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.     

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.     

Vanadium doped ceramic matrix Li6.7La3Zr1.7V0.3O12 enabled PEO-based solid composite electrolyte with high lithium ion transference number and cycling stability

Solid polymer electrolytes (SPEs) have attracted much attention because of their potential in improving energy density and safety. Vanadium doped ceramic matrix Li_6.7La₃Zr_1.7V_0.3O₁₂ (LLZVO) was synthesized by high-temperature annealing, and formed a composite electrolyte with polyethylene oxide (PEO). Compared with pure PEO electrolyte membrane, the composite electrolyte membrane exhibited better ionic conductivity (30 °C: 3.2 × 10^?5 S cm^?1; 80 °C: 3.6 × 10^?3 S cm^?1). The combination of LLZVO was beneficial to improve the lithium ion transference number (t_Li⁺) of SPE, which was as high as 0.81. The Li/SPE/LiFePO₄ battery shows good cycling ability, with a specific capacity of 142 mAh g^?1 after a stable cycle of 150 cycles. Meanwhile, the symmetrical lithium battery with composite electrolyte can work continuously for 1200 h without short circuit at the current density of 0.1 mA cm^?2 at 50 °C, and the capacity is 0.176 mAh. Vanadium doped ceramic matrix LLZVO as an active ionic conductor, improved the overall performance of solid electrolyte.     

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     

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.     

Microporous poly(acrylonitrile-methyl methacrylate) membrane as a separator of rechargeable lithium battery

We studied microporous poly(acrylonitrile-methyl methacrylate), AMMA, membrane as the separator of Li/LiMn₂O₄ cell. The porous AMMA membrane was prepared by the phase inversion method with N,N-dimethylformamide (DMF) as the solvent and water as the non-solvent. We observed that morphology of the resulting membrane was strongly affected by the concentration of polymer solution: low concentration produced finger-like pores with dense skin on two surfaces of the membrane, while high concentration yielded open voids with dense layer on the other surface of the membrane. Regardless of their morphology, both membranes could be rapidly wetted by the liquid electrolyte (1.0 m LiBF₄ dissolved in 1:3 wt.% mixture of ethylene carbonate (EC) and γ-butyrolactone (GBL)), and could be swollen at elevated temperatures, which resulted in the formation of a microporous gel electrolyte (MGE). It was shown that the resulting MGE not only had high ionic conductivity and but also had good compatibility with metal lithium even at 60 °C. Cyclic voltammetric test showed that the MGE had an electrochemical window of 4.9 V versus Li⁺/Li. At room temperature, the Li/MGE/LiMn₂O₄ cell showed excellent cycliability with a specific capacity of 121-125 mA h g⁻¹ LiMn₂O₄. It was shown that even at 60 °C good mechanical strength of the MGE remained. Therefore, the MGE is suitable for the application of battery separator at elevated temperatures.     

新能源汽车固态电池中的锂枝晶抑制研究

相比于商业化的锂离子电池,固态电池具有更高的能量密度和更好的安全性。然而,固体电解质依旧面临锂枝晶生长的问题。以目前已大规模工业化的聚氧化乙烯（PEO）基电解质作为研究对象,通过将PEO与高杨氏模量的石榴石型电解质复合,抑制了锂枝晶在PEO基复合电解质中的生长,不仅使电解质膜的离子电导率从9.8×10^-6 S/cm增加到了3.8×10^-4 S/cm,还使锂/锂对称电池的临界电流密度从0.4 mA/cm²提高到1.6 mA/cm²。与此同时,组装的基于金属锂负极与传统石墨负极的软包电池可分别获得334.5 W·h/kg与218.2 W·h/kg的能量密度。其中,钴酸锂/复合电解质/石墨软包全电池循环1 000次后的容量保持率可达92.3%,能够满足新能源汽车的需求。     

A microporous gel electrolyte based on poly(vinylidene fluoride-co-hexafluoropropylene)/fully cyanoethylated cellulose derivative blend for lithium-ion battery

