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     

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]     

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.     

Gel electrolyte membranes derived from co-continuous polymer blends

Polymer gel electrolyte membranes were prepared by first casting films of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, and poly(ethylene glycol) (PEG) monomethacrylate and dimethacrylate macromonomers. Polymerization of the macromonomers initiated by UV-irradiation then generated solid films having phase-separated morphologies with a microporous PVDF-HFP phase embedded in PEG-grafted polymethacrylates. Gel electrolyte membranes were finally prepared by allowing the films to take up solutions of LiTFSI in γ-butyrolactone (γ-BL). The PEG-grafted polymethacrylate in the membranes was found to host the largest part of the liquid electrolyte, giving rise to a highly swollen ionic conductive phase. Results by FTIR spectroscopy showed that the Li⁺ ions preferentially interacted with the ether oxygens of the PEG chains. The properties of the membranes were studied as a function of the ratio of PVDF-HFP to PEG-grafted polymethacrylate, as well as the degree of crosslinking, LiTFSI concentration, and liquid electrolyte content. The self-supporting and elastic gel membranes had ionic conductivities of 10⁻³ S cm⁻¹ and a mechanical storage modulus in the range of 2.5 MPa in the tension mode at room temperature. Variation of the salt concentration showed the greatest effect on the membrane properties.     

Temperature‐dependent transition of crystal phases in the electrospinning process of poly(vinylidene fluoride‐co‐hexafluoropropylene)

The temperature‐dependent transition of the crystal phases of poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) was investigated in the electrospinning process. A solution of PVDF‐HFP in N,N‐dimethyl acetamide (DMAc) produced only the β‐phase‐dominant crystal up to 70 °C, irrespective of the spinneret temperature. In a mixed solvent of DMAc and acetone, however, the crystal phase of the electrospun fibers was dependent on temperature: β‐phase‐dominant at 30 and 50 °C and α‐phase‐dominant at 70 °C. The transition was related to a change of the coagulation rate during electrospinning, because the less perfect α phase is preferable to the β phase at a higher coagulation rate. The temperature‐dependent increase of the coagulation rate was more drastic in the presence of acetone, so the transition took place only in the mixed solvent. At elevated temperature, acetone not only raised the evaporation rate of the solvent but promoted the phase separation of the polymer resulting from the lower critical solution temperature behavior, which was rheologically traced. © 2019 Society of Chemical Industry     

A microporous gel electrolyte based on poly(vinylidene fluoride-co-hexafluoropropylene)/fully cyanoethylated cellulose derivative blend for lithium-ion battery

A gel polymer electrolyte based on the blend of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and fully cyanoethylated cellulose derivative (DH-4-CN) was prepared and characterized. Thermal, mechanical, swelling, liquid electrolyte retention and electrochemical properties, as well as microstructures of the prepared polymer electrolytes, were investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results showed that the addition of DH-4-CN could obviously improve the conductivity of PVDF-HFP based electrolyte. The maximum ionic conductivity of 4.36 mS cm⁻¹ at 20 °C can be obtained for PVDF-HFP/DH-4-CN 14:1 in the presence of 1 M LiPF₆ in EC and DMC (1:1, w/w). The dry blend membranes exhibit excellent thermal behavior. All the blend electrolytes are electrochemically stable up to about 4.8 V vs. Li/Li⁺ for all compositions. The results reveal that the composite polymer electrolyte qualifies as a potential application in lithium-ion battery.     

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)。     

Partially Sulfonated Poly(vinylidene fluoride) Induced Enhancements of Properties and DMFC Performance of Nafion Electrolyte Membrane

Partially sulfonated poly(vinylidene fluoride) (SPVdF) has been prepared by incorporation of sulfonic acid groups within poly(vinylidene fluoride), using chlorosulfonic acid as the sulfonating agent. The degree of sulfonation (DS) has been varied by modulating the duration of the sulfonation reaction. Blending of SPVdF (having DS = 36.78%) with Nafion at a constituent wt.% ratio of SPVdF:Nafion = 70:30 has resulted in the fabrication of polymer electrolyte membrane with superior properties compared to pristine Nafion‐117 membrane. This particular blend composition exhibited a proton conductivity value of 3.6 × 10⁻² S cm⁻¹ (i.e. ∼12.5% increase over Nafion‐117), a methanol permeability value of 6.81 × 10⁻⁷ cm² s⁻¹ at 6M methanol concentration (i.e. ∼99.31% decrease from Nafion‐117) and a corresponding membrane selectivity value of 5.29 × 10⁴ Ss cm⁻³ (i.e. an increase of approximately two‐orders of magnitude over Nafion‐117) at 20 °C. In addition, this blend composition has also exhibited (a) better heat stability at temperatures as high as 160 °C by virtue of it possessing higher glass transition temperature, (b) higher storage modulus, (c) higher stress relaxation at high angular frequency and (d) superior DMFC performance at high methanol feed concentration in presence of humidified, as well as, non‐humidified air as the catholyte, compared to Nafion‐117 membrane.     

