The effect of Zr substitution for Ti on the microstructures and electrochemical properties of electrode alloys Ti1−xZrxV1.6Mn0.32Cr0.48Ni0.6

The effect of Zr substitution for Ti on the microstructures and electrochemical properties of the electrode alloys Ti_1−xZr_xV_1.6Mn_0.32Cr_0.48Ni_0.6 (x=0.2,0.3,0.4,0.5) has been studied. It is found by X-ray powder diffraction and energy dispersive X-ray spectroscope analyses that all the alloys consist of a C14 Laves main phase with hexagonal structure and a V-based solid solution secondary phase with b.c.c. structure. A small amount of TiNi-based third phase with b.c.c. structure has been found precipitated in the C14 Laves main phase in addition. With the increase in the amount of Zr substitution, the lattice parameters of the main phase and secondary phase are found increased and decreased, respectively. The electrochemical PCT curves indicate that the maximum hydrogen absorption capacity [H/M]_max decreases with increasing Zr substitution, which may be attributed to the decrease in the content of V-based solid solution. The maximum discharge capacity and high rate dischargeability of the alloy electrodes both decrease, while the cyclic durability increases with the increasing amount of Zr substitution.     

Effect of rare earth elements on electrochemical properties of La–Mg–Ni-based hydrogen storage alloys

La_0.60R_0.20Mg_0.20(NiCoMnAl)_3.5 (R = La, Ce, Pr, Nd) alloys were prepared by inductive melting. Variations in phase structure and electrochemical properties due to partial replacement of La by Ce, Pr and Nd, were investigated. The alloys consist mainly of LaNi₅ phase, La₂Ni₇ phase and LaNi₃ phase as explored by XRD and SEM. The maximum discharge capacity decreases with Ce, Pr and Nd substitution for La. However, the cycling stability is improved by substituting Pr and Nd at La sites, capacity retention rate at the 100th cycle increases by 13.4% for the Nd-substituted alloy. The electrochemical kinetics measurements show that Ce and Pr substitution improves kinetics and thus ameliorates the high rate dischargeability (HRD) and low temperature dischargeability. The HRD at 1200 mA g⁻¹ increases from 22.1% to 61.3% and the capacity at 233 K mounts up from 90 mAh g⁻¹ to 220 mAh g⁻¹ for the Ce-substituted alloy.     

The effect of particle size on the electrode performance of Ti–V-based hydrogen storage alloys

The effect of particle size ranging from 100 mesh to below 500 mesh on the electrochemical properties of _{Ti0.8Zr0.2V2.7Mn0.5Cr0.8Nix}(x=0.75,1.75)${\mathrm{Ti}}_{0.8}{\mathrm{Zr}}_{0.2}{\mathrm{V}}_{2.7}{\mathrm{Mn}}_{0.5}{\mathrm{Cr}}_{0.8}{\mathrm{Ni}}_x(x=0.75,1.75)$ hydrogen storage alloy electrodes was investigated. SEM observation on the surface of the alloy electrodes after charge/discharge cycles revealed that the abilities of anti-pulverization and anti-corrosion of the x=0.75$x=0.75$ alloy were much lower than those of the x=1.75$x=1.75$ alloy. For both of the two alloys, the electrode performance is affected markedly by the particle size. With the increase of the initial particle size, the initial discharge capacity of the alloy electrode decreases and the pulverization of the alloy particles aggravates, especially for the particles of the x=0.75$x=0.75$ alloy with size larger than 400 mesh, the size of which was minimized obviously compared with their initial size. However, the maximum discharge capacity and the cycling stability almost do not correlate to the initial particle size but relate with their actual particle size. As the actual particle size decreases, the maximum discharge capacity increases and the cycling stability declines.     

