Nanocomposite polymer electrolytes for solid-state lithium-ion batteries with enhanced electrochemical properties

Solid-state polymer electrolytes (SPEs) have attracted significant attention owing to their improvement in high energy density and high safety performance. However, the low lithium-ion conductivity of SPEs at room temperature restricts their further application in lithium-ion batteries (LIBs). Herein, we propose a novel poly (ethylene oxide) (PEO)-based nanocomposite polymer electrolytes by blending boron-containing nanoparticles (BNs) in the PEO matrix (abbreviated as: PEO/BNs NPEs). The boron atom of BNs is sp²-hybridized and contains an empty p-orbital that can interact with the anion of lithium salt, promoting the dissociation of the lithium salts. In addition, the introduction of the BNs could reduce the crystallinity of PEO. And thus, the ionic conductivity of PEO/BNs NPEs could reach as high as 1.19 × 10⁻³ S cm⁻¹ at 60°C. Compared to the pure PEO solid polymer electrolyte (PEO SPEs), the PEO/BNs NPEs showed a wider electrochemical window (5.5 V) and larger lithium-ion migration number (0.43). In addition, the cells assembled with PEO/BNs NPEs exhibited good cycle performance with an initial discharge capacity of 142.5 mA h g⁻¹ and capacity retention of 87.7% after 200 cycles at 2 C (60°C).     

Novel PEO-based solid composite polymer electrolytes with inorganic–organic hybrid polyphosphazene microspheres as fillers

Novel solid-state composite polymer electrolytes based on poly (ethylene oxide) (PEO) by using LiClO₄ as doping salts and inorganic–organic hybrid poly (cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres as fillers were prepared. Electrochemical and thermal properties of PEO-based polymer electrolytes incorporated with PZS microspheres were studied. Differential scanning calorimetry (DSC) results showed there was a decrease in the glass transition temperature of the electrolytes and the crystallinity of the samples in the presence of the fillers. Maximum ionic conductivity values of 1.2 × 10⁻⁵ S cm⁻¹ at ambient temperature and 7.5 × 10⁻⁴ S cm⁻¹ at 80° were obtained and lithium ion transference number was 0.29. Compared with traditional ceramic fillers such as SiO₂, the addition of PZS microspheres increased the ionic conductivity of the electrolytes slightly and led to remarkable enhancement in the lithium ion transference number.     

Li‐ion conductivity in PEO‐graphene oxide nanocomposite polymer electrolytes: A study on effect of the counter anion

Graphene oxide (GO) has been prepared by modified Hummer's method for their incorporation as nanofiller in designing nanocomposite polymer electrolytes (NCPEs). Prior to use the GO nanofillers has been characterized by TEM, FTIR, and Raman studies to elucidate their nanostructure, functionality, and purity. The various poly(ethylene oxide) (PEO)‐based NCPEs has been prepared by incorporating GO nanofillers in presence of three different lithium salts, viz., CF₃SO₃Li, LiTFSI, and LiNO₃ as the source of Li‐ions and then casted into free standing polymeric films. The change in PEO crystallinity has been studied considering their full width half maximum values of respective diffraction peaks in the XRD spectra. The Li‐ion conductivity of various NCPEs has been studied from impedance spectroscopy. All the NCPE films show optimum value of Li‐ion conductivity with 0.3% GO nanofiller content irrespective of the source of Li‐ions used. But, variation of the Li‐ion conductivity values is occurred for all the three studied lithium salts. Both LiTFSI and LiNO₃ salts display Li‐ion conductivity in the order of 10^?4 S cm^?1 whereas CF₃SO₃Li in the order of 10^?6 S cm^?1, all in presence of 0.3% GO nanofillers. The change in conductivity values of the NCPEs has been explained by correlating with Argand plots and also with change in PEO crystallinity, which occurs due to various relaxation processes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46336.     

