CN113209541B - Novel lithium battery fire extinguishing agent and preparation method thereof - Google Patents
Novel lithium battery fire extinguishing agent and preparation method thereof Download PDFInfo
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- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
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Abstract
The invention discloses a novel lithium battery fire extinguishing agent and a preparation method thereof, wherein the novel lithium battery fire extinguishing agent consists of a fire retardant, an adsorbent, sodium bicarbonate, a foaming agent, a foam stabilizer and water; the flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate; the adsorbent is at least one of aluminum hydroxide, activated carbon, vermiculite and modified vermiculite. The novel lithium battery extinguishing agent disclosed by the invention has the advantages of lasting foam, strong cooling capacity and capability of effectively adsorbing harmful gases such as hydrogen fluoride and the like.
Description
Technical Field
The invention relates to the technical field of lithium battery extinguishing agents, in particular to a novel lithium battery extinguishing agent and a preparation method thereof.
Background
With the increasing emphasis on environmental protection in China and the great reduction of the production cost of lithium batteries, the adoption of lithium ion batteries as new energy to replace traditional energy has become the first step of low-carbon economy in China, and the lithium ion batteries are widely applied to the fields of traffic, energy storage and the like. Although the large-scale application of the lithium battery improves the environment and realizes the beneficial effects of low carbon, energy conservation, environmental protection and the like, the safety problem caused by the large-scale application of the lithium battery is not ignored.
Lithium ion battery fire is different from common fire greatly, and is used as an energy aggregate, after thermal runaway occurs, the fire is caused by heat generated in the center of the battery, the conventional method for isolating oxygen through physical dilution or cutting off a combustion chain cannot completely extinguish the lithium battery fire, and water extinguishment can cause short circuit and cause greater danger. The existing fire extinguishing agent such as heptafluoropropane only can extinguish open fire, cannot fundamentally inhibit fire from happening, frequently causes re-ignition later, and the repeated re-ignition of lithium batteries is a great challenge for the existing fire extinguishing system. And a large amount of toxic gases, such as PF3 (phosphorus trifluoride), PF5 (phosphorus pentafluoride), HF (hydrogen fluoride, also called hydrofluoric acid) and POF3 (phosphorus oxyfluoride), are released by the combustion of the lithium battery, so that the lithium battery pollutes the environment and is harmful to human health.
At present, the safe and efficient lithium battery extinguishing agent capable of effectively preventing the fire re-burning of the lithium battery and preventing the diffusion of harmful gases is a difficult problem.
CN 110368631A discloses a lithium ion battery foam extinguishing agent and a preparation method thereof, wherein a traditional fluorocarbon surfactant is used as a foaming agent for forming a film by water, so that the problem of environmental pollution is solved, the temperature is reduced by using the heat absorption and gasification principle of dodecafluoro-2-methyl-3-pentanone, the cooling rate is poor, the performance of isolating oxygen is weaker, and the problem of environmental pollution caused by harmful gases such as HF (hydrogen fluoride) and the like generated by battery combustion is not solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel lithium battery fire extinguishing agent and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a novel lithium battery fire extinguishing agent comprises the following raw materials: flame retardant, adsorbent, sodium bicarbonate, foaming agent, foam stabilizer and water.
As a preferred scheme, the novel lithium battery fire extinguishing agent is prepared from the following raw materials in parts by weight: 4-7 parts of flame retardant, 10-14 parts of adsorbent, 5-8 parts of sodium bicarbonate, 18-21 parts of foaming agent, 11-13 parts of foam stabilizer and 42-53 parts of water.
The flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate.
As a preferable scheme, the flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate in a mass ratio of (6-9): 1.
The adsorbent is at least one of aluminum hydroxide, activated carbon, vermiculite and modified vermiculite.
Preferably, the adsorbent is a mixture of aluminum hydroxide, activated carbon and modified vermiculite in a mass ratio of (6-10) to (1-5) to (10-23).
The foaming agent is at least one of hexadecyl sulfobetaine and 3-sulfopropyl dodecyl dimethyl betaine.
Preferably, the foaming agent is a mixture of hexadecyl sulfobetaine and 3-sulfopropyl dodecyl dimethyl betaine according to the mass ratio of (1-6) to (1-6).
The foam stabilizer is at least one of ethylene glycol, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether.
As a preferable scheme, the foam stabilizer is a mixture of ethylene glycol, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether according to the mass ratio of (1-4) to (1-4).
