Study on ionic conductivity of polymer electrolyte plasticized with PEG–aluminate ester for rechargeable lithium ion battery

We have synthesized poly(ethylene glycol) (PEG)-aluminate ester as a plasticizer for solid polymer electrolytes. The thermal stability, ionic conductivity and electrochemical stability of the polymer electrolyte which consist of poly(ethylene oxide) (PEO)-based copolymer, PEG–aluminate ester and lithium bis-trifluoromethanesulfonimide (LiTFSI) were investigated. Addition of PEG–aluminate ester increased the ionic conductivity of the polymer electrolyte, showing greater than 10^− 4 S cm^− 1 at 30 °C. The polymer electrolyte containing PEG–aluminate ester retained thermal stability of the non-additive polymer electrolyte and exhibited electrochemical stability up to 4.5 V vs. Li⁺/Li at 30 °C.     

Effect on ion dissociation in MWCNT-based polymer nanocomposite

Polymer nanocomposite has been proven to improve the property of polymer salt complex. Organo-modified clay and inorganic oxides are the most commonly used filler for polymer nanocomposite (PNC). However, single wall carbon nanotube (SWCNT)/multiwall carbon nanotube (MWCNT) are becoming popular filler for PNC for their high surface area and high mechanical stability. In this work, a series of PNC sample has been prepared by using polyethylene oxide (PEO)-polydimethylsiloxane (PDMS) blend as polymer matrix, an optimized salt stoichiometry of Ö/Li ~15, and surface-modified MWCNT as filler. The effect of ion-polymer and ion-MWCNT interaction in the polymer nanocomposite has been investigated by using XRD, SEM, FTIR, and electrical study. X-ray diffraction pattern confirms the dispersion of MWCNT inside the polymer chain and modifies the structural parameter of the polymer matrix. FTIR spectra indicate inclusion of MWCNT inside the polymer salt complex which changes the ion dissociation/association in the polymer host matrix. Further, the changes in structural, thermal, and electrical property of the polymer salt complex system have been studied by using SEM, DSC, and impedance analysis. Dc conductivity study shows that optimized PNC sample has conductivity of 8.04 × 10⁻⁵ S cm⁻¹. This is almost two order enhancement from pure polymer salt system (10⁻⁶ S cm⁻¹).

     

Single ion conductors—polyphosphazenes with sulfonimide functional groups

A novel single ion conductive polymer electrolyte was developed by covalently linking an arylsulfonimide substituent to the polyphosphazene backbone. Polymeric single-ion conductors incorporate the anion of a salt either into the polymer backbone or as a pendent group linked to the polymer backbone. Immobilization of the anion could provide access to electrochemical devices that would be less vulnerable to increased resistance associated with salt concentration gradients at the interfaces during charging and discharging. In this work, an immobilized sulfonimide lithium salt is the source of lithium cations, while a cation-solvating cosubstituent, 2-(2-methoxyethoxy)ethoxy, was used to increase free volume and assist cation transport. The ionic conductivities showed a dependence on the percentage of lithiated sulfonimide substituent present. Increasing amounts of the lithium sulfonimide component increased the charge carrier concentration but decreased the ionic conductivity due to decreased macromolecular motion and possible increased shielding of the nitrogen atoms in the polyphosphazene backbone. Maximum ionic conductivity values of 2.45 × 10^− 6 S/cm at ambient temperature and 4.99 × 10^− 5 S/cm at 80 °C were obtained. Gel polymer electrolytes containing N-methyl-2-pyrrolidone gave ionic conductivities in the 10^− 3 S/cm range. The ion conduction process was investigated through model polymers that contained the non-immobilized sulfonimide — systems that had higher conductivities than their single ion counterparts.     

