Thermodynamic analysis of ammonia storage materials

Thermodynamic analysis of ammonia storage materials such as metal halides, sodium borohydride, water and ammonium hydrogen sulfate was carried out to clarify the stability in the ammoniates. The standard entropy change ΔS⁰ by ammonia absorption decreased with increase of the electronegativity of cation in metal chlorides and the electronegativity difference in metal halides. It was suggested that the stronger the binding energy, the smaller the entropy change by ammonia absorption. ΔS⁰ linearly increased with the natural logarithm of the volume difference ΔV of the ammonia storage materials before and after ammonia absorption, whose slope is 11 times of the slope between the entropy and the natural logarithm of the volume of ideal gas. The standard enthalpy change ΔH⁰ was increased with ΔS⁰. Based on these experimental relations, we can calculate the ammonia vapor pressure P_NH3 by ΔV.     

Investigation of the thermodynamic and kinetic properties of La–Fe–B system hydrogen-storage alloys

La–Fe–B hydrogen-storage alloys were prepared using a vacuum induction-quenching furnace with a rotating copper wheel. The thermodynamic and kinetic properties of the La–Fe–B hydrogen-storage alloys were investigated in this work. The P–C–I curves of the La–Fe–B alloys were measured over a H₂ pressure range of 10⁻³ MPa to 2.0 MPa at temperatures of 313, 328, 343 and 353 K. The P–C–I curves revealed that the maximum hydrogen-storage capacity of the alloys exceeded 1.23 wt% at a pressure of approximately 1.0 MPa and temperature of 313 K. The standard enthalpy of formation ΔH and standard entropy of formation ΔS for the alloys' hydrides, obtained according to the van't Hoff equation, were consistent with their application as anode materials in alkaline media. The alloys also exhibited good absorption/desorption kinetics at room temperature.     

Effect of measurement parameters on thermodynamic properties of La-based metal hydrides

Pressure–concentration isotherms (PCIs) of LaNi_5−xAl_x (x = 0.3 and 0.4) hydrides were measured using a volumetric method. Two important thermodynamic properties, enthalpy of formation (ΔH) and entropy of formation (ΔS), were calculated using the van't Hoff equation. The effects of the Al content on the hydrogen storage capacity, plateau pressure and thermodynamic properties were studied. Additionally, the effects of the charging/discharging pressure difference (ΔP_s) during each step of the absorption/desorption PCI measurement on the hydrogen storage capacity (wt%), equilibrium pressure (P_e), plateau slope, reaction enthalpy (ΔH) and entropy (ΔS) were studied for LaNi_4.6Al_0.4 hydride. All of these properties (P_e, ΔH, ΔS, etc.) showed a significant variation with ΔP_s. The effect of the temperature range on the estimation of the enthalpy of formation was investigated. It was observed that ΔH depends on the experimental temperature range.     

Alloy selection for multistage metal-hydride hydrogen compressors: A thermodynamic model

A thermodynamic model is presented to aid the selection of compatible pairs of hydrogen storage alloys for service in a multi-stage metal-hydride compressor. The model is built around the concept of an ideal compressor in which all pairs of hydrides operate between the same working temperatures. The key feature of the model is a link between the thermodynamic characteristics of the hydrides in each pair (the entropy change ΔS and enthalpy change ΔH when the hydride is formed from the metal) that results from requiring that the heated low-pressure hydride is able to desorb to the cooled high-pressure metal at a unique intermediate pressure. This necessary linking places severe constraints on the choice of alloys, since ΔS and ΔH cannot be freely chosen and are in fact strongly correlated for hydrides with similar operating temperatures. The model is based on the van ‘t Hoff relation, which is derived from first principles and shown to be only approximately valid at the high hydrogen pressures of interest for vehicle filling stations. Pressure hysteresis and plateau slope are incorporated into the model. A case study of a two-stage compressor is presented, based on the curved van ‘t Hoff line and the experimentally determined effects of pressure hysteresis and plateau slope.     

