Laser Raman and ac impedance spectroscopic studies of PVA: NH4NO3 polymer electrolyte

Ion conducting polymer electrolyte PVA:NH₄NO₃ has been prepared by solution casting technique and characterized using XRD, Raman and ac impedance spectroscopic analyses. The amorphous nature of the polymer films has been confirmed by XRD and Raman spectroscopy. An insight into the deconvoluted Raman peaks of υ₁ vibration of NO₃^? anion for the polymer electrolyte reveals the dominancy of ion aggregates at higher NH₄NO₃ concentration. From the ac impedance studies, the highest ion conductivity at 303 K has been found to be 7.5 × 10^?3 S cm^?1 for 80PVA:20NH₄NO₃. The conductivity of the polymer electrolytes has been found to depend on the degree of dissociation of the salt in the host polymer matrix. The combination of the above-mentioned analyses has proven worth while and in fact necessary in order to achieve better understanding of these complex systems.     

The structure and electric characters of proton‐conducting chitosan membranes with various ammonium salts as complexant

The structural and electric properties of chitosan electrolytes doped by three different ammonium salts [CH₃COONH₄, NH₄Cl, and (NH₄)₂SO₄] were discussed. The chitosan electrolytes were prepared by solution casting technique. The results show that the addition of ammonium salts leads to: The formation of complexation between ammonium salts and chitosan matrix, the destruction of crystal forms, and the enhancement of amorphous nature. With the rise of salt content, both the glass transition temperature and the activation energy show a “V”‐type trend, whereas the conductivity exhibits a reverse trend. For different ammonium salts, the electric properties of the chitosan electrolyte are different due to the Coulomb force between anion of salts and functional groups. The CH₃COONH₄ doped chitosan electrolyte exhibits the optimum electric properties, whereas those of (NH₄)₂SO₄ doped chitosan electrolyte are worst. The chitosan electrolyte doped with 40 wt % CH₃COONH₄ has the lowest glass transition temperature of 369 K, the lowest activation energy of 0.19 eV, and the highest ionic conductivity of 2.87 × 10^?4 S cm^?1 at room temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 880–885, 2010     

Proton-conducting membranes: poly (N-vinyl pyrrolidone) complexes with various ammonium salts

The present study focuses on the proton-conducting polymer electrolytes; poly (N-vinyl pyrrolidone)–ammonium thiocyanate and poly (N-vinyl pyrrolidone)–ammonium acetate prepared by solution casting technique. The XRD analysis indicates the amorphous nature of the polymer electrolytes. The Raman spectra of the C=O vibration of pure polymer PVP at 1,663 cm^?1 has been appeared as doublet in the polymer electrolytes. The introduction of this new peak in the salt-doped polymer electrolytes may be due to interaction of the cation with the polymer. The room temperature ionic conductivity σ _303κ has been found to be high, 1.7?×?10^?4 S cm^?1 for 80 mol% PVP–20 mol% NH₄SCN and 1.5?×?10^?6 S cm^?1 for 75 mol% PVP–25 mol% CH₃COONH₄. The polymer electrolytes have been tested for their application in Zn–air battery.     

Studies on ionic liquid-based corn starch biopolymer electrolytes coupling with high ionic transport number

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF₆) and ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BmImTf) were prepared by solution casting technique. The ionic conductivity was found to increase with increasing ionic liquid concentration. Upon doping with 80 wt% of BmImTf, the ionic conductivity increased by three orders of magnitude. The highest ionic conductivity of (3.21 ± 0.01) × 10^?4 S cm^?1 was achieved at ambient temperature. The complexation between corn starch, LiPF₆ and BmImTf was further proven in attenuated total reflectance-Fourier transform infrared findings. The highest conducting biopolymer electrolyte was stable up to 230 °C, as proven in thermogravimetric analysis.     

The Micellization and Clouding Phenomena of a Nonionic Surfactant,Poly(ethylene glycol) t-octylphenyl ether (Triton X-100): Effect of (Chloride Salt) Electrolytes

Herein, we report the micellization and the clouding of a nonionic surfactant, poly(ethylene glycol) t-octylphenyl ether (Triton X-100), in aqueous solutions in the absence and presence of (chloride salt) electrolytes. In the absence and presence of electrolytes, the critical micelle concentration (CMC) of Triton X-100 was measured by surface tension measurements. Upon increasing the temperature as well as the concentration of electrolytes, the CMCs decreased. The surface properties and the thermodynamic parameters of the micellar systems were evaluated. From these evaluated thermodynamic parameters, it was found that in the presence of an electrolyte, the stability of the micellar system is high. The cloud points (CPs) of Triton X-100 were also measured in the absence and presence of metallic ions of electrolytes. Upon the addition of metallic ions of chloride salts (electrolytes), the decrease in CP values was observed and the order was found to be: K⁺ > Na⁺ > Li⁺ > NH⁺₄.     

