Effects of tetrabutylammonium hydrogen sulfate as an electrolyte additive on the electrochemical behavior of lead acid battery

Tetrabutyl ammonium hydrogen sulfate is an ion-paring reagent that has similar properties with ionic liquid. Ionic liquids belong to new branch of salts with unique properties that have ever increasing applications in electrochemical systems especially lithium-ion batteries. For the first time, the effects of tetrabutylammonium hydrogen sulfate (TBAHS) as an electrolyte additive in battery’s electrolyte was studied on the hydrogen and oxygen evolution overpotential and anodic layer formation on lead–antimony–tin grid alloy of lead acid battery by using cyclic voltammetry and linear sweep voltammetry in aqueous sulfuric acid solution. The grid surface morphology after cyclic redox reaction was studied by using scanning electron microscopy. The results show that, by increasing TBAHS concentration in the electrolyte, hydrogen and oxygen overpotential were increased, and so the crystalline structure of PbSO₄ layer changed. Also, cyclic voltammogram on carbon–PbO paste electrode shows that with presence of TBAHS in the electrolyte, oxidation and reduction peak current intensively increased and peak potential for oxidation and reduction of PbO were dependent on TBAHS concentration.     

Effect of solidification temperature of lead alloy grids on the electrochemical behavior of lead-acid battery

One of the main electrochemical characteristics of a lead-acid battery is amount of water consumption. The effect of solidification temperature on electrochemical behavior (mainly hydrogen overvoltage) of Pb–Ca–Sn–Al (0.09%, Ca; 0.9%, Sn; 0.02%, Al) and Pb–Sb–Sn (1.7%, Sb; 0.24%, Sn) alloys, which are used in making the grid of lead-acid batteries, has been studied by cyclic voltammetry (CV) and linear sweep voltammety for different concentrations of sulfuric acid (ranging from 0.5 mol L^–1 to 4.0 mol L^–1). The morphology of the grid at some solidification temperatures was studied by optical microscopy. After one sweep of CV the surface of the electrode was investigated by using scanning electron microscopy.The results show that the potential of hydrogen evolution depends on the solidification temperature of the grids during production (mold temperature of grid casting). Also, at different solidification temperatures, different passivation phenomena, electrode surface constituents, and structure were observed.     

Electrochemical corrosion kinetics of tin and tin amalgams in NaCl aqueous solutions

Electrochemical techniques were used to determine the corrosion rate of pure tin metal as compared to 80 Sn/20 Hg tin amalgam. X-ray diagrams showed that this amalgam was a crystalline γ₂ phase, whereas a 50 Sn/50 Hg amalgam contained liquid alloy embedded in the same γ₂ phase. Open circuit potential measurements, combined with narrow range potential scanning voltammetry, lead to the conclusion that amalgamation resulted in enhancement of the corrosion current, mainly by increasing the cathodic electron transfer reaction kinetics both in deaerated and in oxygen-saturated NaCl solution. When maintained at zero current potential in a solution containing dissolved O₂ gas, the samples were gradually covered with an insulating oxide layer which was identified by a series of electrochemical impedance diagrams recorded at different time intervals. The oxide layer was firmly adherent to the bulk tin metal but was poor at protecting the amalgam electrode. Finally, at potential values where the anodic current reached a few mA/cm², the pure tin metal surface was suddenly deteriorated by the formation of extremely deep pinhole corrosion pits, while this effect was smoothed down by amalgamation. Electronic Publication     

不同碱溶液表面处理对稀土镁镍基储氢合金的影响

采用相同浓度即6 mol·L^-1 LiOH、NaOH和KOH对稀土镁镍基储氢合金进行表面处理,研究了不同碱溶液和不同处理时间对合金表面形貌、组成和电极电化学性能的影响。研究表明,合金经6 mol·L^-1 NaOH溶液处理10 min后具有最好的综合电化学性能。但随着处理时间的延长,采用6 mol·L^-1 NaOH溶液处理的合金放电容量衰减明显,实验证明这是由合金表面稀土元素和Al元素的大量溶解进入碱溶液造成的。3种碱溶液比较,LiOH溶液能有效去除合金表面镁元素减少合金在碱溶液处理过程中的氧化,虽然形成的表面不利于H在合金表面的吸脱附,却能有效提高合金在碱溶液中的抗腐蚀能力,提高合金的循环稳定性。     

