Regulating the Water Molecular in the Solvation Structure for Stable Zinc Metal Batteries

Rechargeable aqueous zinc batteries are promising energy storage devices because of their low cost, high safety, and high energy density. However, their performance is plagued by the unsatisfied cyclability due to the dendrite growth and hydrogen evolution reaction (HER) at the Zn anode. Herein, it is demonstrated that the concentrated hybrid aqueous/non-aqueous ZnCl₂ electrolytes constitute a peculiar chemical environment for not only the Zn-ions but also water molecules. The high concentration of chloride ions substitutes the H₂O molecular in the solvation structure of Zn²⁺, while the acetonitrile further interacts with H₂O to decrease its activity. The hybrid electrolytes both inhibit the dendrite formation and HER, enabling an ultrahigh average Coulombic efficiency of 99.9% in the Zn||Cu half-cell and a highly reversible Zn plating/stripping with a low overpotential of 21 mV. Using this hybrid electrolyte, the Zn||polytriphenylamine (PTPAn) full cell deliveres a high discharge capacity of 110 mAh g⁻¹, a high power density of 9200 W kg⁻¹ at 100 °C and maintains 85% of the capacity for over 6000 cycles at 10 °C. This study provides a deep understanding between the solvation structure and columbic efficiency of Zn anode, thus inspiring the development for stable Zn batteries.     

A Dual-Mode Electrochromic Platform Integrating Zinc Anode-Based and Rocking-Chair Electrochromic Devices

The complementary electrochromic device, where the optical transmittance changes upon the flow of cations back and forth between anodic and cathodic electrodes, operates in a rocking-chair fashion if it can inherently self-discharge. Herein, the first demonstration of a dual-mode electrochromic platform having self-coloring and self-bleaching characteristics is reported, which is realized by sandwiching zinc metal within a newly-designed Prussian blue (PB)-WO₃ rocking-chair type electrochromic device. It is demonstrated that the redox potential differences between the zinc metal and the WO₃/PB electrodes endow the self-color-switching of these electrodes. By employing a hybrid electrolyte of Zn²⁺/K⁺, it is further shown that the colored PB-WO₃ rocking-chair device is capable of spontaneously bleaching when the anodic and cathodic electrodes are coupled. This dual-mode light-control strategy enables the electrochromic devices to exhibit four distinct optical states with the highest optical contrast of 72.6% and fast switching times (<5 s for the bleaching/coloration processes). Furthermore, the built-in voltage of the dual-mode electrochromic devices not only promotes energy efficiency, but also augments the bistability of the devices. It is envisioned that the broad implication of the present platform is in the development of self-powered smart windows, colorful displays, optoelectronic switches, and optical sensors.     

Regulation of Ionic Distribution and Desolvation Activation Energy Enabled by In Situ Zinc Phosphate Protective Layer toward Highly Reversible Zinc Metal Anodes

Despite the merits of high specific capacity, low cost, and high safety, the practical application of aqueous Zn metal batteries (AZMBs) is plagued by the dendritic growth and corrosion reaction of Zn metal anodes. To solve these issues, a Zn₃(PO₄)₂·4H₂O protective layer is in-situ constructed on Zn foil (Zn@ZnPO) by a simple hydrothermal method, avoiding the traditional slurry-casting process. The insulating and conformable ZnPO layer improves the wettability of Zn@ZnPO and aqueous electrolyte via decreasing the contact angle to 11.7^o. Compared with bare Zn, the Zn@ZnPO possesses a lower desolvation activation energy of 35.25 kJ mol^-1, indicating that the ZnPO fasters the desolvation of hydrated Zn²⁺ ions and thereby ameliorates their transport dynamics. Micro-morphology and structural characterization show that there are no dendrites forming on the post-cycling Zn@ZnPO anodes, and the interfacial ZnPO layer remains almost identical before and after cycles. It can be explained that the electrochemically stable ZnPO layer acts as an ionic modulator to enable the homogeneous distribution of Zn²⁺ ions, inhibiting the growth of Zn dendrites. Benefiting from these advantages, the Zn@ZnPO based symmetric and full cells deliver highly reversible Zn plating/stripping behavior and long cycling lifespans.     

A pH-switched mesoporous nanoreactor for synergetic therapy

Zinc oxide nanoparticles (ZnO NPs),as a new type of pH-sensitive drug carrier,have received much attention.ZnO NPs are stable at physiological pH,but can dissolve quickly in the acidic tumor environment (pH ＜ 6) to generate cytotoxic zinc ions and reactive oxygen species (ROS).However,the protein corona usually causes the non-specific degradation of ZnO NPs,which has limited their application considerably.Herein,a new type of pH-sensitive nanoreactor (ZnO-DOX@F-mSiO2-FA),aimed at reducing the non-specific degradation of ZnO NPs,is presented.In the acidic tumor environment (pH ＜ 6),it can release cytotoxic zinc ions,ROS,and anticancer drugs to kill cancer cells effectively.In addition,the fluorescence emitted from fluorescein isothiocyanate (FITC)-labeled mesoporous silica (F-mSiO2) and doxorubicin (DOX) can be used to monitor the release behavior of the anticancer drug.This report provides a new method to avoid the non-specific degradation of ZnO NPs,resulting in synergetic therapy by taking advantage of ZnO NPs-induced oxidative stress and targeted drug release.     