The preparation method of the novel lithium battery fire extinguishing agent comprises the following steps:
p1 mixing foaming agent, foam stabilizer and water, heating and stirring, and filtering to obtain intermediate A;
adding an adsorbent and a flame retardant into the intermediate product A obtained from P1 by using P2, stirring, and cooling to obtain an intermediate product B;
and P3, adding sodium bicarbonate into the intermediate product B obtained from P2, and stirring to obtain the novel lithium battery extinguishing agent.
As a preferable scheme, the preparation method of the novel lithium battery fire extinguishing agent comprises the following steps:
p1 mixing foaming agent, foam stabilizer and water according to the raw material formula, heating to 68-73 ℃, stirring at the rotating speed of 100-150r/min for 3-5min, and filtering to obtain an intermediate product A;
adding an adsorbent and a flame retardant into the intermediate product A obtained from P1 by P2, stirring at the temperature of 38-43 ℃ at the rotating speed of 80-120r/min for 1-3min, and cooling to 22-28 ℃ to obtain an intermediate product B;
and (3) adding sodium bicarbonate into the intermediate product B obtained from the P2 at the temperature of 22-28 ℃, and stirring at the rotating speed of 80-120r/min for 1-5min to obtain the novel lithium battery extinguishing agent.
The preparation method of the modified vermiculite comprises the following steps:
n1, ball milling vermiculite by a planetary ball mill through a wet milling method to obtain vermiculite powder; the wet grinding auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B to obtain the vermiculite powder;
n2 mixing and homogenizing a modifier, a dispersant and an alcohol amine solvent to obtain a modified treatment solution; the alcohol amine solvent is a mixture of at least one of isopropanolamine, N-butyldiethanolamine and diisopropanolamine and water; the modifier is at least one of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane; the dispersant is at least one of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened and acidized aluminum hydroxide;
n3 mixing the vermiculite powder with the denaturation treatment liquid, then treating with ultrasonic wave and ultra-high frequency ultraviolet radiation, filtering to obtain precipitate C, and drying the precipitate C to obtain the denaturation vermiculite.
As a preferable scheme, the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain 1000-mesh 1100-mesh vermiculite powder; in the ball milling process, zirconia grinding balls with two sizes of 0.8-1mm and 1.5-1.8mm in diameter are mixed according to the mass ratio of (0.8-1.2) to 2, the ball material ratio is (15-18) to 1, the rotating speed of the planetary ball mill is 600-900r/min, the ball milling time is 16-20h, a wet milling aid is a mixture of polyoxyethylene sorbitan monooleate and water according to the mass ratio of 1 (6-8), and the mass ratio of the wet milling aid to vermiculite is (1.5-1.8) to 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 72-77 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1 (10-14), the water temperature is 35-45 ℃, ultrasonic wave with power of 330-;
n2 at 20-30 ℃, mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of (6-8) to (0.2-0.5) to (16-19) and homogenizing at the rotation speed of 10000-; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of (4-6) to (2-4) to (1-2.2) to (8-12); the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of (1-3) to (1-3); the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of (1-4) to (1-3) to (1.5-2.2);
n3 mixing the vermiculite powder and the denaturation treatment liquid according to the mass ratio of 1 (7-10), then treating for 5-7h by combining ultrasonic wave and ultrahigh frequency ultraviolet radiation, then filtering to obtain precipitate C, and drying the precipitate C at 75-85 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 380-420W, and the frequency is 38-43 kHz; the wavelength of the ultrahigh frequency ultraviolet light is 82-87nm, and the power is 320-370W; the drying time is 4-6 h.
