Composite polymer electrolytes based on electrospun thermoplastic polyurethane membrane and polyethylene oxide for all‐solid‐state lithium batteries

To improve the electrochemical properties and enhance the mechanical strength of solid polymer electrolytes, series of composite polymer electrolytes (CPEs) were fabricated with hybrids of thermoplastic polyurethane (TPU) electrospun membrane, polyethylene oxide (PEO), SiO₂ nanoparticles and lithium bis(trifluoromethane)sulfonamide (LiTFSI). The structure and properties of the CPEs were confirmed by SEM, XRD, DSC, TGA, electrochemical impedance spectroscopy and linear sweep voltammetry. The TPU electrospun membrane as the skeleton can improve the mechanical properties of the CPEs. In addition, SiO₂ particles can suppress the crystallization of PEO. The results show that the TPU‐electrospun‐membrane‐supported PEO electrolyte with 5 wt% SiO₂ and 20 wt% LiTFSI (TPU/PEO‐5%SiO₂‐20%Li) presents an ionic conductivity of 6.1 × 10^?4 S cm^?1 at 60 °C with a high tensile strength of 25.6 MPa. The battery using TPU/PEO‐5%SiO₂‐20%Li as solid electrolyte and LiFePO₄ as cathode shows an attractive discharge capacity of 152, 150, 121, 75, 55 and 26 mA h g^?1 at C‐rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C, respectively. The discharge capacity of the cell remains 110 mA h g^?1 after 100 cycles at 1C at 60 °C (with a capacity retention of 91%). All the results indicate that this CPE can be applied to all‐solid‐state rechargeable lithium batteries. © 2018 Society of Chemical Industry     

Synthesis and characterization of SrBi4Ti4O15ferroelectric filler based composite polymer electrolytes for lithium ion batteries

Composite polymer electrolytes (CPEs) based on poly (ethylene oxide) (PEO) (Mol.Wt ∼6×10⁵) complexed with LiN(CF₃SO₂)₂ lithium salt and SrBi₄Ti₄O₁₅ ferroelectric ceramic filler have been prepared as films. Citrate gel technique and conventional solid state technique were employed for the synthesis of the ferroelectric fillers in order to study the effect of particle size of the filler on ionic conductivity of the polymer electrolyte. Characterization techniques such as X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscopy (SEM) and temperature dependant DC conductivity studies were taken for the prepared polymer composite electrolytes. The broadening of DTA endotherms on addition of ceramic fillers to the polymer salt complex indicated the reduction in crystallinity. An enhancement in conductivity was observed with the addition of SrBi₄Ti₄O₁₅ as filler to the (PEO)₈-LiN(CF₃SO₂)₂ polymer salt complexes. Among the investigated samples (PEO)₈-LiN(CF₃SO₂)₂ +10 wt% SrBi₄Ti₄O₁₅ (citrate gel) polymer composite exhibits a maximum conductivity.     

Preparation and physicochemical performances of poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolytes doped with modified carbon nanotubes

Modified carbon nanotubes (m‐CNTs) were successfully prepared by the interactions between nitric and sulfuric acids and CNTs, which was confirmed using Fourier transform infrared spectroscopy. Poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolyte (CPE) membranes doped with various amounts of m‐CNTs were prepared by phase inversion method. The desired CPEs were obtained by soaking the liquid electrolytes for 30 min. The physicochemical and electrochemical properties of the CPE membranes were investigated using scanning electron microscopy, X‐ray diffraction, thermogravimetry, electrochemical impedance spectroscopy and linear sweep voltammetry. The results show that the CPE membranes doped with 2.2 wt% m‐CNTs possess the smoothest surface and the highest decomposition temperature about 450 °C. Obviously, adding an appropriate amount of m‐CNTs into the polymer matrix can decrease the crystallinity and enhance the ionic conductivity; the temperature dependence of ionic conductivity follows the Arrhenius relation and the ionic conductivity at room temperature is up to 4.9 mS cm^?1. The interfacial resistance can reach a stable value of about 415 Ω cm^?2 after 10 days storage. The excellent rate and cycle performances with an electrochemical working window up to 5.4 V ensure that the CPEs doped with 2.2 wt% m‐CNTs can be considered as potential candidates as polymer electrolyte for lithium ion batteries. © 2013 Society of Chemical Industry     

