Correlation between electrochemical properties of the CNTs/AB5 composite hydrogen storage alloys and their catalytic properties for KBH4

Searching for non-precious metal anode catalysts with high catalytic activity and capable of inhibiting hydrolysis side reactions is very important for direct borohydride fuel cell (DBFC). In this work, the as-cast AB₅ alloy powders are firstly mixed with CNTs in a ratio of 1:9. Then the mixture of AB₅ alloy and CNTs is ball milled in different milling time. Finally, the CNTs/AB₅ composite alloys are obtained. Not only the catalytic properties of the CNTs/AB₅ composite alloys used as anode catalysts in DBFC, but also the electrochemical properties of the alloys have been investigated in detail. The research results indicate that, as the ball milling time is extended, the electrochemical properties and catalytic properties on ΒΗ₄⁻ of the CNTs/AB₅ composite alloys become better first and then worsen. The CNTs/AB₅ alloy milled 2 h exhibits the best electrochemical properties and catalytic properties. Furthermore, we predict that the electrochemical properties of the composite alloy are positively correlated with the catalytic properties as anode catalyst for DBFC.     

The development of hydrogen storage electrode alloys for nickel hydride batteries

The development of hydrogen storage electrode alloys in the 1980s resulted in the birth and growth of the rechargeable nickel hydride (Ni/MH) battery. In this paper we describe briefly a semi-empirical electrochemical/thermodynamic approach to develop/screen a hydrogen storage alloy for electrochemical application. More specifically we will discuss the AB_x Ti/Zr-based alloys. Finally, the current state of the Ni/MH batteries including commercial manufacture processes, cell performance and applications is given.     

Insights into the structure–performance relationship in La–Y–Ni-based hydrogen storage alloys

La–Y–Ni-based alloys with different phase structures possess various physicochemical properties and thereby different hydrogen storage performances. In this work, the hydrogen storage and electrochemical properties of LaY_1·9Ni₁₀Mn_0·5Al_0.2 alloys with different phase structures (2H-A₂B₇, 3R-A₂B₇ and 2H-A₅B₁₉) are investigated. All the investigated phases present two plateaus in pressure-composition-temperature (PCT) curves, which is induced by the different hydrogen location (A₂B₄ or AB₅) during the hydrogen absorption process. All of the LaY_1·9Ni₁₀Mn_0·5Al_0.2 series alloys possess good hydrogen storage capacities and electrochemical properties. The cyclic stability of the alloys is determined by the anti-corrosive properties of the alloys to electrolyte, neither the phase transition nor the previously believed pulverization. This work, by systematically investigating phase transitions during the annealed process and elucidating the key factors of influencing the cyclic stability, is useful for the design of La–Y–Ni-based alloy for the application of hydrogen storage and beyond.     

The structure, hydrogen storage, and electrochemical properties of Fe-doped C14-predominating AB2 metal hydride alloys

A series of Fe-substituting cobalt C14-predoninating AB₂ alloys with the general formula Ti₁₂Zr_21.5V₁₀Cr_7.5Mn_8.1Fe_xCo_8−xNi_32.2Sn_0.3Al_0.4 (x = 0-5) were studied for the impacts of Fe to structure, gaseous, and electrochemical hydrogen storage properties. All alloys exhibit hyper-stoichiometric C14 main phase due to the formation of A-rich non-Laves secondary phases and the loss of Zr and Ti in the melt. Lattice parameters together with the unit cell volume increases and then decreases with increasing Fe-content which indicates the existence of anti-site defects. The amount of TiNi secondary phase increases with the increase of Fe-content up to 4% and shows a detrimental effect to the high-rate dischargeability of the alloys. Most of the gaseous storage characteristics remain unchanged with the addition of Fe. In the electrochemical properties, Fe-addition in the AB₂ alloys facilitates activation, increases the total electrochemical capacity and effective surface reaction area, decreases the half-cell high-rate dischargeability and bulk hydrogen diffusion, and deteriorates both −10 and −40 °C low-temperature performance. Fe-substituting Co in AB₂ alloys as negative electrode of nickel metal hydride battery can reduce the raw material cost with the trade-off being mainly in the low-temperature performance.     

