Novel polymeric systems for lithium-ion batteries gel electrolytes: I. Cross-linked polyfluorosilicone

The investigation of chemically cross-linked, self-supporting gel-type electrolyte membranes, based on hybrid polyfluorosilicone polymers reinforced with nanosized silica, for lithium-ion battery systems is reported. The polyfluorosilicone materials were selected on the basis of their high chemical and thermal stabilities. The precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional polymer matrices. The latter were undergone to swelling processes in (non-aqueous, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. Several kinds of membranes, based on different types of polyfluorosilicone precursor, were prepared and characterized in terms of swelling behavior, ionic conductivity and electrochemical stability. The properties of the swelled matrices were evaluated as a function of dipping time, temperature, kind of electrolytic solution and cross-linking initiator content.     

Charge-discharge characteristics of the lithium electrode in mixed ether electrolytes

Mixed ether solutions of 1,2-dialkoxyethanes with 1,3-dioxolane or tetrahydrofuran containing some lithium salts have been examined as electrolytes for ambient temperature, rechargeable lithium (Li) batteries. The electrolytic conductivity and the charge-discharge behaviour of the Li electrode were investigated in the alkoxyethane-based electrolytes. The solutions containing LiPF₆ showed high conductance. The polarization behavoiur and the charge-discharge efficiency of the Li electrode were markedly affected by the size of an alkoxy group of ether. The cycling efficiency also depended on the electrolytic salt and the blended co-solvent. The highest efficiency was observed in the mixed system of 1,2-dimethoxyethane-tetrahydrofuran containing LiPF₆.     

Ionic conductivity and electrochemical properties of nanocomposite polymer electrolytes based on electrospun poly(vinylidene fluoride-co-hexafluoropropylene) with nano-sized ceramic fillers

A series of nanocomposite polymer electrolytes (NCPEs) comprising nanoparticles of BaTiO₃, Al₂O₃ or SiO₂ were prepared by electrospinning technique. The nano-sized ceramic fillers were incorporated into poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HEP)] membranes during the electrospinning process. The resultant porous membranes are good absorbent of the liquid electrolyte and exhibit high electrolyte retention capacity. The presence of the ceramic nanoparticles has positive effect on the mechanical properties of the membranes. The ionic conductivity and the electrochemical stability window of the electrospun P(VdF-HFP)-based polymer are enhanced by the presence of the fillers. The cell Li/LiFePO₄ based on the NCPE containing BaTiO₃ delivers a discharge capacity of 164 mAh/g, which corresponds to 96.5% utilization of the active material. In comparison, the performance of Li/LiFePO₄ cells with NCPEs containing Al₂O₃ and SiO₂ was observed to be lower with respective discharge capacities of 153 and 156 mAh/g. The enhanced performance of the BaTiO₃-based-NCPE is attributed mainly to its better interaction with the host polymer and compatibility with lithium metal.     

Physical and electrochemical characterizations of poly(vinylidene fluoride‐co‐hexafluoropropylene)/SiO2‐based polymer electrolytes prepared by the phase‐inversion technique

Highly porous poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF–HFP)‐based polymer membranes filled with fumed silica (SiO₂) were prepared by a phase‐inversion technique, and films were also cast by a conventional casting method for comparison. N‐Methyl‐2‐pyrrolidone as a solvent was used to dissolve the polymer and to make the slurry with SiO₂. Phase inversion occurred just after the impregnation of the applied slurry on a glass plate into flowing water as a nonsolvent, and then a highly porous structure developed by mutual diffusion between the solvent and nonsolvent components. The PVdF–HFP/SiO₂ cast films and phase‐inversion membranes were then characterized by an examination of the morphology, thermal and crystalline properties, absorption ability of an electrolyte solution, ionic conductivity, electrochemical stability, and interfacial resistance with a lithium electrode. LiPF₆ (1M) dissolved in a liquid mixture of ethylene carbonate and dimethyl carbonate (1:1 w/w) was used as the electrolyte solution. Through these characterizations, the phase‐inversion polymer electrolytes were proved to be superior to the cast‐film electrolytes for application to rechargeable lithium batteries. In particular, phase‐inversion PVdF–HFP/SiO₂ (30–40 wt %) electrolytes could be recommended to have optimum properties for the application. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 140–148, 2006     

Electrochemical performance of electrospun poly(vinylidene fluoride-co-hexafluoropropylene)-based nanocomposite polymer electrolytes incorporating ceramic fillers and room temperature ionic liquid

In view of the safety concerns and the requirements of high energy density lithium batteries, the room temperature ionic liquids (RTILs) are being investigated as suitable candidates to substitute organic electrolytes in polymer electrolytes. In this article, we report synthesis, characterization, and electrochemical properties of nanocomposite polymer electrolytes (NCPEs) comprising of a RTIL [n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI)] and nano-sized ceramic fillers (SiO₂, Al₂O₃ or BaTiO₃) hosted in electrospun poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HFP)] membranes. The addition of BMITFSI and ceramic fillers in polymer electrolytes results in high ionic conductivity at room temperature. The cells prepared with BMITFSI and different NCPEs show good interfacial stability and oxidation stability at >5.5 V with the highest value of 6.0 V for the NCPE incorporating BaTiO₃. The cell with the NCPE containing BaTiO₃ delivers high initial discharge capacity of 165.8 mA h g⁻¹, which corresponds to 97.5% utilization of active material under the test conditions, and showed the least % capacity fade after prolonged cycling.     

