Transference Number Data Research Articles

Measurement of Transport Number of Lithium in Glycerol Assisted by Fourier Transform Spectroscopy Analysis: Progress towards Elaboration of Optimal Electrolyte of Friendly Environmental Battery

Up to now, a great deal of research investigations on lithium ion conductors has been carried out, because they are potentially utilized in the solid electrolytes of the batteries and the electrochemical devices. However, in order to elaborate new ecological batteries of lithium, it becomes primordial to study and understand the properties of transport of the lithium electrolytes using eco-friendly solvents, with view perhaps to find out the best electrolyte for such devices. In fact, the electromotive forces (EMFs) of lithium chloride electrolyte in the hydrogen-bonded solvents glycerol, were measured using the concentration cells (CCs) 0.005/0.05 and 0.05/0.5. Then the transport numbers of the lithium-ion were deduced by means of the Nernst equation in combination with the Debye-Huckel limiting law. Whilst the activation energy values were calculated from the parameters of the fitting of the transference number data to the empirical power law, yielding a regression coefficient of 95.9% for the most concentrated concentration cell. The structure and interactions in the lithium electrolyte solution were studied by vibrational Infra-Red spectroscopy. The experimental data were discussed and compared to those obtained previously, using impedance spectroscopy of glass-forming glycerolate lithium electrolytes for the same purpose. Despite the enormous difference between their viscosities; glycerol shows similar activation energy (i.e. 31.40 kJ.mol–1) with water (i.e. 31.73 kJ.mol–1), in particular at very low concentration, confirming both solvents being hydrogen-bonded. Besides, this study suggests the utilization of the glycerol-lithium ion electrolyte for future conception of ecological lithium-ion battery, rather than those using ion electrolyte polymer currently on the market. Similarly to relaxation and conductivity, the transport number data suggests that the diffusion of conformational states is also monitoring the overall lithium ion transport mechanism.

DC Conductivity and Transference number in pure and potassium thiocyanate-doped polyvinyl alcohol films

Poly (vinyl alcohol) (PVA) – based solid electrolyte films with potassium thiocyanate (KSCN) were prepared by solution-cast technique. The pure and KSCN- doped PVA films have been investigated for the charge transport mechanism in the polymer electrolyte system by using the DC conductivity (The composition dependence and temperature dependence in 300-385K range) and transference number measurements. The graphs related to conductivity – temperature shows that an increase in conductivity with respect to rise in the temperature. At room temperature, the conductivity of the (PVA+KSCN) electrolyte is 102 times greater than that of pure PVA. The transference number data exhibit that the charge transport in this polymer electrolyte system is predominantly due to ions. The ionic transference numbers (tion) lies in the range of 0.92 to 0.99 for the films of PVA with KSCN in the wt% ratios (90:10), (80:20) and (70:30).

Electrical and solid-state battery performance of a new PVC/PEO + KBr blend-based polymer electrolyte system

Solid polymer blend electrolyte based on polyvinyl chloride (PVC) and polyethylene oxide (PEO) complexed with potassium bromide (KBr) for different weight percent ratios were prepared using solution cast technique. Various experimental techniques such as X-ray diffraction (XRD), AC conductivity, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transference number measurements were employed to characterize these polymer blend electrolyte system. The conductivity analysis shows that the 15 wt% of potassium bromide-doped polymer blend electrolyte exhibits high ionic conductivity, and it has been found to 2.56 × 10−5 S cm−1 at room temperature. The temperature dependence of ionic conductivity and transference number data indicated the dominance of ion-type charge transport in these specimens. The electrochemical cells have been fabricated using PVC + PEO + KBr electrolyte for which the open-circuit voltage and short-circuit current are 3.2 V and 1380 μA, respectively.

Magnesium ion conducting solid polymer blend electrolyte based on biodegradable polymers and application in solid-state batteries

Magnesium ion conducting solid polymer blend electrolyte based on biodegradable polymers polyvinyl alcohol (PVA) and polyvinyl pyrrolidone (PVP) mixed with different molecular weight percentages (wt.%) of magnesium nitrate (Mg(NO3)2) was prepared by using solution casting technique. X-ray diffraction studies lead the reduction of crystalline nature by the addition of magnesium nitrate to the polymeric matrix. The complex formation between polymer and salt confirmed by Fourier transform infrared spectroscopy studies. Differential scanning calorimetry shows that the glass transition temperature decreases with increase in magnesium salt concentration and the thermal stability of PVA–PVP–Mg(NO3)2 complexes. The maximum ionic conductivity σ ~ 3.78 × 10−5 S cm−1 was obtained for 50PVA–50PVP–30 wt.% of Mg(NO3)2 polymer blend electrolyte at room temperature (303 K). The conductivity–temperature plot is found to follow the Arrhenius behavior, which showed the decrease in activation energy with the increasing salt concentration. The transference number data indicated the dominance of ion-type charge transport in these polymer blend electrolytes. The solid-state electrochemical cells were fabricated, and their discharge profiles were studied for this polymer blend electrolyte system under a constant load of 100 kΩ.

