Ionic liquid-based electrolyte with dual-functional LiDFOB additive toward high-performance LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> batteries

Manganese oxide-based cathodes are one of the most promising lithium-ion battery (LIB) cathode materials due to their cost-effectiveness, high discharge voltage plateau (above 4.0 V vs. Li/Li⁺), superior rate capability, and environmental benignity. However, these batteries using conventional LiPF₆-based electrolytes suffer from Mn dissolution and poor cyclic capability at elevated temperature. In this paper, the ionic liquid (IL)-based electrolytes, consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfon)imidate (PYR_1,4-TFSI), propylene carbonate (PC), lithium bis(trifluoromethanesulfon)imide (LiTFSI), and lithium oxalyldifluoroborate (LiDFOB) additive, were explored for improving the high temperature performance of the LiMn₂O₄ batteries. It was demonstrated that LiTFSI-ILs/PC electrolyte associated with LiDFOB addition possessed less Mn dissolution and Al corrosion at the elevated temperature in LiMn₂O₄/Li batteries. Cyclic voltammetry and electrochemical impedance spectroscopy implied that this kind of electrolyte also contributed to the formation of a highly stable solid electrolyte interface (SEI), which was in accordance with the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. Cyclic voltammetry and electrochemical impedance spectroscopy implied that the cells using this kind of electrolyte exhibited better interfacial stability, which was further verified by the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. These unique characteristics would endow this kind of electrolyte a very promising candidate for the manganese oxide-based batteries.     

Theoretical studies on structure and performance of [1,2,5]‐oxadiazolo‐[3,4‐d]‐pyridazine‐based derivatives

Based on energetic compound [1,2,5]‐oxadiazolo‐[3,4‐d]‐pyridazine, a series of functionalized derivatives were designed and first reported. Afterwards, the relationship between their structure and performance was systematically explored by density functional theory at B3LYP/6‐311 g (d, p) level. Results show that the bond dissociation energies of the weakest bond (N–O bond) vary from 157.530 to 189.411 kJ · mol^?1. The bond dissociation energies of these compounds are superior to that of HMX (N–NO_2, 154.905 kJ · mol^?1). In addition, H1, H2, H4, I2, I3, C1, C2, and D1 possess high density (1.818–1.997 g · cm^?3) and good detonation performance (detonation velocities, 8.29–9.46 km · s^?1; detonation pressures, 30.87–42.12 GPa), which may be potential explosives compared with RDX (8.81 km · s^?1, 34.47 GPa ) and HMX (9.19 km · s^?1, 38.45 GPa). Finally, allowing for the explosive performance and molecular stability, three compounds may be suggested as good potential candidates for high‐energy density materials. Copyright © 2016 John Wiley & Sons, Ltd.     

深度探究浓度对化学平衡的影响

就Fe3++SCN-Fe(SCN)2+平衡而言,向该平衡体系中加入一定浓度的FeCl3溶液,通过改进浓度对化学平衡影响的实验和对实验的深入探究,借助实验的功能解决了平衡移动的方向、Fe(SCN)2+的浓度和溶液的颜色是如何变化的等问题,进而使学生对“外界条件对化学平衡的影响”有了更全面的认识.     

New Strategy Targeting Well‐Defined Polymethylene‐block‐Polystyrene Copolymers: The Combination of Living Polymerization of Ylides and Atom Transfer Radical Polymerization

Well‐defined polymethylene‐block‐polystyrene (PM‐b‐PS) diblock copolymers were synthesized via a combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) of styrene. A series of hydroxyl‐terminated polymethylenes (PM‐OHs) with different molecular weight and narrow molecular weight distribution were prepared using living polymerization of ylides following efficient oxidation in a quantitive functionality. Then, the macroinitiators (PM‐MIs ( = 1 900–15 000; PDI = 1.12–1.23)) transformed from PM‐OHs in ≈ 100% conversion initiated ATRPs of styrene to construct PM‐b‐PS copolymers. The GPC traces indicated the successful extension of PS segment ( of PM‐b‐PS = 5 000–41 800; PDI = 1.08–1.23). Such copolymers were characterized by ¹H NMR and DSC.

     

Fluorescence‐Amplifying Assay for Irradiated DNA Lesions Using Water‐Soluble Conjugated Polymers

A new platform has been developed for DNA lesion detection using a cationic conjugated polymer (CCP). DNA that contains two adjacent thymine bases is irradiated with ultraviolet light to allow for the formation of cyclobutane pyrimidine dimers and pyrimidine–pyrimidone dimers. The DNA lesions block the primer extension, and the base labeled with fluorescein cannot be incorporated into the DNA strand. Addition of the CCP leads to inefficient fluorescence resonance energy transfer (FRET) from CCP to fluorescein. For the case without DNA lesions, successful primer extension allows for efficient FRET between them. In view of the FRET signal changes, the DNA lesions can be detected. This new protocol offers a convenient detection for DNA lesions in aqueous solution without any isolation and washing steps.

