Preparation and ionic conductivity of solid polymer electrolyte based on polyacrylonitrile‐polyethylene oxide

The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO₄ complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10^?4 S/cm with an [Li⁺]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006     

Characterization of PEO-PAN hybrid solid polymer electrolytes

Hybrid solid polymer electrolytes (HSPE) of high ionic conductivity were prepared using polyethylene oxide (PEO), polyacrylonitrile (PAN), propylene carbonate (PrC), ethylene carbonate (EC), and LiClO₄. These electrolyte films were dry, free standing, and dimensionally stable. The HSPE films were characterized by constructing symmetrical cells containing nonblocking lithium electrodes as well as blocking stainless steel electrodes. Studies were made on ionic conductivity, electrochemical reaction, interfacial stability, and morphology of the films using alternating current impedance spectroscopy, infrared spectroscopy, and scanning electron microscopy. The properties of HSPE were compared with the films prepared using (i) PEO, PrC, and LiClO₄; and (ii) PAN, PrC, EC, and LiClO₄. The specific conductivity of the HSPE films was marginally less. Nevertheless, the dimensional stability was much superior. The interfacial stability of lithium was similar in the three electrolyte films. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2191–2199, 1997     

Conformational,thermal, and ionic conductivity behavior of PEO in PEO/PMMA miscible blend: Investigating the effect of lithium salt

In this research, influence of incorporating LiClO₄ salt on the crystallization, conformation, and ionic conductivity of poly(ethylene oxide) (PEO) in its miscible blend with poly(methyl methacrylate) (PMMA) is studied. Differential scanning calorimetry showed that the incorporation of salt ions into the blend suppresses the crystallinity of PEO. The X‐ray diffraction revealed that the unit‐cell parameters of the crystals are independent of the LiClO₄ concentration despite of the existence of ionic interactions between PEO and Li cations. In addition, the complexation of the Li⁺ ions by oxygen atoms of PEO is investigated via Fourier transform infrared spectroscopy. The conformational changes of PEO segments in the presence of salt ions are studied via Raman spectroscopy. It is found that PEO chains in the blend possess a crown‐ether like conformation because of their particular complexation with the Li⁺ ions. This coordination of PEO with lithium cations amorphize the PEO and is accounted for suppressed crystallinity of PEO in the presence of salt ions. Finally, electrochemical impedance spectroscopy is used to characterize the ionic conductivity of PEO in the PEO/PMMA/LiClO₄ ternary mixture at various temperatures. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology and electrochemical and mechanical properties of polyethylene‐oxide‐based nanofibrous electrolytes applicable in lithium ion batteries

We report the synthesis of all‐solid‐state polymeric electrolytes based on electrospun nanofibers. These nanofibers are composed of polyethylene oxide (PEO) as the matrix, lithium perchlorate (LiClO₄) as the lithium salt and propylene carbonate (PC) as the plasticizer. The effects of the PEO, LiClO₄ and PC ratios on the morphological, mechanical and electrochemical characteristics were investigated using the response surface method (RSM) and analysis of variance test. The prepared nanofibrous electrolytes were characterized using SEM, Fourier transform infrared, XRD and DSC analyses. Conductivity measurements and tensile tests were conducted on the prepared electrolytes. The results show that the average diameter of the nanofibers decreased on reduction of the PEO concentration and addition of PC and LiClO₄. Fourier transport infrared analysis confirmed the complexation between PEO and the additives. The highest conductivity was 0.05 mS cm^?1 at room temperature for the nanofibrous electrolyte with the lowest PEO concentration and the highest ratio of LiClO₄. The optimum nanofibrous electrolyte showed stable cycling over 30 cycles. The conductivity of a polymer film electrolyte was 29 times lower than that of the prepared nanofibrous electrolyte with similar chemical composition. Furthermore, significant fading in mechanical properties was observed on addition of the PC plasticizer. The results obtained imply that further optimization might lead to practical uses of nanofibrous electrolytes in lithium ion batteries. © 2019 Society of Chemical Industry     

Review on composite polymer electrolytes for lithium batteries

This paper reviews the state of the art of composite polymer electrolytes (CPE) in view of their electrochemical and physical properties for the applications in lithium batteries. This review mainly encompasses on composite polymer electrolyte hosts namely poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA) and poly(vinylidene fluoride) (PVdF) studied so far. Also the ionic conductivity, transference number, compatibility and the cycling behavior of poly(vinylidene fluoride-hexafluoro propylene) (PVdF-HFP)-[AlO(OH)]_n-LiPF₆/LiClO₄ composite electrolytes have been studied and the results are discussed.     

