Plasticized magnesium ion conducting polymer blend electrolytes based on chitosan (CS): polyvinyl alcohol (PVA) was synthesized with a casting technique. The source of ions is magnesium triflate Mg(CF3SO3)2, and glycerol was used as a plasticizer. The electrical and electrochemical characteristics were examined. The outcome from X-ray diffraction (XRD) examination illustrates that the electrolyte with highest conductivity exhibits the minimum degree of crystallinity. The study of the dielectric relaxation has shown that the peak appearance obeys the non-Debye type of relaxation process. An enhancement in conductivity of ions of the electrolyte system was achieved by insertion of glycerol. The total conductivity is essentially ascribed to ions instead of electrons. The maximum DC ionic conductivity was measured to be 1.016 × 10-5 S cm-1 when 42 wt.% of plasticizer was added. Potential stability of the highest conducting electrolyte was found to be 2.4 V. The cyclic voltammetry (CV) response shows the behavior of the capacitor is non-Faradaic where no redox peaks appear. The shape of the CV response and EDLC specific capacitance are influenced by the scan rate. The specific capacitance values were 7.41 F/g and 32.69 F/g at 100 mV/s and 10 mV/s, respectively. Finally, the electrolyte with maximum conductivity value is obtained and used as electrodes separator in the electrochemical double-layer capacitor (EDLC) applications. The role of lattice energy of magnesium salts in energy storage performance is discussed in detail.
The structure and optical properties of polyethylene oxide (PEO) doped with tin titanate (SnTiO3) nano-filler were studied by X-ray diffraction (XRD) and UV-Vis spectroscopy as non-destructive techniques. PEO-based composed polymer electrolytes inserted with SnTiO3 nano-particles (NPs) were synthesized through the solution cast technique. The change from crystalline phase to amorphous phase of the host polymer was established by the lowering of the intensity and broadening of the crystalline peaks. The optical constants of PEO/SnTiO3 nano-composite (NC), such as, refractive index (n), optical absorption coefficient (α), dielectric loss (εi), as well as dielectric constant (εr) were determined for pure PEO and PEO/SnTiO3 NC. From these findings, the value of n of PEO altered from 2.13 to 2.47 upon the addition of 4 wt.% SnTiO3NPs. The value of εr also increased from 4.5 to 6.3, with addition of 4 wt.% SnTiO3. The fundamental optical absorption edge of the PEO shifted toward lower photon energy upon the addition of the SnTiO3 NPs, confirming a decrement in the optical band gap energy of PEO. The band gap shifted from 4.78 eV to 4.612 eV for PEO-doped with 4 wt.% SnTiO3. The nature of electronic transitions in the pure and the composite material were studied on the basis of Tauc's model, while optical εi examination was also carried out to calculate the optical band gap.
Polymer electrolytes and composites have prevailed in the high performance and mobile marketplace during recent years. Polymer-based solid electrolytes possess the benefits of low flammability, excellent flexibility, good thermal stability, as well as higher safety. Several researchers have paid attention to the optical properties of polymer electrolytes and their composites. In the present review paper, first, the characteristics, fundamentals, advantages and principles of various types of polymer electrolytes were discussed. Afterward, the characteristics and performance of various polymer hosts on the basis of specific essential and newly published works were described. New developments in various approaches to investigate the optical properties of polymer electrolytes were emphasized. The last part of the review devoted to the optical band gap study using two methods: Tauc's model and optical dielectric loss parameter. Based on recently published literature sufficient quantum mechanical backgrounds were provided to support the applicability of the optical dielectric loss parameter for the band gap study. In this review paper, it was demonstrated that both Tauc's model and optical dielectric loss should be studied to specify the type of electron transition and estimate the optical band gap accurately. Other parameters such as absorption coefficient, refractive index and optical dielectric constant were also explored.
