高比能锂离子电池层状富锂正极材料改性策略研究进展

层状富锂材料具有超过250 mAh∙g⁻¹的高可逆比容量,被认为是下一代高比能锂离子电池最具商业化前景的正极材料之一。然而,层状富锂材料在实际应用之前仍需解决诸多挑战,如高电压氧释放、层状到岩盐相的结构变化、过渡金属离子迁移等结构劣化,并由此带来了较低的初始库伦效率、电压/容量的衰减以及循环寿命的不足。针对以上问题,进行层状富锂材料改性无疑是一种行之有效的方法。本综述全面介绍了层状富锂材料的结构、组分以及电化学性能,在此基础上对材料改性策略进行了系统阐述,详细介绍了体相掺杂、表面包覆、缺陷设计、离子交换和微结构调控等一系列改性策略的现状以及发展趋势,最终提出了高容量和长循环层状富锂材料和高比能锂离子电池的设计思路。     

钾改性氧化铝基羰基硫水解催化剂及其失活机理

天然气、油田伴生气、高炉煤气等化工生产过程中伴生COS气体,不仅会腐蚀管道和毒害催化剂,还会严重污染环境并危害人类健康。COS催化水解反应可在温和条件下高效的将COS脱除,是最具应用前景的COS脱除技术之一。碱金属元素因其具有独特的电子供体性质、表面碱性和静电吸附等特性,常被用作助催化剂以提高Al₂O₃的COS催化水解性能。近年来,以钾为助剂改性的Al₂O₃催化剂(K₂CO₃/Al₂O₃)在COS催化水解反应中得到广泛的应用,但由于负载在Al₂O₃上的K物种的组成复杂,目前研究者对K₂CO₃/Al₂O₃催化剂上COS水解机理的理解仍存在一定的困惑和争议。本论文通过湿法浸渍法合成出一系列钾盐和钠盐改性的Al₂O₃催化剂,并利用各类先进的表征技术对这些催化剂进行分析。活性测试表明,以K₂CO₃、K₂C₂O₄、NaHCO₃、Na₂CO₃和NaC₂O₄改性Al₂O₃催化剂均有助于COS的水解。其中K₂CO₃/Al₂O₃拥有最佳的COS水解性能,连续运行20 h后其COS转化率仍高于~93%,远远优于未改性的Al₂O₃ (~58%)。我们利用原位红外光谱和X射线光电子能谱探明了反应过程中催化剂的化学结构特征,阐明了H₂O分子在K₂CO₃/Al₂O₃上的水解作用机制。原位红外表明COS在K₂CO₃/Al₂O₃上的水解过程中形成了硫代碳酸氢盐中间产物。X射线光电子能谱表征证明催化剂的失活主要是因为催化剂表面积累了硫酸盐和单质硫。此外,我们还研究了水蒸气含量对COS水解性能的影响,研究发现,由于H₂O和COS分子在催化剂表面存在竞争吸附,过量的H₂O会引起催化活性的下降。上述研究表明,K₂CO₃/Al₂O₃催化剂上COS水解性能的提高主要是形成了HO-Al-O-K界面活性位。更为重要的是,所制备的催化剂都是在模拟工业工况条件下进行的,这为后续的工业应用提供了宝贵理论指导。本工作为理解助剂钾在Al₂O₃催化剂上COS水解活性的增强提供了新的见解,这为未来设计稳定高效的COS水解催化剂打开了新的发展方向。     

