Compound fire extinguishing agent for lithium ion battery and preparation method thereof

Abstract

The application relates to the technical field of lithium ion battery fire extinguishing agents, and discloses a compounded lithium ion battery fire extinguishing agent and a preparation method thereof, which comprises the following raw materials in parts by mass: vermiculite 30-35 parts, fire extinguishing filler 5-7 parts, modified zeolite 6-8 parts, stabilizer 0.5-1 part, dispersant 1.5-2 parts, thickening agent 1-2 parts, foaming agent 1-3 parts and water 40-50 parts. The fire extinguishing filler can form a barrier layer on the surface of the battery, prevents oxygen and heat from being transmitted, achieves the fire extinguishing purpose, and the starch and polydopamine in the fire extinguishing filler can form a dense carbon layer, so that the wrapped combustible molecules are distributed between the carbon layers, oxygen is further isolated, and the fire extinguishing efficiency is improved; the modified zeolite can complete the fire extinguishing through physical and chemical synergistic effects, and the modified zeolite can form silicon dioxide distributed on the surface of the zeolite in the fire extinguishing process, so that the zeolite is prevented from being subjected to heat shock and thermal stress to cause the collapse of the zeolite framework and affect the fire extinguishing performance.

Description

Technical Field

[0001] This invention relates to the field of lithium-ion battery fire extinguishing agent technology, specifically to a compound lithium-ion battery fire extinguishing agent and its preparation method. Background Technology

[0002] Lithium-ion batteries are rechargeable batteries that use graphite or other carbon materials as the negative electrode and lithium-containing compounds as the positive electrode. Because lithium-ion batteries rely on internal chemical reactions for charging and discharging, when a short circuit or overheating occurs, the temperature of the lithium-ion battery rises rapidly, and the battery undergoes electrolyte decomposition, lithium metal deposition, redox reactions, etc., releasing a large amount of flammable gas and heat, thereby causing a fire. Currently, when lithium battery thermal runaway causes a fire, water-based fire extinguishing agents, dry powder fire extinguishing agents, carbon dioxide fire extinguishing agents, heptafluoropropane fire extinguishing agents, aerosol fire extinguishing agents, and perfluorohexanone fire extinguishing agents are commonly used to extinguish lithium battery fires.

[0003] Existing fire extinguishing agents can isolate oxygen and cool the battery, but they cannot completely stop the chemical reaction inside the battery. After the fire is extinguished, the high temperature and active materials inside the battery can cause thermal runaway again, leading to reignition. Adding montmorillonite and zeolite to the battery fire extinguishing agent can form a barrier layer on the battery surface, preventing the transfer of oxygen and heat, and can adsorb a large number of combustion free radicals, interrupting the chain reaction of combustion. This can extinguish the fire quickly and prevent reignition, and can complete the extinguishing in a short time. However, during the extinguishing process, the expanded montmorillonite barrier layer is prone to cracking at high temperatures, affecting the extinguishing efficiency. Furthermore, zeolite is susceptible to thermal shock and thermal stress, which can cause the zeolite skeleton to collapse, affecting the extinguishing performance. Summary of the Invention

[0004] This invention provides a compound lithium-ion battery fire extinguishing agent and its preparation method, which solves the problem that lithium-ion battery fire extinguishing agents cannot completely terminate the chemical reaction inside the battery, and that the fire reignites after extinguishing due to the high temperature and active materials inside the battery.

[0005] The technical solution of the present invention:

[0006] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 30-35 parts vermiculite, 5-7 parts fire extinguishing filler, 6-8 parts modified zeolite, 0.5-1 part stabilizer, 1.5-2 parts dispersant, 1-2 parts thickener, 1-3 parts foaming agent, and 40-50 parts water.

[0007] The fire extinguishing filler is made by intercalating graphene oxide with montmorillonite, modifying the surface with dopamine, and then mixing it with amphoteric starch, saponins and potassium perfluorobutyl sulfonate.

[0008] The modified zeolite is obtained by mixing hydrochloric acid-activated zeolite with ferric chloride hexahydrate, and then mixing it with organosilicon.

[0009] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0010] Mix vermiculite, fire extinguishing filler, modified zeolite and water, stir evenly, add stabilizer, dispersant, thickener and foaming agent, stir at 500-700 r / min for 30-50 min to obtain battery fire extinguishing agent.