The challenge in front of EDLC device is their low energy density compared to their battery counter parts. In the current study, a green plasticized nanocomposite sodium ion conducting polymer blend electrolytes (PNSPBE) was developed by incorporating plasticized Chitosan (CS) blended with polyvinyl alcohol (PVA), doped with NaBr salt with various concentration of CaTiO3 nanoparticles. The most optimized PNSPBE film was subsequently utilized in an EDLC device to evaluate its effectiveness both as an electrolyte and a separator. Structural and morphological changes were assessed using XRD and SEM techniques. The PNSPBE film demonstrated a peak ionic conductivity of 9.76×10-5 S/cm, as determined through EIS analysis. The dielectric and AC studies provided further confirmation of structural modifications within the sample. Both TNM and LSV analyses affirmed the suitability of the prepared electrolyte for energy device applications, evidenced by its adequate ion transference number and an electrochemical potential window of 2.86 V. Electrochemical properties were assessed via CV and GCD techniques, confirming non-Faradaic ion storage, indicated by the rectangular CV pattern at low scan rates. The parameters associated with the designed EDLC device including specific capacitance, ESR, power density (1950 W/kg) and energy density (12.3 Wh/kg) were determined over 1000 cycles.
This research paper investigates the electrochemical performance of chitosan (CS): dextran (DX) polymer-blend electrolytes (PBEs), which have been developed successfully with the incorporation of ammonium hexafluorophosphate (NH4PF6). X-ray diffraction (XRD) analysis indicates that the plasticized electrolyte system with the highest value of direct current (DC) ionic conductivity is the most amorphous system. The glycerol addition increased the amorphous phase and improved the ionic dissociation, which contributed to the enhancement of the fabricated device's performance. Transference number analysis (TNM) has shown that the charge transport process is mainly by ions rather than electrons, as tion = 0.957. The CS:DX:NH4PF6 system was found to decompose as the voltage goes beyond 1.5 V. Linear sweep voltammetry (LSV) revealed that the potential window for the most plasticized system is 1.5 V. The fabricated electrochemical double-layer capacitor (EDLC) was analyzed with cyclic voltammetry (CV) and charge-discharge analysis. The results from CV verify that the EDLC in this work holds the characteristics of a capacitor. The imperative parameters of the fabricated EDLC such as specific capacitance and internal resistance were found to be 102.9 F/g and 30 Ω, respectively. The energy stored and power delivered by the EDLC were 11.6 Wh/kg and 2741.2 W/kg, respectively.
In this report, a facile solution casting technique was used to fabricate polymer blend electrolytes of chitosan (CS):poly (ethylene oxide) (PEO):NH4SCN with high electrochemical stability (2.43V). Fourier transform infrared (FTIR) spectroscopy was used to investigate the polymer electrolyte formation. For the electrochemical property analysis, cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) techniques were carried out. Referring to the FTIR spectra, a complex formation between the added salt and CS:PEO was deduced by considering the decreasing and shifting of FTIR bands intensity in terms of functional groups. The CS:PEO:NH4SCN electrolyte was found to be electrochemically stable as the applied voltage linearly swept up to 2.43V. The cyclic voltammogram has presented a wide potential window without showing any sign of redox peaks on the electrode surface. The proved mechanisms of charge storage in these fabricated systems were found to be double layer charging. The EIS analysis showed the existence of bulk resistance, wherein the semicircle diameter decreased with increasing salt concentration. The calculated maximum DC conductivity value was observed to be 2.11 × 10-4 S/cm for CS:PEO incorporated with 40 wt% of NH4SCN salt. The charged species in CS:PEO:NH4SCN electrolytes were considered to be predominantly ionic in nature. This was verified from transference number analysis (TNM), in which ion and electron transference numbers were found to be tion = 0.954 and tel = 0.045, respectively. The results obtained for both ion transference number and DC conductivity implied the possibility of fabricating electrolytes for electrochemical double layer capacitor (EDLC) device application. The specific capacitance of the fabricated EDLC was obtained from the area under the curve of the CV plot.
