The thermal behavior of a commercial lithium-ion cell with the cathode material LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) was investigated during the cycling process using a Tian-Calvet calorimeter (C80, SETARAM Instrumentation, France). Various current flows of 42.5, 85, and 170 mA corresponding to charging rates of 0.5, 1, and 2 C, respectively, were applied in the measurements. The corresponding heat flow rates were measured by the C80 calorimeter at 30 °C. The reversible heat effect due to the reversible electrochemical reaction was quantified by the entropy change measurement. The irreversible heat effect due to internal resistances was determined by the electrochemical impedance spectroscopy (EIS) and the galvanostatic intermittent titration technique (GITT). The results were compared with the direct measurement of the heat effect by calorimetry during electrochemical cycling.

Over the last decade, the demand for safer batteries with excellent performance and lower costs has been intensively increasing. The abundantly available precursors and environmental friendliness are generating more and more interest in sodium ion batteries (SIBs), especially because of the lower material costs compared to Li-ion batteries. Therefore, significant efforts are being dedicated to investigating new cathode materials for SIBs. Since the thermal characterization of cathode materials is one of the key factors for designing safe batteries, the thermophysical properties of a commercial layered P2 type structure Na_0.53MnO₂ cathode material in powder form were measured in the temperature range between −20 and 1200 °C by differential scanning calorimetry (DSC), laser flash analysis (LFA), and thermogravimetry (TG). The thermogravimetry (TG) was combined with mass spectrometry (MS) to study the thermal decomposition of the cathode material with respect to the evolved gas analysis (EGA) and was performed from room temperature up to 1200 °C. The specific heat (C_p) and the thermal diffusivity (α) were measured up to 400 °C because beyond this temperature, the cathode material starts to decompose. The thermal conductivity (λ) as a function of temperature was calculated from the thermal diffusivity, the specific heat capacity, and the density. Such thermophysical data are highly relevant and important for thermal simulation studies, thermal management, and the mitigation of thermal runaway.

The sodium ion cells were assembled by using Na_0.53MnO₂ as cathode material, pure sodium metal as anode in case of half coin cells and coconut shell-derived hard carbon in case of full coin cells. Cyclic voltammetry, galvanostatic charge-discharge, and self-discharge analysis were conducted. A good rate capability, capacity retention, coulombic efficiency (99.5%), reproducibility and reversible Na-ion intercalation revealed a satisfactory performance of this cathode material. The safety related parameters including the heat generation during charging-discharging and thermal abuse tests have been executed by the means of sophisticated calorimetry instruments. It was observed that during the charging process less heat was generated than during discharging process. The exothermic reactions during thermal runaway were identified by using an accelerating rate calorimeter and pressure measurements during this thermal abuse test were performed as well. The thermal runaway of full coin cells occurred beyond 190 °C with a temperature rate (dT/dt) of 2.5 °C min⁻¹. Such detailed analysis of heat generation and thermal abuse helps finding new and quantitative correlations between different critical thermal and safety related issues in future post Li batteries that are a prerequisite for the design of safer batteries, the safe upscaling and for the adaptation of the thermal management system.

NaMnPO₄ and NaFePO₄, polyanion cathode materials, exist in two different phases maricite/natrophilite and maricite/olivine, respectively. Both natrophilite NaMnPO₄ and olivine NaFePO₄ are electrochemically active and possess a one-dimensional tunnel for sodium-ion migration; however, these two phases are thermodynamically unstable. Therefore, they can be synthesized through an electrochemical route. On the contrary, maricite (m)-NaMnPO₄ and maricite (m)-NaFePO₄ are thermodynamically stable forms but have a huge activation energy of their diffusion pathways for sodium extraction and insertion in the crystal structure, which hinders electrochemical reactions. Therefore, the electrochemical behaviour of commercial m-NaMnPO₄ and m-NaFePO₄ has been studied to find a way for enabling them electrochemically. Ball milling and thermal/mechanical carbon coating are employed to reduce the particle size to enhance the electrochemical performance and shorten the diffusion pathway. Moreover, ball milling leads to defects and partial phase transformation. The electrochemical performance of milled-coated NaMnPO₄ and NaFePO₄ has been thoroughly investigated and compared. The phase transition of NaFePO₄ is revealed by a differential scanning calorimeter. As a result, the achievable capacities of both cathode materials are significantly enhanced up to 50 mAh.g⁻¹ via the particle size reduction as well as by carbon coating. However, the side reactions and agglomeration problems in such materials need to be minimized and must be considered to enable them for applications.

Commercial coin cells with LiNi_0.6Mn_0.2Co_0.2O₂ positive electrode material were investigated using an accelerating rate calorimeter and a Tian-Calvet calorimeter. After cycling and charging to the selected states of charge (SOCs), the cells were studied under thermal abuse conditions using the heat-wait-seek (HWS) method with the heating step of 5 K and a threshold for self-heating detection of 0.02 K/min. The onset temperature and the rate of the temperature rise, i.e., the self-heating rate for thermal runaway events, were determined. The morphology of the positive electrode, negative electrode and the separator of fresh and tested cells were compared and investigated with scanning electron microscopy (SEM). Furthermore, the microstructure and the chemical compositions of the individual components were investigated by X-ray diffraction (XRD) and inductively coupled plasma with optical emission spectrometry (ICP-OES), respectively. In the Tian-Calvet calorimeter, the coin cells with the selected SOCs and the individual components (positive electrode, negative electrode and separator) were heated up with a constant heating rate of 0.1 °C/min (ramp heating mode). Simultaneously, the heat flow signals were recorded to analyze the heat generation. The combination of the three different methods—the HWS method using the ES-ARC, ramp heating mode on both cells and the individual components using the Tian-Calvet calorimeter—together with a post-mortem analysis, give us a complete picture of the processes leading to thermal runaway.