Zinc Deposits Research Articles

Constructing an ion‐oriented channel on a zinc electrode through surface engineering

AbstractThe inherent shortcomings of a zinc anode in aqueous zinc‐ion batteries (ZIBs) such as zinc dendrites and side reactions severely limit their practical application. Herein, to address these issues, an ion‐oriented transport channel constructed by graphdiyne (GDY) nanowalls is designed and grown in situ on the surface of a zinc electrode. The vertically stacked GDY nanowalls with a unique hierarchical porous structure and mechanical properties form a nanomesh‐like interface on the zinc electrode, acting as an ion‐oriented channel, which can efficiently confine the segmented growth of zinc metal in microscopic regions of hundreds of nanometers. In those microscopic regions, the uniform domain current density is effortlessly maintained compared with a large surface area, thereby inhibiting zinc dendrites effectively. Besides, due to the presence of the ion‐oriented channel, the modified zinc anode demonstrates long‐term stable zinc plating/stripping performance for more than 600 h at 1 mAh cm−2 in an aqueous electrolyte. In addition, full‐cells coupled with MnO2 show high specific capacity and power density, as well as excellent cycling stability with a capacity retention of 82% after 5000 cycles at 1 A g−1. This work provides a feasible and accessible surface engineering approach to modify the electrode interface for confined and dendrite‐free zinc deposition in aqueous ZIBs.

Use of zinc deposited in deciduous teeth as a retrospective measurement of dietary zinc exposure during early development.

We proposed that zinc (Zn) deposition in deciduous teeth would be a timed record of exposure to this essential micronutrient over very early life. We tested this hypothesis by gathering information on the maternal and child's diet during pregnancy and early infancy and measuring mineral deposition in the dentine at points during deciduous tooth development. We developed a short food frequency questionnaire (S-FFQ) to record consumption of food containing Zn during pregnancy and over the first year of life of the child in an Indonesian population. Zn, Sr and Ca were measured by laser ablation ICP-MS in a series of points across the developmental timeline in deciduous teeth extracted from 18 children undergoing the process as part of dental treatment whose mothers completed the SFFQ. Mothers and children were classified into either high Zn or low Zn groups according to calculated daily Zn intake. The Zn/Sr ratio in dentine deposited over late pregnancy and 0-3 months post-partum was higher (p < 0.001, 2-way ANOVA; p < 0.05 by Holm-Sidak post hoc test) in the teeth of children of mothers classified as high Zn consumers (n = 10) than in children of mothers classified as low Zn consumers (n = 8). The S-FFQ was validated internally as adequately accurate to measure zinc intake retrospectively during pregnancy and post-partum (∼7 years prior) by virtue of the correlation with measurements of zinc in deciduous teeth. The ratio of Zn/Sr in deciduous teeth appears to be a biomarker of exposure to zinc nutrition during early development and offers promise for use as a record of prior exposure along a timeline for research studies and, potentially, to identify individuals at heightened risk of detrimental impacts of poor early life zinc nutrition on health in later life and to implement preventative interventions.

Dendrite-Free Engineering toward Efficient Zinc Storage: Recent Progress and Future Perspectives.

Zinc-based energy storage has lately gained popularity due to natural abundance, operational safety, high energy density. Unfortunately, dendrite growth is a common and intractable issue faced in existing zinc-ion batteries to shorten cycle lifespan/stability. This review summarizes recent progress in assembly component (e. g., anode, electrolyte, separator) engineering for dendrite-free zinc-ion batteries. First, diversiform strategies of Zn surface modification and Zn host design are presented to shield the fundamental adverse effect aroused by uneven zinc deposition on the anode. Then, subtle deployments of electrolyte constituents are illustrated to optimize the Zn2+ solvation structure for ultimate dendrite control and Coulombic efficiency elevation in aqueous systems and beyond (e. g., eutectic electrolytes). Furthermore, rational manipulation of advanced separators and the upgrade of zinc metal-free Zn2+ -storage devices are briefly discussed to explore the dendrite-free and high-level Zn2+ -storage. Finally, challenges and perspectives are proposed to offer research inspirations toward safe, high-efficiency and long-lifespan zinc storage.