Effect of Mo–Ni treatment on electrochemical kinetics of La–Mg–Ni-based hydrogen storage alloys

In order to improve kinetic properties of La–Mg–Ni-based hydrogen storage alloys, Mo–Ni treatment was applied to La_0.88Mg_0.12Ni_2.95Mn_0.10Co_0.55Al_0.10 alloy powders. FESEM results showed that after Mo–Ni treatment some network-shaped substance with nano-size formed on the surface of the alloy particles. The EDS results revealed increase in Ni content and emerge of Mo element. EIS and Linear polarization showed that charge-transfer resistance decreased and exchange current density increased for the treated alloy electrode, and the high rate dischargeability (HRD) was consequently improved. HRD at 1500 mA/g increased from 22.5% to 39.5%. Mo- and Ni-single treatments were performed compared with the Mo–Ni treatment, and the results showed that the single treatment improved HRD slightly, far less than the Mo–Ni treatment.     

Effect of carbon coating on the electrochemical properties of La–Y–Ni-based hydrogen storage alloys

The A₂B₇-type (LaSmY) (NiMnAl)_3.5 alloys were prepared by induction melting, and then the alloy samples coated with different contents of nano-carbon were prepared by the mixing and sintering method using pitch as carbon source. The effects of the contents and structure of the coated-carbon on the electrochemical properties of alloy samples were investigated. With the carbon content increase from 0.1 to 1.0 wt%, the cyclic stability is improved and the high-rate dischargeabilitiy (HRD) of the alloy electrodes first increase and then decrease. The kinetic results show that the carbon coating improves the electrocatalytic activity and electrical conductivity of the alloy electrodes. The alloy electrode with 0.5 wt% carbon coating exhibits the best electrochemical properties. The maximum discharge capacity (C_max) is 345.7 mAh·g⁻¹, the HRD₁₂₀₀ is 72.49%, and the capacity retention rate (S₃₀₀) is 79.44%.     

Effect of Sm on hydrogen storage performance of La–Sm–Mg–Ni alloys

Abstract

In this study, Sm was adopted in order to completely replace the expensive Pr/Nd elements in the A2B7 type alloy. The results indicate that Sm is a favourable element for forming Ce2Ni7 type and Ce5Co19 type phases. With the increasing amount of Sm, the discharge capacity of the alloy retains a value of 283·3 mAh g^?1 at the current density of 1200 mA g^?1. The maximum discharge capacity of the alloys increases with the increasing Sm content when Mg content is relatively low. By optimising the composition and processing technology, the cycle life the alloy enhances from 74 cycles to more than 540 cycles, and the maximum discharge capacity also increases from 300 to 355 mAh g^?1.     

Phase structures and electrochemical properties of the Laves phase hydrogen storage alloys Zr1−xTix(Ni0.6Mn0.3V0.1Cr0.05)2

The effects of the partial substitution of Ti for Zr in Zr_1−xTi_x(Ni_0.6Mn_0.3V_0.1Cr_0.05)₂ alloys are reported in this paper. The main phases C15 and C14 Laves phases, and secondary phase Zr₇Ni₁₀ were found. With increasing Ti content, abundance of C15 phase decreases and that of C14 phase increases. Increase of Ti content leads to decrease of the lattice parameters of both C15 and C14 phases. Pressure-composition isotherms show a decrease of the stability of the alloy hydride. Ti substitution for Zr in the alloys is effective to improve the activation and high-rate dischargeability. A critical substitution content of Ti is found at x=0.2. The cycling stability and the high rate dischargeability are deteriorated for the alloy electrodes with high Ti content (x>0.3).     

Structures and properties of Mg–La–Ni ternary hydrogen storage alloys by microwave-assisted activation synthesis

It is a challenge to prepare a material meeting two conflicting criteria – absorbing hydrogen strongly enough to reach a stable thermodynamic state and desorbing hydrogen at moderate temperature with a fast reaction rate. With the guide of the Mg–La–Ni phase diagram, microwave sintering (MS) was successfully applied to preparing Mg–La–Ni ternary hydrogen storage alloys from the powder mixture of Mg, La and Ni. Their phase structures, morphologies and hydrogen absorption and desorption (A/D) properties have been studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-isotherm (PCI) and differential scanning calorimetry (DSC). The metal hydride of 70 Mg–9.72 La–20.28 Ni (wt pct) has the best comprehensive hydriding and dehydriding (H/D) properties, which can absorb 4.1 wt.% H₂ in 600 s and desorb 3.9 wt.% H₂ in 1500 s at 573 K. The DSC results reveal its onset temperatures of hydrogen A/D are the lowest among all the samples, which are 671.4 and 600.9 K. Its activation energy of dehydriding reaction is 113.5 kJ/mol H₂, which is the smallest among all the samples. Also, Chou model was used to analyze the reaction kinetic mechanism.     