[0011] Furthermore, the vermiculite is expanded vermiculite with a particle size of 25-35 μm.

[0012] Furthermore, the stabilizer is selected from ethylene glycol-butyl ether or ethylene glycol.

[0013] Furthermore, the dispersant is selected from polyvinylpyrrolidone or alkyl polyoxyethylene ether.

[0014] Furthermore, the thickener is carboxymethyl cellulose.

[0015] Furthermore, the foaming agent is selected from sodium dodecyl sulfonate or pine oil.

[0016] Furthermore, the fire extinguishing filler is specifically prepared by the following steps:

[0017] A1. Add graphene oxide and montmorillonite to deionized water, heat to 50-60℃, sonicate at 40-60KHz for 5-6 hours, filter, wash, and dry to obtain the composite.

[0018] A2. Add the complex to Tris-HCl buffer, stir until homogeneous, add dopamine, continue stirring, filter, wash, and dry to obtain the modified complex;

[0019] A3. Mix starch and sodium silicate solution, stir evenly, let stand, add dodecenyl succinic anhydride and ethanol, stir evenly, seal, let stand for a while, heat to 65-75℃ and react for 1-3 hours, cool to room temperature, take out, wash and dry to obtain amphoteric starch.

[0020] A4. Add the modified compound and amphoteric starch to ethanol, stir evenly, add saponins and potassium perfluorobutyl sulfonate, stir at room temperature, then heat and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0021] Furthermore, during the A1 reaction described above, ultrasonic treatment can disrupt the interlayer structure of graphene oxide, forming sheet-like graphene oxide intercalated into the montmorillonite interlayer. The silanol groups in the montmorillonite interlayer can be chemically bonded to the carboxyl groups in the sheet-like graphene oxide, so that graphene oxide and montmorillonite are connected by covalent and hydrogen bonds to form graphene oxide intercalated into montmorillonite, i.e., a composite.

[0022] Furthermore, during the A2 reaction described above, in the Tris-HCl buffer solution, dopamine can self-polymerize on the surface of the complex to form polydopamine, thus forming a polydopamine-modified complex, i.e., a modified complex.

[0023] Furthermore, during the A3 reaction described above, the hydroxyl groups in starch can react with the succinic anhydride groups of dodecenyl succinic anhydride, causing the dodecenyl succinic anhydride to be grafted onto the starch molecular chain. This introduces lipophilic alkenyl long chains and hydrophilic carboxylic acid groups into the starch molecular structure, resulting in amphiphilic starch with both hydrophilic and lipophilic properties.

[0024] Furthermore, during the A4 reaction process described above, the surface of the modified composite contains a large number of phenolic hydroxyl groups, which have excellent adhesion properties and can be chemically bonded to amphiphilic starch. This allows the surface of the modified composite coated with amphiphilic starch to be chemically bonded to saponins and potassium perfluorobutyl sulfonate, forming a mixture that serves as a fire extinguishing filler.

[0025] Further, in step A1, the ratio of graphene oxide, montmorillonite, and deionized water is (1-2)g:(5.5-5.9)g:(130-170)mL.

[0026] Further, in step A2, the ratio of the complex, Tris-HCl buffer, and dopamine is (3-4)g:(80-120)mL:(0.7-0.9)g.

[0027] Further, in step A3, the ratio of starch, sodium silicate solution, dodecenyl succinic anhydride and ethanol is (4-6)g:(2-4)mL:(0.5-0.7)mL:(0.5-0.7)mL.

[0028] Further, in step A4, the ratio of the modified complex, amphoteric starch, ethanol, saponins and potassium perfluorobutyl sulfonate is (5-6)g:(2-2.4)g:(45-55)mL:(8-10)g:(9-11)g.

[0029] Furthermore, the modified zeolite is prepared by the following steps:

[0030] B1. Add ferric chloride hexahydrate to hydrochloric acid, stir evenly, add hydrochloric acid to activate the zeolite, sonicate, let stand, filter, wash, and dry to obtain ferric ion-loaded zeolite.

[0031] B2. Add organosilicon to ethanol and deionized water, stir well, add ammonia to adjust the pH to 8-9, stir well, add ferric-loaded zeolite, stir at 45-55℃ until gel-like, filter, wash, and dry to obtain modified zeolite.

