟离子掺杂ZIF-8涂层修饰锌电极实现锌离子混合电容器长循环寿命

doi:10.6023/A26010015

摘要/Abstract

水系锌离子混合电容器具备超级电容器与电池的双重优势, 展现出高功率密度、低成本以及高安全性能, 成为极具开发潜力的储能器件之一. 但水系锌离子混合电容器仍面临一系列挑战, 尤其是锌负极的问题, 包括枝晶生长、腐蚀以及析氢反应. 鉴于金属有机框架(MOF)材料高孔隙率、高导电性的特性, 其被广泛用于锌负极改性. 本研究以MOF典型材料ZIF-8为基底, 合成过程中掺杂铟离子构建ZIF-8-In(III)人工界面保护层: ZIF-8的三维规整孔道可定向引导Zn²⁺迁移, In³⁺则调节孔道表面电荷增强正电性, 避免Zn²⁺团聚. 电化学测量和原位光学图像显示, ZIF-8-In(III)界面促进了锌离子均匀沉积, 同时有助于锌负极的防腐. 并且与ZIF-8@Zn和裸锌相比, 通过组装扣式电池, 对称的ZIF-8-In(III)@Zn涂层改性的锌电极电池表现出极低的极化电压, 并在2 mA•cm⁻²达到900 h的工作时间, 同时组装成锌离子电容器, 在1 A•g⁻¹比容量约达到39.05 mAh•g⁻¹, 可获得20000次的长循环寿命, 容量保持率接近100%.

关键词: 锌离子混合电容器, 锌负极改性, 界面修饰, ZIF-8-In(III), 循环稳定性

Aqueous zinc-ion hybrid capacitors (AZHCs) integrate the inherent merits of supercapacitors and secondary batteries, featuring high power density, low manufacturing cost and excellent intrinsic safety, thereby emerging as one of the most promising advanced electrochemical energy storage devices. Nevertheless, their large-scale commercial applications are severely hindered by inherent defects of zinc anodes, including uncontrollable dendrite growth, severe surface corrosion and parasitic hydrogen evolution reactions. Among various MOF materials, ZIF-8 has been widely employed for zinc anode modification on account of its abundant zinc-philic coordination sites and superior compatibility with zinc anodes. Herein, a functional composite modification layer integrating physical confinement and ion-regulating ability is successfully fabricated by doping In³⁺ into ZIF-8 via a facile one-step low-temperature hydrothermal method (35 ℃, 24 h). The intrinsic three-dimensional ordered pores of ZIF-8 serve as oriented ion transport channels to guide directional Zn migration and physically isolate the zinc foil from corrosive electrolyte, effectively restraining adverse interfacial side reactions. Moreover, the doped In³⁺ significantly optimizes pore surface charge distribution and increases surface positive charge, which prevents excessive Zn²⁺ accumulation inside pores and drives migrating Zn²⁺ toward the zinc substrate to eliminate undesirable zinc dendrite growth and accumulation. Electrochemical measurements and in-situ optical observations distinctly verify that the ZIF-8-In(III) interfacial layer enables uniform zinc deposition and effectively improves the anticorrosion performance of the anode. Compared with bare Zn and ZIF-8@Zn electrodes, the optimized ZIF-8-In(III)@Zn symmetric coin cell delivers remarkably low polarization and maintains an ultralong cycle life of 900 h at 2 mA•cm⁻². Furthermore, the assembled AZHCs with an activated carbon cathode achieve a specific capacity of 39.05 mAh•g⁻¹ at 1 A•g⁻¹, retaining nearly 100% capacity after 20000 long-term cycles. Besides, they possess a maximum energy density of 36.96 Wh•kg⁻¹ at a power density of 90 W•kg⁻¹. This work provides an innovative and feasible route for high-efficiency zinc anode stabilization via ex-situ artificial interface engineering.

Key words: zinc-ion hybrid capacitors, zinc anode modification, interface modification, ZIF-8-In(Ⅲ), cycling stability

引用此文

马洪芳, 邓玉雪, 周平凡, 黄鹏, 吴岭, 曲会鑫, 李金焕, 申来法, 张校刚, 佟浩. 铟离子掺杂ZIF-8涂层修饰锌电极实现锌离子混合电容器长循环寿命[J]. 化学学报, 2026, 84(6): 840-848.

Hongfang Ma, Yuxue Deng, Pingfan Zhou, Peng Huang, Ling Wu, Huixin Qu, Jinhuan Li, Laifa Shen, Xiaogang Zhang, Hao Tong. Indium-Ion-Doped ZIF-8 Coating Modified Zinc Electrode for Long Cycle Life of Zinc-Ion Hybrid Capacitors[J]. Acta Chimica Sinica, 2026, 84(6): 840-848.

