Understanding Heat Generation of LNMO Cathodes in Lithium-Ion Batteries via Entropy and Resistance

The heat generation of lithium-ion batteries is a critical parameter, as it significantly affects cell temperature. Poor thermal management can lead to elevated cell temperatures, accelerating side reactions, reducing cell lifetime, and, in extreme cases, causing thermal runaway. Therefore, understanding heat generation is crucial for the commercialization of emerging battery materials. Due to its high energy density, lithium–nickel–manganese–oxide (LNMO) is an attractive candidate for next-generation cathode materials; however, the composition of its heat generation is not yet fully understood. To address this, the state-of-charge (SoC)-dependent entropy coefficient and resistance of disordered LNMO cathodes are determined using the potentiometric method. The results show that both values are strongly influenced by the redox reactions of Ni and Mn. The entropy coefficient varies between 5.2 and −32.4 J mol−1 K−1, depending on the SoC. Furthermore, the resistance exhibits a switching dependence on kinetics and mass transfer. The resulting heat flux calculations indicate that, at SoC < 20%, heat generation is dominated by the kinetic behavior of LNMO, leading to two exothermal peaks during discharge and one exothermal peak during charge. This behavior is validated through a comparison with a low-current calorimetric measurement.