In the prior art, most of the fire extinguishing agents for the lithium battery have poor cooling capability and cannot effectively prevent the secondary damage phenomenon of toxic gases such as hydrogen fluoride and the like generated by the combustion of the lithium battery. The vermiculite has a loose porous structure, and the surface tension and the capillary action of the inner cavity of the vermiculite ensure that the vermiculite has extremely strong adsorption effect on various harmful gases; however, since vermiculite is an inorganic crystalline mineral composed of silicate crystals, sharp crystal face corners exist whether ground to be finer, and these sharp corners weaken the integrity and stability of the foam, causing the foam to be punctured prematurely at the physical level, and greatly compromising the fire extinguishing effect of the foam extinguishing agent. Accordingly, the present invention is directed to a modified vermiculite and a method for preparing the same, which is used in a lithium battery fire extinguishing agent to obtain a modified vermiculite powder that can adsorb toxic gases such as hydrogen fluoride generated by combustion of a lithium battery, without impairing the stability of thermal insulation/oxygen barrier foam inherent in a foam fire extinguishing agent. In addition, the modified vermiculite powder prepared by the specific method has good synergistic effect with the activated carbon and the aluminum hydroxide, and the absorption capacity of toxic gases including hydrogen fluoride can be further improved by combining the modified vermiculite powder, the activated carbon and the aluminum hydroxide. According to the invention, polyoxyethylene sorbitan monooleate and water are combined to be used as a wet grinding aid, so that the particle size of the vermiculite powder obtained after ball milling is smaller, the particle size distribution is more concentrated, the uniformity is higher, and the obtained vermiculite powder has the surface structure characteristics of more roundness and less sharp edges and corners, and the problem that foams are easily scratched by inorganic crystal minerals is effectively solved on a physical level. The invention adopts the combination of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane as a modifier for the surface modification treatment of the vermiculite powder; the hexaphenylcyclotrisiloxane is centrosymmetric and contains a structure with rich benzene rings and a silicon-oxygen circular ring structure of decamethylcyclopentasiloxane can be grafted on the corner of a vermiculite crystal face with higher free energy and more active chemical activity, so that the modifier can be used for wrapping a sharp crystal face angle on the layer of a chemical bond, and the modified vermiculite powder is ensured not to damage the stability of foam. The invention adopts the alcohol amine solvent consisting of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water as the liquid atmosphere generated by the modified vermiculite powder, which is beneficial to the attraction orientation relation and the attraction magnitude relation of negative electricity centers formed between oxygen atoms and nitrogen atoms in the molecules of the three alcohol amines, and can promote the modifier to be grafted on the surface of the vermiculite powder. The bis (sec-butyl alcohol) tetraethylorthosilicate aluminum salt in the dispersant adopted by the invention can improve the dispersibility of the vermiculite powder in a denaturation treatment reaction atmosphere, and the sec-butyl alcohol branched chain structure of the aluminum salt can improve the surface tension in a porous cavity inside the vermiculite, so that the adsorption capacity of the denatured vermiculite powder on toxic gases such as hydrogen fluoride is further improved. The invention adopts the combined treatment of ultrasonic waves and ultrahigh frequency ultraviolet rays to provide necessary excitation capability for the modification process of vermiculite, fully promotes the modification treatment process of the surface of the vermiculite powder on the dynamic level, and obtains the fire extinguishing agent with better foam stability. In addition to being used as a conventional foam stabilizer, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether have the size relationship between topological molecular polarity surface areas, so that the triethylene glycol monobutyl ether and the tetraethylene glycol monobutyl ether have a synergistic effect with the modified vermiculite prepared by the specific method, the foam stability is enhanced, the adsorption effect of the modified vermiculite on hydrogen fluoride is promoted, and an unexpected technical effect is generated.
The invention has the beneficial effects that:
1. the invention provides a novel lithium battery fire extinguishing agent, wherein a mixture of (trimethylsilyl) phosphite and zinc borate is used as a fire retardant, at least one of aluminum hydroxide, activated carbon, vermiculite and modified vermiculite is used as an adsorbent, and at least one of ethylene glycol, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether is used as a foam stabilizer.
2. The adsorbent adopts modified vermiculite, hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane are used as modifiers in the preparation method, aluminum starch octenylsuccinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened and esterified aluminum hydroxide are used as dispersants, a mixture of ethylene glycol, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether and water is used as a dispersant, and the modified vermiculite is enabled to obtain a more round particle micro surface structure and charge distribution of a porous inner cavity which is more favorable for adsorbing harmful gases including hydrogen fluoride through a wet grinding method, ultrasonic waves and an ultrahigh frequency ultraviolet lamp means, so that the foam stability, fire extinguishing and cooling capacities of the fire extinguishing agent and the adsorption capacity of the fire extinguishing agent on the harmful gases including hydrogen fluoride are improved.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
aluminum hydroxide, particle size: 1 μm, sandisk material ltd, hong kong.
(trimethylsilyl) phosphite, CAS No.: 1795-31-9, Hubei, Spanish technologies, Inc.
Zinc borate, CAS No.: 1332-07-6, west Asia chemical technology (Shandong) Ltd, particle size 1 μm.
