Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Achieving a highly robust zinc(Zn)metal anode is extremely important for improving the performance of aqueous Zn-ion batteries(AZIBs)for advancing“carbon neutrality”society,which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction,corrosion,and passivation,etc.Herein,an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups(COF-S-F)is developed on Zn metal(Zn@COF-S-F)as the artificial solid electrolyte interface(SEI).Sulfonic acid group(-SO_(3)H)in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions,and the three-dimensional channel with fluoride group(-F)can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects,endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions.Consequently,Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage(50.5 m V)at the current density of 1.5 m A cm^(-2).Zn@COF-S-F|Mn O_(2)cell delivers the discharge specific capacity of 206.8 m Ah g^(-1)at the current density of 1.2 A g^(-1)after 800 cycles with high-capacity retention(87.9%).Enlightening,building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

Stabilization of flake Zn powder anodes via designing functional additives in electrolytes for aqueous Zn ion batteries

Zn powder anodes have attracted much attention in aqueous Zn ion battery applications due to advantages such as low cost and processability.However,the high-activity Zn powder anode faces problems such as side reactions,hydrogen evolution,and dendrites,which limit the cycling stability of the cell.In this work,the high activity of Zn powder is weakened by introducing low-cost erythritol as a functional additive in the ZnSO_(4) electrolyte to improve the cycle life of the cell.Both theoretical calculations and empirical evidence demonstrate that the incorporation of erythritol alters the coordination sphere of Zn^(2+)and modifies the local molecular architecture of the electrolyte.This modification serves to diminish the reactivity of water molecules,thereby efficaciously suppressing dendrite formation and deleterious ancillary reactions on the zinc powder anode surfaces.Concurrently,erythritol functions as an interfacial cationic captor,enhancing reaction dynamics and facilitating the development of a favorable protective layer throughout the zinc plating/stripping process.Consequently,the symmetric cell paired with an erythritol-containing electrolyte manifests stable cycling performance for an extended duration of 850 h at a current density of 0.288 mA cm^(-2)and areal capacity of 0.144 mAh cm^(-2).Notably,it maintains a cycling life of 400 h even under intensified conditions (2.88 mA cm^(-2)/1.44 mA h cm^(-2)).Furthermore,the constructed Na_(2)V_(6)O_(16)·3H_(2)O full cell illustrated remarkable capacity retention of 155.8 mA h g^(-1)following 800 cycles at a high rate of 5 A g^(-1).

Removal of Zn (II) from Aqueous Solution onto Kaolin by Batch Design

The Algerian kaolin clay was investigated to remove Zn(II) heavy metal ion from aqueous solution. The effect of contact time, initial metal ion concentration, pH and temperature was experimentally studied in batch mode to evaluate the adsorption capacity, kinetic, thermodynamic and equilibrium. The extent of zinc adsorption increased with increasing initial concentration of adsorbat, pH and temperature. The linear Langmuir and Freundlich models were applied to describe equilibrium isotherms and both models fitted well. The monolayer adsorption capacity for Zn(II) ions was 12.23 mg per g of kaolin clay at pH 6.1 and 25°C. Dubinin-Radushkevich (D-R) isotherm model was also applied to the equilibrium data. Thermodynamic parameters showed that the adsorption of Zn(II) onto kaolin clay was spontaneous and endothermic process in nature. Furthermore, the Lagergren-first-order and pseudo-second-order models were used to describe the kinetic data. The experimental data fitted well the pseudo-second-order kinetic. As a result, the kaolin clay may be used for removal of zinc from aqueous media.

