PVDF-HFP接枝PEG聚合物电解质的制备和性能研究

以聚偏二氟乙烯-六氟丙烯(PVDF-14VP)接枝聚乙二醇(PEG)为基质,用萃取法制备了均相结构的微孔型聚合物电解质.对此共聚物电解质和纯PVDF-HFP电解质进行比较表征,并以接枝共聚物电解质组装扣式电池进行了性能检测.结果表明,PVDF-HFP接枝PEG后可提高吸液率、保液能力和电导率.20℃时PVDF-HFP和PVDF-HFP-g-PEG的电导率分别为2.60×10-3S/cm和3.28×10-3S/cm.0.2 C充放电时,电池首次放电比容量为119.3 mAh/g.50次充放电循环过程中,充放电效率为99%.初始放电比容鼍为120.7 mAh/g,终止放电容量为115.9 mAh/g.0.5、1、2 C的放电比容量分别为0.2 C放电容量的96.2%、94.5%和81.3%.     

PVDF-HFP凝胶型固体聚合物电解质改性研究进展

固体聚合物电解质具有质轻、安全、易加工等优点,在锂离子电池中具有巨大的应用价值。主要综述了以PVDF-HFP共聚物为基的聚合物电解质的研究工作,介绍了PVDF-HFP固体电解质的制备方法,主要讨论了PVDF-HFP电解质的改性措施,对今后的发展方向作了简单展望。     

纳米TiO2/PVDF-HFP微孔膜的制备与性能

采用溶剂挥发法并以N,N二甲基甲酰胺为溶剂制备出聚偏氟乙烯-六氟丙烯（PVDF-HFP）/二氧化钛（TiO₂）聚合物微孔膜。通过对微孔膜的红外光谱、吸液率、力学性能及热重性能的测试分析,结果表明TiO₂含量为15%的微孔膜的吸液率为190%,拉力为46 N,断裂延伸率为130%,分解温度为250℃。可以满足锂离子电池的商业使用要求,具有广阔的应用前景。     

新型共混的PEO/TPU/PVDF-HFP基聚合物电解质的制备及性能

通过相转化法制备基于聚氧化乙烯（PEO）/热塑性聚氨酯（TPU）/聚偏氟乙烯-六氟丙烯（PVDF-HFP）三种高聚物共混形成的电解质隔膜, 浸泡在1 mol/L六氟磷酸锂（LiPF6）的碳酸乙烯酯（EC）: 碳酸二甲酯（DMC）: 碳酸甲乙酯（EMC）=1:1:1的电解液中形成一种新型的凝胶态聚合物电解质（GPE）。采用SEM、FTIR、XRD、TG、DSC、拉伸性能和电化学性能进行了表征。结果表明，聚合物配比为3:1:4的隔膜具备均匀的多孔形貌，结晶峰面积最低，拉伸强度达到了15 MPa，离子电导率为7.9?10^(-3) S?cm，综合性能最佳。将聚合物配比为3:1:4的隔膜装配成CR2032纽扣电池进行电池循环性能测试，结果表明，在0.2 C下电池的充放电比容量分别达到了164 mAh/g和161 mWh/g，在150次循环后，放电比容量仍能保持在152 mAh/g 左右，库仑效率保持97%以上，是一种优异的电池材料。     

浸没沉淀法制备多孔聚合物电解质膜及其性能

先以偏氟乙烯-六氟丙烯的共聚物(PVDF–HFP)作为成膜物质、丙酮作为溶剂,采用浸没沉淀法制得多孔聚合物膜,再将多孔膜浸入含有1 mol/L LiPF₆的碳酸乙烯酯(EC)-碳酸二甲酯(DMC)-碳酸甲乙酯(EMC)的离子液体电解液中获得多孔聚合物电解质膜(PPEM)。研究了PVDF–HFP质量分数和凝固浴温度对PPEM吸液率、离子电导率和电化学稳定窗口的影响。结果表明,当聚合物溶液的PVDF–HFP质量分数为20%、凝固浴温度为25℃时,所得的PPEM电化学稳定窗口为5V,吸液率达到40.2%,但离子电导率为1.52×10^-4 S/cm,有待进一步提高。     

