纳米纤维素/碳纳米管/纳米银线柔性电极的制备

目的以竹粉为原料制备纳米纤维素,并将其作为基底材料制备纳米纤维素/碳纳米管/纳米银线复合电极,应用于柔性超级电容器。方法采用化学机械处理法,将竹粉通过化学处理以及研磨、超声等处理,制备成纳米纤维素悬浮液;分别将多壁碳纳米管和纳米银线超声分散于溶剂中;最后,通过层层自组装制备纳米纤维素/碳纳米管/纳米银线复合电极,同时,作为对照组,制备纳米纤维素/碳纳米管复合电极。结果纳米纤维素纤丝的直径大约为30~100 nm,相互之间缠绕成网状结构,是很好的支撑材料,纳米纤维素/碳纳米管/纳米银线复合电极具有很好的成膜性和电化学性能,在扫描速率为30 m V/s时,面积比电容达到77.95 m F/cm~2。结论以纳米纤维素为基底,通过层层自组装方法制备的纳米纤维素/碳纳米管/纳米银线复合电极具有较好的电化学性能,可作为柔性超级电容器的电极。     

含碳纳米管微波吸收材料的制备及其微波吸收性能研究

用竖式炉流动法,以二茂铁为催化剂,噻吩为助催化剂,苯为碳源通过催化裂解反应制备了碳纳米管,碳纳米管的外径为20-50nm,内径10-30nm,长度50-1000μm.分别以碳纳米管、羰基铁粉、碳纳米管与羰基铁粉的混合物为吸收剂制备了微波吸收材料,研究了上述三种微波吸收材料在2-18GHz的吸波性能,与纯碳纳米管和纯羰基铁粉微波吸收材料相比, 碳纳米管与羰基铁粉复合微波吸收材料在2-18GHz的吸收峰明显向低频移动.在含碳纳米管的微波吸收材料中,碳纳米管作为偶极子在交变电场的作用下,产生极化电流,电磁波的能量转换为其他形式的能量,瑞利散射效应和界面极化也是含碳纳米管微波吸收材料的主要吸波机理.     

Conversion of potassium titanate nanowires into titanium oxynitride nanotubes

Tunnel-structured potassium titanate with a K(3)Ti(8)O(17) phase was synthesized by direct oxidation of titanium powder mixed with KF(aq) in water vapor at 923 K. The reaction conditions were adjusted so that uniform single crystalline potassium titanate nanowires with [010] growth direction (length: 5-30 μm, diameter: 80-100 nm) were obtained. Nitridation of the nanowires by NH(3)(g) at 973-1073 K converted the titanate nanowires into rock-salt structured cubic phase single crystalline titanium oxynitride TiN(x)O(y) nanotubes (x = 0.88, y = 0.12, length = 1-10 μm, diameter = 150-250 nm, wall thickness = 30 - 50 nm) and nanorods (x = 0.5, y = 0.5, length = 1-5 μm, diameter = 100-200 nm) with rough surfaces and [200] growth direction. The overall conversion of the titanate nanowires into the nanotubes and the nanorods can be rationalized by Ostwald ripening mechanism. We fabricated an electrode by adhering TiN(x)O(y) nanotubes (0.2 mg) on a screen-printed carbon electrode (geometric area: 0.2 cm(2)). Electrochemical impedance spectroscopy demonstrated its charge transfer resistance to be 20Ω. The electrochemical surface area of the nanotubes on the electrode was characterized by cyclic voltammetry to be 0.32 cm(2). This property suggests that the TiN(x)O(y) nanostructures can be employed as potential electrode materials for electrochemical applications.     

Etching processes of transparent carbon nanotube thin films using laser technologies

Carbon nanotubes (CNTs) have potential as a transparent conductive material with good mechanical and electrical properties. However, carbon nanotube thin film deposition and etching processes are very difficult to pattern the electrode. In this study, transparent CNT film with a binder is coated on a PET flexible substrate. The transmittance and sheet resistance of carbon nanotube film are 84% and 1000 Ω/□, respectively. The etching process of carbon nanotube film on flexible substrates was investigated using 355 nm and 1064 nm laser sources. Experimental results show that carbon nanotube film can be ablated using laser technology. With the 355 nm UV laser, the minimum etched line width was 20 μm with a low amount of recast material of the ablated sections. The optimal conditions of laser ablation were determined for carbon nanotube film.     

