表面限域掺杂提升高比能正极材料稳定性

Lithium ion batteries (LIBs) have broad applications in a wide variety of a fields pertaining to energy storage devices. In line with the increasing demand in emerging areas such as long-range electric vehicles and smart grids, there is a continuous effort to achieve high energy by maximizing the reversible capacity of electrode materials, particularly cathode materials. However, in recent years, with the continuous enhancement of battery energy density, safety issues have increasingly attracted the attention of researchers, becoming a non-negligible factor in determining whether the electric vehicle industry has a foothold. The key issue in the development of battery systems with high specific energies is the intrinsic instability of the cathode, with the accompanying question of safety. The failure mechanism and stability of high-specific-capacity cathode materials for the next generation of LIBs, including nickel-rich cathodes, high-voltage spinel cathodes, and lithium-rich layered cathodes, have attracted extensive research attention. Systematic studies related to the intrinsic physical and chemical properties of different cathodes are crucial to elucidate the instability mechanisms of positive active materials. Factors that these studies must address include the stability under extended electrochemical cycles with respect to dissolution of metal ions in LiPF₆-based electrolytes due to HF corrosion of the electrode; cation mixing due to the similarity in radius between Li⁺ and Ni²⁺; oxygen evolution when the cathode is charged to a high voltage; the origin of cracks generated during repeated charge/discharge processes arising from the anisotropy of the cell parameters; and electrolyte decomposition when traces of water are present. Regulating the surface nanostructure and bulk crystal lattice of electrode materials is an effective way to meet the demand for cathode materials with high energy density and outstanding stability. Surface modification treatment of positive active materials can slow side reactions and the loss of active material, thereby extending the life of the cathode material and improving the safety of the battery. This review is targeted at the failure mechanisms related to the electrochemical cycle, and a synthetic strategy to ameliorate the properties of cathode surface locations, with the electrochemical performance optimized by accurate surface control. From the perspective of the main stability and safety issues of high-energy cathode materials during the electrochemical cycle, a detailed discussion is presented on the current understanding of the mechanism of performance failure. It is crucial to seek out favorable strategies in response to the failures. Considering the surface structure of the cathode in relation to the stability issue, a newly developed protocol, known as surface-localized doping, which can exist in different states to modify the surface properties of high-energy cathodes, is discussed as a means of ensuring significantly improved stability and safety. Finally, we envision the future challenges and possible research directions related to the stability control of next-generation high-energy cathode materials.     

亚硫酸盐无氰电沉积金新工艺及机制

直接以氯金酸作为主盐、 羟基乙叉二膦酸（HEDP）作为镀液稳定剂和镀层细化剂、 结合添加剂, 组成亚硫酸盐无氰镀金新工艺; 研究镀液稳定性、 镀层形态及金电沉积机制。结果表明, HEDP可明显提升镀液稳定性;不含HEDP的亚硫酸盐镀金液中, 镀层呈棒状晶粒并随沉积时间延长而逐渐生长,导致镀层外观随镀层厚度增加由金黄色转变为红棕色。镀液含有HEDP时, 金晶粒形态由棒状转变为棱锥状, 且棱锥状晶粒随沉积时间延长生长速率较小, 镀层厚度为1 μm时仍呈现金外观。电化学实验表明金电沉积不经历成核过程。     

Chiral separation using cyclodextrins as mobile phase additives in open-tubular liquid chromatography with a pseudophase coating

The chiral separation of various analytes (dichlorprop, mecoprop, ibuprofen, and ketoprofen) was demonstrated with different cyclodextrins as mobile phase additives in open-tubular liquid chromatography using a stationary pseudophase semipermanent coating. The stable coating was prepared by a successive multiple ionic layer approach using poly(diallyldimethylammonium chloride), polystyrene sulfonate, and didodecyldimethyl ammonium bromide. Increasing concentrations (0–0.2 mM) of various native and derivatized cyclodextrins in 25 mM sodium tetraborate (pH 9.2) were investigated. Chiral separation was achieved for the four test analytes using 0.05–0.1 mM β-cyclodextrin (resolution between 1.11 and 1.34), γ-cyclodextrin (resolution between 0.78 and 1.27), carboxymethyl-β-cyclodextrin (resolution between 1.64 and 2.59), and 2-hydroxypropyl-β-cyclodextrin (resolution between 0.71 and 1.76) with the highest resolutions obtained with 0.1 mM carboxymethyl-β-cyclodextrin. %RSD values were <10%. This is the first demonstration of chiral open-tubular liquid chromatography using achiral chromatographic coatings and cyclodextrins as mobile phase additives.     

