Zinc Research Articles

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.

Harnessing biological insights: Integrating proton regulation, pH buffer and zincophility for highly stable Zn anode

Zinc anodes are severely threatened by hydrogen evolution, dendrite growth and by-products. Inspired by the mechanisms of L-carnosine (L-car) in maintaining intracellular pH stability and fostering mucosal repair in biological systems, this study innovatively proposed a comprehensive strategy integrating proton regulation, pH buffer and zincophility by introducing L-car as an electrolyte additive to achieve remarkable stability of zinc anode. Experimental validations and theoretical calculations demonstrate that the abundant N and O sites in L-car can form robust hydrogen bonds with protons, effectively impeding interfacial proton transport and substantially mitigating HER. Moreover, dual pH buffering sites of L-car facilitate dynamic modulation of proton concentration, stabilizing the pH of electrolyte, and suppressing Zn corrosion/passivation/by-product. Concurrently, the robust chelation between L-car and Zn2+ orchestrates uniform zinc ion deposition. This synergistic trifecta of L-car endows Zn ion batteries with an extraordinary cycling stability, extending to an ultralong duration of 5500 h. Furthermore, the Zn//MnO2 full battery, demonstrates remarkable stability, retaining a specific capacity of 106.1 mAh/g with 79.2 % retention after 1000 cycles at 3 A/g. This study pioneers the interdisciplinary application of L-car in electrolyte modification, presenting a novel paradigm for stabilizing zinc anodes.

Zinc and copper effect mechanical cell adhesion properties of the amyloid precursor protein.

The amyloid precursor protein (APP) can be modulated by the binding of copper and zinc ions. Both ions bind with low nanomolar affinities to both subdomains (E1and E2) in the extracellular domain of APP. However, the impact of ion binding on structural and mechanical trans-dimerization properties is yet unclear. Using a bead aggregation assay (BAA), we found that zinc ions increase the dimerization of both subdomains, while copper promotes only dimerization of the E1 domain. In line with this, scanning force spectroscopy (SFS) analysis revealed an increase in APP adhesion force up to three-fold for copper and zinc. Interestingly, however, copper did not alter the separation length of APP dimers, whereas high zinc concentrations caused alterations in the structural features and a decrease of separation length. Together, our data provide clear differences in copper and zinc mediated APP trans-dimerization and indicate that zinc binding might favor a less flexible APP structure. This fact is of significant interest since changes in zinc and copper ion homeostasis are observed in Alzheimer's disease (AD) and were reported to affect synaptic plasticity. Thus, modulation of APP trans-dimerization by copper and zinc could contribute to early synaptic instability in AD.

Discovery of peroxynitrite elevation in zinc ion-induced acute lung injury with an activatable near-infrared fluorogenic probe

Particulate matter derived from environmental pollution might contain zinc ions (Zn2+), and inhaling these particles exacerbates lung tissue's inflammatory response, impairing lung function and increasing the risk of acute lung injury (ALI). Zn2+ is known to contribute to oxidative stress, leading to elevated levels of reactive oxygen species such as peroxynitrite (ONOO-), which play a key role in the pathogenesis of ALI. Herein, a novel near-infrared fluorogenic probe, DCI-BT, was prepared for the specific detection of ONOO- based on the strategy of oxidative hydrolysis of imine to break into aldehyde. The response of DCI-BT to ONOO- was found to be extremely fast, and the addition of ONOO- would enhance its fluorescence intensity. Cell experiments showed that DCI-BT could efficiently indicate the changes in cellular ONOO- levels. Furthermore, employing DCI-BT, the Zn2+-induced endogenous ONOO- production in cells was successfully visualized, confirming that prolonged exposure to Zn2+ triggered cellular oxidative stress. Finally, the application of DCI-BT in the mice model of ALI was evaluated, and the results revealed that it had good biosafety and could effectively track the changes in ONOO- levels in the Zn2+-induced ALI model. Therefore, DCI-BT held promise as a valuable chemical tool for diagnosing and treating environmentally induced oxidative stress-related diseases.

