Effect of plasticizers (EC or PC) on the ionic conductivity and thermal properties of the (PEO)9LiTf: Al2O3 nanocomposite polymer electrolyte system

A new plasticized nanocomposite polymer electrolyte based on poly (ethylene oxide) (PEO)-LiTf dispersed with ceramic filler (Al₂O₃) and plasticized with propylene carbonate (PC), ethylene carbonate (EC), and a mixture of EC and PC (EC+PC) have been studied for their ionic conductivity and thermal properties. The incorporation of plasticizers alone will yield polymer electrolytes with enhanced conductivity but with poor mechanical properties. However, mechanical properties can be improved by incorporating ceramic fillers to the plasticized system. Nanocomposite solid polymer electrolyte films (200–600 μm) were prepared by common solvent-casting method. In present work, we have shown the ionic conductivity can be substantially enhanced by using the combined effect of the plasticizers as well as the inert filler. It was revealed that the incorporating 15 wt.% Al₂O₃ filler in to PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity [σ _RT (max)?=?7.8?×?10^?6 S cm^?1]. It was interesting to observe that the addition of PC, EC, and mixture of EC and PC to the PEO: LiTf: 15 wt.% Al₂O₃ CPE showed further conductivity enhancement. The conductivity enhancement with EC is higher than PC. However, mixture of plasticizer (EC+PC) showed maximum conductivity enhancement in the temperature range interest, giving the value [σ _RT (max)?=?1.2?×?10^?4 S cm^?1]. It is suggested that the addition of PC, EC, or a mixture of EC and PC leads to a lowering of glass transition temperature and increasing the amorphous phase of PEO and the fraction of PEO-Li⁺ complex, corresponding to conductivity enhancement. Al₂O₃ filler would contribute to conductivity enhancement by transient hydrogen bonding of migrating ionic species with O–OH groups at the filler grain surface. The differential scanning calorimetry thermograms points towards the decrease of T _g , crystallite melting temperature, and melting enthalpy of PEO: LiTf: Al₂O₃ CPE after introducing plasticizers. The reduction of crystallinity and the increase in the amorphous phase content of the electrolyte, caused by the filler, also contributes to the observed conductivity enhancement.     

Effect of NiO nanofiller concentration on the properties of PEO-NiO-LiClO4 composite polymer electrolyte

Composite polymer electrolyte films comprising polyethylene oxide (PEO) as the polymer host, LiClO₄ as the dopant, and NiO nanoparticle as the inorganic filler was prepared by solution casting technique. NiO inorganic filler was synthesized via sol-gel method. The effect of NiO filler on the ionic conductivity, structure, and morphology of PEO-LiClO₄-based composite polymer electrolyte was investigated by AC impedance spectroscopy, X-ray diffraction, and scanning electron microscopy, respectively. It was observed that the conductivity of the electrolyte increases with NiO concentration. The highest room temperature conductivity of the electrolyte was 7.4?×?10^?4 S cm^?1 at 10 wt.% NiO. The observation on structure shows the highest conductivity appears in amorphous phase. This result has been supported by surface morphology analysis showing that the NiO filler are well distributed in the samples. As a conclusion, the addition of NiO nanofiller improves the conductivity of PEO-LiClO₄ composite polymer electrolyte.     

Investigation on the effect of nanosilica towards corn starch–lithium perchlorate-based polymer electrolytes

Biodegradable corn starch–lithium perchlorate (LiClO₄)-based solid polymer electrolytes with addition of nano-sized fumed silica (SiO₂) were prepared by solution casting technique. Ionic conductivity at ambient temperature was measured by AC impedance spectroscopy. Upon addition of nano-sized SiO₂, the ionic conductivity at room temperature is increased. The optimum ionic conductivity value obtained was 1.23?×?10^?4?S?cm^?1 at 4?wt% SiO₂. This may be attributed to the low crystallinity of the polymer electrolytes resulting from the dispersed nanosilica particles. Fourier–transform infrared spectroscopy studies confirmed the complexation between corn starch, lithium perchlorate, and silica. The thermal properties of the prepared samples were investigated with differential scanning calorimetry and thermogravimetric analysis. The surface morphology of the polymer electrolytes confirmed the agglomeration of particles after excess dispersion of inorganic filler. This was proven in the scanning electron microscopy studies.     

