Structural investigation and hydrogen storage properties of Ca3-xLaxMg2Ni13 alloys

The phase structures and hydrogen storage properties of the Ca_3-xLa_xMg₂Ni₁₃ alloys were investigated. It was found that the La substitution is unfavorable for the formation of the Ca₃Mg₂Ni₁₃-type phase. The La-substituted alloys consist of multiple phases. Increasing La content to x = 2.25 leads to a disappearance of Ca₃Mg₂Ni₁₃-type phase. Among these alloys, the Ca_1.5La_1.5Mg₂Ni₁₃ alloy has highest equilibrium pressures of hydrogen absorption–desorption and a highest hydrogen desorption capacity of 1.34 wt.% at 318 K. The discharge capacity decreases for La-substituted alloys. However, the cycling capacity retention rate (S₃₀) increases from 13.7 to 67.6% when x increases from 0 to 3.     

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.     

Order-disorder transformation and enhanced oxide-ionic conductivity of (Sm1−xDyx)2Zr2O7 ceramics

(Sm_1−xDy_x)₂Zr₂O₇ (0 ≤ x ≤ 1) ceramics are prepared by a solid state reaction process at 1973 K for 10 h in air. (Sm_1−xDy_x)₂Zr₂O₇ (0 ≤ x ≤ 0.3) ceramics exhibit a single phase of pyrochlore-type structure, while (Sm_1−xDy_x)₂Zr₂O₇ (0.5 ≤ x ≤ 1.0) possess a defective fluorite-type structure. The full width at half-maxima in the Raman spectra increases with increasing Dy content, which indicates that the degree of structural disorder increases as the Dy content increases. The ionic conductivity of (Sm_1−xDy_x)₂Zr₂O₇ ceramics is investigated by impedance spectroscopy over a frequency range of 0.2 Hz to 8 MHz in the temperature range of 873-1173 K in air and hydrogen atmospheres, respectively. The ionic conductivity has a maximum near the phase boundary between the pyrochlore- and the defective fluorite-type phases under identical temperature levels. The ionic conductivity is determined by the degree of structural disorder or unit cell free volume, which is depending on the Dy content. As the ionic conductivity in the hydrogen atmosphere is almost the same as that obtained in air, the conduction of (Sm_1−xDy_x)₂Zr₂O₇ is purely ionic with negligible electronic conduction.     

Hydrogen storage properties of Mg1−xCaxNi2−y defect solid solutions

Ternary Mg_1−xCa_xNi_2−y solid solutions were synthesized by powder sintering. The phase structures and hydrogen storage properties of the sintered samples were investigated. In a certain range of x and y values, the samples are a single C15 Laves phase with various types of defects. The reduction of Ni content leads to the formation of omission solid solution with vacancies on the sites of Ni. These vacancies increase the hydrogen storage capacity, but decrease the reversibility of hydrogen absorption and desorption.     

Microstructure and electrochemical hydrogen storage characteristics of La0.67Mg0.33−xCaxNi2.75Co0.25 (x = 0-0.15) electrode alloys

The microstructure and electrochemical hydrogen storage characteristics of La_0.67Mg_0.33−xCa_xNi_2.75Co_0.25 (x = 0, 0.05, 0.10 and 0.15) alloys are investigated. The results show that all alloys mainly consist of (La, Mg)Ni₃ and LaNi₅ phases, besides a small amount of (La, Mg)₂Ni₇ phase. The cycle stability (S₈₀) after 80 charge/discharge cycles of all alloy electrodes first increases from 60.1% (x = 0) to 64.2% (x = 0.05), then decreases to 45.9% (x = 0.15). The high rate dischargeability of all alloy electrodes first increases from 52.6% (x = 0) to 61.4% (x = 0.10), then decreases to 57.2% (x = 0.15). Moreover, the charge-transfer resistance (R_ct) first decreases from 168.2 mΩ (x = 0) to 125.7 mΩ (x = 0.10), then increases to 136.6 mΩ (x = 0.15). All the results indicate that the substitution of Mg with a certain amount of Ca can improve the overall electrochemical characteristics.     