Performance study of bimetallic Mn-Zn porous flower-like nanosheets as supercapacitor positive electrode materials

As environmental and carbon emission issues become increasingly severe, electrochemical energy storage systems have gained attention. Compared to traditional supercapacitors, zinc-ion hybrid capacitors (ZIHCs) are not only environmentally friendly but also cost-effective. MnO2, with its low cost, eco-friendliness, high theoretical capacity, and stable crystal structure, is considered a promising positive electrode material. In this study, the morphology of MnO2 was optimized using electrodeposition. During cycling, zinc ions reversibly intercalate and extract from MnO2, forming a cactus-like nanoflower structure. This structure is loose and porous, providing ample reaction space for active materials. The assembled device exhibits excellent performance in both energy density (85.68 Wh kg−1) and stability (91.60 %).

Synergistic insights to ion-doped hydroxyapatite: bridging XRD, electrical impedance, dielectric characteristics, and antibacterial properties

ABSTRACT In this work, ion-doped hydroxyapatite materials were synthesized using the sol-gel technique. XRD analysis confirmed the purity of the products, with no secondary peaks observed. Doping with manganese, lithium, potassium, and zinc ions resulted in a crystalline size of 47–48 nm. Fourier transform infrared spectroscopy validated the structural bands, while scanning electron microscopy and energy-dispersive X-ray spectroscopy revealed nano-rod-like particles with sizes ranging from 30 to 80 nm in length and 13 to 40 nm in width. Impedance spectroscopy and dielectric relaxation studies showed electrical behaviour following the Maxwell-Wagner mechanism and non-Debye type relaxation. The materials exhibited strong antibacterial properties, making them promising for medical implant applications.

Comprehensive Understanding of Steric‐Hindrance Effect on the Trade‐Off Between Zinc Ions Transfer and Reduction Kinetics to Enable Highly Reversible and Stable Zn Anodes

AbstractThe electrode interface concentration polarization attributed to the contradiction between sluggish mass transfer process and rapid electrochemical reduction kinetics significantly restricts the practical application of Zn anode. Creating a moderate Zn ions transfer and reduction chemistry is essential for durable zinc‐ion batteries. In this work, this trade‐off effect is realized by selecting large‐size 4‐Aminomethyl cyclohexanecarboxylic acid (AMCA) molecule as the electrolyte additive. Intriguingly, AMCA molecules reorganize the Zn2+ solvation structure via the robust coordination with Zn2+ and reconstruct H‐bond networks, giving a pulled desolvation process. Meanwhile, AMCA enlarges the Zn2+ solvation size with a push force, confining the rapid electrochemical reduction kinetics. The balanced chemical environment is maintained via the moderate pull‐push interplay. Besides, AMCA can anchor on zinc surface to create a water‐poor microenvironment, fostering homogeneous Zn (002) deposition and effectively restricting water‐induced side‐reactions. Notably, the Zn||Zn symmetric cell with AMCA operates stably over 167 days at 20 mA cm−2. Moreover, the Zn||VOX full cell employed AMCA ensures outstanding capacity retention of 99.15% after 590 cycles at 2 A g−1, even with low N/P (4.3), lean electrolyte (50 µL mAh−1) and ultrathin Zn foil of 10 µm. This work reveals unique insights into the balanced interfacial chemistry design toward high‐performance zinc batteries.

Efficient Preparation of Metal-Ion Intercalated Vanadium-Based Cathodes for High-Performance Aqueous Zinc-Ion Batteries: Na2V6O16·3H2O as an Example.

The inherent challenges associated with aqueous zinc ion batteries (AZIBs), such as low energy density and slow diffusion kinetics, pose significant obstacles to their widespread adoption as energy storage systems. These limitations mainly stem from the nongreen and complex preparation process of high-quality cathode materials. In this study, we propose an approach utilizing microwave-assisted ball milling to expedite the fabrication of vanadium-based intercalated nanomaterials, aiming at solving the problem of prolonged reaction at high temperatures, which is unavoidable in the preparation of anode materials. Na2V6O16 (NVO) nanorods were synthesized in just 40 min under aqueous solvent conditions. These nanorods exhibit remarkable electrochemical properties, including a high specific capacity of 564 mA h g-1 at 0.1 A g-1 and an excellent cycle life, maintaining 164.2 mA h g-1 after 5000 cycles at 5 A g-1. Additionally, the incorporation of Na+ into the electrolyte effectively mitigates the stripping of Na+ and the deposition of Zn dendrimers from NVO, further contributing to enhanced cycling stability. The findings of this study offer a promising approach to the rapid and efficient synthesis of high-quality ZIB cathode materials.

