电极活性物质球形氢氧化镍的结构特征研究

球形氢氧化镍的微结构对氢镍电池（MH—Ni）镍电极的电化学性能有重要的影响。本文通过扫描电镜（SEM）和透射电镜（TEM）研究了用控制沉淀-结晶法制备的球形氢氧化镍的结构特征,并与传统非球形氢氧化镍进行了比较,同时讨论了球形氢氧化镍活性物质的电化学行为。研究结果表明,球形氢氧化镍粉体由微球颗粒组成,每一个微球由片状氢氧化镍叠砌而成,这种片状氢氧化镍晶粒又由约0．5nm厚的40层晶片组成,因而球形氢氧化镍是一种纳米结构材料。片状氢氧化镍晶粒在微球内基本上沿径向排列,晶粒之间相互连接形成三维网络结构,晶粒解理面之间存在许多孔隙或缝隙。这种结构在电池的充放电过程中具有良好的力学稳定性,微球内存在的孔隙或缝隙可以用作质子传递的通道而有利于缩短质子在固相中扩散的距离,从而降低电极极化和提高电极的电化学性能及使用寿命。     

球形Ni(OH)2控制结晶过程中的陈化研究

利用控制结晶方法在连续搅拌反应器中制备了球形氢氧化镍,通过电子显微技术表征了球形氢氧化镍的内外结构并研究了其生长过程中的陈化现象.随着反应物过饱和度的下降,反应器内部按功能不同可分成成核区、生长区与熟化区等.在球形氢氧化镍控制结晶生长过程中存在Ostwald熟化,它在粒子之间及粒子表面发生;同时亦存在晶相转变α→β,表现为重结晶作用,在团聚粒子内部进行.Ostwald熟化与相转变构成的陈化作用在促使氢氧化镍粒子团聚密实、重结晶长大、形态向球形转变并使其表面光滑和内部结构呈放射状等微结构的形成过程中发挥重要作用.这一认识深化了球形工业结晶研究,并对反应器设计具有指导意义.     

生物模板法制备具有特殊表面形貌的二氧化硅中空微球

利用油菜花粉作为生物模板,通过溶胶在花粉颗粒表面包裹,再经高温烧结去除花粉颗粒的方法制备了具有特殊表面形貌的二氧化硅中空微球. 并通过调节溶胶中醇盐与水的比例,实现了不同表面形貌的二氧化硅中空微球的制备. 利用差热（DSC）、热重（TG）、X射线能谱仪（EDS）、扫描电子显微镜（SEM）等对花粉颗粒和所制备的二氧化硅中空微球进行了表征,并对不同表面形貌的形成机理进行了探讨. 结果表明,花粉内壁在200℃时即可完全消除,从而形成中空结构,而外壁及其表面的网格状结构在较高温度仍能保持完好,从而保证该结构在微球表面的复制,而溶胶浓度则是形成微球表面不同形貌的决定因素,随着胶体粒子在花粉表面沉积量的不同,微球表面的微孔结构也将随之变化.     

静电凝聚法制备苯乙烯-丙烯酸共聚物/氧化铈核壳纳米复合材料

致力于苯乙烯-丙烯酸共聚物(P(St-co-AA))微球/氧化铈核壳纳米结构的制备,以无皂乳液聚合制备的P(St-co-AA)微球为负电组成,水热法合成的氧化铈纳米粉体为正电组成,设计了静电凝聚法复合工艺,对复合工艺条件进行了初步的探索。结果表明:采用无皂乳液聚合制备的P(St-co-AA)微球呈正球形,颗粒尺寸均一,尺寸在160~390nm范围内可控;以CTAB为表面活性剂,采用水热法在100℃条件下成功制得了颗粒尺寸在10~20nm的氧化铈纳米粉体。在水溶液体系中,在静电凝聚作用下,所制备氧化铈在P(St-co-AA)微球表面紧密堆积,形成了P(St-co-AA)/氧化铈核壳结构。可通过调节P(St-co-AA)微球的尺寸与负电性以及复合过程中pH值来调控所得核壳结构形貌。正负颗粒电性的匹配是构筑核壳结构的关键,一味地增加颗粒表面正电性或负电性对于实现调控复合过程形成纳米核壳结构并非有利。当苯乙烯与丙烯酸单体比例为10∶1时所得P(St-co-AA)微球在pH 2.0~3.0下所得核壳结构形貌均一,分散性较好。     

