Effect of temperature on the conductivity, structural, and morphology of PVA-based alkaline solid polymer electrolyte

Alkaline polymer electrolytes (ASPE) have been prepared by using poly(vinyl alcohol) (PVA) polymer and which different weight percentages of potassium hydroxide (KOH), ceramic filler (α-Al₂O₃), and propylene carbonate (PC) have been added. The pure PVA/H₂O weight ratio (1.00:1.49), the PVA/KOH/H₂O (1.00:0.67:2.22), the PVA/KOH/α-Al₂O₃/H₂O (1.00:0.67:0.09:7.56), and PVA/KOH/α-Al₂O₃/PC/H₂O (1.00:0.67:0.09:2.64:1.32) were studied. The hysteresis phenomena in the conductivity temperature of ASPE were investigated. The polymer electrolytes prepared were characterized using X-ray diffraction and scanning electron microscopy.     

Effect of storage time on the properties of PVA–KOH alkaline solid polymer electrolyte system

Polyvinyl alcohol (PVA) and potassium hydroxide (KOH) have been used to prepare alkaline solid polymer electrolytes (ASPE) films. The films were stored in a dry environment for 30 and 100 days. The highest room temperature conductivity for the PVA:KOH film with weight percentage ratio of 1:0.67 during storage for 30 and 100 days were (8.5±0.2)×10⁻⁴ and (1.3±0.1)×10⁻⁷ S cm⁻¹, respectively. The conductivity–temperature behaviour after 30 and 100 days of storage of the alkaline polymer electrolytes is Arrhenian and liquid-like. The structural, morphological and thermal studies of the ASPE films are also presented in this paper.     

Degradation in polymer Ni-MH battery

The alkaline solid polymer electrolyte system with the conductivity of (8.5±0.2) × 10⁻⁴ Scm⁻¹ composes of polyvinyl alcohol (PVA) and potassium hydroxide (KOH) have been used in fabrication of Mg₂Ni/Ni(OH)₂ nickel metal hydride cell. The self-dehydriding of the cell during storage was presented by open circuit voltage study. Cell degradation after charge-discharge cycling is characterized by means of X-ray diffraction and scanning electron microscopic analyses. The failure of the cell can be ascribed by a small formation of Mg(OH)₂ oxide layer and surface resistance between electrode-electrolyte.     

Impedance spectroscopy studies of poly (methyl methacrylate)-lithium salts polymer electrolyte systems

In the present work, five systems of samples have been prepared by the solution casting technique. These are the plasticized poly(methyl methacrylate) (PMMA-EC) system, the LiCF₃SO₃ salted-poly(methyl methacrylate) (PMMA-LiCF₃SO₃) system, the LiBF₄ salted-poly(methyl methacrylate) (PMMA-LiBF₄) system, the LiCF₃SO₃ salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiCF₃SO₃) system, and the LiBF₄ salted-poly(methyl methacrylate) containing a fixed amount of plasticizer ([PMMA-EC]-LiBF₄) system. The conductivities of the films from each system are characterized by impedance spectroscopy. The room temperature conductivity in the pure PMMA sample and (PMMA-EC) system is 8.57 × 10⁻¹³ and 2.71 × 10⁻¹¹ S cm⁻¹, respectively. The room conductivity for the highest conducting sample in the (PMMA-LiCF₃SO₃), (PMMA-LiBF₄), ([PMMA-EC]-LiCF₃SO₃), and ([PMMA-EC]-LiBF₄) systems is 3.97 × 10⁻⁶, 3.66 × 10⁻⁷, 3.40 × 10⁻⁵, and 4.07 × 10⁻⁷ S cm⁻¹, respectively. The increase in conductivity is due to the increase in number of mobile ions, and decrease in conductivity is attributed to ion association. The increase and decrease in the number of ions can be implied from the dielectric constant, ɛ_r-frequency plots. The conductivity–temperature studies are carried out in the temperature range between 303 and 373 K. The results show that the conductivity is increased when the temperature is increased and obeys Arrhenius rule. The plots of loss tangent against temperature at a fixed frequency have showed a peak at 333 K for the ([PMMA-EC]-LiBF₄) system and a peak at 363 K for the ([PMM-EC]-LiCF₃SO₃) system. This peak could be attributed to β-relaxation, as the measurements were not carried out up to glass transition temperature, T _g. It may be inferred that the plasticizer EC has dissociated more LiCF₃SO₃ than LiBF₄ and shifted the loss tangent peak to a higher temperature. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006     

Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries

To improve the cycle performance of spinel LiMn₂O₄ as the cathode of 4-V-class lithium secondary batteries, spinel phases LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) were successfully prepared using the sol–gel method. The spinel materials were characterized by powder X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. Electrochemical studies were carried out using the Li|LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) cells. These cathodes were more tolerant to repeated lithium extraction and insertion than a standard LiMn₂O₄ spinel electrode in spite of a small reduction in the initial capacity. The improvement in cycling performance is attributed to the stabilization in the spinel structure by the doped metal cations.     

The production of nickel–alumina composite coating via electroplating

A series of electroplating works have been conducted to investigate the best condition for the coelectrodeposition of nickel–alumina (Ni/α–Al₂O₃) composite coating. Co-electrodeposition was done onto mild steel as cathode at ambient temperature (27°C) with current density of 30 mA/cm² under α-Al₂O₃ concentration of 2 g/l and various agitation speeds of 50, 100, 150, 200, and 250 rpms. The cross-section of the composite coatings portrayed α-Al₂O₃ particles was co-deposited. Under field emission scanning electron microscopy analysis, the coating shows a coarse surface morphology, while cross-sectional microstructures shows a compact embedding of α-Al₂O₃ particle in the Ni matrix. Elemental analysis by EDX detected the presence of Ni and α-Al₂O₃. Vickers microhardness testing shows that the coating hardness increases almost 60% at the highest agitation speed, i.e., 250 rpm.     

Structural and electrical properties of pure and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> doped (PVA)<Subscript>0.7</Subscript>(NaI)<Subscript>0.3</Subscript> solid polymer electrolyte

Solid polymer electrolytes (SPE) based on poly-(vinyl alcohol) (PVA)_0.7 and sodium iodide (NaI)_0.3 complexed with sulfuric acid (SA) at different concentrations were prepared using solution casting technique. The structural properties of these electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD data revealed that sulfuric acid disrupt the semi-crystalline nature of (PVA)_0.7(NaI)_0.3 and convert it into an amorphous phase. The proton conductivity and impedance of the electrolyte were studied with changing sulfuric acid concentration from 0 to 5.1 mol/liter (M). The highest conductivity of (PVA)_0.7(NaI)_0.3 matrix at room temperature was 10⁻⁵ S cm⁻¹ and this increased to 10⁻³ S cm⁻¹ with doping by 5.1 M sulfuric acid. The electrical conductivity (σ) and dielectric permittivity (ε′) of the solid polymer electrolyte in frequency range (500 Hz–1 MHz) and temperature range (300–400) K were carried out. The electrolyte with the highest electrical conductivity was used in the fabrication of a sodium battery with the configuration Na/SPE/MnO₂. The fabricated cells give open circuit voltage of 3.34 V and have an internal resistance of 4.5 kΩ.     