Ionic buffer layer design for stabilizing Zn electrodes in aqueous Zn-based batteries

Aqueous Zn-based batteries(AZBs)are hindered by issues associated with the Zn electrodeposition process(ZEDP)on electrode surfaces,including passivation,dendrite formation,and hydrogen evolution.One of the important reasons is the drastic fluctuation in the concentration of Zn^(2+)ions on the electrode surface during the charging and discharging process.In this work,an electrolyte with Zn^(2+)ion buffer layer(EZIBL)is proposed to regulate the ZEDP.First,numerical simulations and corresponding experiments are conducted to assess the impact of different thicknesses of the Zn^(2+)ion buffer layer(ZIBL)on the variation in Zn^(2+)ion concentration,from which the optimal thickness of the ZIBL is determined.Then,the regulation role of EZIBL in the cycling process is demonstrated by a Zn-Cu half cell.Further,combined with the potential profile of the symmetric cell and the experimental phenomena,the regulation role of EZIBL in ZEDP is systematically explained at the mechanistic level through the analysis of key parameters.Finally,a full battery composed of Zn-LiMn2O4 is assembled to evaluate the practical applicability of the EZIBL in real battery cycles,which shows great enhancement in capacity retention and coulombic efficiency.This work proposes the design of the EZIBL used to regulate the ZEDP and provides a simple,low-cost regulation method for the development of high-performance AZBs.

Demineralised Lignite Fly Ash for the Removal of Zn(II) Ions from Aqueous Solution

Among the various possibilities of limiting the disposal of fly ashes (lignite), their reutilization as adsorbent materials is worthy of consideration. To this end, proper ashes beneficiation techniques can be put into practice. The adsorption of toxic compounds from industrial wastewater is an effective method for both treating these effluents and recycling lignite fly ash. The aim of this paper is to give a contribution for understanding the relationships among beneficiation treatments, adsorbent properties and adsorption mechanism and efficiency. In this context, the lignite fly ash was demineralised using concentrated HCl and HF (FA-DEM) and was used as adsorbent for Zn(II) ions from aqueous solutions. Batch experiments were carried out under various adsorbent dosages, pH, contact time and different metal ion concentrations. For FA-DEM, the 57.7% removal of Zn(II) ion was achieved under the optimum conditions of adsorbent dosages of 4 g/L, pH at 6, temperature at 303 K and the contact time of 1.15 h. The adsorption of Zn(II) ions onto FA-DEM followed the pseudo second order kinetics. The Langmuir isotherm model best represented the equilibrium data.

Genotypic Variations in Phenolic, Flavonoids and Their Antioxidant Activities in Maize Plants Treated with Zn (II) HEDTA Grown in Salinized Media

Zinc (Zn (II) HEDTA) was used to determine their effect on salt-induced damages in maize plants. The aim of this study was to investigate the antioxidant capacity and the levels of enhanced total phenolic (TPC), total flavonoid (TFC) contents and their antioxidant activity in leaves of two maize cultivars Single cross 10 (SC10) and Single cross 162 (SC162) grown in two levels of salinity 0.00 and 100 mmol in response to 20 μmol Zn (II) HEDTA foliar spray treatments. Significant differences (P ≤ 0.05) in amounts of TPC ranged from (2.55 to 4.62 mg/gdw as Gallic) in Single cross 10 (SC10) and from (2.53 to 4.38 mg/gdw as Gallic) in Single cross 162 (SC162), TFC (ranged 1.53 to 2.41 mg/gdw as qurestien) in Single cross 10 (SC10) and from (1.28 to 2.41 mg/gdw as qurestien) in Single cross 162 (SC162) among all treated plants were observed. The levels of their compounds increase related to foliar spraying of Zn (II) HEDTA. A significant positive correlation between TPC, TFC and DPPH scavenging activity and iron chelating activity was observed which shows that phenolic compounds were involved in the mechanism of salt tolerance of the two cultivars by showing enhanced antioxidant activity which resulted in reduced membrane damage and hence improved growth. According to the results obtained, the adverse effects of salt stress on maize plants can partly be alleviated with application of Zn (II)-HEDTA chelates. It is concluded that the application of Zn (II) HEDTA to maize plants grown in salt conditions leads to the increase of antioxidant compounds and maize tolerance.

