CN117797443A - A nanographene-doped organic pillared vermiculite dispersion and its preparation and application - Google Patents
A nanographene-doped organic pillared vermiculite dispersion and its preparation and application Download PDFInfo
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- CN117797443A CN117797443A CN202311742187.8A CN202311742187A CN117797443A CN 117797443 A CN117797443 A CN 117797443A CN 202311742187 A CN202311742187 A CN 202311742187A CN 117797443 A CN117797443 A CN 117797443A
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
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Abstract
The invention belongs to the technical field of fire extinguishing agents, and provides a nano graphene doped organic pillared vermiculite dispersion liquid and preparation and application thereof; preparing an organic pillared vermiculite suspension, and co-filtering the organic pillared vermiculite suspension and the nano graphene dispersion to prepare composite pillared vermiculite; and (3) taking the composite pillared vermiculite, the foaming agent and the dispersing agent as raw materials, and sanding to prepare the nano graphene doped organic pillared vermiculite dispersion liquid. When the nano graphene doped organic pillared vermiculite dispersion liquid prepared by the invention is applied to a foam extinguishing agent, the nano graphene doped organic pillared vermiculite dispersion liquid has the advantages of high efficiency in extinguishing fire, good anti-burning capability, good stability, difficult re-burning and the like, and is suitable for extinguishing fire of lithium batteries.
Description
Technical Field
The application relates to the technical field of fireproof and fire extinguishing materials, in particular to a nano graphene doped organic pillared vermiculite dispersion liquid, and preparation and application thereof.
Background
Vermiculite is a silicate mineral with a layered structure, and has the advantages of good thermal expansion characteristic, low density, high melting point, small heat conductivity coefficient, good chemical insulation, strong adsorptivity, good sound insulation effect, environmental protection and low cost after expansion, so that the vermiculite is widely applied to the fields of agriculture and animal husbandry, gardening, building, environmental protection, energy conservation and the like, and has a huge application prospect in the field of fireproof and fire extinguishing materials.
However, since vermiculite is an inorganic mineral, is insoluble in water and has oleophobic property, and is limited to be widely applied to the fields of uniform systems and the like, the vermiculite needs to be modified to increase the hydrophilicity and the lipophilicity; while due to vermiculiteMonoclinic system is a double-layer silicon-oxygen tetrahedron formed by combining two layers of laminated silicon-oxygen frameworks through a brucite layer. Due to A1 in tetrahedra 3+ Instead of Si 4+ Creating an excess negative charge and causing the interlayer to charge up with exchangeable cations and water molecules.
The pillared technology is a process technology for improving the interlayer spacing, stability, specific surface area, surface activity (including surface acidity, catalytic performance, adsorption performance) and the like of a substance with a layered structure, and is a special activation mode. Thus, vermiculite may be organically pillared by cation exchange methods.
The foam extinguishing agent is an effective extinguishing agent for extinguishing flammable and combustible liquid, and mainly generates a condensed foam floating layer on the surface of the liquid to play a role in choking and cooling. The current foam extinguishing agent for extinguishing lithium battery fire is mainly water film-forming foam extinguishing agent. The water film-forming foam extinguishing agent is an ideal extinguishing agent at present, but after the fire outside the lithium battery is extinguished, the lithium battery is easy to re-burn within a period of time. And the existing water film-forming foam extinguishing agent contains perfluorooctane sulfonate (PFOS) and ammonium Perfluorooctanoate (PFOA) and other fluorocarbon surfactants which are difficult to degrade in the environment, and has potential environmental pollution risks.
In view of the above problems, the prior research and development of an aqueous film-forming foam extinguishing agent containing modified vermiculite, for example, the patent application document with publication number CN113440785a discloses the preparation of a nano-scale vermiculite dispersion liquid and the application thereof in the foam extinguishing agent. The vermiculite dispersion liquid is prepared by performing cation exchange on vermiculite through quaternary ammonium salt, washing, filtering to remove halogen salt, adding a dispersing agent, and sanding in a sand mill to obtain the nano vermiculite dispersion liquid with the average particle size of 100 nanometers. The nano vermiculite dispersion liquid is applied to a foam extinguishing agent without containing fluorocarbon surfactant, increases the toughness of foam, and has the characteristics of high inactivation speed, strong burning resistance, environmental friendliness, no pollution, low cost and the like. However, the nanoscale vermiculite is a interlaminar environment in which single-column supporting molecules enter the vermiculite, the prepared foam extinguishing agent has limited improvement on the burning resistance, and a larger re-burning probability still exists when aiming at a large-scale serial-parallel lithium battery module fire disaster.
