Thioacetamide Additive Homogenizing Zn Deposition Revealed by In Situ Digital Holography for Advanced Zn Ion Batteries

doi:10.1007/s40820-023-01310-3

Abstract

Abstract:

Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost, high-safety, and high theoretical capacity. However, dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization. These problems can be tackled through the optimization of the electrolyte. However, the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive. Herein, a fast and simple method based on the digital holography is developed. It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer. It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth, thus able to value the applicability of electrolyte additives. The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive. Based on systematic characterization, it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition, but also construct adsorption molecule layers to inhibit side reactions of Zn anode. Being easy to operate, capable of in situ observation, and able to endure harsh conditions, digital holography method will be a promising approach for the interfacial investigation of other battery systems.

Key words: Digital holographic microscopy, In situ observation, Electrode/electrolyte interface, Zn dendrites, Screening electrolyte additives

Kaixin Ren, Min Li, Qinghong Wang, Baohua Liu, Chuang Sun, Boyu Yuan, Chao Lai, Lifang Jiao, Chao Wang. Thioacetamide Additive Homogenizing Zn Deposition Revealed by In Situ Digital Holography for Advanced Zn Ion Batteries[J]. Nano-Micro Letters, 2024, 16(1): 117-.

Kaixin Ren, Min Li, Qinghong Wang, Baohua Liu, Chuang Sun, Boyu Yuan, Chao Lai, Lifang Jiao, Chao Wang. [J]. Nano-Micro Letters, 2024, 16(1): 117-.

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URL: https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-023-01310-3

https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/117

Figures/Tables 6

Scheme 1 The observation setup of the DHM system and a schematic diagram of the dynamic Zn deposition at the electrode/electrolyte interface. R reference electrode, C counter electrode, W working electrode, CCD charge-coupled device

Fig. 1 a The voltage profiles of galvanostatic Zn deposition at different current densities in 2 M ZnSO₄ electrolyte. b The phase maps corresponding to points (i-iii) in (a). (i-iii): 0.1 mA cm⁻², (i₁-iii₁): 0.5 mA cm⁻², (i₂-iii₂): 1.0 mA cm⁻², (i₃-iii₃): 2.0 mA cm⁻², (i₄-iii₄): 4.0 mA cm⁻²

Fig. 2 a The phase maps corresponding to different Zn deposition time at the current density of 1.0 mA cm⁻² in (i-iv) blank ZnSO₄ and (i₁-iv₁) ZnSO₄-10 mM TAA electrolytes. b In situ optical microscopic observation of Zn deposition at 1 mA cm⁻² in blank ZnSO₄ and ZnSO₄-10 mM TAA electrolytes. SEM images and AFM images of the Zn anodes after 3 cycles: c, e in blank ZnSO₄, d, f in ZnSO₄-10 mM TAA electrolytes. g Electrostatic potential mapping of the TAA molecule. The radial distribution functions of h Zn-O (H₂O) and i Zn-TAA and their radius-dependent coordination numbers in ZnSO₄-10 mM TAA electrolyte. j Snapshot of the MD simulation cells for TAA-based electrolyte

Fig. 3 a Adsorption energies of H₂O and TAA on Zn (002) surface, and adsorption energy of H₂O on Zn (002) surface adsorbed TAA. High-resolution XPS spectra: b C 1s, and c N 1s for the Zn electrode after 3 cycles in ZnSO₄-10 mM TAA electrolyte. d LUMO and HOMO isosurfaces of H₂O molecules and TAA molecules. e The linear sweep voltammetry curves and f linear polarization curves of Zn anode obtained in the electrolytes with/without TAA additive. g Ionic conductivities of the electrolytes with/without TAA. Nyquist plots of the Zn-Zn symmetric cells before and after CA test and the corresponding CA curves obtained at an overpotential of 25 mV in the electrolytes: h blank ZnSO₄, i ZnSO₄-10 mM TAA electrolyte

Fig. 4 a Galvanostatic cycling property of Zn-Zn symmetric cells in the electrolytes with and without TAA at the current density of 1 mA cm⁻² with the areal capacity of 1 mAh cm⁻², and b the enlarged charge-discharge curves of the initial 3 cycles. c Cycling performance of the symmetric cells at high current density of 10 mA cm⁻² with the areal capacity of 1 mAh cm⁻². d Coulombic efficiency measurements of the Zn-Cu cells at a current density of 1 mA cm⁻² with the areal capacity of 1 mAh cm⁻². SEM images of the Zn anode after 50 cycles in ZnSO₄-10 mM TAA electrolytes: e top view, f side view. g XRD patterns of the Zn anode after 50 cycles in the electrolytes. h Schematic illustration of effect mechanism of TAA on Zn deposition in electrode/electrolyte interface in blank ZnSO₄ and ZnSO₄-TAA electrolytes

Fig. 5 Performance comparison of Zn-V₂O₅ full cells between 2 M ZnSO₄ and 2 M ZnSO₄-10 mM TAA electrolytes. a GCD curves under a current density of 2 A g⁻¹. b GCD curves of different cycling times. c Rate capacities under different current densities ranging from 0.2 to 2 A g⁻¹. d Nyquist plots and the fitting results obtained in 2 M ZnSO₄ and 2 M ZnSO₄-10 mM TAA electrolytes (insertion is the equivalent circuit). e Cycling stability of the full cells under a current density of 2 A g⁻¹

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