Electrochemical energy storage fire extinguishing agent definition method and graded protection application thereof
By using an electrochemical energy storage fire extinguishing agent based on a six-dimensional performance parameter system, the problems of low extinguishing efficiency, slow response, and high cost in fire protection in the electrochemical energy storage industry have been solved, achieving efficient fire extinguishing and safety protection.
Patent Information
- Application Number
- CN202511265287.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-05
- Publication Date
- 2025-12-12
AI Technical Summary
Existing fire extinguishing agents in the electrochemical energy storage industry suffer from problems such as low extinguishing efficiency, delayed response, high risk of reignition, and high cost, making it difficult to meet safety and economic requirements.
Electrochemical energy storage fire extinguishing agents based on a six-dimensional performance parameter system are adopted, including perfluoroketone-nanocerium composite fire extinguishing agents and organophosphorus-aerogel fire extinguishing agents. Through the design of the six-dimensional performance parameter system, efficient free radical scavenging, interruption of combustion chain reaction, rapid cooling, long-term inerting and cost optimization are achieved.
It achieves a free radical scavenging rate of ≥98%, a cooling rate of ≥15℃/s, an oxygen concentration of ≤12% and a maintenance time of ≥5 minutes, toxicity control with HF generation ≤15ppm and CO generation ≤100ppm, extinguishing time ≤8 seconds, and supply density ≤2.5kg/m³, meeting both safety and economic requirements.
Smart Images
Figure CN121102845A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the interdisciplinary field of new energy safety materials and systems engineering, and more specifically, to a method for defining electrochemical energy storage fire extinguishing agents and their graded protection applications. Background Technology
[0002] With the rapid development of the electrochemical energy storage industry (covering energy storage scenarios such as lithium-ion batteries, sodium-ion batteries, and flow batteries), fire safety protection has become a core bottleneck restricting the large-scale application of the industry. As a key material for fire protection, fire extinguishing agents have many defects in existing technical solutions, making it difficult to meet the industry's safety and economic needs. The specific problems are as follows. During the chain reaction phase, relying solely on chemical adsorption to remove free radicals has a removal efficiency of less than 85%, which cannot effectively interrupt the chain reaction, leading to the rapid spread of the fire. During the heat spread phase, the penetration of the agent has a significant lag, with a response time > 5 seconds, which cannot suppress the thermal runaway of the battery in time and is prone to causing module-level fires. During the reignition risk period, there is no long-term inertization mechanism, and the oxygen concentration can easily rise rapidly after the fire is extinguished, resulting in a high risk of reignition and making it impossible to completely eliminate the fire hazard. In terms of cost control, the lack of optimization in material selection and spraying strategy, coupled with excessively high supply density, has resulted in high material costs, hindering large-scale application.
[0003] In view of this, we propose a definition method for electrochemical energy storage fire extinguishing agents and their graded protection applications. Summary of the Invention
[0004] One of the objectives of this invention is to provide a method for defining electrochemical energy storage fire extinguishing agents and their graded protection applications, aiming to solve the problem that existing technologies cannot meet the industry's safety and economic needs.
[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for defining an electrochemical energy storage fire extinguishing agent, which is based on a six-dimensional performance parameter system, specifically satisfying the following performance indicators; A1. Free radical scavenging rate ≥98%. Based on the battery thermal runaway chain reaction mechanism, when the scavenging rate is ≥98%, active free radicals such as •OH and •H can be effectively quenched, interrupting the combustion chain reaction. A2. Cooling rate ≥15℃ / s. For the critical temperature of thermal runaway of battery module, a cooling rate of 15℃ / s can reduce the temperature to below 100℃ within 10s, suppressing heat spread. A3. The asphyxiation effect is that the oxygen concentration is ≤12% after the fire is extinguished and maintained for ≥5 minutes. When the oxygen concentration is ≤12%, the combustibles cannot continue to burn. Maintaining it for 5 minutes can ensure that the core area of thermal runaway is completely cooled. A4. Toxicity is controlled at HF generation ≤15ppm and CO generation ≤100ppm, ensuring that personnel are not at risk of acute toxicity within 30 minutes of exposure in the fire extinguishing area. A5. The fire extinguishing time is ≤8 seconds for a 1kWh standard battery module, which can prevent the thermal runaway of the battery module from spreading to adjacent units. A6. Supply density ≤ 2.5 kg / m³, which can balance fire extinguishing efficiency and cost.