[0032] Furthermore, during the B1 reaction process described above, the iron ions in ferric chloride hexahydrate can combine with the active groups in the hydrochloric acid-activated zeolite, allowing the iron ions to be embedded into the zeolite framework, thus obtaining zeolite loaded with iron ions.

[0033] Furthermore, during the B2 reaction process described above, the silanol groups generated by the hydrolysis of organosilicon can combine with the active groups on the surface of the zeolite loaded with iron ions, thereby embedding the zeolite loaded with iron ions into the organosilicon gel to obtain modified zeolite.

[0034] Further, in step B1, the ratio of the amount of ferric chloride hexahydrate, hydrochloric acid, and hydrochloric acid activated zeolite is (1.2-1.3)g:(20-30)mL:(4-6)g.

[0035] Further, in step B2, the ratio of the amount of organosilicon, ethanol, deionized water and iron-loaded zeolite is (7-8)g:(55-65)mL:(15-25)mL:(3-4)g.

[0036] Furthermore, the organosilicon is tetraethyl orthosilicate.

[0037] Furthermore, the hydrochloric acid activated zeolite is prepared by the following steps: adding zeolite to hydrochloric acid, ultrasonic treatment, allowing it to stand, filtering, washing, and drying to obtain the hydrochloric acid activated zeolite.

[0038] Furthermore, during the above reaction process, the basic groups on the surface of the zeolite framework are neutralized and reduced by hydrochloric acid, introducing hydrogen ions into the zeolite framework. This increases the content of acidic functional groups on the zeolite surface, and some impurities and amorphous substances in the zeolite pores are dissolved, increasing the internal porosity of the zeolite and reducing pore resistance, which is conducive to the insertion of iron ions into the zeolite framework.

[0039] Furthermore, the ratio of zeolite to hydrochloric acid is (4-6) g: (20-30) mL.

[0040] Furthermore, the zeolite particle size was 6-7μm, and it was purchased from Linyi Jinyuan Environmental Protection Equipment Co., Ltd.

[0041] The present invention has the following beneficial effects:

[0042] (1) In the technical solution of the present invention, graphene oxide and montmorillonite are connected by covalent bonds and hydrogen bonds to form graphene oxide intercalated montmorillonite. On the one hand, the graphene oxide intercalated montmorillonite forms a layered material, which can form a barrier layer to prevent the transfer of oxygen and heat, block the combustion of lithium-ion batteries, and achieve the purpose of fire extinguishing. On the other hand, graphene oxide and montmorillonite can capture free radicals in the battery combustion reaction, thereby improving the fire extinguishing efficiency. In addition, graphene oxide, as a support structure of montmorillonite, improves the mechanical strength of montmorillonite after expansion, preventing the expanded montmorillonite barrier layer from cracking at high temperature, leading to reignition and affecting the fire extinguishing efficiency. Dopamine can self-polymerize on the surface of the composite to form polydopamine, forming a modified composite, which is beneficial to the formation of a fire extinguishing layer in lithium-ion batteries.

[0043] (2) In the technical solution of the present invention, the surface of the modified composite coated with amphiphilic starch is then chemically bonded with saponins and potassium perfluorobutyl sulfonate to form a mixture, which serves as a fire extinguishing filler. On the one hand, saponins and potassium perfluorobutyl sulfonate enable the fire extinguishing agent to form a uniform water film on the battery surface, blocking oxygen without wetting the battery, thus achieving a good fire extinguishing effect. On the other hand, the amphiphilic starch in the modified composite contains hydrophobic carbon chains that can repel water molecules, capture combustible molecules, and encapsulate them, forming a microcapsule structure deposited on the surface of graphene oxide intercalated montmorillonite. It prevents the continued combustion of combustibles and interrupts the chain reaction of combustion free radicals to achieve the purpose of fire extinguishing. Its hydrophilic groups can be adsorbed into the water film covering the surface of the battery, so that the graphene oxide intercalated montmorillonite composite and microcapsule structure form a dense barrier layer on the surface of the battery, preventing the transfer of oxygen and heat, thus achieving the purpose of fire extinguishing. In addition, as the temperature rises, the starch and polydopamine contained in the fire extinguishing filler can form a dense char layer, so that the encapsulated combustible molecules are distributed between the char layer, further isolating oxygen, preventing reignition, and improving the fire extinguishing efficiency.

