基于β-FeOOH纳米棒制备LiFePO_4/C和Fe_2O_3纳米电极材料及其电池性能

自制直径为90nm、长为500nm的β-FeOOH纳米棒为前驱物,通过碳热还原法和热分解法分别制备出形貌均匀、粒径为300nm的LiFePO4/C正极材料和粒径为100nm的Fe2O3负极材料,并研究它们对金属锂组成半电池和构造LiFePO4/C vs.Fe2O3全电池的电化学性能。结果表明：LiFePO4/C半电池在0.1C、0.5C、1.0C、5.0C、10.0C和15.0C（1C=170 mA g–1）倍率下放电比容量分别为158.8、153.2、144.3、126.8、111.0 mA h g–1和92.9mA h g–1。经过不同倍率循环后,返回0.1 C放电比容量为157.5mA h g–1,为初始0.1 C放电比容量的99.2%。Fe2O3半电池在50mA g–1电流密度下首次放电比容量为1655.5mA h g–1,循环50次后,仍保持460mA h g–1的放电比容量。LiFePO4/C vs.Fe2O3全电池在0.1 C倍率下,相对于LiFePO4活性物质,首次放电比容量为148.7mA h g–1;相对于Fe2O3活性物质,首次放电比容量为441.7mA h g–1。由LiFePO4/C纳米粒子作为正极材料、Fe2O3纳米粒子作为负极材料组成的全电池在0.1 C到2.0 C不同倍率下均表现出了良好的循环性能,且返回0.1 C后其放电比容量相对于初始0.1 C放电比容量无衰减。可见,以β-FeOOH纳米棒为前驱物控制制备的LiFePO4/C正极纳米材料和Fe2O3负极纳米材料可以有效地提升电池的性能。     

V_2O_5/石墨烯复合电极材料的制备与储锂性能

采用溶胶-凝胶法制备了V_2O_5/石墨烯复合电极材料。利用SEM、XRD、Raman和TGA表征了其微观结构。结果表明,该复合电极材料是含有质量分数0.55%石墨烯的片状正交相V_2O_5。电化学测试表明,与未复合石墨烯的纯V_2O_5样品相比,V_2O_5/石墨烯复合材料具有更高的储锂活性和优异的大电流放电性能。在200 m A/g的电流密度下,V_2O_5/石墨烯复合材料和纯V_2O_5样品的放电比容量分别为283和253 m A·h/g;当电流密度增加到5 A/g时,V_2O_5/石墨烯复合材料依然保持有150 m A·h/g的放电比容量,而纯V_2O_5样品的放电比容量仅为114 m A·h/g;V_2O_5/石墨烯和纯V_2O_5电极的电荷传递电阻分别为142和293Ω。V_2O_5/石墨烯//Li4Ti5O12全电池测试结果表明,在1.0~2.5 V电压内,循环初期全电池正极材料的放电比容量从110 m A·h/g衰减到96 m A·h/g,随后又出现上升,循环100次后,正极材料的放电比容量稳定在102 m A·h/g,库伦效率接近100%,表明V_2O_5/石墨烯复合电极材料是一种非常有应用前景的锂离子电池电极活性材料。     

锂离子负极材料NiFe_2O_4/Graphene复合材料的制备和电化学性能

通过水热法合成了NiFe2O4/Graphene纳米复合材料,采用XRD和SEM对其晶相结构和形貌进行了表征,并将其作为锂离子电池活性材料组装成模拟电池,考查电化学性能。结果表明NiFe2O4/Graphene复合材料在100mA/g的电流密度下首次放电容量达970mAh/g,循环20次后,容量保持在668mAh/g,相比纯的NiFe2O4,具有较好的循环稳定性,这种优异的电化学性能归因于复合材料的纳米结构和NiFe2O4与Graphene的协同作用。     

高活性Fe2O3@Ni复合电极制备及电化学性能研究

以六水三氯化铁为铁源，采用水热法合成了高活性Fe2O3@Ni复合电极材料。运用X射线衍射、拉曼光谱、扫描电镜对产物的物相及微观形貌进行了表征。结果表明在泡沫镍表面原位合成的氧化铁是由直径约为5~20 nm的纳米丝交织而成的，从而构成有序三维网状结构，分布均匀紧密。采用循环伏安测试、恒电流充放电测试研究了Fe2O3@Ni复合电极材料的电化学性能，Fe2O3@Ni复合电极呈现赝电容的特性，在电流密度为1 A/g时，Fe2O3@Ni复合电极材料比电容可达532 F/g。     

