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

Abstract 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.