In situ composite of nano SiO2-P(VDF-HFP) porous polymer electrolytes for Li-ion batteries

Nano SiO₂-P(VDF-HFP) composite porous membranes were prepared as the matrix of porous polymer electrolytes through in situ composite method based on hydrolysis of tetraethoxysilane and phase inversion. SEM, TEM, DSC and AC impedance analysis were carried out. It is found that the in situ prepared nano silica was homogeneously dispersed in the polymeric matrix, enhanced conductivity and electrochemical stability of porous polymer electrolytes, and improved the stability of the electrolytes against lithium metal electrodes. The in situ composite method was found to be much better than the direct composite method in lowering the interfacial resistance between electrolyte and lithium metal electrode. Moreover, cycle test of lithium batteries using lithium metal as anode and sulfur composite material as cathode showed that the electrolyte based on in situ composite of silica presented stable charge-discharge behavior and little capacity loss of battery.     

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.     

Polymer electrolytes based on poly(ethylene glycol) and cyanoresin

Polymer electrolytes based on a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresins with lithium salt and plasticizer were prepared with an in situ blending process to improve both the mechanical properties and the ionic conductivity (σ). The PEG/lithium perchlorate (LiClO₄) complexes, including blends of cyanoethyl pullulan (CRS) and cyanoethyl poly(vinyl alcohol) (CRV), exhibited higher σ's than a simple PEG/LiClO₄ complex when the blend compositions of CRS/CRV were 5 : 5 or 3 : 7 or than CRV alone. When the CRS/CRV blend was compared with a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) (CRM) in the same molar ratio, the σ values of the polymer electrolytes containing the CRM copolymer series were slightly higher than those of the CRS/CRV blends containing PEG/LiClO₄ complexes. Moreover, the addition of cyanoresin to PEG/LiClO₄/(ethylene carbonate–propylene carbonate) polymer electrolytes provided better thermal stability and dynamic mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2402–2408, 2007     

Highly ionic conducting methacrylic-based gel-polymer electrolytes by UV-curing technique

Today, special interest is focused on polymer systems showing high ionic conductivity at ambient and/or sub ambient temperatures, since they find unique practical applications, such as separators in high power, versatile, rechargeable Li-based batteries. Thermo-set membranes prepared by free radical photo polymerisation (UV-curing) could be an interesting alternative to existing polymer electrolytes. In the present paper, we report the application of this technique to the synthesis of gel-polymer membranes which can be used as electrolytes for lithium battery application. These membranes are prepared by mixing a dimethacrylic (BEMA) and/or a diacrylic monomer (PEGDA), a methacrylic reactive diluent (PEGMA) and a radical photo-initiator with the in situ addition of a EC/DEC solution. The above mixtures are UV irradiated to obtain transparent, flexible, easy to handle gel-polymer films. The gel-polymer electrolytes (GPEs) are then prepared by swelling these membranes in different liquid electrolytes. The results obtained indicate some superior and satisfactory performances in terms of ionic conductivity at ambient temperature for various GPEs prepared with different lithium salt solutions. The relevance of these features in view of practical application is here demonstrated by the response of lithium cells based on prepared GPEs.     

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     

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.     

Lithium fuel cells:: I. Lithium/poly(organophosphazene) membrane anodes in KOH and seawater