[0044] (3) In the technical solution of the present invention, iron ions are embedded into the hydrochloric acid activated zeolite framework. On the one hand, the hydrochloric acid activated zeolite has a porous structure and a large specific surface area, which can adsorb a large number of combustion free radicals, consume the free radicals in the combustion reaction, and drastically reduce the number of free radicals, interrupt the chain reaction of combustion, and achieve the purpose of extinguishing fire. On the other hand, the loaded iron ions can react with the active free radicals in the flame, inhibit the flame propagation through chemical action, and better complete the extinguishing through physical and chemical synergy.

[0045] (4) In the technical solution of the present invention, zeolite loaded with iron ions is embedded into organosilicon gel to obtain modified zeolite. During the fire extinguishing process, the organosilicon on the surface of the modified zeolite dehydrates to form high-temperature resistant silica, which enhances the stability and heat resistance of the fire extinguishing agent, reduces viscosity and conductivity, and the formed silica is distributed on the surface of the zeolite, which avoids the zeolite from being subjected to thermal shock and thermal stress, causing the zeolite skeleton to collapse and affecting the fire extinguishing performance. Detailed Implementation

[0046] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0047] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0048] The vermiculite is expanded vermiculite with a particle size of 30 μm.

[0049] The stabilizer is ethylene glycol-butyl ether, the dispersant is polyvinylpyrrolidone, the thickener is carboxymethyl cellulose, and the foaming agent is sodium dodecyl sulfonate.

[0050] The graphene oxide has a thickness of 20 nm, an interlayer spacing of 0.6 nm, and a particle size of 10 μm.

[0051] Montmorillonite is a quaternary ammonium salt modified montmorillonite with an apparent density of 0.3 g / cm³. 3 Thickness 25nm, interlayer spacing 2.4nm, purchased from Zhejiang Fenghong Clay Chemical Co., Ltd.

[0052] The starch was tapioca starch, purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0053] The zeolite particles had a diameter of 6.5 μm and were purchased from Linyi Jinyuan Environmental Protection Equipment Co., Ltd.

[0054] The organosilicon is tetraethyl orthosilicate.

[0055] Hydrochloric acid activated zeolite is prepared by the following steps:

[0056] Add 5g of zeolite to 25mL of 0.25mol / L hydrochloric acid, sonicate at 40KHz for 15min, let stand at 25℃ for 24h, filter, wash with deionized water until the pH of the washing solution is neutral, and dry in an oven at 105℃ for 15min to obtain hydrochloric acid activated zeolite.

[0057] Example 1

[0058] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 30 parts expanded vermiculite, 5 parts fire extinguishing filler, 6 parts modified zeolite, 0.5 parts ethylene glycol-butyl ether, 1.5 parts polyvinylpyrrolidone, 1 part carboxymethyl cellulose, 1 part sodium dodecyl sulfonate, and 40 parts water.

[0059] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0060] Expanded vermiculite, fire extinguishing filler, modified zeolite, and water were mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose, and sodium dodecyl sulfonate were then added, and the mixture was stirred at 500 r / min for 30 min to obtain the battery fire extinguishing agent.

[0061] Fire extinguishing filler is prepared by the following steps:

[0062] A1. Add 1g of graphene oxide and 5.5g of quaternary ammonium salt modified montmorillonite to 130mL of deionized water, heat to 50℃, sonicate at 40KHz for 5h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0063] A2. Add 3g of the complex to 80mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.7g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0064] A3. Mix 4g of cassava starch with 2mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.5mL of dodecenyl succinic anhydride and 0.5mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 65℃ and react for 1h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0065] A4. Add 5g of the modified compound and 2g of amphoteric starch to 45mL of ethanol, stir well, add 8g of saponins and 9g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0066] Modified zeolite is prepared by the following steps:

[0067] B1. Add 1.2g of ferric chloride hexahydrate to 20mL of 0.25mol / L hydrochloric acid, stir well, add 4g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0068] B2. Add 7g of tetraethyl orthosilicate to 55mL of ethanol and 15mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 8, stir well, add 3g of iron-loaded zeolite, stir at 45℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0069] Example 2

[0070] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 33 parts expanded vermiculite, 6 parts fire extinguishing filler, 7 parts modified zeolite, 0.8 parts ethylene glycol-butyl ether, 1.8 parts polyvinylpyrrolidone, 1.5 parts carboxymethyl cellulose, 2 parts sodium dodecyl sulfonate, and 45 parts water.

