Zinc Deposits Research Articles

Modulation of Interfacial Characteristics of Copper Electrode by Electrodeposited Cu@Ti for High-Performance Anode-Free Zinc Ion Batteries.

Preparation of the NC-Cu@Ti electrode involved electrochemical deposition of nanocrystalline copper on the surface of titanium foil using a constant potential method, intended for high stability anode-free zinc ion battery (ZIB) anode material applications. This paper examines the effect of Cu2+ concentration in the electrodeposition solution on the structure and morphology of copper crystals on the NC-Cu@Ti electrode surface. The study also assesses how the interfacial properties of the NC-Cu@Ti electrode affect the process of anodic zinc deposition without anodic ZIBs. Our data suggest that with a voltage setting of -0.95 V and a copper ion concentration of 0.5 M in the solution, the deposition rate of copper crystals on the NC-Cu@Ti-0.5 electrode remains consistent. The resultant crystal phase surface appears smooth with a fine grain size. The NC-Cu@Ti-0.5 electrodes have increased hydrogen potentials and superior corrosion resistance; noting zinc nucleation sites at a mere 21.4 mV, it can provide stable electrochemical conditions for the zinc deposition interface of ZIBs and accelerate the process of zinc desolvation and nucleation. The constructed Zn//NC-Cu@Ti-0.5 asymmetric cell displays swift zinc deposition/stripping kinetics, elevated Coulombic efficiency, and prolonged stability (maintaining nearly 99% after 200 cycles). This performance significantly extends the service life relative to the Zn//Zn symmetric cell, which operates stably for 400 h at 1 mA/cm2. Moreover, the NC-Cu@Ti-0.5//MnO2 ZIBs offer enhanced conductivity and magnification performance to the pure zinc anode ZIBs. This study presents a novel approach for the low-cost and rapid preparation of anode materials for high-performance free-anode ZIBs.

Effects of supplementation with different zinc-based products on the growth and health of Nile tilapia

Zinc is one of the essential microelements for the metabolism of animals. Zinc nanoparticles may have higher bioavailability due to their low specific surface area, facilitating absorption by fish. The present study aimed to evaluate the effects of supplementation with different zinc-based products on the growth and health of Nile tilapia Oreochromis niloticus. Zinc, in different sizes (nanoparticles or bulk) and forms (inorganic or organic), were used as a supplement in the tilapia diet at a dose of 15 mg kg feed−1 for 60 days. At the end of the feeding trial, production performance, hemato-immunological parameters, activity of antioxidant system enzymes, exposure to Streptococcus agalactiae and zinc concentration in the muscle were examined. After the bacterial challenge, the mean corpuscular hemoglobin concentration (MCHC) significantly increased in the fish treated with organic zinc, inorganic nano zinc, and organic nano zinc, while in the control group (inorganic zinc), MCHC remained unchanged. Regarding defense cells, dietary inorganic nano zinc increased the number of basophils (1.50 ± 1.10) compared to organic zinc (0.80 ± 0.90). Lymphocyte count increased after the challenge only in the organic zinc treatments (bulk and nanoparticles). Neutrophils decreased in the control (inorganic zinc) (2.20 ± 1.70) and inorganic nano zinc (2.60 ± 2.70) treatments after the challenge. When compared before and after the bacterial challenge, the plasma antimicrobial titer significantly increased after the bacterial challenge in all treatments. No significant differences were observed for total proteins, enzymes (SOD and CAT), cumulative survival and zinc deposition on fillet. In conclusion, organic zinc in nanoparticles or bulk size increased Nile tilapia innate defense during bacterial infection. However, the other parameters evaluated were not affected by zinc particle size or form (organic or inorganic), indicating that further evaluations should be conducted with organic zinc in nanoparticles or bulk size in the tilapia diet.

