Investigation on compositional effect of PEG:BaTiO<Subscript>3</Subscript> in plasticized PVC–LiBETi polymer composite electrolytes

The blend-based polymer electrolyte comprising poly(vinyl chloride) (PVC) and poly(ethylene glycol) (PEG) as host polymer and lithium bis(perfluoroethanesulfonyl)imide as complexing salt have been prepared. Ethylene carbonate and dimethyl carbonate (50:50 v/v) are used as plasticizer for the system. The barium titanate is used as a filler, and the ratio of (PEG:BaTiO₃) is varied to study its effect on the conductivity behavior of the electrolyte. XRD and ac impedance studies are carried out on the prepared samples. The ac impedance measurements show that the conductivity of the prepared samples depends on the (PEG:BaTiO₃) ratio, and its value is higher for (15:5) wt.% of (PEG:BaTiO₃)-incorporated film. The temperature dependence of the conductivity of the polymer films obeys VTF relation. The role of ferroelectric filler in enhancing the conductivity is studied. The thermal stability of the film is ascertained from TG/DTA studies. The phase morphological study reveals that the porous nature of the polymer electrolyte membranes depends on the (PEG:BaTiO₃) ratio.     

Combined effect of nanochitosan and succinonitrile on structural, mechanical, thermal, and electrochemical properties of plasticized nanocomposite polymer electrolytes (PNCPE) for lithium batteries

A sequence of novel plasticized polymer nanocomposite electrolyte systems based on polyethylene oxide (PEO) as polymer host, LiCF₃SO₃ as salt, and a variety of concentrations of nanochitosan as inert filler, succinonitrile as a solid non-ionic plasticizer has been prepared. The prepared membranes were subjected to X-ray diffraction, FT-IR, tensile strength, morphological studies, thermal analysis, AC ionic conductivity measurement, and interfacial analyses. The combined effect of succinonitrile and nanochitosan on the electrochemical properties of polymer electrolytes has been studied, and it was confirmed that the ionic conductivity is significantly increased. The maximum ionic conductivity of the plasticized nanocomposite polymer electrolytes are found to be in the range of 10^?2.8?S/cm. Besides, the interfacial stability also shows a significant improvement. The tensile measurement and thermal analysis results illustrate that the electrolytes based on that polymer host possess good mechanical and thermal stabilities.     

A study on LiBOB-based nanocomposite gel polymer electrolytes (NCGPE) for Lithium-ion batteries

Lithium bis(oxalato)borate (LiBOB) salt-based nanocomposite gel polymer blend electrolyte (PVdF/PVC) membranes have been prepared by solution casting technique for various concentrations of TiO₂. The effect of anatase structure of nanosized titanium dioxide in the plasticized PVC/PVdF + LiBOB matrix has been observed in the 2:1 salt filler ratio in the impedance measurements that the conductivity is increased one order of magnitude higher than the filler-free electrolyte (1:0 salt:filler ratio). The phase morphology of this electrolyte membrane represents the appearance of the free volume sites for ionic migration.     

Characterization of PEO/PVP/GO nanocomposite solid polymer electrolyte membranes: microstructural,thermo-mechanical,and conductivity properties

Poly (ethylene oxide) (PEO)/polyvinylpyrrolidone (PVP) blended nanocomposite polymers, incorporating graphene oxide (GO) nano-sheets and embedded with NaIO₄ salt, were prepared using solution casting technique. The as-prepared nanocomposite electrolyte membranes were characterized by SEM, TEM, XRD, and Raman vibrational spectroscopic techniques to confirm the dispersion of GO nano-sheets and to understand the synergistic properties of GO/polymer interactions as a function of GO nano-sheets concentration. GO fillers incorporated electrolyte membranes demonstrated distinctive surface morphology composed of circular-shaped protuberances of different dimensions. The decrease of Raman intensity ratio (I_D/I_G) and in-plane crystallite size (L_a) values of the nanocomposites suggested the good dispersion and confinement of the GO nano-sheets. The optical properties of blend electrolyte films were studied as a function of GO filler concentration using optical absorption and diffuse reflectance spectra. In reference to PEO/PVP/NaIO₄, the resultant PEO/PVP/NaIO₄/GO (0.4% in weight) electrolyte membrane demonstrated both an increase in tensile strength of ca. 42% and in Young’s modulus of ca. 40%, improvements coupled with a maximum fractured elongation of 3%. Through impedance spectroscopy analysis, the role of the GO nano-sheets onto the room temperature conductivity properties of the prepared electrolyte membranes has been probed.     

