Metallic-lithium, LiFePO4-based polymer battery using PEO—ZrO2 nanocomposite polymer electrolyte

A study of the electrochemical properties of a PEO-based polymer electrolyte with nanometric ZrO₂ as ceramic filler has been carried out in order to confirm an earlier reported model dealing with the role of ceramic fillers within PEO-based polymer electrolytes as components that enhance such properties as conductivity, lithium transference number, compatibility with lithium metal electrodes and cyclability. A prototype of a lithium polymer battery, based on a membrane made from a nanocomposite polymer electrolyte doped with ZrO₂, utilizing LiFePO₄ + 1%Ag as cathode, has been assembled and galvanostatically cycled, resulting in excellent performance at temperatures ranging from 100 °C to 60 °C (close to the crystallization temperature of PEO).     

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     

Ionic conductivity studies of poly(ethylene oxide)-lithium salt electrolytes in high-pressure carbon dioxide

We have measured ionic conductivity of PEO-LiX [anion X=N(CF₃SO₂)₂ (TFSI), ClO₄, CF₃SO₃, BF₄, NO₃, and CH₃SO₃] polymer electrolytes in CO₂ at pressures varied from 0.1 to 20 MPa. From the temperature dependence in supercritical CO₂, a large increase in the conductivity for PEO-LiBF₄ and LiCF₃SO₃ electrolytes has been observed. Permeation of the CO₂ molecules gave rise to the plasticization for crystal domains in the electrolytes, which is related to the reduction in transition point of the Arrhenius plot corresponding to the melting of crystal PEO. Relation between the conductivity and CO₂ reduced density revealed that the electrolytes containing fluorinated anions such as ‘CO₂-philic’ BF₄ and CF₃SO₃ increase in the conductivity with increasing the density. This indicates that the salt dissociation was promoted by the CO₂ permeation and the Lewis acid-base interactions between fluorinated anions and CO₂ molecules.     

New type of lithium poly(polyfluoroalkoxy)sulfonylimides as salts for PEO‐based solvent‐free electrolytes

A new type of lithium salts, —SO₂NLiSO₂OCH₂(CF₂)_nCH₂O_m— (LiPPFASI, where n = 2, 3, 4, 6, and 7), was used as salts in poly(ethylene oxide) (PEO)‐based solvent‐free electrolytes. The conductivity and electrochemical stability behaviors were studied. The results showed the electrolytes almost have a similar conductivity and the PEO–LiPPFASI (n = 3, EO/Li = 10) was the relatively better system under the experiment conditions. Moreover, most systems were found to be oxidatively stable up to 5.5 V versus Li/Li⁺ and the lithium deposition‐stripping process on the electrode was reversible for all the polymer electrolytes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1882–1885, 2001     

Electrochemical studies on nanofiller incorporated poly(vinylidene fluoride–hexafluoropropylene) (PVdF–HFP) composite electrolytes for lithium batteries

Composite polymer electrolytes (CPE), comprising poly(vinylidene fluoride–hexafluoropropylene) (PVdF–HFP), aluminum oxyhydroxide, (AlO[OH] _n – of 40 nm and 7 μm) as filler and LiN(C₂F₅SO₂)₂ or LiClO₄ as lithium salt were prepared using a solution casting technique. The membranes were subjected to XRD, impedance spectroscopy, compatibility and transport number studies. The incorporation of nanofiller greatly enhanced the ionic conductivity and the compatibility of the composite polymer electrolyte. The electrochemical properties of CPE with nano sized fillers are better than those of micron size. Charge- discharge studies of Li Cr_0.01Mn_1.99O₄/CPE/Li cells were made at 70 °C and are discussed.     

New solid polymer electrolytes based on PEO/PAN hybrids

Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO₄ were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO₄‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO₄‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N₂, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006     

Development of non-stoichiometric SrBi4+2xTi4O15+3x (−0·04 ≤x≤ 0·04) ceramics

Abstract

The non-stoichiometric compositions of Bi layered structural SrBi₄Ti₄O₁₅ ferroelectric materials (SrBi_4+2xTi₄O_15+3x, x=?0·04, ?0·02, 0, 0·02 and 0·04) are investigated as the main precursors to find the influence of Bi₂O₃ content on the characteristics of SrBi₄Ti₄O₁₅ ceramics. The effect of compositional variation on the sintering and the dielectric characteristics of SrBi₄Ti₄O₁₅ ceramics are deduced with the aid of X-ray diffraction patterns, scanning electron microscopy observation and dielectric–temperature curves. From the scanning electron microscopy observations, the SrBi_3·92Ti₄O_14·88 and SrBi_3·96Ti₄O_14·94 ceramics reveal two phased grain growth, bar typed and irregularly disc typed grains coexist; the other SrBi_4+2xTi₄O_15+3x ceramics reveal irregularly disc typed grains. From the X-ray patterns, the Bi₂Ti₂O₇ and SrTiO₃ phases are observed in the SrBi_3·92Ti₄O_14·88 and SrBi_3·96Ti₄O_14·94 ceramics. Except the SrBi_3·96Ti₄O_14·94 ceramics, the other SrBi_4+2xTi₄O_15+3x ceramics have revealed a splitting peak in the (119) plane. It is also shown that the compositional variation has apparent influences on the grain morphologies, the bulk densities, the Curie temperatures and the maximum dielectric constants of SrBi_4+2xTi₄O_15+3x ceramics.     

