Comparative structural and electrochemical study of high density spherical and non-spherical Ni(OH)2 as cathode materials for Ni-metal hydride batteries

In this paper we compare the behavior of non-spherical and spherical β-Ni(OH)₂ as cathode materials for Ni-MH batteries in an attempt to explore the effect of microstructure and surface properties of β-Ni(OH)₂ on their electrochemical performances. Non-spherical β-Ni(OH)₂ powders with a high-density are synthesized using a simple polyacrylamide (PAM) assisted two-step drying method. X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric/differential thermal analysis (TG-DTA), Brunauer-Emmett-Teller (BET) testing, laser particle size analysis, and tap-density testing are used to characterize the physical properties of the synthesized products. Electrochemical characterization, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and a charge/discharge test, is also performed. The results show that the non-spherical β-Ni(OH)₂ materials exhibit an irregular tabular shape and a dense solid structure, which contains many overlapped sheet nano crystalline grains, and have a high density of structural disorder and a large specific surface area. Compared with the spherical β-Ni(OH)₂, the non-spherical β-Ni(OH)₂ materials have an enhanced discharge capacity, higher discharge potential plateau and superior cycle stability. This performance improvement can be attributable to a higher proton diffusion coefficient (4.26 × 10⁻⁹ cm² s⁻¹), better reaction reversibility, and lower electrochemical impedance of the synthesized material.     

Synthesis and crystal structure analysis of complex hydride Mg(BH4)(NH2)

Complex hydride Mg(BH₄)(NH₂), which consists of double anion BH₄⁻ and NH₂⁻, was synthesized and the crystal structure was analyzed by synchrotron X-ray diffraction. The mixture sample of Mg(BH₄)₂ + Mg(NH₂)₂ prepared by ball milling was reacted and crystallized to Mg(BH₄)(NH₂) by heating at about 453 K. This crystal phase transforms into amorphous phase above 473 K and subsequently the dehydrogenation begins. The crystal structure of Mg(BH₄)(NH₂) was determined from measurement data at 453 K (chemical formula: Mg_0.94(BH₄)₁(NH₂)_0.88, crystal system: tetragonal, space group: I4₁ (No.80), Z = 8, lattice constants: a = 5.814(1), c = 20.450(4) Å at 453 K). Mg(BH₄)(NH₂) is ionic crystal which the cation (Mg²⁺) and the anions (BH₄⁻ and NH₂⁻) are stacking alternately along the c-axis direction. Two BH₄⁻ and two NH₂⁻ tetrahedrally coordinate around Mg²⁺ ion.     

Decreasing the thermal dehydrogenation temperature of methylamine borane (MeAB) by mixing with poly(methyl acrylate) (PMA)

This paper reports on a hydrogen storage material of poly(methyl acrylate) and methylamine borane (PMA/MeAB) composite, which is synthesized by a simple solution-blending process at room temperature. The thermal decomposition process of the as-prepared composite is investigated by temperature programmed desorption/mass spectrometer (TPD/MS), thermogravimetry (TG) measurements and water displacement method. It is found that PMA/MeAB100 (100 mg PMA with 100 mg MeAB) starts to release H₂ at the temperature of 90.5 °C with the dehydrogenation peak centered at 120.7 °C. This is about 20 °C lower than that of neat MeAB. Meanwhile, the evaporation of MeAB and the volatile byproducts from the dehydrogenation stage of PMA/MeAB100 are also suppressed. The present result shows that the dehydrogenation property of MeAB is enhanced by using PMA/MeAB composite.     

The influence of different additives on the solid-state reaction of magnesium hydride (MgH2) with Si

The possibility of increasing the solid-state reaction rate of MgH₂ with Si by modifying the mixture preparation method and adding chemical compounds or elements, such as niobium pentafluoride (NbF₅), nano-titanium (IV) oxide (TiO₂), nano-chromium (III) oxide Cr₂O₃, yttrium, and nano- and microsized nickel, was investigated. The results show that changing the milling parameters of the MgH₂ and Si mixture in a planetary ball mill greatly affects the rate of direct reaction between them and allows the reaction to take place at temperatures as low as 200 °C with an equilibrium pressure over 1 bar. Moreover, all additives significantly enhanced the reaction speed. The reaction pathway was found to be different for decomposition in a hydrogen vacuum and pressures of several bars. Reactions of the powders investigated did not occur at temperatures below 150 °C.     