Spatial Distribution of Physical and Chemical Properties of Deep Sea Water in Xisha, South China Sea

Deep sea water (DSW) is a globally utilized source of renewable energy and other resources. To understand the characteristics of DSW resources in the South China Sea, in July 2022, the Guangzhou Marine Geological Survey (GMGS) investigated temperature, salinity, pH, dissolved oxygen (DO), inorganic salts (DIN, PO43−-P, and SiO3-Si), heavy metals (Hg, Pb, As, and Cd), trace elements (Cu, Zn, Fe, Mn, Ni, Se, and Mo), and other related indicators. The results of this investigation elucidate the horizontal and vertical changes in the physical and chemical properties of deep sea water in the Xisha Sea. The surface seawater quality in Xisha was found to be excellent and to meet first-class seawater survey standards. However, the concentrations of various nutrient salts in the surface layer were relatively low. As the seawater depth increased, different trace elements and heavy metals exhibited variations, and the concentrations of various nutrients also gradually increased.

Effective CuO/Cu7S4 nanospheres heterostructures for advanced “rocking-chair” zinc-ion battery

Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted considerable attention for energy storage owing to their environmental friendliness and high safety. However, the adverse side reactions and unsatisfactory cycle life brought by Zn-metal anodes limit their large applications. Herein, CuO/Cu7S4 (CSO) heterostructured hollow nanospheres is proposed as an attractive conversion-type Zn-metal-free anode for “rocking-chair” ZIBs. The CSO/graphite self-supporting electrode delivers a high capacity of 271 mAh/g at current density of 0.1 A/g and a superior cyclic stability of 1200 cycles. Based on the excellent electrochemical performance of CSO/graphite electrode, we have constructed a self-powered pressure sensor integrated system using the “rocking-chair” zinc ion battery as the power source, demonstrating significant practicality. This work provides a high-performance conversion type anode material for aqueous multivalent metal ion batteries.

Experimental Validation of Density Functional Theory Predictions on Structural Water Impact in Vanadium Oxide Cathodes for Zinc-Ion Batteries.

This study combines experimental methods with density flooding theory (DFT) calculations to investigate the enhancement of the electrochemical performance of vanadium oxide cathodes for aqueous zinc ion batteries (AZIBs) through strategic water content management. DFT predictions indicated that a moderate presence of structural water optimizes electrical conductivity and facilitates zinc ion diffusion. These theoretical insights are empirically validated by synthesizing AlVO-1.6 H2O using a hydrothermal method, which exhibited superior electrochemical properties. This material demonstrated an impressive initial capacity of 316 mAh g-1 at 0.2 A g-1, with robust capacity retention after extended cycling. Remarkably, even at an elevated current density of 10 A g-1, it sustains a capacity of 161.6 mAh g-1, while maintaining a capacity retention of 97.6% over 2000 cycles. The results confirm that adjusting the structural water content in vanadium oxides significantly boosts their electrochemical capabilities, aligning experimental outcomes with computational forecasts and showcasing a novel approach for developing high-performance cathodes in energy storage technologies.

Structural Changes in Copper Slags During Slow Cooling

The objects of the study were converter slags from the Balkhash copper plant in their initial state and after heat treatment. Using mineralogical and X-ray phase analysis, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA), it was found that the initial converter slag and its thermally treated samples have identical matrices with almost complete coincidence in mineral and phase compositions. The distinguishing feature is the quantitative ratio of mineral components in the slag mass. Almost all of the iron is oxidized and present in the form of fayalite, magnetite, and magnetite, with other elements (silicon, copper, zinc, and aluminum) incorporated into its lattice. The structure of all slag samples indicates an association of sulfur exclusively with copper. Copper in the slags was identified in both metallic and sulfide forms. Slow cooling of the converter slag after its remelting contributes to the reduction in the sulfide–metal suspension in the volume of the melt and its coarsening. During slow cooling, structural changes occur not only in the main oxide part of the slag but also in the polymetallic globules.

