The Effect of Additives on the Reaction Mechanism of the Pb∕PbSO[sub 4] Electrode

Simon, Adam C.; Caulder, S. M.; Gurlusky, P. J.; Pierson, John R.

doi:10.1149/1.2401839

Cited by 33 publications

(14 citation statements)

References 10 publications

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“…The formation of many smaller crystals instead of a few large ones should be favoured. This is the opposite of what is generally observed with the addition of lignins [1][2][3][4][5][6][7]. Clearly other effects of the lignins must be more important [6].…”

Section: Surface Tensionmentioning

confidence: 82%

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Interactions between lignosulphonates and the components of the lead acid battery. Part 2. Interactions with the electrolyte and lead sulphate growth

Myrvold

2005

J Appl Electrochem

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Several lignin based expanders underwent various physical and chemical tests. The results were compared with life time measurements for batteries with the same expanders. The aim was to gain understanding of the interactions between the expanders and the other components in the lead acid battery, and also, if possible, to find a quick and reliable screening test for the life time of batteries. The low pH of the sulphuric acid electrolyte will give both hydrolysis of the lignins and condensation. Hydrolysis seems to be detrimental to the performance. The lignosulphonate expanders seem to promote a dissolution-precipitation mechanism for lead sulphate formation. BackgroundExpanders in lead acid batteries influence the size and shape of the lead sulphate particles formed during discharge [1][2][3][4][5][6][7]. In previous work [8] we looked at the interactions between the lignosulphonate expander and the different solid phases present in a lead acid battery. In this work we will look at the interaction with the electrolyte, that is sulphuric acid, and the lead ions dissolved in the sulphuric acid.The expander greatly improves the performance of starter, lightning and ignition (SLI) batteries. The cold cranking ability is greatly improved, and the life time of the battery is several times longer than without the expander. Many natural and synthetic organic compounds have been used for this purpose [1]. Lignosulphonates have proven to be very well suited as expanders [1,2,9].The construction and testing of batteries is a time and energy consuming process. Several simple tests to screen the expander have been suggested. In this work we investigate whether simple properties of the expander can be used to predict to expander performance, and thus speed up the development time for new expanders. Understanding of the mechanism responsible for the performance of the expanders is also needed. Experimental Surface tensionThe surface tension was determined by a Cenco de Nou¨y tensiometer with a platinum ring. The solutions used were 0.01-5% lignin in a phosphate buffer at pH approximately 6, or in unbuffered sulphuric acid solutions. The temperature was 23°C. The values given are the average of three measurements. The experimental uncertainty is less than 0.2%. The surface tension is a measure of the surface activity of the lignins. Precipitation pHThe precipitation pH was determined by dissolving the lignosulphonates in water and adding sulphuric acid until a precipitate or cloudy solution formed. Solutions with lignin in 6% sulphuric acid were filtered and the molecular weight distribution determined for the soluble fraction in this acid. High temperature stabilityThe high temperature stability was determined in two different ways. 2500 ppm of the lignosulphonates were dissolved in sulphuric acid at three different strengths, e.g. pH 1, pH 3 and pH 5. The solutions were kept at room temperature, at 65°C, and at 105°C. The molecular weight distributions were checked at different times.The high temperature stability was also d...

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Section: Surface Tensionmentioning

confidence: 82%

“…Expanders in lead acid batteries influence the size and shape of the lead sulphate particles formed during discharge [1][2][3][4][5][6][7]. In previous work [8] we looked at the interactions between the lignosulphonate expander and the different solid phases present in a lead acid battery.…”

Section: Introductionmentioning

confidence: 99%

Interactions between lignosulphonates and the components of the lead acid battery. Part 2. Interactions with the electrolyte and lead sulphate growth

Myrvold

2005

J Appl Electrochem

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“…Pit propagation involves consistent anodic dissolution by diffusion due to high concentration of metallic and chloride ions within corrosion pits, hence a high concentration of hydrogen ions due to hydrolysis [21]. The corrosion process within the pit is a specific type of anodic reaction whose conditions enables and is necessary for electrochemical reactions within the pit.…”

Section: Pitting Corrosion Mechanism In the Presence Of Chloridesmentioning

confidence: 99%

Pitting Corrosion Resistance and Inhibition of Lean Austenitic Stainless Steel Alloys