Effect of various electrophoretically deposited nano‐silica contents on the properties of poly(vinylidene fluoride‐co‐hexafluoropropylene)‐based electrospun polymer electrolytes

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (P(VDF‐HFP)) based composite polymer electrolyte (CPE) membranes were successfully prepared by electrospinning followed by electrophoretic deposition processes, and desirable polymer electrolytes were obtained after being activated in liquid electrolytes. The physicochemical properties of the CPEs with different electrophoretically deposited nano‐SiO₂ contents were investigated by SEM, XRD, TGA, linear sweep voltammetry and electrochemical impedance spectroscopy measurements. When the ratio of electrophoretically deposited nano‐SiO₂ to P(VDF‐HFP) is up to 4 wt%, the results show that the CPE membrane presents a very uniform surface with abundant interconnected micropores and possesses excellent mechanical tensile strength with high thermal and electrochemical stability; the ionic conductivity at room temperature can reach 3.361 mS cm^?1 and the reciprocal temperature dependence of the ionic conductivity follows a Vogel ? Tamman ? Fulcher relationship. The interfacial resistance of the assembled Li/CPE/Li simulated cell can rapidly increase to a steady value of about 950 Ω from the initial value of about 700 Ω at 30 °C during 15 days' storage. The battery performance test suggests that the CPE also shows excellent compatible properties with commercial LiCoO₂ and graphite materials. © 2015 Society of Chemical Industry     

Influence of Barium Titanate on poly(vinyl pyrrolidone)‐based composite polymer blend electrolytes for lithium battery applications

Nanocomposite polymer blend electrolytes based on poly (ethylene oxide), poly (vinyl pyrrolidone) that contained lithium perchlorate as a dopant, propylene carbonate (PC) as a plasticizer and Barium Titanate (BaTiO₃) as a filler were prepared for various concentrations of BaTiO₃ using solvent casting technique. The structural and complex formations of the composite electrolyte membranes were confirmed by X‐ray diffraction and FTIR analysis. The addition of BaTiO₃ nanofillers improved the ionic conductivity of the polymer electrolytes to some extent when the content of the BaTiO₃ is 10 wt%. The addition of BaTiO₃ also enhanced the thermal stability of the electrolyte. The surface morphology of the sample having a maximum ionic conductivity was studied by AFM. Molecular motion in the polymeric media was supported by fluorescence studies. The charge transfer arises between the polymer blend and Li‐ions were confirmed by UV‐Vis analysis. POLYM. COMPOS., 36:302–311, 2015. © 2014 Society of Plastics Engineers     

Physicochemical properties of poly(ethylene oxide)-based composite polymer electrolytes with a silane-modified mesoporous silica SBA-15

Mesoporous silica SBA-15 was surface-modified by γ-glycidoxypropyltrimethoxy silane (GPTMS), and novel poly(ethylene oxide) (PEO)-based composite polymer electrolytes (CPE) using the silane-modified SBA-15 (SBA-15-GPTMS) as filler were prepared and characterized. The results of the low-angle X-ray diffraction (XRD) patterns and Fourier-transform infrared (FT-IR) spectroscopy indicated that GPTMS has been successfully attached to the surface of SBA-15 with a high degree of mesoscopic hexagonal pore structure. The incorporation of SBA-15-GPTMS in the PEO-LiClO₄ matrix effectively reduced the PEO crystallinity and obviously improved the conductivity and electrochemical stability of the CPEs. The CPE with 10 wt.% SBA-15-GPTMS provided the highest conductivity among all the tested CPEs, about 2-3 orders of magnitude higher than that of the PEO-LiClO₄ matrix below the melting temperature of PEO. The reasons that the CPEs using SBA-15-GPTMS as filler showed higher conductivity than that with SBA-15 were discussed.     

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.     

Synthesis of quaternized ammonium iodide‐containing conjugated polymer electrolytes and their application in dye‐sensitized solar cells

A series of conjugated polymer electrolytes (CPEs) comprising fluorene/carbazole or thiophene/carbazole backbones with quaternized ammonium iodide groups were synthesized and used in polymer solution and polymer gel electrolytes in dye‐sensitized solar cells (DSSCs). The photovoltaic (PV) performances became markedly poorer with increasing CPE content for the DSSCs based on polymer solution electrolytes. However, the PV performances were not significantly affected with increasing CPE content for the DSSCs fabricated from poly(ethylene oxide) (PEO)/CPE blend‐based gel‐type electrolytes. Moreover, higher PV efficiencies and stabilities were obtained for the DSSCs based on PEO/CPE blend gel electrolytes as compared to the DSSCs based on PEO gel electrolyte. The electrochemical impedance and PV properties of the DSSCs based on polymer solution electrolytes and on polymer gel electrolytes were determined as a function of the CPE concentration. Copyright © 2010 Society of Chemical Industry     

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⁺.     

