CN113350730B - Lithium ion battery extinguishing agent and preparation method and application thereof - Google Patents
Lithium ion battery extinguishing agent and preparation method and application thereof Download PDFInfo
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- CN113350730B CN113350730B CN202110453115.6A CN202110453115A CN113350730B CN 113350730 B CN113350730 B CN 113350730B CN 202110453115 A CN202110453115 A CN 202110453115A CN 113350730 B CN113350730 B CN 113350730B
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a lithium ion battery fire extinguishing agent which comprises a fire extinguishing material, a cooling material and an anticorrosive material, wherein the mass ratio of the fire extinguishing material to the cooling material to the anticorrosive material is (0.5-2): (0.2-2): (0.1 to 0.3); the fire extinguishing material is a fluorine-containing organic matter with the heat of vaporization not more than 100kJ/kg, the cooling material is a fluorine-containing organic matter with the heat of vaporization higher than 100kJ/kg, and the anticorrosive material is montmorillonite loaded with active alumina and urea. Through reasonable compounding, this lithium ion battery fire extinguishing agent has suitable boiling point, high heat of vaporization and high specific heat, has the performance of putting out a fire and cooling down concurrently, can prevent to take place the after combustion when effectively putting out the lithium ion battery conflagration fast, can not corrode electrical equipment at the in-process of putting out a fire simultaneously, causes the secondary damage.
Description
Technical Field
The invention relates to the technical field of fire safety, in particular to a lithium ion battery extinguishing agent and a preparation method and application thereof.
Background
The lithium ion battery is the commercial battery with the highest energy density at present, and has the advantages of long cycle life, no memory effect, no toxic substance and the like. Its application relates to many production, life fields; such as mobile phones, computers, new energy automobile power systems, and smart grid energy storage which is getting more and more attention now. However, the lithium ion battery brings benefits to human beings, and meanwhile, the safety problem is more and more prominent.
At present, no special fire extinguishing agent is available for lithium ion batteries. Because the lithium ion battery is a high-energy material, the lithium ion battery has the characteristics of strong combustion, fast heat diffusion, strong toxicity and the like, and the fire hazard of the lithium ion battery is greatly different from the common fire hazard, the existing fire extinguishing agent for fire prevention can not effectively inhibit the fire hazard of the lithium ion battery, can reburn for multiple times, and has no applicability to the fire hazard of the lithium ion battery. At present, the commonly used fluorine-containing fire extinguishing agent is easy to generate corrosivity in the fire extinguishing process, so that a lithium ion battery is corroded, and secondary damage is caused.
Disclosure of Invention
Therefore, a lithium ion battery fire extinguishing agent which can avoid afterburning and has low corrosivity, and a preparation method and application thereof are needed.
In one aspect of the invention, the invention provides a lithium ion battery fire extinguishing agent, which comprises 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): (0.2-2): (0.1 to 0.3);
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.
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 temperature reducing 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 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.
in some embodiments, 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).
In some embodiments, the loading amount of the activated alumina in the anticorrosive material is 3 to 5 percent, and the loading amount of the urea in the anticorrosive material is 6 to 10 percent.
In some of these embodiments, the corrosion protection material is prepared by:
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.
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%, 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.
The invention also provides a preparation method of the lithium ion battery fire extinguishing agent, which comprises 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.
In another aspect of the invention, a lithium ion battery fire extinguisher is also provided, which is loaded with the lithium ion battery fire extinguishing agent.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) aiming at the characteristics of the lithium ion battery fire, the invention can lead the lithium ion battery fire extinguishing agent to have fire extinguishing and cooling capabilities by compounding the fire extinguishing material which has stronger fire extinguishing capability but is easy to vaporize with the cooling material which has higher vaporization heat and is difficult to vaporize, has proper boiling point, high vaporization heat and high specific heat, and can effectively extinguish the lithium ion battery fire so as to meet the requirements of practical application. The lithium ion battery fire extinguishing agent prepared by the invention is applied to lithium ion battery fires, can effectively extinguish the lithium ion battery fires and efficiently cool the lithium ion battery fires at the same time, and prevents the fires from reburning, so that the use safety of the lithium ion battery is guaranteed, and the lithium ion battery fire extinguishing agent has important significance for promoting the application of the lithium ion battery.
