Hiroyuki Oguchi

Complex Hydrides with (BH4)− and (NH2)− Anions as New Lithium Fast-Ion Conductors

Some of the authors have reported that a complex hydride, Li(BH(4)), with the (BH(4))(-) anion exhibits lithium fast-ion conduction (more than 1 x 10(-3) S/cm) accompanied by the structural transition at approximately 390 K for the first time in 30 years since the conduction in Li(2)(NH) was reported in 1979. Here we report another conceptual study and remarkable results of Li(2)(BH(4))(NH(2)) and Li(4)(BH(4))(NH(2))(3) combined with the (BH(4))(-) and (NH(2))(-) anions showing ion conductivities 4 orders of magnitude higher than that for Li(BH(4)) at RT, due to being provided with new occupation sites for Li(+) ions. Both Li(2)(BH(4))(NH(2)) and Li(4)(BH(4))(NH(2))(3) exhibit a lithium fast-ion conductivity of 2 x 10(-4) S/cm at RT, and the activation energy for conduction in Li(4)(BH(4))(NH(2))(3) is evaluated to be 0.26 eV, less than half those in Li(2)(BH(4))(NH(2)) and Li(BH(4)). This study not only demonstrates an important direction in which to search for higher ion conductivity in complex hydrides but also greatly increases the material variations of solid electrolytes.

Experimental and computational studies on structural transitions in the LiBH4–LiI pseudobinary system

Structural transition properties of the LiBH4+xLiI (x=0–1.00) pseudobinary system were examined by powder x-ray diffraction and differential scanning calorimetry combined with periodic density functional theory calculations. We experimentally and computationally confirmed the stabilization of the high-temperature [hexagonal, lithium super(fast-)ionic conduction] phase of LiBH4 with x=0.33 and 1.00, and the results also imply the existence of intermediate phases with x=0.07–0.20. The studies are of importance for further development of LiBH4 and the derived hydrides as solid-state electrolytes.

Self-Assembly Strategy for Fabricating Connected Graphene Nanoribbons

We use self-assembly to fabricate and to connect precise graphene nanoribbons end to end. Combining scanning tunneling microscopy, Raman spectroscopy, and density functional theory, we characterize the chemical and electronic aspects of the interconnections between ribbons. We demonstrate how the substrate effects of our self-assembly can be exploited to fabricate graphene structures connected to desired electrodes.

Sodium ionic conduction in complex hydrides with [BH4]− and [NH2]− anions

We report the experimental results of structural and sodium ionic conductive properties of the Na(BH4)–Na(NH2)–NaI system. Na(BH4)0.5(NH2)0.5 with [BH4]− and [NH2]− complex anions formed by combining Na(BH4) and Na(NH2) complex hydrides shows the most superior sodium ionic conductivity of 2 × 10−6 S/cm at 300 K because of the specific antiperovskite-type structure with vacancies in the Na+ site Furthermore, Na(BH4)0.5(NH2)0.5 shows a high electrochemical stability of at least 6 V (vs Na+/Na). The result suggests that Na(BH4)0.5(NH2)0.5 could be a potential candidate for solid electrolyte.

Lithium-ion conduction in complex hydrides LiAlH4 and Li3AlH6

Lithium-ion conduction in complex hydrides LiAlH4 and Li3AlH6 was investigated using ac complex impedance measurements. The conductivities at room temperature were 8.7×10−9 S/cm in the case of LiAlH4 and 1.4×10−7 S/cm in the case of Li3AlH6. To enhance the conductivity of Li3AlH6 having good thermal stability in heating/cooling cycles, mechanical milling, and addition of lithium halides (LiCl, LiI) were implemented. The maximum value of 2.5×10−4 S/cm at 393 K was observed when 0.33 M ratio of LiI was added to Li3AlH6. This study demonstrated two research directions to enhance the lithium-ion conductivity in a variety of complex hydrides.