Some Hybrid Systems of Chiral Schiff Base Zn(II) Complexes and Photochromic Spiropyrans for Environmental Ion Sensing

This is a review article including our recent results and some previous photo functional hybrid system having potential applications for environmental ion sensing. We have prepared several new and known chiral Schiff base Zn(II) complexes and measured (and also calculated) absorption and fluorescence spectra for sole complexes. After assembling hybrid systems with 1,3,3-trime- thylindolino-6’-nitrobenzopyrylospiran (SP) in methanol solutions, we measured spectral changes before and after alternate irradiation of UV and visible light. Intensity of fluorescence spectra for pale yellow Zn(II) complexes (λem = 450 nm, λex = 270 and 360 nm) was quenched by colorless SP (λem = 533 nm, λex = 612 nm). After UV light irradiation to form purple merocyanine (MC), photoisomerization resulted in changes of the intensity of absorption spectra as well as fluorescence spectra. Thus the hybrid systems could successfully act as molecular logic circuit by input (excitation by light) and output (intensity of fluorescence peaks). Moreover, we investigated concentration dependence of doped Zn(II) and Cu(II) ions to confirm quenching of intensity of fluorescence peaks by Zn(II) and Cu(II) MC complexes for metal ion sensing in solutions.

α-Glucosidase Inhibition by New Schiff Base Complexes of Zn(II)

There are many reports that divalent alkaline earth, first-row transition metals, and Zn(II) ions have α-glucosidase inhibitory effects. Cu(II) and Zn(II) ions, in particular, have strong α-glucosidase inhibitory effects. Several Schiff bases also display α-glucosidase inhibitory effects. In this study, we focused on safe and highly effective complexes including Zn(II) ion. We prepared and characterized the Zn(II) complexes with four different Schiff bases (N-salicylidene-β-alanine (N-sβ), N-N’-bis (salicylidene) ethylenediamine (N-bsE), N, N’-bis (salicylidene)-phenylenediamine (N-bsP), and 1-[(2-dimethylaminoethylimino) methyl]naphtholate (DMN)) and investigated their α-glucosidase inhibitory effects in vitro, using α-glycosidases from Saccharomyces sp. and rat small intestine, and in vivo, using a sucrose tolerance test. The Zn(II) complexes with DMN showed the highest in vitro and in vivo α-glucosidase inhibitory effects in this study.

改性累托石对水溶液中Zn(II)吸附作用的研究

采用天然累托石粘土,经十二烷基二甲基苄基氯化胺(1227)有机改性后对水溶液中Zn(II)进行了吸附研究。考察了pH值、吸附剂用量、吸附平衡时间等因素对Zn(II)吸附效果的影响。结果表明,吸附最佳条件是:pH为8,吸附剂用量8g/L,吸附平衡时间40min。从吸附等量线和吸附等温线得知,该吸附满足Freundlich吸附机理,在常温下可自发进行,温度升高对吸附不利。

Zn(II)-NH_4·HCO_3-NH_3-H_2O体系雾化干燥机理研究

以Zn(II)-NH4·HCO3-NH3-H2O溶液为原料,通过雾化干燥、煅烧获得超细氧化锌。试验表明,雾化溶液中游离氨浓度对干燥过程的固体形貌影响较大,随着溶液中游离氨浓度的降低,干燥产物由针状颗粒按照针状颗粒与球形颗粒混合物、球形颗粒顺序演变。对干燥机理进行分析,干燥过程按照氨与水的挥发、前躯体析出、水分蒸发及前躯体分解四个环节依次进行。NH3分子在干燥过程中,先后起Zn2+配体、传递Zn2+及控制Zn的析出方向等作用。液滴与热空气接触后,雾滴与热空气基本保持同步运动,干燥产品基本为碱式碳酸锌。