Enthalpy change (ΔH) and entropy change (ΔS) measurement of CeMn1−xAl1−xNi2x (x=0.00, 0.25, 0.50 and 0.75) hydrides by electrochemical P–C–T curve

The thermodynamic properties of CeMn_1−xAl_1−xNi_2x (x=0.00, 0.25, 0.50 and 0.75) hydrides have been investigated in this paper. With increasing Ni substitution content, the hydrogen concentration (H/M) in CeMn_1−xAl_1−xNi_2x (x=0.00, 0.25, 0.50 and 0.75) hydride increases from 0.129 wt% for x=0.00 to 0.421 wt% for x=0.75 at 293 K. The pressure–concentration isotherm (P–C–T) curves show that no hydrogen equilibrium pressure plateau has been observed for CeMnAl hydride while the slope of the plateau become flatter and longer with increasing Ni content. Meanwhile, the enthalpy change (ΔH⁰) and the entropy change (ΔS⁰) of the hydrides for dehydrogenization shift from −67.44 kJ mol⁻¹ (x=0.00) to 21.16 kJ mol⁻¹ (x=0.75) and from −0.24 kJ mol⁻¹ K⁻¹ (x=0) to −0.03 kJ mol⁻¹ K⁻¹ (x=0.75), respectively. With increasing Ni content, both ΔH⁰ and ΔS⁰ for dehydrogenization shift to the positive direction and make alloy hydrides more stable and hydrogen desorption much easier.     

Evaluation of thermodynamic parameters for hydrogen in the storage device ST-90®

The thermodynamic parameters such as partial molar enthalpy (ΔH_H), partial molar entropy (ΔS_H), and partial molar excess entropy (ΔS^E_H) of the dissolved hydrogen in the hydrogen storage unit ST-90^® containing 18.6 kg of misch metal based AB₅ alloy are evaluated based on the calculation of Sieverts constant and from Clausius–Clapeyron equation. The partial molar enthalpy at infinite dilution (ΔH⁰_H) and the partial molar excess entropy at infinite dilution (ΔS^E,0_H) have been obtained from the dependence of and on the hydrogen concentration. The nature of metal-hydrogen and hydrogen interactions are also evaluated for the three single phases namely α, β and γ. The hydrogen–hydrogen interaction is attractive in the α phase and repulsive in the β and γ phases. For the mixed phases α+β and β+γ, it is very difficult to predict the nature of the interactions either as attractive or repulsive.     

Hydrogen storage thermodynamic and dynamic properties of as-milled CeMgNi-based CeMg12-type alloys

Ni was chosen to partially substitute the Mg of alloys to investigate the effect on hydrogen storage dynamics of NdMg₁₂-type alloy. The amorphous and nanocrystalline alloys were synthesized by mechanical milling technology based on CeMg₁₁Ni + x wt% Ni (x = 100, 200) alloys. This paper systematically narrates and investigates the influences of Ni content and milling duration on hydrogen storage performance. Sievert apparatus and differential scanning calorimetry (DSC) were utilized for investigating the de-/hydriding performances of samples. Both Arrhenius and Kissinger methods were utilized in this paper for estimating the dehydrogenation activation energy of hydrides, and found that enhancing Ni content can decrease the thermodynamic parameters (ΔH and ΔS) of alloys slightly and improve the dehydriding dynamics significantly. Furthermore, the hydrogen storage property can be affected significantly by adjusting milling time. With varying milling time, the hydrogen storage capacities can reach the maximum values of 5.691 and 5.904 wt% for x = 100 and 200 alloys separately. The hydrogen absorption saturation ratio (R^a(10)) at 573 K and 3 MPa also obtains maximum values with the variation of milling time, namely 90.17% and 99.32% for x = 100 and 200 alloys separately. The hydrogen desorption ratio (R^d(20)) always increases with milling time increasing. To be specific, prolonging milling time from 5 to 60 h results in the increase of R^d(20) at 593 K from 37.55% to 47.21% for x = 100 alloy and 47.29%–61.70% for x = 200 alloy.     

