A mixed fire extinguishing agent composition, a mixed fire extinguishing agent and a preparation method thereof, and a fire extinguishing system for energy storage lithium batteries

Abstract

The application relates to the technical field of electric power energy storage, and discloses a mixed fire extinguishing agent composition, a mixed fire extinguishing agent, a preparation method thereof and a fire extinguishing system of an energy storage lithium battery. The composition contains a fluorine-based fire extinguishing agent, a solubilizer and an anti-reignition fire extinguishing agent; the content volume ratio of the solubilizer, the fluorine-based fire extinguishing agent and the anti-reignition fire extinguishing agent is 1:1-3:1-6; the fluorine-based fire extinguishing agent is at least one selected from perfluorohexanone and dichlorotrifluoropropylene; the anti-reignition fire extinguishing agent is at least one selected from liquefied carbon dioxide and liquefied sulfur dioxide; and the solubilizer is a fluorine-containing amine compound. The mixed fire extinguishing agent can simultaneously achieve rapid extinguishing of battery open fire and prevention of battery reignition, and solves the thermal runaway safety problem of the energy storage lithium ion battery.

Description

Technical Field

[0001] This invention relates to the field of power energy storage technology, specifically to a mixed fire extinguishing agent composition, a mixed fire extinguishing agent and its preparation method, and a fire extinguishing system for energy storage lithium batteries. Background Technology

[0002] Lithium-ion battery energy storage boasts advantages such as short response time, rapid deployment, and good economic efficiency, leading to its rapid development in recent years. In the first half of 2023, my country's newly installed lithium-ion battery energy storage capacity reached 8.63 GW / 17.73 GWh, approaching the total cumulative installed capacity of all previous years. However, lithium-ion batteries are highly susceptible to thermal runaway fires and explosions induced by internal or external faults. Therefore, the safety of lithium-ion batteries has become a key factor restricting the development of the lithium-ion battery energy storage industry.

[0003] Battery thermal runaway fires differ from conventional solid fires. After a battery experiences thermal runaway, internal chemical reactions continue, making it highly susceptible to reignition. Domestically and internationally, traditional fire extinguishing technologies such as heptafluoropropane and perfluorohexanone are mainly used to combat battery thermal runaway. However, heptafluoropropane has low heat absorption capacity and poor reignition prevention performance.

[0004] CN114344774A uses perfluorohexanone, which has a higher boiling point, for fire extinguishing. Perfluorohexanone is more effective than heptafluoropropane in extinguishing fires, but its high boiling point results in a slower vaporization rate. Therefore, it is slow to extinguish open flames on batteries and has poor resistance to reignition.

[0005] CN114515402A proposes a method to prevent the reignition of lithium-ion batteries by spraying inert gases such as carbon dioxide after the open flame has been extinguished in the battery compartment. However, inert gases such as carbon dioxide are gaseous at room temperature and are immiscible with liquid high-boiling-point fluorochlorobromo-based fire extinguishing agents. Therefore, when using fluorochlorobromo-based fire extinguishing agents to quickly extinguish open flames and inert gases to prevent reignition, two sets of fire extinguishing devices need to be used simultaneously or sequentially, which increases the complexity of the system and the cost of the fire extinguishing system.

[0006] In summary, there is an urgent need to develop a new extinguishing agent to enhance the reignition prevention capability of high-boiling-point fluorochlorobromo-based extinguishing agents, as well as a fire extinguishing system that can simultaneously extinguish open flames and prevent reignition. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of slow extinguishing speed and poor ability to prevent reignition in existing lithium battery fire extinguishing agents.

[0008] Normally, liquid substances are difficult to dissolve gaseous substances without a chemical reaction. However, through extensive experimental research, the inventors discovered that certain types of fluorinated fire extinguishing agents and reignition-preventing fire extinguishing agents can achieve a certain proportion of miscibility with certain types of solubilizers in a liquefied state, forming mixed fire extinguishing agents. Therefore, fluorinated fire extinguishing agents and reignition-preventing fire extinguishing agents can be sprayed using the same set of pipelines during fire extinguishing, improving the system's economy and reducing the complexity of the fire extinguishing system compared to traditional application methods. Furthermore, after the fluorinated fire extinguishing agents and reignition-preventing fire extinguishing agents are sprayed, the reignition-preventing fire extinguishing agents, being gases with low boiling points, promote heat and mass transfer in the higher-boiling-point fluorinated fire extinguishing agents during volatilization, increasing the vaporization rate of the fluorinated fire extinguishing agents and thus enhancing their extinguishing rate.