The main goal of our research project is to design safe, high energy and power density lithium/water systems. We explored the feasibility of substituting the natural bilayer (formed on the lithium surface when lithium is in contact with water), for a thin polymeric film. By substituting the natural bilayer film we hope to reduce the parasitic reactions occurring at the lithium/water interface, thus yielding an increase in the anodic efficiency. We investigated the effect of placing or casting a thin, (lithium/ion-conducting) polymer layer on the lithium metal surface. This paper is part one in a series of two papers. Paper I presents the results obtained with a lithium/polymer system, where the polymer was a monolayer of a polyphosphazene with 90% trifluoromethylphenoxy and 10% lithium carboxyphenoxy side groups (Polymer 4), or a multilayer film formed of one layer of poly[bis(methoxyethoxyethoxy)phosphazene] (MEEP) and one to three layers of Polymer 4 containing from 0 to 75 wt.% of lithium triflate salts. Paper II presents results obtained when the polymer layers were prepared using a polymer with equal amounts of methoxyethoxyethoxy and phenoxy side groups containing from 0 to 75 wt.% of lithium triflate salts. Phosphazene membranes have been designed and tailored to allow lithium ion conduction and prevent water migration to the surface of lithium metal. The phosphazene membranes enhance the safety of an aqueous lithium cell by inhibiting (or reducing) the reaction of lithium with water that evolves hydrogen at the anode. Original tests of lithium/phosphazene systems led to unpredictable open circuit voltages (OCVs). When the adhesion of the membrane to the lithium metal was improved, the OCV stabilized. The OCVs for the half-cell of lithium polymer aqueous electrolytes varies between −3.1 and −2.8 V_SCE, depending on the membrane. The current densities for this polymer system are in the range of 10⁻⁶-10⁻³ A/cm². The Columbic anodic efficiency is assumed to be near 100%—as hydrogen evolution is not measurable. Some of the polymeric membranes developed pinholes with use. Layered systems have also been designed to avoid the development of pinholes over time. In this paper, we present the results obtained by using polyphosphazenes with a 9:1 ratio of trifluoromethylphenoxy and p-carboxyphenoxy side groups and the lithium salt of the carboxylate function. Poly(organophosphazene) membranes with a single layer and a multilayer structure were tested in 8 M KOH or synthetic seawater for up to 5 days.     

Morphological characterization of γ-LiAlO2-filled composite polymer electrolytes containing LiPF6

Morphological properties of composite polymer electrolytes based on blends of polyethylene oxide (PEO) and a perfluorinated polyphosphazene (PPz) containing LiPF₆ as lithium salt and a finely divided ceramic filler, γ-LiAlO₂, were studied by using polarizing optical microscopy and differential scanning calorimetry (DSC). A parallel study was performed on propylene carbonate plasticized composite polymer electrolytes. Results indicate that both the morphology and the thermal properties depend upon the composition of the polymer host, a result not observed in composite polymer electrolytes having the same polymer composition containing LiCF₃SO₃ as lithium salt. The incorporation of the ceramic filler at the lower concentration tested (10% by wt) has practically no effect on the thermal behavior of the samples; whereas, differences were clearly distinguished at a concentration of ceramic material of 20 wt %. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1023–1030, 1999     

Poly(methyl methacrylate) based nanocomposite gel polymer electrolytes with enhanced safety and performance

The study presents preparation of poly methyl methacrylate (PMMA) based nanocomposite gel polymer electrolytes consisting of, salt lithium perchlorate (LiClO₄), plasticizer PC/DEC and different proportions of SiO₂ nanofiber by solution casting process. The effect of the composition of the electrolytes on their ionic, mechanical and thermal characteristics was investigated. Morphology of the nanocomposite electrolyte films has been observed by scanning and transmission electron microscopes. Interactions among the constituents of the composite and structural changes of the base polymer were investigated by Fourier Transform Infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques. The maximum conductivity i.e. 10^?3 Scm^?1 at room temperature is obtained with the electrolyte composition of 0.6(PMMA)-0.15(PC + DEC)-0.1LiClO₄ (wt%) containing 10 wt% SiO₂ nanofiber and the temperature dependent conductivity data of the electrolyte follows Vogel-Tamman-Fulcher (VTF) behavior.     

Effects of simultaneous chemical cross-linking and physical filling on separation performances of PU membranes

The novel modified polyurethane (PU) membranes were prepared by β-cyclodextrin (CD) cross-linking and SiO₂/carbon fiber filler, simultaneously. The structures, thermal stabilities, morphologies, and surface properties were characterized by FTIR, TGA, SEM, and contact angle. The results showed that the addition of inorganic particles increased the thermal stabilities of PU membranes. The modified PU membranes possessed more hydrophobic surfaces than pure PU. In the swelling investigation, PU and its modified membranes were swelled gradually with increasing phenol content in the mixture. The membranes modified by CD cross-linking (PUCD) demonstrated the highest swelling degree. Pervaporation (PV) performances were investigated in the separation of phenol from water. Three kinds of modified membranes obtained better permeability and selectivity than PU membranes. With the feed mixture of 0.5 wt% phenol at 60 °C, the modified PU membrane by CD cross-linking and SiO₂ filler (PUCD-S) obtained the total flux of 5.92 kg μm m^?2 h^?1 which was above doubled that of PU (2.90 kg μm m^?2 h^?1). The modified PU membrane by CD cross-linking and carbon fiber filling (PUCD-C) obtained the separation factor of 51.31 which was nearly tripled that of PU (17.72). The PUCD membranes showed both better permeability and selectivity than the pure PU membranes. The increased phenol content induced an increased separation factor of PUCD and PU, but a decreased selectivity of PUCD-S and PUCD-C. The methods of CD cross-linking and inorganic particle filling were effective to develop the overall separation performances, greatly.     

