Poly(vinylidene fluoride)/poly(acrylonitrile) blend fibrous membranes by centrifugal spinning for high‐performance lithium ion battery separators

Fibrous membranes are promising as high‐performance lithium ion battery separators because of high porosity and superior electrolyte uptake. Electrospinning is a popular approach to produce fibrous membranes, but its production rate is very low. As a comparison, mass production of fibrous membranes can be achieved by centrifugal spinning. This study reports fibrous membranes based on poly(vinylidene fluoride)/poly(acrylonitrile) blends by centrifugal spinning and their application as lithium ion battery separators. The blend fibrous membranes have high electrolyte uptake of about 300%, excellent dimensional stability at 180 °C and good mechanical strength over 18 MPa. The coin cells with the blend fibrous membranes as separators show high discharge capacity of 147.7 mAh/g at 0.2 C and superior C‐rate performance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44515.     

Preparation and characterization of novel chitosan‐based mixed matrix membranes resistant in alkaline media

In this work, mixed matrix membranes (MMMs) based on chitosan (CS) and different fillers (room temperature ionic liquid [emim][OAc] (IL), metallic Sn powder, layered titanosilicate AM‐4 and layered stannosilicate UZAR‐S3) were prepared by solution casting. The room temperature electrical conductivity and electrochemical response in strong alkaline medium were measured by electrochemical impedance spectroscopy and cyclic voltammetry (CV). The ionic conductivity of pure CS membranes was enhanced, from 0.070 to 0.126 mS cm^?1, for the pristine CS and Sn/CS membranes, respectively, as a function of the hydrophilic nature of the membrane and the coordination state of Sn. This hydrophilic and charge nature was corroborated by water uptake measurements, where only the introduction of IL in the CS membrane led to a water uptake of 3.96 wt %, 20 or 30 times lower than the other membranes. Good thermal and chemical stability in alkaline media were observed by thermogravimetric analyses and X‐ray photoelectron spectroscopy analyses, respectively, and good interaction between CS and the fillers observed by X‐ray diffraction, scanning electron microscopy and CV. Thus, thin CS‐based MMMs (40–139 µm), resistant in high alkaline media, show higher conductivity than pure CS membranes, especially those fillers containing tin, and although the electrochemical performance is lower than commercially available anion‐exchange membranes they have potential in pervaporation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42240.     

Preparation of 4A zeolite coated polypropylene membrane for lithium-ion batteries separator

This study aims to improve wettability and thermal resistance of lithium-ion batteries separators. For this purpose, a commercial polypropylene (PP) separator was coated by 4A zeolite using poly(vinylidene fluoride) as binder and effects of the separators' zeolite content was investigated. All the coated separators showed lower contact angles, higher electrolyte uptakes, and less thermal shrinkages compared to the neat commercial separator. The coated PPA8 separator (zeolite to binder ratio of 8) showed the lowest wettability (contact angle of 0°) and electrolyte uptake (270%) due to its surface porosity resulting from the zeolite particles interstitial cavities as well as their internal cavities. Also, the PPA8 separator ion conductivity was found as 2.25 mS cm⁻¹ and C-rate and cycling performance of its assembled battery were higher compared to those of the commercial PP separator assembled battery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47841.     

Resin-silica composite nanoparticle grafted polyethylene membranes for lithium ion batteries

To avoid the peeling-off of ceramic nanoparticles (NPs) from polyolefin membranes usually occurred in commercially available ceramic NPs coated polyolefin separators for lithium batteries, we propose a simple one-pot in-situ reaction method to modify commercial polyethylene (PE) separators by surface grafting 3-Aminophenol/formaldehyde (AF)/silica (SiO₂) composite NPs. The AF/SiO₂ composite NPs form self-supporting connected pores on the modified layer of the separator surface, which ensures the transportation of Li⁺. Moreover, the PE@AF/SiO₂ separators has higher electrolyte wettability and compatibility than neat PE separators attributed to the plentiful polar functional groups in the AF/SiO₂ layer and AF/SiO₂ composite NPs, resulting in higher lithium ion transference number (= 0.62) and ionic conductivity (σ = 0.722 mS cm⁻¹). More importantly, the discharge capacity, capacity retention rate and coulombic efficiency (136.2 mA h g⁻¹, 87.9% and 99%, respectively) after 200 cycles of Li|NMC half batteries with PE@AF/SiO₂ separators, are all more excellent than that with the pure PE separator (125 mA h g⁻¹, 83.1% and 85%, respectively). Our results show that the PE@AF/SiO₂ separators obtained by this modification method have higher electrochemical stability in the lithium battery system.     

