Effect of branching in base polymer on ionic conductivity in hyperbranched polymer electrolytes

Novel hyperbranched polymer, poly[bis(diethylene glycol)benzoate] capped with a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group (poly-Bz1a), was prepared, and its polymer electrolyte with LiN(CF₃SO₂)₂, poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte, was all evaluated in thermal properties, ionic conductivity, and electrochemical stability window. The poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte exhibited higher ionic conductivity compared with a polymer electrolyte based on poly[bis(diethylene glycol)benzoate] capped with an acetyl group (poly-Ac1a), and the ionic conductivity of poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte was to be 7×10⁻⁴ S cm⁻¹ at 80 °C and 1×10⁻⁶ S cm⁻¹ at 30 °C, respectively. The existence of a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group as a branching unit present at ends in the base polymer improved significantly ionic conductivity of the hyperbranched polymer electrolytes. The polymer electrolyte exhibited the electrochemical stability window of 4.2 V at 70 °C and was stable until 300 °C.     

Blended lithium ion conducting polymer electrolytes based on boroxine polymers

A new series of blended polymer electrolytes based on a boroxine polymer (BP) with poly(ethylene oxide) (PEO), an ethylene oxide–propylene oxide copolymer or poly(methyl methacrylate) were prepared. Good room temperature mechanical properties were exhibited by electrolytes containing in excess of 30% PEO. Cationic transference number measurements indicated that a slight improvement in lithium ion conductivity could be achieved by using a mixture of LiCF₃SO₃ and LiN(CF₃SO₂)₂ as the electrolyte salt. Electrolytes incorporating significant proportions of BP exhibited reduced lithium–polymer electrolyte interfacial resistance.     

Effect of molecular weight on conductivity of polymer electrolytes

The ionic conductivity, σ, of mixtures of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfone)imide (LiTFSI) was measured as a function of molecular weight of the PEO chains, M, over the range 0.2-5000 kg/mol. Our data are consistent with an expression σ = σ₀ + K/M proposed by Shi and Vincent [Solid State Ionics 60 (1993)] where σ₀ and K are exponential and linear functions of inverse temperature respectively. Explicit expressions for σ₀ and K are provided.     

Polymer electrolyte plasticized with PEG-borate ester having high ionic conductivity and thermal stability

We have focused on the PEG-borate ester as a new type of plasticizer for solid polymer electrolyte composed of poly(ethyleneglycol) methacrylate (PEGMA) and lithium bis-trifluoromethanesulfonimide (LiTFSI). The PEG-borate ester shows good thermal stability and high flash point. Ionic conductivity of the polymer electrolyte increases with increasing amount of the PEG-borate ester and exhibits values greater than 10⁻⁴ S cm⁻¹ at 30 °C and 10⁻³ S cm⁻¹ at 60 °C. Furthermore, PEG-borate ester has three EO chains whose lengths are variable, and various ionic conductivities are expected to depend on EO chain length. As a result, polymer electrolyte containing the PEG-borate ester whose EO chain length is n=3 shows highest ionic conductivity. Furthermore, polymer electrolytes containing PEG-borate esters show excellent thermal and electrochemical stability. The electrolytes are thermally stable up to 300 °C and electrochemically up to 4.5 V vs. Li⁺/Li.     

Ionic conduction in plasticized PVC/PAN blend polymer electrolytes

Blended polymer electrolytes with poly(vinyl chloride) (PVC)–poly(acrylonitrile) (PAN) were prepared with different plasticizer concentrations and constant lithium perchlorate (LiClO₄) ratio by the solution-casting technique. The structure and complexation of the prepared films were studied by X-ray diffraction and Fourier transform infrared spectroscopy. The effect of the plasticizer on the ionic conduction in these electrolytes was investigated using alternating current impedance measurement and discussed. The temperature-dependant ionic conductivity was carried out in the range 302–373 K. The prepared films were also examined by thermogravimetry/differential thermal analysis to determine their thermal stability.     

Effects of plasticizer and nanofiller on the dielectric dispersion and relaxation behaviour of polymer blend based solid polymer electrolytes

Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF₃SO₃) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li⁺ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF₃SO₃ electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10⁻⁵ S cm⁻¹, confirming their use in preparation of all-solid-state ion conducting devices.     