Synthesis and properties of unsaturated polyoxyethylene and its graft copolymers with styrene

The unsaturated polyoxyethylene (PEO) was synthesized by copolymerization of ethylene oxide with allyl glycidyl ether in toluene using bimetallic-oxo-alkoxide as a catalyst. The effects of polymerization conditions on conversion and intrinsic viscosity of the copolymer were studied. The unsaturated copolymer was characterized with infrared spectra, ¹H NMR, and wide-angle X-ray diffraction. The relationship between crystallinity of the copolymers and conductivity of their LiClO₄ complexes were investigated. The copolymer with ∼ 65 wt % PEO content exhibits a room temperature conductivity of 1 × 10⁻⁴ S cm⁻¹ at a molar ratio of EO/Li = 20. The unsaturated PEO was graft-copolymerized with styrene using 2,2′-azobis(isobutyronitrile) as initiator in toluene, with grafting efficiency ∼ 50%. The purified graft copolymer was characterized with infrared spectra, ¹H NMR, and wide-angle X-ray diffraction, and was shown to have good emulsifying properties and a phase-transfer catalytic property. LiClO₄ complex of the graft copolymer with 70 wt % PEO content exhibits a room temperature conductivity approaching 1 × 10⁻⁴ S cm⁻¹ at molar ratio of EO/Li = 20/1. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2417–2425, 1998     

Composite polymer electrolyte incorporating WO3 nanofillers with enhanced performance for dendrite-free solid-state lithium battery

All solid-state lithium batteries (ASS-LBs) with polymer-based solid electrolytes are a prospective contender for the next-generation batteries because of their high energy density, flexibility, and safety. Among all-polymer electrolytes, PEO-based solid polymer electrolytes received huge consideration as they can dissolve various Li salts. However, the development of an ideal PEO-based solid polymer electrolyte is hindered by its insufficient tensile strength and lower ionic conductivity due to its semi-crystalline and soft chain structure. In order to lower the crystallization and improve the performance of PEO-based solid polymer electrolyte, tungsten trioxide (WO₃) nanofillers were introduced into PEO matrix. Herein, a PEO₂₀/LiTFSI/x-WO₃ (PELI-xW) (x = 0%, 2.5%, 5%, 10%) solid composite polymer electrolyte was prepared by the tape casting method. The solid composite polymer electrolyte containing 5 wt% WO₃ nanofillers achieved the highest ionic conductivity of 7.4 × 10^-4 S cm^-1 at 60 °C. It also confirms a higher Li-ion transference number of 0.42, good electrochemical stability of 4.3V, and higher tensile strength than a PEO/LiTFSI (PELI-0W) fillers-free electrolyte. Meanwhile, the LiFePO₄│PELI-xW│Li ASS-LBs demonstrated high performance and cyclability. Based on these findings, it can be considered a feasible strategy for the construction of efficient and flexible PEO-based solid polymer electrolytes for next-generation solid-state batteries.     

Preparation and application of poly(ethylene oxide)-based all solid-state electrolyte with a walnut-like SiO2 as nano-fillers

Poly(ethylene oxide) (PEO) is one of the most promising candidates in polymer solid-state electrolyte. However, the polymer matrix has a high degree of crystallinity and thus manifests low conductivity, which restricts its application in all solid-state lithium-ion battery. Herein, a new composite polymer electrolyte (PLWLS), which is comprised of PEO, LiClO₄, and the independently synthetized walnut-like SiO₂ (WLS) as nano-fillers, is designed and prepared by the tape-casting way. The optimum mass fraction of walnut-like SiO₂ is determined by physical and electrochemical characterization. The result shows that the PLWLS-15 with 15 wt % walnut-like SiO₂ nanoparticles has a crystallinity of 13.7%. Similarly, the maximum tensile strength is improved greatly. The assembled all-solid-state lithium-ion battery with LiFePO₄/PLWLS-15/Li exhibits a higher discharge capacity of 167 mAh g⁻¹ at 0.1 C (1C = 170 mAh g⁻¹) and 143 mAh g⁻¹ at 0.5 C in first cycle, lower voltage polarization and better cycle performance. Therefore, adding nanoparticle into PEO-based solid-state electrolyte could effectively promote the mechanical property and electrochemical performance, and thus provide a possibility of application for PLWLS-15 in next generation all solid-state lithium battery. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48810.     

