Lithium ion conducting solid polymer blend electrolyte based on bio-degradable polymers

Lithium ion conducting polymer blend electrolyte films based on poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) with different Mwt% of lithium nitrate (LiNO₃) salt, using a solution cast technique, have been prepared. The polymer blend electrolyte has been characterized by XRD, FTIR, DSC and impedance analyses. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR study confirms the complex formation between the polymer and salt. The shifts in T _g values of 70 PVA–30 PVP blend and 70 PVA–30 PVP with different Mwt% of LiNO₃ electrolytes shown by DSC thermograms indicate an interaction between the polymer and the salt. The dependence of T _g and conductivity upon salt concentration has been discussed. The ion conductivity of the prepared polymer electrolyte has been found by a.c. impedance spectroscopic analysis. The PVA–PVP blend system with a composition of 70 wt% PVA: 30 wt% PVP exhibits the highest conductivity of 1·58 × 10^???6 Scm^???1 at room temperature. Polymer samples of 70 wt% PVA–30 wt% PVP blend with different molecular weight percentage of lithium nitrate with DMSO as solvent have been prepared and studied. High conductivity of 6·828 × 10^???4 Scm^???1 has been observed for the composition of 70 PVA:30 PVP:25 Mwt% of LiNO₃ with low activation energy 0·2673 eV. The conductivity is found to increase with increase in temperature. The temperature dependent conductivity of the polymer electrolyte follows the Arrhenius relationship which shows hopping of ions in the polymer matrix. The relaxation parameters (ω) and (τ) of the complexes have been calculated by using loss tangent spectra. The mechanical properties of polymer blend electrolyte such as tensile strength, elongation and degree of swelling have been measured and the results are presented.     

Anodic behaviour and passivation of a lead electrode in sodium carbonate solutions

Cyclic voltammograms of a lead electrode were obtained in Na₂CO₃ solution as a function of the starting potential, electrolyte concentration and voltage scanning rate. The shape of the voltammograms was found to depend on the starting potential as well as the sweep number. This is probably due to changes in the activation state of the electrode surface. The first anodic portion of the voltammograms is characterized by a shoulder and two peaks corresponding to the formation of PbCO₃, PbO and PbO₂, respectively. The cathodic portion shows the occurrence of two peaks corresponding to the reduction of PbO₂ to PbO and PbO to Pb, successively, followed by the formation of PbH₂. An increase in concentration of CO ₃ ^2– ions leads to a negative shift in the values of the peak potentials, E_p, accompanying the formation of PbO and PbO₂. In addition, the current density for both the anodic oxidation peaks showed marked dependence on the concentration of the electrolyte. An increase in the scanning rate was observed to lead an increase in the size of the voltammograms. The current density of both the anodic peaks and the anodic passivation region were proportional to v^1/2. Such behaviour is expected in a diffusion-controlled processes. In addition, the anodic peaks are shifted towards more positive values of potential, whereas the cathodic peaks are shifted in the negative direction, indicating irreversible formation of the passive film on the electrode surface.     

Hydrothermal synthesis of lead dioxide/multiwall carbon nanotube nanocomposite and its application in removal of some organic water pollutants

Lead dioxide/multiwall carbon nanotube (PbO₂/MWCNT) nanocomposite was synthesized by hydrothermal formation of lead dioxide on functionalized MWCNT. PbO₂ nanoparticles were formed from 0.015 M Pb(OH) ₃ ^? (75 ml) solution in the presence of polyvinyl pyrrolidone (0.1 g). The solution was mixed with ammonium persulfate (NH₄)₂S₂O₈ as oxidizing agent and transferred to 100 ml Teflon-lined stainless steel autoclave heating it to 60 °C for 3 h. To prepare nanocomposite, PbO₂ formation was carried out in the presence of ultrasonically dispersed MWCNT. A black-brown product was formed in reaction vessel. The product was collected and then dried in an oven at 70 °C for 24 h. The morphology and composition of precipitate were investigated by X-ray power diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and transmission electron microscopy (TEM). The results of XRD and TEM show globular α-PbO₂ nanoparticles immobilize on the surface of the MWCNTs. Also, TGA results demonstrated the presence of CNT in nanocomposite. The prepared PbO₂/MWCNT nanocomposite is used to construct the solid-phase cartridge. The performance of solid phase in the removal of pesticides from drinking water is determined by gas chromatography–mass spectroscopy (GC–MS) analysis. The average adsorption depends on concentration of spiked pollutants and their relative standard deviations were between 1.4 and 11 %.     