(2) The anticorrosive material in the lithium ion battery extinguishing agent is montmorillonite loaded with active aluminum oxide and urea, the load of the active aluminum oxide and the urea improves the adsorption effect of the montmorillonite, moisture and hydrogen fluoride can be effectively adsorbed, and the lithium ion battery extinguishing agent is not easy to generate high-corrosivity hydrogen fluoride during storage. In the fire extinguishing process, anticorrosive material covers can also play the effect of isolated air on lithium ion battery surface, further improves lithium ion battery fire extinguishing agent's fire extinguishing effect, simultaneously, the aluminium oxide and the urea of load can be with the hydrogen fluoride reaction that the fire extinguishing material decomposes the production in the heating process to the realization is to the high-efficient absorption of water and hydrogen fluoride, is favorable to avoiding moisture and hydrogen fluoride to the corruption of electrical equipment, prevents the secondary damage of fire extinguishing process to electrical equipment.
Drawings
FIG. 1 is a graph showing the cooling curves of comparative examples 1 to 4 of the present invention;
FIG. 2 is a graph showing the temperature drop curves of comparative examples 1, 4 and 5 and example 1 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, 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 terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a lithium ion battery fire extinguishing agent, which comprises 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): (0.2-2): (0.1 to 0.3);
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 has lower boiling point and vaporization heat, can block free radical chain reaction in the combustion process as the fire extinguishing material, and in the fire extinguishing process, the material absorbs heat and vaporizes fast to achieve the effect of fast cooling, but the vaporization process is fast, so that the electrical equipment can not be cooled continuously, and the waste heat in the battery can cause re-combustion. The cooling material has higher boiling point and high heat of vaporization, slowly vaporizes in the fire extinguishing process, can continuously cool the electrical equipment to prevent after combustion, is also a fluorine-containing organic matter, and has certain fire extinguishing performance.
Above-mentioned lithium ion battery fire extinguishing agent includes fire extinguishing material, cooling material and anticorrosive material, and through selecting the fluorine-containing organic matter that heat of vaporization is no longer than 100kJ/kg as fire extinguishing material, the heat of vaporization is higher than the fluorine-containing organic matter of 100kJ/kg as cooling material, makes lithium ion battery fire extinguishing agent have suitable boiling point, high heat of vaporization and high specific heat capacity, has the fire extinguishing performance concurrently simultaneously, can cool down to it at the electrical equipment surface, avoids taking place the risk of reburning. Montmorillonite loaded with active alumina and urea is taken as an anticorrosive material, and can adsorb moisture and hydrogen fluoride in the fire extinguishing agent during storage so as to prevent the container from being corroded; on the other hand, when using, anticorrosive material covers on electrical equipment surface, plays the effect of isolated air, can adsorb the hydrogen fluoride that fire extinguishing material decomposes the production simultaneously, avoids extinguishing agent to produce the secondary damage to 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 temperature reducing 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 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.
in some embodiments, 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).
In some embodiments, the loading amount of the activated alumina and the loading amount of the urea in the anticorrosive material are respectively 3-5% and 6-10% by mass percent.
In some of these examples, the corrosion protection material is prepared according to the following steps S10-S14:
step S10: dispersing montmorillonite in water, adding aluminum isopropoxide, uniformly mixing, and carrying out hydrothermal reaction;
step S12: filtering, drying and calcining the hydrothermal reaction product to obtain montmorillonite loaded with active alumina;
step S14: and soaking the montmorillonite loaded with the active alumina in a urea solution, taking out the montmorillonite, and drying to obtain the anticorrosive material.
In some embodiments, the mass ratio of montmorillonite to water to aluminum isopropoxide is (4-8): (15-25): 1.
in some embodiments, the calcination is performed in an air atmosphere, the calcination temperature is 400-600 ℃, and the calcination time is 3-5 hours.
In some embodiments, the mass concentration of the urea solution is 30-50%, and each 1g of the activated alumina-loaded montmorillonite is soaked in 0.8-1.2 mL of the urea solution for 3-5 h.
