Motoo Yumura

Extracting the Full Potential of Single‐Walled Carbon Nanotubes as Durable Supercapacitor Electrodes Operable at 4 V with High Power and Energy Density

Supercapacitors are electrochemical energy storage systems that store energy directly and physically as charge, whereas batteries, for example Li-ion cells, store energy in chemical reactants capable of generating charge. [ 1 ] Accordingly, the energy density of supercapacitors ( < 10 Wh kg − 1 ) is lower than batteries ( > 100 Wh kg − 1 ). However, their power is signifi cantly higher and their lifetime longer. As such, supercapacitors are expected to play a crucial role where superior power performance is required. The importance of supercapacitors is highlighted by a report from the US Department of Energy assigning equal importance to batteries and supercapacitors. [ 2 ] Examples of envisioned largescale applications of supercapacitors are load-leveling in solar, wind, and other energy sources and energy recovery from regenerative braking in automobiles. [ 2 , 3 ] To emerge as an important energy storage technology in the future, advanced supercapacitors must be developed with higher operating voltage and higher energy and power delivery, while maintaining high cyclability. Hitherto, activated carbon (AC) has been the electrode material of choice due to its high surface area (1000–2000 m 2

Conical beams from open nanotubes

Electron guns are indispensable devices that are widely used in household and industrial appliances. Field electron-emitting sources (which emit electrons by tunnelling effects in electric fields), with their small size, small energy spread, high current density and no requirement for heat, have distinct advantages over thermionic emitters. We have made a field electron emitter from hollow, open-ended carbon nanotubes.

Integrated three-dimensional microelectromechanical devices from processable carbon nanotube wafers.

In order to be useful as microelectromechanical devices, carbon nanotubes with well-controlled properties and orientations should be made at high density and be placed at predefined locations. We address this challenge by hierarchically assembling carbon nanotubes into closely packed and highly aligned three-dimensional wafer films from which a wide range of complex and three-dimensional nanotube structures were lithographically fabricated. These include carbon nanotube islands on substrates, suspended sheets and beams, and three-dimensional cantilevers, all of which exist as single cohesive units with useful mechanical and electrical properties. Every fabrication step is both parallel and scalable, which makes it easy to further integrate these structures into functional three-dimensional nanodevice systems. Our approach opens up new ways to make economical and scalable devices with unprecedented structural complexity and functionality.

Carbon Nanotubes with Temperature-Invariant Viscoelasticity from –196° to 1000°C

Shake It to Wake It Viscoelastic materials combine the recoverable stretchiness found in elastic materials with the slow-flowing behavior of a thick fluid, like honey. When subjected to an oscillatory motion, the response will depend on the frequency. At low frequencies, the viscous behavior will dominate and lead to a dissipation of the applied energy as heat, while at fast frequencies the elastic behavior dominates. Xu et al. (p. 1364; see the Perspective by Gogotsi) developed a viscoelastic material with an exceptionally broad operating temperature range, based on a network of carbon nanotubes. The responsiveness of the material was probably caused by the “zipping” and “unzipping” of the nanotubes at points of contact. A dense carbon-nanotube network shows nearly constant viscoelastic properties over an exceptionally wide temperature range. Viscoelasticity describes the ability of a material to possess both elasticity and viscosity. Viscoelastic materials, such as rubbers, possess a limited operational temperature range (for example, for silicone rubber it is –55° to 300°C), above which the material breaks down and below which the material undergoes a glass transition and hardens. We created a viscoelastic material composed from a random network of long interconnected carbon nanotubes that exhibited an operational temperature range from –196° to 1000°C. The storage and loss moduli, frequency stability, reversible deformation level, and fatigue resistance were invariant from –140° to 600°C. We interpret that the thermal stability stems from energy dissipation through the zipping and unzipping of carbon nanotubes at contacts.