Evaluation of Bunsen reaction at elevated temperature and high pressure in continuous co-current reactor in iodine-sulfur thermochemical process

Bunsen reaction is one of the three reaction steps of iodine-sulfur process. In present study, Bunsen reaction is carried out in co-current reactor to identify effect of different operating conditions on concentrations of Bunsen reaction product mixture. Bunsen reaction studies have been done in tubular reactor, which is made of tantalum tube and stainless steel jacket, in 50–80 °C temperature range, 2–6 bar (g) pressure range. Feed flow rates are varied for HIx (mixture of hydroiodic acid, water and iodine) 1.2 l/h - 3 l/h, SO₂ 0.02 g/s – 0.24 g/s and O₂ 0.008 g/s ?0.016 g/s. It has been observed that, increasing SO₂ feed flow rate and pressure results in increased mole fraction of HI in HIx phase and H₂SO₄ in sulfuric acid phase. Increase in temperature increased the mole fraction of HI in HIx phase but decreased the mole fraction of H₂SO₄ in sulfuric acid phase. Increase in feed I₂/H₂O ratio and HIx feed flow rate, decreased the mole fraction of HI in HIx phase. Higher pressure improved the conversion of Bunsen reactants to products.     

Texture/phase evolution during microwave fabrication of nanocrystalline multicomponent (Cu/Zn/Al)O metal oxides with varying diethylene glycol content applied in hydrogen production

A series of Cu/Zn/Al mixed oxides, as steam methanol reforming catalysts, were synthesized via the microwave assisted combustion synthesis method using diethylene glycol as the organic fuel. The nanocatalysts were analyzed by XRD, FESEM, EDX, BET, H₂-TPR and FTIR techniques to ensure authenticity of the synthesis steps and pursuing the effect of the fuel/nitrate ratio on their physicochemical properties. The results proved the necessity of defining an optimum fuel/nitrate ratio for the combustion synthesis method. Fuel/nitrate ratio affects significantly on crystal growth and crystalline facets size. Proper crystallography of CuO/ZnO/Al₂O₃ (DEG/Nitrate = 3) nanocatalyst along with higher specific surface area and distributed particle size, made it predictable that it could result in higher methanol conversion in the steam methanol reforming process. The catalytic performance studies justified assumptions, since the CZA (DEG/N = 3) presented higher methanol conversion and selectivity toward desired products as well as its high stability.     

Insights into the reaction mechanisms of methanol decomposition,methanol oxidation and steam reforming of methanol on Cu(111): A density functional theory study

Cu-based catalysts have been widely used for hydrogen production from methanol decomposition, methanol oxidation and steam reforming of methanol (MSR). In this study, we have systematically identified possible reaction paths for the thermodynamics and dynamics involved in the three reactions on a Cu(111) surface at the molecular level. We find that the reaction paths of the three reactions are the same at the beginning, where methanol scission is favourable involving O–H bond scission followed by sequential dehydrogenation to formaldehyde. Formaldehyde is an important intermediate in the three reactions, where direct dehydrogenation of formaldehyde to CO is favourable for methanol decomposition; for methanol oxidation, formaldehyde tends to react with oxygen to form dioxymethylene through C–H bond breaking and finally the end products are mainly CO₂ and hydrogen; for MSR, formaldehyde tends to react with hydroxyl to form hydroxymethoxy through formic acid and formate formation, followed by dissociation to CO₂. CH₂O formation from methoxy dehydrogenation is considered to be the rate-limiting step for the three reactions. In general, the thermodynamic and kinetic preference of the three reactions shows the order methanol oxidation > MSR > methanol decomposition. Methanol oxidation and MSR are faster than methanol decomposition by about 500 and 85 times at typical catalytic conditions (e.g., 523 K), respectively. The result may be useful for computational design and optimization of Cu-based catalysts.     

