新型单离子聚醚/聚氨酯固体电解质制备及其离子导电性

磺化聚醚;离子电导率;聚合物;新型单离子聚醚/聚氨酯固体电解质制备及其离子导电性     

高分子固体电解质设计的新概念

高分子固体电解质是开发零释放能源－－高性能电池的关键材料。本文详细介绍了20世纪90年代以来高分子固体电解质结构设计的新概念，包括高分子凝胶电解质，两相高分子电解质，盐掺聚合物（Polymer-in-salt)，有机／无机纳米复合型电解质，悬挂柔性短聚醚侧链的网格聚合物电解质。     

一种新型固体电解质的导电性的研究

对多种新型Ｌｉ离子导电的ｐｏｌｙｍｅｒ－ｉｎ－ｓａｌｔ固体电解质的导电性及其影响因素进行了研究。这种固体电解质是将很少量的单离子聚合物电解质－聚丙烯酸锂熔于低温共熔锂盐中得到的,室温电导率为１０＾－５Ｓ／ｃｍ（２９℃）,较由聚氧化乙烯（ＰＥＯ）制造的ｐｏｌｙｍｅｒ－ｉｎ－ｓａｌｔ固体电解质,电导率有明显地提高。     

脂肪族聚酯与高氯酸锂络合物的结构与导电性

本文通过酯交换反应合成了一系列脂肪族聚丁二酸酯,对他们的结构和性能作了表征。发现聚酯存在多晶现象,其熔点有奇偶性变化规律。探索了由此系列聚酯与高氯酸锂形成的固体电解质的结构和离子导电性。无机盐的加入提高了电解质的玻璃化温度但降低了聚酯的熔点及结晶度。聚酯电解质的晶体类似于聚酯,其无机盐主要溶解于聚酯的无定形区域。聚酯系列电解质的导电率也有偶奇效应,与熔点变化相反;熔点高的电解质导电率低,熔点低的电解质导电率高。电解质的导电率随温度改变而变化,在室温下电解质的导电率可达10~(-6)s/cm。高分子链上侧基的引入将大大降低电解质的导电性。     

聚氨酯型固体电解质的离子导电性和红外光谱研究

聚醚聚氨酯;聚合物固体电解质;络合;离子导电率     

聚醚聚氨酯/低聚醚硫酸盐电解质的导电性能

聚合物固体电解质;聚二氧戊环;聚醚聚氨酯/低聚醚硫酸盐电解质的导电性能;离子电导率;     

硬段聚醚掺杂聚氨酯的合成及其离子导电性能

低分子量聚醚;聚氨酯固体电解质;离子电导率;硬段聚醚掺杂聚氨酯的合成及其离子导电性能     

脂肪族聚脂与高氯酸锂络合物的结构与导电性

本文通过酯交换反应合成了一系列脂肪族聚丁二酸酯，对他们的结构和性能作了表征。发现聚酯存在多晶现象，其熔点有奇偶性变化规律。探索了由此系列聚酯与高氯酸锂形成的固体电解质的结构和离子导电性。无机盐的加入提高了电解质的玻璃化温度但降低了聚酯的熔点及结晶度。聚酯电解质的晶体类似于聚酯，其无机盐主要溶解于聚酯的无定形区域。聚酯系列电解质的导电率也有偶奇效应，与熔点变化相反；熔点高的电解质导电率低，熔点低的电解质导电率高。电解质的导电率随温度改变而变化，在室温下电解质的导电率可达10^-6s/cm。高分子链上侧基的引入将大大降低电解质的导电性。     

交替马来酸酐共聚物多缩乙二醇酯盐络合物中阳离子－高分子相互作用的研究

交替马来酸酐共聚物多缩乙二醇酯盐络合物中阳离子－高分子相互作用的研究丁黎明，林云青，周子南（中国科学院长春应用化学研究所长春１３００２２）关键词高分子固体电解质，离子传输，电子轨道结合能高分子固体电解质（ＳＰＥ）可塑性强，易制成大面积均匀薄膜，并具有...     