Highly selective sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene)/poly(ether sulfone) blend proton exchange membranes for direct methanol fuel cells

Proton exchange membranes (PEMs) based on blends of poly(ether sulfone) (PES) and sulfonated poly(vinylidene fluoride‐co‐hexafluoropropylene) (sPVdF‐co‐HFP) were prepared successfully. Fabricated blend membranes showed favorable PEM characteristics such as reduced methanol permeability, high selectivity, and improved mechanical integrity. Additionally, these membranes afford comparable proton conductivity, good oxidative stability, moderate ion exchange capacity, and reasonable water uptake. To appraise PEM performance, blend membranes were characterized using techniques such as Fourier transform infrared spectroscopy, AC impedance spectroscopy; atomic force microscopy, and thermogravimetry. Addition of hydrophobic PES confines the swelling of the PEM and increases the ultimate tensile strength of the membrane. Proton conductivities of the blend membranes are about 10^?3 S cm^?1. Methanol permeability of 1.22 × 10^?7cm² s^?1 exhibited by the sPVdF‐co‐HFP/PES10 blend membrane is much lower than that of Nafion‐117. AFM studies divulged that the sPVdF‐co‐HFP/PES blend membranes have nodule like structure, which confirms the presence of hydrophilic domain. The observed results demonstrated that the sPVdF‐co‐HFP/PES blend membranes have promise for possible usage as a PEM in direct methanol fuel cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43907.     

Preparation and characterization of antifouling poly(vinylidene fluoride) blended membranes

Poly(vinylidene fluoride) (PVDF) membranes have been widely used in microfiltration and ultrafiltration because of their excellent chemical resistance and thermal properties. However, PVDF membranes have exhibited severe membrane fouling because of their hydrophobic properties. In this study, we investigated the antifouling properties of PVDF blended membranes. Antifouling PVDF blended membranes were prepared with a PVDF‐g‐poly(ethylene glycol) methyl ether methacrylate (POEM) graft copolymer. The PVDF‐g‐POEM graft copolymer was synthesized by the atom transfer radical polymerization (ATRP) method. The chemical structure and properties of the synthesized PVDF‐g‐POEM graft copolymer were determined by NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. To investigate the antifouling properties of the membranes, we prepared microfiltration membranes by using the phase‐inversion method, which uses various PVDF/PVDF‐g‐POEM concentrations in dope solutions. The pure water permeabilities were obtained at various pressures. The PVDF/PVDF‐g‐POEM blended membranes exhibited no irreversible fouling in the dead‐end filtration of foulants, including bovine serum albumin, sodium alginate, and Escherichia coli broth. However, the hydrophobic PVDF membrane exhibited severe fouling in comparison with the PVDF/PVDF‐g‐POEM blended membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and performance of aramid nanofiber membrane for separator of lithium ion battery

Stable and uniform dispersions of para‐aramid nanofibers have been prepared by adding methoxypolyethylene glycol (mPEG) in the polymerization process, followed by strong shear and dispersion. Aramid membranes are fabricated by vacuum‐assisted filtration of the nanofiber dispersion and assembled into batteries as separator. The membrane properties and battery performances are characterized in detail and the effect of mPEG content on these properties is explored. It is demonstrated that aramid membranes possess good electrolyte wettability, excellent mechanical properties, and superior thermal stability, which improve the safety of lithium ion batteries. The mPEG is critical to the formation of aramid nanofibers and improves the porosity and ionic conductivity of the membranes. These fascinating characteristics and facile papermaking method endow aramid membrane potential application as separator in lithium ion batteries with superior safety. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43623.     

