CN113350730B - Lithium ion battery extinguishing agent and preparation method and application thereof - Google Patents

Abstract

The invention provides a lithium ion battery fire extinguishing agent, which includes fire extinguishing material, cooling material and anticorrosion material, and the mass ratio of fire extinguishing material, cooling material and anticorrosion material is (0.5-2): (0.2-2): (0.1-0.3 ); the fire extinguishing material is a fluorine-containing organic compound with a heat of vaporization not exceeding 100kJ/kg, the cooling material is a fluorine-containing organic compound with a heat of vaporization higher than 100kJ/kg, and the anti-corrosion material is a montmorillonite loaded with activated alumina and urea. Through reasonable compounding, the lithium ion battery fire extinguishing agent has suitable boiling point, high vaporization heat and high specific heat, and has both fire extinguishing and cooling performance. It can effectively and quickly extinguish lithium ion battery fires while preventing re-ignition. During the fire extinguishing process, the electrical equipment will not be corroded, causing secondary damage.

Description

Lithium-ion battery fire extinguishing agent and preparation method and application thereof

technical field

The invention relates to the technical field of fire safety, in particular to a lithium ion battery fire extinguishing agent and a preparation method and application thereof.

Background technique

Lithium-ion batteries are currently the commercial batteries with the highest energy density, and have the advantages of long cycle life, no memory effect, and no toxic substances. Its applications involve many fields of production and life; such as mobile phones, computers, new energy vehicle power systems, and smart grid energy storage, which is now attracting more and more attention. However, while lithium-ion batteries benefit mankind, safety issues are becoming more and more prominent.

At present, there is no special fire extinguishing agent for lithium-ion batteries. Because lithium-ion battery is a high-energy material, it has the characteristics of strong combustion, fast thermal diffusion, and strong toxicity. Lithium-ion battery fires are very different from ordinary fires, resulting in existing fire extinguishing agents that cannot effectively suppress lithium-ion battery fires. It will reignite many times and is not suitable for lithium-ion battery fires. The commonly used fluorine-containing fire extinguishing agents are usually corrosive during the fire extinguishing process, thereby corroding lithium-ion batteries and causing secondary damage.

SUMMARY OF THE INVENTION

Based on this, it is necessary to provide a lithium-ion battery fire extinguishing agent that can avoid re-ignition and has low corrosion, and a preparation method and application thereof.

In one aspect of the present invention, a lithium-ion battery fire extinguishing agent is provided, which includes a fire extinguishing material, a cooling material and an anti-corrosion material; the mass ratio of the fire-extinguishing material, the cooling material and the anti-corrosion material is (0.5-2): (0.2～2): (0.1～0.3);

Wherein, the fire extinguishing material is a fluorine-containing organic compound with a heat of vaporization not exceeding 100kJ/kg; the cooling material is a fluorine-containing organic compound with a heat of vaporization higher than 100kJ/kg; the anti-corrosion material is a Mongolian compound loaded with activated alumina and urea Destone.

In some of these embodiments, the fire extinguishing material is selected from at least one of heptafluoropropane, perfluorohexanone and 2-bromo-3,3,3-trifluoropropene.

In some embodiments, the cooling material is at least one of pentafluorobutane and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether.

In some embodiments, the fire extinguishing material is selected from at least one of heptafluoropropane, perfluorohexanone and 2-bromo-3,3,3-trifluoropropene, and the cooling material is pentafluorobutane and 1 ,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, the mass ratio of the fire extinguishing material to the cooling material is (0.5～2): 1 .

In some embodiments, the fire extinguishing material is selected from at least one of heptafluoropropane, perfluorohexanone and 2-bromo-3,3,3-trifluoropropene, and the cooling material is pentafluorobutane and 1 ,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether mixture, the fire extinguishing material, the pentafluorobutane and the 1,1,2,2- The mass ratio of tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether is (0.5-2):(0.1-1):(0.1-1).

In some of the embodiments, in the anti-corrosion material, the loading amount of the activated alumina is 3%-5%, and the loading amount of the urea is 6%-10% according to the mass percentage.