[0071] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0072] Expanded vermiculite, fire extinguishing filler, modified zeolite, and water were mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose, and sodium dodecyl sulfonate were then added, and the mixture was stirred at 600 r / min for 40 min to obtain the battery fire extinguishing agent.

[0073] Fire extinguishing filler is prepared by the following steps:

[0074] A1. Add 1.5g of graphene oxide and 5.7g of quaternary ammonium salt modified montmorillonite to 150mL of deionized water, heat to 55℃, sonicate at 50KHz for 5.5h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0075] A2. Add 3.5g of the complex to 100mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.8g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0076] A3. Mix 5g of cassava starch with 3mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.6mL of dodecenyl succinic anhydride and 0.6mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 70℃ and react for 2h, cool to room temperature, take out, wash 3 times with ethanol, and dry in a 70℃ oven for 10min to obtain amphoteric starch;

[0077] A4. Add 5.5g of the modified compound and 2.2g of amphoteric starch to 50mL of ethanol, stir well, add 9g of saponins and 10g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0078] Modified zeolite is prepared by the following steps:

[0079] B1. Add 1.25g of ferric chloride hexahydrate to 25mL of 0.25mol / L hydrochloric acid, stir well, add 5g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0080] B2. Add 7.5g of tetraethyl orthosilicate to 60mL of ethanol and 20mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 8.5, stir well, add 3.5g of ferric-loaded zeolite, stir at 50℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0081] Example 3

[0082] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0083] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0084] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0085] Fire extinguishing filler is prepared by the following steps:

[0086] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0087] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0088] A3. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0089] A4. Add 6g of the modified compound and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 10g of saponins and 11g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0090] Modified zeolite is prepared by the following steps:

[0091] B1. Add 1.3g of ferric chloride hexahydrate to 30mL of 0.25mol / L hydrochloric acid, stir well, add 6g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0092] B2. Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of iron-loaded zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0093] Comparative Example 1

[0094] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0095] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0096] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0097] Fire extinguishing filler is prepared by the following steps:

[0098] A1. Mix 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to obtain a composite;

[0099] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0100] A3. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0101] A4. Add 6g of the modified compound and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 10g of saponins and 11g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0102] Modified zeolite is prepared by the following steps:

[0103] B1. Add 1.3g of ferric chloride hexahydrate to 30mL of 0.25mol / L hydrochloric acid, stir well, add 6g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0104] B2. Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of iron-loaded zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0105] Comparative Example 2

[0106] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0107] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0108] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0109] Fire extinguishing filler is prepared by the following steps:

[0110] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0111] A2. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0112] A3. Add 6g of the complex and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 10g of saponins and 11g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0113] Modified zeolite is prepared by the following steps:

[0114] B1. Add 1.3g of ferric chloride hexahydrate to 30mL of 0.25mol / L hydrochloric acid, stir well, add 6g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0115] B2. Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of iron-loaded zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0116] Comparative Example 3

[0117] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0118] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0119] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0120] Fire extinguishing filler is prepared by the following steps:

[0121] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0122] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0123] A3. Add 6g of the modified compound and 2.4g of cassava starch to 55mL of ethanol, stir well, add 10g of saponins and 11g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0124] Modified zeolite is prepared by the following steps:

[0125] B1. Add 1.3g of ferric chloride hexahydrate to 30mL of 0.25mol / L hydrochloric acid, stir well, add 6g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0126] B2. Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of iron-loaded zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0127] Comparative Example 4

[0128] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0129] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0130] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0131] Fire extinguishing filler is prepared by the following steps:

[0132] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0133] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0134] A3. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0135] A4. Add 6g of the modified compound and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 21g of saponins, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0136] Modified zeolite is prepared by the following steps:

[0137] B1. Add 1.3g of ferric chloride hexahydrate to 30mL of 0.25mol / L hydrochloric acid, stir well, add 6g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0138] B2. Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of iron-loaded zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0139] Comparative Example 5

[0140] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0141] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0142] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0143] Fire extinguishing filler is prepared by the following steps:

[0144] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0145] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0146] A3. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0147] A4. Add 6g of the modified compound and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 21g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0148] Modified zeolite is prepared by the following steps:

[0149] B1. Add 1.3g of ferric chloride hexahydrate to 30mL of 0.25mol / L hydrochloric acid, stir well, add 6g of hydrochloric acid to activate the zeolite, sonicate at 40KHz for 10min, let stand at 25℃ for 2h, filter, wash 3 times with deionized water, and dry in an oven at 80℃ for 10min to obtain ferric ion-loaded zeolite.

