Aqueous electrolytes have great potential to improve the safety and production costs of Li-ion batteries. Our recent materials exploration led to the discovery of the Li-salt dihydrate melt Li­(TFSI)0.7(BETI)0.3·2H2O, which possesses an extremely wide potential window. To clarify the detailed liquid structure and electronic states of this unique aqueous system, a first-principles molecular dynamics study has been conducted. We found that water molecules in the hydrate melt exist as isolated monomers or clusters consisting of only a few (at most five) H2O molecules. Both the monomers and the clusters have electronic structures largely deviating from that in bulk water, where the lowest unoccupied states are higher in energy than that of the Li-salt anions, which preferentially cause anion reduction leading to formation of an anion-derived stable solid-electrolyte interphase. This clearly shows the role of characteristic electronic structure inherent to the peculiar water environment for the extraordinary electrochemical stability of hydrate melts.

Boron-doped diamond (BDD) has attracted much attention as a promising electrode material especially for electrochemical sensing systems, because it has excellent properties such as a wide potential window and low background current. It is known that the electrochemical properties of BDD electrodes are very sensitive to the surface termination such as to whether it is hydrogen- or oxygen-terminated. Pretreating BDD electrodes by cathodic reduction (CR) to hydrogenate the surface has been widely used to achieve high sensitivity. However, little is known about the effects of the CR treatment conditions on surface hydrogenation. In this Article, we report on a systematic study of CR treatments that can achieve effective surface hydrogenation. As a result, we found that the surface hydrogenation could be improved by applying a more negative potential in a lower pH solution. This is because hydrogen atoms generated from protons in the CR treatment contribute to the surface hydrogenation. After CR treatments, BDD surface could be hydrogenated not completely but sufficiently to achieve high sensitivity for electrochemical sensing. In addition, we confirmed that hydrogenation with high repeatability could be achieved.

To study the influence of crystal orientation on the electrochemical properties of boron-doped diamond (BDD), electrodes comprising ( 100) and ( 111) homoepitaxial single-crystal layers of BDD were investigated and these were compared with a thin polycrystalline BDD electrode. The BDD samples with similar amounts of boron of around 10 20 cm −3 and resistivity of around 6 × 10 −3 Ω cm were prepared. Evaluation of the electrochemical reactivity of each of the samples with both H-and O-terminated surfaces showed that polycrystalline BDD was the most reactive, whereas the (111) samples proved to be more reactive than the (100) ones for single-crystal BDD. Moreover, considering the results of firstprinciples molecular dynamics simulations, it is proposed that surface transfer doping is the dominating factor for H-terminated surfaces, whereas the degree of band bending and the thickness of the space-charge layer are the dominating factors for O-terminated surfaces.

Carbon-based materials are regarded as an environmentally benign alternative to the conventional metal electrode used in electrochemistry from the viewpoint of sustainable chemistry. Among various carbon electrode materials, boron-doped diamond (BDD) exhibits superior electrochemical properties. However, it is still uncertain how surface chemical species of BDD influence the electrochemical performance, because of the difficulty in characterizing the surface species. Here, we have developed in situ spectroscopic measurement systems on BDD electrodes, i.e., in situ attenuated total reflection infrared spectroscopy (ATR-IR) and electrochemical X-ray photoelectron spectroscopy (EC-XPS). ATR-IR studies at a controlled electrode potential confirmed selective surface hydroxylation. EC-XPS studies confirmed deprotonation of C–OH groups at the BDD/electrolyte interface. These findings should be important not only for better understanding of BDD’s fundamentals but also for a variety of applications.

The tunnel field-effect transistor (TFET) is one of the candidates replacing conventional metal-oxide-semiconductor field-effect transistors to realize low-power-consumption large-scale integration (LSI). The most significant issue in the practical application of TFETs concerns their low tunneling current. Si is an indirect-gap material having a low band-to-band tunneling probability and is not favored for the channel. However, a new technology to enhance tunneling current in Si-TFETs utilizing the isoelectronic trap (IET) technology was recently proposed. IET technology provides a new approach to realize low-power-consumption LSIs with TFETs. The present paper reviews the state-of-the-art research and future prospects of Si-TFETs with IET technology.