Zinc Deposits Research Articles

Simultaneous Inhibition of Vanadium Dissolution and Zinc Dendrites by Mineral‐Derived Solid‐State Electrolyte for High‐Performance Zinc Metal Batteries

Designing solid electrolyte is deemed as an effective approach to suppress the side reaction of zinc anode and active material dissolution of cathodes in liquid electrolytes for zinc metal batteries (ZMBs). Herein, kaolin is comprehensively investigated as raw material to prepare solid electrolyte (KL‐Zn) for ZMBs. As demonstrated, KL‐Zn electrolyte is an excellent electronic insulator and zinc ionic conductor, which presents wide voltage window of 2.73 V, high ionic conductivity of 5.08 mS cm‐1, and high Zn2+ transference number of 0.79. For the Zn//Zn cells, superior cyclic stability lasting for 2200 h can be achieved at 0.2 mA cm‐2. For the Zn//NH4V4O10 batteries, stable capacity of 245.8 mAh g‐1 can be maintained at 0.2 A g‐1 after 200 cycles along with high retention ratio of 81%, manifesting KL‐Zn electrolyte contributes to stabilize the crystal structure of NH4V4O10 cathode. These satisfying performances can be attributed to the enlarged interlayer spacing, zinc (de)solvation‐free mechanism and fast diffusion kinetics of KL‐Zn electrolyte, availably guaranteeing uniform zinc deposition for zinc anode and reversible zinc (de)intercalation for NH4V4O10 cathode. Additionally, this work also verifies the application possibility of KL‐Zn electrolyte for Zn//MnO2 batteries and Zn//I2 batteries, suggesting the universality of mineral‐based solid electrolyte.

Electroplating of zinc onto polyelectrolyte complex membranes as anode for aqueous zinc-ion batteries

Conventionally, the anode of a primary Aqueous zinc-ion batteries (ZIBs) is metallic and rigid, which made it difficult to integrate into flexible designs. In this research, a composite polyelectrolyte complex (PEC) with cationic poly(diallyldimethylammonium chloride), anionic poly(sodium-4-styrenesulfonate) and carbon black (CB) as conductive filler (PEC-CB) was developed as an anode substrate for zinc deposition via electroplating technique. The Zinc-electroplated PEC-CB (Zn-PEC-CB) anode was characterized using electron microscopy and X-Ray diffraction analysis to verify the successful zinc coating. The Zn-PEC-CB was then assembled with PEC-CB-MnO cathodes in an ZIB setup. The results demonstrated the potential of PEC-based electrodes as a promising alternative to conventional materials in ZIBs, encouraging further exploration in energy storage applications.

Simultaneous Inhibition of Vanadium Dissolution and Zinc Dendrites by Mineral-Derived Solid-State Electrolyte for High-Performance Zinc Metal Batteries.

Designing solid electrolyte is deemed as an effective approach to suppress the side reaction of zinc anode and active material dissolution of cathodes in liquid electrolytes for zinc metal batteries (ZMBs). Herein, kaolin is comprehensively investigated as raw material to prepare solid electrolyte (KL-Zn) for ZMBs. As demonstrated, KL-Zn electrolyte is an excellent electronic insulator and zinc ionic conductor, which presents wide voltage window of 2.73 V, high ionic conductivity of 5.08 mS cm-1, and high Zn2+ transference number of 0.79. For the Zn//Zn cells, superior cyclic stability lasting for 2200 h can be achieved at 0.2 mA cm-2. For the Zn//NH4V4O10 batteries, stable capacity of 245.8 mAh g-1 can be maintained at 0.2 A g-1 after 200 cycles along with high retention ratio of 81%, manifesting KL-Zn electrolyte contributes to stabilize the crystal structure of NH4V4O10 cathode. These satisfying performances can be attributed to the enlarged interlayer spacing, zinc (de)solvation-free mechanism and fast diffusion kinetics of KL-Zn electrolyte, availably guaranteeing uniform zinc deposition for zinc anode and reversible zinc (de)intercalation for NH4V4O10 cathode. Additionally, this work also verifies the application possibility of KL-Zn electrolyte for Zn//MnO2 batteries and Zn//I2 batteries, suggesting the universality of mineral-based solid electrolyte.