[0150] B2. Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of iron-loaded zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0151] Comparative Example 6

[0152] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts modified zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0153] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0154] Expanded vermiculite, fire extinguishing filler, modified zeolite and water are mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose and sodium dodecyl sulfonate are added and stirred at 700 r / min for 50 min to obtain battery fire extinguishing agent.

[0155] Fire extinguishing filler is prepared by the following steps:

[0156] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0157] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0158] A3. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0159] A4. Add 6g of the modified compound and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 10g of saponins and 11g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0160] Modified zeolite is prepared by the following steps:

[0161] Add 8g of tetraethyl orthosilicate to 65mL of ethanol and 25mL of deionized water, stir well, add 45% ammonia water to adjust the pH to 9, stir well, add 4g of hydrochloric acid to activate the zeolite, stir at 55℃ until gel-like, filter, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain modified zeolite.

[0162] Comparative Example 7

[0163] A compound lithium-ion battery fire extinguishing agent comprises the following raw materials in parts by weight: 35 parts expanded vermiculite, 7 parts fire extinguishing filler, 8 parts iron-loaded zeolite, 1 part ethylene glycol-butyl ether, 2 parts polyvinylpyrrolidone, 2 parts carboxymethyl cellulose, 3 parts sodium dodecyl sulfonate, and 50 parts water.

[0164] A method for preparing a compound lithium-ion battery fire extinguishing agent includes the following preparation steps:

[0165] Expanded vermiculite, fire extinguishing filler, iron-loaded zeolite, and water were mixed and stirred evenly. Ethylene glycol-butyl ether, polyvinylpyrrolidone, carboxymethyl cellulose, and sodium dodecyl sulfonate were then added, and the mixture was stirred at 700 r / min for 50 min to obtain the battery fire extinguishing agent.

[0166] Fire extinguishing filler is prepared by the following steps:

[0167] A1. Add 2g of graphene oxide and 5.9g of quaternary ammonium salt modified montmorillonite to 170mL of deionized water, heat to 60℃, sonicate at 60KHz for 6h, filter, wash 3 times with deionized water, and dry in an oven at 60℃ for 15min to obtain the composite.

[0168] A2. Add 4g of the complex to 120mL of Tris-HCl buffer at pH 8.5, stir for 20min at 25℃ and 2000r / min, add 0.9g of dopamine, stir for 2h at 30℃ and 2000r / min, filter, wash three times with deionized water, and dry in an oven at 70℃ for 10min to obtain the modified complex;

[0169] A3. Mix 6g of cassava starch with 4mL of 20% sodium silicate solution, stir well, let stand at 25℃ for 1h, add 0.7mL of dodecenyl succinic anhydride and 0.7mL of ethanol, stir well, seal, let stand at 25℃ for 3h, then heat to 75℃ and react for 3h, cool to room temperature, take out, wash 3 times with ethanol, and dry in an oven at 70℃ for 10min to obtain amphoteric starch;

[0170] A4. Add 6g of the modified compound and 2.4g of amphoteric starch to 55mL of ethanol, stir well, add 10g of saponins and 11g of potassium perfluorobutyl sulfonate, stir at 25℃ for 1.5h, raise the temperature to 70℃, and continue stirring until the solvent evaporates to obtain the fire extinguishing filler.

[0171] Iron-loaded zeolites are prepared by the following steps:

[0172] 1.3 g of ferric chloride hexahydrate was added to 30 mL of 0.25 mol / L hydrochloric acid and stirred until homogeneous. 6 g of hydrochloric acid was added to activate the zeolite. The mixture was ultrasonically treated at 40 kHz for 10 min, allowed to stand at 25 °C for 2 h, filtered, washed three times with deionized water, and dried in an oven at 80 °C for 10 min to obtain ferric-loaded zeolite.

[0173] The performance of the battery fire extinguishing agents prepared in Examples 1-3 and Comparative Examples 1-7 was then tested.

[0174] The battery extinguishing agent prepared above was encapsulated in a fire extinguishing container to form a pressurized fire extinguisher. The container was filled with 1 kg of the battery extinguishing agent, the nozzle pressure was set to 0.5 MPa, the flow rate was controlled at 5 L / min, and the nozzle outlet diameter was 3 mm. The fire extinguisher filled with the battery extinguishing agent prepared above was subjected to the following fire extinguishing simulation experiment.