Theoretical model on the electronic properties of multi-element AB5-type metal hydride

Nowadays, multi-element alloys are preferred over binary alloys for application point of view. The hydrogenation properties strongly depend on the thermodynamic, structural and electronic properties of the alloys. At present, no model is available which can predict the hydrogen storage properties of the multi-element alloy, before actual synthesis of the alloy. In the present investigation, efforts are made to develop a theoretical mathematical model to predict the hydrogenation properties of multi-element AB₅-type metal hydride. The present investigation deals with the various electronic parameters which may affect the hydrogenation characteristics of the metal hydride. Based on all such parameters, an electronic factor has been proposed for AB₅-type alloys. Electronic factor has been combined with the structural and thermodynamical factor to propose a new combined factor, which was further correlated with the hydrogen storage capacity of the alloy. Atomic radius and electronic configuration of substituted elements in the multi-element AB₅-type hydrogen storage alloy have been found as key players to predict the hydrogenation properties of the alloys before synthesis. It has been shown that in the case of alloy series with multiple substitutions, the combined factor is more relevant in deciding the hydrogen storage capacity in comparison to electronic factor alone. Combined factor is directly proportional to the hydrogen storage capacity. All the three factors thermodynamic, structural and electronic together may lead to the prediction of pressure-composition isotherm of the multi-element AB₅-type hydrogen storage alloy.     

Activation and de/ hydriding behavior in Ti23V40Mn37 alloy by Hf and Hf/Cr substitutions

To improve absorption/desoprtion rate and hydrogen desorption capacity of Ti–V–Mn alloy, Ti₂₃V₄₀Mn₃₇ alloys by Hf and Hf/Cr substitutions were prepared, the activation and hydriding/dehydriding behaviors of the alloys are investigated. Results show that the lattice parameter of BCC phase increases and the ratio of C14 Laves phase also increases by the substitutions. Ti₁₉Hf₄V₄₀Mn₃₅Cr₂ alloy exhibits the rapid absorption/desoprtion rate and the highest hydrogen desorption capacity of 1.58 wt% H₂ at 293 K. The Hydrogenation kinetic mechanism of the alloys is transformed from nucleation-growth to diffusion, and the dehydrogenation kinetic mechanism is only nucleation-growth. The activation energy of Hf/Cr substituted alloy is lower than that of Hf-free alloy, with the values of 53.79 kJ mol⁻¹ H₂ and 90.13 kJ mol⁻¹ H₂ respectively, which is accounted for the easily absorption of hydrogen molecules on the particle surface and the rapid H diffusion of the interior of alloy, thus the substituted alloys have rapid absorption/desoprtion rate.     

Effect of polyaniline on hydrogen absorption–desorption properties and discharge capacity of AB3 alloy

A series of AB₃/PANI composites were prepared by adding polyaniline (PANI) into La_0.7Mg_0.25Ti_0.05Ni_2.975Co_0.525 (AB₃) hydrogen storage alloy, which was prepared by magnetic levitation melting, and the composites were investigated by XRD and SEM. The effects of PANI concentration on the hydrogen absorption–desorption properties and discharge capacities of AB₃ alloy were systematically studied by P–C–T isotherms and LAND battery test system, respectively. The results indicated that the addition of PANI did not change the hydrogen absorption capacity of AB₃ alloy distinctly, while the hydrogen desorption plateau pressure of AB₃ alloy decreased firstly, and then increased with the increase in the PANI concentration, the minimum plateau pressures of 0.022, 0.1, 0.321 and 0.55 MPa were obtained with PANI concentration of 2 wt% at 25, 50, 80 and 100 °C, respectively. It was theoretically verified by the changes in enthalpy and entropy of AB₃/PANI hydrides dehydrogenation which were calculated by Van’t Hoff equation. In the present paper, the phenomenon that PANI improved the hydrogen absorption kinetics of AB₃ alloy was found; the influence of PANI concentration on hydrogen absorption kinetics of AB₃ alloy was more apparent at higher temperature. The activation energies of dissolved hydrogen in AB₃/PANI hydrides were calculated from hydrogen absorption kinetics and the Arrhenius equation. LAND experiments demonstrated that, the AB₃/PANI electrodes composites possessed higher cycling discharge capacity retention rates than AB₃ electrode alloy.     