Low voltage operating OFETs based on solution-processed metal phthalocyanines

The class of sodium salts of sulphonated metal phthalocyanines (MePCS _x , S = SO₃Na, x=1–4) was investigated as a p-type channel component in organic field-effect transistors (OFETs). The solubility of these materials appears to be enhanced compared to their non-sulphonated counterparts (MePCs). We fabricated transistors based on MePCS _x varying the central metal atom (Me = Ni, Co, Zn, Al) and we evaluated the dependence of transistor performance on the nature of the central atom and the degree of sulphonation. The best results were obtained in the case of Ni and low sulphur content. In this case the mobility value is μ=1.08 cm² V⁻¹ s⁻¹ and the on/off current ratio ∼10³. The degree of sulphonation affects the electric field inside the active film in a way analogous to the case of polyelectrolyte-gated OFETs. The Na⁺ counter ions present in the channel contribute to the device characteristics but their concentration should be controlled in order to optimize device performance.     

Physicochemical properties of LiAl x Mn2 − x O4 and LiAl0.05Mn1.95O4 − y F y cathode material by the citric acid-assisted sol–gel method

LiAl _x Mn_2 − x O₄ and LiAl_0.05Mn_1.95O_4 − y F _y spinel have been successfully synthesized by citric acid-assisted sol–gel method. The structure and physicochemical properties of this as-prepared powder were investigated by electronic conductivity test, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge test in detail. The electronic conductivity decreases with increasing of the content of doped Al. XRD patterns show that the diffraction of LiAl_0.05Mn_1.95O_4 − y F _y samples is similar, with all the peaks indexable in the Fd3m space group, and a little impurity appears in the LiAl_0.05Mn_1.95O_3.8F_0.2 sample. SEM reveals that all LiAl_0.05Mn_1.95O_4 − y F _y powders have the uniform, nearly cubic structure morphology with narrow size distribution which is less than 500 nm. Galvanostatic charge–discharge test indicates that LiAl_0.05Mn_1.95O₄ has the highest discharge capacity and electrochemical performance among all LiAl _x Mn_2 − x O₄ samples after 50 cycles, and the initial discharge capacity of LiAl_0.05Mn_1.95O_4 − y F _y (y = 0, 0.02, 0.05, 0.1) is 123.9, 124.6, 124.9, and 125.0 mAh g⁻¹, respectively, and their capacity retention ratios are 94.2%, 94.9%, 91.7%, and 89.9% after 50 cycles, respectively. EIS indicates that LiAl_0.05Mn_1.95O_3.98F_0.02 have smaller charge transfer resistance than that of LiAl_0.05Mn_1.95O₄ corresponding to the extraction of Li⁺ ions.     

A novel anode-supported stable BaCe0.7Ta0.1Y0.2O3− δ membrane prepared by all-solid-state process for solid oxide fuel cells

BaCe_0.7Ta_0.1Y_0.2O_{3− δ} (BCTY) and BaCe_0.8Y_0.2O_{3− δ} (BCY) were synthesized by solid-state reaction method at 1,300 °C for 20 h. After being exposed in 3% CO₂ + 3% H₂O + 94% N₂ at 700 °C for 20 h, the BCTY exhibited adequate chemical stability against carbonations while BCY decomposed into BaCO₃ and CeO₂. The BCTY showed the similar thermal expansion behavior to BCY from room temperature to 1,000 °C in air. The BCTY displayed a conductivity of 0.007 S/cm at 700 °C in humid hydrogen, lower than that of BCY (0.009 S/cm). A fuel cell with 10-μm thick BCTY membrane prepared through an all-solid-state process exhibited 1.004 V for OCV, 330 mW/cm² for maximum output at 700 °C, respectively. Short-term test shows that the fuel cell performance does not degrade after 20 h.     