[0009] To achieve the above objectives, the first aspect of the present invention provides a mixed fire extinguishing agent composition containing a fluorine-based fire extinguishing agent, a solubilizer, and a reignition-preventing fire extinguishing agent;

[0010] The volume ratio of the solubilizer, fluorinated fire extinguishing agent, and reignition-preventing fire extinguishing agent is 1:1-3:1-6;

[0011] The fluorine-based fire extinguishing agent is selected from at least one of perfluorohexanone and dichlorotrifluoropropylene;

[0012] The fire extinguishing agent for preventing reignition is selected from at least one of liquefied carbon dioxide and liquefied sulfur dioxide;

[0013] The solubilizer is a fluorinated amine compound.

[0014] A second aspect of the present invention provides a method for preparing a mixed fire extinguishing agent, using the components of the composition described in the first aspect, comprising:

[0015] (1) The solubilizer, fluorine-based fire extinguishing agent and anti-reignition fire extinguishing agent are liquefied to obtain liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied anti-reignition fire extinguishing agent respectively;

[0016] (2) The liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied fire extinguishing agent are mixed to obtain a mixed fire extinguishing agent.

[0017] A third aspect of the present invention provides a mixed fire extinguishing agent prepared by the method described in the second aspect.

[0018] The fourth aspect of the present invention provides a fire extinguishing system for energy storage lithium batteries. The system includes: a thermal runaway monitoring module, a fire extinguishing agent delivery pipeline, a nozzle system arranged around each energy storage lithium battery pack, a fire extinguishing agent storage tank, a control module for regulating the opening and closing of the control valve of the fire extinguishing agent storage tank, and a pressure stabilizing module for stabilizing the pressure inside the fire extinguishing agent storage tank.

[0019] The pressure stabilizing module is connected to the fire extinguishing agent storage tank;

[0020] The extinguishing agent stored in the extinguishing agent storage tank is the mixed extinguishing agent described in the third aspect.

[0021] Compared with the prior art, the advantages of the present invention are as follows:

[0022] (1) The fluorine-based fire extinguishing agent and the anti-reignition fire extinguishing agent in the mixed fire extinguishing agent provided by the present invention can act on the battery at the same time, so as to simultaneously extinguish the open flame of the battery and prevent the battery from reigniting, thus solving the thermal runaway safety problem of energy storage lithium-ion batteries.

[0023] (2) In the mixed fire extinguishing agent provided by the present invention, the fluorine-based fire extinguishing agent and the anti-reignition fire extinguishing agent use the same set of fire extinguishing pipelines when extinguishing fire, which saves costs and is economical.

[0024] (3) The fire extinguishing agent in the mixed fire extinguishing agent provided by the present invention can increase the vaporization rate of the high-boiling-point fluorine-based fire extinguishing agent, improve its ability to extinguish open flames, and ultimately improve the fire extinguishing speed. Attached Figure Description

[0025] Figure 1 A schematic diagram of the process for extinguishing fires using a mixed extinguishing agent.

[0026] Figure 2 This is a schematic diagram of the fire extinguishing system of the energy storage lithium battery in Embodiment 1 of the present invention.

[0027] Figure 3 This is a photograph of the fluorine-based fire extinguishing agent, solubilizer, and reignition-preventing fire extinguishing agent after they have been mixed in Example 1. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] As mentioned above, a first aspect of the present invention provides a mixed fire extinguishing agent composition containing a fluorine-based fire extinguishing agent, a solubilizer, and a reignition-preventing fire extinguishing agent;

[0030] The volume ratio of the solubilizer, fluorinated fire extinguishing agent, and reignition-preventing fire extinguishing agent is 1:1-3:1-6;

[0031] The fluorinated fire extinguishing agent is selected from at least one of perfluorohexanone and dichlorotrifluoropropylene (2-chloro-3,3,3-trifluoropropylene);

[0032] The fire extinguishing agent for preventing reignition is selected from at least one of liquefied carbon dioxide and liquefied sulfur dioxide;

[0033] The solubilizer is a fluorinated amine compound.

[0034] Preferably, the volume ratio of the solubilizer, fluorinated fire extinguishing agent, and reignition-preventing fire extinguishing agent is 1:1-2:2-4. The inventors of this invention have discovered that under these preferred conditions, the resulting mixed fire extinguishing agent has a faster extinguishing speed and better reignition-preventing capability.

