Role of Dielectric Constant on Ion Transport: Reformulated Arrhenius Equation

Solid and nanocomposite polymer electrolytes based on chitosan have been prepared by solution cast technique. The XRD results reveal the occurrence of complexation between chitosan (CS) and the LiTf salt. The deconvolution of the diffractogram of nanocomposite solid polymer electrolytes demonstrates the increase of amorphous domain with increasing alumina content up to 4 wt.%. Further incorporation of alumina nanoparticles (6 to 10 wt.% Al2O3) results in crystallinity increase (large crystallite size). The morphological (SEM and EDX) analysis well supported the XRD results. Similar trends of DC conductivity and dielectric constant with Al2O3 concentration were explained. The TEM images were used to explain the phenomena of space charge and blocking effects. The reformulated Arrhenius equation (σ(ε′,T)=σoexp(-Ea/KBε′T)) was proposed from the smooth exponential behavior of DC conductivity versus dielectric constant at different temperatures. The more linear behavior of DC conductivity versus 1000/(ɛ′×T) reveals the crucial role of dielectric constant in Arrhenius equation. The drawbacks of Arrhenius equation can be understood from the less linear behavior of DC conductivity versus 1000/T. The relaxation processes have been interpreted in terms of Argand plots

Structure, Dielectric Properties and AC Behavior of Commercial Polytetrafluroethylene (PTFE) Polymer

In this work the relative permittivity (ε''), dielectric loss (ε'') and AC-conductivity for commercial polytetrafluroethylene (PTFE) have been measured at different temperatures (20-110°С) and over the frequency range from 10 KHz to 1 MHz. The infrared (IR) spectra of PTFE also been investigated to detect the presence of polar groups and carbon double bonds. The relative permittivity had observed to decrease with increasing frequency and temperature. Some loss peaks were observed in the dielectric loss spectra, which referred to the relaxation, arises from the orientation of unsaturated double (C=C) bond and polar additives. The diameter of the semicircles in Cole-Cole (ε' versus ε'') plots are not coincides with x-axis at different temperature which reveals that the relaxation processes are non-Debye type. The AC-conductivity increases with increasing of frequency and almost independent on the temperature

From green remediation to polymer hybrid fabrication with improved optical band gaps

The present work proposed a novel approach for transferring high-risk heavy metals tometal complexes via green chemistry remediation. The method of remediation of heavy metals developed in the present work is a great challenge for global environmental sciences and engineering because it is a totally environmentally friendly procedure in which black tea extract solution is used. The FTIR study indicates that black tea contains enough functional groups (OH and NH), polyphenols and conjugated double bonds. The synthesis of copper complex was confirmed by the UV-vis, XRD and FTIR spectroscopic studies. The XRD and FTIR analysis reveals the formation of complexation between Cu metal complexes and Poly (Vinyl Alcohol) (PVA) host matrix. The study of optical parameters indicates that PVA-based hybrids exhibit a small optical band gap, which is close to inorganic-based materials. It was noted that the absorption edge shifted to lower photon energy. When Cu metal complexes were added to PVA polymer, the refractive index was significantly tuned. The band gap shifts from 6.2 eV to 1.4 eV for PVA incorporated with 45 mL of Cu metal complexes. The nature of the electronic transition in hybrid materials was examined based on the Taucs model, while a close inspection of the optical dielectric loss was also performed in order to estimate the optical band gap. The obtained band gaps of the present work reveal that polymer hybrids with sufficient film-forming capability could be useful to overcome the drawbacks associated with conjugated polymers. Based on the XRD results and band gap values, the structure-property relationships were discussed in detail. © 2019 by the authors. Licensee MDPI, Basel, Switzerland

New Method for the Development of Plasmonic Metal-Semiconductor Interface Layer: Polymer Composites with Reduced Energy Band Gap

Silver nanoparticles within a host polymer of chitosan were synthesized by using in situ method. Ultraviolet-visible spectroscopy was then carried out for the prepared chitosan : silver triflate (CS : AgTf) samples, showing a surface plasmonic resonance (SPR) peak at 420 nm. To prepare polymer composites with reduced energy band gap, different amounts of alumina nanoparticles were incorporated into the CS : AgTf solution. In the present work, the results showed that the reduced silver nanoparticles and their adsorption on wide band gap alumina (Al2O3) particles are an excellent approach for the preparation of polymer composites with small optical band gaps. The optical dielectric loss parameter has been used to determine the band gap experimentally. The physics behind the optical dielectric loss were interpreted from the viewpoint of quantum mechanics. From the quantum-mechanics viewpoint, optical dielectric loss was also found to be a complex equation and required lengthy numerical computation. From the TEM investigation, the adsorption of silver nanoparticles on alumina has been observed. The optical micrograph images showed white spots (silver specks) with different sizes on the surface of the films. The second semicircle in impedance Cole-Cole plots was found and attributed to the silver particles