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图/表 5

图1. (a)分别为ZIF-8-In(III)粉末、ZIF-8粉末XRD图谱; (b~d)分别为ZIF-8-In(III)粉末XPS谱: N 1s、C 1s、In 3d; (e) ZIF-8-In(III)@Zn及ZIF-8-In(III)粉末的XRD谱图; (f) ZIF-8-In(III)@Zn、裸Zn及ZIF-8@Zn电极在1 mol•L−1 Na2SO4溶液中的LSV图; (g) ZIF-8-In(III)@Zn、裸Zn及ZIF-8@Zn电极在1 mol•L−1 Na2SO4溶液中的Tafel图; (h)将ZIF-8-In(III)@Zn、裸Zn及ZIF-8@Zn电极分别与AC组装成锌离子电容后的EIS对比图; (i)在电流密度为0.5 mA•cm−2时Zn//Zn和ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn对称电池的成核过电位

Figure 1. (a) XRD patterns of ZIF-8-In(III) powder and ZIF-8 powder, respectively; (b~d) XPS spectra of ZIF-8-In(III) powder: N 1s, C 1s and In 3d; (e) XRD patterns of ZIF-8-In(III)@Zn and ZIF-8-In(III) powder; (f) LSV curves of ZIF-8-In(III)@Zn, bare Zn, and ZIF-8@Zn electrodes in 1 mol•L−1 Na2SO4 solution, respectively; (g) Tafel plots of ZIF-8-In(III)@Zn, bare Zn, and ZIF-8@Zn electrodes in 1 mol•L−1 Na2SO4 solution, respectively; (h) Comparison of EIS spectra of zinc-ion capacitors assembled with ZIF-8-In(III)@Zn, bare Zn and ZIF-8@Zn electrodes paired with AC, respectively; (i) Nucleation overpotentials of Zn//Zn and ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn symmetric cells at a current density of 0.5 mA•cm−2

图2. (a)裸Zn和ZIF-8-In(III)@Zn涂层结构循环示意图; (b) ZIF-8-In(III)粉末的SEM图; (c) ZIF-8粉末的SEM图; (d~g) ZIF-8-In(III)粉末的EDS mapping图; (h) ZIF-8-In(III)@Zn电极与裸Zn电极的接触角测试

Figure 2. (a) Schematic diagrams illustrating the cycling processes of bare Zn and ZIF-8-In(III)@Zn coating structures; (b) SEM image of ZIF-8-In(III) powder; (c) SEM image of ZIF-8 powder; (d~g) EDS mapping images of ZIF-8-In(III) powder; (h) Contact angle measurements of bare Zn electrode and ZIF-8-In(III)@Zn electrode, respectively

图3. (a) ZIF-8-In(III)@Zn电极与AC组装成锌离子电容器后在2 A•g−1的电流密度下循环50圈后的SEM图; (b)将ZIF-8-In(III)@Zn电极浸泡在2 mol•L−1 ZnSO4溶液中5 d后的SEM图; (c)裸Zn电极与AC组装成锌离子电容器后在2 A•g−1的电流密度下循环50圈后的SEM图; (d)将裸Zn电极浸泡在2 mol•L−1 ZnSO4溶液中5 d后的SEM图; (e)将ZIF-8-In(III)@Zn、裸Zn电极分别与AC组装成锌离子电容器后在2 A•g−1下循环50圈后的XRD图; (f)裸Zn、ZIF-8-In(III)@Zn电极在10 mA•cm−2的电流密度下电镀的原位光学显微镜图像

Figure 3. (a) SEM image of ZIF-8-In(III)@Zn electrode assembled with activated carbon (AC) in a zinc-ion capacitor after 50 cycles at a current density of 2 A•g−1; (b) SEM image of ZIF-8-In(III)@Zn electrode after immersion in 2 mol•L−1 ZnSO4 solution for 5 d; (c) SEM image of bare Zn electrode assembled with AC in a zinc-ion capacitor after 50 cycles at a current density of 2 A•g−1; (d) SEM image of bare Zn electrode after immersion in 2 mol•L−1 ZnSO4 solution for 5 d; (e) XRD patterns of ZIF-8-In(III)@Zn and bare Zn electrodes paired with AC for zinc-ion hybrid capacitors after 50 cycles at 2 A•g−1; (f) In-situ optical microscopy images of electrodeposition on bare Zn and ZIF-8-In(III)@Zn electrodes at a current density of 10 mA•cm−2

