Effects of cathode fabrication conditions and cycling on the electrochemical performance of LiNiO2 synthesized by combustion and calcination

LiNiO₂ was synthesized by the combustion method with various excess lithium amount z in Li_1 + zNiO₂ (z = 0.04, 0.08, 0.10, 0.12, and 0.15). The sample with z = 0.10 has the largest first discharge capacity of 195 mAh/g at 0.1 C rate and voltage range 2.7-4.4 V with the weight ratio of active material:acetylene black:binder = 85:10:5. The LiNiO₂ cathodes, in which the excess lithium amount z for the synthesis of LiNiO₂ was 0.10, were fabricated with various weight ratios of active material:acetylene black:binder (85:10:5, 85:12:3, and 90:7:3). The cathode with the ratio of active material:acetylene black:binder 85:10:5 has the best electrochemical properties. The variation, with C-rate, of discharge capacity vs. number of cycles curve for the LiNiO₂ cathode with the weight ratio of active material:acetylene black:binder = 85:10:5 was investigated. At 0.1 C rate, the LiNiO₂ cathode has the largest first discharge capacity, the discharge capacity degradation rate of 0.70 mAh/g/cycle and a discharge capacity at n = 50 of 134 mAh/g.     

Effects of Zn or Ti substitution for Ni on the electrochemical properties of LiNiO2

LiNiO₂ and LiNi_1−yM_yO₂ (M = Zn and Ti, y = 0.005, 0.01, 0.025, 0.05, and 0.1) were synthesized with a solid-state reaction method by calcination at 750 °C for 30 h under oxygen stream after preheating at 450 °C for 5 h in air. LiNi_0.995Zn_0.005O₂ among the Zn-substituted samples and LiNi_0.995Ti_0.005O₂ among the Ti-substituted samples showed the best electrochemical properties. For similar values of y, LiNi_1−yTi_yO₂ had in general better electrochemical properties than LiNi_1−yZn_yO₂. Electrochemical properties seem to be closely related to R-factor but less related to I_0 0 3/I_1 0 4 value. In the FT-IR absorption spectra of LiNiO₂ and LiNi_1−yM_yO₂ (M = Zn and Ti, y = 0.005, 0.01, 0.025, 0.05 and 0.1), Li₂CO₃ was detected even if it is not observed from XRD pattern, with the samples LiNi_1−yZn_yO₂ (y = 0.05 and 0.1) showing Li₂ZnO₂ additionally. The smaller cation mixing of the Ti-substituted samples is considered to lead to their better electrochemical properties than the Zn-substituted samples.     

An electromechanical perspective on the metal/solution interfacial region during the metallic zinc electrodeposition

The difficulty of studying the metal/solution interfacial region makes the use of non-conventional measurement techniques indispensable. In this way, a careful in situ study by means of acoustic impedance techniques coupled with nano-electrogravimetric techniques allowed this interface to be monitored during the metallic zinc electrodeposition process. This paper proves the formation of a viscoelastic layer consisting of ultra-hydrated Zn(II)/Zn(I) salts as a key step in the metallic zinc electrodeposition mechanism in sulfate aqueous solutions. Surprisingly, this layer is located in the metal/solution interfacial region and not on the reaction substrate. The chloride ions effect on the metallic zinc electrodeposition mechanism at these experimental conditions lies mainly in the stabilization of the zinc ions inside this layer.     

Metal-carbonate formation from ammonia solution by addition of metal salts—An effective method for CO2 capture from landfill gas (LFG)

The absorption of CO₂ from LFG in different weight concentration ammonia solution and metal salts (Zinc and Barium) is investigated in this study. Addition of metal salts results in useful metal carbonates when LFG is passed through the solution. Barium salts show a better potential of removing CO₂ as compared to Zinc salts. Addition of Barium salts to ammonia solution results in a new absorbent as no study has been focused on it till date. Also metal salts are added to alkaline wastewater which not only decreases the pH of the wastewater but also useful metal carbonates are obtained from wastewater when LFG is passed through it. Different parameters like CO₂ loading, reaction rate and change in pH are investigated. Formation of carbonates is proved by using SEM and XRD analysis. Raman spectroscopy was performed on the discarded liquid after removal of carbonates to understand the formation of bicarbonates, carbonates and carbamates.     