Effects of burial powder configuration on the microstructure,composition, and ion conductivity of perovskite Li3xLa1/3-xTaO3 ion conductors

A combustion synthesis methodology for the preparation of perovskite Li_3xLa_1/3-xTaO₃ lithium-ion conductors with x = 0.033 is presented. Bulk ceramic specimens were sintered under combinations of burial powder and cover crucibles to provide different lithium vapor overpressure conditions. A maximum total lithium ion conductivity of 6 × 10^-6 S cm^-1 at room temperature was found for the pellet covered by a crucible whose lip was sealed using parent powder (moderate overpressure), with agreement to the maximum in the intergranular ion conductivity. Intragranular conductivity was maximized at the low overpressure condition. The trend in ion conductivity was found to correspond to the lithium content in the samples through a combination nuclear reaction analysis and energy dispersive X-ray spectroscopy phase constitution measurements. The mechanism impacting ion conductivity was determined to be changes in the amount of LaTaO₄ secondary phase as driven by the processing conditions during sintering.     

Hyperbranched Poly(Glycidol)-Grafted Silica Nanoparticles for Enhancing Li-Ion Conductivity of Poly(Ethylene Oxide)

Silica nanoparticles bearing hyperbranched polyglycidol (hbP) grafts are synthesized and blended with poly(ethylene oxide) (PEO) for the fabrication of composite solid polymer electrolytes (SPEs) for enhancing Li-ion conductivity. Different batches of hbPs are prepared, namely, the 5th, 6th, and 7th with increasing molecular weights using cationic ring-opening polymerization and grafted the hbPs onto the silica nanoparticles using quaternization reaction. The effect of end functionalization of hbP-grafted silica nanoparticles with a nitrile functional group (CN–hbP–SiO₂) on the ionic conductivity of the blends with PEO is further studied. High dipole moments indicate polar nature of nitriles and show high dielectric constants. Among all the hbPs, the 6th-batch CN–hbP–SiO₂ nanoparticles exhibit better ionic conductivity on blending with PEO showing ionic conductivity of 2.3 × 10⁻³ S cm⁻¹ at 80 °C. The blends show electrochemical stability up to 4.5 V versus lithium metal.     

Novel composite polymer electrolyte comprising poly(ethylene oxide) and triblock copolymer/mesostructured silica hybrid used for lithium polymer battery

Ordered mesoporous materials, due to its potential applications in catalysis, separation technologies, and nano-science have attracted much attention in the past few years. In this work, a novel PEO-based composite polymer electrolyte by using organic-inorganic hybrid EO₂₀PO₇₀EO₂₀ @ mesoporous silica (P123 @ SBA-15) as the filler has been developed. The interactions between P123 @ SBA-15 hybrid and PEO chains are studied by X-ray diffraction (XRD), differential scanning calorimeter (DSC), and FT-IR techniques. The effects of P123 @ SBA-15 on the electrochemical properties of the PEO-based electrolyte, such as ionic conductivity, lithium ion transference number are studied by electrochemical ac impedance spectroscopy and steady-state current method. The experiment results show that P123 @ SBA-15 can enhance the ionic conductivity and increase the lithium ion transference number of PEO-based electrolyte, which are induced by the special topology structure of P123 in P123 @ SBA-15 hybrid, at the same time. The excellent lithium transport properties and broad electrochemical stability window suggesting that PEO-LiClO₄/P123 @ SBA-15 composite polymer electrolyte can be used as candidate electrolyte materials for lithium polymer batteries.     

Fabrication and characterization of PEO/PPC polymer electrolyte for lithium‐ion battery

A new poly(propylene carbonate)/poly(ethylene oxide) (PEO/PPC) polymer electrolytes (PEs) have been developed by solution‐casting technique using biodegradable PPC and PEO. The morphology, structure, and thermal properties of the PEO/PPC polymer electrolytes were investigated by scanning electron microscopy, X‐ray diffraction, and differential scanning calorimetry methods. The ionic conductivity and the electrochemical stability window of the PEO/PPC polymer electrolytes were also measured. The results showed that the T_g and the crystallinity of PEO decrease, and consequently, the ionic conductivity increases because of the addition of amorphous PPC. The PEO/50%PPC/10%LiClO₄ polymer electrolyte possesses good properties such as 6.83 × 10^?5 S cm^?1 of ionic conductivity at room temperature and 4.5 V of the electrochemical stability window. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication and properties of crosslinked poly(propylene carbonate maleate) gel polymer electrolyte for lithium‐ion battery

