Ultrathin Zincophilic Interphase Regulated Electric Double Layer Enabling Highly Stable Aqueous Zinc-Ion Batteries

doi:10.1007/s40820-023-01312-1

Abstract

Abstract:

The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions. Regulating the electrical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes. Herein, we report an ultrathin zincophilic ZnS layer as a model regulator. At a given cycling current, the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer (stern layer) and a suppressed diffuse layer, indicating the regulated charge distribution and decreased electric double layer repulsion force. Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance. Consequently, the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm⁻² with a lower overpotential of 25 mV. When coupled with an I₂/AC cathode, the cell demonstrates a high rate performance of 160 mAh g⁻¹ at 0.1 A g⁻¹ and long cycling stability of over 10,000 cycles at 10 A g⁻¹. The Zn||MnO₂ also sustains both high capacity and long cycling stability of 130 mAh g⁻¹ after 1,200 cycles at 0.5 A g⁻¹.

Key words: Zinc anode, Electric double-layer regulation, Multifunction SEI layer, Inhibited side reactions and dendrite, Rapid kinetics

Yimei Chen, Zhiping Deng, Yongxiang Sun, Yue Li, Hao Zhang, Ge Li, Hongbo Zeng, Xiaolei Wang. Ultrathin Zincophilic Interphase Regulated Electric Double Layer Enabling Highly Stable Aqueous Zinc-Ion Batteries[J]. Nano-Micro Letters, 2024, 16(1): 96-.

Yimei Chen, Zhiping Deng, Yongxiang Sun, Yue Li, Hao Zhang, Ge Li, Hongbo Zeng, Xiaolei Wang. [J]. Nano-Micro Letters, 2024, 16(1): 96-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-023-01312-1

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/96

Figures/Tables 6

Scheme 1 Schematic of zinc deposition process at the Zn and Zn@ZnS surface

Fig. 1 Morphology and properties of ZnS Layer. a Atomic force microscopy image of the electrode (right part: without ZnS; left part: with ZnS deposition). b, c XPS of Zn and Zn@ZnS electrodes. d, e SEM images of pure Zn electrode. f, g SEM images of Zn@ZnS electrode. h EDX- mapping of Zn@ZnS surface

Fig. 2 Simulations of Zn and ZnS properties. a The potential difference between the blue dot (yellow dot) and the value of the blue line (yellow line) at x = 0 represents the potential difference over the Helmholtz layer. b, c Scheme of EDL structure of b Zn/electrolyte and c Zn@ZnS/electrolyte interphase. d Zeta potential of zinc powder and ZnS powder. e Zeta potential of zinc deposits from Zn and Zn@ZnS surface. f EDL capacitance of Zn and Zn@ZnS symmetric batteries. g, h EIS of g Zn@ZnS||Zn@ZnS and h pure Zn||Zn symmetric cell at various temperatures. i The activation energy (E_a) of Zn and Zn@ZnS symmetric cell. j Adsorption energy, k Bader charge, and l electron density difference of Zn adatom toward Zn or Zn@ZnS electrode (For charge density difference, the blue color indicates a decrease in charge, and yellow represents an increase in charge)

Fig. 3 Characterizations of Side Reactions and Zinc Dendrite. a LSV curves and b Tafel plot. c XPS of electrodes after cycling. d CE of Zn-Cu cell. e, f Charge and discharge curves of e Zn@ZnS /Cu and f Zn/Cu cell. g Band structure of Zn@ZnS interface. h, i SEM images of h bare Zn surface and i Zn@S after 50 cycles at 1 mA cm⁻² and 1 mAh cm⁻². j CA curves. k, l COMSOL simulation of electrolyte current density distribution of k the pure Zn and l Zn@ZBO during the zinc deposition process

Fig. 4 Electrochemical performance of symmetric cells. a Rate performance and b Voltage hysteresis of symmetric cells. c Voltage hysteresis comparison at various current densities. d Long cycling performance at 1 mA cm⁻². e Lifetime comparison at various current densities with different coating thicknesses. f Long cycling performance at 3 mA cm⁻². g Long cycling performance with a DOD of 34.3%

Fig. 5 Electrochemical performance of full cells. a CV curves, b EIS, and c Rate performance of Zn//I₂@AC battery. d Galvanic curves of Zn@ZnS //I₂@AC full cell. e Long cycling performance of Zn//I₂@AC full cell at 1A g⁻¹ with N/P ratio of 3. f Galvanic curves of Zn@ZnS //MnO₂ full cells. g Long cycling performance of the Zn//MnO₂ full cells with a current density of 0.5A g⁻¹

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