Amorphous and crystalline TiO2 nanotube arrays for enhanced Li-ion intercalation properties

We have employed a simple process of anodizing Ti foils to prepare TiO2 nanotube arrays which show enhanced electrochemical properties for applications as Li-ion battery electrode materials. The lengths and pore diameters of TiO2 nanotubes can be finely tuned by varying voltage, electrolyte composition, or anodization time. The as-prepared nanotubes are amorphous and can be converted into anatase nanotubes with heat treatment at 480 degrees C. Rutile crystallites emerge in the anatase nanotube when the annealing temperature is increased to 580 degrees C, resulting in TiO2 nanotubes of mixed phases. The morphological features of nanotubes remain unchanged after annealing. Li-ion insertion performance has been studied for amorphous and crystalline TiO2 nanotube arrays. Amorphous nanotubes with a length of 3.0 microm and an outer diameter of 125 nm deliver a capacity of 91.2 microA h cm(-2) at a current density of 400 microA cm(-2), while those with a length of 25 microm and an outer diameter of 158 nm display a capacity of 533 microA h cm-2. When the 3-microm long nanotubes become crystalline, they deliver lower capacities: the anatase nanotubes and nanotubes of mixed phases show capacities of 53.8 microA h cm-2 and 63.1 microA h cm(-2), respectively at the same current density. The amorphous nanotubes show excellent capacity retention ability over 50 cycles. The cycled nanotubes show little change in morphology compared to the nanotubes before electrochemical cycling. All the TiO2 nanotubes demonstrate higher capacities than amorphous TiO2 compact layer reported in literature. The amorphous TiO2 nanotubes with a length of 1.9 microm exhibit a capacity five times higher than that of TiO2 compact layer even when the nanotube array is cycled at a current density 80 times higher than that for the compact layer. These results suggest that anodic TiO2 nanotube arrays are promising electrode materials for rechargeable Li-ion batteries.     

Bioactivity of zirconia nanotube arrays fabricated by electrochemical anodization

Zirconia nanotubes with a diameter of 50 nm and a length of 20 μm were fabricated by anodic oxidation of zirconium in (NH₄)₂SO₄ electrolyte containing NH₄F. The structure and phase composition of the zirconia nanotube layers were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The bioactivity was assessed by investigating the formation of apatite on the surface of zirconia nanotubes after soaking in simulated body fluids (SBF) for 20–30 days. The results indicate that bone-like apatite can be formed on the surface of the zirconia nanotube layers in our SBF immersion experiments. Microstructure of zirconia nanotubes with apatite layer was observed by SEM. Substance and phase compositions were characterized respectively by energy dispersive X-ray spectrometer (EDS) and XRD. Our results show that zirconia nanotube layers fabricated by electrochemical anodization exhibit favorable bioactivity.     

CeO2修饰的透明TiO2纳米管电极的电致变色器件

采用电化学沉积法在阳极氧化制备的TiO2纳米管阵列管壁上沉积一层CeO2纳米颗粒,再将CeO2修饰的透明TiO2纳米管阵列薄膜对电极与聚三甲基噻吩变色电极组装成透过型电致变色器件.实验结果表明:CeO2修饰的TiO2纳米管阵列薄膜仍保持良好的光透过性,其电荷存储能力比纯TiO2纳米管电极提高了30%.经CeO2修饰的TiO2纳米管改善了器件的性能,与对电极为单一TiO2纳米管阵列的器件相比,其对比度仍保持在38%左右,其褪色时间由1.3 s缩短为0.8 s.电致变色器件快速响应得益于纳米管与纳米颗粒组成的复合结构的高比表面积和快速的电荷传输过程.     

Nanocrystallized steel surface by micro-shot peening for catalyst-free carbon nanotube growth

Nanocrystallized steel surface by micro-shot peening (MSP) were applied to carbon nanotube growth in this study. Micro-shot peening treatment severely deformed steel surface and nanocrystallized surface layer was formed by the plastic deformation. The grain sizes of the nanocrystallized layer were 10-30 nm after 300 s of MSP treatment. On the nanocrystallized surface, carbon nanotubes were formed with thermal chemical vapour deposition without catalysts. Before carbon nanotube growth, the nanocrystallized steel surface was reduced with H₂/N₂ gas at 600 °C. The carbon nanotube growth was performed at 600 °C with C₂H₂ gas carried by H₂/N₂ gas. The carbon nanotubes formed on the nano-structured surface was multi-walled carbon nanotube and the diameter was 10-20 nm. The reduction process before carbon nanotube growth was essential to form carbon nanotubes on the nanocrystallized surface with MSP.     