Milk osteopontin mediates zinc uptake in intestinal cells in the presence of phytic acid

The bioavailability and the intestinal absorption of the essential mineral zinc are challenged by the food matrix and especially the content of zinc chelating antinutrients. Many milk proteins and peptides affect zinc bioavailability. Osteopontin (OPN) is an acidic and highly phosphorylated whey protein that has been shown to bind calcium, magnesium and iron. Here we report the zinc binding properties of OPN, and the effect of OPN-Zn complexes on zinc absorption in Caco-2 cells. By isothermal titration calorimetry milk OPN was shown to bind approximately 36 zinc ions (KD of ∼70 μM). The binding was mainly mediated by the phosphorylations in the protein. OPN retained zinc bound after in vitro simulated gastrointestinal transit. Interestingly the OPN-Zn complex enhanced zinc bioavailability in the presence of phytic acid, compared to inorganic zinc salts. Zinc uptake mediated by OPN significantly upregulated the gene expression of MT1G and ZnT1 which are crucial proteins involved in preserving enterocyte zinc homoeostasis. These results indicate that OPN could be incorporated into functional foods and infant formulas to increase zinc bioavailability and uptake.

NASICON-structured Na3Ti0.8V1.2(PO4)3/C as a high-performance cathode for aqueous sodium-zinc hybrid batteries

Phosphate cathode materials have a stable and open backbone structure and are expected to be one of the ideal cathode materials for aqueous zinc ion batteries (ZIBs). In this work, a new compound Na3Ti0.8V1.2(PO4)3 is synthesised by sol-gel method and used as a cathode material for ZIBs. The battery delivered a reversible and stable capacity of 120.1 mA h g−1 over 100 cycles at 0.5 C. Impressively, the battery demonstrated exceptional cycling performance and outstanding rate performance, maintaining a capacity retention of 95.6 % after 1000 cycles at 5.0 C. It is demonstrated that the dissolution of V in water is effectively inhibited by partial Ti ion occupancy at the V site, which accelerates the ion diffusion rate and greatly improves the electrochemical performance. In this work, the charging and discharging process of NASICON structured Na3Ti0.8V1.2(PO4)3 cathode was investigated to show the mechanism of Na+ and Zn2+ co-doping. This discovery offers a novel phosphate cathode material for ZIBs, as well as a fresh approach to enhancing the specific capacity and stability of phosphate cathode materials.

Hyperstable low-tortuosity fast ion nanochannels for MXene electrodes

The development of flexible MXene-based electrodes with hyperstable ion nanochannels and low tortuosity, remains daunting challenging for long-term wearable electronic devices. This paper presents a hydrogen-bonding enhanced holey MXene (HC-HMXene) electrode with maximum ion accessibility, optimized ion transport pathways, and hyperstable ion nanochannels. Specifically, three roles of introducing in-plane mesopores, reducing the lateral dimensions, and increasing the interlayer spacing in HMXene film notably enhance the electrolyte permeation efficiency and shorten the ion transport paths of the electrode (resulting in a 78.7-fold decrease in tortuosity). Thus, the constructed HC-HMXene electrode exhibits 41.1 times higher diffusion coefficient and 2.3 times higher specific capacitance than those of closely restacked film electrode with the same mass loading of MXene. Furthermore, the aramid nanofibers introduced among the MXene layers as interlocking agents bond the nanosheets via hydrogen interaction and significantly enhance the stability of the ion channel. Consequently, the HC-HMXene film effectively resists swelling behavior and maintains good structural stability in aqueous media. Moreover, the flexible sensing integrated system, powered by a HC-HMXene-based zinc ion microcapacitor, exhibits promising application prospects in real-time monitoring human physiological characteristics.

Human biomonitoring of essential and toxic trace elements (heavy metals and metalloids) in urine of children, teenagers, and young adults from a Central European Cohort in the Czech Republic.