The effect of rapid solidification on the microstructure and hydrogen storage properties of V35Ti25Cr40 hydrogen storage alloy

The microstructures and hydrogen storage properties of as-cast and rapidly solidified V₃₅Ti₂₅Cr₄₀ alloys have been investigated in this paper. The results showed that the rapid solidification refined the dendritic microstructure and altered the element distribution of the alloy. And through the positron annihilation measurements of the vacancy trapping rate (K_d1) and vacancy-trapped positron annihilation lifetime (τ₂), it was found that the rapid solidification increased the vacancy concentration and at the same time decreased the vacancy size in the alloy. The XRD results showed that the rapid solidification also significantly enlarged the alloy's lattice parameter. As a result of the microstructure change, the hydrogen absorption capacity and hydrogen absorption rate were increased; and the kinetic mechanism of hydrogen absorption was changed from 3-D diffusion control in the as-cast alloy to chemical reaction control in the rapidly solidified alloy; but the activation property was to some extent weakened after the rapid solidification.     

Hydrogen storage and electrochemical properties of annealed low-Co AB5 type intermetallic compounds

The structure, hydrogen storage and electrochemical properties of annealed low-Co AB₅-type intermetallic compounds have been investigated. La-alloy, Nd-alloy and Cr-alloy are used to represent La_0.8Ce_0.2Ni₄Co_0.4Mn_0.3Al_0.3, La_0.6Ce_0.2Nd_0.2Ni₄Co_0.4Mn_0.3Al_0.3 and La_0.6Ce_0.2Nd_0.2Ni_3.8Co_0.4Mn_0.3Al_0.3Cr_0.2, respectively. The XRD results indicated that annealed samples are all single-phase alloys with CaCu₅ type structure. The maximum of both hydrogen content and discharge capacity is obtained for La-alloy 1.23 wt%H₂ and 321.1 mA h/g, respectively. All the investigated alloys are quiet stable with ΔH of hydrogen desorption about 36–38 kJ/mol H₂. Cycle life of alloy electrode has been improved by partial substitution of La for Nd and Ni for Cr. The highest capacity retention of 92.2% after 100 charge/discharge cycles at 1C has been observed for Nd-alloy. The hydrogen diffusion coefficient measured by PITT is higher at the start of charging process and dramatically reduces by 2–3 order of magnitude with saturation of β-hydride. The highest value 6.9 × 10^?13 cm²/s is observed for La alloy at 100% SOC. Partial substitution La for Nd and Cr for Ni in low-Co AB₅ metal hydride alloys slightly reduces maximum discharge capacity, HRD performance and hydrogen diffusion kinetics. Low-Co alloys show good overall electrochemical properties compared to high-Co alloys and might be perspective materials for various electrochemical applications.     

Electrode characteristics of the Cr and La doped AB2-type hydrogen storage alloys

AB₂-type alloy, a kind of hydrogen storage alloys used as an anode of Ni-MH batteries, has a large discharge capacity but still has several problems such as initial activation, cycle life and self-discharge. In this study, we have investigated the effects of Cr addition and fluorination after La addition on AB₂-type alloy with Zr_0.7Ti_0.3V_0.4Mn_0.4Ni_1.2 composition. The EPMA and SEM surface analysis techniques were used and the crystal structure was characterized by XRD analysis. Metal hydride negative was characterized by galvanostatic cycling test, electrochemical impedance spectroscopy and potentiodynamic polarization. Cr-addition is found to be effective to improve cycle life and self-discharge characteristics but ineffective to promote initial activation due to the formation of stable oxide film on alloy surface. Highly reactive particles have been formed by fluorination after La-addition to the alloys and those particles may remarkably improve the initial activation of MH-negative electrodes.     

