FTIR, XRD and ac impedance spectroscopic study on PVA based polymer electrolyte doped with NH4X (X = Cl, Br, I)

The present study focuses on characterizing PVA: NH₄X (X = Cl, Br, I) proton conducting polymer electrolyte prepared by solution casting technique using XRD, FTIR and ac impedance spectroscopic studies. The XRD patterns of all the prepared polymer electrolytes reveal the amorphous nature of the films. The FTIR spectroscopic study indicates the detailed interaction of PVA with proton. From ac impedance spectroscopic studies, it has been found that PVA doped with NH₄I have high ionic conductivity (2.5 × 10⁻³S cm⁻¹) than PVA doped with NH₄Br (5.7 × 10⁻⁴S cm⁻¹) and NH₄Cl (1.0 × 10⁻⁵S cm⁻¹) polymer electrolytes. This is due to the large anionic size and low lattice energy of NH₄I (in comparison with NH₄Br and NH₄Cl).The temperature dependence of ionic conductivity for all the PVA: NH₄X (X = Cl, Br, I) polymer films obey Arrhenius equation. Ionic transference number measured has been found to be in the range of 0.93-0.96 for all the polymer electrolytes proving that the total conductivity is mainly due to ions.     

Evaluation and investigation on the effect of ionic liquid onto PMMA-PVC gel polymer blend electrolytes

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl imide), BmImTFSI based poly(methyl methacrylate)-poly (vinyl chloride), PMMA-PVC gel polymer electrolytes were prepared by solution casting technique. These ionic liquid-based gel polymer electrolytes exhibit Arrhenius type temperature dependence of ionic conductivity. The highest ionic conductivity of (8.08 ± 0.01) × 10^− 4 Scm⁻¹ was achieved at 80 °C upon addition of 60 wt.% of BmImTFSI. X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies revealed the amorphous nature and morphology of these polymer electrolytes, respectively. The lower coherence length of the peak inferred the higher amorphous degree in these polymer matrices. Decreases in T_g and T_m indicate the flexibility of polymer backbone. The amorphous behavior of these ionic liquid-based gel polymer electrolytes are also enhanced as shown in differential scanning calorimetry (DSC) analysis. On the contrary, thermogravimetric analysis (TGA) divulges that the thermal stability of polymer electrolytes has been improved upon impregnation of BmImTFSI.     

Characterization of SBA-15 doped (PEO + LiClO4) polymer electrolytes for electrochemical applications

SBA-15 mesoporous material was prepared by the simple hydrothermal process and added to poly(ethylene oxide) (PEO) and lithium percholorate (LiClO₄) as a filler. X-ray Diffractometry (XRD), Differential Scanning Calorimetry (DSC) and Scanning Electron Microscopy (SEM) were used to determine the characteristics of the composite polymer electrolyte. The SEM of the electrolyte containing 10 wt% of SBA-15 confirms the highest miscibility and amorphous nature. SBA-15 doped (PEO + LiClO₄) polymer electrolytes have shown improved conductivity over the pure PEO and (PEO + LiClO₄) electrolyte. The mesoporous SBA-15 acted as crystal cores and fined the crystallites thus decreasing the crystallinity, which provided a much more continuous amorphous domain for Li⁺ ions to move easily in the (PEO + LiClO₄) electrolyte.     

Preparation and physical properties of (PVA)0.75(NH4Br)0.25(H2SO4)xM solid acid membrane

In this work, solid acid membrane consisting of poly(vinyl alcohol) (PVA), ammonium bromide (NH₄Br) and sulfuric acid (SA) has been prepared by a solution casting technique method. X-ray diffraction of the (PVA)_0.75(NH₄Br)_0.25(H₂SO₄)_xM polymer matrix and pure (PVA)_0.75(NH₄Br)_0.25 revealed the difference in crystallinity between them. The effect of different amounts of SA on the conductivity of the polymer electrolytes was studied. The ionic conductivity of the prepared electrolytes can reach 3.1 × 10⁻² S cm⁻¹ at room temperature. The conductivity measurements carried out at different temperatures indicate that all the films follow Arrhenius behavior and that the activation energy decreases with the increase in SA concentration. The a.c. conductivity seems to follow the universal power law.     