[0006] This invention also discloses a graded protection application of an electrochemical energy storage fire extinguishing agent, including the following application steps; B1. Pre-loading step: The extinguishing agent is pre-loaded into a storage tank, which is equipped with a digital certificate chip. The chip stores the initial authentication values of the six-dimensional performance parameters of the extinguishing agent. B2. Monitoring steps: Real-time monitoring of free radical concentration within the protected area using 94GHz millimeter-wave radar, and calculation of real-time free radical scavenging rate based on a pre-calibrated concentration-scavenging rate mapping model; B3. Dynamic calibration steps: By monitoring the deviation of six-dimensional parameters in real time, the spraying state of the extinguishing agent is automatically adjusted.
[0007] Preferably, in step B3 above, the logic of the dynamic calibration spray includes increasing the spray flow rate of the extinguishing agent by 10%-20% to improve the scavenging efficiency when the free radical scavenging rate is <98% based on real-time monitored six-dimensional performance data.
[0008] Preferably, in step B3 above, the logic of the dynamic calibration injection further includes simultaneously monitoring the oxygen concentration when the free radical scavenging rate is <98%, and if the oxygen concentration is >12%, activating the nitrogen replenishment system to reduce the oxygen concentration to below 12%.
[0009] Preferably, in step B3 above, the logic of the dynamic calibration spray further includes calculating the supply density. When the supply density is >2.5 kg / m³, dendrite growth is suppressed by the radio frequency ion trap array to reduce the consumption of extinguishing agent.
[0010] Preferably, step B3 above further includes optimizing the six-dimensional parameter balance using a response surface model, with the objective function being: ; in, Free radical scavenging rate, For the cooling rate, To ensure supply density, a weighted allocation is used, with the clearance rate having the highest weight, ensuring that core performance targets are met first.
[0011] The present invention also discloses an electrochemical energy storage fire extinguishing agent, including a perfluoroketone-nanocerium nanocomposite fire extinguishing agent and an organophosphorus-aerogel fire extinguishing agent.
[0012] Preferably, the perfluoroketone-nanocerium composite fire extinguishing agent is composed of perfluoro-2-methyl-3-pentanone, CeO2@SiO2 core-shell nanoparticles and perfluoropolyether surfactant in a mass ratio of 92:6:2; The organophosphorus-aerogel fire extinguishing agent is composed of melamine polyphosphate, tris(2-chloropropyl) phosphate and SiO2 aerogel in a mass ratio of 20:70:10.
[0013] Compared with the prior art, the beneficial effects of the present invention are: 1. Based on a six-dimensional performance parameter system, the present invention improves the free radical scavenging rate to ≥98% during the chain reaction period, interrupting the combustion chain; during the thermal spread period, it suppresses diffusion with a cooling rate of ≥15℃ / s and a fire extinguishing time of ≤8s (1kWh module); during the reignition risk period, it constructs long-term inerting by maintaining an oxygen concentration of ≤12% for ≥5min; and on the cost side, it reduces costs with a supply density of ≤2.5kg / m³ and optimization strategies, meeting both safety and economic requirements.
