Study of the Charge Acceptance of Small-Size Sealed Lead-Acid Batteries

ＳｔｕｄｙｏｆｔｈｅＣｈａｒｇｅＡｃｃｅｐｔａｎｃｅｏｆＳｍａｌｌ－ＳｉｚｅＳｅａｌｅｄＬｅａｄ－ＡｃｉｄＢａｔｔｅｒｉｅｓＤＯＮＧＢａｏｇｕａｎｇ；ＺＨＡＮＧＱｉｕｄａｏ；ＭＵＪｕｎｊｉａｎｇ（董保光，张秋道，穆俊江）（Ｄｅｐｔ．ｏｆＡｐｐｌｉｅｄ...

Self-Discharge in Valve-Regulated Sealed Lead-Acid Batteries

Factors that cause the self-discharge in valve-regulated sealed lead-acid batteries are discussed and measures to inhibit the self-discharge are put forward.

Reductive smelting of spent lead–acid battery colloid sludge in a molten Na_2CO_3 salt

Lead extraction from spent lead–acid battery paste in a molten Na2CO3 salt containing Zn O as a sulfur-fixing agent was studied. Some influencing factors, including smelting temperature, reaction time, Zn O and salt dosages, were investigated in detail using single-factor experiments. The optimum conditions were determined as follows: T = 880°C; t = 60 min; Na2CO3/paste mass ratio = 2.8:1; and the Zn O dosage is equal to the stoichiometric requirement. Under the optimum conditions, the direct recovery rate of lead reached 98.14%. The results suggested that increases in temperature and salt dosage improved the direct recovery rate of lead. XRD results and thermodynamic calculations indicated that the reaction approaches of lead and sulfur were Pb SO4→Pb and Pb SO4→Zn S, respectively. Sulfur was fixed in the form of Zn S, whereas the molten salt did not react with other components, serving only as a reaction medium.

Addition of Ce as additive to Pb-Ca-Sn-Al grid alloy for lead acid battery

The study on three Pb Ca Sn Al alloys with 0.08%, 0.4% and 1.0% of Ce indicates that the addition of Ce results in an obvious increase in the tensile strength and hardness of the alloys, an increase in the overpotentials of hydrogen and oxygen evolution and the corrosion resistance as well. The study on the corrosion film formed on the alloys by cyclic voltammetry shows that the addition of Ce slows down the formation of corrosion film. It is therefore concluded from the experimental results that the addition of Ce can increase the tensile strength and HB of Pb Ca alloy and the tensile strength and HB of the alloy increase with the increase of Ce; the addition of Ce also increases the hydrogen and oxygen evolution overpotentials of Pb Ca alloy, and when the content of Ce is 1.0%, the alloy has the highest hydrogen and oxygen evolution overpoteatials; the addition of Ce improves the anticorrosion capability of the alloy, and when the content Ce is 1.0%, the alloy has the best anticorrosion capability; and the addition of Ce also slows down the formation of corrosion film.

Effect of lead foam grid on performance of lead-acid battery

In order to increase the specific energy and specific power of a lead-acid battery, lead foam grid was prepared by electrodepositing Pb-Sn alloy on a copper foam substrate and used as negative current collector for a lead acid battery whose capacity was limited by the negative plate. Comparing the effect of the cast grid, under the same conditions, the mass of lead foam grid decreases by 35%, and the area of lead foam contacted with active material increases by about 20 times. Under 2 h rate discharge condition, with a high current （3 0 I2） e and low-temperature （-10 ℃, I2） discharge system, the lead foam grid markedly boosts the discharge performance of lead acid battery. It increases not only the negative electrode mass specific capacity by 27%,37% and 29%,but also the utilization efficiency of the negative active material by 5%. Compared with the negative electrode of cast grid, XRD and SEM results show that after 20 cycles at the state of charge, the sponge lead in the negative lead foam electrode has smaller crystals and less PbSO4 on its surface. Meanwhile, at the state of full discharge, the PbSO4 crystals are smaller and occur less on the surface of lead foam electrode. This indicates its active material reacts more uniformly.

