The influence of formation conditions on the electrochemical behavior of lead oxide in sulfuric acid solution

In course of anodic oxidation of lead in chloride-nitrate melt it has been formed β-PbO either in the form of nanopowder with the average size of the particles 20-70 nm or in the form of nanofibers with the thickness of 20 nanometers and length 500 nm. Synthesis is easily reproduced and can become a basis of industrial production lead nano-oxide. Lead oxide nanopowders and nanofibers tested in a course of potentiodynamic cycling in working conditions of a positive electrode of the acid lead battery, have shown good reproducibility of results and high values of currents density that can be unequivocally connected with increase in the true area of a surface of active mass of electrodes.     

Power assisted fuel cell

A hybrid fuel cell demonstrated pulse power capability at pulse power load simulations synonymous with electronics and communications equipment. The hybrid consisted of a 25.0 W Proton Exchange Membrane Fuel Cell (PEMFC) stack in parallel with a two-cell lead-acid battery. Performance of the hybrid PEMFC was superior to either the battery or fuel cell stack alone at the 18.0 W load. The hybrid delivered a flat discharge voltage profile of about 4.0 V over a 5 h radio continuous transmit mode of 18.0 W.     

Influence of measurement procedure on quality of impedance spectra on lead-acid batteries

Many battery simulation models, but also electrochemical interpretations are based on impedance spectroscopy. However, the impedance of a battery is influenced by various factors, e.g. in the case of a lead-acid battery: state of charge (SOC), charging or discharging, superimposed dc current, short-term history or homogeneity of the electrolyte. This paper analyses the impact of those factors on impedance spectra of lead-acid batteries. The results show that very detailed information about the conditions during the measurement is crucial for the correct interpretation of a spectrum.     

Lead-acid battery use in the development of renewable energy systems in China

Policies and laws encouraging the development of renewable energy systems in China have led to rapid progress in the past 2 years, particularly in the solar cell (photovoltaic) industry. The development of the photovoltaic (PV) and wind power markets in China is outlined in this paper, with emphasis on the utilization of lead-acid batteries. The storage battery is a key component of PV/wind power systems, yet many deficiencies remain to be resolved. Some experimental results are presented, along with examples of potential applications of valve regulated lead-acid (VRLA) batteries, both the absorbed glass mat (AGM) and gelled types.     

Corrosion of Pb–Ca–Sn alloy during potential step cycles

Potential step was applied to Pb–Ca–Sn alloy electrode at various potential and time regimes. No severe corrosion was observed during potential step cycle with cathodic potential under −140 mV or over −40 mV versus Pb/PbSO₄ (3.39 M H₂SO₄), or at constant potential without stepping. On the other hand, the Pb–Ca–Sn alloy was severely corroded during potential step with cathodic potential from −120 mV to −60 mV and with anodic potential of +40 mV or more positive. The corrosion could not be decreased with periodical rest at 0 mV, while it could be decreased with periodical reduction at high polarization of, e.g. −160 mV. It was found out that the severe corrosion occurs when the oxidation of Pb to PbSO₄ and partial reduction of passive film of PbSO₄ take turns many times.     

Lead-acid battery capacity in solar home systems—Field tests and experiences in Lundazi, Zambia

Batteries in solar home systems can cause problems and costs for the users and/or operators of the systems. In Zambia the Lundazi Energy Service Company (LESCO) operates 150 solar home systems on a fee for service basis. The aim of the study was to investigate how the capacity of lead-acid flat plate batteries had changed after one year of operation under real conditions. The results indicate that the batteries capacity has been significantly reduced in comparison to new unused batteries of the same type. Changes in battery management and maintenance, along with additional education of customers on correct use of SHS is advised in order to improve the life span of batteries in practical use.     