In some of these embodiments, the anti-corrosion material is prepared according to the following steps:

Disperse the montmorillonite in water, add aluminum isopropoxide, and mix to carry out a hydrothermal reaction;

After filtering, drying and calcining the hydrothermal reaction product, the activated alumina-loaded montmorillonite is obtained;

The activated alumina-loaded montmorillonite is soaked in a urea solution, and then the montmorillonite is taken out and dried to obtain the anti-corrosion material.

In some embodiments, the mass ratio of the montmorillonite, the water and the aluminum isopropoxide is (4-8):(15-25):1; the mass concentration of the urea solution is 30 %～50%, every 1 g of the activated alumina-loaded montmorillonite is soaked in 0.8 mL～1.2 mL of the urea solution, and the soaking time is 3h～5h.

Another aspect of the present invention also provides a preparation method of the above-mentioned lithium ion battery fire extinguishing agent, comprising the following steps:

The fire-extinguishing material, the cooling material and the anti-corrosion material are evenly mixed to obtain the lithium-ion battery fire-extinguishing agent.

In another aspect of the present invention, a lithium ion battery fire extinguisher is also provided, which is loaded with the above lithium ion battery fire extinguishing agent.

Compared with the prior art, the present invention at least has the following beneficial effects:

(1) The present invention is aimed at the characteristics of lithium-ion battery fires. By compounding a fire-extinguishing material that has strong fire-extinguishing ability but is easy to vaporize and a cooling material that has high vaporization heat and is not easy to vaporize, the lithium-ion battery fire-extinguishing agent can have both Fire extinguishing and cooling capabilities, with suitable boiling point, high vaporization heat and high specific heat, can effectively extinguish lithium-ion battery fires to meet the needs of practical applications. When the lithium ion battery fire extinguishing agent prepared by the invention is applied to a lithium ion battery fire, the lithium ion battery can be effectively cooled while being effectively extinguished, and the fire can be prevented from re-ignition, so as to ensure the use safety of the lithium ion battery, and promote the promotion of the lithium ion battery. The application of lithium-ion batteries is of great significance.

(2) The anti-corrosion material in the above-mentioned lithium-ion battery fire extinguishing agent is montmorillonite loaded with activated alumina and urea. The loading of activated alumina and urea improves the adsorption effect of montmorillonite and can effectively adsorb moisture and hydrogen fluoride. , Li-ion battery fire extinguishing agent is not easy to produce highly corrosive hydrogen fluoride during storage. During the fire extinguishing process, the anti-corrosion material covering the surface of the lithium-ion battery can also isolate the air, which further improves the fire-extinguishing effect of the lithium-ion battery fire extinguishing agent. At the same time, the loaded alumina and urea can be decomposed with the fire extinguishing material during the heating process. The generated hydrogen fluoride reacts to achieve efficient adsorption of water and hydrogen fluoride, which is beneficial to avoid the corrosion of water and hydrogen fluoride to electrical equipment, and prevent secondary damage to electrical equipment during the fire extinguishing process.

Description of drawings

Fig. 1 is the cooling curve diagram of comparative examples 1～4 of the present invention;

FIG. 2 is a cooling curve diagram of Comparative Examples 1, 4, 5 and Example 1 of the present invention.

Detailed ways

In order to facilitate understanding of the present invention, the present invention will be described more fully hereinafter with reference to the related drawings. Preferred embodiments of the invention are shown in the accompanying drawings. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that a thorough and complete understanding of the present disclosure is provided.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

An embodiment of the present invention provides a lithium-ion battery fire extinguishing agent, including fire extinguishing material, cooling material and anti-corrosion material; the mass ratio of fire-extinguishing material, cooling material and anti-corrosion material is (0.5～2):(0.2～2):( 0.1～0.3);

Among them, the fire extinguishing material is a fluorine-containing organic compound with a heat of vaporization not exceeding 100kJ/kg; the cooling material is a fluorine-containing organic compound with a heat of vaporization higher than 100kJ/kg; the anti-corrosion material is a montmorillonite loaded with activated alumina and urea.

