锂离子电池用聚合物电解质的最新进展II.含液聚合物电解质

由于干态聚合物电解质目前还不能满足聚合物锂离子电池的应用要求,人们致力于开发含液体增塑剂的聚合物电解质,包括凝胶型和微孔型两类体系。本文综述了含液聚合物电解质的最新进展,重点论述了各种新体系和新方法。     

Time-resolved spectroscopy of infrared active vibrations in 2,5-dioctyloxy poly(phenylene vinylene) films

We report on picosecond time resolved spectroscopy of photogenerated infrared active vibrations in thin films of 2,5-dioctyloxy poly(phenylene vinylene). We excited the films by ?4 ps long pulses of 565 nm laser light with 2×10¹³ photons/cm² per pulse and repetition rate of 76 MHz. We then followed the temporal evolution of the infrared active vibrational (IRAV) spectrum using a subsequent, variably delayed, weak tunable IR probe pulses of similar temporal duration. Under these conditions, we show clear spectroscopic evidence for photogenerated infrared active vibrations at times which are shorter than our temporal resolution (<4 ps). We suggest that the transient IRAV absorption is due to secondary polarons formation following exciton dissociation.     

Quantum chemical studies of Li cation binding to polyalkyloxides

A quantum chemical study of the binding of Li⁺ cation to polyalkyloxides has been carried out. The lithium cation interaction with three polyalkyloxides (polyethylene oxide (PEO), polytrimethylene oxide (PTMO), and polypropylene oxide (PPO)) has been investigated using ab initio molecular orbital theory at the HF/6-31G^* level with molecular models for the polymers. Coordination by one to six oxygens was considered. In addition, higher level calculations were carried out using G3(MP2) theory for coordination of Li⁺ by one oxygen. For coordination of lithium by one oxygen, the binding energy ordering is PTMO>PPO>PEO, with PTMO having the largest lithium cation affinity. The same ordering is found for larger coordination numbers with the exception of coordination by six oxygens, where the ordering changes due to the steric interactions.     

Specific interactions in blends containing Chitosan and functionalized polymers. Molecular dynamics simulations

Chitosan (CS)/poly(vinyl alcohol) (PVA) and Chitosan/poly(2-hydroxyethyl methacrylate) (P2HEM) blends have been studied through molecular dynamic simulations. In a previous work it was found miscibility between these polymers and it was attributed to hydrogen bonding formation. However, the experimental information obtained was not enough to know which of the interacting groups of Chitosan, i.e. -CH₂OH or -NH₂, are responsible of the interaction. Therefore, we have performed molecular dynamics simulation runs of 1 ns in order to calculate radial distribution functions (RDF) for the groups tentatively involved in the interaction. The results are correlated with our previous experimental data. This way, we have obtained a more precise conclusive information about the interactions involved as function of the blends composition. For low compositions of PVA and P2HEM the interaction is predominantly with the hydroxymethyl groups of CS while as the composition of PVA and P2HEM increases, the interaction with the amine groups increases.     

Preparation of one-dimensional polymer films by modification of a hydroxymethylbenzene self-assembled monolayer on iron with alkyltriethoxysilanes for preventing iron corrosion

A self-assembled monolayer (SAM) of p-hydroxymethylbenzene HOCH₂C₆H₄ - (HOMB) moiety adsorbed on iron by the formation of a covalent bond between carbon and iron atoms was prepared by electrochemical derivatization of an iron electrode with p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH₂C₆H₄N₂BF₄. The electrode covered with the HOMB SAM was modified with alkyltriethoxysilanes C_nH_2n+1Si(OC₂H₅)₃ (C_nTES, n = 8 or 18) to prepare a film of one-dimensional polymer. The protective ability of the polymer film was determined by polarization measurement of the covered electrode in an aerated 0.5 M NaCl solution. The ability was enhanced by modification of the HOMB SAM with C_nTES markedly. The iron surface coated with the one-dimensional polymer film of the HOMB SAM modified with C₈TES was characterized by contact angle measurement and FTIR reflection and X-ray photoelectron spectroscopies. The persistence in the protective ability of the polymer film against iron corrosion in 0.5 M NaCl may be associated with the strong adsorption via the covalent bond, revealed by electron-probe microanalysis.     

Low Electrical Percolation Threshold of Silver and Copper Nanowires in Polystyrene Composites

Silver and copper nanowires have been synthesized using a scalable method of AC electrodeposition into porous aluminum oxide templates, which produces gram quantities of metal nanowires ca. 25 nm in diameter and up to 5 and 10 μm in length for Ag and Cu, respectively. The nanowires have been used to prepare polystyrene nanocomposites by solution processing. Electrical resistivity measurements performed on polymer nanocomposites containing different volume fractions of metal indicate that low percolation thresholds of nanowires are attained between compositions of 0.25 and 0.75 vol %.     

华北油田鄚东地区深井钻井液技术

鄚东地区钻井过程中经常发生垮塌、卡钻、井漏等复杂事故。该地区深井钻井采用了抑制性及封堵性较强的铵基沥青树脂高密度钻井液体系,并根据地层特点,对不同井段制定了相应的钻井液维护处理措施。结果表明,该钻井液体系抑制性好,抗温、抗污染能力强,性能稳定,成功地控制了复杂事故的发生,满足了该地区深层钻井的要求。     

Numerical study on PEMFC’s geometrical parameters under different humidifying conditions

Steady-state and three-dimensional simulations were carried out to study the influences of geometrical parameters on the performance of PEMFC under different hydrating conditions. Flow fields, species transport, transport of water in polymer membrane and movement of liquid water in cathode and anode porous layers were determined, in order to accomplish a complete estimation of ohmic and concentration losses of PEMFC power. The geometrical parameters were thickness of the polymer membrane, cathode catalyst layer as well as gas channel to rib width ratio. Every simulation was made under different relative humidities of inlet flows (50 and 100%) for every change of characteristic length. Results show that the influence of the geometrical parameters on ohmic and concentration losses is of considerable importance. The performance of PEMFC is seriously affected under dehydrating conditions. However, such performance may be considerably improved by using suitable geometrical parameters. Cathode and anode liquid saturation may not only affect the transport of species, but also the polymer electrolyte water content. These results show the importance of simultaneously calculating both the water absorption and desorption through the polymer electrolyte and the liquid saturation in the cathode and anode porous mediums to obtain an actual view of ohmic and concentration losses of the PEMFC performance.     

Improvement of emission efficiency in polymer light-emitting devices based on phosphorescent polymers

We report improvement of emission efficiency in polymer light-emitting devices (PLEDs) employing phosphorescent polymers. A hole-blocking layer was inserted between the emissive layer and the cathode to enhance recombination efficiency for the injected holes and electrons. Aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolato (BAlq) was used for the hole-blocking layer. The resultant PLEDs exhibited significant improvement of emission efficiency. The respective external quantum efficiencies for red, green and blue PLEDs were 6.6, 11 and 6.9%. These values are very high compared with those based on conventional fluorescent polymers.