Concentrated electrolytes usually demonstrate good electrochemical performance and thermal stability, and are also supposed to be promising when it comes to improving the safety of lithium-ion batteries due to their low flammability. Here, we show that LiN(SO₂F)₂-based concentrated electrolytes are incapable of solving the safety issues of lithium-ion batteries. To illustrate, a mechanism based on battery material and characterizations reveals that the tremendous heat in lithium-ion batteries is released due to the reaction between the lithiated graphite and LiN(SO₂F)₂ triggered thermal runaway of batteries, even if the concentrated electrolyte is non-flammable or low-flammable. Generally, the flammability of an electrolyte represents its behaviors when oxidized by oxygen, while it is the electrolyte reduction that triggers the chain of exothermic reactions in a battery. Thus, this study lights the way to a deeper understanding of the thermal runaway mechanism in batteries as well as the design philosophy of electrolytes for safer lithium-ion batteries.

During thermal runaway (TR), lithium-ion batteries (LIBs) produce a large amount of gas, which can cause unimaginable disasters in electric vehicles and electrochemical energy storage systems when the batteries fail and subsequently combust or explode. Therefore, to systematically analyze the post-thermal runaway characteristics of commonly used LIBs with ${\mathrm{LiFePO}}_4$ (LFP) and ${\mathrm{LiNi}}_x{\mathrm{C}\mathrm{o}}_{\mathrm{y}}{\mathrm{M}\mathrm{n}}_{\mathrm{z}}{\mathrm{O}}_2$ (NCM) cathode materials and to maximize the in situ gas generation during battery thermal runaway, we designed experiments using an adiabatic explosion chamber (AEC) under an inert atmosphere to test LIBs. Additionally, we conducted in situ analysis of the gas components produced during thermal runaway. Our research findings indicate that after thermal runaway, NCM batteries produce more gas than LFP batteries. Based on battery gas production, the degree of harm caused by TR can be ranked as follows: NCM9 0.5 0.5 > NCM811 > NCM622 > NCM523 > LFP. The primary gas components during thermal runaway for both NCM and LFP batteries include ${\mathrm{H}}_2,\mathrm{C}\mathrm{O},{\mathrm{C}\mathrm{O}}_2,{\mathrm{C}}_2{\mathrm{H}}_4$, and ${\mathrm{C}\mathrm{H}}_4$. The gas produced by LFP batteries contains a high proportion of ${\mathrm{H}}_2$. The high concentration of ${\mathrm{H}}_2$ results in a lower flammability limit (LFL) for the gas generated by LFP batteries during TR compared to the mixed gas produced by NCM batteries. Therefore, in terms of battery TR gas composition, the order of hazard level is LFP > NCM811 > NCM622 > NCM523 > NCM9 0.5 0.5 0.5. Although experimental results show that LFP batteries have superior thermal stability and lower gas production during large-scale battery thermal runaway events, considering gas generation composition and thermal runaway products, the thermal runaway risk of LFP batteries may be higher than that of NCM batteries. Although LFP batteries are considered very safe, our research results have once again drawn researchers’ attention to LFP batteries. These gases can also serve as detection signals for battery thermal runaway warnings, providing a cautionary note for the future development of electrochemical energy storage and the renewable energy sector.

Lithium-ion batteries (LIBs) are widely used in electric vehicles (EV) and energy storage stations (ESS). However, combustion and explosion accidents during the thermal runaway (TR) process limit its further applications. Therefore, it is necessary to investigate the uncontrolled TR exothermic reaction for safe battery system design. In this study, different LIBs are tested by lateral heating in a closed experimental chamber filled with nitrogen. Moreover, the relevant thermal characteristic parameters, gas composition, and deflagration limit during the battery TR process are calculated and compared. Results indicate that the TR behavior of NCM batteries is more severe than that of LFP batteries, and the TR reactions becomes more severe with the increase of energy density. Under the inert atmosphere of nitrogen, the primarily generated gases are H₂, CO, CO₂, and hydrocarbons. The TR gas deflagration limits and characteristic parameter calculations of different cathode materials are refined and summarized, guiding safe battery design and battery selection for power systems.