AbstractInvestigations on the effect of flame retardant additives (FRs) on the abuse tolerance of large scale lithium ion battery (LIB) cells (5 Ah) are of high relevance in battery science and industry but rarely performed as they are cost and time consuming. In addition, even though FRs are frequently investigated, their positive effect on the safety properties of larger full LIB cells under abusive condition has not been proven yet. The promising FR (phenoxy) pentafluorocyclotriphosphazene (FPPN) is known to exhibit excellent flame retardant‐ and electrochemical properties at the same time. Therefore, FPPN is investigated towards abuse tolerance in 5 Ah LIB cells in this study. Calorimetric investigations show that a mass percentage of 5 wt % FPPN mixed to a standard electrolyte, significantly reduces the self‐heating rate of 5 Ah cells in the temperature range from 80 °C to 110 °C. While nail penetration and external short circuit experiments provide no significant difference between standard and FPPN‐containing cells, an increased overcharge tolerance and a favorable thermal stability at ≈120 °C in overcharge and oven experiments could be shown.