锂离子电池用Fe_3O_4/纳米碳复合材料的制备及性能

以苯甲醇为溶剂和还原剂,溶剂热法一步合成四氧化三铁/石墨烯-碳纳米管(Fe3O4/r-GOCNTs)三元复合材料。X射线衍射仪(XRD)、傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)和高倍透射电镜(HRTEM)测试显示,Fe3O4纳米晶体的生成与氧化石墨烯的还原是同时发生的,Fe3O4的尺寸约为10 nm,均匀且稳固地生长在r-GO片层和CNTs组成的三维网络结构上。电极材料在0.1 A/g下循环100次之后可逆比容量为840 mA·h/g,循环稳定性明显优于纯Fe3O4电极。     

烧结温度对Fe(OH)3胶体制备Fe2O3材料储锂性能的影响

以Fe(OH)_3胶体为铁源,探索了一步烧结法制备二维片状结构Fe_2O_3电极材料,考察了烧结温度(400、500、600和700℃)对材料微观结构和储锂性能的影响。结果表明:400℃烧结的样品为α-Fe_2O_3/Fe_3O_4复合材料,其他温度烧结得到的是纯的α-Fe_2O_3;随着烧结温度的升高,组成片状结构致密相连的不规则颗粒逐渐分离,二维片状结构接近坍塌。电化学性能研究发现:500℃下得到的样品电极具有相对较好的储锂性能,在1 A/g的电流密度下循环450圈后放电比容量达628.6 mA·h/g,当电流密度为4 A/g时,放电比容量仍有352.3 mA·h/g。动力学及电极稳定性分析发现,500℃烧结的样品Li~+扩散系数最大(还原峰和氧化峰对应的扩散系数值分别为:1.57×10~(–13)和4.60×10~(–13) cm~2/s),充放电循环过程中结构稳定性最好。     

Co–MOFs纳米片/碳布复合材料的制备及在锂离子电池中的应用

采用液相沉积法在导电碳布表面原位生长Co–MOFs纳米片,制得了Co–MOFs/CF复合材料。通过红外光谱、X射线衍射、扫描电子显微镜、恒流充放电、循环伏安、电化学阻抗等手段对材料的组成、结构形貌和电化学性能进行了表征。结果表明:当用作无黏结剂型锂离子电池电极时,在50 mA/g电流密度下,Co–MOFs/CF的首次放电比容量为1 621.3 mA·h/g,100次循环后,其放电比容量仍可达445.1 mA·h/g。相比于纯Co–MOFs,Co–MOFs/CF的首次Coulomb效率和循环性能均有明显改善,主要归因于Co–MOFs的二维片状结构与碳布良好导电性之间的协同作用,Co–MOFs/CF优异的电化学性能使其成为很好的锂离子电池电极候选材料。     

新型煅烧法制备分级多孔NiO/Ni及其电化学性能研究

采用新型煅烧法制备分级多孔Ni O/Ni纳米复合材料,考察不同冷冻条件对该纳米复合材料的结构形貌及电化学性能的影响。当冷冻温度为-20℃时,材料具有微孔-介孔分级多孔结构,比表面积为337.6 m~2/g,孔体积为1.37 cm~3/g。此外,材料表面均匀负载纳米Ni颗粒,可有效改善Ni O的导电性。电化学性能测试结果表明,0.1 C放电比容量为983 m A·h/g,首次库伦效率高达86%。该方法中引入冷冻步骤,大幅降低了固相法制备Ni O基纳米复合材料的煅烧温度,是一种环保低能耗制备纳米材料的新方法。     

Fe_3O_4/石墨烯复合材料的制备及其电化学性能研究

以FeCl_3·6H_2O和FeCl_2·4H_2O为铁源,以Na OH溶液为沉淀剂,选择共沉淀法制备Fe_3O_4∕石墨烯复合物。以Fe⁽²⁺⁾和Fe(2+)和Fe⁽³⁺⁾的浓度作为变量制得5种不同比例的Fe_3O_4/石墨烯纳米复合材料,然后将所得复合材料压制成电极片,组装成超级电容器后进行循环伏安(CV)、恒电流充放电(GCD)、交流阻抗(EIS)测试,探究Fe_3O_4与石墨烯的含量比对复合材料电化学性能的影响。结果表明,当FeCl_3·4H_2O和FeCl_2·4H_2O用量分别为0.456 g和0.665 g,氧化石墨烯用量为150 mg时,所制备复合材料的电化学性能最佳,比电容可达510 F/g。     

空心球状Fe_3O_4纳米晶的制备与电催化性能

采用微乳-溶剂热法制备了空心球状Fe3O4纳米晶。利用X射线衍射(XRD)和扫描电子显微镜(SEM)对所制备的样品进行晶型结构表征和形貌观察。制备的Fe3O4颗粒为粒径550 nm的空心球状。对以纳米Fe3O4空心球为电催化剂的锂-空气电池进行恒流充放电和交流阻抗测试。在50 m A·g-1的电流密度下,电池的首次放电容量高达1602 m Ah·g-1,放电电压平台为2.8~2.2 V,充电电压平台为3.8 V左右。     

