聚合物/TiO2杂化纳米纤维微孔膜的制备及其在染料敏化太阳能电池中的应用

利用静电纺丝技术,制备了不同的聚合物/TiO2杂化纳米纤维微孔膜,吸附液体电解质后形成聚合物/TiO2杂化纳米纤维微孔膜准固态电解质,应用于制备准固态染料敏化太阳能电池(DSSCs).测试了电纺聚合物纳米纤维微孔膜电解质的吸液率、孔隙率、离子电导率等参数,研究了纳米纤维微孔膜准固态电解质DSSCs的光伏性能.结果显示,TiO2的掺入可提高聚合物/TiO2杂化纳米纤维微孔膜对液态电解质的浸润扩散性能,从而提高纳米纤维微孔膜对液态电解质的吸附能力.组装的DSSCs的光电转换效率可达液态电解质的90%以上,并具有较好的长期工作稳定性.     

重离子辐照制备电池用微孔膜及其阻抗性质

利用离子辐照结合径迹蚀刻方法制备聚丙烯(PP)微孔膜.用加速器产生的单核能为11.4MeV·u-1(总能量2245.8MeV)的197Au离子束辐照PP膜,剂量为1×108ions·cm-2.辐照后PP膜沿离子路径产生损伤区域,用硫酸与重铬酸钾的混合液进行蚀刻(5-30min),制备出孔径为380-1610nm的聚丙烯微孔膜.对膜的表面和断面形貌进行表征,微孔膜的孔径大小及空间分布均匀,孔道上下贯通,形状近似为圆柱形.给出了微孔膜的孔隙率理论公式.将制备的聚丙烯微孔膜用作锂离子电池隔膜,用电化学阻抗谱(EIS)测定浸满电解液的微孔膜的离子电导率,并与商用隔膜进行比较.分析表明辐照剂量和孔径大小均会影响膜的孔隙率和离子电导率,选择合适的辐照剂量和蚀刻时间,可以制备出孔隙率和离子电导率符合应用标准的聚丙烯微孔膜.     

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.     

聚偏氟乙烯电纺膜及其电化学性能的研究

用电纺的方法制备了聚偏氟乙烯纳米纤维膜,它们具有多微孔结构,能够作为锂电池聚合物电解质.电纺中聚合物溶液的浓度对制备的电纺膜的结构形态有很大的影响,低浓度(10 wt%)时得到珠丝结构的膜,浓度15 wt%时则为纤维结构,而高浓度(18 wt%)时,电纺膜为交联的网状结构.用电纺法制备的聚偏氟乙烯纳米纤维微孔膜具有较高的孔隙率,而且它们与锂金属电极具有良好的界面稳定性;在25℃时吸液率最高可达340%,以这种膜制备的聚合物电解质室温电导率可达到1.57×10-3S.cm-1;由该电解质组装的扣式电池以0.5 mA.cm-2恒流充放电,25℃时50次循环后几乎无容量损失,具有良好的循环性能;即使60℃时,电池仍能保持良好的工作稳定性.     

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.     

水蒸气沉淀法制备SiO2/偏氟乙烯-六氟丙烯共聚物复合微孔型聚合物电解质的研究

用水蒸气沉淀法制备了SiO2 偏氟乙烯 六氟丙烯共聚物 [P(VDF HFP) ]复合微孔型聚合物电解质 ,并研究了纳米SiO2 的加入对微孔结构及复合微孔型聚合物电解质性能的影响 .SEM观察发现当纳米SiO2 的添加量大于 0 1倍聚合物质量时 ,可以在微孔中观察到纳米粒子的严重团聚现象 .电导率的测量表明添加 0 0 5倍聚合物质量的纳米SiO2 后 ,微孔型聚合物电解质的电导率有明显提高 ,但进一步增大添加量后 ,电导率有所下降 .另外 ,实验发现添加纳米SiO2 可以明显提高微孔型聚合物电解质与锂金属电极之间的界面稳定性 ,特别是添加量为 0 0 5倍聚合物质量时的效果良好 .     

