水热合成时间对纳米MnO_2超电容性能的影响

以KMnO_4和MnSO_4·H_2O为原料,利用水热合成纳米MnO_2。采用X射线衍射(XRD)、场发射扫描电镜(SEM)、比表面积测试(BET)、循环伏安(CV)、恒流充放电以及交流阻抗(EIS)等方法研究水热合成时间对产物结构以及电化学性能的影响。结果表明水热合成为棒状纳米级α-MnO_2,随着水热合成时间增加,结晶度增加;水热合成纳米α-MnO_2在1 mol/L Na_2SO_4水溶液中具有良好的电化学电容性能,其中水热合成24 h制备棒状纳米MnO_2具有较高比电容,其真实电容量达到189 F/g;交流阻抗测试表明水热合成24 h制备的纳米MnO_2样品法拉第电荷传递能力和离子在电解液与活性材料界面的扩散能力得到提高,具有良好的电化学性能。     

泡沫镍负载球状NiCo_2O_4电极的制备及超级电容性能研究

采用水热法在泡沫镍上生长了球状钴酸镍(NiCo_2O_4)电极材料,利用扫描电镜(SEM)观测了纳米球的表面形貌,利用X射线衍射(XRD)分析了纳米球的结构,通过循环伏安、恒流充放电测试了电极的超级电容性能。结果表明:球状NiCo_2O_4直径500~600nm,均匀生长在泡沫镍骨架上,球状之间存在空隙,可以增大与电解液的接触面积。在电流密度为1A/g,NiCo_2O_4/泡沫镍复合电极放电比电容为970F/g,循环1000次后比电容仍保持在844F/g,放电比容量保持率为82.5%,具有优异的超级电容性能。     

NiCo_2O_4微球的制备及其电化学性能

通过简单的水热法以及后续热处理,成功合成介孔NiCo_2O_4微球。利用FESEM、TEM、XPS和电化学工作站对样品的表面形貌、元素价态和电化学性能进行表征。结果表明:合成的NiCo_2O_4拥有丰富的多孔纳米针状结构,表现出较高的比表面积。由于这种三维多孔纳米结构,当NiCo_2O_4微球作为电极材料时,展现出优异的电容特性,在1A·g-1的电流密度下比电容高达1 554F·g-1,而且当电流密度增加到20A·g-1时,电容保持率为87.5%。另外,在5A·g-1的电流密度下,经过2 000次的充放电循环后,比电容仍能保持初始电容的90.4%。良好的电化学性能表明,NiCo_2O_4微球是一种理想的超级电容器电极材料。     

聚吡咯包覆NiCo_2S_4纳米管阵列的制备及其赝电容性能北大核心CSCD

使用两步水热法在泡沫镍表面生长NiCo_2S_4纳米管阵列,再通过电化学聚合技术将聚吡咯包覆在NiCo_2S_4纳米管表面形成核壳式复合材料。通过多种手段表征复合材料的物相与微结构,表明管外径约130nm,管壁厚约15nm,聚吡咯包覆膜平均厚度约8nm。研究聚吡咯包覆对NiCo_2S_4纳米管赝电容性能的影响,揭示聚吡咯改善了NiCo_2S_4纳米管的比电容、充放电性能、倍率性能和循环性能。放电比容量与未包覆的相比从1123F·g^(-1)增长到1524F·g^(-1),增加了36%;3000次循环后,聚吡咯包覆NiCo_2S_4仍释放比容量1096F·g^(-1),相比于第一次的保持率为78.5%,而未包覆的比容量只有22%的保持率。赝电容性能的改善主要是由于聚吡咯提高了NiCo_2S_4纳米管的电导率和结构稳定性。     

发射状OMS2型MnO2的制备及其超级电容性能

在不同的反应时间下水热法控制制备发射状超级电容器用MnO2电极材料,采用X射线衍射光谱(XRD)、扫描电镜(SEM)表征其结构,采用循环伏安、恒流充放电和交流阻抗研究其电化学电容性能。结果表明,制备的MnO2为隐钾锰矿型,具有发射状结构,随着反应时间的延长,MnO2的晶型从不完善逐渐变得完善,发射状结构逐渐明显、增大,并且MnO2辐射出的每根单枝从较细的纳米刺逐渐生长为四方结构的纳米棒;在5mA/cm2的电流密度下,最高比电容达到了448F/g;随着反应时间的增加,MnO2电极的比容量先增长再降低。     

锂空气电池α-MnO2纳米线催化剂的合成及表征

锂空气电池具有与汽油相当的理论能量密度,成为电动汽车最具潜力的动力源。通过水热法制备了锂空气电池的空气电极催化剂α-MnO_2纳米线。利用X射线衍射仪、扫描电子显微镜等仪器对催化剂的结构与表面形貌进行了表征。通过充放电测试和循环伏安测试,研究并比较了α-MnO_2、商业二氧化锰和导电炭黑(Super P)电化学性能的区别。测试结果表明,以α-MnO_2作为催化剂的锂空气电池首次放电比容量可达10163.2mAh/g,首次充放电库伦效率为87.6%,可稳定循环超过15次,具有良好的电化学性能。     