Ion conducting corn starch biopolymer electrolytes doped with ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

Biodegradable corn starch-lithium hexafluorophosphate (LiPF₆) based biopolymer electrolytes were prepared by solution casting technique. Ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF₆) was doped into the polymer matrix. Upon addition of 50 wt.% BmImPF₆, the maximum ionic conductivity of (1.47 ± 0.02) × 10^− 4 Scm^− 1 was achieved due to its higher amorphous region. This result had been further proven in ATR-FTIR study. Frequency dependence of conductivity and dielectric studies reveal the occurrence of polarization at the electrolyte-electrode interface and thus form the electrical double layer, asserting the non-Debye characteristic of polymer electrolytes. This result is in good agreement with dielectric loss tangent study. Based on the changes in shift, changes in intensity, changes in shape and existence of some new peaks, attenuated total reflectance-Fourier Transform Infrared (ATR-FTIR) divulged the complexation between corn starch, LiPF₆ and BmImPF₆, as shown in the spectra.     

Investigation on dielectric relaxations of PVP-NH4SCN polymer electrolyte

Poly (N-vinyl pyrrolidone) (PVP) and ammonium thiocyanate (NH₄SCN) based polymer films with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The FTIR analysis confirms the complex formation of the polymer with the salt. The conductivity analysis shows that the 20 mol% ammonium thiocyanate doped polymer electrolyte has high ionic conductivity and it has been found to be 1.7 × 10⁻⁴ S cm⁻¹, at room temperature. From the admittance plot, the activation energy has been found to be low for 20 mol% salt doped polymer electrolyte. The dielectric behavior has been analyzed using dielectric permittivity (ε^∗), dissipation factor (tan δ) and electric modulus (M^∗) of the samples.     

Transport property and structural characterization studies on (1 − x)[0.75AgI:0.25AgCl]:xTiO2 conducting composite electrolyte system

Transport property and structural investigation have been carried out on newly synthesized Ag⁺ ion conducting composite electrolyte system. The composite electrolyte system (1 − x)[0.75AgI:0.25AgCl]:xTiO₂, where 0 ? x ? 0.5 (in molar weight fraction) has been synthesized by melt quenching and annealing methods. The chemical compound TiO₂ (second phase dispersoid) dispersed in different compositions in a quenched (0.75AgI:0.25AgCl) mixed system/solid solution; this solid solution was used as a first phase host salt in place of AgI. The different preparation routes were adopted for the composite electrolyte system. Composition x = 0.1 exhibited highest conductivity at room temperature. The composite system 0.9[0.75AgI:0.25AgCl]:0.1TiO₂ was synthesized at different soaking times by melt quenching method. The system exhibited optimum conductivity at 20 min soaking time (σ_rt ≈ 1.4 × 10⁻³ S/cm). The ac conductivity has been measured from Z′-Z″ (Cole-Cole) complex impedance plots using impedance spectroscopic (IS) technique. The electrical conductivity as a function of temperature and frequency has been studied, and activation energy E_a, was calculated from Arrhenius plots for all compositions (0 ? x ? 0.5). The dc conductivity value has been evaluated from Log σ vs. log f plots. Structural characterization studies were carried out by X-ray diffraction (XRD) and differential thermal analysis (DSC) techniques.     

Iron redox equilibrium, structure and properties of zinc iron phosphate glasses

Iron redox equilibrium, structure and properties were investigated for the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glasses melted at different temperatures. The structure and valence states of the iron ions in these glasses were investigated using Mössbauer spectroscopy, Raman spectroscopy and differential thermal analysis. Mössbauer spectroscopy indicated that the concentration of Fe²⁺ ions increased in the 10ZnO-30Fe₂O₃-60P₂O₅ (mol%) glass with increasing melting temperature. The Fe²⁺/(Fe²⁺ + Fe³⁺) ratio increased from 0.18 to 0.38 as the melting temperature increased from 1100 to 1300 °C. The measured isomer shifts showed that both Fe²⁺ and Fe³⁺ ions are in octahedral coordination. It was shown that the dc conductivity strongly depended on Fe²⁺/(Fe²⁺ + Fe³⁺) ratio in glasses. The dc conductivity increases with the increasing Fe²⁺ ion content in these glasses. The conductivity arises from the polaron hopping between Fe²⁺ and Fe³⁺ ions which suggests that the conduction is electronic in nature in zinc iron phosphate glasses.     

