Effect of electrolyte on electrochemical characteristics of MmNi3.55Co0.72Al0.3Mn0.43 alloy electrode for hydrogen storage

A series of experiments have been performed to investigate the effects of three electrolytes of different compositions (EO, EA and EM) on the electrochemical characteristics of MmNi_3.55Co_0.72Al_0.3Mn_0.43 hydrogen storage alloy electrode. Electrolytes EA and EM were obtained by adding appropriate amounts of Al₂(SO₄)₃ and MnSO₄ to the original electrolyte EO (6 M KOH + 1 wt% LiOH), respectively. Electrode activation, maximum capacity, cycle life, self-discharge and high-rate discharge characteristics have been studied. It was found that a maximum capacity of about 260 mA h/g has been obtained for the alloy electrodes in all these electrolytes after 5–7 cycles of charging/discharging. The alloy electrodes have a good durability in electrolytes EA and EM, especially after 175 cycles. Using the capacity retention as an indication of self-discharge resistance, almost identical degree of capacity retention (82% after 4 days and 45% after 16 days) has been observed at 298 K, regardless of the electrolytes used. When tested at higher temperature, however, a higher capacity retention (46% after 3 days) at 333 K has been observed for electrodes in electrolyte EA, and about 32% for electrodes in both electrolytes EO and EM. As to high-rate discharge behavior of the results of high-rate discharge tests indicated that about 50% of discharge efficiencies were obtained in the three electrolytes at 333 K by continuous-model high-rate discharge method, at a discharge rate of 7C, and 22% in 298 K. The alloy electrode in electrolyte EM has the best durability, in which about 50% of discharge efficiency at DC = 9C was obtained by step-model high-rate discharge method at 333 K, which was even higher than that at 298 K.     

Electrochemical performance of TiVNi-Quasicrystal and AB3-Type hydrogen storage alloy composite materials

The Ti_1.4V_0.6Ni ribbon alloy and AB₃-type (La_0.65Nd_0.12Mg_0.23Ni_2.9Al_0.1) alloy ingot are prepared by melt-spinning technique and induction levitation melting technique, respectively. The Ti_1.4V_0.6Ni + 20 wt.% AB₃ mixture powders are synthesized by ball-milling the above prepared alloy ingots, and their structures and the electrochemical hydrogen storage properties are investigated. It is found that the icosahedral quasicrystal, Ti₂Ni, BCC structural solid solution and AB₃-type phases are all presented in the composite material. The maximum electrochemical discharge capacity of the composite electrode is 294.7 mAh/g at the discharge current density of 30 mA/g and 303 K. In addition, the electrode made of Ti_1.4V_0.6Ni and AB₃ composite holds better high-rate discharge ability than that of Ti_1.4V_0.6Ni.     

Enhanced high-rate discharge properties of La11.3Mg6.0Sm7.4Ni61.0Co7.2Al7.1 with added graphene synthesized by plasma milling

In order to improve the high-rate discharge properties of La_11.3Mg_6.0Sm_7.4Ni_61.0Co_7.2Al_7.1 (AB_3.0) alloy electrodes, the effects of plasma milling (PM) and graphene addition on their electrochemical properties and kinetics have been investigated. It was found that the discharge capacity of AB_3.0 at a high discharge current density was significantly improved after the addition of graphene followed by PM for only 10 min. Moreover, the high-rate dischargeability (HRD) and the exchange current density I₀ of the alloy electrodes were also increased. The PM technique exhibits obvious advantages for improving the high-rate discharge properties of hydrogen-storage alloys.     

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.     

MmNi3.55Co0.75Mn0.4Al0.3B0.3 hydrogen storage alloys for high-power nickel/metal hydride batteries

Non-stoichiometric La-rich MmNi_3.55Co_0.75Mn_0.4Al_0.3B_0.3 hydrogen storage alloys using B–Ni or B–Fe alloy as additive and Ce-rich MmNi_3.55Co_0.75Mn_0.4Al_0.3B_0.3 one using pure B as additive have been prepared and their microstructure, thermodynamic, and electrochemical characteristics have been examined. It is found that all investigated alloys show good activation performance and high-rate dischargeability though there is a certain decrease in electrochemical capacities compared with the commercial MmNi_3.55Co_0.75Mn_0.4Al_0.3 alloy. MmNi_3.55Co_0.75Mn_0.4Al_0.3B_0.3 alloys using B–Ni alloy as additive or adopting Ce-rich mischmetal show excellent rate capability and can discharge capacity over 190 mAh/g even under 3000 mA/g current density, which display their promising use in the high-power type Ni/MH battery. The electrochemical performances of these MmNi_3.55Co_0.75Mn_0.4Al_0.3B_0.3 alloys are well correlated with their microstructure, thermodynamic, and kinetic characteristics.     

