A predictive theory on thermal runaway of ultrahigh capacity lithium-ion batteries

Ultrahigh capacity lithium-ion batteries (LIBs) with prudent safety measures are key to future transportation. The undesirable thermal events such as thermal runaway (TR) in LIBs can pose a direct risk to battery life and the consumers. In the present study, a set of new TR criteria are established by closely inspecting the relation between the rate of heat generation and dissipation to anticipate the TR at an early stage. From the proposed criteria, three alarming temperatures prior to TR are identified, such as the safe temperature limit TE (an intersection between heat generation curve and heat removal line), the maximum temperature limit TM (where second derivative of heat generation is zero), and the low temperature TC from the Semenov theory. For a safer battery operation, both the low and upper limit temperatures have to remain below the safety zone, i.e. TM < TE with TC < TE. The criteria are validated by implementing them on the ultrahigh capacity LIBs, which are subjected to the thermal abuse, wherein the rate of heat generation was determined from calorimetry. The state TM < TE indicates the first precursor to TR where a controlled measure can be taken to prevent the runaway. However, TE ≤ TM regarded as the critical state during which a self-sustaining reaction involving delithiated nickel-rich cathode, intercalated anode, and dissociated electrolyte progresses, resulting in an irreversible TR in the system. The validity of the proposed criteria is demonstrated, while additional work is considered in a broad class of batteries subjected to thermal abuse conditions for establishing a safety margin of operation.