The poly(propylene carbonate maleate) (PPCMA) was synthesized by the terpolymerization of carbon dioxide, propylene oxide, and maleic anhydride. The PPCMA polymer can be readily crosslinked using dicumyl peroxide (DCP) as crosslinking agent and then actived by absorbing liquid electrolyte to fabricate a novel PPCMA gel polymer electrolyte for lithium‐ion battery. The thermal performance, electrolyte uptake, swelling ratio, ionic conductivity, and lithium ion transference number of the crosslinked PPCMA were then investigated. The results show that the T_g and the thermal stability increase, but the absorbing and swelling rates decrease with increasing DCP amount. The ionic conductivity of the PPCMA gel polymer electrolyte firstly increases and then decreases with increasing DCP ratio. The ionic conductivity of the PPCMA gel polymer electrolyte with 1.2 wt % of DCP reaches the maximum value of 8.43 × 10⁻³ S cm⁻¹ at room temperature and 1.42 × 10⁻² S cm⁻¹ at 50°C. The lithium ion transference number of PPCMA gel polymer electrolyte is 0.42. The charge/discharge tests of the Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3O₂ cell were evaluated at a current rate of 0.1C and in voltage range of 2.8–4.2 V at room temperature. The results show that the initial discharge capacity of Li/PPCMA GPE/LiNi_1/3Co_1/3Mn_1/3 O₂ cell is 115.3 mAh g⁻¹. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An investigation of lithium ion conductivity of copolymers based on P(AMPS-co-PEGMA)

In this work, a series of novel lithium ion-conducting copolymer electrolytes based on 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) and poly(ethyleneglycol) methacrylate (PEGMA) were produced and characterized. The copolymers were synthesized by free-radical polymerization of the corresponding monomers with three different feed ratios to form P(AMPS-co-PEGMA)-based electrolytes. After the polymerization, AMPS units of the copolymers were lithiated via ion exchange. The characterization of the electrolytes was done by ¹H-NMR, FTIR, differential scanning calorimetry (DSC), thermogravimetric analysis, X-ray diffraction, scanning electron microscopy (SEM), and impedance analyzer. The copolymers were thermal stable approximately to 200 °C. Single T_g transitions in DSC curves verified the homogeneity as well as amorphous characteristics. SEM further confirmed the homogeneity of the electrolytes. The lithium ion conductivity of these new polymer electrolytes was studied by impedance dielectric impedance analyzer and the effect of PEGMA contents onto the ionic conductivity of these copolymer electrolytes were investigated. It was observed that the temperature dependence of ionic conductivity was interpreted over Vogel Tammann Fulcher model. The Li ion conductivity increased by PEGMA content and S3 has maximum conductivity of 3 × 10⁻³ mS cm⁻¹ at 100 °C. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47798.     

Crystallinity,ion conductivity,and thermal and mechanical properties of poly(ethylene oxide)–illite nanocomposites with exfoliated illite as a filler

Illite particles were exfoliated by the intercalation and subsequent deintercalation of dimethyl sulfoxide (DMSO) in the interlayer of illite, and the exfoliated illite particles were used to prepare a novel poly(ethylene oxide) (PEO)–illite nanocomposite. The resulting exfoliated illite and PEO–illite nanocomposites were characterized by X‐ray diffraction (XRD), fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry, ion conductivity testing, thermogravimetry analysis, and mechanical testing. The XRD results showed that the acid treatment of illite to exchange K⁺ in the interlayer of illite with H⁺ was a necessary condition for the DMSO intercalation. SEM micrographs confirmed the exfoliation of the illite particles in the process of DMSO deintercalation from the interlayer of the illite–DMSO intercalation complex. A good dispersion of exfoliated illite in the PEO matrix was also confirmed. A gradual decrease in the PEO crystallinity in the PEO–illite nanocomposites was observed with increasing exfoliated illite concentration. The ion conductivity of the nanocomposites gradually increased with the filler content and reached 3.21 × 10⁻⁵ S/cm at an illite concentration of 20 wt %. The formation of an amorphous region around the exfoliated illite was beneficial for Li⁺‐ion conduction. The ion conductivity significantly increased when the amorphous regions were connected to each other to form a conducting path for Li⁺ ions with a high filler concentration of greater than 10 wt %. Meanwhile, the thermooxidative stability and mechanical properties of the PEO–illite nanocomposites were also enhanced when exfoliated illite was introduced into the polymer matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44226.     

