Rational screening of metal coating on Zn anode for ultrahigh-cumulative-capacity aqueous zinc metal batteries

Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.

MXene-assisted polymer coating from aqueous monomer solution towards dendrite-free zinc anodes

Coating polymer on the surface is an effective way to realize functional modification of the materials for diverse applications,which has been proved to enhance the stability of metal anodes in batteries.However,given the limited operability of coating from polymer dispersions,it is imperative to develop simple aqueous-based strategies from monomers for versatile polymer coating.Herein,a Ti_(3)C_(2)Tx MXene-assisted approach is proposed to construct polymer coating on zinc metal surfaces directly from the aqueous solution of monomers in an ice bath.By combining a doctor-blading method with spontaneous polymerization of monomers on the substrates at room temperature,a uniform,adhesive,and versatile coating layer assisted by a small amount of MXene is produced in one step.Additionally,MXene nanosheets serve as nanofillers to further enhance the mechanical strength and ionic conductivity of the polymer coating.Benefiting from good film formation and improved interfacial contact,the coated zinc anode exhibits a long cycling lifespan of over 1900 h.The assembled full cells show excellent cycling stability with a high capacity retention of 85.0%at 16 A g^(-1)over 2600 cycles.This work provides a simple and efficient way to produce polymer coatings directly from monomers,which may give new insights into design multifunctional polymer coatings for various applications.

Properties of Al/Conductive Coating/α-PbO2-CeO2-TiO2/β-PbO2-WC-ZrO2 Composite Anode for Zinc Electrowinning

The properties of Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-WC-ZrO2 composite anode for zinc electrowinning were investigated. The electrochemical performance was studied by Tafel polarization curves（Tafel）, electrochemical impedance spectroscopy（EIS） and corrosion rate obtained in an acidic zinc sulfate electrolyte solution. Scanning electron microscopy（SEM）, X-ray diffraction（XRD）, and energy dispersive X-ray spectroscopy（EDXS） were used to observe the microstructural features of coating. Anodes of Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2, Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-WC, Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-ZrO2, and Pb-1%Ag anodes were also researched. The results indicated that the Al/conductive coating/α-PbO2-CeO2-TiO2/β-PbO2-WC-ZrO2 showed the best catalytic activity and corrosion resistant performance; the intensity of diffraction peak exhibited the highest value as well as a new PbWO4 phase; the content of WC and ZrO2 in coating showed the highest value as well as the finest grain size.

Growth and corrosion resistance of molybdate modified zinc phosphate conversion coatings on hot-dip galvanized steel

The modified zinc phosphate conversion coatings(ZPC) were formed on hot-dip galvanized(HDG) steel when 1.0 g/L sodium molybdate were added in a traditional zinc phosphate solution. The growth performance and corrosion resistance of the modified ZPC were investigated by SEM, open circuit potential(OCP), mass gain, potentiodynamic polarization and electrochemical impedance spectroscopy(EIS) measurements and compared with those of the traditional ZPC. The results show that if sodium molybdate is added in a traditional zinc phosphate solution, the nucleation of zinc phosphate crystals is increased obviously; zinc phosphate crystals are changed from bulky acicular to fine flake and a more compact ZPC is obtained. Moreover, the mass gain and coverage of the modified ZPC are also boosted. The corrosion resistance of ZPC is increased with an increase in coverage, and thus the corrosion protection ability of the modified ZPC for HDG steel is more outstanding than that of the traditional ZPC.

Electrodeposition of Compositionally Modulated Zinc-cobalt Alloy Multilayer Coatings

The effects of pulse parameters on the cobalt content, surface morphologies and grain size of Zn-Co alloy deposits were studied using a pulse plating technique with a square-wave current containing reverse pulse. Average current density and reverse anodic current density amongst the variables investigated have very strong effects on the cobalt content in the Zn-Co alloy deposits. Grain size, surface appearance and internal stress in the deposit were improved significantly by introducing the reverse current. Varieties of Zn-Co alloy compositionally modulated multilayer (CMM) coatings with large differences in cobalt contents for different sublayers were electrodeposited by designing corresponding waveforms using a computer-aided pulse plater and characterized in terms of surface morphologies. Cross-sectional morphologies of the Zn-Co alloy CMM coatings, examined using field emission gun scanning electron microscopy (FEGSEM), confirmed the layered structure.