Activated carbon, CAS No.: 64365-11-3, particle size: 325 mesh, Shanghai Xinhui activated carbon Co., Ltd.
Hexadecylsultaine, CAS No.: 2281-11-0, available from Hippocampus Chemicals, Inc.
3-sulfopropyl dodecyl dimethyl betaine, CAS No.: 14933-08-5, west Asia chemical technology (Shandong) Inc.
Vermiculite, CAS number: 1318-00-9, Bailingwei science and technology Limited, particle size 750 mesh, impurity content less than or equal to 1 wt.%.
Polyoxyethylene sorbitan monooleate, CAS number: 9005-65-6, Bailingwei technologies, Inc.
Isopropanolamine, CAS No.: 78-96-6, Bailingwei technologies, Inc.
N-butyldiethanolamine, CAS No.: 102-79-4, welenger technologies ltd.
Diisopropanolamine, CAS No.: 110-97-4, Bailingwei technologies, Inc.
Hexaphenylcyclotrisiloxane, CAS No.: 512-63-0, Bailingwei technologies, Inc.
Decamethylcyclopentasiloxane, CAS No.: 541-02-6, Bailingwei Technology Ltd.
Aluminum starch octenyl succinate, CAS No.: 9087-61-0, Saen chemical technology, Inc.
Bis (sec-butanol) orthosilicate triethyl orthosilicate aluminum salt, CAS: 68959-06-8, Sahn chemical science and technology, Inc.
Benzoic acid stearic acid aluminum hydroxide, CAS: 54326-11-3, Saen chemical technology, Inc.
Example 1
A novel lithium battery fire extinguishing agent is composed of the following raw materials in parts by weight:
6 parts by weight of a flame retardant, 12 parts by weight of an adsorbent, 6 parts by weight of sodium bicarbonate, 20 parts by weight of a foaming agent, 12 parts by weight of a foam stabilizer, and 44 parts by weight of water.
The flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate according to a mass ratio of 7: 1.
The adsorbent is a mixture of aluminum hydroxide, activated carbon and modified vermiculite in a mass ratio of 8:4: 17.
The foaming agent is a mixture of hexadecyl sulfobetaine and 3-sulfopropyl dodecyl dimethyl betaine according to a mass ratio of 5: 3.
The foam stabilizer is a mixture of ethylene glycol, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether according to the mass ratio of 1:3: 2.
The preparation method of the novel lithium battery fire extinguishing agent comprises the following steps:
p1 mixing foaming agent, foam stabilizer and water according to the formula of the raw materials, heating to 70 ℃, stirring for 4min at the rotating speed of 140r/min, and filtering to obtain an intermediate product A;
p2 adding adsorbent and fire retardant into intermediate product A obtained from P1, stirring at 40 deg.C at 100r/min for 2min, and cooling to 25 deg.C to obtain intermediate product B;
and P3, adding sodium bicarbonate into the intermediate product B obtained from P2 at 25 ℃, and stirring at the rotating speed of 100r/min for 3min to obtain the novel lithium battery extinguishing agent.
The preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 2
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is hexaphenylcyclotrisiloxane; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 3
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is decamethylcyclopentasiloxane; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 4
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture of starch octenyl succinic acid aluminum and benzoic acid hard ester acidification aluminum hydroxide in a mass ratio of 3: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 5
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the ethanol water solution at the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the mass fraction of ethanol in the ethanol water solution is 40%; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 6
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then irradiating for 6 hours by ultrahigh frequency ultraviolet rays, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 7
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out ultrasonic treatment for 6h, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the drying time is 5 h.
Example 8
Essentially the same as in example 1, except that:
the preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a dry milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, and the ball milling time is 18 h; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 9
A novel lithium battery fire extinguishing agent is composed of the following raw materials in parts by weight:
6 parts by weight of a flame retardant, 12 parts by weight of an adsorbent, 6 parts by weight of sodium bicarbonate, 20 parts by weight of a foaming agent, 12 parts by weight of a foam stabilizer, and 44 parts by weight of water.
The flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate according to a mass ratio of 7: 1.
The adsorbent is a mixture of aluminum hydroxide, activated carbon and modified vermiculite in a mass ratio of 8:4: 17.
The foaming agent is a mixture of hexadecyl sulfobetaine and 3-sulfopropyl dodecyl dimethyl betaine according to a mass ratio of 5: 3.
