高分子固体电解质

固体电解质是全塑固态电池不可缺少的一个组成部分，近年来得到了迅速的发展。高分子固体电解质由于质量轻，可塑性强，并具且良好的力学性能和机械加工性能，在固体电解质领域内越来越受到人们的重视和关注。高分子固体电解质一般是由聚醚类的高分子主体物和无机盐形成的复合物。聚氧化乙烯（PEO）是高分子主体物中比较优秀的代表，其盐复合物在高温（100 ℃）时电导率可达2 * 10~(-3)Scm~(-1)，但由于结晶，其室温电导率很低(10~(-8) ～ 10~(-7)Scm~(-1))，远远满足不了室温电池的要求。本工作的目的是利用接技和共聚对PEO进行改性，提高复合物室温电导率。主要工作和结论有下列几点：（1）采用二步法合成了列三种单体：CH_2-CH CH_2O(CH_2CH_2O)_nCH_3 (n = 0,1,2)，通过改进反应条件，提高了产物收率。（2）考察了不同烷基铝多元催化剂对上述单体聚合的催化性能，发现只有Al(i-Bu)_3-Zn(acac)_2-H_2O和AlEt_3-Hacac-H_2O对单体聚合的催化效果较好。（3）DSC分析的结果表明，上述单体的均聚物不易结晶；聚合物玻璃化温度分别为-64 ℃(n = 0)，-75 ℃ (n = 1)和-86 ℃(n = 2)，都比PEO(Tg = -57 ℃)低，这对提高复合物电导率应该是有利的。（4）利用环氧丙烷（Po）与环氧烷（Eo）共聚，大幅度降低了聚合物的结晶性，当共聚物中Po含量达到40％时，聚合物几乎是完全非晶的。（5）利用DSC、X－射线衍射、偏光显微镜等手段对均聚物和共聚物的 NaScN和LiClO_4复合物的聚集态结构进行了研究，发现复合物中没有结晶络合物相存在，这与PEO体系是不同的。复合物结晶度随聚合物结构和盐含量的不同而变化。（6）共聚改性是提高复合物室温电导率的有效手段。共聚物与NaScN和LiClO_4复合物在25 ℃时的电导率分别达到了5 * 10~(-5)Scm~(-1)和1.1 * 10~(-4)Scm~(-1)，与PEO体系相比提高了2 ～ 3个数量级。（7）梳状均聚物虽然结晶度和玻璃化温度都很低，但其盐复合物的室温电导率不高，只有10~(-6)Scm~(-1)数量级，这与我们预期的结果不一致。（8）聚合物一盐复合物的电导率随聚合结构以及盐的种类和含量的变化而不同。对于无机盐来说，阴离子相同时，复合物电导率随阳离子半径的增大而增大，随着盐浓度的变化，复合物电导率出现一个极大值。另外，成膜溶剂、水份等都对复合物电尼率有很大的影响。（9）考察了复合物电导率随温度的变化情况。高温(～100 ℃)时，复合物电导率都比PEO体系低，说明为提高复合物室温电导率而对PEO进行的改性是以牺牲其高温电导率为代价的。