Solid electrolyte membranes from semi-interpenetrating polymer networks of PEG-grafted polymethacrylates and poly(methyl methacrylate)

Solid polymer electrolyte membranes were prepared as semi-interpenetrating networks by photo-induced polymerization of mixtures of poly(ethylene glycol) (PEG) methacrylate macromonomers in the presence of poly(methyl methacrylate) (PMMA) and lithium bis(trifluoromethanesulfonyl)imide salt. The composition of the membranes was varied with respect to the PMMA content, the degree of cross-linking, and the salt concentration. Infrared analysis of the membranes indicated that the lithium ions were coordinated by the PEG side chains. Calorimetry results showed a single glass transition for the blend membranes. However, dynamic mechanical measurements, as well as a closer analysis of the calorimetry data, revealed that the blends were heterogeneous systems. The ionic conductivity of the membranes increased with the content of PEG-grafted polymethacrylate, and was found to exceed 10^− 5 S cm^− 1 at 30 °C for membranes containing more than 85 wt.% of this component in the polymer blend.     

Ionic conductivity of polymer electrolytes based on phosphate and polyether copolymers

Linear polyphosphate random copolymers (LPC) composed of phosphate as a linking agent with poly(ethylene glycol) (PEG) and/or poly(tetramethylene glycol) (PTMG) were synthesized to increase local segmental motion for improved ion transport. Ionic conductivity and thermal behavior of LPC series–LiCF₃SO₃ complexes were investigated with various compositions, salt concentrations and temperatures. The PEG(70)/PTMG(30)/LiCF₃SO₃ electrolyte exhibited ionic conductivity of 8.04×10⁻⁵ S/cm at 25°C. Salt concentration with the highest ionic conductivity was considerably dependent on EO/TMO compositions in LPC series–salt systems. Relationship between solvating ability and chain flexibility with various compositions and salt concentrations was investigated through theoretical aspects of the Adam–Gibbs configurational entropy model. Temperature dependence on the ionic conductivity in LPC6 series–salt systems suggested the ion conduction follows the Williams–Landel–Ferry (WLF) mechanism, which is confirmed by Vogel–Tamman–Fulcher (VTF) plots. The ionic conductivity was affected by segmental motion of the polymer matrix. VTF parameters and apparent activation energy were evaluated by a non-linear least square minimization method. These results suggested that the solvating ability of the host polymer might be a dominant factor to improve the ionic conductivity rather than chain mobility.     

Preparation and characterization of a new PEO-PPG blend polymer electrolyte system

This paper reports on preparation and characterization of thin films of a new zinc ion conducting blended polymer electrolyte system containing polyethylene oxide [PEO] and polypropylene glycol [PPG] complexed with zinc triflate [Zn(CF₃SO₃)₂] salt. The room temperature ionic conductivity (σ _298K) data of such PEO-PPG polymer blends prepared by solution casting technique were found to be of the order of 10^?5 S cm^?1, whereas the optimized composition containing 90:10 wt% ratio of PEO and PPG possessed an appreciably high ionic conductivity of 7.5?×?10^?5 S cm^?1. Subsequently, six different weight percentages of zinc triflate viz., 2.5, 5, 7.5, 10, 12.5 and 15, respectively, were added into the above polymer blend and resulting polymer-salt complexes were characterized by means of various analytical tools. Interestingly, the best conducting specimen namely 87.5 wt% (PEO:PPG)-12.5 wt% Zn(CF₃SO₃)₂ exhibited an enhanced room temperature ionic conductivity of 6.9?×?10^?4 S cm^?1 with an activation energy of 0.6 eV for ionic conduction. The present XRD results have indicated the occurrence of characteristic PEO peaks and effects of salt concentration on the observed intensity of these diffraction peaks. Appropriate values of degree of crystallinity for different samples were derived from both XRD and DSC analyses, while an examination of surface morphology of the blended polymer electrolyte system has revealed the formation of homogenous spherulites involving a rough surface and relevant zinc ionic transport number was found to be 0.59 at room temperature for the best conducting polymer electrolyte system thus developed.     