Construction of an artificial zinc alloy layer toward stable zinc-metal anode

Aqueous zinc-ion batteries (AZIBs) present a promising option for next-generation batteries given their high safety, eco-friendliness, and resource sustainability. Nonetheless, the practical application of zinc anodes is hindered by inevitable parasitic reactions and dendrite growth. Here, zinc alloy layers (i.e., ZnCo and ZnFe alloys) were rationally constructed on the zinc surface by chemical displacement reactions. The alloying process exposes more (002) planes of the ZnCo anode to guide the preferential and dendrite-free zinc deposition. Furthermore, the ZnCo alloy layer not only effectively inhibits water-induced side reactions but also accelerates electrode kinetics, enabling highly reversible zinc plating/stripping. As a result, the ZnCo anode achieves a Coulombic efficiency of 99.2% over 1300 cycles, and the ZnCo symmetric cell exhibits a long cycle life of over 2000 h at 4.4 mA cm−2. Importantly, the ZnCo//NH4V4O10 full cell retains a high discharge capacity of 218.4 mAh g−1 after 800 cycles. Meanwhile, the ZnFe-based symmetric cell also displays excellent cycling stability over 2500 h at 1.77 mA cm−2. This strategy provides a facile anode modification approach toward high-performance AZIBs.

Dual-functional ionic liquids additive enables dendrite-free Zn anode with ultra-long cycle life over one year

Zn anodes suffer from the formation of uncontrolled dendrites aggravated by the uneven electric field and the insulating by-product accumulation in aqueous zinc-ion batteries (AZIBs). Here, an effective strategy implemented by 1-butyl-3-methylimidazolium hydrogen sulfate (BMIHSO4) additive is proposed to synergistically tune the crystallographic orientation of zinc deposition and suppress the formation of zinc hydroxide sulfate for enhancing the reversibility on Zn anode surface. As a competing cation, BMI+ is proved to preferably adsorb on Zn-electrode compared with H2O molecules, which shields the “tip effect” and inhibits the Zn-deposition agglomerations to inducing the horizontal growth along Zn (002) crystallographic texture. Simultaneously, the protonated BMIHSO4 additives could remove the detrimental OH– in real-time to fundamentally eliminate the accumulation of 6Zn(OH)2·ZnSO4·4H2O and Zn4SO4(OH)6·H2O on Zn anode surface. Consequently, Zn anode exhibits an ultra-long cycling stability of one year (8762 h) at 0.2 mA cm−2/0.2 mAh cm−2, 3600 h at 2 mA cm−2/2 mAh cm−2 with a high plating cumulative capacity of 3.6 Ah cm−2, and a high average Coulombic efficiency of 99.6 % throughout 1000 cycles. This work of regulating Zn deposition texture combined with eliminating notorious by-products could offer a desirable way for stabilizing the Zn-anode/electrolyte interface in AZIBs.

Molecular crowding electrolytes for stabilizing Zn metal anode in rechargeable aqueous batteries

A solid electrolyte interphase (SEI) with a robust mechanical property and a high ionic conductivity is imperative for high-performance zinc metal batteries. However, it is difficult to form such a SEI directly from an electrolyte. In this work, a molecular crowding effect is based on the introduction of Zn(OTF)2 and Zn(ClO4)2 to 2 mol/L ZnSO4 electrolytes. Simulations and experiments indicate that the Zn(OTF)2 and Zn(ClO4)2 not only create a molecularly crowded electrolyte environment to promote the interaction of Zn2+and OTF−, but also participate in the reduction to construct a robust and high ionic-conductive SEI, thus promoting metal zinc deposition to the (002) crystal surface. With this molecular crowding electrolyte, a high current density of 1 mA/cm2 can be obtained by assembling symmetric batteries with Zn as the anode for over 1000 h. And in a temperature environment of −10 °C, a current density of 1 mA/cm2 can be obtained by assembling symmetric batteries with Zn for over 200 h. Zn//Bi2S3/VS4@C cells achieve a CE rate of up to 99.81% over 1000 cycles. Hence, the utilization of a molecular crowding electrolyte is deemed a highly effective approach to fabricating a sophisticated SEI for a zinc anode.