聚醚类聚合物固体电解质的研究

聚合物固体电解质是近几年来引起人们高度重视的一种新型功能材料。由于质轻、可塑性强，可加工成溥膜等特点，使它在固体电池，燃料电池，电化学元件和分离膜等方面的应用上显示了很大的优越性，尤其在全固态高能密锂电池的应用上已成为强有力的竞争者。聚合物固体电解质是一类由聚醚类主体聚合物与无机盐形成的络合物。目前研究的大多是以取环氧乙烷（PEO）为主体聚合物的各种碱金属盐络合物。研究表明，PEO是迄今为止所发现的络合能力最强的主体聚合物，与无机盐络合后高温电导率可达2 * 10~(-3)scm~(-1)，但室温下由于PEO的高结晶性阻碍了离子的迁移，电导率只有10~(-8)-10~(-7)scm~(-1)，从而使其应用范围受到局限，本工作采用共聚、交联及添加低分子增塑剂的方法制得了既具有较高室温电导率又具有良好机械加工性能的聚合物电解质。主要工作及结论如下：1、选择了带有双键的烯丙基缩水甘油醚这一单体与环氧乙烷共聚，制得了P(EO-AGE)二元共聚物。讨论了不同催化剂对产物结构和性能的影响，发现AlEt_3-H_2O-acac的催化效果较好。DSC和X-射线衍射结果表明，共聚使PEO的结晶受阻，其结晶度随着AGE含量的增大而减小。共聚物的玻璃化转变温度及溶点均较纯PEO的低。由二元共聚物和LiClO_4组成的P(EO-AGE)-LiClO_4络合物室温电导率达2*10~(-5)scm~(-1)，较纯PEO-LiClO_4体系高2-3个数量级。2、在二元共聚物的研究基础上，合成了（环氧乙烷-环氧丙烷-烯丙基缩水甘油醚）三元共聚物，P(EO-PO-AGE)。结果表明，三元共聚物具有更低的玻璃化转变温度和更多的无定形结构。P(EO-PO-AGE)-LiClO_4络合物的室温电导率达5 * 10~(-5)scm~(-1)。3、对P(EO-AGE)-LiClO_4和P(EO-PO-AGE)-LiClO_4络合物结构的研究发现，络合物在L:/O=0.20-0.125(mol)范围内呈现完全无定形的结构，当L:/O分别为0.33和0.25(mol)时，在X-射线衍射图上出现了新的结晶衍射峰。证实了组成分别为O/Li=3和O/Li=4的结晶络合物的存在。4、对P(EO-AGE)-LiClO_4和P(EO-PO-AGE)-LiClO_4络合物电导的研究表明，电导对温度的依赖性服从VTF方程：σ=AT~(-1/2)e~(-B/(T-To))，呈现典型的非晶电解质电导行为，但在50-70 ℃范围内lg(σT~(1/2)～1/(T-To)曲线出现转折。络合物电导与盐浓度的关系表现出与理论相一致的结果，即在某一盐浓度下存在一极大值，对P(EO-AGE)-LiClO_4和P(EO-PO-AGE)-LiClO_4体系，电导极大值都出现在O/Li=20处。此处，还讨论了共聚物组成，阴离子，阳离子种类及离子对对络合物电导率的影响。5、采用添加低分子增塑剂聚乙二醇（PEG400）的方法不仅提高了聚合物电解质柔顺性，使分子链段活动性增加，而且增加了体系的无定形区，为离子迁移提供了新的导电通递。增塑P(EO-PO-AGE)-LiClO_4络合物的电导随着增塑剂含量的增大而升高，60%(vol)PEG400增塑的P(EO-PO-AGE)-LiClO_4聚合物电解质膜的电导率可达10~(-4)scm~(-1)(25 ℃)。增塑的电解质膜不仅具有较高的室温电导率，而且具有良好的热稳定性，在700 ℃下无相分离；于干燥气氛下放置一年无蠕变流动现象，电导亦无变化。6、采用硫化和辐射交联法制得具有网络结构的聚合物电解质膜。交联后的电解质膜尺寸稳定性增加，拉伸强度和断裂伸长均成倍增加，抗溶剂性能提高，具有良好的可加工性。硫化交联所得的P(EO-AGE)-LiClO_4和P(EO-PO-AGE)-LiClO_4网络电解质膜的室温电导率仍可达10~(-5)scm~(-1)，而经辐射交联所得的PEG400增塑的P(EO-PO-AGE)-LiClO_4电解质膜的室温电导率可达10~(-4)scm~(-1)。交联电解质膜具有与未交联电解质膜相似的电导行为。

Electro-Optical Effect Measurement of Thin-Film Material Using PM Fiber Mach-Zehnder Interferometer

A polarization-maintaining (PM) fiber Mach-Zehnder (MZ) interferometer has been established to measure the EO effect of very thin film materials with optical anisotropy. Unlike a common MZ interferometer,all the components are connected via polarization-maintaining fibers. At the same time, a polarized DFB laser with a maximum power output of 10mW is adopted as the light source to induce a large extinction ratio. Here, we take it to determine the electro-optical coefficients of a very thin superlattice structure with GaAs, KTP, and GaN as comparative samples. The measured EO coefficients show good comparability with the others.