Influence of solid electrolyte particles size on ionic transport in model composite system (PVdF-HFP–Li1.3Al0.3Ti1.7(PO4)3)

The influence of filler particles size on lithium ion conductivity of composite polymer electrolytes was issued on model system vinylidenefluoride with hexafluoropropylene (PVdF-HFP)–Li_1.3Al_0.3Ti_1.7(PO₄)₃. Model electrolyte objects with filler grains of different sizes were prepared using a modified solvent casting method from a mixture of PVdF-HFP solution in dimethylformamide and Li_1.3Al_0.3Ti_1.7(PO₄)₃ solid electrolyte particles. The percolation threshold was defined and the transport properties of composite polymer electrolytes at different volume concentrations of the solid electrolyte investigated. A significant decrease in conductivity compared to that of ceramic solid electrolytes was observed. The size of the filler particles was found to affect the structure and transport properties of the prepared composite polymer electrolytes. The conductivity of the composite polymer electrolyte at 100 °C was found to increase by two orders of magnitude with the tenfold increase of the size of the filler particles.     

Li ion conduction in TiO2 filled polyvinylidenefluoride-co-hexafluoropropylene based novel nanocomposite polymer electrolyte membranes with LiDFOB

This paper describes, nanocomposite polymer electrolyte (NCPE) based on polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP), which comprises the novel lithium difluoro(oxalato)borate (LiDFOB). Ehtylene carbonate (EC) and diethyl carbonate (DEC) mixture was used as gelling agent and nanoparticulate TiO₂ used as filler. The NCPE membranes were subjected to a.c. impedance, tensile strength, Raman studies, TG/DTA and morphological studies. 5 wt% TiO₂ comprising membranes exhibited enhanced conductivity of 0.56 mS cm⁻¹and the Young’s modulus was increased from 1.32 to 2.74 MPa. The structural change of α to β phase was confirmed by Raman studies. The thermal stability of the NCPE membrane is found to be 130 °C. Calculation of activation energy and synthesis of LiDFOB has also been presented.     

Effect of ZnO nanoparticles filler concentration on the properties of PEO-ENR50-LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript> solid polymeric electrolyte

A solid polymer electrolyte comprising blend of poly(ethylene oxide) and 50% epoxidized natural rubber (ENR50) as a polymer host, LiCF₃SO₃ as a salt and nanoparticle ZnO as an inorganic filler was prepared by solution-casting technique. The effect of filler on the electrolyte properties was characterized and analysed. FESEM analysis showed that the filler was well distributed in the polymer matrix, while the effective interaction between the salt and the polymer host was reduced by the addition of filler. As evidenced by FTIR analysis, which showed the formation of triplet peak at C-O-C stretching region. Ionic conductivity was found to decrease from 1.4 × 10⁻⁴ Scm⁻¹ to 2.5 × 10⁻⁶ Scm⁻¹ upon the addition of filler, due to the blocking effect of filler into the electrolyte conduction pathways. The temperature dependence on the electrolyte conductivity obeys Arrhenius rule in two temperature regions.     

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.     