Research on thin grid materials of lead-acid batteries

A detailed investigation on Pb-Ca-Sn alloys was made in order to choose suitable grid alloys materials for thin plate lead-acid batteries. The electrochemical performances of alloys were investigated by electrochemical corrosion experiment, scanning electron microscope (SEM), and cyclic voltammetry (CV) test. The results indicate that Pb-Ca-Sn-Bi-Cu alloys can be used to make the grids used for thin grid lead-acid batteries, the content of bismuth has primary effects on the corrosion resistance of grid alloys, the composition of alloys plays an important role on batteries performance, and appropriate scale of elements can be choosed to obtain optimal electrochemical performance. The lead-acid batteries using this kind of grid show good performance by cycle life test.

Experiments Study on Charge Technology of Lead-Acid Electric Vehicle Batteries

The basic theory of the fast charge and several charge methods are introduced. In order to heighten charge efficiency of valve-regulated lead-acid battery and shorten the charge time, five charge methods are investigated with experiments done on the Digatron BNT 400-050 test bench. Battery current, terminal voltage, capacity, energy and terminal pole temperature during battery experiment were recorded, and corresponding curves were depicted. Battery capacity-time ratio, energy efficiency and energy-temperature ratio are put forward to be the appraising criteria of lead-acid battery on electric vehicle （EV）. According to the appraising criteria and the battery curves, multistage-current/negative-pulse charge method is recommended to charge lead-acid EV battery.

PREPARATION OF LEAD-ACID BATTERY USING ELECTROPLATED RETICULATED SiC AS THE POSITIVE CURRENT COLLECTOR

The possibility of using Pb-electroplated reticulated SiC as the positive current collector for lead-acid batteries was investigated. Reticulated SiC with two aperture sizes (3 and 2mm) were tested as the substrate of positive electrode. It was found that the reticulated SiC has an excellent corrosion resistance in H2SO4 solution, and the Pb layer electroplated on reticulated SiC showed analogous electrochemical behavior to metal Pb. Preliminary test of the battery performance indicated that the utilization efficiency of the positive active mass of new designed batteries are improved compared with the conventional batteries. The improvement could be ascribed to the high specific surface area of the reticulated structured positive current collector, which was further supported by the even better performance of the battery made from a smaller aperture size (2mm) reticulated SiC as the substrate of the positive electrode.

Mathematical Model and Experiment of Temperature Effect on Discharge of Lead-Acid Battery for PV Systems in Tropical Area

This paper presents Mathematical Model and Experiment of Temperature effect on Charge and Discharge of Lead-Acid Battery performance in PV system power supply. To test temperature effect on battery discharge cycles, a temperature range of tropical area from 25 - 60 degrees Celsius in a simulator is set up for testing. This temperature range is normally practical for battery usage. This allows the battery to determine the parameters of the battery quickly and high accurate. A Mathematical Model with MATLAB Program is written and constructed as block diagram using the equations of battery the parameters. By running program, the effects of various parameters are investigated. The results showed that time of discharge the battery is longer. Then, the experiment is set up by battery VRLA 12 V 20 AH. The results confirmed the mathematical model simulations.

Pb-Ca-Sn-Ba Grid Alloys for Valve-Regulated Lead Acid Batteries

The effect of barium additives on the process of anodic corrosion of lead-tin-calcium alloys in a 4.8 М sulfuric acid solution was studied. Cyclic voltammetry, impedance spectroscopy, weight loss measurements and scanning electronic microscope analysis have allowed exploring the oxidation process and characterizing the formed corrosion layer. According to our results, barium introduction into lead-tin-calcium alloys increases their hardness, reduces their electrochemical activity, and improves their corrosion stability. Reduction of the calcium content in the alloy can be compensated by adding barium. Barium dopation at lead-tin-calcium alloys decreases the resistance of the oxide layer formed on the grid surface, in a deeply discharged state, and raises its resistance during floating conditions and at a charged state of the positive electrode.

Potentiometric Measurement of State-of-Charge of Lead-Acid Batteries Using Polymeric Ferrocene and Quinones Derivatives

Measurement of state-of-charge of lead-acid batteries using potentiometric sensors would be convenient;however, most of the electrochemical couples are either soluble or are unstable in the battery electrolyte. This paper describes the results of an investigation of poly (divinylferrocene) (PDVF) and Poly(diethynylanthraquinone) (PAQ) couples in sulfuric acid with the view to developing a potentiometric sensor for lead-acid batteries. These compounds were both found to be quite stable and undergo reversible reduction/oxidation in sulfuric acid media. Their redox potential difference varied linearly with sulfuric acid concentration in the range of 1 M - 5 M (i.e. simulated lead-acid electrolyte during battery charge/discharge cycles). A sensor based on these compounds has been investigated.