Corrosion behavior of sintered zinc-aluminum coating in NaCl solution

Sintered zinc aluminum coating (SZAC) was prepared using zinc flakes, aluminum flakes and CrO 3 as main raw materials. The corrosion behavior of SZAC in 3.5%NaCl solution was studied by means of SEM, EDS, EIS and so on. Results indicate that aluminum corroded in advance of zinc to produce speculate or spherical substances, which attaches to SZAC and adds mass to it. Corrosion production passivates metal powders in SZAC, causes E corr of SZAC to increase gradually, and causes the arising of the third time constant in EIS, which corresponds to the insulation of corrosion production.

Towards advanced zinc anodes by interfacial modification strategies for efficient aqueous zinc metal batteries

Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.

Effect of Rare Earth on the Corrosion-Resisting Performance of Zinc-Based Alloy Coatings

The corrosion behavior of coatings of pure zinc and Zn-Al,Zn-Al-RE alloys in NaCl solu- tions was studied by salt-spray experiments,even corrosion experiments and electrochemical measurements of bi-directional polarization curves and a.c.impedance in weak polarization region consistent regularities were obtained by these different methods,viz.,the corrosion resistance of Zn could be enhanced by alloying it with Al,and particularly with Al-RE.The causes of enhancement of corrosion resistance by RE were also discussed.

The Alternative Coating Method For Zinc Phosphate Coating before Cold Deformation of High Carbon Steel Wires

The metal surfaces are passed through the pretreatment steps before being subjected to the coating process.One of these steps is zinc phosphate coating.The present process has many disadvantages such as the high number of digits,the difficult and high cost of disposal of the formed sludge,and not being an environmentally friendly approach.In this study,which we planned as an alternative coating for zinc phosphate coating,the effects on the wire were studied by working with stearates in order to be sensitive to the environment.Dipping method was used to compare different pH,time,temperature and concentrations of the obtained data with the zinc phosphate coating.With the alternative coating,the coating time can be reduced.Coating process;it can be completed in 3 stages by alternative coating method while it is finished in 7 steps in zinc phosphate process with surface cleaning.In addition,the corrosion resistance with alternative coating increased and cost decreased by 70-80%.Thus,it has been understood that the alternative coating is a coating type superior to zinc phosphate coating.

Dual Bath Electrodeposition of Alternate Multilayer Coatings of Zinc and Nickel Deposits

The synthesis of zinc and nickel alternate multilayer coatings produced by successive deposition from dual baths containing a revised zinc sulphate electrolyte and a new developed nickel bath has been investigated. Smooth and uniform zinc-nickel compositionally modulated multilayered (CMM) coatings with different multilayer configurations were obtained. The surface and cross-sectional morphologies of samples were examined using scanning electron microscopy (SEM). Cross-sectional morphology showed the layered structure of the coatings clearly.

Microstructure and Performances of Nanocrystalline Zinc-nickel Alloy Coatings

Nanocrystalline zinc-nickel alloy coatings were deposited from an alkaline zincate bath contained an organic additive that can reduce polarization and a complexing agent. SEM and TEM observations and XRD analysis were performed to examine the microstructure and phase composition of the coatings. The nickel content in deposits is 12.0-14.7% and the coating is consisted of single nanocrystalline y-phase structure (Ni5Zn2i), with grain average grain size about 15nm. The nanocrystalline zinc-nickel alloy coatings have better corrosion resistance, less bnttleness and higher microhardness than the conventional zinc coatings.

Effect of heat diffusion on properties of zinc-aluminum coating on AZ91D magnesium alloys

A protecting zinc and aluminum coating on the surface of AZ91D magnesium alloys was obtained by thermal spraying to improve the corrosion and wear resistance performances. In order to enhance the combination between magnesium alloy matrix and zinc and aluminum coating, the sample was heat-treated at 300℃for 2 h, then, the cross-section patterns, XRD pattern, micro-hardness, wear and corrosion resistance abilities were researched. The results indicate that the interface between the coating and substrate is metallurgical bond, and a transitional fusion layer is formed by diffusion. The micro-scale abrasion test and polarization test in 3% NaCl solution show that the diffusion-treated specimen has better wear and corrosion resistance performances in comparison with the undiffusion-treated and substrate magnesium alloys; in addition, it has relatively higher micro-hardness than the undiffusion-treated magnesium alloys.