Morphological,infrared, and ionic conductivity studies of poly(ethylene oxide)–49% poly(methyl methacrylate) grafted natural rubber–lithium perchlorate salt based solid polymer electrolytes

The potential of poly(ethylene oxide) (PEO) and 49% poly(methyl methacrylate) grafted natural rubber (MG49) as a polymer host in solid polymer electrolytes (SPE) was explored for electrochemical applications. PEO–MG49 SPEs with various weight percentages of lithium perchlorate salt (LiClO₄) was prepared with the solution casting technique. Characterization by scanning electron microscopy, Fourier transform infrared spectroscopy, and impedance spectroscopy was done to investigate the effect of LiClO₄ on the morphological properties, chemical interaction, and ionic conductivity behavior of PEO–MG49. Scanning electron microscopy analysis showed that the surface morphology of the sample underwent a change from rough to smooth with the addition of lithium salts. Infrared analysis showed that the interaction occurred in the polymer host between the oxygen atom from the ether group (C? O? C) and the Li⁺ cation from doping salts. The ionic conductivity value increased with the addition of salts because of the increase in charge carrier up to the optimum value. The highest ionic conductivity obtained was 8.0 × 10^?6 S/cm at 15 wt % LiClO₄. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Role of ceramic reinforcement in composite polymer electrolyte

Composite polymer electrolytes were prepared from PEO (polyethylene oxide), lithium perchlorate (LiClO₄), and with three different dielectric reinforcements such as lead zirconium titanate (PZT)‐12000, barium titanate (BT)‐1000, and Alumina (Al₂O₃)‐6. Differential scanning calorimetry and X‐ray diffractometry were employed to reveal the crystalline nature of the electrolytes. The conductivity of the composite polymer electrolytes were measured by impedance spectrometry. Among the three systems, PZT reinforced composite exhibits maximum ionic conductivity of 2.9 × 10⁻⁵ S/cm at room temperature. The ionic conductivity of the polymer composites increases with increase in dielectric constant of the reinforcement. The composite with alumina reinforcement displayed strongly modified properties with very weak temperature dependence of conductivity. POLYM. COMPOS., 36:42–46, 2015. © 2014 Society of Plastics Engineers     

Preparation and performance analysis of barium titanate incorporated in corn starch‐based polymer electrolytes for electric double layer capacitor application

Polymer electrolyte membranes composing of corn starch as host polymer, lithium perchlorate (LiClO₄) as salt, and barium titanate (BaTiO₃) as composite filler are prepared using solution casting technique. Ionic conductivity is enhanced on addition of BaTiO₃ by reducing the crystallinity and increasing the amorphous phase content of the polymer electrolyte. The highest ionic conductivity of 1.28 × 10^?2 S cm^?1 is obtained for 10 wt % BaTiO₃ filler in corn starch‐LiClO₄ polymer electrolytes at 75°C. Glass transition temperature (T_g) of polymer electrolytes decreases as the amount of BaTiO₃ filler is increased, as observed in differential scanning calorimetry analysis. Scanning electron microscopy and thermogravimetric analysis are employed to characterize surface morphological and thermal properties of BaTiO₃‐based composite polymer electrolytes. The electrochemical properties of the electric double‐layer capacitor fabricating using the highest ionic conductivity polymer electrolytes is investigated using cyclic voltammetry and charge‐discharge analysis. The discharge capacitance obtained is 16.22 F g^?1. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43275.     

Structural and dielectric studies of amorphous and semicrystalline polymers blend‐based nanocomposite electrolytes

The solid polymeric nanocomposite electrolyte (SPNE) films based on the blend of amorphous poly(methyl methacrylate) (PMMA) and semicrystalline poly(ethylene oxide) (PEO) (PMMA:PEO = 80:20 wt %) doped with lithium perchlorate (LiClO₄) salt and montmorillonite (MMT) clay nanofiller were prepared by classical solution cast, ultrasonic assisted solution cast and ultrasonication along with microwave irradiated solution cast followed by melt‐pressing methods. The X‐ray diffraction study of these electrolytes revealed the amorphous behavior with intercalated MMT structures. The suppressed crystallinity of PEO in the blend electrolyte complexes confirmed the existence of single discrete PEO chains confined within the PMMA domains. The dielectric relaxation spectroscopy of these materials was performed over the frequency range 20 Hz to 1 MHz, at ambient temperature. The presence of a singular relaxation peak in the loss tangent and electric modulus spectra of these electrolytes confirms a coupled cooperative chain segmental dynamics of the blend polymer owing to their miscible amorphous morphology. The behavior of transient complexes formed between the polymers functional groups, lithium cations and the intercalated MMT nanoplatelets was explored. The ambient temperature ionic conductivity of these electrolytes depends on the structural dynamics and the sample preparation methods. It is revealed that the presence of PEO in the PMMA matrix mainly governs the structural, dielectric, and ionic properties of these SPNE films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41311.     

