Effect of partial substitution of Co with Fe on the properties of LaNi3.55Mn0.4Al0.3Co0.75−xFex (x=0, 0.15, 0.55) alloys electrodes

The effect of iron substitution on the electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x compounds (x=0, 0.15, 0.55) has been studied by chronopotentiometry and cyclic voltammetry techniques. The maximum capacity decreases linearly from 308 to 239 mAhg⁻¹ when the iron content increases from 0 to 7.3 wt.% (x=0.55). This decrease can be explained by the corrosion of the alloy in the aqueous KOH electrolyte. In spite of this decrease and of the long time needed for the activation, a good stability of discharge capacity was observed in LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x compounds. The reversibility of the electrochemical redox reaction of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x alloy electrodes has been observed in the alloys least rich in iron. The hydrogen diffusivity in LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x alloy electrodes decreases when increasing the iron content. The obtained values of the hydrogen diffusion coefficient D_H, varies between 2.1×10⁻⁷ and 8.2×10⁻⁹ cm² s⁻¹ depending on the iron content of the electrode.     

Electrochemical investigation of the iron-containing and no iron-containing AB5-type negative electrodes

The electrochemical behaviour of LaNi_3.55Mn_0.4Al_0.3Co_0.75−xFe_x (x = 0, 0.15, 0.55, 0.75) intermetallic compounds has been studied and presented [C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, Int. J. Hydrogen Energy 29 (2004) 307–311; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 360 (2003) 266–271; C. Khaldi, H. Mathlouthi, J. Lamloumi, A. Percheron-Guégan, J. Alloys Compd. 384 (2004) 249–253]. It has been deduced that the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound has interesting electrochemical properties. In this paper we present the electrochemical study of LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compound properties compared with the parent LaNi_3.55Mn_0.4Al_0.3Co_0.75 compound. Several techniques, such as, the chronopotentiometry, the constant potential discharge (CPD), the cyclic voltammetry (CV) and the linear polarization (LP) were applied to characterize these electrochemical properties. The electrochemical discharge capacity of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 alloy increases to reach 294 mAh g⁻¹ after few cycles only (five cycles). However, the activation of the LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy takes more than 20 cycles to be achieved and the obtained maximum discharge capacity is 194 mAh g⁻¹. The hydrogen diffusion coefficient D_H was determined by constant potential discharge and cyclic voltammetry techniques. The obtained values of the LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 compounds are 6.29 × 10⁻¹¹ and 7.62 × 10⁻¹¹, and 2 × 10⁻⁸ and 7.5 × 10⁻⁸ cm² s⁻¹ by CPD and CV techniques, respectively. The exchange current density values, determined by a linear polarization technique, are 44 and 27 mA g⁻¹, respectively, for LaNi_3.55Mn_0.4Al_0.3Co_0.75 and LaNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloys.     

Electrochemical properties of the MmNi3.55Mn0.4Al0.3Co0.4Fe0.35 compound

In this paper, the electrochemical properties of the MmNi_3.55Mn_0.4Al_0.3Co_0.4Fe_0.35 alloy used as a negative electrode in Ni–MH accumulators, have been investigated by different electrochemical methods such as cyclic voltammetry, chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy. The experimental results indicate that the discharge capacity reaches a maximum value of 260 mAh g⁻¹ after 12 cycles and then decreases to about 200 mAh g⁻¹ after 70 cycles. The value of the mean diffusion coefficient D_H, determined by cyclic voltammetry, is about 3.44 × 10⁻⁹ cm² s⁻¹, whereas the charge transfer coefficient , determined by the same method, is about 0.5 which allows us to conclude that the electrochemical reaction is reversible. The hydrogen diffusion coefficients in this compound, corresponding to 10 and 100% of the charge state, determined by electrochemical impedance spectroscopy, are, respectively, equal to 4.15 × 10⁻⁹ cm² s⁻¹ ( phase) and 2.15 × 10⁻⁹ cm² s⁻¹ (β phase). These values are higher, for the phase and less, for the β phase, than the mean value determined by cyclic voltammetry. We assume that this is related to the number of interstitial sites susceptible to accept the hydrogen atom, which are more numerous in the phase than in the β phase. The chronoamperometry shows that the average size of the particles involved in the electrochemical reaction is about 12 μm.     

