Microstructure and electrochemical corrosion behavior of a Pb-1 wt%Sn alloy for lead-acid battery components

The aim of this study was to evaluate the effect of solidification cooling rates on the as-cast microstructural morphologies of a Pb-1 wt%Sn alloy, and to correlate the resulting microstructure with the corresponding electrochemical corrosion resistance in a 0.5 M H₂SO₄ solution at 25 °C. Cylindrical low-carbon steel and insulating molds were employed permitting the two extremes of a significant range of solidification cooling rates to be experimentally examined. Electrochemical impedance spectroscopy (EIS) diagrams, potentiodynamic polarization curves and an equivalent circuit analysis were used to evaluate the electrochemical corrosion response of Pb-1 wt%Sn alloy samples. It was found that lower cooling rates are associated with coarse cellular arrays which result in better corrosion resistance than fine cells which are related to high cooling rates. The experimental results have shown that that the pre-programming of microstructure cell size of Pb-Sn alloys can be used as an alternative way to produce as-cast components of lead-acid batteries with higher corrosion resistance.     

Cell/dendrite transition and electrochemical corrosion of Pb-Sb alloys for lead-acid battery applications

The aim of this article is focused on a comparative experimental study of the electrochemical feature of as-cast Pb-2.2 wt.% Sb alloy with cellular/dendritic transition for applications in the manufacturing of lead-acid battery parts. A water-cooled unidirectional solidification system is used to obtain the alloy samples. Electrochemical impedance spectroscopy (EIS) plots, potentiodynamic polarization curves and equivalent circuit analysis are used to evaluate corrosion resistance in a 0.5 M H₂SO₄ solution at 25 °C. The cellular Pb-2.2 wt.% Sb alloy is found to have a current density which is of about 3 times lower than that of the dendritic Pb-2.2 wt.% Sb alloy. The Pb-2.2 wt.% Sb alloy has lower current density than both the Pb-1 wt.% Sb and the Pb-6.6 wt.% Sb alloys evidencing its potential for application as positive grid material in lead-acid batteries. It is also verified that a conventional casting with low cooling rate of about 0.6 °C s⁻¹ produces coarser cellular spacings which is more appropriate for the manufacturing of the Pb-2.2 wt.% Sb alloys grids due to its corresponding electrochemical behavior.     

Electrochemical corrosion of Pb–1 wt% Sn and Pb–2.5 wt% Sn alloys for lead-acid battery applications

The aim of this study was to compare the electrochemical corrosion behavior of as-cast Pb–1 wt% Sn and Pb–2.5 wt% Sn alloy samples in a 0.5 M H₂SO₄ solution at 25 °C. A water-cooled unidirectional solidification system was used to obtain the as-cast samples. Electrochemical impedance spectroscopy (EIS) diagrams, potentiodynamic polarization curves and an equivalent circuit analysis were used to evaluate the electrochemical corrosion response. It was found that a coarse cellular array has a better electrochemical corrosion resistance than fine cells. The pre-programming of microstructure cell size of Pb–Sn alloys can be used as an alternative way to produce as-cast components of lead-acid batteries with higher corrosion resistance associated with environmental and economical aspects.     

Electrochemical investigation of the anodic corrosion of Pb–Ca–Sn–Li grid alloy in H2SO4 solution

The steady-state and anodic corrosion of Pb–0.17 wt.% Ca–0.88 wt.% Sn, and Pb–0.17 wt.% Ca–0.88 wt.% Sn–0.06 wt.% Li alloys in 4.5 M H₂SO₄ at 25 °C were studied using cyclic voltammetry, linear sweep voltammetry, and electrochemical impedance spectroscopy. The experimental results show that the lithium added to Pb–Ca–Sn alloy increases corrosion resistance in equilibrium potential and inhibits the growth of the anodic corrosion layer.     