Gaston Planté and his invention of the lead-acid battery—The genesis of the first practical rechargeable battery

In 1860, the Frenchman Gaston Planté (1834-1889) invented the first practical version of a rechargeable battery based on lead-acid chemistry—the most successful secondary battery of all ages. This article outlines Planté’s fundamental concepts that were decisive for later development of practical lead-acid batteries. The ‘pile secondaire’ was indeed ahead its time in that an appropriate appliance for charging the accumulator was not available. The industrial success came after the invention of the Gramme machine. In 1879, Planté obtained acceptance for his work by publishing a book entitled Recherches sur l’Electricité. He never protected his inventions by patents, and spent much of his fortune on assisting impoverished scientists.     

Modeling of the capacity loss of a 12 V automotive lead-acid battery due to ageing and comparison with measurement data

One-dimensional modeling was carried-out to predict the capacity loss of a 12 V automotive lead-acid battery due to ageing. The model not only accounted for electrochemical kinetics and ionic mass transfer in a battery cell, but also considered the anodic corrosion of lead in sulfuric acid. In order to validate the modeling, modeling results were compared with the measurement data of the cycling behaviors of the lead-acid batteries having nominal capacity of 68 Ah that are mounted on the automobiles manufactured by Hyundai Motor Company. The cycling was performed under the protocol of the constant-current discharge and the constant-voltage charge. The discharge rate of C/3 was used. The range of state of charge was between 1 and 0.85. The voltage was kept constant at the gassing voltage until the charge current tapered to 10 mA. The retention capacity of the battery was measured with C/3 discharge rate before the beginning of cycling and after every 40 cycles of cycling. The modeling results were in good agreement with the measurement data.     

Fabrication of porous hollow glass microspheres

Porous hollow glass microspheres have many uses, including porosity enhancers for lead-acid batteries. A fast, facile and high yield synthetic method for fabricating porous hollow glass microspheres with diameters around 45-55 μm is demonstrated. The process involves shaking commercially available hollow glass microspheres in dilute hydrofluoric acid for 20 min. This process yielded two pore morphologies by using different commercially available starting materials; sponge-like submicron pores etched from S38 microspheres, and straight through micron pore etched from K25. Yields were 33% and 40%, respectively. The simplicity of the reported fabrication technique has the potential to be scaled up for large scale production.     

Further demonstration of the VRLA-type UltraBattery under medium-HEV duty and development of the flooded-type UltraBattery for micro-HEV applications

The UltraBattery has been invented by the CSIRO Energy Technology in Australia and has been developed and produced by the Furukawa Battery Co., Ltd., Japan. This battery is a hybrid energy storage device which combines a super capacitor and a lead-acid battery in single unit cells, taking the best from both technologies without the need of extra, expensive electronic controls. The capacitor enhances the power and lifespan of the lead-acid battery as it acts as a buffer during high-rate discharging and charging, thus enabling it to provide and absorb charge rapidly during vehicle acceleration and braking.The laboratory results of the prototype valve-regulated UltraBatteries show that the capacity, power, available energy, cold cranking and self-discharge of these batteries have met, or exceeded, all the respective performance targets set for both minimum and maximum power-assist HEVs. The cycling performance of the UltraBatteries under micro-, mild- and full-HEV duties is at least four times longer than that of the state-of-the-art lead-acid batteries. Importantly, the cycling performance of UltraBatteries is proven to be comparable or even better than that of the Ni-MH cells. On the other hand, the field trial of UltraBatteries in the Honda Insight HEV shows that the vehicle has surpassed 170,000 km and the batteries are still in a healthy condition. Furthermore, the UltraBatteries demonstrate very good acceptance of the charge from regenerative braking even at high state-of-charge, e.g., 70% during driving. Therefore, no equalization charge is required for the UltraBatteries during field trial. The HEV powered by UltraBatteries gives slightly higher fuel consumption (cf., 4.16 with 4.05 L/100 km) and CO₂ emissions (cf., 98.8 with 96 g km⁻¹) compared with that by Ni-MH cells. There are no differences in driving experience between the Honda Insight powered by UltraBatteries and by Ni-MH cells. Given such comparable performance, the UltraBattery pack costs considerably less – only 20–40% of that of the Ni-MH pack by one estimate. In parallel with the field trial, a similar 144-V valve-regulated UltraBattery pack was also evaluated under simulated medium-HEV duty in our laboratories.In this study, the laboratory performance of the 144-V valve-regulated UltraBattery pack under simulated medium-HEV duty and that of the recently developed flooded-type UltraBattery under micro-HEV duty will be discussed. The flooded-type UltraBattery is expected to be favorable to the micro-HEVs because of reduced cost compared with the equivalent valve-regulated counterpart.     