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.     

Studies of solvent effect on the conductivity of 2‐mercaptopyridine‐doped solid polymer blend electrolytes and its application in dye‐sensitized solar cells

Solvents and electrolytes play an important role in the fabrication of dye‐sensitized solar cells (DSSCs). We have studied the poly(ethylene oxide)‐poly(methyl methacrylate)‐KI‐I₂ (PEO‐PMMA‐KI‐I₂) polymer blend electrolytes prepared with different wt % of the 2‐mercaptopyridine by solution casting method. The polymer electrolyte films were characterized by the FTIR, X‐ray diffraction, electrochemical impedance and dielectric studies. FTIR spectra revealed complex formation between the PEO‐PMMA‐KI‐I₂ and 2‐mercaptopyrindine. Ionic conductivity data revealed that 30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂ electrolyte can show higher conductivity (1.55 × 10^?5 S cm^?1) than the other compositions (20, 40, and 50%). The effect of solvent on the conductivity and dielectric of solid polymer electrolytes was studied for the best composition (30% 2‐mercaptopyridine‐doped PEO‐PMMA‐KI‐I₂) electrolyte using various organic solvents such as acetonitrile, N,N‐dimethylformamide, 2‐butanone, chlorobenzene, dimethylsulfoxide, and isopropanol. We found that ac‐conductivity and dielectric constant are higher for the polymer electrolytes processed from N,N‐dimethylformamide. This observation revealed that the conductivity of the solid polymer electrolytes is dependent on the solvent used for processing and the dielectric constant of the film. The photo‐conversion efficiency of dye‐sensitized solar cells fabricated using the optimized polymer electrolytes was 3.0% under an illumination of 100 mW cm^?2. The study suggests that N,N‐dimethylformamide is a good solvent for the polymer electrolyte processing due to higher ac‐conductivity beneficial for the electrochemical device applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42489.     

Effect on properties of PVDF-HFP based composite polymer electrolyte doped with nano-SiO2

Various kinds of nano-SiO₂ using different catalysts were obtained and characterized by scanning electron microscope (SEM) technique. The results showed that the nano-SiO₂ using NH₃·H₂O as catalyst presented the best morphology. Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) based composite polymer electrolyte (CPE) membranes doped with different contents of nano-SiO₂ were prepared by phase inversion method. The as-prepared CPE membranes were immersed into 1.0 M LiPF₆-EC/DMC/EMC electrolytes for 0.5 h to be activated. The physicochemical and electrochemical properties of the CPEs were characterized by SEM, X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) techniques. The results indicate that the CPEs doped with 10 % nano-SiO₂ exhibit the best performance. SEM micrographs showed that the CPE membranes have uniform surface with abundant interconnected micro-pores, and the uptake ratio was up to 104.4 wt%. EIS and LSV analysis also showed that the ionic conductivity at room temperature and electrochemical stability window of the modified membrane can reach 3.372 mS cm^?1 and 4.7 V, respectively. The interfacial resistance R _i was 670 Ω cm^?2 in the first day, then increased to a stable value of about 850 Ω cm^?2 in 10 days storage at room temperature. The Li/As-fabricated CPEs/LiCoO₂ cell also showed good charge–discharge performance, which suggested that the prepared CPE membranes can be used as potential electrolytes for lithium ion batteries.     