A study of the Al content impact on the properties of MmNi4.4−xCo0.6Alx alloys as precursors for negative electrodes in NiMH batteries

AB₅-type hydrogen storage alloys with MmNi_4.4−xCo_0.6Al_x (Mm-mischmetal) composition are synthesized, structurally and thermodynamically characterized, and electrochemically tested in 6 M KOH electrolyte. It is shown that an increase of the Al content in the alloy results in expansion of both the alloy lattice cell size and the unit cell volume. These structural changes lead to decrease of the plateau pressure and increase of the plateau width in the pressure-composition-temperature desorption isotherms. Improvement of the specific electrode capacity is also registered with the increase of the cell parameters. In addition to that the higher Al content is found to enhance the stability of the alloy components’ hydrides. Maximum discharge capacity of 278 mAh g⁻¹ is measured with an electrode made from a MmNi_3.6Co_0.6Al_0.8 alloy. Cycle life tests of the accordingly prepared electrodes suggest a stability that is comparable to the stability of commercially available hydrogen storage electrodes.     

Effects of additions on AB5-type hydrogen storage alloy in MH–Ni battery application

The AB₅-type hydrogen storage alloy of Mm_0.3Ml_0.7Ni_3.55Co_0.75Mn_0.4Al_0.3 were synthesized and mixed with PVA (Polyvinyl Alcohol) or different percentage Ni powder as the test samples. The cycle stabilities of the composites were tested in 6 M KOH electrolyte through electrochemical method. The results indicated that all the samples with Ni powder have better cycle stabilities and flatter discharge voltage platform. The sample of Mm_0.3Ml_0.7Ni_3.55Co_0.75Mn_0.4Al_0.3 + 200 wt.% Ni has the highest capacity conservation rate of 80.5% and the longest discharge time of 5.2 h. The SEM images show that the particle diameters of the alloy decreased by 2 μm and the surface smoothed without sharp edges after adding Ni powder. It can be presumed that adding Ni can improve the cycle stability of the alloy of Mm_0.3Ml_0.7Ni_3.55Co_0.75Mn_0.4Al_0.3 in the alkaline electrolyte and enhance the reaction rate in the charge/discharge cycles.     

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.     

Electrochemical properties of the Mm0.3Ml0.7Ni3.55Co0.75Mn0.4Al0.3 alloy mixed with Ni powder

Composites of Mm_0.3Ml_0.7Ni_3.55Co_0.75Mn_0.4Al_0.3 alloy and Ni powders were mechanically synthesized and electrochemically tested in 6 M KOH electrolyte. In this work, the electrochemical properties of the alloys were greatly improved by mixing them with Ni, which plays a corrosion-resistance role in the alkali electrolyte and helps electron conduction. It has been shown that the numbers of activation cycles decreased compared with the alloys without Ni powder. All the alloys were activated after the second cycle. Improvements of the maximum discharge capacities were also found in this work. A maximum discharge capacity of 358 mAh g⁻¹ was measured in the Mm_0.3Ml_0.7Ni_3.55Co_0.75Mn_0.4Al_0.3 + 250 wt.% Ni composite. In addition to that, adding Ni was found to enhance the high-rate discharge ability of the alloys, which appear to be good candidates for the realization of MH battery electrodes.     

Effect of Al content on structure and electrochemical properties of LaNi4.4 − xCo0.3Mn0.3Alx hydrogen storage alloys