[0035] Preferably, the fluorinated amine compound is selected from at least one of perfluorotriethylamine, perfluorodiethylamine, N,N-dimethyl-2-(perfluorophenyl)ethylamine, perfluorophenylethylamine, perfluoroethylcyclohexylamine, and perfluorotributylamine.

[0036] More preferably, the fluorinated amine compound is perfluorotriethylamine. The inventors of this invention have discovered that, under this preferred condition, the fluorinated fire extinguishing agent and the reignition-preventing fire extinguishing agent exhibit better miscibility, resulting in a mixed fire extinguishing agent with superior fire extinguishing performance.

[0037] In this invention, the reignition prevention mechanism of the fire extinguishing agent is that active lithium, oxygen, carbon dioxide, and / or sulfur dioxide in the battery react to produce inert lithium carbonate.

[0038] 2Li + CO₂ + 1 / 2O₂ (oxygen in the air) → Li₂CO₃;

[0039] 2Li + SO₂ + 1 / 2O₂ (oxygen in the air) → Li₂SO₃.

[0040] The specific mechanism of action of the mixed fire extinguishing agent described in this invention is as follows: (1) Promoting heat transfer: When the fire extinguishing agent for preventing reignition evaporates from the high-boiling-point fluorine-based fire extinguishing agent, it will generate tiny bubbles. When the bubbles are generated, their surface area is very large. The heat of phase change is transferred out through the surface, thereby promoting the heat transfer process. The formation of bubbles can increase the contact area between the liquid and the heated surface, thereby increasing the heat transfer rate. (2) Promoting mass transfer: The rapid rise of the bubbles will generate eddies and flow, which will increase the mass transfer rate.

[0041] As previously described, a second aspect of the present invention provides a method for preparing a mixed fire extinguishing agent, using the components of the composition described in the first aspect, comprising:

[0042] (1) The solubilizer, fluorine-based fire extinguishing agent and anti-reignition fire extinguishing agent are liquefied to obtain liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied anti-reignition fire extinguishing agent respectively;

[0043] (2) The liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied fire extinguishing agent are mixed to obtain a mixed fire extinguishing agent.

[0044] It should be noted that the definitions and dosages of the solubilizers, fluorinated fire extinguishing agents, and reignition-preventing fire extinguishing agents described in this invention are the same as the definitions and contents of the corresponding components described in the first aspect, and will not be repeated here. Those skilled in the art should not understand this as a limitation of the invention.

[0045] It should be noted that in this invention, if the selected solubilizer or fluorinated fire extinguishing agent is in a liquid state at room temperature, it does not need to be liquefied or liquefied at room temperature.

[0046] According to a preferred embodiment, the liquefaction method is selected from at least one of pressurization and cooling.

[0047] Preferably, the liquefaction is achieved by pressurization and cooling. This liquefaction method ensures that the storage state of the mixed extinguishing agent does not fluctuate with changes in room temperature.

[0048] Preferably, the conditions for liquefying the fire extinguishing agent to prevent reignition include: a temperature of -25 to 25°C and a pressure of 2 to 10 MPa.

[0049] According to another preferred embodiment, in step (2), the mixing conditions include: a temperature of -25 to 25°C, a time of 10 to 20 minutes, and a stirring speed of 20 to 100 rpm.

[0050] As previously described, a third aspect of the present invention provides a mixed fire extinguishing agent prepared by the method described in the second aspect.

[0051] As mentioned above, the fourth aspect of the present invention provides a fire extinguishing system for energy storage lithium batteries. The system includes: a thermal runaway monitoring module, a fire extinguishing agent delivery pipeline, a nozzle system arranged around each energy storage lithium battery pack, a fire extinguishing agent storage tank, a control module for regulating the opening and closing of the control valve of the fire extinguishing agent storage tank, and a pressure stabilizing module for stabilizing the pressure inside the fire extinguishing agent storage tank.

[0052] The pressure stabilizing module is connected to the fire extinguishing agent storage tank;

[0053] The extinguishing agent stored in the extinguishing agent storage tank is the mixed extinguishing agent described in the third aspect.

[0054] Preferably, the extinguishing agent delivery pipeline includes a main extinguishing agent delivery pipeline and branch extinguishing agent delivery pipelines; the extinguishing agent storage tank is connected to the inlet of the main extinguishing agent delivery pipeline, the outlet of the main extinguishing agent delivery pipeline is connected to the inlet of each of the branch extinguishing agent delivery pipelines, and the outlet of each branch extinguishing agent delivery pipeline is connected to the nozzle system.