PAN/PMMA凝胶聚合物电解质膜导电动力学分析

采用静电纺丝法制备PAN/PMMA(聚丙烯腈/聚甲基丙烯酸甲酯)凝胶聚合物电解质膜,用交流阻抗法测试其在不同温度下的电导率,研究温度对凝胶聚合物电解质膜离子传输性能的影响规律;并与溶液浇铸法制得的平滑膜进行对比,分析两种不同形式凝胶聚合物电解质膜的导电动力学规律,探索其导电机理与微观形貌的关系.结果发现,两种薄膜的导电机理符合Arrhenius公式,其中纺丝薄膜的离子导电活化能较低.     

聚(丙烯腈-甲氧基聚乙二醇单丙烯酸酯-丙烯酸锂)的制备与表征

采用乳液聚合方法制备了锂离子电池凝胶电解质用丙烯腈-甲氧基聚乙二醇(350)单丙烯酸酯-丙烯酸锂共聚物. 利用红外光谱(IR), 差示扫描量热法(DSC)对共聚物结构进行了表征. 利用倒相法制备了共聚物微孔膜, 使聚(丙烯腈-甲氧基聚乙二醇(350)单丙烯酸酯)共聚物的溶解性能得到了显著提高, 同时, 还改善了膜的收缩性. 采用交流阻抗方法测试了凝胶电解质膜在室温下的电导率, 结果表明, 该凝胶电解质具有较高的离子电导率, 能满足现有锂离子电池使用要求.     

静电纺丝纳米纤维基凝胶聚合物电解质的研究进展

凝胶聚合物电解质(GPEs)可以解决传统电池的漏液问题和低能量密度问题,提高电池的安全性能,使电池轻便化,薄型化和外形多样化。静电纺丝技术可以控制纤维的直径和孔隙率,平衡GPEs离子电导率和力学性能,实现两者的共同提高,引起众多学者的研究兴趣。重点对聚偏氟乙烯(PVDF)电纺膜基凝胶聚合物电解质和聚丙烯腈(PAN)电纺膜基凝胶聚合物电解质的制备工艺和性能的研究进展进行了介绍,并对静电纺丝纳米纤维基凝胶聚合物电解质存在的问题和研究方向进行了探讨。     

静电纺丝法制备PAN/HNTs混杂纤维增强热塑性聚氨酯复合材料

静电纺丝方法制备了聚丙烯腈/埃洛石纳米管(PAN/HNTs)混杂纤维增强体,通过改变接收装置、热拉伸处理得到5种不同的PAN/HNTs混杂纤维增强体。采用浸渍法将5种增强体用于改性热塑性聚氨酯,得到PAN/HNTs/TPU复合材料。结果表明,PAN/HNTs混杂纤维增强体可显著提高复合材料的力学性能。将平板接收制备的PAN/HNTs混杂纤维增强体以及另外两种由1050r/m滚筒接收制备的PAN/HNTs混杂纤维增强体(前者不采用热拉伸,后者采用热拉伸),三者制成PAN/HNTs/TPU复合材料。与通过平板接收制备的复合材料相比,通过由1050r/m滚筒接收制备的两种复合材料性能要优于前者,相较于前者,其复合材料的拉伸强度分别增加了19%和43%,弹性模量分别增加了44%和122%,断裂伸长率分别增加了19%和24%。当定向接收的PAN/HNTs纤维膜的含量为5.6%时所得到的PAN/HNTs/TPU复合材料力学性能为最佳;通过热拉伸处理PAN/HNTs纤维膜,当含量为4.5%时,复合材料的力学性能为最佳。这种力学增强的主要原因是PAN/HNTs纤维与热塑性聚氨酯材料之间的相容性得到了改...     

