Hydrothermally Oxidized Single‐Walled Carbon Nanotube Networks for High Volumetric Electrochemical Energy Storage

Improving volumetric energy density is one of the major challenges in nanostructured carbon electrodes for electrochemical energy storage device applications. Herein, a simple hydrothermal oxidation process of single‐walled carbon nanotube (SWNT) networks in dilute nitric acid is reported, enabling simultaneous physical densification and chemical functionalization of the as‐assembled randomly‐packed SWNT films. After the hydrothermal oxidation process, the density of the SWNT films increases from 0.63 to 1.02 g cm^?3 and a considerable amount of redox‐active oxygen functional groups are introduced on the surface of the SWNTs. The functionalized SWNT films are used as positive electrodes against Li metal negative electrodes for potential Li‐ion capacitors or Li‐ion battery applications. The functionalized SWNT electrodes deliver high volumetric as well as gravimetric capacities, 154 Ah L^?1 and 152 mAh g^?1, respectively, owing to the surface redox reactions between the introduced oxygen functional groups and Li ions. In addition, these electrodes exhibit a remarkable rate‐capability by retaining its high capacity of 94 Ah L^?1 (92 mAh g^?1) at a high discharge rate of 10 A g^?1. These results demonstrate the simple hydrothermal oxidation process as an attractive strategy for improving the volumetric performance of nanostructured carbon electrodes.     

Ultralong aligned multi-walled carbon nanotube for electrochemical sensing

We have investigated electrochemical sensing properties of electrodes fabricated with ultralong aligned multi-walled carbon nanotube (MWNT) bundles synthesized using water-assisted chemical vapor deposition on aluminum (Al) and iron (Fe) coated silicon wafer with ethylene and argon/hydrogen gas as carbon source and buffer gas respectively. Cyclic voltammograms performed on these electrodes show diffusion-controlled-reversible reaction. The dominance of radial diffusion mass transport at these electrodes was also indicated by sigmoidal-shaped voltammograms obtained at various scan rates. These electrodes were able to sense very low concentration of ascorbic acid (approximately 0.7 microM) and dopamine (approximately 1.87 microM), two model species often used in electro-analysis. The excellent electrochemical properties along with good single species detection ability suggest that these MWNTs are promising electrode materials for developing very sensitive chemical and/or biological sensors.     

以预锂化多壁碳纳米管为负极的锂离子电容器性能

采用内部短路方式对多壁碳纳米管负极进行不同程度的预嵌锂处理,预嵌锂时间为5,30,60min,以预嵌锂多壁碳纳米管极片作为负极,活性炭极片作为正极,组装成锂离子电容器。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)对多壁碳纳米管及电极极片进行表征分析,采用恒流充放电(GCD)和交流阻抗谱(EIS)研究预嵌锂多壁碳纳米管负极和未预嵌锂处理多壁碳纳米管负极锂离子电容器的性能。电化学测试结果表明,多壁碳纳米管负极预嵌锂大幅提高了电容器充放电性能,对比未嵌锂多壁碳纳米管电容器,在相同的电流密度下(100mA/g),能量密度提高400%。预嵌锂60min,电流密度100mA/g时,其比容量达到57F/g。在电流密度为100～3200mA/g范围内,其最高能量密度与功率密度分别达到90Wh/kg,4130W/kg。1000次充放电循环后,容量保持率维持在85%以上,表现出良好的超级电容器性能。     

Dimethyl methylphosphonate detection with a single-walled carbon nanotube capacitive sensor fabricated by airbrush technique

Single-walled carbon nanotube (SWNT) films were prepared on interdigitated electrodes by airbrush technique, and their sensing properties to dimethyl methylphosphonate (DMMP) were studied. The SWNT films were characterized by field-emission scanning electron microscope. The response to different concentrations of DMMP vapors were investigated at room temperature. The results showed that the capacitance of airbrush SWNT sensor decreased rapidly in varying concentrations ranging from 12 to 60 mg/m³ (2.4–12 ppm). The capacitance sensitivity was about 12.5 % when exposed to 12 mg/m³ DMMP vapor. The capacitance sensitivity was higher when the initial capacitance and loss tangent were higher and the SWNT film was denser. It was found that the capacitance sensitivity was nearly 10 times to the resistance sensitivity. The airbrush SWNT sensor exhibited highly and fast capacitance response, good repeatability and selectivity for DMMP vapor.     