Effects of partial substitutions of cerium and aluminum on the hydrogenation properties of La(0.65−x)CexCa1.03Mg1.32Ni(9−y)Aly alloy

Hydrogen in metal hydrides could be one of the promising energy storage mediums to address the intermittent nature of renewable energy. To convert the hydrogen energy to electricity, the storage system has to be coupled with a fuel cells system. Hence, it is important to design a hydrogen storage system that meets the operating requirements for a fuel cell system. In this work, the effects of partial substitution of both cerium and aluminum on the hydrogenation properties of La_(0.65−x)Ce_xCa_1.03Mg_1.32Ni_(9−y)Al_y alloys were investigated simultaneously using factorial design. Both Ce and Al additions greatly improved the reversibility of hydrogen storage capacity. However, the maximum hydrogen storage capacity and absorption kinetics can be reduced by the additions. As Ce and Al gave opposite effects on the absorption and desorption plateaus, they could be used to tune the properties of the alloys to the desired operating conditions for fuel cell applications.     

Microstructure and electrochemical hydrogen storage characteristics of (La0.7Mg0.3)1−xCexNi2.8Co0.5 (x = 0-0.20) electrode alloys

The microstructure and electrochemical hydrogen storage characteristics of (La_0.7Mg_0.3)_1−xCe_xNi_2.8Co_0.5 (x = 0, 0.05, 0.10, 0.15 and 0.20) alloys have been investigated. The results show that all alloys consist of (La, Mg)Ni₃ and LaNi₅ phases. The cyclic stability (S₁₀₀) of the alloy electrodes increases from 58.7% (x = 0) to 69.8% (x = 0.20) after 100 charge/discharge cycles. The high rate dischargeability (HRD) increases from 66.8% (x = 0) to 69.6% (x = 0.10), then decreases to 65.1% (x = 0.20) at the discharge current density of 1200 mA/g. Moreover, the electrochemical kinetic characteristics of the alloy electrodes are also improved by increasing Ce content.     

Microstructure and electrochemical investigations of La0.76−xCexMg0.24Ni3.15Co0.245Al0.105 (x = 0, 0.05, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys

The effects of substitution of Ce for La on the microstructure and electrochemical performance of La_0.76−xCe_xMg_0.24Ni_3.15Co_0.245Al_0.105 (x = 0, 0.05, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were investigated. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) analyses showed that the main phases of the alloys consist of (La, Mg)Ni₃ phase (PuNi₃-type rhombohedral structure), LaNi₅ phase (CaCu₅-type hexagonal structure) and (La, Mg)₂Ni₇ phase (Ce₂Ni₇-type hexagonal structure). The cell volume of the (La, Mg)Ni₃ phase, (La, Mg)₂Ni₇ phase and LaNi₅ phase decreased monotonously with increasing Ce content. Electrochemical investigations showed a decrease in the discharge capacity, while high rate dischargeability (HRD) first increased and then decreased with increasing Ce content. The Ce substitution for La slightly enhanced the cyclic stability of the alloy electrodes. The pressure–composition (P–C) isotherms showed that the plateau region was broadened with Ce content increased in the alloys, meanwhile, two plateaus appeared and pressure of the hydrogen absorption and desorption increased accordingly.     