Activity,stability and deactivation behavior of Au/CeO2 catalysts in the water gas shift reaction at increased reaction temperature (300 °C)

The effect of increasing the reaction temperature to 300 °C on the activity, stability and deactivation behavior of a 4.5 wt.% Au/CeO₂ catalyst in the water gas shift (WGS) reaction in idealized reformate was studied by kinetic and spectroscopic measurements at 300 °C and comparison with previously reported data for reaction at 180 °C under similar reaction conditions [A. Karpenko, Y. Denkwitz, V. Plzak, J. Cai, R. Leppelt, B. Schumacher, R.J. Behm, Catal. Lett. 116 (2007) 105]. Different procedures for catalyst pretreatment were used, including annealing at 400 °C in oxidative, reductive or inert atmospheres as well as redox processing. The formation/removal of stable adsorbed reaction intermediates and side products (surface carbonates, formates, OH_ad, CO_ad) was followed by in situ IR spectroscopy (DRIFTS), the presence of differently oxidized surface species (Au⁰, Au^0′, Au³⁺, Ce³⁺) was evaluated by XPS. The reaction characteristics at 300 °C generally resemble those at 180 °C, including (i) significantly higher reaction rates, (ii) comparable apparent activation energies (44 ± 1/50 ± 1 kJ mol⁻¹ vs. 40 ± 1 kJ mol⁻¹ at 180 °C), (iii) a correlation between deactivation of the catalyst and the build-up of stable surface carbonates, and (iv) a decrease of the initially significant differences in activity after different pretreatment procedures with reaction time. Different than expected, the tendency for deactivation did not decrease with higher temperature, due to enhanced carbonate decomposition, but increases.     

Numerical modeling and investigation of gas crossover effects in high temperature proton exchange membrane (PEM) fuel cells

A gas crossover model is developed for a high temperature proton exchange membrane fuel cell (HT-PEMFC) with a phosphoric acid-doped polybenzimidazole membrane. The model considers dissolution of reactants into electrolyte phase in the catalyst layers and subsequent crossover of reactant gases through the membrane. Furthermore, the model accounts for a mixed potential on the cathode side resulting from hydrogen crossover and hydrogen/oxygen catalytic combustion on the anode side due to oxygen crossover, which were overlooked in the HT-PEMFC modeling works in the literature. Numerical simulations are carried out to investigate the effects of gas crossover on HT-PEMFC performance by varying three critical parameters, i.e. operating current density, operating temperature and gas crossover diffusivity to approximate the membrane degradation. The numerical results indicate that the effect of gas crossover on HT-PEMFC performance is insignificant in a fresh membrane. However, as the membrane is degraded and hence gas crossover diffusivities are raised, the model predicts non-uniform reactant and current density distributions as well as lower cell performance. In addition, the thermal analysis demonstrates that the amount of heat generated due to hydrogen/oxygen catalytic combustion is not appreciable compared to total waste heat released during HT-PEMFC operations.     

Synthesis of mesoporous silica (SBA-16) nanoparticles using silica extracted from stem cane ash and its application in electrocatalytic oxidation of methanol

