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

摘要

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 PbSO_4 crystals dissolve and precipitate onto the bigger crystals. The latter have low solubility and hence PbSO_4 accumulates progressively in the negative plates causing capacity loss. In order to suppress this process, the rate of the charge process should be increased.rnIn a previous publication of ours we have established that reduction of Pb~(2+) 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 BaSO_4 (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. BaSO_4 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 (< 180nm), 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 BaSO_4 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.