聚丁二酸丁二醇酯与碱金属盐络合物的离子导电性

某些聚合物经特殊加工可制成具有半导体、导体,甚至超导体性质的材料。最近高分子固体电解质材料引起科学家们极大的兴趣和重视,其研究主要集中在聚醚体系,对聚酯研究甚少。本文对聚丁二酸丁二醇酯体系作了研究。     

多嵌段聚醚氨酯脲类固态离子导体的X光电子能谱研究

固态离子导体作为一种高能密度电池中的电解质在传感器中的实际应用受到了普遍关注。聚氧化乙烯与碱金属盐的复合物是其中研究得最早、最多的一类。但它在室温下电导率较低、力学性能不理想,人们正着力于研制综合性能优良的高分子固态离子导     

IONIC CONDUCTIVITIES OF SEGMENTED POLYETHER POLYURETHANEUREA COMPLEXES WITH LiClO4

Ionic conductivity values for segmented polyether polyurethaneurea (PEUU) complexes with LiClO_4 were determined and values as high as～1.1×10~(-4) S·cm~(-1) at 353K and～1.0×10~(-5)S·cm~(-1) at 306K were achieved. The ionic conductivity data were analyzed using the VTF (Vogel-Tamman-Fulcher) equation and WLF (Williams-Landel-Ferry) type equation. Values have been estimated for the "apparent" activation energies of ion transport from VTF equation and they lie in the range 2.70—5.53 kJ·mol~(-1).     

Solid polymer electrolytes. IV. Preparation and characterization of novel crosslinked epoxy‐siloxane polymer complexes as polymer electrolytes

Two series of novel crosslinked siloxane‐based polymers and their complexes with lithium perchlorate (LiClO₄) were prepared and characterized by Fourier transform infrared spectroscopy, solid‐state NMR (¹³C, ²⁹Si, and ⁷Li nuclei), and differential scanning calorimetry. Their thermal stability and ionic conductivity of these complexes were also investigated by thermogravimetric and AC impedance measurements. In these polymer networks, poly(propylene oxide) chains with different molecular weights were introduced through self‐synthesized epoxy‐siloxane precursors cured with two curing agents. The glass‐transition temperature (T_g) of these copolymers is dependent on the length of the ether units. The dissolution of LiClO₄ considerably increases the T_g of the polyether segments. The dependence of the ionic conductivity was investigated as a function of temperature, LiClO₄ concentration, and the molecular weight of the polyether segments. The ion‐transport behavior was affected by the combination of the ionic mobility and number of carrier ions. The ⁷Li solid‐state NMR line shapes of these polymer complexes suggest a significant interaction between Li⁺ ions and the polymer matrix, and temperature‐ and LiClO₄ concentration‐dependent chemical shifts are correlated with ionic conductivity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1226–1235, 2002     

Poly(ionic liquids)‐coated stainless‐steel wires packed into a polyether ether ketone tube for in‐tube solid‐phase microextraction

An in‐tube solid‐phase microextraction device was developed by packing poly(ionic liquids)‐coated stainless‐steel wires into a polyether ether ketone tube. An anion‐exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)‐coated stainless‐steel wires were characterized by scanning electron microscopy and energy dispersive X‐ray spectrometry. The extraction device was connected to high‐performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03–20 μg/L, detection limits of 0.010–0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1–118.9%.     

Current Scenario and Future Prospective of Ionic-Liquid Doped Polymer Electrolyte for Energy Application

Solid polymer electrolyte (SPE) films based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF–HFP) with salt and ionic-liquid (IL) are synthesized using the solution-cast technique and summarized in this review. Doping ILs or salts increases ionic conductivity up to the device level. This is further confirmed using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements. Polarized optical microscopy (POM) affirms that enhancement in ionic conductivity is due to increase in amorphous nature of film. The complex nature of polymer electrolyte films is confirmed using Fourier transform infrared (FT-IR) spectroscopy. Overall results show that doping IL into polyether matrix is advantageous material playing a dominant role in electrochemical devices.     