Preparation of poly(vinylidene fluoride)/poly(methyl methacrylate) membranes by novel electrospinning system for lithium ion batteries

Fibrous membranes of poly(vinylidene fluoride)/poly(methyl methacrylate) (PVdF/PMMA) were fabricated by electrospinning method with different concentrations of polymer solution: 14, 16, and 18 wt %. The morphology of the electrospun membranes was observed by scanning electron microscopy. The images revealed that the nanofibers showed uniform diameter and no bead formation was observed with the concentration of 16 wt %. Also, the structure, crystallinity, ionic conduction, and electrochemical stability of the electrospun membranes were characterized. The results suggested that electrolyte uptake, ionic conduction, and electrochemical stability were improved by the addition of PMMA. Furthermore, with the 16 wt % concentration of the polymer solution, the membrane showed a high ionic conductivity of 3.5 mS cm^?1 at room temperature and electrochemical stability of up to 5.1 V. We predicted that this new method may be very promising for preparing microporous PVdF/PMMA polymer electrolytes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Preparation and characterization of mixed matrix membranes based on poly(vinylidene fluoride) and zeolite 4A for gas separation

Zeolite 4A was incorporated into poly(vinylidene fluoride) (PVDF) matrix to prepare mixed matrix membranes (MMMs). The objective of this study was to investigate the effects of the inorganic filler on the structural properties of the MMMs. The resulting membranes were characterized using thermogravimetric analysis, differential scanning calorimetry, X‐ray diffraction, contact angle tests, and scanning electron microscopy (SEM). The mechanical properties of the membranes were determined using a tensile stress–strain machine. To fully study the interface properties between the inorganic fillers and polymer chains, the densities of the membranes were experimentally determined and compared with the theoretical values. The experimental densities of the composite membranes were lower than those of the theoretical values. The void volume fractions were calculated accordingly. The single gas (He, CO₂, O₂, and N₂) permeabilities of the resulting membranes were carried out. The highest permeabilities of 14.65, 6.62, 1.01, and 0.3 Barrer for He, CO₂, O₂, and N₂, respectively, were obtained by PVDF/4A 32% composite membrane; whereas the highest selectivities of 105.5, 31.5, and 3.3 for He/N₂, CO₂/N₂, and O₂/N₂, respectively, were obtained using PVDF/4A 16% composite membrane. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Branched poly(biphenylene-co-sulfone)ether ion exchange membranes containing perfluorocyclobutane groups for fuel cell applications

A series of branched poly(biphenylene-co-sulfone) ion exchange membranes containing perfluorocyclobutane groups were prepared for fuel cells. Two bifunctional trifluorovinyloxy-terminated monomers (sulfonable 4,4′-bis(trifluorovinyloxy)biphenyl and insulfonable 4,4′-sulfonyl-bis(trifluorovinyloxy)biphenyl) and a trifunctional trifluorovinyloxy-terminated branching agent (1,1,1-tris(4′-trifluorovinyloxyphenyl)ethane) were synthesized and terpolymerized via thermal [2π + 2π] cyclodimerization to obtain partially fluorinated and branched polymers containing 0–5 mol% of the branching agent. They were then postsulfonated by chlorosulfonic acid at room temperature, cast as membranes, and characterized to evaluate their electrochemical properties for fuel cell applications. As the branching agent content was increased, their polydispersity values highly increased, indicating they became highly branched. It was confirmed that higher branching agent content also increased the ion exchange capacity, water uptake, and proton conductivity of the branched ion exchange membranes containing perfluorocyclobutane groups. This indicates that their electrochemical properties can be easily controlled by the degree of branching. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48373.     

The influence of poly(3,4-ethylenedioxythiophene) modification on the transport properties and fuel cell performance of Nafion-117 membranes

Nafion-117/PEDOT composite membranes were synthesized by in situ chemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using ammonium persulfate as an oxidant. The polymerization of EDOT in Nafion membranes for various EDOT/oxidant treatment sequences was studied for the first time. PEDOT introduction leads to a slight decrease in both the ion-exchange capacity and water uptake of the composite membranes, as well as to an increase in cationic transport. Membranes initially treated with an oxidant exhibit better conductivity and lower hydrogen permeability. The effect of both modification of Nafion-117 membranes by PEDOT and hot-pressing of hydrogen-oxygen membrane-electrode assemblies (MEAs) on the performance of proton-exchange membrane fuel cells was studied. The maximum power density of the fabricated MEAs increases 1.5-fold: from 510 (for a pristine Nafion-117 membrane) to 810 mW cm⁻² (for a membrane modified by PEDOT). The current density at a voltage of 0.4 V reaches 1248 and 2246 mA cm⁻², respectively.     