Preparation and characterization of PEG–Mg(CH3COO)2–CeO2 composite polymer electrolytes for battery application

Composite polymer electrolytes based on poly(ethylene glycol) (PEG), magnesium acetate [Mg(CH3COO)2], and x wt% of cerium oxide (CeO2) ceramic fillers (where x = 0, 5, 10, 15 and 20, respectively) have been prepared using solution casting technique. X-ray diffraction patterns of PEG–Mg(CH3COO)2 with CeO 2 ceramic filler indicated the decrease in the degree of crystallinity with increasing concentration of the filler. DSC measurements of PEG–Mg(CH3COO)2–CeO2 composite polymer electrolyte system showed that the melting temperature is shifted towards the lower temperature with increase of the filler concentration. The conductivity results indicate that the incorporation of ceramic filler up to a certain concentration (i.e. 15 wt%) increases the ionic conductivity and upon further addition the conductivity decreases. The transference number data indicated the dominance of ion-type charge transport in these specimens. Using this (PEG–Mg(CH3COO)2–CeO2) (85-15-15) electrolyte, solid-state electrochemical cell was fabricated and their discharge profiles were studied under a constant load of 100 kΩ.

Effect Of Al2O3 ceramic Filler On PEG-based Composite Polymer electrolytes For Magnesium Batteries

Composite polymer electrolyte films consisting of polyethylene glycol (PEG), Mg(CH3COO)2 and Al2O3 particles have been prepared by solution casting technique. The X-ray diffraction patterns of PEG-Mg(CH3COO)2 with Al2O3 ceramic filler, indicates the decrease in the degree of crystallinity with increasing concentration of the filler. The role of ceramic phase is to reduce the melting temperature which is ascertained from the DSC. The effect of ceramic filler on the conductivity of the polymer electrolyte was studied. The maximum ionic conductivity has been observed for 10 wt% of Al2O3 at room temperature (303 K). The transference number data indicated the dominance of ion-type charge transport in these composite polymer electrolytes. Using this (PEG-Mg(CH3COO)2-Al2O3) (85–15–10) electrolyte, solid-state electrochemical cell was fabricated and their discharge profiles were studied under a constant load of 100 kΩ. Several cell profiles associated with this cell were evaluated and are reported.

Ionic Conductivity and Discharge Characteristic Studies of PVA-Mg(CH3COO)2 Solid Polymer Electrolytes

Ion conducting solid polymer electrolytes based on a polymer polyvinyl alcohol (PVA) complexed with magnesium acetate (Mg(CH3COO)2) were prepared by solution cast technique. Various experimental techniques, such as XRD, DSC, composition-dependent conductivity, temperature-dependent conductivity, and transport number measurements are used to characterize these polymer electrolyte films. The transference number data indicated the dominance of ion-type charge transport in these polymer electrolyte systems. An electrochemical cell with the configuration Mg/(80PVA + 20Mg(CH3COO)2)/(I2 + C + electrolyte) has been fabricated and its discharge characteristics were studied. The Open Circuit Voltage (OCV) is 1.84 V.

Effect of propylene carbonate as a plasticizer on (PEO)50AgCF3SO3:SnO2 nanocomposite polymer electrolyte