[0014] 2. The perfluoroketone-cerium nanocomposite fire extinguishing agent of this invention is composed of perfluoro-2-methyl-3-pentanone, CeO2@SiO2 core-shell nanoparticles and perfluoropolyether surfactant in a mass ratio of 92:6:2. Perfluoro-2-methyl-3-pentanone provides suffocation and cooling effects, CeO2@SiO2 core-shell nanoparticles catalyze the removal of free radicals, and perfluoropolyether surfactant improves dispersibility and wettability. The organophosphorus-aerogel fire extinguishing agent is made of melamine polyphosphate, tris(2-chloropropyl) phosphate and SiO2 aerogel in a mass ratio of 20:70:10. The components work synergistically to achieve multiple functions such as free radical removal, cooling and suffocation. Attached Figure Description
[0015] Figure 1 This is a schematic diagram of the overall architecture of the present invention; Figure 2 This is a schematic diagram of system integration in this invention; Figure 3 This is a scientific basis diagram of the six-dimensional performance parameter system in this invention; Figure 4 This is a flowchart of the dynamic calibration algorithm in this invention. Figure 5 This is the complete engineering process of the present invention, from the preparation of the fire extinguishing agent to its final application in the energy storage compartment. Detailed Implementation
[0016] Example 1 In this embodiment, the extinguishing agent is a perfluoroketone-nanocerium composite extinguishing agent based on a six-dimensional performance parameter system, which meets the following requirements: free radical scavenging rate ≥98%, cooling rate ≥15℃ / s, asphyxiation efficacy ≤12% oxygen concentration after extinguishing and maintained for ≥5 minutes, toxicity control ≤15ppm HF generation and ≤100ppm CO generation, extinguishing time ≤8 seconds for a 1kWh standard battery module, and supply density ≤2.5kg / m³. Among them, the free radical scavenging rate is ≥98%, which is tested at 200℃ by electron spin resonance spectroscopy according to ISO22007-2023 standard. Based on the battery thermal runaway chain reaction mechanism, when the scavenging rate is ≥98%, active free radicals such as ・OH and ・H can be effectively quenched and the combustion chain reaction can be interrupted. The cooling rate is ≥15℃ / s. According to the ISO12156-1:2022 standard, it is tested at the geometric center of the battery module. For the critical temperature of thermal runaway of the battery module, the cooling rate of 15℃ / s can reduce the temperature to below 100℃ within 10s, suppressing heat spread. The asphyxiation efficacy is that the oxygen concentration is ≤12% after fire extinguishing and maintained for ≥5 minutes. According to the EN3-7:2018 Annex D standard, it was verified in a 1m³ closed chamber. When the oxygen concentration is ≤12%, the combustibles cannot continue to burn. Maintaining it for 5 minutes can ensure that the core area of thermal runaway is completely cooled. Toxicity is controlled at HF generation ≤15ppm and CO generation ≤100ppm. According to NFPA 70-2023 §500.7, gas chromatography-mass spectrometry can be used for detection to ensure that there is no risk of acute toxicity to personnel within 30 minutes of exposure in the fire extinguishing area. The fire extinguishing time is ≤8 seconds for a 1kWh standard battery module. According to UL9540AEd.3-2024AnnexB, high-speed video recording can prevent the thermal runaway of the battery module from spreading to adjacent units. With a supply density ≤2.5kg / m³, and tested according to NFPA 2010-2022 Chapter 4 under the conditions of a spray pressure of 0.5MPa and a nozzle diffusion angle ≤15°, it can balance fire extinguishing effectiveness and cost; The perfluoroketone-nanocerium composite fire extinguishing agent is prepared by dispersing CeO2@SiO2 core-shell nanoparticles (50nm in diameter, used for catalytic scavenging of free radicals) in a perfluoropolyether surfactant (used to improve the dispersibility of nanoparticles and the wettability of the agent), ultrasonically treating for 30 minutes (300W power) to form a nano-dispersion, and then slowly adding the nano-dispersion to perfluoro-2-methyl-3-pentanone (as the main fire extinguishing component, providing suffocation and cooling), stirring at a rate of 500r / min, and mixing for 1 hour. In this process, the mass ratio of perfluoro-2-methyl-3-pentanone, CeO2@SiO2 core-shell nanoparticles and perfluoropolyether surfactant is 92:6:2.