One hundred fold increase in current carrying capacity in a carbon nanotube-copper composite

Increased portability, versatility and ubiquity of electronics devices are a result of their progressive miniaturization, requiring current flow through narrow channels. Present-day devices operate close to the maximum current-carrying-capacity (that is, ampacity) of conductors (such as copper and gold), leading to decreased lifetime and performance, creating demand for new conductors with higher ampacity. Ampacity represents the maximum current-carrying capacity of the object that depends both on the structure and material. Here we report a carbon nanotube–copper composite exhibiting similar conductivity (2.3–4.7 × 105 S cm−1) as copper (5.8 × 105 S cm−1), but with a 100-times higher ampacity (6 × 108 A cm−2). Vacuum experiments demonstrate that carbon nanotubes suppress the primary failure pathways in copper as observed by the increased copper diffusion activation energy (∼2.0 eV) in carbon nanotube–copper composite, explaining its higher ampacity. This is the only material with both high conductivity and high ampacity, making it uniquely suited for applications in microscale electronics and inverters.

A black body absorber from vertically aligned single-walled carbon nanotubes

Among all known materials, we found that a forest of vertically aligned single-walled carbon nanotubes behaves most similarly to a black body, a theoretical material that absorbs all incident light. A requirement for an object to behave as a black body is to perfectly absorb light of all wavelengths. This important feature has not been observed for real materials because materials intrinsically have specific absorption bands because of their structure and composition. We found a material that can absorb light almost perfectly across a very wide spectral range (0.2–200 μm). We attribute this black body behavior to stem from the sparseness and imperfect alignment of the vertical single-walled carbon nanotubes.

Revealing the Secret of Water-Assisted Carbon Nanotube Synthesis by Microscopic Observation of the Interaction of Water on the Catalysts

We elucidated the secret of water-assisted chemical vapor deposition (CVD) by elucidating the influence of water on the catalysts, through ex situ microscopic and spectroscopic analysis. We unambiguously showed that catalyst deactivation readily occurs due to carbon coating and that water acted to remove this coating and revive catalysts activity. This represents the central point of water-assisted CVD.

Dispersion of metal nanoparticles for aligned carbon nanotube arrays

We report that Co metal nanoparticles (an average diameter of 4 nm) chemically synthesized by a reverse micelle method catalyzes the growth of multiwall carbon nanotubes (MWNTs) aligned perpendicular to a substrate. The surface of the nanoparticles is covered with surfactants so that the nanoparticles can be dispersed in organic solvent. The dispersion of the nanoparticles was cast directly onto a plane Si substrate for thermal pyrolysis of acetylene. We have found that the pretreatment of the metal nanoparticles with hydrogen sulfide before the pyrolysis straightens the MWNTs, suggesting sulfurization of the nanoparticle catalyst plays an important role in regular growth of the MWNTs. The dispersion of the nanoparticles offers a conventional and processible approach to synthesize large area aligned MWNT arrays.

Improved and Large Area Single-Walled Carbon Nanotube Forest Growth by Controlling the Gas Flow Direction

A gas shower system was introduced to improve the growth of single-walled carbon nanotube (SWNT) forests by controlling the gas flow direction. Delivery of gases from the top of the forest enabled direct and precise supply of ethylene and water vapor to the Fe catalysts. As such, this approach solved one of the limiting factors of water-assisted chemical vapor deposition method (CVD), that is, delivery of the very small optimum water level to the catalysts. Consequently, this approach improved SWNT forests growth stability, uniformity, reproducibility, carbon efficiency (32%), and catalyst lifetime. With this improved growth, we could synthesize a 1 cm tall forest with 1 x 1 cm size. Also we employed this approach to grow an A4 size SWNT forest to highlight the scalability of water-assisted CVD.

Alignment control of carbon nanotube forest from random to nearly perfectly aligned by utilizing the crowding effect.

Alignment represents an important structural parameter of carbon nanotubes (CNTs) owing to their exceptionally high aspect ratio, one-dimensional property. In this paper, we demonstrate a general approach to control the alignment of few-walled CNT forests from nearly random to nearly ideally aligned by tailoring the density of active catalysts at the catalyst formation stage, which can be experimentally achieved by controlling the CNT forest mass density. Experimentally, we found that the catalyst density and the degree of alignment were inseparably linked because of a crowding effect from neighboring CNTs, that is, the increasing confinement of CNTs with increased density. Therefore, the CNT density governed the degree of alignment, which increased monotonically with the density. This relationship, in turn, allowed the precise control of the alignment through control of the mass density. To understand this behavior further, we developed a simple, first-order model based on the flexural modulus of the CNTs that could quantitatively describe the relationship between the degree of alignment (HOF) and carbon nanotube spacing (crowding effect) of any type of CNTs.