Capacitive carbon and electrochemical lead electrode systems at the negative plates of lead–acid batteries and elementary processes on cycling

Batteries in hybrid electric vehicles operate in High-Rate Partial-State-of-Charge (HRPSoC) cycling duty. To make lead–acid batteries suitable for this duty, carbon is added to the negative active material. As a result of this technological change, two electrical systems form at the negative plates: (a) a capacitive carbon system comprising high-rate charging and discharging of the electric double layer; low Ah capacity, and (b) a lead electrochemical system, comprising oxidation of Pb to PbSO4 during discharge and vice versa during charge; this system is slow to accept charge, but has high Ah capacity. Through cycling lead–acid cells under HRPSoC conditions with short current pulses of various durations we have established that the processes involved in the capacitive system proceed highly reversibly and complete hundreds of thousands HRPSoC cycles. The number of cycles achieved by the electrochemical system is limited to tens of thousands and lead to progressive sulfation. Carbon added to the negative active material changes the latter's structure. The specific surface of NAM increases and the median pore radius decreases. Some carbon additives may reduce the radius of the pores in NAM to membrane sizes, which may change the chemistry of the electrochemical system. •Capacitive carbon and electrochemical lead systems operate in NAM with carbon additives.•The capacitive carbon system has small Ah capacity but high rate of operation.•The electrochemical lead system is slow to accept charge but has high Ah capacity.•Some carbons reduce the median pore radius of NAM to membrane sizes.•Carbon additives alter the structure and may change the chemistry of negative plates.