A dual-functional rare earth halide additive for high-performance aqueous zinc ion batteries

Aqueous zinc ion batteries have received much attention due to their high theoretical capacity, inherent safety, and low cost. However, the growth of zinc dendrites and side reactions hinder its practical application. In this study, a rare-earth metal salt, europium chloride (EuCl3), is used as a new electrolyte additive to regulate the uniform deposition of zinc and inhibit the interfacial side reactions. The EuCl3 additive benefits for preferentially Zn2+ deposition along the (002) crystal plane, as well as suppress the hydrogen evolution reaction (HER) at electrode-electrolyte interface. As a result, the capacity retention of the Zn//NaV3O8 full cell assembled with the modified electrolyte much better than that without additives, showing a long-term cycling life and high coulombic efficiency at a current density of 10 A g−1. This new dual-functional rare earth halide additive strategy provides great potential for the development of practical aqueous zinc ion batteries and other battery systems.

Modulation of water reactivity by ethyl acetate/water co-solvent for zinc-metal batteries

The realization of durable aqueous zinc-metal batteries is hindered by uncontrollable Zn dendrite growth and serious parasitic reactions. Here, a miscible ethyl acetate (EA)/H2O co-solvent electrolyte is constructed by salting-in effect of Zn(OTf)2 to manipulate the solvation structures of Zn2+ and disrupt the original strong H-bond networks built by H2O. It reveals that EA molecules and OTf- jointly forms EA-H2O-OTf- co-dominated solvation sheath structure, weakening the coordination between Zn2+ and water molecules, meanwhile promoting Zn2+ immigration in reconstructed co-solvent H-bond environment. Besides, de-solvation water molecules with higher ionization barrier significantly inhibits H2O reactivity. Further, the introduced EA molecules are prone to preferentially adsorbed in Holmhertz Electrical Double Layers, which forms a hydrophobic interphase to regulate the uniform distribution of Zn2+ fluxes by steric structure. Therefore, it realizes dendrite-free zinc deposition with long plating/stripping stability of over 1300 h at 1 mA cm−2. In particular, the low temperature (600 cycles at −40 ℃) and ultra-long durable (20,000 cycles with 100 % capacity retention) electrochemical performance in Zn||Active Carbon zinc-ion capacitors, as well as long cycling stability (average coulombic efficiency of 99.91 % at 1 A g−1 after 1000 cycles) in Zn|| NaV3O8·1.5H2O batteries are also achieved.

Ultrafast laser one-step construction of 3D micro-/nanostructures achieving high-performance zinc metal anodes

Aqueous zinc-ion batteries provide a most promising alternative to the existing lithium-ion batteries due to their high theoretical capacity, intrinsic safety, and low cost. However, commercializing aqueous zinc-ion batteries suffer from dendritic growth and side reactions on the surface of metallic zinc, resulting in poor reversibility. To overcome this critical challenge, here, we report a one-step ultrafast laser processing method for fabricating three-dimensional micro-/nanostructures on zinc anodes to optimize zinc nucleation and deposition processes. It is demonstrated that the three-dimensional micro-/nanostructure with increased specific surface area significantly reduces nucleation overpotential, as well as preferentially absorbs zinc ions to prevent dendritic protuberances and corrosion. As a result, the presence of three-dimensional micro-/nanostructures on the zinc metal delivers stable zinc plating/stripping beyond 2500 h (2 mA cm-2/1 mAh cm-2) in symmetric cells, a high Coulombic efficiency (99.71%) in half cells, and moreover an improved capacity retention (71.8%) is also observed in full cells. Equally intriguingly, the pouch cell with three-dimensional micro-/nanostructures can operate across various bending states without severely compromising performance. This work provides an effective strategy to construct ultrafine and high-precision three-dimensional micro-/nanostructures achieving high-performance zinc metal anodes and is expected to be of immediate benefit to other metal-based electrodes.

On the Electrodeposition of Zinc in Low Magnetic Fields

Abstract While aqueous zinc-based batteries have garnered much research on account of their improved safety, lower cost, and easier fabrication over lithium-ion batteries, they remain held back by dendrite growth on the anode. While many different solutions have been proposed, these solutions often greatly complicate the synthesis or materials in the battery. The application of a magnetic field across the battery has been shown to inhibit dendrite formation without the need for any materials or interface engineering. Herein, we provide a study on the effects of low magnetic fields on the electrodeposition and cycling of zinc in various aqueous systems. We demonstrate that although stronger fields have more immediate impacts on the morphology of zinc deposits, low magnetic fields are still suitable for inhibiting dendrite growth over long periods of cycling. Magnetic field strengths as low as 29 mT were shown to decrease charge transfer resistance of zinc ion deposition by up to 54% and to stabilize the cycling of Zn/Zn symmetric cells. Furthermore, the versatility of magnetic field application was demonstrated by affecting the morphology of zinc deposits on both copper and single-walled carbon nanotubes, which are both compatible with anode-free configurations of aqueous zinc-ion batteries.