The Influence of Microscopic Fungi on Chromated Galvanized Zinc Coatings

A solution containing Cr(VI), Cr(NO3)3 and its complex with an organic acid as well as several commercial solutions containing Cr(III) complexes with an organic acid and additionally CO2+, F-, SO42- ions were used for the studies. Results of the studies obtained in the following commercial solutions: Likonda 2AT, Cr(NO3)3 + malonic acid;Likonda 3Cr5 and Likonda 3CrMC are discussed. Steel coated with chromated Zn coatings was contaminated by some microscopic fungi. The variety of fungi on chromated plates diminished, however the propagules of fungi did not disappear completely. The Likonda 3Cr5 solution diminishes fungi contamination on chromated steel most effectively. In water used to rinse the surface of chromated plates the number of fungi propagules was detected to be higher as compared to that on the plate surface. The least quantity of fungi propagules was detected in water used to rinse plates coated in the Likonda 3Cr5 solution. The main part of fungi detected on chromated plates treated in the Likonda 3Cr5 solution were the fungi of Cladosporium species (C.herbarum, C.cladosporioides). The latter species also dominated on chromated plates coated with zinc and treated with the other solution. It should be mentioned, that on these plates chromated in this solution, Actinomycetes of the Streptomyces group were abundant. After comparison of surfaces of the plates treated in four solutions it has been determined that the surface of the plates treated in the Likonda 3Cr5 passivation solution and exposed to modelling conditions changed least of all. It has been noticed that on the subject studied white porous rust accumulates, the intensity of this process on the surface studied determines both the probability of corrosion and the resistance of the used safety means to the external factors.

Self-healing Performance of Composite Coatings Prepared by Phosphating and Cerium Nitrate Post-sealing

The phosphated and cerium nitrate post-sealed galvanized steel was firstly scratched to expose zinc layer and then placed in neutral salt spray （NSS） chamber for different durations. The microstructure and compositions of the scratches were investigated using SEM and EDS. The phases of the corrosion products were examined through XRD. The self-healing mechanism of the composite coatings was discussed. The experimental results show that the composite coatings have an excellent corrosion resistance. The corrosion products increase with corrosion time and finally cover the whole scratch. They contain phosphorous, cerium, oxygen, chloride and zinc, and are fine needle and exceedingly compact. The composite coatings are favorable self-healing. During corrosion, the self-healing ions such as Ce3＋, Ce4＋, PO43-, Zn2＋ in the composite coatings were dissolved, migrated, recombined, and covered the exposed zinc, impeding zinc corrosion. The self-healing process of the scratches on the composite coatings can be divided into three stages, about 2 h, 4 h, and 24 h, respectively.

Review on the phosphate-based conversion coatings of magnesium and its alloys

Magnesium(Mg)and its alloys are lightweight as well as biocompatible and possess a high strength-to-weight ratio,making them suitable for many industries,including aerospace,automobile,and medical.The major challenge is their high susceptibility to corrosion,thereby limiting their usability.The considerably lower reduction potential of Mg compared to other metals makes it vulnerable to galvanic coupling.The oxide layer on Mg offers little corrosion resistance because of its high porosity,inhomogeneity,and fragility.Chemical conversion coatings(CCs)belong to a distinct class because of underlying chemical reactions,which are fundamentally different from other types of coating.Typically,a CC acts as an intermediate sandwich layer between the base metal and an aesthetic paint.Although chromate CCs offer superior performance compared to phosphate CCs,yet still they release carcinogenic hexavalent chromium ions(Cr^(6+));therefore,their use is prohibited in most European nations under the Registration,Evaluation,Authorization and Restriction of Chemicals legislation framework.Phosphate-based CCs are a cost-effective and environment-friendly alternative.Accordingly,this review primarily focuses on different types of phosphate-based CCs,such as zinc,calcium,Mg,vanadium,manganese,and permanganate.It discusses their mechanisms,current status,pretreatment practices,and the influence of various parameters-such as pH,temperature,immersion time,and bath composition-on the coating performance.Some challenges associated with phosphate CCs and future research directions are also elaborated.