Effect of Pt addition on the isomerization properties of MoO2 − x(OH)y deposited on TiO2

Isomerization of n-hexane and n-pentane were studied using equivalent 5 monolayers of MoO₃ deposited on TiO₂. Addition of 2.5% Pt by weight of MoO₃ on the Mo catalyst resulted in an increase in the catalytic activity of the system in favor of hydrocracking products. Surface characterization by XPS-UPS and ISS reveal that the sample surface contains Oxygen, Molybdenum, Platinum and Titanium. Apparently, the metallic properties of the deposited Pt favors the hydrocracking reactions and becomes dominant at reaction temperatures higher than 623 K. Balanced metal-acid functions in MoO_2 − x(OH)_y phase seems to be in optimized condition toward the hydroisomerization process. The contribution of Platinum addition to this catalytic reaction is not obvious. Combination of surface XPS-UPS, ISS and catalytic reactions carried out at similar experimental conditions enabled us to have better insight concerning the catalytic activities of the different chemical species present on the sample surface.     

Segmented copolymers with monodisperse crystallizable hard segments: Novel semi-crystalline materials

Segmented block copolymers with short monodisperse crystallizable hard segments have interesting structures and properties. In the melt, such short monodisperse segments are miscible with the matrix segments. Moreover, upon cooling, they crystallize fast, demonstrating a very high crystallinity, and only a small crystallization window is needed. The melting temperature of the short segments is high, provided that they can H-bond and/or contain aromatic groups. The melting temperature was found to decrease with increasing matrix segment concentration, due to the solvent effect of the matrix segments. At concentrations of crystallizable segment of 4-35 wt%, good dimensional and solvent stabilities were obtained.The monodisperse segments crystallized into nano-ribbons with uniform thickness and high aspect ratio, and these dispersed nano-ribbon crystallites constituted physical crosslinks, while acting also as reinforcing fillers. At concentrations of the monodisperse segments below 20 wt% no spherulitic ordering took place, and the semi-crystalline polymers were transparent. The monodisperse crystallizable segments can be used in combination with matrix segments of either low or high glass transition temperature, and may even contain (bio)functional units.     

Synthesis and characterization of ZnxMg1 − xGa2O4:Co fabricated by low-temperature burning method

A series of Zn_xMg_1 − xGa₂O₄:Co²⁺ spinels (x = 0, 0.25, 0.5, 0.75, and 1.0) was successfully produced through low-temperature burning method by using Mg(NO₃)₂·4H₂O, Zn(NO₃)₂·6H₂O, Ga(NO₃)₃·6H₂O, CO(NH₂)₂, NH₄NO₃, and Co(NO₃)₂·6H₂O as raw materials. The product was characterized by X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The product was not merely a simple mixture of MgGa₂O₄ and ZnGa₂O₄; rather, it formed a solid solution. The lattice constant of Zn_xMg_1 − xGa₂O₄:Co²⁺ (0 ≤ x ≤ 1.0) crystals has a good linear relationship with the doping density, x. The synthesized products have high crystallinities with neat arrays. Based on an analysis of the form and position of the emission spectrum, the strong emission peak around the visible region (670 nm) can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴A₂(⁴F)] of Co²⁺ in the tetrahedron. The weak emission peak in the near-infrared region can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴T₂(⁴F)] of Co²⁺ in the tetrahedron.     

Evaluation of embeddable potential sensor for corrosion monitoring in concrete structures

Embeddable potential sensor based on MnO₂ was assembled and characterised in concrete. The stability, reversibility, polarisability and impedance characteristics have been studied with respect to known reference. The corrosion performance of reinforced steel with respect to MnO₂ sensor was monitored by different electrochemical techniques. Reversibility of MnO₂ sensor indicated that difference of ±5 mV between the forward and reverse scan indicates the better reversibility characteristics in concrete. The rebar potentials (E_R) of steel with respect to MnO₂ are −315 and −525 mV for passive and active conditions of rebar in concrete. The corrosion current from potentiodynamic polarisation and R_ct from a.c. impedance technique clearly differentiated the behaviour of steel embedded in chloride contaminated concrete (active condition) from uncontaminated concrete (passive condition) with respect to MnO₂ sensor. All these studies revealed that corrosion monitoring of steel in concrete using embedded MnO₂ as a better potential sensor for steel in concrete. In addition it is easy to fabricate for amenable miniaturisation, varied configuration as demanded for corrosion monitoring in concrete structures.     