A New Concept in Antidiabetic Therapeutics: A Concerted Removal of Labile Iron and Intracellular Deposition of Zinc.

A New Concept in Antidiabetic Therapeutics: A Concerted Removal of Labile Iron and Intracellular Deposition of Zinc.

In-situ growth of hydrophobic zinc succinate interphase with high ionic conductivity toward stable zinc anodes

Aqueous zinc-ion batteries (ZIBs) are a promising solution for energy storage due to their affordability, high performance, environmental friendliness, and excellent safety features. However, zinc metal anodes are prone to capacity degradation and short circuits due to side reactions and dendrite growth during cycling. To address this issue, a dual-function artificial solid electrolyte interphase (SEI) made of zinc succinate complex (ZnSA) is in-situ constructed on zinc anodes by a simple and cost-effective soaking approach. This interphase is hydrophobic and highly ionic conductive (4.5 mS cm−1). It has a low electronic conductivity (1.6 mS cm−1) and a large Zn2+ transfer number (0.63). The hydrophobic SEI progressively represses water-induced side reactions, lowers zinc nucleation overpotential, accelerates zinc ion diffusion, and regulates homogeneous zinc deposition. As a result, the ZnSA@Zn symmetric cell achieves an impressive lifespan of 4450 h at 1 mA cm−2 for 0.5 mAh cm−2, which is significantly better than the bare zinc cell and superior to many recently reported zinc anodes. Furthermore, the V2O5//ZnSA@Zn batteries exhibit outstanding rate performance and remarkable long-term operation stability for 2000 cycles at 1 A/g. This innovative and cost-effective strategy opens up new possibilities for developing high-performance aqueous zinc-ion batteries.

In Situ Grown Coordination-Supramolecular Layer Holding 3D Charged Channels for Highly Reversible Zn Anodes.

Dynamic reversible noncovalent interactions make supramolecular framework (SF) structures flexible and designable. A three-dimensional (3D) growth of such frameworks is beneficial to improve the structure stability while maintaining unique properties. Here, through the ionic interaction of the polyoxometalate cluster, coordination of zinc ions with cationic terpyridine, and hydrogen bonding of grafted carboxyl groups, the construction of a 3D SF at a well-crystallized state is realized. The framework can grow in situ on the Zn surface, further extending laterally into a full covering without defects. Relying on the dissolution and the postcoordination effects, the 3D SF layer is used as an artificial solid electrolyte interphase to improve the Zn-anode performance. The uniformly distributed clusters within nanosized pores create a negatively charged nanochannel, accelerating zinc ion transfer and homogenizing zinc deposition. The 3D SF/Zn symmetric cells demonstrate high stability for over 3000 h at a current density of 5 mA cm-2.

β''-Al2O3 protecting layer for stable zinc metal anodes

Aqueous zinc-ion batteries (AZIB) has attracted considerable attention on account of its low cost, high security and environmental friendliness. Nevertheless, the growing dendrites and corrosion reactions on the surface of zinc anode limit the development of AZIB. Herein, β''-Al2O3 with high ion conductivity was firstly employed as an efficient artificial layer for stabilizing the zinc anode. The optimized β''-Al2O3 layer enables homogeneous ion flux and uniform zinc deposition, significantly suppressing dendrite growth and parasitic reactions. Symmetric cells based on this unique protective layer can stably operate for 1600 h under 1 mA cm−2/1 mAh cm−2. Benefiting from the high-performance zinc metal anode, the full cell paired with the NH4V4O10 cathode delivers a high discharge initial capacity of 400 mAh g−1 at 1 A g−1 and good cycling stability. This simple protecting layer provides a new strategy for the modification of zinc metal anode and accelerates the practical application of AZIB.