Modified silicone–PVDF composite hollow‐fiber membrane preparation and its application in VOC separation

Polydimethylsiloxane^vi–poly(vinylidene fluoride) (PDMS^vi–PVDF) composite membranes were prepared using asymmetric PVDF hollow‐fiber membranes as the substrate where a very thin layer of silicone‐based coating material was deposited via a developed dip coating method. The preparation of the composite membranes under various conditions were investigated. In the optimal coating procedure, homogenous and stable oligo‐PDMS^vi coating layers as thin as 1–2 μm were successfully deposited on the surface of PVDF membranes. The developed PDMS^vi–PVDF composite membranes were applied for separation of a wide variety of volatile organic compounds (benzene, chloroform, acetone, ethyl acetate, and toluene). The results showed that the PDMS^vi–PVDF hollow‐fiber composite membranes that had been developed exhibited very high removal efficiency (>96%) for all the VOCs examined under favorable operating conditions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effect of storage on film-formation property of vinylidene chloride-acrylonitrile-methyl acrylate terpolymer latex

Latex prepared from 91 : 5 : 4 wt % vinylidene chloride-acrylonitrile-methyl acrylate monomer mixture by seeded semicontinuous emulsion polymerization was investigated for a change in minimum film-formation temperature (MFFT) during storage, with focus placed on polymer crystallinity in the dispersed state. MFFT rose from 20°C to 32°C, with storage at 20°C for 49 weeks. Infrared absorption of fresh and stored latexes in the dispersed state indicated an increase in absorbance at 1048 cm⁻¹, which is characteristic of a crystalline vinylidene chloride polymer, that correlated with the MFFT rise with storage. This suggested that the MFFT rise with storage was caused by increasing crystallinity of the polymer in the dispersed state. X-ray wide-angle diffraction and infrared absorption of powder polymers obtained by lyophilization of fresh and stored latexes also indicated increasing crystallinity with latex storage. Oxygen gas permeabilities of films coated with fresh and stored latexes were measured. Latex stored for long periods exhibited poor barrier property, indicating that such latex is unsuitable as an industrial barrier coating material for films and papers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 573–579, 1998     

Effect of Casting Solution on Morphology and Performance of PVDF Microfiltration Membranes

The effects of preparation‐influencing parameters such as polymer concentration, thickness of casting solution, and type of solvent on morphology and performance of poly(vinylidene difluoride) (PVDF) microfiltration membranes for the treatment of emulsified oily wastewater were investigated. Flat‐sheet membranes were prepared from a casting solution of polymer and additive in various solvents by immersing the prepared films in nonsolvent‐containing mixtures of water and 2‐propanol. The membranes were characterized using scanning electron microscopy. Increasing the polymer concentration and membrane thickness significantly affected the pore size, leading to permeate flux decrease. An attempt was made to correlate the effect of the solvent on membrane morphology and performance employing solubility parameters between solvent and nonsolvent).     

Thermoresponsive surface prepared by atom transfer radical polymerization directly from poly(vinylidene fluoride) for control of cell adhesion and detachment

Thermoresponsive surface was prepared from commercial poly(vinylidene fluoride) (PVDF) films via surface‐initiated atom transfer radical polymerization. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the N‐isopropylacrylamide (NIPAAm) monomer. The PVDF surfaces grafted with poly(N‐isopropylacrylamide) [P(NIPAAm)] were characterized by X‐ray photoelectron spectroscopy. Kinetics study revealed that the P(NIPAAm) chain growth from the PVDF surface was consistent with a “controlled” process. The temperature‐dependent swelling behavior of the surfaces in aqueous solution was studied by atomic force microscope. At 37°C [above the lower critical solution temperature (LCST, about 32°C) of NIPAAm], the seeded cells adhered and spread on the NIPAAm grafted PVDF surface. Below the LCST, the cells detached from the P(NIPAAm)‐grafted PVDF surface spontaneously. The thermoresponsive surfaces are potentially useful as stimuli‐responsive adhesion modifiers in the biomedical fields.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