[0055] Preferably, the thermal runaway monitoring module is used to locate the location of a fire within the energy storage battery compartment.

[0056] In a preferred embodiment, the connection point between the pressure stabilizing module and the fire extinguishing agent storage tank is located above the liquid surface of the mixed fire extinguishing agent in the fire extinguishing agent storage tank.

[0057] Preferably, the system further includes a cooling and insulation system for maintaining the temperature inside the extinguishing agent storage tank and a control valve for controlling the extinguishing agent storage tank.

[0058] Preferably, the cooling and insulation system is connected to the extinguishing agent storage tank. This system can ensure that the internal temperature of the extinguishing agent storage tank is maintained at -20°C for an extended period of time.

[0059] In a preferred embodiment, the pressure stabilizing module is a gas booster pump and / or a pressure stabilizing gas cylinder; the pressure stabilizing gas cylinder uses nitrogen or argon as the gas pressure source.

[0060] According to a preferred embodiment, such as Figure 1 As shown, a method for extinguishing a fire using the aforementioned energy storage lithium battery fire extinguishing system includes the following steps:

[0061] After liquefying the fluorinated extinguishing agent, solubilizer, and reignition-preventing extinguishing agent, they are mixed in a volume ratio of 1:1-3:1-6 to form a mixed extinguishing agent, which is then placed in an extinguishing agent storage tank. A thermal runaway monitoring module is then used to locate the fire within the energy storage battery compartment. A control module opens the control valve of the extinguishing agent storage tank, allowing the mixed extinguishing agent to travel through the extinguishing agent delivery pipeline to the nozzle system for spraying and fire extinguishing.

[0062] The present invention will be described in detail below through examples. Unless otherwise specified, the instruments, reagents, and materials involved in the following examples are all conventional instruments, reagents, and materials, which can be obtained through legitimate commercial channels. Unless otherwise stated, all reagents used are commercially available products. Room temperature mentioned in the examples refers to a temperature of 22±3℃.

[0063] Solubilizer:

[0064] Perfluorotriethylamine, purchased from Wuhan Lanabai Company, CAS No. 359-70-6.

[0065] Perfluorophenylethylamine, purchased from Zhengzhou Alpha Chemical Co., Ltd., CAS No. 1583-76-2.

[0066] Fluorine-based fire extinguishing agents:

[0067] Perfluorohexanone: purchased from Sinochem Lantian Company, brand name FK-5-1-12.

[0068] Dichlorotrifluoropropylene: purchased from 3M, CAS number 2730-62-3.

[0069] Example 1

[0070] The mixed fire extinguishing agent is prepared using a method including the following steps:

[0071] (1) The solubilizer, fluorine-based fire extinguishing agent and anti-reignition fire extinguishing agent are liquefied to obtain liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied anti-reignition fire extinguishing agent respectively;

[0072] The solubilizer is perfluorotriethylamine, and its liquefaction conditions are: temperature 20°C and pressure 0.1 MPa.

[0073] The fluorine-based fire extinguishing agent is perfluorohexanone, which is a liquid at room temperature;

[0074] The fire extinguishing agent used to prevent reignition is carbon dioxide, and its liquefaction conditions are: temperature 20℃ and pressure 5.7MPa.

[0075] (2) The liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied fire extinguishing agent are mixed in a high-pressure volumetric flask at a volume ratio of 1:2:2 to obtain a mixed fire extinguishing agent;

[0076] The mixing conditions were: temperature 20°C, time 15 min, and stirring speed 20 rpm.

[0077] like Figure 2 As shown, a fire extinguishing system for energy storage lithium batteries includes: a thermal runaway monitoring module, a fire extinguishing agent delivery pipeline, a nozzle system arranged around each energy storage lithium battery pack, a fire extinguishing agent storage tank, a control valve for controlling the fire extinguishing agent storage tank, a control module for regulating the opening and closing of the control valve of the fire extinguishing agent storage tank, and a pressure stabilizing module for stabilizing the pressure inside the fire extinguishing agent storage tank.

[0078] The extinguishing agent delivery pipeline includes a main extinguishing agent delivery pipeline and branch extinguishing agent delivery pipelines.

