Ionic conductivity and physical stability study of gel nework polymer electrolytes

Gel polymer electrolytes (GPE) were prepared by a crosslinking reaction between poly(ethylene glycol) and a crosslinking agent with three isocyanate groups in the presence of propylene carbonate (PC) and ethylene carbonate (EC) or their mixture, and their ionic conducting behavior was carefully investigated. When the plasticizer amount was fixed, the ionic conductivity was greatly influenced by the nature of plasticizers. It was found that the conductivity data followed the Arrhenius equation in the GPE. Whatever plasticizer was used, a maximum ambient conductivity was found at a salt concentration near [Li⁺]/[EO] equal to 0.20. The physical stability of GPE was studied qualitatively by weight loss of GPE under pressure. It was shown that the stability was greatly affected by the network structure of the GPE and the most stable one in our research was the GPE containing the PEO₁₀₀₀ segment, which has a strong interaction between network and plasticizers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2957–2962, 2000     

Crystallinity,thermal properties,morphology and conductivity of quaternary plasticized PEO‐based polymer electrolytes

Quaternary plasticized solid polymer electrolyte (SPE) films composed of poly(ethylene oxide), LiClO₄, Li_1.3Al_0.3Ti_1.7(PO₄)₃, and either ethylene carbonate or propylene carbonate as plasticizer (over a range of 10–40 wt%) were prepared by a solution‐cast technique. X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) indicated that components such as LiClO₄ and Li_1.3Al_0.3Ti_1.7(PO₄)₃ and the plasticizers exerted important effects on the plasticized quaternary SPE systems. XRD analysis revealed the influence from each component on the crystalline phase. DSC results demonstrated the greater flexibility of the polymer chains, which favored ionic conduction. SEM examination revealed the smooth and homogeneous surface morphology of the plasticized polymer electrolyte films. EIS suggested that the temperature dependence of the films' ionic conductivity obeyed the Vogel–Tamman–Fulcher (VTF) relation, and that the segmental movement of the polymer chains was closely related to ionic conduction with increasing temperature. The pre‐exponential factor and pseudo activation energy both increased with increasing plasticizer content and were maximized at 40 wt% plasticizer content. The charge transport in all polymer electrolyte films was predominantly reliant on lithium ions. All transference numbers were less than 0.5. Copyright © 2006 Society of Chemical Industry     

Nuclear magnetic resonance and conductivity study of hydroxyethylcellulose based polymer gel electrolytes

Polymer gel electrolytes formed by hydroxyethylcellulose (HEC) plasticized with glycerol and containing lithium perchlorate were studied by nuclear magnetic resonance spectroscopy (NMR) and complex impedance spectroscopy. In heavily plasticized samples, results show that the addition of solvent enhances the conductivity, which reaches 6 × 10⁻⁵ S/cm at room temperature. The ⁷Li NMR results indicate that this enhancement is associated with a decoupling of the lithium-ion dynamics from the local motion of the polymer host, with the increase in the mobility of the ionic species, and with the increase of the charge carrier concentration resulting from the salt dissociation after addition of the solvent. The temperature dependence of the lithium NMR spin-lattice relaxation is interpreted assuming that there are two distinct lithium-ion dynamics. The corresponding NMR relaxation processes are characterized by activation energies of 0.3 and 0.12 eV, respectively.     

Ionic conductivity of solid polymer electrolytes for dye‐sensitized solar cells

We developed an ionic conductivity model of solid polymer electrolytes for dye‐sensitized solar cells (DSSCs) based on the Nernst–Einstein equation in which the diffusion coefficient is derived from the molecular thermodynamic model. We introduced concentration‐dependence of the diffusion coefficient into the model, and the diffusion coefficient was expressed by differentiating the chemical potential by concentration. The ionic conductivities of polymer electrolytes (PEO/LiI/I₂ system) were investigated at various temperatures and compositions. We prepared a set of PEO in which an EO : LiI mole ratio of 10 : 1 was kept constant for PEO·LiI·(I₂)_n compositions with n = 0.02, 0.05, 0.1, 0.15, 0.2, and 0.3 (mole ratio of LiI : I₂). The ionic conductivities of the electrolytes were measured using a stainless steel/polymer‐electrolyte/stainless steel sandwich‐type electrode structure using alternating current impedance analysis. The values calculated using the proposed model agree well with experimental data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Conductivity studies of solid polymer electrolytes based on polyethers and polyphosphazene blends

In this work, electrical characteristics of several polymer electrolytes based on polyether and polyphosphazene blends are reported by means of complex impedance spectroscopy. In addition, a statistical analysis was conducted applying a mathematical model to a previously designed pattern to the purpose of gaining insight into the effect exerted on the conductivity of the electrolyte by the portion of each component in the blend. Evidence was obtained to prove that the dependence of conductivity on blend composition adjusts to a reduced cubic model, whose regression coefficients are determined in this work. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2181–2186, 1998     