镍纳米管阵列的电沉积合成及其磁学性能表征

以氧化铝膜为模板、金属汞为电阴极,采用简单的直流电沉积方法制备出高度有序的镍纳米管阵列。利用扫描电子显微镜、透射电子显微镜、选区电子衍射、能谱仪、X射线粉末衍射和样品振动磁强计对样品进行形貌表征、成分及磁性能分析。结果表明,阵列中的镍纳米管彼此平行,尺寸均匀,纳米管外径为260～360nm;镍纳米管阵列表现出良好的磁各向异性,其易磁化方向垂直于镍纳米管阵列。以金属汞为电阴极是易形成纳米管的关键条件。     

Basal plane pyrolytic graphite modified electrodes: comparison of carbon nanotubes and graphite powder as electrocatalysts

The oxidations of NADH, epinephrine, and norepinephrine are studied using carbon nanotube and graphite powder-modified basal plane pyrolytic graphite electrodes. Immobilization is achieved in two ways: first, via abrasive attachment of multiwall carbon nanotubes or graphite powder by gently rubbing the electrode surface on a fine quality paper supporting the desired material; second, via "film" modification from dispersing either graphite powder or nanotubes in acetonitrile and pipeting a small volume onto the electrode surface and allowing the solvent to volatilize. While electrocatalytic behavior of both types of nanotube-modified electrodes is shown, with enhanced currents and reduced peak-to-peak separations in the voltammetry in comparison with naked basal plane pyrolytic graphite, similar catalytic behavior is also seen at the graphite powder-modified electrodes. Caution is, therefore, suggested in assigning unique catalytic properties to carbon nanotubes.     

Chemical optimization of self-assembled carbon nanotube transistors

We present the improvement of carbon nanotube field effects transistors (CNTFETs) performances by chemical tuning of the nanotube/substrate and nanotube/electrode interfaces. Our work is based on a method of selective placement of individual single walled carbon nanotubes (SWNTs) by patterned aminosilane monolayer and its use for the fabrication of self-assembled nanotube transistors. This method brings a relevant solution to the problem of systematic connection of self-organized nanotubes. The aminosilane monolayer reactivity can be used to improve carrier injection and doping level of the SWNT. We show that the Schottky barrier height at the nanotube/metal interface can be diminished in a continuous fashion down to an almost ohmic contact through these chemical treatments. Moreover, sensitivity to 20 ppb of triethylamine is demonstrated for self-assembled CNTFETs, thus opening new prospects for gas sensors taking advantages of the chemical functionality of the aminosilane used for assembling the CNTFETs.     

Nickel Oxide/Carbon Nanotubes Nanocomposite for Electrochemical Capacitance

A nanocomposite of nickel oxide/carbon nanotubes was prepared through a simple chemical precipitation followed by thermal annealing. The electrochemical capacitance of this electrode material was studied. When the mass fraction of CNTs (carbon nanotubes) in NiO/CNT composites increases, the electrical resistivity of nanocomposites decreases and becomes similar to that of pure CNTs when it reaches 30%. The specific surface area of composites increases with increasing CNT mass fraction and the specific capacitance reaches 160 F/g under 10 mA/g discharge current density at CNT mass fraction of 10%.     

Fabrication of an aluminum–carbon nanotube metal matrix composite by accumulative roll-bonding

Accumulative roll-bonding was adapted to fabricate a carbon nanotube (CNT)-reinforced aluminum matrix composite. Its microstructure was investigated by transmission electron microscopy, and it was confirmed that the nanotubes were embedded into the metal matrix while maintaining their multiwalled structure. Measurements revealed that the as-received CNTs had a bimodal diameter size distribution, while only nanotubes with diameters >30 nm and >30 walls were retained during four consecutive rolling operations at 50% reduction.     

Pt-TiO2纳米管电极的制备及电催化性能

采用电化学阳极氧化-阴极还原法制备Pt-TiO2纳米管电极.扫描电镜(SEM)结果显示TiO2纳米管平均管径100nm,管长470nm,管壁厚20nm,且其比表面积大,同时纳米Pt微粒分散在TiO2纳米管上,且粒径细小,Pt微粒充分裸露,使得Pt-TiO2纳米管电极活性点多,电催化性能高.对甲醇的电催化性能测试表明:同纯Pt电极和Pt-TiO2电极(Pt微粒固定在TiO2致密膜上)相比,Pt-TiO2纳米管电极对甲醇具有更高的电催化活性,其氧化峰电流密度是在纯Pt片电极上的20倍以上.     

Alignment of glycolipid nanotubes on a planar glass substrate using a two-step microextrusion technique

We have developed a two-step microextrusion technique to align lipid nanotubes of 200 nm in diameter in parallel on planar glass substrates. This technique is useful to align self-assembled molecular nanofibers or nanotubes with diameters ranging from 100 to 300 nm. In the first step, we applied relatively large air pressure (approximately 40 hPa) onto a microcapillary filled with aqueous dispersion of lipid nanotubes to push them out. An aqueous droplet with 60 microm diameter was then extruded from the tip of the microcapillary. After one end of the lipid nanotube moved out, we changed the air pressure to be smaller, approximately 20 hPa to reduce the flow rate of the dispersion. The decrease in size of the droplet allowed us to fix the exposed end of the lipid nanotube onto the planar substrate. By dragging the microcapillary along the planar surface, we were able to align the whole nanotube onto the substrate. Using this technique, we have achieved the parallel alignment of the lipid nanotubes on the glass substrate.     