Nanocrystalline LaNi4−xMn0.75Al0.25Cox electrode materials prepared by mechanical alloying (0≤x≤1.0)

Polycrystalline hydrogen storage alloys based on lanthanum (La) are commercially used as negative electrode materials for the nickel–metal hydride (Ni–MH_x) batteries. In this paper, mechanical alloying (MA) was used to synthesize nanocrystalline LaNi_4−xMn_0.75Al_0.25Co_x (x=0, 0.25, 0.5, 0.75 and 1.0) hydrogen storage materials. XRD analysis showed that, after 30 h milling, the starting mixture of the elements decomposed into an amorphous phase. Following the annealing in high purity argon at 700 °C for 0.5 h, XRD confirmed the formation of the CaCu₅-type structures with a crystallite sizes of about 25 nm. The nanocrystalline materials were used as negative electrodes for a Ni–MH_x battery. Cobalt substituting nickel in LaNi₄Mn_0.75Al_0.25 greatly improved the discharge capacity and cycle life of the LaNi₅ material. For example, in the nanocrystalline LaNi_3.75Mn_0.75Al_0.25Co_0.25 powder, discharge capacities up to 258 mA h g⁻¹ (at 40 mA g⁻¹ discharge current) were measured. Mechanical alloying is a suitable procedure to obtain LaNi₅-type alloy powders for electrochemical energy storage.     

Study of the structural, thermodynamic and electrochemical properties of LaNi3.55Mn0.4Al0.3(Co1−xFex)0.75 (0 ≤ x ≤ 1) compounds used as negative electrode in Ni-MH batteries

This study concerns the influence of iron for cobalt substitution on the structural, thermodynamic and electrochemical properties of the hydrides of poly-substituted LaNi_3.55Mn_0.4Al_0.3(Co_1−xFe_x)_0.75 (0 ≤ x ≤ 1) alloys used as material for negative electrode in Ni-MH batteries. The Fe substitution leads to an increase of the cell parameter, this increase is linear according to the rate of substitution, and a decrease of the equilibrium pressure in agreement with the geometric law. Nevertheless, it is observed that the Fe substitution leads to a deviation from the linear variation between the logarithm of the pressure and the cell volume observed for Co, Mn and Al for Ni substitution. The Fe for Co substitution leads also to a decrease of the solid–gas and electrochemical capacity.     

Power factor of La1−xSrxFeO3 and LaFe1−yNiyO3

The electrical conductivity (σ), Seebeck coefficient (S), and power factor (σS²) of perovskite-type LaFeO₃, La_1−xSr_xFeO₃ [0.1 ≤ x ≤ 0.4] and LaFe_1−yNi_yO₃ [0.1 ≤ y ≤ 0.6] were investigated in the temperature range of 300–1100 K to explore their possibility as thermoelectric materials. The electrical conductivity of LaFeO₃ showed semiconducting behavior, and its Seebeck coefficient changed from positive to negative around 650 K with increasing temperature. The electrical conductivity of LaFeO₃ increased with the substitutions of Sr and Ni atoms, while its Seebeck coefficient decreased. The Seebeck coefficient of La_1−xSr_xFeO₃ was positive, whereas that of LaFe_1−yNi_yO₃ changed from positive to negative with increasing Ni content. The substitutions of Sr and Ni were effective in increasing the power factor of LaFeO₃; 0.0053 × 10⁻⁴ Wm⁻¹ K⁻² for LaFeO₃ (1050 K), 1.1 × 10⁻⁴ Wm⁻¹ K⁻² for La_1−xSr_xFeO₃ (x = 0.1 at 1100 K) and 0.63 × 10⁻⁴ Wm⁻¹ K⁻² for LaFe_1−yNi_yO₃ (y = 0.1 at 1100 K).     

Influence of the rare earth composition on the properties of Ni–MH electrodes

Lattice parameters, hydrogen absorption properties and electrochemical cycling properties up to 240 cycles have been measured as a function of the Ce content for alloys of composition La_0.82−xCe_xNd_0.15Pr_0.03Ni_3.55Mn_0.4Al_0.3Co_0.75 (0≤x≤0.82). The results show the strong increase of the plateau pressure correlated to the cell volume decrease as a function of x. On the other hand, the hydrogen capacity measured in solid–gas reaction as well as the electrochemical capacity decreases slightly. The results show that both La and Ce have to be present to achieve a good cycle life, the cycling degradation being almost independent of their relative quantities in a broad range of concentrations.     