Effect of solvent on thermal transitions and conductivity of poly (vinylidene fluoride) gel electrolytes

ABSTRACT

The melting (T_m) and crystallization (T_c) temperature increased with increasing solvent phenyl propanol (PhP) concentration in the mixture of solvent propylene carbonate and phenyl propanol (PC/PhP). It is also a little enhances of Tm and Tc with adding ethylene carbonate (EC) to propylene carbonate (PC). The melting (T_m) and softening temperature (T_soft) follows the following order of solvents PC<EC:PC<PhP:PC. There was a small change of modulus was observed with the addition of PhP. The conductivity falls with increasing PhP concentration and viscosity and re-calculate free ion concentration. The adding EC to PC raises temperatures slightly, but conductivity much the same. The overall, adding poorer solvent PhP increases the melting and crystallization temperatures at the expense of conductivity, but a little changes was observed in storage modulus, much better gel network, thereby securing the continuity of the complex leads to more flexible ductile and crystalline phase serves better mechanical properties. The crystallinity of PVDF gel electrolyte is about 50%, which facilitate to changes gel network structure slightly with PhP concentration. The formation of fully interconnected three dimensional frame work structure uniformly distributed pores with large surface area can function as efficient channels for ion conduction.     

A study on polyurethane/acrylate crosslinked gel polymer electrolytes

2,4‐Toluene diisocyanate, poly(propylene glycol), poly(ethylene glycol) (PEG) and 2‐hydroxyethyl methacrylate were used to synthesize PEG–UA (urethane acrylate) monomer. The crosslinked polymer and gel polymer electrolytes were prepared in dioxane by free radical polymerization. The swelling behaviour, thermal degradation properties, morphology and ionic conductivity of the gel polymer electrolytes were investigated. With decrease in the proportion of dioxane used, the synthesized polymer's network density increased, its affinity with a solution of 1 M LiClO₄ in propylene carbonate (PC) decreased, and more microgel which diffused in the network. At the same time, the conductivity increased and reached 4 × 10^?4 S cm^?1 at 25 °C. Copyright © 2003 Society of Chemical Industry     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007     

Application of liquid gel polymer electrolyte based on chitosan–NH4NO3 for proton batteries

Liquid gel polymer electrolyte (LGPE) based on chitosan, ammonium nitrate, and acetic acid with a ratio of 1.9 : 0.17 : 96.3 wt % gives the highest conductivity of (1.46 ± 0.07) ´ 10⁻¹ S cm⁻¹ at room temperature. This optimized composition of electrolyte is then used in proton batteries with the configuration of Zn + ZnSO₄·H₂O/LGPE/MnO₂. The open circuit voltage of battery is 1.41 V during 48 h of storage. The battery obtained a discharge capacity of 27.90 mA h⁻¹ upon discharge at 1.0 mA current. The maximum power density for the battery is 3.67 mW cm⁻². © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of PBMA on PVC‐based polymer blend electrolytes

Poly(vinyl chloride) (PVC)—poly(butyl methacrylate) (PBMA) blended polymer electrolytes with lithium perchlorate (LiClO₄) as the complexing salts are prepared by solution casting technique. The addition of PBMA into PVC matrix is found to induce considerable changes in physical and electrical properties of the polymer electrolytes. Addition of PBMA into PVC matrix is found to increase the conductivity by two orders of magnitude (1.108 × 10^?5 S cm^?1) when compared with that of the pristine PVC polymer electrolyte (10^?7 S cm^?1). Structural, thermal, mechanical, morphological, and polymer–salt interactions are ascertained from X‐ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), mechanical analysis, scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) respectively. A thermal stability upto 250 °C is asserted from the TG/DTA analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44939.     

Solid polymer electrolytes. XI. Preparation,characterization and ionic conductivity of new plasticized polymer electrolytes based on chemical‐covalent polyether–siloxane hybrids

