Nido-Hydroborate-Based Electrolytes for All-Solid-State Lithium Batteries

Hydroborate-based solid electrolytes have recently been successfully employed in high voltage, room temperature all-solid-state sodium batteries. The transfer to analogous lithium systems has failed up to now due to the lower conductivity of the corresponding lithium compounds and their high cost. Here LiB₁₁H₁₄ nido-hydroborate as a cost-effective building block and its high-purity synthesis is introduced. The crystal structures of anhydrous LiB₁₁H₁₄ as well as of LiB₁₁H₁₄-based mixed-anion solid electrolytes are solved and high ionic conductivities of 1.1 × 10⁻⁴ S cm⁻¹ for Li₂(B₁₁H₁₄)(CB₁₁H₁₂) and 1.1 × 10⁻³ S cm⁻¹ for Li₃(B₁₁H₁₄)(CB₉H₁₀)₂ are obtained, respectively. LiB₁₁H₁₄ exhibits an oxidative stability limit of 2.6 V versus Li⁺/Li and the proposed decomposition products are discussed based on density functional theory calculations. Strategies are discussed to improve the stability of these compounds by modifying the chemical structure of the nido-hydroborate cage. Galvanostatic cycling in symmetric cells with two lithium metal electrodes shows a small overpotential increase from 22.5 to 30 mV after 620 h (up to 0.5 mAh cm⁻²), demonstrating that the electrolyte is compatible with metallic anodes. Finally, the Li₂(B₁₁H₁₄)(CB₁₁H₁₂)  electrolyte is employed in a proof-of-concept half cell with a TiS₂ cathode with a capacity retention of 82% after 150 cycles at C/5.     

以辉锑矿为原料放电等离子烧结快速制备黝铜矿Cu_(12)Sb_4S_(13)及反应机理

采用辉锑矿为原料成功制备出Cu_(12)Sb_4S_(13)块体。研究以Sb_2S_3矿物为原料时烧结工艺对Cu_(12)Sb_4S_(13)合成的影响。在400 ～ 440℃温度区间内均可快速合成Cu_(12)Sb_4S_(13)块体且二次烧结能够进一步减小中间相CuSbS_2和Cu_3SbS_3。第二相Cu_3SbS_4和残留相CuS随着烧结时间的延长而降低。二次烧结前进行机械化球磨处理,干磨比湿磨更容易减小残留相。初次烧结块体的断面SEM和EDS能谱分析表明内部存在Cu或Cu_2S颗粒团聚现象。适当降低Cu或CuS摩尔量(化学计量比0.1 mol)能促进烧结块表面反应进行。烧结过程中,硫磺蒸汽压的导致烧结块表面成分和内部粉末的成分不同。     

Two Triterpene Synthases from Imperata cylindrica Catalyzing the Formation of a Pair of Diastereoisomers through Boat or Chair Cyclization

Imperata cylindrica is known to produce a pair of triterpenes, isoarborinol and fernenol, that exhibit identical planar structures but possess opposite stereochemistry at six of the nine chiral centers. These differences arise from a boat or a chair cyclization of the B-ring of the substrate. Herein, we report the characterization of three OSC genes from I. cylindrica. IcOSC1 and IcOSC5 were identified as isoarborinol and fernenol synthases, respectively, while IcOSC3 was characterized as a multifunctional enzyme that produces glutinol and friedelin as its major products. Mutational studies of isoarborinol and fernenol synthases revealed that the residues surrounding the DCTAE motif partially affected the conformation of the B-ring during cyclization. Additionally, the IcOSC1-W255H mutant produced the rare triterpene boehmerol. The introduced histidine residue presumably abstracted a proton from the intermediary carbocation at C18 during the 1,2-rearrangement. Expression analysis indicated that all OSC genes were highly expressed in stems.     

Improvement of the Nelder-Mead method using Direct Inversion in Iterative Subspace

Optimization and Engineering - The Nelder-Mead (NM) method is a popular derivative-free optimization algorithm owing to its fast convergence and robustness. However, it is known that the method...     

Quantitative Elemental Analysis of a Single Cell by Using Inductively Coupled Plasma-Mass Spectrometry in Fast Time-Resolved Analysis Mode

The elemental composition of a single yeast, green alga, or red blood cell (RBC) was precisely determined by using inductively coupled plasma-mass spectrometry (ICP-MS) operating in fast time-resolved analysis (TRA) mode. The technique is known as single-cell (SC)-ICP-MS. Phosphorus, sulfur, magnesium, zinc, and iron were detected in the three types of cell. The elemental composition of yeast and green alga obtained by SC-ICP-MS was consistent with results obtained from conventional ICP-MS measurements following acid digestion of the cells. Slight differences were found in the measured values between SC-ICP-MS and the conventional ICP-MS results for RBC. However, the SC-ICP-MS results for S and Fe in RBC were closer to the estimated values for these elements that were calculated from the level of hemoglobin in RBCs. The data suggest that SC-ICP-MS is suitable for the analysis of various cell types, namely, fungus, plant, and animal cells.     