Hydrophobic Organic–Inorganic Hybrid Surface Modification-Induced Uniform Zinc Deposition and Prohibited Side Reactions toward a Ultra-stable Zinc Anode

Zinc-ion batteries (ZIBs) are ideal candidates for new ideal energy devices due to large theoretical capacity, scale production, and handleability. However, the problem of dendrite growth and side reactions originated from an uneven Zn plating/stripping process, and the direct contact of the Zn metal with the electrolyte reduces the cycle stability and lifetime of ZIBs. In this research, organic hydrophobic polyvinylidene fluoride and uniformly distributed nano-silicon particles (PVDF-Si) was constructed as a functional protection layer to promote the cycle stability of the Zn anode. Silicon nanoparticles can uniformly distribute electric field and Zn2+ flux on the Zn anode surface which can guide the uniform Zn deposition and avoid dendrite growth. The hydrophobic PVDF can reduce the free water content on the Zn anode surface, which significantly inhibits side reactions. With the coordinate inhibition of the PVDF-Si modification layer, the PVDF-Si@Zn anode displays dendrite-free Zn plating/stripping with a low overpotential of 38 mV after 3080 h in PVDF-Si@Zn||PVDF-Si@Zn batteries. Meanwhile, the PVDF-Si@Zn||V2O5 battery also achieved a high stability with a 79.38% capacity retention and nearly 100% of the coulomb efficiency after 500 cycles. The hydrophobic polymer–nanomaterial interface modification provides a new strategy for the protection of the Zn anode.

Концентрация меди и цинка в органах березы повислой (Betula pendula roth.) и пырея ползучего (Elytrigia repens L.) в условиях их естественного произрастания

The influence of man-made pollution on the accumulation of copper and zinc in the soil and plants of the forest park zones of Yelets is studied on the example of the woody and plant objects of the natural environment prevailing in them-hanging birch (Betula pendula Roth) and creeping wheatgrass (Elytrigia repens). As a result of the conducted studies, the features of the deposition of copper and zinc in plant organs were revealed, and the total accumulation of the studied elements in the soil under green plantations was estimated. Keywords: PARK, HANGING BIRCH, CREEPING WHEATGRASS, COPPER, ZINC, LEAVES, ROOTS, SOIL

Retaining the reversible capacity by Lorentz forces for enhanced cyclability of aqueous zinc-bromide batteries using internal magnets

Despite the high safety and low-cost of aqueous zinc-bromide batteries (AZBBs), their widespread application in portable and stationary energy storage systems is hindered by deleterious zinc-dendrite growth and cross-diffusion of tribromide (Br3−) ions. Here, we, for the first time demonstrate the effect of Lorentz force using internal magnets to retain the reversible capacity for mitigated cross-diffusion of Br3−, dendrite-free zinc deposition, enhanced cycle life, improved voltage efficiency and energy efficiency of AZBBs via magnetohydrodynamics. Of the magnetic field strengths investigated (0 – 70 ± 1 mT), cells incorporating 50 ± 1 mT achieved a high energy efficiency of 88.8 % (coulombic efficiency of 99.3 %) with a small decay of 7.6 % after 550 cycles. Interestingly, batteries with internal magnets resist self-discharge and exhibit an improved rate-capability (up to 3C rate) compared to batteries without magnets. Scanning electron microscopy images and energy dispersive X-ray analysis of zinc electrodes (after 100 cycles) of AZBBs containing 50 ± 1 mT revealed the suppressed amount of cross-diffused bromine and dendrite-free zinc deposits without any passivation layer. Operando UV–vis spectroscopic data of membrane electrode assembly (MEA) of AZBB confirmed the retention of Br3− ions at 50 ± 1 mT, whereas the MEA without magnets suffered severe leaching of Br3− ions into the electrolyte.