The structure and electrochemical properties of LaNi_4.4 − xCo_0.3Mn_0.3Al_x hydrogen storage alloys have been investigated by XRD and simulated battery test, including maximum capacity, cyclic stability, self-discharge, high-rate dischargeability (HRD). Samples A, B, C and D were used to represent alloys LaNi_4.4Co_0.3Mn_0.3Al, LaNi_4.3Co_0.3Mn_0.3Al_0.1, LaNi_4.2Co_0.3Mn_0.3Al_0.2 and LaNi_4.1Co_0.3Mn_0.3Al_0.3 respectively. The results indicated that as-prepared LaNi_4.4 − xCo_0.3Mn_0.3Al_x alloys are all single-phase alloys with hexagonal CaCu₅ type structure. The maximum discharge capacity is 330.4 mAh g⁻¹ (Alloy C). With the increase of Al content from A to D, cycle life of alloy electrode has been improved. Higher capacity retention of 89.29% (after 50 charge/discharge cycles) has been observed for electrode D, while with a smaller capacity loss of 12.5% in its self-discharge test. Better high-rate charge/discharge behaviors have been observed in electrode B, and the maximum data is 54.7% at charge current of 900 mA/g) and 68.54% at discharge current of 1800 mA/g). Furthermore, the electrochemical impedance spectroscopy (EIS) analysis shown that the reaction of alloy electrode is controlled by charge-transfer step. The addition of Al results in the formation of protective layer of aluminum oxides on the surface of the alloy electrode, which is good for the improvement of electrode properties in alkaline solution and is detrimental for the charge-transfer process. Therefore, a suitable addition of Al is needed to improve its electrode properties.     

Electrocatalytic characteristics of the metal hydride electrode for advanced Ni/MH batteries

The electrocatalytic characteristics of a metal hydride (MH) electrode for advanced Ni/MH batteries include the hydrogen adsorption/desorption capability at the electrode/electrolyte interface. The hydrogen reactions at the MH electrode/electrolyte interface are also related to factors such as the surface area of the MH alloy powder and the nature of additives and binder materials. The high-rate discharge capability of the negative electrode in a Ni/MH battery is mainly determined by the mass transfer process in the bulk MH alloy powder and the charge transfer process at the interface between the MH alloy powder and the electrolyte. In this study, an AB₅-type hydrogen-absorbing alloy, Mm (Ni, Co, Al, Mn)_5.02 (where Mm denotes Mischmetal, comprising 43.1 wt.% La, 3.5 wt.% Ce, 13.3 wt.% Pr and 38.9 wt.% Nd), was used as the negative MH electrode material. The MH electrode was charged and discharged for up to 200 cycles. The specific discharge capacity of the alloy electrode decreases from a maximum value of 290–250 mAh g⁻¹ after 200 charge/discharge cycles. A cyclic voltammetry technique is used to analyze the charge transfer reactions at the electrode/electrolyte interface and the hydrogen surface coverage capacity.     

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.     

Effect of electrolyte concentration on the electrochemical properties of an AB5-type alloy for Ni/MH batteries

This publication is the first of a series of three that we have undertaken to study the effect of electrolyte concentration on electrode performance. Here, the electrochemical properties of an AB₅-type alloy, namely LaNi_3.6Co_0.7Mn_0.4Al_0.3, are investigated using different KOH electrolyte concentrations (i.e. 2 M, 4 M, 6 M and 8 M). The next two publications will be concerned with an AB₂-type alloy and a Mg-based alloy, respectively.     

Effects of particle size and type of conductive additive on the electrode performances of gas atomized AB5-type hydrogen storage alloy

The phase composition, morphology, structure, and state of the surface of gas atomized LaNi_4.5Al_0.5 alloy powders constituting a fine (≤50 μm), a medium (160–316 μm), and a coarse (630–1000 μm) fraction have been investigated. The electrochemical and storage characteristics of electrodes made from these powders with addition of electrolytic copper powder or a carbon composite (1 wt.% carbon nanotubes + 7 wt.% nanosized carbon black) as a conductive additive have been studied. In the work, X-ray diffraction, scanning electron microscopy, electron-probe microanalysis, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and several electrochemical methods have been used. It has been established that, in the initial state, the coarse-fraction gas atomized powders show a better kinetics of the hydrogen exchange reactions and higher discharge capacity (∼300 mA h/g). It is shown that electrodes made from the powders of all the fractions have a good high-rate discharge capability. Hydrogen diffusion coefficients during discharge of the electrodes made from the alloy powders of all the fractions and conductive additives have been calculated. It is shown that, for LaNi_4.5Al_0.5 alloy electrodes with the composite carbon additive, the hydrogen diffusion coefficients during discharge computed from data obtained by the electrochemical impedance spectroscopy method agree well with those calculated from cyclic current–voltage curves (2–4 × 10⁻⁹ cm²/s).     

