微孔型聚丙烯腈固体电解质的结构与导电性能研究

用蒸汽相沉析法和液相沉析法分别制备了两类高孔隙率的聚丙烯腈 (PAN)微孔膜 .用扫描电子显微镜对微孔膜的形态进行了观察 ,发现前者为均匀的蜂窝状结构 ,而后者则具有不对称的三层次结构 .又用这两类微孔膜分别制备了两个系列的微孔型PAN电解质 .电性能测试表明前者的室温电导率较高 ,可以达到 4×10 - 3 S cm ,后者的电导率则相对较低 .微孔膜本身诸因素对微孔型PAN电解质电导率的影响顺序为微孔膜结构—孔隙率—微孔孔径     

纳米碳酸钙/庚二酸复合成核剂对热致相分离法制备聚丙烯微孔膜的影响

以大豆油/邻苯二甲酸二丁酯(DBP)为混合稀释剂,采用热致相分离法(TIPS)制备聚丙烯(PP)微孔膜.研究了纳米碳酸钙成核剂、纳米碳酸钙/庚二酸复合成核剂对PP/大豆油/DBP(30/42/28,质量比)混合体系中PP结晶、熔融性能和PP微孔膜微观结构的影响.结果表明,单一纳米碳酸钙成核剂加入量为PP的0%~4%(质量百分率)时,PP/DBP/大豆油体系中PP熔融曲线上对应的峰值温度(Tpm)降到150.7~151.3℃,而纯PP的熔融峰值温度为165℃;DSC实验结果还显示加入1%~4%纳米碳酸钙和0.5%庚二酸后,导致PP的熔融曲线上出现了熔融双峰,说明纳米碳酸钙/庚二酸复合成核剂与单一成核剂相比有明显地促进β晶生成的作用,宽角X射线衍射(WAXD)实验进一步证实了β晶的存在.单一纳米碳酸钙成核剂对PP微孔膜的球晶结构和微观孔结构影响不大;加入纳米碳酸钙/庚二酸复合成核剂明显影响PP微孔膜的球晶结构和微观孔结构,其中0.5%庚二酸和1%纳米碳酸钙组成的复合成核剂制得的PP微孔膜的球晶结构明显,微孔膜孔径小且分布均匀;进一步增加纳米碳酸钙用量,PP微孔膜生成了许多细小的边界模糊的不规则结晶,微孔膜孔径不规则且尺寸较大,这与此时PP形成β晶结构有关.     

聚丙烯中空纤维膜的微孔结构的控制

通过熔纺／冷拉伸法制备了微孔聚丙烯中空纤维膜。研究了工艺条件对微孔聚丙烯中空纤维膜的微孔结构与性能的影响。结果表明：随着纺丝温度的下降或熔体拉伸比的提高，最大可几孔径及孔隙率增大；熔纺中冷却风速提高，最大可几孔径及孔隙率较大；温度低于110℃时，热处理对最大可几孔径及孔隙率的影响较小，在120－130℃时，随着热处理温度的增加，最大孔径及孔隙率有明显增加的趋势；随着初纺中空纤维拉伸倍数的增加，孔隙率先增加而后下降。     

高分子量级分含量对熔体挤出拉伸法制备聚丙烯微孔膜的影响

通过熔体挤出拉伸法以两种聚丙烯为原料制备微孔膜.通过考察原料分子量数据发现高分子量聚丙烯(PPH)在高分子量级分(重均分子量>106)含量上大于低分子量聚丙烯(F401).PPH的弛豫时间在相同条件下也远大于F401.红外二向光法结果表明,PPH在相同熔体牵伸比下片晶取向度较F401高.相同加工条件下PPH微孔膜片较F401成孔分布更均匀,孔径尺寸也更均匀.2种微孔膜孔隙率都随熔体牵伸比的增加而提高,微孔分布随着熔体牵伸比的提高和片晶取向度的增加而趋于均匀,孔尺寸也随之区域均匀.研究表明,聚合物树脂中高分子量级分含量是影响预制膜中片晶取向度、冷热拉伸成孔分布和尺寸均匀度的重要影响因素.     

工艺条件对 LLDPE/POE/CaCO3微孔膜的孔结构及防水透湿性能的影响

用拉伸致孔法制备了 LLDPE/POE/CaCO3防水透湿微孔膜,研究了拉伸倍数及体系组成对微孔膜的微孔结构及防水透湿性能的影响.用 SEM 对微孔膜的微孔结构进行考察,用压汞法对微孔膜的孔径及其分布和微孔的孔隙率进行研究.用静水压法及正杯法分别研究了微孔膜的防水和透湿性能.结果表明:拉伸倍数及 CaCO3用量对微孔膜的孔径、孔隙率及防水透湿性能有明显影响.     

新型锂电池用复合隔膜的制备及其电化学性能表征

利用浸渍法在聚丙烯微孔膜(Celgard2400)表面涂覆掺有纳米二氧化硅的聚氧乙烯(PEO),制备了新型锂电池用复合隔膜.采用交流阻抗法、扣式电池充放电等实验技术测试了复合隔膜的电化学性能.     