Hole doping and surface functionalization of single-walled carbon nanotube chemiresistive sensors for ultrasensitive and highly selective organophosphor vapor detection

We developed a chemiresistive sensor based on doped and functionalized semiconducting single-walled carbon nanotube (SWNT) networks for ultrasensitive and rapid detection of dimethyl methylphosphonate (DMMP) (simulant of nerve agent sarin) vapor. The semiconducting SWNT network was deposited between interdigitated electrodes and modified by solid organic acid tetrafluorohydroquinone (TFQ). The TFQ molecules could not only selectively bind DMMP onto the sidewalls of SWNTs via the strong hydrogen bonding interaction, but also tailor the electronic properties of SWNTs via heavy hole doping. This synergetic effect significantly improved the sensitivity of the devices, and enabled the sensors to easily detect DMMP at 20 parts-per-trillion (ppt) concentration with a response time of less than 2 min, without the need for pre-concentration of the analytes. This sensitivity is about five orders of magnitude higher than that of the unmodified SWNT chemiresistor, and also significantly higher than that of the functionalized SWNT chemiresistors previously reported. Moreover, the SWNT-TFQ sensors could be recovered when DMMP is replaced with referencing gas. The SWNT-TFQ sensors also show excellent selectivity toward DMMP over some interfering organic vapors. The response mechanism, i.e. charge transfer and dedoping was investigated.     

Poly-cobalt[tetrakis(o-aminophenyl)porphyrin] nanowire and single-walled carbon nanotube for the analysis of hydrogen peroxide

Nanowires of poly-cobalt[tetrakis(o-aminophenyl)porphyrin] (PCoTAPPNW) were fabricated by electrochemical polymerization by the cyclic voltammetric method in anodic aluminum oxide membranes. A glassy carbon electrode (GCE) modified by PCoTAPPNW and single-walled carbon nanotubes (SWNT) without any binder was investigated with voltammetric methods in phosphate buffer saline (PBS) at pH 7.4. The PCoTAPPNW + SWNT/GCE exhibited strongly enhanced voltammetric and amperometric sensitivity towards hydrogen peroxide (H2O2), which shortened the response time (< 5 seconds), showed detection limit of 1.0 microM and enhanced the sensitivity for H2O2 detection with 194 microA mM(-1) cm(-2). The PCoTAPPNW + SWNT/GCE can be used to monitor H2O2 at very low concentration in physiological pH as an efficient electrochemical H2O2 sensor.     

Polydiphenylamine/carbon nanotube composites for applications in rechargeable lithium batteries

Polydiphenylamine/single walled carbon nanotube (PDPA/SWNT) composites were synthesized electrochemically aiming at their application as active electrode materials for rechargeable lithium batteries. The electrochemical polymerization of diphenylamine (DPA) on a SWNT film immersed in a 1 M HCl solution was studied by cyclic voltammetry. Comparing cyclic voltammograms recorded on a blank Pt electrode with those obtained for a SWNT film deposited on Pt electrode one observes in the latter case a decrease of the DPA reduction potential. To elucidate electrochemical polymerization mechanism, photoluminescence studies on DPA/SWNT and PDPA/SWNT systems were carried out. Additional information concerning the functionalization process of SWNT with PDPA was obtained by Raman and IR spectroscopy. Using the PDPA/SWNT composite as active material for the positive electrode of a rechargeable lithium cell (LiPF₆ electrolyte), the charge-discharge tests show a specific discharge capacity of ca. 245 mA h g⁻¹, much higher than the 35 mA h g⁻¹ for pure PDPA.     