The effect of Na addition on the first hydrogen absorption kinetics of cast hypoeutectic Mg–La alloys

With superior properties of Mg such as high hydrogen storage capacity (7.6 wt% H/MgH₂), low price, and low density, Mg has been widely studied as a promising candidate for solid-state hydrogen storage systems. However, a harsh activation procedure, slow hydrogenation/dehydrogenation process, and a high temperature for dehydrogenation prevent the use of Mg-based metal hydrides for practical applications. For these reasons, Mg-based alloys for hydrogen storage systems are generally alloyed with other elements to improve hydrogen sorption properties. In this article, we have added Na to cast Mg–La alloys and achieved a significant improvement in hydrogen absorption kinetics during the first activation cycle. The role of Na in Mg–La has been discussed based on the findings from microstructural observations, crystallography, and first principles calculations based on density functional theory. From our results in this study, we have found that the Na doped surface of Mg–La alloy systems have a lower adsorption energy for H₂ compared to Na-free surfaces which facilitates adsorption and dissociation of hydrogen molecules leading to improvement of absorption kinetic. The effect of Na on the microstructure of these alloys, such as eutectic refinement and a density of twins is not highly correlated with absorption kinetics.     

Effect of Al content on the structural and electrochemical properties of A2B7 type La–Y–Ni based hydrogen storage alloy

LaY_1.9Ni_10.2−xAl_xMn_0.5 (x = 0–0.6) hydrogen storage alloys have been prepared using a vacuum induction-quenching furnace and annealed at 1148 K for 16 h. The alloys are composed of Ce₂Ni₇- and Gd₂Co₇-type phases and an extra Pr₅Co₁₉-type phase appears when x = 0.6. Aluminum tends to enter the inner AB₅ slabs of Ce₂Ni₇- and Gd₂Co₇-type phases and promotes the generation of new AB₅ slabs. The maximum discharge capacity of the alloy electrodes is stable at approximate 375 mA h/g as x increases from 0 to 0.4 and then decreases to 364.2 mA h/g (x = 0.6). The cycling capacity retention rate at the 300^th cycle is 59.4%, 62.0%, 62.7% and 58.7% for x = 0, 0.2, 0.4 and 0.6, respectively, indicating that the function of aluminum on improving the cyclic stability of the alloy electrodes is limited. The main reason is that the similar pulverization degrees of the alloys are presented during the charge/discharge cycles.     

Microstructure characteristics,hydrogen storage thermodynamic and kinetic properties of Mg–Ni–Y based hydrogen storage alloys

In this paper, the Mg_95-X-Ni_x-Y₅ (x = 5, 10, 15) alloy were prepared by vacuum induction melting. The X-ray diffraction was used to analytical phase composition in different states, and the Scanning Electron Microscope and Transmission Electron Microscope were used to characterize the microstructure and crystalline state. Meanwhile, the kinetic properties of isothermal hydrogen adsorption and desorption at different temperatures also were tested by the Sievert isometric volume method. The results indicate that the hydrogenated Mg–Ni–Y samples is a nanocrystalline structure consists of MgH₂, Mg₂NiH₄, and YH₃ phases. And, the in-situ formed YH₃ phase not decompose in the process of dehydrogenation and evenly dispersed in the mother alloy, which plays a paly a positive the catalytic role for the reversible cyclic reaction of Mg and Mg₂Ni phases. In addition, the Ni elements are effectively to improve the thermodynamic properties of the Mg-based hydrogen storage alloy, the desorption enthalpy of the Ni₅, Ni₁₀, and Ni₁₅ samples successively decrease to 84.5, 69.1, and 63.5 kJ/mol H₂. The hydrogen absorption and desorption kinetics of the Mg–Ni–Y alloy are improved obviously with the increase of Ni content, especially for Mg₈₀Ni₁₅Y₅ alloy, which the optimal hydrogenated temperature is reduced to 200 °C, and the 90% of the maximum hydrogen storage capacity can be absorbed within 1 min, about 5.4 wt % H₂. Besides, the dehydrogenated activation energy of the Mg₈₀Ni₁₅Y₅ alloy also is reduced to 67.0 kJ/mol, and it can completely release hydrogen at 320 °C within 5 min, which is almost reached the hydrogen desorption capability of Ni₅ alloy at 360 °C. This means that Ni element is a very positive element to reduce the hydrogen desorption temperature.     