Improved electrochemical properties of amorphous Mg65Ni27La8 electrodes: Surface modification using graphite

Amorphous Mg₆₅Ni₂₇La₈ alloy is prepared by melt-spinning. The alloy surface is modified using different contents of graphite to improve the performances of the Mg₆₅Ni₂₇La₈ electrodes. In detail, the electrochemical properties of (Mg₆₅Ni₂₇La₈) + xC (x = 0–0.4) electrodes are studied systematically, where x is the mass ratio of graphite to alloy. Experimental results reveal that the discharge capacity, cycle life, discharge potential characteristics and electrochemical kinetics of the electrodes are all improved. The surface modification enhances the electrocatalytic activity of the alloy, reduces the contact resistance of the electrodes and obstructs the formation of Mg(OH)₂ on the alloy surface. An optimal content of graphite has been obtained. The (Mg₆₅Ni₂₇La₈) + 0.25 C electrode has the largest discharge capacity of 827 mA h g⁻¹, which is 1.47 times as large as that of the electrode without graphite, and the best electrochemical kinetics. Further increasing of graphite content will lead to the increase of contact resistance and activation energy for charge-transfer reaction of the electrode, resulting in the degradation of electrode performance.     

Influence of CaO on structure and electrical conductivity of pyrochlore-type Sm2Zr2O7

(Sm_1−xCa_x)₂Zr₂O_7−x (0 ≤ x ≤ 0.100) ceramics were prepared by a solid state reaction process at 1973 K for 10 h in air, and were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). (Sm_1−xCa_x)₂Zr₂O_7−x (0 ≤ x ≤ 0.025) ceramics have a single phase of pyrochlore-type structure; however (Sm_1−xCa_x)₂Zr₂O_7−x (0.050 ≤ x ≤ 0.100) consist of pyrochlore phase and a small amount of perovskite-like CaZrO₃. The electrical conductivity of (Sm_1−xCa_x)₂Zr₂O_7−x ceramics was investigated by complex impedance spectroscopy over a frequency range of 0.1 Hz to 20 MHz in the temperature range of 573–873 K. The measured electrical conductivity obeys the Arrhenius relation. Both the activation energy and pre-exponential factor for grain conductivity increase with increasing the CaO content; however, electrical conductivity of (Sm_1−xCa_x)₂Zr₂O_7−x decreases with increasing the CaO content, which is due to the increase in structural disordering at 0 ≤ x ≤ 0.025 and the presence of the poorly conducting CaZrO₃ phase at 0.050 ≤ x ≤ 0.100, respectively.     

Characterization of (Y1-xCax)BaCo4-yZnyO7 as cathodes for intermediate temperature solid oxide fuel cells

The effects of Ca and Zn substitution, respectively, for Y and Co in (Y_1-xCa_x)BaCo_4-yZn_yO₇ (0.25 ≤ x ≤ 0.75 and 1.0 ≤ y ≤ 1.75) on the structure, high-temperature phase stability, thermal expansion coefficient (TEC), and electrochemical performance for intermediate temperature solid oxide fuel cells (IT-SOFC) have been investigated. The (Y_1-xCa_x)BaCo_4-yZn_yO₇ oxides crystallize in a trigonal P31c symmetry similar to YBaCo₄O₇. The substitution of Zn for Co improves the long-term phase stability at high temperatures, but at the expense of the electrochemical performance. In contrast, the substitution of Ca for Y is improves electrochemical performances, but deteriorates the long-term phase stability at high temperatures at high Ca contents (x = 0.75 and 1.0). Among the various chemical compositions investigated in the (Y_1-xCa_x)BaCo_4-yZn_yO₇ system, the (Y_0.5Ca_0.5)BaCo_2.5Zn_1.5O₇ composition offers a combination of good electrochemical performance and low TEC, while maintaining the phase stability at 600-800 °C for 120 h. The (Y_0.5Ca_0.5)BaCo_2.5Zn_1.5O₇ + GDC (50 : 50 wt. %) composite cathodes exhibit a maximum power density of ∼ 450 mW cm⁻² at 700 °C in anode-supported single SOFC.     