Graphene is a new material with a single-layer lamellar structure composed of carbon atoms, and is a planar film with a hexagonal honeycomb lattice composed of carbon atoms in sp2 hybridization orbits, and is a two-dimensional material with a thickness of only one carbon atom. The unique two-dimensional layered structure of the graphene has an excellent flame retardant effect, and the two-dimensional layered structure of the graphene has a lamellar blocking effect, so that heat transfer, diffusion and escape of pyrolysis products and diffusion and mixing of oxygen can be delayed. Therefore, the preparation of efficient and environment-friendly fire extinguishing agents by using graphene is studied.
In sum, if graphene and organic pillared vermiculite can be utilized to prepare composite pillared vermiculite and prepare the water film-forming foam extinguishing agent, the synergistic effect of the graphene and the organic pillared vermiculite can be utilized to achieve the effects of rapidly extinguishing fire and effectively avoiding re-combustion when aiming at lithium battery fire, and the water film-forming foam extinguishing agent has no pollution to the environment, so that the practicability of the water film-forming foam extinguishing agent in lithium battery fire is improved.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a nano graphene doped organic pillared vermiculite dispersion liquid and preparation and application thereof, so as to solve the problems that the existing water film-forming foam extinguishing agent in the prior art is fast in extinguishing speed, is easy to cause a re-combustion phenomenon, contains fluorocarbon surfactant and causes environmental pollution and the like when being used for extinguishing a lithium battery.
In order to achieve the above and related objects, the present invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of a nano graphene doped organic pillared vermiculite dispersion, which comprises the following steps:
(1) Modifying vermiculite by using quaternary ammonium salt to prepare organic pillared vermiculite;
(2) Preparing an organic pillared vermiculite suspension, and co-filtering the organic pillared vermiculite suspension and the nano graphene dispersion to prepare composite pillared vermiculite;
(3) And (3) taking the composite pillared vermiculite, the foaming agent and the dispersing agent as raw materials, and sanding to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
In one embodiment of the present application, the preparation conditions of step (1) are selected from at least one of (i) to (iii):
the quaternary ammonium salt is any one of dodecyl, tetradecyl, hexadecyl and octadecyl trimethyl ammonium bromide;
(ii) vermiculite is expanded vermiculite;
(III) the mass ratio of the quaternary ammonium salt to the vermiculite is (1-2): (1-3).
In one embodiment of the present application, step (1) includes:
(a) Grinding vermiculite, sieving, adding into deionized water, and stirring;
(b) Adding quaternary ammonium salt, stirring once every 15-20 min, reacting for 2-3 h at constant temperature, performing ultrasonic treatment for 20-30 min, aging, separating, washing and drying to obtain the organic pillared vermiculite.
In one embodiment of the present application, the reaction conditions of step (2) are selected from at least one of (iv) to (vi):
(IV) preparing an organic pillared vermiculite suspension with the solid content of 10-20wt%;
(V) preparing nano graphene dispersion liquid with solid content of 20-25 wt% by taking water, nano graphene and a dispersing agent as raw materials;
the volume ratio of the organic pillared vermiculite suspension to the nano graphene dispersion is (2-3): (1-2).
In one embodiment of the present application, the raw material in step (3) further includes a wetting agent and water.
In one embodiment of the present application, the dispersing agent is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and hexadecyl ammonium bromide.
In one embodiment of the present application, the reaction conditions of step (3) are selected from at least one of (vii) to (viii):
(VII) the mass ratio of the composite pillared vermiculite to the foaming agent to the dispersing agent to the wetting agent to the water is (5-10): (1 to) to (1 to 8) to (2 to 6) to (74 to 89);
(VIII) sanding for 10-20 h.
In one embodiment of the present application, the foaming agent is at least one of dodecyl dimethyl betaine, cocamidopropyl betaine, alkyl glycoside, and octyl amidopropyl betaine;
the wetting agent is at least one of alkyl monohydric alcohol, alkyl dihydric alcohol, alkyl polyhydric alcohol and alkyl dihydric alcohol polyether derivative.