Investigation of hydrogen embrittlement of Sn–Al alloy during contact with water vapour

The humid air induced processes of embrittlement of the Sn–Al alloy and hydrogen emission have been investigated. Using the secondary-ion mass spectrometry, X-ray, scanning electron microscopy and energy-dispersive X-ray spectrometry techniques it was found that the brittleness is caused by a failure of phase adhesion due to accumulation of hydrogen and formation of oxidized layers on phase boundaries during contact of the alloy with water vapour. Specific physical and electrochemical properties of the Sn/Al phase boundary satisfy conditions for the formation of atomic hydrogen and its reaction with Sn. Electrochemical corrosion plays an important role at the stage of formation of atomic hydrogen. The penetration of hydrogen and its accumulation in the bulk of the alloy is due to the high energy of the phase boundary and the low energy of formation of unstable tin hydride. Electronic Publication     

Electrochemical studies on Zn deposition and dissolution in sulphate electrolyte

The electrochemical deposition and dissolution of Zn on Pt electrode in sulphate electrolyte was investigated by electrochemical methods in an attempt to contribute to the better understanding of the more complex Zn–Cr alloy electrodeposition process. A decrease of the Zn electrolyte pH (from 5.4 to 1.0) so as to minimise/avoid the formation of hydroxo-products of Cr in the electrolyte for deposition of alloy coatings decreases the current efficiency for the Zn reaction, but the rate of the cathode reaction increases significantly due to intense hydrogen evolution. The results of the investigations in Zn electrolytes with pH 1.0–1.6 indicate that Zn bulk deposition is preceded by hydrogen evolution, stepwise Zn underpotential deposition (UPD) and formation of a Zn–Pt alloy. Hydrogen evolution from H₂O starts in the potential range of Zn bulk deposition. Data obtained from the electrochemical quartz crystal microbalance (EQCM) measurements support the assumption that electrochemical deposition of Zn proceeds at potentials more positive than the reversible potential of Zn. Anodic potentiodynamic curves for galvanostatically and potentiostatically deposited Zn layers provide indirect evidence about the dissolution of Zn from an alloy with the Pt substrate. The presumed potential of co-deposition of Cr (−1.9 V vs. Hg/Hg₂SO₄) is reached at a current density of about 300 mA cm⁻².     

High-efficiency ozone generation via electrochemical oxidation of water using Ti anode coated with Ni–Sb–SnO<Subscript>2</Subscript>

Ozone (O₃) has been generated on Ni–Sb–SnO₂/Ti electrode as anode immersed in acidic media at 25 °C by electrochemical process. The anode was electrochemically characterized by cyclic voltammetry and morphologically characterized by scanning electron microscopy (SEM) and X-ray diffraction. The concentration of dissolved ozone was determined by a UV/Vis spectrophotometer. The type of electrode with different times coating on the titanium mesh and different acid type and various concentrations (C _acid) were used, and the stability of the electrode was investigated under the experimental conditions by SEM images. Results shows that higher efficiency (53.7%) for O₃ generation by electrochemical oxidation of water were obtained in HClO₄ (1 M) and an applied potential of 2.4 V vs. Ag/AgCl in 150 ml volume undivided electrochemical cell.     

Electrochemical behavior of Pd–Rh alloys

Pd–Rh alloys were prepared by electrochemical codeposition. Bulk compositions of the alloys were determined by the energy dispersive X-ray analysis method, while surface compositions were determined from the potential of the surface oxide reduction peak. Cyclic voltammograms, recorded in 0.5 M H₂SO₄ for Pd–Rh alloys of different bulk and surface compositions, are intermediate between curves characteristic of Pd and Rh. The influence of potential cycling on electrochemical properties and surface morphologies of the alloys was studied. Due to electrochemical dissolution of metals, both alloy surface and bulk become enriched with Pd. Carbon oxides were adsorbed at a constant potential from the range of hydrogen adsorption. The presence of adsorbed CO₂ causes remarkable diminution of hydrogen adsorption but it does not significantly influence hydrogen insertion into the alloy bulk. On the other hand, in the presence of adsorbed CO, both hydrogen absorption and adsorption are strongly suppressed. Oxidative removal of the adsorbates results in a characteristic voltammetric peak, whose potential increases with the decrease in Rh surface content. Electron per site (eps) values calculated for the oxidation of the adsorbates change with alloy surface composition, more for CO₂ than CO adsorption, indicating the variation of the structure and composition of CO₂ and CO adsorption products. The course of the dependence of eps values on surface composition suggests that the products of CO₂ and CO adsorption on Pd–Rh alloys are similar but not totally identical.     

