Journal of Power Sources, Vol.113, No.2, 255-270, 2003
Strap grid tubular plate - a new positive plate for lead-acid batteries - Processes of residual sulphation of the positive plate
For almost a century now the tubular plate design has been based on cylindrical tubes and spines. The contact surface between the positive active mass (PAM) and the spine is small, which results in high polarisation of the plate at high discharge currents and low power output of the cell. In an attempt to eliminate these disadvantages, the shape of the tubes has been changed to flattened elliptic and the spines have been replaced by strap grids. The thickness of this new type of tubular plate, strap grid tubular plate (SGTP), is between 3 and 5 mm. Batteries with tubular plates of the new design (SGTP batteries) can be used in electric vehicle (EV) and photovoltaic (PV) system applications. This paper presents results of SGTP battery tests according to the European standards for EV, hybrid electric vehicle (HEV) and photovoltaic (PV) system batteries. SGTP batteries have a cycle life of 1000 ECE-15-EV cycles, 6000 ECE-HEV cycles and more than eight gross PV cycles. The optimum battery charge algorithm for VRLA batteries with strap grid tubular plates has been established and the mechanism of disintegration of the positive active mass has been disclosed. The following phenomena are responsible for the decline in capacity of the positive plates. First, when the PAM is built up of globules adhering closely to each other, a strong skeleton with thick aggregates (branches) with a membrane surface is formed. The surface layer of the branches impedes the access of H2O and H2SO4 to their interior thus reducing the utilisation of the PAM. Besides, internal stresses are created in the aggregates, which cause them to crack. Secondly, when the PAM is built up of individual agglomerates with micropores in between, a porous mass with large surface is formed. The tubes keep the aggregates together and prolong the cycle life of the battery. During discharge, the contacts between the aggregates weaken and the capacity declines. Third, during discharge, the H2SO4 concentration in the pores of the plate inner layers (close to the straps) increases. In concentrated H2SO4 solution the solubility of PbSO4 crystals decreases. This slows down the rate of oxidation of PbSO4 to PbO2. Some parts of the PbSO4 crystals in the PAM of the charged plate remain unoxidised (residual sulphation). Thus, the capacity of the plate is lower. Strap corrosion is the phenomenon that may limit the cycle life of SGT plates.
Keywords:lead-acid battery;tubular lead dioxide plates;structure of lead dioxide active mass;electric vehicle batteries;photovoltaic batteries