Model prediction for ranking lead-acid batteries according to expected lifetime in renewable energy systems and autonomous power-supply systems

Predicting the lifetime of lead-acid batteries in applications with irregular operating conditions such as partial state-of-charge cycling, varying depth-of-discharge and different times between full charging is known as a difficult task. Experimental investigations in the laboratory are difficult because each application has its own specific operation profile. Therefore, an experimental investigation is necessary for each application and, moreover, for each operation strategy.     

A novel flow battery—A lead-acid battery based on an electrolyte with soluble lead(II): Part VI. Studies of the lead dioxide positive electrode

The structure of thick lead dioxide deposits (approximately 1 mm) formed in conditions likely to be met at the positive electrode during the charge/discharge cycling of a soluble lead-acid flow battery is examined. Compact and well adherent layers are possible with current densities >100 mA cm⁻² in electrolytes containing 0.1–1.5 M lead(II) and methanesulfonic acid concentrations in the range 0–2.4 M; the solutions also contained 5 mM hexadecyltrimethylammonium cation, C₁₆H₃₃(CH₃)₃N⁺. From the viewpoint of the layer properties, the limitation is stress within the deposit leading to cracking and lifting away from the substrate; the stress appears highest at high acid concentration and high current density. There are, however, other factors limiting the maximum current density for lead dioxide deposition, namely oxygen evolution and the overpotential associated with the deposition of lead dioxide. A strategy for operating the soluble lead-acid flow battery is proposed.     

One-dimensional dynamic modeling and validation of maintenance-free lead-acid batteries emphasizing temperature effects

Lead acid batteries are still widely used for SLI (Starting-Lighting-Ignition) systems in vehicles because of the cost advantage. The batteries are frequently charged and discharged under different operation conditions, which continuously changes distribution of inner temperature of batteries. Variation of the temperature distributions significantly affects performance and durability of the battery. We developed a one-dimensional dynamic model based on the first principle of thermal dynamics and electrochemistry. The thermal model incorporates control volumes for each of the major constituents of the battery cells that is casing, electrolyte, and electrodes. The model was extended for a six-cell battery and used to analyze effects of discharging currents on the performances and temperature, compared with results from a three-dimensional finite element analysis and tested against experimental results obtained from a thermal chamber and using thermal imaging.     

Lead-acid batteries in micro-hybrid vehicles

More and more vehicles hit the European automotive market, which comprise some type of micro-hybrid functionality to improve fuel efficiency and reduce emissions. Most carmakers already offer at least one of their vehicles with an optional engine start/stop system, while some other models are sold with micro-hybrid functions implemented by default.But these car concepts show a wide variety in detail—the term “micro-hybrid” may mean a completely different functionality in one vehicle model compared to another. Accordingly, also the battery technologies are not the same. There is a wide variety of batteries from standard flooded and enhanced flooded to AGM which all are claimed to be “best choice” for micro-hybrid applications.A technical comparison of micro-hybrid cars available on the European market has been performed. Different classes of cars with different characteristics have been identified. Depending on the scope and characteristics of micro-hybrid functions, as well as on operational strategies implemented by the vehicle makers, the battery operating duties differ significantly between these classes of vehicles.Additional laboratory investigations have been carried out to develop an understanding of effects observed in batteries operated in micro-hybrid vehicles pursuing different strategies, to identify limitations for applications of different battery technologies.     