[0017] The following table is a performance verification table for the fire extinguishing agent in this embodiment:
[0018] Example 2 This embodiment is basically the same as Embodiment 1, except that the extinguishing agent in this embodiment is an organophosphorus-aerogel extinguishing agent based on a six-dimensional performance parameter system that meets the following requirements: free radical scavenging rate ≥98%, cooling rate ≥15℃ / s, asphyxiation efficacy ≤12% oxygen concentration after extinguishing and maintained for ≥5 minutes, toxicity control ≤15ppm HF generation and ≤100ppm CO generation, extinguishing time ≤8 seconds for a 1kWh standard battery module, and supply density ≤2.5kg / m³. The organophosphorus-aerogel fire extinguishing agent in this embodiment is obtained by mixing melamine polyphosphate with tris(2-chloropropyl) phosphate, heating and stirring at 80°C for 1 hour (rate 300 r / min), then adding SiO2 aerogel (particle size 100 nm), and vacuum degassing for 30 minutes (vacuum degree -0.09 MPa). In this process, the mass ratio of melamine polyphosphate, tri(2-chloropropyl) phosphate and SiO2 aerogel is 20:70:10.
[0019] The following table shows the formulation and performance of the extinguishing agent in this embodiment:
[0020] Example 3 A graded protection application of an electrochemical energy storage fire extinguishing agent includes the following application steps; B1. Pre-loading step: The extinguishing agent is pre-loaded into a storage tank, which is equipped with a digital certificate chip. The chip stores the initial authentication values of the six-dimensional performance parameters of the extinguishing agent. B2. Monitoring steps: The concentration of free radicals in the protected area is monitored in real time using a 94GHz millimeter-wave radar, and the real-time free radical scavenging rate is calculated based on a pre-calibrated concentration-scavenging rate mapping model. B3. Dynamic calibration steps: By monitoring the deviation of six-dimensional parameters in real time, the spraying state of the extinguishing agent is automatically adjusted.
[0021] In step B3 above, the logic for dynamic calibration of the spray includes increasing the spray flow rate of the extinguishing agent by 10%-20% to improve the scavenging efficiency when the free radical scavenging rate is <98% based on real-time monitoring of six-dimensional performance data.
[0022] In step B3 above, the logic of dynamic calibration injection also includes synchronously monitoring the oxygen concentration when the free radical scavenging rate is <98%, and if the oxygen concentration is >12%, the nitrogen replenishment system is activated to reduce the oxygen concentration to below 12%.
[0023] In step B3 above, the logic for dynamic calibration of the spray also includes calculating the supply density. When the supply density is >2.5 kg / m³, dendrite growth is suppressed by the radio frequency ion trap array to reduce the consumption of extinguishing agent.
[0024] Step B3 above also includes optimizing the six-dimensional parameter balance using a response surface model, with the objective function being: ; in, Free radical scavenging rate, For the cooling rate, To ensure supply density, a weighted allocation is used, with the clearance rate having the highest weight, ensuring that core performance targets are met first.
[0025] The embodiments disclosed in this invention are preferred embodiments, but are not limited thereto. Those skilled in the art can easily understand the spirit of this invention based on the above embodiments and make different extensions and variations, but as long as they do not depart from the spirit of this invention, they are all within the protection scope of this invention.