The invention also provides a preparation method of the lithium ion battery fire extinguishing agent, which comprises 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.
The invention also provides a lithium ion battery fire extinguisher loaded with the lithium ion battery fire extinguishing agent.
The following are specific examples.
Example 1:
the embodiment provides a special fire extinguishing agent for a lithium ion battery, which comprises perfluorohexanone, 1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (HFE458 for short) and montmorillonite loaded with active alumina and urea, wherein the mass ratio of the perfluorohexanone to the HFE458 to the montmorillonite loaded with the active alumina and the urea is 1:1: 0.2; the loading of the activated alumina in the montmorillonite was 4 wt% and the loading of the urea was 8 wt%.
The preparation method of the special fire extinguishing agent for the lithium ion battery comprises the following steps:
(1) the fire extinguishing material perfluorohexanone and the cooling material HFE458 are mixed according to the mass ratio of 1:1, mixing and uniformly stirring to obtain a compound fire extinguishing agent raw material;
(2) dispersing montmorillonite in water, adding aluminum isopropoxide, controlling the mass ratio of montmorillonite to water to aluminum isopropoxide to be 6:20:1, fully stirring, carrying out hydrothermal reaction in a high-pressure kettle, controlling the temperature of the hydrothermal reaction to be 120 ℃, filtering a product after the reaction is carried out for 48 hours, drying at 80 ℃, calcining in an air atmosphere, heating to 500 ℃ at the heating rate of 1 ℃/min, and calcining for 4 hours to obtain the montmorillonite loaded with active alumina;
(3) fully soaking the activated alumina-loaded montmorillonite obtained in the step (2) in a urea solution with the mass concentration of 40 wt% for 3 hours, and controlling the ratio of the activated alumina-loaded montmorillonite to the urea solution to be 1 g: 1mL, taking out and drying to obtain montmorillonite loaded with active alumina and urea as an anticorrosive material for later use;
(4) and (3) adding the anticorrosive material obtained in the step (3) into the compound fire extinguishing agent raw material, and controlling the mass ratio of the compound fire extinguishing agent raw material to the anticorrosive material to be 2:0.2 to obtain the lithium ion battery fire extinguishing agent.
And (3) sealing and filling the lithium ion battery fire extinguishing agent into a high-pressure container to obtain the lithium ion battery fire extinguisher.
In order to verify the actual fire extinguishing effect of the lithium ion battery fire extinguishing agent prepared by the embodiment on the lithium ion battery, the 32650 ternary lithium battery is subjected to simulated heating at first, and then the special fire extinguishing agent for the lithium ion battery prepared by the embodiment is used for extinguishing the fire. The lithium ion battery starts to generate open fire after being heated for 5 minutes, the lithium ion battery extinguishing agent prepared by the embodiment is sprayed out, the open fire does not exist after 10 seconds, the extinguishing agent is continuously sprayed out for 20 seconds to cool the lithium ion battery, and the flame can be observed to be completely extinguished after 40 seconds and does not re-ignite any more. The observation that the ternary lithium battery is removed shows that the position of the middle part below the lithium battery, in which the heating rod is inserted, is burnt, but under the action of the fire extinguishing agent, flame is extinguished and does not re-burn any more, and other parts of the lithium battery are basically unaffected and do not show corrosion. Therefore, the lithium ion battery fire extinguishing agent prepared by the embodiment can effectively extinguish lithium ion battery fire in time, inhibit re-combustion, avoid corrosion of hydrogen fluoride generated by decomposition of the fire extinguishing agent on the lithium ion battery, effectively avoid fire spreading and harm caused by corrosion, and play an effective protection role on electrical equipment.
Comparative examples 1 to 5:
compared with the fire extinguishing agent in the embodiment 1, the fire extinguishing agent has the difference that the components and the proportion of the raw materials of the compound fire extinguishing agent are changed, the preparation and the corresponding addition of the anticorrosive material are consistent with those of the fire extinguishing agent in the embodiment 1, and the details are not repeated. The components and the mass percentages of the components in the raw materials of the compound fire extinguishing agent of the comparative examples 1-5 are respectively shown in table 1.