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     

Impedance of interface between PEO:LiTFSI polymer electrolyte and blocking electrodes

The impedance spectra of electrolytes comprising poly(ethylene oxide) (PEO) with LiN(CF₃SO₂)₂ (LiTFSI) salt were measured for a wide range of concentration of salt in polymer electrolyte (from pure PEO to molar ratio of 1:1 EO:Li) and in various states (amorphous and semicrystalline). The measurements were performed on membranes placed between gold-plated stainless steel electrodes. Investigations of crystallization and melting with simultaneous observations in a polarizing microscope were performed between glass plates covered with film of indium tin oxide. The impedance data were analyzed by least squares fitting of equivalent circuit. Two different equivalent circuits were proposed for modeling of interfacial impedance for electrolytes with low and high concentration of salt, respectively. The decrease of the contact area due to the increase of stiffness of electrolyte and changes of electrical properties of the interfacial layer due to the presence of crystalline lamellae were identified as the major causes for changes of impedance of the interface layer taking place during crystallization.     

Effects of the surface treatment of the Al2O3 filler on the lithium electrode/solid polymer electrolyte interface properties

The lithium deposition-dissolution process in solid polymer electrolytes containing Al₂O₃ filler treated under different conditions has been investigated comparing with the ionic conduction behavior of the electrolyte. The composite electrolytes were prepared from poly(ethylene oxide) (PEO), LiBF₄ and α-Al₂O₃ filler by using a dry process, where the surface of α-Al₂O₃ was beforehand modified by a wet process. The exchange current densities, i₀, of the lithium electrode process in P(EO)₂₀LiBF₄ with and without Al₂O₃ filler were determined by a micro-polarization method. The temperature dependence of i₀ provided similar values for activation energy, ca. 25 and 70 kJ mol⁻¹ in both temperature regions above and below 60 °C, respectively. The effect of the surface treatment of the filler on the lithium electrode process gave a different tendency from that on the ionic conductivity. The Al₂O₃ surface treated by alkali solution enhanced the electrode process to the largest extent among the fillers used here, while it led to rather poor cycling stability in voltammetry. The enhanced reaction rate at the lithium electrode/solid polymer electrolyte interface has probably resulted in the improved ion dissociation by the surface groups of the Al₂O₃ filler.     

Effect of silicone dioxide and poly(ethylene glycol) on the conductivity and relaxation dynamics of poly(ethylene oxide)–silver triflate solid polymer electrolyte

The conducting and relaxation dynamics of Ag⁺ ions in poly(ethylene oxide) (PEO)–silver triflate (AgCF₃SO₃) solid polymer electrolytes (SPEs) containing nanosize SiO₂ filler and poly(ethylene glycol) (PEG) as a plasticizer were studied in the frequency range 10 Hz to 10 MHz and in the temperature range 303–328 K. The comparatively lower conductivity of the plasticized (PEG) PEO–AgCF₃SO₃–SiO₂ nanocomposite electrolyte system was examined by analysis of the Fourier transform infrared (FTIR) spectroscopy and conductivity data. The electric modulus (M″) properties of the SPE systems were investigated. A shift of the M″ peak spectra with frequency was found to depend on the translation ion dynamics and the conductivity relaxation of the mobile ions. The value of the conductivity relaxation time was observed to be lower for the PEO–AgCF₃SO₃ system only with nanofiller SiO₂. The scaling behavior of the M″ spectra showed that the dynamical relaxation processes was temperature-independent in the PEO–AgCF₃SO₃ and PEO–AgCF₃SO₃–SiO₂–PEG polymer systems, whereas they were temperature-dependent for the PEO–AgCF₃SO₃–SiO₂ system. However, the relaxation processes of all of theses systems were found to be dependent on their respective compositions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Novel PEO-based solid composite polymer electrolytes with inorganic–organic hybrid polyphosphazene microspheres as fillers

Novel solid-state composite polymer electrolytes based on poly (ethylene oxide) (PEO) by using LiClO₄ as doping salts and inorganic–organic hybrid poly (cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) microspheres as fillers were prepared. Electrochemical and thermal properties of PEO-based polymer electrolytes incorporated with PZS microspheres were studied. Differential scanning calorimetry (DSC) results showed there was a decrease in the glass transition temperature of the electrolytes and the crystallinity of the samples in the presence of the fillers. Maximum ionic conductivity values of 1.2 × 10⁻⁵ S cm⁻¹ at ambient temperature and 7.5 × 10⁻⁴ S cm⁻¹ at 80° were obtained and lithium ion transference number was 0.29. Compared with traditional ceramic fillers such as SiO₂, the addition of PZS microspheres increased the ionic conductivity of the electrolytes slightly and led to remarkable enhancement in the lithium ion transference number.     