Lithium garnet based free-standing solid polymer composite membrane for rechargeable lithium battery

Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (W_avg ~?5?×?10⁶) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO₄) and lithium garnet oxide Li_6.28Al_0.24La₃Zr₂O₁₂ (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li⁺ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li⁺ conductivity of 4.40?×?10^?4 S cm^?1 and wide electrochemical window (4.5 V) is observed for PEO₈/LiClO₄?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO₂ as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g^?1/142 mAh g^?1 at 25 °C with 0.06 C-rate.     

Polyethyleneoxide (PEO)-based, anion conducting solid polymer electrolyte for PEC solar cells

Solid polymer electrolyte membranes were prepared by complexing tetrapropylammoniumiodide (Pr₄N⁺I^?) salt with polyethylene oxide (PEO) plasticized with ethylene carbonate (EC), and these were used in photoelectrochemical (PEC) solar cells fabricated with the configuration glass/FTO/TiO₂/dye/electrolyte/Pt/FTO/glass. The PEO/Pr₄N⁺I^?+I₂?=?9:1 ratio gave the best room temperature conductivity for the electrolyte. For this composition, the plasticizer EC was added to increase the conductivity, and a further conductivity enhancement of four orders of magnitude was observed. An abrupt increase in conductivity occurs around 60–70 wt% EC; the room temperature conductivity was 5.4?×?10^?7 S cm^?1 for 60 wt% EC and 4.9?×?10^?5 S cm^?1 for the 70 wt% EC. For solar cells with electrolytes containing PEO/Pr₄N⁺I^?+I₂?=?9:1 and EC, IV curves and photocurrent action spectra were obtained. The photocurrent also increased with increasing amounts of EC, up to three orders of magnitude. However, the energy conversion efficiency of this cell was rather low.     

Electrical Properties of Carboxyl Methylcellulose/Chitosan Dual-Blend Green Polymer Doped with Ammonium Bromide

This present work discusses dual-blend green polymer electrolyte (GPE)–based natural polymers, composed of carboxyl methylcellulose (CMC) and chitosan (CS), created by introducing various compositions of ammonium bromide (NH₄Br) as a dopant in the system. These GPEs were successfully prepared by the solution casting technique and characterized using electrical impedance spectroscopy (EIS). From EIS measurement, the highest room-temperature conductivity is 1.21 × 10^?5 Scm^?1 for the sample containing 20 wt.% of NH₄Br. Plot of the temperature dependence of the GPEs revealed that the system obeys the Arrhenius rule and was thermally assisted. Besides that, dielectric studies were also conducted and the data were analyzed using complex permittivity, ?^*, and complex electrical modulus, M*, to determine the sample with the highest conductivity value. Thus, this study confirmed non-Debye behavior in the sample.     

Surface Modification of Low-Carbon Steels by Plasma Electrolytic Nitrocarburising

This study investigates the effect of the plasma electrolytic nitrocarburising conditions and electrolyte composition (NH₄Cl, NH₄NO₃ and glycerol) on steel structure and properties. The cross-sectional microstructure, composition and phase constituents of a modified layer are characterized. The thickness of each layer is determined by carbon and nitrogen diffusion, anode dissolution, and oxidation that occur simultaneously. These processes are affected by the concentration of electrolyte components. The aqueous solution containing NH₄NO₃, NH₄Cl and glycerol enables to obtain the modified layer with the thickness of 0.20 mm and hardness of 930 HV, the decrease in the surface roughness from 1.01 to 0.15 µm, the corrosion rate by a factor of 4.4 and the weight loss after lubricate wear testing by a factor of 14.     

Cross-linking copolymers of acrylates’ gel electrolytes with high conductivity for lithium-ion batteries

The cross-linking gel copolymer electrolytes containing alkyl acrylates, triethylene glycol dimethacrylate, and liquid electrolyte were prepared by in situ thermal polymerization. The gel polymer electrolytes containing 15 wt% polymer content and 85 wt% liquid electrolyte content with sufficient mechanical strength showed the high ionic conductivity around 5?×?10^?3 Scm^?1 at room temperature. The gel electrolytes containing different polymer matrices were prepared, and their physical observation and conductivity were discussed carefully. The cross-linking copolymer gel electrolytes of alkyl acrylates with other monomers were designed and synthesized. The results showed that copolymerization can improve the mechanical properties and ionic conductivities of the gel electrolytes. The polymer matrices of gels had excellent thermal stability and electrochemical stability. The scanning electron microscope analysis showed the gel electrolyte was the homogeneous structure, and the cross-linking polymer host was the porous three-dimensional network structure, which demonstrated the high conductivity of the gel electrolytes. The gel polymer Li-ion battery was prepared by this in situ thermal polymerization. The cell exhibited high charge-discharge efficiency at 0.1 C. The results of LiFePO4-PEA-Li cell and graphite-PEA-Li cell showed that gel polymer electrolytes have good compatibility with the battery electrodes materials.     