The comparative structure, properties, and ionic conductivity of LiI + Li2S + GeS2 glasses doped with Ga2S3 and La2S3

The well known and characterized fast ion conducting (FIC) LiI + Li₂S + GeS₂ glass-forming system has been further optimized for higher ionic conductivity and improved thermal and chemical stability required for next generation solid electrolyte applications by doping with Ga₂S₃ and La₂S₃. These trivalent dopants are expected to eliminate terminal and non-bridging sulfur (NBS) anions thereby increasing the network connectivity while at the same time increasing the Li⁺ ion conductivity by creating lower basicity [(Ga or La)S_4/2]⁻ anion sites. Consistent with the finding that the glass-forming range for the Ga₂S₃ doped compositions is larger than that for the La₂S₃ compositions, the addition of Ga₂S₃ is found to eliminate NBS units to create bridging sulfur (BS) units that not only gives an improvement to the thermal stability, but also maintains and in some cases increases the ionic conductivity. The compositions with the highest Ga₂S₃ content showed the highest T_gs of ∼325 °C. The addition of La₂S₃ to the base glasses, by comparison, is found to create NBS by forming high coordination octahedral LaS₆³⁻ sites, but yet still improved the chemical stability of the glass in dry air and retained its high ionic conductivity and thermal stability. Significantly, at comparable concentrations of Li₂S and Ga₂S₃ or La₂S₃, the La₂S₃-doped glasses showed the higher conductivities. The addition of the LiI to the glass compositions not only improved the glass-forming ability of the compositions, but also increased the ionic conductivity glasses. LiI concentrations from 0 to 40 mol% improved the conductivities of the Ga₂S₃ glasses from ∼10⁻⁵ to ∼10⁻³ (Ω cm)⁻¹ and of the La₂S₃ glasses from ∼10⁻⁴ to ∼10⁻³ (Ω cm)⁻¹ at room temperature. A maximum conductivity of ∼10⁻³ (Ω cm)⁻¹ at room temperature was observed for all of the glasses and this value is comparable to some of the best Li ion conductors in a sulfide glass system. Yet these new compositions are markedly more thermally and chemically stable than most Li⁺ ion conducting sulfide glasses. LiI additions decreased the T_gs and T_cs of the glasses, but increased the stability towards crystallization (T_c − T_g).     

Structure study of multi-component borosilicate glasses from high-Q neutron diffraction measurement and RMC modeling

A neutron diffraction structure study has been performed on multi-component borosilicate glasses with compositions (65 − x)SiO₂ · xB₂O₃ · 25Na₂O · 5BaO · 5ZrO₂, x = 5-15 mol%. The structure factor has been measured up to a rather high momentum transfer value of 30 Å⁻¹, which made high r-space resolution available for real space analyses. Reverse Monte Carlo simulation was applied to calculate the partial atomic pair correlation functions, nearest neighbor atomic distances and coordination number distributions. The Si-O network consists of tetrahedral SiO₄ units with characteristic first neighbor distances at r_Si-O = 1.60 Å and r_Si-Si = 3.0 Å. The boron environment contains two well-resolved B-O distances at 1.40 and 1.60 Å and both 3- and 4-fold coordinated B atoms are present. A chemically mixed network structure is proposed including ^[4]B-O-^[4]Si and ^[3]B-O-^[4]Si chain segments. The O-O and Na-O distributions suggest partial segregation of silicon and boron rich regions. The highly effective ability of Zr to stabilize glassy and hydrolytic properties of sodium-borosilicate materials is interpreted by the network-forming role of Zr ions.     

Electrical conductivity of NbN-SiO2 films obtained by ammonolysis of Nb2O5-SiO2 sol-gel derived coatings

The studies of electrical conductivity of NbN-SiO₂ films are reported. To obtain these films, sol-gel derived xNb₂O₅-(100 − x)SiO₂ (where x = 100, 90, 80, 70, 60, 50 mol%) coatings were nitrided at 1200 °C. The nitridation process leads to the formation of some disordered structures, with NbN metallic grains dispersed in insulating SiO₂ matrix. The structure of the samples was studied using X-ray diffraction (XRD) and atomic force microscopy (AFM). The electrical conductivity was measured with the conventional four-terminal method in the temperature range from 5 to 280 K. The superconducting transition was not observed even for the sample that does not contain silica. All the samples exhibit negative temperature coefficient of resistivity. The results of conductivity versus temperature may be described on the grounds of a model proposed for a weakly disordered system.     