Investigation on the effects of addition of SiO<Subscript>2</Subscript> nanoparticles on ionic conductivity,FTIR, and thermal properties of nanocomposite PMMA–LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>

Composite polymer electrolyte systems composed of poly(methyl methacrylate) (PMMA) as the host polymer, lithium trifluoromethanesulphonate (also known as lithium triflate; LiCF₃SO₃) as dopant salt, and a variety of different concentrations of nano-sized fumed silica (SiO₂) as inorganic filler were studied. The effect upon addition of SiO₂ on the ionic conductivity of the composite polymer electrolytes was investigated, and it was proven that the ionic conductivity had been enhanced. In addition, the interfacial stability also showed improvement. Maximum conductivity was obtained upon addition of 2 wt.% SiO₂. The complexation of PMMA and LiCF₃SO₃ was verified through Fourier transform infrared studies. The thermal stability of the polymer electrolytes was also found to improve after dispersion of inorganic filler. This was proven in the thermogravimetric studies.     

Structural, vibrational, thermal, and electrical properties of PVA/PVP biodegradable polymer blend electrolyte with CH3COONH4

A biodegradable solid polymer blend electrolyte was prepared by using polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) polymers with different molecular weight percentages (wt.%) of ammonium acetate, and its structural, thermal, vibrational, and electrical properties were evaluated. The polymer blend electrolyte is prepared using solution casting technique, with water as a solvent. X-ray diffraction shows that the incorporation of ammonium acetate into the polymeric matrix causes decrease in the crystallinity degree of the samples. The Fourier transform infrared spectroscopy and laser Raman studies confirm the complex formation between the polymer and salt. Differential scanning calorimerty shows that the thermal stability of the polymer blend electrolyte and the glass transition temperature decreased as the concentration of ammonium acetate increased. The ionic conductivity of the prepared polymer electrolyte was found by AC impedance spectroscopic analysis. A maximum conductivity of 8.12?×?10^?5 Scm^?1 was observed for the composition of 50 PVA/50 PVP/30 wt.% of CH₃COONH₄.     

Structural, conductivity, and dielectric characterization of PEO–PEG blend composite polymer electrolyte dispersed with TiO2 nanoparticles

A solid polymer electrolyte (SPE) composites consisting blend of poly(ethylene oxide) (PEO) and poly(ethylene glycol) (PEG) as the polymer host with LiCF₃SO₃ as a Li⁺ cation salt and TiO₂ nanoparticle which acts as a filler were prepared using solution-casting technique. The SPE films were characterized by X-ray diffraction and Fourier transform infrared analysis to ensure complexation of the polymer composites. Frequency-dependent impedance spectroscopy observation was used to determine ionic conductivity and dielectric parameters. Ionic conductivity was found to vary with increasing salt and filler particle concentrations in the polymer blend complexes. The optimum ambient temperature conductivity achieved was 2.66?×?10^?4?S?cm^?1 for PEO (65 %), PEG (15 %), LiCF₃SO₃ (15 %), ethylene carbonate (5 %), and TiO₂ (3 %) using weight percentage. The dielectric relaxation time obtained from a loss tangent plot is fairly consistent with the conductivity studies. Both Arrhenius and VTF behaviors of all the composites confirm that the conductivity mechanism of the solid polymer electrolyte is thermally activated.     

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.     

Thermal and electrical properties of solid polymer electrolyte PEO9 Mg(ClO4)2 incorporating nano-porous Al2O3 filler

Solid polymer electrolyte PEO₉ Mg(ClO₄)₂ incorporating 10 wt.% nano-porous Al₂O₃ filler grains has been prepared by the solvent casting technique using acetonitrile as the common solvent. Al₂O₃ powder (activated acidic, Aldrich) with grain size 104 μm and pore size 5.8 nm were incorporated as an inert filler. Electrolyte films have been characterized by differential scanning calorimetry, complex impedance and dc polarization measurements. The nano-composite electrolyte as well as the filler-free electrolyte appear to be predominantly anionic conductors with ClO₄⁻ ions being the migrating species. The presence of the alumina filler has enhanced the ionic conductivity significantly. The conductivity enhancement has been attributed to Lewis acid–base type interactions between H groups at the filler grain surface and the ClO₄⁻ ions. Transient H-bonding through these interactions is expected to provide additional hopping sites and favourable conducting pathways for migrating ionic species.     