Hierarchical Pore Structure Composite Electrode by Electrospinning for Dendrite‐free Zinc‐Based Flow Battery

AbstractIn the pursuit of sustainable energy solutions, zinc‐based flow batteries stand out for their potential in large‐scale energy storage, offering a blend of cost efficiency and safety. Although the porous electrode provides an increased specific surface area for reaction, the non‐uniform deposition of zinc, attributed to uneven concentration distribution within the porous electrode, has been a pivotal issue in accelerating the formation of zinc dendrites, which hinders the enhancement of energy density. A composite electrode with a strategic hierarchical pore structure has been developed with aligned nitrogen‐doped carbon fibers and traditional carbon felt. This structure takes advantage of the large pores of the carbon felt for efficient through‐flow paths, ensuring higher flow rates, while the dual‐scale pores within the electrospun film enhance mass transfer and increase the specific surface area. At 320 mA cm−2, it achieved an ≈11.4% improvement in the battery's energy efficiency. Moreover, the nitrogen doping and the optimized reaction uniformity within the composite electrode have been instrumental in reducing the generation of zinc dendrites. The battery, integrated with the innovative composite electrode, maintained an energy efficiency of 59.2% at 320 mA cm−2 after 300 cycles, which is a substantial improvement in operational longevity.

Stable Zn metal anode enabled via ferroelectric nanotube arrays

Aqueous zinc-ion batteries are receiving increasing attention owing to their markedly high safety and low cost. However, the uncontrolled zinc dendrite growth and the side reactions at Zn-electrolyte interfaces hinder the practical application of aqueous rechargeable zinc-based batteries. Therefore, regulating the electrode/electrolyte interface to achieve dense zinc deposition is crucial for improving the electrochemical performance of zinc-ion batteries. Herein, ferroelectric composite nanotube arrays (BaTiO3 modified TiO2 nanotubes, TiO2@BaTiO3) are designed and fabricated as the three-dimensional current collector for Zn metal anode. Abundant zincophilic sites on the surface of BaTiO3 induce zinc nucleation, enabling a compact and horizontally-aligned Zn morphology. At external electric field, the depolarization field produced the ferroelectric BaTiO3 layer on the electrode surface can accelerate the dissociation of ZnSO4 and regulate the Zn-ion desolvation process at the interfaces, leading to dendrite-free Zn deposition and less byproducts. As a result, the TiO2@BaTiO3/Zn anode achieves reversible Zn plating/stripping with low overpotential for over 3000 h at 3 mA cm−2 in symmetric cells, and the assembled full battery exhibits a significantly enhanced cycling stability over 1800 cycles at 1 A g−1. Ferroelectric nanotube arrays brings new opportunities for next-generation aqueous zinc-ion batteries.

Molecule Engineering of Sugar Derivatives as Electrolyte Additives for Deep-Reversible Zn Metal Anode.

The cycling performance of zinc-ion batteries is greatly affected by dendrite formation and side reactions on zinc anode, particularly in scenarios involving high depth of discharge (DOD) and low negative/positive capacity (N/P) ratios in full cells. Herein, drawing upon principles of host-guest interaction chemistry, we investigate the impact of molecular structure of electrolyte additives, specifically the -COOH and -OH groups, on the zinc negative electrode through molecular design. Our findings reveal that molecules containing these groups exhibit strong adsorption onto zinc anode surfaces and chelate with Zn2+, forming a H2O-poor inner Helmholtz plane. This effectively suppresses side reactions and promotes dendrite-free zinc deposition of exposed (002) facets, enhancing stability and reversibility of an average coulombic efficiency of 99.89 % with the introduction of Lactobionic acid (LA) additive. Under harsh conditions of 92 % DOD, Zn//Zn cells exhibit stable cycling at challenging current densities of 15 mA ⋅ cm-2. Even at a low N/P ratio of 1.3, Zn//NH4V4O10 full cells with LA electrolyte exhibit high-capacity retention of 73 % after 300 cycles, significantly surpassing that of the blank electrolyte. Moreover, in a conversion type Zn//Br static battery with a high areal capacity (~5 mAh ⋅ cm-2), LA electrolyte sustains an improved cycling stability of 700 cycles.