Influence of annealing treatment on the hydrogen storage properties of La2−xTixMgNi9 (x = 0.2, 0.3) alloys

La_2−xTi_xMgNi₉ (x = 0.2, 0.3) alloys have been prepared by magnetic levitation melting under an Argon atmosphere, and the as-cast alloys were annealed at 800 °C, 900 °C for 10 h under vacuum. The effects of annealing on the hydrogen storage properties of the alloys were investigated systematically by XRD, PCT and electrochemical measurements. For the La_2−xTi_xMgNi₉ (x = 0.2, 0.3) alloys, LaNi₅, LaMg₂Ni₉ and LaNi₃ are the main phases and a Ti₂Ni phase appears at 900 °C. The effective hydrogen storage capacity increases from 1.10, 1.10 wt.% (as-cast) to 1.22, 1.16 wt.% (annealed 800 °C) and 1.31, 1.27 wt.% (annealed 900 °C), respectively. The annealing not only improves the hydrogen absorption/desorption kinetics but also increases the maximum discharge capacity and enhances the cycling stability. The La_1.8Ti_0.2MgNi₉ alloy annealed at 900 °C exhibits good electrochemical properties, and the discharge capacities decrease from 366.1 mA h/g to 219.6 mA h/g after 177 charge-discharge cycles.     

The interrelation between mechanical properties, corrosion resistance and microstructure of Pb-Sn casting alloys for lead-acid battery components

It is well known that there is a strong influence of thermal processing variables on the solidification structure and as a direct consequence on the casting final properties. The morphological microstructural parameters such as grain size and cellular or dendritic spacings will depend on the heat transfer conditions imposed by the metal/mould system. There is a need to improve the understanding of the interrelation between the microstructure, mechanical properties and corrosion resistance of dilute Pb-Sn casting alloys which are widely used in the manufacture of battery components. The present study has established correlations between cellular microstructure, ultimate tensile strength and corrosion resistance of Pb-1 wt% Sn and Pb-2.5 wt% Sn alloys by providing a combined plot of these properties as a function of cell spacing. It was found that a compromise between good corrosion resistance and good mechanical properties can be attained by choosing an appropriate cell spacing range.     

Electrochemical hydrogen storage characteristics of nanocrystalline and amorphous Mg20Ni10-xCox(x=0−4) alloys prepared by melt spinning

Nanocrystalline and amorphous Mg₂Ni-type alloys with nominal compositions of Mg₂₀Ni_10-xCo_x (x = 0, 1, 2, 3, 4) were synthesized by melt-spinning technique. The microstructures of the as-cast and spun alloys were characterized by XRD, SEM and HRTEM. The electrochemical hydrogen storage characteristics of the as-cast and spun alloys were measured. The obtained results show that the substitution of Co for Ni does not change the major phase of Mg₂Ni, but it leads to the formation of secondary phase MgCo₂ and Mg. No amorphous phase forms in the as-spun alloy (x = 0), whereas the as-spun alloy (x = 4) holds a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni significantly heightens the glass forming ability of the Mg₂Ni-type alloy. The substitution of Co for Ni and melt spinning significantly improve the electrochemical hydrogen storage performances of the alloys. When Co content x increases from 0 to 4, the maximum discharge capacity of the as-cast alloy increases from 30.3 to 113.3 mAh/g, and from 135.5 to 402.5 mAh/g for as-spun (30 m/s) alloy. The capacity retaining rate of the as-cast alloy after 20 cycles rises from 36.71 to 37.04%, and from 27.06 to 83.35% for as-spun (30 m/s) alloy, respectively.     

Electrochemical behavior and application of lead–lanthanum alloys for positive grids of lead-acid batteries

The effects of different lanthanum content (0, 0.00600, 0.0112, 0.0195 and 0.0540 wt.%) on the electrochemical behavior of lead–lanthanum alloy in sulfuric acid solutions were investigated by linear potential sweep (LSV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The morphology of the corrosion layer and corrosion section of Pb and Pb–La alloys were analyzed by scanning electron microscope (SEM) after corrosion testing. It was found that the addition of La inhibits the oxygen evolution reaction on the surface of Pb alloy electrodes, and La amounts of 0.00600 and 0.0540 wt.% in Pb–La alloy electrodes can lead to a more effective inhibition. The results of the LSV, CV and EIS experiments show that the addition of La can inhibit the growth of the anodic Pb(II) oxides and PbO₂ film. The resistance of the anodic film on the Pb–La electrodes is much lower than that on the Pb electrode. SEM for the corrosion layer indicates that the corrosion product on pure Pb and Pb–0.0195% La alloy is uniform and compact. The corrosion products on the alloys with La contents of 0.00600, 0.0112 and 0.0540 are loose and porous that the active materials can easily sit in the apertures to contact the grid surface intimately with the effective. The results demonstrate that Pb–La alloys show the potential for application as the positive grid material in maintenance-free lead-acid batteries.     