Effect of ball milling time on microstructure and electrochemical properties of CeMg12+100%Ni hydrogen storage alloy

Abstract

In order to improve hydrogen storage performances of CeMg₁₂ type alloys, ball milling technology was used for preparing nanocrystalline/amorphous CeMg₁₂+100%Ni composite hydrogen storage alloys. The microstructures and morphologies of alloy samples were characterised by X-ray diffraction, scanning electron microscopy and high resolution transmission electron microscopy. The electrochemical hydrogen storage characteristics of as milled alloys were tested by an automatic galvanostatic system. The electrochemical impedance spectra were plotted by an electrochemical workstation (PARSTAT2273). The hydrogen diffusion coefficients D in the alloys were calculated by virtue of potential step method. The results show that the amount of nanocrystalline/amorphous Mg₂Ni phase and Ni phase within alloy samples increase with prolonging milling time. Prolonging of ball milled duration markedly improves the electrochemical discharge properties and cyclic stability of alloy samples. The amorphisation degree of the milling alloys increases with rising milling duration. Furthermore, the high rate dischargeability, electrochemical impedance spectra and potential step measurement all indicate that electrochemical kinetics of alloy electrodes first increases and then decreases with increasing ball milling.     

Improved tolerance of Pd/Cu-treated metal hydride alloys towards air impurities

Electroless copper plating and colloidal Pd nanoparticle impregnation were shown to greatly improve the tolerance of a multi-component AB₅-type alloy towards air impurities. Treated alloys demonstrated improved hydrogen absorption and desorption rates and tolerance towards air impurities when exposed to 0.5 MPa initial hydrogen pressure at room temperature. In addition, the readily-activated response was retained after the treated alloys had been exposed to air for 24 h. The removal of the surface oxide species and the spillover mechanism may have accounted for the enhanced hydrogenation kinetics of the alloys after treatment. Slight degradation of the hydrogen absorption rates with increasing air exposure was observed and was attributed to limitations in the protection provided by the Pd–Cu layer, resulting in a slow growth of an oxide layer on the alloy surface, which acted as a barrier for the transport of hydrogen atoms, towards the core of the AB₅-type alloy material after hydrogen spillover.     

Study of hydrogen storage properties of oxygen modified Ti- based AB2 type metal hydride alloy

A multi component AB₂ type hydrogen storage intermetallic alloy (A = Ti_0.85Zr_0.15, B₂ = Mn_1.22Ni_0.22Cr_0.2V_0.3Fe_0.06; was investigated in this work. The intermetallic specified above was modified by oxygen to yield the composition AB₂O_0.05. The oxygen was introduced by adding TiO₂ to the charge, with corresponding decrease of the Ti amount, followed by arc melting and annealing at the same conditions as for the oxygen free AB₂-type alloy. The addition of oxygen to the alloy did not change much the PCT properties; the only difference was that the plateau pressure for the oxygen-modified alloy increased slightly. Both alloys have shown to be excellent candidates for H₂ storage, particularly for utility vehicles, due to their relatively high reversible H₂ storage capacity (1.6 wt%) and low plateau pressure at room temperature (<5 bar). The addition of oxygen improved hydrogen absorption kinetics in the AB₂ alloy allowing it to immediately absorb H₂ without activation while for the non-modified sample an incubation period (30 min) was observed at the same conditions.     

Machine learning analysis of alloying element effects on hydrogen storage properties of AB2 metal hydrides

Zirconium-titanium-based AB₂ is a potential candidate for hydrogen storage alloys and NiMH battery electrodes. Machine learning (ML) has been used to discover and optimize the properties of energy-related materials, including hydrogen storage alloys. This study used ML approaches to analyze the AB₂ metal hydrides dataset. The AB₂ alloy is considered promising owing to its slightly high hydrogen density and commerciality. This study investigates the effect of the alloying elements on the hydrogen storage properties of the AB₂ alloys, i.e., the heat of formation (ΔH), phase abundance, and hydrogen capacity. ML analysis was performed on the 314 pairs collected and data curated from the literature published during 1998–2019, comprising the chemical compositions of alloys and their hydrogen storage properties. The random forest model excellently predicts all hydrogen storage properties for the dataset. Ni provided the most contribution to the change in the enthalpy of the hydride formation but reduced the hydrogen content. Other elements, such as Cr, contribute strongly to the formation of the C14-type Laves phase. Mn significantly affects the hydrogen storage capacity. This study is expected to guide further experimental work to optimize the phase structure of AB₂ and its hydrogen sorption properties.     