Effect of ethylene carbonate plasticizer on agar-agar: NH<Subscript>4</Subscript>Br-based solid polymer electrolytes

Proton-conducting polymer electrolytes based on biopolymer, agar-agar as the polymer host, ammonium bromide (NH₄Br) as the salt and ethylene carbonate (EC) as the plasticizer have been prepared by solution casting technique with dimethylformamide as solvent. Addition of NH₄Br and EC with the biopolymer resulted in an increase in the ionic conductivity of polymer electrolyte. EC was added to increase the degree of salt dissociation and also ionic mobility. The highest ionic conductivity achieved at room temperature was for 50 wt% agar/50 wt% NH₄Br/0.3% EC with the conductivity 3.73?×?10^?4 S cm^?1. The conductivity of the polymer electrolyte increases with the increase in amount of plasticizer. The frequency-dependent conductivity, dielectric permittivity (ε′) and modulus (M′) studies were carried out.     

Solid polymer electrolytes in a poly(butadiene-acrylonitrile)–LiBr system

Poly(nitriles) are among the polymer matrices providing high salt solubility and, in some cases, superionic lithium conductivity at ambient temperatures observed in highly concentrated solvent-free polymer electrolytes. However, the properties of these electrolytes in which ionic aggregation prevails remain difficult to reproduce and predict, as current theories do not adequately model their attributes. The development of new concepts for ion transport in highly concentrated solid polymer electrolytes (SPEs) requires a better understanding of the fundamentals of structure formation in a polymer–salt system over a wide concentration range including salt precipitation. In an attempt to approach this goal, a series of fundamental studies was carried out on the systems based on a rubbery random copolymer of butadiene and acrylonitrile (abbreviated as PBAN). In the present work, LiBr with monatomic halide anion was used as a lithium salt. The effect of LiBr concentration (0.05 to 3.35 mol kg^?1) on phase composition, ion–molecular interactions, glass transition temperature, and ionic conductivity was studied by optical microscopy, FTIR, X-ray diffraction, DSC, and impedance measurements. The results were compared with those of PBAN–LiClO₄ and PBAN–LiAsF₆ studied previously. Low salt solubility and separation of a metastable cubic CsCl-type polymorph of LiBr were established. The highest conductivity of ～10^?4 S cm^?1 at >50 °C was observed for heterogeneous samples comprising this phase. While the conductivity of PBAN–LiBr was lower than that of PBAN–LiClO₄ and PBAN–LiAsF₆, this study provides a new insight into the nature of polymer electrolyte systems.     

Conductivity studies of plasticized proton conducting PVA–PVIM blend doped with NH4BF4

The proton conducting solid-state polymer electrolyte comprising blend of poly(vinyl alcohol) (PVA) and poly(N-vinylimidazole) (PVIM), ammonium tetrafluoroborate (NH₄BF₄) as salt, and polyethylene glycol (PEG) (molecular weight 300 and 600) as plasticizer is prepared at various compositions by solution cast technique. The prepared films are characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy analysis. The conductivity–temperature plots are found to follow an Arrhenius nature. The conductivity of solid polymer electrolytes is found to depend on salt and plasticizer content and also on the dielectric constant value and molecular weight of the plasticizer. Maximum ionic conductivity values of 2.20?×?10^?4 and 1.28?×?10^?4?S?cm^?1 at 30 °C are obtained for the system (PVA–PVIM)?+?20 wt.% NH₄BF₄?+?150 wt.% PEG300 and (PVA–PVIM)?+?20 wt.% NH₄BF₄?+?150 wt.% PEG300, respectively. The blended polymer, complexed with salt and plasticizer, is shown to be a predominantly ionic conductor. The proton transport in the system may be expected to follow Grotthuss-type mechanism.     