Electrodeposition of dicalcium phosphate dihydrate coatings on stainless steel substrates

Cathodic reduction of an aqueous solution containing dissolved calcium and phosphate ions results in the deposition of micrometer thick CaHPO₄·2H₂O (dicalcium phosphate dihydrate) coatings on stainless steel substrates. The coating obtained at a low deposition current (8 mA cm^???2) comprises lath-like crystallites oriented along 020. The 020 crystal planes are non-polar and have a low surface energy. At a high deposition current (12 mA cm^???2), platelets oriented along 121? are deposited. CaHPO₄·2H₂O is an important precursor to the nucleation of hydroxyapatite, the inorganic component of bones. Differently oriented CaHPO₄·2H₂O coatings transform to hydroxyapatite with different kinetics, the transformation being more facile when the coating is oriented along 121?. These observations have implications for the development of electrodeposited biocompatible coatings for metal endoprostheses for medical applications.     

Studies on electrical double layer capacitor with a low-viscosity ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate as electrolyte

The performance of an electrical double layer capacitor (EDLC) composed of high surface area activated carbon electrodes and a new ionic liquid, 1-ethyl-3-methylimidazolium tetracyanoborate, [EMIm]TCB, as the electrolyte has been investigated by impedance spectroscopy, cyclic voltammetry and galvanostatic charge–discharge studies. The high ionic conductivity (~1·3 × 10^???2 S cm^???1 at 20 °C) and low viscosity (~22 cP) of the ionic liquid, [EMIm]TCB, make it attractive as electrolyte for its use in EDLCs. The optimum capacitance value of 195·5 F g^???1 of activated carbon has been achieved with stable cyclic performance.     

Effect of phosphoric acid on the performance of low antimony grid of Pb‐acid cell under constant current charging and discharging

Effect of phosphoric acid on the performance of Pb‐1.7%Sb grid of lead‐acid cell is studied in 5 M H₂SO₄ by cyclic galvanostatic polarization and impedance spectroscopy. An increase in capacitance to a maximum is recorded during the initial stages of the electro‐reduction of PbO₂ into Pb(II) compounds and attributed to concurrent compositional and dimensional changes. These changes include removal of O₂ bubbles, insertion of large amounts of H₂SO₄ and H₂O. Efficiency of PbO₂ formation decreases, while its rate of self‐discharge increases with increasing the charging current and in the presence of H₃PO₄. The charge capacity increases with increasing the discharging current due to the decrease in the self‐discharge. The charge capacity is lower in the presence of H₃PO₄. On increasing the cycle number, the corrodibility of the grid increases, because more layers of the surface Pb are involved in the self‐discharge. H₃PO₄ significantly retards the effect of cycle number.     

Magneto-dielectric effect in Pb(Zr0·52Ti0·48)O3 filled nanoporous Ni 0 ·5Zn 0 ·5Fe 2 O 4 composite

Nanoporous Ni_0·5Zn_0·5Fe₂O₄ particles of diameter, ~ 9·5 nm, were synthesized by citric acid assisted thermal decomposition in an autoclave. The BET surface area measured was 80 m² g^???1 and the average pore diameter was 2·5 nm. By soaking the particles in a suitable precursor solution and then subjecting them to a heat treatment at 923 K for 3 h, Pb(Zr_0·52Ti_0·48)O₃ was grown within the nanopores. X-ray and electron diffraction studies confirmed the presence of both these phases. The nanocomposites showed ferromagnetic behaviour over the temperature range 2–300 K. No ferroelectric hysteresis loop could be found which was consistent with the earlier theoretical prediction of loss of ferroelectricity below a critical thickness of 2·4 nm. Good magneto-dielectric response of the order of 7% at a magnetic field of 9 kOe was recorded for the present system. This is believed to arise due to a negative magnetostriction coefficient of Ni_0·5Zn_0·5Fe₂O₄ which exerted a compressive strain on Pb(Zr_0·52Ti_0·48)O₃ thereby lowering the tetragonality in its crystal structure.     