Table 1 ingredients and contents of raw materials of compound fire extinguishing agents provided in comparative examples 1-5
| Comparative example | Raw material components and content of compound fire extinguishing agent |
| Comparative example 1 | Perfluorohexanone (100 wt%) |
| Comparative example 2 | Heptafluoropropane (100 wt%) |
| Comparative example 3 | Pentafluorobutane (100 wt%) |
| Comparative example 4 | 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (HFE458) (100 wt%) |
| Comparative example 5 | Perfluorohexanone (75 wt%) and HFE458(25 wt%) |
In order to compare the cooling effect of the fire extinguishing agents provided in example 1 and comparative examples 1 to 5, a cooling experiment was performed on the heating plate using the fire extinguishing agents, and the cooling curves of the fire extinguishing agents in comparative examples 1 to 4 are shown in fig. 1, and the cooling curves of the fire extinguishing agents in comparative examples 1, 4 and 5 and example 1 are shown in fig. 2. Referring to fig. 1, it can be seen that compared to perfluorohexanone and heptafluoropropane, pentafluorobutane and HFE-458 have better long-acting cooling effect, and the temperature still drops significantly after 100 seconds, while perfluorohexanone and heptafluoropropane have only short-acting cooling effect, and the temperature drops more in 100 seconds, and the temperature drops only slightly after 100 seconds. Referring to fig. 2, the fire extinguishing agent of comparative example 5 has perfluorohexanone to HFE-458 mass ratio of 3:1, and the cooling effect is the same as that of comparative example 1. The mass ratio of the perfluorohexanone to the HFE-458 in the fire extinguishing agent of the example 1 is 1:1, and the temperature reduction effect is better than that of the fire extinguishing agent of the comparative example 1 and the fire extinguishing agent of the comparative example 5. See table 2 for cooling data for example 1, comparative example 4, and comparative example 5.
TABLE 2 Cooling data for example 1, comparative example 4 and comparative example 5
In order to further test the ability of the fire extinguishing agent provided by the embodiment 1 and the comparative example to extinguish an open fire, taking the comparative example 4 as an example, and carrying out a fire extinguishing test on the open fire together with the fire extinguishing agent provided by the embodiment 1, it is found that after 30 seconds of ignition, the fire extinguishing agent provided by the comparative example 4 needs 15 seconds to extinguish flames, while the fire extinguishing agent provided by the embodiment 1 needs 8 seconds to extinguish the open fire, so that the fire extinguishing efficiency is higher, and the fire extinguishing agent provided by the embodiment 1 is added with a proper amount of cooling material, so that the cooling effect can be improved while the fire extinguishing effect is ensured, and re-ignition is avoided.
Examples 2 to 10:
embodiments 2 to 10 respectively provide a lithium ion battery fire extinguishing agent, and compared with embodiment 1, the difference lies in that the components and mass ratio of each compound substance in the compound fire extinguishing agent raw materials are changed, and the preparation and corresponding addition of the anticorrosive material are consistent with those of embodiment 1, and are not described herein again. The components and mass ratios of the raw materials of the compound fire extinguishing agents corresponding to examples 2 to 10 are shown in table 3.
Table 3 raw material components of a compound fire extinguishing agent in the fire extinguishing agent for lithium ion batteries provided in embodiments 2 to 10 and corresponding mass ratios thereof
| Examples | Each component of the raw materials of the compound fire extinguishing agent and the corresponding mass ratio thereof |
| Example 2 | Perfluorohexanone pentafluorobutane ═ 0.5:1 |
| Example 3 | Perfluorohexanone HFE 458-2: 1 |
| Example 4 | Heptafluoropropane pentafluorobutane 1:1 |
| Example 5 | HFE458 ═ 1:1, heptafluoropropane |
| Example 6 | 2-bromo-3, 3, 3-trifluoropropene-pentafluorobutane ═ 1:1 |
| Example 7 | HFE458 ═ 1:1, 2-bromo-3, 3, 3-trifluoropropene |
| Example 8 | Perfluorohexanone pentafluorobutane HFE 458: 1:0.5 |
| Example 9 | Heptafluoropropane pentafluorobutane HFE 458: 1:0.5 |
| Example 10 | 2-bromo-3, 3, 3-trifluoropropene pentafluorobutane HFE458 ═ 1:0.5 |
After the fire extinguishing performance test of the lithium ion battery fire extinguishing agent provided by the embodiment 2-10, the lithium ion battery fire extinguishing agent provided by the embodiment 2-10 can enable the prepared fire extinguishing agent to have good fire extinguishing effect and cooling effect, and the effect of effectively extinguishing the lithium ion battery fire and enabling the lithium ion battery fire to be not reburning is achieved. And the lithium ion battery has no obvious corrosion after the fire extinguishing agent is used.