Preparation of high-resolution 238U α-sources by electrodeposition: a comprehensive study

In this paper the source preparation procedures for high-resolution ²³⁸U sources are described and compared. This work was done within collaboration between CIEMAT and IRMM in the frame of MetroFission, a project of the European Metrology Research Programme, in order to determine the alpha-emission probabilities of ²³⁸U. ²³⁸U was deposited from organic (iso-propanol) and inorganic-H₂SO₄/(NH₄)₂SO₄, saturated NH₄NO₃-electrolyte solutions on metal backings. The parameters affecting electrodeposition were studied and optimized. The activity distribution of uranium was checked by autoradiography. Results show that the ²³⁸U source quality is significantly better using the saturated NH₄NO₃ than the two other electrolytes. By this method, sources of 18.6–22 mm diameter, 26 μg cm^?2 surface density, ~15–18 keV resolution and a peak to valley ratio higher than 50 could be made. This reconciles the inherently opposing requirements of high resolution and sufficient count rate needed to determine the alpha–emission probabilities accurately.     

Nanocomposite blend gel polymer electrolyte for proton battery application

A proton-conducting nanocomposite gel polymer electrolyte (GPE) system, [35{(25 poly(methylmethacrylate) (PMMA) + 75 poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP))?+?xSiO₂}?+?65{1 M NH₄SCN in ethylene carbonate (EC) + propylene carbonate (PC)}], where x?=?0, 1, 2, 4, 6, 8, 10, and 12, has been reported. The free standing films of the gel electrolyte are obtained by solution cast technique. Films exhibit an amorphous and porous structure as observed from X-ray diffractometry (XRD) and scanning electron microscopy (SEM) studies. Fourier transform infrared spectrophotometry (FTIR) studies indicate ion–filler–polymer interactions in the nanocomposite blend GPE. The room temperature ionic conductivity of the gel electrolyte has been measured with different silica concentrations. The maximum ionic conductivity at room temperature has been observed as 4.3?×?10^?3?S?cm^?1 with 2 wt.% of SiO₂ dispersion. The temperature dependence of ionic conductivity shows a typical Vogel-Tamman-Fulcher (VTF) behavior. The electrochemical potential window of the nanocomposite GPE film has been observed between ?1.6 V and 1.6 V. The optimized composition of the gel electrolyte has been used to fabricate a proton battery with Zn/ZnSO₄·7H₂O anode and PbO₂/V₂O₅ cathode. The open circuit voltage (OCV) of the battery has been obtained as 1.55 V. The highest energy density of the cell has been obtained as 6.11 Wh?kg^?1 for low current drain. The battery shows rechargeability up to 3 cycles and thereafter, its discharge capacity fades away substantially.     

Effect of plasticizers (EC or PC) on the ionic conductivity and thermal properties of the (PEO)9LiTf: Al2O3 nanocomposite polymer electrolyte system

A new plasticized nanocomposite polymer electrolyte based on poly (ethylene oxide) (PEO)-LiTf dispersed with ceramic filler (Al₂O₃) and plasticized with propylene carbonate (PC), ethylene carbonate (EC), and a mixture of EC and PC (EC+PC) have been studied for their ionic conductivity and thermal properties. The incorporation of plasticizers alone will yield polymer electrolytes with enhanced conductivity but with poor mechanical properties. However, mechanical properties can be improved by incorporating ceramic fillers to the plasticized system. Nanocomposite solid polymer electrolyte films (200–600 μm) were prepared by common solvent-casting method. In present work, we have shown the ionic conductivity can be substantially enhanced by using the combined effect of the plasticizers as well as the inert filler. It was revealed that the incorporating 15 wt.% Al₂O₃ filler in to PEO: LiTf polymer electrolyte significantly enhanced the ionic conductivity [σ _RT (max)?=?7.8?×?10^?6 S cm^?1]. It was interesting to observe that the addition of PC, EC, and mixture of EC and PC to the PEO: LiTf: 15 wt.% Al₂O₃ CPE showed further conductivity enhancement. The conductivity enhancement with EC is higher than PC. However, mixture of plasticizer (EC+PC) showed maximum conductivity enhancement in the temperature range interest, giving the value [σ _RT (max)?=?1.2?×?10^?4 S cm^?1]. It is suggested that the addition of PC, EC, or a mixture of EC and PC leads to a lowering of glass transition temperature and increasing the amorphous phase of PEO and the fraction of PEO-Li⁺ complex, corresponding to conductivity enhancement. Al₂O₃ filler would contribute to conductivity enhancement by transient hydrogen bonding of migrating ionic species with O–OH groups at the filler grain surface. The differential scanning calorimetry thermograms points towards the decrease of T _g , crystallite melting temperature, and melting enthalpy of PEO: LiTf: Al₂O₃ CPE after introducing plasticizers. The reduction of crystallinity and the increase in the amorphous phase content of the electrolyte, caused by the filler, also contributes to the observed conductivity enhancement.     