Balancing current density and electrolyte flow for improved zinc-air battery cyclability

Zinc-air batteries (ZABs), known for their high energy density and environmental friendliness, are emerging as promising solutions for sustainable energy storage. However, the irregular deposition of zinc on electrodes hinders the widespread utilization of rechargeable ZABs due to limited durability and stability. This study investigates the role of electrolyte flow in enhancing zinc electrodeposition and overall performance in zinc-air flow batteries (ZAFBs) at high current densities. We explore the interplay between current density, flow rate, and their influence on electrode surface morphology and the removal of the passivating zinc oxide layer to improve battery efficiency and lifespan. Using advanced in-situ synchrotron radiation x-ray tomography, we found that incorporating flowing electrolyte at specific current densities results in rounded dendrite tips, thinner and more uniform deposition layers, and improved zinc adhesion. Imaging and electrochemical analyses further reveal that flowing electrolyte enhances zinc morphology, reduces charge transfer resistance, diminishes passivation, and lowers galvanostatic charge/discharge polarization across various current densities, thereby improving battery cycling performance. Notably, the impact of flowing electrolyte is more pronounced at a moderate current density of 50 mA/cm2 compared to lower or higher currents. Our findings underscore the importance of electrolyte flow and current density management in developing high-performance ZAFBs, providing valuable insights for their future commercialization.

A Cu-Zn bimetallic organic framework as protective interlayer for dendrite-free Zn deposition in zinc-based flow batteries

Zinc-based flow batteries hold great promise for grid-scale energy storage. However, the formation of zinc dendrites challenges their lifespan and safety. In this work, we devise a bimetallic organic framework material on carbon cloth (CuZn@MOF-CC) using a one-step dip coating method to address the dendrite issue. The prepared CuZn@MOF-CC promotes the creation of zincophilic sites on the electrode surface, facilitating smooth and uniform zinc deposition. Electrochemical csharacterizations and density functional theory (DFT) calculations reveal much stronger electronic interactions between CuZn@MOF and the zinc atoms compared to the commonly used anode material through an obvious electron interaction between the Zn atom and the Cu sites linked in the CuZn@MOF chain. By mitigating the zinc dendrite problem, this approach effectively improves the coulombic efficiency, cycle life, and safety of zinc-based flow batteries. The battery incorporating the prepared material demonstrates impressive stability, exceeding 450 cycles without dendrites at a high current density of 320 mA cm−2, paving the way for efficient and reliable energy storage solutions and a sustainable future.

Homogeneous Deposition of Zinc on N-Doped Carbon Fibers Interconnected with Sn Nanoparticles for Advanced Aqueous Zinc Batteries.

Currently, inhomogeneous distribution of Zn2+ on the surface of the Zn anode is still the essential reason for dendrite formation and unsatisfactory stability of zinc ion batteries. Given the merits of strong interaction between Sn and Zn, as well as a low nucleation barrier during Zn deposition, the combination of metallic Sn with carbon material is expected to improve the deposition of zinc ions and inhibit the growth of zinc dendrites by guiding the homogeneous plating/stripping of zinc on the electrode surface. In this article, zincophilic Sn nanoparticles with low nucleation barriers and strong interaction with Zn2+ were embedded into 3D N-doped carbon nanofibers using a simple electrostatic spinning technique. Accordingly, when serving as an artificial coating layer for the zinc metal anode, an ultrastable Sn@NCNFs@Zn||Sn@NCNFs@Zn symmetric cell can be achieved for over 3500 h with a low nucleation overpotential of 29.1 mV. Significantly, the full cell device assembled with the as-prepared anode and MnO2 cathode exhibits desirable electrochemical behaviors. Moreover, this simple method could be extended to other metal-carbon composites, and to ensure ease in scaling up as required. Such significant approach can provide an effective strategy for the design of high-performance zinc anodes.