Examples 11 to 17 and comparative examples 6 to 8:
examples 11 to 17 and comparative examples 6 to 8 each provide a lithium ion battery fire extinguishing agent, and compared with example 1, examples 11 to 14 are different in that the loading amounts of activated alumina and urea in montmorillonite are changed by adjusting the mass ratio of montmorillonite to water to aluminum isopropoxide and the concentration of urea solution; the difference between the embodiments 15-16 lies in that the calcining condition in the preparation process of the anticorrosive material is changed; example 17 is different in that a mixture of activated alumina, urea and montmorillonite mechanically mixed is used as an anticorrosive material, and the relative contents of activated alumina, urea and montmorillonite in example 17 are the same as those in example 1; comparative example 6 is different in that montmorillonite loaded with no active alumina and urea was used as the anticorrosive material, comparative example 7 is different in that only active alumina was loaded on montmorillonite, and comparative example 8 is different in that only urea was loaded on montmorillonite. The specific preparation method adjusts the corresponding steps according to the differences from embodiment 1, which is not repeated herein.
The loading amounts of activated alumina and urea and the calcination conditions for examples 11 to 16 are shown in Table 4.
TABLE 4 Loading amounts of activated alumina and urea and calcination conditions in examples 11 to 16
The method comprises the steps of carrying out simulated heating on a 32650 ternary lithium battery according to the mode provided by the embodiment 1, and extinguishing the fire of the lithium battery subjected to simulated heating by using the fire extinguishing agents prepared in the embodiments 11-16 respectively, wherein after the fire extinguishing agents are continuously sprayed for 40 seconds, the fire extinguishing agents prepared in the embodiments 11-16 can completely extinguish flames without re-combustion, which shows that the fire extinguishing and cooling effects of the fire extinguishing agents are not greatly influenced by properly adjusting the loading amounts of active alumina and urea and corresponding calcination conditions within a certain range, and the fire extinguishing agents prepared in the embodiments can effectively extinguish the lithium ion battery fire in time and inhibit the re-combustion.
In order to further compare the corrosion resistance differences among the examples 1, 11 to 17 and 6 to 8, the corrosion of the fire extinguishing agents prepared in the above examples and comparative examples on the metal steel sheet was tested by taking the metal steel sheet as an example, and the fluorine ion concentration of the fire extinguishing agent after spraying was tested. The specific test steps are as follows:
test I, corrosion test on metal steel sheet
A Q355 metal steel sheet was selected for the test, and after being polished, cleaned and dried, the weight thereof was weighed. And then placing a metal steel sheet between the high-pressure steel cylinder filled with the fire extinguishing agent to be detected and the simulated heating ternary lithium battery, so that the metal steel sheet is positioned 50cm under the fire extinguishing agent nozzle. And after the ternary lithium battery is ignited, spraying a fire extinguishing agent for 40s, waiting for 2h, weighing the metal steel sheet again, and calculating the weight loss rate of the metal steel sheet.
Test II, fluorine ion concentration test after spraying fire extinguishing agent
Mixing 10mL of 0.1mol/L fluorine ion standard solution with 10mL of total ion intensity adjusting buffer solution, and diluting to 100mL with fluorine-free distilled water to obtain 10-2A mol/L fluorine ion solution; the obtained 10mL solution was adjusted to a concentration of 10-2mixing the mol/L fluoride ion solution with 10mL total ion intensity adjusting buffer solution, and metering to 100mL according to the same method to obtain the product with the concentration of 10-3A mol/L fluorine ion solution; then, the concentration is respectively prepared to be 10 in the same way-4、10-5、10-6、10-7The fluorine ion solution of mol/L is measured, and the concentration is respectively 10-2、10-3、10-4、10-5、10-6、10-7The steady state potential values of the mol/L fluorine ion solution are 351mV, 338mV, 287mV, 227mV, 166mV and 109mV respectively, thereby obtaining the relationship between the fluorine ion concentration and the steady state potential value of the fluorine ion solution.