Zn^(2+)促进TiO_(2)煅烧过程晶型转变的掺杂机制研究

硫酸法钛白生产工艺中,高温煅烧是生成稳定晶型的重要阶段。锌盐处理剂的加入可以降低锐钛晶型向金红石转变的温度,然而其促进作用的内在机理目前尚不明确。以钛白工艺中间物料二洗偏钛酸为原料,硫酸锌为盐处理剂,在马弗炉里高温煅烧至600~900℃。利用XRD、HRTEM和XPS等分析手段研究了Zn^(2+)在煅烧过程中对TiO_(2)晶型转变的影响和掺杂机制。结果表明,不同的Zn^(2+)初始浓度以及煅烧温度对Zn^(2+)在TiO_(2)晶型转变的作用机制和Zn^(2+)的存在状态具有显著影响。当Zn^(2+)质量分数小于1%时,Zn^(2+)以取代模式掺入TiO_(2)晶格中,置换Ti^(4+),使晶胞参数变大并形成氧空位;且随着Zn^(2+)浓度的增加,过量的Zn^(2+)在TiO_(2)表面形成新物种ZnTiO_(3)。取代掺杂和ZnTiO_(3)通过不同的作用机理都可以降低相变温度,促进锐钛向金红石的相转变。

Highly Efficient and Selective Removal of Pb（II） ions by Sulfur-Containing Calcium Phosphate Nanoparticles

A facile one-step co-precipitation method was demonstrated to fabricate amorphous sulfurcontaining calcium phosphate （SCP） nanoparticles, in which the sulfur group was in-situ introduced into calcium phosphate. The resulting SCP exhibited a noticeable enhanced performance for Pb（II） removal in comparison with hydroxyapatite （HAP）, being capable of easily reducing 20 ppm of Pb（II） to below the acceptable standard for drinking water within less than 10 min. Remarkably, the saturated removal capacities of Pb（II） on SCP were as high as 1720.57 mg/g calculated by the Langmuir isotherm model, exceeding largely that of the previously reported absorbents. Significantly, SCP displayed highly selective removal ability toward Pb（II） ions in the presence of the competing metal ions （Ni（II）, Co（II）, Zn（II）, and Cd（II））. Further investigations indicated that such ultra-high removal efficiency and preferable affinity of Pb（II） ions on SCP may be reasonably ascribed to the formation of rodlike hydroxypyromorphite crystals on the surface of SCP via dissolution-precipitation and ion exchange reactions, accompanied by the presence of lead sulfide precipitates. High removal efficiency, fast removal kinetics and excellent selectivity toward Pb（II） made the obtained SCP material an ideal candidate for Pb（II） ions decontamination in practical application.

Regulating Zn Deposition via an Artificial Solid–Electrolyte Interface with Aligned Dipoles for Long Life Zn Anode

Aqueous zinc ion batteries show prospects for next-generation renewable energy storage devices.However,the practical applications have been limited by the issues derived from Zn anode.As one of serious problems,Zn dendrite growth caused from the uncontrollable Zn deposition is unfavorable.Herein,with the aim to regulate Zn deposition,an artificial solid–electrolyte interface is subtly engineered with a perovskite type material,BaTiO3,which can be polarized,and its polarization could be switched under the external electric field.Resulting from the aligned dipole in BaTiO3 layer,zinc ions could move in order during cycling process.Regulated Zn migration at the anode/electrolyte interface contributes to the even Zn stripping/plating and confined Zn dendrite growth.As a result,the reversible Zn plating/stripping processes for over 2000 h have been achieved at 1 mA cm^(−2) with capacity of 1 mAh cm−2.Furthermore,this anode endowing the electric dipoles shows enhanced cycling stability for aqueous Zn-MnO2 batteries.The battery can deliver nearly 100%Coulombic efficiency at 2 Ag^(−1) after 300 cycles.