The foam stabilizer is ethylene glycol.
The preparation method of the novel lithium battery fire extinguishing agent comprises the following steps:
p1 mixing foaming agent, foam stabilizer and water according to the formula of the raw materials, heating to 70 ℃, stirring for 4min at the rotating speed of 140r/min, and filtering to obtain an intermediate product A;
p2 adding adsorbent and fire retardant into intermediate product A obtained from P1, stirring at 40 deg.C at 100r/min for 2min, and cooling to 25 deg.C to obtain intermediate product B;
and P3, adding sodium bicarbonate into the intermediate product B obtained from P2 at 25 ℃, and stirring at the rotating speed of 100r/min for 3min to obtain the novel lithium battery extinguishing agent.
The preparation method of the modified vermiculite comprises the following steps:
n1 ball milling vermiculite with a planetary ball mill by a wet milling method to obtain vermiculite powder with the grain size of 1100 meshes; in the ball milling process, zirconia grinding balls with diameters of 0.9mm and 1.7mm are mixed according to a mass ratio of 1:2, the ball-material ratio is 17:1, the rotating speed of the planetary ball mill is 800r/min, the ball milling time is 18 hours, a wet milling auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water according to a mass ratio of 1:7, and the mass ratio of the wet milling auxiliary agent to vermiculite is 1.8: 1; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B at 75 ℃ to obtain the vermiculite powder; the mass ratio of the sediment A to water is 1:12, the water temperature is 40 ℃, ultrasonic assistance with the power of 350W and the frequency of 45kHz is adopted during cleaning, and the drying time is 6 hours;
n2 mixing the modifier, the dispersant and the alcohol amine solvent according to the mass ratio of 7:0.5:18 at 25 ℃, and homogenizing at the rotating speed of 14000r/min for 2min to obtain a modified treatment solution; the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water in a mass ratio of 5:3:2: 10; the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane in a mass ratio of 3: 2; the dispersing agent is a mixture consisting of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened esterification hydroxide in a mass ratio of 3:1: 2;
n3 mixing the vermiculite powder and the denaturation treatment liquid in a mass ratio of 1:9, then carrying out combined treatment on the mixture for 6 hours by ultrasonic waves and ultrahigh frequency ultraviolet irradiation, then filtering to obtain precipitate C, and drying the precipitate C at 80 ℃ to obtain the denaturation vermiculite; the power of the ultrasonic wave is 400W, and the frequency is 40 kHz; the wavelength of the ultrahigh frequency ultraviolet ray is 86nm, and the power of the ultrahigh frequency ultraviolet ray is 350W; the drying time is 5 h.
Example 10
A novel lithium battery fire extinguishing agent is composed of the following raw materials in parts by weight:
6 parts by weight of a flame retardant, 12 parts by weight of an adsorbent, 6 parts by weight of sodium bicarbonate, 20 parts by weight of a foaming agent, 12 parts by weight of a foam stabilizer, and 44 parts by weight of water.
The flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate according to a mass ratio of 7: 1.
The adsorbent is a mixture of aluminum hydroxide, activated carbon and vermiculite in a mass ratio of 8:4: 17.
The foaming agent is a mixture of hexadecyl sulfobetaine and 3-sulfopropyl dodecyl dimethyl betaine according to a mass ratio of 5: 3.
The foam stabilizer is a mixture of ethylene glycol, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether according to the mass ratio of 1:3: 2.
The preparation method of the novel lithium battery fire extinguishing agent comprises the following steps:
p1 mixing foaming agent, foam stabilizer and water according to the formula of the raw materials, heating to 70 ℃, stirring for 4min at the rotating speed of 140r/min, and filtering to obtain an intermediate product A;
p2 adding adsorbent and fire retardant into intermediate product A obtained from P1, stirring at 40 deg.C at 100r/min for 2min, and cooling to 25 deg.C to obtain intermediate product B;
and P3, adding sodium bicarbonate into the intermediate product B obtained from P2 at 25 ℃, and stirring at the rotating speed of 100r/min for 3min to obtain the novel lithium battery extinguishing agent.