Ferrocene-modified dendrimers as support of copper nanoparticles: evaluation of the catalytic activity for the decomposition of ammonium perchlorate

Ferrocene (Fc)-based systems are frequently used as burning rate catalysts in the decomposition of ammonium perchlorate (AP)-based propellants. However, small Fc derivatives migrate to the surface of the propellant resulting in undesirable changes in the designed burning parameters and unstable combustion. To retard the migration and to increase the combustion rate of AP, fourth-generation polyamidoamine (PAMAM) dendrimers modified with Fc (PAMAM generation 4 [G4]-Fc) were synthetized and used as support for the obtention of copper nanoparticles (CuNPs). PAMAM G4 produced smaller nanoparticles (1–2 nm) with lower aggregation than PAMAM G4-Fc (12–14 nm). X-ray photoelectron spectroscopy (XPS) characterization confirmed the superior stabilizing and protecting effect against oxidation of CuNPs by PAMAM G4 in comparison to PAMAM G4-Fc, whereas molecular dynamics simulations have shown less flexibility and lower presence of stabilizing sites for nanoparticles in PAMAM G4-Fc. Antimigration tests confirmed the negligible migration of PAMAM G4-Fc compared with Fc, whereas PAMAM G4-Fc|CuNP affected the high-temperature decomposition of AP positively, decreasing the decomposition temperature in 87 °C owing to a synergistic effect between CuNPs and Fc. PAMAM G4-Fc can act both as an effective antimigration system of Fc and as a stabilizing framework of metal nanoparticles with application as catalysts of AP.     

One step nanoencapsulation of corrosion inhibitors for gradual release application

The direct application of corrosion inhibitors on metal surfaces is potentially dangerous for the environment and the restoration operators, thus new conservation strategies are mandatory. In this study, two copper corrosion inhibitors, 1H-benzotriazole (BTA) and 5-phenyl-1H-tetrazole (PT), are encapsulated in a silica nanocontainer, for future application in smart coatings, with the aim to reduce the amount of chemicals used in treatments, their dispersion in the environment and the direct exposure of the operators to these chemicals. In particular, composite silica nanocapsules, containing the corrosion inhibitors, are prepared via one-step synthesis, based on mini-emulsion polymerisation processes.The morphology, structure, and texture of these loaded silica nanocontainers are characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ physisorption (BET/BJH). Micro-Raman spectroscopy (RS) is performed to characterise the composition. UV–visible spectroscopy and thermal analysis (TG/DSC) are performed for the loading and encapsulation efficiency (L%, EE%) study.Synthesised nanocapsules show a core-shell structure and, when loaded with the inhibitors, have size ranging from about 130 to 170 nm and a BET surface area of the order of 800 m²/g. The EE% is maximum in the case of BTA and decreases to ～52% in the case of PT.     

New polymer electrolyte membrane for medium-temperature fuel cell applications based on cross-linked polyimide Matrimid and hydrophobic protic ionic liquid

New hydrophobic protic ionic liquid, 2-butylaminoimidazolinium bis(trifluoromethylsulfonyl)imide (BAIM-TFSI), has been synthesized. The ionic liquid showed good thermal stability to at least 350 °C. The conductivity of BAIM-TFSI determined by electrochemical impedance method was found to be 5.6 × 10^?2 S/cm at 140 °C. Homogeneous composite films based on commercial polyimide (PI) Matrimid and BAIM-TFSI containing 30–60 wt% of ionic liquid were prepared by casting from methylene chloride solutions. Thermogravimetric analysis data indicated an excellent thermal stability of PI/BAIM-TFSI composites and thermal degradation points in the temperature range 377 °C–397 °C. The addition of ionic liquid up to 50 wt% in PI films does not lead to any significant deterioration of the tensile strength of the polymer. The dynamic mechanical analysis results indicated both an increase of storage modulus E′ of PI/BAIM-TFSI composites at room temperature and a significant E′ decrease with temperature compared with the neat polymer. The cross-linking of the PI with polyetheramine Jeffamine D-400 allowed to prepare PI/Jeffamine/BAIM-TFSI (50%) membrane with E′ value of 300 MPa at 130 °C. The ionic conductivity of this cross-linked composite membrane reached the level of 10^?2 S/cm at 130 °C, suggesting, therefore, its potential use in medium-temperature fuel cells operating in water-free conditions.     