Characterization of carboxy methylcellulose doped with DTAB as new types of biopolymer electrolytes

The investigation of new solid biopolymer electrolyte (BEs) system based on carboxy methylcellulose (CMC) is creating opportunity for new types of electrochemical devices, which may themselves, in turn, revolutionize many industrial areas. Biodegradable carboxy methylcellulose (CMC) doped with dodecyltrimethyl ammonium bromide (DTAB) as BEs were prepared via solution-casting method. Upon addition of 35 wt. % of DTAB, highest ionic conductivity of 7·72 × 10^???4 Scm^???1 was achieved due to its higher amorphous region compared to other samples prepared. This result had been further proven in FTIR study. Temperature dependence relationship obeys the Arrhenius rule from which the activation energy, E _a, for ionic conductivity and activation energy for relaxation process, E _τ , were evaluated. The divergent values between E _a for ionic conductivity and relaxation process E _τ shows that the ions hop by jumping over a potential barrier.     

GITT studies on oxide cathode LiNi1/3Co1/3Mn1/3O2 synthesized by citric acid assisted high-energy ball milling

Layered LiNi_1/3Co_1/3Mn_1/3O₂ was synthesized by a citric acid assisted solid-state method. The structure and electrochemical properties of the LiNi_1/3Co_1/3Mn_1/3O₂ materials were investigated. XRD analysis indicated the as-synthesized LiNi_1/3Co_1/3Mn_1/3O₂ was with the layered α-NaFeO₂ structure. The discharge capacity was about 154 m·Ahg^???1 at 0·1 °C rate in the range of 2·0–4·5 V. The kinetics of the LiNi_1/3Co_1/3Mn_1/3O₂ materials was investigated by the galvanostatic intermittent titration technique (GITT) method. The lithium ion diffusion coefficient of the LiNi_1/3Co_1/3Mn_1/3O₂ was determined in the range of 10^???8??? 10^???9 cm²· s^???1 as a function of voltage of 3·7?4·5 V.     

An investigation into the effect of rate of stirring of bath electrolyte on the properties of electrodeposited CdTe thin film semiconductors

Electrodeposition (ED) has been recognized as a low cost and scalable technique available for fabrication of CdS/CdTe solar cells. Photovoltaic activity of these electrodeposited semiconductor materials drastically depends on the ED growth parameters namely; electrodeposition potential, concentrations and ratios of concentrations of precursors used to prepare the bath electrolyte, pH of the electrolyte, deposition temperature and rate of stirring of the electrolyte. In order to grow thin films with good photovoltaic properties, it is essential to maintain these variables at their optimum ranges of values during electrodepositions. Hence, this study was conducted to investigate the dependence of the properties of electrodeposited CdTe thin film material on the rate of stirring of the bath electrolyte. The CdTe material was grown on glass/FTO (2?×?3 cm²) and glass/FTO/CdS (2?×?3 cm²) surfaces in bath electrolytes containing 1.0 mol/L CdSO₄ and 1.0 mmol/L TeO₂ solutions at different rates of stirring within the range of 0–350 rpm while keeping the values of pH of the electrolyte, deposition temperature and cathodic deposition potential with respect to the saturated calomel electrode at 2.3, 65 °C and 650 mV respectively. After the heat treatment at 400 °C in air atmosphere, the deposited samples with a good visual appearance were selected and evaluated based on their morphological, elemental, structural, optical and electrical properties in order to identify the optimum range of rate of stirring for electrodeposition of CdTe thin film semiconductors. Results revealed that, rates of stirring in the range of 60–85 rpm in a 100 mL volume of electrolyte containing the substrate and the counter electrodes in the center of the bath with a separation of 2.0 cm between them can electrodeposit CdTe layers exhibiting required levels of morphological, structural, optical and electrical properties on both glass/FTO and glass/FTO/CdS surfaces.     