[0079] The extinguishing agent storage tank is connected to the inlet of the main extinguishing agent delivery pipeline, the outlet of the main extinguishing agent delivery pipeline is connected to the inlet of each of the branch extinguishing agent delivery pipelines, and the outlet of each of the branch extinguishing agent delivery pipelines is connected to the nozzle system.

[0080] The pressure stabilizing module is connected to the fire extinguishing agent storage tank, and its connection point is located at the top of the fire extinguishing agent storage tank;

[0081] The fire extinguishing agent stored in the fire extinguishing agent storage tank is the mixed fire extinguishing agent prepared in Example 1. The pressure inside the fire extinguishing agent storage tank is 6 MPa, the pressure resistance level of the fire extinguishing agent storage tank is 7 MPa, and the pressure stabilizing module is a gas booster pump.

[0082] Example 2

[0083] The mixed fire extinguishing agent is prepared using a method including the following steps:

[0084] (1) The solubilizer, fluorine-based fire extinguishing agent and anti-reignition fire extinguishing agent are liquefied to obtain liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied anti-reignition fire extinguishing agent respectively;

[0085] The solubilizer is perfluorotriethylamine, and its liquefaction conditions are: temperature 20°C and pressure 0.1 MPa.

[0086] The fluorine-based fire extinguishing agent is dichlorotrifluoropropylene, and its liquefaction conditions are: temperature 20°C and pressure 2MPa.

[0087] The fire extinguishing agent for preventing reignition is carbon dioxide, and its liquefaction conditions are: temperature -20℃ and pressure 2MPa.

[0088] (2) The liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied fire extinguishing agent are mixed in a high-pressure volumetric flask at a volume ratio of 1:2:4 to obtain a mixed fire extinguishing agent;

[0089] The mixing conditions were: temperature -20℃, time 15 min, and stirring speed 30 rpm.

[0090] Example 3

[0091] This embodiment uses a method similar to that in Embodiment 1 to prepare a mixed fire extinguishing agent. The difference is that in step (2), the liquefied solubilizer, liquefied fluorine-based fire extinguishing agent, and liquefied reignition prevention fire extinguishing agent are mixed in a high-pressure volumetric flask at a volume ratio of 1:3:6.

[0092] The remaining steps are the same as in Example 1.

[0093] Example 4

[0094] This embodiment uses a method similar to that in Example 1 to prepare a mixed fire extinguishing agent. The difference is that in step (1), the solubilizer is perfluorophenylethylamine.

[0095] The remaining steps are the same as in Example 1.

[0096] Comparative Example 1

[0097] This comparative example uses a similar method to Example 1 to prepare a mixed fire extinguishing agent, except that no reignition prevention fire extinguishing agent is added to this comparative example;

[0098] The remaining steps are the same as in Example 1.

[0099] Comparative Example 2

[0100] This comparative example uses a similar method to Example 1 to prepare a mixed fire extinguishing agent, except that no fluorine-based fire extinguishing agent is added.

[0101] The remaining steps are the same as in Example 1.

[0102] Comparative Example 3

[0103] This comparative example uses a similar method to Example 1 to prepare a mixed fire extinguishing agent, except that no solubilizer is added in this comparative example;

[0104] The remaining steps are the same as in Example 1.

[0105] Application Examples

[0106] The mixed extinguishing agent prepared in the above example was used to conduct fire extinguishing performance tests on a 280Ah energy storage lithium iron phosphate battery module. The test conditions were as follows: 280Ah energy storage lithium-ion battery modules with 100% SOC were used for testing. Each battery module had 16 batteries connected in series. Thermal runaway of the battery module was triggered by heating with a heating plate measuring 135mm × 220mm × 2mm with a rated power of 900W. The fire extinguishing system of the energy storage lithium battery in Example 1 was used for fire extinguishing. When the battery module experienced thermal runaway, the thermal runaway monitoring module located the fire location in the energy storage battery compartment. The control module opened the control valve of the extinguishing agent storage tank, allowing the mixed extinguishing agent to reach the nozzle system through the extinguishing agent delivery pipeline and spray the mixed extinguishing agent, achieving rapid extinguishing of open flames and prevention of reignition. The final battery thermal runaway suppression effect is shown in Table 1.

