Aqueous Zinc Research Articles

Reveal the Influence of Conductive Carbon on Sulfur Crystallization: Key to High-Performance Aqueous Zinc–Sulfur Batteries

Reveal the Influence of Conductive Carbon on Sulfur Crystallization: Key to High-Performance Aqueous Zinc–Sulfur Batteries

High‐Entropy Electrolyte Driven by Multi‐Solvation Structures for Long‐Lifespan Aqueous Zinc Metal Pouch Cells

Aqueous zinc metal batteries (AZMBs) are promising for grid‐scale energy storage due to their low cost and high safety. However, poor stability and an unfavorable freezing point hinder their actual application. Herein, a ternary salts‐based high‐entropy electrolyte (HEE) composed of Zn0.2Na0.4Li0.4(ClO4)1.2·7H2O is proposed to address the above issues. The addition of perchlorate salts with different cations reduces the size of ion clusters, significantly increases the solvation structure species, and promotes the anion‐rich Zn2+ solvation structures, resulting in an enlarged electrochemical stability window, favorable viscosity and ionic conductivity, and low freezing point. Furthermore, characterization and calculations confirm that multiple types of solvation structures effectively increase the electrolyte entropy. As a consequence, the Zn/Zn symmetric cells in HEE can sustainably cycle for at least 1000 hours and 1500 hours under room and subzero temperatures, respectively. The Na0.33V2O5/Zn and polyaniline/Zn full cells can even last for 30000 and 20000 cycles without capacity decay at −20 °C, respectively. The pouch cells employing HEE deliver promising capacity and stability, even at high mass loading of active materials. This strategy of introducing multiple salts with different cations to construct a high‐entropy environment provides a facile approach for high‐performance and long‐lifespan AZMBs across a wide temperature range.

High-Entropy Electrolyte Driven by Multi-Solvation Structures for Long-Lifespan Aqueous Zinc Metal Pouch Cells.

Aqueous zinc metal batteries (AZMBs) are promising for grid-scale energy storage due to their low cost and high safety. However, poor stability and an unfavorable freezing point hinder their actual application. Herein, a ternary salts-based high-entropy electrolyte (HEE) composed of Zn0.2Na0.4Li0.4(ClO4)1.2·7H2O is proposed to address the above issues. The addition of perchlorate salts with different cations reduces the size of ion clusters, significantly increases the solvation structure species, and promotes the anion-rich Zn2+ solvation structures, resulting in an enlarged electrochemical stability window, favorable viscosity and ionic conductivity, and low freezing point. Furthermore, characterization and calculations confirm that multiple types of solvation structures effectively increase the electrolyte entropy. As a consequence, the Zn/Zn symmetric cells in HEE can sustainably cycle for at least 1000 hours and 1500 hours under room and subzero temperatures, respectively. The Na0.33V2O5/Zn and polyaniline/Zn full cells can even last for 30000 and 20000 cycles without capacity decay at -20 °C, respectively. The pouch cells employing HEE deliver promising capacity and stability, even at high mass loading of active materials. This strategy of introducing multiple salts with different cations to construct a high-entropy environment provides a facile approach for high-performance and long-lifespan AZMBs across a wide temperature range.

Optimized Tungsten Disulfide via Pyrolytic Deposition for Improved Zn‐Ion Batteries

AbstractThe selection and optimization of cathode materials are crucial for enhancing the performance of aqueous zinc‐ion batteries. In this work, different active materials were created by combining Sulfur powder and polydopamine in four different mass ratios. The novel N‐doped carbon/WS2 is obtained. Thanks to the optimization of the dopamine‐carrying tungsten ion precursor and Sulfur powder (1 : 2, 1 : 4, 1 : 6 and 1 : 8), the four samples exhibited different morphology. The N−C/WS2‐6‐based zinc ion batteries with the highest specific capacity, 120.0 mAh/g in the first discharge at 2.0 A/g, and 78.0 mAh/g after 2500 cycles, with a capacity retention of 65 %, had a relatively good overall performance, according to the results. The reaction kinetics characteristics of the N−C/WS2‐6 cathode reveal that diffusion has a significant impact on the processes in the aqueous zinc ionic material N−C/WS2‐6.

