Aqueous zinc-ion batteries are largely restricted by the unsatisfactory performance of zinc (Zn) anodes, including their poor stability and irreversibility. In particular, the mechanism behind the electrochemical contrast caused by the surface crystal plane, which is a decisive factor of the electrochemical characteristics of the hostless Zn anode, is still relatively indistinct. Hence, new insight into a novel anode with a surface-preferred (002) crystal plane is provided. The interfacial reaction and morphology evolution are revealed by theoretical analysis and post-mortem/operando experimental techniques, indicating that Zn anodes with more exposed (002) basal planes exhibit free dendrites, no by-products, and weak hydrogen evolution, in sharp contrast to the (100) plane. These features benefit the Zn (002) anode by enabling a long cyclic life of more than 500 h and a high average coulombic efficiency of 97.71% for symmetric batteries, along with delivering long cycling stability and reversibility with life spans of over 2000 cycles for full batteries. This work provides new insights into the design of high-performance Zn anodes for large-scale energy storage and can potentially be applied to other metal anodes suffering from instability and irreversibility.

Surface-Preferred Crystal Plane for a Stable and Reversible Zinc Anode

Principals and strategies for constructing a highly reversible zinc metal anode in aqueous batteries

Zn–Fe, Zn–Ni and Zn–Ni–Fe coatings were electrodeposited galvanostatically on mild steel from acidic baths (pH 3.5) consisted of ZnCl 2 , NiCl 2 , FeCl 2 , gelatin, sulfanilic ( p -aminobenzenesulfonic) acid and ascorbic acid. Cyclic voltammetry showed that the effect of gelatin was more pronounced than that of sulfanilic acid, and that the deposition of the ternary alloy behaved differently from the deposition of the binary alloys. In all three systems, the Faradaic efficiency was higher than 88%, the rate of Zn deposition was heavily influenced by mass-transport limitation at high applied current densities, and the deposition was of anomalous type. For each applied current density, the concentrations of Ni and Fe in the ternary alloy were higher than the corresponding concentrations in the binary alloys. The hardness of Zn–Ni coatings was the highest, while that of Zn–Fe coatings was the lowest. The Zn–Ni–Fe coatings were the smoothest, had distinguished surface morphology, and contained ZnO in the bulk, not just on the surface. The lowest corrosion rate in each alloy system (214, 325 and 26 μm year −1 for Zn–Ni, Zn–Fe and Zn–Ni–Fe, respectively) was characteristic of coatings deposited at 30, 30 and 40 mA cm − 2 , respectively. The higher corrosion resistance of the ternary alloy was also reflected by a higher corrosion potential, a higher impedance and a higher slope of the Mott-Schottky line. The enhanced corrosion behavior of the ternary alloy was thus attributed to its chemical composition, phase content, roughness and the synergistic effect of Ni and Fe on the n -type semiconductor surface film.

Electrodeposition of Zn–Ni, Zn–Fe and Zn–Ni–Fe alloys

Zn–Ni, Zn–Co and Zn–Ni–Co coatings were electrodeposited on mild steel from an acidic chloride bath containing p-aminobenzenesulphonic acid (SA) and gelatin. These additives changed the phase content in the coatings, most likely as a result of their adsorption at the surface of the cathode. The effect of gelatin was more pronounced than that of SA. The Faradaic efficiency was higher than 90%. As the current density was increased or the bath temperature was decreased, the concentration of the nobler metal in the coating increased. Both concentrations of Ni and Co in the ternary alloy increased as the applied current density was increased. Nickel and cobalt were found to have a synergistic catalytic effect. The thickness of all coatings increased as the applied current density was increased. The hardness increased with current density to a peak value, and then decreased. The rate of Zn deposition was heavily influenced by mass-transport limitation at high applied current densities, while the rates of Ni and Co deposition were not. The anomalous codeposition was explained by the great difference between the exchange current densities of Zn and the iron-group metal. Potentiodynamic polarization scans and electrochemical impedance spectroscopy showed that the corrosion resistance of the ternary Zn–Ni–Co alloy coatings was approximately 10 times higher than that of Zn–Ni and 7 times higher than that of Zn–Co. The improved corrosion resistance of the ternary alloy was attributed to its surface chemistry, phase content, texture, and surface morphology. The ternary Zn–Ni–Co coating may thus replace the conventional Zn–Ni and Zn–Co coatings in a variety of applications.

Electroplating and characterization of Zn–Ni, Zn–Co and Zn–Ni–Co alloys

Electrodeposition of Zn–Ni coatings as Cd replacement for corrosion protection of high strength steel

A heat treatment effect on the microstructure and corrosion properties of electrodeposited Zn, Zn-Co, Zn-Fe and Zn-Ni alloy coatings was studied. Surface morphology examinations were carried with AFM, while XRD was used to determine metal lattice parameters, texture and phase composition. Low-temperature annealing (at 225 °C) caused the formation of intermetallic Fe/Zn compounds, a transformation of amorphous oxide inclusions to the crystalline form and a decrease in the Zn lattice parameter for Zn-Co and Zn-Fe alloys. The mentioned structural modifications were not accompanied, however, by corrosion behavior changes of these coatings. On the Zn-Ni alloy, the annealing caused a significant reduction in the diffraction peak width and simultaneous considerable augmentation of the corrosion current. This effect is related to the formation of a less disordered lattice for this alloy.

Microstructure and corrosion resistance of electrodeposited zinc alloy coatings

The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn21Ni5 phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity of grain distribution were established to be the main factors determining corrosion behaviour of the coating.

R. Juškėnas

Papers

Microstructure and corrosion resistance of electrodeposited zinc alloy coatings

Pulse plating effect on microstructure and corrosion properties of Zn–Ni alloy coatings