Influence of molar mass on the thermal properties,conductivity and intermolecular interaction of poly(ethylene oxide) solid polymer electrolytes

The sample preparation pathway of solid polymer electrolytes (SPEs ) influences their thermal properties, which in turn governs the ionic conductivity of the materials especially for systems consisting of a crystallizable constituent. Majority of poly(ethylene oxide) (PEO)‐based SPEs with molar masses of PEO well above 10⁴ g mol^?1 (where PEO is crystallizable and should reach an asymptote in thermal behaviour) display molar mass dependence of the thermal properties and ionic conductivities in non‐equilibrium conditions, as reported in the literature. In this study, PEO of different viscosity‐molar masses (M _η = 3 × 10⁵, 6 × 10⁵, 1 × 10⁶, 4 × 10⁶ g mol^?1) and LiClO₄ salt (0 to 16.7 wt%) were used. The SPEs were thermally treated under inert atmosphere above the melting temperature of PEO and then cooled down for subsequent isothermal crystallization for sufficient experimental time to develop morphology close to equilibrium conditions. The thermal properties (e.g. glass transition temperature, melting temperature, crystallinity) according to differential scanning calorimetry and the ionic conductivity obtained from impedance spectroscopy at room temperature (σ _DC ～ 10^?6 S cm^?1) demonstrate insignificant variation with respect to the molar mass of PEO at constant salt concentration. These findings are in agreement with the PEO crystalline structures using X‐ray diffraction and ion ? dipole interaction by Fourier transform infrared results. © 2017 Society of Chemical Industry     

Lithium ionic conductivity in poly(ether urethanes) derived from poly(ethylene glycol) and lysine ethyl ester

Poly(ether urethanes) obtained by the copolymerization of poly(ethylene glycol) (PEG) and lysine ethyl ester (LysOEt) are elastomeric materials that can be processed readily to form flexible, soft films. In view of these desirable physicomechanical properties, the potential use of these new materials as solid polymer electrolytes was explored. Solid polymer electrolytes were prepared with copolymers containing PEG blocks of different lengths and with different concentrations of lithium triflate (LiCF₃SO₃). Correlations between the length of the PEG block, the concentration of lithium triflate in the formulation, and the observed Li⁺ ion conductivity were investigated. Solid electrolyte formulations were characterized by differential scanning calorimetry for glass transition temperatures (T_g), melting points (T_m), and crystallinity. Ionic conductivity measurements were carried out on thin films of the polymer electrolytes that had been cast on a microelectrode assembly using conventional ac-impedance spectroscopy. These polymer electrolytes showed inherently high ionic conductivity at room temperature. The optimum concentration of lithium triflate was about 25–30% (w/w), resulting at room temperature in an ionic conductivity of about 10⁻⁵ S cm⁻¹. For poly(PEG₂₀₀₀-LysOEt) containing 30% of LiCF₃SO₃, the activation energy was ∼ 1.1 eV. Our results indicate that block copolymers of PEG and lysine ethyl ester are promising candidates for the development of polymeric, solvent-free electrolytes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1449–1456, 1997     

Gas permeation properties of a composite membrane filled with poly(ethylene oxide) into a porous membrane

The permeability coefficients of O₂, N₂, and CO₂ gases at 25°C were examined for composite membranes that were prepared by filling poly(ethylene oxide)(PEO) with different molecular weights into a porous membrane. The permeability coefficients of O₂, N₂, and CO₂ were 2 × 10⁻¹⁰ – 4 × 10⁻¹⁰, 5 × 10⁻¹¹ – 9.5 × 10⁻¹¹, and 6 × 10⁻¹⁰ – 1 × 10⁻⁹ (cm³ STPcm/cm² s cmHg), respectively. The higher permeability coefficients of CO₂ are explained in terms of high solubility of CO₂ in filled PEO. The permeability coefficient of CO₂ was affected by the degree of crystallinity of PEO in the composite. On the other hand, there was little effect of crystallinity on O₂ and N₂ permeability coefficients. Some probable relationships between selectivities of O₂ to N₂ and CO₂ to N₂ and the degree of crystallinity of PEO were observed. The CO₂ gas permeability coefficients of the composite membrane for PEO50000 (M_w = 5 × 10⁴) showed a marked change due to melting or crystallization of PEO. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2733–2738, 1999     