Regulating the Zn electrode/electrolyte interface with lactose additive for high performance Zn anode

The practical utilization of rechargeable aqueous zinc metal batteries (AZMBs) has been constrained by the formation of zinc dendrites and other associated issues. This article introduces lactose, a compound rich in hydroxyl groups, as an electrolyte additive into the aqueous solution of the electrolyte with the objective of suppressing the harmful growth of zinc dendrites. The lactose additive, with its strong zincophilicity, robust intermolecular hydrogen bonding, and a large number of exposed high electronegativity hydroxyl groups, enables lactose to effectively modulate the electrode/electrolyte interface in a dynamic manner, thereby achieving the stability and reversibility of the zinc anode. The findings presented in this work demonstrate the uniform deposition and stripping of zinc in a 2 M ZnSO4 electrolyte with the addition of lactose, thereby enhancing the cycling performance of Zn||Zn batteries. The alteration of the zinc ion environment on the surface of the zinc electrode, in conjunction with the dynamic modulation of the Gouy-Chapman-Stern (GCS) layer by lactose, increases the nucleation overpotential, thereby facilitating to a uniform deposition morphology in lieu of the formation of large-scale dendrites. Furthermore, the formation of hydrogen bonds serves to prevent the occurrence of side reactions. These factors act in concert to enhance the electrochemical performance of AZMBs. The addition of lactose to the electrolyte has resulted in a significant enhancement in the Coulombic efficiency of the card-type Zn||Cu asymmetric battery, reaching 99.7 %. The biodegradability of lactose and the sustainability of its source make this research conducive to the development of environmentally friendly battery electrolyte additives.

A donor-acceptor conjugated bipolar polymer with multielectron redox sites for long-cycle-life and high-rate aqueous zinc dual-ion batteries

A donor-acceptor conjugated bipolar polymer with multielectron redox sites for long-cycle-life and high-rate aqueous zinc dual-ion batteries

Bifunctional electrolyte additive enabling long cycle life of vanadium-based cathode aqueous zinc ion batteries

Aqueous zinc ion batteries have received extensive attention due to their many advantages, but they still face problems such as dendrite growth and interface reaction of Zn anode and collapse of vanadium-based cathode structure. Here, a bifunctional electrolyte additive Methionine (MET) is proposed, which exhibits a unique role in inducing uniform deposition of zinc anode and inhibiting the failure of vanadium-based cathode materials. MET affects the solvated structure of the electrolyte to inhibit water activity and reduce HER and other related parasitic reactions. At the same time, it regulates the flux of Zn2+, improves the deposition kinetics of Zn2+ on the zinc anode side, and induces the preferential growth of the Zn (1 0 1) crystal plane to promote ordered Zn deposition. In particular, MET can in-situ generate a CEI containing such as ZnF2 on the surface of the vanadium-based cathode to inhibit the failure of the vanadium-based cathode, while adjusting the surface electronic state and Zn2+ diffusion behavior, and reducing the structural damage of the vanadium-based cathode caused by the Zn2+ intercalation process by inducing a strengthened surface pseudocapacitive reaction. Compared with the bare electrolyte, the capacity retention rate of the K2V8O21||Zn full-cell with OTF-M50 electrolyte increased from 10.2 % to 99.8 % after 800 cycles at a low current density of 1 A/g. Therefore, MET exhibits considerable application prospects as a bifunctional additive that can improve the stability of vanadium-based cathode and promote the stable deposition of zinc anode.

Impacts of distorted local chemical coordination on electrochemical performance in hydrated vanadium pentoxide

Modulating and elevating the operating voltage of a given cathode is a significant challenge to enhance the energy density of secondary batteries without sacrificing power output. The chemical coordination strongly influences the energy levels of d-orbitals of redox cations in cathode materials, which tie to their operating voltage. In contrast to concentrated studies on enhancing the specific capacity, in this study, we choose bi-layered hydrated vanadium pentoxide as the model to modulate the d-orbital energy levels through local chemical coordination manipulation, achieving a higher operating voltage in rechargeable aqueous zinc ion batteries. Here we show that, by employing X-ray absorption spectroscopy (XAS) and pair distribution function (PDF) techniques, we can analyze the distortion of [VO6] octahedra and extract chemical bond information, deciphering the correlation between the chemical coordination and operating voltage in cathode materials. The fundamentals could guide the designing and developing RAZIBs with higher energy and power density.