熔融-拉伸法制备亲水聚丙烯/聚乙烯醇缩丁醛中空纤维膜

以聚丙烯(PP)为基材,聚乙烯醇缩丁醛(PVB)为亲水改性剂,聚丙烯接枝马来酸酐(PP-g-MAH)为增容剂,通过熔融-拉伸法(MS-S)制备亲水PP/PVB中空纤维膜.采用差示扫描量热(DSC)和水接触角(WCA)测试考察了PVB添加量对PP/PVB共混物结晶行为及亲水性的影响;采用广角X射线衍射(WAXD)和小角X射线散射(SAXS)研究了PP/PVB中空纤维热处理后片晶微观结构;采用场发射扫描电镜(FESEM)观察了PP/PVB中空纤维膜内表面孔结构的变化,测试了PP/PVB中空纤维膜的孔隙率及纯水通量.研究结果表明,随着PVB含量的增加,PP/PVB共混物的WCA从103°降低到76°,表明PP/PVB共混物亲水性得到明显改善.同时,PVB可以起到异相成核作用,但由于MAH与PVB发生键合作用,过量添加PVB会阻碍PP分子链段运动,导致晶体结构不完善,这与WAXD和SAXS分析结果相同.PP/PVB2.5(PVB质量分数为2.5%)中空纤维膜热处理后结晶度、片晶取向度、厚度及Shish-kebab结构完善度均高于纯PP样品.对应膜孔隙率为66%,纯水通量达到320 L/(m2·h),比纯PP膜提高了76.8%.     

辐照交联法制备锂离子电池用凝胶聚合物电解质及其性能

采用γ-射线辐照交联法制备了具有网络结构的聚偏氟乙烯-六氟丙烯/新戊二醇二丙烯酸酯(PVDF-HFP/NPGDA)基凝胶聚合物电解质(GPE). 考察了不同辐照剂量对凝胶电解质形貌结构、热稳定性和电化学性能的影响以及不同辐照剂量和不同温度下电导率的变化. 结果表明, 随辐照剂量的增加, 凝胶电解质的固化程度提高, 电导率下降. 电导率随温度的变化符合VTF方程. 当辐照剂量为5 kGy 时, 制备的凝胶电解质具有较高的离子电导率和电化学稳定窗口, 室温下分别为7.8×10-3 S·cm-1和4.7 V(vs Li/Li+). 以其为电解质制备的LiMn2O4∣GPE∣Li聚合物锂离子电池具有较好的循环性能.     

丁苯橡胶为黏合剂的聚丙烯硫酸钡复合膜的制备

以丁苯橡胶(SBR)为黏合剂、羧甲基纤维素钠(CMC)为分散剂、聚丙烯(PP)膜为基体,在其两侧涂覆厚度2μm的硫酸钡(BaSO_4)颗粒,得到一种复合电池隔膜。对复合膜的形貌、润湿性、热稳定性、电导率等进行了研究。结果表明:BaSO_4涂层均匀涂布于PP膜表面,使复合膜中小于200nm的孔增多。同PP膜相比,复合膜具有较小的热收缩率和较好的润湿性。而与聚偏氟乙烯(PVDF)黏合剂相比,SBR具有更强的黏合性。以复合膜做为隔膜的电池在不同电流密度下具有更高的容量保持率。     

用于聚合物镍氢电池的新型PVA/SiO2碱性微孔聚合物电解质

采用溶胶凝胶法,结合相转移法和碱液活化法制备了PVA/SiO2碱性微孔聚合物电解质,通过SEM、XRD、交流阻抗法和循环伏安法表征了电解质的结构与电化学性能.研究表明,PVA/5ωSiO2(ω为质量分数)共混膜上的微孔大小合适,聚合物电解质的离子电导率最大可达1.62×10-2 S·cm-1,电化学稳定窗口2V以上;将PVA/SiO2碱性微孔电解质组装成聚合物镁基镍氢电池,与传统镍氢电池相比,循环稳定性大大增加.     

锂离子二次电池用隔膜的制备及其性质

本文采用倒相法制备了锂离子二次电池用的PVDF HFP共聚物型多孔聚合物隔膜 ,该聚合物膜具有良好的机械性能 ,其孔隙率可达 75% ,吸附电解液后增重 4 50 % ,电导率为 10 - 3S/cm ,组装成电池后表现出良好的循环性能和较低的极化率     

Sulfonated polystyrene grafted polypropylene composite electrolyte membranes for direct methanol fuel cells

Polypropylene (PP)-g-sulfonated polystyrene (SPS) composite membranes were prepared by grafting polystyrene (PS) on microporous polypropylene membranes via plasma-induced polymerization. Grafting of polystyrene was established not only inside the pores but also on the surface of PP membranes, followed by the sulfonation reaction. The chemical and physical structure of PS-g-PP membranes was investigated using FTIR and SEM. The thickness and weight of the composite membrane increased with increasing grafting time. Ion exchange capacity (IEC), ion conductivity, and methanol permeability coefficient were measured and analyzed according to grafting reaction and sulfonation time. While both the ion conductivity and methanol permeability coefficient increased with grafting amount, the characteristic factor was comparable to that of Nafion^®.     