Syntheses of alkali-metal carbazolides for hydrogen storage

Metalorganic hydrides are a new class of hydrogen storage materials. Replacing the H of N–H or O–H functional groups using metal hydrides have been recently reported, which substantially improved the dehydrogenation properties of heteroaromatic organic hydrides by lowering their enthalpies of dehydrogenation (ΔH_d), enabling dehydrogenation at much lower temperatures. Among the reported metalorganic hydrides, lithium carbazolide and sodium carbazolide appear to be the most attractive hydrogen storage/delivery material owing to its high hydrogen capacity (>6.0 wt%) and ideal ΔH_d. Nevertheless, the interaction of carbazole and corresponding metal hydride to form metallo-carbazolide is a multistep process involving intensive ball milling and high temperature treatment, where the interaction was not investigated in detail. In this paper, both alkali metal hydrides and amides were employed to react with carbazole to synthesize corresponding carbazolides, aiming to broaden and optimize the synthetic method and understand the reaction mechanism. Our experimental results showed that around one equivalent of H₂ or NH₃ could be released from the reactions of carbazole and corresponding hydrides or amides, respectively. Instrumental spectroscopic analyses proved that metallo-carbazolides were successfully synthesized from all precursors. It is found that the alkali metal amides (i.e., LiNH₂ and NaNH₂) with stronger Lewis basicities as metal precursors could synthesize the metallo-carbazolides under milder conditions. Furthermore, quasi in situ nuclear magnetic resonance results revealed that alkali metal could replace H (H–N) gradually, donating more electrons to carbazole ring. Additionally, the solubilized alkali cation may unselectively interact with π-electron of aromatic systems of both carbazole molecules and carbazolide anions via electrostatic cation-π interactions.     

Structural characteristics and hydrogen storage properties of Ca3.0−xMgxNi9 (x = 0.5, 1.0, 1.5 and 2.0) alloys

The effect of Mg content on the structural characteristics and hydrogen storage properties of the Ca_3.0−xMg_xNi₉ (x = 0.5, 1.0, 1.5 and 2.0) alloys was investigated. The lattice parameters and unit cell volume of the PuNi₃-type (Ca, Mg)Ni₃ main phase decreased with increasing Mg content. The 6c site of PuNi₃-type structure was occupied by both Ca and Mg atoms. Moreover, the occupation factor of Ca on the 6c site decreased with the increase of Mg content. The hydrogen absorption capacity of the alloys decreased due to higher Mg content. However, the thermodynamic properties of hydrogen absorption and desorption were improved and the plateau pressures were increased. When x = 1.5–2.0, the Ca_3.0−xMg_xNi₉ alloys had favorable enthalpy (ΔH) and entropy (ΔS) of hydride formation.     

Benzimidazole and imidazole lithium salts for battery electrolytes

The intrinsic anion oxidation potential (ΔE_v) and lithium ion pair dissociation energy (ΔE_d) are two important properties for predicting the potential use of new lithium salts for battery electrolytes. In this work several cyano substituted fluoroalkylated benzimidazole and imidazole anions have been investigated computationally to obtain ΔE_v and ΔE_d. Varying the number and position of cyano substituents results in large effects on the electrochemical stability of the anion and on the possible lithium ion pair configurations. The lengthening of the fluoroalkyl group introduces several new stable ion pair configurations and a small increase in anion oxidation stability. The most promising fluoroalkylated anions in the present work are the 4,5,6,7-tetracyano-2-fluoroalkylated benzimidazolides (TTB and PTB), with oxidation potentials suitable for high voltage Li-ion battery applications (<4.2 V) and much improved ΔE_d compared to PF₆⁻—a benchmark for commercially available anions. Further improvements in ΔE_d, with maintained stability towards oxidation, are obtainable by replacing the fluoroalkyl group by an additional cyano group, but possibly demanding increased synthesis efforts.     