Adsorptive crystallization of benzoic acid in aerogels from supercritical solutions

In this work, adsorption and crystallization of benzoic acid in different porous carriers (silica aerogel, MCM41, Trisopor glass, zeolite) from supercritical CO₂ solutions is studied. The main purpose is to reveal the influence of the adsorptive properties of the carrier on the crystallization behavior of the solute. Therefore, both adsorption and crystallization processes are studied as a function of carrier's surface properties. Adsorption of the solute and CO₂ is measured in situ using a magnetic suspension balance, whereas crystallization is realized in a high pressure view cell. The carriers could be loaded with up to ∼35 wt.% of benzoic acid, depending on the nature and the amount of the functional groups of the carrier. The size of the benzoic acid particles obtained inside the aerogel matrix depends on the crystallization conditions and is in the range of ∼20 nm-50 μm. The crystallinity of the particles was studied and it is shown that the physical state of the loaded benzoic acid inside the pores of aerogels is influenced by benzoic acid-aerogel surface interactions: strong interactions favor the amorphous form, weak interactions favor crystalline particles. The amorphous form of benzoic acid is shown to be stable over a long time period. Thus, silica aerogels can be used for stabilizing amorphous forms of organic compounds, which can be used for instance in pharmaceutical applications for the improvement of drug bioavailability.     

Zingerone Modulates Neuronal Voltage-Gated Na+ and L-Type Ca2+ Currents

Zingerone (ZO), a nontoxic methoxyphenol, has been demonstrated to exert various important biological effects. However, its action on varying types of ionic currents and how they concert in neuronal cells remain incompletely understood. With the aid of patch clamp technology, we investigated the effects of ZO on the amplitude, gating, and hysteresis of plasmalemmal ionic currents from both pituitary tumor (GH₃) cells and hippocampal (mHippoE-14) neurons. The exposure of the GH₃ cells to ZO differentially diminished the peak and late components of the I_Na. Using a double ramp pulse, the amplitude of the I_Na(P) was measured, and the appearance of a hysteresis loop was observed. Moreover, ZO reversed the tefluthrin-mediated augmentation of the hysteretic strength of the I_Na(P) and led to a reduction in the I_Ca,L. As a double ramp pulse was applied, two types of voltage-dependent hysteresis loops were identified in the I_Ca,L, and the replacement with BaCl₂-attenuated hysteresis of the I_Ca,L enhanced the I_Ca,L amplitude along with the current amplitude (i.e., the I_Ba). The hysteretic magnitude of the I_Ca,L activated by the double pulse was attenuated by ZO. The peak and late I_Na in the hippocampal mHippoE-14 neurons was also differentially inhibited by ZO. In addition to acting on the production of reactive oxygen species, ZO produced effects on multiple ionic currents demonstrated herein that, considered together, may significantly impact the functional activities of neuronal cells.     

Carbon monoxide oxidation and nitrous oxide reduction on Rh/Pt(1 1 1) electrodes

Rhodium adlayers on Pt(1 1 1) substrates have been prepared by electrodeposition from dilute Rh³⁺ acidic solutions. Resulting deposition rates are lower than 0.03 ML min⁻¹. Pseudomorphic growth of the first monolayer has been confirmed by scanning tunneling microscopy (STM) as well as the formation of small compact islands in the submonolayer range. Carbon monoxide oxidation and nitrous oxide reduction have been studied on Rh/Pt(1 1 1) electrodes. The oxidation of carbon monoxide is catalyzed by the presence of very low coverages of rhodium as demonstrated by the negative shift of the CO oxidation profile. Results are compatible with a bifunctional mechanism for catalysis including CO diffusion in the Pt domains toward the edges of the islands (splitting of the voltammetric oxidation profile). The reduction of nitrous oxide occurs at different potential and with different rates on Pt domains, at the center of the Rh islands and at their edges, being the latter sites especially active. In any case, the adsorptive and catalytic activity of the adlayers differ from those of the bulk Pt(1 1 1) and Rh(1 1 1) electrodes. The existence of strain in the film together with a diminution in the coordination number for adatoms at the edges of the islands are considered to be at the origin of the observed behavior.     