Wet spinning of fiber-shaped flexible Zn-ion batteries toward wearable energy storage

High-performance flexible one-dimensional(1D)electrochemical energy storage devices are crucial for the applications of wearable electronics.Although much progress on various 1D energy storage devices has been made,challenges involving fabrication cost,scalability,and efficiency remain.Herein,a highperformance flexible all-fiber zinc-ion battery(ZIB)is fabricated using a low-cost,scalable,and efficient continuous wet-spinning method.Viscous composite inks containing cellulose nanofibers/carbon nanotubes(CNFs/CNTs)binary composite network and either manganese dioxide nanowires(MnO_(2) NWs)or commercial Zn powders are utilized to spinning fiber cathodes and anodes,respectively.MnO_(2) NWs and Zn powders are uniformly dispersed in the interpenetrated CNFs/CNTs fibrous network,leading to homogenous composite inks with an ideal shear-thinning property.The obtained fiber electrodes demonstrate favorable uniformity and flexibility.Benefiting from the well-designed electrodes,the assembled flexible fiber-shaped ZIB delivers a high specific capacity of 281.5 m Ah g^(-1) at 0.25 A g^(-1) and displays excellent cycling stability over 400 cycles.Moreover,the wet-spun fiber-shaped ZIBs achieve ultrahigh gravimetric and volumetric energy densities of 47.3 Wh kg^(-1) and 131.3 m Wh cm^(-3),respectively,based on both cathode and anode and maintain favorable stability even after 4000 bending cycles.This work offers a new concept design of 1D flexible ZIBs that can be potentially incorporated into commercial textiles for wearable and portable electronics.

Stable and dendrite-free Zn anode with artificial desolvation interface layer toward high-performance Zn-ion capacitor

Aqueous Zn-based energy storage devices possess tremendous advantages, such as low cost, high safety,and competitive energy density, due to employing a Zn metal anode and aqueous electrolyte. However,the cycling stability and rate ability of a Zn anode are hindered by Zn dendrite growth and sluggish ion transfer in the electrode/electrolyte interface. Herein, the interfacial properties of Zn anodes are improved through the introduction of a silver(Ag) protective layer, which facilitates uniform Zn deposition and regulates Zn ion transport. As a result, Ag-coated Zn anodes display stable cycling performance(600 h at 1 m A cm^(-2)) and low overpotential(150 mV at 50 mA cm^(-2)after 2000 cycles). The Ag layer in situ electrochemically converts into an AgZn_(3) layer and promotes Zn ion desolvation and threedimensional diffusion processes. Moreover, a Zn-ion capacitor assembled with an Ag-coated Zn anode and active carbon cathode shows a capable cycling lifespan and rate performance. This study provides a feasible strategy for constructing a stabilized and dendrite-free Zn anode for the development of high-performance Zn-based energy storage devices.

FeHCF/Zn电池的电化学性能研究

水性可充电锌离子电池因其低成本和安全性而备受关注,然而,水性锌离子电池的正极材料极易劣化,限制了电池稳定的能量输出。在水系锌离子电池中,正极材料尤其是普鲁士蓝类化合物(FeHCF)因其三维开放结构、高工作电压、简单的合成方法等优点而成为竞争力非常强的候选正极材料。本工作采用沉淀法制备了普鲁士蓝类似物FeHCF,测试它的物化性能,组装扣式全电池,进行电化学测试,结果表明,水电解质在1C时可提供80 m Ah/g的比容量,并显示出良好的循环稳定性(在1C下循环50次后容量保持率为90%),这种普鲁士蓝基水系锌离子电池的成本低、能量密度高、循环寿命长,在中小规模储能应用中大有可为。

Bi_(2)S_(3) for Aqueous Zn Ion Battery with Enhanced Cycle Stability

Aqueous Zn ion batteries(ZIBs)are promising in energy storage due to the low cost,high safety,and material abundance.The development of metal oxides as the cathode for ZIBs is limited by the strong electrostatic forces between O2−and Zn2+which leads to poor cyclic stability.Herein,Bi2S3 is proposed as a promising cathode material for rechargeable aqueous ZIBs.Improved cyclic stability and fast diffusion of Zn2+is observed.Also,the layered structure of Bi2S3 with the weak van der Waals interaction between layers offers paths for diffusion and occupancy of Zn2+.As a result,the Zn/Bi2S3 battery delivers high capacity of 161 mAh g−1 at 0.2 A g−1 and good cycling stability up to 100 cycles with ca.100%retention.The battery also demonstrates good cyclic performance of ca.80.3%over 2000 cycles at 1 A g−1.The storage mechanism in the Bi2S3 cathode is related to the reversible Zn ion intercalation/extraction reactions and the capacitive contribution.This work indicates that Bi2S3 shows great potential as the cathode of ZIBs with good performance and stability.