Towards the mechanism of Li<Superscript>+</Superscript> ion transfer in the net solid polymer electrolyte based on polyethylene glycol diacrylate–LiClO<Subscript>4</Subscript>

Ion transport in the new three-dimensional network polymer electrolytes that are completely amorphous in the solid state has been studied on the example of the matrix model with a monomer—polyethylene glycol diacrylate, cross-linked by radical polymerization. The nature of ionic conductivity in solid polymer electrolytes based on polyethylene glycol diacrylate at different concentrations of salt LiClO₄ was studied by methods of electrochemical impedance, differential scanning calorimetry analysis, Fourier transform infrared spectroscopy and quantum chemical modeling. The maximum value of conductivity in the range of 20–100 °C is realized at 20 wt% content of LiClO₄. The reason for the low conductivity of the SPE studied is the small degree of dissociation of contact ion pairs. At the increase in the salt content associates of contact pairs Li⁺ClO ₄ ^? , dimers and trimers (at LiClO₄ >20 wt%) are formed. The appearances of trimers are accompanied by a decrease in conductivity due to lowering of contact pair content.     

Novel fast lithium-ion conductor LiTa2PO8 enhances the performance of poly(ethylene oxide)-based polymer electrolytes in all-solid-state lithium metal batteries

At present, replacing the liquid electrolyte in a lithium metal battery with a solid electrolyte is considered to be one of the most powerful strategies to avoid potential safety hazards. Composite solid electrolytes (CPEs) have excellent ionic conductivity and flexibility owing to the combination of functional inorganic materials and polymer solid electrolytes (SPEs). Nevertheless, the ionic conductivity of CPEs is still lower than those of commercial liquid electrolytes, so the development of high-performance CPEs has important practical significance. Herein, a novel fast lithium-ion conductor material LiTa₂PO₈ was first filled into poly(ethylene oxide) (PEO)-based SPE, and the optimal ionic conductivity was achieved by filling different concentrations (the ionic conductivity is 4.61 × 10^?4 S/cm with a filling content of 15 wt% at 60 °C). The enhancement in ionic conductivity is due to the improvement of PEO chain movement and the promotion of LiTFSI dissociation by LiTa₂PO₈. In addition, LiTa₂PO₈ also takes the key in enhancing the mechanical strength and thermal stability of CPEs. The assembled LiFePO₄ solid-state lithium metal battery displays better rate performance (the specific capacities are as high as 157.3, 152, 142.6, 105 and 53.1 mAh/g under 0.1, 0.2, 0.5, 1 and 2 C at 60 °C, respectively) and higher cycle performance (the capacity retention rate is 86.5% after 200 cycles at 0.5 C and 60 °C). This research demonstrates the feasibility of LiTa₂PO₈ as a filler to improve the performance of CPEs, which may provide a fresh platform for developing more advanced solid-state electrolytes.     

Ionic conductivities of the complexes of LiClO4 and alternating copolymers of oligomeric poly(ethylene oxide) having biphenyl units in the backbone

A series of copolymers of predominantly poly(ethylene oxide) (PEO) with biphenyl (BP) units in the backbone were synthesized. The solid polymer electrolytes (SPEs) were prepared from these copolymers (BP-PEG) employing lithium perchlolate (LiClO₄) as a lithium salt and their ionic conductivities were investigated to exploit the structure–ionic conductivity relationships as a function of chain length ratio between the flexible PEO chains and rigid BP units. The ionic conductivity increases with increasing PEO length in BP-PEG. The salt concentrations in BP-PEG/LiClO₄ complexes were also changed and the results show that maximum conductivity is obtained at [EO]/[Li⁺]≈8. The reasons for these findings are discussed in terms of the number of charge carriers and the mobility of the polymer chain.     

Influence of DC electric field on both crystalline structure and conductivity of poly(ethylene oxide)10:LiClO4 electrolyte

The dynamic ionic conductivity and polarizing morphology of poly(ethylene oxide)₁₀:LiClO₄ (PEO₁₀:LiClO₄) electrolyte membranes under different direct current electric fields (EFs) were simultaneously investigated. PEO molecular chains were found to rearrange during the migration of charge carriers, and the rearrangement of PEO molecular chains dramatically affected the conductivity of the electrolyte membrane. No noticeable differences of conductivity and polarizing morphology between the heating and cooling process were observed when the EF was absent. However, the conductivity of the membrane was remarkably enhanced after applying an EF and after carrying out a heating–cooling loop. Differential scanning calorimetry and wide‐angle X‐ray diffraction of the sample with different treatments of both EFs and heating–cooling loops showed that the conductivity enhancement or reduction after loading special EFs and heating–cooling loops were attributed to the change of both the crystallite size of certain diffraction planes and the thickness of PEO lamellae. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Temperature dependence of the conductivity of plasticized poly(vinyl chloride)-low molecular weight liquid 50% epoxidized natural rubber solid polymer electrolyte