Studies on electrical conductivity and dielectric behaviour of PVdF–HFP–PMMA–NaI polymer blend electrolyte

Polymer blend electrolytes composed of poly(vinylidene fluoride-co-hexafluoro-propylene), poly(methyl methacrylate) and 1·0 M NaI as salt have been synthesized using solution caste technique by varying the PVdF(HFP)–PMMA blend concentration ratio systematically. A.c. impedance studies were performed to evaluate the ionic conductivity of the polymer electrolyte films. The highest ionic conductivity at room temperature for [PVdF(HFP)–PMMA(4:1)](20 wt%) – [NaI(1·0 M)](80 wt%) system is found to be 1·67 × 10^???2 S cm^???1. XRD studies reveal complete complexation of the salt in the polymeric blend systems. The temperature dependence conductivity has been performed in the range of 303–373 K and it is observed that it obeys the Arrhenius behaviour. It has been observed that the dielectric constant, ε _r and dielectric loss, ε _i, increases with temperature in the lower frequency region and is almost negligible in the higher frequency region. This behaviour can be explained on the basis of electrode polarization effects. Plot of real part, M _r and imaginary part, M _i vs frequency indicates that the systems are predominantly ionic conductors. The phenomenon suggests a plurality of relaxation mechanism.     

Synthesis and optimization of P(MMA-BA-MAA)/PEG-based polymer gel electrolytes

A polymer gel electrolyte based on poly(methyl methacrylate-butyl acrylate-methacrylic acid)/polyethylene glycol 400 blend (P(MMA-BA-MAA)/PEG400) was successfully prepared by a simple and efficient procedure. The optimal ionic conductivity was achieved to be 3.12 mS cm^?1 at the temperature of 30 °C when the electrolyte has the composition of 20 wt% P(MMA-BA-MAA)/PEG400 blend, 0.6 M NaI, and 0.06 M I₂ in the solvent γ-butyrolactone (GBL). For tuning the ionic conductivity, various additives were introduced into the polymer gel electrolytes. The measured values of open circuit voltage, short circuit current, and total photovoltaic efficiency indicates that the adding of pyridine (PY) leads to better performance of the final dye-sensitized solar cells (DSSCs), while the adding of Guanidine thiocyante (GuSCN) leads to a worse one. 4-Tert-butylpyridine (TBP) additive takes a more complex effect on the performance of the final DSSCs. For polymer gel electrolyte with 0.5 M pyridine, the final fabricated dye-sensitized solar cell has overall energy conversion efficiency (η) of 3.63 % (0.16 cm² active area) under AM 1.5 at irradiation of 100 mW cm^?2, which reached the level of the liquid electrolyte based device (η = 3.83 % at 0.16 cm² active area). Meanwhile, this gel electrolyte exhibits well long-term stability. The mechanism analysis revealed the dependences of ionic conductivity on the concentration of polymer and NaI and the temperatures.     

Electrical,electrochemical and photo-electrochemical studies on the electrodeposited n-type semiconductor hexagonal crystalline CdS thin film on nickel substrate

Electrodeposited cadmium sulfide (CdS) on nickel substrate of new properties from aqueous solutions of Cd²⁺ and S₂O₃ ^2? at 313 K has been obtained using cyclic voltammetric and potentiostatic techniques. The mechanism of the electrode reactions for the electrodeposition of CdS has been evaluated and proposed. Energy dispersive X-ray florescence elemental analysis and X-ray diffraction investigations demonstrate that, the electrodeposited CdS is pure and hexagonal polycrystalline in nature, at our optimal conditions. Furthermore, the electrodeposited CdS is of n-type semiconductor was investigated and confirmed by Mott–Schotky test. Donor concentration (N_D) was determined to be 1.0 × 10¹⁷ cm^?3. In this research we discovered that, the electrodeposited semiconductor CdS on Ni substrate has low resistivity and magnetic properties (became as a strong magnet) at the mentioned conditions. The photoelectrochemical measurements of the electrodeposited CdS on nickel electrode had been investigated at room temperature and under illumination giving good results.     