The fire extinguishing material has a low boiling point and vaporization heat. As a fire extinguishing material, it can block the free radical chain reaction during the combustion process. During the fire extinguishing process, it quickly absorbs heat and vaporizes to achieve a rapid cooling effect. The cooling of electrical equipment and the residual heat inside the battery may cause re-ignition. The cooling material has a high boiling point and high heat of vaporization, and vaporizes slowly during the fire extinguishing process, which can continuously cool the electrical equipment and prevent re-ignition, and the cooling material is also a fluorine-containing organic compound, which has a certain fire extinguishing performance.

The above-mentioned fire extinguishing agent for lithium ion batteries includes fire extinguishing materials, cooling materials and anti-corrosion materials. The ion battery fire extinguishing agent has a suitable boiling point, high vaporization heat and high specific heat capacity. It has both fire extinguishing performance and can cool it on the surface of electrical equipment to avoid the risk of re-ignition. The montmorillonite loaded with activated alumina and urea is used as the anti-corrosion material, which can absorb the moisture and hydrogen fluoride in the fire extinguishing agent during storage, so as not to corrode the container; It can be used to isolate the air, and at the same time, it can absorb the hydrogen fluoride generated by the decomposition of the fire extinguishing material, so as to avoid the secondary damage of the fire extinguishing agent to the electrical equipment.

In some of these embodiments, the fire extinguishing material is selected from at least one of heptafluoropropane, perfluorohexanone, and 2-bromo-3,3,3-trifluoropropene.

In some embodiments, the cooling material is at least one of pentafluorobutane and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether.

In some embodiments, the fire extinguishing material is selected from at least one of heptafluoropropane, perfluorohexanone and 2-bromo-3,3,3-trifluoropropene, and the cooling material is pentafluorobutane and 1,1,2 , a kind of 2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, the mass ratio of fire extinguishing material and cooling material is (0.5～2):1.

In some embodiments, the fire extinguishing material is selected from at least one of heptafluoropropane, perfluorohexanone and 2-bromo-3,3,3-trifluoropropene, and the cooling material is pentafluorobutane and 1,1,2 ,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether mixture, fire extinguishing material, pentafluorobutane and 1,1,2,2-tetrafluoroethyl-2,2,3 , The mass ratio of 3-tetrafluoropropyl ether is (0.5～2):(0.1～1):(0.1～1).

In some of the embodiments, calculated by mass percentage, in the anti-corrosion material, the loading of activated alumina is 3% to 5%, and the loading of urea is 6% to 10%.

In some of the embodiments, the anti-corrosion material is prepared according to the following steps S10-S14:

Step S10: dispersing the montmorillonite in water, adding aluminum isopropoxide, and mixing to conduct a hydrothermal reaction;

Step S12: after filtering, drying and calcining the hydrothermal reaction product, the activated alumina-loaded montmorillonite is obtained;

Step S14: soaking the activated alumina-loaded montmorillonite in the urea solution, then taking out the montmorillonite and drying to obtain the anti-corrosion material.

In some embodiments, the mass ratio of montmorillonite, water and aluminum isopropoxide is (4-8):(15-25):1.

In some of the embodiments, the calcination is performed in an air atmosphere, the calcination temperature is 400°C to 600°C, and the calcination time is 3 to 5 hours.

In some of the embodiments, the mass concentration of the urea solution is 30% to 50%, and each 1 g of activated alumina-loaded montmorillonite is soaked in 0.8 mL to 1.2 mL of the urea solution, and the soaking time is 3 h to 5 h.

Another embodiment of the present invention also provides a preparation method of the above-mentioned lithium ion battery fire extinguishing agent, comprising the following steps:

The fire-extinguishing material, the cooling material and the anti-corrosion material are evenly mixed to obtain a lithium-ion battery fire-extinguishing agent.

Another embodiment of the present invention also provides a lithium ion battery fire extinguisher loaded with the above lithium ion battery fire extinguishing agent.

The following are specific examples.

Example 1:

This embodiment provides a special fire extinguishing agent for lithium ion batteries, including perfluorohexanone, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (abbreviated as HFE458 ) and montmorillonite loaded with activated alumina and urea, and the mass ratio of perfluorohexanone, HFE458 and montmorillonite loaded with activated alumina and urea is 1:1:0.2; activated alumina in montmorillonite The loading of urea is 4wt%, and the loading of urea is 8wt%.