Preparation and properties of gel‐filled PVDF separators for lithium ion cells

Polyether gel‐filled poly(vinylidene fluoride) separators (GF‐PVDF separators) were prepared by means of thermal crosslinking of poly(ethylene glycol) methyl ether acrylate (PEGMEA) and poly(ethylene glycol) diacrylate (PEGDA) as gel constituents. The intrinsic properties of GF‐PVDF and their corresponding gel polymer electrolyte (GPE) were characterized by SEM, DSC, and electrochemical methods. It was found a relatively better GPE could be got when the filled polyether content no more than 60 wt % and its ion conductivity could reach 1.3 × 10^?3 S cm^?1. The GPE is compatible with anode and cathode of lithium ion battery at high voltage and its electrochemical window is 4.6 V (vs. Li/Li⁺). The coulombic efficiency could reach 94% after 100 cycles for the cells using such GPE. The results reveal that the composite polymer electrolyte qualifies as a potential application in lithium cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44473.     

Preparation and properties of hydrophobic poly(vinylidene fluoride)–SiO2 mixed matrix membranes for dissolved oxygen removal from water

The application of the membrane method for removing dissolved oxygen (DO) from water on the laboratory scale was studied. Flat mixed matrix membranes were composed of poly(vinylidene fluoride) (PVDF) and hydrophobic nanosilica particles, which were used to improve the DO removal process. The SiO₂ particles were modified by a silane coupling agent and examined by Fourier transform infrared spectroscopy. It was shown that the surface of the SiO₂ particles was bonded to hydrophobic long‐chain alkane groups through chemical bonding. The effects of adding SiO₂ particles on the membrane properties and morphology were examined. The results show that the porosity and pore size of the membrane were affected by the introduction of SiO₂ particles, and the cross‐sectional morphology of the PVDF composite membranes changed from fingerlike macrovoids to a spongelike structure. The membrane performance of DO removal was evaluated through the membrane unit by a vacuum degassing process. It was found that the SiO₂/PVDF hybrid membranes effectively improved the oxygen removal efficiency compared with the original PVDF membranes. The maximum permeation flux was obtained when the loading amount was 2.5 wt %. The effect of the downstream vacuum level was also investigated. The experimental results show that the SiO₂/PVDF hybrid membranes had superior performances and could be an alternative membrane for removing DO from water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40430.     

Preparation and characterization of porous poly(vinylidene fluoride) membranes for dehumidification with poly(ethylene glycol) as an additive

Porous poly(vinylidene fluoride) (PVDF) membranes for dehumidification were prepared from a PVDF/dimethylformamide/water system by phase inversion with poly(ethylene glycol) (PEG) as an additive at various concentrations (1.2, 1.8, and 2.4%) and with various molecular weights (1000, 2000, and 6000). The surface morphologies of the resultant membranes were characterized with scanning electron microscopy and atomic force microscopy, and the pore diameter, porosity, and pore size distribution of the membranes were also determined by a gas‐sorption method. The influence of the concentration and molecular weight of PEG on water‐vapor transport through the membranes was evaluated. The moisture‐transport property of the membranes was improved significantly with increases in the concentration and molecular weight of PEG, and a membrane with good moisture permeability was obtained with 2.4% PEG‐6000 as an additive. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrochemical performance and thermal stability of the electrospun PTFE nanofiber separator for lithium‐ion batteries

Separator is a very important set of lithium‐ion batteries. At present, low porosity and poor thermal stability are two major disadvantages of separator. In this work, we first apply electrospinning method to prepare the Polytetrafluoroethylene (PTFE) nanofiber separator, which has the advantages of electrospinning method and PTFE materials. The effect of the PTFE nanofiber separator is investigated by scanning electron microscope, Capillary Flow Porometer, thermogravimetric–differential scanning calorimeter, linear sweep voltammeter, AC impedance, and charge/discharge cycling tests. The results demonstrate that the PTFE nanofiber separator has a special fiber structure made from PTFE particles gathering one by one along the fibers. Moreover, the PTFE nanofiber separator exhibits several advantages, including suitable pore diameter, uniform pore size distribution, high porosity, and electrolyte uptake, which enhance the ionic conductivity. The thermal stability of the PTFE nanofiber separator is much better than that of the conventional polyolefin separator. The Li/LiCoO₂ cell equipped with PTFE nanofiber separator exhibits excellent rate performance and first charge–discharge specific capacity of 142 and 131 mA h g^?1, respectively, accompanied by relatively stable cycle performance at 0.2 C rate. It is supposed to be a candidate for application in lithium‐ion batteries. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46508.     