Controlled assembly of CdSe/MWNT hybrid material and its fast photoresponse with wavelength selectivity

We report the novel assembly method of CdSe quantum dot (QD)/pyridine/multi-walled carbon nanotube (CdSe-py-MWNT) hybrid material between electrodes using two-step dielectrophoresis (DEP). At the first step, we assembled the individual MWNT between electrodes by the DEP method. At the second step, the CdSe-py materials were assembled onto the MWNT by DEP method again, which enables site specific and density controlled assembly of QDs. As the photoresponse results, the recovery time of the device fabricated was about 250 times faster than that of a similar CdSe-py-SWNT device using a single-walled carbon nanotube (SWNT) instead of a MWNT. Moreover, it was demonstrated that the optoelectronic property of the device could be modulated by the size of CdSe NQD assembled on a MWNT. We characterized the material and the device by using SEM, TEM, absorption spectroscopy, and optoelectronic instruments.     

Optical anisotropy in single-walled carbon nanotube thin films: implications for transparent and conducting electrodes in organic photovoltaics

Optical anisotropy in single-walled carbon nanotube thin film networks is reported. We obtain the real and imaginary parts of the in-(parallel) and out-of-plane (perpendicular) complex dielectric functions of the single-walled carbon nanotube (SWNT) thin films by combining transmission measurements at several incidence angles with spectroscopic ellipsometry data on different substrates. In sparse networks, the two components of the real part of the complex dielectric constant (epsilon1 parallel and epsilon1 perpendicular) were found to differ by 1.5 at 2.25 eV photon energy. The resulting angular dependence (from 0 to 70 degrees incidence angles) of transmittance is reflected in the conversion efficiency of organic solar cells utilizing SWNT thin films as the hole conducting electrodes. Our results indicate that, in addition to the transparency and sheet resistance, factors such as the optical anisotropy must be considered for optical devices incorporating SWNT networks.     

Detection of a nerve agent simulant using single-walled carbon nanotube networks: dimethyl-methyl-phosphonate

Single-walled carbon nanotube (SWNT) networks were used to detect hazardous dimethyl-methyl-phosphonate (DMMP) gas in real time, employing two different metals as electrodes. Random networks of SWNTs were simply obtained by drop-casting a SWNT-containing solution onto a surface-oxidized Si substrate. Although the electrical responses to DMMP at room temperature were reversible for both metals, the Pd-contacting SWNT network sensors exhibited a higher response and a shorter response time than those of the Au-contacting SWNT network sensors at the same DMMP concentration, due to the stronger interactions between the SWNTs and Pd surface atoms. In Pd-contacting SWNT network sensors, the response increased linearly with increasing DMMP concentration and reproducible response curves were obtained for DMMP levels as low as 1 ppm. These results indicate that SWNT networks in contact with Pd electrodes can function as good DMMP sensors at room temperature with scalable and fast response and excellent recovery.     

气相沉积生长单壁纳米碳管束

采用流动催化热解碳氢化合物方法制备出具有一定取向的单壁纳米碳管束。研究了单壁纳米碳管束的生长过程,发现单壁纳米碳管的生长过程是在气流飘浮单个催化剂颗粒中完成。这与热解碳氢化合物制备定向的多壁纳米碳管在基体催化上生长过程有所不同。根据单壁纳米碳管生长过程,推测出单壁纳米碳管束生长速度的数量级为10^-5m/s。     

Polyethylene crystallization nucleated by carbon nanotubes under shear

Polyethylene crystallization under shear has been studied in the presence of single-wall, few-wall, and multiwall carbon nanotubes (SWNT, FWNT, and MWNT). Polyethylene crystal d-spacings for (110) and (200) planes in polyethylene/carbon nanotubes (CNT) are smaller than in the control polyethylene without CNT and the polymer chain is oriented along the CNT axis. The single-wall carbon nanotube templated polyethylene crystals do not redissolve in boiling xylenes; instead, the chain morphology transforms to an amorphous conformation but remains oriented along the nanotube axis. SWNT crystal peaks were also observed in polyethylene/SWNT fibers.     