Elaboration and electrochemical characterization of Mg–Ni hydrogen storage alloy electrodes for Ni/MH batteries

Mg–Ni hydrogen storage alloy electrodes with composition of Mg–33, 50, 67 Ni at. % in amorphous phase were prepared by means of mechanical alloying (MA) process using a planetary ball mill. The electrochemical hydrogen storage characteristics and mechanisms of these electrodes were investigated by electrochemical measurements, X–ray diffraction (XRD) and scanning electron microscope (SEM) analyses. The relationship between alloy composition and electrochemical properties was evaluated. In addition, optimum milling time and composition of Mg–Ni hydrogen storage alloy with acceptable electrochemical performance were determined. XRD results show that the alloys exhibit dominatingly amorphous structures after milling of 20 h. The electrochemical measurements revealed that the discharge capacity of Mg₃₃Ni₆₇ and Mg₆₇Ni₃₃ alloy electrodes reached a maximum when alloys were prepared after 20 h of milling time (260 and 381 mAhg^?1, respectively). The maximum discharge capacity of Mg₅₀Ni₅₀ alloy was observable after 40 h milling (525 mAhg^?1). It was also found that the cyclic stability of the alloys increased with increasing Ni content. Among these alloys, the amorphous Mg₅₀Ni₅₀ alloy presents the best overall electrochemical performance. In this paper, electrode process kinetics of Mg₅₀Ni₅₀ alloy electrode was also studied by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The impedance spectra of electrodes were measured at different depths of discharge (DODs). The observed spectra were fit well with the equivalent circuit model used in the paper. The electrochemical parameters calculated from electrochemical impedance were also compared. The electrochemical discharge and cyclic performance of 20, 40 and 60 h milled Mg₅₀Ni₅₀ alloy electrodes were demonstrated by the fitted charge transfer resistance and Warburg impedance obtained at various DODs. It was further observed that the controlling-step of the discharge process changed from a mixed rate-determining process at lower DODs to a mass-transfer controlled process at higher DODs. The fitted results demonstrated that charge–transfer resistance (R_ct) increased with DOD. The R_ct of 40 h milled Mg₅₀Ni₅₀ alloy (29.27 Ω) was lower than that of 20 h (41.89 Ω) and 60 h milled alloys (92.43 Ω) at fully discharge state.     

An improvement on cycling stability of Ti–V–Fe-based hydrogen storage alloys with Co substitution for Ni

In this work, the effects of Co substitution for Ni on the microstructures and electrochemical properties of Ti_0.8Zr_0.2V_2.7Mn_0.5Cr_0.6Ni_1.25−xCo_xFe_0.2 (x = 0.00–0.25) alloys were investigated systematically by XRD, SEM and electrochemical measurements. The structural investigations revealed that the main phases of all of the alloys were the C14 Laves phase in a three-dimensional network and the V-based solid solution phase with a dendritic structure. The lattice parameters and unit cell volumes of the two phases gradually increased with the increase of Co concentration. The relative abundance of the C14 Laves phase slightly increased from 47.3% to 49.6%, accordingly that of the V-based solid solution phase decreased, with the increase of x from 0.00 to 0.25. The crystal grain of the V-based solid solution phase was obviously refined after Co substitution. The electrochemical investigations showed that the proper substitution of Co for Ni improved the cycling durability of the alloy electrodes mainly due to the suppression of both the pulverization of the alloy particles and the dissolution of the main hydrogen absorbing elements (V and Ti) into the KOH solution. The cycling stability of the alloy electrode with x = 0.1 was 79.8% after 200 cycles. However, the maximum discharge capacity (C_max) was decreased from 340.5 to 305.6 mAh g⁻¹, and the high rate dischargeability (HRD) gradually decreased from 66.8% to 55.0% with increasing x from 0.00 to 0.25.     