Influence of crystalline complexes on electrical properties of PEO:LiTFSI electrolyte

Polymer electrolytes of poly(ethylene oxide) matrix with lithium imide salt LiN(CF₃SO₂)₂ were prepared by casting from solution. Thin films with compositions corresponding to molar ratios 6:1, 3:1 and 2:1 EO:Li were investigated by impedance spectroscopy, impedance spectroscopy simultaneous with polarizing microscope observation, X-ray diffraction and differential scanning calorimetry. The presence of PEO:LiTFSI stoichiometric complexes was found to significantly decrease conductivity at temperature of crystallization, which indicates that those complexes should be regarded as poorly conductive. Changes of properties of amorphous phase related to crystallization were also observed. Crystallization induced phase segregation, which in some cases caused considerable shift of the glass transition temperature of amorphous phase remaining in a semicrystalline system. For PEO:LiTFSI electrolyte with molar ratio of 3:1 EO:Li this effect was found to be responsible for enhancement of conductivity of semicrystalline sample in respect to the amorphous one, which was observed at low temperatures. Phase separation involving precipitation of LiTFSI salt was also found to be a likely explanation for significant enhancement of conductivity for PEO:LiTFSI 2:1 electrolyte subjected to rapid cooling below the glass transition temperature.     

Simple introduction of anion trapping site to polymer electrolytes through dehydrocoupling or hydroboration reaction using 9-borabicyclo[3.3.1]nonane

Organoboron-based anion trapping polymer electrolytes were synthesized through hydroboration or dehydrocoupling reaction between poly(propylene oxide) (PPO) oligomer (M_n = 400, 1200, 2000 and 4000) and 9-borabicyclo[3.3.1]nonane (9-BBN). Obtained oligomers were added various lithium salts (LiN(CF₃SO₂)₂, LiSO₃CF₃, LiCO₂CF₃ or LiBr) to analyze the ionic conductivity and lithium ion transference number (tLi⁺). The ionic conductivity of the oligomer in the presence of LiN(CF₃SO₂)₂ showed higher ionic conductivity than other systems, however, the tLi⁺ was less than 0.3. When LiSO₃CF₃ or LiCO₂CF₃, was added high tLi⁺ over 0.6 was obtained. Such difference in tLi⁺ can be explained by HSAB principle. Since boron is a hard acid, soft (CF₃SO₂)₂N⁻ anion can not be trapped effectively. High ionic conductivity of 1.3 × 10⁻⁶ S cm⁻¹ and high tLi⁺ of 0.73 was obtained when PPO chain length was 2000. These values of facilely prepared polymer electrolytes are comparable to those of the PPOs having covalently bonded salt moieties on the chain ends.     

Assessment on the mechanical,structural, and thermal attributes of green graphene-based water soluble polymer electrolyte composites

In the current study, graphene oxide (GO) was prepared using green chemistry with modified Hummer's method without incorporating sodium nitrate (NaNO₃). Solvent casting was employed to fabricate GO-doped poly(ethylene oxide) (PEO), that is, PEO/GO composites with various proportion of Na₂SO₄ and were then subjected to characterization via advanced spectroscopic techniques for different physicochemical aspects to estimate their potential applications as marketable products. XRD analysis explored that fabricated composites are more crystalline than neat PEO. PEO/GO/Na₂SO₄ composite films offered maximum crystallinity. SEM displayed the same trend. TG/DTA thermogram exposed better thermal stability than pristine polymer. FTIR studies confirmed complexation among hybrid's components. Elongation-at-break and Young's modulus displayed an enhancing behavior with an incremental loading of salt and filler. In terms of mechanical performance, composite of PEO with 0.37 wt % GO and 0.08 g salt was found to be an ideal composition during the course of study. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48376.     

Effect of grafting degree and side PEO chain length on the ionic conductivities of NBR-g-PEO based polymer electrolytes

Comb-shaped graft polymers were synthesized and complexed with a LiCF₃SO₃ salt to form a new class of polymer electrolytes. The polymers based on an acrylonitrile-butadiene copolymer (NBR) have pendant, short-chain poly(ethylene oxide) (PEO) grafted onto a butadiene unit. The characteristics of these polymer electrolytes were investigated in terms of number of pendant EO groups and grafting degree in the graft copolymer. The maximum conductivity was observed at the optimum side PEO chain length, and the PEO chain length for the maximum conductivity decreased with an increase in the grafting degree. And a solid ⁷Li NMR relaxation technique was used to study the local environments and dynamics of the ions in the polymer electrolytes. The maximum conductivity value obtained from our study was three orders of magnitude higher than that of classical PEO-based electrolytes at ambient temperature. These improved low temperature conducting polymers with higher relative mechanical strength are expected to be suitable for practical applications, such as in rechargeable lithium batteries or electrochromic devices.     

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

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

Effect of 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.     

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.