动力锂离子二次电池聚偏氟乙烯隔膜的制备及性能表征

采用浸没沉淀相转化法,以聚酯(PET)无纺布为底膜,在其上涂覆聚偏氟乙烯(PVDF)制备复合隔膜,应用于动力锂离子二次电池隔膜。将制备的复合隔膜与Celgard隔膜进行了孔结构分析、电化学性质、热性能等理化性质及电池性能检测对比。结果显示,复合隔膜孔径尺寸较大且分布均一,孔隙率达到48.5%,可以承受250.8℃的高温,离子电导率达0.346 mS·cm^-1,使用该隔膜的锂离子电池具有很好的倍率特性,初次放电容量达48.7 mA·h,循环100次后仍保持77.9%的容量,其性能与市售Celgard隔膜基本相当,能满足实际应用的要求。     

Imidazole/(HPO3)3‐doped sulfonated poly (ether ether ketone) composite membrane for fuel cells

A novel gel of imidazole/(HPO₃)₃ was synthesized and incorporated into sulfonated poly (ether ether ketone) (SPEEK) to fabricate composite proton exchange membranes. The composite membranes were characterized by alternating current impedance (AC), thermogravimetry (TG), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), scanning electron microscope (SEM) and mechanical property test. Based on the electrochemical performance investigation, the proton conductivity of the membrane is intimately correlated with the temperature and the mass ratio of imidazole/(HPO₃)₃ in the composite. The SPEEK/imidazole/(HPO₃)₃?4 composite membrane (with 44.4 wt % of imidazole/(HPO₃)₃) has the optimized performance at 135°C. Mover, the strength of the composite membranes is almost comparable to that of Nafion membrane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41946.     

Preparation and characterization of novel poly(vinylidene fluoride) membranes using self-assembled dibenzylidene sorbitol for membrane distillation

We proposed a method for the preparation of novel poly(vinylidene fluoride) (PVDF) membranes with self-assembled 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS). The vapor-induced phase separation (VIPS) method with a dry/wet process was used to produce DMDBS/PVDF composite membranes. The resulting membranes exhibited the coexistence of PVDF cellular pores and crystalline particles. The DMDBS molecules self-assembled into nanofibril structures, and a large number of nanofibrils were found on the surfaces and in the cross-sections of the prepared membranes. The DMDBS nanofibril networks in the PVDF matrix acted as reinforcing materials that enhance the hardness and stiffness of the membranes. Moreover, because of the entangled DMDBS networks, a greater strain was required to induce sample failure; therefore, the ductility of the membranes increased with increasing amounts of DMDBS. In addition, in a membrane distillation process, our composite membranes exhibited a good permeate flux that was comparable to that of commercial PVDF membranes.     

Fabrication of poly(vinylidene fluoride)-based composite powder coating with enhanced adhesion performance

Given the environmental benefits, poly(vinylidene fluoride) (PVDF)-based composite powder coating was developed without using any harmful solvent. However, it still remains poor adhesion to substrates and low compatibility to acrylic resin issues. To address these challenges, PVDF was grafted with glycidyl methacrylate (GMA) through a facile and scalable reactive extrusion method. The resulting product, PVDF-g-GMA, was then mixed with different contents of polymethyl methacrylate (PMMA), and the mixing was sprayed onto aluminum substrates. The PVDF-g-GMA/PMMA powder coating shows the excellent adhesion and corrosion resistance, particularly when the PMMA content is 30 wt%, owning to the good compatibility of PVDF-g-GMA and PMMA. This work opens up a new possibilities for the development of advanced composite powder coatings with improved performance characteristics.     

Surface modification of polyamide and poly(vinylidene fluoride) membranes

Experimental results from the gas‐plasma treatment and electron‐beam irradiation of polyamide (PA) and poly(vinylidene fluoride) (PVDF) membranes to improve their wettability and to evaluate protein adsorption at their surface are presented. The wettability of the membrane surface was determined by contact angle measurements; the analysis of the surface composition was performed by X‐ray photoelectron spectroscopy (XPS). We observed that a reduction in the water contact angle was not always indicative of a reduction in the protein adsorption and, furthermore, that a charge at the surface of the modified membrane seemed to be a major factor in the protein adsorption process. Furthermore, the XPS results shed some light on the modification mechanism of PVDF and PA by electron‐beam irradiation. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013