快速调控在半导体基底上的锌沉积实现高性能水系锌电池

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近日，安徽大学张朝峰教授课题组等人在Advanced Functional Materials上发表重要文章，论文题为“Fast and Regulated Zinc Deposition in a Semiconductor Substrate toward High-Performance Aqueous Rechargeable Batteries”。可充电水锌离子电池具有安全、环保、成本低等优点，被认为是大规模储能的理想选择。而锌阳极在阳极-电解质界面处容易产生枝晶生长和寄生反应，阻碍了电池的实际实现。在这项工作中，作者提出了通过使用三维ZnTe半导体基底来改善锌金属负极的电化学性能。该衬底具有高亲锌性、高电子导电性和高电子亲和性，以及较低的锌成核能垒，可以促进锌沿(002)晶面的防枝晶沉积，同时在表面保持较高的化学稳定性，防止寄生金属腐蚀和析氢反应，并保持稳定的骨架结构，防止负极体积的变化。基于碲基底的锌金属负极具有超过3300小时的长循环寿命，在1和30 mA cm^-2处电压滞回分别为48和320 mV。在贫电解质(18 µL mAh^-1)和有限锌金属(N:P容量比为3:1，正极质量负载高的实际条件下，ZnTe@Zn//MnO2全电池可以运行超过500个循环。

第一作者：Rui Wang

通讯作者：Chaofeng Zhang

通讯单位：安徽大学

论文DOI：10.1002/adfm.202207751

Figure 1. Illustrations of zinc-stripping/plating behaviors on bare Zn foil and 3D ZnTe@Zn electrode in 1 m ZnSO4 aqueous electrolyte. a) Bare Zn electrode suffers serious chemical corrosion, side reactions, and dendrite growth. b) The ZnTe@Zn electrode can obtain uniform and compact Zn plating. FESEM images of c) the bare Zn foil and (d) as-prepared ZnTe@Zn product, with the inset showing the digital image of ZnTe@Zn electrode. The corresponding elemental mapping results of the ZnTe@Zn surface for e) Te and f) Zn. g,h) The FESEM images of the cross-sectional ZnTe@Zn electrode, with the thickness of the ZnTe layer ≈4 µm. i,j) The corresponding elemental mappings of the ZnTe@Zn from the cross-sectional view. k) XRD patterns of anodic Zn, electrodeposited Zn, and ZnTe@Zn. High-resolution spectra of l) Zn 2p and m) Te 3d for the bare Zn and ZnTe@Zn.

Figure 2. Electrochemical characterizations of the bare Zn and ZnTe@Zn electrodes: a) CE tests of Zn-Cu and ZnTe@Zn-Cu cells at a current density of 2 mA cm−2. The charge/discharge curves of b) ZnTe@Zn-Cu and c) Zn-Cu cells. d) The time–voltage curves of Zn-Zn and ZnTe@Zn-ZnTe@Zn symmetrical cells at 1 mA cm−1. e) The first time-voltage profiles of Zn-Zn and ZnTe@Zn-ZnTe@Zn symmetrical cells at 1 mA cm−1. f) Comparison of the cycling time and voltage hysteresis of ZnTe@Zn electrodes with the reported Zn anodes at the current density of 1 mA cm−2. g) Time–voltage curves for Zn-Zn and ZnTe@Zn-ZnTe@Zn symmetrical cells at 30 mA cm−1.

Figure 3. Electric field simulation of a) the bare Zn and b) ZnTe@Zn electrode. Zn2+ concentration field simulation of c) the bare Zn and d) ZnTe@Zn electrode. FESEM images of e) the bare Zn and f) the ZnTe@Zn electrode after cycling for 50 cycles. g) XRD patterns of the bare Zn and ZnTe@Zn electrode after 50 cycles in 1 m ZnSO4 electrolyte. h) Adsorption energies of Te atom on Zn (002) plane and Zn (100) plane. i) Illustrations of Zn (002) crystal.

Figure 4. a) The FESEM images and the corresponding elemental mapping results of the cross-sectional electrodes after Zn deposition on ZnTe coated Cu substrate in 1 m ZnSO4 at 0.3 and 3 mAh cm−2. b) The cross-sectional image of a 2D ZnTe@Zn electrode after plating and corresponding elemental mapping results. c) Comparison of the binding energy of Zn atom with bare Zn (001) and ZnTe (111). d) Comparison of the binding energy of Zn atom with bare Zn (101) and ZnTe (111). e) Illustrations of zinc-plating behaviors on ZnTe@Zn electrode.

Figure 5. Electrochemical properties of the Zn//MnO2 and ZnTe@Zn//MnO2 cells: a) Rate performance of the both cells. b) The second charge/discharge plots of both cells at 1 C. c) The second CV curves of Zn//MnO2 and ZnTe@Zn//MnO2 cells. d) The different ratio values of N:P and E/C at experimental and practical conditions. e) Cycling performance at N:P capacity ratio conditions of 5:1 and 3:1

【总结】

作者通过简单的电沉积和原位气固反应法制备了可充电AZIBs的3D ZnTe@Zn电极。ZnTe层促进了改进的电荷转移动力学，有效地降低了重复循环过程中固体-电解质界面的内部电池极化，并提供了显著的光滑镀/剥离曲线。该ZnTe涂层不仅能作为亲锌宿主有效地引导Zn²⁺均匀的(002)沉积，还能提供三维结构限制进一步的无枝晶Zn沉积。因此，ZnTe@Zn电极在对称电池中表现出超平坦的电镀/剥离曲线和低电压滞后。此外，在固定电流密度为1 mA cm^-2的情况下，它在> 3300小时内表现出优越的速率能力和稳定性性能。即使在10 mA cm^-2的超高电流密度下，对称电池也能实现超过1100小时的无枝晶镀/剥离循环。此外，使用MnO2作为正极的全电池在贫电解液(电解液与容量之比为18 µL mAh^-1)、高负极质量负载和有限的锌负极(N:P比为3:1)的实际条件下表现出超过500次的长期寿命。这些显著的电化学性能使这种3D ZnTe@Zn候选材料成为有前途的下一代先进AZIBs负极。此外，该工作还指导了设计半导体材料作为高性能衬底用于抑制金属电极(如Zn/Li/Na电极)的枝晶生长。

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