The preparation method of the special fire extinguishing agent for lithium ion batteries comprises the following steps:

(1) Mix the fire extinguishing material perfluorohexanone and the cooling material HFE458 according to the mass ratio of 1:1, and stir evenly to obtain the compound fire extinguishing agent raw material;

(2) disperse montmorillonite in water, then add aluminum isopropoxide, control the mass ratio of montmorillonite, water and aluminum isopropoxide to be 6:20:1, and carry out hydrothermal reaction in the autoclave after fully stirring , the temperature of the hydrothermal reaction was controlled to be 120 °C, the product was filtered after 48 h of reaction, dried at 80 °C and then calcined in an air atmosphere, heated to 500 °C at a heating rate of 1 °C/min, and calcined for 4 h. Obtain the montmorillonite loaded with activated alumina;

(3) placing the montmorillonite loaded with activated alumina obtained in step (2) in a urea solution with a mass concentration of 40 wt % and fully immersing it for 3 hours, and controlling the ratio of the montmorillonite loaded with activated alumina to the urea solution to be 1g: 1mL, then take it out and dry it to obtain a montmorillonite loaded with activated alumina and urea, which is used as an anti-corrosion material for later use;

(4) adding the anti-corrosion material obtained in step (3) to the compound fire-extinguishing agent raw material, and controlling the mass ratio of the compound fire-extinguishing agent raw material to the anti-corrosion material to be 2:0.2 to obtain a lithium-ion battery fire-extinguishing agent.

The above-mentioned lithium ion battery fire extinguishing agent is sealed and filled in a high pressure container to obtain a lithium ion battery fire extinguisher.

In order to verify the actual fire extinguishing effect of the lithium ion battery fire extinguishing agent prepared in this example on the lithium ion battery, the 32650 ternary lithium battery was first simulated and heated, and then the lithium ion battery special fire extinguishing agent prepared in this example was used to extinguish the fire. The lithium-ion battery began to generate an open flame after being heated for 5 minutes. At this time, the lithium-ion battery fire extinguishing agent prepared in this example was sprayed. After 10 seconds, there was no open fire. The fire extinguishing agent was continuously sprayed for 20 seconds to cool the lithium-ion battery. After 40 seconds It can be observed that the flame is completely extinguished and does not reignite. After removing the ternary lithium battery, it was observed that the position where the heating rod was inserted in the middle of the lower part of the lithium battery was burned, but under the action of the fire extinguishing agent, the flame was extinguished and no longer reignited, and other parts of the lithium battery were basically unaffected and not affected. There are signs of corrosion. It can be shown that the lithium-ion battery fire extinguishing agent prepared in this example can timely and effectively extinguish the lithium-ion battery fire, and suppress the re-ignition, and at the same time avoid the corrosion of the lithium-ion battery by the hydrogen fluoride generated by the decomposition of the fire extinguishing agent. The hazards caused by fire spread and corrosion have played an effective role in protecting electrical equipment.

Comparative Examples 1 to 5:

Comparative Examples 1 to 5 respectively provide a fire extinguishing agent. Compared with Example 1, the difference is pointed out that the composition and ratio of the compound fire extinguishing agent raw materials have been changed, and the preparation and corresponding addition of anti-corrosion materials are consistent with Example 1 , and will not be repeated here. The components in the compound fire extinguishing agent raw materials of Comparative Examples 1 to 5 and the mass percentage of each component are shown in Table 1, respectively.

Table 1 Composition and content of compound fire extinguishing agent raw materials provided by Comparative Examples 1 to 5

Comparative ratio Composition and content of compound fire extinguishing agent raw materials Comparative Example 1 Perfluorohexanone (100wt%) Comparative Example 2 Heptafluoropropane (100wt%) Comparative Example 3 Pentafluorobutane (100wt%) Comparative Example 4 1,1,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE458) (100wt%) Comparative Example 5 Perfluorohexanone (75wt%) and HFE458 (25wt%)