[0107] Table 1

[0108] Example 1 3.5 510 No reignition Example 2 3 490 No reignition Example 3 6 630 No reignition Example 4 5 590 No reignition Comparative Example 1 4 / Reignition occurred at 120 seconds. Comparative Example 2 10 920 No reignition Comparative Example 3 8 640 No reignition

[0109] This invention is in Figure 3 The document provides, exemplarily, physical images of the miscible fluorinated fire extinguishing agent, solubilizer, and reignition-preventing fire extinguishing agent in Example 1. Figure 3 It can be seen that fluorinated fire extinguishing agents and reignition prevention fire extinguishing agents are well miscible in the presence of a solubilizer. Furthermore, the results show that the mixed fire extinguishing agent provided by this invention can simultaneously achieve rapid fire extinguishing and reignition prevention. In Comparative Example 1, the use of a single fluorinated fire extinguishing medium makes it difficult to achieve a good reignition prevention effect. In Comparative Example 2, the absence of a fluorinated fire extinguishing agent results in low extinguishing efficiency and a long extinguishing time in the initial stage of the battery fire, leading to a slow temperature drop after extinguishing the battery, which is detrimental to rapid and efficient fire extinguishing. In Comparative Example 3, the lack of a solubilizer reduces the miscibility of the fluorinated fire extinguishing agent and the reignition prevention fire extinguishing agent, causing them to separate into layers, resulting in reduced extinguishing and cooling capabilities, which is also detrimental to rapid and efficient fire extinguishing and reignition prevention.

[0110] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A mixed fire extinguishing agent composition, characterized in that, The composition contains fluorine-based fire extinguishing agents, solubilizers, and reignition-preventing fire extinguishing agents; The volume ratio of the solubilizer, fluorinated fire extinguishing agent, and reignition-preventing fire extinguishing agent is 1:1-2:2-4. The fluorine-based fire extinguishing agent is selected from at least one of perfluorohexanone and dichlorotrifluoropropylene; The fire extinguishing agent for preventing reignition is selected from at least one of liquefied carbon dioxide and liquefied sulfur dioxide; The solubilizer is a fluorinated amine compound, which is perfluorotriethylamine and / or perfluorophenylethylamine.

2. The composition according to claim 1, characterized in that, The fluorine-containing amine compound is perfluorotriethylamine.

3. A method for preparing a mixed fire extinguishing agent, characterized in that, The application of each component of the composition according to claim 1 or 2 includes: (1) The solubilizer, fluorine-based fire extinguishing agent and fire extinguishing agent for preventing reignition are liquefied to obtain liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied fire extinguishing agent for preventing reignition; (2) The liquefied solubilizer, liquefied fluorine-based fire extinguishing agent and liquefied fire extinguishing agent are mixed to obtain a mixed fire extinguishing agent.

4. The method according to claim 3, characterized in that, The liquefaction method is selected from at least one of pressurization and cooling.

5. The method according to claim 4, characterized in that, The conditions for liquefying the fire extinguishing agent to prevent reignition include: a temperature of -25 to 25°C and a pressure of 2 to 10 MPa.

6. The method according to any one of claims 3-5, characterized in that, In step (2), the mixing conditions include: a temperature of -25 to 25°C, a time of 10 to 20 minutes, and a stirring speed of 20 to 100 rpm.

7. A mixed fire extinguishing agent prepared by the method according to any one of claims 3-6.

8. A fire extinguishing system for an energy storage lithium battery, characterized in that, The system includes: a thermal runaway monitoring module, a fire extinguishing agent delivery pipeline, a nozzle system deployed around each energy storage lithium battery pack, a fire extinguishing agent storage tank, a control module for regulating the opening and closing of the control valves of the fire extinguishing agent storage tank, and a pressure stabilizing module for stabilizing the pressure inside the fire extinguishing agent storage tank. The pressure stabilizing module is connected to the fire extinguishing agent storage tank; The fire extinguishing agent stored in the fire extinguishing agent storage tank is the mixed fire extinguishing agent as described in claim 7.

9. The fire extinguishing system according to claim 8, characterized in that, The pressure stabilizing module is a gas booster pump and / or a pressure stabilizing gas cylinder; the pressure stabilizing gas cylinder uses nitrogen or argon as a gas pressure source; and / or The extinguishing agent delivery pipeline includes a main extinguishing agent delivery pipeline and branch extinguishing agent delivery pipelines; the extinguishing agent storage tank is connected to the inlet of the main extinguishing agent delivery pipeline, the outlet of the main extinguishing agent delivery pipeline is connected to the inlet of each of the branch extinguishing agent delivery pipelines, and the outlet of each branch extinguishing agent delivery pipeline is connected to the nozzle system.

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