The second aspect of the invention provides a nano graphene doped organic pillared vermiculite dispersion prepared by the preparation method of the nano graphene doped organic pillared vermiculite dispersion.
The third aspect of the invention provides application of the nano graphene doped organic pillared vermiculite dispersion liquid in a foam extinguishing agent.
The beneficial technical effects of the invention are as follows:
firstly, modifying vermiculite, and expanding interlayer spacing of the vermiculite through an organic column support; and depositing nano graphene in the interlayer spacing of the vermiculite by co-suction filtration to prepare the composite pillared vermiculite. And preparing nano graphene doped organic pillared vermiculite dispersion liquid by taking the composite pillared vermiculite as a raw material, so as to prepare the water film-forming foam extinguishing agent.
The synergistic effect of the nano graphene and the organic pillared vermiculite is utilized, so that the burning resistance of the water-formed film foam extinguishing agent is improved. The prepared foam extinguishing agent is suitable for large-scale serial-parallel lithium battery module fires, and can quickly extinguish fires and effectively avoid re-burning. Meanwhile, the foam extinguishing agent does not contain fluorocarbon surfactant, so that the foam extinguishing agent has no pollution to the environment.
When the foam extinguishing agent is used for extinguishing fire of the lithium battery, a protective layer is formed on the lithium battery through the covering and isolating effects of the organic pillar supporting vermiculite, and the supply of oxygen is pressed, so that the chemical reaction process of flame is blocked or slowed down, and the first extinguishing effect is achieved. Then, the nano graphene in the composite pillar vermiculite plays a role in blocking, heat of the lithium battery is delayed from being transmitted outwards, and pyrolysis products and/or oxygen are diffused and mixed in the combustion process, so that a second fire extinguishing effect is achieved, and further, the occurrence of reburning after a period of time of first re-extinguishing is effectively avoided.
The foam extinguishing agent can extinguish fire through the two modes, and achieves the purpose of rapid fire extinguishment and thorough fire extinguishment.
The preparation method of the nano graphene doped organic pillared vermiculite dispersion liquid is simple and low in cost.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Detailed Description
Unless defined otherwise, all technical and/or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable combination or in any other described embodiment of the invention as appropriate. Certain features described in the context of various embodiments will not be considered essential features of those embodiments unless the embodiments are not operable without those elements. The present invention will be further described with reference to the following specific examples, but it should be understood that the specific process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention, and are not intended to limit the scope of the present invention, and all equivalent changes or modifications according to the spirit of the present invention should be included in the scope of the present invention.
The invention provides a preparation method of a nano graphene doped organic pillared vermiculite dispersion liquid, which comprises the following steps:
(1) Grinding expanded vermiculite serving as a raw material, sieving with a 80-100 mesh sieve, adding the crushed vermiculite into deionized water, wherein the mass ratio of the vermiculite to the deionized water is (1-2): (10-15), stirring for 10-15 min;
the quaternary ammonium salt is any one of dodecyl, tetradecyl, hexadecyl and octadecyl trimethyl ammonium bromide, and the mass ratio of the quaternary ammonium salt to the vermiculite is (1-2): (1-3), adding quaternary ammonium salt into the aqueous solution of vermiculite, stirring once every 15-20 min, reacting for 2-3 h at the constant temperature of 60-80 ℃, transferring the reaction solution into an ultrasonic scrubber, ultrasonically treating for 20-30 min, taking out, aging for 5 days at room temperature, separating and washing by a centrifuge, repeatedly washing with deionized water for 3 times, and drying to obtain the organic pillared vermiculite.
(2) Adding organic pillared vermiculite into water to prepare an organic pillared vermiculite suspension with the solid content of 10-20wt%;
preparing nano graphene dispersion liquid with solid content of 20-25 wt% by taking water, nano graphene and a dispersing agent as raw materials, wherein the dispersing agent is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and hexadecyl ammonium bromide;
the volume ratio is (2-3): mixing the organic pillared vermiculite suspension of the (1-2) with the nano graphene dispersion liquid, and carrying out vacuum suction filtration to obtain the composite pillared vermiculite.