This work deals with the incorporation of propylene carbonate (PC) as a plasticizer in conjunction with poly (ethylene oxide) (PEO), silver triflate (AgCF3SO3) and nanocrystalline tin oxide (SnO2) for obtaining the nanocomposite polymer electrolyte system (PEO)50AgCF3SO3:2 wt% SnO2 + x wt% PC (x = 10, 20, 30 and 40) by solution casting method. The present electrical conductivity data extracted by means of complex impedance spectroscopic analysis in the frequency range 20 Hz–1 MHz and over the temperature domain 298–373 K have demonstrated that the maximum electrical conductivity value of 5.9 × 10−5 S cm−1 at 298 K would be possessed by the specimen containing 30 wt% PC incorporated into the optimized nanocomposite system (PEO)50AgCF3SO3:2 wt% SnO2. Silver ionic transference number (tAg+) data evaluated using AC/DC polarization technique have indicated that the highest tAg+ value of 0.52 could be realized in the case of the specimen (PEO)50AgCF3SO3:2 wt% SnO2 + 30 wt% PC, whereas the complexation of the plasticizer within the nanocomposite electrolyte has been deduced from the detailed Fourier transform infrared spectroscopic investigation owing to the fact that such results have revealed the appearance of absorption bands corresponding to free triflate ions (CF3SO3−) and PC. Surface morphological features of pure PEO and (PEO)50AgCF3SO3:2 wt% SnO2 + 30 wt% PC nanocomposite systems were analysed through scanning electron microscope. The feasibility of a reduction in the degree of crystallinity of the plasticized system has been indicated by the X-ray diffraction data and confirmed from differential scanning calorimetric results obtained in terms of quantification of crystallinity and reduction in the glass transition temperature due to the addition of the chosen plasticizer into the nanocomposite polymer electrolyte matrix. Interestingly, the all solid-state cell based on the nanocomposite polymer electrolyte, namely, (PEO)50AgCF3SO3:2 wt% SnO2 + 30 wt% PC and silver anode has exhibited an open circuit voltage of 676 mV and short circuit current of 192 μA at room temperature.

Characterization of poly(vinyl alcohol)/potassium chloride polymer electrolytes for electrochemical cell applications

AbstractA solid polymer electrolyte system based on poly(vinyl alcohol) (PVA) complexed with potassium chloride (KCl) salt was prepared by using solution cast technique. The complexation of KCl salt with the polymer was confirmed by X‐ray diffractrometer and Fourier transform infrared spectroscopy. Differential scanning calorimetry was used to determine the melting temperatures and crystallinity of the pure PVA and complexed films. Ionic conductivities of the electrolytes have been determined by AC impedance studies in the temperature range 303–373 K. The conductivity was found to increase with the increase in dopant concentration and temperature. Transference number data suggests that the charge transport in this polymer electrolyte system is mainly due to ions. Optical absorption studies were made in the wavelength range 200–800 nm on pure and KCl doped PVA films. The absorption edge, direct band, and indirect band gap values were evaluated. It was found that the energy gaps and band edge values shifted to lower energies on doping. Electrochemical cells were fabricated with the configuration of K/(PVA + KCl)/(I2 + C + electrolyte) and discharge characteristics were studied under a constant load of 100 kΩ. Various cell parameters, such as open circuit voltage, short circuit current, power density, and energy density were determined. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers

Electrical and optical properties of (PEMA/PVC) polymer blend electrolyte doped with NaClO4

Sodium ion conducting polymer blend electrolytes based on poly (vinyl chloride)/poly (ethyl methacralyte) complexed with NaClO4 were prepared using a solution casting technique. The features of complexation of the electrolytes were studied by X-ray diffraction (XRD). DC conductivity of the films was measured in the temperature range 303–398K. The electrical conductivity increased with increasing dopant concentration, which is attributed to the formation of charge transfer complexes. The polymer complexes exhibited Arrhenius type dependence of conductivity with temperature. In the temperature range studied, two regions with different activation energies were observed. Transference number data showed that the charge transport in this system is predominantly due to ions. Electrochemical cells of configuration Na/(PEMA+PVC+NaClO4)/(I2+C+electrolyte) were fabricated and the discharge characteristics of these cells were studied under a constant load of 100KΩ. Several cell parameters associated with the cells were evaluated and compared with earlier reports. Optical properties such as absorption edge, direct band gap and indirect band gap were estimated for pure and doped films from their optical absorption spectra in the wavelength region 200–600nm. It was found that the energy gap and band edge values shifted to lower energies on doping with NaClO4 salt.

Charge transport and discharge mechanism in (PVC+KClO 3) polymer electrolyte films

This paper presents results of the studies on ionic conductivity and transference number measurements on potassium chlorate (KClO 3) complexed polyvinyl chloride (PVC) films prepared by solution-cast technique. Temperature dependence of ionic conductivity and transference number data indicated the dominance of ion-type charge transport in these specimens. The magnitude of conductivity increased with increase in the concentration of the salt and temperature. Using this (PVC+KClO 3) electrolyte, solid-state electrochemical cells were fabricated and their discharge profiles were studied under a constant load of 100 kΩ. Several cell profiles associated with these cells were evaluated and are reported.