Improved hydrogen storage behaviours of nanocrystalline and amorphous Mg2Ni-type alloy by Mn substitution for Ni

The nanocrystalline and amorphous Mg₂Ni-type alloys with nominal compositions of Mg₂Ni_1−xMn_x (x = 0, 0.1, 0.2, 0.3, 0.4) were synthesized by melt spinning technique. The structures of the as-cast and spun alloys were characterized by XRD, SEM and HRTEM. The hydrogen absorption and desorption kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system. The results show that the as-spun (x = 0) alloy holds a typical nanocrystalline structure, whereas the as-spun (x = 0.4) alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg₂Ni-type alloy. The hydrogen absorption capacity of the alloys first increases then decreases with rising Mn content, but the hydrogen desorption capacity of the alloys grows with increasing Mn content. Furthermore, the substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving both the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn from 0 to 0.4, the discharge capacity of as-spun (30 m/s) alloy grows from 116.7 to 311.5 mAh/g, and its capacity retaining rate at 20th charging and discharging cycle rises from 36.7 to 78.7%.     

Cooperative effect of Co and Al on the microstructure and electrochemical properties of AB3-type hydrogen storage electrode alloys for advanced MH/Ni secondary battery

The crystal structure and electrochemical properties of the La₂MgMn_0.3Ni_8.7−x(Co_0.5Al_0.5)_x (x = 0, 1.0, 2.0 and 3.0, at%) hydrogen storage alloys are investigated systematically. The results show that all the alloys consist of (La, Mg)Ni₃ and LaNi₅ phases, the cyclic stability S₆₀ increases from 61.2% (x = 0) to 78.7% (x = 3.0) after 60 charge/discharge cycles, and the peak high rate dischargeability (HRD) at the discharge current density of 1200 mA/g appears at the alloy of x = 2.0 with the value of 68.3%. Moreover, the electrochemical kinetic properties of the alloys are also improved at different extent with increasing x. All the results indicate that the substitution of Co and Al for Ni in AB₃-type hydrogen storage alloys is effective to improving the overall electrochemical properties, and the optimum content is x = 2.0.     

Gaseous phase hydrogen storage and electrochemical properties of Zr8Ni21, Zr7Ni10, Zr9Ni11, and ZrNi metal hydride alloys

A systematic study of four important non-Laves phase alloys, Zr₈Ni₂₁, Zr₇Ni₁₀, Zr₉Ni₁₁, and ZrNi, commonly seen in the Zr-based AB₂ metal hydride alloys was presented. In order to investigate the synergetic effect between the major and secondary phases, an annealing treatment was used to change the abundances of various phases in the alloys. The structure, gaseous phase hydrogen storage, and electrochemical properties were obtained for each of the four alloy compositions before and after annealing, and the correlations among these properties were explored. Annealing generally suppressed secondary phases except for the case of Zr₉Ni₁₁, where its secondary ZrNi phase abundance increased. As the Zr/Ni ratio in the average composition increased, the maximum gaseous phase hydrogen storage capacity increased but maximized at Zr:Ni = 9:11. Comparing the properties before and after annealing, it was established that the change in phase distribution influenced the gaseous phase storage. Through the electrochemical measurements, it was found that the highest full discharge capacity was obtained at Zr:Ni = 7:10, which represents a compromise between the hydrogen desorption/discharge rate and the theoretical maximum gaseous phase hydrogen storage. As the Zr/Ni ratio increased, the high-rate dischargeability decreased, which followed the trend of the amount of metallic Ni in the surface oxide determined by magnetic susceptibility measurement. The synergetic effect was observed in the electrochemical environment by comparing the results before and after annealing. In general, annealing deteriorated and improved the electrochemical discharge capacity and high-rate dischargeability, respectively, due to the reduction in secondary phase abundance and consequent synergetic effect. Among all alloys investigated, the unannealed Zr₇Ni₁₀ demonstrated the best overall gaseous phase hydrogen storage and electrochemical capacity and could be considered as a candidate to replace the AB₅ and AB₂ metal hydride alloys in Ni/MH battery applications. Furthermore, the unannealed Zr₈Ni₂₁ showed a good balance between high-rate dischargeability and ease of formation.     