Comparison among the performance of LiBOB,LiDFOB and LiFAP impregnated polyvinylidenefluoride-hexafluoropropylene nanocomposite membranes by phase inversion for lithium batteries

This paper describes the physico-chemical and electrochemical properties of polyvinylidenefluoride-hexafluoropropylene (PVdF-HFP) membranes (GPM) prepared by phase inversion technique. Nanocomposite polymer membranes (NCPM) are also prepared by the same technique using AlO(OH)_n nanoparticles. The prepared GPM and NCPM are gelled with liquid electrolyte containing three different salts namely, lithium bis(oxalate)borate, lithium fluoroalkylphosphate and lithium difluoro(oxalato)borate. Prepared membranes were subjected to various physico-chemical characterizations likely, mechanical stability, ionic conductivity, morphological studies, surface area and thermal analysis. Electrochemical chemical properties of membranes are evaluated in half-cell configurations (Li/NCPM or GPM/LiFePO₄) at room temperature conditions. Galvanostatic cycling profiles clearly indicates the improved performance of chelato borate based anions i.e. BOB and DFOB when compared to fluoroalkyl group (FAP).     

Conductivity, dielectric behaviour and thermal stability studies of lithium ion dissociation in poly(methyl methacrylate)-based gel polymer electrolytes

Thin films of poly(methyl methacrylate) (PMMA) with lithium triflate (LiCF₃SO₃) were prepared by using the solution-casting method with PMMA as the host polymer. Ionic conductivity and dielectric measurements were carried out on these films. The highest conductivity for polymer electrolyte with a ratio of 65:35 was found to be 9.88 × 10⁻⁵ S cm⁻¹, which is suitable for the production of mobile phone battery. Thermal gravimetric analysis was carried out to evaluate the thermal stability of the polymer electrolyte. The addition of salts will increase thermal stability of the polymer electrolyte.     

Solvent-free nanocomposite proton-conducting membranes composed of cesium salt of phosphotungstic acid doped PVDF–CTFE/PEO blend

In this research, novel nanocomposite membranes were prepared using polymer blend of polyethylene oxide (PEO) and polyvinylidene fluoride–chloro tetrafluoro ethylene (PVDF–CTFE) copolymer with cesium salt of phosphotungstic acid (Cs_2.5H_0.5PWO₄₀) as proton conductor. Nanocomposite membranes were prepared by solvent-free procedure. The DSC studies show a decrease in crystalinity of polymer matrix with increasing PEO to PVDF–CTFE proportional ratio and the filler. The TGA studies show that membranes are stable up to 180 °C. The TGA also indicates that addition of cesium salt of phosphotungstic acid increases the thermal stability of membranes. The SEMs exhibit that membranes are non-porous and the additive components are homogenously dispersed. Conductivity tests for membranes were carried out in the range of 25–100 °C in dry and hydrated states. Results show that by increasing the temperature, membranes conductivities are increased. In dry state, except at the temperature of 45 °C, membranes which have the highest crystalinity, have the highest conductivity. The alteration of the conductivity in the range of temperatures in dry condition may be attributed to segmental motion of polymer which resulted in proton hopping from one site to another or increasing free volume for proton motion. In fully hydrated state, dynamic equilibrium between different proton moieties determines the mode of proton conductivity which can be described by Grothuss mechanism. In the presence of water molecule, the free proton may be formed. The conductivity for the membrane in hydrated state with the blend ratio of PVDF:PEO = 95:5 w/w and 10% addition of cesium salt of phosphotungstic acid at the temperature of 90 °C is 1.05 × 10⁻⁴ S cm⁻¹.     