Hexamethylenetetramine additive with zincophilic head and hydrophobic tail for realizing ultra-stable Zn anode

Aqueous zinc batteries are regarded as one of the promising next-generation energy storage batteries due to their high safety and low cost, however, one of the most important problems limiting their commercialization is the cyclic stability of the zinc anode. Therefore, in this work, we first employed hexamethylenetetramine (HMT) as the electrolyte additive to in-situ construct a Zn-HMT complex film to stabilize the zinc anode. After adding the HMT, its zincophilic head will be prior to adsorbing on the zinc foil to form Zn-HMT complex film and then introduce uniform zinc deposition, and simultaneously the formed Zn-HMT complex with hydrophobic alkyl tail will repel the H2O from combining with Zn2+ to form Zn4SO4(OH)6·nH2O by-product as well as the hydrogen evolution reaction (HER). As a result, the HMT-based electrolyte promotes ultra-stable zinc anode cycling for as long as 2000 h with extremely high average Coulombic efficiency (99.51 %). When applied in the Zn-V2O5 full cell, it also demonstrates outstanding electrochemical performances with a reversible capacity as high as 197.8 mAh/g after 500 cycles. This work provides a simple and effective method for the implementation of high-safety and high-stable aqueous zinc-ion batteries.

The Effects of Phytase and Non-Starch Polysaccharide-Hydrolyzing Enzymes on Trace Element Deposition, Intestinal Morphology, and Cecal Microbiota of Growing-Finishing Pigs.

This study investigated the effects of supplementing phytase and non-starch polysaccharide-degrading enzymes (NSPases) to corn-soybean meal-based diet on the growth performance, trace element deposition, and intestinal health of growing-finishing pigs. Fifty pigs were randomly assigned into the control (basal diet), phytase (basal diet + 100 g/t of phytase), β-mannanase (basal diet + 40 g/t of β-mannanase), β-glucanase (basal diet + 100 g/t of β-glucanase), and xylanase (basal diet + 100 g/t of xylanase) groups. The results show that the supplementation of phytase and NSPases had no impacts (p > 0.05) on the growth performance of pigs. Compared with the control group, pigs fed with xylanase had higher (p < 0.05) Zn concentrations in the ileum and muscle and those fed with phytase had higher (p < 0.05) Zn concentrations in the ileum. Phytase and xylanase supplementation decreased (p < 0.05) fecal Zn concentrations in pigs compared with the control group (p < 0.05). In addition, phytase, β-mannanase, β-glucanase, and xylanase supplementation up-regulated (p < 0.05) the FPN1 expression, whereas xylanase up-regulated (p < 0.05) the Znt1 expression in the duodenum of pigs compared with the control group. Moreover, phytase, β-glucanase, and xylanase supplementation up-regulated (p < 0.05) the jejunal Znt1 expression compared with the control group. The intestinal morphology results show that the phytase, β-mannanase, and xylanase groups had increased villus heights (VHs), an increased villus height-crypt depth ratio (VH:CD), and decreased crypt depths (CDs) in the duodenum, whereas phytase, β-mannanase, β-glucanase, and xylanase groups had decreased VH and VH:CD, and increased CD in the jejunum compared with the control group (p < 0.05). Pigs fed with exogenous enzymes had decreased bacterial diversity in the cecum. The dietary supplementation of NSPases increased the relative abundance of Firmicutes and decreased spirochaetes (p < 0.05). Compared with the control group, dietary NSPase treatment decreased (p < 0.05) the opportunistic pathogens, such as Treponema_2 and Eubacterium_ruminantium. Moreover, the relative abundances of Lachnospiraceae_XPB1014 and Lachnospiraceae were enriched in the β-glucanase and β-mannanase groups (p < 0.05), respectively. In conclusion, phytase and xylanase supplementation may promote zinc deposition in pigs. Additionally, the supplementation of NSPases may improve the gut health of pigs by modulating the intestinal morphology and microbiota.

Safety and efficacy of a feed additive consisting of a zinc(II)-betaine complex for all animal species (Biochem Zusatzstoffe Handels- und Produktionsges. mbH).