钕-铝系稀土色料的研制

通过钕-铝系列色料合成实验,分析不同配比及不同矿化剂等对色料呈色效果的影响,确定最佳工艺方法。对实验结果进行XRD及色度分析,确定其主晶相为钕酸铝,试样的明度均在70以上,色彩鲜艳亮丽。     

Polycrystalline In2O3 and In2O3/Y2O3 photoanodes

Single crystal In₂O₃ shows promise as a photoanode for the decomposition of water. Because of various difficulties in the preparation of the single crystal material, two simple techniques were developed for the preparation of polycrystalline In₂O₃ anodes. One method involves the thermal decomposition of the nitrate while the other utilizes the chemical vapour deposition technique. Voltammograms and photoresponse spectra of these anodes are compared to the single crystal material. Among other observations, it is noted that the quantum efficiencies of the thermally decomposed films are comparable to the single crystal material. It is also shown that the on-set potential can be shifted to more negative values by forming the mixed oxide In₂O₃/Y₂O₃.     

Phase equilibrium in binary La2O3-Dy2O3 and ternary CeO2-La2O3-Dy2O3 systems

Cerium oxide doped with oxides of rare earth elements is a multifunctional material, a wide range of uses which is associated with its unique physicochemical properties. Phase diagrams of multicomponent systems are the physicochemical basis for the creation of new materials with improved characteristics.In this work, phase equilibria in ternary CeO₂–La₂O₃–Dy₂O₃ and binary La₂O₃–Dy₂O₃ systems in the whole concentration range were studied. No new phases have been identified in these systems. An isothermal section of the phase diagram of the CeO₂–La₂O₃–Dy₂O₃ system at a temperature of 1500 °С is constructed. No new phases have been detected in the system. It was found that in the studied ternary system solid solutions are formed on the basis of (F) modification of CeO₂ with structure of fluorite type, monoclinic (B), cubic (C) and hexagonal (A) modifications of Ln₂O₃.In the La₂O₃–Dy₂O₃ binary system (1500–1100 °С) three types of solid solutions are formed: based on hexagonal modification A-La₂O₃, monoclinic modification B-Dy₂O₃ and cubic modification C-Dy₂O₃ separated by two-phase fields (A+B) and (B+C), respectively. The boundaries of the regions of homogeneity of solid solutions based on A-La₂O₃ are determined by compositions containing 35–40, 20–25, 15–20 mol% Dy₂O₃ at 1500, 1250, 1100 °C, respectively. From the obtained data it follows that the solubility of Dy₂O₃ in the hexagonal modification of lanthanum oxide is 39 mol% at 1500 °C, 23 mol. % at 1250 °C and 16 mol% at 1100 °C. The limits of existence of solid solutions based on monoclinic B-modification are determined by compositions containing 30–35, 65–60 (1250 °С), 35–40, 55–60 (1100 °С) 40–45, 70–75 (1500 °C) mol% Dy₂O₃.In the studied system, with a decrease in temperature from 1500° to 1100°C, there is a decrease in the solubility of La₂O₃ in the crystal lattice of cubic solid solutions of C-type from 16 to 10 mol%.     

Bactericidal Effectiveness of O3, O3/H2O2 and O3/TiO2 on Clostridium perfringens

The purpose of this research is to evaluate the bactericidal capacity of different Advanced Oxidation Treatments (AOTs) based on ozone: ozone, ozone/hydrogen peroxide and ozone/titanium dioxide on a wild strain of Clostridium perfringens, a fecal bacterial indicator in drinking water. The dose of ozone consumed ranges from 0.6 mg L^?1 min^?1 to 5.13 mg L^?1 min^?1 depending on the process and on the sample. In the treatments combined with O₃, H₂O₂ dose utilized is 0.04 mM and TiO₂ dose, 1 g L^?1. In order to evaluate the influence of natural organic matter and suspension solids over the disinfection rate, treatments are performed with two types of water – natural water from Ebro River (Zaragoza, Spain) and NaCl solution 0.9%. To achieve 4 log units of inactivation, 3.6 mg O₃ L^?1 is necessary in O₃ treatment, 4.25 mg O₃ L^?1 in O₃/TiO₂ system and 2.7 mg O₃ L^?1 in O₃/H₂O₂ after processing the natural water. In NaCl solution, to get the same inactivation, 0.42 mg O₃ L^?1 is necessary in O₃ treatment, 1.15 mg O₃ L^?1 in O₃/TiO₂ system and 0.06 mg O₃ L^?1 in O₃/H₂O₂ process. Even though the three treatments studied have a high bactericidal activity due to the number of surviving bacteria decreases to non-detectable levels, O₃/H₂O₂ is the most effective system for eliminating C. perfringens cells in a lower contact time, followed by O₃ and finally O₃/TiO₂ system.     