MoO3和Nb2O5助剂对Pt/ZrO2催化剂上短链烷烃燃烧反应的不同促进作用

贵金属Pt催化剂具有高活性和热稳定性,广泛应用于催化挥发性有机物的完全氧化反应(燃烧反应).短链烷烃(甲烷、乙烷、丙烷等)化学性质稳定,是最难氧化的一类有机物,常用作考察燃烧反应催化剂性能的模型反应物.然而,目前报道的研究工作通常仅限于针对某一种烷烃底物的催化燃烧,系统考察催化剂以及助剂对不同短链烷烃的催化燃烧活性鲜有报道.在短链烷烃中,甲烷只有C–H键;而其它烷烃除了C–H键;还有C–C键.因此,研究催化剂对甲烷、乙烷和丙烷燃烧反应催化性能的差异性,对于认识催化剂上C–H键和C–C键的活化具有非常重要的意义.本文制备了MoO3或Nb2O5修饰的Pt/ZrO2催化剂并用于短链烷烃的燃烧反应.研究发现,MoO3助剂对甲烷燃烧有明显的抑制作用,但对乙烷,丙烷和正己烷燃烧反应具有促进作用,促进作用随着烷烃碳链的增长逐渐增加;Nb2O5助剂对甲烷、乙烷、丙烷和正己烷燃烧反应均具有促进作用,然而促进作用随着碳链的增长而逐渐减弱.MoO3和Nb2O5助剂的不同促进作用与助剂影响催化剂表面酸性以及Pt物种的氧化或还原态有关.NH3-TPD结果表明,MoO3助剂可以显著增加Pt/ZrO2催化剂表面强酸位点数量,而Nb2O5助剂可以显著增加Pt/ZrO2催化剂表面中强酸位点数量.HTEM结果表明,两种助剂的添加都不会明显改变Pt物种的颗粒尺寸.在Pt-Mo/ZrO2催化剂上,MoO3覆盖部分Pt物种形成丰富的Pt-MoO3界面,促进了金属Pt物种和强表面酸性位点的生成,提高了丙烷燃烧反应活性;Pt-Nb/ZrO2催化剂上载体表面的部分Nb2O5被Pt物种包覆,使得生成的表面Pt-Nb2O5界面低于Pt-Mo/ZrO2催化剂,但由于催化剂表面酸性位的提升,也促进了丙烷燃烧反应活性的提高.XPS结果表明,在甲烷燃烧反应中,Pt-Nb/ZrO2催化剂上Ptn+物种能够更加稳定地存在,这可能是Nb2O5助剂提高Pt-Nb/ZrO2催化剂上甲烷燃烧活性的关键.而Pt-Mo/ZrO2催化剂上Ptn+物种在甲烷反应中可以更容易地被还原,并且由于MoO3的包裹导致暴露的Pt位点数量降低,使催化剂催化甲烷燃烧的活性受到抑制.可见,MoO3助剂更有利于C–C键活化,而Nb2O5助剂更有利于高键能的C–H键活化.综上,本文系统性地研究MoO3助剂和Nb2O5助剂对Pt/ZrO2催化剂上不同短链烷烃的燃烧反应的影响,证实了两种助剂的促进作用与碳链长度的关系是截然不同的.     

6S现场管理方法在计量检测实验室中的应用

6S现场管理的方法已经在多个领域得以运用并取得较好的效果。结合计量检测实验室的特点,从整理、整顿、清扫、清洁、素养、安全6各方面讨论了6S现场管理在计量检测实验室中的应用。该管理模式可以提高工作效率,降低物品遗失率,减少寻找物品的时间等,提高计量检测质量。     

介质层厚对含负折射率介质Bragg微腔的影响

研究了介质层厚对含负折射率介质一维光子晶体Bragg微腔的缺陷模和双稳态的影响.在中心频率附近将传输矩阵各矩阵元采用泰勒级数展开并取一级近似,得到了缺陷模频率与介质层厚的关系式及品质因子公式.研究结果表明：一级近似法能很好地解释中心频率附近介质层厚对缺陷模频率的影响.理想Bragg微腔结构的缺陷模品质因子最大;递增正折射率介质层厚和增大缺陷层介质层厚、递减负折射率介质层厚及同时等量递减正和负折射率介质层厚,均可使缺陷模红移,双稳态阈值降低.     

Research on the defect structure and g factors for the tetragonal (CrO4)3− impurity center in ZrSiO4: Cr5+ crystal

ABSTRACT

The EPR g factors g// and g⊥ for the tetragonal (CrO₄)^3? impurity center in ZrSiO4: Cr⁵⁺ crystal are studied from the high-order perturbation formulas based on the two-mechanism (the crystal field and charge-transfer mechanisms) model. The studies indicate that differing from the tetragonally-elongated host (SiO4)^4- tetrahedron, the dominant defect structure of the substitutional (CrO₄)^3? tetrahedron is tetragonally- compressed with the ground state |d_z² due to the Jahn-Teller distortion. Furthermore, the agreement of g factors between calculation and experiment requires a small admixture of the first excited state |d_x²_?y² to the ground state |d_z² due to the vibrational motion of ligands, which leads a compressed (CrO₄)^3? tetrahedron to become a twinkling elongated one, These results are discussed.     

Defect structure of quenched γ-BICOVOX by combined X-ray and neutron powder diffraction

A detailed investigation of the defect structure of the Co doped BIMEVOX solid electrolyte, Bi₂V_{1 − x}Co_xO_{5.5 − 3x/2} (x = 0.1 and x = 0.2), quenched from high temperature, has been carried out using X-ray and neutron powder diffraction data measured at room temperature. The structure is built up from alternating layers of [Bi₂O₂]_n²ⁿ⁺ and [V_{1 − x}Co_xO_{3.5 − 3x/2}]_n²ⁿ⁻ with disorder limited to the vanadate layer. The ideal V/Co co-ordination is octahedral with corner sharing of equatorial oxygens. The refinements show that the true structure is distorted, with disorder in both apical and equatorial oxygens and oxygen vacancies concentrated in the equatorial positions. Detailed analysis of the oxygen site occupancies reveals two main types of V/Co co-ordination viz. distorted octahedral and distorted tetrahedral. The majority of the sites in both compositions are tetrahedral.     