Following a request from the European Commission, EFSA was asked to deliver a scientific opinion on the safety and efficacy of a zinc(II)-betaine complex as nutritional additive for all animal species. The EFSA Panelon Additives and Products or Substances used in Animal Feed (FEEDAP) concluded that the additive is safe for chickens for fattening. This conclusion could be extrapolated to all animal species and categories provided that the maximum authorised levels in the EU for total zinc in feed are not exceeded. The FEEDAP Panelconcluded that the use of the zinc(II)-betaine complex in animal nutrition is of no concern for consumer safety provided that the maximum authorised total zinc levels in feed are respected. The additive is considered to be a skin and respiratory sensitiser due to the presence of nickel; it is irritant to the eyes, but not to the skin. The use of the additive in animal nutrition for terrestrial animals and land-based aquaculture at the proposed use levels is considered safe for terrestrial and aquatic ecosystems. The available data do not allow the conclusion to be made on the safety of the additive for the marine sediment when it is used in sea cages. Based on the deposition of zinc in edible tissues/organs in chickens for fattening, the FEEDAP Panelconcluded that the additive is a source of bioavailable zinc, comparable to the standard inorganic zinc source, and therefore, the additive is efficacious in meeting the birds zinc requirements. This conclusion can be extrapolated to all animal species and categories.

Mineralogical and geochemical study of hydrothermal dolomite from the Daliang zinc deposit in Guizhou, Southwest China: new evidence for the genesis

Mineralogical and geochemical study of hydrothermal dolomite from the Daliang zinc deposit in Guizhou, Southwest China: new evidence for the genesis

Controllable CF4 Plasma In Situ Modification Strategy Enables Durable Zinc Metal Anode.

Zn metal with high specific capacity and low redox potential is deemed to be an ideal anode material for aqueous zinc-ion batteries (ZIBs). However, the serious dendrite problems induced by the uneven deposition of zinc shorten the service life and hinder the development of ZIBs. According to the nucleation and growth mechanism, the charge distribution at the anode interface is the critical factor affecting the deposition morphology. Herein, CF4 plasma technology is applied for the first time to in situ modification of the Zn anode, and then, the uniform nanoscale ZnF2 particles are formed. Due to the excellent ionic conductivity and poor electronic conductivity of ZnF2, the ion and electron distribution at the anode interface is orderly regulated, thus guiding uniform and reversible deposition behavior and restraining the dendrite growth. As a result, the Zn@ZnF2-5 anode exhibits low nucleation overpotential (16 mV), long cycle life (2500 h at 1 mA cm-2 and 1 mA h cm-2), and excellent resistance to high current density (20 mA cm-2) and high discharge depth (16%). Meanwhile, the Zn@ZnF2-5|I2@AC full battery shows remarkable cycle stability (1000 cycles) with ∼10% discharge depth of the anode. The novel and practical CF4 plasma in situ modification strategy provides a new idea for the interface modification of zinc anode.

Stabilizing zinc deposition through solvation sheath regulation and preferential adsorption by electrolyte additive of lithium difluoro(oxalato)borate

Aqueous zinc ion batteries have become one of the most promising energy storage technologies due to intrinsic safety, low price, and high capacity. However, zinc metal anode suffers from severe dendrites and harmful side reactions in aqueous electrolytes, resulting in low coulombic efficiency and short life span. Although organic electrolyte additives have proven to be very effective in improving zinc plating/stripping reversibility, they would not only reduce the ionic conductivity of electrolytes but also bring about toxic and flammable issues. Herein, an inorganic lithium salt, i.e., lithium difluoro(oxalate)borate (LiODFB), is utilized and the following benefits can be realized. Firstly, ODFB− ions can be preferentially adsorbed at the surface of Zn metal to restraint “tip-effect”, resist corrosion, and mitigate side reactions. Secondly, the water activity can be significantly weakened through intense interaction between ODFB− and H2O. Thirdly, the desolvation process can be promoted. Hence, the LiODFB additive with a very low concentration of 30 mM endows Zn//Zn cell with long lifespan (1000 h at 4 mAh cm−2) and enables Zn//Cu cell to deliver very high coulombic efficiency (average value of 99.74 % during 1500 cycles). Moreover, the rate and cycling performances of Zn//MnO2 and Zn//V2O5 full batteries can be dramatically improved by the LiODFB additive. This work extends our knowledge of interfacial engineering for aqueous batteries.

