Certain polymers, such as polyvinylidene fluoride (PVDF), polyimide (PI), and poly (phthalazinone ether sulfone ketone) (PPESK), are commonly used separator materials in batteries. However, during the thermal runaway (TR) processing of batteries, significant heat is released by the combustion of the polymer separator. Therefore, analysis of the fire behaviors of polymer separator materials will facilitate a more comprehensive quantitative evaluation of battery thermal risk. This paper investigated the combustion properties of three types of polymers, namely, PVDF, PI, and PPESK, as potential separator materials by cone calorimetry and thermogravimetry (TG). A series of characteristic parameters, including ignition time (TTI), heat release rate (HRR), smoke production rate (SPR), and total heat release (THR), were evaluated for three polymers and blends (PI/PVDF, PPESK/PVDF) under an external heat flux of 45 or 60 kW/m2, respectively. The combustion characteristics and fire hazards of the three polymers and corresponding mixtures were analyzed through the comparative analysis of experimental data and phenomena. Under 60 kW/m2, the HRR curves of all polymers presented two peaks, while PI/PVDF and PPESK/PVDF mixtures exhibited one obvious peak. Moreover, the peak HRR (pHRR) for the mixed polymers was higher, indicating a relatively higher fire risk. However, in the application scenario, the mixed state represents the main polymer form as the active separator materials in batteries. The results showed that the specific coupling behaviors were related primarily to the component type. This work will help evaluate the fire risk of polymeric separator materials based on the combustion characteristics to predict the safety of mixtures in batteries and develop new methods for fire suppression.
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