[0175] Twelve test lithium batteries were connected in parallel and placed on a heating plate with a power of 1kW, a temperature of 600℃, and dimensions of 210mm×170mm×15mm. After the batteries were charged to 100%, the power was turned off. The heating plate was heated evenly at a rate of 20℃ / min. When the batteries started to heat up, smoked, or even showed open flames, a lithium-ion battery fire was triggered.

[0176] Fire extinguishing performance test: After the battery is exposed to open flame, keep it burning for 10 seconds, use a fire extinguisher filled with the battery extinguishing agent prepared above, stand 1.5m away from the fire source and continuously spray the extinguishing agent until the flame is completely extinguished, and record the extinguishing time; and observe whether the battery re-ignites 0.5h, 1h and 1.5h after the fire is extinguished.

[0177] The test results are shown in Table 1 below.

[0178] Table 1 Performance testing of battery fire extinguishing agents prepared in Examples 1-3 and Comparative Examples 1-5

[0179]

[0180] As can be seen from the data in Table 1, the battery fire extinguishing agents prepared in Examples 1-3 have high fire extinguishing performance and are not easily reignited.

[0181] When the fire extinguishing filler prepared in step A of Comparative Example 1 without ultrasonic treatment was added to the battery fire extinguishing agent, its fire extinguishing performance decreased. This proves that ultrasonic treatment of graphene oxide and montmorillonite allows graphene oxide to intercalate between montmorillonite layers to form a layered material. This material can form a barrier layer, preventing the transfer of oxygen and heat, thus blocking the combustion of lithium-ion batteries and achieving the purpose of fire extinguishing. Furthermore, graphene oxide, as a support structure for montmorillonite, improves the mechanical strength of montmorillonite after expansion, preventing the expanded montmorillonite barrier layer from cracking at high temperatures and affecting the fire extinguishing efficiency.

[0182] In Comparative Example 2, when the modified composite was replaced with the fire extinguishing filler prepared from the composite and added to the battery fire extinguishing agent, its fire extinguishing performance decreased. This proves that dopamine can self-polymerize on the surface of the composite to form polydopamine, thus forming a modified composite. This is beneficial for forming a fire extinguishing layer in lithium-ion batteries. Furthermore, the presence of polydopamine in the fire extinguishing filler can form a dense char layer, allowing the encapsulated combustible molecules to be distributed between the char layers, further isolating oxygen and improving fire extinguishing efficiency.

[0183] In Comparative Example 3, when the fire extinguishing filler prepared by replacing the amphoteric starch with cassava starch was added to the battery fire extinguishing agent, its fire extinguishing performance decreased. This proves that the surface of the modified composite coated with amphiphilic starch contains hydrophobic carbon chains that can repel water molecules, capture combustible molecules, and encapsulate them to form a microcapsule structure, interrupting the chain reaction of combustion free radicals. Its hydrophilic groups can be adsorbed into the water film covering the battery surface, so that the graphene oxide intercalated montmorillonite composite and the microcapsule structure form a dense barrier layer on the battery surface, preventing the transfer of oxygen and heat, and achieving the purpose of fire extinguishing.

[0184] When fire extinguishing fillers prepared using only saponins in Comparative Example 4 and only potassium perfluorobutyl sulfonate in Comparative Example 5 were added to the battery fire extinguishing agent, their fire extinguishing performance decreased. This proves that saponins and potassium perfluorobutyl sulfonate enable the fire extinguishing agent to form a uniform water film on the battery surface, blocking oxygen without wetting the battery, resulting in a better fire extinguishing effect. Furthermore, they facilitate the adsorption of the fire extinguishing filler into the water film, forming a dense barrier layer on the battery surface to prevent the transfer of oxygen and heat.

[0185] Comparative Example 6 showed that when the iron-loaded zeolite was replaced with hydrochloric acid-activated zeolite, the modified zeolite was added to the battery fire extinguishing agent, and its fire extinguishing performance decreased. This proves that hydrochloric acid-activated zeolite can adsorb a large number of combustion free radicals, and the loaded iron ions can react with the active free radicals in the flame, inhibiting the spread of the flame through chemical action and thus better extinguishing the fire.