高压均质法制备枸橼酸喷托维林纳米颗粒

采用高压均质法制备枸橼酸喷托维林纳米颗粒,分析均质压力、均质次数和储存过程对药物颗粒形貌与粒径的影响,通过喷雾干燥制得微粉。结果表明:最优高压均质条件是均质压力为75 MPa、循环5次,制得的纳米颗粒是粒径为100~200 nm的片状结晶,储存稳定;枸橼酸喷托维林纳米颗粒悬浊液喷雾干燥微粉颗粒呈粒径小于1μm的球形,由保持原微观形貌与结构的纳米片状结晶聚集而成。     

反相水性乳液法制备聚酰亚胺微球形貌调控及影响因素

利用聚酰胺酸三乙胺盐可溶于水的特性,利用反相乳液技术,以液体石蜡为连续相,含水的聚酰胺酸盐为分散相,非离子型表面活性剂Span 80/Span 85为乳化剂,通过化学酰亚胺法制备聚酰亚胺微球。重点研究聚酰亚胺分子链结构和HLB值对聚酰亚胺微球形貌的调控作用。研究结果表明,随着聚酰亚胺分子链结构刚性降低,分别得到半球、多孔球以及带凹陷的微球。针对均苯四甲酸酐(PMDA)/4,4′-二氨基二苯醚(ODA)体系,当乳化剂体系的HLB值从1.8增加到4.3时,微球形貌从微球逐渐转变成半球,球表面的凹陷逐渐减少。此外,还对比研究了酰亚胺方法和搅拌速率对微球形态的影响。研究表明热酰亚胺化只能得到粘结严重的纳米微球;搅拌速度过快或过慢都可能造成微球破裂或变形。     

改进Stoeber法制备光子晶体用SiO2微球

为获得光子晶体用单分散性较好、表面光滑的SiO2球形颗粒,对传统Stoeber法进行改进,分析了氨水和正硅酸乙酯（TEOS）浓度对SiO2微球粒径的影响,提出了单分散SiO2微球的形成机理,利用X射线衍射分析仪（XRD）和场发射扫描电子显微镜（SEM）对样品结构和形貌进行了表征。XRD分析表明,合成的SiO2微球为无定形态;SEM照片显示SiO2微球粒径在292-750nm范围内,微球粒径偏差均在5％以下。     

核壳结构喷墨微滴珠液开发研究

用微乳液界面反应制备了含油溶性颜料、酚醛树脂的纳米核壳微球彩色乳液,TEM和激光散射粒度仪测定了微球形态粒径为80～120 nm球形.通过IR和DSC测定了壁材的结构,表明微球外壳为聚脲壳,芯为酚醛树脂.SEM观察了微球喷涂到电解氧化的铝版基上成膜前后的形态,成膜前为球形;成膜后为团聚片状.把制成的纳米核壳微球彩色乳液经计算机直接喷墨成像,在电解氧化形成砂目的铝版上制成喷墨CTP版,并在胶印机上进行了印刷,耐印率超过2万印以上.分辨率取决于喷墨打印机.     

交联聚合物磁性复合微球的制备与性能研究

由共沉淀法制备磁性FeaO4纳米颗粒,并用油酸钠对其表面进行改性,得到了平均直径为12.7nm的油基Fe3O4纳米颗粒.在该纳米颗粒存在的条件下,通过分散共聚制得了内部为Fe3O4,外层为二乙烯基苯(DVB)交联的聚丙烯酸-co-聚甲基丙烯酸甲酯(PAA-co-PMMA)磁性复合微球.研究了介质乙醇/水的比例、引发剂、分散剂、交联剂用量对形成复合微球的影响,得出了制备复合微球的优化实验条件,并对复合微球的结构、形态、尺寸及磁含量进行了考察.     

载银SnO2复合微球的制备及表征

以结晶四氯化锡(SnCl4·5H2O)和尿素为原料,采用溶剂热法在180℃下反应12h制备出了单分散性良好的SnO2微球,并通过原位化学还原法在SnO2微球表面沉积银纳米颗粒制备表面载银的SnO2复合微球。考察了表面活性剂的种类及SnCl4·5H2O的浓度对微球形貌的影响,分析了Ag纳米颗粒在微球表面分布的均匀性。通过XRD、SEM、EDS、TEM等分析手段对产物进行了表征。结果表明,以PEG6000为模板导向剂,SnCl4浓度为2mmol时,可以得到分散性良好、直径约为1μm的SnO2微球,微球由平均晶粒尺寸约为5nm的SnO2纳米晶粒组装而成;以Sn2+活化处理SnO2微球,弱还原剂聚乙烯吡咯烷酮(PVP)还原Ag+,可以得到Ag纳米颗粒均匀沉积的载银SnO2复合微球。     