Conductivity and thermal behavior of proton conducting polymer electrolyte based on poly (N-vinyl pyrrolidone)

The polymer electrolytes based on poly N-vinyl pyrrolidone (PVP) and ammonium thiocyanate (NH₄SCN) with different compositions have been prepared by solution casting technique. The amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. The shift in T_g values and the melting temperatures of the PVP-NH₄SCN electrolytes shown by DSC thermo-grams indicate an interaction between the polymer and the salt. The dependence of T_g and conductivity upon salt concentration have been discussed. The conductivity analysis shows that the 20 mol% ammonium thiocyanate doped polymer electrolyte exhibit high ionic conductivity and it has been found to be 1.7 × 10⁻⁴ S cm⁻¹, at room temperature. The conductivity values follow the Arrhenius equation and the activation energy for 20 mol% ammonium thiocyanate doped polymer electrolyte has been found to be 0.52 eV.     

Characteristics of proton conducting polymer electrolyte based on chitosan acetate complexed with CH3COONH4

The polymer electrolytes based on chitosan and ammonium acetate (CH₃COONH₄) were prepared by solution casting technique and the properties were studied. With the addition of CH₃COONH₄, the amorphous nature of the polymer electrolytes was promoted. The glass transition temperature, activation energy, and conductivity are closely related. Lower the glass transition temperature, lower the activation energy, higher the conductivity. The 40 wt % ammonium acetate doped polymer electrolyte has the lowest glass transition temperature of 369 K, the lowest activation energy of 0.19 eV, and the highest ionic conductivity of 2.87 × 10^?4 S cm^?1 at room temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 549–554, 2009     

Effect of alkaline and alkaline–earth cations on the supercapacitor performance of MnO2 with various crystallographic structures

The electrochemical performances of the α-, γ-, and δ-MnO₂ with different crystallographic structures were systematically investigated in 0.5 mol/L Li₂SO₄, 0.5 mol/L Na₂SO₄, 1 mol/L Ca(NO₃)₂, and 1 mol/L?Mg(NO₃)₂ electrolytes. The results showed that the electrochemical performances of the manganese dioxides depended strongly on the crystallographic structures of MnO₂ as well as the cation in the electrolytes. Because the δ-MnO₂ consists with layers of structure and the interlayer separation is 7 Å, which is suitable for insertion/extraction of some alkaline and alkaline–earth cations, the δ-MnO₂ electrode showed the higher specific capacitance than that of α-MnO₂ and γ-MnO₂. We also found that the α-, γ-, and δ-MnO₂ electrodes in the Mg(NO₃)₂ electrolyte showed a higher specific capacitance, while all the α-, γ-, and δ-MnO₂ electrodes in the Li₂SO₄ electrolyte exhibited a better cycle life. The reason for the different behavior of Li⁺ and Mg²⁺ during the charge/discharge process can be ascribed to the charge effect of the cations in the electrolytes. The ex situ X-ray diffraction (XRD) and long-time cyclic voltammogram measurements were used to systematically study the energy storage mechanism of MnO₂-based electrodes. A progressive crystallinity loss of the materials is also observed upon potential cycling at the oxidized states. A reasonable charge/discharge mechanism is proposed in this work.     