Inkjet printing of single-walled carbon nanotube/RuO<Subscript>2</Subscript> nanowire supercapacitors on cloth fabrics and flexible substrates

Single-walled carbon nanotube (SWNT) thin film electrodes have been printed on flexible substrates and cloth fabrics by using SWNT inks and an off-the-shelf inkjet printer, with features of controlled pattern geometry (0.4–6 cm²), location, controllable thickness (20–200 nm), and tunable electrical conductivity. The as-printed SWNT films were then sandwiched together with a piece of printable polymer electrolyte to form flexible and wearable supercapacitors, which displayed good capacitive behavior even after 1,000 charge/discharge cycles. Furthermore, a simple and efficient route to produce ruthenium oxide (RuO₂) nanowire/SWNT hybrid films has been developed, and it was found that the knee frequency of the hybrid thin film electrodes can reach 1,500 Hz, which is much higher than the knee frequency of the bare SWNT electrodes (˜158 Hz). In addition, with the integration of RuO₂ nanowires, the performance of the printed SWNT supercapacitor was significantly improved in terms of its specific capacitance of 138 F/g, power density of 96 kW/kg, and energy density of 18.8 Wh/kg. The results indicate the potential of printable energy storage devices and their significant promise for application in wearable energy storage devices.      

Carbon nanotube DNA sensor and sensing mechanism

We report the fabrication of single-walled carbon nanotube (SWNT) DNA sensors and the sensing mechanism. The simple and generic protocol for label-free detection of DNA hybridization is demonstrated with random sequence 15mer and 30mer oligonucleotides. DNA hybridization on gold electrodes, instead of on SWNT sidewalls, is mainly responsible for the acute electrical conductance change due to the modulation of energy level alignment between SWNT and gold contact. This work provides concrete experimental evidence on the effect of SWNT-DNA binding on DNA functionality, which will help to pave the way for future designing of SWNT biocomplexes for applications in biotechnology in general and also DNA-assisted nanotube manipulation techniques.     

In Situ One-Step Grown Fe/Suspended Single-Wall Carbon Nanotube/Fe Junction and Their Controllable Carrier Transport Properties

We demonstrated the in situ one-step fabrication of suspended single wall carbon nanotube transistors with Fe/Al bi- layered film electrodes for practical integrated quantum phase devices. At 300 K, the devices show field effect transistor operation with an excellent subthreshold swing of S ~ 90 mV/decade for a long channel of 3 mum. In the low temperature regime, we observed four clear peaks corresponding to the four-fold degeneracy of the quantum energy levels at 3.7 K. These four clear peaks indicated that both of the contacts between the SWNT and Fe/Al are highly transparent and that a high-quality SWNT bridge is formed. The dl/dV characteristics under an applied external magnetic field indicate that the modulation of the bandgap of the nanotube with the oscillation of the conductance can be achieved by varying the magnetic field, due to the quantum interference of the electrons. In summary, the simple one-step grown SWNT junction between Fe electrodes can be utilized as a promising element for integrated quantum electronic devices.     

Decarboxylation of oxidized single-wall carbon nanotubes

A classical protocol widely used in organic chemistry of aromatic and polyaromatic molecules has been successfully applied in this work for the decarboxylation of oxidized single-wall carbon nanotube (SWNT) to rend C-H SWNT derivatives. SWNT produced by arc discharge method have been oxidized during a purification process using strongly oxidant agents, such as hydrogen peroxide and nitric acid. The decarboxylation of oxidized SWNT has been conduced with copper(I) oxide in a 50:50 solution of N-methylpyrrolidone and quinoline. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and acid-base potentiometric titration analyses were carried out to characterize quali and quantitatively the changes in the chemical environment on the SWNT surface in each step of the purification and the decarboxylation process. Those techniques showed the appearance of mainly carboxylic and phenolic groups after the purification process and the disappearance of the carboxylic groups after the decarboxylation reaction. Fourier transform infrared spectroscopy analysis indicated also the formation of aliphatic and aromatic C-H groups. X-ray photoelectron spectroscopy and potentiometric titration results determined an efficiency higher than 90% for our decarboxylation procedure. The purity and structural quality of the SWNT sample used in the decarboxylation process were evaluated by thermogravimetry and Raman spectroscopy. Thermogravimetric analysis identified a purified sample with approximately 80 wt% of SWNT, in fractions distributed in highly structured SWNTs (25 wt%), with distribution in composition, length and structural quality (35 wt%) and with very defective and short tubes (25 wt%). The damages on the purified SWNT walls were characterized by the Raman scattering analysis.     