The effect of number of vacuum thermal evaporation cycles to the optoelectronic and morphological properties of ZnO

Zinc oxide (ZnO) is a wide band gap material (~3.37 eV) which has small exciton Bohr radius ~2.34 nm. In dye-sensitized solar cell, ZnO thin film is used as photoelectrode. Light-sensitive organic/ inorganic fluorophores could be adsorbed on the surface of the ZnO film, which later will be sandwiched with electrolyte and a counter electrode. The aim of this paper is to study the effect of number of evaporation cycle to the yielded morphology and size of ZnO building blocks; deposited using one, two, and three cycles of vacuum thermal evaporation technique. The ZnO thin films have been deposited on ITO glass substrate at vacuum pressure of 5 ´ 10-5 Torr, 116 A, and 2.6 V. The morphology of the thin films has been examined under Field Emission Scanning Electron Microscope (FESEM), which showed nanosphere morphology. The morphological observation is supported by a simulation; which calculated based on the crystallographic properties of the synthesized ZnO – characterized by X-ray diffractometer (XRD). Three sets of the ZnO thin films consists of ZnO particles in the range of 8 – 20 nm, 11 – 37 nm, and 6 – 16 nm respectively. According to the optical properties characterized by absorption spectrometer, it has been observed that the band gap of the thin films increased with increasing number of evaporation cycles. The values of the optical bandgap, Eg evaluated from Tauc’s plot, were found in the range between 2.40 eV to 2.60 eV

Electrochemical impedance spectroscopy as a novel approach to investigate the influence of metal complexes on electrical properties of poly (vinyl alcohol)(PVA) composites

In the current study, black tea leaves extract solution (TES) as a new green technique is used to fabricate metal-polyphenols complexes (X-polyphenols complex; X= Cu+2, Ce+3, and Cd+2). The metal-complexes are integrated with poly (vinyl alcohol) (PVA) to prepare PVA composite films. The electrical properties of pure PVA and composites are characterized using the electrochemical impedance spectroscopy (EIS) method. The EIS data are fitted to the electrical equivalent circuit to evaluate the impedance parameters of pure PVA and composite films. The trend of DC conductivity is further verified by dielectric analysis. The electrical parameters are considerably improved upon incorporating with the metal-complexes. The effects of the metal-complexes on the modification of PVA are compared together. The PVA composite incorporated with the Cu+2-complex shows the highest DC conductivity and dielectric constant, which is important for application in electrochemical energy storage devices such as batteries and supercapacitors, in comparison with the Ce+3- and Cd+2- complexes

Metal framework as a novel approach for the fabrication of electric double layer capacitor device with high energy density using plasticized Poly(vinyl alcohol): Ammonium Thiocyanate based Polymer Electrolyte

High performance electric double-layer capacitors (EDLCs) based on poly (vinyl alcohol) (PVA): ammonium thiocyanate (NH4SCN):Cu(II)-complex plasticized with glycerol (GLY) have been fabricated. The maximum DC ionic conductivity (σDC) of 2.25 × 10-3 S cm-1 is achieved at ambient temperature. The X-ray diffraction (XRD) patterns confirmed that the addition of both Cu(II)–complex and GLY enhanced the amorphous region within the samples. Through the Fourier transform infrared (FTIR) the interactions between the host polymer and other components of the prepared electrolyte are observed. The FESEM images reveal that the surface morphology of the samples showed a uniform smooth surface at high GLY concentration. This is in good agreement with the XRD and FTIR results. Transference numbers of ion (tion) and electron (tel) for the highest conducting composite polymer electrolyte (CPE) are recognized to be 0.971 and 0.029, respectively. The linear sweep voltammetry (LSV) revealed that the electrochemical stability window for the CPE is 2.15 V. These high values of tion and potential stability established the suitability of the synthesized systems for EDLC application. Cyclic voltammetry (CV) offered nearly rectangular shape with the lack of Faradaic peak. The specific capacitance and energy density of the EDLC are nearly constant within 1000 cycles at a current density of 0.5 mA/cm2 with average of 155.322 F/g and 17.473 Wh/Kg, respectively. The energy density of the EDLC in the current work is in the range of battery specific energy. The EDLC performance was found to be stable over 1000 cycles. The low value of equivalent series resistance reveals that the EDLC has good electrolyte-electrode contact. The EDLC exhibited the initial high power density of 4.960 × 103 W/K

