Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection

In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL^?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Interlayer Engineering of Molybdenum Trioxide toward High‐Capacity and Stable Sodium Ion Half/Full Batteries

Orthorhombic molybdenum trioxide (MoO₃) is one of the most promising anode materials for sodium‐ion batteries because of its rich chemistry associated with multiple valence states and intriguing layered structure. However, MoO₃ still suffers from the low rate capability and poor cycle induced by pulverization during de/sodiation. An ingenious two‐step synthesis strategy to fine tune the layer structure of MoO₃ targeting stable and fast sodium ionic diffusion channels is reported here. By integrating partially reduction and organic molecule intercalation methodologies, the interlayer spacing of MoO₃ is remarkably enlarged to 10.40 Å and the layer structural integration are reinforced by dimercapto groups of bismuththiol molecules. Comprehensive characterizations and density functional theory calculations prove that the intercalated bismuththiol (DMcT) molecules substantially enhanced electronic conductivity and effectively shield the electrostatic interaction between Na⁺ and the MoO₃ host by conjugated double bond, resulting in improved Na⁺ insertion/extraction kinetics. Benefiting from these features, the newly devised layered MoO₃ electrode achieves excellent long‐term cycling stability and outstanding rate performance. These achievements are of vital significance for the preparation of sodium‐ion battery anode materials with high‐rate capability and long cycling life using intercalation chemistry.     

Study of metal assisted anisotropic chemical etching of silicon for high aspect ratio in crystalline silicon solar cells

Textured surface is commonly used to enhance the efficiency of silicon solar cells by reducing the overall reflectance and improving the light scattering. In this study, a comparison between isotropic and anisotropic etching methods was investigated. The deep funnel shaped structures with high aspect ratio are proposed for better light trapping with low reflectance in crystalline silicon solar cells. The anisotropic metal assisted chemical etching (MACE) was used to form the funnel shaped structures with various aspect ratios. The funnel shaped structures showed an average reflectance of 14.75% while it was 15.77% for the pillar shaped structures. The average reflectance was further reduced to 9.49% using deep funnel shaped structures with an aspect ratio of 1:1.18. The deep funnel shaped structures with high aspect ratios can be employed for high performance of crystalline silicon solar cells.     

煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

Charge injection in metal/organic/metal structures with ZnO:Al/organic interface modified by Zn1−xMgxO:Al layer

Aluminum-doped zinc oxide (ZnO:Al, AZO) electrodes were covered with very thin (∼6 nm) Zn_1−xMg_xO:Al (AMZO) layers grown by atomic layer deposition. They were tested as hole blocking/electron injecting contacts to organic semiconductors. Depending on the ALD growth conditions, the magnesium content at the film surface varied from x = 0 to x = 0.6. Magnesium was present only at the ZnO:Al surface and subsurface regions and did not diffuse into deeper parts of the layer. The work function of the AZO/AMZO (x = 0.3) film was 3.4 eV (based on the ultraviolet photoelectron spectroscopy). To investigate carrier injection properties of such contacts, single layer organic structures with either pentacene or 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine layers were prepared. Deposition of the AMZO layers with x = 0.3 resulted in a decrease of the reverse currents by 1–2 orders of magnitude and an improvement of the diode rectification. The AMZO layer improved hole blocking/electron injecting properties of the AZO electrodes. The analysis of the current-voltage characteristics by a differential approach revealed a richer injection and recombination mechanisms in the structures containing the additional AMZO layer. Among those mechanisms, monomolecular, bimolecular and superhigh injection were identified.     

A Multiscale-Porous Anion Exchange Membrane for Convenient and Scalable Electrokinetic Concentration of Cationic Species

A device able to electrokinetically concentrate cationic samples has many potential medical and industrial applications, but until now has remained undeveloped due to the lack of a commercial anion-permselective material leading to a prohibitively complex fabrication procedure. Herein, a novel multiscale-porous anion exchange membrane (MP-AEM) that enables the convenient and scalable electrokinetic concentration of cationic species is proposed. A mechanically enhanced multiscale-porous structure with a solid framework is realized by adopting polyester resin as an additive to overcome the intrinsic limitations of the AEM material. The scalable MP-AEM-embedded electrokinetic concentrator is devised based on the peculiar properties of the MP-AEM that for allow both ion and fluid transport. With the MP-AEM, the concentrator is fabricated in a highly streamlined manner consisting only of a simple insertion and assembly. The concentration performance of the MP-AEM-embedded electrokinetic concentrator is demonstrated with a positively charged fluorescent dye and a fluorescein-labeled protein, and the results show enrichment factors of 250 and 500, respectively. The MP-AEM makes cationic electrokinetic concentration more accessible and scalable, thereby enabling further progress in a wide range of fields.     

RF磁控溅射制备钛酸锶钡BST纳米薄膜

钛酸锶钡(BST)薄膜作为一种高K介质材料在微电子和微机电系统等领域具有广阔的应用前景,人们已对BST薄膜的制备工艺技术和介电性能进行了大量的研究。BST纳米薄膜的制备工艺直接影响和决定着薄膜的介电性能(介电常数、漏电流密度、介电强度等)。对RF磁控反应溅射制备BST纳米薄膜的工艺技术进行了综述。从溅射靶的制备、溅射工艺参数的优化、热处理、薄膜组分的控制,及制备工艺对介电性能的影响等方面,对现有研究成果进行了较全面的总结。     

半导体传感器在生物分析科学中的应用(英文)

回顾了半导体生化传感器 (ISFET 和 LA PS)在医学监测、免疫检测、免疫分析、D N A 杂交以及细胞培养等方面应用的进展。为使半导体器件适用于生化检测,对其中所采用的检测手段和取得的研究结果进行了分析。展望了通过与微流体网络相结合,基于半导体传感器的实验室芯片化的可行性。