Comparison of aggregation behaviors between branched and linear block polyethers: MesoDyn simulation study

The comparison of aggregation behaviors between the branched block polyether T1107 (polyether A) and linear polyether (EO)(60)(PO)(40)(EO)(60) (polyether B) in aqueous solution are investigated by the MesoDyn simulation. Polyether A forms micelles at lower concentration and has a smaller aggregation number than B. Both the polyethers show the time-dependent micellar growth behaviors. The spherical micelles appear and then change to rod-like micelles with time evolution in the 10 vol% solution of polyether A. The micellar cluster appears and changes to pseudo-spherical micelles with time evolution in the 20 vol% solution of polyether A. However, the spherical micelles appear and change to micellar cluster with time evolution in the 20 vol% polyether B solution. The shear can induce the micellar transition of both block polyethers. When the shear rate is 1x10(5) s(-1), the shear can induce the sphere-to-rod transition of both polyethers at the concentration of 10 and 20 vol%. When the shear rate is lower than 1x10(5) s(-1), the huge micelles and micellar clusters can be formed in the 10 and 20 vol% polyether A systems under the shear, while the huge micelles are formed and then disaggregated with the time evolution in the 20 vol% polyether B system.

An Electro-osmotic Fuel Pump for Dircet Methanol Fuel Cells

This work reports on the design and performance evaluation of a miniature direct methanol fuel cell(DMFC)integrated with an electro_osmotic(EO)pump for methanol delivery.Electro-osmotic pumps require minimal parasitic power while boasting no moving parts and simple fuel cell integration.Here ,aneletro-osmotic pump is realized from a commercially available porous glass frit.We characterize a custom-fabricated DMFC with a free convection cathode and coupled to an extennal electro-osmotic pump operated at applied potentials of 4.0,7.0,and 10V.Maximum gross power density of our free convection DMFC(operated at 50°)is 55 mW/cm2 using 4.0 mol/L concentration methanol solution supplied by the EO pump.Experimental results show that electro-osmotic pumps can deliver 2.0,4.0 and 8.0mol/L methanol/water mixtures to DMFCs while utilizing ~5.0% of the fuel cell power.Furthermore ,we discuss pertinent design considerations when using electro-osmotic pumps with DMFCs and areas of further study.

用高级氧化技术去除植物油中的多环芳烃

应用植物油淋洗可去除土壤中高浓度多环芳烃,为进一步去除多环芳烃,采用高级氧化(臭氧氧化、过氧化氢和紫外线联合氧化)对两种含多环芳烃植物油进行处理,并考察了运行参数对多环芳烃去除效果的影响.结果表明臭氧具有氧化植物油中多环芳烃的能力,对蒽和荧蒽的氧化能力强于菲.用紫外线、10%过氧化氢,在pH=3的条件下处理MO植物油,总多环芳烃的去除率最高,为81%;按此条件对含高浓度多环芳烃EO植物油处理8 h,总多环芳烃去除率为76.5%,达到良好效果.

Tethered diblock copolymer chains on platelets prepared by semicrystalline ABC triblock copolymers in toluene with trace amounts of water

Lamellar platelets of triblock copolymers grown in dilute toluene solution with trace amounts of water can be used as templates for tethered diblock copolymer chain preparation and analysis. Polystyrene-bpoly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two different block fractions were used as model templates to generate tethered P2VP-b-PS chains on the platelet basal surfaces. In toluene solution the aggregation states of PS-b-P2VP-b-PEO were sensitive to the water content in the solution. For toluene with trace amount of water, spherical micelles were formed in the early stage and large square platelets would gradually grow from these spherical micelles. The hydrogen bonding between water and EO units was responsible for the formation of micelles and subsequent square platelets in the solution. Tethered P2VP-b-PS chains on basal surface of PEO platelets could be regarded as diblock copolymer brushes and the density (or: 0.086-0.36) and height (d: 3.5-14.3 nm) of these tethered chains could be easily modulated by changing the crystallization condition and/ or the molecular weight of each block. The tethered P2VP-b-PS chains were responsive to different solvent vapor.