Thermoelectric properties of A-site doped perovskites (Sr0.6Ba0.4)1−xMxPbO3 (M = La, K)

La- and K-doped perovskite-type ceramics, (Sr_0.6Ba_0.4)_1−xLa_xPbO₃ with x = 0.0−0.1 and (Sr_0.6Ba_0.4)_1−xK_xPbO₃ with x = 0.00−0.15, were prepared to modify thermoelectric properties of semi-metallic Sr_0.6Ba_0.4PbO₃ via the doping of electrons and holes, respectively. The electrical conductivity σ and Seebeck coefficient S for the ceramics were measured at temperatures of 373–1073 K in air. With the La doping, electron carriers were successively doped and the material changed from a semi-metal for the undoped Sr_0.6Ba_0.4PbO₃ to a metal for the (Sr_0.6Ba_0.4)_0.9La_0.1PbO₃. With the K doping, the thermoelectric properties were essentially unchanged probably due to the carrier compensation effect by the generation of oxygen deficiencies. The thermoelectric power factor S²σ was maximized to a value of 3.1 × 10⁻⁴ Wm⁻¹ K⁻² at 773 K for the undoped Sr_0.6Ba_0.4PbO₃ ceramic.     

Rechargeable hydrogen batteries using rare-earth-based hydrogen storage alloys

Electrochemical properties of low cost MmNi₅-based-hydrogen storage alloys (Mm ≡ mischmetal) were extensively examined. The alloy MmNi_3.5Co_0.7Al_0.8 showed a very long cycle life with reasonable discharge capacity (250 mA h g⁻¹) and rate capability. An ingot with a very high endurance and low lattice strain was obtained under controlled conditions, including high rate cooling in the casting process for obtaining a columnar structure, no heat treatment and prevention of stoichiometric deviation. A columnar structure was formed so that the c-axis of the hexagonal structure was oriented parallel to the cooling plane. This alloy was significantly distinguished in crystal growth from a manganese-containing alloy (MmNl_3.5Co_0.5Al_0.3Mn_0.4) which had an equiaxial structure with considerable lattice strain, which needed conventional heat treatment. Deviation from stoichiometric composition to the nickel-rich side caused a significant decrease in capacity and cycle life owing to the precipitation of AlNi₃ at grain boundaries. The decay in capacity of the MH electrode using MmNi_3.6Co_0.7Al_0.8 was only 10% after 2000 cycles. The cylindrical sealed cell also showed a very long cycle life (a capacity decay of 6% after 2000 cycles). The high capacity sealed cell had a 1.5–2 times higher energy density (210 W h dm⁻³; 65 W h kg⁻¹) with a longer cycle life and better rate capability than the high capacity Ni-Cd battery.     

Preparation and bulk thermal expansion studies in M1−xCexSiO4 (M = Th, Zr) system, and stabilization of tetragonal ThSiO4

Two series of compositions with the general formula M_1−xCe_xSiO₄ (M = Th, Zr; x = 0.0–0.5; 1.0) were prepared by a standard solid state route and characterized by powder XRD. About 10 mol% of ceria could be dissolved in the lattice of ThSiO₄. A striking observation was the stabilization of tetragonal modification of ThSiO₄, which is metastable, by ceria substitution. There was no solubility of ceria in zircon (ZrSiO₄) lattice. The average linear thermal expansion coefficient (293–1123 K) of ZrSiO₄, ThSiO₄ and Th_0.9Ce_0.1SiO₄ are 4.65 × 10⁻⁶, 4.97 × 10⁻⁶ and 5.14 × 10⁻⁶ K⁻¹, respectively.     

Hydrogen disproportionation by reactive milling and recombination of Nd2(Fe1−xCox)14B alloys

Stoichiometric Nd₂(Fe_1−xCo_x)₁₄B alloys (x=0, 0.25, 0.5, 0.75 and 1) have been disproportionated into NdH_2+δ and bcc–(Fe,Co) (0≤x≤0.75) or fcc–Co (x=1), respectively, by milling in hydrogen at enhanced temperatures. Reactive milling leads to the disproportionation of the thermodynamically very stable Nd₂Co₁₄B alloy. This reaction is not possible via the conventional hydrogenation disproportionation desorption and recombination (HDDR) process. Grain sizes of disproportionated and recombined Nd₂(Fe,Co)₁₄B materials were found to be <10 nm and 40–50 nm, respectively — approximately an order of magnitude smaller than those of conventional-HDDR processed alloys. The recombined Nd₂Co₁₄B alloy shows on average slightly smaller grain sizes than the Nd₂Fe₁₄B compound. A more effective exchange coupling leading to enhanced remanences, possibly due to the slightly smaller grain size, has been observed for Nd₂Co₁₄B powders recombined at 600–700°C.     

