氧化还原法制备氧化锰超级电容器电极材料

以高锰酸钾(KMnO4)和聚乙烯吡络烷酮(PVP)为原料,采用氧化还原法制备介孔氧化锰.研究发现,产物的晶型和微观结构受KMnO4溶液浓度的影响.当KMnO4溶液浓度从0.1 mol·L-1增加到0.3 mol·L-1,产物从比表面积13.6 m2·g-1的晶态Mn3O4转变成比表面积约60 m2·g-1的非晶态MnO2.电化学测试表明:非晶MnO2具有最佳电化学性能,在2 mol·L-1 KOH溶液中,1 A·g-1的电流密度下的比电容可达442 F·g-1,5 A·g-1的电流密度下循环1100次后比电容保有率为72.6;.     

介孔氧化锌的微乳液法制备及表征

以十六烷基三甲基溴化铵(CTAB)/苯乙烯/硝酸锌溶液/过硫酸钾组成的聚苯乙烯微乳液为模板,提出一种制备介孔氧化锌的简易方法,研究了煅烧温度对介孔氧化锌结构特性的影响,提出了介孔形成的可能机制.结果表明:煅烧温度较高时,所得介孔氧化锌的孔径较大,比表面积较小;当煅烧温度为 500℃时,所得纳米氧化锌的比表面积为 11.013 m2·g-1,孔容为0.135 cm3·g-1,介孔分布在40.2 nm左右.此外,光催化降解亚甲基蓝的实验表明所制备的介孔 ZnO 具有较高的光催化性能.     

三维还原氧化石墨烯的制备及超级电容性能

以氧化石墨凝胶制备的氧化石墨烯溶胶为前驱体,一步水热法制备三维还原氧化石墨烯,采用XRD、Raman、XPS、SEM和TEM对其结构和形貌进行表征;将其作为超级电容器的电极材料时,采用直接压片法制备工作电极,在三电极体系中测试了材料的超级电容性能.结果表明:经一步水热法对氧化石墨烯溶胶进行还原处理,可去除结构中大部分的含氧官能团,所得三维还原氧化石墨烯呈多孔网状结构,层数为3～7层;比电容在0.5A·g-1的电流密度下可达294 F·g-1,且在1A·g-1电流密度下循环1000次后仍高达247 F·g-1,保持率为88.85;;欧姆电阻Rs约为0.52 Ω,界面电阻Rc约为1.53 Ω.相对于热还原法和化学还原法所制备的石墨烯材料具有更好的超级电容性能.     

腐植酸钾一步炭化活化制备孔径可调的活性炭材料及其电化学性能

以腐植酸钾为碳源,乙酸钾(CH3COOK)、氢氧化钾(KOH)、碳酸钙(CaCO3)分别为活化剂,在800℃氮气气氛下碳化活化1h制备出了具备不同孔结构的三种活性炭材料.利用N2吸附-脱附分析、扫描电子显微镜(SEM)分析了所得活性炭材料的孔结构和微观形貌,并利用循环伏安(CV)和恒流充放电(GCD)测试方法评价了其作为超级电容器电极材料的电化学性能.结果表明:不同活化剂对活性炭材料的比表面积和孔径分布影响显著,而后者又进一步决定了炭材料的比电容特性.其中,尤其是直径小于1 nm的超微孔炭材料可以获得很高的比电容.在三种不同结构的活性炭中,以CH3COOK为活化剂制备的活性炭具有最优的电化学性能,其比表面积约为1100m2/g,孔径集中在0.4 ～0.6 nm;在2 mol/L KOH电解液中,电流密度为0.1 A/g时比电容高达270 F/g;经3000次充放电循环后,该材料的比电容保持率仍超过87;,是一种性能较为理想的超级电容器用电极材料.     

氮掺杂酸角衍生多孔碳的制备及电容性能研究

随着化石燃料的加速消耗和能源危机的日益加剧,作为新型储能元件的超级电容器引起了研究人员极大的关注.本文通过水热法制备了生物质衍生多孔碳,并对该材料的微观结构和元素组成进行分析,研究了其作为超级电容器电极材料的电化学性能.结果表明,经过掺氮处理的酸角衍生多孔碳材料其比电容从166 F·g-1提高到了232 F·g-1,说明掺杂能有效提高生物质衍生多孔碳材料的电容性能.     

硅溶胶-硅微粉对层状托贝莫来石物化性质的影响

以硅溶胶和硅微粉为混合硅源,采用动态水热合成法成功制备了层状托贝莫来石催化剂,借助XRD、BET和NH3/CO2-TPD等手段对托贝莫来石进行分析表征,研究了不同硅源比例对托贝莫来石晶相结构、比表面积、孔结构性质及表面酸碱性质的影响.结果 表明:随非晶态硅溶胶占比增大,托贝莫来石比表面积和孔容呈逐渐增大趋势,但结晶度和表面酸碱量及弱酸弱碱强度逐渐下降.硅溶胶占比增至20;,托贝莫来石结晶度由81.65;下降至73.66;,总酸量由0.18 mmol·g-1降至0.14 mmol·g-1,总碱量由0.47 mmol·g-1降至0.40 mmol·g-1,比表面积由65 m2·g-1增至174 m2·g-1,孔容由0.15cm3·g-1增至0.60 cm3·g-1,出现介孔-大孔特征;硅溶胶占比增至30;,制得托贝莫来石产物出现少量SiO2晶相.     