Effect of ethylene carbonate in poly (methyl methacrylate)-lithium tetraborate based polymer electrolytes

Thin films composed of poly (methyl methacrylate) (PMMA), lithium tetraborate (Li₂B₄O₇) and ethylene carbonate (EC) were prepared by solution casting method. The highest ionic conductivity at room temperature was achieved for the composition PMMA:Li₂B₄O₇:EC (42:18:40) with the value 1.29 × 10⁻⁵ S cm⁻¹. The presence of plasticizer in the polymer complex is crucial in improving the ionic conductivity by increasing the concentration of free mobile ions through the structural conversion from crystalline to amorphous phase. This conversion lowers the viscosity of the polymer complex. Conductivity-temperature plots were found to obey Williams-Landel-Ferry (WLF) mechanism. Dielectric data was analyzed using the dielectric permittivity (ε′) and dielectric modulus (M′) of the samples. Fourier transform infrared (FTIR) studies confirmed that complexation occurs between PMMA, Li₂B₄O₇ and EC. Thermal stability of the polymer complex, which decreases with the addition of plasticizer (EC), was determined using thermal gravimetric analysis (TGA).     

Microstructure and percolation threshold characteristics of reactive sputtered Au-TiO2 granular composite films

The Au/TiO₂ composite films were prepared by using reactive co-sputtering technique. The size and shape of the embedded Au particles and the absorption spectra of the composite films were investigated by using SEM, XRD, and UV-VIS-NIR spectrophotometer, respectively. The average size of Au particles and the electrical conductivity decrease as the sputtering pressure increases. The normalized conductivity of the films deposited at five different pressures with the Au concentration in the range of 0.15-0.91 were measured. The percolation threshold increases from 0.21 to 0.90 as the sputtering pressure increases from 2 × 10⁻² Torr to 9.5 × 10⁻² Torr.     

Different substrate materials effect on structure of ta-C films by Raman spectroscopy for magnetic recording sliders

Raman spectra, using visible (514 nm) and ultraviolet (244 nm) excitation, of tetrahedral amorphous carbon (ta-C) films of thickness of 5 nm have been studied as a function of different substrates materials. These materials are Fe-Co (Fe: 67 at.%, Co: 33 at.%) alloy, Fe-Ni alloy (Fe: 18 at.%, Ni: 82 at.%), Au and Al₂O₃-TiC (Al₂O₃: 64 at.%, TiC: 36 at.%), which are mainly used in magnetic recording sliders. The spectra show that the films deposited on Al₂O₃-TiC contain the highest sp³ content, with a lower sp³ content observed in films deposited to Fe-Co and Fe-Ni alloys. The lowest sp³ content was observed in films on the Au substrate. The results also indicate that the anti-wear performance of ta-C film on different substrates varies as Al₂O₃-TiC (the best) > Fe-Co and Fe-Ni alloy > Au (the worst). Also mechanisms are proposed to explain the effect of substrate material on these thin film properties.     

Polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP)-based composite polymer electrolyte containing LiPF3(CF3CF2)3

This paper describes the preparation and characterization of lithium fluoroalkylphosphate-containing composite polymer electrolyte based on a polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) matrix. A mixture of ethylene carbonate and diethyl carbonate was used as a plasticizing agent and nanoscopic Al₂O₃ as a filler. The membranes were characterized by ac impedance, SEM, DSC, FTIR and fluorescence. An electrolyte with 2.5 wt% Al₂O₃ exhibited a conductivity of 9.8 × 10⁻⁴ S cm⁻¹ at ambient temperature. It was found that filler contents above 2.5 wt% rendered the membranes less conducting.     

A novel route of synthesis of WS2 thin film and its characterization

WS₂ thin films have been deposited by chemical deposition technique using citric acid as a complexing agent at 343 K. X-ray pattern shows that crystalline nature with hexagonal- and orthorhombic-mixed phase. The films show that good optical properties high absorption and band gap value was found to be 1.31 eV. The specific conductivity of the film was found to be in order of 10⁻³ (Ω cm)⁻¹.     