共混改性的PEO/TPU/PVDF-HFP基聚合物电解质的制备及性能

通过相转化法制备基于聚氧化乙烯(PEO)/热塑性聚氨酯(TPU)/聚偏氟乙烯-六氟丙烯(PVDF-HFP)3种高聚物共混形成的电解质隔膜,将其浸泡在浓度为1 mol/L六氟磷酸锂(LiPF6)的碳酸乙烯酯(EC)-碳酸二甲酯(DMC)-碳酸甲乙酯(EMC)(三者体积比为1:1:1)电解液中形成一种凝胶态聚合物电解质(GPE).采用SEM、EDS、FTIR、XRD、TG、DSC、万能拉力机和交流阻抗法对隔膜进行了表征.结果表明,m(PEO):m(TPU):m(PVDF-HFP)=3:1:4的隔膜具有均匀的多孔形貌,结晶峰面积最低,拉伸强度达到15 MPa左右,离子电导率为7.9×10–3 S/cm,综合性能最佳.将该隔膜装配成CR2032纽扣电池进行电池循环性能测试,结果表明,在0.2 C倍率下电池的充放电比容量分别达到了164和161 mA·h/g,在150次循环后,放电比容量仍能保持在152 mA·h/g左右,库伦效率保持97％以上,表明该GPE是一种优异的电池材料.     

PVDF/TiO2复合膜的性能研究

采用流延成膜的加工工艺,制备了聚偏氟乙烯/二氧化钛(PVDF/TiO2)复合膜,研究了TiO2含量对复合膜的热稳定性、力学性能、结晶形态、热性能以及耐候性的影响。结果表明,TiO2含量为2%时,共混制得的复合膜拉伸强度高达59.5MPa,起始分解温度为340℃;加入TiO2对PVDF结晶度的影响不大,通过紫外照射实验证明加入TiO2改善了PVDF的耐候性。     

聚合物电解质的研究进展

介绍了锂离子电池的特点、市场前景及聚合物锂离子电池的种类,综述了聚合物电解质的发展历程,重点阐述了近来研究较多的几种聚合物电解质的研究进展,包括:聚偏氟乙烯基(PVDF基)、聚丙烯腈基(PAN基)、聚甲基丙烯酸甲酯基(PMMA基)和聚乙烯类(PE)聚合物电解质。     

P（VDF—HFP）基凝胶聚合物电解质的研究进展

概述影响凝胶聚合物电解质性能的的因素;重点介绍P(VDF-HFP)多孔凝胶聚合物电解质作为锂离子电池聚合物电解质的研究进展,包括该类聚合物电解质的的制备方法及其离子电导率;展望了凝胶聚合物电解质在锂离子电池中的应用前景.     

全固态聚合物电解质的性能研究

聚合物电解质由于本身的优点,已成为锂离子电池研究的一个热点.聚合物电解质由聚合物、锂盐及添加剂组成,本文综述了聚合物电解质研究的新体系,论述了聚合物电解质中各组分对其性能的影响.     

Enhanced high-temperature polymer electrolyte membrane for fuel cells based on polybenzimidazole and ionic liquids

Polybenzimidazole (PBI)/ionic liquid (IL) composite membranes were prepared from an organosoluble, fluorine-containing PBI with ionic liquid, 1-hexyl-3-methylimidazolium tri?uoromethanesulfonate (HMI-Tf). PBI/HMI-Tf composite membranes with different HMI-Tf concentrations have been prepared. The ionic conductivity of the PBI/HMI-Tf composite membranes increased with both the temperature and the HMI-Tf content. The composite membranes achieve high ionic conductivity (1.6 × 10⁻² S/cm) at 250 °C under anhydrous conditions. Although the addition of HMI-Tf resulted in a slight decrease in the methanol barrier ability and mechanical properties of the PBI membranes, the PBI/HMI-Tf composite membranes have demonstrated high thermal stability up to 300 °C, which is attractive for high-temperature (>200 °C) polymer electrolyte membrane fuel cells.     

Lithium polymer batteries using the highly porous membrane filled with solvent-free polymer electrolyte

Solid polymer electrolyte supported by a microporous membrane was prepared and characterized. The polymer electrolyte was prepared by penetrating the highly conductive solvent-free polymer electrolyte based on poly(oligo [oxyethylene] oxyterephthaloyl) into the pores of the highly porous membrane. The electrochemical characteristics of the solid polymer electrolytes are presented, and we discuss the possibility of them as an electrolyte material for lithium polymer batteries.     