图4. (a, b)裸Zn与ZIF-8-In(III)@Zn电极组装的对称电池在不同温度下的EIS图; (c)裸Zn和ZIF-8-In(III)@Zn的Arrhenius曲线图; (d, e) Zn//Zn和ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn对称电池在恒压极化为10 mV时的电流-时间曲线图(其中恒压极化前后的阻抗谱图作为插图); (f) Cu//Zn和Cu//ZIF-8@Zn、Cu//ZIF-8-In(III)@Zn不对称电池在0.5 mA•cm−2, 0.5 mAh•cm−2条件下的库伦效率图; (g) Zn//Zn和ZIF-8@Zn//ZIF-8@Zn、ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn对称电池在2 mA•cm−2, 1 mAh•cm−2条件下的循环稳定性对比图; (h) Zn//Zn、ZIF-8@Zn//ZIF-8@Zn及ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn对称电池在10 mA•cm−2, 0.5 mAh•cm−2条件下的循环稳定性对比图; (i)不同扫速下ZIF-8-In(III)@Zn电极组装的锌离子混合电容器的CV图

Figure 4. (a, b) The EIS spectra of symmetric cells assembled with bare Zn and ZIF-8-In(III)@Zn electrodes at different temperatures; (c) Arrhenius plots of bare Zn and ZIF-8-In(III)@Zn electrodes; (d, e) Current-time curves of Zn//Zn and ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn symmetric cells under a constant voltage polarization of 10 mV (the insets show the impedance spectra before and after constant voltage polarization); (f) Coulombic efficiency of Cu//Zn, Cu//ZIF-8@Zn and Cu//ZIF-8-In(III)@Zn asymmetric cells at 0.5 mA•cm−2 and 0.5 mAh•cm−2; (g) Cycling stability comparison of Zn//Zn, ZIF-8@Zn//ZIF-8@Zn, and ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn symmetric cells at 2 mA•cm−2 and 1 mAh•cm−2; (h) Cycling stability of Zn//Zn, ZIF-8@Zn//ZIF-8@Zn, and ZIF-8-In(III)@Zn//ZIF-8-In(III)@Zn symmetric cells tested at 10 mA•cm−2 and 0.5 mAh•cm−2; (i) Cyclic voltammetry (CV) curves of zinc-ion hybrid capacitors based on ZIF-8-In(III)@Zn electrodes at various scan rates

图5. (a)不同扫速下ZIF-8-In(III)@Zn组装电容器的表面控制电容和扩散电容占总电容的比例; (b) ZIF-8-In(III)@Zn//AC锌离子混合电容器的拉贡曲线图; (c)组装Zn//AC、ZIF-8@Zn//AC及ZIF-8-In(III)@Zn//AC电容器后的循环倍率对比图; (d~f) Zn//AC、ZIF-8@Zn//AC和ZIF-8-In(III)@Zn//AC电容器在1 A•g−1的电流密度下进行长循环性能测试图; (g~i) Zn//AC、ZIF-8@Zn//AC和ZIF-8-In(III)@Zn//AC电容器在10 A•g−1的电流密度下进行长循环性能测试图

Figure 5. (a) Proportions of surface-controlled capacitance and diffusion-controlled capacitance to the total capacitance of capacitors assembled with ZIF-8-In(III)@Zn electrodes at different scan rates; (b) Ragone plot of ZIF-8-In(III)@Zn//AC zinc-ion hybrid capacitors; (c) Rate capability comparison of Zn//AC, ZIF-8@Zn//AC, and ZIF-8-In(III)@Zn//AC capacitors, respectively; (d~f) Long-term cycling performance of Zn//AC, ZIF-8@Zn//AC and ZIF-8-In(III)@Zn//AC capacitors at a current density of 1 A•g−1; (g~i) Long-term cycling performance of Zn//AC, ZIF-8@Zn//AC and ZIF-8-In(III)@Zn//AC capacitors at a current density of 10 A•g−1

