Don N. Futaba

High-Power Supercapacitor Electrodes from Single-Walled Carbon Nanohorn/Nanotube Composite

A novel composite is presented as a supercapacitor electrode with a high maximum power rating (990 kW/kg; 396 kW/l) exceeding power performances of other electrodes. The high-power capability of the electrode stemmed from its unique meso-macro pore structure engineered through the utilization of single-walled carbon nanotubes (20 wt %) as scaffolding for single-walled carbon nanohorns (80 wt %). The novel composite electrode also exhibited durable operation (6.5% decline in capacitance over 100 000 cycles) as a result of its monolithic chemical composition and mechanical stability. The novel composite electrode was benchmarked against another high-power electrode made from single-walled carbon nanotubes (Bucky paper electrode). While the composite electrode had a lower surface area compared to the Bucky paper electrode (280 vs 470 m(2)/g from nitrogen adsorption), it had a higher meso-macro pore volume (2.6 vs 1.6 mL/g from mercury porosimetry) which enabled the composite electrode to retain more electrolyte, ensuring facile ion transport, hence achieving a higher maximum power rating (970 vs 400 kW/kg).

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.

Exploring Advantages of Diverse Carbon Nanotube Forests with Tailored Structures Synthesized by Supergrowth from Engineered Catalysts

We explored advantages of diverse carbon nanotube forests with tailored structures synthesized by water-assisted chemical vapor deposition (CVD) growth (supergrowth) from engineered catalysts. By controlling the catalyst film thickness, we synthesized carbon nanotube (CNT) forests composed from nanotubes with different size and wall number. With extensive characterizations, many interesting dependencies among CNT forest structures and their properties, which were unknown previously, were found. For example, multiwalled carbon nanotubes (MWNTs) showed superior electronic conductivity while single-walled carbon nanotubes (SWNTs) showed superior thermal diffusivity, and sparse MWNTs achieved lower threshold voltage for field emission than dense SWNTs. These interesting trends highlight the complexity in designing and choosing the optimum CNT forest for use in applications.

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.

Ion diffusion and electrochemical capacitance in aligned and packed single-walled carbon nanotubes.

Direct measurement of ion diffusion in aligned, densified single-walled carbon nanotube electrodes showed that the diffusion coefficient for transport of ions (KSCN in acetonitrile) parallel to the alignment direction of the nanotubes was close to the theoretical limit of perfectly straight pores, achieving a value 20 times larger than that of activated carbon electrodes (1 × 10(-5) vs 5 × 10(-7) cm(2)/s). In contrast, the diffusion coefficient for ion transport perpendicular to the alignment direction was an order of magnitude smaller (8 × 10(-7) cm(2)/s). As an example of the ramifications of this anisotropic diffusion phenomenon, the difference in performance of the aligned carbon nanotubes as electrochemical-capacitor electrodes was evaluated. At low discharge rates, the performances of the two orientations were identical, but as the discharge rate was increased, a more rapid decline in capacitance was observed for the perpendicular orientation (66 vs 14% decline in capacitance when the discharge current was increased from 0.01 to 1 A/g). Furthermore, the maximum power rating of the perpendicular electrode was lower than that of the parallel electrode (1.85 vs 3 kW/kg during operation at 1 V).

Role of subsurface diffusion and Ostwald ripening in catalyst formation for single-walled carbon nanotube forest growth.

Here we show that essentially any Fe compounds spanning Fe salts, nanoparticles, and buckyferrocene could serve as catalysts for single-walled carbon nanotube (SWNT) forest growth when supported on AlO(x) and annealed in hydrogen. This observation was explained by subsurface diffusion of Fe atoms into the AlO(x) support induced by hydrogen annealing where most of the deposited Fe left the surface and the remaining Fe atoms reconfigured into small nanoparticles suitable for SWNT growth. Interestingly, the average diameters of the SWNTs grown from all iron compounds studied were nearly identical (2.8-3.1 nm). We interpret that the offsetting effects of Ostwald ripening and subsurface diffusion resulted in the ability to grow SWNT forests with similar average diameters regardless of the initial Fe catalyst.

Existence and kinetics of graphitic carbonaceous impurities in carbon nanotube forests to assess the absolute purity.

We present an approach that can identify and assess carbonaceous impurities in carbon nanotube (CNT) forests. First, the kinetics of the impurity accumulation was elucidated by investigating the time evolution of both the height and weight of the forests. Second, the kinetics was used to extract a power scaling law revealing the carbonaceous impurity level to solely depend on the total volume of carbon exposure. Third, the power scaling law allowed for a quantitative model describing both the growth of CNTs and accumulation of the carbonaceous impurities. Lastly, from the model the absolute purities of the SWNT forests were evaluated as above 95% with a high of 99.5%.