Hydrogen bonding effect on the poly(ethylene oxide), phenolic resin,and lithium perchlorate–based solid‐state electrolyte

The interaction behavior of solid‐state polymer electrolytes composed of poly(ethylene oxide) (PEO)/novolac‐type phenolic resin and lithium perchlorate (LiClO₄) was investigated in detail by DSC, FTIR, ac impedance, DEA, solid‐state NMR, and TGA. The hydrogen bonding between the hydroxyl group of phenolic and ether oxygen of the PEO results in higher basicity of the PEO. The higher basicity of the ether group can dissolve the lithium salts more easily and results in a greater fraction of “free” anions and thus higher ionic conductivity. DEA results demonstrated that addition of the phenolic increases the dielectric constant because of the partially negative charge on the ether group induced by the hydrogen bonding interaction between ether oxygen and the hydroxyl group. The study showed that the blend of PEO(100)/LiClO₄(25)/phenolic(15) possesses the highest ionic conductivity (1.5 × 10^?5 S cm^?1) with dimensional stability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1207–1216, 2004     

Effect of the addition of hydrophobic clay on the electrochemical property of polyacrylonitrile/LiClO4 polymer electrolytes for lithium battery

In this study, an organoclay, ALA-MMT, was prepared by the ionic exchange reaction of montmorillonite (MMT) with 12-aminododecanoic acid (ALA). ALA-MMT was then used as a filler to prepare a series of composite polymer electrolytes based on polyacrylonitrile (PAN) and LiClO₄. The effect of the addition of ALA-MMT on the properties of the composite polymer electrolytes (CPEs) was investigated by XRD, FT-IR, DSC, tensile strength, AC impedance, and cyclic voltammetry measurements. It was found that the ALA-MMT particles were well dispersed in the CPEs. Owing to the incorporation of ALA-MMT, a higher fraction of the free anions was obtained, indicating that the lithium salt dissolved in the PAN matrix more effectively for the CPE than in the PAN/LiClO₄ polymer electrolyte. Moreover, the glass-transition temperature was reduced, benefiting the ion transport. The best ionic conductivity at room temperature was obtained from the CPE with 7 wt% of the modified clay and 0.6 M LiClO₄ per PAN repeat unit (CPE-7) and was more than seven times higher than that from the corresponding PAN/LiClO₄ polymer electrolyte (CPE-0). The mechanical property and the cation transference number, t₊, of CPE-7 are largely increased compared to that of CPE-0. Besides, the CPEs were electrochemically stabilized up to 4.75 V and the corresponding cell exhibited excellent electrochemical stability and cyclability over the potential range between 0 V and 4.0 V vs. Li/Li⁺.     

Effect of additives in PEO/PAA/PMAA composite solid polymer electrolytes on the ionic conductivity and Li ion battery performance

Polyethylene oxide (PEO) based-solid polymer electrolytes were prepared with low weight polymers bearing carboxylic acid groups added onto the polymer backbone, and the variation of the conductivity and performance of the resulting Li ion battery system was examined. The composite solid polymer electrolytes (CSPEs) were composed of PEO, LiClO_4, PAA (polyacrylic acid), PMAA (polymethacrylic acid), and Al₂O₃. The addition of additives to the PEO matrix enhanced the ionic conductivities of the electrolyte. The composite electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 exhibited a low polarization resistance of 881.5 ohms in its impedance spectra, while the PEO:LiClO₄ film showed a high value of 4,592 ohms. The highest ionic conductivity of 9.87 × 10⁻⁴ S cm⁻¹ was attained for the electrolyte composed of PEO:LiClO₄:PAA/PMAA/Li_0.3 at 20 °C. The cyclic voltammogram of Li⁺ recorded for the cell consisting of the PEO:LiClO₄:PAA/PMAA/Li_0.3:Al₂O₃ composite electrolyte exhibited the same diffusion process as that obtained with an ultra-microelectrode. Based on this electrolyte, the applicability of the solid polymer electrolytes to lithium batteries was examined for an Li/SPE/LiNi_0.5Co_0.5O₂ cell.     

Synthesis and characterization of novel crosslinked polyurethane–acrylate electrolyte

Flexible, transparent, and crosslinked polymer films were synthesized by polymerization of PEG‐modified urethane acrylate using a simple method. A series of novel solid polymer electrolytes and gel electrolytes were prepared based on this type of polymer film. To understand the interactions among salt, solvent, and polymer, the swelling behaviors of the crosslinked polymer in pure propylene carbonate (PC) and liquid electrolyte solutions (LiClO₄/PC) were investigated. The results showed that the swelling rate in the electrolyte solution containing moderate LiClO₄ was greater than that in pure PC. Thermogravimetric analysis (TGA) also supported the interaction between the solvent and polymer. The morphology and crystallinity of the crosslinked polymer and polymer electrolytes were studied using atomic force microscopy (AFM) and wide‐angle X‐ray diffraction (WAXD) spectroscopy. The effects of the content of the electrolyte solution on the ionic conductivity of gel electrolytes were explored. The dependence of the conductivity on the amount of the electrolyte solution was nonlinear. With a different content of the plasticizer, the ionic conduction pathway of the polymer electrolytes would be changed. The best ionic conductivity of the gel electrolytes, which should have good mechanical properties, was 4 × 10^r?3 S cm^?1 at 25°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 340–348, 2003     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007     