A gel polymer electrolyte based on the blend of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and fully cyanoethylated cellulose derivative (DH-4-CN) was prepared and characterized. Thermal, mechanical, swelling, liquid electrolyte retention and electrochemical properties, as well as microstructures of the prepared polymer electrolytes, were investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results showed that the addition of DH-4-CN could obviously improve the conductivity of PVDF-HFP based electrolyte. The maximum ionic conductivity of 4.36 mS cm⁻¹ at 20 °C can be obtained for PVDF-HFP/DH-4-CN 14:1 in the presence of 1 M LiPF₆ in EC and DMC (1:1, w/w). The dry blend membranes exhibit excellent thermal behavior. All the blend electrolytes are electrochemically stable up to about 4.8 V vs. Li/Li⁺ for all compositions. The results reveal that the composite polymer electrolyte qualifies as a potential application in lithium-ion battery.     

Blending poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile) as composite polymer electrolyte

A blend of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (PSAN) has been evaluated as a composite polymer electrolyte by means of differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, ac impedance measurements, and linear sweep voltammetry (LSV). The blends show an interaction with the Li⁺ ions when complexed with lithium perchlorate (LiClO₄), which results in an increase in the glass‐transition temperature (T_g) of the blends. The purpose of using PSAN as another component of the blend is to improve the poor mechanical properties of PMMA‐based plasticized electrolytes. The mechanical property is further improved by introducing fumed silica as inert filler, and hence the liquid electrolyte uptake and ionic conductivity of the composite systems are increased. Room‐temperature conductivity of the order of 10^?4 S/cm has been achieved for one of the composite electrolytes made from a 1/1 blend of PSAN and PMMA containing 120% liquid electrolyte [1M LiClO₄/propylene carbonate (PC)] and 10% fumed silica. These systems also showed good compatibility with Li electrodes and sufficient electrochemical stability for safe operation in Li batteries. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1319–1328, 2001     

Synthesis,characterization, and electrochemical properties of poly(ethylene oxide)-based polyaniline electrolyte complex

The polymer electrolyte based poly(ethylene oxide) complexed with conducting polyaniline (PANI) has been prepared in different weight percentages. The complexation is confirmed by Fourier transform infrared spectroscopy (FTIR).The change in morphology is studied by using scanning electron microscopy. The DC conductivity measurements are carried out using Keithley digital multimeter. It is seen that DC conductivity shows exponential behavior for all PEO : PANI complexes. It is observed that among all the PEO : PANI complexes, 50 wt % of PEO in PANI shows highest conductivity. Electrochemical cell parameters for battery applications at room temperature also have been determined. The samples are fabricated for battery application in the configuration of Na:(PEO : PANI):(I₂ + C + sample), and their experimental data are measured using Wagner polarization technique. The cell parameters results in an open-circuit voltage of 0.4 V and a short-circuit current of 902 μA for PEO : PANI (50 : 50) composite. Hence, these composites can be better candidates for the polymer electrolyte studies. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Non-woven fabric supported poly(acrylonitrile-vinyl acetate) gel electrolyte for lithium ion battery use

This paper reported on a new gel polymer electrolyte (GPE) based on polyethylene (PE) non-woven fabric supported poly(acrylonitrile-vinyl acetate) (P(AN-VAc)/PE) membrane for lithium ion battery use. The preparation and performances of the P(AN-VAc)/PE membrane and its GPE based on 1 M LiPF₆ in dimethyl carbonate/diethylene carbonate/ethylene carbonate (1:1:1 in volume) were investigated with a comparison of the unsupported P(AN-VAc) membrane. It is found that the P(AN-VAc)/PE membrane shows better mechanical strength and pore structure for electrolyte uptake than the P(AN-VAc) membrane, and subsequently the GPE based on P(AN-VAc)/PE exhibits higher ionic conductivity and electrochemical stability on cathode than the GPE based on P(AN-VAc). With the support of the non-woven fabric, the ionic conductivity of the GPE at room temperature increases from 1.4 to 3.8 mS cm⁻¹, the oxidation decomposition potential of the GPE on a stainless steel is improved from 5.0 to 5.6 V (vs. Li/Li⁺). The mesocarbon microbeads (MCMB)/LiMn₂O₄ battery using P(AN-VAc)/PE as separator retains 94% of its initial discharge capacity after 100 cycles at C/2 rate, showing that the P(AN-VAc)/PE membrane is a possible alternative to the expensive separator for current liquid lithium ion battery.     