An investigation on PAN-PVC-LiTFSI based polymer electrolytes system

Polymer-salt complex with poly(vinyl chloride) (PVC) and poly(acrylonitrile) (PAN) as host polymers blended with lithium bis-(trifluoro methanesulfonyl)imide, LiTFSI [LiN(CF₃SO₂)₂] as dopant salt were prepared in the form of thin film. Fourier transform infrared (FTIR) studies show the evidence of the complexation between PVC, PAN and LiTFSI. Ionic conductivity studies reveal that polymer electrolyte with 30 wt.% LiTFSI has the highest ionic conductivity of 4.39 × 10^− 4 S/cm at room temperature. The polymer electrolytes are also found to be stable up to 315 °C before they decompose. Thermal stability of the polymer electrolytes was also found to increase with increase in salt content. This was proven through thermogravimetric studies.     

PEG crosslinked poly(vinylbenzene boronic acid) polymer electrolytes for Li-ion batteries

Poly(4-vinylbenzeneboronic acid), PVBBA was synthesized via free-radical polymerization of 4-vinylbenzeneboronic acid (4-VBBA) and followed by crosslinking with polyethylene glycol (PEG) with different molecular weights to produce boron containing crosslinked polymers. Prior to crosslinking, the materials were doped with CF₃SO₃Li at several stoichiometric ratios to get PVBBAPEGX-Y where X is the molecular weight of PEG and Y is the EO/Li ratio. The materials were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). The ionic conductivity of these novel crosslinked electrolytes was studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of the side units as well as the doping ratio. PVBBAPEG200-10 illustrated a satisfactory ionic conductivity of 3.1 × 10^?5 S/cm at 20 °C and 1.8 × 10^?3 S/cm at 100 °C.     

Solid polymer electrolytes based on poly(lithium carboxylate) salts

The ionic conductivity, lithium ion transference number, electrochemical stability, and thermal property of solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and poly(lithium carboxylate)s, (poly(lithium acrylate) (Poly(Li-A)) or poly(lithium fumarate) (Poly(Li-F)), with and without BF₃·OEt₂ were investigated. The ionic conductivities of all solid polymer electrolytes were enhanced by one to two orders of magnitude with addition of BF₃·OEt₂ because the dissociation of lithium ion and carboxylate anion was promoted by the complexation with BF₃. The lithium ion transference number in the solid polymer electrolytes based on poly(lithium carboxylate)s showed relatively high values of 0.41–0.70, due to the suppression of the transport of counter anion by the use of a polymeric anion. The solid polymer electrolytes with addition of BF₃·OEt₂ showed good electrochemical stability.     

Polymer electrolytes based on ethylene oxide–epichlorohydrin copolymers

In this work we studied the ionic conductivity for three copolymers of the title co-monomers as a function of LiClO₄ content, temperature and ambient relative humidity. We also investigated the interactions between the salt and the co-monomer blocks in the copolymers and its effect on the morphology and thermal properties of the copolymer/salt complexes. Our data indicate that the Li⁺ ion predominantly interacts with the ethylene oxide repeating units of the copolymers. The copolymer with the highest ionic conductivity was obtained with an ethylene oxide/epichlorohydrin ratio of 84/16 containing 5.5% (w/w) of LiClO₄. It showed a conductivity of 4.1×10⁻⁵ S cm⁻¹ (30°C, humidity< 1 ppm) and 2.6×10⁻⁴ S cm⁻¹ at 84% relative humidity (24°C). The potential stability window of the copolymer/salt complex is 4.0 V, as measured by cyclic voltammetry. For comparison, we also prepared a blend of the corresponding homopolymers containing LiClO₄; it showed higher crystallinity and lower ionic conductivity.     

Studies on the structure and transport properties of hexanoyl chitosan-based polymer electrolytes

Polymer electrolytes composed of hexanoyl chitosan as the host polymer, lithium trifluoromethanesulfonate (LiCF₃SO₃) as the salt, diethyl carbonate (DEC)/ethylene carbonate (EC) as the plasticizers were prepared and characterized by X-ray diffraction and impedance spectroscopy. The X-ray diffraction results reveal the variation in conductivity from structural aspect. This is reflected in terms of amorphous content. Sample with higher amorphous content exhibits higher conductivity. In order to further understand the source of the conductivity variation with varying plasticizers compositions as well as temperatures, the ionic charge carrier concentration and their mobility in polymer electrolyte were determined. The Rice and Roth model was proposed to be used to estimate the ionic charge carrier concentration, n. Knowing n and combining the result with dc conductivity, the mobility of the ionic charge carrier can be calculated. It is found that the conductivity change with DEC/EC composition is due mainly to the change in ionic charge carrier concentration while the conductivity change with temperature is due primarily to the change in mobility.     