Mechanistic Understanding of Long Duration Fast Charge Aqueous Zinc Batteries Using Physically Adsorbed Oligomers as Interphases.

Polymers have been used as additives in the liquid electrolytes typically used for secondary batteries that utilize metals as anode. Such additives are conventionally argued to improve long-term anode performance by suppressing morphological and hydrodynamic instabilities thought to be responsible for out-of-plane and dendritic metal deposition during battery charging. More recent studies have reported that the polymer additives provide even more fundamental mechanisms for stabilizing metal electrodeposition through their ability to regulate metal electrodeposit crystallography and, thereby, morphology. Few studies explore how polymers carried in a liquid electrolyte achieve these functions, and fewer still provide rules for choosing among the various polymer types, the additive polymer molecular weight (Mw), and concentration in the electrolyte. Here, we investigate how these generally easy-to-control variables influence electrochemical interphase formation inside battery cells and their impact on the morphology and reversibility of Zn electrodes in aqueous electrolytes. We focus on aqueous Zn-iodine electrochemical cells containing linear polyethylene glycol (PEG) chains as additives and find that in electrolytes where the polymer concentration is maintained in the dilute solution regime there is an optimum polymer molecular weight (Mw ≈ 1000 Da), above which beneficial effects of polymers on Zn electrode reversibility and Zn-I2 battery lifetime are progressively lost. By means of optical ellipsometry and theoretical calculations, we show that the optimal Mw is associated with saturation of the thickness of a physiosorbed PEG coating on the Zn metal electrode. Electron microscopy and X-ray photoelectron spectroscopy analysis of Zn electrodeposits formed in such electrolytes reveal that the physiosorbed polymer coating has two primary effects─it regulates the deposit morphology and suppresses parasitic reactions between the electrode and electrolyte components. The parasitic reactions produce species like ZnO, which are known to passivate the Zn electrode and promote nonuniform deposition. Galvanostatic cycling measurements in aqueous Zn-I2 cells containing the PEG additives at the optimal Mw show that the cells maintain very high Coulombic efficiencies (≥99%) at current densities as high as 50 mA/cm2─close to the maximum values permissible across the Celgard separator membranes used in our studies.

Phase Engineering of ZnSe by Small Molecules as a High-Performance Protective Layer for Zn Anode.

The practical application of aqueous zinc ion batteries is still hampered by the side reactions and dendrite growth on Zn anode. Herein, the phase engineering of ZnSe coating layer by incorporating small molecules is developed to enhance the performance of Zn anode. The unique electronic structure of ZnSe⋅0.5N2H4 promises strong adsorption for Zn atoms and enhanced ability to inhibit hydrogen evolution, thereby promoting uniform Zn deposition and preventing by-product and dendrite growth. Meanwhile, fast Zn2+ transfer and deposition kinetics are also demonstrated by ZnSe⋅0.5N2H4. As a result, the ZnSe⋅0.5N2H4@Zn symmetric cell achieves long-term cycling stability up to 1900 h and 300 h at high current densities of 5 mA cm-2 and 20 mA cm-2, respectively. The assembled ZnSe⋅0.5N2H4@Zn||NH4V4O10 full cell presents outstanding cycling stability and rate capability. This work highlights the key role of crystal phase control of protective layer for high-performance zinc anode.