In order to compare the cooling effect of the fire extinguishing agent provided in Example 1 and Comparative Examples 1 to 5, a cooling experiment was performed on the heating plate by using the fire extinguishing agent, and the cooling curves of the fire extinguishing agents in Comparative Examples 1 to 4 were obtained as shown in Figure 1. Comparative Examples 1, 4, 5 and the cooling curves of the fire extinguishing agent in Example 1 are shown in Figure 2. Referring to Figure 1, it can be seen that compared with perfluorohexanone and heptafluoropropane, pentafluorobutane and HFE-458 have better long-term cooling effect. After 100 seconds, the temperature still drops significantly, while perfluorohexanone and Heptafluoropropane has only a short-acting cooling effect, and the temperature drops more within 100 seconds, and after 100 seconds, the temperature only decreases slightly. Referring to Figure 2, the mass ratio of perfluorohexanone to HFE-458 in the fire extinguishing agent of Comparative Example 5 is 3:1, and its cooling effect is no different from that of Comparative Example 1. The mass ratio of perfluorohexanone and HFE-458 in the fire extinguishing agent of Example 1 is 1:1, and its cooling effect is better than that of Comparative Example 1 and Comparative Example 5. For the cooling data of Example 1, Comparative Example 1, Comparative Example 4 and Comparative Example 5, please refer to Table 2.

The cooling data of table 2 embodiment 1, comparative example 1, comparative example 4 and comparative example 5

In order to further test the ability of the fire extinguishing agent provided in Example 1 and Comparative Example to extinguish an open fire, taking Comparative Example 4 as an example, the fire extinguishing test on open fire was carried out together with the fire extinguishing agent of Example 1. It was found that after 30 seconds of ignition, the Comparative Example was used. 4. It takes 15 seconds for the fire extinguishing agent provided to be able to put out the flame, and the fire extinguishing agent provided in Example 1 only needs 8 seconds to extinguish the open fire, which has a higher fire extinguishing efficiency, indicating that the fire extinguishing agent provided in Example 1 is added with an appropriate amount. The cooling material can improve the cooling effect while ensuring the fire extinguishing effect and avoid re-ignition.

Examples 2 to 10:

Embodiments 2 to 10 respectively provide a fire extinguishing agent for lithium ion batteries. Compared with Example 1, the difference is that the composition and mass ratio of each compound material in the compound fire extinguishing agent raw material are changed, and the preparation of anti-corrosion material is changed. The corresponding addition amounts are the same as those in Example 1, and are not repeated here. Table 3 shows the composition and mass ratio of the compound fire extinguishing agent raw materials corresponding to Examples 2 to 10.

The raw material components of the compound fire extinguishing agent in the special fire extinguishing agent for lithium ion batteries provided by Examples 2 to 10 in Table 3 and their corresponding mass ratios

Example The components of the compound fire extinguishing agent and their corresponding mass ratios Example 2 Perfluorohexanone:Pentafluorobutane=0.5:1 Example 3 Perfluorohexanone:HFE458=2:1 Example 4 Heptafluoropropane:Pentafluorobutane=1:1 Example 5 Heptafluoropropane:HFE458=1:1 Example 6 2-Bromo-3,3,3-trifluoropropene:Pentafluorobutane=1:1 Example 7 2-Bromo-3,3,3-trifluoropropene:HFE458＝1:1 Example 8 Perfluorohexanone:Pentafluorobutane:HFE458=1:0.5:0.5 Example 9 Heptafluoropropane:Pentafluorobutane:HFE458=1:0.5:0.5 Example 10 2-Bromo-3,3,3-trifluoropropene:Pentafluorobutane:HFE458＝1:0.5:0.5

After testing the fire-extinguishing performance of the lithium-ion battery fire extinguishing agents provided in Examples 2-10, it was found that the lithium-ion battery fire-extinguishing agents provided in Examples 2-10 can make the prepared fire-extinguishing agents have good fire-extinguishing effect and cooling effect at the same time. The effect of effectively extinguishing lithium-ion battery fires and preventing them from re-igniting. And the lithium-ion battery has no obvious corrosion after using fire extinguishing agent.