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.
In this work, plasticized polymer electrolyte films consisting of chitosan, ammonium nitrate (NH4NO3) and glycerol for utilization in energy storage devices was presented. Various microscopic, spectroscopic and electrochemical techniques were used to characterize the concerned electrolyte and the electrical double-layer capacitor (EDLC) assembly. The nature of complexation between the polymer electrolyte components was examined via X-ray diffraction analysis. In the morphological study, field emission scanning electron microscopy (FESEM) was used to investigate the impact of glycerol as a plasticizer on the morphology of films. The polymer electrolyte (conducting membrane) was found to have a conductivity of 3.21 × 10-3 S/cm. It is indicated that the number density (n), mobility (μ) and diffusion coefficient (D) of ions are increased with the glycerol amount. The mechanism of charge storing was clarified, which implies a non-Faradaic process. The voltage window of the polymer electrolyte is 2.32 V. It was proved that the ion is responsible for charge-carrying via measuring the transference number (TNM). It was also determined that the internal resistance of the EDLC assembly lay between 39 and 50 Ω. The parameters associated with the EDLC assembly are of great importance and the specific capacitance (Cspe) was determined to be almost constant over 1 to 1000 cycles with an average of 124 F/g. Other decisive parameters were found: energy density (18 Wh/kg) and power density (2700 W/kg).
In the present work, a novel polymer composite electrolytes (PCEs) based on poly(vinyl alcohol) (PVA): ammonium thiocyanate (NH4SCN): Cd(II)-complex plasticized with glycerol (Gly) are prepared by solution cast technique. The film structure was examined by XRD and FTIR routes. The utmost ambient temperature DC ionic conductivity (σDC) of 2.01 × 10-3 S cm-1 is achieved. The film morphology was studied by field emission scanning electron microscopy (FESEM). The trend of σDC is further confirmed with investigation of dielectric properties. Transference numbers of ions (tion) and electrons (tel) are specified to be 0.96 and 0.04, respectively. Linear sweep voltammetry (LSV) displayed that the PCE potential window is 2.1 V. The desired mixture of activated carbon (AC) and carbon black was used to fabricate the electrodes of the EDLC. Cyclic voltammetry (CV) was carried out by sandwiching the PCEs between two carbon-based electrodes, and it revealed an almost rectangular shape. The EDLC exhibited specific capacitance, energy density, and equivalent series resistance with average of 160.07F/g, 18.01Wh/kg, and 51.05Ω, respectively, within 450 cycles. The EDLC demonstrated the initial power density as 4.065 × 103 W/Kg.
In this work, analysis of ion transport parameters of polymer blend electrolytes incorporated with magnesium trifluoromethanesulfonate (Mg(CF3SO3)2) was carried out by employing the Trukhan model. A solution cast technique was used to obtain the polymer blend electrolytes composed of chitosan (CS) and poly (2-ethyl-2-oxazoline) (POZ). From X-ray diffraction (XRD) patterns, improvement in amorphous phase for the blend samples has been observed in comparison to the pure state of CS. From impedance plot, bulk resistance (Rb) was found to decrease with increasing temperature. Based on direct current (DC) conductivity (σdc) patterns, considerations on the ion transport models of Arrhenius and Vogel-Tammann-Fulcher (VTF) were given. Analysis of the dielectric properties was carried out at different temperatures and the obtained results were linked to the ion transport mechanism. It is demonstrated in the real part of electrical modulus that chitosan-salt systems are extremely capacitive. The asymmetric peak of the imaginary part (Mi) of electric modulus indicated that there is non-Debye type of relaxation for ions. From frequency dependence of dielectric loss (ε″) and the imaginary part (Mi) of electric modulus, suitable coupling among polymer segmental and ionic motions was identified. Two techniques were used to analyze the viscoelastic relaxation dynamic of ions. The Trukhan model was used to determine the diffusion coefficient (D) by using the frequency related to peak frequencies and loss tangent maximum heights (tanδmax). The Einstein-Nernst equation was applied to determine the carrier number density (n) and mobility. The ion transport parameters, such as D, n and mobility (μ), at room temperature, were found to be 4 × 10-5 cm2/s, 3.4 × 1015 cm-3, and 1.2 × 10-4 cm2/Vs, respectively. Finally, it was shown that an increase in temperature can also cause these parameters to increase.
