Boron-Doped Edges as Active Sites for Water Adsorption in Activated Carbons.

Investigating the surface properties of heteroatom-doped carbon materials is essential because these versatile materials have found use in a variety of energy and environmental applications; an understanding of these properties would also lead to an improved appreciation of the direct interaction between the reactant and the functionalized surface. Herein, we explore the effect of boron (B) doping on the surface properties of activated carbon (AC) materials based on their water adsorption behavior and oxygen reduction reaction. In the high-temperature B doping process, B-doped AC materials at 1400 °C exhibit an open pore structure with B-O bonds, whereas at a temperature of 1600 °C, a nonporous structure containing a large amount of B-C bonds prevails. The B-O species act as active sites for water adsorption on the carbon surface. On the basis of the isothermal adsorption heat, we suggest that B atoms are present at the pore openings and on the surfaces. The B-O moieties at the open edges improve the electrocatalytic activity, whereas the B-C bonds at the closed edges decrease the electrocatalytic activity because of the stable structure of these bonds. Our findings provide new evidence for the electrocatalytic properties associated with the structure of B-doped edges.

Characterization of Sn4P3-Carbon Composite Films for Lithium-Ion Battery Anode Fabricated by Aerosol Deposition.

We fabricated tin phosphide-carbon (Sn4P3/C) composite film by aerosol deposition (AD) and investigated its electrochemical performance for a lithium-ion battery anode. Sn4P3/C composite powders prepared by a ball milling was used as raw material and deposited onto a stainless steel substrate to form the composite film via impact consolidation. The Sn4P3/C composite film fabricated by AD showed much better electrochemical performance than the Sn4P3 film without complexing carbon. Although both films showed initial discharge (Li+ extraction) capacities of approximately 1000 mAh g-1, Sn4P3/C films retained higher reversible capacity above 700 mAh g-1 after 100 cycles of charge and discharge processes while the capacity of Sn4P3 film rapidly degraded with cycling. In addition, by controlling the potential window in galvanostatic testing, Sn4P3/C composite film retained the reversible capacity of 380 mAh g-1 even after 400 cycles. The complexed carbon works not only as a buffer to suppress the collapse of electrodes by large volume change of Sn4P3 in charge and discharge reactions but also as an electronic conduction path among the atomized active material particles in the film.

Properties of Lithium Trivanadate Film Electrodes Formed on Garnet-Type Oxide Solid Electrolyte by Aerosol Deposition.

We fabricated lithium trivanadate LiV3O8 (LVO) film electrodes for the first time on a garnet-type Ta-doped Li7La3Zr2O12 (LLZT) solid electrolyte using the aerosol deposition (AD) method. Ball-milled LVO powder with sizes in the range of 0.5⁻2 µm was used as a raw material for LVO film fabrication via impact consolidation at room temperature. LVO film (thickness = 5 µm) formed by AD has a dense structure composed of deformed and fractured LVO particles and pores were not observed at the LVO/LLZT interface. For electrochemical characterization of LVO film electrodes, lithium (Li) metal foil was attached on the other end face of a LLZT pellet to comprise a LVO/LLZT/Li all-solid-state cell. From impedance measurements, the charge transfer resistance at the LVO/LLZT interface is estimated to be around 10³ Ω cm² at room temperature, which is much higher than at the Li/LLZT interface. Reversible charge and discharge reactions in the LVO/LLZT/Li cell were demonstrated and the specific capacities were 100 and 290 mAh g-1 at 50 and 100 °C. Good cycling stability of electrode reaction indicates strong adhesion between the LVO film electrode formed via impact consolidation and LLZT.

Determination of the stacking order of curved few-layered graphene systems.

We report a facile method to efficiently visualize the atomic carbon network of curved few-layered graphitic systems including folded bi-layer graphene, nanoribbon edges and multi-walled carbon nanotubes (straight and bent), via the processing of aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) images. This technique is also able to atomically resolve the structure of overlapping graphene layers with different orientations, thus enabling us to determine the stacking order of multiple graphene layers. To the best of our knowledge, we are the first to identify the stacking order of a misoriented 4-layer closed-edge graphene and a metal-semiconductor double-walled carbon nanotube junction.

Unusually high dispersion of nitrogen-doped carbon nanotubes in DNA solution.

The dispersibility in a DNA solution of bundled multiwalled carbon nanotubes (MWCNTs), having different chemical functional groups on the CNT sidewall, was investigated by optical spectroscopy. We observed that the dispersibility of nitrogen (N)-doped MWCNTs was significantly higher than that of pure MWCNTs and MWCNTs synthesized in the presence of ethanol. This result is supported by the larger amount of adsorbed DNA on N-doped MWCNTs, as well as by the higher binding energy established between nucleobases and the N-doped CNTs. Pure MWCNTs are dispersed in DNA solution via van der Waals and hydrophobic interactions; in contrast, the nitrogenated sites within N-doped MWCNTs provided additional sites for interactions that are important to disperse nanotubes in DNA solutions.

Enhanced electrical conductivities of N-doped carbon nanotubes by controlled heat treatment.

The thermal stability of nitrogen (N) functionalities on the sidewalls of N-doped multi-walled carbon nanotubes was investigated at temperatures ranging between 1000 °C and 2000 °C. The structural stability of the doped tubes was then correlated with the electrical conductivity both at the bulk and at the individual tube levels. When as-grown tubes were thermally treated at 1000 °C, we observed a very significant decrease in the electrical resistance of the individual nanotubes, from 54 kΩ to 0.5 kΩ, which is attributed to a low N doping level (e.g. 0.78 at% N). We noted that pyridine-type N was first decomposed whereas the substitutional N was stable up to 1500 °C. For nanotubes heat treated to 1800 °C and 2000 °C, the tubes exhibited an improved degree of crystallinity which was confirmed by both the low R value (I(D)/I(G)) in the Raman spectra and the presence of straight graphitic planes observed in TEM images. However, N atoms were not detected in these tubes and caused an increase in their electrical resistivity and resistance. These partially annealed doped tubes with enhanced electrical conductivities could be used in the fabrication of robust and electrically conducting composites, and these results could be extrapolated to N-doped graphene and other nanocarbons.

Chirality-dependent transport in double-walled carbon nanotube assemblies: the role of inner tubes.

A fundamental understanding of the electrical properties of carbon nanotubes is vital when fabricating high-performance polymeric composites as well as transparent conductive films. Herein, the chirality-dependent transport mechanisms in peapod- and chemical vapor deposition-grown double-walled carbon nanotubes (DWNTs) films are discussed by identifying the chiralities of the inner and the outer tubes using fast Fourier transform image processing, as well as optical studies (e.g., Raman, UV, and photoluminescence spectroscopies). The observed conduction mechanisms are strongly dependent on the total fraction of the metallic inner and outer tubes within the DWNT samples. Furthermore, the contribution of the inner tubes to the electronic transport properties of DWNT films is confirmed by photochemically deactivating the outer tubes in both types of DWNT samples.