Synthesis and crystallization behaviors of poly(styrene-b-isoprene-b-epsilon-caprolactone) triblock copolymers

The triblock copolymers, poly(styrene-b-isoprene-b-epsilon-caprolactone)s (PS-b-PI-b-PCL) have been synthesized successfully by combination of anionic polymerization and ring-opening polymerization. Diblock copolymer capped with hydroxyl group, PS-b-PI-OH was synthesized by sequential- anionic polymerization of styrene and isoprene and following end-capping reaction of EO, and then it was used as macro initiator in the ring-opening polymerization of CL. The results of DSC and WAXD show big effect of amorphous PS-b-PI on the thermal behaviors of PCL block in the triblock copolymers and the lower degree of crystalline in the triblock copolymer with higher molecular weight of PS-b-PI was observed. The real-time observation on the polarized optical microscopy shows the spherulite growth rates of PCL27, PCL328 and PS-b-PI-b-PCL344 are 0.71, 0.46 and 0.07 mu m s(-1), respectively. The atomic force microscopy (AFM) images of the PS90-b-PI66-b-PCL-(28) show the columns morphology formed by it's self-assembling.

马来酸酐封端聚碳酸亚丙酯的大分子偶联反应

自从 1 969年井上祥平[1] 发现二氧化碳 (CO2 )可以同环氧化合物直接共聚合成脂肪族聚碳酸酯(APC)以来 ,这一学科领域受到科学家的广泛关注[2～ 8] .这是因为CO2 所产生的温室效应 ,成为使全球变暖的主要因素[9,10 ] .已经确定CO2 使气侯变暖占诸多因素中的 66% .目前大气中CO2 的体积浓度为 345ppmv,由于人类的各类活动每年以 1ppmv的速度递增 .因此 ,降低CO2 排放量已成为全人类共同关注的热点之一 .另一方面 ,CO2 的固定化以及消耗、利用显然是一个应积极鼓励的研究课题 .目前人们已经将CO2 同环氧乙烷 (EO)、环氧丙烷 (PO)、环氧环己烷 (CHO)等环氧化合物实现共聚 ,制得一类脂肪族碳酸酯新材料 .特别是自从人们发现戊二酸锌等高效催化剂可以得到具有高分子量的APC以来 ,APC做为一种新的塑料材料使用已具有现实意义 .由于APC的加工热稳定性较差 ,在高温条件下 ,很容易产生大分子主链的断裂及从端基开始的解拉链式降解 ,因此 ,研究其物理特性及提高其热稳定性的方法具有重要的科学意义和实际应用价值 .本文采用熔体反应的办法 ,实现了马来酸酐(MA...

Thermodynamical study on pressure-induced compatibility in UCST polymer-containing mixtures

The present calculations were performed on the basis of the Sanchez-Lacombe lattice fluid theory and the new combinatorial rules for block copolymer according to the experimental results on the pressure-induced compatibility in poly(ethylene oxide) (PEO) and poly(ethylene oxide-b-dimethylsiloxane) (P(EO-b-DMS)) mixtures with UCST behavior. The study on enthalpy, combinatorial entropy, vacancy entropy and Gibbs energy upon mixture shows that Sanchez-Lacombe fluid theory and the new combinatorial rules could describe the pressure-induced compatibility (PIC) of polymer mixtures with UCST behavior well.

Ring-opening polymerization of epsilon-caprolactone and L-lactide using organic amino calcium catalyst

Poly (6-caprolactone) (PCL) and poly (L-lactide) (PLA) were prepared by ring-opening Polymerization catalyzed by organic amino calcium catalysts (Ca/PO and Ca/EO) which were prepared by reacting calcium ammoniate Ca(NH3)(6) with propylene oxide and ethylene oxide, respectively. The catalysts exhibited high activity and the ring-opening polymerization behaved a quasi-living characteristic. Based on the Fr-IR spectra and the calcium contents of the catalysts, and based on the H-1 NMR end-group analysis of the low molecular weight PCL prepared using catalysts Ca/PO and Ca/EO, it was proposed that the catalysts have the structure of NH2-Ca-O-CH(CH3)(2) and NH2-CaO-CH2CH3 for Ca/PO and Ca/EO, respectively. The ring-opening polymerization of CL and LA follows a coordination-insertion mechanism and the active site is the Ca-O bond.