Structural change and hydrogenation behavior of (Sr,Ca)2Al alloys

The phase structure and hydrogenation behavior of the (Sr_1−xCa_x)₂Al (x = 0.5, 0.6, 0.7, 0.8 and 0.9) alloys were investigated. It was found that the (Sr_1−xCa_x)₂Al alloys have different phase components with the change of Ca content. When x = 0.6 and 0.7, the single (Sr, Ca)₂Al phase can be obtained. The lattice parameters of (Sr, Ca)₂Al compound in the (Sr_1−xCa_x)₂Al alloys decrease gradually with the increase of Ca content. The (Sr, Ca)₂Al phase can absorb hydrogen even at 303 K. During hydrogenation, the (Sr, Ca)₂Al compound transforms into distinct phases at different temperatures.     

High-throughput studies of Li1−xMgx/2FePO4 and LiFe1−yMgyPO4 and the effect of carbon coating

A two-dimensional sample array synthesis has been used to screen carbon-coated Li_(1−x)Mg_x/2FePO₄ and LiFe_(1−y)Mg_yPO₄ powders as potential positive electrode materials in lithium ion batteries with respect to x, y and carbon content. The synthesis route, using sucrose as a carbon source as well as a viscosity-enhancing additive, allowed introduction of the Mg dopant from solution into the sol–gel pyrolysis precursor. High-throughput XRD and cyclic voltammetry confirmed the formation of the olivine phase and percolation of the electronic conduction path at sucrose to phosphate ratios between 0.15 and 0.20. Measurements of the charge passed per discharge cycle showed that the capacity deteriorated on increasing magnesium in Li_(1−x)Mg_x/2FePO₄, but improved with increasing magnesium in LiFe_(1−y) Mg_yPO₄, especially at high scan rates. Rietveld-refined XRD results on samples of LiFe_(1−y)Mg_yPO₄ prepared by a solid-state route showed a single phase up to y = 0.1 according to progressive increases in unit cell volume with increases in y. Carbon-free samples of the same materials showed conductivity increases from 10⁻¹⁰ to 10⁻⁸ S cm⁻¹ and a decrease of activation energy from 0.62 to 0.51 eV. Galvanostatic cycling showed near theoretical capacity for y = 0.1 compared with only 80% capacity for undoped material under the same conditions.     

Effect of non-stoichiometry on hydrogen storage properties of La(Ni3.8Al1.0Mn0.2)x alloys

The La(Ni_3.8Al_1.0Mn_0.2)_x (x = 0.94, 0.96, 0.98, 1.0) hydrogen storage alloys have been investigated to examine the effect of non-stoichiometry on the crystal structure, activation performance, hydrogen absorption/desorption properties and cycle life. It was found that for the stoichiometric compound, only single phase with CaCu₅ type structure exists. However, for B-poor compounds of AB₅ alloys, there is a principal CaCu₅ type phase with a small amount of second phase and the amount of second phase increased with decreasing x when x ≥ 0.96 and reached a maximum when x = 0.96. The activation becomes harder with decreasing x until x = 0.96 and easier when x decreased to 0.94. The plateau pressure increased and the hydrogen uptake capacity decreased with decreasing x when x ≥ 0.96, and then decreased and increased, respectively, when x further decreased to 0.94. Both the change in the lattice strain which could be estimated by FWHM (full width at half maximum) and the degree of slope factor S_f in the alloys show the same trend with the change of x, exhibiting a maximum at x = 0.96. The ΔH decreased with decreasing x when x ≥ 0.96 and then increased when x = 0.94 and it was found that the larger the cell volume, the larger the absolute value of the enthalpy. The pulverization resistance of the alloys was greatly improved by the non-stoichiometric. The kinetics of the alloys was very fast and almost not influenced by the change of non-stoichiometric x. After 300 absorption/desorption cycles, the hydrogen uptake capacity of the stoichiometric and non-stoichiometric alloys almost kept the same, but the particle size decreased greatly.     