(3) The method comprises the steps of taking composite pillared vermiculite, a foaming agent, a dispersing agent, a wetting agent and water as raw materials, wherein the foaming agent is at least one of dodecyl dimethyl betaine, cocamidopropyl betaine, alkyl glycoside and octyl amidopropyl betaine; the wetting agent is at least one of alkyl monohydric alcohol, alkyl dihydric alcohol, alkyl polyhydric alcohol and alkyl dihydric alcohol polyether derivative;
the mass ratio is (5-10): (1-2): (3-8): (2-6): mixing the composite pillared vermiculite of (74-89), the foaming agent, the dispersing agent, the wetting agent and the water, stirring by using a high-speed stirrer for pre-dispersing for 30min, and transferring into a sand mill for sand milling for 10-20 h to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
The invention provides a nano graphene doped organic pillared vermiculite dispersion prepared by the preparation method of the nano graphene doped organic pillared vermiculite dispersion.
The invention provides application of the nano graphene doped organic pillared vermiculite dispersion liquid in a foam extinguishing agent.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) Grinding the expanded vermiculite, sieving with an 80-mesh sieve, and adding the crushed vermiculite into deionized water, wherein the mass ratio of the expanded vermiculite to the deionized water is 1:10, stirring for 10min;
adding octadecyl trimethyl ammonium bromide into an aqueous solution of expanded vermiculite, wherein the mass ratio of the octadecyl trimethyl ammonium bromide to the expanded vermiculite is 1:1, stirring once every 15min, reacting for 2h at the constant temperature of 70 ℃, transferring the reaction liquid into an ultrasonic scrubber, performing ultrasonic treatment for 20min, taking out, aging for 5 days at room temperature, separating and washing by a centrifuge, repeatedly washing by deionized water for 3 times, and drying at 80 ℃ to obtain the organic pillared vermiculite.
(2) Adding organic pillared vermiculite into water to prepare an organic pillared vermiculite suspension with the solid content of 10 weight percent; preparing nano graphene dispersion liquid with solid content of 20wt% by taking water, nano graphene and sodium dodecyl sulfate as raw materials;
the volume ratio is 1: and 1, mixing the organic pillared vermiculite suspension with the nano graphene dispersion liquid, and carrying out vacuum suction filtration to obtain the composite pillared vermiculite.
(3) The mass ratio is 5:1:3:2:89, mixing the composite pillared vermiculite, the dodecyl dimethyl betaine, the sodium dodecyl sulfate, the propylene glycol and the water, stirring by using a high-speed stirrer for pre-dispersing for 30min, and transferring into a sand mill for sand milling for 10h to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
(4) And adding the nano graphene doped organic pillared vermiculite dispersion liquid into water, and diluting until the mass concentration is 6%, thus obtaining the foam extinguishing agent.
Example 2
(1) Grinding the expanded vermiculite, sieving with a 100-mesh sieve, adding the crushed vermiculite into deionized water, wherein the mass ratio of the expanded vermiculite to the deionized water is 1:12, stirring for 15min;
adding cetyltrimethylammonium bromide into an aqueous solution of expanded vermiculite, wherein the mass ratio of the cetyltrimethylammonium bromide to the expanded vermiculite is 2:3, stirring once every 15min, reacting at the constant temperature of 70 ℃ for 2.5h, transferring the reaction liquid into an ultrasonic scrubber, performing ultrasonic treatment for 25min, taking out, aging for 5 days at room temperature, separating and washing by a centrifuge, repeatedly washing with deionized water for 3 times, and drying at 80 ℃ to obtain the organic pillared vermiculite.
(2) Adding organic pillared vermiculite into water to prepare an organic pillared vermiculite suspension with the solid content of 15 wt%; preparing nano graphene dispersion liquid with solid content of 20wt% by taking water, nano graphene and sodium dodecyl benzene sulfonate as raw materials;
the volume ratio is 2: and 1, mixing the organic pillared vermiculite suspension with the nano graphene dispersion liquid, and carrying out vacuum suction filtration to obtain the composite pillared vermiculite.
(3) The mass ratio is 8:2:6:2:82, dodecyl dimethyl betaine, sodium dodecyl benzene sulfonate, propylene glycol and water, pre-dispersing for 30min by using a high-speed stirrer, and sanding for 15h by using a sand mill to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
(4) And adding the nano graphene doped organic pillared vermiculite dispersion liquid into water, and diluting until the mass concentration is 6%, thus obtaining the foam extinguishing agent.