A study on the blending effect of polyvinyledene fluoride in the ionic transport mechanism of plasticized polyvinyl chloride + lithium perchlorate gel polymer electrolytes

The gel polymer electrolytes composed of the blend of polyvinylchloride (PVC) and polyvinylidene fluoride (PVdF) as host polymers, the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizer, and LiClO₄ as a salt was studied. An attempt was made to investigate the effect of PVdF in the plasticized PVC + LiClO₄ system in three blend ratios. The differential scanning calorimetry study confirms the formation of polymer–salt complex and miscibility of the PVC and PVdF. The X-ray diffraction results of plasticized PVC (S1, S2, S3) and PVdF-blended films (S4, S5, S6) were compared, in that an increase in PVC concentration decreases the degree of crystallinity for S1 and S3, respectively, but drastically increases for PVC (S2). The increase in PVC content has not accounted in the conductivity studies also noted. However, the blending effect of PVdF showed decreases in crystallinity homogeneously for (S6 > S5 > S4), which were reflected in ionic conductivity measurements. The surface morphology of the films were also studied by scanning electron microscope, and it corroborates the same. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Investigation on PVDF-HFP microporous membranes prepared by TIPS process and their application as polymer electrolytes for lithium ion batteries

Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) microporous membranes were prepared via thermally induced phase separation (TIPS) process. Then they were immersed in a liquid electrolyte to form polymer electrolytes. The effects of polymer content in casting solution on the morphology, crystallinity, and porosity of the membranes were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and a mercury porosimeter, respectively. Ionic conductivity, lithium-ion transference number, and electrochemical stability window of corresponding polymer electrolytes were characterized by AC impedance spectroscopy, DC polarization/AC impedance combination method, and linear sweep voltammetry, respectively. The results showed that spherulites and “net-shaped” structure coexisted for the membranes. Polymer content had no effect on crystal structure of the membranes. The maximum transference number was 0.55. The temperature dependence of ionic conductivity followed the Vogel–Tammann–Fulcher (VTF) relation. The maximum ionic conductivity was 2.93 × 10⁻³ Scm⁻¹ at 20 °C. Electrochemical stability window was stable up to 4.7 V (vs. Li⁺/Li).     

Star-shaped oligo(ethylene glycol) ethers (OEGE) as a new type of plasticizer for polymer gel electrolytes

Star-shaped oligo(ethylene glycol) methyl ethers (three and four arm molecules of various molecular weights) were synthesized and characterized with regard to viscosity, thermal transitions, ability to solvate the electrolyte LiCF₃SO₃ and the ionic conductivity of their LiCF₃SO₃ solutions in comparison to linear oligo(ethylene glycol) methyl ethers. Polymer gel electrolytes were prepared by photopolymerization of tri(ethylene glycol) dimethacrylate (EG₃DMA) or its copolymerization with the polar comonomer cyanomethyl methacrylate (CyMA) in the presence of the oligo(ethylene glycol) ethers mentioned above and of the electrolyte LiCF₃SO₃. The gels were characterized concerning their thermal transitions, thermo-mechanical properties, their ability to solvate the electrolyte and their ionic conductivity. In comparison to the linear plasticizers the star-shaped ones show a distinctly lower tendency to crystallize, which is even completely suppressed in several cases. Intensified ion association was found in LiCF₃SO₃ solutions of the star-shaped plasticizers, if the number of the ethylene glycol units per arm was lower than 4. Therefore, the conductivity of the solutions and the gels was lower than that with linear plasticizers at room temperature. The modification of the polymer matrix by copolymerization with 20 mol% CyMA resulted in a maximum of the ionic conductivity σ≈1×10⁻⁵ S/cm of gels with star-shaped plasticizers at 25 °C.     