In this work, a new catalyst based on modified mesoporous silica SBA-16 is proposed and used for electrochemical oxidation of methanol. Mesoporous silica SBA-16 nanoparticles are synthesized hydrothermally under the acidic medium using SiO₂/F127/BuOH/HCl/H₂O gel. Pure SiO₂ powder is prepared from inexpensive and environmentally friendly silica source of stem cane ash (SCA). The synthesized SBA-16 is characterized using X-ray diffraction, scanning electronic microscopy, transmission electron microscopy, Brumauer–Emmett–Teller (BET) and FT-IR techniques. The synthesized SBA-16 is modified with Ni(II) by dispersion in a 0.1 M nickel chloride solution. A modified carbon paste electrode (CPE) is prepared by mixing of NiSBA-16 to carbon paste (NiSBA-16CPE). The electrocatalytic oxidation of methanol was studied on modified electrode by cyclic voltammetry and chronoamperometry. From cyclic voltammetry, it is observed that the oxidation current is extremely increased by using NiSBA-16CPE compared to the nonmodified CPE. The incorporation of Ni²⁺ into SBA-16 channels provides the active sites for catalysis of methanol oxidation. Also, the rate constant for the catalytic reaction (k) of methanol is obtained.     

Characteristics and performance of the Co–CeO2 catalyst as a function of the promoter (La,Pr, and Zr) used in high temperature water gas shift reaction

The catalysts used to facilitate the water gas shift reaction (WGSR) are generally harmful to the environment. Therefore, catalysts that have high activity and stability in WGSR and do not pollute the environment need to be fabricated. Herein, three promoters (La, Pr, and Zr) are added into Co–CeO₂ (CoCe) catalyst to improve catalytic performance in a high temperature WGSR to produce high-purity hydrogen from waste-derived synthesis gas. Various techniques are employed to confirm the changes in the properties that affect the catalytic performance. The catalytic reaction is performed at a high gas hourly space velocity to screen the performance of the promoted CoCe catalysts. The CoCeZr catalyst shows the highest CO conversion (X_CO = 88% at 450 °C) due to its high Co dispersion and oxygen vacancy resulting from the addition of Zr to the CoCe catalyst; thus, it is most suitable for use in high temperature WGSR.     

Mechano-chemical synthesis of manganese borohydride (Mn(BH4)2) and inverse cubic spinel (Li2MnCl4) in the (nLiBH4 + MnCl2) (n = 1, 2, 3, 5, 9 and 23) mixtures and their dehydrogenation behavior

Manganese borohydride (Mn(BH₄)₂) was successfully synthesized by a mechano-chemical activation synthesis (MCAS) from lithium borohydride (LiBH₄) and manganese chloride (MnCl₂) by applying high energy ball milling for 30 min. For the first time a wide range of molar ratios n = 1, 2, 3, 5, 9 and 23 in the (nLiBH₄ + MnCl₂) mixture was investigated. During ball milling for 30 min the mixtures release only a very small quantity of H₂ that increases with the molar ratio n but does not exceed ∼0.2 wt.% for n = 23. However, longer milling duration leads to more H₂ released. For the equimolar ratio n = 1 the principal phases synthesized are Li₂MnCl₄, an inverse cubic spinel phase, and the Mn(BH₄)₂ borohydride. For n = 2 a LiCl salt is formed which coexists with Mn(BH₄)₂. With the n increasing from 3 to 23 LiBH₄ is not completely reacted and its increasing amount is retained in the microstructure coexisting with LiCl and Mn(BH₄)₂. Gas mass spectrometry during Temperature Programmed Desorption (TPD) up to 450 °C shows the release of hydrogen as a principal gas with a maximum intensity around 130–150 °C accompanied by a miniscule quantity of borane B₂H₆. The intensity of the B₂H₆ peak is 200–600 times smaller than the intensity of the corresponding H₂ peak. In situ heating experiments using a continuous monitoring during heating show no evidence of melting of Mn(BH₄)₂ up to about 270–280 °C. At 100 °C under 1 bar H₂ pressure the ball milled n = 2 and 3 mixtures are capable of desorbing quite rapidly ∼4 wt.% H₂ which is a very large amount of H₂ considering that the mixture also contains 2 mol of LiCl salt. The H₂ quantities experimentally desorbed at 100 and 200 °C do not exceed the maximum theoretical quantities of H₂ expected to be desorbed from Mn(BH₄)₂ for various molar ratios n. It clearly confirms that the contribution from B₂H₆ evolved is negligibly small (if any) when desorption occurs isothermally in the practical temperature range 100–200 °C. It is found that the ball milled mixture with the molar ratio n = 3 exhibits the highest rate constant k and the lowest apparent activation energy for dehydrogenation, E_A ∼ 102 kJ/mol. Decreasing or increasing the molar ratio n below or above 3 increases the apparent activation energy. Ball milled mixtures with the molar ratio n = 2 and 3 discharge slowly H₂ during storage at room temperature and 40 °C. The addition of 5 wt.% nano-Ni with a specific surface area of 60.5 m²/g substantially enhances the rate of discharge at 40 °C.     