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     

Influences of poly(ether urethane) introduction on poly(ethylene oxide) based polymer electrolyte for solvent-free dye-sensitized solar cells

A poly(ether urethane) (PEUR)/poly(ethylene oxide) (PEO)/SiO₂ based nanocomposite polymer is prepared and employed in the construction of high efficiency all-solid-state dye-sensitized nanocrystalline solar cells. The introduction of low-molecular weight PEUR prepolymer into PEO electrolyte has greatly enhance the electrolyte performance by both improving the interfacial contact properties of electrode/electrolyte and decreasing the PEO crystallization, which were confirmed by XRD and SEM characteristics. The effects of polymer composition, nano SiO₂ content on the ionic conductivity and I₃⁻ ions diffusion of polymer-blend electrolyte are investigated. The optimized composition yields an energy conversion efficiency of 3.71% under irradiation by white light (100 mW cm⁻²).     

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     

“Pore/bead” membrane for rechargeable lithium ion batteries

A special “pore/bead” membrane was prepared with a mesoporous inorganic filler (MCM‐41) and a P(VDF‐HFP) binder. The special “pore/bead” structure of the MCM‐41 filler not only enhanced the puncture strength of the membrane but also improved its ionic conductivity. The puncture strength of the dried “pore/bead” membrane (MCM‐41 : P(VDF‐HFP) = 1 : 1.5) was 18 N, and showed a slight decrease (16 N) after the membrane was wetted by liquid electrolyte. Additionally, the composite membrane showed excellent thermal dimensional stability. The composite membrane could be activated by adding 1M LiClO₄‐EC/DMC (1 : 1 by volume). The activated membrane displayed a high ionic conductivity about 3.4 × 10^?3 S cm^?1 at room temperature. Its electrochemical stability window was up to 5.3 V vs. Li/Li⁺, indicating that it was very suitable for lithium‐ion battery application. The battery assembled using the composite electrolyte also showed reasonably good high‐rate performance. The approach of preparing a “pore/bead” membrane provides a new avenue for improving both the conductivity and the mechanical strength of polymer electrolytes for lithium batteries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhanced mechanical strength and conductivity of PVFM based membrane and its supporting polymer electrolytes

Polyvinyl formal based polymer electrolyte membranes are prepared via the optimized phase inversion method with poly(ethylene oxide) (PEO) blending. The physical properties of blend membranes and the electrochemical properties of corresponding gel polymer electrolytes (GPEs) are characterized by field emission scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, mechanical strength test, electrolyte uptake test, AC impedance spectroscopy, cyclic voltammetry, and galvanostatic charge–discharge test. The comparative study shows that the appearance of PEO obviously enhances the tensile strength of membranes and the ionic conductivity of corresponding GPEs. When the weight ratio of PEO is 30%, the tensile strength of membrane achieves 12.81 MPa, and its GPE shows high ionic conductivity of 2.20 × 10⁻³ S cm⁻¹, wide electrochemical stable window of 1.9–5.7 V (vs. Li/Li⁺), and good compatibility with LiFePO₄ electrode. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41839.     

PVdF-HFP/P123 hybrid with mesopores: a new matrix for high-conducting, low-leakage porous polymer electrolyte