Integration of carbon nanotubes as hole transport electrode in polymer/fullerene bulk heterojunction solar cells

Transparent and conductive single-walled carbon nanotube (SWNT) thin films were fabricated onto glass substrates and their optical and electrical properties were evaluated. Particular attention was given to the dependence of the conductivity and optical transparency on the thickness of the films. Furthermore, the SWNT thin films were integrated in organic photovoltaic devices as the hole transport electrode. The best photovoltaic performance was observed for the devices utilizing 80 nm SWNT films with a sheet resistance of 362 Ω/sq, and a transmittance of 64% at 520 nm. The experiments reveal that SWNTs films can be used as transparent electrodes for efficient, flexible organic photovoltaic devices.     

Carbon nanotube purification: preparation and characterization of carbon nanotube paste electrodes

Paste electrodes have been constructed using single-wall carbon nanotubes mixed with mineral oil. The electrochemical behavior of such electrodes prepared with different percentages of carbon nanotubes has been compared with that of graphite paste electrodes and evaluated with respect to the electrochemistry of ferricyanide with cyclic voltammetry. Carbon nanotubes were purified by a treatment with concentrated nitric acid, then oxidized in air. In addition, electrochemical pretreatments were carried out to increase the selectivity of carbon nanotube electrodes. Performances of carbon nanotube paste and carbon paste electrodes were evaluated by studying such parameters as current peak, deltaEp, anodic and cathodic current ratio, and charge density toward several different electroactive molecules. Data interpretation based on the carbon nanotubes and carbon surface area is presented. Carbon nanotube paste and carbon paste electrodes were tested as H2O2 and NADH probes, and several analytical parameters were evaluated. The oxidative behavior of dopamine was examined at these electrodes. The two-electron oxidation of dopamine to dopaminequinone showed an excellent reversibility in cyclic voltammetry that was significantly better than that observed at carbon paste electrodes.     

Electrochemical organization of monolayer protected gold nanoclusters on single-walled carbon nanotubes: significantly enhanced double layer capacitance

This paper reports a novel electrochemical route for anchoring monolayer protected gold nanoclusters (size 8 +/- 0.2 nm) on single-walled carbon nanotube bundles, resulting in the formation of hybrid materials. Monolayer protected gold nanoclusters prepared by modified Brust synthesis route were organized on SWNT bundles by cycling the potential in dichloromethane between -1 to +1 V at a scan rate of 50 mV/s. Monolayer protected nanoclusters in electrolyte solutions possess ionic space charge around them (double layer charging), making them suitable for organization on nanotube bundles, by tuning the electrostatic interactions. More significantly, analysis of the double layer capacitance of these hybrid materials shows almost ten times increase in capacitance compared to that of bare SWNT bundles. We believe that these hybrid materials are potentially useful in nanoelectronics.     

Screen-printed single-walled carbon nanotube networks and their use for dimethyl methylphosphonate detection

Single-walled carbon nanotube (SWNT) films were prepared on silicon/silica substrates by screen-printed technique at a wafer scale, and their sensing properties to dimethyl methylphosphonate (DMMP) were studied. The SWNT networks were characterized by field-emission scanning electron microscope. The resistance responses to different concentrations of DMMP vapors were investigated at room temperature. The results showed that the resistance changes of the screen-printed SWNT films increased rapidly in varying concentrations ranging from 20 to 200?ppm. The sensor exhibited high resistance responses, good reproducibility and excellent long-term stability for DMMP vapor detection. The screen-printed SWNT networks would be potentially extended to large-scale, low cost and simple manufacturing sensor applications.