Evolution of physicochemical and electrocatalytic properties of NiCo2O4 (AB2O4) spinel oxide with the effect of Fe substitution at the A site leading to efficient anodic O2 evolution in an alkaline environment

Within the framework of this work, spinel-type ternary transition metal oxides of nickel, cobalt and iron with the composition Fe_xNi_1−xCo₂O₄ (0 ≤ x ≤ 1) were prepared and tested as promising electrocatalysts for the oxygen evolution reaction (OER) in alkaline water electrolysis. The hydroxide precipitation method was used for the synthesis. The morphology, structure and specific surface area of the prepared electrocatalysts were determined by means of scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, the Brunauer Emmet Teller method and X-ray photo electron spectroscopy. The electrochemical properties were tested by thin-film technique on a rotating disk electrode and in a single-cell laboratory water electrolyzer coupled with electrochemical impedance spectroscopy. The OER studies indicate that substitution of Ni by Fe increases the electrocatalytic activity of the resulting material significantly. The highest activity was achieved for x = 0.1. Whereas the current density obtained using a pure nickel anode in the water electrolysis test was 54 mA cm⁻² at a cell voltage of 1.85 V, in the case of the anode modified with NiCo₂O₄ catalyst the value was 87 mA cm⁻². Using ternary transition metal oxides in the water electrolysis test and under identical conditions, the catalyst with the highest activity displayed a current density of 115 mA cm⁻².     

Structural and thermal stabilities of layered Li(Ni1/3Co1/3Mn1/3)O2 materials in 18650 high power batteries

The structural and thermal stabilities of the layered Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni_1/3Co_1/3Mn_1/3)O₂/graphite high power batteries. The Li(Ni_1/3Co_1/3Mn_1/3)O₂ materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10 C discharge rate at temperatures of 25 and 50 °C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode and the Joule heat that results from the great increase in the total resistance (R_cell) of batteries. The reactions of fully charged Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140 °C in the fully charged batteries during oven test, which is much lower than the temperature of about 240 °C required for the reactions outside batteries.     

Studies on dehydrogenation characteristic of Mg(NH2)2/LiH mixture admixed with vanadium and vanadium based catalysts (V,V2O5 and VCl3)

In the present study, we have investigated the effect of vanadium and its compounds (V, V₂O₅ and VCl₃) on desorption characteristics of 1:2 magnesium amide (Mg(NH₂)₂) and lithium hydride (LiH) mixture. The hydrogen storage characteristics of 1:2 Mg(NH₂)₂/LiH mixture gets enhanced with admixing of V, V₂O₅ and VCl₃ separately. The VCl₃ has been found to be the most effective followed by V and V₂O₅. The activation energy for dehydrogenation process of 1:2 Mg(NH₂)₂/LiH mixture with and without catalyst has been evaluated using a method suggested by Ozawa et al. [25]. Based on the experimental results, schematic reaction scheme for decomposition of Mg(NH₂)₂ in the presence of VCl₃ has also been proposed.     