A new hybrid polymer electrolyte system based on chemical‐covalent polyether and siloxane phases is designed and prepared via the sol–gel approach and epoxide crosslinking. FT‐IR, ¹³C solid‐state NMR, and thermal analysis (differential scanning calorimetry (DSC) and TGA) are used to characterize the structure of these hybrids. These hybrid films are immersed into the liquid electrolyte (1M LiClO₄/propylene carbonate) to form plasticized polymer electrolytes. The effects of hybrid composition, liquid electrolyte content, and temperature on the ionic conductivity of hybrid electrolytes are investigated and discussed. DSC traces demonstrate the presence of two second‐order transitions for all the samples and show a significant change in the thermal events with the amount of absorbed LiClO₄/PC content. TGA results indicate these hybrid networks with excellent thermal stability. The EDS‐0.5 sample with a 75 wt % liquid electrolyte exhibits the ionic conductivity of 5.3 × 10^?3 S cm^?1 at 95°C and 1.4 × 10^?3 S cm^?1 at 15°C, in which the film shows homogenous and good mechanical strength as well as good chemical stability. In the plot of ionic conductivity and composition for these hybrids containing 45 wt % liquid electrolyte, the conductivity shows a maximum value corresponding to the sample with the weight ratio of GPTMS/PEGDE of 0.1. These obtained results are correlated and used to interpret the ion conduction behavior within the hybrid networks. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1000–1007, 2006     

Electrochemical properties of Li ion polymer battery with gel polymer electrolyte based on polyurethane

Gel polymer electrolyte (GPE) was prepared using polyurethane acrylate as polymer host and its performance was evaluated. LiCoO₂/GPE/graphite cells were prepared and their electrochemical performance as a function of discharge currents and temperatures was evaluated. The precursor containing a 5 vol % curable mixture had a viscosity of 4.5 mPa s. The ionic conductivity of the GPE at 20 °C was about 4.5 × 10^–3 S cm^–1. The GPE was stable electrochemically up to a potential of 4.8 V vs Li/Li⁺. LiCoO₂/GPE/graphite cells showed a good high rate and low-temperature performance. The discharge capacity of the cell was stable with charge–discharge cycling.     

Gel polymer electrolytes based on a novel quaternary ammonium salt for dye-sensitized solar cells

Gel polymer electrolytes were prepared with polyacrylonitrile (PAN) and solutions of a novel quaternary ammonium salt, polysiloxane with quaternary ammonium side groups (PSQAS), in a mixture of ethylene carbonate (EC) and propylene carbonate (PC). The influences of PAN content and salt concentration on the ionic conductivity have been investigated. The ionic conductivity can be further improved with the use of the mixtures of KI and PSQAS, which can be expected as inorganic-organic salts. The gel polymer electrolytes were used in the fabrication of the dye-sensitized solar cells with a nanoporous TiO₂ working electrode, cis-di(thiocyanato)-N,N-bis(2,2-bipyridyl-4,4-dicarboxylic acid) ruthenium(II) complex dye and a counter electrode based on platinized conducting glass. The cells showed open-circuit voltages (V _oc) around 0.6 V and short-circuit current densities (J _sc) larger than 7.5 mA cm^–2 under 60 mW cm^–2 irradiation. The fill factors (FF) and energy conversion efficiencies () of the cells were calculated to be higher than 0.56 and 4.4%, respectively.     

Ionically conductive polymer gel electrolytes consisting of crosslinked methacrylonitrile and organic electrolyte

To develop a highly ion‐conductive polymer electrolyte, we copolymerized methacrylonitrile (MAN) with ethylene glycol dimethacrylate (EGDMA) in propylene carbonate that contained tetraethylammonium tetrafluoroborate (TEATFB), changing the TEATFB concentration and the MAN/EGDMA molar ratio. We characterized the obtained polymer gel electrolytes with complex impedance analysis and cyclic voltammetry, intending to apply them to electric double‐layer capacitors. The ionic conductivities of the polymer gel electrolytes were dependent on the TEATFB concentration, the temperature, and particularly the crosslinking degree. The polymer gel electrolytes in this system exhibited high room‐temperature conductivities (>10^?3 S/cm). Furthermore, these polymer electrolytes showed good electrochemical stability windows ranging from ?4.0 to +4.0 V versus Ag. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2655–2659, 2002     

Partial crystallisation in liquid polymer electrolytes based on co-polymers of ethylene oxide/propylene oxide

Solutions of lithium perchlorate in a low molecular weight ethylene oxide/propylene oxide (EO/PO) co-polymer were studied by differential scanning calorimetry. The pure co-polymer was found to crystallise partially, while addition of the salt impaired crystallisation first by slowing crystal growth then by slowing nucleation. At high salt concentrations (～1·0 molal) no crystallisation occurred. The solvation of Li⁺-ions and the introduction of ‘transient crosslinking’ between cations and anions effectively suppresses the separation of the polymer into microregions of EO and PO. The crystallisation phenomena are relevant to the use of these copolymers as ‘model’ polymer electrolyte systems.     