Electrical studies on ionic liquid-based gel polymer electrolyte for its application in EDLCs

Ionic liquid-based gel polymer electrolyte (GPE) has been synthesized using standard solution cast technique. Different weight percent of ionic liquid, 1-Butyl-3-methylimidazolium chloride (BMIMCl) and liquid electrolyte, ethylene carbonate (EC)–propylene carbonate (PC)–tetra ethyl ammonium tetra fluoro borate (TEABF₄) was incorporated in polymer, poly(vinylidene fluoride-co-hexafluoro propylene (PVdF-HFP) to obtain mechanically stable gel polymer electrolyte film (GPE) having maximum conductivity of ~10⁻³ S cm⁻¹ at room temperature, which is acceptable from device fabrication point of view. Potential window and ionic transference number has been obtained to examine the potential limit and ionic characteristics of optimized GPE system. Temperature dependence behavior of electrical conductivity curve follows Arrhenius nature in the temperature range of 303–373 K. Pattern of dielectric constant and its loss as a function of frequency and temperature have been studied and is being explained on the basis of electrode interfacial polarization effect. Frequency-dependent conductivity spectra obey the Jonscher’s power law. Further, optimized composition of GPE has been tested successfully for its application in supercapacitor fabrication with activated charcoal as an electrode material. Maximum specific capacitance of 118.6 mF cm⁻² equivalent to single electrode specific capacitance of 61.7 F g⁻¹ have been observed for the optimized GPE film.

     

New polymer electrolyte based on (PVA–PAN) blend for Li-ion battery applications

A polymer blend electrolyte based on polyvinyl alcohol (PVA) and polyacrylonitrile (PAN) was prepared by a simple solvent casting technique in different compositions. The ionic conductivity of polymer blend electrolytes was investigated by varying the PAN content in the PVA matrix. The ionic conductivity of polymer blend electrolyte increased with the increase of PAN content. The effect of lithium salt concentrations was also studied for the polymer blend electrolyte of high ionic conductivity system. A maximum ionic conductivity of 3.76×10⁻³ S/cm was obtained in 3 M LiClO₄ electrolyte solution. The effect of ionic conductivity of polymer blend electrolyte was measured by varying the temperature ranging from 298 to 353 K. Linear sweep voltammetry and DC polarization studies were carried out to find out the stability and lithium transference number of the polymer blend electrolyte. Finally, a prototype cell was assembled with graphite as anode, LiMn₂O₄ as cathode, and polymer blend electrolyte as the electrolyte as well as separator, which showed good compatibility and electrochemical stability up to 4.7 V.     

Electrical characterization of nano-composite polymer gel electrolytes containing NH4BF4 and SiO2: role of donor number of solvent and fumed silica

Nano-composite polymer gel electrolytes were synthesized by using polyethylene oxide (PEO), ammonium tetrafluoroborate (NH₄BF₄), fumed silica (SiO₂), dimethylacetamide (DMA), ethylene carbonate (EC), and propylene carbonate (PC) and characterized by conductivity studies. The effect of donor number of solvent on ionic conductivity of polymer gel electrolytes has been studied. The mechanical strength of the gel electrolytes has been increased with the addition of nano-sized fumed silica along with an enhancement in conductivity. Maximum room temperature ionic conductivity of 2.63 × 10⁻³ and 2.92 × 10⁻³ S/cm has been observed for nano-composite gel electrolytes containing 0.1 and 0.5 wt% SiO₂ in DMA+1 M NH₄BF₄+10 wt% PEO, respectively. Nano-composite polymer gel electrolytes having DMA have been found to be thermally and electrically stable over 0 to 90 °C temperature range. Also, the change in conductivity with the passage of time is very small, which may be desirable to make applicable for various smart devices.

     

Ionic conduction behavior in PVC–PEG blend polymer electrolytes upon the addition of TiO2

The blend-based polymer electrolyte consisting of poly (vinyl chloride) (PVC) and poly (ethylene glycol) (PEG) as host polymers and lithium perchlorate (LiClO₄) as the complexing salt was studied. An attempt was made to investigate the effect of TiO₂ concentration in the unplasticized PVC–PEG polymer electrolyte system. The XRD and FTIR studies confirm the formation of a polymer–salt complex. The conductivity results indicate that the incorporation of ceramic filler up to a certain concentration (15 wt.%) increases the ionic conductivity and upon further addition the conductivity decreases. The maximum ionic conductivity 0.012 × 10⁻⁴ S cm⁻¹ is obtained for PVC–PEG–LiClO₄–TiO₂ (75–25–5–15) system. Thermal stability of the polymer electrolyte is ascertained from TG/DTA studies.     