A study on the role of BaTiO<Subscript>3</Subscript> in lithum bis(perfluoroethanesulfonyl)imide-based PVDF-HFP nanocomposites

Lithium bis(perfluoroethanesulfonyl)imide (BETI; guest species)-based polyvinylidenefluoride-hexafluoropropylene (PVDF-HFP) (host matrix) polymer nanocomposites (PNC) films by loading barium titanate (BaTiO₃) as a filler in ascending proportions with plasticizer (mixture of EC + DMC) while keeping host and guest content as constants has been investigated by employing AC impedance, thermal, X-ray diffraction (XRD), phase morphology, and Fourier transform infrared (FTIR) studies. The ionic conductivity measurements on these PNC show that 2.5% BaTiO₃-loaded polymer nanocomposites (PNC) showed mitigation in magnitude of the conductivity compared with that of 0 wt.% loaded PNC; but increase in conductivity is noted thereafter with increase in filler content of up to 7.5 wt.%. The higher conductivity is observed for 7.5% filler-loaded membrane. The XRD study identifies suppression of polymer phase associated with (200) plane. The SEM image illustrates inhomogeneity in surface morphologies for PNCs with the filler dispersed. The thermal profile registers the endothermic changes associated with polymer host indicating a varying heat of fusion ∆Hm with filler increase. FTIR studies confirm possible interaction between various constituents of the PNCs.     

PVC–PMMA composite electrospun membranes as polymer electrolytes for polymer lithium-ion batteries

Composite nanofibrous membranes based on poly (vinyl chloride) (PVC)?Cpoly (methyl methacrylate) (PMMA) were prepared by electrospinning and then they were soaked in liquid electrolyte to form polymer electrolytes (PEs). The introduction of PMMA into the PVC matrix enhanced the compatibility between the polymer matrix and the liquid electrolyte. The composite nanofibrous membranes prepared by electrospinning involved a fully interconnected pore structure facilitating high electrolyte uptake and easy transport of ions. The ion conductivity of the PEs increased with the increase in PMMA content in the blend and the ion conductivity of the polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend was 1.36?×?10^?3 S cm^?1 at 25?°C. The polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend presented good electrochemical stability up to 5.0?V (vs. Li/Li⁺) and good interfacial stability with the lithium electrode. The promising results showed that nanofibrous PEs based on PVC?CPMMA were of great potential application in polymer lithium-ion batteries.     

Effects of MnO<Subscript>2</Subscript> nano-particles on the conductivity of PMMA-PEO-LiClO<Subscript>4</Subscript>-EC polymer electrolytes

Li-ion rechargeable batteries based on polymer electrolytes are of great interest for solid state electrochemical devices nowadays. Many studies have been carried out to improve the ionic conductivity of polymer electrolytes, which include polymer blending, incorporating plasticizers and filler additives in the electrolyte systems. This paper describes the effects of incorporating nano-sized MnO₂ filler on the ionic conductivity enhancement of a plasticized polymer blend PMMA–PEO–LiClO₄–EC electrolyte system. The maximum conductivity achieved is within the range of 10⁻³ S cm⁻¹ by optimizing the composition of the polymers, salts, plasticizer, and filler. The temperature dependence of the polymer conductivity obeys the VTF relationship. DSC and XRD studies are carried out to clarify the complex formation between the polymers, salts, and plasticizer.     

Preparation and characterization of anhydrous polymer electrolyte membranes based on poly(vinyl alcohol-<Emphasis Type="Italic">co</Emphasis>-ethylene) copolymer

Anhydrous polymer electrolyte membranes with cross-linked structure have been prepared based on poly(vinyl alcohol-co-ethylene) (PVA-co-PE) copolymer. The PVA units of copolymer served to induce thermal cross-linking with 4,5-imidazole dicarboxylic acid (IDA) via esterification while PE units controlled the membrane swelling and the mechanical properties of films. Upon doping with phosphoric acid (PA, H₃PO₄) to form imidazole-PA complexes, the proton conductivity of membranes continuously increased with increasing PA content. As a result, proton conductivity reached 0.01 S/cm at 100 °C under anhydrous conditions. X-ray diffraction analysis revealed that both the d-spacing and crystalline peak of membranes were reduced upon introduction of IDA/PA due to the cross-linking effect. The PVA-co-PE/IDA/PA membranes exhibited good mechanical properties, e.g., 150 MPa of Young’s modulus, as determined by a universal testing machine. Thermal gravimetric analysis also represented that the thermal stability of membranes was increased up to 200 °C upon introduction of IDA/PA.