This report presents the preparation of plasticized sodium ion-conducting polymer electrolytes based on polyvinyl alcohol (PVA)via solution cast technique. The prepared plasticized polymer electrolytes were utilized in the device fabrication of electrical double-layer capacitors (EDLCs). On an assembly EDLC system, cyclic voltammetry (CV), electrical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), transfer number measurement (TNM) and charge-discharging responses were performed. The influence of plasticization on polymer electrolytes was investigated in terms of electrochemical properties applying EIS and TNM. The EIS was fitted with electrical equivalent circuit (EEC) models and ion transport parameters were estimated with the highest conductivity of 1.17 × 10-3 S cm-1 was recorded. The CV and charge-discharging responses were used to evaluate the capacitance and the equivalent series resistance (ESR), respectively. The ESR of the highest conductive sample was found to be 91.2 Ω at the first cycle, with the decomposition voltage of 2.12 V. The TNM measurement has shown the dominancy of ions with tion = 0.982 for the highest conducting sample. The absence of redox peaks was proved via CV, indicating the charge storing process that comprised ion accumulation at the interfacial region. The fabricated EDLC device is stable for up to 400 cycles. At the first cycle, a high specific capacitance of 169 F/g, an energy density of 19 Wh/kg, and a power density of 600 W/kg were obtained.
The current work shows the preparation of plasticized chitosan-magnesium acetate Mg(CH3COO)2-based polymer electrolyte dispersed with nickel (Ni) metal complexes via solution casting. Investigations of electrical and electrochemical properties of the prepared polymer composite electrolyte were carried out. The structural and optical properties of the samples were studied using X-ray diffraction (XRD) and UV-Vis spectroscopy techniques. The structural and optical outcomes revealed a clear enhancement in both absorbance and amorphous nature of the samples upon the addition of Ni metal complexes. Through the simulation of impedance data, various ion transport parameters were calculated. The electrochemical performance of the sample was examined by means of transference number measurement (TNM), linear sweep voltammetry (LSV) and cyclic voltammetry (CV) measurements. The TNM analysis confirmed the dominance of ions as the main charge carrier in the electrolyte with tion of (0.96) compared to only (0.04) for tel. The present electrolyte was stable in the range of 0 V to 2.4 V, which was obtained from linear sweep voltammetry (LSV). A result from CV proved that the electrical double-layer capacitor (EDLC) has a capacitive behavior as no redox peaks could be observed. The presence of Ni improved the charge-discharge cycle of the EDLC due to its amorphous behavior. The average performances of the EDLC were recorded as 41.7 F/g, 95%, 5.86 Wh/kg and 628 W/kg for specific capacitance, coulombic efficiency, energy and power densities, respectively. The fabricated EDLC device was found to be stable up to 1000 cycles.