Effects of polymer matrix and salt concentration on the ionic conductivity of plasticized polymer electrolytes

Two polar polymers with different dielectric constants, poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO), were each blended with a chlorine-terminated poly(ethylene ether) (PEC) and one of the two salts, LiBF₄ and LiCF₃CO₂, to form PEC plasticized polymer electrolytes. The room-temperature ionic conductivity of the PEC plasticized polymer electrolytes reached a value as high as 10^?4 S/cm. The room-temperature ionic conductivity of the PVDF-based polymer electrolytes displayed a stronger dependence on the PEC content than did the PEO-based polymer electrolytes. In PVDF/PEC/LiBF₄ polymer electrolytes, the dynamic ionic conductivity was less dependent on temperature and more dependent on the PEC content than it was in PEO/PEC/LiBF₄ polymer electrolytes. The highly plasticized PVDF-based polymer electrolyte film with a PEC content greater than CF4 (CF4 defined as the molar ratio of the repeat units of PEC to those of PVDF equal to 4) was self-supported and nonsticky, while the corresponding PEO-based polymer electrolyte film was sticky. In these highly plasticized PVDF-based polymer electrolytes, the curves of the room-temperature ionic conductivity vs. the salt concentration were convex because the number of carrier ions and the chain rigidity both increased with increase of the salt content. The maximum ionic conductivity at 30°C was independent of the PEC content, but it depended on the anion species of the lithium salts in these highly plasticized polymer electrolytes. © 1995 John Wiley & Sons, Inc.     

Effect of modified montmorillonites on the ionic conductivity of (PEO)16LiClO4 electrolytes

Three kinds of modified montmorillonites were prepared by ion exchange method, and added into (PEO)₁₆LiClO₄ matrix to study the effect on the ionic conductivity of (PEO)₁₆LiClO₄ electrolytes. The structure of the modified montmorillonites and polymer composites were characterized by wide-angle X-ray diffraction. HP 4192A was used to measure the ionic conductivity of the polymer electrolytes. The results show that the addition of optimum content of 250-Li-mont enhances the ionic conductivity of the PEO based electrolyte by nearly 30 times more than the plain system and that is much higher than the other two modified montmorillonites. The difference of enhancement in conductivity caused by adding these three montmorillonites can be attributed to the difference in structure of the samples as characterized by wide-angle X-ray diffraction.     

Calcium phosphate incorporated poly(ethylene oxide)‐based nanocomposite electrolytes for lithium batteries. I. Ionic conductivity and positron annihilation lifetime spectroscopy studies

Nanocomposite polymer electrolytes (NCPEs) composed of poly(ethylene oxide), calcium phosphate [Ca₃(PO₄)₂], and lithium perchlorate (LiClO₄)/lithium bis(trifluoromethane sulfonyl)imide [LiN(CF₃SO₂)₂ or LiTFSI] in various proportions were prepared by a hot‐press method. The membranes were characterized by scanning electron microscopy, differential scanning calorimetry, thermogravimetry–differential thermal analysis, ionic conductivity testing, and transference number studies. The free volume of the membranes was probed by positron annihilation lifetime spectroscopy at 30°C, and the results supported the ionic conductivity data. The NCPEs with LiClO₄ exhibited higher ionic conductivities than the NCPE with LiTFSI as a salt. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

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     

Morphology,crystallinity, and electrochemical properties of in situ formed poly(ethylene oxide)/TiO2 nanocomposite polymer electrolytes

A method to produce nanocomposite polymer electrolytes consisting of poly(ethylene oxide) (PEO) as the polymer matrix, lithium tetrafluoroborate (LiBF₄) as the lithium salt, and TiO₂ as the inert ceramic filler is described. The ceramic filler, TiO₂, was synthesized in situ by a sol–gel process. The morphology and crystallinity of the nanocomposite polymer electrolytes were examined by scanning electron microscopy and differential scanning calorimetry, respectively. The electrochemical properties of interest to battery applications, such as ionic conductivity, Li⁺ transference number, and stability window were investigated. The room‐temperature ionic conductivity of these polymer electrolytes was an order of magnitude higher than that of the TiO₂ free sample. A high Li⁺ transference number of 0.51 was recorded, and the nanocomposite electrolyte was found to be electrochemically stable up to 4.5 V versus Li⁺/Li. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2815–2822, 2003