Characterization of opto-electronic properties of thermally evaporated ZnO

Photoelectrode plays significant role in excitonic solar cells i.e., (i) as an acceptor and (ii) transport media of excited state electron from the fluorophore upon absorption of energy of photon; which prevents from electron-hole recombination in the fluorophore. The evolution of opto-electronic properties of the ZnO upon change of size, however, receives insufficient attention from researchers. Therefore, the aim of this paper is to establish few realistic clusters of (ZnO)n (n = 3, 6, 12, 13, and 21) to study their opto-electronic properties using quantum chemical calculations at the level of B3LYP functional and lanl2dz basis set. Geometry of the clusters were optimized to the lowest energy structures; evaluated as realistic using a combination of harmonic frequency calculations, and experimental works. A device structure of cadmium selenide-based solar cell was used in the study to analyze the energy level alignment, and compatibility of the ZnO realistic clusters

Effect of ohmic-drop on electrochemical performance of EDLC fabricated from PVA:dextran:NH4I based polymer blend electrolytes

Proton conducting solid polymer blend electrolytes based on poly(vinyl alcohol)(PVA):dextran that were doped with different quantities of ammonium iodide (NH4I) were prepared. The X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) study were carried out to examine the compatibility of NH4I withPVA:dextran polymers. FTIR spectroscopy assessment was used to establish the presence of a complex formation between the PVA:dextran and added salt through the modification and reduction in the intensity of FTIR bands relevant to the functional groups. The field emission scanning electron microscopy (FESEM) examination was used to assess the channels for proton transport. Electrical impedance spectroscopy (EIS) was used to analyse the samples conductivity behaviour. The sample with 20 wt.% of added salt has shown a high DC conductivity which can be employed in electrochemical devices such as EDLC. It is also demonstrated by the transference number (TNM) and linear sweep voltammetry (LSV) that it is appropriate to use the largest conducting sample for electrochemical device. There was electrochemical stability of the electrolyte sample with voltage sweeping linearly to 1.3 V. It is shown by the outcome of cyclic voltammetry (CV) plot that charge storage at the site of electrode-electrolyte is non-Faradiac. A high drop voltage (Vd=IR) is implied by the usual galvanostatic charge-discharge. The equivalent series resistance (Res) increases as a result of the increase in Vd all the way through the charge-discharge cycle. Specific capacitance (Csp) is nearly constant from the foremost cycle to the 100th cycle, with average of 4.2 F/g

Tea from the drinking to the synthesis of metal complexes and fabrication of PVA based polymer composites with controlled optical band gap

In the present study black tea extract (BTE) solution which is familiar for drinking was used to prepare cerium metal-complexes (Ce(III)-complex). The prepared Ce(III)-complex was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and UV–Vis spectroscopy. The results indicate that BTE solution is a novel green coordination chemistry approach for the synthesis of metal complexes. The outcomes signify that coordination occurs between cerium cations and polyphenols. The synthesis of metal-complexes with superior absorption performance in the visible region is a challenge for optoelectronic device applications. The suspended Ce(III)-complex in distilled water was mixed with poly (vinyl alcohol) (PVA) polymer to fabricate PVA/ Ce(III)-complex composites with controlled optical properties. The PVA/Ce(III)-complexes composite films were characterized by FTIR, XRD, and UV–Vis spectroscopy. The XRD findings confirms the amorphous structure for the synthesized Ce(III)-complexes. The addition of Ce(III)-complex into the PVA host polymer led to the growth of polymer composites with controllable small optical band gaps. It is shown by the FTIR spectra of the composite films that the functional groups of the host PVA have a vigorous interaction with the Ce(III)-complex. The XRD deconvolution on PVA composites reveals the amorphous phase enlargement with increasing Ce(III)-complex concentration. It is indicated in the atomic force microscopy (AFM) that the surface roughness in the doped PVA films increases with the increase of the Ce(III)-complex. There is a decrease in absorption edge from 5.7 to 1.7 eV. It becomes possible to recognize the type of electron transition by studying both the Tauc's model and optical dielectric loss (ɛi) parameter