Example 3
(1) Grinding the expanded vermiculite, sieving with a 100-mesh sieve, adding the crushed vermiculite into deionized water, wherein the mass ratio of the expanded vermiculite to the deionized water is 1:10, stirring for 10min;
adding tetradecyl trimethyl ammonium bromide into an aqueous solution of the expanded vermiculite, wherein the mass ratio of the tetradecyl trimethyl ammonium bromide to the expanded vermiculite is 2:1.5, stirring every 15min, reacting at the constant temperature of 70 ℃ for 3h, transferring the reaction liquid into an ultrasonic scrubber, performing ultrasonic treatment for 25min, taking out, aging for 5 days at room temperature, separating and washing by a centrifuge, repeatedly washing with deionized water for 3 times, and drying at 80 ℃ to obtain the organic pillared vermiculite.
(2) Adding organic pillared vermiculite into water to prepare an organic pillared vermiculite suspension with the solid content of 18 weight percent; preparing a nano graphene dispersion liquid with the solid content of 22wt% by taking water, nano graphene and sodium dodecyl benzene sulfonate as raw materials;
the volume ratio is 3:2, mixing the organic pillared vermiculite suspension with the nano graphene dispersion liquid, and carrying out vacuum suction filtration to obtain the composite pillared vermiculite.
(3) The mass ratio is 8:2:8:4:78, mixing the composite pillared vermiculite, cocoamidopropyl betaine, sodium dodecyl benzene sulfonate, propylene glycol and water, pre-dispersing for 30min by using a high-speed stirrer, and transferring into a sand mill for sand milling for 15h to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
(4) And adding the nano graphene doped organic pillared vermiculite dispersion liquid into water, and diluting until the mass concentration is 6%, thus obtaining the foam extinguishing agent.
Example 4
(1) Grinding the expanded vermiculite, sieving with a 100-mesh sieve, adding the crushed vermiculite into deionized water, wherein the mass ratio of the expanded vermiculite to the deionized water is 1:10, stirring for 10min;
adding tetradecyl trimethyl ammonium bromide into an aqueous solution of the expanded vermiculite, wherein the mass ratio of the tetradecyl trimethyl ammonium bromide to the expanded vermiculite is 1:1, stirring once every 15min, reacting for 3h at a constant temperature of 70 ℃, transferring the reaction liquid into an ultrasonic scrubber, performing ultrasonic treatment for 25min, taking out, aging for 5 days at room temperature, separating and washing by a centrifuge, repeatedly washing by deionized water for 3 times, and drying at 80 ℃ to obtain the organic pillared vermiculite.
(2) Adding organic pillared vermiculite into water to prepare an organic pillared vermiculite suspension with the solid content of 20 weight percent; preparing a nano graphene dispersion liquid with solid content of 25wt% by taking water, nano graphene and sodium dodecyl benzene sulfonate as raw materials;
the volume ratio is 3:2, mixing the organic pillared vermiculite suspension with the nano graphene dispersion liquid, and carrying out vacuum suction filtration to obtain the composite pillared vermiculite.
(3) The mass ratio is 5:2:8:2:83, mixing the composite pillared vermiculite, cocoamidopropyl betaine, sodium dodecyl benzene sulfonate, diethylene glycol and water, stirring by using a high-speed stirrer for pre-dispersing for 30min, and transferring into a sand mill for sand milling for 20h to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
(4) And adding the nano graphene doped organic pillared vermiculite dispersion liquid into water, and diluting until the mass concentration is 6%, thus obtaining the foam extinguishing agent.
Example 5
The difference between the present example and example 1 is that the above nano graphene doped organic pillared vermiculite dispersion is added into water, and diluted to a mass concentration of 4%, so as to prepare the foam extinguishing agent.
Comparative example 1
(1) Grinding the expanded vermiculite, sieving with an 80-mesh sieve, and adding the crushed vermiculite into deionized water, wherein the mass ratio of the expanded vermiculite to the deionized water is 1:10, stirring for 10min;
adding octadecyl trimethyl ammonium bromide into an aqueous solution of expanded vermiculite, wherein the mass ratio of the octadecyl trimethyl ammonium bromide to the expanded vermiculite is 1:1, stirring once every 15min, reacting for 2h at the constant temperature of 70 ℃, transferring the reaction liquid into an ultrasonic scrubber, performing ultrasonic treatment for 20min, taking out, aging for 5 days at room temperature, separating and washing by a centrifuge, repeatedly washing by deionized water for 3 times, and drying at 80 ℃ to obtain the organic pillared vermiculite.