Na ions doped Fe2VO4 cathode for high performance aqueous zinc‐ion batteries

Aqueous zinc ion batteries are thought to be a new generation of secondary batteries that will replace lithium ion batteries due to their great safety and inexpensive cost. In the cathode materials of aqueous zinc ion batteries with long life and high capacity, abundant active sites and crystal structure stability play an important role. In the present work, the strategy of Na+ intercalation of Fe2VO4 (FVO) is proposed, aiming at the insertion of Na+, which not only enriches the active sites, but also sodium and iron ions act as guest species with the negatively charged VOx lattice to provide strong electrostatic attraction to stabilize the lamellar structure. In terms of electrochemical performance, the discharge specific capacity is 370 mAh g‐1 at a current density of 0.1 A g‐1, and when the current density is arising 5 A g‐1, the specific capacity also reaches 200 mAh g‐1 after cycling 2000 with a capacity retention of 99%, which is better than the electrochemical performance of Fe2VO4 (FVO) alone at 50 mAh g‐1. The superior electrochemical performance proves that FVO‐Na is an ideal cathode material for zinc ion batteries.

Mechanism-Guided Rational Design of Anode Coatings for Aqueous Zinc Ion Batteries.

Aqueous zinc ion batteries (ZIBs) hold promises as a safer, more cost-effective, and environmental-friendly alternative to lithium-ion batteries, especially for stationary energy storage. Recent advancements in protective anode coatings, which fine-tune zinc ion solvation structure, have yielded significant improvements in the aqueous ZIB performance, addressing dendrite formation and side reactions, thereby prolonging cycle lifetime. Understanding the underlying mechanisms of these coatings as ions sieves is crucial for further optimization and achieving long-term stability, which is a key requirement for practical applications. This concept explores recent developments in ZIB anode coatings from the view of molecular mechanisms and points out future research directions.

Biogenic synthesis and physicochemical characterization of metal nanoparticles based on Calotropis procera as promising sustainable materials against skin cancer

The UAE harbors a rich diversity of wild medicinal plants, such as Calotropis procera (CP), that are renowned for their extensive use in traditional medicine due to their abundance of bioactive phytochemicals. Zinc and iron metals possess significant pharmacological effects including antioxidant and anticancer properties. In this study, nanoparticles (NPs) containing zinc and iron were green synthesized utilizing ethanolic and aqueous extracts of CP aerial parts. UV-Vis spectra revealed absorption peaks around 270–275 nm, while FT-IR analysis confirmed successful coating of the NPs with plant’s phytochemicals. SEM/EDX analysis indicated a more potent reducing effect of the aqueous extract, whereas the alcoholic extract demonstrated more effective coating of the NPs. DLS showed monodispersed NPs with average sizes of 32.67–202 nm. The alcoholic extract-based zinc and iron NPs exhibited the highest phenolic and flavonoid contents (51.06 ± 2.82 µg of GAE/mg of DW and 66.26 ± 1.12 µg of Qu/mg of DW, respectively) and the strongest antioxidant effect against ABTS and DPPH radicals (IC50 = 52.81 and 148.46 µg/mL, respectively). The aqueous extract-based zinc NPs demonstrated the greatest cytotoxicity against A-431 cell lines (IC50 = 188.97 µg/mL). The findings highlight promising potential of these sustainable materials for therapeutic applications, indicating a need for continued research and development in this area.

Rational design of α-MnO2@TiO2 composites for high-performance zinc ions batteries

Aqueous zinc ions batteries (AZIBs) have attracted widespread interest due to their remarkable energy density, non-toxicity, environmental friendliness and low cost. However, the application of MnO2 cathode materials for AZIBs is limited owing to the dissolution of Mn2+, structural collapse and intrinsic poor conductivity. Herein, α-MnO2@TiO2 composites were synthesized via simple hydrothermal and calcination approaches. Some smaller TiO2 were coated on the MnO2 nanorods to form the protective layer. The TiO2 protective layer not only prevents the dissolution of Mn2+ and structural collapse of MnO2, but also enhances the conductivity of the material due to the presence of Ti3+ defects, which increased electrode materials wettability, specific surface area and diffusion rate of Zn2+. In addition, the coating TiO2 causes surface adsorbed oxygen and surface binding defects in α-MnO2@TiO2, and increases surface reactivity and electrochemically active sites, which provides abundant channels and available insertion electrochemically active sites for H+/Zn2+ transport. As a result, α-MnO2@TiO2–2 delivers a high specific capacity of 182.90 mAh g−1 at 1 A g−1 after 600 cycles and outstanding rate capacity of 127.91 mAh g−1 at 5 A g−1. This work provides an idea for exploring high-performance cathode materials for AZIBs.