Generation and annealing of defects in virgin fused silica (type III) upon ArF laser irradiation: Transmission measurements and kinetic model

The transmission of ArF laser pulses in virgin fused silica (type III) samples changes during N = 10⁶ pulses at an incoming fluence H_in = 5 mJ cm⁻² pulse⁻¹. The related absorption is determined by the pulse energy absorption coefficient α(N, H_in) using a modified Beer’s law, yielding initial values α_ini around 0.005 cm⁻¹, a maximum α_max ? 0.02 cm⁻¹ at N = 10³-10⁴ and stationary values 0.0045 cm⁻¹ ? α_end ? 0.0094 cm⁻¹ after N ≈ 6 × 10⁵ pulses. The development α(N, H_in = const.) is simulated by a rate equation model assuming a pulse number dependent E′ center density E′(N). E′(N) is determined by a dynamic equilibrium between E′ center generation and annealing. Generation occurs photolytically from the precursors ODC II and unstable SiH structures upon single photon absorption and from strained SiO bonds via two-photon excitation. Annealing in the dark periods between the laser pulses is dominated by the reaction of E′ with H₂ present in the SiO₂ network. The development α(N, H_in = const.) is observed for the very first sample irradiation only (virgin state). The values α_end are not accessible by simple spectrophotometer measurements.     

Production of CN(BΣ) state from dissociative excitation reaction of BrCN with microwave discharge flow of Ar

The mechanism of the dissociative excitation reaction of BrCN with the microwave discharge flow of Ar was investigated based on the CN(B²Σ⁺-X²Σ⁺) emission-spectroscopic and the electrostatic-probe measurements. By passing Ar and BrCN through P₂O₅, the contamination of H₂O molecules into the reaction region was reduced to ≈30%, being confirmed by monitoring the reduction of the OH(A²Σ⁺-X²Π) emission intensity. The variation of the CN(B²Σ⁺-X²Σ⁺) emission intensity on the pressure of Ar, P_Ar, of 0.1-0.3 Torr was compared with that of the density of electrons whose kinetic energy was lower than the ionization energy of BrCN, 11.9 eV. The dissociation of BrCN was found to proceed predominantly via the charge transfer from Ar⁺ followed by the BrCN⁺ − e⁻ recombination. When the contamination of H₂O molecules in the reaction region was not reduced, the dissociation via the energy transfer from metastable Ar atoms became significant. The present study shows that the contamination of H₂O molecules in the reaction system makes significant effect onto the gas-phase plasma process.     

Three-dimensional structure of fast ion conducting 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses from high-energy X-ray diffraction and reverse Monte Carlo simulations

A high-energy X-ray diffraction study has been carried out on a series of 0.5Li₂S + 0.5[(1 − x)GeS₂ + xGeO₂] glasses with x = 0.0, 0.1, 0.2, 0.4, 0.6 and 0.8. Structure factors were measured to wave vectors as high as 30 Å⁻¹ resulting in atomic pair distribution functions with high real space resolution. The three dimensional atomic-scale structure of the glasses was modeled by reverse Monte Carlo simulations based on the diffraction data. Results from the simulations show that at the atomic-scale 0.5Li₂S + 0.5[(1 − x)GeS₂ + xGeO₂] glasses may be viewed as an assembly of independent chains of (Li^+-S)₂GeS_2/2 and (Li^+-O)₂GeO_2/2 tetrahedra as repeat units, where the Li ions occupy the open space between the chains. The new structure data may help understand the reasons for the sharp maximum in the Li⁺ ion conductivity at x ∼ 0.2.     

Structural, thermal and electrical properties of PVA-LiCF3SO3 polymer electrolyte

The development of polymeric systems with high ionic conductivity is one of the main objectives in Li rechargeable battery. In the present study, the different composition of PVA-LiCF₃SO₃ polymer electrolyte has been prepared by solution cast technique using DMSO as solvent. The FTIR study confirms the polymer-salt complex formation. The amorphous nature of the polymer has been confirmed by XRD analysis. DSC measurements show decrease in T_g with increasing salt concentration. The temperature dependent conductivity obeys Arrhenius relationship. The maximum conductivity has been observed in the order of 7 × 10^− 4 S cm^− 1 for 25 mol% of LiCF₃SO₃. The activation energy has been found to be 0.16 eV. The two peaks have been observed in the dielectric loss spectrum which shows two types of relaxation α and β.