参考文献 40

[1]	Ji, H.; Xie, C.; Zhang, Q.; Li, Y.; Li, H.; Wang, H. Acta Chim. Sinica 2023, 81, 29 (in Chinese). doi: 10.6023/A22100413
	(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
[2]	Zhang, L.; Wang, W.; Zhang, H.; Han, S.; Wang, L. Acta Chim. Sinica 2021, 79, 158 (in Chinese). doi: 10.6023/A20090409
	(张璐, 王文凤, 张洪明, 韩树民, 王利民, 化学学报, 2021, 79, 158.) doi: 10.6023/A20090409
[3]	Man, G. T.; Iordache, A. M.; Zgavarogea, R.; Nechita, C. Membranes 2024, 14, 277. doi: 10.3390/membranes14120277
[4]	Guo, D. F.; Chu, S. Y.; Zhang, B.; Li, Z. J. Small Methods 2024, 8, 2400587. doi: 10.1002/smtd.v8.12
[5]	Su, Y.; Yuan, G.; Hu, J.; Zhang, G.; Tang, Y.; Chen, Y.; Tian, Y.; Wang, S.; Shakouri, M.; Pang, H. Adv. Mater. 2024, 36, 2406094. doi: 10.1002/adma.v36.32
[6]	Guo, X.; Xu, H.; Qiu, Z.; Li, Q.; Li, N.; Yang, Z.; Li, W.; Lian, Y.; Li, Q.; Sui, Y.; Shakouri, M.; Chen, H‑C.; Zhang, Y.; Pang, H. Adv. Mater. 2025, 37, e14035. doi: 10.1002/adma.v37.45
[7]	Ling, W.; Wang, P.; Chen, Z.; Wang, H.; Wang, J.; Ji, Z.; Fei, J.; Ma, Z.; He, N.; Huang, Y. ChemElectroChem 2020, 7, 2957. doi: 10.1002/celc.v7.14
[8]	Huh, S. H.; Choi, Y. J.; Kim, S. H.; Bae, J. S.; Lee, S. H.; Yu, S. H. J. Mater. Chem. A 2023, 11, 19384. doi: 10.1039/D3TA01943H
[9]	Kang, D. H.; Lee, E.; Youn, B. S.; Ha, S.; Hyun, J. C.; Yoon, J.; Jang, D.; Kim, K. S.; Kim, H.; Lee, S. M.; Lee, S. Carbon Energy 2022, 4, 1080. doi: 10.1002/cey2.v4.6
[10]	Bui, H. T.; Tan, K. H. J. Build. Eng. 2025, 108, 112915.
[11]	Çamurcu, T.; Demirbas, E.; Ates, M. N. ACS Appl. Mater. Interfaces 2024, 16, 23209. doi: 10.1021/acsami.4c01028
[12]	Ma, H.; Tian, X.; Wang, T.; Hou, S.; Jin, H. ACS Appl. Mater. Interfaces 2023, 15, 57049.
[13]	Luo, H.; Li, C.; Sheng, W.; Yuan, W.; Chen, X.; Ma, Q.; Li, X.; Sun, Z.; Li, P. Solid State Ionics 2025, 421, 116790. doi: 10.1016/j.ssi.2025.116790
[14]	Li, B.; Zhao, Y.; Gao, X.; Sun, Y.; Zhao, B.; Luo, Q.; Fan, X. 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, 樊小勇, 化学学报, 2025, 83, 237.) doi: 10.6023/A24120389
[15]	Lu, M.; Xiao, B. H.; Lu, Y. X.; Xiao, K.; Liu, Z. Q. Adv. Energy Mater. 2025, 15, 2500785. doi: 10.1002/aenm.v15.30
[16]	Hao, Z.; Zhao, J.; Li, H.; 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
[17]	Liu, J.; Luo, Q.; Xia, S.; Yang, X.; Lei, J.; Sun, Q.; Chen, X.; Shao, J.; Tang, X.; Zhou, G. J. Colloid Interf. Sci. 2024, 665, 163. doi: 10.1016/j.jcis.2024.03.126
[18]	Zhou, P.; Deng, Y.; Huang, P.; Ma, H.; Wu, L.; Qu, H.; Shen, L.; Xu, Z.; Zhang, X.; Tong, H. Acta Chim. Sinica 2026, 84, 324 (in Chinese). doi: 10.6023/A25120395
	(周平凡, 邓玉雪, 黄鹏, 马洪芳, 吴岭, 曲会鑫, 申来法, 许真铭, 张校刚, 佟浩, 化学学报, 2026, 84, 324.) doi: 10.6023/A25120395
[19]	Jang, J.; Lim, W. G.; Jo, C. Batteries & Supercaps 2024, 7, e202400365. doi: 10.1002/batt.v7.12
[20]	Wang, C.; Tang, W.; Xu, J.; Zu, Y.; Sun, Y.; Wei, A.; Nie, W. Mater. Lett. 2025, 385, 138182. doi: 10.1016/j.matlet.2025.138182
