1. Introduction
Driven by the energy crisis and climate change, carbon-neutrality targets have been proposed in more than half of the countries worldwide [
1,
2], and sustainable, low-carbon energy resources are being actively pursued [
3]. As a representative of emerging energy carriers, LIBs are characterized by high energy density, long service life, excellent cycling performance, and negligible memory effect [
4,
5,
6], and have therefore been widely deployed in electric vehicles and stationary energy-storage systems. However, owing to their specific chemical compositions and electrochemical energy-storage characteristics, LIBs may undergo rupture, ignition, or even explosion when subjected to abusive conditions such as overheating, overcharging, penetration, or compression [
7]. With the rapid development of energy-storage stations toward larger scale and higher energy density, the consequences of fire incidents have become increasingly severe. For example, a fire occurred at the Gateway energy-storage station in California, USA, on 15 May 2024, and persisted for nearly two weeks with multiple re-ignitions. Therefore, it is of critical importance to develop fire-suppression strategies capable of rapidly and effectively mitigating TR.
For LIB fire suppression technologies, current research can be broadly classified into solid extinguishing agents, gaseous extinguishing agents, water-based agents, and novel agents. Solid agents such as dry powder and aerosol have been shown to lack sufficient cooling capability. Meng et al. [
8] attempted to extinguish LiFePO
4 battery fires using a dry-powder agent and found that, under certain conditions, the fire could be extinguished; however, the suppression effect was limited. Only the regions in direct contact with the battery experienced noticeable cooling, and the internal thermal runaway reactions could not be completely suppressed. In addition, shorter discharge distance and longer discharge duration were found to enhance the suppression performance, whereas the spray angle had little influence.
Gaseous extinguishing agents mainly include CO
2, heptafluoropropane (HFC-227ea) and perfluorohexanone (Novec1230). Xu et al. [
9] conducted experiments on the combustion and explosion characteristics and fire suppression of 94 Ah Li(NiCoMn)O
2 batteries to evaluate the performance of CO
2, HFC-227ea and water mist. The results indicated that all three agents were capable of suppressing LIB fires; however, water mist outperformed the other two agents in both suppression effectiveness and cooling capability. Liu et al. [
10] reported that Novec1230 initially exhibited a negative inhibition effect in LIB fires. It first promoted the progression of thermal runaway; as the injection quantity increased, this negative effect was converted into a positive inhibition effect and was gradually enhanced. Zhang et al. [
11] proposed a synergistic suppression strategy in which gaseous agents (Novec1230, CO
2 and HFC-227ea) were combined with water mist to suppress LIB fires. Experimental results showed that the composite agents provided stronger suppression than any single agent, and among the composite agents, the combination of Novec1230 and water mist was the most effective. Although gaseous agents can effectively inhibit flaming combustion, they are not suitable for LIB fires if adequate cooling cannot be provided.
Water-based extinguishing agents are typically formulated by adding additives to water to enhance its fire-extinguishing performance, such as water gel, F-500 and foam concentrates. Liu et al. [
12] compared the suppression effects of water and water gel on LIB TR, and it was shown that, owing to its special three-dimensional network structure, water gel exhibited superior performance in extinguishing LIB fires. F-500 encapsulator technology, developed by Hazard Control Technologies (HCT) in the United States, has been shown to significantly enhance the extinguishing effectiveness of plain water and to improve its penetration and cooling capabilities when F-500 is mixed with water at an appropriate ratio. In comparative experiments [
13,
14], F-500 aqueous solutions demonstrated better extinguishing and cooling performance than pure water, while requiring a smaller amount of water. Andersson et al. [
15] evaluated the performance of foam extinguishing agents on LiFePO
4 battery fires and found that foam agents could extinguish open flames; low-expansion foam, with its higher water content compared with high-expansion foam, provided superior cooling. Overall, compared with solid and gaseous agents, liquid extinguishing agents offer greater advantages in suppressing lithium-ion battery fires.