Hydrogenation-induced microstructure evolution in as cast and severely deformed Mg-10 wt.% Ni alloy

We determined the kinetics of hydrogen absorption of the hypoeutectic Mg-10 wt.% Ni alloy in the as-cast state and after processing by four passes of equal channel angular pressing (ECAP). While during the first hydrogenation cycle the ECAP-modified alloy exhibited faster absorption than its as-cast counterpart, this advantage was lost after the second hydrogenation cycle; parity was regained after six cycles. We attributed these differences in the hydrogen absorption kinetics to the formation of large (tens of micrometers) faceted Mg crystals observed during the first hydrogenation cycle. These crystals were significantly larger in the ECAP-modified alloy than in its as-cast counterpart. We discussed the growth of large Mg crystals during hydrogenation in terms of self-diffusion of Mg atoms driven by the metal-hydride transformation stress. The larger size of these crystals in the ECAP-processed alloy was attributed to the acceleration of diffusion by ECAP. Our metallographic studies revealed a number of microstructural changes in the alloys upon hydrogenation, such as cracking, accumulation of plastic strain in large Mg crystals, and re-distribution of the dispersed particles of Mg₂Ni phase in the partly hydrogenated alloys.     

Hydriding/dehydriding properties of MgH2/5 wt.% Ni coated CNFs composite

In this paper, we reported that the prepared nickel coated carbon nanofibers (NiCNFs) by electroless plating method exhibited superior catalytic effect on hydrogen absorption/desorption of magnesium (Mg). It is demonstrated that the nanocomposites of MgH₂/5 wt.% NiCNFs prepared by ball milling could absorb hydrogen very fast at low temperatures, e.g. absorb ∼6.0 wt.% hydrogen in 5 min at 473 K and ∼5.0 wt.% hydrogen in 10 min even at a temperature as low as 423 K. More importantly, the desorption of hydrogen was also significantly improved with additives of NiCNFs. Diffraction scanning calorimetry (DSC) measurement indicated that the peak desorption temperature decreased 50 K and the on-set temperature for desorption decreased 123 K. The composites also desorbed hydrogen fast, e.g. desorb 5.5 wt.% hydrogen within 20 min at 573 K. It is suggested that the new phase of Mg₂Ni, and the nano-sized dispersed distribution of Ni and carbon contributed to this significant improvement. Johnson–Mehl–Avrami (JMA) analysis illustrated that hydrogen diffusion is the rate-limiting step for hydrogen absorption/desorption.     

Electrochemical performance of melt-spinning Al–Mg–Sn based anode alloys

Rapidly solidified Al–0.5Mg–0.1Sn–0.02In (0.02Ga)–0.1Si (wt. %) alloys were prepared as anode alloys for Al–air battery by the single roller melt-spinning method. The corrosion behavior of the alloys and the Al–air battery performance were investigated in both 2 M NaCl and 4 M NaOH solutions. Results obtained have shown that the Al–0.5Mg–0.1Sn–0.02Ga–0.1Si alloy has a better electrochemical performance in the 2 M NaCl solution, while Al–0.5Mg–0.1Sn–0.02In–0.1Si alloy shows a better electrochemical performance in the 4 M NaOH solution. In the 2 M NaCl solution, both alloys suffer from a uniform corrosion. In the 4 M NaOH solution, the corrosion morphology of the alloys evolves from an intergranular corrosion to a uniform corrosion. SEM and EIS results are in good agreement with electrochemical characteristics.     

Hydrogen storage properties of Mg–30 wt.% LaNi5 composite prepared by hydriding combustion synthesis followed by mechanical milling (HCS + MM)

A Mg–30 wt.% LaNi₅ composite was prepared by hydriding combustion synthesis followed by mechanical milling (HCS + MM), and the hydriding and dehydriding properties of the HCS + MM product were compared with those of the HCS product and the MM product. The dehydriding temperature onsets of the MM and HCS + MM products were both 470 K, which were lower than that of the HCS product by 100 K. Moreover, the HCS + MM product desorbed faster than the MM product, e.g., the former desorbed completely upon heating to 510 K, whereas the latter did not decompose completely until 590 K. Additionally, the HCS + MM product reached a saturated hydrogen absorption capacity of 3.80 wt.% at 373 K in 50 s, but both the HCS product and the MM product absorbed less than 1.50 wt.% of hydrogen at 373 K in 1800 s. These results suggest the potential of the HCS + MM processing in preparing Mg-based hydrogen storage materials.     