Examples 11-17 and Comparative Examples 6-8:

Examples 11 to 17 and Comparative Examples 6 to 8 respectively provide a fire extinguishing agent for lithium ion batteries. Compared with Example 1, the difference between Examples 11 to 14 is that by adjusting montmorillonite, water and isopropanol The aluminum mass ratio and the concentration of the urea solution have changed the loading of activated alumina and urea in the montmorillonite; the difference of Examples 15 to 16 is that the calcination conditions in the preparation process of the anti-corrosion material have been changed; the difference of Example 17 The place is that the mixture of activated alumina, urea and montmorillonite is mechanically mixed as the anti-corrosion material, and the relative contents of activated alumina, urea and montmorillonite in Example 17 are consistent with those in Example 1; The difference is that the montmorillonite without adding active alumina and urea is used as the anti-corrosion material, the difference of the comparative example 7 is that only activated alumina is loaded on the montmorillonite, and the difference of the comparative example 8 is that the montmorillonite is on the montmorillonite. Loaded with urea only. The specific preparation method adjusts the corresponding steps according to the difference from Example 1, and will not be repeated here.

Table 4 lists the corresponding activated alumina, urea loading and calcination conditions of Examples 11-16.

Table 4 Loads and calcination conditions of activated alumina and urea in Examples 11 to 16

The 32650 ternary lithium battery was simulated and heated according to the method provided in Example 1, and the fire extinguishing agents prepared in Examples 11 to 16 were used to extinguish the simulated heated lithium battery. After continuously spraying the extinguishing agent for 40s, Example 11 The fire extinguishing agent prepared by ~16 can completely extinguish the flame, and no re-ignition occurs, indicating that the appropriate adjustment of the activated alumina and urea loading and the corresponding calcination conditions within a certain range has little effect on the fire extinguishing and cooling effect of the fire extinguishing agent. , the fire extinguishing agent prepared in each embodiment can effectively extinguish the lithium ion battery fire in time and suppress the re-ignition.

In order to further compare the difference in anti-corrosion performance between Example 1, Examples 11-17 and Comparative Examples 6-8, taking a metal steel sheet as an example, the fire extinguishing agents prepared in the above-mentioned examples and comparative examples were tested against the metal steel sheet. Corrosive, and test the fluoride ion concentration after the fire extinguishing agent is sprayed. The specific test steps are as follows:

Test 1. Corrosion test on metal steel sheets

Select Q355 metal steel sheet for testing, and weigh it after grinding, cleaning and drying. Then, a metal steel sheet is placed between the high-pressure steel cylinder containing the fire extinguishing agent to be tested and the simulated heated ternary lithium battery, so that the metal steel sheet is located 50cm directly below the fire extinguishing agent nozzle. After the ternary lithium battery is ignited, spray fire extinguishing agent for 40s, wait for 2h, weigh the metal steel sheet again, and calculate the weight loss rate of the metal steel sheet.

Test 2. Fluoride ion concentration test after spraying fire extinguishing agent

Mix 10 mL of fluoride ion standard solution with a concentration of 0.1 mol/L and 10 mL of total ionic strength adjustment buffer solution, and dilute to 100 mL with fluoride-free distilled water to obtain a fluoride ion solution with a concentration of 10 ^-2 mol/L; Mix 10 mL of fluoride ion solution with a concentration of 10 ^-2 mol/L with 10 mL of total ionic strength adjusting buffer solution, and dilute to 100 mL in the same way to obtain a fluoride ion solution with a concentration of 10 ^-3 mol/L; The fluoride ion solutions with concentrations of 10 ^-4 , 10 ^-5 , 10 ^-6 , and 10 ^-7 mol/L were prepared in a different way, and the measured concentrations were 10 ^-2 , 10 ^-3 , 10 ^-4 , 10 ^-5 , The steady-state potential values of 10 ^-6 and 10 ^-7 mol/L fluoride ion solutions are 351mV, 338mV, 287mV, 227mV, 166mV, and 109mV, respectively. The relationship between the fluoride ion concentration and the steady-state potential value of the fluoride ion solution is obtained. .

Then place the collection container at the position corresponding to the metal steel sheet in Test 1, collect the sprayed fire extinguishing agent, filter it and take 10 mL as the solution to be tested, mix it with 10 mL of the total ionic strength adjustment buffer solution, and use a fluorine-free solution. Distilled water to 100mL, and then measure the steady-state potential value, and estimate the fluoride ion concentration according to the relationship between the obtained fluoride ion concentration and the steady-state potential value of the fluoride ion solution.