Test example 1
And (3) testing a combustion test: 12 lithium batteries for testing are connected in parallel and then placed on a heating plate, wherein the power of the heating plate is 1kW, the temperature is set to be 600 ℃, and the size is 210mm multiplied by 170mm multiplied by 15 mm; turning off the power supply after the battery is charged to 100% SOC; the heating plate is heated up uniformly, and the heating rate is 20 ℃/min. A thermal imaging camera which is produced by Philier corporation of America and has the model of FLIR T540 is adopted to record the central temperature change of the lithium battery, and the temperature measuring range is 0-1200 ℃. When the battery is out of control due to heat until the shell explodes for 20s, the fire extinguishing agent obtained by each embodiment of the invention is sprayed on the heating plate, and the central temperature of the lithium battery is measured and recorded at the same time and is recorded once every 1 min; the spraying flow rate is 0.4L/s, and the spraying time is 5 s. Set up a set of parallel contrast experiment, adopt water to put out a fire, the spraying time to the hot plate is 5s together. The test results are shown in table 1. The technical parameters of the lithium batteries for the test are shown in table 2.
TABLE 1 internal temperature of lithium batteries as a function of time
TABLE 2 technical parameters of lithium batteries for testing
Therefore, the fire extinguishing agent obtained by the embodiments of the invention has good effects of extinguishing fire, reducing temperature and restraining secondary disasters (such as smoldering and reburning) for the thermal runaway phenomenon of the lithium battery.
Test example 2
Hydrogen fluoride adsorption test: spraying the fire extinguishing agent obtained in each example into a glass tank filled with hydrogen fluoride gas at 25 ℃; after spraying, waiting for 10min, respectively testing the light absorption value of the gas in the glass tank, and calculating the residual amount M of the hydrogen fluoride in the gas in the glass tank after spraying1(unit is mol/L); the content of hydrogen fluoride in the glass tank gas before spraying is M0（M0=0.3 mol/L), from which the adsorption rate of the fire extinguishing agent to hydrogen fluoride can be calculated as (M)0-M1）/M0X is 100%; straight of the glass tankThe diameter is 1m, the height is 1.6m, the air pressure inside and outside the glass tank is consistent, and the air is the rest except the hydrogen fluoride in the glass tank; the spraying flow rate of the fire extinguishing agent in each example is 0.4L/s, and the spraying time is 2 s. The test results are shown in table 2.
TABLE 2 test results of adsorption rate of novel lithium battery fire extinguishing agent to hydrogen fluoride
Therefore, the fire extinguishing agent prepared by the specific methods has excellent adsorption effect on hydrogen fluoride gas, and can prevent the hydrogen fluoride gas generated by the combustion of the lithium battery from diffusing and damaging people.
The vermiculite has a loose porous structure, and the surface tension and the capillary action of the inner cavity of the vermiculite ensure that the vermiculite has extremely strong adsorption effect on various harmful gases; however, since vermiculite is an inorganic crystal mineral composed of silicate crystals, sharp crystal face edges exist no matter the vermiculite is ground to be fine, and the sharp edges weaken the integrity and stability of foam, so that the foam is punctured prematurely at a physical layer, and the fire extinguishing effect of the foam extinguishing agent is greatly reduced; accordingly, the present invention is directed to provide a modified vermiculite powder which can adsorb toxic gases such as hydrogen fluoride generated by combustion of a lithium battery, without impairing the stability of heat insulating/oxygen insulating foam inherent in a foam extinguishing agent, and a method for preparing the same. According to the invention, polyoxyethylene sorbitan monooleate and water are combined to be used as a wet grinding aid, so that the particle size of the vermiculite powder obtained after ball milling is smaller, the particle size distribution is more concentrated, the uniformity is higher, and the obtained vermiculite powder has the surface structure characteristics of more roundness and less sharp edges and corners, and the problem that foams are easily scratched by inorganic crystal minerals is effectively solved on a physical level. In addition, the modified vermiculite powder prepared by the specific method has good synergistic effect with the activated carbon and the aluminum hydroxide, and the absorption capacity of toxic gases including hydrogen fluoride can be further improved by combining the modified vermiculite powder, the activated carbon and the aluminum hydroxide. The invention adopts the combination of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane as a modifier for the surface modification treatment of the vermiculite powder; the hexaphenylcyclotrisiloxane is centrosymmetric and contains a structure with rich benzene rings and a silicon-oxygen circular ring structure of decamethylcyclopentasiloxane can be grafted on the corner