Investigation on a Non-cyanide Plating Process of Ni-P Coating on Magnesium Alloy AZ91D

In this research we presented a non-cyanide plating process of Ni-P alloy coating on Mg alloy AZ91D. By applying a new process flow of electroless nickel plating in which zinc coating is used as transition of Ni-P coating on Mg alloy AZ91D, the process of copper transition coating plated in the cyanides bath can be replaced. A new bath composed of NiSO4 was established by orthogonal test. The results show that zinc transition coating can increase the adhesion and protect the Mg alloy substrate from the bath corrosion. The optimal plating bath composition is NiSO4·6H2O 20 g/L, NaH2PO2·H2O20g/L and C6H8O7·H2O 2.5 g/L, and optimal bath acidity and optimal plating temperature are pH 4.0 and 95℃, respectively. The present process flow is composed of ultrasonic cleaning→alkaline cleaning→acid pickling→activation→double immersing zinc→electroplating zinc→electroless nickel plating→passivation treatment. The present non-cyanide process of electroless nickel plating is harmless to our surroundings and Ni-P coating on Mg alloy AZ91D produced by present process possesses good adhesion and corrosion resistance.

Modification of ZnS∶Mn Phosphors by Sb-Doped SnO2 Coating

The coating of ZnS∶Mn by Sb-doped SnO2 using an co-precipitation process was reported. ZnS∶Mn phosphor particles were prepared by solid reaction with ZnS and MnCl2·4H2O. Surface modification of the ZnS∶Mn powders was carried out by coating transparent conductive films of Sb-doped tin oxides which were formed by co-precipitation and heat treatment process. Tin tetrachloride and antimony trichloride were used as the precursor materials for the co-precipitation. The influences of coating molar ratio, Sb concentration in the coatings, annealing temperature and time on the resistivity of coated ZnS∶Mn phosphors were investigated. The optimum co-precipitation processing parameters and annealing conditions were determined. The phosphors were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence(PL) observation and conductance measurements. An improvement in phosphors conductivity was observed while the respective photoluminescence intensity is analogous to the as-prepared ZnS∶Mn phosphors.

Carbon-coated manganese dioxide nanoparticles and their enhanced electrochemical properties for zinc-ion battery applications

In this study, we report the cost-effective and simple synthesis of carbon-coated α-MnOnanoparticles(α-MnO@C) for use as cathodes of aqueous zinc-ion batteries(ZIBs) for the first time. α-MnO@C was prepared via a gel formation, using maleic acid(CHO) as the carbon source, followed by annealing at low temperature of 270 °C. A uniform carbon network among the α-MnOnanoparticles was observed by transmission electron microscopy. When tested in a zinc cell, the α-MnO@C exhibited a high initial discharge capacity of 272 m Ah/g under 66 m A/g current density compared to 213 m Ah/g, at the same current density, displayed by the pristine sample. Further, α-MnO@C demonstrated superior cycleability compared to the pristine samples. This study may pave the way for the utilizing carbon-coated MnOelectrodes for aqueous ZIB applications and thereby contribute to realizing high performance eco-friendly batteries.

Influence of sodium metanitrobenzene sulphonate on structures and surface morphologies of phosphate coating on AZ91D

The gray phosphate coating was formed on AZ91D magnesium alloy from the zinc phosphating bath containing sodium metanitrobenzene sulphonate in about 4 min. The structure, surface morphologies and phase compositions of the phosphate coatings were observed and analyzed by using SEM, XRD and EDS. It is shown that the phosphate coating becomes denser and has less micro holes with increasing the concentration of sodium metanitrobenzene sulphonate in the bath in the range of 2.0 to 6.0 g/L. The addition of sodium metanitrobenzene sulphonate greatly increases the micro cathode sites for the formation of the phosphate coating and decreases the porosity of the coating.