Studies on the Fluorescence Fiber-Optic DNA Biosensor Using <Emphasis Type="Italic">p</Emphasis>-Hydroxyphenylimidazo[f]1,10-phenanthroline Ferrum(III) as Indicator

A complex Fe(phen)₂·PHPIP·3ClO₄·2H₂O, where phen = 1,10-phenanthroline and PHPIP = p-hydroxyphenylimidazo[f]1,10-phenanthroline, was synthesized and acted as a good fluorescence indicator based on its interaction with double-duplex DNA. Then a fiber-optic DNA biosensor of fluorimetric detection was developed based on the recognition of target DNA in DNA hybridization assays. A probe ssDNA was covalently immobilized onto the surface of quartz optical fibers and then the probe ssDNA hybridized with complementary ssDNA introduced into the local environment of the sensor. The hybridization with complementary strands was monitored in real time by fluorimetric detection. Several factors affecting the probe immobilization, target DNA hybridization, and indicator binding reactions were optimized to maximize the sensitivity and shorten the assay time. Using this method, a sequence of the 16-mer oligonucleotides could be quantified over the range from 4.98 × 10⁻⁷ to 4.88 × 10⁻⁶ M and a detection limit of 1.08 × 10⁻⁷ M. And the designed optic-fiber biosensor could be conveniently regenerated by thermal denature. The utility of the novel hybridization indicator could provide a simple, rapid, low toxicity and reusable detection.     

Impedance and FTIR studies on plasticized PMMA–LiN(CF<Subscript>3</Subscript>SO<Subscript>2</Subscript>)<Subscript>2</Subscript> nanocomposite polymer electrolytes

Plasticized polymer electrolytes composed of poly(methyl methacrylate) (PMMA) as the host polymer and lithium bis(trifluoromethanesulfonyl)imide LiN(CF₃SO₂)₂ as a salt were prepared by solution casting technique at different ratios. The ionic conductivity varied slightly and exhibited a maximum value of 3.65 × 10⁻⁵ S cm⁻¹ at 85% PMMA and 15% LiN(CF₃SO₂)₂. The complexation effect of salt was investigated using FTIR. It showed some simple overlapping and shift in peaks between PMMA and LiN(CF₃SO₂)₂ salt in the polymer electrolyte. Ethylene carbonate (EC) and propylene carbonate (PC) were added to the PMMA–LiN(CF₃SO₂)₂ polymer electrolyte as plasticizer to enhance the conductivity. The highest conductivities obtained were 1.28 × 10⁻⁴ S cm⁻¹ and 2.00 × 10⁻⁴ S cm⁻¹ for EC and PC mixture system, respectively. In addition, to improve the handling of films, 1% to 5% fumed silica was added to the PMMA–LiN(CF₃SO₂)₂–EC–PC solid polymer electrolyte which showed a maximum value at 6.11 × 10⁻⁵ S cm⁻¹ for 2% SiO₂.     

In situ FTIR study of oxygen adsorption on nanostructured RuO2 thin-film electrode

In situ Fourier transform spectroscopy (FTIR) was used to study interactions of nanostructured ruthenium oxide (RuO₂) thin-film sensing electrode with O₂ at room temperature. RuO₂ nanostructures were pretreated at 1,000 °C for 1 h in order to obtain good crystallinity of amorphous RuO₂ nanoparticles. Morphology and properties of nanostructured RuO₂ were characterized by X-ray diffraction, thermo-gravimetric/differential thermal analysis, scanning electron microscopy, and FTIR. It was shown that pretreated RuO₂ is quite active for O₂ ⁻, O₂ ²⁻, and O²⁻ adsorption with clear 722 cm⁻¹ band for superoxide ions (O₂ ⁻) adsorption for the different oxygen concentrations. The results of in situ FTIR measurements revealed that the active sites for oxygen adsorption are not limited to the triple boundaries, but extended to surfaces of RuO₂ electrodes. Fundamental vibration frequencies of ruthenium–oxygen bond at a temperature of 23 °C as well as region above fundamental frequencies for the nanostructured RuO₂ were identified.     

