Electrocatalytic and structural properties and computational calculation of PAN-EC-PC-TPAI-I2 gel polymer electrolytes for dye sensitized solar cell application.

In this study, gel polymer electrolytes (GPEs) were prepared using polyacrylonitrile (PAN) polymer, ethylene carbonate (EC), propylene carbonate (PC) plasticizers and different compositions of tetrapropylammonium iodide (TPAI) salt. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) measurements were done using non-blocking Pt-electrode symmetric cells. The limiting current (J lim), apparent diffusion coefficient of triiodide ions and exchange current were found to be 12.76 mA cm-2, 23.41 × 10-7 cm2 s-1 and 11.22-14.24 mA cm-2, respectively, for the GPE containing 30% TPAI. These values are the highest among the GPEs with different TPAI contents. To determine the ionic conductivity, the EIS technique was employed with blocking electrodes. The GPE containing 30% TPAI exhibited the lowest bulk impedance, R b (22 Ω), highest ionic conductivity (3.62 × 10-3 S cm-1) and lowest activation energy. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) techniques were utilized for structural characterization. Functional group interactions among PAN, EC, PC and TPAI were studied in the FTIR spectra of the GPEs. An up-shift of the XRD peak indicates the polymer-salt interaction and possible complexation of the cation (TPA+ ion) with the lone pair of electrons containing site -C[triple bond, length as m-dash]N at the N atom in the host polymer matrix. On the other hand, computational study shows that TPAI-PAN based GPE possesses the lowest frontier orbital bandgap, which coincided with the enhanced electrochemical and electrocatalytic performance of GPE. The dye-sensitized solar cell (DSSC) fabricated with these GPEs showed that the J SC (19.75 mA cm-2) and V OC (553.8 mV) were the highest among the GPEs and hence the highest efficiency, η (4.76%), was obtained for the same electrolytes.

Jahn-Teller effect in LiMn2O4: influence on charge ordering, magnetoresistance and battery performance.

The phase transition near room temperature in LiMn2O4 was studied using thermal expansion measurements, and directly compared with the electrochemical performance of the material. Studies based on thermal expansion indicate the onset of a first-order phase transition at Tc ∼ 220 K for the nearly half-doped material, with [Mn3+]/[Mn4+] ≈ 1. The Tc shifts to a higher temperature, ∼290 K, and signatures for Verwey-type charge ordering at 290 K can be observed when the fraction of Jahn-Teller Mn3+ in LiMn2O4 is increased, i.e., [Mn3+]/[Mn4+] > 1. These studies show that the first-order phase transition near room temperature in LiMn2O4 is associated with charge ordering, which ultimately is a consequence of the Jahn-Teller effect. In addition, the Jahn-Teller effect is proven to be an important cause of magnetoresistance and electrochemical capacity fading in LiMn2O4. Electrochemical measurements show that both materials, either with a Tc ∼ 220 K or Tc ∼ 290 K, exhibit capacity fading to almost the same extent. Electrochemical capacity retention is observed only in nanosized LiMn2O4, for which the phase transition anomalies are completely absent.

Improvement of N-phthaloylchitosan based gel polymer electrolyte in dye-sensitized solar cells using a binary salt system.

A binary salt system utilizing lithium iodide (LiI) as the auxiliary component has been introduced to the N-phthaloylchitosan (PhCh) based gel polymer electrolyte consisting of ethylene carbonate (EC), dimethylformamide (DMF), tetrapropylammonium iodide (TPAI), and iodine (I2) in order to improve the performance of dye-sensitized solar cell (DSSC) with efficiency of 6.36%, photocurrent density, JSC of 17.29mAcm-2, open circuit voltage, VOC of 0.59V and fill factor, FF of 0.62. This efficiency value is an improvement from the 5.00% performance obtained by the DSSC consisting of only TPAI single salt system. The presence of the LiI in addition to the TPAI improves the charge injection rates and increases the iodide contribution to the total conductivity and both factors contribute to the increase in efficiency of the DSSC. The interaction behavior between polymer-plasticizer-salt was thoroughly investigated using EIS, FTIR spectroscopy and XRD.

Vibrational studies of flexible solid polymer electrolyte based on PCL-EC incorporated with proton conducting NH4SCN.

A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50 wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94 × 10(-7) Scm(-1) to 3.82 × 10(-5) Scm(-1). Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN(-) stretching mode (2030-2090 cm(-1)). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4(+) complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.

Prediction of conductivity by adaptive neuro-fuzzy model.

Electrochemical impedance spectroscopy (EIS) is a key method for the characterizing the ionic and electronic conductivity of materials. One of the requirements of this technique is a model to forecast conductivity in preliminary experiments. The aim of this paper is to examine the prediction of conductivity by neuro-fuzzy inference with basic experimental factors such as temperature, frequency, thickness of the film and weight percentage of salt. In order to provide the optimal sets of fuzzy logic rule bases, the grid partition fuzzy inference method was applied. The validation of the model was tested by four random data sets. To evaluate the validity of the model, eleven statistical features were examined. Statistical analysis of the results clearly shows that modeling with an adaptive neuro-fuzzy is powerful enough for the prediction of conductivity.