[0186] Comparative Example 7 showed that when the modified zeolite was replaced with iron-loaded zeolite and added to the battery fire extinguishing agent, its fire extinguishing performance decreased. This proves that when iron-loaded zeolite is embedded in organosilicon gel, the organosilicon dehydrates during the fire extinguishing process to form high-temperature resistant silica distributed on the zeolite surface, which avoids the zeolite being subjected to thermal shock and thermal stress, which would cause the zeolite skeleton to collapse and affect the fire extinguishing performance.

[0187] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0188] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the scope defined by the invention, and all such modifications and additions should fall within the protection scope of the present invention.

Claims

1. A compound lithium-ion battery fire extinguishing agent, characterized in that, The raw materials include the following parts by weight: 30-35 parts vermiculite, 5-7 parts fire extinguishing filler, 6-8 parts modified zeolite, 0.5-1 part stabilizer, 1.5-2 parts dispersant, 1-2 parts thickener, 1-3 parts foaming agent, and 40-50 parts water; The fire extinguishing filler is prepared by the following steps: A1. Add graphene oxide and montmorillonite to deionized water, heat to 50-60℃, sonicate at 40-60 KHz for 5-6 hours, filter, wash, and dry to obtain the composite. A2. Add the complex to Tris-HCl buffer, stir until homogeneous, add dopamine, continue stirring, filter, wash, and dry to obtain the modified complex; A3. Mix starch and sodium silicate solution, stir evenly, let stand, add dodecenyl succinic anhydride and ethanol, stir evenly, seal, let stand for a while, heat to 65-75℃ and react for 1-3 hours, cool to room temperature, take out, wash and dry to obtain amphoteric starch. A4. Add the modified compound and amphoteric starch to ethanol, stir evenly, add saponins and potassium perfluorobutyl sulfonate, stir at room temperature, then heat up and continue stirring until the solvent evaporates to obtain the fire extinguishing filler. The modified zeolite is prepared by the following steps: B1. Add ferric chloride hexahydrate to hydrochloric acid, stir evenly, add hydrochloric acid to activate the zeolite, sonicate, let stand, filter, wash, and dry to obtain ferric ion-loaded zeolite. B2. Add organosilicon to ethanol and deionized water, stir well, add ammonia to adjust the pH to 8-9, stir well, add ferric-loaded zeolite, stir at 45-55℃ until gel-like, filter, wash, and dry to obtain modified zeolite.

2. The compound lithium-ion battery fire extinguishing agent according to claim 1, characterized in that, In step A1, the ratio of graphene oxide, montmorillonite and deionized water is (1-2)g:(5.5-5.9)g:(130-170)mL.

3. The compound lithium-ion battery fire extinguishing agent according to claim 1, characterized in that, In step A2, the ratio of the complex, Tris-HCl buffer, and dopamine is (3-4)g:(80-120)mL:(0.7-0.9)g.

4. The compound lithium-ion battery fire extinguishing agent according to claim 1, characterized in that, In step A3, the ratio of starch, sodium silicate solution, dodecenyl succinic anhydride and ethanol is (4-6)g:(2-4)mL:(0.5-0.7)mL:(0.5-0.7)mL.

5. A compound lithium-ion battery fire extinguishing agent according to claim 1, characterized in that, In step A4, the ratio of the modified complex, amphoteric starch, ethanol, saponins and potassium perfluorobutyl sulfonate is (5-6)g:(2-2.4)g:(45-55)mL:(8-10)g:(9-11)g.

6. The compound lithium-ion battery fire extinguishing agent according to claim 1, characterized in that, In step B1, the ratio of ferric chloride hexahydrate, hydrochloric acid, and hydrochloric acid activated zeolite is (1.2-1.3)g:(20-30)mL:(4-6)g.

7. The compound lithium-ion battery fire extinguishing agent according to claim 1, characterized in that, In step B2, the ratio of the amount of organosilicon, ethanol, deionized water and iron-loaded zeolite is (7-8)g:(55-65)mL:(15-25)mL:(3-4)g.

8. A method for preparing a compound lithium-ion battery fire extinguishing agent according to any one of claims 1-7, characterized in that, The preparation steps include the following: Mix vermiculite, fire extinguishing filler, modified zeolite and water, stir evenly, add stabilizer, dispersant, thickener and foaming agent, stir at 500-700 r / min for 30-50 min to obtain battery fire extinguishing agent.

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