     

Corrosion resistance and blood compatibility of lanthanum ion implanted pure iron by MEVVA

Pure iron is a potential material applying for coronary artery stents based on its biocorrodible and nontoxic properties. However, the degradation characteristics of pure iron in vivo could reduce the mechanical stability of iron stents prematurely. The purpose of this work was to implant the lanthanum ion into pure iron specimens by metal vapor vacuum arc (MEVVA) source at an extracted voltage of 40 kV to improve its corrosion resistance and biocompatibility. The implanted fluence was up to 5 × 10¹⁷ ions/cm². The X-ray photoelectron spectroscopy (XPS) was used to characterize the chemical state and depth profiles of La, Fe and O elements. The results showed lanthanum existed in the +3 oxidation state in the surface layer, most of the oxygen combined with lanthanum and form a layer of oxides. The lanthanum ion implantation layer could effectively hold back iron ions into the immersed solution and obviously improved the corrosion resistance of pure iron in simulated body fluids (SBF) solution by the electrochemical measurements and static immersion tests. The systematic evaluation of blood compatibility, including in vitro platelets adhesion, prothrombin time (PT), thrombin time (TT), indicated that the number of platelets adhesion, activation, aggregation and pseudopodium on the surface of the La-implanted samples were remarkably decreased compared with pure iron and 316L stainless steel, the PT and TT were almost the same as the original plasma. It was obviously showed that lanthanum ion implantation could effectively improve the corrosion resistance and blood compatibility of pure iron.     

相分离Eu0.5Sr0.5MnO3体系中的场诱导磁相变及输运特性研究

研究了半掺杂相分离锰氧化物Eu0.5Sr0.5MnO3样品的结构和电磁输运特性.在半掺杂情况下,该样品呈O′型正交结构,表明样品存在典型的Jahn-Teller畸变;在75 K附近样品的顺磁/反铁磁背景中开始出现铁磁相,在更低的温度42 K,4000 A/m磁场下M-T的场冷曲线和零场冷曲线出现明显分岔,样品的交流磁化率实部随温度的变化曲线中也在42 K观察到尖峰的出现,表现出团簇玻璃行为.在无外加磁场下该样品在整个测量温区均呈现绝缘体型导电行为,而在外加磁场1.6×106 A/m下出现磁场诱导的绝缘体-金属 (I-M)转变,其电输运特性符合可变程跳跃模型;研究表明,半掺杂Eu0.5Sr0.5MnO3样品的基态存在多种复杂而丰富的磁相互作用之间的竞争机理,其研究将为强关联锰氧化物体系物理机理的理解提供丰富的实验资料.     

LNG液化装置冷箱降温过程的动态模拟

冷箱的降温是MRC天然气液化装置运行调试过程的重点。文中对此过程进行了动态仿真,除降温后期偏差稍大外,结果基本令人满意。冷箱降温前期中期主要受冷箱本身的显热容影响,而后期降温过程主要取决于冷箱的换热能力。     

Bulk Modulus and Electronic Band Structure of ZnGa2X4(X=S,Se): a First-Principles Study

First-principles local density functional calculations are presented for the compounds ZnGa₂X₄ (X=S,Se). We investigate the bulk moduli and electronic band structures in a defect chalcopyrite structure. The lattice constants and internal parameters are optimized. The electronic structures are analysed with the help of total and partial density of states. The relation between the cohesive energy and the unit cell volume is obtained by fully relaxed structures. We derive the bulk modulus of ZnGa₂X₄ by fitting the Birch-Murnaghan's equation of state. The extended Cohen's empirical formula agrees well with our ab initio results.     

Bulk Modulus and Electronic Band Structure of ZnGa2Xa （X=S,Se）： a First-Principles Study

First-principles local density functional calculations are presented for the compounds ZnGa2X4 （X = S, Se）. We investigate the bulk moduli and electronic band structures in a defect chalcopyrite structure. The lattice constants and internal parameters are optimized. The electronic structures are analysed with the help of total and partial density of states. The relation between the cohesive energy and the unit cell volume is obtained by fully relaxed structures. We derive the bulk modulus of ZnGa2Xa by fitting the Birch-Murnaghan＇s equation of state. The extended Cohen＇s empirical formula agrees well with our ab initio results.