Effect of Additives on the Performance of Lead Acid Batteries

Effect of titanium dioxide （TiO2） and carbon additives in the respective positive and negative material properties and the influence on the performance of the battery were investigated. The electrode samples were characterized by BET （Brunauer Emmett Teller）, XRD （X-ray diffractometer）, SEM （scanning electron microscopy） and EIS （electrochemical impedance spectroscopy） to understand the surface area, phase, structure, morphology and electrical conductivity of the respective electrode material. The surface area was obtained as 2.312 m2＂g＂l and 0.892 m2＂g＂1, respectively for 12% of activated carbon in the expander of negative and 0.70% of TiO2 （Titanium dioxide） in the PAM （positive active material）. The structural analysis reveals an increase in the tetrabasic lead sulfate and also evidenced by well grown crystals in the PAM with the TiO2, respectively obtained by XRD and SEM techniques. The impedance spectra analysis shows an increase of electrical conductivity of negative active mass with temperature. The battery results showing two fold enhancements in the charge acceptance were attributed to the high surface area activated carbon in the NAM （negative active material）. The materials properties of electrodes and their influence on the battery performance were discussed.

ACID ELECTROLYTIC TREATMENT PROCESS OF SCRAP BATTERY SLUDGE

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Development of Management Systems for Electric Vehicle Battery Series

A kind of management system for electric vehicle (EV) battery series was developed. The system can predict residual capacity for EV battery series and mileages. The system can determine if it is necessary for the battery series to be charged. The system can determine which battery is necessary to be updated for the reason of damage or aging. The system can display the total voltage of battery series, extreme voltage and temperature of every battery in the series. The system can display the accumulative discharge for every battery in the series. The system can alarm when both total or extreme voltage is at low level, or temperature of a battery in the series is at high level. The system provided with a microprocessor as key part can collect and record signal of charging and discharging current, total voltage, extreme voltage and temperature for every battery. The mathematical model of residual capacity for EV lead acid batteries was discussed in details. The system operates well in the laboratory and meets the requirement.

Effect of Properties of Carbon Materials on Performance of VRLA Batteries

In the present study, the relationship between properties of different carbon materials and their impact on performance of VRLA （valve regulated lead acid） battery was studied. The material properties undertaken for the study are： surface area, conductivity and water absorption of the carbon. The electrode morphology revealed the uniform distribution of active material when high surface area carbon was added to NAM （negative active material）. The porosity of the plate also exhibited changes with respect to type of carbon materials added. The study further revealed that, the addition of high surface area carbon （-1,400 m^2/g） improves the charge acceptance of the battery with higher loading. Further improvement in charge acceptance was observed with addition of graphite to higher surface area carbon. Nevertheless, the float current of the battery got affected due to graphite loading and found there was no impact on shelf life of the battery in all the cases. The study demonstrates the need for customized ＂carbon formulation＂ to obtain the maximum performance out of the battery.

Application of Power Electronics and Control for Dual Battery Packs Management with Voltage Balancing and State of Charge Estimation

Energy storage, such as lead acid batteries, is necessary for renewable energy sources’ autonomy because of their intermittent nature, which makes them more frequently used than traditional energy sources to reduce operating costs. The battery storage system has to be monitored and managed to prevent serious problems such as battery overcharging, over-discharging, overheating, battery unbalancing, thermal runaway, and fire dangers. For voltage balancing between batteries in the pack throughout the charging period and the SOC estimate, a modified lossless switching mechanism is used in this research’s suggested battery management system. The OCV state of charge calculation, in the beginning, was used in conjunction with the coulomb counting approach to estimate the SOC. The results reveal that correlation factor K has an average value of 0.3 volts when VM ≥ 12 V and an average value of 0.825 when VM ≤ 12 V. The battery monitoring system revealed that voltage balancing was accomplished during the charging process in park one after 80 seconds with a SOC difference of 1.4% between Batteries 1 and 2. On the other hand, the system estimates the state of charge during the discharging process in two packs, with a maximum DOD of 10.8 V for all batteries. The project’s objectives were met since the BMS estimated SOC and achieved voltage balance.

