Indium-Ion-Doped ZIF-8 Coating Modified Zinc Electrode for Long Cycle Life of Zinc-Ion Hybrid Capacitors

doi:10.6023/A26010015

Abstract

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

Cite this article

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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Fig. & Tab. 5

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

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

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

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

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

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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