Li4Ti2.5Cr2.5O12 as anode material for lithium battery

Chromium-substituted Li₄Ti₅O₁₂ has been investigated as a negative electrode for future lithium batteries. It has been synthesized by a solid-state method followed by quenching leading to a micron-sized material. The minimum formation temperature of Li₄Ti_2.5Cr_2.5O₁₂ was found to be around 600 °C using thermogravimetric and differential thermal analysis. X-ray diffraction, scanning electron microscopy, cyclic voltammetry (CV), impedance spectroscopy, and charge–discharge cycling were used to evaluate the synthesized Li₄Ti_2.5Cr_2.5O₁₂. The particle size of the powder was around 2–4 μm. CV studies reveal a shift in the deintercalation potential by about 40 mV, i.e., from 1.54 V for Li₄Ti₅O₁₂ to 1.5 V for Li₄Ti_2.5Cr_2.5O₁₂. High-rate cyclability was exhibited by Li₄Ti_2.5Cr_2.5O₁₂ (up to 5  C) compared to the parent compound. The conduction mechanism of the compound was examined in terms of the dielectric constant and dissipation factor. The relaxation time has been evaluated and was found to be 0.07 ms. The mobility was found to be 5.133 × 10⁻⁶ cm² V⁻¹ s⁻¹.     

Structural,thermal and ion transport studies on nanocomposite polymer electrolyte-{(PEO + SiO<Subscript>2</Subscript>):NH<Subscript>4</Subscript>SCN} system

Development and characterisation of polyethylene oxide (PEO)-based nanocomposite polymer electrolytes comprising of (PEO-SiO₂): NH₄SCN is reported. For synthesis of the said electrolyte, polyethylene oxide has been taken as polymer host and NH₄SCN as an ionic charge supplier. Sol–gel-derived silica powder of nano dimension has been used as ceramic filler for development of nanocomposite electrolytes. The maximum conductivity of electrolyte ∼2.0 × 10⁻⁶ S/cm is observed for samples containing 30 wt.% silica. The temperature dependence of conductivity seems to follow an Arrhenius-type, thermally activated process over a limited temperature range.     

Low thermal expansion behavior and transport properties of Ni and Ge co-doped manganese nitride materials at cryogenic temperatures

A series of Ni and Ge co-doped manganese nitride materials were fabricated by mechanical ball milling followed by solid-state sintering. Their thermal expansion properties and electrical and thermal conductivities were investigated in the temperature range of 77–300 K. The results show that Ni and Ge co-doped manganese nitride materials have negative thermal expansion (NTE), and the operation-temperature window of NTE shifts toward the lower temperature region and the variation of linear thermal expansion (ΔL/L _(300K)) in the operation-temperature window of NTE decreases with increasing Ni content. The combination of these two factors results in a low coefficient of thermal expansion (CTE) at cryogenic temperatures. The average CTE of Mn₃(Cu_0.2Ni_0.4Ge_0.4)N drops to ‘zero’ in the temperature range of 190–77 K. The values of electrical and thermal conductivities of the Ni and Ge co-doped manganese nitride materials are in the ranges of 2–3×10³ (ohm cm)⁻¹ and 1.6–3.4 W (m K)⁻¹, respectively.     

Grafted natural rubber-based polymer electrolytes: ATR-FTIR and conductivity studies

Attenuated total reflectance–Fourier transformed infrared spectroscopy measurement is employed to study the interactions between the components of 30% methyl-grafted natural rubber (MG30), lithium trifluromethanesulfonate (LiCF₃SO₃ or LiTF), and propylene carbonate (PC). Vibrational spectra data of LiTF reveals that the ν_s(SO₃) at 1,045 cm⁻¹, δ_s(CF₃) at 777 cm⁻¹, and C=O stretching mode at 1,728 cm⁻¹ for MG30 have shifted to lower wave numbers in MG30–LiTF complexes indicating that complexation has occurred between MG30 and LiTF. The solvation of lithium ion is manifested in Li⁺ ← O=C interaction as shown by the downshifting and upshifting of C=O mode at 1,788 to 1,775 cm⁻¹ and ν_as(SO₃) at 1,250 to 1258 cm⁻¹, respectively, in LiTF–PC electrolytes. There is no experimental evidence of the interaction between MG30 and PC. Competition between MG30 and PC on associating with lithium ion is studied, and the studies show that the interaction between MG30–LiTF is stronger than that of the PC–LiTF in plasticized polymer–salt complexes. The effect of PC on the ionic conductivity of the MG30–LiTF system is explained in terms of the polymer, plasticizer, and salt interactions. The temperature dependence of conductivity of the polymer films obeys the Vogel–Tamman–Fulcher relation. Values of conductivity and activation energy of the MG30-based polymer electrolyte systems are presented and discussed.     