System dynamic model and charging control of lead-acid battery for stand-alone solar PV system

The lead-acid battery which is widely used in stand-alone solar system is easily damaged by a poor charging control which causes overcharging. The battery charging control is thus usually designed to stop charging after the overcharge point. This will reduce the storage energy capacity and reduce the service time in electricity supply. The design of charging control system however requires a good understanding of the system dynamic behaviour of the battery first. In the present study, a first-order system dynamics model of lead-acid battery at different operating points near the overcharge voltage was derived experimentally, from which a charging control system based on PI algorithm was developed using PWM charging technique.The feedback control system for battery charging after the overcharge point (14 V) was designed to compromise between the set-point response and the disturbance rejection. The experimental results show that the control system can suppress the battery voltage overshoot within 0.1 V when the solar irradiation is suddenly changed from 337 to 843 W/m². A long-term outdoor test for a solar LED lighting system shows that the battery voltage never exceeded 14.1 V for the set point 14 V and the control system can prevent the battery from overcharging. The test result also indicates that the control system is able to increase the charged energy by 78%, as compared to the case that the charging stops after the overcharge point (14 V).     

Influence of expander components on the processes at the negative plates of lead-acid cells on high-rate partial-state-of-charge cycling. Part II. Effect of carbon additives on the processes of charge and discharge of negative plates

Lead-acid batteries operated in the high-rate partial-state-of-charge (HRPSoC) duty rapidly lose capacity on cycling, because of sulfation of the negative plates. As the battery operates from a partially discharged state, the small PbSO₄ crystals dissolve and precipitate onto the bigger crystals. The latter have low solubility and hence PbSO₄ accumulates progressively in the negative plates causing capacity loss. In order to suppress this process, the rate of the charge process should be increased.In a previous publication of ours we have established that reduction of Pb²⁺ ions to Pb may proceed on the surface of both Pb and carbon black particles. Hence, the reversibility of the charge-discharge processes improves, which leads to improved cycle life performance of the batteries in the HRPSoC mode. However, not all carbon forms accelerate the charge processes. The present paper discusses the electrochemical properties of two groups of carbon blacks: Printex and active carbons. The influence of Vaniseprse A and BaSO₄ (the other two components of the expander added to the negative plates) on the reversibility of the charge-discharge processes on the negative plates is also considered. It has been established that lignosulfonates are adsorbed onto the lead surface and retard charging of the battery. BaSO₄ has the opposite effect, which improves the reversibility of the processes on cycling and hence prolongs battery life in the HRPSoC duty. It has been established that the cycle life of lead-acid cells depends on the type of carbon black or active carbon added to the negative plates. When the carbon particles are of nano-sizes (<180 nm), the HRPSoC cycle life is between 10,000 and 20,000 cycles. Lignosulfonates suppress this beneficial effect of carbon black and activated carbon additives to about 10,000 cycles. Cells with active carbons have the longest cycle life when they contain also BaSO₄ but no lignosulfonate. A summary of the effects of the three expander components on the elementary processes during charge of negative lead-acid battery plates is presented at the end of the paper.     

A novel electrochemical approach on the effect of alloying elements on self-discharge and discharge delivered current density of Pb-Ca-Ag lead-acid battery plates

The aim of this research is to examine the effect of alloying elements in positive plate composition of a lead-acid battery on its self-discharge and delivered current density in discharge state performances. To elucidate, a positive and negative lead-acid battery plates of two alloys namely Pb-Ca-Ag and Pb-Sb are investigated through electrochemical measurements in battery solution. Higher delivered current density of Pb-Ca-Ag cell in compare with Pb-Sb cell is observed for 25 days of 33 measurement days. The evolution of couple potential for both cases shows that the Pb-Ca-Ag cell potential achieves a value in the potential range of water stability after 25 days while in case of Pb-Sb cell, it remains well beyond the water stability potential domain for 33 days of measurements. Further investigations demonstrate that Pb-Sb cell current density is mainly caused by Pb oxidation reaction on negative plate while both anodic and cathodic polarizations (mixed polarization) are responsible in the case of Pb-Ca-Ag cell.