Characterizations were carried out to study on a new plasticized solid polymer electrolyte that was composed of blends of poly(vinyl chloride) (PVC), liquid 50% epoxidized natural rubber (LENR50), ethylene carbonate, and polypropylene carbonate. This freestanding solid polymer electrolyte (SPE) was successfully prepared by solution casting technique. Further analysis and characterizations were carried out by using scanning electron microscopy (SEM), X-ray diffraction, differential scanning calorimeter (DSC), Fourier transform infrared (ATR-FTIR), and impedance spectroscopy (EIS). The SEM results show that the morphologies of SPEs are compatible with good homogeneity. No agglomeration was observed. However, upon addition of salt, formation of micropores occurred. It is worth to note that micropores improve the mobility of ions in the SPE system, thus increased the ionic conductivity whereas the crystallinity analysis for SPEs indicates that the LiClO₄ salt is well complexed in the plasticized PVC-LENR50 as no sharp crystallinity peak was observed for 5–15% wt. LiClO₄. This implies that LiClO₄ salt interacts with polymer host as more bonds are form via coordination bonding. In DSC study, it is found that the glass temperature (T _g) increased with the concentration of LiClO₄. The lowest T _g was obtained at 41.6 °C when incorporated with 15% wt. LiClO₄. The features of complexation in the electrolyte matrix were studied using ATR-FTIR at the peaks of C=O, C–O–C, and C–Cl. In EIS analysis, the highest ionic conductivity obtained was 1.20?×?10^?3 S cm^?1 at 15% wt. LiClO₄ at 353 K.     

Ionic conductivity enhancement in the solid polymer electrolyte PEO9LiTf by nanosilica filler from rice husk ash

Rice husk ash is a cheap raw material available in abundance in rice-growing countries. It contains around 85–90 % amorphous silica. Rice husk ash, when subjected to a simple chemical precipitation method, will produce nanosilica which can be used for many industrial and technological applications. In this work, we have successfully synthesized nano-sized silica from local rice husk ash and prepared the nanocomposite solid polymer electrolyte, PEO₉LiTf:SiO₂. The resulting electrolyte has been characterized by X-ray diffraction, differential scanning calorimetry, atomic force microscopy, Fourier transform infrared spectroscopy, and complex impedance spectroscopy. The electrolyte shows about a 12-fold increase in ionic conductivity at room temperature due to the silica filler. In the nanocomposite electrolyte, nanosilica particles obtained from rice husk ash behaved very similarly to the commercial grade nanosilica and had a size distribution in the 25- to 40-nm range. As already suggested by us and by others, the O^2? and OH^? surface groups in the filler surface interact with the Li⁺ ions and provide hopping sites for migrating Li⁺ ions through transient H bonding, creating additional high-conducting pathways. This would contribute to a substantial conductivity enhancement through increased ionic mobility. An additional contribution to conductivity enhancement, particularly at temperatures below 60 °C, appears to come from the increased fraction of the amorphous phase, as evidenced from the reduced crystallite melting temperature and the reduced enthalpy of melting due to the presence of the filler.     

A novel PEO-based composite solid-state polymer electrolyte with methyl group-functionalized SBA-15 filler for rechargeable lithium batteries

Functionalized molecular sieve SBA-15 with trimethylchlorosilane was used as an inorganic filler in a poly(ethyleneoxide) (PEO) polymer matrix to synthesize a composite solid-state polymer electrolyte (CSPE) using LiClO₄ as the doping salts, which is designated to be used for rechargeable lithium batteries. The methyl group-functionalized SBA-15 (^fSBA-15) powder possesses more hydrophobic characters than SBA-15, which improves the miscibility between the ^fSBA-15 filler and the PEO matrix. The interaction between the ^fSBA-15 and PEO polymer matrix was investigated by scanning electron microscopy, X-ray diffraction, and differential scanning calorimetry. Linear sweep voltammetry and electrochemical impedance spectroscopy were employed to study the electrochemical stability windows, ionic conductivity, and interfacial stability of the CSPE. The temperature dependence of the change of the PEO polymer matrix in the CSPE from crystallization to amorphous phase was surveyed, for the first time, at different temperature by Fourier transform infrared emission spectroscopy. It has demonstrated that the addition of the ^fSBA-15 filler has improved significantly the electrochemical compatibility of the CSPE with a lithium metal electrode and enhanced effectively the ion conductivity of the CSPE. Dedicated to Professor Oleg Petrii on the occasion of his 70th birthday on August 24th, 2007.     