Surface Functionalization of PEO Nanofibers Using a TiO2 Suspension as Sheath Fluid in a Modified Coaxial Electrospinning Process

Convenient and integration fabrication process is a key issue for the application of functional nanofibers. A surface functionalization method was developed based on coaxial electrospinning to produce ultraviolet(UV) protection nanofibers. The titanium dioxide(TiO₂) nanoparticles suspension was delivered through the shell channel of the coaxial spinneret, by which the aggregation of TiO₂ nanoparticles was overcome and the distribution uniformity on the surface of polyethylene oxide(PEO) nanofiber was obtained. With the content of TiO₂ increasing from 0 to 3%(mass fraction), the average diameter of nanofibers increased from (380±30) nm to (480±100) nm. The surface functionalization can be realized during the electrospinning process to gain PEO/TiO₂ composite nanofibers directly. The uniform distribution of TiO₂ nanoparticles on the surface of nanofibers enhanced the UV absorption and resistance performance. The maximum UV protection factor(UPF) value of composite nanofibers reaches 2751. This work presented a novel surface-functionalized way for the preparation of composite nanofiber, which has great application potential in the field of micro/nano system integration fabrication.     

“功能涂料”课程的教学改革:打造趣味性、互动性和挑战性的课堂*

本着培养涂料行业精英人才的宗旨,针对涂料行业对人才需求的特点,结合多年教学经验,从教材的选择、教学内容设置、教学方法改进以及考核方法改革等4个方面探索了“功能涂料”课程的教学方法改革与课程实践。通过自编教材,精心设置授课内容,将科研成果、前沿知识、生活场景、新闻事件与书本知识相结合,提高课堂的趣味性;通过讨论法和交换式互动上课来加强课堂的互动性;通过过程性评价提高课程的学业挑战度。通过教学改革,本课程的选课率和出勤率得到了大幅提高,学生对涂料的兴趣明显增加,毕业后选择进入涂料领域工作的学生也越来越多。     

大口径反射镜高反射膜研究进展

大口径反射镜是大型反射式光学系统中关键的光学元件,在工作波段的反射率直接决定了光学系统的性能。随着地基、天基观测设备的发展,对大口径反射镜高反射膜提出了更宽的工作波段、更高的反射率、更好的环境适应性等要求。针对这些挑战,各种新的膜系结构、新的镀制方法、新的膜层材料纷纷出现,满足了大口径反射镜高反射膜的各种需求。本文对近些年国内外的大口径反射镜高反射膜研究进展予以综述,并预测大口径反射镜高反膜制备的技术趋势将由铝反射膜向银反射膜、由热蒸发向磁控溅射发展。     

二维材料用于渗透能转换的研究进展

在河水与海水的交界处实现渗透能提取与捕获是解决未来能源危机的重要方式之一. 渗透能因为储量大, 容易获取以及绿色可持续的优势受到广泛关注. 反向电渗析技术是一种能够有效捕获渗透能的方法之一, 目前已经得到了深入的研究与发展. 离子交换膜是反向电渗析技术转换渗透能的关键组件, 其性能的优异程度决定能量转换效率的高低. 常见的膜材料主要是高分子聚合物及其改性化合物, 最近一些二维材料如石墨烯、 氧化石墨烯、 二硫化钼、 各种框架材料及其改性复合物因优异的选择性离子传输、 纳米级通道、 丰富的表面功能基团以及可修饰性成为捕获渗透能的重要膜材料. 本文综合评述了二维材料作为离子传输通道的类型以及相应的传输机理; 例举了二维材料及其复合物的设计方案和在渗透能转换方面的具体应用; 最后提出了目前二维材料在渗透能转换领域中面临的挑战以及未来的发展方向.