Optimizing the charging rate is crucial for enhancing lithium iron phosphate (LFP) battery performance. The substantial heat generation during high C-rate charging poses a significant risk of thermal runaway, necessitating advanced thermal management strategies. This study systematically investigates the coupling mechanism between charging rates and ambient temperatures in overcharge-induced thermal runaway, filling the knowledge gaps associated with multi-indicator thermal management approaches. Through experiments on prismatic LFP cells across five operational conditions (1C/35 °C, 1.5C/5 °C, 1.5C/15 °C, 1.5C/25 °C, and 1.5C/35 °C), synchronized infrared thermography and electrochemical monitoring quantitatively characterize the thermal–electric coupling dynamics throughout overcharge-to-runaway transitions. The experimental findings reveal three key observations: (1) Charge rate and temperature have synergistic amplification effects on triggering thermal runaway. (2) Contrary to intuition, while low-current/high-temperature charging enhances safety versus high-current/high-temperature conditions, low-temperature/high-current charging triggers thermal runaway faster than high-temperature/high-current scenarios. (3) Staged multi-indicator lithium battery thermal runaway warning signals would be more accurate (first peaks > 0.5 °C/s temperature rise rate + >10 V/s voltage drop rate). These findings collectively demonstrate the imperative for next-generation battery management systems integrating real-time ambient temperature compensation with adaptive C-rate control, fundamentally advancing beyond conventional single-variable thermal regulation strategies. Intelligent adaptation is critical for mitigating thermal runaway risks in LFP battery operations.

The increasing prevalence of lithium-ion batteries in energy storage and electric transportation has led to a rise in overcharge-induced thermal runaway (TR) incidents. Particularly, the TR of Lithium Iron Phosphate (LFP) batteries demonstrates distinct evolutionary stages and multimodal hazard signals. This study investigated the TR process of LFP batteries under various charging rates through five sets of gradient C-rate experiments, collecting multimodal data (temperature, voltage, gas, sound, and deformation). Drawing on the collected data, this study proposes a three-stage evolution model that systematically identifies key characteristic signals and tracks their progression pattern through each stage of TR. Subsequently, fusion-based models (for both single- and multi-rate scenarios) and a time-series-based LSTM model were developed to evaluate their classification accuracy and feature importance in the classification of TR stages. Results indicate that the fusion-based models offer greater generalization, while the LSTM model excels at modeling time-dependent dynamics. These models demonstrate complementary strengths, providing a comprehensive toolkit for risk assessment. Furthermore, for the severe TR stage, this study proposes an innovative three-dimensional dynamic emergency decision matrix comprising a toxicity index (TI), flammability index (FI), and visibility (V) to provide quantitative guidance for rescue operations in the post-accident phase. Ultimately, this study establishes a comprehensive, closed-loop framework for LFP battery safety, extending from multimodal signal acquisition and intelligent early warning to quantified emergency response. This framework provides both a robust theoretical basis and practical tools for managing TR risk throughout the entire battery lifecycle.