Samarium-doped Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles with improved magnetic and supercapacitive performance: a novel preparation strategy and characterization

Sm³⁺-doped magnetite (Fe₃O₄) nanoparticles were synthesized through a one-pot facile electrochemical method. In this method, products were electrodeposited on a stainless steel (316L) cathode from an additive-free 0.005 M Fe(NO₃)₃/FeCl₂/SmCl₃ aqueous electrolyte. The structural characterizations through X-ray diffraction, field-emission electron microscopy, and energy-dispersive X-ray indicated that the deposited material has Sm³⁺-doped magnetite particles with average size of 20 nm. Magnetic analysis by VSM revealed the superparamagnetic nature of the prepared nanoparticles (Ms = 41.89 emu g^?1, Mr = 0.12 emu g^?1, and H _Ci = 2.24 G). The supercapacitive capability evaluation of the prepared magnetite nanoparticles through cyclic voltammetry and galvanostat charge–discharge showed that these materials are capable to deliver specific capacitances as high as 207 F g^?1 (at 0.5 A g^?1) and 145 F g^?1 (at 2 A g^?1), and capacity retentions of 94.5 and 84.6% after 2000 cycling at 0.5 and 1 A g^?1, respectively. The results proved the suitability of the electrosynthesized nanoparticles for use in supercapacitors. Furthermore, this work provides a facile electrochemical route for the synthesis of lanthanide-doped magnetite nanoparticles.     

Formulated quasi-solid state electrolyte based on polypyrrole/polyaniline–polyurethane nanocomposite for dye-sensitized solar cell

A polymer-based quasi-solid state electrolyte using polyurethane (PU) matrix was applied for dye-sensitized solar cell (DSSC). To further improve the performance of the electrolyte, 10 wt% of conductive polymer [polypyrrole (PPy) and polyaniline (PANi)] nanoparticles were introduced into the matrix. The samples were named PU-10%PPy and PU-10%PANi, and characterized using ATR–FTIR, TEM, DLS, a transmitted light microscope, a reflected light microscope, and TGA. The formulated polymeric nanocomposites were immersed in the liquid electrolyte and the polymer matrix absorbency, conductivity (σ), ion diffusion coefficient (D_ff), and photovoltaic performance in the DSSC were measured. Polymer matrix absorbency and D_ff of PU-10%PPy (1.72 g g^?1, 1.52 µcm² s^?1) and PU-10%PANi (1.74 g g^?1, 1.31 µcm² s^?1) were lower than the PU matrix (2.01 g g^?1, 1.68 µcm² s^?1). However, the conductivity of PU-10%PPy and PU-10%PANi was higher than the PU matrix (2.64, 2.69, and 2.59 mS cm^?1, respectively). The efficiency of the DSSC based on PU-10%PANi was the highest, with open circuit voltage of 709 mV, short circuit current of 3.67 mA cm^?2, fill factor of 0.62, and light-to-energy conversion efficiency of 2.68%.     

Pb/S/1,2-ethanedithiol composite thin films for efficient solid-state quantum-dot sensitized TiO<Subscript>2</Subscript> nanorod array solar cells

The Pb/S/1,2-ethanedithiol composite thin films were successfully deposited on TiO₂ nanorod arrays by spin-coating step-by-step 5 mmol dm^?3 Pb(NO₃)₂, Na₂S and 1% 1,2-ethanedithiol solution and their chemical compositions can be easily adjusted by changing the concentration of Na₂S solution from 5 to 3.5 mmol dm^?3 and 2 mmol dm^?3. The average crystal sizes of Pb/S/1,2-ethanedithiol quantum-dots decreased from 7.9 to 7.1 nm and 6.5 nm with the decrease of the concentration of Na₂S solution and the chemical bonding of Pb²⁺ and S in EDT was chelation of the penta-heterocycle in Pb/S/1,2-ethanedithiol composite thin films. All solid-state Pb/S/1,2-ethanedithiol composite thin film sensitized TiO₂ nanorod array solar cells using 5, 3.5, 2 mmol dm^?3 Na₂S solution exhibited the photoelectric conversion efficiency of 2.68, 3.41 and 4.51% under the illumination of simulated AM 1.5 sunlight (100 mA cm^?2).     

