聚偏氟乙烯共混隔膜的制备与性能

以乙二醇二甲基丙烯酸酯和丙烯腈为单体,合成了聚合物poly(AN-co-PEGDMA),然后与聚偏氟乙烯(PVDF)共混,制备了不同poly(AN-co-PEGDMA)含量的PVDF/poly(AN-co-PEGDMA)共混隔膜,利用X射线衍射、扫描电子显微镜(SEM)、差示扫描量热对共混隔膜的性能进行表征。结果表明,随着poly(AN-co-PEGDMA)含量的增加,PVDF/poly(AN-co-PEGDMA)的玻璃化转变温度逐渐提高,衍射峰的谱峰强度逐渐降低,隔膜的结晶度降低。SEM结果显示,随着poly(AN-co-PEGDMA)含量的增加共混隔膜的孔隙变大,有利于电解液的有效吸收。通过对PVDF/poly(AN-co-PEGDMA)共混隔膜电导率、吸液率的测定,表明在poly(AN-co-PEGDMA)质量分数为30%时,制得的共混隔膜的性能较佳。在此基础上,对共混隔膜构建的聚合物锂离子电池的电化学稳定窗口、电池容量和循环性能进行测试,其电化学稳定窗口为0～4.7 V(vs Li+/Li),放电电容为1.433～1.151 mAh,可以满足商业使用要求,具有广阔的应用前景。     

四苯基氯化鏻对聚偏氟乙烯电活性相的诱导作用

通过简单的熔体共混方法,将不同质量分数的高熔点高活性的四苯基氯化鏻(TPPC)与聚偏氟乙烯(PVDF)混合,探究了TPPC对PVDF极性相的诱导作用,并研究了此体系与熔体结晶过程最为相近的非等温结晶过程。结果表明,添加极少量(0.4%)的TPPC即可以使PVDF直接从熔体中全部以极性相结晶,这归因于TPPC固体表面的电荷与PVDF分子链之间强烈的相互作用。TPPC的加入使PVDF的非等温结晶行为发生了很大的变化,当TPPC含量达到0.4%时,降温结晶曲线出现两个结晶峰,也是这种反常的结晶行为才能使PVDF几乎全部以极性相结晶。     

Stable composite electrolytes of PVDF modified by inorganic particles for solid-state lithium batteries

Polymer electrolytes have been attracting much attention because of their flexibility and easy follow-up processing, but their Li⁺ conductivity in lithium-metal batteries (LIBs) is unsatisfactory. Stable composite electrolytes of poly (vinylidene fluoride) (PVDF) polymer with high lithium-ion conductivity have been prepared by a trigger structural modification of Li_6.5La₃Zr_1.5Nb_0.25Ta_0.25O₁₂ (LLZNTO) garnet ceramic and TiO₂ oxide. The influences of various amounts of TiO₂ and LLZNTO on electrochemical performance were systematically examined. These composite electrolytes exhibited maximal Li⁺ conductivity of 2.89 × 10⁻⁴ S cm⁻¹, which is consistent with the value of pure ceramic electrolytes. Furthermore, it possessed the stable long-term Li cycling and the wide electrochemical window, involving repeated Li plating/stripping at 0.2 mA cm⁻² over 280 h without failure. The discharge specific capacity and Coulomb efficiency for all-solid-state LIBs assembled with these membranes delivered outstanding cycling stability with high discharge capacities (117.9 mA h g⁻¹) at 0.1 C rate and Coulomb efficiency reached 99.9% after 25 cycles. The high Li⁺ conduction capability can be ascribed function of introducing TiO₂ and LLZNTO to restrain tremendously the crystalline behavior of the polymer. Furthermore, the LLZNTO can be complex with PVDF for dehydrofluorination, and it can also offer a burst transportation route for lithium ions. This system might serve as an attractive use for polymer solid electrolytes and open up new possibilities for safe all-solid-state LIBs.     

PVDF/TiO2杂化纤维膜的制备及其性能分析

采用静电纺丝的方法制备聚偏氟乙烯（PVDF）/二氧化钛（TiO2）杂化纤维膜,并利用扫描电子显微镜、X射线衍射仪和可见分光光度计等仪器对杂化纤维膜的微观形貌、晶体结构、力学性能以及光催化性能进行研究与分析。结果表明,随着TiO2添加量的增加,PVDF/TiO2杂化纤维膜表面暴露的TiO2增加;杂化纤维膜的拉伸强度呈现先增后减的趋势;且杂化纤维膜的光催化降解能力逐渐增强;同时PVDF/TiO2杂化纤维膜具有良好的重复利用性。     