“Smart” membrane materials: Preparation and characterization of PVDF‐g‐PNIPAAm graft copolymer

In this research, a smart membrane material of graft copolymer of poly(vinylidene fluoride) with poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) was synthesized by atom transfer radical polymerization (ATRP) using poly(vinylidene fluoride) (PVDF) as a macroinitiator and direct initiation of the secondary fluorinated site PVDF facilitates grafting the N‐isopropylacrylamide comonomer. The copolymers were characterized by Fourier transform infrared (FTIR), ¹H NMR, gel‐permeation chromatography (GPC), and X‐ray photoelectron spectroscopy (XPS). The temperature‐sensitive membrane was prepared from the PVDF‐g‐PNIPAAm graft copolymers by the phase inversion method. The effects of temperature on the flux of pure water of membrane was investigated. The results showed that alkyl fluorides were successfully applied as ATRP initiators in the synthetic condition and the flux of pure water through the PVDF‐g‐PNIPAAm membrane depended on the temperature change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1482–1486, 2007     

Sulfonated polyether sulfone‐poly(vinylidene fluoride) blend membrane for DMFC applications

Direct methanol fuel cell (DMFC) proton exchange membranes were prepared by blending poly (vinylidene fluoride) (PVDF) with sulfonated poly(ether sulfone) (SPES). Using a diffusion cell and gas chromatographic technique, the effects of PVDF content on methanol permeability in the blended membranes were investigated. The thermal resistance and proton conductivity of the membranes were also determined by using a thermal gravimetric analysis (TGA) and an impedance analysis technique respectively. The presence of sulfonic acid groups in SPES was confirmed by Fourier transform infrared (FTIR). It was found that the methanol permeability in the blended membranes decreased with PVDF content at the expense of proton conductivity. Blended membranes show methanol permeability values much lower than that of Nafion 115, whereas the proton conductivities of the membranes are comparable with that of Nafion. The thermal stability of these blended membranes is above 250°C, which is sufficiently high for use in DMFC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Porous biodegradable polyesters. I. Preparation of porous poly(L‐lactide) films by extraction of poly(ethylene oxide) from their blends

Porous poly(L ‐lactide) (PLLA) films were prepared by water extraction of poly(ethylene oxide) (PEO) from solution‐cast PLLA and PEO blend films. The dependence of blend ratio and molecular weight of PEO on the porosity and pore size of films was investigated by gravimetry and scanning electron microscopy. The film porosity and extracted weight ratio were in good agreement with the expected for porous films prepared using PEO of low molecular weight (M_w = 1 × 10³), but shifted to lower values than expected when high molecular weight PEO (M_w = 1 × 10⁵) was utilized. The maximum pore size was larger for porous films prepared from PEO having higher molecular weight, when compared at the same blending ratio of PLLA and PEO before water extraction. Differential scanning calorimetry of as‐cast PLLA and PEO blend films revealed that PLLA and PEO were phase‐separated at least after solvent evaporation. On the other hand, comparison of blend films before and after extraction suggested that a small amount of PEO was trapped in the amorphous region between PLLA crystallites even after water extraction and hindered PLLA crystallization during solvent evaporation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 629–637, 2000     

In situ crosslinking of hyperbranched polyglycerol in casting solutions and its effect on the structure and properties of porous PVDF membranes

Porous membranes were prepared via phase inversion process from casting solutions composed of poly(vinylidene fluoride), hyperbranched polyglycerol (HPG), and N,N‐dimethylacetamide. To seek a stable presence of HPG in the resulting membranes, it was crosslinked in the casting solutions using 4,4′‐oxydiphthalic anhydride as the crosslinking agent. The membranes were characterized in terms of morphology, surface and bulk chemical compositions, water contact angle, porosity, water flux, and bovine serum albumin (BSA) adsorption experiments. The effects of HPG content and crosslinking degree on the membrane structure and properties were investigated. The increasing of crosslinking degree resulted in a significant improvement in HPG stability in the membrane matrix, and a remarkable enrichment of the crosslinked HPG at the separation surface was observed when the membrane was shaken in water at a relatively high temperature (60°C). This enrichment led to a decrease in the value of water contact angle and an improvement in fouling‐resistance. To optimize the membrane performance, a small amount of poly(vinylpyrrolidone) (PVP) was used as an additive, and it was found that the addition of PVP led to a considerable increase in water flux. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(lactic acid)-Based Film with Excellent Thermal Stability for High Energy Density Capacitor Applications