Intermediate temperature ionic conduction in Sn1−xGaxP2O7

A novel series of samples Sn_1−xGa_xP₂O₇ (x = 0.00, 0.01, 0.03, 0.06, 0.09, 0.12, 0.15) are synthesized by solid state reaction. XRD patterns indicate that the samples of x = 0.00 − 0.09 exhibit a single cubic phase structure, and the doping limit of Ga³⁺ in Sn_1−xGa_xP₂O₇ is x = 0.09. The protonic and oxide-ionic conduction in Sn_1−xGa_xP₂O₇ are investigated using some electrochemical methods at intermediate temperatures (323-523 K). It is found that the samples exhibit appreciable protonic conduction in hydrogen atmosphere, and a mixed conduction of oxide-ion and electron hole in dry oxygen-containing atmosphere. The highest conductivities are observed for the sample of x = 0.09 to be 4.6 × 10⁻² S cm⁻¹ in wet H₂ and 2.9 × 10⁻² S cm⁻¹ in dry air at 448 K, respectively. The H₂/air fuel cell using x = 0.09 as electrolyte (thickness: 1.45 mm) generates a maximum power density of 19.2 mW cm⁻² at 423 K and 22.1 mW cm⁻² at 448 K, respectively.     

Effect of substituting Mn for Ni on the hydrogen storage and electrochemical properties of ReNi2.6−xMnxCo0.9 alloys

ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys were prepared by induction melting. The effects of partially substituting Mn for Ni on the phase structure and electrochemical properties of the alloys were investigated systematically. In the alloys, (La, Ce)₂Ni₇ phase with a Ce₂Ni₇-type structure, (Pr, Ce)Co₃ phase with a PuNi₃-type structure, and (La, Pr)Ni₅ phase with a CaCu₅-type structure were the main phases. The (La,Pr)Ni phase appeared when x increased to 0.45, and the (La, Pr)Ni₅ phase disappeared with further increasing x (x > 0.45). The hydrogen-storage capacity of the ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloys initially increased and reached a maximum when Mn content was x = 0.45, and then decreased with further increasing Mn content. The ReNi_2.6−xMn_xCo_0.9 (x = 0.0, 0.225, 0.45, 0.675, 0.90) alloy exhibited a hydrogen-storage capacity of 0.81, 0.98, 1.04, 0.83 and 0.53 wt.%, respectively. Electrochemical studies showed that the maximum discharge capacity of the alloy electrodes initially increased from 205 mAh/g (x = 0.0) to 352 mAh/g (x = 0.45) and then decreased to 307 mAh/g (x = 90). The hydrogen absorption rate first increased and then decreased with addition of Mn element. The ReNi_2.15Mn_0.45Co_0.9 alloy showed faster hydrogen absorption kinetics than that of the other alloys. The presence of Mn element slowed hydrogen desorption kinetics.     

Ionic conduction in Sn1−xScxP2O7 for intermediate temperature fuel cells

A novel series of mixed ion conductors, Sn_1−xSc_xP₂O₇ (x = 0.03, 0.06, 0.09, 0.12), were synthesized by a solid-state reaction method. The conduction behaviors of the ion conductors in wet hydrogen atmosphere were investigated by some electrochemical methods including AC impedance spectroscopy, gas concentration cells in the temperature range of 323-523 K. It was found that the doping limit of Sc³⁺ in SnP₂O₇ was between 9 mol% and 12 mol%. The highest conductivity was observed to be 2.76 × 10⁻² S cm⁻¹ for the sample of x = 0.06 under wet H₂ atmosphere at 473 K. The ionic conduction was contributed mainly to proton and partially to oxide ion in wet hydrogen atmosphere from 373 K to 523 K. The H₂/air fuel cells using Sn_1−xSc_xP₂O₇ (x = 0.03, 0.06, 0.09) as electrolytes (1.7 mm in thickness) generated the maximum power densities of 11.16 mW cm⁻² for x = 0.03, 25.02 mW cm⁻² for x = 0.06 and 14.34 mW cm⁻² for x = 0.09 at 423 K, respectively. The results indicated that Sn_1−xSc_xP₂O₇ is a promising solid electrolyte system for intermediate temperature fuel cells.     