Effect of surface modified porous inorganic-organic hybrid polyphosphazene nanotubes on the properties of polyethylene oxide based solid polymer electrolytes

2-(2-methyloxyethoxy)ethanol modified poly (cyclotriphosphazene-co-4,4′-sufonyldiphenol) (PZS) nanotubes were synthesized and solid composite polymer electrolytes based on the surface modified polyphosphazene nanotubes added to PEO/LiClO₄ model system were prepared. Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to investigate the characteristics of the composite polymer electrolytes (CPE). The ionic conductivity, lithium ion transference number and electrochemical stability window can be enhanced after the addition of surface modified PZS nanotubes. The electrochemical investigation shows that the solid composite polymer electrolytes incorporated with PZS nanotubes have higher ionic conductivity and lithium ion transference number than the filler SiO₂. Maximum ionic conductivity values of 4.95 × 10⁻⁵ S cm⁻¹ at ambient temperature and 1.64 × 10⁻³ S cm⁻¹ at 80 °C with 10 wt % content of surface modified PZS nanotubes were obtained and the lithium ion transference number was 0.41. The good chemical properties of the solid state composite polymer electrolytes suggested that the inorganic-organic hybrid polyphosphazene nanotubes had a promising use as fillers in solid composite polymer electrolytes and the PEO₁₀-LiClO₄-PZS nanotubes solid composite polymer electrolyte can be used as a candidate material for lithium polymer batteries.     

Polymer electrolytes based on poly(ethylene glycol) dimethyl ether and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate: Preparation, physico-chemical characterization, and theoretical study

Polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) and the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF₆) have been prepared and characterized by different techniques. Coordination of the IL by the polymer occurs mainly in the amorphous phase. This finding was correlated with previous theoretical investigations of a similar model for polymer electrolytes based on poly(ethylene oxide), PEO, and IL. It has been obtained ionic conductivity σ ∼ 10⁻³ S cm⁻¹ for the polymer electrolyte with 35 wt% of IL at 100 °C. The same order of magnitude for σ was obtained by molecular dynamics simulation of PEO/IL. This work demonstrates consistency between experimental and theoretical results for polymer electrolytes containing ionic liquids.     

Preparation and performance study on P(St‐MMA)‐SiO2 doped P(VDF‐HFP) based composite polymer electrolyte

The organic–inorganic hybrid material poly(styrene‐methyl methacrylate)‐silica (P(St‐MMA )‐SiO₂) was successfully prepared by in situ polymerization confirmed by Fourier transform infrared spectroscopy and was employed to fabricate poly(vinylidene fluoride‐hexafluoropropylene) (P(VDF‐HFP )) based composite polymer electrolyte (CPE ) membrane. Desirable CPEs can be obtained by immersing the CPE membranes into 1.0 mol L^?1 LiPF₆‐EC /DMC /EMC (LiPF₆ ethylene carbonate + dimethyl carbonate + ethylmethyl carbonate) liquid electrolyte for about 0.5 h for activation. The corresponding physicochemical properties were characterized by SEM , XRD , electrochemical impedance spectroscopy and charge–discharge cycle testing measurements. The results indicate that the as‐prepared CPEs have excellent properties when the mass ratio of the hybrid P(St‐MMA )‐SiO ₂ particles to polymer matrix P(VDF‐HFP ) reaches 1:10, at which point the SEM analyses show that the as‐prepared P(St‐MMA )‐SiO ₂ particles are uniformly dispersed in the membrane and the CPE membrane presents a homogeneous surface with abundant interconnected micropores. The XRD results show that there may exist interaction forces between the P(St‐MMA )‐SiO ₂ particles and the polymer matrix, which can obviously decrease the crystallinity of the composite membrane. Moreover, the ionic conductivity at room temperature and the electrochemical working window of the CPE membrane can reach 3.146 mS cm^?1 and 4.7 V, respectively. The assembled LiCoO₂/CPE /Li coin cell with the CPE presents excellent charge–discharge and C ‐rate performance, which indicates that P(St‐MMA )‐SiO ₂ hybrid material is a promising additive for the P(VDF‐HFP ) based CPE of the lithium ion battery. © 2016 Society of Chemical Industry     

Study of a new polymer electrolyte poly(ethylene oxide): NaClO3 with several plasticizers for battery application

Sodium ion conducting thin film polymer electrolytes based on poly(ethylene oxide) (PEO) complexed with NaClO₃ were prepared by a solution‐casting method. Characterization by XRD, IR spectroscopy and AC conductivity has been carried out on these thin film electrolytes to analyse their properties. The conductivity studies show that the conductivity value of PEO:NaClO₃ complex increases with the increase in salt concentrations. Increase in conductivity was found in the electrolyte system by the addition of low molecular weight polymer poly(ethylene glycol) (PEG) and the organic solvents dimethylformamide (DMF) and propylene carbonate (PC). Using these electrolyte systems, cell parameters were measured from the discharge study with the application of load 100 kΩ at room temperature with common cell configuration Na|electrolyte|C:I₂:electrolyte. The open circuit voltage (OCV) ranges from 2.81 to 3.23 V and the short circuit current (SCC) ranges from 340 to 1180 µA. © 2001 Society of Chemical Industry     