Mossbauer study of ferrite systems Co x Mn1−x Fe2O4 and Ni x Mn1−x Fe2O4

Mössbauer spectra of Co _x Mn_1?x Fe₂O₄ and Ni _x Mn_1?x Fe₂O₄ ferrites withx values ranging from 0·1 to 0·8 in steps of 0·1 have been recorded at room temperature. All spectra exhibit well-defined Zeeman hyperfine patterns. It has been observed that hyperfine field at Fe³⁺ nucleus increases more rapidly by nickel substitution than by cobalt substitution. This has been explained in terms of exchange interactions and cation distribution in the spinels. Hyperfine fields, isomer shifts and quadrupole splittings have been determined.     

高熵纳米合金在电化学催化中的应用

The implementation of clean energy techniques, including clean hydrogen generation, use of solar-driven photovoltaic hybrid systems, photochemical heat generation as well as thermoelectric conversion, is crucial for the sustainable development of our society. Among these promising techniques, electrocatalysis has received significant attention for its ability to facilitate clean energy conversion because it promotes a higher rate of reaction and efficiency for the associated chemical transformations. Noble-metal-based electrocatalysts typically show high activity for electrochemical conversion processes. However, their scarcity and high cost limit their applications in electrocatalytic devices. To overcome this limitation, binary catalysts prepared by alloying with transition metals can be used. However, optimization of the activity of the binary catalysts is considerably limited because of the presence of the miscibility gap in the phase diagram of binary alloys. The activity of binary electrocatalysts can be attributed to the adsorption energy of molecules and intermediates on the surface. High-entropy alloys (HEAs), which consist of diverse elements in a single NP, typically exhibit better physical and/or chemical properties than their single-element counterparts, because of their tunable composition and inherent surface complexity. Further, HEAs can improve the performance of binary electrocatalysts because they exhibit a near-continuous distribution of adsorption energy. Recently, HEAs have gained considerable attention for their application in electrocatalytic reactions. This review summarizes recent research advances in HEA nanostructures and their application in the field of electrocatalysis. First, we introduce the concept, structure, and four core effects of HEAs. We believe that this part will provide the basic information about HEAs. Next, we discuss the reported top-down and bottom-up synthesis strategies, emphasizing on the carbothermal shock method, nanodroplet-mediated electrodeposition, fast moving bed pyrolysis, polyol process, and dealloying. Other methods such as combinatorial co-sputtering, ultrashort-pulsed laser ablation, ultrasonication-assisted wet chemistry, and scanning-probe block copolymer lithography are also highlighted. Among these methods, wet chemistry has been reported to be effective for the formation of nano-scale HEAs because it facilitates the concurrent reduction of all metal precursors to form solid-solution alloys. Next, we present the theoretical investigation of HEA nanocatalysts, including their thermodynamics, kinetic stability, and adsorption energy tuning for optimizing their catalytic activity and selectivity. To elucidate the structure–property relationship in HEAs, we summarize the research progress related to electrocatalytic reactions promoted by HEA nanocatalysts, including the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, methanol oxidation reaction, and CO₂ reduction reaction. Finally, we discuss the challenges and various strategies toward the development of HEAs.     

Ultrasonic techniques for nondestructive testing of standing trees

The aim of this study is to assess wood quality of standing trees with ultrasonic velocity methods. The ultrasonic techniques currently used are: scattering based techniques that use travel time and other wave parameters for measuring the elastic constants of wood, and ultrasonic tomographic imaging techniques which seek to provide a high resolution picture of the defect. Scattering based techniques were firstly used as nondestructive techniques with increment cores of 5 mm diameter. On these specimens measurements with bulk waves--longitudinal and shear were used to detect the influence of sylvicultural treatment (pruning) on wood quality and also to detect defects (slope of grain, wavy figures). High resolution imaging techniques were developed for imaging abnormalities induced by biological attacks of fungi or insects in standing trees. In this case, ultrasonic tomography refers to cross-sectional imaging of trees from data collected by illuminating the tree from different directions. Ultrasonic images were reconstructed from the time of flight. The images were reconstructed from 120 measurements in situ and through the bark with direct transmission technique, using 1 MHz transducers. The resolution is 5 cm.