Development of proton conducting biopolymer membrane based on agar–agar for fuel cell

A proton-conducting polymer electrolyte based on agar and ammonium nitrate (NH₄NO₃) has been prepared through solution casting technique. The prepared polymer electrolytes were characterized by impedance spectroscopy, X-ray diffraction, and Fourier transform infra-red spectroscopy. Impedance analysis shows that sample with 60 wt.% NH₄NO₃ has the highest ionic conductivity of 6.57 × 10⁻⁴ S cm⁻¹ at room temperature. As a function of temperature, the ionic conductivity exhibits an Arrhenius behaviour increasing from 6.57 × 10⁻⁴ S cm⁻¹ at room temperature to 1.09 × 10⁻³ S cm⁻¹ at 70 °C. Transport parameters of the samples were calculated using Wagner’s polarization method and thus shows that the increase in conductivity is due to the increase in the number of mobile ions. Fuel cell has been constructed with the highest proton conductivity polymer 40agar/60NH₄NO₃ and the open circuit voltage is found to be 558 mV.

     

AC impedance studies on proton-conducting PAN : NH4SCN polymer electrolytes

Solid polymer electrolytes based on polyacrylonitrile (PAN) doped with ammonium thiocyanate (NH₄SCN) in different molar ratios of polymer and salt have been prepared by solution-casting method using DMF as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. A shift in glass transition temperature (T _g) of the PAN?:?NH₄SCN electrolytes has been observed from the DSC thermograms which indicates the interaction between the polymer and the salt. From the AC impedance spectroscopic analysis, the ionic conductivity has been found to increase with increasing salt concentration up to 30 mol% of NH₄SCN beyond which the conductivity decreases and the highest ambient temperature conductivity has been found to be 5.79?×?10^?3 S cm^?1. The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship which shows hopping of ions in the polymer matrix. The dielectric loss curves for the sample 70 mol% PAN?:?30 mol% NH₄SCN reveal the low-frequency β-relaxation peak pronounced at high temperature, and it may be caused by side group dipoles. The ionic transference number of polymer electrolyte has been estimated by Wagner’s polarization method, and the results reveal that the conductivity species are predominantly ions.     

Proton-conducting biopolymer electrolytes based on pectin doped with NH4X (X=Cl,Br)

Research has been undertaken to develop polymer electrolytes based on biodegradable natural polymers such as cellulose acetate, starch, gelatin, and chitosan, which are being used as polymer hosts for obtaining new polymer electrolytes for their applications in various electrochemical devices such as batteries, sensors, and electrochromic windows. Pectin is a naturally available material which is extracted from the skin of citrus fruits. Pectins, also known as pectic polysaccharides, are rich in galacturonic acid. The present study focuses on the proton-conducting polymer electrolytes based on the biopolymer pectin doped with ammonium chloride (NH₄Cl) and ammonium bromide (NH₄Br) prepared by solution casting technique. The prepared membranes are characterized using XRD, FTIR, and AC impedance techniques to study their complexation behavior, amorphous nature, and electrical properties. The conductivity of pure pectin membrane has been found to be 9.41 × 10⁻⁷ S cm⁻¹. The polymer systems with 30 mol% NH₄Cl-doped pectin and 40 mol% NH₄Br-doped pectin have been found to have maximum ionic conductivity of 4.52 × 10⁻⁴ and 1.07 × 10⁻³ S cm⁻¹, respectively. The conductivity value has increased by three orders of magnitude compared to pure pectin membrane. The dielectric behavior of both the systems has been explained using dielectric permittivity and electric modulus spectra.