Manipulating Horizontal Zn Deposition with Graphene Interpenetrated Zn Hybrid Foils for Dendrite-Free Aqueous Zinc Ion Batteries

Aqueous zinc ion batteries(ZIBs)with intrinsic safety have great potentials in portable devices,but suffer from limited cycling life mainly caused by serious dendrite growth and unavoidable side reactions of Zn anodes.Herein,graphene interpenetrated Zn(GiZn)hybrid foils are developed for dendrite-free and long-term Zn anodes for high-performance ZIBs.The GiZn anode is prepared by interfacial assembly of reduced graphene oxide(rGO)on the skeletons of zinc foams,followed by mechanical compression into hybrid foils and drying process.The presence of the rGO nanosheets in the GiZn hybrid foils provides abundant zincophilic sites to induce horizontal Zn deposition for Zn metal anodes without the growth of dendrites.Meanwhile,the uniform distribution of rGO nanosheets endows the hybrid foils with superior conductivity and wetting ability with electrolytes for reduced interfacial resistances.As a result,GiZn-based symmetric cells exhibit a small voltage hysteresis of 30.4 mV and remarkable areal capacity of 30 mAh cm^(-2)at 0.5 mA cm^(-2).Further,GiZn anodes also enable the corresponding aqueous Zn||MnO_(2)batteries with high capacity of 168.5 mAh g^(-1)at 8 C,superior to the counterpart with pure Zn foil anodes(72.7 mAh g^(-1)).Therefore,GiZn hybrid foil anodes will shed light on the rational construction of 2D material-interpenetrated Zn hybrid foil anodes for high-performance ZIBs.

Bioadsorption of Cd (II) from Contaminated Water on Treated Sawdust: Adsorption Mechanism and Optimization

Sawdust (SD) a very low cost material has been utilized as adsorbent material for the removal of Cd (II) from aqueous solutions after treatment with mono methylol urea (MMU) in the presence of zinc chloride as a catalyst to form MMU-SD. The reaction of MMU-SD was carried out under different conditions including MMU/SD molar ratio, catalyst concentration, and reaction time and temperature. Adsorption studies have been carried out to determine the effect of agitation time, pH, adsorbent and adsorbate concentrations on the adsorption capacity of Cd (II) ions onto MMU-SD. Langmuir, Freundlich and Redlich-Peterson isotherm models were applied in the adsorption studies. The experimental data were analyzed using various sorption kinetic models. The removal processes of Cd (II) onto MMU-SD particles could be well described by the pseudo-second order model. The maximum adsorption capacity of Cd(II) onto MMU-SD was 909 mg/g. Similarly, the Freundlich constant 1/n value was 0.45.

Host-guest supramolecular interaction behavior at the interface between anode and electrolyte for long life Zn anode

The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of H_(3)O^(+) is inhibited by the supramolecular host–guest complex composed of H_(3)O^(+) as guest and 18-crown-6 as host.The even Zn plating is induced by the host–guest complex electrostatic shielding layer on Zn anode,as detected by in-situ optical microscopy.The lamellar Zn is plated which profits from the improved Zn plating behavior.Density functional theory (DFT) calculation presents the stable structure of complex.The less produced H_(2) content is monitored online by a mass spectrometer during Zn plating/stripping,which indicates HER can be hampered by the host–guest behavior.Thus,the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6.The proposed host–guest supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.