Highly conducting porous polymer electrolytes comprised of poly(vinylidene-fluoride-co-hexafluoropropylene) (PVdF-HFP), polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (P123), ethylene carbonate (EC), propylene carbonate (PC), and LiClO₄ were fabricated. The PVdF-HFP/P123 hybrid polymer membranes were made with a phase inverse method and the electrolyte solution uptake was carried out in glove box to avoid the moisture contamination. It was found that when a small amount of polymer surfactant (P123) was blended into the PVdF-HFP, mesopores with well-defined sizes were formed. Impedance spectroscopy showed that the room temperature conductivity of (PVdF-HFP)/P123 polymer electrolytes increased as the content of P123 increased up to 4×10⁻³ S/cm. Nitrogen adsorption isotherms, electrolyte solution uptake, porosity measurements, and SEM micrographs showed that the enhanced conductivity was due to increase the pore volume, pore density, and electrolyte uptake. The highest conduction was found when the weight ratio of P123 to PVdF-HFP was 70%, when big channels were formed in the hybrid polymer membrane. Furthermore, blending P123 in PVDF-HFP reduced the pore size of polymer membrane, therefore, the solution leakage was also reduced. These polymer electrolytes were stable up to 4.5 V (vs Li/Li⁺) and the performance of the model lithium ion battery made by sandwiching the polymer electrolyte between a LiCoO₂ anode and a MCMB cathode, showed great promise for the use of these polymer electrolytes in lithium ion batteries.     

Preparation and performance of poly(ethylene oxide)-based composite solid electrolyte for all solid-state lithium batteries

Poly(ethylene oxide)-based solid electrolyte is attractive for using in all solid-state lithium batteries. However, the polymer has a certain degree of crystallization, which is adverse to the conduction of lithium ions. In order to overcome this drawback, a flexible composite polymer electrolyte (CPE) containing TiO₂ nanoparticles is elaborately designed and synthesized by tape casting method. The effects of different molar ratios of EO: Li and mass fraction of TiO₂ on the physical and electrochemical performances are carefully studied. The results show the CPE10 having 10 wt % TiO₂ has the lowest degree of crystallinity of 9.04%, the lowest activation energy of 8.63 × 10⁻⁵ eV mol⁻¹. Besides, the CPE10 shows a lower polarization and higher decomposition voltage. Thus, prepared all solid-state battery LiFePO₄/CPE10/Li shows a high initial capacity of 160 mAh g⁻¹ at 0.1 C, 134 mAh g⁻¹ at 0.5 C and higher capacity retention of 93.2% after 50 cycles at 0.5 C (1 C = 170 mAh g⁻¹). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47498.     

Preparation of poly(acrylonitrile-butyl acrylate) gel electrolyte for lithium-ion batteries

Poly(acrylonitrile-butyl acrylate) gel polymer electrolyte was prepared for lithium ion batteries. The preparation started with synthesis of poly(acrylonitrile-butyl acrylate) by radical emulsion polymerization, followed by phase inversion to produce microporous membrane. Then, the microporous gel polymer electrolytes (MGPEs) was prepared with the microporous membrane and LiPF₆ in ethylene carbonate/diethyl carbonate. The dry microporous membrane showed a fracture strength as high as 18.98 MPa. As-prepared gel polymer electrolytes presented ionic conductivity in excess of 3.0 × 10⁻³ S cm⁻¹ at ambient temperature and a decomposition voltage over 6.6 V. The results showed that the as-prepared gel polymer electrolytes were promising materials for Li-ion batteries.     

Physical and electrochemical properties of low molecular weight poly(ethylene glycol)‐bridged polysilsesquioxane organic–inorganic composite electrolytes via sol–gel process

A new class of ionic conducting organic/inorganic hybrid composite electrolyte with high conductivity, better electrochemical stability and mechanical behavior was prepared through the sol–gel processing between ethylene‐bridged polysilsesquioxane and poly(ethylene glycol) (PEG). The composite electrolyte with 0.05 LiClO₄ per PEG repeat unit has the best conductivity up to 10^?4 S/cm at room temperature with the transference number up to 0.48 and an electrochemical stability window as high as 5.5 V versus Li/Li⁺. Moreover, the effect of the PEG chain length on the properties of the composite electrolyte has also been studied. The interactions between ions and polymer have also been investigated for the composite electrolyte in the presence of LiClO₄ by means of FTIR, DSC, and TGA. The results indicated the interaction of Li⁺ ions with the ether oxygen of the PEG, and the formation of transient crosslinking with LiClO₄, resulting in an increase of the T_g of the composite electrolyte. The VTF‐type behavior of the ionic conductivity implied that the diffusion of the charge carriers was assisted by the segmental motions of the polymer chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2752–2758, 2007