The Indium-tin Bimetallic Modification Layer Synergistically Inhibited Zinc Dendrite Growth

doi:10.6023/A24120389

Abstract

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

Cite this article

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.

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Fig. & Tab. 6

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

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)

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

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

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

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

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