Preparation and electrocatalytic property of Au-Pt/SnO2/GC composite electrode

Au-Pt/SnO2/GC composite electrode was prepared by self-assembling Au-Pt nanoparticles on SnO2 film, which was deposited on actived glassy carbon (GC). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images revealed that dense and uniform Au-Pt particles with 25-nm diameter were dispersed on SnO2 film. X-ray photoelectron spectroscopy (XPS) results proved that there was an interaction between Au-Pt nanoparticles and SnO2 support. Electrochemical experiments showed that Au-Pt/SnO2/GC composite electrode had a good electrocatalytic activity to the oxidation of methanol.     

Charge-discharge induced phase transformation of RuO<Subscript>2</Subscript> electrode for thin film supercapacitor

We report on the preparation of an all solid-state thin film micro-supercapacitor using RuO₂ electrode film and LiPON electrolyte film on a Pt/Ti/Si substrate with dual target dc and rf reactive sputtering. Room temperature charge-discharge measurements based on a symmetrical RuO₂/LiPON/RuO₂ structure clearly demonstrated the cyclibility dependence of the RuO₂ electrode on the microstructure. Using both glancing angle X-ray diffraction (GXRD) and transmission electron microscopy (TEM) analysis, it was found that the characteristics of the thin film supercapacitor are dependent on the microstructure of the RuO₂ film. In addition, high-resolution electron transmission microscopy (HREM) analysis after cycling demonstrates that the interface layer formed by interfacial reaction between the LiPON and RuO₂ acts as the main factor in the degradation of the performance of the thin film micro-supercapacitor. This article is based on a presentation made in the 2002 Korea-US symposium on the “Phase Transformations of Nano-Materials”, organized as a special program of the 2002 Annual Meeting of the Korean Institute of Metals and Materials, held at Yonsei University, Seoul, Korea on October 25–26, 2002.     

Au-Pt双金属纳米粒子的制备及其电催化性质

在PEG10000/Vc/HAuCl4体系中,用Vc还原HAuCl4制备金纳米粒子,以所制备的金纳米粒子为晶种,通过控制HAuCl4与H2PtCl6的质量比,制备不同Pt/Au比的双金属纳米粒子,并进一步研究其对H2O2电化学氧化的催化作用。紫外-可见光谱(Uv-vis)、透射电子显微镜(TEM)、选区电子衍射(SAED)、X射线粉末衍射(XRD)等实验结果表明：Au-Pt双金属纳米粒子为面心立方结构的合金。用循环伏安法对Au-Pt双金属纳米粒子修饰的玻碳电极的电化学性能进行测试,结果表明：Au-Pt双金属纳米粒子对H2O2电化学氧化有一定的催化作用。催化效率随Au-Pt双金属粒子中Pt含量的增加而增加。     

Synthesis and electrochemical properties of Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C nanoparticles via polyol process

Carbon-coated lithium manganese silicate (Li₂MnSiO₄/C) nanoparticles were synthesized by polyol process. X-ray diffraction (XRD) patterns of the obtained materials exhibit a good fit with that of the Li₂MnSiO₄ phase. Field emission scanning electron microscopy (FESEM) images of the obtained samples show that the particle size is only tens of nanometers. The high resolution transmission electron microscopy (HRTEM) analysis shows that the Li₂MnSiO₄ nanoparticles are surrounded by a very thin film of amorphous carbon. The composite prepared through polyol process shows good performance as cathode materials in lithium cells at room temperature. The charge capacity of the Li₂MnSiO₄/C samples is 219 mAh/g (about 1.3 Li⁺ per unit formula extracted), and the discharge capacity is 132 mAh/g (about 0.8 Li⁺ per unit formula inserted) in the first cycle in the voltage range of 1.5–4.8 V. A good capacity cycling maintenance of 81.8% after 10 cycles was obtained.     