Zinc-doped phosphate coatings for enhanced corrosion resistance, antibacterial properties, and biocompatibility of AZ91D Mg alloy

Magnesium and its alloys have been foreseen as promising bone-implant owing to good biocompatibility, high strength, mechanical properties, and biodegradability to replace the conventional bio-metals (Titanium, stainless-steel, Co-Cr alloys) in orthopedic applications. However, high corrosion rate and high degradation rates adversely effects like abrupt evolution of H2 gas and localized alkalization in a physiological environment limit its medical applications. To overcome these issues, phosphate-based surface coating is developed on Mg-alloy to resist the high biodegradation and corrosion rate utilizing magnesium substrate as source of magnesium ion through a single-step hydrothermal process. Controlling the fast corrosion rate and localized alkalization would reduce the antibacterial character of magnesium-based implants therefore, the simple phosphate-based coatings has been induced by doping it with zinc ions due to its physiological tolerance and excellent antibacterial efficacy. The doping of zinc ions may provide a sustained drug-free antibacterial characteristic for potential application in orthopedics. The synthesized phosphate-based coating was characterized using advanced techniques like Scanning Electron Microscopy, X-ray Diffraction, and wettability test, followed by comprehensive electrochemical testing to assess its corrosion behavior. The in vitro immersion test in simulated body fluid (SBF) indicates that deposition of phosphate and zinc doped phosphate coatings reduces the degradation rate consequently minimized the fast dissolution of Mg2+ ions and OH- in physiological environment. Additionally, cytotoxicity and biocompatibility were evaluated using Alamar Blue and live/dead assays on the MC3T3-E1 mouse osteoblast cell line. These assays demonstrated good cell viability, indicating the coatings possess favorable cytocompatibility and support cellular metabolic activity.

Manipulation of facet zincophilicity of protective coatings for long lifetime zinc anodes

Aqueous zinc-ion batteries are considered to be a promising technology for large scale energy storage deployment due to their advantages of low cost and high security. However, the zinc anodes suffer long-standing problems of uncontrollable dendrite growth and unstable interfacial chemistry that hinder their industrial applications. In this work, we manage to manipulate the facet zincophilicity of commercial titanium oxide (TiO2) by nitrogen implanting as a protective coating to realize long-term zinc plating/stripping. The nitrogen-implanting significantly increases the habitual facet zincophilicity of TiO2 layer to enable uniform and fast zinc deposition kinetics. Impressively, the as-protected Zn anode could be operated for a long lifespan of 2400 h accompanying with a high cumulative capacity of 4.1 Ah cm-2 and a stable Coulombic efficiency of 99.53 % over 900 cycles. This work will shed new insight on the importance of manipulating the facet zincophicility of protective coatings for dendrite-free metal anodes beyond zinc chemistry.

Low-Cost Anode-Free Aqueous Batteries Using Permanent Magnets

The rise in portable electronics has created an ever growing demand for more electrochemical energy storage (EES) systems. Lithium-ion batteries have achieved widespread commercial use because of their high energy density, but concerns about their safety and the sustainability of lithium have created a search for alternatives. Aqueous batteries present a much safer option, and they are cheaper both in materials and fabrication. The zinc-ion battery is among the most researched aqueous batteries, but problems remain with the formation of zinc dendrites during plating on the anode. A number of solutions to this problem have been proposed, including the use of a permanent magnet placed behind a zinc-foil anode, which creates uniform zinc deposition via the magnetohydrodynamic (MHD) effect. Herein, we expand this concept to zinc deposition on other substrates for the so-called anode-free configuration, in which an inactive current collector is used for the zinc to plate and strip off of during cycling. This anode-free configuration is a promising way to reduce the cost and increase the energy density of batteries by removing active material and allowing a cheaper, inactive material to serve as the substrate for metal plating and stripping, and the use of a permanent magnet precludes the need for a complicated material or over-engineered solution interface to prevent dendrite growth.