Preparation and characterization of PVDF/silica hybrid membranes containing sulfonic acid groups

Organic–inorganic hybrid membranes of poly(vinylidene fluoride)‐cohexafluoropropylene (PVDF‐HFP) and silica composites containing sulfonic acid groups were prepared via in situ polymerization of tetraethoxysilane (TEOS) and sulfosuccinic acid (SSA) using the sol‐gel process. The membranes containing more sulfonic acid groups showed a higher vapor sorption and greater swelling behavior. The bound and free water content of the membrane is proportional to the SSA concentration. However, the hybrid membranes without SSA do not have free water. The ion conductivity of the membranes is proportional to the SSA concentration. Silica content in the hybrid membrane without SSA had great effect on their mechanical properties. Tensile modulus and yield stress increased and yield strain and elongation at break decreased with increased silica content. However, in the case of the hybrid membrane containing SSA modulus, yield stress decreased and yield strain and elongation at break increased with increased silica content due to the weak interactions between the hydrophobic polymer chain and the hydrophilic group of SSA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 209–218, 2004     

Effects of mixed diluent compositions on poly(vinylidene fluoride) membrane morphology in a thermally induced phase‐separation process

The effects of a mixed diluent (MD) composition [dibutyl phthalate/dioctyl phthalate (DOP)] on poly (vinylidene fluoride) (PVDF) membrane morphology were investigated with scanning electron microscopy, and a bicontinuous morphology could be obtained with MD in a thermally induced phase‐separation process. The reasons for the morphology formation were explained according to the effect of MD on the phase diagrams. In addition, the effects of the PVDF concentration on the membrane morphology were examined. For the system with less DOP, the large spherulite morphology was obvious under all investigated concentrations, whereas no large spherulite structure existed in the membrane as the DOP content increased to concentrations other than 20%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

锂电池用聚偏氟乙烯粘结剂

锂电池用粘结剂是制造锂电池的重要材料之一,可直接影响其性能.介绍了锂电池用粘结剂应具备的特性、种类及存在的问题;叙述了日本专利中,偏氟乙烯作为锂电池用粘结剂和用偏氟乙烯与第二及第三单体的共聚改性、聚偏氟乙烯与其他聚合物共混改性等的方法.     

锂离子电池用溶剂型PVDF混涂隔膜制备及性能

将聚偏氟乙烯(PVDF)粉末和氧化铝(Al2O3)加入二甲基乙酰胺中进行高速分散,得到溶剂型PVDF涂布液,将涂布液涂覆在聚乙烯多孔基膜上,通过浸渍相反转的方法得到锂离子电池用PVDF混涂隔膜.将Al2O3、粘结剂、助剂和水混合搅拌均匀得到水系陶瓷浆料,在上述水系陶瓷浆料中添加PVDF得到水系PVDF混涂浆料,使用研磨...     

膜蒸馏用PDMS/PVDF/PTFE三元共混微孔膜制备

采用浸没沉淀相转化法制备了聚二甲基硅氧烷/聚偏氟乙烯/聚四氟乙烯（PDMS/PVDF/PTFE）三元共混微孔膜,并用于20 g/L NaCl水溶液的膜蒸馏脱盐实验。通过扫描电子显微镜观察以及接触角、膜孔隙率和膜平均孔径分析,研究了PTFE含量对膜结构与性能的影响。结果表明,随着PTFE含量的增加,共混微孔膜断面的指状孔逐渐被海绵状取代,平均孔半径由0.234 μm增加到0.354 μm,膜孔隙率由53.4 %增加到81.3 %;膜下表面与水接触角从118.52 °增加到131.11 °;膜蒸馏过程中通量逐渐增加,截留率先稳定后降低,PTFE含量为40 %（质量分数,下同） 时达最大,为99.99 %,此时膜蒸馏通量达16.60 kg/(m2·h)。     

Preparation and properties of gel membrane containing porous PVDF-HFP matrix and cross-linked PEG for lithium ion conduction

Lithium ion conducting membranes are the key materials for lithium batteries. The lithium ion conducting gel polymer electrolyte membrane (Li-GPEM) based on porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix and cross-linked PEG network is prepared by a typical phase inversion process. By immersing the porous PVDF-HFPmembrane in liquid electrolyte containing poly(ethylene glycol) diacrylate (PEGDA) and an initiator to absorb the liquid electrolyte at 25°C, and then thermally cross-linking at 60°C, the Li-GPEMis fabricated successfully. The measurements on its weight loss, mechanical and electrochemical properties reveal that the obtained Li-GPEM has better overall performance than the liquid and blend gel systems used as conductive media in lithium batteries. The ionic conductivity of the fabricated Li-GPEM can reach as high as 2.25 × 10⁻³ S/cm at 25°C. __________ Translated from Journal of Functional Materials, 2007, 38(2): 234–242 [译自: 功能材料]     