Capacitance performance enhancement of TiO<Subscript>2</Subscript> doped with Ni and graphite

Nano-amorphous TiO₂ was prepared by a sol-gel method. The results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the composite electrode material (TiO₂-NiO-C) is made of powder with a grain size of 36.2 nm. Doping of nickel and graphite can increase the electrical conductivity and the specific surface area of nano-amorphous TiO₂. The electrochemical properties of TiO₂-NiO-C, such as self-discharge, leakage current, and cycle life, were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. With a charge-discharge current density of 500 mA/g, the specific capacity of the TiO₂-NiO-C composite material reaches 12.88 mAh/g. Also, the expense of capacity is only 3.88% after 500 cycles. The electrochemical capacitor with the electrode material of TiO₂-NiO-C shows excellent capacity and cycling performance.     

Synthesis and characterization of SnO2/polyaniline nanocomposites by sol–gel technique and microemulsion polymerization

Nanostructured SnO₂ was prepared based on the sol–gel method. Aniline monomer was polymerized by microemulsion polymerization in the presence of nanocrystalline SnO₂ to form inorganic–organic nanocomposite materials, in which SnO₂ nanoparticles were embedded within porous polyaniline (PANI). Structural and morphological characterization of SnO₂ and SnO₂/PANI was carried out using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The XRD pattern suggested that PANI did not modify the crystal structure of SnO₂. FT-IR spectrum proved that aniline was successfully composited with the nanostructured SnO₂. TEM analysis showed that the SnO₂ nanoparticles with a diameter of ca. 15 nm were embedded well in the porous PANI. Conductivity analysis indicated that the SnO₂/PANI nanocomposites had a higher conductivity than that of the pure SnO₂ nanopowders.     

直流电弧等离子体法制备In(Sn)-O及Sn(In)(Sb)-O系纳米颗粒

采用一种新的直流电弧等离子体法,通过对熔融的金属进行爆破(或气化),制备出了单相SnO₂、In₂O₃纳米颗粒以及In₂O₃:Sn (ITO)、SnO₂:Sb (ATO)和SnO₂:In:Sb (IATO)多元复合纳米颗粒。XRD结果表明,所制备的SnO₂和In₂O₃基多元复合纳米颗粒均为单相结构,没有其它杂相;TEM结果表明,直流电弧等离子体所制备的单相纳米颗粒分散性好,尺寸约20-50nm。该法合成的纳米ITO和ATO颗粒所制备的ITO靶材和SnO₂电极密度高、电阻率低,表明所制备的ITO和ATO纳米颗粒可以应用于平板显示和导电电极领域。     

碳纳米管修饰的空心多孔NiO/SnO2纳米复合材料对丙酮传感性能的优化

通过静电纺丝法制备中空多孔的NiO/SnO2复合纳米纤维,在复合纤维表面装饰碳纳米管,在此基础上制备气敏传感器器件。利用TGA确定了复合材料热分解温度,得到热处理工艺;利用SEM、XRD、TEM、XPS分别对复合材料的形貌、结构、尺寸、表面成分进行了表征。使用WS-30A气敏元件测试仪对气敏元件响应进行测试,结果表明CNTs装饰的NiO/SnO2复合纳米材料制备的气敏传感器降低了丙酮检测最佳工作温度,为160℃,提高了检测灵敏度,对50 ppm丙酮的响应达到25.25,对检测丙酮有快速的响应(~8.2 s)以及恢复性能(~10.5 s),同时在30天的长期稳定性测试中也体现了良好的稳定性。证明了装饰CNTs 的 NiO/SnO₂复合材料在检测丙酮方面的潜在价值,同时本文也进一步讨论了CNTs, 中空多孔结构的NiO/SnO₂提高检测性能的作用机理。     

Controllable Low-Temperature Hydrothermal Synthesis and Gas-Sensing Investigation of Crystalline SnO<Subscript>2</Subscript> Nanoparticles

SnO₂ nanoparticles have been successfully synthesized by a facile hydrothermal method from SnCl₂·2H₂O, hexamethylenetetramine, and trisodium citrate in water at 120 °C for 12 h. The effects of surfactant and precipitant on SnO₂ synthesis were investigated. SnO₂ nanoparticles can be synthesized in the temperature range of 120-180 °C with long reaction time in the presence of trisodium citrate. When NaOH was used as precipitant instead of hexamethylenetetramine, it is difficult to obtain SnO₂ nanoparticles at 120 °C in the presence of trisodium citrate. SnO₂ nanoparticles with an average size of about 5 nm show good crystallinity and excellent sensitivity to ethanol and acetaldehyde in about 55% relative humidity.     