Superporous P(2-hydroxyethyl methacrylate) cryogel-M (M:Co,Ni, Cu) composites as highly effective catalysts in H2 generation from hydrolysis of NaBH4 and NH3BH3

Highly porous p(2-hydroxyethyl methacrylate) p(HEMA) cryogels were synthesized via cryopolymerization technique and used as template for Co, Ni, and Cu nanoparticle preparation, then as composite catalyst systems in H₂ generation from hydrolysis of both NaBH₄ and NH₃BH₃. Due to their highly porous and open microstructures, p(HEMA)-Co cryogel composites showed very effective performances in H₂ production from hydrolysis of both chemical hydrides. The characterization of p(HEMA) cryogels, and their metal composites was determined via various techniques including swelling experiments, digital camera images, SEM and TEM images, AAS and TGA measurements. The effect of various parameters on the hydrolysis reaction of NaBH₄ such as metal types, concentration of chemical hydrides, amounts of catalyst, alkalinity of reaction medium and temperature were investigated in detail. It was found that Co nanoparticles are highly active catalysts in H₂ generation reactions from both hydrides. The hydrogen generation rate (HGR) of p(HEMA)-Co was 1596 (mL H₂) (min)⁻¹ (g of Co)⁻¹ which is quite good in comparison to reported values in the literature. Furthermore, kinetic parameters of p(HEMA)-Co metal composites such as energy, enthalpy and entropy were determined as Ea = 37.01 kJmol⁻¹, ΔH# = 34.26 kJmol⁻¹, ΔS# = −176,43 Jmol⁻¹ K⁻¹, respectively.     

Effects of Zr doping on activation capability and hydrogen storage performances of TiFe-based alloy

Activation difficulty is the key problem limiting the application of TiFe-based hydrogen storage alloys. The addition of transition group elements helps to improve the activation properties of TiFe-based hydrogen storage alloy. In our previous work, the Ti_1.08Y_0.02Fe_0.8Mn_0.2 alloy exhibits extremely high hydrogen storage capacity (1.84 wt%) at room temperature with excellent kinetic properties, but it still needs an incubation period of about 1500s. In this study, the composition of Ti_1.08Y_0.02Fe_0.8Mn_0.2Zr_x (x = 0, 0.02, 0.04, 0.06, 0.08) alloys was prepared by electromagnetic induction melting. The quantitative analysis of elements by energy dispersive spectrometer shows that in the second phase region containing Zr, the content of Ti element is significantly higher than that of Fe. Meanwhile, the first-principle calculation on Zr-doped TiFe system indicates that Zr is more attractive to substitute Ti than Fe. Therefore, the doping of Zr partially replaces the Ti. The solubility of Zr in TiFe is limited, when x ≤ 0.04, the alloy consists of pure TiFe phase. When x > 0.4, the excess Zr forms precipitates, which reduces the reversible hydrogen absorption and desorption capacity of the TiFe alloy. The addition of Zr significantly shortens the activation time and reduces the plateau pressure of TiFe alloys. The Ti_1.08Y_0.02Fe_0.8Mn_0.2Zr_0.04 alloy can be directly activated without the incubation period and its absolute values of enthalpy change (ΔH) and entropy change (ΔS) are minima (ΔH for 23.2 kJ/mol and ΔS for 83.1 J/mol/K).     