Fabrication of BSCF-based mixed oxide ionic-electronic conducting multi-layered membrane by sequential electrophoretic deposition process

The Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF)-based multi-layered oxygen separation membrane was fabricated by the sequential electrophoretic deposition (EPD) process. A thin porous/dense bi-layer of BSCF was formed on a thick porous support of BSCF. The porous support prepared by a sacrificial template method using BSCF powder mixed with wheat starch (30 wt%) as a pore-forming agent, followed by uniaxial pressing and low-temperature sintering, was directly used as an EPD electrode. A thin BSCF layer was first formed on the porous support, and then a thin BSCF + PMMA (polymethyl methacrylate) layer was sequentially formed on the thin BSCF layer using a bimodal suspension of BSCF and PMMA. A 30-μm thin porous/dense bi-layer of BSCF of which the total thickness was obtained by optimizing the processes of EPD and subsequent co-sintering. The oxygen separation performance of 3.7 ml (STP) min^?1 cm^?2 at 860 °C was achieved for the BSCF-based multi-layered oxygen separation membrane.     

Surface Analysis of Cr2O3‐, CoO‐, and Al2O3‐Doped Iron–Phosphate Glasses at High Temperature

Surface structures of iron–phosphate glasses were examined using X‐ray photoelectron spectroscopy (XPS). Cr₂O₃, CoO, and Al₂O₃ were introduced to the glass by the replacement of a part of Fe₂O₃, and the simulated fission products are also added. The obtained glasses showed high chemical durabilities by MCC‐1 test. In situ high‐temperature and room‐temperature XPS measurements were conducted on the polished sample surfaces and also those after 1‐week chemical durability test. Unique trends were observed in XPS spectra on heating and after the chemical durability test, respectively. Nature of the glass surface of iron–phosphate glasses was explained from the point of view of surface energy, and the origin of high chemical durability and the effect of chromium ions were discussed based on the changes on surface composition and valence states of transition‐metal ions.     

Applicability of the generalized scaling law to a pile-inclined ground system subject to liquefaction-induced lateral spreading

The generalized scaling law is based on the concept of two-stage scaling and allows currently available centrifuge facilities to model a large-scale prototype expanding over the spatial dimension ranging from 30 m or larger subject to earthquake motions. This paper presents the results of investigation on the applicability of the generalized scaling law to the fully nonlinear regime of soil-structure system with the induced strain level of 10% in the order of magnitude. The centrifuge model tests performed in this study under the modeling of models scheme consist of a pile model embedded in a inclined ground subject to liquefaction-induced lateral spreading. Four different centrifugal accelerations ranging from 13g to 50g are used whereas the actual size of the physical model is kept constant with an overall scaling factor of 1/100. The models are exposed to tapered sinusoidal input accelerations of frequency 0.59 Hz and amplitude 3.0 m/s² in prototype scale, and the results are compared in terms of prototype by applying the generalized scaling law. As for the response of the ground during shaking, essentially identical accelerations and excess pore water pressures are recorded for all cases, while the lateral displacement shows a variation ranging from 5% to 9% in terms of shear strain due to a slight variation in experimental conditions (e.g., input peak acceleration, achieved density distribution). Practically the same responses are measured among the cases in the dissipation phase of excess pore water pressure. With regard to pile behavior, nearly identical responses for the lateral displacements and bending moments are obtained for all cases both during and after shaking. These results demonstrated that the generalized scaling law is applicable to the fully nonlinear regime of soil-structure system subject to the cumulative shear strain in the order of 10% due to cyclic mobility of sands during earthquakes.     

Characterization of the Oxide Scale Formed on T12 Water Wall Tube After Long-term Service in Supercritical Power Plant

Oxidation of Metals - Oxide scale control is one of the critical maintenance issues in fossil fuel power plant. Hence, the water treatment of the feed water has been changed from all-volatile...     

Bioconcentration potential of polydimethylsiloxane (PDMS) fluids by fish

The water solubilities (S), octanol/water partition coefficients (K_ow) and bioconcentration factors (BCF) of four polydimethylsiloxane (PDMS) fluids covering a wide range of molecular weight were measured. It is shown that a previously described correlation between S and K_ow for organic chemicals may be invalid for PDMS fluids; an alternative correlation is proposed. Some PDMS fluids tend to have a bioconcentration potential in silver carp.