In this work, we introduce a method based on impedance spectroscopy and the equations developed to evaluate, with a good degree of accuracy, the number density, mobility and diffusion coefficient of mobile ions. Nyquist plots of electrolytes based on poly(acrylonitrile) or PAN and methyl cellulose (MC) incorporated with lithium bis(oxalato)borate have been established from impedance measurements. Equivalent circuits based on a resistor and "leaky capacitor(s)" have been determined and the relevant impedance equations derived. The values of the parameters required in the equation are obtained from the Nyquist plots and the parameters that cannot be obtained from the respective plots have been obtained by trial and error in order to fit the Nyquist plots. The transport parameters are calculated using the developed equations and the results have been compared with those obtained from the broadband dielectric response (BDR) method. Finally, Fourier transform infrared (FTIR) spectroscopy has been used to verify the results obtained from the two approaches at room and elevated temperatures.
A poly(vinyledene difluoride)-lithium bis(oxalato)borate solid polymer electrolyte prepared by a solvent casting method has been irradiated with different doses of gamma-rays. Differential scanning calorimetry reveals that the polymer electrolyte irradiated with 35 kGy of γ-rays is the most amorphous sample. This is also supported by the results obtained from X-ray diffraction. The Fourier transform infrared spectrum of each irradiated sample has been deconvoluted in the wavenumber region between 1830 and 1758 cm(-1) in order to predict the percentage of free and contact ions in the samples. The sample exposed to 35 kGy of γ-rays contains the highest percentage of free ions and the lowest amount of contact ions. This sample also exhibits the highest room temperature conductivity of 3.05 × 10(-4) S cm(-1), which is 15% higher relative to the virgin sample. The number density of free ions is observed to have more control on the conductivity variation with the γ-radiation dose compared to ionic mobility. This study confirms that γ-irradiation can be a potential way to obtain highly conductive and mechanically stable polymer electrolytes.
Gel polymer electrolytes (GPEs) with polyacrylonitrile (PAN)-based polymer, ethylene carbonate (EC) and propylene carbonate (PC) plasticizers, and different amounts of tetrabutylammonium iodide (TBAI) salt and iodine (I2) have been prepared and used in dyesensitized solar cells (DSSCs). The maximum room temperature conductivity of 5.14 mS cm−1 is obtained for electrolyte with a composition of 8 wt% PAN-30 wt% EC-30 wt% PC-30 wt% TBAI-2 wt% I2 (S3 electrolyte) which influenced by the highest charge carrier density of 7.93 × 1020 cm−3 estimated from fitting the impedance Nyquist plot. The DSSC fabricated with S3 electrolyte revealed the highest power conversion efficiency of 3.45% with open-circuit voltage (Voc) of 582 mV and short-circuit current density (Jsc) of 12.9 mA cm−2. The incident photon-to-current conversion efficiency of the DSSC with highest efficiency is 54.01%. The electrical impedance spectroscopy of the same cell shows the lowest series resistance indicating the superiority of electrolyte charge transport characteristics in DSSC. In addition, electron transfer time constant and electron recombination time , charge collection efficiency , electron diffusion coefficient and diffusion length of DSSC fabricated with GPEs prepared have been estimated by intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy techniques. The DSSC with highest efficiency shows lowest of 34.46 ms and highest of 90.41 ms due to the huge amount of TBA+ ions that covered the surface area of mesoporous TiO2. The of 0.62, D of 4.00 × 10−5 cm2 s−1 and of 19.02 μm further support the photovoltaic efficiency of DSSC.
In this paper, we report the effect of doping sodium iodide (NaI) salt into a polymer blend matrix of sodium carboxymethyl cellulose (NaCMC) and poly(vinyl alcohol) (PVA). Solution casting approach was used to prepare solid polymer electrolyte (SPE) films. The films were characterized by Fourier-transform infrared spectroscopy (FTIR), X-Ray diffraction (XRD), electrical impedance spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). XRD showed that NaI incorporation decreased the crystallinity of NaCMC/PVA-based SPE. FTIR technique confirmed the complexation of salt with polymer matrix due to the formation of the coordination bond between Na+ and –OH group and hydrogen bond between I− and –CH group. The sample with 30 wt% NaI showed the highest conductivity of 2.52 × 10–3 S cm−1, strongly influenced by the highest charge concentration $$(n)$$
(
n
)
, not its mobility (μ). DSC analysis revealed an increase in glass transition temperature $$({T}_{g})$$
(
T
g
)
with increasing salt content. TGA studies showed a decrease in thermal stability with salt inclusion. The transference number was found to be 0.99 for the highest conducting sample showing the primary charge carriers are ions. The highest conducting sample exhibited a mechanical strength of 15.42 MPa at room temperature, and it has been used to fabricate a battery to evaluate its suitability in energy storage devices.
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