Influence of 2-(4-chlorophenyl)-2-oxoethyl benzoate on the hydrogen evolution and corrosion inhibition of 18 Ni 250 grade weld aged maraging steel in 1.0 M sulfuric acid medium

Electrochemical corrosion behavior and hydrogen evolution reaction of weld aged maraging steel have been investigated, in 1.0 M sulfuric acid solution containing different concentrations of 2-(4-chlorophenyl)-2-oxoethyl benzoate (CPOB). The data obtained from polarization technique showed that the corrosion current density (i_corr) and the hydrogen evolution rate decrease, indicating a decrease in the corrosion rate of weld aged maraging steel as well as an increase in the inhibition efficiency (η%) with the increase in inhibitor concentration. Changes in impedance parameters were indicative of adsorption of CPOB on the metal surface, leading to the formation of protective film. Both activation (E_a) and thermodynamic parameters (ΔG_ads⁰, ΔH_ads⁰ and ΔS_ads⁰) were calculated and discussed. The adsorption of CPOB on the weld aged maraging steel surface obeyed the Langmuir adsorption isotherm model. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) study confirmed the formation of an adsorbed protective film on the metal surface.     

Comparative investigation on the hydrogenation/dehydrogenation characteristics and hydrogen storage properties of Mg3Ag and Mg3Y

The hydrogenation/dehydrogenation characteristics and hydrogen storage properties of nominal Mg₃Ag and Mg₃Y alloys prepared by induction melting were investigated. The as-melted Mg₃Ag alloy was composed of Mg₅₄Ag₁₇ phase, while Mg₃Y consisted of Mg₂₄Y₅ and Mg₂Y phases. Mg₅₄Ag₁₇ transformed into MgAg and MgH₂ during the first hydrogenation, and the phase transition of the following hy/dehydrogenation cycles was Mg₃Ag + 2H₂ ↔ MgAg + 2MgH₂. Both Mg₂₄Y₅ and Mg₂Y undertook disproportion reactions and decomposed into MgH₂ and YH₃. Experimental and calculated results demonstrated that there was no necessary relation between the thermodynamic stabilities and the size interstices in these alloys. The dehydrogenation enthalpy change (ΔH) and entropy change (ΔS) of Mg₃Ag were calculated and compared with that of pure Mg, which indicated that the increase of ΔS could counteract the stabilization effect of ΔH, which offered a method for tuning the thermodynamic properties of Mg-based alloys.     

Crystal structures of MgyTi100−y thin film alloys in the as-deposited and hydrogenated state

In situ X-ray diffraction was used to identify the crystal structures of as-deposited and hydrogenated Mg_yTi_100-y thin film alloys containing 70, 80 and 90 at.% Mg. The preferred crystallographic orientation of the films in both the as-prepared and hydrogenated state made it difficult to unambiguously identify the crystal structure up to now. In this work, identification of the unit cells was achieved by in situ recording diffraction patterns at various tilt angles. The results reveal a hexagonal closed packed structure for all alloys in the as-deposited state. Hydrogenating the layers under 10⁵ Pa H₂ transforms the unit cell into face-centered cubic for the Mg₇₀Ti₃₀ and Mg₈₀Ti₂₀ compounds, whereas the unit cell of hydrogenated Mg₉₀Ti₁₀ has a body-centered tetragonal symmetry. The (de)hydrogenation kinetics changes along with the crystal structure of the metal hydrides from rapid for fcc-structured hydrides to sluggish for hydrides with a bct symmetry and emphasizes the influence of the crystal structure on the hydrogen transport kinetics.     

Substitutional effect of Ti-based AB2 hydrogen storage alloys: A density functional theory study

Stability of AB₂ alloy in Laves phases C14 and C15 were studied by first-principle density functional theory simulations. A range of different combinations of B and C elements in the Ti_1−xC_xB₂ alloys were considered. The formation energies of these alloys generally increase with the unit cell volumes of alloys. The volume also affects the stability of the corresponding metal hydride. We find that the formation energies and the hydrogenation enthalpies of AB₂ alloys are likely to be determined by at least three factors: electronegativity, atomic radius and covalent radius. The enthalpies of AB₂ hydrides increase with increasing compositionally-averaged electronegativity and volume change upon hydrogenation. However, the enthalpies of AB₂ hydrides decrease with increasing compositionally-averaged atomic and covalent radii. This study provides useful insights for future exploration of AB₂-type alloys for hydrogen storage applications.     