强疏水性PDMS/PVDF微孔膜的制备及其性能研究

利用非溶剂相转化法（NIPS）,通过在聚偏氟乙烯(PVDF)铸膜液中加入聚二甲基硅氧烷(PDMS),制备了PDMS/PVDF共混疏水微孔膜,并研究了凝胶浴组成（水/乙醇）对铸膜液凝胶动力学、膜形貌、疏水性及力学性能的影响。结果表明,随着凝胶浴中乙醇百分含量由零增加至100 %时,PDMS/PVDF共混膜的断面上指状孔基本消失,海绵状孔结构贯穿断面;当凝胶浴中乙醇含量为100 %时,PDMS与PVDF发生分相;膜表面疏水性能增加,水接触角达到139.68 °;弹性模量、拉伸强度、断裂伸长率分别由（48.06±4.20）、（2.82±0.15） MPa、（92.90±2.53） %下降至（15.70±2.83）、（0.72±0.13） MPa、（15.47±1.63） %。     

Thermal behaviour and annealing of poly(vinylidene fluoride)

In this study, we report the melting behavior of poly(vinylidene fluoride) (PVF₂) annealed in a differential scanning calorimeter. PVF₂ annealed under isothermal conditions often shows double or triple melting endotherms depending on the annealing temperature (T_a) and the heating rate. The lower melting peak temperature increases as T_a increases. When the annealing time is varied, there is a systematic increase in the size of the lower endotherms. This suggests that a portion of the main endothermic response is due to reorganization during the scan. Annealing PVF₂ not only increases the degree of crystallinity, but also improves the crystal perfection. The ability of an annealing sample to reorganize decreases as the annealing time increases. However, an additional third melting peak appears when PVF₂ is annealed at 140°C for a sufficiently long time. The existence of this peak suggests that more than one kind of distribution of crystal perfection may occur when PVF₂ is quenched from the melt into liquid nitrogen and subsequently annealed.     

Formation of multilayer poly(acrylic acid)/poly(vinylidene fluoride) composite membranes for pervaporation

Dual‐ and multilayer composite membranes, consisting of poly(acrylic acid) (PAA) and poly(vinylidene fluoride) (PVDF), were synthesized by the plasma‐induced polymerization technique. The dual‐layer membrane had a dense PAA layer grafted onto a microporous PVDF substrate, whereas in the multilayer membranes, the grafted PAA and the PVDF layers were arranged in an alternating sequence (e.g., PAA/PVDF/PAA and PAA/PVDF/PAA/PVDF/PAA). These membranes were used in a pervaporation process to separate ethanol–water solutions. For the dual‐layer membranes, the results indicated that the separation factor increased and the permeation flux decreased with increasing amounts of grafted PAA. For the case of grafting yield < 0.6 mg/cm², the composite membrane demonstrated poor separation. As the grafting yield reached 0.85 mg/cm², a sharp increase of the separation factor was observed. For the multilayer membranes, the pervaporation performances were very good, with high separation factors (on the order of 100) and reasonable permeation fluxes over a wide ethanol concentration range. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2266–2274, 2004     

Preparation of temperature sensitive poly(vinylidene fluoride) hollow fiber membranes grafted with N‐isopropylacrylamide by a novel approach

In the present study, the temperature sensitive PVDF‐g‐NIPAAm HFM was prepared by grafting N‐isopropylacrylamide (NIPAAm) on poly(vinylidene fluoride) (PVDF) hollow fiber membrane (HFM) using a novel approach, alkaline treatment method. The structures of PVDF‐g‐NIPAAm HFM were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. The effects of alkaline treatment time and grafting yield on the mechanical properties of PVDF HFM were measured and analyzed. In addition, the temperature sensitive behavior of PVDF‐g‐NIPAAm HFM and the effect of grafting yield on the temperature sensitive behavior were investigated by the flux of pure water and the rejection of ovalbumin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 833–837, 2006     

Preparation and characterization of poly(vinylidene fluoride) nanocomposites containing multiwalled carbon nanotubes