The effect of deposition temperature on the catalytic activity of Ni–P alloys toward the hydrogen reaction

The deposition of Ni–P alloys in the temperature range from 0°C to 60°C has been studied. At low temperatures only Ni was deposited. With increasing temperature the amount of P in the deposited alloy increases. The proposed explanation is based on the known reaction mechanisms for electrodeposition and electroless deposition. The catalytic activity of the deposited alloys towards the hydrogen reaction was determined. The highest activity was found at 25°C.     

Highly active and novel A-site deficient symmetric electrode material (Sr0.3La0.7)1−x (Fe0.7Ti0.3)0.9Ni0.1O3−δ and its effect on electrochemical performance of SOFCs

A-site deficient (Sr_0.3La_0.7)_1-x (Fe_0.7Ti_0.3)_0.9Ni_0.1O_3-δ ((SL)_1-xFTN) symmetrical electrodes with compositions x = 0.1, 0.2 and 0.3 denoted as SLFTN-01, SLFTN-02, and SLFTN-03 respectively were synthesized via modified Pechini method. The as prepared samples were further coated on LGSM electrolyte through screen-printing technique. Electrochemical performance was significantly improved for A-site deficient (SL)_1-xFTN due to increased concentration of oxygen vacancy. XRD patterns revealed better reversibility for (SL)_1-xFTN with rhombohedral structure. Low polarization resistance (Rp) ~0.210, 0.195 and 0.165 Ωcm² (in dry H₂) and 0.069, 0.046 and 0.043 Ωcm² (in air) was measured for SLFTN-01, SLFTN-02, and SLFTN-03 respectively at a temperature of 750 °C. Highest conductivities ~326, 338 and 342 Scm^?1 were calculated in air and the conductivities obtained in dry H₂ were ~0.64, 0.81 and 1.01 Scm^?1 at 700 °C. It was observed that small polaron mechanism was responsible for the decreased conductivity with the increased temperature range. The fabricated symmetrical cell ((SL)_1-xFTN/LDC|LSGM|LDC/(SL)_1-xFTN), maintained good stability without any degradation during the test time ~500 h (in air) and 100 h (in dry H₂). The detailed investigations categorized the fabricated cells well suited as anode and cathode with improved performance and excellent stability both in oxidizing and reducing atmospheres.     

An investigation of the borohydride oxidation reaction on La–Ni-based hydrogen storage alloys

In this study, LaNi_4.7Sn_0.2Cu_0.1 metal hydride alloys, with and without surface deposits of Pt, are investigated as electrocatalysts for the borohydride oxidation reaction (BOR) in alkaline media. Results obtained for LaNi_4.78Al_0.22 and LaNi_4.78Mn_0.22 are used for comparison. It is observed that wet exposition to hydrogen or sodium borohydride lead to some hydriding of the metal hydride alloy particles, particularly that with a coating of Pt. In the presence of borohydride ions, the hydrided charged alloys present more negative potentials for the (boro)hydride oxidation process, and these enhancements are significantly larger for the Pt-coated material. In the potential range of interest, the results demonstrate considerable activity for the BOR, but just for the alloy with Pt. In the presence of borohydride ions in the solution there is a continuous hydriding the alloy during the discharge of the metal hydride electrode. Differential electrochemical mass spectrometry (DEMS) measurements showed that there is formation of H₂, either by hydrolysis or by partial oxidation of the borohydride ions, but in the absence of Pt the hydrolysis process is quite slow.