Preparation and electrochemical performance of nano-scale nickel hydroxide with different shapes

Platelet-like, flake-like, and needle-like nano-scale β-Ni(OH)₂ particles were prepared by coordination homogeneous precipitation method in this paper. X-ray diffraction (XRD), transmission electron microscopy (TEM) and infrared absorption spectra (IR) were used to characterize the microstructure and morphology of the products. The nano-scale Ni(OH)₂ composite electrodes were prepared by mixing 10 wt.% samples with spherical Ni(OH)₂ to carry out charge-discharge test. The results show that the nano-scale Ni(OH)₂ composite electrodes have higher discharge specific capacity, and the nickel hydroxide nanoneedles show a better adulteration performance than the others.     

Fabrication and properties of spray-dried nanofeatured spherical Ni(OH)2 materials

Spherical agglomerates of nanostructured beta-phase Ni(OH)2 with the general formula Ni1-xCox(OH)2 (x = 0, 0.1, 0.3) for use as cathode materials were produced by a modified method including coprecipitation of Ni or Ni composite hydroxide and further spray drying of the precipitated and washed slurry. This process leads to the formation of spherical agglomerate particles with a narrow Gaussian-type distribution range. The method permits faster and cheaper production of cathode materials with a higher specific surface area and similar or better capacity and cycle life compared with the materials prepared via conventional technology.     

镍电极的固相掺杂及在非对称电容中的应用

应用CoO、Zn粉对镍电极进行固相掺杂,电极经若干次充放电循环,Co、Zn元 素在Ni(OH)₂颗粒表层以固溶体的形式富集,可优化活性物质表面的组成和结构,提高活性物 质表层的快速反应能力,从而使镍电极更适用于C／Ni(OH)₂非对称电容器体系.实验结果表 明:在高倍率充放电条件下,掺杂10％CoO的镍电极,其容量为未掺杂电极的2倍;用5％的 Zn粉替代部分导电剂Ni粉,镍电极大电流条件下的循环性能和容量性质将明显改善.     

Mechanically alloyed Ni/8YSZ powder mixtures: preparation, powder characterization and sintering behavior

A state of the art anode for the solid oxide fuel cell (SOFC)consists of a mixture of 8 mol % Y2O3-stabilized zirconia (8YSZ) andnickel particles, which form an interconnected porous structure after sintering. Coarsening of the Ni particles under SOFC workingconditions has to be avoided, hence it leads to a deterioration of the anode's performance. In the present work the aim was to improve thestability of the Ni particles by a reduction of the sinteringactivity of nickel. For this purpose between 10 and 50 % by volume of nano-sized zirconia particleshave been dispersed in the nickel matrix by dry ball milling in a planetary mill.Forpressed samples made of mechanically alloyed Ni with 10 vol % of 8YSZ,a homogeneous dispersion of 8YSZ particles in the Ni matrix wasconfirmed by transmission electron microscopy. It was confirmed bymercury porosity penetration and optical microscopy that thisdispersoid structure leads to a retardation of recrystallization.Also, an essentially lowered densification during sintering was found, compared to samples made of the pure Ni powder. Samples made of mechanically alloyed Ni with a higher zirconia amountshowed a higher densification during sintering and annealing thansamples containing 10 vol % 8YSZ. It is assumed that this results frominsufficient dispersion in these systems. The results show that mechanically alloyed nickel,with a homogeneous dispersion of 8YSZ crystallites, is a promising candidate for high temperature catalysts.     

Morphology and crystallographic phase of V–C particles formed in Fe–Cr–Ni–V–C alloys

Abstract

The morphology and crystallographic phase of V–C carbide particles formed in cast Fe–Cr–Ni–V–C alloys were investigated by means of X-ray diffraction, scanning electron microscopy and transmission electron microscopy (TEM). The combination of results obtained with these techniques revealed that cuboidal, cruciform and spherical carbide particles were formed, depending on the alloy composition, all having the cubic-VC_1?x structure (Fm-3m). Detailed TEM observations suggested that small carbide particles were initially cubic in shape and became spherical with increasing particle size. All cuboidal and spherical carbides were single crystallites with no grain boundary at any particle sizes, even after growing to 6 μm in diameter.     