Enhancing electrochemical performance and stabilizing zinc anode in mild acidic electrolyte using combined additive

Rechargeable zinc-based batteries having aqueous electrolytes are renowned as promising alternatives for large scale energy storage systems (ESSs). However, in mild acidic electrolytes, zinc anodes pose several issues that have yet to be overcome. For tackling the major difficulties of zinc anodes, electrolyte engineering is the most practical and cost-effective strategy. Notwithstanding the broad variety of mechanisms associated with different electrolyte additives, the function of a single additive is straightforward. Finding combined additives with broader functionalities and greater efficacy is crucial. In this work, the combination of ionic liquid (IL) 1-butyl-1-methylpyrrolidinium dicyanamide ([BMPY][DCN]) and ethylene glycol (EG) as additives in an aqueous electrolyte 3 M ZnSO4 proves to be an effective strategy for simultaneously enhancing both zinc dissolution and deposition. IL significantly enhances zinc (Zn) dissolution and deposition while EG plays an important role in suppressing hydrogen evolution reaction (HER)and corrosion. Thus, 13.50 % improvement in capacity is achieved by the mixed additive EG + IL/ZnSO4 compared with the 3 M ZnSO4 electrolyte. In the Zn//Zn symmetrical system at 2 mA cm−2, the mixed additive greatly augments the cyclability of zinc, reaching over 400 h while maintaining excellent coulombic efficiency (CE). In-situ XAS and FT-EXAFS analyses confirm the high activities of both zinc oxidation/reduction in the mixed additive electrolyte. Results demonstrate that EG + IL/ZnSO4 can be applied to increase the cyclability of aqueous zinc-based batteries while sustaining high performance.

НОВЫЕ ДАННЫЕ О ГЕНЕЗИСЕ ГЮМУШЛУГСКОГО СВИНЦОВО-ЦИНКОВОГО МЕСТОРОЖДЕНИЯ НАХЧЫВАНСКОЙ АР АЗЕРБАЙДЖАНА

As a result of long-term geological and sedimentological investigation of the Gyumushlug stratiform lead and zinc deposit in the carbonate strata of the Middle Devonian and study of the geological structure of the Sharur massive of the territory and adjacent areas, it became possible to develop its sedimentary ore genesis. The source of metals for the formation of the deposit was not hypothetical hydrothermal solutions, as was confirmed by previous researchers, but polymetallic deposits and manifestations developed on the Baikal basement of the Zangezur microcontinent. The formation of ore deposits of the Gyumushlug tested a difficult and long path, amounting to several hundred million years. Three stages of ore formation were established: sedimento-logical-diagenetic; catagenetic with the participation of hot highly mineralized chloride-sulfate-calcium-magnesium groundwater; tectonic, which manifestate on the border of the Late Triassic and Early Jurassic as a result of the activation of the Early Alpine phase of tec-togenesis...

Adjusting zinc deposition behaviors by a modified separator to acquire zinc anodes for aqueous rechargeable zinc-ion batteries.

Aqueous rechargeable zinc ion batteries (ARZIBs) are ideal for massive and longstanding energy storage applications because of their excellent security and low operation cost. Nevertheless, ARZIBs are subject to the severe corrosion reaction of zinc metal anodes that is derived from the thermodynamic unsteadiness of the zinc anodes in aqueous solution, as well as zinc dendrite growth originating from uncontrolled zinc deposition. Herein, we created a separator by coating a thin piece of polypropylene (PP) with a compound consisting of zinc trifluoromethanesulfonate [Zn(OTf)2] and poly(vinylidene fluoride-hexafluoropropylene (PVDF-HFP). Consequently, the severe corrosion reaction of the zinc metal anodes and the profuse formation of zinc dendrites were effectively mitigated by the novel PP separator, which prolonged the lifetime of the zinc metal anodes. When a zinc metal plating layer was used with preferential (002) crystallographic orientation, the cyclic performance over 1100 h of the symmetrical Zn∥Zn battery based on the novel separator was steady. Additionally, the Zn∥MnO2 batteries exhibited an impressive specific capacity and competitive long durability of 75.5% over 500 cycles at a current density of 0.1 A g-1. With this work, we intend to set the standard for designing novel separators in the construction of advanced zinc anodes for high-performance ARZIBs.