Evaluations of hydrogen permeation on TiN-5 wt.%Ni membrane by spark plasma sintering

The TiN-5 wt.%Ni membrane was researched for gasification of coal technique, separating hydrogen from fossil fuel. In general, Pd and Pd-based alloy membranes of separating hydrogen were reported to have the good property of hydrogen selectivity at high temperature, but they has some problems such as hydrogen embrittlement and high material costs. Therefore, materials with good properties of hydrogen selectivity are needed instead of Pd. In this research, we fabricated membranes for hydrogen permeation that are highly resistant to acids, chemically steady, and composed of the economical substance, TiN. Our laboratory investigated hydrogen selectivity. TiN powder was milled for 30, 60, and 240 min by a vibration mill, respectively. Afterwards, the samples underwent operate spark plasma sintering and was characterized by XRD, BET, and SEM. Also, hydrogen selectivity was measured by Sievert’s type hydrogen permeation membrane equipment. In this report, the hydrogen permeability of the TiN-5 wt.%Ni membrane was measured to be 7.8 × 10⁻⁸, 1.7 × 10⁻⁷, and 1.4 × 10⁻⁷ mol/m·s·Pa^1/2 at 473, 573, and 673K under 0.2 MPa H₂ atmosphere, respectively.     

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

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

Structures and electrochemical hydrogen storage behaviours of La0.75−xPrxMg0.25Ni3.2Co0.2Al0.1 (x = 0–0.4) alloys prepared by melt spinning

In order to improve the electrochemical performance of the La–Mg–Ni system A₂B₇-type electrode alloys, La in the alloy was partially substituted by Pr and melt spinning technology was used for preparing La_0.75−xPr_xMg_0.25Ni_3.2Co_0.2Al_0.1 (x = 0, 0.1, 0.2, 0.3, 0.4) electrode alloys. The microstructures and electrochemical performance of the as-cast and spun alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the as-cast and spun alloys have a multiphase structure which consists of two main phases (La, Mg)Ni₃ and LaNi₅ as well as a residual phase LaNi₂. The substitution of Pr for La leads to an obvious increase of the (La, Mg)Ni₃ phase and a decrease of the LaNi₅ phase in the alloys. The results of the electrochemical measurement indicate that the discharge capacity of the alloys first increases and then decreases with variation of the Pr content. The cycle stability of the alloy monotonically rises with increasing Pr content. When the Pr content rises from 0 to 0.4, the discharge capacity increases from 389.4 (x = 0) to 392.4 (x = 0.1) and then drops to 383.7 mAh/g (x = 0.4) for the as-cast alloy. Discharge capacity increases from 393.5 (x = 0) to 397.9 (x = 0.1), and then declines to 382.5 mAh/g for the as-spun (5 m/s) alloys. The capacity remaining after 100 cycles increases from 65.32 to 79.36% for the as-cast alloy, and from 73.97 to 93.08% for the as-spun (20 m/s) alloy.     

Influence of temperature on corrosion behavior of PbCaSnCe alloy in 4.5 M H2SO4 solution

The temperature effect on corrosion behaviors of PbCaSnCe alloy in 4.5 M H₂SO₄ solution was investigated by using potentiodynamic curve, electrochemical impedance spectra (EIS), Mott-Schottky plot and photocurrent response methods. It was found that PbCaSnCe alloy was in passive state in sulfuric acid solution, a passive film can be formed on alloy surface. The compositions of passive films formed at 0.9 V for 2 h under different temperatures were detected by X-ray photoelectron spectroscopy (XPS). The results showed that the film resistance and the transfer resistance decreased with the increment of the solution temperature. Mott-Schottky analysis and the photocurrent response revealed that the passive film exhibited n-type semi-conductive character, the donor density of the passive film decreased with increasing the solution temperature. Photocurrent response revealed that the photocurrent increased with increasing temperature. XPS results indicated that the PbO₂ content in passive films may increase with increasing the solution temperature.     