The microstructure and wear resistance characteristics of electroformed nickel and partially stabilized zirconia composite coatings

Ni-PSZ composite coatings with various PSZ particle content were prepared by the electroforming technique. The microstructure and surface components of the coatings have been examined by optical microscopy, electron microscopy and X-ray photoelectron spectroscopy analysis and the wear properties of the coatings tested on a reciprocating wear test machine. The results show that the PSZ particles are uniformly dispersed in the coatings and thus increase the wear resistance of the coatings by inhibiting plastic deformation of the nickel matrix. The co-deposition of the PSZ particles in the electrolyte is mainly in the form of agglomeration and is accompanied by the incorporation of Ni(OH)₂. When the PSZ content in a coating is higher than a critical value, the wear resistance of the coating could deteriorate because of the decrease in the integrity of the nickel matrix. After heat-treatment at high temperature, Ni(OH)₂ in the coating is turned into Ni₂O₃ and NiO which can wet the PSZ particles and increase the bonding strength between the PSZ and nickel. In addition, the agglomerated PSZ particles are sintered when heat-treated. These are all beneficial to increasing the wear resistance of the coating.     

Analysis of the Phenomena of Diamond Synthesis by Seeding with Diamond

Synthesizing diamond single crystal by diamond seed particles which were electroplated with nickel film as catalyst under high pressure and high temperature （HPHT） was described. The microstructure of nickel film after synthesis and morphology of grown diamond were investigated by means of X-ray diffraction （XRD） and scanning electron microscopy （SEM）, respectively. The phase structure in nickel film were graphite, NiC, Ni, and diamond structure hadn＇t been found. A lot of recrystallized graphite pits appear in interface between the inner surface of nickel film and the surface diamond. It is shown that the new-grown diamond was developed epitaxially on the crystal planes of seeds. Also, the new-grown diamond grew by two-dimensional nucleation and by a layer growth mechanism. The growth process of crystal was microaggregate→step→expansion→new crystal layers, and the flat growth interface transformed into a cellular interface at the same time.     

Transparent conducting properties of Ni doped zinc oxide thin films prepared by a facile spray pyrolysis technique using perfume atomizer

Undoped and Ni doped zinc oxide (Ni–ZnO) thin films were prepared by a facile spray pyrolysis technique using perfume atomizer from aqueous solution of anhydrous zinc acetate (Zn(CH₃COOH)₂ and hexahydrated nickel chloride (NiCl₂·6H₂O) as sources of zinc and nickel, respectively. The films were deposited onto the amorphous glass substrates kept at (450 °C). The effect of the [Ni]/[Zn] ratio on the structural, morphological, optical and electrical properties of Ni doped ZnO thin film was studied. It was found from X-ray diffraction (XRD) analysis that both the undoped and Ni doped ZnO films were crystallized in the hexagonal structure with a preferred orientation of the crystallites along the [002] direction perpendicular to the substrate. The scanning electron microscopy (SEM) images showed a relatively dense surface structure composed of crystallites in the spherical form whose average size decreases when the [Ni]/[Zn] ratio increases. The optical study showed that all the films were highly transparent. The optical transmittance in the visible region varied between 75 and 85%, depending on the dopant concentrations. The variation of the band gap versus the [Ni]/[Zn] ratio showed that the energy gap decreases from 2.95 to 2.72 eV as the [Ni]/[Zn] ratio increases from 0 to 0.02 and then increases to reach 3.22 eV for [Ni]/[Zn] = 0.04. The films obtained with the [Ni]/[Zn] ratio = 0.02 showed minimum resistivity of 2 × 10⁻³ Ω cm at room temperature.     

New route for synthesis of electrocatalytic Ni(OH)2 modified electrodes—electrooxidation of borohydride as probe reaction

Immobilization of redox species like Ni(OH)₂ onto the electrode surface is important in the application areas such as super capacitor, electrochromic displays and electrocatalysis. Nickel hexacyanoferrate (NiHCF) modified glassy carbon could be further derivatized with Ni(OH)₂ by electrochemical cycling in alkali. The electrodeposition of Ni(OH)₂ was usually carried out onto the electrode surface from nickel salt at high interfacial pH. This paper reports the preparation of Ni(OH)₂ from insoluble nickel tetracyanonickelate supported on carbon (NTN/C). This insoluble precursor complex was decomposed by two methods. (1) By potential cycling of modified electrode with the above complex in alkali. (2) By thermal decomposition of the precursor complex (NTN/C) to form metallic nickel followed by cycling in alkali. Ni(OH)₂ modified electrodes formed using both methods were characterized by cyclic voltammetry and also by Fourier transform infrared spectroscopy, X-ray diffraction and scanning electron microscopy. Further, electrocatalytic properties of Ni(OH)₂/C modified electrodes formed by the above two methods were studied and compared using borohydride oxidation as probe reaction.