Exposure to toxic trace elements, which include metals and metalloids, can induce adverse health effects, including life-threatening diseases. Conversely, essential trace elements are vital for bodily functions, yet their excessive (or inadequate) intake may pose health risks. Therefore, identifying levels and determinants of exposure to trace elements is crucial for safeguarding human health. The present study analyzed urinary concentrations of 14 trace elements (arsenic, cadmium, cobalt, chromium, copper, mercury, manganese, molybdenum, nickel, lead, antimony, selenium, thallium, and zinc) and their exposure determinants in 711 individuals, spanningfrom children to young adults from a Central European population from the Czech Republic. Multivariate linear regression and non-parametric Kruskal-Wallis ANOVA were used to investigate exposure determinants. Estimates of 95th percentile concentrations and confidence intervals were carried out to establish reference values(RV95). The study also assessed the percentage of population exceeding health-based guidance values (GVs) to gauge health risks. Young adults showed elevated toxic element concentrations, whereas children exhibited higher concentrations of essential elements. Mercury concentrations were associated with both dental amalgam filling count and seafood intake; arsenic concentrations were associated with seafood, rice, and mushroom consumption. Mushroom consumption also influenced lead concentrations. Sex differences were found for cadmium, zinc, nickel, and cobalt. Between 17.9% and 25% of the participants exceeded recommended GV for arsenic, while 2.4% to 2.8% exceeded GV for cadmium. Only one participant exceeded the GV for mercury, and none exceeded GVs for chromium and thallium. Essential trace elements' GVs were surpassed by 38% to 68.5% participants for zinc, 1.3% to 1.8% for molybdenum, and 0.2% to 0.3% for selenium. The present study examines trace element exposure in a Central European population from the Czech Republic, unveiling elevated exposure levels of toxic elements in young adults and essential elements in children. It elucidates key determinants of trace element exposure, including dietary and lifestyle indicators as well as dental amalgam fillings. Additionally, the study establishes novel reference values and acomparison with established health-based human biomonitoring guidance values, which are crucial for public health decision-making. This comprehensive biomonitoring study provides essential data to inform public health policies and interventions.

Determination of nutritional sufficiency ranges for pomelo (Citrus grandis Osbeck) grown on alluvial soils using DRIS.

Pomelo is an important tropical fruit with a high nutrient content and economic value in the Vietnamese Mekong Delta (VMD). The Diagnosis and Recommendation Integrated System (DRIS) helps determine the leaf nutrient status of various plants worldwide. However, the DRIS-based nutritional balance in pomelo leaves remains to be established. Therefore, in this study, we aimed to (i) construct the DRIS norms and indices for nutrients, including macronutrients (N, P, K, Ca, and Mg) and trace elements (Cu, Fe, Zn, and Mn) in pomelo leaves, and (ii) establish nutrient sufficiency value ranges for sustainable pomelo cultivation in the VMD. We collected 270 leaf samples at three stages of pomelo growth, i.e., flowering, fruit development, and postharvest, and calculated DRIS indices for various nutrients. The DRIS indices established for various nutrients in pomelo leaves were accurate and reliable, as indicated by the high coefficient of determination (R2 = 0.43-0.93, p < 0.05) between nutrient concentrations and their DRIS indices. We observed that pomelo leaves were deficient in N (IN = -6.82), P (IP = -24.0), and Fe (IFe = -0.40) at the flowering stage and most deficient in P (IP = -15.6), K (IK = -11.7), Fe (IFe = -0.50), and Mn (IMn = -2.31) at the fruit development stage. However, only N (IN = -2.64) and P (IP = -13.4) shortages were observed at the postharvest stage. Thus, in this study, we evaluated nutrient value ranges (deficient, balanced, and excess) in pomelo leaves at their different growth stages and established DRIS indices for various nutrients. The results contribute to our understanding of the nutritional status of pomelo leaves, which can help growers improve plant health for sustainable pomelo production.

Constructing Cyclic Hydrogen Bonding to Suppress Side Reactions and Dendrite Formation on Zinc Anodes.

The high electrochemical reactivity of H2O molecules and zinc metal results in severe side reactions and dendrite formation on zinc anodes. Here we demonstrate that these issues can be addressed by using N-hydroxymethylacetamide (NHA) as additives in 2 M ZnSO4 electrolytes. The addition of NHA molecules, acting as both a hydrogen bond donor and acceptor, enables the formation of cyclic hydrogen bonding with H2O molecules. This interaction disrupts the existing hydrogen bonding networks between H2O molecules, hindering proton transport, and containing H2O molecules within the cyclic hydrogen bonding structure to prevent deprotonation. Additionally, NHA molecules show a preference for adsorption on the (101) crystal surface of zinc metal. This preferential adsorption reduces the surface energy of the (101) plane, facilitating the homogeneous Zn deposition along the (101) direction. Thus, the NHA enables Zn||Zn symmetric cell with a cycle lifespan of 1100 hours at 5 mA cm-2 and Zn||Cu asymmetric cell with a high Coulombic efficiency over 99.5 %. Moreover, the NHA-modified Zn||AC zinc ion hybrid capacitor is capable of sustaining 15000 cycles at 2 A g-1. This electrolyte additive engineering presents a promising strategy to enhance the performance and broaden the application potential of zinc metal-based energy storage devices.