Simple Rational Model for Discharge of Batteries with Aqueous Electrolytes, Based on Nernst Equation

A simple rational model is proposed for discharge of batteries with aqueous electrolytes, based on Nernst equation. Details of electrode kinetics are not taken into account. Only a few overall parameters of the battery are considered. A simple algorithm, with variable time step-length Δt, is presented, for proposed model. The model is first applied to Daniel cell, in order to clarify concepts and principles of battery operation. It is found that initial pinching, in time-history curve of voltage E-t, is due to initial under-concentration of product ion. Then, model is applied to a lead-acid battery. In absence of an ion product, and in order to construct nominator of Nernst ratio, such an ion, with coefficient tending to zero, is assumed, thus yielding unity in nominator. Time-history curves of voltage, for various values of internal resistance, are compared with corresponding published experimental curves. Temperature effect on voltage-time curve is examined. Proposed model can be extended to other types of batteries, which can be considered as having aqueous electrolytes, too.

Electrochemical behavior and electrolytic preparation of lead in eutectic NaCl−KCl melts

A novel molten salt extraction process consisting of chlorination roasting and molten salt electrolysis was proposed to develop a more efficient and environmental friendly technology for recovering lead from spent lead acid batteries(LABs).The feasibility of this process was firstly assessed based on thermodynamics fundamentals.The electrochemical behavior of Pb(II)on a tungsten electrode in the eutectic NaCl−KCl melts at 700℃ was then investigated in detail by transient electrochemical techniques.The results indicated that the reduction reaction of Pb(II)in NaCl−KCl melts was a one-step process exchanging two electrons,and it was determined to be a quasi-reversible diffusion-controlled process.Finally,potentiostatic electrolysis was carried out at−0.6 V(vs Ag/AgCl)in the NaCl−KCl−PbCl2 melts,and the obtained cathodic product was identified as pure Pb by X-ray diffraction analysis.This investigation demonstrated that it is practically feasible to produce pure Pb metal by electrochemical reduction of PbCl2 in eutectic NaCl−KCl melts,and has provided important fundamental for the further study on lead recovery from spent LABs via molten salt extraction process.

Studies on the Behaviors of PbSO_4/Pb and PbO_2/PbSO_4 Electrodes Prepared from Lead Carbonate by Powder Microelectrode Technique

The behaviors ot PbSO4/Pb and PbO4/PbSO4 electrode prepared from PbCO3 have been examined using powder microelectrode(PME) technique and cyclic voltammetry(CV). Firstly, PMEs parked with Pb- CO3 transformed into PtSO4 PME in 1. 0 mol/L H2SO4 solution at 30 C, and then the PbSO4 in the PMEs were formed to Pb or PbO2 using an unsymmetrical signal(Qa/Qe for PbSO4/Pb electrode and Qe/Qa for PsO2/ PbSO4 electrode being 0. 1-0. 3) in 2. S mol/L H2SO4 solution. The results show that the CV characteristic of either PbSO4/Pb or PsO2/PbSO4 PME prepared from PhCO3 are as good as that of both electrodes made from lead oxide powder produced by ball mill.

Comparison of Alkaline Treatment of Lead Contaminated Wastewater Using Lime and Sodium Hydroxide

A lead-acid storage battery manufacturing industry in India produces several thousand liters of lead con-taminated acidic wastewater on a daily basis and uses hydrated lime to render the lead-contaminated acidic wastewater alkaline (pH = 8.0). Alkaline treatment of the acidic wastewater with lime though a cost-effective method, generates copious amount of lead-contaminated gypsum sludge. Other alkali agents such as sodium hydroxide, sodium carbonate and dolomite are also used for alkali treatment of the acid wastewaters. The present paper compares the relative efficiency of hydrated lime and 0.05 M to 1 M NaOH solutions with re-spect to 1) amounts of sludge produced, 2) immobilization of the soluble lead in the acidic wastewater (AWW) and 3) increase in TDS (total dissolved solids) levels upon treatment of AWW with NaOH solutions and lime. The study also performs equilibrium speciation upon alkaline treatment of AWW with lime and NaOH (sodium hydroxide) solutions using the Visual MINTEQ program to understand the chemical reac-tions occurring during treatment process.