NMR, conductivity and DSC study of Li transport in ethylene glycol/citric acid polymer gel

In this present paper the influence of viscosity on the ionic dynamics of polymer gel electrolytes prepared by the Pechini polymeric precursor method is investigated by impedance spectroscopy, differential scanning calorimetric (DSC) and NMR techniques. Polymer gel electrolytes are formed by ethylene glycol (EG) and citric acid (CA) and lithium perchlorate. Room temperature conductivity of the order of 2.3 × 10⁻⁴ S/cm was obtained for the sample of EG/CA:LiClO₄ with lower viscosity (η = 197 cP). The results show that the ionic conductivity of the electrolytes increases for decreasing viscosity. Proton (¹H) and Lithium (⁷Li) NMR lineshapes and spin-lattice relaxation times were measured as a function of temperature and viscosity (197-868 cP). The ⁷Li relaxation process was found to be dominated by quadrupolar couplings. The activation energy extracted from the ¹H and ⁷Li relaxation data (∼0.23 eV) was found to be independent of the viscosity of the gel electrolyte. The ⁷Li NMR relaxation results indicate an increase of the lithium ion mobility with decreasing viscosity.     

Ionically conductive polymer gel electrolytes prepared from vinyl acetate and methyl methacrylate for electric double layer capacitor

In order to obtain highly conductive polymer electrolytes for an electric double layer capacitor, three kinds of polymer gel electrolytes were prepared. Vinyl acetate (VAc) and methyl methacrylate (MMA) were copolymerized with divinyl adipate (DA) and ethylene glycol dimethacrylate (EGDMA), respectively, in propylene carbonate (PC) containing tetraethylammonium tetrafluoroborate (TEATFB) to form network polymer gel electrolytes. MMA was also copolymerized with butylene glycol DMA for comparison. The polymer gel electrolytes obtained were characterized by means of thermogravimetry, complex impedance analysis, and cyclic voltammetry for use in the electric double layer capacitor. The ionic conductivities of the polymer gel electrolytes were dependent on the TEATFB concentration, temperature, and crosslinking degree. The polymer gel electrolytes in the VAc‐DA system exhibited higher room temperature conductivities (10⁻² S/cm) than those in the MMA‐EGDMA system. Further, the polymer gel electrolytes in the VAc‐DA system showed good electrochemical stability windows ranging from −4.0 to 4.0 V versus Ag. Thermal analysis revealed that the polymer gel electrolytes in both systems were stable up to 150°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 12–18, 2000     

Mechanical properties and ionic conductivity of gel polymer electrolyte based on poly(vinylidene‐fluoride‐co‐hexafluoropropylene)

The main thermodynamic parameters were evaluated for the dextran/methoxy ethylene glycol (MEG) system by viscosity measurements at 25, 30, 35, 40, and 45°C. The long-range and short-range interaction parameters were determined by extrapolation methods, i.e, Kurata-Stockmayer-Fixman, Berry, and Inagaki-Suzuki-Kurata equations. Calculated values, as well as the unperturbed root-mean-square end-to-end distance and hydrodynamic expansion factor, were interpreted mainly on the basis of hydrogen-bond formation between polymer segments and dextran/MEG molecules in solution. The thermodynamic interaction parameter was also evaluated for the same system. The theta temperatures were obtained from the temperature dependence of the interaction parameter, dependence of (1/2-χ) and the second virial coefficient in the temperature interval of 25 and 45°C for the system and quite a good accordance was indicated with the calculated values evaluated via extrapolation and interpolation methods. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 948–953, 2001     

Preparation and ionic conductivity of solid polymer electrolyte based on polyacrylonitrile‐polyethylene oxide

The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO₄ complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10^?4 S/cm with an [Li⁺]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006     

FTIR, 1H‐NMR spectra,and thermal characterization of water‐based polyurethane/acrylic hybrids

Polyurethane (PU) polymer was synthesized following a prepolymer mixing process, by polyaddition of isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), 2‐hydroxyethyl methacrylate (HEMA), and 2,2‐bis(hydroxymethyl)propionic acid (DMPA). The PU anionomer having 2‐ethoxymethacrylate terminal groups was dispersed in water by prior neutralization of carboxylic acid groups of DMPA with triethylamine (TEA), chain extended with hydrazine (HZM) in water and a dispersion polymerization with methyl methacrylate/n‐butyl acrylate/acrylic acid mixture was performed. The above polymerization reactions lead to the formation of PU/acrylic hybrids having a chemical bond between PU and acrylic moieties. Acrylic content was varied from 0 to 50 wt % and samples were purified to eliminate oligomers and impurities before characterization. The FTIR and ¹H‐NMR spectra of these purified hybrid samples were obtained and bands and peaks assignments were discussed. Thermal properties (DSC and TGA) were also discussed. Breaking hydrogen bonds is the main reason for changes in properties with increasing acrylic content. Particle size data of dispersions is also presented and discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008