Enhancing the performance of electrodeposited CuInSe2 solar cells by suppressing secondary phases using sodium dodecyl sulfate

CuInSe₂ thin films were prepared on Mo-coated glass substrates using pulse electrodeposition with an aqueous solution containing sodium dodecyl sulfate (SDS) as an additive. The effect of SDS on the electrochemistry mechanism that inhibits secondary phases (Cu_xSe_y) was examined using cyclic voltammetry, which indicated that SDS can inhibit the reduction of Cu²⁺ and H₂SeO₃ and prohibit the formation of secondary phases. Scanning electron microscopy and atomic force microscopy revealed that the cracks and roughness of CuInSe₂ films decreased considerably after adding SDS into the electrolyte. The suppression of secondary phases was also observed using X-ray diffraction and Raman spectroscopy. The optical bandgap values of the CuInSe₂ films were measured using a UV–vis–NIR spectrophotometer; the bandgap values of the films deposited in the electrolyte with 0 and 1 mM SDS were approximately 0.96 and 1.05 eV, respectively. As expected, based on these differences, the CuInSe₂ solar cell with the Al/AZO/i-ZnO/CdS/CuInSe₂/Mo/glass structure derived from precursor film deposited in an electrolyte containing SDS demonstrated greater efficiency (η = 2.51 %) than that of the cell derived from precursor film deposited in an electrolyte without SDS (η = 0.63 %).     

Brush plated copper indium sulphide films and their properties

Copper indium sulphide films were deposited for the first time by the brush plating technique at different electrolyte temperatures in the range of 30–80 °C and at a constant deposition current density of 5.0 mA cm^?2. The Films exhibited single phase copper indium sulphide. The grain size increased with increase of electrolyte temperature. Optical band gap of the films varied in the range of 1.30–1.42 eV. Atomic force microscopy studies indicated that the grain size vary from 600 to 1,000 nm, with increase of substrate temperature. Solar cells fabricated with the films exhibited V_oc of 650 mV, J_sc of 19.5 mA cm^?2, ff of 0.73 and efficiency of 9.50 %.     

Effect of nitric acid modification on the lead(II) adsorption of mesoporous biochars with different mesopore size distributions

Two mesoporous biochars AC-1 and AC-2 with similar chemical properties but different mesopore size distributions were prepared to study the effect of HNO₃ modification on the lead(II) adsorption. AC-2 possesses higher mesopore volume and broader pore diameter than AC-1, while their surface area and micropore volume are similar. Adsorption experiments showed that AC-2 had far better removal efficiency, indicating the important role of mesopores played in the adsorption. HNO₃ modification enhanced the adsorption capacity of lead AC-1 and AC-2 by 15 and 27 mg g^?1, respectively. In particular, the removal rate of lead for AC-1 was improved from 46 to 99 % by HNO₃ treatment at a low initial lead concentration of 10 mg L^?1. Results of Boehm’s titration demonstrated that the amounts of oxygenic acid groups of AC-1 and AC-2 increased to 2.456 and 2.705 mmol g^?1 after HNO₃ treatment, respectively. Analyses of FTIR spectrum revealed that AC-2 was more likely to graft oxygen-containing acidic functional groups than AC-1, indicating that higher mesoporosity takes advantage of grafting more oxygenic functional groups, thus forming more active adsorption sites. The above results indicate that mesoporous biochars with wider pore width are more favorable to be introduced with oxygenic groups for enhanced lead removal efficiency.     

Improvement of hydrothermally synthesized MnO2 electrodes on Ni foams via facile annealing for supercapacitor applications

Nanostructured manganese dioxide (MnO₂) is deposited on nickel foams by a hydrothermal synthesis route. As-deposited MnO₂ thin films are largely amorphous. Facile post-deposition annealing significantly improves the electrochemical performance of the MnO₂ thin films via changing their morphology, phase, and crystallinity. The specific capacitance of the MnO₂ electrode increases with the annealing temperature and reaches an optimal value of 244 F g^?1 (at the current density of 1 A g^?1) in a neutral 1 M Na₂SO₄ electrolyte for a specimen annealed at 500 °C. Furthermore, when an alkaline 5 M KOH electrolyte is used, an exceptionally high capacitance of 950 F g^?1 is achieved at the current density of 2 A g^?1. The cost-effective facile synthesis, high specific capacitance, and good cycle stability of these MnO₂-based electrodes enable their applications in high-performance supercapacitors.