In this study, plasticized films of polyvinyl alcohol (PVA): chitosan (CS) based electrolyte impregnated with ammonium thiocyanate (NH4SCN) were successfully prepared using a solution-casting technique. The structural features of the electrolyte films were investigated through the X-ray diffraction (XRD) pattern. The enrichment of the amorphous phase with increasing glycerol concentration was confirmed by observing broad humps. The electrical impedance spectroscopy (EIS) portrays the improvement of ionic conductivity from 10-5 S/cm to 10-3 S/cm upon the addition of plasticizer. The electrolytes incorporated with 28 wt.% and 42 wt.% of glycerol were observed to be mainly ionic conductor as the ionic transference number measurement (TNM) was found to be 0.97 and 0.989, respectively. The linear sweep voltammetry (LSV) investigation indicates that the maximum conducting sample is stable up to 2 V. An electrolyte with the highest conductivity was used to make an energy storage electrical double-layer capacitor (EDLC) device. The cyclic voltammetry (CV) plot depicts no distinguishable peaks in the polarization curve, which means no redox reaction has occurred at the electrode/electrolyte interface. The fabricated EDLC displays the initial specific capacitance, equivalent series resistance, energy density, and power density of 35.5 F/g, 65 Ω, 4.9 Wh/kg, and 399 W/kg, respectively.
In this study, porous cationic hydrogen (H+) conducting polymer blend electrolytes with an amorphous structure were prepared using a casting technique. Poly(vinyl alcohol) (PVA), chitosan (CS), and NH4SCN were used as raw materials. The peak broadening and drop in intensity of the X-ray diffraction (XRD) pattern of the electrolyte systems established the growth of the amorphous phase. The porous structure is associated with the amorphous nature, which was visualized through the field-emission scanning electron microscope (FESEM) images. The enhancement of DC ionic conductivity with increasing salt content was observed up to 40 wt.% of the added salt. The dielectric and electric modulus results were helpful in understanding the ionic conductivity behavior. The transfer number measurement (TNM) technique was used to determine the ion (tion) and electron (telec) transference numbers. The high electrochemical stability up to 2.25 V was recorded using the linear sweep voltammetry (LSV) technique.
In this study, structural characterization, electrical properties and energy storage performance of plasticized polymer electrolytes based on polyvinyl alcohol/methylcellulose/ammonium thiocyanate (PVA/MC-NH4SCN) were carried out. An X-ray diffraction (XRD) study displayed that the plasticized electrolyte system with the uppermost value of direct current (DC) ionic conductivity was the most amorphous system. The electrolyte in the present work realized an ionic conductivity of 2.903 × 10-3 Scm-1 at room temperature. The main charge carrier in the electrolyte was found to be the ions with the ionic transference number (tion) of 0.912, compared to only 0.088 for the electronic transference number (telec). The electrochemical stability potential window of the electrolyte is 2.1 V. The specific capacitance was found to reduce from 102.88 F/g to 28.58 F/g as the scan rate increased in cyclic voltammetry (CV) analysis. The fabricated electrochemical double layer capacitor (EDLC) was stable up to 200 cycles with high efficiency. The specific capacitance obtained for the EDLC by using charge-discharge analysis was 132.7 F/g at the first cycle, which is slightly higher compared to the CV plot. The equivalent series resistance (ESR) increased from 58 to 171 Ω throughout the cycles, which indicates a good electrolyte/electrode contact. Ions in the electrolyte were considered to have almost the same amount of energy during the conduction process as the energy density is approximately at 14.0 Wh/kg throughout the 200 cycles. The power density is stabilized at the range of 1444.3 to 467.6 W/kg as the EDLC completed the cycles.
In this study, solid polymer blend electrolytes (SPBEs) based on chitosan (CS) and methylcellulose (MC) incorporated with different concentrations of ammonium fluoride (NH4F) salt were synthesized using a solution cast technique. Both Fourier transformation infrared spectroscopy (FTIR) and X-ray diffraction (XRD) results confirmed a strong interaction and dispersion of the amorphous region within the CS:MC system in the presence of NH4F. To gain better insights into the electrical properties of the samples, the results of electrochemical impedance spectroscopy (EIS) were analyzed by electrical equivalent circuit (EEC) modeling. The highest conductivity of 2.96 × 10-3 S cm-1 was recorded for the sample incorporated with 40 wt.% of NH4F. Through transference number measurement (TNM) analysis, the fraction of ions was specified. The electrochemical stability of the electrolyte sample was found to be up to 2.3 V via the linear sweep voltammetry (LSV) study. The value of specific capacitance was determined to be around 58.3 F/g. The stability test showed that the electrical double layer capacitor (EDLC) system can be recharged and discharged for up to 100 cycles with an average specific capacitance of 64.1 F/g. The synthesized EDLC cell was found to exhibit high efficiency (90%). In the 1st cycle, the values of internal resistance, energy density and power density of the EDLC cell were determined to be 65 Ω, 9.3 Wh/kg and 1282 W/kg, respectively.