Preparation and electrical characterization of (PVC + KBrO3) polymer electrolytes for solid state battery applications

This paper presents results of studies on dc electrical conductivity and transference number measurements on potassium bromate (KBrO3) complexed polyvinyl chloride (PVC) films prepared by solution cast technique. Temperature dependence of dc electrical conductivity and transference number data indicated the dominance of ion type charge transport in these specimens. The magnitude of conductivity increased with increase in concentration of the salt and temperature. Using this (PVC + KBrO3) electrolyte, solid-state electrochemical cells were fabricated, and their discharge profiles were studied under a constant load of 100 kΩ. Several cell profiles such as open circuit voltage, short circuit current, power density, and energy density associated with these cells were evaluated and were reported. The features of complexation of the electrolytes were studied by X-ray diffraction and Fourier transform infrared spectroscopy.

Structural and electrical properties of pure and NaBr doped poly (vinyl alcohol) (PVA) polymer electrolyte films for solid state battery applications

A sodium ion conducting polymer electrolyte based on poly (vinyl alcohol) (PVA) complexed with sodium bromide (NaBr) was prepared using solution cast technique. Several experimental techniques such as XRD, FTIR, SEM, temperature-dependant conductivity and transference number measurements have been performed. XRD and FTIR studies confirm the complexation of salt with the polymer. Surface morphology was studied using Scanning Electron Microscopy. DC conductivity was measured in the temperature range of 303–373 K, and the conductivity was found to increase with the increase of dopant concentration as well as temperature. Transference number data suggests that the charge transport in this polymer electrolyte system is mainly due to ions. Using these polymer electrolyte films, electrochemical cells were fabricated with configuration Na/(PVA:NaBr)/V2O5 and Na/(PVA:NaBr)/(I2+C+electrolyte) and their discharge characteristics like open circuit voltage (OCV), short circuit current (SCC), power density, energy density were evaluated and compared.

Electrical, optical, and structural characterization of polymer blend (PVC/PMMA) electrolyte films

Ion-conducting solid polymer blend electrolytes based on polyvinyl chloride (PVC)/poly methyl methacrylate (PMMA) complexed with sodium perchlorate (NaClO4) were prepared in various concentrations by solution cast technique. The features of complexation of the electrolytes were studied by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. DC conductivity of the films was measured in the temperature range 303–398 K. Transference number measurements were carried out to investigate the nature of charge transport in the polymer blend electrolyte system. The electrical conductivity increased with increasing dopant concentration, which is attributed to the formation of charge transfer complexes. The polymer complexes exhibited Arrhenius type dependence of conductivity with temperature. In the temperature range studied, two regions with different activation energies were observed. Transference number data showed that the charge transport in this system is predominantly due to ions. Optical properties like absorption edge, direct band gap, and indirect band gap were estimated for pure and doped films from their optical absorption spectra in the wavelength region 200–600 nm. It was found that the energy gap and band edge values shifted to lower energies on doping with NaClO4 salt.

Ion transport and battery discharge characteristics of polymer electrolyte based on PEO complexed with NaFeF4 salt

Ion-conducting solvent-free solid polymer electrolytes based on polyethylene oxide (PEO) complexed with sodium ferric tetrafluoride (NaFeF4) were prepared using a solution casting technique. The complexation of the films was investigated through X-ray diffraction and Fourier transform infrared spectroscopic studies. Measurements of DC conductivity in the temperature range 300–370 K and the transference numbers were carried out to investigate the nature of charge transport in the polymer electrolyte system. Transference number data shows that the charge transport in this system is found to be predominantly due to ions. Using these polymer electrolytes, electrochemical cells were fabricated with the configuration of Na/(PEO+NaFeF4)/(I2+C+electrolyte). Various cell parameters, such as open circuit voltage, short circuit current, power density, and energy density of the device were evaluated and reported.

Preparation and characterization of (PVP + NaClO4) electrolytes for battery applications

A sodium ion-conducting polymer electrolyte based on polyvinyl pyrrolidone (PVP) complexed with NaClO(4) was prepared using the solution-cast technique. The cathode film of V(2)O(5) xerogel modified with polyvinyl pyrrolidone was prepared using the sol-gel method. Investigations were conducted using X-ray diffractometry (XRD), Fourier transformation infrared (FT-IR) spectroscopy. The ionic conductivity and transference number measurements were performed to characterize the polymer electrolyte for battery applications. The transference number data indicated that the conducting species in these electrolytes are the anions. Using the electrolyte, electrochemical cells with a configuration Na/(PVP + NaClO(4))/V(2)O(5) modified by (PVP) were fabricated and their discharge profiles studied.