Evaluating the electrochemical properties of PEO‐based nanofibrous electrolytes incorporated with TiO2 nanofiller applicable in lithium‐ion batteries

In the present work, nanofibrous composite polymer electrolytes consist of polyethylene oxide (PEO), ethylene carbonate (EC), propylene carbonate (PC), lithium perchlorate (LiClO₄), and titanium dioxide (TiO₂) were designed using response surface method (RSM) and synthesized via an electrospinning process. Morphological properties of the as‐prepared electrolytes were studied using SEM. FTIR spectroscopy was conducted to investigate the interaction between the components of the composites. The highest room temperature ionic conductivity of 0.085 mS.cm^?1 was obtained with incorporation of 0.175 wt. % TiO₂ filler into the plasticized nanofibrous electrolyte by EC. Moreover, the optimum structure was compared with a film polymeric electrolyte prepared using a film casting method. Despite more amorphous structure of the film electrolyte, the nanofibrous electrolyte showed superior ion conductivity possibly due to the highly porous structure of the nanofibrous membranes. Furthermore, the mechanical properties illustrated slight deterioration with incorporation of the TiO₂ nanoparticles into the electrospun electrolytes. This investigation indicated the great potential of the electrospun structures as all‐solid‐state polymeric electrolytes applicable in lithium ion batteries.     

Conductivity enhancement mechanism of the poly(ethylene oxide)/modified‐clay/LiClO4 systems

This study demonstrates that adding clay that was organically modified by dimethyldioctadecylammonium chloride (DDAC) and d2000 surfactants increases the ionic conductivity of polymeric electrolyte. A.C. impedance, differential scanning calorimetric (DSC), and Fourier transform infrared (FTIR) studies revealed that the silicate layers strongly interact with the dopant salt lithium perchlorate (LiClO₄) within a poly(ethylene oxide) (PEO)/clay/LiClO₄ system. DSC characterization verified that the addition of a small amount of the organic clay reduces the glass‐transition temperature of PEO as a result of the interaction between the negative charge in the clay and the lithium cation. Additionally, the strength of such a specific interaction depends on the extent of PEO intercalation. With respect to the interaction between the silicate layer and the lithium cation, three types of complexes are assumed. In complex I, lithium cation is distributed within the PEO phase. In complex II, lithium cation resides in an PEO/exfoliated‐clay environment. In complex III, the lithium cation is located in PEO/agglomerated‐clay domains. More clay favors complex III over complexes II and I, reducing the interaction between the silicate layers and the lithium cations because of strong self‐aggregation among the silicate layers. Notably, the (PEO)₈LiClO₄/DDAC‐modified clay (DDAC‐mClay) composition can form a nanocomposite electrolyte with high ionic conductivity (8 × 10^?5 S/cm) at room temperature. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1342–1353, 2002     

Nanocomposite blend gel polymer electrolyte for proton battery application

A proton-conducting nanocomposite gel polymer electrolyte (GPE) system, [35{(25 poly(methylmethacrylate) (PMMA) + 75 poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP))?+?xSiO₂}?+?65{1 M NH₄SCN in ethylene carbonate (EC) + propylene carbonate (PC)}], where x?=?0, 1, 2, 4, 6, 8, 10, and 12, has been reported. The free standing films of the gel electrolyte are obtained by solution cast technique. Films exhibit an amorphous and porous structure as observed from X-ray diffractometry (XRD) and scanning electron microscopy (SEM) studies. Fourier transform infrared spectrophotometry (FTIR) studies indicate ion–filler–polymer interactions in the nanocomposite blend GPE. The room temperature ionic conductivity of the gel electrolyte has been measured with different silica concentrations. The maximum ionic conductivity at room temperature has been observed as 4.3?×?10^?3?S?cm^?1 with 2 wt.% of SiO₂ dispersion. The temperature dependence of ionic conductivity shows a typical Vogel-Tamman-Fulcher (VTF) behavior. The electrochemical potential window of the nanocomposite GPE film has been observed between ?1.6 V and 1.6 V. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO₄·7H₂O anode and PbO₂/V₂O₅ cathode. The open circuit voltage (OCV) of the battery has been obtained as 1.55 V. The highest energy density of the cell has been obtained as 6.11 Wh?kg^?1 for low current drain. The battery shows rechargeability up to 3 cycles and thereafter, its discharge capacity fades away substantially.     