Template-free hydrothermal synthesis of single-crystalline SnO<Subscript>2</Subscript> nanocauliflowers and their optical properties

Large-scale single-crystalline SnO₂ nanocauliflowers were successfully synthesized using a hydrothermal growth method without any template. The samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). FE-SEM images show that the as-grown SnO₂ nanocauliflowers are constructed of tetragonal prisms with a width of 500–600 nm. XRD, EDS, and SAED results indicate that the as-grown SnO₂ nanocauliflowers are single crystalline with the tetragonal rutile crystalline structure. The growth mechanism of SnO₂ nanocauliflowers is also preliminarily discussed on the basis of different Sn(OH)₆²⁻ concentrations, and it is found that Sn(OH)₆²⁻ concentration plays an important role in determining the shape of the prepared SnO₂. Room temperature photoluminescence was further carried out on SnO₂ nanocauliflowers to investigate their optical properties. An intense blue luminescence centered at a wavelength of 424 nm is observed in the as-grown SnO₂ nanocauliflowers.     

Fabrication and characterization of a SnO2−RuO2 composite anode for a hybrid thin film battery

A SnO₂−RuO₂ composite (SnRuO) thin film possesses unique electrochemical properties for a hybrid between batteries and supercapacitors due to the fact that the SnRuO system shows battery and supercapacitor characteristics simultaneously. SnRuO thin films were prepared through the magnetron co-sputtering method in order to investigate the feasibility of a monolithic thin film hybrid battery. The SnRuO thin film as an anode film for a secondary battery demonstrated a first discharge capacity of 1557 μAh/cm²·μm; the second discharge capacity was 52% of the first discharge capacity. The degree of capacity fade of the SnRuO thin film was almost the same as that of the SnO₂ thin film, even though the capacity of the SnRuO thin film was larger than that of the pure SnO₂. In addition, the SnRuO thin film showed a supercapacitor behavior and exhibited a specific capacitance of 14 mF/cm² μm during 1000 cycles. These results suggest that SnRuO thin film could be used as a thin film supercapacitor as well as a thin film battery. Furthermore, this composite thin film holds promise for the fabrication of a monolithic thin film high power hybrid battery based on micro-processes.     

Performance and capacity fading reason of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries after storing at high temperature

Spinel LiMn₂O₄ was synthesized by a solid-state method. A 204468-size battery was fabricated and stored at 55°C. The structure and morphology of the LiMn₂O₄ cathode were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) technique. Energy dispersive spectroscopy (EDS) was used to analyze the surface component of the carbon anode. The discharge capacities of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 106, 98, 96, and 92 mAh·g⁻¹, respectively. The cyclic performance is improved after storage. The capacity retentions of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 83.8%, 85.8%, 86.9%, and 88.6% after 180 cycles. The intensity of all the LiMn₂O₄ diffraction peaks is weakened. Mn is detected from the carbon electrode when the battery is stored for 96 h. Cyclic voltammograms and electrochemical impedance spectroscopy (EIS) were used to examine the surface state of the electrode after storage. The results show that the resistance and polarization of LiMn₂O₄/electrolyte is increased after storage, which is responsible for the fading of capacity.     