The weight loss rate, steady-state potential value and fluoride ion concentration of the metal steel sheet measured according to the above test method are shown in Table 5.

Table 5 Corrosion and fluoride ion concentration test of the fire extinguishing agents of Example 1, Examples 11-17 and Comparative Examples 6-8 to metal steel sheets

Combining with Table 5, it can be seen that by properly adjusting the loading of activated alumina and urea and the corresponding calcining conditions within a certain range, the prepared fire extinguishing agent can achieve a better anticorrosion effect while ensuring the fire extinguishing and cooling effects. The lower steel sheet weight loss rate and fluoride ion concentration indicated that both the moisture and hydrogen fluoride contained in the fire extinguishing agent can be effectively adsorbed by the anti-corrosion material and will not cause secondary damage to electrical equipment including lithium-ion batteries. However, when natural montmorillonite was used as the anti-corrosion material in the fire extinguishing agent of Comparative Example 6, the weight loss rate and fluoride ion concentration were significantly higher than those of the examples, indicating that when the unmodified montmorillonite was used as the anti-corrosion material, the The absorption of moisture and hydrogen fluoride is limited, and the moisture and hydrogen fluoride in the fire extinguishing agent cause serious corrosion to electrical equipment. After the fire is extinguished, it still causes corrosive damage to the unburned lithium-ion battery, which affects its normal use. The anti-corrosion material added by mechanical mixing in Example 17 can achieve a certain anti-corrosion effect, but the measured weight loss rate and steady-state potential value are still higher than those in Examples 11-16, mainly because the mechanical mixing process cannot The modification of montmorillonite results in limited adsorption of montmorillonite at high temperature, and the dispersion effect of each raw material is not good, resulting in the overall anti-corrosion effect still weaker than that of Examples 11-16. When comparative example 7 and comparative example 8 are loaded with a single activated alumina or urea respectively, the measured weight loss rate and steady-state potential value are significantly higher than those of the embodiments of the present invention, mainly because their single loading mode not only leads to The raw materials for the reaction of water and hydrogen fluoride are reduced, and it is difficult to effectively modify the montmorillonite, thereby affecting its overall anti-corrosion effect.

The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can also be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (8)

1. A lithium ion battery fire extinguishing agent is characterized by comprising a fire extinguishing material, a cooling material and an anticorrosive material; the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is (0.5-2): 1: 0.2;

wherein the fire extinguishing material is fluorine-containing organic matter with heat of vaporization not more than 100 kJ/kg; the cooling material is fluorine-containing organic matter with the heat of vaporization higher than 100 kJ/kg; the anticorrosive material is montmorillonite loaded with active alumina and urea; the fire extinguishing material is at least one of heptafluoropropane, perfluorohexanone and 2-bromo-3, 3, 3-trifluoropropene; the cooling material is at least one of pentafluorobutane and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether;

the anticorrosive material is prepared according to the following steps:

dispersing the montmorillonite in water, adding aluminum isopropoxide, uniformly mixing, and carrying out hydrothermal reaction;

filtering, drying and calcining the hydrothermal reaction product to obtain montmorillonite loaded with active alumina;

and soaking the montmorillonite loaded with the active alumina in a urea solution, taking out the montmorillonite, and drying to obtain the anticorrosive material.

2. The lithium ion battery fire extinguishing agent according to claim 1, wherein the fire extinguishing material is at least one selected from heptafluoropropane, perfluorohexanone and 2-bromo-3, 3, 3-trifluoropropene, the temperature reducing material is one selected from pentafluorobutane and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and the mass ratio of the fire extinguishing material to the temperature reducing material is (0.5-2): 1.

3. the lithium ion battery fire extinguishing agent according to claim 1, wherein the fire extinguishing material is at least one selected from heptafluoropropane, perfluorohexanone and 2-bromo-3, 3, 3-trifluoropropene, the temperature reducing material is a mixture of pentafluorobutane and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and the mass ratio of the fire extinguishing material to the pentafluorobutane to the 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether is (0.5-2): (0.1-1): (0.1 to 1).