of a vermiculite crystal face with higher free energy and more active chemical activity, so that the modifier can be used for wrapping a sharp crystal face angle on the layer of a chemical bond, and the modified vermiculite powder is ensured not to damage the stability of foam. The invention adopts the alcohol amine solvent consisting of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water as the liquid atmosphere generated by the modified vermiculite powder, which is beneficial to the attraction orientation relation and the attraction magnitude relation of negative electricity centers formed between oxygen atoms and nitrogen atoms in the molecules of the three alcohol amines, and can promote the modifier to be grafted on the surface of the vermiculite powder. The bis (sec-butyl alcohol) tetraethylorthosilicate aluminum salt in the dispersant adopted by the invention can improve the dispersibility of the vermiculite powder in a denaturation treatment reaction atmosphere, and the sec-butyl alcohol branched chain structure of the aluminum salt can improve the surface tension in a porous cavity inside the vermiculite, so that the adsorption capacity of the denatured vermiculite powder on toxic gases such as hydrogen fluoride is further improved. The invention adopts the combined treatment of ultrasonic waves and ultrahigh frequency ultraviolet rays to provide necessary excitation capability for the modification process of vermiculite, fully promotes the modification treatment process of the surface of the vermiculite powder on the dynamic level, and obtains the fire extinguishing agent with better foam stability. In addition to being used as a conventional foam stabilizer, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether have the size relationship between topological molecular polarity surface areas, so that the triethylene glycol monobutyl ether and the tetraethylene glycol monobutyl ether have a synergistic effect with the modified vermiculite prepared by the specific method, the foam stability is enhanced, the adsorption effect of the modified vermiculite on hydrogen fluoride is promoted, and an unexpected technical effect is generated.
Claims (5)
1. A preparation method of a novel lithium battery fire extinguishing agent is characterized by comprising the following steps:
the novel lithium battery extinguishing agent is prepared from the following raw materials in parts by weight: 4-7 parts of flame retardant, 10-14 parts of adsorbent, 5-8 parts of sodium bicarbonate, 18-21 parts of foaming agent, 11-13 parts of foam stabilizer and 42-53 parts of water;
p1 mixing foaming agent, foam stabilizer and water, heating and stirring, and filtering to obtain intermediate A;
adding an adsorbent and a flame retardant into the intermediate product A obtained from P1 by using P2, stirring, and cooling to obtain an intermediate product B;
adding sodium bicarbonate into the intermediate product B obtained from the step P2 by the step P3, and stirring to obtain the novel lithium battery extinguishing agent;
the flame retardant is a mixture of (trimethylsilyl) phosphite and zinc borate;
the adsorbent is a mixture of aluminum hydroxide, activated carbon and modified vermiculite;
the foaming agent is a mixture of hexadecyl sulfobetaine and 3-sulfopropyl dodecyl dimethyl betaine;
the foam stabilizer is a mixture of ethylene glycol, triethylene glycol monobutyl ether and tetraethylene glycol monobutyl ether;
the preparation method of the modified vermiculite comprises the following steps:
n1, ball milling vermiculite by a planetary ball mill through a wet milling method to obtain vermiculite powder; the wet grinding auxiliary agent is a mixture of polyoxyethylene sorbitan monooleate and water; filtering to obtain a precipitate A after the ball milling is finished, washing the precipitate A with water, filtering again to obtain a precipitate B, and drying the precipitate B to obtain the vermiculite powder;
n2 mixing and homogenizing a modifier, a dispersant and an alcohol amine solvent to obtain a modified treatment solution;
n3 mixing the vermiculite powder with the denaturation treatment liquid, then treating with ultrasonic wave and ultra-high frequency ultraviolet radiation, filtering to obtain precipitate C, and drying the precipitate C to obtain the denaturation vermiculite.
2. The method for preparing a novel lithium battery fire extinguishing agent as claimed in claim 1, wherein: the modifier is a mixture of hexaphenylcyclotrisiloxane and decamethylcyclopentasiloxane.
3. The method for preparing a novel lithium battery fire extinguishing agent as claimed in claim 1, wherein: the dispersant is a mixture of aluminum starch octenyl succinate, aluminum bis (sec-butyl alcohol) orthosilicate triethyl orthosilicate and aluminum benzoate hardened and acidized aluminum hydroxide.
4. The method for preparing a novel lithium battery fire extinguishing agent as claimed in claim 1, wherein: the alcohol amine solvent is a mixture of isopropanolamine, N-butyldiethanolamine, diisopropanolamine and water.
5. A novel lithium battery fire extinguishing agent is characterized in that: obtained by the production method according to any one of claims 1 to 4.
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