Loto¹

2017

Austenitic Stainless Steels - New Aspects

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The pitting corrosion behavior of 301, 304 and 316 austenitic stainless steels in 2M H 2 SO 4 at 0-1.5% NaCl concentrations was investigated through potentiodynamic polarization and optical microscopy analysis. Electrochemical analysis of the pitting corrosion inhibition and surface protection properties of rosemary oil and aniline on the stainless was also performed. The corrosion rate, pitting potential, passivation potential, metastable pitting potential and surface morphology of both steels where significantly altered by changes in chloride concentration, differences in alloy composition and metallurgical properties of the steels. 316 steel had the lowest corrosion rate and highest pitting corrosion resistance followed by 301 steel. The surface morphology of 316 steel was slightly altered at 1.5% NaCl concentration while 301 steel appears to etch with grain boundaries appearing at higher chloride concentration. 304 steel showed no resistance to pitting after 0% NaCl coupled with relatively significant increase in corrosion rate values. Its surface morphology showed the presence of corrosion pits with respect to chloride and inhibitor concentration. Rosemary oil and aniline significantly reduced the corrosion rates values of the stainless steels and with consequent increase in their pitting corrosion resistance; however the compounds had no positive influence on the pitting corrosion behavior of 304 steel.

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“…The geometric models for 2D and 3D nucleation and growth of anodic films that have been developed (1 1,12) treat the growth kinetics in terms of two growth rates and the nucleation rate. The growth rates involved are the lateral growth rate, kl, representing the crystal growth parallel to the plane surface of the electrode, and the vertical growth rate, k2, describing the growth perpendicular to the electrode surface.…”

Section: (B) Potential Step Dependencementioning

confidence: 99%

“…During the discharge process, the expander affects the PbSO, film formed making it more porous (1 -3). The PbSO, crystals were more loosely attached and they extended further from the electrode surface (1). ' The size of the PbS04 crystals was also reduced due to the adsorption of the expander onto the growing PbS0, crystal (3).…”

Section: Introductionmentioning

confidence: 99%

The influence of ammonium lignosulphonate as an expander on the formation of PbSO₄ on lead amalgam electrodes

Barradas¹,

Rennie²,

VanderNoot³

1985

Can. J. Chem.

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. Linear potential sweeps and potentiostatic pulse perturbations have been employed to investigate the influence of the expander ammonium lignosulphonate, on the anodic formation of PbS04 on lead amalgam electrodes in sulphuric acid solutions at 24°C. It was found that the expander strongly adsorbs onto the clean amalgam surface thus affecting the formation of the PbS0, film. The expander increased the charge necessary for passivation, inhibited the cathodic reduction of the film, and produced a more porous film. Evidence is given for the presence of an optimum concentration of expander. Some speculations concerning the mode of action of the expander onto the amalgam surface are presented. [Traduit par le journal]

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The Effect of Additives on the Reaction Mechanism of the Pb∕PbSO[sub 4] Electrode

Cited by 33 publications

References 10 publications

Interactions between lignosulphonates and the components of the lead acid battery. Part 2. Interactions with the electrolyte and lead sulphate growth

Interactions between lignosulphonates and the components of the lead acid battery. Part 2. Interactions with the electrolyte and lead sulphate growth

Pitting Corrosion Resistance and Inhibition of Lean Austenitic Stainless Steel Alloys

The influence of ammonium lignosulphonate as an expander on the formation of PbSO₄ on lead amalgam electrodes

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The Effect of Additives on the Reaction Mechanism of the Pb∕PbSO[sub 4] Electrode

Cited by 33 publications

References 10 publications

Interactions between lignosulphonates and the components of the lead acid battery. Part 2. Interactions with the electrolyte and lead sulphate growth

Interactions between lignosulphonates and the components of the lead acid battery. Part 2. Interactions with the electrolyte and lead sulphate growth

Pitting Corrosion Resistance and Inhibition of Lean Austenitic Stainless Steel Alloys

The influence of ammonium lignosulphonate as an expander on the formation of PbSO4 on lead amalgam electrodes

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The influence of ammonium lignosulphonate as an expander on the formation of PbSO₄ on lead amalgam electrodes