Evolution of Frustrated Coordination in Eutectic Electrolyte Driven by Ligand Asymmetry toward High-Performance Zinc Batteries.

Eutectic electrolytes hold promise for aqueous zinc metal batteries in sustainable energy storage chemistries, yet improvement from perspective of molecule configurational engineering are ambiguous. Herein, we propose design strategy of increasing asymmetric molecular geometry in organic ligands to regulate frustrated coordination and disordered structure for eutectic electrolytes toward enhanced zinc metal batteries. The introduced asymmetry in eutectic component gives rise to relatively weak coordination strength and configurational disorder interaction among cation-anion-ligand, leading to suppressed local aggregation, steady eutectic phase and improved Zn2+diffusion kinetics. Such highly frustrated coordination state also enables disruption of hydrogen bonding network and reinforcement of anion participation, which results in confined side reactions, decreased water activity and the formation of inorganic-enriched solid electrolyte interphase. In comparison to highly symmetric ligands, asymmetric ligand-involved eutectic electrolytes with configurational disorderdeliver high Coulombic efficiency of 99.4 %, stabilized Zn plating/stripping of 5000 h and impressive rate capability even under harsh conditions such as small N/P, low temperature. The rationale in this work advances the deep understanding of asymmetric molecular engineering in eutectic electrolytes and showcases suitability of frustrated coordination to achieve high-performance zinc metal batteries.

Effect of probiotics 'Bio-health' and foliar fertilization with zinc sulfate on growth and yield of okra (Abelmoschus esculentus (L.) Moench)

The experiment was conducted in a private field in Jaflawiya, Al-Mishkhab District, Najaf Governorate, for the spring season 2021, to study the effect of soil application with probiotics Bio health and foliar fertilization with aqueous zinc sulfate on some vegetative growth characteristics and yield of okra Husainawia variety. The experiment was a factorial experiment according to Randomized Complete Block Design (R.C.B.D.) with 2 factors and 3 replicates. The first factor was ground application with probiotics Bio health at 3 levels (0, 2500, 5000 g ha-1) and the second factor is the foliar spraying of zinc in (ZnSO4.7H20) using 3 concentrations (0, 75 and 150 mg L-1). Both factors were applied 3 times during the growing season. The first application was in the stage of 4 true leaves and zinc was sprayed a week later. The second and third were 30 and 60 days after the first addition respectively. Analysis of variance (ANOVA) was performed and the averages were compared using the least significant difference test. Least Significant Difference Test (L.S.D.) at 0.05 probability level. The highest results were recorded in the treatment of adding the Bio health at a level of 5000 g ha-1, which led to the highest rates of vegetative growth indicators, quantitative and qualitative yield and chemical indicators, including plant height, leaf area, knot ratio, number of pods, total yield, nitrogen and phosphorous ratio in pods, zinc content in pods and protein % in pods. In general, the ground application of Bio health at 5000 g ha-1 with zinc 150 mg L-1 significantly outperformed most of the single and interaction treatments. It gave the highest significant increase in vegetative growth indicators, yield, chemical and qualitative indicators.

Trace Amounts of Multifunctional Electrolyte Additives Enhance Cyclic Stability of High-Rate Aqueous Zinc-Ion Batteries.

Aqueous zinc ion batteries (AZIBs) are renowned for their exceptional safety and eco-friendliness. However, they face cycling stability and reversibility challenges, particularly under high-rate conditions due to corrosion and harmful side reactions. This work introduces fumaric acid (FA) as a trace amount, suitable high-rate, multifunctional, low-cost, and environmentally friendly electrolyte additive to address these issues. FA additives serve as prioritized anchors to form water-poor Inner Helmholtz Plane on Zn anodes and adsorb chemically on Zn anode surfaces to establish a unique in situ solid-electrolyte interface. The combined mechanisms effectively inhibit dendrite growth and suppress interfacial side reactions, resulting in excellent stability of Zn anodes. Consequently, with just tiny quantities of FA, Zn anodes achieve a high Coulombic efficiency (CE) of 99.55 % and exhibit a remarkable lifespan over 2580 hours at 5mA cm-2, 1 mAh cm-2 in Zn//Zn cells. Even under high-rate conditions (10mA cm-2, 1 mAh cm-2), it can still run almost for 2020 hours. Additionally, the Zn//V2O5 full cell with FA retains a high specific capacity of 106.95 mAh g-1 after 2000 cycles at 5 A g-1. This work provides a novel additive for the design of electrolytes for high-rate AZIBs.