Effects of defects generated in ALD TiO<Subscript>2</Subscript> films on electrical properties and interfacial reaction in TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>/Si system upon annealing in vacuum

Thin TiO₂ layers grown at 130°C on SiO₂-coated Si substrates by atomic layer deposition (ALD) using TTIP and H₂O as precursors were annealed, and the effects of the annealing temperature on the resulting electrical properties of TiO₂ and the interface properties between a Pt electrode and TiO₂ were examined using transmission line model (TLM) structures. The as-deposited TiO₂ thin film had an amorphous structure with OH groups and a high resistivity of 6×10³Ω-cm. Vacuum annealing at 700 °C transformed the amorphous film into an anatase structure and reduced its resistivity to 0.04Ω-cm. In addition, the vacuum-annealing of the TiO₂/SiO₂ structure at 700°C produced free silicon at the TiO₂-SiO₂ interface as a result of the reaction between the Ti interstitials and SiO₂. The SiO₂ formed on the TiO₂ surface caused a Schottky contact, which was characterized by the TLM method. The use of the TLM method enabled the accurate measurement of the resistivity of the vacuum-annealed TiO₂ films and the characterization of the Schottky contacts of the metal electrode to the TiO₂.     

Synthetically Controlled,Carbon-Coated Co<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/SnO<Subscript>2</Subscript> Composite Anode for Lithium-ion Batteries

The inherent drawbacks of Co₂SnO₄ in demonstrating the closer-to-theoretical capacity value behavior and the inadmissible volume-expansion-related capacity fade behavior have been surpassed by choosing a tailor-made material composition of Co₂SnO₄/SnO₂, prepared at two different temperatures such as 400°C and 600°C to obtain residual carbon-containing and carbon-free compositions, respectively. Among the products, carbon-coated Co₂SnO₄/SnO₂ composite exhibits better electrochemical performance compared with that of the carbon-free product mainly because of the beneficial effect of carbon in accommodating the volume-expansion-related issues arising from the alloying/de-alloying mechanism. A combination of conversion reaction and alloying/de-alloying mechanism is found to play a vital role in exhibiting closer-to-theoretical capacity values. In other words, an appreciable specific capacity value of 834 mAh g^?1 has been exhibited by Co₂SnO₄/SnO₂ anode containing carbon coating, thus, demonstrating the possibility to improve the electrochemical performance of the title anode through carbon coating, which is realized as a result of the addition of carefully manipulated synthesis conditions.     

Effect of a surface treatment for LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> cathode material in lithium secondary batteries

LiNi_1/3Co_1/3Mn_1/3O₂ cathode material was surface-treated to improve its electrochemical performance. Al₂O₃ nanoparticles were coated onto the surface of LiNi_1/3Co_1/3Mn_1/3O₂ powder using a sol-gel method. The as-prepared Al₂O₃ nano-particle was identified as the cubic structure of Al₂O₃. XRD showed that the LiNi_1/3Co_1/3Mn_1/3O₂ structure was not affected by the Al₂O₃ coating. With a coating of 3 wt.% Al₂O₃ on LiNi_1/3Co_1/3Mn_1/3O₂, the cyclic-life performance and rate capability were improved. However, heavier coatings (5 wt.%) on LiNi_1/3Co_1/3Mn_1/3O₂ resulted in a considerable decrease of the discharge capacity and rate capability. The thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂ materials was greatly improved by the 3 wt.% Al₂O₃ coating.     

Electrophoretic impregnation of porous anodizing layer by synthesized TiO<Subscript>2</Subscript> nanoparticles

This paper deals with the elaboration of a stable suspension of TiO₂ nanoparticles and their incorporation by electrophoretic deposition into pores of an anodized 5754 aluminum alloy. The as-synthesized TiO₂ nanopowder was characterized by the X-ray diffraction, scanning and transmission electron microscopy, energy dispersive X-ray spectroscopy and IR spectroscopy. During this work, both the transmission electron microscopy and particle analysis showed that the resulting particles had a narrow size distribution with a crystallite size of about 15 nm. The zeta potential and stability of TiO₂ nanoparticles dispersed with poly(acrylic acid) in an aqueous solution were also measured. A porous anodic film was synthesized in the phosphoric acid-base electrolyte and then filled by 15 nm TiO₂ particles via electrophoresis. In addition, the effect of poly(acrylic acid) and pH on the suspension stability has been investigated. It was also demonstrated that by adding glycine in buffered suspension gelating phenomenon can be avoided that inhibits the insertion of nanoparticles inside the pores of an anodic film. It was also noted that an applied electric field greatly influences the electrophoretic deposition process. The field emission gun-scanning electron microscopy observations showed that larger (125 nm in diameter) and linear (6 μm in length) pores are successfully filled in 5 min.     