[21]	Lv, D.; Li, Q.; Wu, P.; Zhang, X.; Wang, L.; Li, B.; Gao, N.; Liu, Z.; Wang, L. Langmuir 2024, 40, 11287. doi: 10.1021/acs.langmuir.4c01037
[22]	Chen, X.; Li, W.; Hu, S.; Akhmedov, N. G.; Reed, D.; Li, X.; Liu, X. Nano Energy 2022, 98, 107269. doi: 10.1016/j.nanoen.2022.107269
[23]	Wang, Y.; Fan, Y.; Liao, D.; Wu, Y.; Yu, Y.; Hu, C. Energy Storage Mater. 2022, 51, 212.
[24]	Wang, G. Int. J. Electrochem. Sci. 2025, 20, 101023. doi: 10.1016/j.ijoes.2025.101023
[25]	Guo, C.; Xue, P.; Duan, F.; Chen, Y.; Lan, Y. Q. Acc. Chem. Res. 2025, 58, 2229. doi: 10.1021/acs.accounts.5c00226
[26]	Zhang, W. W.; Qi, W. T.; Yang, K.; Hu, Y. Y.; Jiang, F. Y.; Liu, W. B.; Du, L. Y.; Yan, Z. H.; Sun, J. C. Energy Storage Mater. 2024, 71, 103616.
[27]	Zhou, H. R.; Li, Y. Y, Ren, J. X, Qu, J. N, Zhang, Y. H, Lin, C.; Liang, X. L, Lei, J. H, Chen, J. H, Li, J. Y, Zhang, Y. Electrochim. Acta 2025, 530, 146423. doi: 10.1016/j.electacta.2025.146423
[28]	Du, C.; Xiong, H.; Xiang, Y.; Zhao, H.; Yu, L.; Liang, J.; Nie, Z.; Wan, G.; Dou, Z.; Wang, G. J. Power Sources 2025, 656, 238084. doi: 10.1016/j.jpowsour.2025.238084
[29]	Long, Y.; Huang, X.; Li, Y.; Yi, M.; Hou, J.; Zhou, X.; Hu, Q.; Zheng, Q.; Lin, D. J. Colloid Interf. Sci. 2022, 614, 205. doi: 10.1016/j.jcis.2022.01.072
[30]	Wang, Q.; Ina, T.; Chen, W. T.; Shang, L.; Sun, F.; Wei, S.; Sun-Waterhouse, D.; Telfer, S. G.; Zhang, T.; Waterhouse, G. I. Sci. Bull. 2020, 65, 1743. doi: 10.1016/j.scib.2020.06.020
[31]	Liu, P.; Dong, Y.; Li, X.; Zhang, Y.; Liu, Z.; Lu, Y.; Peng, X.; Zhai, R.; Chen, Y. J. Hazard. Mater. 2024, 470, 134150. doi: 10.1016/j.jhazmat.2024.134150
[32]	Bui, N. T.; Kang, H.; Teat, S. J.; Su, G. M.; Pao, C. W.; Liu, Y. S.; Zaia, E. W.; Guo, J.; Chen, J. L.; Meihaus, K. R.; Dun, C. Nat. Commun. 2020, 11, 3947. doi: 10.1038/s41467-020-17757-6
[33]	Lee, J. S.; Kitchamsetti, N.; Cho, J. S. Chem. Eng. J. 2024, 487, 150465. doi: 10.1016/j.cej.2024.150465
[34]	Xie, X.; Deng, L.; Li, L.; Pan, A.; Liang, S.; Fang, G. Energy Storage Mater. 2024, 73, 103834.
[35]	Menon, S.; Dutta, S.; Madaboosi, N.; Sai, V. V. R. ACS Appl. Nano Mater. 2023, 7, 18346. doi: 10.1021/acsanm.3c04104
[36]	Ding, R.; Qi, L.; Jia, M.; Wang, H. Electrochim. Acta 2013, 107, 494. doi: 10.1016/j.electacta.2013.05.114
[37]	Wang, W.; Zhang, L.; Xu, G.; Song, H.; Yang, L.; Zhang, C.; Xu, J.; Jia, D. Inorg. Chem. 2018, 57, 10287. doi: 10.1021/acs.inorgchem.8b01524
[38]	Xiao, Z.; Mei, Y.; Yuan, S.; Mei, H.; Xu, B.; Bao, Y.; Fan, L.; Kang, W.; Dai, F.; Wang, R.; Wang, L. ACS Nano 2019, 13, 7024. doi: 10.1021/acsnano.9b02106
[39]	Tao, K.; Han, X.; Ma, Q.; Han, L. Dalton Trans. 2018, 47, 3496. doi: 10.1039/C7DT04942K
[40]	Yu, P.; Liang, Y.; Dong, H.; Hu, H.; Liu, S.; Peng, L.; Zheng, M.; Xiao, Y.; Liu, Y. ACS Sustain. Chem. Eng. 2018, 6, 15325. doi: 10.1021/acssuschemeng.8b03763