Basalt fibers grafted with a poly(ionic liquids) coating for in‐tube solid‐phase microextraction

To improve the durability and extraction efficiency of an ionic liquid coating, 1‐dodecyl‐3‐vinylimidazolium bromide was polymerized and grafted onto basalt fibers for in‐tube solid‐phase microextraction. To develop an extraction tube, basalt fibers grafted with the poly(ionic liquids) coating were filled into a polyether ether ketone tube with a 0.75 mm inner diameter. The extraction tube was connected to high‐performance liquid chromatography system equipped with a sampling pump to build an online enrichment and analysis system. Using four common phthalates as model analytes, the extraction tube was investigated by the online analysis system. Good enrichment performance was exhibited by high enrichment factors ranging from 851 to 1858. Under the optimum conditions, an online analysis method was established, and good linearity (0.03–12 and 0.15–12 μg/L) and low limits of detection (0.01–0.05 μg/L) were achieved. This analysis method was applied to real samples including water in a disposable plastic box and the bottled water, some targets were detected but not quantified, and the relative recoveries spiked at 2, 5 and 10 μg/L were in the range of 86.4–119.5%.     

Syntheses and characterizations of soft‐segment ionic polyurethanes

Novel soft‐segment ionic polyurethane (linear and crosslinking) have been prepared based up on sodium sulfonate–side chains poly(ethylene oxide) (SPEO). SPEO was synthesized by grafting the sodium sulfonate onto the chain of poly(ethylene oxide) with molecular weights of 400, 600, 800, and 1000. The SPEO and the ionic polyurethane were characterized by elemental analysis, ¹H‐NMR, ¹³C‐NMR, gel permeation chromatography, and impedance analysis. The effect of plasticizer on the ionic conductivity of the polyurethane was also investigated. These solid polymer electrolytes possess a higher ionic conductivity (about 10⁻⁶ S/cm at room temperature) than the corresponding sulfonated hard‐segment polyurethane electrolytes. The presence of the hydroxyl group in the electrolyte tends to lower the ionic conductivity. Crosslinking of polyurethane results in the enhancement of the dimensional stability, while maintaining the same level of the ionic conductivity. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 837–845, 1999     

聚离子液体材料在分离科学中的研究进展

离子液体作为新型离子化试剂,具有诸多优越的物理化学性质,比如:良好的溶解性、导电性、热稳定性、生物相容性及低蒸气压和不易燃等特点,近年来在分析化学领域得到广泛关注。聚离子液体材料结合了离子液体和聚合物的双重性质,已经成为分离科学研究的前沿领域。本文详细讨论了离子液体与目标物之间的多种作用机制,比如亲/疏水作用、氢键作用、离子交换、π - π 堆积及静电吸附作用等等,总结了聚离子液体材料在固相萃取、液相色谱、气相色谱、毛细管电泳及毛细管电色谱等领域的研究进展;最后,对聚离子液体材料的发展前景进行了展望。     

羧酸型聚乙二醇聚氨酯离聚物及其导电性能

以聚环氧乙烷（ＰＥＯ）为软段，与４，４’－二苯甲烷二异氰酸酯（ＭＤＩ）预聚，以２，２’－二羟甲基丙酸（ＤＭＰＡ）扩链合成了含羧酸基团的聚氨酯，并经中和形成了含不同金属离子的离聚物．测定了样品的热分析数据和力学性能，利用交流阻抗分析仪测定了样品的阻抗谱，由此计算出样品的离子电导率．这类样品由于阴离子（－ＣＯＯ－）固定在聚合物分子链上，因此只有单一阳离子迁移．结果表明，羧酸型聚氨酯离聚物既有较高的单一离子电导率又具有优良的力学性能．讨论了不同软段分子量、硬段含量和金属抗衡离子对离子电导性能的影响     

Amphiphilic segmented polyurethanes as surface modifying additives

Amphiphilic segmented polyetherurethanes were prepared from methylene diphenylene diisocyanate (MDI), poly(ethylene glycol) 1500 (PEG), and a fatty acid monoglyceride as a chain extender. The polymers were not soluble in water or methanol, but dissolved readily in organic solvents. The amphiphilic properties were demonstrated as a large hysteresis in the water contact angles, exceeding 110°. The amphiphilic polymers were shown to modify the surface properties of a poly(ether urethane) (PEU) and a poly(ether urethane urea) (PEUU) when added in 1–10 wt %, presumably due to migration of the additive to the surface. The surfaces of particularly the PEU blends became highly amphiphilic, exhibiting contact angles hystereses up to 90–100°. A surface saturation effect was observed at 5% added amphiphilic polymer. A difference in the behavior of PEU and PEUU was ascribed to differences in solubility of the additive in the matrix. On long-term exposure to water the PEUU blends increased their amphiphilic behavior.