Evaluation of Composition,Microstructure Characterization and Interfacial Properties of Zn—SnO<Subscript>2</Subscript> Metal Matrix Composite Coating

In this paper the microstructure and tribological behavior of Zn—SnO₂ (Zn—Sn) alloys produced through chloride and sulphates co-deposition is presented for comparison. 7.0 wt % SnO₂ was added to Zn bath and deposited at 0.3 V. The interfacial effect and microchemistry of the fabricated composite was studied by optical microscope, X-ray diffraction (XRD), scanning electron microscope (SEM) equipped with energy disperse spectrum (EDS). The tribological behavior of the metal composites with SnO₂ particles as reinforcement was studied using reciprocating sliding tester. The scanning electron microscopy (SEM) and atomic force microscope (AFM) of the composite surfaces indicates that there is good interfacial interaction between the alloy formulated matrixes made from the two baths and the substrate. Reasonable uniform distribution of Sn metal phase particulates is shown for both coating alloy. Increases in hardness and wear resistance are attributed to the uniform and coherent precipitation in the metal interface especially for Zn—7Sn—S—0.3V. In general, 7 wt % Sn additions to the bath showed more hastening to improved surface properties and better mechanical characteristics.     

In situ synthesis of Co3O4/graphene nanocomposite material for lithium-ion batteries and supercapacitors with high capacity and supercapacitance

Co₃O₄/graphene nanocomposite material was prepared by an in situ solution-based method under reflux conditions. In this reaction progress, Co²⁺ salts were converted to Co₃O₄ nanoparticles which were simultaneously inserted into the graphene layers, upon the reduction of graphite oxide to graphene. The prepared material consists of uniform Co₃O₄ nanoparticles (15-25 nm), which are well dispersed on the surfaces of graphene nanosheets. This has been confirmed through observations by field emission scanning electron microscopy, transmission electron microscopy and atomic force microscopy. The prepared composite material exhibits an initial reversible lithium storage capacity of 722 mAh g⁻¹ in lithium-ion cells and a specific supercapacitance of 478 F g⁻¹ in 2 M KOH electrolyte for supercapacitors, which were higher than that of the previously reported pure graphene nanosheets and Co₃O₄ nanoparticles. Co₃O₄/graphene nanocomposite material demonstrated an excellent electrochemical performance as an anode material for reversible lithium storage in lithium ion cells and as an electrode material in supercapacitors.     

Primary investigation of corrosion resistance of Ni-P/TiO2 composite film on sintered NdFeB permanent magnet

In this paper, an electroless nickel plating and sol-gel combined technique used to prepare the Ni-P/TiO₂ composite film on sintered NdFeB permanent magnet is described and the composite film was characterized by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM), and energy dispersive X-ray spectrometer (EDX). The corrosion resistance of Ni-P/TiO₂ film was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The self-corrosion current density (i_corr) of Ni-P/TiO₂ composite film is 2.38μA/cm² in 0.5mol/L H₂SO₄ solution about 33% of that of Ni-P coating and 0.22μA/cm² in 0.5mol/L NaCl solution about 14% of that of Ni-P coating, respectively. In 0.5mol/L H₂SO₄ and 0.5mol/L NaCl solutions, the polarization resistance (Rp) of the composite film is 12.5kΩ cm² and 120kΩ cm², about 1.6 and 2 times that of Ni-P coating, respectively. The results indicate that Ni-P/TiO₂ composite film has a better corrosion resistance than Ni-P coating.