Hiroyuki Itoi

Three-Dimensionally Arrayed and Mutually Connected 1.2-nm Nanopores for High-Performance Electric Double Layer Capacitor

Zeolite-templated carbon is a promising candidate as an electrode material for constructing an electric double layer capacitor with both high-power and high-energy densities, due to its three-dimensionally arrayed and mutually connected 1.2-nm nanopores. This carbon exhibits both very high gravimetric (140-190 F g(-1)) and volumetric (75-83 F cm(-3)) capacitances in an organic electrolyte solution. Moreover, such a high capacitance can be well retained even at a very high current up to 20 A g(-1). This extraordinary high performance is attributed to the unique pore structure.

Enhancement Mechanism of Electrochemical Capacitance in Nitrogen-/ Boron-Doped Carbons with Uniform Straight Nanochannels

Anodic aluminum oxide (AAO) with uniform straight nanochannels was completely coated with pure, N-doped, or B-doped carbon layer. Their electric double layer capacitances are measured in aqueous (1 M sulfuric acid) and organic (1 M Et4NBF4/polypropylene carbonate) electrolyte solutions in order to investigate the capacitance enhancement mechanisms caused by N- or B-doping. Since the three types of carbon-coated AAOs (pure, N-doped, or B-doped) have exactly the same pore structure, the observed capacitance enhancement was ascribable to only the following factors: (i) better wettability, (ii) the decrease of equivalent series resistance, (iii) the contribution of space-charge-layer capacitance, and (iv) the occurrence of pseudocapacitance. From the measurements of the wettability and the electrical resistance of the coated AAOs together with the electrochemical investigation (the cyclic voltammetry, the galvanostatic charge/discharge cycling, and the impedance analysis), it is concluded that the pseudocapacitance through faradic charge transfer (factor iv) is the most important factor to enhance the capacitance by N- or B-doping. This can be applied to not only the present carbon-coated AAOs but also any other porous carbons.

Investigation of the ion storage/transfer behavior in an electrical double-layer capacitor by using ordered microporous carbons as model materials.

An ordered microporous carbon, which was prepared with zeolite as a template, was used as a model material to understand the ion storage/transfer behavior in electrical double-layer capacitor (EDLC). Several types of such zeolite-templated carbons (ZTCs) with different structures (framework regularity, particle size and pore diameter) were prepared and their EDLC performances were evaluated in an organic electrolyte solution (1 M Et(4)NBF(4)/propylene carbonate). Moreover, a simple method to evaluate a degree of wettability of microporous carbon with propylene carbonate was developed. It was found that the capacitance was almost proportional to the surface area and this linearity was retained even for the carbons with very high surface areas (>2000 m(2) g(-1)). It has often been pointed out that thin pore walls limit capacitance and this usually gives rise to the deviation from linearity, but such a limitation was not observed in ZTCs, despite their very thin pore walls (a single graphene, ca. 0.34 nm). The present study clearly indicates that three-dimensionally connected and regularly arranged micropores were very effective at reducing ion-transfer resistance. Despite relatively small pore diameter ZTCs (ca. 1.2 nm), their power density remained almost unchanged even though the particle size was increased up to several microns. However, when the pore diameter became smaller than 1.2 nm, the power density was decreased due to the difficulty of smooth ion-transfer in such small micropores.

Reversible Pore Size Control of Elastic Microporous Material by Mechanical Force

Nanoporous materials, such as zeolites, activated carbons, and metal-organic frameworks (MOFs), are peculiar platforms in which a variety of guest molecules are stored, reacted, and/or separated. The size of the nanopores is essential to realize advanced functions. In this work, we demonstrate a very simple but innovative method for the control of nanopore size, that is, reversible and continuous control by mechanical force loaded to soft nanoporous materials. The elastic properties of several microporous materials, including zeolites, zeolite-templated carbon (ZTC), activated carbon, and MOFs (e.g., ZIF-8), are examined and it is found that ZTC is a material that is suitable for the aforementioned idea thanks to its extraordinary soft properties compared to the others. The original pore size of ZTC (1.2 nm) can be contracted to 0.85 nm by using a relatively weak loading force of 135 MPa, whereas the other microporous materials barely contracted. To demonstrate the change in the physical properties induced by such artificial deformation, in situ gas adsorption measurements were performed on ZTC with and without loading mechanical force, by using CO2, CH4, and H2, as adsorbates. Upon the contraction by loading 69 or 135 MPa, CO2 adsorption amount is increased, due to the deepening of the physisorption potential well inside the micropores, as proved by the increase of the heat of adsorption. Moreover, the adsorption amount is completely restored to the original one after releasing the mechanical force, indicating the fully reversible contraction/recovery of the ZTC framework against mechanical force. The experimental results are theoretically supported by a simulation using Grand Canonical Monte Carlo method. The similar adsorption enhancement is observed also on CH4, whereas H2 is found as an exception due to the weak interaction potential.

Enhanced hydrogen chemisorption and spillover on non-metallic nickel subnanoclusters

Very fine Ni nanoparticles including subnanoclusters are dispersed in zeolite-templated carbon (ZTC), by thermal decomposition (573 K) of nickelocene pre-loaded on ZTC which functions as a high-surface area support. X-ray absorption fine structure reveals that the Ni species formed by the thermal decomposition is in a unique oxidized state. It is different from nickelocene, Ni metal, or any other inorganic Ni species. The unique Ni species can dissociatively adsorb H2, and enhance the following spillover even under ambient conditions. The spillover activity of the non-metallic Ni subnanoclusters is superior to that of Ni-metal nanoparticles and even comparable to that of Pt nanoparticles.