PVDF/PAN/SiO<Subscript>2</Subscript> polymer electrolyte membrane prepared by combination of phase inversion and chemical reaction method for lithium ion batteries

PVDF/PAN/SiO₂ polymer electrolyte membranes based on non-woven fabrics were prepared via introducing a chemical reaction into Loeb-Sourirajan (L-S) phase inversion process. It was found that physical properties (porosity, electrolyte uptake and ionic conductivity) and electrochemical properties were obviously improved. A favorable membrane structure with fully connective porous and uniform pore size distribution was obtained. The effects of PVDF/PAN weight ratio on the morphology, crystallinity, porosity, and electrochemical performances of membranes were studied. The optimized PVDF/PAN (70/30 w/w) (designated as M_pc30) polymer electrolyte membrane delivered excellent electrolyte uptake of 246.8 % and the highest ionic conductivity of 3.32 × 10^?3 S/cm with electrochemical stability up to 5.0 V (vs. Li/Li⁺). In terms of cell performance, the Li/M_pc30 polymer electrolyte/LiFePO₄ battery exhibited satisfactory electrochemical properties including high discharge capacity of 149 mAh/g at 0.2 C rate and good discharge performance at different current densities. The promising results reported here clearly indicated that PVDF/PAN/SiO₂ polymer electrolyte membranes prepared by the combination of phase inversion and chemical reaction method were promising enough to be applied in power lithium ion batteries.     

MICROPOROUS PVDF-HFP-BASED POLYMER MEMBRANES FORMED FROM SUPERCRITICAL CO2 INDUCED PHASE SEPARATION

Microporous poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)membranes following supercritical CO_2 induced phase separation process were prepared using four solvents.The solid electrolytes of PVDF-HFP were formed by microporous PVDF-HFP membranes filled and swollen by a liquid electrolyte.The effect of the solvents on the morphology and structure,electrolyte absorptions and lithium ionic conductivity of the activated membranes were investigated.It was approved that all the membrane had the simi...     

Preparation of P(AN–MMA) microporous membrane for Li-ion batteries by phase inversion

A novel process was proposed for preparation of microporous poly(acrylonitrile–methyl methacrylate) (P(AN–MMA)) membranes by phase inversion techniques using ultrasonic humidifier. Being prepared by dissolving the polymer (PAN–MMA) in the N,N-dimethylformamide (DMF) solution with mechanical stirring, the homogenous casting solution was cast onto a clean glass plate. Successively, the glass plate was exposed to the water vapor produced by ultrasonic humidifier, inducing the phase inversion. It is found the pore size is much more uniform across the cross-section of the membrane than that of the porous membrane prepared by conventional water bath coagulation technique. The microporous membranes were directly obtained after the washing and drying. It had about 1–5 μm of pores and presented an ionic conductivity of 2.52 × 10⁻³ S/cm at room temperature when gelled with 1 M LiPF₆/EC-DMC (1:1 vol.%) electrolyte solution. The test cells with the gel electrolytes prepared from as-prepared microporous membranes showed stable cycling capacities, indicating that the microporous membrane, which was prepared from cheap starting materials acrylonitrile and methyl methacrylate, can be used for the gel electrolyte of lithium batteries.     

PREPARATION AND ELECTROCHEMICAL CHARACTERISTICS OF POLYMER ELECTROLYTE MEMBRANES BASED ON SAN/PVDF-HFP BLENDS

A copolymer of poly(acrylonitrile-co-styrene) (SAN) was synthesized via an emulsion polymerization method. Novel polymer electrolyte membranes cast from the blends of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), SAN and fumed silica (SiO2) are microporous and can be used in polymer lithium-ion batteries. The membrane shows excellent characteristics such as high ionic conductivity and good mechanical strength when the mass ratio between SAN and PVDF-HFP and SiO2 is 3.5/31.5/5. The ionic conductivity of the membrane soaked in a liquid electrolyte of 1 mol/L LiPF6/EC/DMC/DEC is 4.9×10-3 S cm-1 at 25℃. The membrane is electrochemical stable up to 5.5 V versus Li /Li in the liquid electrolyte. The influences of SiO2 content on the porosity and mechanical strength of the membranes were studied. Polymer lithium-ion batteries based on the membranes were assembled and their performances were also studied.     

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^®.