The content of copper and zinc in the natural environment components of the park areas

The influence of man-made pollution on the accumulation of copper and zinc in the soil and plants of the forest park zones of Yelets was studied on the example of the woody–plant natural environment components prevailing in them hanging birch (Betula pendula Roth) and creeping wheatgrass (Elytrigia repens). As a result of the conducted studies, the features of the deposition of copper and zinc in the plant organs were revealed, and the total accumulation of the studied elements in the soil under green plantations was estimated.

Regulating zinc deposition behaviors by using a functional PANI modification layer on a separator for high performance aqueous zinc-ion batteries

GF/PANI separators were prepared byin situpolymerization of aniline monomers on GF. A PANI layer homogenizes the electric field distribution and induces the uniform deposition of zinc, thereby improving the electrochemical performance of batteries.

Reliable lateral Zn deposition along (002) plane by oxidized PAN separator for zinc-ion batteries.

Aqueous zinc ion batteries (AZIBs) are the promising candidate for energy storage where safety and low cost are the major concerns. However, the uneven and random electrodeposition of Zn has become a serious impediment to the deep recharging of AZIBs. Conventional modifications on zinc substrate can promote homogenous zinc deposition initially, but not sustainably. Here, an oxidized polyacrylonitrile (OPAN) membrane with a conjugated planar structure is proposed as a zinc ion battery separator. This separator can continuously regulate the growth of Zn with (002) texture to inhibit dendrites. In addition, the separator has a fast Zn2+ ion transfer, which can spontaneously repel SO42- and relieve side reactions. As a result, the Zn-symmetric batteries show cycle lifetime of more than 1300 hours at 1 mA cm-2 and 1 mA h cm-2, and kept stable for more than 160 hours even at 65% high discharge of depth (DOD). The MnO2//Zn full celled assembled with an OPAN separator had very little decay for 5000 cycles at 2 A g-1. This work provides a new method for realizing the continuous and uniform deposition of Zn metals, which also provides a new route for batteries with metallic anodes.

Performance improvement of aqueous zinc batteries by zinc oxide and Ketjen black co-modified glass fiber separators.

Rechargeable aqueous zinc-based batteries (AZBs) are intriguing candidates for next-generation energy storage batteries. However, the dendrites generated plagued their development during charging. To inhibit the dendrite generation, a novel modification method based on the separators was proposed in this study. The separators were co-modified by spraying sonicated Ketjen black (KB) and zinc oxide nanoparticles (ZnO) uniformly. The highly conductive KB homogenizes the anode interface's electric field. The deposited ions are deposited on ZnO preferentially rather than on the anode electrode, and the deposited particles can be refined. The ZnO in the uniform KB conductive network can provide sites for zinc deposition, and the by-products of the zinc anode electrode reduced. The Zn-symmetric cell with the modified separator (Zn//ZnO-KB//Zn) can cycle for 2218 h at 1 mA cm-2 stably (the unmodified Zn-symmetric cell (Zn//Zn) only can cycle for 206 h). With the modified separator, the impedance and polarization of Zn//MnO2 reduced, and the cell can charge/discharge 995 times at 0.3 A g-1. In conclusion, the electrochemical performance of AZBs can be improved effectively after separator modification by the synergistic effect of ZnO and KB.

Enabling uniform zinc deposition by zwitterion additives in aqueous zinc metal anodes

This article proposes a new electrolyte engineering strategy with “zwitterion” molecules, which reduce side reactions by adsorbing onto the zinc surface. The 6-aminohexanoic acid enables uniform zinc deposition and reduces zinc dendrite growth.