And then placing a collecting container at a position corresponding to the metal steel sheet in the first test, collecting the sprayed fire extinguishing agent, filtering the fire extinguishing agent, taking 10mL of the filtered fire extinguishing agent as a solution to be tested, mixing the filtered fire extinguishing agent with 10mL of total ion intensity adjusting buffer solution, using fluorine-free distilled water to fix the volume to 100mL, measuring the steady-state potential value of the solution, and estimating the concentration of the fluorine ions according to the relation between the obtained concentration of the fluorine ions and the steady-state potential value of the fluorine ion solution.
The weight loss ratio, the steady-state potential value and the fluorine ion concentration of the metal steel sheet measured according to the above-mentioned test methods are shown in Table 5.
TABLE 5 corrosiveness and fluorine ion concentration of the fire extinguishing agents of example 1, examples 11 to 17, and comparative examples 6 to 8 on the metal steel sheet
As can be seen in connection with table 5: the prepared fire extinguishing agent can achieve better anticorrosion effect while ensuring the fire extinguishing and cooling effects by properly adjusting the loading amounts of the activated alumina and the urea and corresponding calcination conditions within a certain range, and the measured lower weight loss rate and fluorine ion concentration of the steel sheet show that moisture and hydrogen fluoride contained in the fire extinguishing agent can be effectively adsorbed by an anticorrosion material, so that secondary damage to electrical equipment including a lithium ion battery can be avoided. However, the fire extinguishing agent of comparative example 6, which uses natural montmorillonite as the anticorrosive material, has a weight loss rate and a fluorine ion concentration which are obviously higher than those of the examples, which indicates that when unmodified montmorillonite is used as the anticorrosive material, the absorption of moisture and hydrogen fluoride in the fire extinguishing agent is limited, the moisture and hydrogen fluoride in the fire extinguishing agent cause severe corrosion to electrical equipment, and the lithium ion battery which is not burnt out after fire extinguishing still causes corrosive damage to affect the normal use of the lithium ion battery. The anticorrosive material added in the mechanical mixing manner in example 17 can achieve a certain anticorrosive effect, but the weight loss rate and the steady-state potential value measured by the anticorrosive material are still higher than those in examples 11 to 16, mainly because the montmorillonite cannot be modified in the mechanical mixing process, the adsorption effect of the montmorillonite at high temperature is limited, and the dispersion effect of each raw material is poor, so that the overall anticorrosive effect is still weaker than those in examples 11 to 16. When the comparative examples 7 and 8 are respectively loaded with single active alumina or urea, the measured weight loss rate and steady-state potential value are obviously higher than those of the examples of the invention, mainly because the single loading mode not only reduces the raw materials capable of reacting with water and hydrogen fluoride, but also is difficult to effectively modify the montmorillonite, thereby influencing the overall anticorrosion effect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall 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.
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| PCT/CN2021/095631 WO2022227153A1 (en) | 2021-04-26 | 2021-05-25 | Lithium ion battery fire extinguishing agent, preparation method therefor and use thereof |
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| CN115671641B (en) * | 2022-10-27 | 2023-10-20 | 国网浙江省电力有限公司湖州供电公司 | High-vaporization heat porous fire extinguishing medium applied to electrochemical energy storage system and preparation method thereof |
| CN116251324B (en) * | 2022-12-06 | 2024-06-11 | 北京理工大学 | Quick-cooling lithium ion battery extinguishing agent and preparation method thereof |
| CN116459484A (en) * | 2023-03-21 | 2023-07-21 | 广西电网有限责任公司防城港供电局 | Fire extinguishing agent composition, preparation method of fire extinguishing composition and fire extinguishing device |
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| US7223351B2 (en) * | 2003-04-17 | 2007-05-29 | Great Lakes Chemical Corporation | Fire extinguishing mixtures, methods and systems |
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