In this study, biopolymer composite electrolytes based on chitosan:ammonium iodide:Zn(II)-complex plasticized with glycerol were successfully prepared using the solution casting technique. Various electrical and electrochemical parameters of the biopolymer composite electrolytes' films were evaluated prior to device application. The highest conducting plasticized membrane was found to have a conductivity of 1.17 × 10-4 S/cm. It is shown that the number density, mobility, and diffusion coefficient of cations and anions fractions are increased with the glycerol amount. Field emission scanning electron microscope and Fourier transform infrared spectroscopy techniques are used to study the morphology and structure of the films. The non-Debye type of relaxation process was confirmed from the peak appearance of the dielectric relaxation study. The obtained transference number of ions (cations and anions) and electrons for the highest conducting sample were identified to be 0.98 and 0.02, respectively. Linear sweep voltammetry shows that the electrochemical stability of the highest conducting plasticized system is 1.37 V. The cyclic voltammetry response displayed no redox reaction peaks over its entire potential range. It was discovered that the addition of Zn(II)-complex and glycerol plasticizer improved the electric double-layer capacitor device performances. Numerous crucial parameters of the electric double-layer capacitor device were obtained from the charge-discharge profile. The prepared electric double-layer capacitor device showed that the initial values of specific capacitance, equivalence series resistance, energy density, and power density are 36 F/g, 177 Ω, 4.1 Wh/kg, and 480 W/kg, respectively.
In the present work it was shown that low lattice energy ammonium salts are not favorable for polymer electrolyte preparation for electrochemical device applications. Polymer blend electrolytes based on chitosan:poly(ethylene oxide) (CS:PEO) incorporated with various amounts of low lattice energy NH4BF4ammonium salt have been prepared using the solution cast technique. Both structural and morphological studies were carried out to understand the phenomenon of ion association. Sharp peaks appeared in X-ray diffraction (XRD) spectra of the samples with high salt concentration. The degree of crystallinity increased from 8.52 to 65.84 as the salt concentration increased up to 40 wt.%. These are correlated to the leakage of the associated anions and cations of the salt to the surface of the polymer. The structural behaviors were further confirmed by morphological study. The morphological results revealed the large-sized protruded salts at high salt concentration. Based on lattice energy of salts, the phenomena of salt leakage were interpreted. Ammonium salts with lattice energy lower than 600 kJ/mol are not preferred for polymer electrolyte preparation due to the significant tendency of ion association among cations and anions. Electrical impedance spectroscopy was used to estimate the conductivity of the samples. It was found that the bulk resistance increased from 1.1 × 104 ohm to 0.7 × 105 ohm when the salt concentration raised from 20 wt.% to 40 wt.%, respectively; due to the association of cations and anions. The low value of direct current (DC) conductivity (7.93 × 10-7 S/cm) addressed the non-suitability of the electrolytes for electrochemical device applications. The calculated values of the capacitance over the interfaces of electrodes-electrolytes (C2) were found to drop from 1.32 × 10-6 F to 3.13 × 10-7 F with increasing salt concentration. The large values of dielectric constant at low frequencies are correlated to the electrode polarization phenomena while their decrements with rising frequency are attributed to the lag of ion polarization in respect of the fast orientation of the applied alternating current (AC) field. The imaginary part of the electric modulus shows obvious peaks known as conduction relaxation peaks.