Solid polymer electrolytes of blends of polyurethane and polyether modified polysiloxane and their ionic conductivity

Polymer electrolytes based on thermoplastic polyurethane (TPU) and polyether modified polysiloxane (PEMPS) blend with lithium salts were developed via an in-situ polymerization of TPU with the presence of PEMPS and salts. Morphological study of TPU/PEMPS electrolytes showed that TPU and PEMPS were immiscible and TPU/PEMPS electrolytes had a multiphase morphology. The lithium salt enhanced the interfacial compatibilization between TPU and PEMPS via the interaction of lithium ions with different phases. Three lithium salts with different interaction strengths with TPU and PEMPS were used to prepare TPU/PEMPS electrolytes with different levels of phase compatibilization: LiCl, LiClO₄, and LiN(SO₂CF₃)₂ (LiTFSI). The effect of PEMPS on ionic conductivity, dimensional stability and thermal stability of TPU/PEMPS electrolytes and their relationship with the blend morphology were investigated. TPU/PEMPS electrolytes showed good dimensional stability and thermal stability. The addition of PEMPS to TPU increased the ionic conductivity of TPU/PEMPS electrolytes. The room temperature ionic conductivity of TPU/PEMPS electrolytes with LiTFSI can reach up to 2.49 × 10⁻⁵ S/cm.     

A novel polymer electrolyte based on PMAML/PVDF-HFP blend

A gel polymer electrolyte based on the blend of poly(methyl methacrylate-co-acrylonitrile-co-lithium methacrylate) (PMAML) and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was prepared and characterized. The synthesized PMAML were characterized by FTIR and NMR, respectively, and the surface morphology of the PMAML and PVDF-HFP blend membrane was also observed by scanning electron microscope (SEM). The electrochemical properties of composite electrolyte membranes were studied. The ionic conductivity of the polymer electrolyte composed of 75 wt.% 1 M LiBF₄ in ethylene carbonate (EC) and dimethyl carbonate (DMC) (EC:DMC=1:1 by weight) was about 2.6×10⁻³ S cm⁻¹ at ambient temperature. The electrochemical window of the polymer electrolyte was about 4.6 V determined from the linear sweep voltammetry plot. The lithium ion polymer batteries were assembled by sandwiching gel polymer electrolyte between LiCoO₂ cathode and mesophase carbon fibre (MPCF) anode. Charge-discharge test results display that lithium ion batteries with these gel polymer electrolytes have good electrochemical performance.     

Effect of nano‐TiO2 dispersion on PEO polymer electrolyte property

Polymer electrolyte membranes based on poly(ethylene oxide) (PEO) doped with TiO₂ nanoparticles were synthesized by simple solution cast technique. Mesoporous TiO₂ film was prepared by doctor‐blade method. The modified polymer membranes and the mesoporous films were characterized by SEM, TEM, AFM, ionic conductivity, and J‐V measurements. Dye‐sensitized solar cells (DSSC) have been fabricated in which PEO‐polymer electrolyte doped with and without nano‐TiO₂ were sandwiched between porous TiO₂ and counter electrodes. The DSSC with nano‐TiO₂ doped polymer electrolyte shows better performance (1.68%) in comparison with pristine polymer electrolyte (1.07%), which is due to improved ionic conductivity value in polymer electrolyte system by nano‐TiO₂ doping. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ionic conductivity enhancement of the plasticized PMMA/LiClO4 polymer nanocomposite electrolyte containing clay

This work has demonstrated that the addition of an optimum content of dimethyldioctadecylammonium chloride (DDAC)-modified montmorillonite clay (Dclay) enhances the ionic conductivity of the plasticized poly(methyl methacrylate)-based electrolyte by nearly 40 times higher than the plain system. Specific interactions among silicate layer, carbonyl group (CO) and lithium cation have been investigated using Fourier-transform infrared (FTIR), solid-state NMR, alternating current impedance. The FTIR characterization confirms that both of the relative fractions of ‘complexed’ CO sites and ‘free’ anions increase with the increase of the Dclay content, indicating that strong interaction exists between the CO group and the lithium salt. In addition, the solid-state NMR demonstrates that the interaction between the PMMA and the clay mineral is insignificant. The addition of clay mineral promotes the dissociation of the lithium salt and thus, the specific interaction can be enhanced between the CO and the free lithium cation. However, the balanced attractive forces among silicate layers, CO groups, lithium cations and anions is critical to result in the higher ionic conductivity.     