Effect of plasticizer on electrical conductivity and cell parameters of (PVC+KBrO<Subscript>3</Subscript>) polymer electrolyte system

The effect of a plasticizer dimethyl formamide (DMF) on the properties of a potassium ion conducting electrolyte based on polyvinyl chloride (PVC) complexed with potassium bromate (KBrO₃) prepared using solution-cast technique was investigated. Various experimental techniques, such as electrical conductivity (composition and temperature dependence) and transport number measurements, were used to characterize these polymer electrolyte films. It was found that the addition of plasticizer (DMF) significantly improved the ionic conductivity. Transport number for K⁺ ion ranged from 0.95 to 0.97 depending on the composition and temperature. Electrochemical cells of configuration K/PVC+KBrO₃/(I₂+C+electrolyte) and K/PVC+KBrO₃+plasticizer/(I₂+C+electrolyte) were fabricated. The discharge characteristics of the cells were studied under a constant load of 100 kΩ. The open-circuit voltage, short-circuit current, and discharge time for the plateau region were measured. The PVC+KBrO₃ polymer electrolyte system with added plasticizer showed an increased discharge time with respect to pure PVC+KBrO₃ electrolyte system. The features of complexation of the electrolytes were studied by X-ray diffraction.     

An investigation of the proton conductivities of hydrated poly(vinyl alcohol)/boric acid complex electrolytes

Proton-conducting polymer complex electrolytes were prepared by incorporation of boric acid, H₃BO₃ into poly(vinylalcohol), PVA, to form hydrated PVAxH₃BO₃ where x denotes the number of moles of boric acid per polymer repeat unit. The dried materials were characterized via Fourier transform infrared spectroscopy, thermogravimetry, and X-ray diffraction. The proton conductivity of the hydrated complex electrolytes was measured by AC impedance spectroscopy. PVA2H₃BO₃ with RH ∼25% was found to be optimum composition that exhibited proton conductivity of 1.3 × 10⁻³ S/cm at 80 °C.     

Effect of radiation on conductivity of solid PVA–KOH–PC composite polymer electrolytes

The aim of this work is to enhance the room temperature conductivity of solid alkaline composite polymer electrolytes (ACPEs) based on polyvinyl alcohol/potassium hydroxide/propylene carbonate (PVA–KOH–PC) composites by cross-linking the PVA and bond scission of the PC by γ-radiation. The ACPEs were prepared by solvent-casting technique and irradiated with doses up to 200 kGy at room temperature. The microstructure of the ACPEs was measured using XRD spectrometer, and the results show the structural change from semicrystalline to amorphous, indicating that the cross-linking has been achieved at higher doses. It was found that the PKOH composite at 40 wt% KOH and PPC composite at 60 wt% PC show higher conductivities. The conductivity of the PKPC composites is dominated by dc conductivity at higher frequencies and that PC with 60 wt% has the highest conductivity at a dose of 200 kGy.Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6–8, 2005.     

Characterization of pTMCnLiPF6 solid polymer electrolytes

In this study the results of our characterization of a solid polymer electrolyte based on poly(trimethylene carbonate), henceforth designated as p(TMC), and lithium hexafluorophosphate (LiPF₆) are described. Samples of solvent-free electrolytes were prepared with a range of concentration of guest salt using solvent casting from tetrahydrofuran and characterized by conductivity measurements, thermal analysis and electrochemical stability. Electrolytes based on this host polymer, with LiPF₆, were obtained as mechanically robust, flexible, transparent and completely amorphous films.     

Effect of hot pressing on the ionic conductivity of the PEO/LiCF3SO3 based electrolyte membranes

PEO/LiCF₃SO₃ (LiTFS) /Ethylene carbonate (EC) polymer electrolyte membranes were prepared with a solution casting method followed by a hot pressing process. The effect of the hot pressing process on the in-plane conductivity of the PEO electrolyte membranes was evaluated using a four-electrode AC impedance method. The composition, morphology, and microstructure of the composite polymer electrolyte were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The AC impedance measurement results indicate that the hot pressing process can increase the room temperature conductivity of the membranes 14 times to 1.7 × 10^− 3 S cm^− 1 depending upon the duration of the hot pressing process. The SEM, FTIR, XRD, and DSC results indicate that the hot pressing process could increase the amorphous part of the polymer electrolyte membrane or convert large spherulite crystals into nano-sized crystals.     

Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps

Sodium ion conducting polymer blend electrolyte films, based on polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP) complexed with NaF salt, were prepared using solution casting technique. The complexation of the salt with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy. Electrical conductivity of the films was measured with impedance analyzer in the frequency range of 1 Hz to 1 MHz and in the temperature range of 303-348 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. UV-vis absorption spectra in wavelength region of 200-800 nm were used to evaluate the optical properties like direct and indirect optical energy band gaps, optical absorption edge. The optical band gaps decreased with the increase in Na⁺ ion concentration. This suggests that NaF, as a dopant, is a good choice to improve the electrical properties of PEO/PVP polymer blend electrolytes.