New solid polymer electrolytes based on PEO/PAN hybrids

Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO₄ were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO₄‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO₄‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N₂, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006     

Preparation and electrochemical behaviors of polymeric composite electrolytes containing mesoporous silicate fillers

In the present study, poly(ethylene oxide) (PEO)-based polymeric composite electrolytes (PCEs) had been prepared by using a different content of mesoporous silicate MCM-41, in order to examine the filler addition effect on the microstructural and electrochemical properties. The interactions between MCM-41 and PEO matrix were studied by XRD, DSC, and SEM techniques. The electrochemical properties of the PCEs, such as ionic conductivity, its temperature dependence, and lithium transference number were investigated. MCM-41 could maintain the pore structure effectively, resulting in nanocomposites that were homogeneously complexed with the PEO chains. The PCEs with 8 wt.% MCM-41 showed the smallest crystallinity, 30.4%. Accordingly, those PCEs showed the highest ion conductivity, 1.2 × 10⁻⁴ S/cm, a two-order-of-magnitude higher value than that of the pristine PEO-LiClO₄. This might have reflected decreased crystallinity and improved ion transport. Furthermore, those PCEs showed an increased Li ion transference number of ∼0.5. In conclusion, the filler addition could enhance the ionic conductivity and increase the Li ion transference number at the same time.     

Ionic liquid mediated magnesium ion conduction in poly(ethylene oxide) based polymer electrolyte

Magnesium ion conduction in poly(ethylene oxide) (PEO) based polymer electrolyte incorporated with room temperature ionic liquid (RTIL) is reported. The electrolyte films comprise the PEO complexed with magnesium trifluoromethanesulfonate (or magnesium triflate) added with different amount of ionic liquid, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMITf). The polymer electrolyte with ∼50 wt.% of ionic liquid offers a maximum electrical conductivity of ∼5.6 × 10⁻⁴ S cm⁻¹ at room temperature (∼25 °C) with improved thermal and electrochemical stabilities. The Mg²⁺ ion conduction in the PEO-complex is confirmed from cyclic voltammetry, impedance and transport number measurements. A significant increase in the Mg²⁺ ion transport number (tMg2+) is observed with increasing content of the ionic liquid in PEO–Mg salt complex and the maximum value is obtained to be ∼0.45 for ∼50 wt.% of ionic liquid. The interaction of imidazolium cations with ether oxygen of PEO, as evidenced from FTIR and Raman studies, play an important role in the substantial enhancement in the tMg2+ value.     

Preparation of anion exchange membranes based on pyridine functionalized poly(vinyl alcohol) crosslinked by 1,4-dichlorobutane

A series of anion exchange membranes [pyridine functionalized-poly(vinyl alcohol)-1,4-dichlorobutane (PVA-PY-DL_x)] were synthesized by using PVA-PY as polymer matrix and DL as crosslinker and iodomethane as quaternization reagent. During the experiment, pyridine groups grafted on PVA were transformed into quaternary ammonium group during the formation process of the crosslinked structure and the quaternization routine by iodomethane. The characterization results revealed that the PVA-PY-DL_x membranes have been successfully prepared and the crystallinity increases with increase of DL. PVA-PY-DL_x membranes have smooth and uniform morphology. The introduction of crosslinked structure improves the mechanical properties and dimensional stability of the PVA-PY-DL_x membrane, enhances the alkali resistance. When the mass content of DL was 4.0%, composite membrane had the maximum tensile strength (44.2 MPa), and the OH⁻ conductivity reaches 1.05 × 10⁻² S cm⁻¹ at 70 °C. The accelerated aging experiment was carried out in 3 mol L⁻¹ potassium hydroxide (KOH) solution for 120 h at 80 °C, which revealed that the anionic conductivity of PVA-PY-DL_4.0 membrane retains 79.6% of its initial conductivity, showing better stability of alkali stability. Methanol permeability of PVA-PY-DL_x membranes was only the 0.37–0.72% of the Nafion-117 membrane in 3 mol L⁻¹ methanol at 60 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47395.