Dielectric capacitors play a key role in high power electronics, electric vehicles, and medical devices. Due to the biodegradability, high thermal stability, and ease of processing, poly(lactic acid)-based (PLA) films are widely used in applications of tissue engineering, actuators, and sensors. In this investigation, PLA films are prepared using a solution casting method for high energy density capacitor applications. It is found that the stretched poly(d -lactic acid) (PDLA) film exhibits an energy density and charge discharge efficiency of 18.5 J cm⁻³ and 95%, respectively, at room temperature. Furthermore, after a heating time of 30 min at 100 °C, it is found that the energy density and chargedischarge efficiency of the stretched PDLA films are maintained at 11.2 J cm⁻³ and 76%, respectively. In comparison, the energy density and efficiency of the stretched PDLA film are 1.03-fold and 53% higher, respectively, than those of the stretched poly(vinylidene fluoride-hexafluoropropylene) film at 100 °C with the same heat treatment. Compared with a high temperature polyimide material, the energy density of the stretched PDLA film is 1.98-fold higher at 100 °C. The PLA-based material shows great promise for application in high energy density capacitors operating at a high temperature (100 °C).     

EB‐crosslinked Polymer Electrolyte Membranes Based on Highly Sulfonated Poly(ether ether ketone) and Poly(vinylidene fluoride)/Triallyl Isocyanurate

In this study, crosslinked polymer electrolyte membranes for polymer electrolyte membrane fuel cell (PEMFC) applications are prepared using electron beam irradiation with a mixture of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and triallyl isocyanurate (TAIC) at a dose of 300 kGy. The gel‐fraction of the irradiated SPEEK/PVDF/TAIC (95/4.5/0.5) membrane is 87% while the unirradiated membrane completely dissolves in DMAc solvent. In addition, the water uptake of the irradiated membrane is 221% at 70 °C while that of the unirradiated membrane completely dissolves in water at above 70 °C. The ion exchange capacity and proton conductivity of the crosslinked membrane are 1.57 meq g⁻¹, and 4.0 × 10⁻² S cm⁻¹ (at 80 °C and RH 90%), respectively. Furthermore, a morphology study of the membranes is conducted using differential scanning calorimetry and X‐ray diffractometry. The cell performance study with the crosslinked membrane demonstrates that the maximum power density is 518 mW cm⁻² at 1036 mA cm⁻² and the maximum current density at applied voltage of 0.4 V is 1190 mA cm⁻².     

Proton exchange membranes based on poly(vinylidene fluoride) and sulfonated poly(ether ether ketone)

Blend membranes were obtained by solution casting from poly(vinylidene fluoride) (PVDF) and sulfonated poly(ether ether ketone) (SPEEK) in N,N-dimethylacetamide (DMAc). DSC and XRD were used to characterize the structure of the blend membranes. The effect of PVDF content on the membrane properties was investigated. The methanol permeability, water uptake and the swelling ratio of blend membranes decreased with the increase of PVDF content. Though the proton conductivity decreased upon the addition of PVDF, they were still comparable to that of Nafion^® 117 membrane. Higher selectivities were also found for most blend membranes in comparison with Nafion^® 117 membrane. The effect of methanol concentration on solution uptake, swelling ratio and methanol permeability of the blend membranes was also studied.     

PVDF/CB composites prepared by novel solvent casting method for low voltage PTC temperature regulation applications

A novel solvent casting preparation technique utilizing three variants of poly(vinylidene fluoride) (PVDF) to achieve a thermal cut off and a self regulation effect at a low applied voltage is reported in this study. The positive temperature coefficient (PTC) composites were prepared by dissolving PVDF in 1‐methyl‐2‐pyrrolidone (NMP) solvent, blending with Vulcan® XC72 carbon black (CB) filler, crosslinking with vinyl trimethoxysilane (VTMOS) and quenching in water. All composites displayed a highly macrovoidal structure that promoted a PTC effect when subjected to a thermal expansion effect via an electrical current. Subsequently the current was cut off and self regulation behavior was exhibited. Kynar® 761A PVDF resulted in the strongest PTC effect, and displayed temperature regulation at around 100°C which may be attributed to the highly semi crystalline nature and the larger molecular weight of this polymer in comparison with the other PVDF composites studied. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011