Claims
1. A method for defining an electrochemical energy storage fire extinguishing agent, characterized in that, This method is based on a six-dimensional performance parameter system, specifically satisfying the following performance indicators; A1. Free radical scavenging rate ≥98%. Based on the battery thermal runaway chain reaction mechanism, when the scavenging rate is ≥98%, active free radicals such as •OH and •H can be effectively quenched, interrupting the combustion chain reaction. A2. Cooling rate ≥15℃ / s. For the critical temperature of thermal runaway of battery module, a cooling rate of 15℃ / s can reduce the temperature to below 100℃ within 10s, suppressing heat spread. A3. The asphyxiation effect is that the oxygen concentration is ≤12% after the fire is extinguished and maintained for ≥5 minutes. When the oxygen concentration is ≤12%, the combustibles cannot continue to burn. Maintaining it for 5 minutes can ensure that the core area of thermal runaway is completely cooled. A4. Toxicity is controlled at HF generation ≤15ppm and CO generation ≤100ppm, ensuring that personnel are not at risk of acute toxicity within 30 minutes of exposure in the fire extinguishing area. A5. The fire extinguishing time is ≤8 seconds for a 1kWh standard battery module, which can prevent the thermal runaway of the battery module from spreading to adjacent units. A6. Supply density ≤ 2.5 kg / m³, which can balance fire extinguishing efficiency and cost.
2. A graded protection application of an electrochemical energy storage fire extinguishing agent, wherein the application is based on the fire extinguishing agent defined using the electrochemical energy storage fire extinguishing agent definition method described in claim 1, characterized in that, The following application steps are included; B1. Pre-loading step: The extinguishing agent is pre-loaded into a storage tank, which is equipped with a digital certificate chip. The chip stores the initial authentication values of the six-dimensional performance parameters of the extinguishing agent. B2. Monitoring steps: The concentration of free radicals in the protected area is monitored in real time using a 94GHz millimeter-wave radar, and the real-time free radical scavenging rate is calculated based on a pre-calibrated concentration-scavenging rate mapping model. B3. Dynamic calibration steps: By monitoring the deviation of six-dimensional parameters in real time, the spraying state of the extinguishing agent is automatically adjusted.
3. The graded protection application of an electrochemical energy storage fire extinguishing agent according to claim 2, characterized in that, In step B3 above, the logic of the dynamic calibration spray includes increasing the spray flow rate of the extinguishing agent by 10%-20% to improve the scavenging efficiency when the free radical scavenging rate is <98% based on real-time monitoring of six-dimensional performance data.
4. The graded protection application of an electrochemical energy storage fire extinguishing agent according to claim 3, characterized in that, In step B3 above, the logic of the dynamic calibration injection also includes simultaneously monitoring the oxygen concentration when the free radical scavenging rate is <98%, and if the oxygen concentration is >12%, activating the nitrogen replenishment system to reduce the oxygen concentration to below 12%.
5. The graded protection application of an electrochemical energy storage fire extinguishing agent according to claim 3, characterized in that, In step B3 above, the logic of the dynamic calibration spray also includes calculating the supply density. When the supply density is >2.5kg / m³, dendrite growth is suppressed by the radio frequency ion trap array to reduce the consumption of extinguishing agent.
6. The graded protection application of an electrochemical energy storage fire extinguishing agent according to claim 2, characterized in that, Step B3 above also includes optimizing the six-dimensional parameter balance using a response surface model, with the objective function being: ； in, Free radical scavenging rate, For the cooling rate, To ensure supply density, a weighted allocation is used, with the clearance rate having the highest weight, ensuring that core performance targets are met first.
7. An electrochemical energy storage fire extinguishing agent, which is a fire extinguishing agent satisfying the definition method of an electrochemical energy storage fire extinguishing agent as described in claim 1, characterized in that, This includes perfluoroketone-nanocerium composite fire extinguishing agents and organophosphorus-aerogel fire extinguishing agents.
8. The electrochemical energy storage fire extinguishing agent according to claim 7, characterized in that, The perfluoroketone-nanocere composite fire extinguishing agent is composed of perfluoro-2-methyl-3-pentanone, CeO2@SiO2 core-shell nanoparticles and perfluoropolyether surfactant in a mass ratio of 92:6:
2. The organophosphorus-aerogel fire extinguishing agent is composed of melamine polyphosphate, tris(2-chloropropyl) phosphate and SiO2 aerogel in a mass ratio of 20:70:10.