Poly(vinylidene fluoride) (PVDF) nanocomposites with different loadings of multiwalled carbon nanotubes (MWNT) were prepared by melt‐compounding technique. A homogeneous dispersion of MWNT throughout PVDF matrix was observed on the cryo‐fractured surfaces by scanning electron microscopy. Thermogravimetric analysis results indicated that the thermal stability of neat PVDF was improved with the incorporation of MWNT. Dynamic mechanical analysis showed a significant improvement in the storage modulus over a temperature range from ?125 to 75°C with the addition of MWNT. The melt‐rheological studies illustrated that incorporating MWNT into PVDF matrix resulted in higher complex viscosities (|η*|), storage modulus (G′), loss modulus (G″), and lower loss factor (tan δ) than those of neat PVDF. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure,properties, and phase transitions of melt‐spun poly(vinylidene fluoride) fibers

Three different experimental techniques were used to study structural phase transitions in melt‐spun poly(vinylidene fluoride) fibers, which were produced with different process parameters and processed in the draw‐winding process at different temperatures and draw ratios. The fibers are examined with the help of wide‐angle X‐ray diffraction at elevated temperatures, differential scanning calorimetry with stochastic temperature modulation, and dynamic mechanical analysis. An oriented mesophase and deformed crystal structures can be observed in all fibers and assigned to the mechanical stress occurring in the processes. Furthermore, several phase transitions during melting and two mechanical relaxation processes could be detected. The observed transitions affect the crystal geometry, the orientation distribution, anisotropic thermal expansion, and the mechanic response of the fiber samples. The relaxation processes can be related with an increasing amount of crystalline β‐phase in fibers drawn at different temperatures. The detailed information about phase transitions and the related temperatures are used to produce fibers with an extended amount of β‐phase crystallites, which are responsible for piezoelectric properties of the material. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

多孔结构耐磨超疏水薄膜的制备及性能

为了获得持久稳定的超疏水材料,本研究将聚偏氟乙烯共六氟丙烯共聚物（P(VDF-HFP)）和疏水改性的纳米三氧化二铝（Al2O3）进行复合并通过溶剂/非溶剂诱导相分离法制备了一种耐磨超疏水薄膜。采用SEM及能谱分析仪和接触角测量仪分别对薄膜的表面微观结构、化学组成和疏水性能进行表征。结果表明：制备的薄膜具有自相似微纳米复合微观结构。并且薄膜具有优异的自清洁性和耐机械摩擦性,即使经历360个周期的砂纸磨损（100 g载重）后仍保持超疏水性。除此之外薄膜具有优异耐化学溶液和紫外灯照射稳定性。     

聚偏氟乙烯-六氟丙烯接枝聚丙烯酸磺酸丙酯制备质子膜

以聚偏氟乙烯(PVDF)-六氟丙烯(HFP)中PVDF的仲氟原子直接引发甲基丙烯酸(3-磺酸钾)丙酯(SPMA)的原子转移自由基聚合,成功得到以PVDF-HFP为主链、侧链含磺酸基团的接枝聚合物(PVDF-HFP-g-PSPMA)质子交换膜. 通过红外、核磁分析方法对PVDF-HFP-g-PSPMA的结构进行表征. 反应不同时间得到的PVDF-HFP-g-PSPMA离子交换容量为0.051~0.59 meq/g,质子传导率为(2.58~30.9)×10-2 S/m.     

A novel electrospun TPU/PVdF porous fibrous polymer electrolyte for lithium ion batteries

Novel blend-based gel polymer electrolyte (GPE) films of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) (denoted as TPU/PVdF) have been prepared by electrospinning. The electrospun thermoplastic polyurethane-co-poly (vinylidene fluoride) membranes were activated with a 1M solution of LiClO₄ in EC/PC and showed a high ionic conductivity about 1.6 mS cm⁻¹ at room temperature. The electrochemical stability is at 5.0 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. Cycling tests of Li/GPE/LiFePO4 cells showed the suitability of the electrospun membranes made of TPU/PVdF (80/20, w/w) for applications in lithium rechargeable batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Solution‐derived ferroelectric vinylidene fluoride oligomer thin films with large polarization

Dense and uniform vinylidene fluoride (VDF) oligomer thin films with a highly polar β phase were prepared for the first time by a low‐cost and scalable solution casting approach, after treatments of substrate surface functionalization and hot‐pressing. Introducing hydrated salt in the precursor solution effectively promoted the ferroelectric β phase. The VDF oligomer thin films obtained with short molecular chains exhibited high crystallinity and high remnant polarization (91 mC m^?2), which is larger than both the polymer and copolymer counterpart films. The reasons for the observed low dielectric constant at low electric field, despite its larger polarization at high field, and the relatively high coercive field are discussed on the basis of the distinct structural characteristics of VDF oligomers. The low polar bulky end‐groups and difficulties in kink formation and propagation may result in the observed low dielectric constant at low electric field and the high coercive field. Copyright © 2011 Society of Chemical Industry