Polyacrylamide-methanesulfonic acid gel polymer electrolytes for tin-air battery

The present work describes the synthesis and characterization of gel polymer electrolytes containing methanesulfonic acid (MSA) with Polyacrylamide (PAAm). The PAAm–MSA gel electrolytes were prepared with different concentrations of MSA. Addition of 0.5 M of MSA into the electrolyte increased the ionic conductivity of PAAm from 1.35 × 10^?3 to 1.56 × 10^?2 S cm^?1. The maximum ionic conductivity of 7.0 × 10^?1 S cm^?1 was obtained with 3 M MSA at room temperature. The chemical interaction between PAAm and MSA was studied by Fourier transformed infra-red. The performance as a polymer electrolyte was evaluated from the cell discharge and open circuit potential measurements of a tin-air cell. The tin-air cell supported relatively high current, up to 12 mA cm^?2 with a maximum power density of 5 mW cm^?2. The open-circuit potential of the cell was 1.27 V for 24 h.     

Novel Bi2O3 nanoporous film fabricated by anodic oxidation and its photoelectrochemical performance

Novel bismuth oxide (Bi₂O₃) nanoporous films were fabricated through anodization of bismuth foil in electrolytes containing glycol, ammonium sulfate ((NH₄)₂SO₄) and deionized (DI) water. Scanning electron microscopy analysis indicated that morphology of the anodized bismuth foil changed markedly along with the changing of oxidation time, water content, electrolyte concentration, temperature, and applied voltages. The optimized morphology was obtained when bismuth was anodized at 20 V, 40 °C for 40 min in glycol solution containing 0.3 wt% (NH₄)₂SO₄ and 5 wt% DI water. The composition and crystal structure of the samples formed in the optimized conditions were characterized by energy-dispersive spectroscopy and X-ray diffraction. Results showed that the as-prepared nanoporous structures were amorphous. β-Bi2O3 was obtained when the samples were annealed at 200 °C. The photocurrent response experiments demonstrated that the Bi₂O₃ nanoporous film can generate photocurrent as large as 2.893 and 6.980 μA/cm² under 0 and 0.5 V bias voltage versus saturated calomel electrode, respectively.     

A polymer electrolyte containing ionic liquid for possible applications in photoelectrochemical solar cells

Various iodide ion conducting polymer electrolytes have been studied as candidate materials for fabricating photoelectrochemical (PEC) solar cells and energy storage devices. In this study, enhanced ionic conductivity values were obtained for the ionic liquid tetrahexylammonium iodide containing polyethylene oxide (PEO)-based plasticized electrolytes. The analysis of thermal properties revealed the existence of two phases in the electrolyte, and the conductivity measurements showed a marked conductivity enhancement during the melting of the plasticizer-rich phase of the electrolyte. Annealed electrolyte samples showed better conductivity than nonannealed samples, revealing the existence of hysteresis. The optimum conductivity was shown for the electrolytes with PEO:salt = 100:15 mass ratio, and this sample exhibited the minimum glass transition temperature of 72.2 °C. For this optimum PEO to salt ratio, the conductivity of nonannealed electrolyte was 4.4 × 10⁻⁴ S cm⁻¹ and that of the annealed sample was 4.6 × 10⁻⁴ S cm⁻¹ at 30 °C. An all solid PEC solar cell was fabricated using this annealed electrolyte. The short circuit current density (I _SC), the open circuit voltage (V _OC), and the power conversion efficiency of the cell are 0.63 mA cm⁻², 0.76 V, and 0.47% under the irradiation of 600 W m⁻² light.     

Conductivity of crosslinked poly(N-vinylpyrrolidone) gel film containing surfactant as electrolyte salt

New polymeric solid electrolyte films, consisting of crosslinked poly(N-vinylpyrrolidone) (PVPD) as matrix, and surfactant, sodium deoxycholate (NaDC), lithium deoxycholate (LiDC), sodium laulylsulfate (R₁₂OSO₃Na), or sodium palmitate (R₁₅COONa) as electrolyte salt, are prepared; their basic structure and conductivity dependence on temperature are reported. The structure of the electrolytes is amorphous. Their conductivity is 3.1 × 10^?5 S cm^?1 (containing NaDC), 8.42 × 10^?6 S cm^?1 (LiDC), 2.18 × 10^?4 S cm^?1 (R₁₂OSO₃Na), and 7.27 × 10^?5 S cm^?1 (R₁₅COONa) at 20°C. Their temperature dependence of the conductivity is similar to that of liquid electrolyte rather than that of usual polymeric solid electrolyte, i.e., the WLF-type dependence. The values of activation energy of conductivity (E_a) were PVPD, 25.5 kJ mol^?1; PVPD/NaDC, 21.4 kJ mol^?1; PVPD/LiDC, 25.3 kJ mol^?1; PVPD/R₁₂OSO₃Na, 17.2 kJ mol^?1; PVPD/R₁₅COONa, 18.7 kJ mol^?1. © 1993 John Wiley & Sons, Inc.