Polymer-based passive layer to stabilize zinc anode in aqueous electrolyte

Metallic zinc holds promise as a cost-effective and scalable material for secondary energy storage applications. However, its inherent reversibility issues hinder its practical implementation. Among various strategies, interface engineering has emerged as a promising approach to enhance the reversibility of zinc anodes. Herein we introduce an innovative method involving the parallel deposition of poly(acrylic acid) (PAA) and zinc metal, creating a composite layer of polymer and zinc, denoted as Zn-PAA. This unique Zn-PAA layer deposition technique remarkably enhances interfacial behavior, ensuring superior cyclic stability in symmetric cells. Moreover, the Zn-PAA layer reduces polarization effects and effectively mitigates interface alterations during plating and stripping processes resulting in increased interface stability. This study highlights the potential of simultaneous electropolymerisation and zinc deposition as a promising strategy to coat and densify interface on zinc anode with intertangled matrix of zinc and polymer for improving the performance and stability of zinc anodes in batteries.

Increasing the Cycle Life of Zinc Metal Anodes and Nickel-Zinc Cells Using Flow-Through Alkaline Electrolytes

Alkaline electrolyte flow through porous Zn anodes and Ni(OH)2 cathodes can overcome diffusion limits, reduce dendrite growth, and improve cycle life. Zinc deposition morphology improves with low flow rates electrolyte in KOH/ZnO electrolytes at current densities near the diffusion-limit regime. Zinc dendrites present without flow are suppressed by micrometer-per-second flow at concentrations ranging from 0.2 to 0.6 M ZnO dissolved in 6 M and 10 M KOH solutions. Zn-Cu asymmetric cell tests reveal that flowing electrolyte increases the lifespan by more than 6 times in the diffusion-limit regime by suppressing gas evolution and dendrite formation. Ni-Zn cell tests show that a flow-assisted battery cycles 1500 times with over 95% Coulombic efficiency (CE) at 35 mA cm−2 current density and 7 mAh/cm2 charge capacity, increasing the battery lifespan by 17 times compared with a stagnant Ni-Zn cell. Flow-through electrolyte also stabilizes the Zn electrode in the over-limiting regime, achieving approximately 4 times increased lifespan and 297 cycles with over 90% CE at 52 mA cm−2.

Dual effect of organic/inorganic artificial protective layer to construct high-performance zinc metal anode

Owing to their high specific capacity, low cost, environmental friendliness and safety, aqueous zinc ion batteries (AZIBs) have been one of the most popular battery systems. Nevertheless, dendrite growth, corrosion, hydrogen evolution and passivation on the anode side can seriously affect the lifetime of AZIBs. In view of this, this work constructs a protective layer compounded from inorganic (titanium silicate molecular sieve, TS) and organic (polyacrylonitrile, PAN) materials to realize the high-performance and dendrite-free zinc anode (Zn@PAN-TS). The cyano group in PAN has a coordination effect with zinc ions, which facilitates the transport of zinc ions. The porous TS can regulate the zinc ion flux through ion-confinement effect. Thus, the PAN-TS composite protective layer provides fast and orderly ion transport channels that modulate the uniform deposition of zinc through dual effect. Moreover, the experimental results show that the Zn@PAN-TS 50:1 anode has the best electrochemical performance. The corresponding MnO2 full cell maintained a high discharge capacity of 217.2 mAh·g−1 with a high retention rate of 81.1 % after 500 cycles at 0.3 A·g−1. This strategy offers fresh insight into constructing multifunctional hybrid interface for dendrite-free AZIBs.

Electroless brassing of historical artefacts

Abstract The topic of this work was the investigation of an alternative brassing technique consisting of electroless zinc plating of a copper object in a strongly alkaline solution and subsequent annealing to achieve a characteristic brass appearance. Within the scope of the work was the determination of the mechanism of zinc deposition on the copper surface, the optimisation of the NaOH concentration (30 and 40 wt. %), time of deposition (5-120 min), as well as temperature (150 and 200 °C) and annealing time (15 – 60 min). Electrochemical methods (potentiodynamic curves and open-circuit potential), metallography, X-ray diffraction (XRD), and glow-discharge optical emission spectroscopy (GD-OES) were used to study the brassing mechanism. Electrochemical measurements have shown that zinc powder significantly decreases the surface potential of copper to the value of zinc itself and also acts as a reducing agent. The diffusion of zinc in copper was found to occur during the primary deposition of zinc with the formation of the γ phase (Cu5Zn8). The optimal NaOH concentration is 40 wt.% and the deposition time is 60 min. The optimal conditions of annealing are 200 °C and 60 min. The primary γ phase is transformed during the annealing process into β and α phases.

