Thermal Runaway of Lithium-Ion Batteries without Internal Short Circuit

We demonstrate herein that not only internal short circuiting, but also chemical crossover, is the mechanism behind thermal runaway that can occur in lithium-ion batteries due to abuse conditions. In situ experiments showed that during thermal runaway, the cathode releases oxygen by a phase transition, and this oxygen is consumed by the lithiated anode. The released highly oxidative gas reacts with reductive LiCx with tremendous heat generation centered at 274.2°C with heat flow of 87.8 W g−1. To confirm the proposed mechanism, we froze a battery undergoing the thermal runaway process by liquid nitrogen and subjected it to detailed post-test analysis. Our results revealed the hidden thermal runaway mechanism of chemical crossover between the battery components without a severe internal short circuit. These findings provide an important insight into the rational design of automotive lithium-ion batteries as well as solid-state batteries.