核壳结构MnCO3@Mn3O4球形颗粒的制备及其电化学性能研究

以硫酸锰为原料合成出球状MnCO3作为前驱体,加入KMnO4,通过化学沉淀法成功制备出粒径范围在0.5～1.0μm的核壳结构MnCO3@Mn3O4球形颗粒。通过对比实验发现,MnCO3、KMnO4和盐酸的添加量对最终产物的形成有很大的影响。电化学性能测试表明,核壳结构MnCO3@Mn3O4球形颗粒兼有双电层电容和赝电容特性,其最大比电容可以达到156F/g。     

“一步法”合成NiCo_2S_4纳米阵列高性能能量存储器件电极的研究

通过简单的"一步低温原位合成"法成功制备出了以泡沫镍为基底的具有自支撑结构的分层三维网络的NiCo_2S_4纳米阵列,采用SEM、XRD对产物的微观结构进行表征,并对其进行电化学性能测试。结果表明,由于这种独特的分层网络结构,该NiCo_2S_4纳米阵列不仅能够为能量存储提供大量的电化学活性位点,而且拥有良好的电子传递性能,NiCo_2S_4@泡沫镍电极在20 m A/cm~2的电流密度下,面积比电容可达到10.15 F/cm~2,且当电流密度增大到100 m A/cm~2时,面积电容仍然为7.29 F/cm~2,显示出优异的电容保持率;当NiCo_2S_4负载量是14.8 mg时,电流密度为20 m A/cm~2,充放电5 000次,电容保持率是72.5%,显示出NiCo_2S_4@泡沫镍电极良好的循环稳定性。     

水热法制备CoFe2O4/石墨烯复合物及其电化学性能

本研究采用水热法制备了质量比为2∶1的CoFe2O4/石墨烯(CoFe2O4/graphene)复合物,利用XRD、FT-IR和TEM对样品的结构和形貌进行了表征,采用循环伏安法(CV)和恒电流充放电测试研究了其电化学性能。结果表明,CoFe2O4均匀的分布在石墨烯表面,粒径大约为10nm。在0.5A/g的电流密度下,比电容为105F/g。1000次循环后,电容保持率在90%以上。     

ZnCo2O4及ZnCo2O4/rGO复合材料的制备与电化学性能

采用一步水热法制备尖晶石型钴酸锌(ZnCo_2O_4)及钴酸锌/石墨烯(ZnCo_2O_4/rGO)复合材料,通过XRD,SEM和RST5000电化学工作站对材料的组分、表面形貌及电化学性能进行表征。通过改变水热温度,制备出具有辐射状花簇团结构、褶皱片层结构和表面光滑的球体结构的ZnCo_2O_4电极材料。结果表明:加入石墨烯后,ZnCo_2O_4呈规则的多边形结构,附着在石墨烯片上,两者的协同作用可有效改善电极材料的电化学性能;钴酸锌与氧化石墨烯的质量比为6∶1时得到的ZnCo_2O_4/rGO复合材料的比电容为205F/g,比纯ZnCo_2O_4的比电容提升了约114%。     

K2(Rb2,Cs2,Tl2)TeBr6(I6) and Rb3(Cs3)Sb2(Bi2)Br9(I9) perovskite compounds

We systematize available experimental data on the crystal structure of the ternary halides K₂(Rb₂,Cs₂,Tl₂)TeBr₆(I₆) and Rb₃(Cs₃)Sb₂(Bi₂)Br₉(I₉), analyze the general trends in the properties of their single crystals, and examine the key features of the physicochemical interaction in related systems.     

Al2O3/SiO2 and HfO2/SiO2 dichroic mirrors for UV solid-state lasers

HfO₂/SiO₂ and Al₂O₃/SiO₂ multilayers to be employed as high reflectance end mirrors in Cerium-doped fluoride solid-state lasers were produced by radio frequency sputtering. The components were designed to have high transmittance at the pumping wavelength and high reflectance in a wavelength band corresponding to the active medium emission. A photoacoustic beam deflection technique and inspection of the irradiated area under a microscope were used to measure the laser induced damage threshold of the mirrors at the pumping wavelength. These coatings were tested in a laser cavity.     

Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films

Sol-gel SiO₂/TiO₂ and TiO₂/SiO₂ bi-layer films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO₂/TiO₂ and CS TiO₂/SiO₂ bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO₂/TiO₂ bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO₂ single-layer component and arrangement of the bi-layer structure, i.e. TiO₂ underlayer or overlayer.     

