Energy balance of the closed oxygen cycle and processes causing thermal runaway in valve-regulated lead/acid batteries

A model for the reactions involved in the closed oxygen cycle in valve-regulated lead/acid batteries and the associated energy transformations is proposed. When electric current flows through the closed oxygen cycle, a certain amount of electric energy is converted via electrochemical processes into chemical energy, i.e. the products obtained may interact spontaneously as a result of which the system returns to its initial state. During these spontaneous reactions, the chemical energy is converted into heat. Depending on the type of the reactions involved in oxygen reduction on the negative plate, the closed oxygen cycle may proceed in two different electrochemical systems: (i) oxygen is reduced through electrochemical reactions yielding the electrochemical system PbO2//H2OO/O2///O2//H2OO/Pb, and (ii) oxygen is reduced through chemical reactions forming the electrochemical system PbO2//H2OO/O2///PbSO4//Pb. The energy introduced into the system for activation of the closed oxygen cycle is different for the two electrochemical systems. The quantity of this energy is calculated in the present work using thermodynamic data. During the closed oxygen cycle the electric energy is transformed into chemical energy which, in turn, is converted into heat. Part of this heat causes the cell temperature to increase and another part dissipates into the surrounding air. The amount of the former heat depends on the heat capacity of the battery and is influenced most strongly by the quantity of the electrolyte. It has been established that the rate of oxygen evolution on the positive plate depends strongly on the temperature. When the heat exchange between the battery and the surrounding medium is poor, the reactions of the closed oxygen cycle may enter (through the heat and oxygen flows between the positive and the negative plates) into self-accelerating interrelations, which may lead to thermal runaway. To avoid this, an adequate heat exchange should be maintained between the battery and the surrounding medium, the rate of the oxygen reaction should be kept down and a high heat capacity of the battery and small water loss on its operation should be ensured.