The electrochemical behavior of highly crystallized single-walled carbon nanotubes (SWCNTs), having a small diameter distribution, is investigated by cyclic voltammetry (CV), using triethylmethylammonium tetrafluoroborate in propylene carbonate as an electrolyte. Unlike the CV curves previously observed by other researchers and referred to as the "butterfly" shape, the CV curve observed in the present study shows large bulges on both sides of the rest potential, thereby resembling a dumbbell. By comparison of the electronic density of states (DOS) of SWCNTs and the dumbbell CV shape, it was determined that the drastic increase of current in the dumbbell shape can be explained by the van Hove singularity in the DOS of the semiconducting SWCNTs in the sample. To validate the explanation, we performed separation of metallic and semiconducting SWCNTs by the density gradient ultracentrifugation method and measured CV curves of the two separated samples. As was expected, the two SWCNT samples showed completely different CV profiles corresponding to each DOS shape. In addition, ion adsorption inside the nanotube is discussed with attention to the change in CV curves with increasing sweep rate.

We investigated the electrochemical lithium-ion storage properties of 9,10-anthraquinone (AQ) and 9,10-phenanthrenequinone (PhQ) molecules encapsulated in the inner hollow core of single-walled carbon nanotubes (SWCNTs). The structural properties of the obtained encapsulated systems were characterized by electron microscopy, synchrotron powder X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. We found that almost all quinone molecules encapsulated in the SWCNTs can store Li-ions reversibly. Interestingly, the undesired capacity fading, which comes from the dissolution of quinone molecules into the electrolyte, was suppressed by the encapsulation. It was also found that the overpotential of AQ was decreased by the encapsulation, probably due to the high-electric conductivity of SWCNTs.

We prepared up to 20 m-thick LiNi1/3Co1/3Mn1/3O2 (NMC)-Li + conductive glass-ceramic solid electrolyte (LATP: Li +~1 0-3 S cm-2 at 298 K) composite cathode films on Li7La3Zr2O12 (LLZ) substrates by aerosol deposition (AD) and investigated their electrochemical properties as all-solid-state batteries. The resultant NMC/LATP interface in the composite film had a thin mutual diffusion layer (~5 nm) and a film had a porosity of ca. 0.15% in volume. The composite films were well adhered to the LLZ substrates even though the films were prepared at room temperature. All-solid-state batteries, consisting of Li/LLZ/NMC-LATP composite film (20 m), repeated charge-discharge reactions for 90 cycles at 100 o C at a 1/10 C rate (capacity retention: 99.97 % / cycle). Rate capability of this battery was improved by modifying both the LATP and electron conductive source amount in the composite film, and a battery with 16 m-thick composite electrode delivered 60 mAh g-1 at 1 mA cm-2 .

In order to understand the reason why polyiodide ions encapsulated in single-walled carbon nanotubes (SWCNTs) drastically improve the electric conductivity and the water dispersibility of SWCNTs at low temperature, we performed in situ Raman measurements of polyiodide ions encapsulated in three kinds of SWCNTs having different mean tube diameters under low temperature down to −100 °C. It was found that, for all the three samples, the Raman peak intensities of polyiodide ions increase and the G-band peak position of SWCNTs shifts toward the higher-wavenumber side with decreasing temperature. It means that the charge-transfer from SWCNTs to encapsulated iodine molecules increases with decreasing temperature and that hole-doping level of SWCNTs increases at low temperature. Furthermore, the peak profiles changed with temperature drastically for polyiodide ions encapsulated in the SWCNT sample having the largest mean tube diameter of 2.5 nm. This change indicates the structural transformation of polyiodide ions in SWCNTs. These experimental results can be explained by the promotion of the chain-like polyiodide ion formation at low temperature. It was discussed with the control experiment using amylose that the promotion of the polyiodide ion formation at low temperature is characteristic for iodine molecules encapsulated in SWCNTs.

We demonstrate that iodine-doping into single-walled carbon nanotubes (SWCNTs) can be effectively done using an electrochemical method. It is shown by in situ Raman measurements that the iodine-doping level can be easily and finely controlled because de-doping is also possible by changing the polarity. In situ synchrotron XRD measurements reveal that iodine molecules are mainly inserted into the hollow core of SWCNTs. The dispersion state of the iodine-doped SWCNTs in water as a function of temperature is also investigated. It is shown that the iodine-doped SWCNTs can be homogeneously dispersed in water at low temperature (ca. <15 °C).