Application of surface electrochemical passivation of lead-antimony alloy for a simple and rapid electrochemical determination of antimony content

A simple, rapid and selective electrochemical method is proposed as a novel and powerful analytical technique for the solid phase determination of less than 4% antimony in lead-antimony alloys without any separation and chemical pretreatment. The proposed method is based on the surface antimony oxidation of Pb/Sb alloy to Sb(III) at the thin oxide layer of PbSO₄/PbO that is formed by oxidation of Pb and using linear sweep voltammetric (LSV) technique. Determination was carried out in concentrate H₂SO₄ solution. The influence of reagent concentration and variable parameters was studied. Antimony of Pb/Sb alloys can be determined in the range of 0.0056–4.00% with a detection limit of 0.0045% and maximum relative standard deviation of 4.26%. This method was applied for the determination of Sb in lead/acid battery grids satisfactory.     

Interface analysis of pure Sn,pure Ag and Sn?Ag binary alloys in H2SO4

The electrochemical and passivation properties of three selected binary xSn? Ag (x = 26, 50 and 70 wt%) alloys were studied by means of open‐circuit potential variation, potentiodynamic curves and a.c. impedance spectroscopy techniques.The specimens were polarized between ?1.0 and 0.5 V versus saturated calomel electrode (SCE) in naturally oxygenated sulfuric acidsolutions of different concentrations The experimental results indicate that i_corr increases with increasing either the acid concentration or the Sn content in the solid phase. Electrochemical impedance spectroscopyresults measured at the free corrosion potential confirm that alloy I (26Sn? Ag) characterizes by thicker passive film with higher protective ability compared to the other two samples richer in tin component. The exponential variation of the relative thickness of the surface film on any of the tested samples assumes an almost constant thickness for a thin barrier layer and a much larger outer porous layer that dominates the total film thickness on the alloy. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and structure of μ-oxo-bis-[(2,5-dimethylbenzenesulfonato)tri-p-tolylantimony(v)]

μ-Oxobis[(2,5-dimethylbenzenesulfonato)tri-p-tolylantimony(v)] was prepared by the reaction of 2,5-dimethylbenzesulfonic acid with tri-p-tolylstibine in the presence of hydrogen peroxide. According to X-ray diffraction data, the linear O bridge links two Sb atoms having a trigonal bipyramidal configuration. The 2,5-dimethylbenzenesufonate group and the bridging O atom occupy the axial positions and the three tolyl substituents are equatorial. The Sb(1)−O−Sb(2) and O−Sb−O angles are 180.0(0)° and 177.2(1)°; the Sb−C(Ph)_eq, Sb−O(SO₂Ar), and Sb−μ−O distances are 2.090(5)–2.095(6), 2.258(3), and 1.9361(5), respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2346–2349, December, 1999.     

Electrochemical behavior of PbO2/PbSO4 electrode in the presence of surfactants in electrolyte

The electrochemical behavior of PbO₂/PbSO₄ electrode is investigated in 4.5 M H₂SO₄ in presence of three surfactants, Sodium Dodecyl Sulfate (SDS), Cetyltrimethylammonium bromide (CTAB) and Sodium tripolyphosphate (STPP), using cyclic voltametry, electrochemical spectroscopy impedance and galvanostatic discharge as techniques. The micro morphology of the surface of the modified PbO₂ electrodes is examined by scanning electron microscopy. The results show that SDS and CTAB when added in the electrolyte could refine the coating particles and change the roughness of the surface of the electrode leading to a thin film of PbO₂ with amorphous character. In addition, SDS and CTAB shift the hydrogen evolution potential towards more negative values, improve the discharge capacity of the anodic layer and accelerate the charge transfer. Under cathodic polarization, CTAB presents the lowest value of the charge transfer resistance R_ct. In the contrary, STPP shifts the oxygen evolution potential towards more positive values, passivates the surface of the electrode and inhibits completely the reaction of PbO₂ formation.     