An Infrared Imaging Method for High-Throughput Combinatorial Investigation of Hydrogenation-Dehydrogenation and New Phase Formation of Thin Films

We have developed an infrared imaging setup enabling in situ infrared images to be acquired, and expanded on capabilities of an infrared imaging as a high-throughput screening technique, determination of a critical thickness of a Pd capping layer which significantly blocks infrared emission from below, enhancement of sensitivity to hydrogenation and dehydrogenation by normalizing raw infrared intensity of a Mg thin film to an inert reference, rapid and systematic screening of hydrogenation and dehydrogenation properties of a Mg-Ni composition spread covered by a thickness gradient Pd capping layer, and detection of formation of a Mg2Si phase in a Mg thin film on a thermally oxidized Si substrate during annealing.

Model, prediction, and experimental verification of composition and thickness in continuous spread thin film combinatorial libraries grown by pulsed laser deposition

Pulsed laser deposition was used to grow continuous spread thin film libraries of continuously varying composition as a function of position on a substrate. The thickness of each component that contributes to a library can be empirically modeled to a bimodal cosine power distribution. We deposited ternary continuous spread thin film libraries from Al(2)O(3), HfO(2), and Y(2)O(3) targets, at two different background pressures of O(2): 1.3 and 13.3 Pa. Prior to library deposition, we deposited single component calibration films at both pressures in order to measure and fit the thickness distribution. Following the deposition and fitting of the single component films, we predict both the compositional coverage and the thickness of the libraries. Then, we map the thickness of the continuous spread libraries using spectroscopic reflectometry and measure the composition of the libraries as a function of position using mapping wavelength-dispersive spectrometry (WDS). We then compare the compositional coverage of the libraries and observe that compositional coverage is enhanced in the case of 13.3 Pa library. Our models demonstrate linear correlation coefficients of 0.98 for 1.3 Pa and 0.98 for 13.3 Pa with the WDS.

Ferroelectric dipole electrets for output power enhancement in electrostatic vibration energy harvesters

We propose a ferroelectric dipole electret composed of polarized lead zirconate titanate. Deep insight into the physics behind the parallel plate capacitor theoretically predicts that we can extract large electric field near the surface of the ferroelectric dipole electret by increasing its surface charge density and thickness. Experiment for ferroelectric dipole electret shows good agreement with the theory. The maximum output power density of electrostatic vibration energy harvesters using the ferroelectric dipole electret was 78 μW/cm3, a three-fold increase over a conventional polymer electret. Our results will pave the way for use of ferroelectrics as electrets.

Sodium-ion conduction in complex hydrides NaAlH4 and Na3AlH6

We have studied sodium-ion conduction in complex hydrides NaAlH4 and Na3AlH6. The electrical conductivities of these complex hydrides were studied using ac impedance measurements at temperatures up to 363 K for NaAlH4 and 433 K for Na3AlH6. Nyquist plots obtained by the measurements indicated the sodium-ion conduction. Also, dc measurements showed that sodium-ion transference numbers of NaAlH4 and Na3AlH6 were almost unity. Na3AlH6 exhibited the sodium-ion conduction of 4.1 × 10−4 S/cm at 433 K. This study will open up research on complex hydrides as solid-state sodium-ion conductors.

Fe-B-Nd-Nb metallic glass thin films for microelectromechanical systems

In the present study, we investigate the mechanical properties, residual stress, and microprocessing compatibility of Fe67.5B22.5Nd6.3Nb3.7 metallic glass thin films (Fe-MGTFs). The mechanical properties are measured using a specially designed microtensile tester. The fracture toughness of the Fe-MGTF (6.36 MPa × m1/2) is more than twice that of Si, and the highest among the thin films developed for microelectromechanical systems (MEMS) to this point. In addition, the fabrication of freestanding microcantilevers illustrates the low residual stress and high microprocessing compatibility of Fe-MGTFs. The present study verifies the great potential of Fe-MGTFs for use in MEMS.