A Water-in-Ester Electrolyte with Controllable Water Activity for Highly Reversible Zinc Anodes

Rechargeable aqueous zinc batteries, featuring intrinsic safety, low cost and terrific recyclability, are an emerging and engaging technology potentially for stationary energy storage. However, this technology is blocked by the instability of zinc anode/electrolyte interface, due to the water-induced hydrogen evolution and dendrite growth. Herein, we formulate a water-in-ester electrolyte to effectively regulate the water activity by controlling the molar ratio of H2O to γ-valerolactone. The γ-valerolactone gets in on the solvation of Zn2+ ions, helping to exclude almost all bound water molecules from the solvation shell, and interacts with free water via forming intermolecular hydrogen bonds, thus completely confining water molecules in γ-valerolactone network. Thanks to the constrained H2O molecules and the reduced water activity, Zn anodes exhibit heighted anti-corrosion abilities in the water-in-ester electrolyte compared with the pure water electrolyte. The zinc deposition morphology evolves from hexagonal dendrites to tense particles, as the pure water electrolyte is transformed to the water-in-ester electrolyte. Water-in-ester electrolytes as well promise less hydrogen production, and eventually improve the average columbic efficiency and cycling stability of asymmetric Zn ‖ Ti cell from less than 85% and merely 10 cycles to 99.6% and over 500 cycles. The cycling lifespan of symmetric Zn ‖ Zn cell is extended to more than 1100 h at 1 mA cm-2 and 1 mAh cm-2 with the water-in-ester electrolyte, fourfold higher than that of the pure water electrolyte. Additionally, superior full cell performance is demonstrated for the newly formulated electrolyte. This work sheds light on the strong correlation between water activity and performance of zinc anodes and contributes to developing more stable aqueous zinc batteries by restricting water activity.

The Range of Influence across Commercial Glass Fiber Separators on the Cycling of the Zinc Metal Anode

Aqueous zinc-ion batteries (AZIBs) have attracted significant research attention due to their promising potential for large-scale energy storage applications in support of the rapid global growth of renewable wind and solar energy generation. However, challenges associated with the limited cycling life and low energy density of AZIBs persist as the critical limiting factors preventing their practical use in utility-scale energy storage applications [1]. Throughout zinc-ion research working to address these challenges, commercial glass fiber (GF) membranes are often used as the separator in studies investigating cathode, electrolyte, and anode designs [2]. Nevertheless, commercial GF membranes are available with a range of physicochemical properties, and the specific details of the selected membrane are often missing in published studies. In our work, we systematically compare Whatman™ GF separators (GF/A, GF/B, GF/C, GF/D, and GF/F) to assess the influence of the separator’s physicochemical properties (i.e., pore size and thickness) on the cycling life and cell-to-cell variability across multiple trials of Zn|Zn cells. Under constant current cycling, significant differences were observed in the cycling life and cell-to-cell consistency depending on the pore size and thickness of the GF separator [3]. In addition, our use of micro-computed X-ray tomography explores the associations between the separator’s pore size and zinc deposition morphology and provides visual identification of the failure mechanism corresponding with an overpotential collapse. The results of this work clarify the importance of GF separator selection and the separator’s influence to support the improvement of other cell components.