Recent Development of Polyolefin‐Based Microporous Separators for Li−Ion Batteries: A Review

Secondary Li?ion batteries have been paid attention to wide‐range applications of power source for the portable electronics, electric vehicle, and electric storage reservoir. Generally, lithium‐ion batteries are comprised of four components including anode, cathode, electrolyte and separator. Although separators do not take part in the electrochemical reactions in a lithium‐ion (Li?ion) battery, they conduct the critical functions of physically separating the positive and negative electrodes to prevent electrical short circuit while permitting the free flow of lithium ions through the liquid electrolyte that fill in their open porous structure. Hence, the separator is directly related to the safety and the power performance of the battery. Among a number of separators developed thus far, polyethylene (PE) and polypropylene (PP) porous membrane separators have been the most dominant ones for commercial Li?ion batteries over the decades because of their superior properties such as cost‐efficiency, good mechanical strength and pore structure, electrochemical stability, and thermal shutdown properties. However, there are main issues for vehicular storage, such as nonpolarity, low surface energy and poor thermal stability, although the polyolefin separators have proven dependable in portable applications. Hence, in this review, we decide to provide an overview of the types of polyolefin microporous separators utilized in Li?ion batteries and the methods employed to modify their surface in detail. The remarkable results demonstrate that extraordinary properties can be exhibited by mono‐ and multilayer polyolefin separators if they are modified using suitable methods and materials.     

Preparation and characterization of antibacterial microporous membranes fabricated by poly(AMS-co-DMAEMA) grafted polypropylene via melt-stretching method

Functional polypropylene (PP) is prepared by graft poly(AMS-co-DMAEMA) onto PP chains through melt blending, and then microporous membranes of functional PP are made by casting and stretching, and finally the polycation microporous membranes are obtained via quaternization. The obtained microporous membranes show good hydrophilicity and antibacterial properties.     

Effect of porosity on the effective electrical conductivity of different ceramic membranes used as separators in eletrochemical reactors

Different microporous ceramic membranes have been investigated to be used as separators in electrochemical reactors. The effect of porosity on the effective electrical conductivity of the ceramic membranes has been studied. The porosity of the membranes has been modified by changing the manufacturing pressure and by the addition of starch to the alumina–kaolin matrix. In the absence of starch the pore size distribution becomes more uniform with the increase of the manufacturing pressure, and lower porosities and average pore sizes are obtained. On the other hand, the porosity and the average pore size increase with the addition of starch to the alumina–kaolin matrix, but pore size distribution is less uniform and becomes bimodal with two different characteristic pore diameters.

The effective electrical conductivity of the membranes, κ_eff, increases with the decrease of manufacturing pressure and with the increase of starch content. The following correlation between the effective electrical conductivity and the porosity has been obtained: f_c = κ_eff/κ = 0.35 ^1.04, where κ is the electrolyte electrical conductivity.     

TiO2/P(VdF-HFP)杂化纤维微孔膜的制备及其电化学性能

用电纺法制备了TiO₂/P(VdF-HFP)(聚偏氟乙烯-六氟丙烯共聚物)杂化纤维微孔膜, 用SEM观察了杂化纤维微孔膜的形貌, 并测算了这类由超细纤维相互搭接而形成的微孔膜的孔隙率. 这种微孔膜吸附LiPF₆/EC-DMC-EMC(碳酸乙烯酯-二甲基碳酸酯-碳酸甲乙酯)电解质溶液后得到凝胶聚合物电解质膜. 用电化学方法测试了聚合物电解质膜的离子电导率、锂离子迁移数等参数, 并研究了TiO₂纳米晶的掺入对聚合物电解质电化学性能的影响. 结果表明, TiO₂的掺入降低了P(VdF-HFP)聚合物基体的结晶度, 改善了凝胶聚合物电解质的低温电化学性能.     

INTERACTION BETWEEN ISOTACTIC POLYPROPYLENE AND ITS NON-SOLVENTS

Polypropylene (PP) microporous film prepared by biaxial stretching of isotactic PPis treated with non-solvent liquid at room temperature. The dimension of the film maychange after the treatment. The degree of area contraction of PP film is dependent on thematch between PP and liquid in solubility parameter and polarity. The fact indicates thatsome interactions do exist between liquid and isotactic PP, and a shrinkable porous film isa sensitive probe to detect the weak interactions.     

Effect of tin concentration on the electrical properties of ceramic membranes used as separators in electrochemical reactors

This paper deals with the study of different microporous ceramic membranes used as separators in electrochemical reactors to treat the activating solutions coming from the electroless plating of polymers. The main component of these solutions is Sn(IV) in HCl as diluting agent, then, the effect of the complex species formed between Sn⁴⁺ and Cl⁻ ions on the electrical properties of the membranes has been studied.