In situ diffraction studies of electrode surface structure during gold electrodeposition

Surface X-ray scattering (SXS) in transmission geometry provides a valuable tool for in situ structural studies of electrochemical interfaces under reaction conditions, as illustrated here for homoepitaxial electrodeposition on Au(1 0 0) and Au(1 1 1) electrodes. Employing diffusion-limited deposition conditions to separate the effects of potential and deposition rate, a mutual interaction between the interface structure and the growth behavior is found. Time-dependent SXS measurements during Au(1 0 0) homoepitaxy show with decreasing potential transitions from step flow to layer-by-layer growth, then to multilayer growth, and finally back to layer-by-layer growth. This complex growth behavior can be explained within the framework of kinetic growth theory by the effect of potential, Cl adsorbates and the Au surface structure, specifically the presence of the surface reconstruction, on the Au surface mobility. Conversely, the electrodeposition process influences the structure of the reconstructed Au surface, as illustrated for Au(1 1 1), where a significant deposition-induced compression of the Au surface layer as compared to Au(1 1 1) surfaces under ultrahigh vacuum conditions or in Au-free electrolyte is found. This compression increases towards more negative potentials, which may be explained by a release of potential-induced surface stress.     

Electrodeposition and characterization of Fe80Ga20 alloy films

Due to its high magnetostriction and good mechanical properties Fe₈₀Ga₂₀ is interesting for magnetostrictive microactuators and sensors. Here we use electrodeposition to grow Fe–Ga films onto Au and Pt coated Si substrates by potentiostatic and pulse potential deposition. Composition, microstructure and structure are analysed. The desired composition of Fe₈₀Ga₂₀ was obtained at −1.4 V_SCE and −1.5 V_SCE, respectively. The origin of low reproducibility and high oxygen content up to 50 at.% is investigated. Optimum deposition conditions to achieve dense, homogeneous films with low oxygen content are identified. In these films the saturation magnetization reaches a maximum value of 1.7 T confirming the high quality of electrodeposited films.     

Variation of discharge capacities with C-rate for LiNi1−yMyO2 (M = Ni,Ga, Al and/or Ti) cathodes synthesized by the combustion method

LiNiO₂, LiNi_0.995Al_0.005O₂, LiNi_0.975Ga_0.025O₂, LiNi_0.990Ti_0.010O₂ and LiNi_0.990Al_0.005Ti_0.005O₂ specimens were synthesized by preheating at 400 °C for 30 min in air and calcination at 750 °C for 36 h in an O₂ stream. The variation of the discharge capacities with C-rate for the synthesized samples was investigated. LiNi_0.990Al_0.005Ti_0.005O₂ has the largest first discharge capacities at the 0.1 and 0.2 C rates. LiNi_0.990Ti_0.010O₂ has the largest first discharge capacity at the 0.5 C rate. In case of LiNiO₂ and LiNi_0.990Ti_0.010O₂, the first discharge capacity decreases slowly as the C-rate increases. LiNiO₂ has the largest discharge capacities at n = 10 (after stabilization of the cycling performance) at the 0.1, 0.2 and 0.5 C rates. This is considered to be related with the largest value of I_0 0 3/I_1 0 4 and the smallest value of R-factor (the least degree of cation mixing) among all the samples. LiNi_0.975Ga_0.025O₂ exhibits the lowest discharge capacity degradation rates at 0.1, 0.2 and 0.5 C rates.     

New binary (1 − x)Ba(Lu1/2Nb1/2)O3-xPbTiO3 solid solution with morphotropic phase boundary

A new ferroelectric solid solution of (1 − x)Ba(Lu_1/2Nb_1/2)O₃-xPbTiO₃ (BLN-PT) (0 ≤ x ≤ 1) has been synthesized by solid state reactions. Its structure and electric properties have been studied by X-ray diffraction and di-/ferro-electric measurements. Based on the investigation, a partial solid state phase diagram of the binary BLN-PT ceramics system has been established, which exhibits a morphotropic phase boundary (MPB) region in the composition range of 0.64 ≤ x ≤ 0.68. The Curie temperature is measured to be around 250 °C in the vicinity of the MPB region, which is much higher than that of PMNT or PZNT system. The dielectric behavior has been discussed based on Curie-Weiss Law and Lorentz-type quadratic relationship. With increasing PT content, a transformation from relaxor to ferroelectric phase has been demonstrated in the solid solution system.     