Studies of off-stoichiometric AB2 metal hydride alloy: Part 2. Hydrogen storage and electrochemical properties

In Part 2 of this two-part series of papers, gaseous hydrogen storage and electrochemical properties of three series of alloys with different combinations of Cr/Mn/Co ratios are studied and compared to the structural properties reported in Part 1. As the B/A stoichiometry in each series of alloys increases from 1.8 to 2.2, systematic trends in certain storage properties are found: the hydrogen dissociation pressure and heat of hydride formation increases; the alloy with a AB_2.0 stoichiometry has the highest electrochemical full capacity; and slightly higher and lower B-contents increase the electrochemical high-rate-dischargeability and gaseous phase maximum storage capacity, respectively. Stoichiometric or slightly hyper-stoichiometric AB₂ alloys have lower PCT hysteresis which are expected to reduce pulverization during cycling. The full and high-rate discharge electrochemical capacities correlate well with the maximum and reversible gaseous hydrogen storages, respectively. Slight hyper-stoichiometry increases the high-rate dischargeability. Open circuit voltage, an important parameter in high-power application, is also found to be more relevant to the surface reaction than to the bulk hydride stability.     

Characteristics of A2B7-type LaYNi-based hydrogen storage alloys modified by partially substituting Ni with Mn

LaY₂Ni_10.5?xMn_x (x = 0.0, 0.5, 1.0, 2.0) alloys are prepared by a vacuum induction-quenching process followed by annealing. The structure, as well as the hydriding/dehydriding and charging/discharging characteristics, of the alloys are investigated via X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), pressure-composition isotherms (PCI), and electrochemical measurement. The alloys have multiphase structures mainly composed of Gd₂Co₇-type (3R) and Ce₂Ni₇-type (2H) phases. Partial substitution of Ni by Mn clearly increases the hydrogen storage capacity of the alloys. The x = 0.5 alloy exhibits a maximum hydrogen storage capacity of 1.40 wt % and a discharge capacity of 392.9 mAh g^?1, which are approximately 1.5 and 1.9 times greater than those of the x = 0.0 alloy, respectively. The high-rate dischargeability (HRD) of the x = 0.5 alloy is higher than that of the other alloys because of its large hydrogen diffusion coefficient D, which is a controlling factor in the electrochemical kinetic performance of alloy electrodes at high discharge current densities. Although the cyclic stability of the x = 0.5 alloy is not as high as that of the other alloys, its capacity retention ratio is as high as 56.3% after the 400th cycle. The thermodynamic characteristics of the x = 0.5 alloy satisfy the requirements of the hydride electrode of metal hydride–nickel (MH–Ni) batteries.     

Effect of rare earth composition on the high-rate capability and low-temperature capacity of AB5-type hydrogen storage alloys

Effects of rare earth composition on the high-rate capability and low-temperature capacity of AB₅-type hydrogen storage alloys have been studied and analyzed with pattern recognition methods. The results show that the increase of Ce and Pr and the decrease of La and Nd concentration improve the high-rate capability and low-temperature capacity of AB₅-type hydrogen storage alloys, Ce exhibiting better favorable influences than Pr. The improvement of both high-rate capability and low-temperature capacity are mainly ascribed to the lower stability of the hydride. The alloy with the rare earth composition of La_0.1645Ce_0.7277Pr_0.0234Nd_0.0845 shows very good high-rate capability and low-temperature capacity.