Synergistic interaction between amphiphilic ion additive groups for stable long-life zinc ion batteries

The uneven deposition of zinc and hydrogen generation at the zinc anode interface constitute major impediments to the lifespan of aqueous zinc-ion batteries. Herein, an amphoteric ion additive, choline phosphate (CP), is proposed to stabilize the battery anode interface. The remarkable interplay between choline ions and phosphate groups assumes a pivotal role in homogenizing zinc ion deposition and regulating the behavior of free water molecules. Due to the negative electric field adsorption on the surface of the zinc anode, the positively charged choline ions will be adsorbed on its surface preferentially and prevent the approach of water molecules. The phosphate group interacts strongly with the zinc ion, permeating the solvated structure of these ions, regulating zinc ion flux, and immobilizing free water molecules through hydrogen bonding to impede unwanted side reactions. In summary, using CP additives yields a profound enhancement in enabling significantly extended cycle lifespans of both Zn//Zn symmetric batteries and LiFePO4 full batteries.

Dendrite-free anodes enabled by MOF-808 and ZIF-8 modified glass microfiber separator for ultralong-life zinc-ion hybrid capacitors

Zinc-ion hybrid capacitors (ZIHCs) have been attracted attention for aqueous electrochemical energy storage systems owing to their high safety, low cost, abundant natural resource of zinc, convenient assembly (in an air atmosphere), robust stability with aqueous electrolytes, and the unique electrochemical characteristics of metallic zinc (Zn) as an anode electrode. Nevertheless, the growth of dendrite is the main challenge of zinc electrode in an aqueous electrolyte, leading to short circuit failure. Herein, metal-organic frameworks (MOFs) have been employed to decorate the separator. The porous nature of MOFs has been identified as beneficial for directing uniform zinc deposition. This study focuses on the operational efficiency and lifecycle of ZIHCs utilizing MOFs, specifically MOF-808 and ZIF-8, to modify glass microfiber separators. The results demonstrated that the symmetrical cell using MOF modified separators exhibited high performance, maintaining stable voltage over 1000 h. attributed to the enhanced uniformity of Zn ion flux during striping/plating processes. Additionally, at the current density of 1.0 A g−1, ZICs with MOFs modified separators exhibited higher specific capacities compared to those using the pristine separator and prolonged the cycle life over 20,000 cycles with capacity retention of 56.73 and 63.89 %, respectively. Because the MOFs modified separators can inhibit non-uniform dendritic zinc growth on a zinc anode surface according to the scanning electron micrographs.

Mineralization processes of the Mount Garnet Zinc deposit, NE Queensland (Australia): Insights from garnet geochemistry and U-Pb geochronology

The Mount Garnet Zinc deposit in NE Queensland, Australia, is located in the region of voluminous magmatism associated with the formation of Palaeozoic continental arcs of Gondwana. Ore-forming events of this deposit are related to the intrusion of the Kennedy Igneous Association (KIA) – a large suite of igneous rocks spanning Late Carboniferous to Early Permian in age – into the Silurian limestone (Chillagoe Formation) in the Hodgkinson Province (Mossman Orogen). Petrographic observations and in situ major and trace element analysis reveal the sequence of garnet growth and fluid-rock interaction during skarn formation. Three types of garnets are identified, Grt I (including IA and IB) and Grt II. Grt IB is related to Zn-Pb mineralization. All garnets have elevated Sn and W and the highest levels of W and Sn are observed in Grt II. Garnet U-Pb ages of Grt IB provide the first direct geochronological result of hydrothermal minerals in the Mount Garnet region. New data argues that the base metal mineralization may take place during early Permian period and be sourced from the Claret Creek Supersuite. Sn-W mineralization may be associated with the O’Briens Creek Supersuite.