Roles of lithium ions and La/Li-site vacancies in sinterability and total ionic conduction properties of polycrystalline Li3xLa2/3−xTiO3 solid electrolytes (0.21 ≤ 3x ≤ 0.50)

The Li_0.33La_0.55TiO₃ solid electrolyte has a maximum grain ionic conductivity of 1.13 × 10⁻³ S cm⁻¹ among the Li_3xLa_2/3−xTiO₃ oxides (0.21 ≤ 3x ≤ 0.50), but the total ionic conductivity of its polycrystalline phase is not the highest. Owing to the grain-boundary resistances controlling the total resistances of bulk samples, an excellent solid electrolyte is mainly characterized by the grain-boundary resistances. With regard to the role of lithium ions, the substitution of La³⁺ ions by the Li⁺ ions weakens the strength of inter-ionic forces, leading to the decrease in the sintering temperature. The presence of La³⁺/Li⁺-site vacancies promotes the densification and grain growth and further results in rapid decreases in porosity and grain-boundary resistances. Li_0.21La_0.60TiO₃ with a larger amount of La³⁺/Li⁺-site vacancies can therefore exhibit the highest total ionic conductivity through rapidly decreasing its grain-boundary resistances by changing its microstructure, and it becomes a better polycrystalline solid electrolyte than Li_0.33La_0.55TiO₃ in the Li_3xLa_2/3−xTiO₃ system studied, in spite of its lower grain ionic conductivity.     

Crystal structure of the new ternary aluminide CeRu3−xAl10+x (x = 0.17)

A large and transparent Yb³⁺:GdYCOB crystal with dimensions up to 30 mm× 58 mm have been grown by the Czochralski method. The spectral properties of Yb³⁺:GdYCOB crystal has been investigated. The absorption cross-section (σ_a) is 1.65 × 10⁻²⁰ cm² at 977 nm. The emission cross-section (σ_e) is 0.25 × 10⁻²⁰ cm² with an FWHM of 37.2 nm at 1020 nm. The fluorescence lifetime is 3.00 ms.     

Tailoring of misfit along interfaces between ZnxMn3−xO4 and Ag

This work is aimed at examining how the tetragonality of Zn_xMn_3−xO₄ spinel structures depends on the chemical composition when Zn_xMn_3−xO₄ is embedded in a metal matrix. The paper focuses on a wide range of Zn_xMn_3−xO₄ precipitates in a Ag matrix with x varying between 0 and 1.5. This variation of x has been obtained by internal oxidation of Ag–2at.%Mn–4at.%Zn in air followed by annealing in vacuo at different temperatures. It will be demonstrated that the Zn concentration x in Zn_xMn_3−xO₄ has a major influence on the interfacial misfit and orientation relation between Ag/Zn_xMn_3−xO₄. The degree of mismatch of 10.4% of 1 1 1 Ag–Mn₃O₄ and 2.4% of Ag–Zn_1.5Mn_1.5O₄ was visualized using the Bragg filtering technique on HRTEM micrographs of those interfaces. It was possible to identify misfit dislocations qualitatively with this technique at 1 1 1 Ag–Zn_xMn_3−xO₄ interfaces with different degree of mismatch.     

Structural, magnetic and magnetostrictive studies of Tb0.27Dy0.73(Fe1 − xAlx)2

Measurements of magnetic properties, X-ray diffraction and magnetostriction were made on Tb_0.27Dy_0.73(Fe_{1 − x}Al_x)₂ (x = 0.1, 0.2, …, 0.7) compounds. It was found that the system has the cubic MgCu₂ structure over almost the whole (Fe,Al) concentration range investigated, except for a narrow intermediate range (x = 0.4–0.6) where the hexagonal MgZn₂ structure appears. With increasing Al content x, the lattice constant a increases linearly with x. The first replacement of Fe results in a marked decrease in the Curie temperature, which is followed by a slight decrease in T_C with x. A linear decrease in magnetostriction of |λ_| − λ| at room temperature with x was also observed from 1530 × 10⁻⁶ for x=0 to 36×10⁻⁶ for x=0.3. The saturation magnetization σ_s exhibits a complex concentration dependence in the Tb_0.27Dy_0.73(Fe)_{1 − x}Al_x)₂ system: in the range x < 0.5, σ_s increases linearly with x and, for x = 0.5–0.6, σ_s decreases and then increases again. An enhancement of the magnetic ‘hardness’ in this system was also observed at low temperature.     