Ion conducting properties of poly(ethylene oxide)-based electrolytes incorporating amorphous silica attached with imidazolium salts

Poly(ethylene oxide) (PEO)-based polymer electrolytes containing amorphous silica attached ionic liquid (IL) were studied in order to improve electrochemical and interfacial properties. An imidazolium salt such as IL was attached to modified ceramic fillers. The modified ceramic fillers were amorphous silica with the immobilized 1-methyl-3-propyl-imidazolium bromide (MPIm-AS). PEO-based polymer electrolytes were prepared by using the solution casting technique. In order to investigate the ionic conductivity, studies on the modified filler addition effects on the ion-conducting behavior of polymer electrolytes having specific amounts of MPIm-AS were carried out. The addition of MPIm-AS in polymer electrolytes has resulted in higher ionic conductivity at room temperature. The structure, crystallinity, and morphology of the solid polymer electrolytes were evaluated using X-ray diffraction, differential scanning calorimetry, and scanning electron microscope measurement. The ionic conductivity was measured by an AC impedance method. The enhanced conductivity was dependent on the decreased crystallinity and the changed morphologies of composites.     

Effects of lithium salt and poly(4‐vinyl phenol) on crystalline and amorphous phases in poly(ethylene oxide)

Effects of a strong‐interacting amorphous polymer, poly(4‐vinyl phenol) (PVPh), and an alkali metal salt, lithium perchlorate (LiClO₄), on the amorphous and crystalline domains in poly(ethylene oxide) (PEO) were probed by differential scanning calorimetry (DSC), optical microscopy (OM), and Fourier transform infrared spectroscopy (FTIR). Addition of lithium perchlorate (LiClO₄, up to 10% of the total mass) led to enhanced T_g's, but did not disturb the miscibility state in the amorphous phase of PEO/PVPh blends, where the salt in the form of lithium cation and ClO anion was well dispersed in the matrix. Competitive interactions between PEO, PVPh, and Li⁺ and ClO ions were evidenced by the elevation of glass transition temperatures and shifting of IR peaks observed for LiClO₄‐doped PEO/PVPh blend system. However, the doping distinctly influenced the crystalline domains of LiClO₄‐doped PEO or LiClO₄‐doped PEO/PVPh blend system. LiClO₄ doping in PEO exerted significant retardation on PEO crystal growth. The growth rates for LiClO₄‐doped PEO were order‐of‐magnitude slower than those for the salt‐free neat PEO. Dramatic changes in spherulitic patterns were also seen, in that feather‐like dendritic spherulites are resulted, indicating strong interactions. Introduction of both miscible amorphous PVPh polymer and LiClO₄ salt in PEO can potentially be a new approach of designing PEO as matrix materials for electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3357–3368, 2006     

Effect of addition of 1-butyl-3-methylimidazolium thiocyanate on conductivity of Na-containing polymer electrolyte

Research in the environmentally friendly energy field has grown rapidly due to severe problems such as global warming and climate change. Sodium-ion technology is one of the most promising alternatives to lithium-ion batteries. Use of ionic liquids containing thiocyanate anion has been considered because of their low cost, low viscosity, and nonhazardous nature. In this work, polyethylene oxide (PEO)–sodium perchlorate (NaClO₄) samples containing different amounts of 1-butyl-3-methylimidazolium thiocyanate ionic liquid were prepared by a solution casting method. Addition of the ionic liquid to the PEO–NaClO₄ electrolyte further increased the ionic conductivity. The electrolyte containing 30 wt% ionic liquid exhibited the maximum ionic conductivity of ~5.0 × 10^?4 S/cm at room temperature. Fourier-transform infrared (FT-IR) spectroscopy revealed the interaction between the polymer chain and salt ion complexes for various sodium salt contents. Differential scanning calorimetry (DSC) demonstrated that the crystallinity was reduced by addition of 1-butyl-3-methylimidazolium thiocyanate ionic liquid.     