Syntheses and structures of Ta2(WO2)0.87H0.26(PO4)4 and Ta2(MoO2)(PO4)4

Tantalum hydrogen phosphate, β-TaH(PO₄)₂, has a three-dimensional structure that is stable to remarkably high temperature (∼600 °C) presumably due to the presence of strong hydrogen bonds. Impedance measurements indicate a low conductivity, 2.0 × 10⁻⁶ S/cm at 200 °C in 5% H₂. In further studies aimed at enhancing the conductivity by aliovalent doping, we have investigated systematically the synthesis of compounds in the TaH(PO₄)₂-W₂P₂O₁₁ system at 380 °C. As a result, a new phase, Ta₂(WO₂)_0.87H_0.26(PO₄)₄, was identified and subsequently the molybdenum analog Ta₂(MoO₂)(PO₄)₄ was also prepared. The structures were determined by single crystal X-ray diffraction techniques. The structures of Ta₂(WO₂)_0.87H_0.26(PO₄)₄ and Ta₂(MoO₂)(PO₄)₄ can be formally derived from the structure of β-TaH(PO₄)₂ by the replacement of two P-OH protons with an MO₂²⁺ (M = Mo and W) group together with a change in the orientation of some phosphate tetrahedra.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Crystal Structure of (H3O)2[(UO2)2(SeO4)3(H2O)2](H2O)3.5

Crystals of (H₃O)₂[(UO₂)₂(SeO₄)₃(H₂O)₂](H₂O)_3.5 were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 11.9402(11), b = 13.6452(14), c = 13.7271(12) Å, β = 109.436(7)°, V = 2109.1(3) ų] was solved by the direct method and refined to R ₁ = 0. 048 (wR ₂ = 0. 082) for 3677 reflections with |F _hkl |F _hkl |. The structure consists of [(UO₂)₂(SeO₄)₃(H₂O)₂]₂₋ layers arranged parallel to the (010) plane. The layers are formed by uranium and selenium coordination polyhedra sharing common vertices and are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups arranged between the layers. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 412–414. Original Russian Text Copyright ? 2005 by Krivovichev, Kahlenberg.     

The role of TiO2 and ZrO2 in Na2OMO2SiO2 glasses

The glass transition temperatures of $\text{(1?x)}\text{Na}{}_2\text{O}\text{·}\text{1}\text{2}\text{x}\text{MO}{}_2\text{·2}\text{SiO}{}_2$ and Na₂O·xMO₂·(2 ?x)SiO₂ glasses, with M = Ti or Zr, have been related to the structural role and coordination of Ti and Zr. The role of network-former, intermediate or modifier of a cation has been fundamentally linked to ionic field strength; T_g values depend on ionic field strength and coordination. Titanium behaves like an intermediate oxide; its coordination ranges between four and six, depending on $\text{Ti}\text{Si}$ ratio. The role of zirconium changes according to the degree of substitution for Na or Si and progressively approaches that of a modifier ion.     

Hydrothermal Crystallization in the Systems La2(CO3)3 ? 6H2O-CaCO3(BaCO3)-R-H2O (R = Na2CO3, K2CO3, NaHCO3, KHCO3, NaCl, NH4Cl, CO(NH2)2)

Crystallization in the systems La₂(CO₃)₃ ⋅ 6H₂O-CaCO₃(BaCO₃)-R-H₂O (R = Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, NaCl, NH₄Cl, CO(NH₂)₂) was studied under hydrothermal conditions (400–450°C). The solid reaction products were found to contain LaOHCO₃ and NaLa(CO₃)₂. Detailed thermal decomposition schemes were proposed for these phases, and their lattice parameters were refined. __________ Translated from Neorganicheskie Materialy, Vol. 41, No. 11, 2005, pp. 1366–1372. Original Russian Text Copyright ? 2005 by Nikol'skaya, Dem'yanets.     

Microstructure control for sputter-deposited ZrO2, ZrO2·CaO and ZrO2·Y2O3

The microstructure of pure and oxide-stabilized cubic ZrO₂ has been determined as a function of the principal deposition conditions for coatings prepared by r.f. diode reactive sputtering. Broad control of crystal structure, phase composition, grain size and crystallographic orientation is obtained by appropriate selection of the target composition, substrate bias and substrate temperature. The crystal structure and phase composition obtained for coatings are compared with predictions based on the equilibrium phase diagrams. The microstructural control demonstrated in this work should make possible rapid, efficient and systematic optimization of ZrO₂ coatings for future engineering applications.     

Reactivity of the H2O2/TiO2 system

The reactivity of the H₂O₂/TiO₂ system for samples treated at atmospheric pressure is studied by means of Auger Electron Spectroscopy. The most significant changes on the TiO₂ ‘final’ state are: (i) The I(O)/I(Ti) peak-to-peak ratio is diminished by 15%. (ii) The LMV transition suffers an energy shift of +2 eV, whereas the peak-to-peak width diminishes 1.5 eV. (iii) Its structure changes with respect to that of the TiO₂ ‘initial’ state although it is not identified with any one of the known stoichiometric oxides. (iv) When the samples that represent the ‘final’ state are heated up to 650 K, the AES spectrum matches quite well that of the TiO₂ ‘initial’ state.