Catalytic properties of monometallic copper and bimetallic copper-nickel systems combined with ceria and Ce-X (X = Gd,Tb) mixed oxides applicable as SOFC anodes for direct oxidation of methane

The present contribution analyses the possibilities of both Cu and bimetallic Cu-Ni formulations combined with CeO₂-based oxides for their use as anodes of solid-oxide fuel cells (SOFC) for direct oxidation of methane. The main objective is related to examining how the metals combination and the presence of dopants like Gd and Tb into the ceria structure could affect the catalytic activity of this type of materials towards reaction with methane. For this purpose, cermets of Cu alone as well as bimetallic Cu-Ni (with 20 and 40 wt.%) have been synthesised in combination with various supports composed by oxides of Ce, Ce-Tb and Ce-Gd. The behaviour of such systems towards interaction with dry methane up to 900 °C was analysed by means of CH₄-TPR tests. Appreciable differences in the catalytic activity are revealed as a function of the presence of nickel as well as Gd or Tb dopants in the systems. The characteristics of carbonaceous deposits formed upon such interaction was analysed by means of TPO and XPS.     

Prediction of vortex penetration depth at thermal stratification by cavity flow in a branch pipe with closed end (effect of heat radiation condition on temperature fluctuations)

In a branch pipe with one closed end, the cavity flow penetrates into the branch pipe from the main loop and a thermal boundary layer occurs because the cavity flow is a hot fluid, but heat removal causes a colder fluid in the branch pipe. This thermal stratification may affect the structural integrity. Therefore, a pipe design standard to suppress thermal fatigue should be established. The pipe design standard consists of the maximum penetration depth L_sv and the minimum penetration depth L_sh. In order to establish an evaluation method for L_sh, a visualization test and a temperature fluctuation test were carried out. A theoretical formula for thermal stratification was introduced from the heat balance model. Then the model was used to obtain an empirical equation from the map of fluid temperature fluctuation. This method can predict the vortex penetration depth by cavity flow in horizontal branch pipes. © 2006 Wiley Periodicals, Inc. Heat Trans Asian Res, 36(1):38–55, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20135     

Effect of Ce on the structural features and catalytic properties of La(0.9−x)CexFeO3 perovskite-like catalysts for the high temperature water-gas shift reaction

La_(0.9−x)Ce_xFeO₃ perovskite-like catalysts were investigated for the production of hydrogen from simulated coal-derived syngas via the water-gas shift reaction in the temperature range 450-600 °C and at 1 atm. These catalysts exhibited higher activity at high temperatures (T ≥ 550 °C), compared to that of a commercial high temperature iron-chromium catalyst at 450 °C. Addition of a low Ce content (x = 0.2), has little influence on the formation of the LaFeO₃ perovskite structure, but enhances catalytic activity especially at high temperatures with 19.17% CO conversion at 550 °C and 40.37% CO conversion at 600 °C. The LaFeO₃ perovskite structure and CeO₂ redox properties play an important role in enhancing the water-gas shift activity. Addition of a high Ce content (x = 0.6) inhibits the formation of the LaFeO₃ perovskite structure and decreases catalyst activity.     

Experimental and numerical study of detailed reaction mechanism optimization for syngas (H2 + CO) production by non-catalytic partial oxidation of methane in a flow reactor

The National Institute of Standards and Technology (NIST) detailed reaction mechanism of methane combustion was optimized based on a flow reactor experiment to obtain syngas (H₂ + CO). The experimental methane partial oxidation was conducted with pre-mixed gas in a flow reactor. Specifically, 0.2% methane and 0.1% oxygen were diluted with 99.7% argon, restraining the exothermic effect. The experiment was conducted from 1223 K to 1523 K under pressure. Through a comparison of the experimental results with calculated values, the NIST mechanism was selected as a starting point. Rate coefficients of O + OH = O₂ + H, CH₃ + O₂ = CH₃O + O, and C₂H₂ + O₂ = HCCO + OH were replaced with results from other studies. The replaced rate coefficient for CH₃ + O₂ = CH₃O + O was again optimized, within its reported uncertainty of 3.16, based on the experimental results of this study. The revised value of the rate coefficient for CH₃ + O₂ = CH₃O + O was k₃₇ = 7.92 × 10¹³ × e^{(−31400/RT)}. The optimized mechanism showed better performance in predicting the results of other studies, as well as this study. The optimization reduced the RMS error for the results of this study from 6.7 to 1.18.