Ion-conducting polymer electrolyte based on poly(ethylene oxide) complexed with Li 1.3Al 0.3Ti 1.7(PO 4) 3 salt

Solid polymer electrolyte films were prepared from poly(ethylene oxide) (PEO) and fine Li 1.3Al 0.3Ti 1.7(PO 4) 3 salt in appropriate ratios of EO/Li ratios (=8–50) by a solution-cast technique. The complexation of Li 1.3Al 0.3Ti 1.7(PO 4) 3 salt with PEO was directly detected by infrared (IR) spectroscopy. A cellular structure formed by the PEO crystallites covered by the amorphous complexed layer was observed under SEM. Differential scanning calorimetry (DSC) showed that in the polymer electrolyte, the PEO crystallization temperature decreased from 63.67 to 52.64 °C with the addition of increasing Li 1.3Al 0.3Ti 1.7(PO 4) 3. The room temperature impedance spectra of the polymer films all exhibited a shape of depressed semicircle in high frequency range and an inclined line in low frequency range, but the high temperature ones were mainly the inclined lines. Measurements of ionic conductivity in the temperature range 298–383K showed that, with EO/Li = 16, the conductivity of the film is ∼10 −6 S cm −1 at room temperature and ∼10 −4 S cm −1 at above 343 K. By the combining EIS measurement of fabricated solid-state electrochemical cells, the transference number data shows that the polymer films was a mixed (ionic + electronic) conductor, and that the charge transport in the polymer electrolyte system was predominantly due to ions.

Development of a new polymer electrolyte (PMMA-CO-P4VPNO+KClO3) for solid state electrochemical cells

Polymer electrolyte films based on a co-polymer polymethyle methacrylate-co-poly 4vinyl pyridine N-oxide (PMMA-CO-P4VPNO) complexed with KClO3 were prepared by solution cast technique. The complexation of KClO3 salt with the polymer was confirmed by infrared studies. Measurements of the dc conductivity in the temperature range 300–410 K and transference numbers were carried out to investigate the charge transport in the polymer electrolyte system. Transference number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. Using the polymer electrolyte solid state electrochemical cells were fabricated with the configuration (K)-(PMMA-CO-P4VPNO+KClO3)-(I2+C+electrolyte) and various parameters of the cells including open circuit voltage (OCV) and short circuit current (SCC) were evaluated.

Behaviour of Some Copper(I) and Cobalt(III) Complexes in Acetonitrile and n-Butyronitrile at 298.15K

Abstract Molar conductances of a large number of copper(I) and cobalt(III) complexes, behaving as strong 1:1 electrolytes, have been measured in acetonitrile (AN) and n-butyronitrile (n-BTN) at 298.15K. The conductance data have been analyzed by the Shedlovsky method to evaluate Λ0 and K A values of these electrolytes. Limiting ion conductances (λ i 0) for various ions in AN have been calculated by using transference number data. In n-BTN, where no transference number data is available, such values have been calculated by an indirect method using Bu4NBPh4 as a reference electrolyte. The actual ionic radii (ri ) for various ions in solution have been calculated using a modified form of Stokes’ law. The ionic radii (ri ) for various complex ions have been compared with the ionic radii of two reference ions, Bu4N+ and Ph4B−, which are not solvated in dipolar aprotic solvents, to throw light on the solvation behaviour of these complex ions.

Conductivity and parametric studies of a (PEO+(glass)(15Na2O–15NaF–70B2O3)) cell

Ion conducting polymer electrolyte films based on poly(ethylene oxide) (PEO) complexed with a glass (15Na 2 O–15NaF–70B 2 O 3 ) are prepared by a solution—cast technique. The complexation of the glass with PEO is confirmed by X-ray diffraction analysis. DC conductivity in the temperature range 303–373 K and transference number measurements are performed in order to investigate the charge transport in the polymer electrolyte system. The conductivity of the (PEO+glass) electrolyte is about 10 4 times larger than that of pure PEO at room temperature. The transference number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. Using these polymer electrolytes, solid-state electrochemical cells are fabricated. Various parameters associated with these cells are evaluated and compared with those of other reported cells.