Preparation of monodispersed ZrO2 nanoparticles and their applications in poly[(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolytes

To improve the electrochemical performance of pure poly[(vinylidene fluoride)‐co‐hexafluoropropylene] (P(VDF‐HFP))‐based gel polymer electrolytes, different amounts of monodispersed ZrO₂ nanoparticles were introduced to fabricate P(VDF‐HFP)/ZrO₂ composite polymer electrolytes (CPEs) using the phase inversion method and activated processes, in which the monodispersed ZrO₂ nanoparticles were synthesized by an easy route without any chelating agents or surfactants, and confirmed using scanning electron microscopy, particle size distribution measurement and X‐ray diffraction. The characterization results show that the as‐fabricated CPE membranes present not only an abundant porous structure, but also an improved mechanical strength. In particular, sample CPE‐5 presents the best properties when the doped content of the monodispersed ZrO₂ nanoparticles reaches 5 wt% in the polymer matrix, in which the liquid uptake and ionic conductivity at room temperature are about 192.4% and 3.926 mS cm^?1, and the electrochemical working window and thermal decomposition temperature can increase to 5.1 V and 420 °C, respectively. Moreover, an assembled LiCoO₂/CPE‐5/Li coin cell can deliver excellent rate and cycling performance, in which the discharge specific capacity of the cell can show about 83.95% capacity retention at 2.0 C after 85 cycles. © 2018 Society of Chemical Industry     

Characterization of SiO2 and Al2O3 incorporated PVdF‐HFP based composite polymer electrolytes with LiPF3(CF3CF2)3

Lithium fluoroalkylphosphate (LiPF₃(CF₃ CF₂)₃) based composite polymer electrolytes (CPE) have been prepared in the matrix of polyvinylidenefluoride‐hexafluoropropylene(PVdF‐HFP), using solvent casting technique. The membranes were gelled with ethylene carbonate and diethyl carbonate as a plasticizer and nanosized SiO₂ and nanoporous Al₂O₃ as fillers. These membranes were subjected to a.c. impedance, DSC, SEM, FTIR, and Fluorescence studies. The a.c. impedance studies and activation energy calculation reveal that 2.5 wt % fillers containing membranes only exhibit maximum conductivity for SiO₂ (1.16 mS cm^?1) and Al₂O₃ (0.98 mS cm^?1), compared to fillers free membranes and beyond 2.5 wt % of such fillers the conductivity tends to decrease. The enhancement of conductivity has been explained in terms of Vogel‐Tamman‐Fulcher (VTF) theory. Molecular interactions by FTIR and local viscosity environment by fluorescence studies have been investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

FT-IR studies on interactions of AlCl3 with PEO-NaSCN polymer electrolytes

Solid polymer electrolytes are potentially useful electrolytes to be applied in high-energy batteries. In the present work, a novel polymer electrolyte, polyethylene oxide (PEO)-NaSCN-AlCl₃, was prepared and investigated by FT-IR spectroscopic techniques. Based on the FT-IR data, the bands in the CN stretching envelope have been assigned and the effect of AlCl₃ on ion-ion and ion-polymer interactions in the polymer electrolyte has been examined. It is shown that the Lewis acid-base interaction of AlCl₃ with SCN¹⁻ leads to the formation of the complex anions AlCl₃SCN⁻ and Al₂Cl₆SCN⁻, depending on the content of AlCl₃ and/or NaSCN in PEO; the preferential interactions of AlCl₃ with crystal complex P(EO)₃NaSCN occur in PEO-NaSCN-AlCl₃ electrolytes; the AlCl₃-NaSCN complex anions can play a plasticization role in PEO-NaSCN-AlCl₃ electrolyte, and are expected to be a important factor to improve the conductivity and to enhance the cation transference number. In addition, the interactions between AlCl₃ and ether oxygen of PEO were analyzed, and their effect on ionic association was also discussed.     

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.