A comparative study on the hydriding kinetics of Zr-based AB2 hydrogen storage alloys

Two kinetic models (Jander model and Chou model) are used to investigate the hydrogen absorption kinetic mechanism of Zr-based AB₂ type Laves phase alloys (Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55). The analysis shows that the rate-controlling step is the diffusion process at high temperatures in the range from 673 K to 923 K with a low hydrogen concentration (solid solution phase). Both models can well describe the experimental data but Chou model is preferred. Chou model is simpler and easier to use for analyzing the experimental results. The activation energies calculated using Chou model with the least square method are 29.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, 43.8 kJ/mol H₂ for Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and 48.5 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55, which are close to the values reported in the literature (28.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5 and 40.3 ± 1.5 kJ/mol H₂ for both Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55).     

Synthesis and characterization of LiGaxMn2−xO4 (0 ≤ x ≤ 0.05) by triethanolamine-assisted sol–gel method

Spinel LiGa_xMn_2−xO₄ (0 ≤ x ≤ 0.05) cathode materials with phase-pure particles and nano-sized distribution were synthesized by sol–gel method using triethanolamine as the chelating agent. The effects of heat treatment on the physicochemical properties of the spinel LiGa_xMn_2−xO₄ powders were examined with thermogravimetric and differential thermal analysis (TG/DTA), powder X-ray diffraction (XRD) and scanning electron micrograph (SEM). The LiGa_xMn_2−xO₄ (0 ≤ x ≤ 0.05) electrodes were characterized electrochemically by charge/discharge experiments under a current rate of 0.5C at 55 °C. Although the Ga-doped spinel electrode showed smaller initial discharge capacity, it exhibited better cycling performance than the undoped-LiMn₂O₄ electrode. The dQ/dV versus potential plots at 55 °C revealed that the improvement in cycling performance of the Ga-doped spinel electrode is attributed to stabilization of the spinel structure by the presence of gallium ion.     

Existence, structure and valence properties of the skutterudites CeyFe4−xCoxSb12

We report on sample preparation, annealing effects, electron microprobe analysis in the series Ce_yFe_4−xCo_xSb₁₂ which shows that a phase separation occurs for substituted samples (0<x<4) annealed at 650 and 550 °C. Single phase samples are obtained for either Ce_yFe₄Sb₁₂ or Ce_yCo₄Sb₁₂ samples annealed at 650 °C and for all compositions when annealed at 700 °C. The valence state of Ce in homogeneous samples has been studied using X-ray absorption spectroscopy (XAS). Ce ions are trivalent throughout the series and the XAS spectra does not show effect of the crystal field on the 5d-final state.     

Preparation and structures of the La1−xKxCo1−xNbxO3 (x = 0–l) system

The La_1−xK_xCo_1−xNb_xO₃ system was performed by conventional solid state reaction technique using metal oxides. By DSC analysis, the activation energy of crystallization of the powders with x = 0.3 is 388.4 kJ/mol. The crystal structure of the compound reveals a transition from rhombohedral to cubic, and then to orthorhombic structure as the amount of the potassium niobate (KNbO₃) increases. It is found that the structure of the samples with x < 0.3 is similar to that of lanthanum cobaltate (LaCoO₃), while at the compositions with 0.7 ≥ x ≥ 0.3, the structure transforms to cubic. Finally, with x ≥ 0.7, the structures were similar to that of KNbO₃. According to the results of selected-area-diffraction (SAD) patterns and X-ray diffraction (XRD) identifications, the lattice parameters were calculated. The direction of superlattice structure along [2 1 0] was found for x = 0.5 as identified from SAD patterns. The dielectric constants were measured with cubic structure. Dielectric constant (K) decreases with increasing x.     

Influence of tin on the electrochemical and gas phase hydrogen sorption in Mg2−xSnxNi (x = 0, 0.1, 0.3)

Mg_2−xSn_xNi (x = 0, 0.1, 0.3) alloys were synthesized by reactive ball milling under protective Ar atmosphere and liquid n-heptane. The microstructure and the morphology of the powders were determined by X-ray diffraction and scanning electron microscopy. The as-milled alloys consist of Mg₂Ni nanocrystals with an average grain size in the range 3–7 nm, depending on the alloy composition. Sn containing phases were not detected even in the Sn-rich alloy. Obviously, Sn is dissolved in the Mg₂Ni intermetallic compound. Gas phase sorption of hydrogen was not observed in the alloys containing Sn (Mg_2−xSn_xNi; x = 0.1, 0.3). It was suggested that Sn impedes the process of hydrogen molecules decomposition. The as-milled alloys absorbed reversibly hydrogen electrochemically. Mg₂Ni alloy showed the highest discharge capacity of 300 mAh/g. The capacity of Mg_1.9Sn_0.1Ni and Mg_1.7Sn_0.3Ni was about 260 mAh/g. It was found that Sn improved the cycle life of the electrode.