Pulse plating effect on microstructure and corrosion properties of Zn–Ni alloy coatings

The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn₂₁Ni₅ phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity of grain distribution were established to be the main factors determining corrosion behaviour of the coating. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005     

Tin corrosion in highly acidic solutions containing ethylene glycol oligomers and halides: An electrochemical quartz crystal microbalance study

Tin corrosion in 1 M H₂SO₄ solutions containing 0.01 M Sn(II), 0.01 M ethylene glycol or its oligomers, and 30 μM of various halides is studied by the electrochemical quartz crystal microbalance method. The current density of the tin electrode corrosion is found to approach a few tens of μA cm^?2. In the presence of Sn(II), the current density is nearly half that in its absence. The corrosion potential steadily increases with time, approaching a certain limit. In solutions containing Sn(II), the limit practically corresponds to the equilibrium potential of the Sn/Sn²⁺ electrode. The corrosion rate barely depends on the oligomer nature even up to tetraethylene glycol. Halides accelerate the corrosion process. Their action intensifies at initial time instants (up to 15–20 min) in the series Cl^? < Br^? < I^?. The corrosion impedance equals ～1000 ohm cm². It may be ignored when analyzing the overall impedance of the tin electrode in the frequency region extending from 0.1 Hz to 50 kHz.     

Inhibition activity of ethyleneglycol and its oligomers on tin electrode

Voltammetry and electrochemical impedance spectroscopy were applied to investigate the inhibition activity of ethyleneglycol and its oligomers on tin electrode in strong acidic sulfate solutions. Tetraethyleneglycol was found to be the most active substance among compounds HO–(CH₂–CH₂–O) _m –H (m≤4) that retards diffusion-controlled Sn(II) reduction due to its inhibitive adsorption. This rather slow process is controlled both by diffusion and electrosorption steps. A comparison of exchange current densities obtained in the presence of different polyethers shows that the length of the hydrocarbon chain is the main factor responsible for inhibition activity of such substances on tin electrode.     

Electrochemical deposition of ternary and binary systems from an alkaline electrolyte—a demanding way for manufacturing p-doped bismuth and antimony tellurides for the use in thermoelectric elements

Alkaline solution, especially diphosphate solutions, can be used as electrolytes for the galvanic deposition of p-type semiconductors. A ternary Bi–Sb–Te alloy semiconductor was deposited at a Ni-covered cathode surface at potentials lower than −0.6 V (Ag/AgCl), under potentiostatic condition in well-stirred solutions. Additionally, it was possible to deposit antimony telluride, a binary p-semiconductor, from the ternary electrolyte. The kinetics of the process was investigated by cyclic voltammetric measurements. The influence of the electrolyte convection on the electrocrystallization was analysed with the help of rotating disc electrode. The semiconductor layers were characterized by electrochemical impedance spectroscopy.Paper presented at the Jahrestagung der Fachgruppe Angewandte Elektrochemie der Gesellschaft Deutscher Chemiker, Düsseldorf, 11.-14.09.2005     

Physicochemical and electrochemical hydriding–dehydriding characteristics of amorphous MgNi x (x=1.0, 1.5, 2.0) alloys prepared by mechanical alloying

 Physicochemical and electrochemical hydriding-dehydriding characteristics of amorphous MgNi _x (x=1.0, 1.5, 2.0) alloys prepared by mechanical alloying have been investigated. It was found that the increase of Ni content in the alloys resulted in greatly enhanced kinetics for both absorption and desorption of hydrogen, while the saturation capacity showed the reverse tendency. Charge–discharge tests showed that the increase in Ni content lead to a significant enhancement in cycle performance of MgNi _x alloy electrodes. X-ray photoelectron spectroscopic and X-ray excited Auger electron spectroscopic investigations indicated the existence of a significantly thicker Ni-enriched layer for the MgNi_1.5 and MgNi_2.0 alloys than for the MgNi alloy. These results reveal that excess of Ni in MgNi _x alloys may improve the cycle performance of alloy electrodes by suppressing the segregation of Mg during electrochemical cycling, and the Ni in the topmost surface layer is mainly responsible for the improvement in the kinetics of hydrogen absorption. Received: 28 August 1999 / Accepted: 23 November 1999     