Thermal, electrical and mechanical properties of plasticized polymer electrolytes based on PEO/P(VDF-HFP) blends

The polymer electrolytes composed of a blend of poly(ethylene oxide) (PEO) and poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) as a host polymer, mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizer, and LiClO₄ as a salt were prepared by a solution casting technique. SEM micrographs show that P(VDF-HFP) is very compatible with PEO. The ionic conductivity of the electrolytes increases with increasing plasticizer content, while the mechanical properties become obviously worse. By addition of a certain content of PEO in P(VDF-HFP) matrix, a good compromise between high ionic conductivity and mechanical stability can be obtained.     

PVdF-HFP/P123 hybrid with mesopores: a new matrix for high-conducting, low-leakage porous polymer electrolyte

Highly conducting porous polymer electrolytes comprised of poly(vinylidene-fluoride-co-hexafluoropropylene) (PVdF-HFP), polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (P123), ethylene carbonate (EC), propylene carbonate (PC), and LiClO₄ were fabricated. The PVdF-HFP/P123 hybrid polymer membranes were made with a phase inverse method and the electrolyte solution uptake was carried out in glove box to avoid the moisture contamination. It was found that when a small amount of polymer surfactant (P123) was blended into the PVdF-HFP, mesopores with well-defined sizes were formed. Impedance spectroscopy showed that the room temperature conductivity of (PVdF-HFP)/P123 polymer electrolytes increased as the content of P123 increased up to 4×10⁻³ S/cm. Nitrogen adsorption isotherms, electrolyte solution uptake, porosity measurements, and SEM micrographs showed that the enhanced conductivity was due to increase the pore volume, pore density, and electrolyte uptake. The highest conduction was found when the weight ratio of P123 to PVdF-HFP was 70%, when big channels were formed in the hybrid polymer membrane. Furthermore, blending P123 in PVDF-HFP reduced the pore size of polymer membrane, therefore, the solution leakage was also reduced. These polymer electrolytes were stable up to 4.5 V (vs Li/Li⁺) and the performance of the model lithium ion battery made by sandwiching the polymer electrolyte between a LiCoO₂ anode and a MCMB cathode, showed great promise for the use of these polymer electrolytes in lithium ion batteries.     

Gel-based composite polymer electrolytes with novel hierarchical mesoporous silica network for lithium batteries

In the present work, novel gel-based composite polymer electrolytes for lithium batteries were prepared by introducing a hierarchical mesoporous silica network to the poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)-based gel electrolytes. As compared with the PVDF-HFP-based gel electrolytes with/without conventional nano-sized silica fillers, the novel electrolytes have shown more homogeneous microstructure, higher ionic conductivity and better mechanical stability, which could be caused by the strong silica network and the effective interactions among the polymer, the liquid electrolytes and the silica. Moreover, the cell with this kind of electrolytes could achieve a discharge capacity as much as 150 mAh g⁻¹ at room temperature (LiCoO₂ as the cathode active material), with high Coulomb efficiency.     

Conductivity relaxation in the PEO-salt polymer electrolytes

The ionic conductivity of polyethylene oxide (PEO)-based electrolytes is complicated due to the coexistence of crystalline and amorphous phase below melting point of PEO complexes. The two-phase characteristics are greatly dependent upon thermal history, exhibiting variety of spherulitic morphology and crystallinity. Further complicacy comes from slow crystallization kinetics of the spherulites. We found that the ionic conductivity of PEO_nLiClO₄ polymer electrolytes under isothermal conditions, after quenching from high-temperature phase, drops significantly for roughly first 10 h and then decreases very slowly thereafter. The conductivity relaxation observed can be assigned to be a consequence of the slow recrystallization kinetics of PEO. It corresponds to a gradual, slow secondary crystallization of PEO and PEO-salt complexes corresponding to thickening of spherulitic aggregates, possibly through a development of subsidiary lamellae which fill in the space between the dominant lamellae crystals. Hence, large inconsistencies in the conductivity values reported in many papers, varying more than three orders of magnitude, are rather obvious, originated from non-equilibrium nature and slow recrystallization kinetics of semicrystalline state.