Preparation and electrochemical properties of nickel oxide by molten-salt synthesis

Well-crystallized NiO nanoparticles with uniform morphology of hexagon plates were first fabricated by molten-salt synthesis method using NaCl as a flux at 1000 °C. The phase of the synthesized NiO powder was confirmed by comparing the obtained XRD pattern with the JCPDS standard. Transmission electron microscopy (TEM) image shows that the morphology of NiO particle is hexagon plate with particle size of 50-80 nm. NiO nanoparticles prepared by molten-salt synthesis method is homogenous and in high purity. The NiO sample has a better particle size distribution than that obtained from liquid precipitation and solid state reaction. The electrochemical behavior was investigated by chronopotentiometry and electrochemical impedance spectroscopy. The nickel oxide sample calcined at 1000 °C exhibited electrochemical supercapacitive behavior. The internal resistance measured at open circuit potential is only 0.5 Ω, which is smaller than that of the NiO prepared by other conventional precipitation. NiO prepared by molten-salt synthesis is a potential electrode material for supercapacitor.     

One-step fabrication of carbon nanotubes decorated with graphitic nanoflakes for energy storage systems

We have used a bias-assisted microwave plasma chemical vapor deposition system to synthesize carbon nanotubes presenting graphitic nanoflakes, named coral-like carbon nanotubes, and well-aligned carbon nanotubes on carbon cloth substrates. Applying an external bias of -100 V led to the growth of well-aligned carbon nanotubes. In the absence of an external bias, the coral-like nanotubes presenting graphite nanoflakes were formed. The specific surface areas of the well-aligned and coral-like carbon nanotubes electrodes were 90.31 and 143.69 m2/g, respectively. In terms of energy storage, we estimated the capacitance of the coral-like carbon nanotube electrode to be ca. 194 F/g in an electrolyte of 1 M H2SO4. This value is almost double that of the well-aligned carbon nanotubes electrode (104 F/g), presumably because the presence of the carbon nanoflakes had a positive influence on the migration and adsorption of ions within the electrode. The fitting results indicated that the coral-like carbon nanotubes electrode behaved as a traditional electrochemical capacitor. Durability tests revealed that the coral-like carbon nanotube electrode was reliable, with a decay of 9% in capacitance over 1000 cycles.     

镀Ni-P和Ni-N合金碳纳米管的磁性能及其复合材料的微波吸收性能

用竖式炉流动法,以二茂铁为催化剂,噻吩为助催化剂,苯为碳源通过催化裂解反应在1100~1200℃制备了直线形碳纳米管,外径为20~50 nm,内径10~30 nm,长度50~1000 μm。用化学镀工艺在碳纳米管表面均匀包覆了Ni-P和Ni-N合金,研究了它们的磁性能及其环氧树脂基复合材料在2~18 GHz的微波吸收性能。与纯碳纳米管相比,镀Ni-P合金碳纳米管复合材料的吸收峰向高频移动,镀Ni-P和Ni-N合金碳纳米管经热处理后,复合材料的吸收峰向低频移动。镀Ni-P合金碳纳米管以及镀Ni-P和Ni-N合金经热处理碳纳米管的矫顽力分别为304.34 Oe、 81.65 Oe、 183.85 Oe。随着矫顽力的增加,在2~18 GHz,复合材料的微波吸收峰向高频移动。在复合材料中,碳纳米管以及镀Ni-P和Ni-N合金的碳纳米管作为偶极子吸收微波。      

碳纳米管的电化学性质及其应用研究

把碳纳米管作为一种新型的电极材料是开发碳纳米管应用的一个新的方向。本文研究了碳纳米管的化学修饰和电化学性质,发现决定碳纳米管电化学性质的两个重要因素。系统地总结了我们在碳纳米管电极的制备、碳纳米管电极的电化学响应、碳纳米管电极的生物电分析和电氧化有毒化成分应用方面的研究成果。     

碳纳米管表面沉积氧化镍及其超电容器的电化学行为

通过催化裂解法制备了碳纳米管并进一步制备了碳纳米管薄膜电极.基于该种材料的超电容器电极比容量达到36F/g.研究了在碳纳米管薄膜基体上使用电化学方法沉积氧化镍的新工艺,制备出碳纳米管和氧化镍的复合电极.电化学测试证明复合电极的比容量提高到52F/g以上且基于这种复合电极的超电容器具有极低的自放电率.