Highly improved electroluminescence from double-layer devices based on a carbazole-functionalized europium<Superscript>3+</Superscript> complex

A novel europium complex Eu(TTA)₃(CPPO)₂ (1) (TTA=thenoyltrifluoroacetone, CPPO=9-[4-(diphenyl-phosphinoyl)-phenyl]-9H-carbazole) based on the phosphine oxide ligand with bipolar structure was used to fabricate double-layer devices. The strong hole injection and transport ability of 1 was proved. The luminance of 414 cd m⁻² was achieved with the device configuration ITO/Eu(TTA)₃(CPPO)₂(40 nm)/BCP (30 nm)/Mg:Ag (BCP = 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline), which is favorable among double-layer organic light emitting devices based on small molecular Eu³⁺ complexes. The maximum current efficiency of 2.44 cd A⁻¹ and external quantum efficiency of 1.55% demonstrate the potential application of 1 as a promising candidate for high-efficiency, simple-structure and pure red-emitting devices.     

Gelatin-based protonic electrolyte for electrochromic windows

Proton-conducting gel polymer electrolytes based on gelatin plasticized with glycerol and containing acetic acid were investigated, characterized, and applied to electrochromic window. For glycerol contents varying from 7% to 48%, the conductivity of the uniform and predominantly amorphous gel electrolyte was found to follow a Vogel–Tamman–Fulcher behavior with the temperature. Typically, for the electrolyte chosen to make 7 × 2 cm² electrochromic smart window with the configuration: glass/fluor-doped tin oxide (FTO)/WO₃/gelatin electrolyte/CeO₂–TiO₂/FTO/glass and containing 28% of glycerol, the conductivities were found to be of the order of 5 × 10⁻⁵ S/cm at room temperature and 3.6 × 10⁻⁴ S/cm at 80 °C. The device was characterized by spectroelectrochemical techniques and was tested up to 10,000 cycles showing a fast coloring/bleaching behavior, where the coloring process was achieved in 10 s and the bleaching in 2 s. The transmission variation at the wavelength of 550 nm was about 15%. The cyclic voltammograms showed a very good reversibility of the cathodic/anodic processes, and the charge density was about 3.5 mC/cm². The memory tests showed that the transmittance in the colored state increased by 8% in 90 min after removing the potential.     

Surface chemistry and catalytic activity of Ni/Al2O3 irradiated with high-energy electron beam

The radiation effects induced effects by electron beam (EB) treatment on the catalytic activity of Ni/γ-Al₂O₃ were studied for the carbon dioxide reforming of methane with different EB energy and absorbed radiation dose. Transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to determine the change in structure and surface states of Ni/γ-Al₂O₃ catalyst before and after the EB treatment. Higher energy EB treatment is useful for increasing the proportion of the active sites (such as Ni⁰ and NiAl₂O₄-phase) on the surface. The increase of Ni/Al-ratio indicates that the Ni dispersion on the surface increased with the EB-treatment, resulting in an increase of the active sites, which leads to improving the catalytic activity. XPS measurement also showed a decrease of the surface carbon with EB dose. The maximum 20% increase in the conversion of CO₂/CH₄-mixture into CO/H₂ gas was observed for the catalyst treated with 2 MeV energy and 600 kGy dose of EB relative to untreated.