Effect of heat treatment and chemical composition on the corrosion behavior of FeAl intermetallics in molten (Li + K)carbonate

The corrosion performance of various Fe–Al alloys in 62 mol. %Li₂CO₃-38 mol.%K₂CO₃ at 650 °C has been studied using the weight loss technique. Alloys included FeAl with additions of 1, 3 and 5 at.% of either Ni or Li with or without a heat treatment at 400 °C during 144 h. For comparison, 316L type stainless steel was also studied. The tests were complemented by X-ray diffraction (XRD), scanning electronic microscopy and microchemical studies. Results showed that FeAl base alloy without heat treatment had the highest corrosion rate but by either heat treating it or by adding either Ni or Li the mass gain was decreased. When the FeAl base alloy was heat treated and alloyed with either 5Ni or 1Li the degradation rate reached as low values as those found for 316L stainless steel which had the lowest degradation rate. Both Ni and Li improved the adhesion of external protective layer either by avoiding the formation of voids or by lowering the number of precipitates and making them more homogenously distributed.     

Influence of the substitution of La for Mg on the microstructure and hydrogen storage characteristics of Mg20−xLaxNi10 (x = 0–6) alloys

In order to enhance the glass forming ability of the Mg₂Ni-type hydrogen storage alloy, the Mg in the alloy was partially substituted by La. The alloys Mg_20−xLa_xNi₁₀ (x = 0, 2, 4, 6) were prepared by casting and rapid quenching. The structures and morphologies of the as-cast and the quenched alloys were studied by XRD, SEM and HRTEM. It was found that no amorphous phase was formed in the as-quenched La-free alloy. But the as-quenched alloys containing La held a major amorphous phase, confirming that the substitution of La for Mg significantly enhances the glass forming ability of the alloys. When La content x ≤ 2, the major phase in the as-cast alloys is Mg₂Ni phase, but with the further increase of La content, the major phase of the as-cast alloys changes into (La,Mg)Ni₃ + LaMg₃ phase. Thermal stability of the as-quenched alloys was studied by DSC, showing that La content engenders a negligible influence on the crystallization temperature of the amorphous phase. The hydrogen absorption and desorption kinetics of the as-cast and the quenched alloys were measured by an automatically controlled Sieverts apparatus. The results showed that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly rise with increasing La content. For La content x = 2, the as-quenched alloy displays an optimal hydrogen desorption kinetics at 200 °C. The electrochemical measurement showed that the discharge capacities of the as-cast alloys rose with the increase of La content, but those of the as-quenched alloys obtained the maximum values with the variation of La content. The cycle stability of the as-cast and the quenched alloys significantly improved with increasing La content.     

Effects of cell size and macrosegregation on the corrosion behavior of a dilute Pb–Sb alloy

The aim of this study was to examine the effect of cooling rate on the cellular growth of a Pb–0.85 wt%Sb alloy and to evaluate the influences of cell size and of the corresponding macrosegregation profile on the resultant corrosion behavior. In order to obtain the as-cast samples a water-cooled unidirectional solidification system was used. Such experimental set-up has permitted the development of a clear cellular structural array even for relative high cooling rates and has allowed a wide range of solidification conditions to be analyzed. Macrostructural and microstructural aspects along the casting were characterized by optical microscopy and scanning electron microscope (SEM) techniques. The electrochemical impedance spectroscopy technique and potentiodynamic curves (Tafel extrapolation) were used to analyze the corrosion resistance of samples collected along the casting length and immersed in a 0.5 M H₂SO₄ solution at 25 °C. It was found that the corrosion rate decreases with increasing cell spacing and that the pre-programming of microstructure cell size can be used as an alternative way to produce as-cast components of Pb–Sb alloys, such as battery grids, with better corrosion resistance.     

Effect of Sn concentration on the corrosion resistance of Pb-Sn alloys in H2SO4 solution

The effect of Sn concentration on the corrosion resistance of Pb-Sn alloy in H₂SO₄ electrolyte was investigated by potentiodynamic polarization. A new approach to calculate the exchange current density, i_corr, was proposed and proved to be in accordance with the experimental results. This study shows that with the increase of alloying Sn, the corrosion rate of the alloy increased and then decreased, with its minimum appearing at 2.60 wt.% Sn. It was also found that the cathodic reaction does not have to be a single-step process, i.e., there are multiple sub-steps involved and complex cations, including H₄³⁺ and H₂⁺, existing in the systems.