溶剂热合成Co(OH)2/活性炭复合电极材料及其电化学性能研究

以Co(NO3)2·6H2O,CO(NH2)2和活性炭(AC)为原料,利用溶剂热法合成了Co(OH) 2/AC复合电极材料.X射线衍射仪、扫描电子显微镜、傅里叶红外光谱和热重分析显示,产物是约为2 μm无定形的Co(OH)2薄片状粒子与AC颗粒复合.电化学测试表明,在6 mol/L KOH电解液中电流密度为1A·g-1时,电极材料的比电容达301F·g-1,倍率特性良好(164 F·g-1,20 A·g-1);比电容值比AC和Co(OH)2分别提高了89;和35;.复合材料电化学性能提升源自于高导电性活性炭和高赝电容比容量Co(OH)2间的协同作用.     

NiTe电极材料的制备及其在超级电容器中的应用

采用二氧化碲(TeO2)为碲源,泡沫镍作为镍源及基底,水合肼(N2H4· H2O)为还原剂,利用一步水热法原位生长片状NiTe材料.将制得的NiTe作为超级电容器的电极材料,研究了水热温度对产物的微观形貌及电化学性能的影响规律,结果表明:当水热温度为180 ℃时,所制得的NiTe为均匀的片状结构,在三电极体系下获得的NiTe电极最大的质量比电容为603.6 F· g-1.利用 NiTe和AC 分别作为正极和负极,制备了非对称超级电容器(ASC).NiTe//AC ASC可以将电位窗口扩展到1.6 V,最大的能量密度和功率密度分别为25.8 Wh· kg-1和3994 W· kg-1.ASC显示出良好的循环稳定性,5000次循环之后保持了初始电容的83.3;.     

不同表面活性剂对合成介孔氧化镁晶体性质的影响

采用液相法,以Mg(NO3)2·6H2O为镁源,NH3·H2O为沉淀剂,研究了不同表面活性剂对介孔MgO晶体性质的影响.采用XRD、FT-IR、SEM、BET和CO2-TPD等手段对介孔MgO晶相组成、骨架结构、微观形貌、孔结构及表面化学性质进行了分析表征.研究结果表明,不同表面活性剂对介孔MgO晶体物化性质影响较大.以非离子型PEG-2000为表面活性剂制得产品表面碱强度和碱总量均大于以阴离子型SDS、阳离子型CTAB制得的产品.以非离子型PEG-2000为表面活性剂制备得到的介孔MgO同时具有弱碱、中强碱特征,碱总量为0.192 mmol·g-1,比表面积、孔容和平均孔径分别为145.42 m2·g-1、0.67 cm3·g-1和18.56 nm.     

沉淀pH值对SAPO-34/CZA复合催化剂物化性质及CO2加氢反应影响

研究了液相沉淀包覆工艺终点pH值对SAPO-34/CZA复合催化剂物化性质和CO2氢还原制低碳烯烃催化性能的影响.借助XRD、SEM、BET、NH3-TPD和CO2-TPD等手段对不同复合催化剂的晶相组成、微观形貌、孔结构及表面酸碱性质进行了分析表征.研究结果表明,沉淀pH值对SAPO-34/CZA复合催化剂物化性质和CO2加氢制低碳烯烃催化性能影响较大.过高或过低的沉淀pH值制得复合催化剂中SAPO-34分子筛结晶度、微孔比表面积及表面碱量均有所下降,呈现以介孔为主的孔结构特征;而当pH值为7时,制得复合催化剂形成了包覆相结构和微-介复合孔结构(微孔比表面积53.1 m2·g-1,介孔比表面积59.8 m2·g-1,总比表面积为112.9 m2·g-1,总孔容0.4 cm3·g-1,平均孔径14.6 nm);在反应温度325℃,还原温度285℃,反应压力3.0 MPa,体积比H2:CO2=3.0,空速3500 mL·g-1·h-1反应条件下,CO2转化率为64.8;,低碳烯烃选择性为49.8;.与pH=9制得催化剂比较,CO2转化率和低碳烯烃选择性分别提高了26.2;和19.2;.     

Modelling of mechanism of agglomeration of KCl crystallization

The article presents an analysis into agglomeration during KCl vacuum crystallization. The theoretical and experimental investigations into the mechanism of agglomeration during mass crystallization result in an extension of the growth phenomena within the known model equations. The basis for this is essentially constituted by the collision model concepts of the theory of floculation in disperse systems. The parameters derived from the microprocess analysis (energy dissipation, content of solids, growth rate of individual grains) lead to model equations which are confirmed by laboratory and test trials.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.     

Mechanism of thermal expansion of structural modifications of zinc pyrovanadate

Crystal chemical characteristics of the α and β modifications of Zn₂V₂O₇ are calculated based on in situ high-temperature X-ray measurements. The expansion of the structure is found to be strongly anisotropic up to the negative volumetric thermal expansion of the α-Zn₂V₂O₇ unit cell in the temperature range of 300–600°С, α _V =–17.94 × 10^–6 1/K. The transformations of the “hard” and “soft” sublattices with an increase temperature and at the phase transition are considered in detail. It is shown that the negative volumetric thermal expansion of α-Zn₂V₂O₇ is due to the degeneracy of the zigzag-like shape of zinc–oxygen columns at constant distances between their vertices.