On the theory of high rate capability of LiMn2O4 with some preferred orientations: insights from the crystal shape algorithm.

The predominant orientation of LiMn2O4 synthesized through the different methods is attributed, using the crystal shape algorithm (a new tool advanced to study the crystal shapes of crystalline materials), to the (331) plane. Existing literature evidence however shows that the (400) plane is the thermodynamically most stable hkl direction of LiMn2O4. Observations from the crystal shape algorithm and literature evidence of the thermodynamic stabilities of the hkl planes of LiMn2O4 point to the operation of a kinetically controlled mechanism governing the LiMn2O4 synthesis reactions currently available in the literature. This finding can have important consequences on the electrochemical characteristics of the material such as its rate capability.

A method based on impedance spectroscopy to determine transport properties of polymer electrolytes.

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.

FTIR studies of plasticized poly(vinyl alcohol)-chitosan blend doped with NH4NO3 polymer electrolyte membrane.

Fourier transform infrared (FTIR) spectroscopy studies of poly(vinyl alcohol) (PVA), and chitosan polymer blend doped with ammonium nitrate (NH(4)NO(3)) salt and plasticized with ethylene carbonate (EC) have been performed with emphasis on the shift of the carboxamide, amine and hydroxyl bands. 1% acetic acid solution was used as the solvent. It is observed from the chitosan film spectrum that evidence of polymer-solvent interaction can be observed from the shifting of the carboxamide band at 1660 cm(-1) and the amine band at 1591 cm(-1) to 1650 and 1557 cm(-1) respectively and the shift of the hydroxyl band from 3377 to 3354 cm(-1). The hydroxyl band in the spectrum of PVA powder is observed at 3354 cm(-1) and is observed at 3343 cm(-1) in the spectrum of the PVA film. On addition of NH(4)NO(3) up to 30 wt.%, the carboxamide, amine and hydroxyl bands shifted from 1650, 1557 and 3354 cm(-1) to 1642, 1541 and 3348 cm(-1) indicating that the chitosan has complexed with the salt. In the PVA-NH(4)NO(3) spectrum, the hydroxyl band has shifted from 3343 to 3272 cm(-1) on addition of salt from 10 to 30 wt.%. EC acts as a plasticizing agent since there is no shift in the bands as observed in the spectrum of PVA-chitosan-EC films. The mechanism of ion migration is proposed for the plasticized and unplasticized PVA-chitosan-NH(4)NO(3) systems. In the spectrum of PVA-chitosan-NH(4)NO(3)-EC complex, the doublet CO stretching in EC is observed in the vicinity 1800 and 1700. This indicates that there is some interaction between the salt and EC.

FTIR studies of PVC/PMMA blend based polymer electrolytes.

The polymer electrolytes composing of the blend of polyvinyl chloride-polymethyl methacrylate (PVC/PMMA) with lithium triflate (LiCF3SO3) as salt, ethylene carbonate (EC) and dibutyl phthalate (DBP) as plasticizers and silica (SiO2) as the composite filler were prepared. FTIR studies confirm the complexation between PVC/PMMA blends. The CCl stretching mode at 834 cm-1 for pure PVC is shifted to 847 cm-1 in PVC-PMMA-LiCF3SO3 system. This suggests that there is interaction between Cl in PVC with Li+ ion from LiCF3SO3. The band due to OCH3 at 1150 cm-1 for PVC-PMMA blend is shifted to 1168 cm-1 in PVC-PMMA-LiCF3SO3 system. This shift is expected to be due to the interaction between Li+ ion and the oxygen atom in PMMA. The symmetric vibration band and the asymmetric vibration band of LiCF3SO3 at 1033 and 1256 cm-1 shifted to 1075 and 1286 cm-1 in the DBP-EC plasticized PVC-PMMA-LiCF3SO3 complexes. The interaction between Li+ ions and SiO2 will lead to an increase in the number of free plasticizers (which does not interact with Li+ ions). When the silica content increases from 2% to 5%, the intensity of the peak at 896 cm-1 (due to the ring breathing vibration of free EC) increases in PVC-PMMA-LiCF3SO3-DBP-EC system.

FT-IR studies on interactions among components in hexanoyl chitosan-based polymer electrolytes.

Fourier transform infrared (FT-IR) spectroscopic studies have been undertaken to investigate the interactions among components in a system of hexanoyl chitosan-lithium trifluoromethanesulfonate (LiCF(3)SO(3))-diethyl carbonate (DEC)/ethylene carbonate (EC). LiCF(3)SO(3) interacts with the hexanoyl chitosan to form a hexanoyl chitosan-salt complex that results in the shifting of the N(COR)(2), CONHR and OCOR bands to lower wavenumbers. Interactions between EC and DEC with LiCF(3)SO(3) has been noted and discussed. Evidence of interaction between EC and DEC has been obtained experimentally. Studies on polymer-plasticizer spectra suggested that there is no interaction between the polymer host and plasticizers. Competition between plasticizer and polymer on associating with Li(+) ions was observed from the spectral data for gel polymer electrolytes. The obtained spectroscopic data has been correlated with the conductivity performance of hexanoyl chitosan-based polymer electrolytes.