温度对燃烧包覆LiMn2O4/ZnO及其电性能的影响

通过葡萄糖辅助低温燃烧制备ZnO包覆型LiMn2O4,利用X射线衍射仪、扫描电子显微镜、循环伏安、交流阻抗以及恒流充放电测试等手段,研究了温度对产物晶体结构、微观形貌及电化学性能的影响。XRD结果表明所有产物均为单相尖晶石型LiMn2O4结构。SEM结果表明产物的颗粒尺寸随温度的升高而增大。电化学性能测试表明400℃和500℃制备的LiMn2O4/ZnO具有相对优异的电化学性能,室温1C条件下首次放电比容量分别为119.3mAh/g、116.3mAh/g,循环100次后容量保持率分别85.6%、87.8%。尖晶石LiMn2O4电极的阻抗谱特征与温度有关,电池的电化学性能主要受电荷转移电阻(Rct)影响。     

Effect of microwave sintering on the microstructure and electrical properties of low-voltage ZnO varistors

Coarse-grained ZnO varistors for low-voltage applications were prepared by microwave sintering technique under different soaking times of 5–150?min. For comparison, a low-voltage ZnO varistor was also prepared through a conventional sintering process. Microwave sintering remarkably enhanced the grain growth rate of ZnO varistors. Average grain size of the sample prepared by microwave sintering in 15?min was about 20?µm, which is similar to the grain size of sample prepared conventionally in 150?min time. In addition to grain growth, an increase in microwave sintering time led to precipitation of zinc titanate (Zn₂TiO₄) on the top surface of samples which sintered for long dwell times. X-ray diffraction and scanning electron microscopy results from different points of the samples declared that precipitation of Zn₂TiO₄ phase is due to the high rate of bismuth evaporation of Bi-rich liquid from top surface and the reaction between remaining titanium ions on the surface with ZnO. The results showed that increasing sintering time from 5 to 150?min increased the grain size from 14 to 33?µm, consequently, the breakdown field decreased from 90 to 27?V/mm, respectively. These changes led to a switch in the varistor application, from low to very low voltage.     

在盐湖地区暴露48个月纯锌的腐蚀行为

采用X射线衍射(XRD)、扫描电子显微镜(SEM)、金相显微镜和电化学阻抗等手段研究了锌在青海盐湖大气环境(富盐干旱型大气环境)中的腐蚀行为。结果表明,在青海盐湖大气环境中锌的腐蚀规律遵循经验公式m=Atn。锌的向地面比向天面腐蚀严重,向天面暴晒48个月出现锈层脱落现象。两个表面的腐蚀产物均由Zn5(OH)8Cl2·H2O,Zn5(CO)3(OH)6和Zn4SO4(OH)6·3H2O组成,锈层均富含SiO2。电化学结果表明,随着暴晒时间的延长向地面的极化电阻Rp逐渐增大,而向天面的Rp逐渐增加,而暴晒48个月时减小。锈层有抑制基体腐蚀的作用,对两个表面锈层的保护性随暴晒时间的延长而增大,而向天面暴晒48个月时保护性减弱。     

Effect of Powder Processing and Sintering Conditions on the Microstructural,Thermal, and Mechanical Properties of Reticulated Zinc Oxide Ceramic Foams

Ceramic foams are made of zinc oxide using different amounts of Sb₂O₃ and Bi₂O₃ as sintering aids. The effect of a ball milling processing of the starting powders and the sintering temperature on the microstructure and the properties of the ZnO foams is investigated. The focus is set on the evolution of the secondary phases formed within the microstructure of ZnO. A determining effect is identified in the amount of an Al₂O₃ impurity which is introduced by abrasion of the milling vessels during ball milling. Alumina is partially dissolved in a spinel α–Zn₇Sb₂O₁₂ secondary phase which is stabilized by a reduction of the unit cell volume. Remaining Al₂O₃ is incorporated into zinc oxide under formation of a defect wurtzite phase. The phase evolution is a complex function of the content of sintering aids, the Al₂O₃ impurity level and the sintering temperature. The shrinkage during sintering and the porosity evolution are correlated to the phase composition within the ZnO material. The thermal conductivity and the compressive strength of the foams are determined, normalized with respect to their porosity, and correlated to the microstructure and phase composition of the ZnO strut material.     

Fabrication and gas-sensing properties of hierarchically porous ZnO architectures

Hierarchically three-dimensional (3D) porous ZnO architectures are synthesized by a template-free, economical aqueous solution method combined with subsequent calcination. First, the precursors of interlaced and monodisperse basic zinc nitrate (BZN) nanosheets are prepared. Then calcination of the precursors produces hierarchically 3D porous ZnO architectures composed of interlaced ZnO nanosheets with high porosity resulting from the thermal decomposition of the precursors. The products are characterized by X-ray diffraction, thermogravimetric-differential thermalgravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller N₂ adsorption-desorption analyses. The BET surface area of the hierarchically porous ZnO nanostructures was calculated to be 12.8 m² g⁻¹. Compared with ZnO rods, the as-prepared porous ZnO nanosheets exhibit a good response and reversibility to some organic gases, such as ethanol and acetone. The responses to 100 ppm ethanol and acetone are 24.3 and 31.6, respectively, at a working temperature of 320 °C. These results show that the porous ZnO architectures are highly promising for gas sensor applications, as the gas diffusion and mass transportation in sensing materials are significantly enhanced by their unique structures. Moreover, it is believed that this solution-based approach can be extended to fabricate other porous metal oxide materials with a unique morphology or shape.