Synthesis and performance of Li3(V1−xMgx)2(PO4)3 cathode materials

In order to search for cathode materials with better performance, Li₃(V_1−xMg_x)₂(PO₄)₃ (0, 0.04, 0.07, 0.10 and 0.13) is prepared via a carbothermal reduction (CTR) process with LiOH·H₂O, V₂O₅, Mg(CH₃COO)₂·4H₂O, NH₄H₂PO₄, and sucrose as raw materials and investigated by X-ray diffraction (XRD), scanning electron microscopic (SEM) and electrochemical impedance spectrum (EIS). XRD shows that Li₃(V_1−xMg_x)₂(PO₄)₃ (x = 0.04, 0.07, 0.10 and 0.13) has the same monoclinic structure as undoped Li₃V₂(PO₄)₃ while the particle size of Li₃(V_1−xMg_x)₂(PO₄)₃ is smaller than that of Li₃V₂(PO₄)₃ according to SEM images. EIS reveals that the charge transfer resistance of as-prepared materials is reduced and its reversibility is enhanced proved by the cyclic votammograms. The Mg²⁺-doped Li₃V₂(PO₄)₃ has a better high rate discharge performance. At a discharge rate of 20 C, the discharge capacity of Li₃(V_0.9Mg_0.1)₂(PO₄)₃ is 107 mAh g⁻¹ and the capacity retention is 98% after 80 cycles. Li₃(V_0.9Mg_0.1)₂(PO₄)₃//graphite full cells (085580-type) have good discharge performance and the modified cathode material has very good compatibility with graphite.     

Structural and electrochemical properties of Ti1.5Zr5.5VxNi10−x

Quaternary alloys with the formula Ti_1.5Zr_5.5V_xNi_10−x (x between 0 and 3.0) were studied as a potential replacement for Laves phase alloys used as the negative electrode active material in nickel metal hydride batteries. The V-containing alloys all show multi-phase structures. The major phase shifts from a Zr₇Ni₁₀ structure to a Zr₉Ni₁₁ structure and finally to a C14 structure as the vanadium content increases. Other minor phases with C15 and ZrNi crystal structures are also present. The solubility of vanadium is high in AB2 phases (both C14 and C15), moderate for the ZrNi phase and very low for Zr₇Ni₁₀ and Zr₉Ni₁₁ phases. The bulk hydrogen transport property of the alloys is dominated by synergetic effects between major and minor phases. Electrochemical testing shows that the highest discharge capacity, 357 mAh/g, was obtained from an alloy with a chemical composition of Ti_1.5Zr_5.5V_2.5Ni_7.5 and mainly C14 structure. Testing also shows the high rate dischargeability is controlled by the surface reaction and Ti_1.5Zr_5.5V_0.5Ni_9.5 has the best high rate dischargeability.     

Reversible de-/hydriding characteristics of a novel Mg18In1Ni3 alloy

The present work demonstrates the reversible hydrogen storage properties of the ternary alloy Mg₁₈In₁Ni₃, which is prepared by ball-milling Mg(In) solid solution with Ni powder. The two-step dehydriding mechanism of hydrogenated Mg₁₈In₁Ni₃ is revealed, namely the decomposition of MgH₂ is involved with different intermetallic compounds or Ni, which leads to the formation of Mg₂Ni(In) solid solution or unknown ternary Mg–In–Ni alloy phase. As a result, the alloy Mg₁₈In₁Ni₃ shows improved thermodynamics in comparison with pure Mg. The Ni addition also results in the kinetic improvement, and the minimum desorption temperature is reduced down to 503 K, which is a great decrease comparing with that for Mg–In binary alloy. The composition and microstructure of Mg–In–Ni ternary alloy could be further optimized for better hydrogen storage properties.