Fire suppression agents represented by LN have emerged in recent years as a novel technology for extinguishing LIB fires. Owing to its strong cooling and inerting capabilities, LN has been widely applied in confined spaces such as coal mines and cable tunnels [
16,
17,
18]. Wang et al. [
19] selected ten commonly used extinguishing agents—water, water mist, dry powder, HFC-227ea, CO
2, a water-based agent, 3% aqueous film-forming foam, HFC-227ea, water gel, and LN—and conducted comparative tests under identical experimental conditions. By establishing an evaluation and scoring system, LN was verified to provide the best overall suppression performance. To obtain a comprehensive understanding of the suppression mechanism of LN on LIB fires, Huang et al. [
20] carried out extinguishing experiments on a commercial 2200 mAh 18650-type LIB module. The following conclusions were drawn: LN can successfully slow down or even block heat transfer between cells, thereby delaying the onset of TRP; cells located further downstream in the propagation chain require less LN for cooling; during the experiments, the maximum cooling rate of LN reached 34.25 °C/s; and the suppression mechanism of LN is mainly reflected in two aspects, namely protecting unreacted cells and cooling already reacted high-temperature cells, thus interrupting the rapid TR propagation between cells. Wang et al. [
21] further investigated the effects of LN injection mass, injection position, state of charge (SOC), and heating power on the suppression of LIB TR in a confined space. The following conclusions were obtained: (1) the average cooling rate of cells in a confined space is lower than that in an open space, indicating more difficult heat dissipation; (2) LN can cool not only the TR cell but also its neighboring cells; (3) the cooling performance of LN is enhanced as the injection mass increases; (4) top injection is more effective than side injection; (5) the average cooling rate of LN is negatively correlated with SOC and positively correlated with heating power; and (6) reducing the spacing between cells enhances inter-cell heat transfer.
Previous studies on fire suppression agents have mainly focused on conventional agents, all of which exhibit certain limitations when dealing with LIB fires. Although extensive research has been conducted on liquid nitrogen fire extinguishing agents. These studies have confirmed the feasibility of liquid nitrogen in mitigating battery thermal runaway. However, liquid nitrogen is highly prone to vaporization at room temperature, and few studies have focused on how to maximize the cooling efficiency of liquid nitrogen. LN is stored at a very low temperature (−196 °C) and vaporizes rapidly after being released into the ambient air, improving its effective utilization on the basis of existing studies has become a new research focus. In this work, by establishing fire compartments, the effective action area of LN is reduced, its cooling capacity per unit volume is increased, and thus the cooling effectiveness of LN is improved to varying degrees. This study proposes a novel synergistic strategy that employs physical compartmentalization to overcome the rapid vaporization of LN.
4. Conclusions
This study focuses on 100 Ah LiFePO4 batteries to investigate the impact of fire compartmentalization on the LN fire suppression effectiveness in LIBs. The main conclusions are as follows:
(1) The TRP can be divided into four stages: the external heating stage, safety valve opening stage, self-heating stage, and cooling phase. Among these, the self-heating stage generates the most heat, with the fastest heat accumulation rate, and the highest danger level. Without fire suppression intervention, the TRP rate within the LIB module gradually accelerates.
(2) LN absorbs a large amount of heat through vaporization, rapidly lowering the temperature and interrupting the internal side reactions of the cell, as the temperature falls below the required reaction threshold, thus halting the TR reaction. The effective utilization rate of 17.4 kg of LN is 0.037, and the effective utilization rate for each cell in the module gradually decreases with the sequence of TRP.
(3) Fire compartments effectively enhance LN fire suppression. Under the controlled LN flow rate of 0.063 kg/s, the addition of fire compartments increased the effective utilization rate from 0.037 to 0.051. The data indicates that for the tested module configurations, the volume reduction effect outweighs the influence of compartment geometry, although the marginal gain in utilization diminishes as the compartment volume decreases further. Future quantitative flow simulations are recommended to strictly decouple these effects.
This study examined the impact of three different fire compartment configurations on the suppression of TRP in large-capacity LIB modules. A method to enhance LN fire suppression effectiveness based on fire compartmentalization was proposed. Future research could explore more types of compartment design methods, as this enhanced design could improve LN fire suppression performance in engineering applications. Moreover, future research will extend the application of this LN suppression strategy to higher energy-density systems, such as high-nickel layered cathodes and lithium metal anodes, to evaluate the method’s efficacy under more aggressive thermal runaway conditions. In addition, future investigations will explore the suppression performance of LN under dynamic operating conditions, including high C-rate charging and active discharge cycles, to assess the system’s effectiveness under varying internal thermal stress levels.