Electrochemical performance of Mg–9Al–1Zn alloy in aqueous medium

A systematic study on the corrosion and passivation behavior of AZ91D alloy in relation to the influence of concentration, temperature, pH, and immersion time was made in aqueous sulfate solution using electrochemical techniques including open-circuit potential, potentiodynamic polarization and impedance spectroscopy. It was found that the corrosion and pitting potentials (E _corr and E _pit) of the alloy drift to more active values with increasing either concentration (0.01–1.0 M) or temperature (278–338 K) of the test solution, suggesting that sulfate solution enhances the alloy dissolution, particularly at higher temperatures. On the other hand, values of the total film resistance (R _T) indicate that neutral solution (pH 7.0) supports the formation of a better protective layer on AZ91D surface than alkaline (pH 12.5) or acidic (pH 1.0) medium. The growth of a protective film on the alloy surface at short immersion times (up to ∼50 h) is evinced by a rapid positive evolution of E _corr and fast decrease in the corrosion rate (i _corr). However, for a long-term exposure (up to 500 h) E _corr drifts negatively and i _corr increases due to breakdown of the protective film, which causes a decrease in the alloy stability. Fitting the impedance data to equivalent circuit models suitable to each behavior assisted to explore the mechanism for the attack of the sample surface at various testing times. The results obtained from the three studied electrochemical techniques are in good agreement.     

Effects of Ca and Ag addition and heat treatment on the corrosion behavior of Mg-7Sn alloys in 3.5 wt.% NaCl solution

The effects of 1 wt.% Ca or 1 wt.% Ca + 1 wt.% Ag addition and heat treatment on the corrosion behavior of Mg-7Sn (wt.%) alloy in 3.5 wt.% NaCl solution were investigated by electrochemical measurements and immersion tests. The alloys were characterized by optical microscope (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). It was found that all alloys were corroded by pitting corrosion and grain boundary corrosion and further corroded with time going. Loose layers of compounds, including Mg (OH)₂, MgO, SnO₂, and other compounds containing Ca and Ag elements, were calibrated on the surface of corroded Mg-7Sn-1Ca-1Ag alloy. The Ca addition improved the corrosion resistance of Mg-7Sn alloy due to the formation of relatively stable compounds containing calcium element and grains refinement. Furthermore, the solid solutioned alloys obtained a superior corrosion resistance due to the dissolve of eutectic Mg₂Sn phase and homogenization treatment. However, the aging treatment is slightly detrimental to the corrosion resistance of Mg-7Sn alloys with the formation of Mg₂Sn precipitates. In conclusion, the aged Mg-7Sn-1Ca-1Ag alloy exhibited a better corrosion resistance and a noticeable micro-hardness property compared with those of as-cast Mg-7Sn alloy. And this study provides an important idea for the research on the comprehensive properties of Mg-Sn alloys.     

Study of the Alkyl Chain Length on Laccase Stability and Enzymatic Kinetic with Imidazolium Ionic Liquids

The activity and stability of laccase and their kinetic mechanisms in water soluble ionic liquids (ILs): 1-butyl-3-methyl imidazolium chloride [C₄mim][Cl], 1-octyl-3-methyl imidazolium chloride [C₈mim][Cl], and 1-decyl-3-methyl imidazolium chloride [C₁₀mim][Cl] were investigated. The results show that an IL concentration up to 10% is satisfactory for initial laccase activity at pH 9.0. The laccase stability was well maintained in [C₄mim][Cl] IL when compared to the control. The inactivation of laccase increases with the length of the alkyl chain in the IL: [C₁₀mim][Cl] > [C₈mim][Cl] > [C₄mim][Cl]. The kinetic studies in the presence of ABTS as substrate allowed calculating the Michaelis–Menten parameters. Among the ILs, [C₄mim][Cl] was the suitable choice attending to laccase activity and stability. Alkyl chains in the ions of ILs have a deactivating effect on laccase, which increases strongly with the length of the alkyl chain.