近日，中南大学-王海燕&张旗研究团队等人在Advanced Energy Materials上发表重要文章，论文题“High-Index Zinc Facet Exposure Induced by Preferentially Orientated Substrate for Dendrite-Free Zinc Anode”。用于含水锌离子电池的最常用的锌箔负极具有差的循环稳定性和低的锌利用率。具有高亲锌性和稳定性的主体材料上的镀锌负极受到越来越多的关注以缓解上述问题。这里，作者通过实验观察和理论计算证实了Cu (2 2 0)的高锌沉积活性，然后通过工业电解策略制备了具有高度择优取向的Cu (2 2 0)衬底。所制备的Cu (2 2 0)衬底可以通过诱导具有最低表面能的Zn (0 0 1)生长和暴露高指数的锌晶面来一致地调节致密的锌生长，这是由于其优异的晶粒尺寸、高沉积活性和均匀的晶体取向，这导致该Cu (22 0)衬底的高镀锌/剥离可逆性。当组装到Zn//MnO2电池中时，在高锌利用率(=20%)下，镀锌Cu (2 2 0)在640次循环后可提供93.9%的容量保持率。这种可扩展的取向设计策略为实现具有特殊织构的无枝晶金属沉积提供了新的视角。
通讯作者：Qi Zhang，Haiyan Wang论文DOI：10.1002/aenm.202203203Figure 1. a) Optical image, b) inverse pole maps of annealed large grain copper foil. c) Optical image, d) inverse pole maps, e) confidence index map, f) electron backscatter image and corresponding EDS (line 1 and line 2) of annealed large grain copper foil with zinc deposition at 5 mA cm-2 for0.1 mAh cm-2. Scale bars: 100 μm.
Figure 2. SEM and CLSM images of a,b) P-Cu and c,d) C-Cu. e) Optical images and f) XRD patterns of P-Cu and C-Cu. g) Inverse pole maps andh) inverse pole figure in the [0 0 1] direction of P-Cu. Scale bars: 5 um.Figure 3. a) CV curves, b) voltage-capacity curves and optical images after zinc deposition, and c) nucleation overpotential-current density curves of C-Cu and P-Cu. Surface and sectional SEM images of zinc deposition on d,e) P-Cu and f,g) C-Cu at 5 mA cm-2 for 4 mAh cm-2. h) CLSM images of zinc deposition on P-Cu and C-Cu. In situ optical microscope surficial observations of zinc deposition on i) P-Cu and j) C-Cu at 5 mA cm-2.Figure 4. Crystallographic information. a) XRD patterns and b) relative texture coefficient (RTC) of each zinc facet on zinc deposited Cu substrate at 5 mA cm-2 for 2 mAh cm-2. c) Electron backscatter image and corresponding inverse pole maps, d) crystal orientation analysis of microdomains, and e) pole figure in the [0 0 1] direction.Figure 5. a) The adsorption model, charge distribution, and binding energy of zinc on different copper facets. b) Simulation of zinc facets growth and exposure. c) Surface energy of zinc facets and binding energy of zinc atom on different zinc facets. d) Schematic diagram of zinc deposition on different copper substrates.Figure 6. a) The Coulombic efficiency of Cu-based half cell and b) the corresponding voltage-capacity curves at 5 mA cm-2 for 2 mAh cm-2. c) Cyclic stability of symmetrical cells using copper plated with 4 mAh cm-2 of zinc as the electrode. d) Optical microscope morphology and e) XRD patterns of the copper electrodes after 50 cycles at 5 mA cm-2 for 2 mAh cm-2. f) Cycling performance of full cell with MnOz as cathode and P-Cu and C-Cu plated with 4 mAh cm-2 of zinc as the anode.【总结】
总之，通过实验观察和理论计算，作者发现锌在Cu (2 2 0)面上的沉积是非常活跃的。提出了一种可扩展的电解策略来制备高度择优取向的Cu (2 20)衬底。所制备的P-Cu由于其优异的晶粒尺寸、高的锌沉积活性和均匀的晶体取向，可以通过诱导具有最低表面能的Zn (0 01)的生长和暴露高指数的锌晶面来一致地调节密集的锌沉积。因此，这种基底在半电池中表现出较高的库仑效率(1100次循环，平均99.77%)和在全电池中的容量保持率(640次循环，93.9%)。这种廉价而有效的晶体取向调控策略可以指导实现特殊织构和无枝晶金属沉积。
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球差电镜 | 有限元模拟 | 理论计算
原位XRD、原位Raman、原位FTIR、原位TEM
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刘老师
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