Fe2O3-MnO-Cr2O3-La2O3系统紫色颜料的制备及表征

采用溶胶均匀共沉淀法于低温下合成了含少量稀土氧化物La2O3的紫色颜料，并采用颜色测定、SEM、XRD等手段对颜料的颜色、检度及结晶构造等进行了表征。     

Separation of Phases by Spinodal Decomposition in the Systems Al2O3−Cr2O3 and Al2O3−Cr2O3−Fe2O3

Separation of phases was investigated in the hexagonal (rhombohedral) systems Al₂O₃−Cr₂O₃ and Al₂O₃−Cr₂O₃−Fe₂O₃. The binary system shows a miscibility gap with a T_c of 950°C; the miscibility gap for the ternary system was determined for a constant Cr₂O₃ content of 16.6 mol%. Dark field transmission electron microscopy of solid solutions annealed within the miscibility gap showed dark and light lamellas ∼50 to 200 Å thick. X-ray diffraction results for the solid solutions in the ternary system indicated that, in the early stages of annealing, broadening occurred only on (hkl) reflections where l≠0. There was no major change in the X-ray diffraction patterns of the annealed solid solutions in the binary system. Electron diffraction results indicated, however, that phase separation in both systems proceeded in the [001] direction. Solid solutions in the binary system separated very slowly; the separation could be enhanced hydrothermally. The mechanism of the separation of phases in both systems is spinodal and proceeds as follows: solid solution→intermediate modulated phase→equilibrium phases.     

Na2O-Al2O3-Fe2O3系烧结过程中铝、铁的反应行为

以Al2O3, Fe2O3和Na2CO3为原料,对Na2O-Al2O3-Fe2O3系烧结过程中的反应行为进行了详细研究. 基于溶出率与时间、温度的关系,证明Na2O×Al2O3和Na2O×Fe2O3的生成反应动力学都服从Zhuralev-Lesokin-Tempelman模型,表观活化能分别为186.59和80.92 kJ/mol,表明Na2O×Fe2O3比Na2O×Al2O3在动力学上更易形成;Al2O3易与Na2O×Fe2O3反应形成Na2O×Al2O3和Fe2O3,在1273 K烧结30 min,所得熟料Al2O3溶出率达98.51%;Fe2O3对Na2O×Al2O3的形成有双重作用,在1273 K下可加速Na2O×Al2O3的形成,超过1323 K,促使Na2O×Al2O3分解成Na2O和b-Al2O3,且随着温度升高或时间延长,分解程度增高,从而导致熟料中Al2O3溶出率显著降低.     

Decomposition of Carboxylic Acids in Water by O3, O3/H2O2, and O3/Catalyst

This paper studies the decomposition of formic, oxalic and maleic acids by O₃, O₃/catalyst, and O₃/H₂O₂. The catalytic effect of Co²⁺, Ni²⁺, Cu²⁺, Mn²⁺, Zn²⁺, Cr³⁺, and Fe²⁺ ions is investigated. The results showed that—Co²⁺ and Mn²⁺ have the highest catalytic activity for the decomposition of oxalic acid while the catalytic effect of the studied ions is insignificant on the rate of decomposition of formic acid. Maleic acid decomposes by ozone into formic acid and glyoxylic acid, which subsequently oxidizes to oxalic acid. Though the studied ions have no effect on the decomposition of maleic acid, they have a significant effect on the produced oxalic and glyoxylic acids. In the presence of Cu²⁺ ions glyoxylic acid is mainly transformed into formic acid and traces of oxalic acid. In such case, a complete decomposition of maleic acid and its degradation products is achieved within 45 min. The results also show that combining H₂O₂ with O₃ results in an increase in the rate of decomposition of oxalic acid. However, O₃/H₂O₂ system is less active than O₃/Co²⁺ or O₃/Mn²⁺.     

ß-Al2O3 synthesis from m-Al2O3

-Al₂O₃ formation fromm-Al₂O₃ was found by a new convenient technique. By thermal decomposition of a complex compound, trioxalatoaluminate Na _x (NH₄)_3–x [Al(C₂O₄)₃]yH₂O(0.091 x 0.333;y= 3), a very fine powder ofm-Al₂O₃ was formed. The decomposition process was examined by thermal analysis and X-ray diffraction and the phase relation of the system Na₂O-Al₂O₃ in the midtemperature region between 600 and 1200° C is discussed briefly. The tablet ofm-Al₂O₃ was fired at 1600° C for 30 min to prepare dense-Al₂O₃ ceramics, the apparent density of which was greater than 95% of the theoretical value. The sintered tablet was examined from the structural point of view and the electrical conductivity was measured by an a.c. method to verify that the procedure of the complex decomposition is a suitable technique for-Al₂O₃ synthesis.