Synthesis and magnetic properties of Cu-doped ZnO nanowire arrays

Arrays of Cu-doped ZnO nanowires were successfully fabricated by electrodeposition of Zn²⁺ and Cu²⁺ into anodic aluminum oxide template and post-oxidation annealing in air atmosphere. The transmission electron microscopy result shows that the nanowires are uniform, about 100 nm in diameter and with the aspect ratio of up to 40. Selected area electron diffraction and X-ray diffraction results indicate that the nanowires are in hexagonal wurtzite structure. Magnetization measurements show that the Zn_1−xCu_xO (x = 0.07 and 0.11) nanowires exhibit room-temperature ferromagnetism and the enhancement of the ferromagnetism is revealed for the Zn_0.93Cu_0.07O nanowires annealed in vacuum.     

Transesterification of palm oil on KyMg1 − xZn1 + xO3 catalyst: Effect of Mg-Zn interaction

The Mg-Zn interaction effect of K_yMg_1 − xZn_1 + xO₃ heterogeneous type catalyst and its performance on transesterification of palm oil have been studied using the response surface methodology and the factorial design of experiments. The catalyst was synthesized using the co-precipitation method and the activity was assessed by transesterification of palm oil into fatty acid methyl esters. The ratio of the Mg/Zn metal interaction, temperature and time of calcination were found to have positive influence on the conversion of palm oil to fatty acid methyl ester (FAME) with the effect of metal to metal ratio and temperature of calcination being more significant. The catalytic activity was found to decrease at higher calcination temperature and the catalyst type K₂Mg_0.34Zn_1.66O₃ with Mg/Zn ratio of 4.81 gave FAME content of 73% at a catalyst loading of 1.404 wt.% of oil with molar ratio of methanol to oil being 6:1 at temperature of 150 °C in 6 h. A regression model was obtained to predict conversions to methyl esters as a function of metal interaction ratio, temperature of calcination and time. The observed activity of the synthesized catalyst was due to its synergetic structure and composition.     

Effect of electrodeposition parameters on the hydrogen permeation during Cu-Sn alloy electrodeposition

The Cu-Sn alloy coatings were synthesized on 27SiMn steel by direct current (DC), pulse current (PC) and pulse reverse current (PRC) electrodeposition techniques from pyrophosphate-based electrolyte. The hydrogen permeation behaviors during the electrodeposition by different techniques were investigated using Devanathan-Stachurski method. The results demonstrated that the hydrogen permeation amount of different electrodeposition techniques decreased in the order: DC > PC > PRC. Frequency and duty cycle have great effect on the sub-surface concentration C_o of atomic hydrogen and hydrogen permeation amount. The minimum of hydrogen permeation amount was observed at the frequency of 1000 Hz or 2500 Hz and the duty cycle of 40%. It indicates that the amount of permeated hydrogen in the steel during deposition can be reduced due to the decrease of C_o by PC and PRC methods.     

Electrical conductivity of samarium-ytterbium zirconate ceramics

(Sm_1 − xYb_x)₂Zr₂O₇ (0 ≤ x ≤ 1.0) ceramic powders were prepared by chemical-coprecipitation and calcination method, and were pressureless-sintered at 1973 K for 10 h to fabricate dense bulk materials. (Sm_1 − xYb_x)₂Zr₂O₇ has a single phase with a pyrochlore or defect fluorite structure, depending mainly upon the Yb content. They are found to be pyrochlores for 0 ≤ x ≤ 0.1, and defect fluorites for 0.3 ≤ x ≤ 1.0. The electrical conductivity of (Sm_1 − xYb_x)₂Zr₂O₇ was investigated by complex impedance spectroscopy over a frequency range of 200 Hz to 20 MHz from 723 to 1173 K in air. The measured electrical conductivity obeys the Arrhenius relation. The grain conductivity of (Sm_1 − xYb_x)₂Zr₂O₇ ceramics gradually increases with increasing temperature. A decrease of about one order of magnitude in grain conductivity is found at all temperature levels when the Yb content increases from x = 0.1 to x = 0.3. The electrical conductivities of defect fluorite-type materials are lower than those of pyrochlore-type materials in (Sm_1 − xYb_x)₂Zr₂O₇ system, whereas activation energies for the conduction process increase monotonically as the structure becomes disordered.