Preparation of nickel modified activated carbon/AB5 alloy composite and its electrochemical hydrogen absorbing properties

Due to the good catalysis of metal nickel for the electrochemical reduction/oxidation reactions between H₂O and H in alkaline electrolyte, it is separately introduced into activated carbon (AC) by ball milling (named AC-1), liquid phase reduction (AC-2) and hydrothermal (AC-3) methods. The results of scanning electron microscopy (SEM) show that different to the aggregation of metal nickel in AC-1 and the coating of metal nickel on the surface of AC-2, metal nickel introduced by the hydrothermal method is uniformly dispersed among the AC-3 particles. The AC-3/AB₅ alloy (90 wt%) composite shows the best electrochemical hydrogen absorbing activity. Its capacity at a 0.2 C rate reaches to 318 mA h/g. Compared to the AB₅ alloy electrode, its discharge capacity separately increases 16% at a 1 C rate and 59% at a 3 C rate, which is particularly suitable for the high-power nickel metal-hydride (Ni–MH) battery.     

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.     

Synergistic effects in an AB5–Co material as an anode for a secondary alkaline battery

The AB₅ alloy and Co powders have been mixed at various weight ratios to form AB₅–Co composite electrodes. The discharge properties such as discharge capacity, discharge plateau, and cycling stability are investigated by charge and discharge testing using Arbin battery testing equipment. Synergistic effects in the composite electrodes contribute to significant improvements of the discharge behavior. For instance, the composite AB₅–25%Co electrode shows a high discharge capacity of 395.1 mAh/g, which is significantly higher than that of AB₅ or Co electrode, and good cycling stability. The discharge process is also characterized by electrochemical impedance spectroscopy. Moreover, the electrochemical discharge mechanism is discussed.     

Effect of La–Mg-based alloy addition on structure and electrochemical characteristics of Ti0.10 Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

Effect of La–Mg-based alloy (AB₅) addition on Structure and electrochemical characteristics of Ti_0.10Zr_0.15V_0.35Cr_0.10Ni_0.30 hydrogen storage alloy has been investigated systematically. XRD shows that the matrix phase structure is not changed after adding AB₅ alloy, however, the amount of the secondary phase increases with increasing AB₅ alloy content. The electrochemical measurements show that the plateau pressure Ti_0.10Zr_0.15V_0.35Cr_0.10Ni_0.30 + x% La_0.85Mg_0.25Ni_4.5Co_0.35Al_0.15 (x = 0, 1, 5, 10, 20) hydrogen storage alloys increase with increasing x, and the width of the pressure plateau first increases when x increases from 0 to 5 and then decreases as x increases further, and the maximum discharge capacity changes in the same trend. The activation performance, the low temperature dischargeabilities, high-rate dischargeability and cyclic stability of composite alloy electrodes increase greatly with increasing x. The improvement of the electrochemical characteristics caused by adding AB₅ alloy seems to be related to formation of the secondary phase.     

Cyclic stability and high rate discharge performance of (La,Mg)5Ni19 multiphase alloy

The cyclic stability and high rate discharge performance of (La,Mg)₅Ni₁₉ multiphase alloy were investigated in this work. The results show that the alloy is composed of Pr₅Co₁₉-type (2H), Ce₅Co₁₉-type (3R), CaCu₅-type and Ce₂Ni₇-type phase after annealing at 1123 K. The total phase abundance of Pr₅Co₁₉-type (2H) and Ce₅Co₁₉-type (3R) is 63.3%. That composition decides the good cyclic stability both in repeated hydriding/dehydriding and charging/discharging process for this alloy. Moreover, the alloy shows the higher high rate discharge capacity at room temperature and it remains 140 mA h/g at the current density of 3600 mA/g.     

Effect of CuO addition on electrochemical properties of AB3-type alloy electrodes for nickel/metal hydride batteries

In order to improve overall electrochemical properties of AB₃-type hydrogen storage alloy electrodes, especially the cycling stability, CuO was added to the electrode. Electrochemical properties of the electrodes with and without additives were studied. Cyclic voltammetry and SEM results show that CuO is reduced to Cu during the charging process and the fine Cu particles deposit at surface of the alloy particles. The as-deposited Cu particles form a protective layer to increase electronic and heat conductivity of the electrodes and thus improve maximum discharge capacity, high rate dischargeability, cycling stability and dischargeability at high temperature of the electrodes. The maximum discharge capacity increases from 314 mAh g⁻¹ (blank electrode) to 341 mAh g⁻¹ (3.0 wt.% CuO) and the capacity retention rate at the 200th cycle increases from 71.6% to 77.2% (2.5 wt.% CuO).