Nonisothermal crystallization kinetics of ethylene terephthalate-ethylene oxide segmented copolymers with two crystallizing segments

The nonisothermal crystallization behavior of ethylene terephthalate-ethylene oxide segmented copolymers has been studied by means of differential scanning calorimetry (DSC). The kinetics of ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed by the Ozawa equation. During the crystallization of the high-T-m segments (PET), the low-T-m segments (PEO) act as a noncrystalline diluent, the crystallization behavior of PET obeys the Ozawa theory. When the PEO segments begin to crystallize, the PET phase is always partially solidified and the presence of the spherulitic microstructure of PET profoundly influences the crystallization behavior, which results in that the overall crystallization process does not obey the Ozawa equation. (C) 2000 Elsevier Science Ltd. All rights reserved.

Nonisothermal crystallization kinetics of PEO in ethylene terephthalate-ethylene oxide segmented copolymers

The nonisothermal crystallization behavior of Ethylene Terephthalate-Ethylene Oxide (ET-EO) segmented copolymers has been studied with the use of differential scanning calorimetry (DSC). The kinetics of PEO in ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed with the Ozawa equation. The results show that there is no agreement with Ozawa's theoretical predictions in the whole crystallization process owing to the constraint of ET segments imposed on the EO segments. A distinct two-crystallization process has been investigated by using the Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. The value of the Avrami exponent n is independent of the length of soft segments. However, the crystallization rate is sensitive to the length of soft segments. The longer the soft segments, the faster the crystallization will be.

Spectrometric investigation on the thermooxidative degradation of ethylene oxide and tetra-hydrofuran co-polyether

The thermooxidative degradtion of ethylene oxide and tetra-hydrofuran (EO-THF) co-polyether has been studied by electron spin resonance (ESR), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy. The initial degradation site was found to be at the a-carbon of the ether bond. Two free radicals which derived from dehydrogenation and oxygen addition were successfully detected by spin-trapping technique which used alpha -phenyl-N-tert-butyl nitrone(PBN) as spin trap. Both FT-IR and NMR have been used to follow structural changes of the copolyether during degradation. Nearly 20 product fragments including formate, carbonate, methyl, alcohol, methylene-dioxy, hydroperoxide and semiformal have been characterized by D-1 and D-2 NMR. The thermooxidtion of co-polyether preferred to occur on the THF units especially at the alternating linkage of EO and THF. Antioxidant (BHT) not only retarded the thermooxidation but also modified the degradation products with less ester and methylene-dioxy groups hut more hydroxyl and methyl groups.

多种谱学方法研究环氧乙烷/四氢呋喃共聚醚的热氧降解

采用电子自旋共振 (ESR)、傅里叶变换红外光谱 (FT IR)和多种核磁共振 (NMR)技术研究了环氧乙烷 /四氢呋喃共聚醚的热氧降解 ,表征了近 2 0种产物结构碎片 ,并对EO和THF两种链节的降解作了定量讨论。共聚醚的氧化降解发生在醚键氧碳上 ,遵循自由基氧化机理 ,最后形成大量的甲酸酯、碳酸酯等酯类以及甲基、亚甲二氧基和醇 ,此外还检测到过氧化氢和半缩甲醛结构。分析表明共聚醚中THF链节的降解程度明显大于EO链节 ,而且降解容易发生在两种链节交替连接处。抗氧剂 2 ,6 二叔丁基 4 甲基酚 (BHT)不仅降低了共聚醚的氧化降解程度 ,还改变了降解产物的结构分布 ,显著抑制了碳酸酯和亚甲二氧基结构的生成 ,相对增加了羟基和端甲基结构