     

Enhancement of ionic conductivity by dispersed oxide inclusions: Influence of oxide isoelectric point and cation size

Doping of a halide salt by dispersion of oxide particles rather than subtitutional impurities is a proven method of enhancing the extrinsic ionic conductivity of the host. The conductivity mechanism in any space-charge layer at the oxide/host interface is determined by the chemical reactions at the interface. These interactions are discussed by analogy with the particle hydrates. The enhancement of the F⁻-ion conductivity in PbF₂ is predicted to be via F⁻-ion vacancies in the space-charge region and to increase with decreasing oxide isoelectric point and increasing normal anion coordination of the oxide cation. This prediction accounts satisfactorily for the relative enhancement factors measured for PbF₂ containing dispersed CeO₂, SiO₂, ZrO₂ and Al₂O₃.     

Preparation and characterization of biodegradable poly(ε-caprolactone)-based gel polymer electrolyte films

Biodegradable polymer electrolyte films based on poly(ε-caprolactone) (PCL) in conjunction with lithium tetrafluoroborate (LiBF₄) salt and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) ionic liquid were prepared by solution cast technique. The structural, morphological, thermal, and electrical properties of these films were examined using X-ray diffraction (XRD), optical microscopy (OM), differential scanning calorimetry (DSC), and impedance spectroscopy. The XRD and OM results reveal that the pure PCL possesses a semi-crystalline nature and its degree of crystallinity decreases with the addition of LiBF₄ salt and EMIMBF₄ ionic liquid. DSC analysis indicates that the melting temperature and enthalpy are apparently lower for the 40 wt% EMIMBF₄ gel polymer electrolyte as compared with the others. The ambient temperature electrical conductivity increases with increasing EMIMBF₄ concentration and reaches a high value of ～2.83?×?10^?4 S cm^?1 for the 85 PCL:15 LiBF₄ + 40 wt% EMIMBF₄ gel polymer electrolyte. The dielectric constant and ionic conductivity follow the same trend with increasing EMIMBF₄ concentration. The dominant conducting species in the 40 wt% EMIMBF₄ gel polymer electrolyte determined by Wagner’s polarization technique are ions. The ionic conductivity of this polymer electrolyte (～2.83?×?10^?4 S cm^?1) should be high enough for practical applications.     

Effect of lithium salt concentration in PVAc/PMMA-based gel polymer electrolytes

Hybrid solid polymer electrolyte films comprising of poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), LiClO₄, and propylene carbonate are prepared by solution casting technique by varying the salt concentration. In this study, PVAc/PMMA polymer blend ratio is fixed as 25:75 on the basis of conductivity and mechanical stability of the film. X-ray diffraction, Fourier transform infrared impedance, thermogravimetry/differential thermal analysis and scanning electron microscopy studies are carried out for the polymer electrolytes. The maximum ionic conductivity is found to be 4.511 × 10⁻⁴ S cm⁻¹ at 303 K for the plasticized polymer electrolyte with 8 wt.% of LiClO₄. The ionic conductivity is found to decrease with an increase of LiClO₄ concentration.     

Synthesis and ionic conductivity of polymeric ion gel containing room temperature ionic liquid and phosphotungstic acid

Composite electrolyte comprising phosphotungstic acid (PWA) filler and 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF₄) room temperature ionic liquid (RTIL) in poly(2-hydroxyethyl methacrylate) (PHEMA) matrix has been prepared. The polymer matrix was formed by free radical polymerization of 2-hydroxyethyl methacrylate (HEMA) monomers. BMImBF₄ was used as both ionic source and plasticizer, and PWA filler provided the proton conductivity in this system. The interactions and structure changes of the PHEMA-RTIL-PWA composites were investigated by Fourier transform infrared spectra, differential scanning calorimetry, and X-ray diffraction. PWA fillers maintained their Keggin structure within a limited range and enhanced the ionic conductivity of the composite electrolyte. The electrolyte with PWA at the 2 wt.% showed the highest ionic conductivity of 8 × 10^− 4 S cm^− 1 at room temperature and 96% relative humidity.