Ti–Ni alloys as MH electrodes in Ni–MH accumulators

In hydrogen solid–gas reaction at 300 K and 1 bar, the hydrogen content for Ti_3.87Ni_1.73Fe_0.7O_x (0.2≤ × ≤0.8) alloys was in range 1.93–0.05 (Cwt.H,%), and discharge capacity of 360–235 A h/kg was achieved accordingly. The ΔHH₂$\Delta H_{{\text{H}}_2}$ and ΔSH₂$\Delta S_{{\text{H}}_2}$ values of −32.29 kJ mol⁻¹ and −111.04 J mol⁻¹ K⁻¹, respectively, for Ti_3.87Ni_1.73Fe_0.7O_0.5 alloy were obtained using experimental PCT relations, where hysteresis effect was only slightly visible. The half-cell potentials (vs. Hg/HgO) of metal hydride (MH) electrodes based on Ti_3.87Ni_1.73Fe_0.7O_x (0.2≤ ×≤ 0.8) alloys were calculated.     

Formation and properties of titanium-manganese alloy hydrides

Hydride formation and hydriding properties of Ti-Mn alloy systems, which have a hexagonal structure of MgZn₂(C14)-type known as the Laves phase, were studied by measuring pressure-composition isotherms in the temperature range 0–80°C. It was found that the Ti-Mn binary alloys whose Ti contents were less than 36 at % absorbed almost no hydrogen (P ? 4.5 MPa), but the alloys containing more Ti did react readily with hydrogen at room temperature without any activation treatment. The maximum absorbed hydrogen content of every Ti-Mn alloy was H/M ～ 1.The TiMn_1.5 hydride showed the most desirable properties of all the Ti-Mn binary alloy hydrides; the dissociation plateau pressure is approximately 0.7 MPa, the maximum amount of absorbed hydrogen is 228 ml g^?1 the maximum amount of released hydrogen is 190 ml g^?1 at 20°C, and ΔHΔH is the molar enthalpy change of hydrogen (i.e. the heat of formation).= ?28.7 kJ(mol H₂)^?1. Also, hydriding properties of TiMn₂ based Ti-Mn multi-component alloys containing other transition metals, such as Zr, V, Cr, Fe, Co, Ni, Cu, Nb, Mo, Ta, La and Ce, were studied. The dissociation plateau pressure at 20°C was obtained in a range from 0.01 MPa (for Ti_0.5Zr_0.5 Mn₂-H) to 1 MPa (for Ti_0.9Zr_0.1Mn_1.4V_0.2Cr_0.4-H).     

Electrochemical PCT isotherm study of hydrogen absorption/desorption in AB5 type intermetallic compounds

The enthalpy (ΔH) and entropy (ΔS) of hydride formation/decomposition could be determined either experimentally or theoretically based on models proposed in the literature. The experimental pathway includes gas/solid-phase measurement of pressure–composition–temperature (PCT) isotherms at different temperatures. This measurement is followed by plotting of van't Hoff dependences and evaluation of the ΔH and ΔS from their slopes and intersects, respectively. In this study we demonstrate the applicability of electrochemical PCT isotherm measurements as an advanced method for thermodynamic analysis of hydrogen adsorption/desorption process. Experimentally this is done by electrochemical charging/discharging of an electrode, prepared from AB₅ type alloy with MmNi_4.6Co_0.6Al_0.8 composition (Mm – mischmetal). In addition, the hydride formation as a result of the electrochemical charging is independently confirmed by ex-situ XRD diffraction. Our work demonstrates that not only the electrochemical approach is a viable alternative of PCT gas/solid-phase measurement but it also represents a safer, cost-effective and faster protocol than its hydrogen gas–solid phase equivalent.