(Invited) Engineering Nanocomposite Substrates for Metal Deposition

Reversible metal plating is at the heart of aqueous based energy storage. Since virtually all metal anodes, e.g., Fe, and Zn, operate outside the stability window of water, it is thus essential to minimize their surface area by controlling the nucleation and growth during deposition and the pit formation during stripping.While epitaxial growth has shown promise as exemplified by the horizontal zinc deposition on graphene, an approximate heteroepitaxy, we will focus our effort in developing a nanocomposite substrate that promotes uniform nucleation sites and fast surface transport. The strategy is potentially highly scalable to address the need for large scale storage. Recently, we have shown that a nanocomposite substrate can induce single crystalline Li growth. By reacting FeF3 with Li, a nanocomposite of Fe and LiF is formed which features Fe nanoparticles of < 2 nm in size uniformly distributed in a matrix of LiF. Despite the global lithiophobility of the substrate, nano Fe domains provide energetically uniform nucleation sites for Li deposition while LiF enables rapid surface transport. Corporative merging of neighboring seeds lead to the formation of single crystalline Li. Unlike single crystal substrates, the nanocomposite features uniformly distributed, energetically equivalent sites for nucleation.We have adopted a similar strategy for Fe and Zn deposition. Preliminary results show that significantly improved macroscopic uniformity is achieved with the nanocomposite substrate. We will discuss materials requirements for operation in an aqueous environment and the general applicability of the approach for other materials.

Suppressing hydrogen evolution and promoting dendrite free zinc deposition by fluorinated triazine framework towards robust aqueous zinc ion batteries

Aqueous zinc-ion batteries (AZIBs) have become a research hotspot, but the inevitable zinc dendrites and parasitic reactions in the zinc anode seriously hinder their further development. In this study, three covalent triazine frameworks (DCPY-CTF, CTF-1 and FCTF) have been synthesized and used as artificial protective coatings, in which the fluorinated triazine framework (FCTF) increases the zinc-philic site, thus better promoting dendritic free zinc deposition and inhibiting hydrogen evolution reactions. Excitingly, both experimental results and theoretical calculations indicate that the FCTF interface adjusts the deposition of Zn2+ along the (002) plane, effectively alleviating the formation of zinc dendrites. As expected, Zn@FCTF symmetric cells exhibit cycling stability of over 4000 h (0.25 mA cm−2), meanwhile Zn@FCTF//NHVO full cells provide a high specific capacity of 280 mAh/g at 1.0 A/g, which are superior to those of bare Zn anode. This work provides new insights for suppressing hydrogen evolution and promoting dendrite-free zinc deposition to construct highly stable and reversible AZIBs.

Emerging strategies for the improvement of modifications in aqueous rechargeable zinc–iodine batteries: Cathode, anode, separator, and electrolyte

AbstractAqueous rechargeable zinc–iodine batteries have gained traction as a promising solution due to their suitable theoretical energy density, cost‐effectiveness, eco‐friendliness, and safety features. However, challenges such as the polyiodide shuttle effect, low iodine cathode conductivity, zinc anode dendritic growth, and the requirement for efficient separators and electrolytes hinder their commercial prospects. Hence, this review highlights recent progress in refining the core optimization strategies of zinc–iodine batteries, focusing on enhancements to the cathode, anode, separator, and electrolyte. Cathode improvements involve the addition of inorganic, organic, and hybrid materials to counteract the shuttle effect and boost redox kinetics, where these functional materials also are applied in anode modifications to curb dendritic growth and enhance cycling stability. Meanwhile, cell separator design approaches that effectively block polyiodide shuttle while promoting uniform zinc deposition are also discussed, while electrolyte innovations target zinc corrosion and polyiodide dissolution. Ultimately, the review aims to map out a strategy for developing zinc–iodine batteries that are efficient, safe, and economical, aligning with the demands of contemporary energy storage.

Resilient and Reversible Phosphotungstic Acid Passivated Zinc Anode.

Aqueous zinc ion batteries (ZIBs) present a compelling solution for grid-scale energy storage, which is crucial for integrating renewable energy resources into the electric infrastructure. The cycling stability of ZIBs hinges on the electrochemical reversibility of the zinc anode, which is often compromised by corrosion and dendritic zinc deposition. Here, we present a straightforward surface passivation strategy that significantly enhances the cycling stability of zinc anodes. By immersing zinc in a solution of phosphotungstic acid, we promoted the dominance of the 002 plane of zinc's hexagonal structure. This process facilitates the creation of a uniform nucleation and protective layer on the native zinc surface, resulting in a more uniform plating-stripping process and increased corrosion resistance. In symmetric cells, the passivated zinc exhibits a capacity retention of 68.7% after 1000 cycles at a current density of 1.0 Ag1-, whereas untreated zinc anodes retain only 7.4% of capacity under identical conditions. In full cell zinc iodine batteries employing the passivated zinc anode, over 1000 stable charge-discharge cycles were achieved at a current density of 20 mA cm-2, with approximately 96% Coulombic efficiency (CE), 86% voltage efficiency (VE), and 82% energy efficiency (EE). This study demonstrates a promising pathway for the construction and upscaling of flow batteries with high capacity and low cost.