Structural and transport characteristics of polyethylene oxide/phenolic resin blend solid polymer electrolytes

Details on the structure and transport characteristics of the solid polymer electrolyte polyethylene oxide (PEO)/lithium salt (LiClO₄) modified by novolac phenolic resin are presented here. From IR spectra it could be concluded that complex formation occurred through multiple interactions between the ether oxygen of PEO–lithium, phenolic lithium, and the phenolic ether oxygen of PEO. The free hydroxyl band in phenolic reflected that phenolic closely interacted with both the PEO polymer and ionic salt. With increasing salt content in PEO, the vibration band corresponding to the ClO anion (～623 cm^?1) displayed growth of a shoulder at ～635 cm^?1, suggesting the formation of Li⁺…ClO₄^? ion pairing. However, in the presence of phenolic, ion‐pairing formation was effectively suppressed, which suggested that the phenolic moiety facilitated a greater degree of LiClO₄ salt dissociation. Activation energy analysis revealed two conducting pathways: one through the amorphous PEO and the other through the PEO/phenolic amorphous matrix. The high ion conductivity originated from effective salt dissociation and the establishment of a new conduction network formed by PEO and phenolic. Furthermore, the structural modification also extended the thermal stability and mechanical strength of the solid polymer electrolyte composite. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3866–3875, 2004     

Enhanced ionic conductivity in PEO/PMMA glassy miscible blends: Role of nano‐confinement of minority component chains

AC impedance spectroscopy was used to investigate the ionic conductivity of solution cast poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends doped with lithium perchlorate. At low PEO contents (below overlap weight fraction w^*), ionic conductivities are almost low. This could be due to nearly distant PEO chains in blend, which means ion transportation cannot be performed adequately. However, at weight fractions well above w^*, a significant increase in ionic conductivity was observed. This enhanced ionic conductivity mimics the PEO segmental relaxation in rigid PMMA matrix, which can be attributed to the accelerated motions of confined PEO chains in PMMA matrix. At PEO content higher than 20 wt % the conductivity measured at room temperature drops due to crystallization of PEO. However by increasing temperature to temperatures well above the melting point of PEO, a sudden increase of conductivity was observed which was attributed to phase transition from crystalline to amorphous state. The results indicate that some PEO/PMMA blends with well enough PEO content, which are structurally solid, can be considered as an interesting candidate for usage as solid‐state electrolytes in Lithium batteries. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2065–2071, 2010     

Effects of PEO length and phenyl unit structure on ionic conductivities of the complexes of LiClO4 and alternating copolymers of PEO having various phenyl units in the backbone

A series of copolymers of predominantly poly(ethylene oxide) (PEO) with mono-phenyl (HQ), biphenyl (BP) units, or both of them (HQ/BP) in the backbone were synthesized. The solid polymer electrolytes (SPEs) were prepared from three different types of copolymers (HQ-PEG, BP-PEG, and HQ/BP-PEG) employing lithium perchlorate (LiClO₄) as a lithium salt at a fixed salt concentration of [EO]/[Li⁺]=8. Their ionic conductivities were investigated to exploit the structure–ionic conductivity relationships as a function of structural change in rigid phenyl units and chain length ratio between flexible PEO chain and rigid phenyl units. As more rigid phenyl units were incorporated in the backbone chain, the formation inter- and intra-molecular complex with LiClO₄ became weaker and lower ionic conductivities were observed. And it was also found that higher ionic conductivity is obtained with increasing PEO chain length because inter- and intra-molecular dissociation power of PEO increases.     

Influence of barium titanate nanofiller on PEO/PVdF-HFP blend-based polymer electrolyte membrane for Li-battery applications

Organic-inorganic hybrid membranes based on poly(ethylene oxide) (PEO) 6.25 wt%/poly(vinylidene fluoride hexa fluoro propylene) [P(VdF-HFP)] 18.75 wt% were prepared by using various concentration of nanosized barium titanate (BaTiO₃) filler. Structural characterizations were made by X-ray diffraction and Fourier transform infrared spectroscopy, which indicate the inclusion of BaTiO₃ in to the polymer matrix. Addition of filler creates an effective route of polymer-filler interface and promotes the ionic conductivity of the membranes. From the ionic conductivity results, 6 wt% of BaTiO₃-incorporated composite polymer electrolyte (CPE) showed the highest ionic conductivity (6 × 10^?3 Scm^?1 at room temperature). It is found that the filler content above 6 wt% rendered the membranes less conducting. Morphological images reveal that the ceramic filler was embedded over the membrane. Thermogravimetric and differential thermal analysis (TG-DTA) of the CPE sample with 6 wt% of the BaTiO₃ shows high thermal stability. Electrochemical performance of the composite polymer electrolyte was studied in LiFePO₄/CPE/Li coin cell. Charge-discharge cycle has been performed for the film exhibiting higher conductivity. These properties of the nanocomposite electrolyte are suitable for Li-batteries.