(2) The mass ratio is 5:1:3:2:89, mixing the organic pillared vermiculite, the dodecyl dimethyl betaine, the sodium dodecyl sulfate, the propylene glycol and the water, stirring by using a high-speed stirrer for pre-dispersing for 30min, and transferring into a sand mill for sand milling for 10h to prepare the organic pillared vermiculite dispersion liquid.
(3) And (3) adding the organic pillared vermiculite dispersion liquid into water, and diluting until the mass concentration is 6%, thus obtaining the foam extinguishing agent.
Comparative example 2
The mass ratio is 3:3:2:8:3:2:0.5:8:70.5, mixing vermiculite, graphene, dodecyl dimethyl betaine, sodium dodecyl sulfate, propylene glycol, sodium dodecyl benzene sulfonate, sodium citrate, urea and water, and uniformly stirring to obtain the foam extinguishing agent.
Comparative example 3
Commercial foam extinguishing agents.
Performance testing
Fire extinguishing performance: the fire extinguishing performance of the foam extinguishing agents of examples 1 to 5 and comparative examples 1 to 3 was tested according to GB 15308-2006 foam extinguishing agent, and the test results are shown in Table 1.
Fire extinguishing by using a lithium battery: placing 12 lithium batteries for testing on a heating plate after being connected in parallel, wherein the power of the heating plate is 1kW, the temperature is set to 600 ℃, and the sizes are 210mm multiplied by 170mm multiplied by 15mm; the power supply is turned off after the battery is charged to 100% SOC; the heating plate was heated uniformly at a heating rate of 20 c/min, and the battery was thermally run away to 20s after the explosion of the housing, and the heating plate was sprayed with the foam extinguishing agent according to each example of the present invention and each comparative example, and the time period required for extinguishing the open fire and whether the post-combustion was performed after 2min were measured, and the test results are shown in table 2. (the lithium battery adopted in the test is a soft-package ternary lithium ion NCM 811/graphite system power battery, and the outer membrane material of the battery is an aluminum membrane)
Table 1 test of fire extinguishing performance of foam extinguishing agent of examples and comparative examples
| Test object | Injection time/s | Expansion ratio/multiple | 25% liquid separation time/s | Time/s of fire control | 25% burn time/s |
| Example 1 | 120 | 8.2 | 230 | 49 | 284 |
| Example 2 | 120 | 8.5 | 234 | 44 | 293 |
| Example 3 | 120 | 8.0 | 227 | 54 | 275 |
| Example 4 | 120 | 7.8 | 221 | 57 | 270 |
| Example 5 | 120 | 8.8 | 237 | 42 | 302 |
| Comparative example 1 | 120 | 5.3 | 170 | 82 | 213 |
| Comparative example 2 | 120 | 5.6 | 189 | 73 | 237 |
| Comparative example 3 | 120 | 4.2 | 121 | 98 | 158 |
Table 2 lithium battery fire suppression test for foam extinguishing agents of examples and comparative examples
As can be seen from Table 1, the foam extinguishing agent prepared by doping the organic pillared vermiculite dispersion liquid with the nano graphene is a low-multiple foam extinguishing agent, and the 25% liquid separation time of the foam extinguishing agent prepared in the examples 1-5 is 3-4 min, which is obviously higher than that of the foam extinguishing agent prepared in the comparative examples 1-3, and has better stability. The foam extinguishing agents prepared in the embodiments 1 to 5 have the advantages of high-efficiency fire extinguishing when the 100% fire control time is within 1min, and the foam extinguishing agents in the comparative examples 1 to 3 have low fire extinguishing speed and can ensure 100% fire control within 2 min. In addition, under the action of the organic pillared vermiculite and the nano graphene, the foam fire extinguishing agent prepared in the embodiments 1-5 has a good blocking effect, the burning resistance of the foam fire extinguishing agent is remarkably improved, and the burning resistance time is kept above 4 minutes, so that the prepared foam fire extinguishing agent is not easy to re-burn after extinguishing a fire source. And the fire-resistant time of the foam extinguishing agent in comparative examples 1-3 is in the range of 2-4 min, after the fire source is extinguished, the fire source is easy to re-burn after a period of time, and the fire-resistant capability is poor. In conclusion, the foam extinguishing agent prepared by the application has better stability, burning resistance and high-efficiency fire extinguishing capability.