4. The lithium ion battery fire extinguishing agent according to any one of claims 1 to 3, wherein the loading amount of the activated alumina in the anticorrosive material is 3-5% and the loading amount of the urea in the anticorrosive material is 6-10% by mass percentage.

5. The lithium ion battery fire extinguishing agent according to any one of claims 1 to 3, wherein the mass ratio of the montmorillonite, the water and the aluminum isopropoxide is (4-8): (15-25): 1; the mass concentration of the urea solution is 30-50%, and every 1g of the montmorillonite loaded with the active alumina is soaked in 0.8-1.2 mL of the urea solution for 3-5 h.

6. The lithium ion battery fire extinguishing agent according to claim 1, wherein the fire extinguishing material is perfluorohexanone, the temperature reducing material is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, and the load of the active alumina and the load of the urea are 4% and 8% respectively in the anticorrosive material in percentage by mass, and the mass ratio of the fire extinguishing material to the temperature reducing material to the anticorrosive material is 1:1: 0.2;

or the fire extinguishing material is perfluorohexanone, the cooling material is pentafluorobutane, the loading capacity of the activated alumina and the loading capacity of the urea in the anticorrosive material are respectively 4% and 8%, and the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is 0.5:1: 0.2;

or the fire extinguishing material is perfluorohexanone, the cooling material is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, the loading amount of the active alumina and the loading amount of the urea in the anticorrosive material are respectively 4% and 8%, and the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is 2:1: 0.2;

or the fire extinguishing material is heptafluoropropane, the cooling material is pentafluorobutane, the loading capacity of the active alumina in the anticorrosive material is 4%, the loading capacity of the urea in the anticorrosive material is 8%, and the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is 1:1: 0.2;

or the fire extinguishing material is heptafluoropropane, the cooling material is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, the loading of the active alumina and the loading of the urea in the anticorrosive material are respectively 4% and 8%, and the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is 1:1: 0.2;

or the fire extinguishing material is 2-bromo-3, 3, 3-trifluoropropene, the cooling material is pentafluorobutane, the loading amount of the active alumina in the anticorrosive material is 4% and the loading amount of the urea in the anticorrosive material is 8% according to the mass percentage, and the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is 1:1: 0.2;

or the fire extinguishing material is 2-bromo-3, 3, 3-trifluoropropene, the cooling material is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, the loading amount of the active alumina in the anticorrosive material is 4%, the loading amount of the urea in the anticorrosive material is 8%, and the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is 1:1: 0.2;

or the fire extinguishing material is perfluorohexanone, the cooling material is a mixture of pentafluorobutane and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, the loading amount of the active alumina in the anticorrosive material is 4% and the loading amount of the urea in the anticorrosive material is 8% by mass percent, and the mass ratio of the fire extinguishing material to the pentafluorobutane to the 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether to the anticorrosive material is 1:0.5:0.5: 0.2;

or the fire extinguishing material is heptafluoropropane, the temperature reducing material is a mixture of pentafluorobutane and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, the loading amount of the active alumina and the loading amount of the urea in the anticorrosive material are respectively 4% and 8%, and the mass ratio of the fire extinguishing material to the pentafluorobutane to the 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether to the anticorrosive material is 1:0.5:0.5: 0.2;

or the fire extinguishing material is 2-bromo-3, 3, 3-trifluoropropene, the cooling material is a mixture of pentafluorobutane and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, the loading amount of the active alumina in the anticorrosive material is 4% and the loading amount of the urea in the anticorrosive material is 8% by mass percentage, and the mass ratio of the fire extinguishing material to the pentafluorobutane to the 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether to the anticorrosive material is 1:0.5:0.5: 0.2.

7. The preparation method of the lithium ion battery fire extinguishing agent according to any one of claims 1 to 6, characterized by comprising the following steps:

and uniformly mixing the fire extinguishing material, the cooling material and the anticorrosive material to obtain the lithium ion battery extinguishing agent.

8. A lithium ion battery fire extinguisher, characterized in that it is loaded with a lithium ion battery fire extinguishing agent according to any one of claims 1 to 6.

Images