A Feasible Strategy for High-Performance Aqueous Zinc-Ion Batteries: Introducing Conducting Polymer.

Aqueous zinc ion batteries (AZIBs) offer great potential for large-scale energy storage because of their high safety, low cost and acceptable energy density. However, the cycle life of AZIBs is inevitably affected by parasitic reactions and dendritic growth caused by multiple factors such as electrode, electrolyte and separator, which pose significant obstacles to the practical application of AZIBs. To address these challenges, conducting polymer (CP) based materials have gained widespread attention in the realm of rechargeable batteries due to the adjustable band gap, controllable morphology, and excellent flexibility of CPs. In particular, CPs exhibit remarkable conductivity, low dimensionality, and doping characteristics, making them highly promising for integration into the AZIB system. In this review, the problems associated with the cathode, anode, electrolyte, and separator of AZIBs are discussed, and the application of CPs for their modification is summarized. The review provides a comprehensive analysis of the action mechanisms involved in the CP modification process and offers valuable insights for the design and development of CPs that can be effectively utilized in AZIBs. Additionally, the review presents a promising outlook of this research field, aiming to further advance the application of low-cost and high-performance CPs and their composites in AZIBs.

Organic Electrolyte Additives for Aqueous Zinc Ion Batteries:Progress and Outlook.

Aqueous zinc ion batteries (AZIBs) are considered one of the most prospective new-generation electrochemical energy storage devices with the advantages of high specific capacity, good safety, and high economic efficiency. Nevertheless, the enduring problems of low Coulombic efficiency (CE) and inadequate cycling stability of zinc anodes, originating from dendrites, hydrogen precipitation and passivation, are closely tied to their thermodynamic instability in aqueous electrolytes, which significantly shortens the cycle life of the battery. Electrolyte additives can solve the above difficulties and are important for the advancement of affordable and reliable AZIBs. Organic electrolyte additives have attracted widespread attention due to their unique properties, however, there is a lack of systematic discussion on the performance and mechanism of action of organic electrolyte additives. In this review, a comprehensive overview of the application of organic electrolyte additives in AZIBs is presented. The role of organic electrolyte additives in stabilizing zinc anodes is described and evaluated. Finally, further potential directions and prospects for improving and directing organic electrolyte additives for AZIBs are presented.

Innovative Zinc Anodes: Advancing Metallurgy Methods to Battery Applications.

Aqueous zinc metal batteries (AZMBs) are emerging as a powerful contender in the realm of large-scale intermittent energy storage systems, presenting a compelling alternative to existing ion battery technologies. They harness the benefits of metal zinc's high safety, natural abundance, and favorable electrochemical potential (-0.762V vs Standard hydrogen electrode, SHE), alongside an impressive theoretical capacity (820mAhg-1 and 5655mAhcm-3). However, the electrochemical performance of ZMBs is impeded by several challenges, including poor compatibility with high-loading cathodes and persistent side reactions. These issues are intricately linked to the inherent physicochemical properties of the zinc metal anodes (ZMAs). Here, this review delves into the traditional methods of ZMAs production, encompassing extraction, electrodeposition, and rolling processes. The discussion then progresses to an exploration of cutting-edge methodologies designed to enhance the electrochemical performance of ZMAs. These methods are categorized into alloying, pre-treatment of substrate, advanced electrodeposition techniques, and the development of composite anodes utilizing zinc powder. The review offers a comparative analysis of the merits and drawbacks of various optimization strategies, highlighting the beneficial outcomes achieved. It aspires to inspire novel concepts for the advancement and innovation of next-generation zinc-based energy storage solutions.