High-rate Partial-state-of-charge Research Articles

Mechanism of action of electrochemically active carbons on the processes that take place at the negative plates of lead-acid batteries

It is known that negative plates of lead-acid batteries have low charge acceptance when cycled at high rates and progressively accumulate lead sulphate on high-rate partial-state-of-charge (HRPSoC) operation in hybrid-electric vehicle (HEV) applications. Addition of some carbon or graphite forms to the negative paste mix improves the charge efficiency and slows down sulfation of the negative plates. The present investigation aims to elucidate the contribution of electrochemically active carbon (EAC) additives to the mechanism of the electrochemical reactions of charge of the negative plates. Test cells are assembled with four types of EAC added to the negative paste mix in five different concentrations. Through analysis of the structure of NAM (including specific surface and pore radius measurements) and of the electrochemical parameters of the test cells on HRPSoC cycling, it is established that the electrochemical reaction of charge Pb 2+ + 2e − → Pb proceeds at 300–400 mV lower over-potentials on negative plates doped with EAC additives as compared to the charge potentials of cells with no carbon additives. Hence, electrochemically active carbons have a highly catalytic effect on the charge reaction and are directly involved in it. Consequently, the reversibility of the charge/discharge processes is improved, which eventually leads to longer battery cycle life. Thus, charging of the negative plates proceeds via a parallel mechanism on the surfaces of both Pb and EAC particles, at a higher rate on the EAC phase. Cells with EAC in NAM have the longest cycle life when their NAM specific surface is up to 4 m 2 g −1 against 0.5 m 2 g −1 for the lead surface. The proposed parallel mechanism of charge is verified experimentally on model Pb/EAC/PbSO 4 and Pb/EAC electrodes. During the charge and discharge cycles of the HRPSoC test, the EAC particles are involved in dynamic adsorption/desorption on the lead sulfate and lead surfaces. Another effect of electrochemically active carbons is also evidenced namely that, above a definite concentration, some EAC forms reduce the mean pore radius of NAM. When it diminishes to less than 1.5 μm, access of sulfuric acid into the pores is impeded and PbO forms instead of PbSO 4 in the pores of NAM during discharge. Thus, it may be presumed that electrochemically active carbons change the overall electrochemical reaction of charge and discharge of lead-acid cells when operated under HRPSoC cycling conditions.

Spiral wound valve-regulated lead-acid batteries for hybrid vehicles

Future vehicle applications require the development of reliable and long life batteries operating under high-rate partial-state-of-charge (HRPSoC) working conditions. This paper updates work carried out to develop spiral wound valve-regulated lead-acid (VRLA) batteries for vehicles with different hybridisation degrees, ranging from stop-start to mild hybrid applications. Former work on design optimisation and active material formulations has been implemented in two spiral wound VRLA batteries, rated 12 V 50 Ah and 6 V 24 Ah, and these two products are currently being tested both in benches and in vehicles with different hybridisation degrees within a demonstration project funded by the Advanced Lead Acid Battery Consortium and in collaboration with several European vehicle and electrical component manufacturers.

Advanced valve-regulated lead-acid batteries for hybrid vehicle applications

Future vehicle applications require the development of reliable and long life batteries operating under high-rate partial-state-of-charge (HRPSoC) working conditions. Work presented in this paper deals with the study of different design parameters, manufacturing process and charging conditions of spiral wound valve-regulated lead-acid (VRLA) batteries, in order to improve their reliability and cycle life for hybrid vehicle applications. Test results show that both electrolyte saturation and charge conditions have a strong effect on cycle life at HRPSoC performance, presumably because water loss finally accelerates battery failure, which is linked to irreversible sulphation in the upper part of the negative electrodes. By adding expanded graphite to the negative active mass formulation, increasing the electrolyte saturation degree (>95%) and controlling overcharge during regenerative braking periods (voltage limitation and occasional boosting) it is possible to achieve up to 220,000 cycles at 2.5% DOD, equivalent to 5500 capacity throughput. These results could make lead acid batteries a strong competitor for HEV applications versus other advanced systems such as Ni–MH or Li-ion batteries.

Optimization of the cycle life performance of VRLA batteries, working under high rate, partial state of charge (HRPSOC) conditions

On hybrid vehicle applications, batteries must work in a rather low state of charge (SOC), in order to be able to recover as much of the regenerative braking energy as possible. Usually SOC values around 60% are used, which promotes the development of new unexpected failure modes not previously found, mainly associated with heavy sulphation of the negative plates. In order to try to optimise the cycle life performance to the point of making these batteries a real alternative for the application of hybrid vehicles, a series of tests have been undertaken, aimed to optimise the key parameters that from previous experience are known to determine life duration in high rate low state of charge (HRPSOC) conditions. Previous works have been focused on trying to determine the optimum composition of positive and negative active material, concerning paste density in the positive, and additives in negative. In order to overcome the deleterious effect of heavy sulphation in negative plates on cycle life, the use of conductivity enhancers additives such as graphite has been proposed. The objective of this project is to optimize the performance of the glass microfiber separators, in order to maintain a high degree of compression in the group, as well as to avoid acid stratification and development of short circuits along the battery life. To do this, different glass microfiber separators with inert additives, as well as different fiber composition have been tested. Results obtained up to now, indicate a remarkable good performance of the VRLA batteries with the new separators containing very fine fiberglass and silica fillers as an additive.

Development of additives in negative active-material to suppress sulfation during high-rate partial-state-of-charge operation of lead–acid batteries

Additives in the negative active-material of lead–acid batteries were examined to determine whether they could prevent progressive accumulation of lead sulfate (PbSO 4) in negative plates during high-rate partial-state-of-charge (HRPSoC) operation. This phenomenon is caused by progressive growth of PbSO 4 particles and a lack of conductive paths near these PbSO 4 particles. Barium sulfate (BaSO 4) particles in various sizes and synthetic lignin were added to the negative active-material to control PbSO 4 particle size during HRPSoC cycle-life. Some types of carbon fibres were also added to form conductive paths around the PbSO 4 particles. Synthetic lignin was found to be the most effective additive for improving battery life in HRPSoC cycle-life tests, whereas the other factors such as BaSO 4 size or carbon fibre extended less influence. The growth rate of PbSO 4 particles per cycle was much lower in a cell with synthetic lignin than in a cell with natural lignin.

Requirements for future automotive batteries – a snapshot

Introduction of new fuel economy, performance, safety, and comfort features in future automobiles will bring up many new, power-hungry electrical systems. As a consequence, demands on automotive batteries will grow substantially, e.g. regarding reliability, energy throughput (shallow-cycle life), charge acceptance, and high-rate partial state-of-charge (HRPSOC) operation. As higher voltage levels are mostly not an economically feasible alternative for the short term, the existing 14 V electrical system will have to fulfil these new demands, utilizing advanced 12 V energy storage devices. The well-established lead–acid battery technology is expected to keep playing a key role in this application. Compared to traditional starting–lighting–ignition (SLI) batteries, significant technological progress has been achieved or can be expected, which improve both performance and service life. System integration of the storage device into the vehicle will become increasingly important. Battery monitoring systems (BMS) are expected to become a commodity, penetrating the automotive volume market from both highly equipped premium cars and dedicated fuel-economy vehicles (e.g. stop/start). Battery monitoring systems will allow for more aggressive battery operating strategies, at the same time improving the reliability of the power supply system. Where a single lead–acid battery cannot fulfil the increasing demands, dual-storage systems may form a cost-efficient extension. They consist either of two lead–acid batteries or of a lead–acid battery plus another storage device.