A study on sulfonated poly(arylene ether sulfone) membranes containing two different types of SiO2 for a high temperature and low-humidified polymer electrolyte fuel cell

Two different types of silica oxide were prepared as filler in sulfonated polymers for fuel cell applications operated under water deficient environment. SiO₂ nanoparticle and thiol-embedded SiO₂ nanoparticles were mechanically mixed with sulfonated (arylene ether sulfone) solutions, and then the mixtures were cast to prepare composite membranes. The composite membranes with different amount of SiO₂ were prepared to investigate the effect of two types of SiO₂ nanoparticles on ionic conductivity with relative humidity at 120 °C. In addition, ion exchange capacity, water uptake, thermogravitational analysis, differential scanning calorimetry were studied. As results, the composite membranes containing thiol-embedded SiO₂ showed better water-channel forming ability at low relative humidity less than 50% in this study. Under full hydration of the composite membranes, the composite membranes containing pure SiO₂ nano-particles have higher ionic conductivity since the thiol-embedded SiO₂ might cause steric hindrance to make water channel well connected. Thus, below 50% relative humidity, the composite membranes containing 10 wt% of thiol-embedded SiO₂ showed the best ionic conductivity. It is very promising for polymer electrolyte fuel cells operated normally under 50% relative humidity at cathode.     

Characteristics of PVdF-HFP/TiO2 composite membrane electrolytes prepared by phase inversion and conventional casting methods

Porous poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP)-based polymer membranes filled with various contents of titania (TiO₂) nanocrystalline particles are prepared by phase inversion technique and, along with conventional casting method for comparison. N-methyl-2-pyrrolidone (NMP) as a solvent is used to dissolve the polymer and to make the slurry with TiO₂. Cast film is obtained by spreading the slurry and evaporating NMP in a dry oven, while phase inversion membrane by promptly immersing the spread slurry into flowing water as a non-solvent. Physical and electrochemical characterizations, such as morphology, thermal and crystalline behavior, and other transport properties of lithium ionic species, are carried out for the polymer films/membranes and the polymer electrolytes with absorbing an electrolyte solution. Phase inversion polymer electrolytes are proved to show superior behaviors in electrochemical properties, such as ionic conductivity, electrochemical and interfacial stability, than cast film electrolytes. This is greatly owed to highly porous structure of phase inversion membranes. Even including the feature of interfacial resistance with lithium electrode, phase inversion polymer electrolytes of PVdF-HFP/(5-20 wt.% TiO₂) can be optimized as the adequate ones in applying to the electrolyte medium of lithium rechargeable batteries.     

Structure, transport properties and interfacial stability of PVdF/HFP electrolytes containing modified inorganic filler

Gel polymer electrolyte membranes composed of poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) and surface modified aluminum or titanium oxide were prepared according to the so-called Bellcore process. Modifications were done by impregnating ceramic powder with 1-8% sulphuric acid aqueous solutions. Filler grain size varied from 10 to 12 μm. The membranes were conditioned in liquid electrode—1 mol/l LiClO₄ in PC.The ionic conductivity of polymer membrane increased by more than one order of magnitude upon the addition of filler into polymer host. For electrolyte membrane containing modified aluminum or titanium oxide, the interfacial resistance is stable in time as opposed to unmodified gel electrolytes. An increase in lithium transference number is observed upon the addition of filler. Lithium transference number also increases with the fraction of acidic surface groups.     

Solid polymer electrolytes. VII. Preparation and ionic conductivity of gelled polymer electrolytes based on poly(ethylene glycol) diglycidyl ether cured with α,ω‐diamino poly(propylene oxide)

Crosslinked polymer electrolyte networks were prepared from poly(ethylene glycol) diglycidyl ether blended with an epoxy resin (diglycidyl ether of bisphenol A) in different ratios and then cured with α,ω‐diamino poly(propylene oxide) in the presence of lithium perchlorate (LiClO₄) as a lithium salt. The ionic conductivities of these polymer electrolytes were determined by alternating current (AC) impedance spectroscopy. Propylene carbonate (PC) was used as a plasticizer to form gelled polymer electrolyte networks. The conductivities of the polymer electrolytes containing 46 wt % PC plasticizer were approximately 5 × 10^?4 S cm^?1 at 25°C and approximately 10^?3 S cm^?1 at 85°C. These polymer electrolytes were homogeneous and exhibited good mechanical properties. The effects of the polymer composition, plasticizer content, salt concentration, and temperature on the ionic conductivities of the polymer electrolytes were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1264–1270, 2004     

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

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