Integrated Interfacial Modulation Strategy: Trace Sodium Hydroxyethyl Sulfonate Additive for Extended-Life Zn Anode Based on Anion Adsorption and Electrostatic Shield.

Aqueous zinc-ion batteries (AZIBs) are poised to play a pivotal part in meeting the growing demands for energy storage and powering portable electronics for their superior security, affordability, and environmentally friendly characteristics. However, the detrimental side reactions occurring at the zinc anode and the dendrite caused by uneven zinc plating/stripping have greatly compromised the cycling life of AZIBs, thereby impeding their practical prospects. In this study, the interfacial comodulation strategy was employed by combining the "electrostatic shielding" effect of cations with the characteristic adsorption of anions. Two molar ZnSO4 served as the matrix, and sodium hydroxyethyl sulfonate (SHES) was selected as a low-cost, nontoxic additive. Experimental results confirm that SHES and zinc anode exhibit robust interactions that lead to the formation of an electrostatic shield and a dynamic adsorption layer at the interface, thereby suppressing hydrogen evolution and corrosion. The combined "electrostatic shielding" effect of sodium ions and the robust characteristic adsorption of hydroxyethyl sulfonate anions serve to guide the directed three-dimensional (3D) diffusion of Zn2+, facilitating rapid, stable, and uniform deposition of zinc. Due to these effects, incorporating 0.2 M SHES as an additive extends the cycle life beyond 3600 h and enables a highly reversible process of deposition and stripping in symmetric cells. Additionally, the Zn-Cu half-cell exhibits reliable cycling for over 1400 cycles, achieving an average Coulombic efficiency of 99.6%. Moreover, the introduction of this additive substantially enhances the performance of Zn-MnO2 and Zn-NH4V4O10 full cells. This study demonstrates the practical feasibility of achieving anodes with high reversibility in AZIBs through the implementation of a strategy that involves anion adsorption at the interface, which holds paramount significance for the practical application of AZIBs.

Geochronology and metallogenic mechanism of the Ashele copper–zinc deposit in the Altay, Xinjiang, Northwest China: Insights from pyrite Re–Os dating, trace elements and sulfur isotopes

The Ashele Cu–Zn deposit is the largest volcanogenic massive sulfide (VMS) type deposit in the Xinjiang Central Asian Orogenic Belt (XCAOB). This deposit is located in the Devonian volcanic–sedimentary basin on the South Altay, Xinjiang. The Nos. I and II mineralized belts are the largest in the ore district consist of two parts: concordant massive sulfide lenses and discordant vein-type sulfide mineralization. This study mainly focuses on the mineralization during the submarine exhalative–sedimentary period. In situ trace element analysis showed that sphalerite is an important host for In and Cd, and tennantite is the main host for Au, Ag, As, Cd, Sb, Zn, Bi, and Se in base metal sulfides system. The concentration fluctuation of Bi and Se may be caused by galena. Pyrite and chalcopyrite are not enriched with specific elements, except for occasional inclusions of other minerals. Seven stratified pyrite samples display a Re–Os weighted average age of 389.1 ± 9.9 Ma (MSWD = 0.15). This data can represent the formation time of the No. I mineralized belt. The geothermometer of sulfur isotope shows sulfide mainly formed at 113 to 362 °C (avg. 214 °C), and sphalerite formed at 133 to 194 °C (avg. 175 °C) based on GGIMFis geothermometer. The δ34S values are between −1.84 to 5.51 ‰, suggestting sulfur mainly comes from magmatic sulfur, followed by seawater sulfate.