As can be seen from Table 2, when the foam extinguishing agents prepared in examples 1 to 5 of the present application are aimed at lithium battery extinguishment, extinguishment can be completed rapidly within 1.5min, and after a period of time, no re-combustion is performed, so that thorough extinguishment is realized, and the safety is high. And when the foam extinguishing agent of comparative examples 1-3 is used for extinguishing fire by aiming at a lithium battery, the fire extinguishing time is more than 2 minutes, the speed is low, and the foam extinguishing agent has the possibility of re-burning after a period of time and cannot achieve the effect of thoroughly extinguishing the fire. Therefore, the foam extinguishing agent prepared by utilizing the nano graphene doped organic pillared vermiculite dispersion liquid is suitable for lithium battery fire extinguishment, has the advantages of high efficiency, thorough fire extinguishment and no reburning during fire extinguishment, and is safer and more environment-friendly without fluorocarbon surfactant.
In addition, through experimental detection, the soft-package ternary lithium battery generates the following gas components after thermal runaway: hydrogen, oxygen, methane, ethane, ethylene, nitrogen, propane, propylene, carbon dioxide, isobutane, n-butane, propadiene, acetylene, fumaric, n-butene, isobutylene, cis-butene, carbon monoxide, isopentane, n-pentane, 1, 3-butadiene, 3-methyl-1-butene, propyne, trans-2-pentene, 2-methyl-2-butene, pentene, 2-methyl-1-butene, cis-2-pentene, butyne, vinylacetylene, isoprene. Wherein, the hydrogen, nitrogen, carbon dioxide and carbon monoxide account for relatively high, and the total content is about 89 percent. The total content of oxygen, methane and ethylene is about 9.8%, and the rest gas components are very small.
When the foam extinguishing agent is used for soft-package ternary lithium battery thermal runaway extinguishment, the organic pillar supporting vermiculite firstly adsorbs a fire source, and through the covering and isolating functions, the supply of oxygen is suppressed, so that the gas generated by the lithium battery thermal runaway is prevented from reacting with each other at high temperature, a large amount of heat is released again, for example, the oxygen and ethylene react exothermically at high temperature. And secondly, the porous organic pillar vermiculite is adsorbed by the porous organic pillar vermiculite surface, the edges and corners of the laminate edges and the like, so that the organic pillar vermiculite can achieve an adsorption effect similar to that of activated carbon, and can further adsorb gases such as ethylene, carbon dioxide, carbon monoxide and the like.
Meanwhile, the composite column supports the nano graphene in the vermiculite to achieve a blocking effect, so that heat of the lithium battery is further delayed from being transmitted outwards, and pyrolysis products and/or oxygen in the combustion process of the lithium battery are diffused and mixed, so that secondary heat release and explosion are avoided. And the nano graphene is used for absorbing flammable and explosive gases such as hydrogen, methane and the like which are emitted by the lithium battery in a thermal runaway way and gases with more contents such as oxygen, nitrogen and the like in a physical adsorption or chemical adsorption mode.
Therefore, when most inflammable and explosive gases generated by thermal runaway of the lithium battery and combustion-supporting gases are adsorbed, the foam extinguishing agent can block or slow down the chemical reaction process in the lithium battery, so that the extinguishing effect is achieved, the internal temperature of the lithium battery is further reduced, and the secondary re-combustion is avoided. In addition, most of gas generated by thermal runaway of the lithium battery is absorbed by the foam extinguishing agent, and a very small amount of unabsorbed isopentane and other gases possibly exist, but the internal temperature of the lithium battery is reduced, the combustion temperature and the explosion temperature of the residual gas cannot be reached, no gas is assisted, and secondary reburning cannot be caused.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The preparation method of the nano graphene doped organic pillared vermiculite dispersion liquid is characterized by comprising the following steps of:
(1) Modifying vermiculite by using quaternary ammonium salt to prepare organic pillared vermiculite;
(2) Preparing an organic pillared vermiculite suspension, and co-filtering the organic pillared vermiculite suspension and the nano graphene dispersion to prepare composite pillared vermiculite;
(3) And sanding the composite pillared vermiculite, the foaming agent and the dispersing agent serving as raw materials to prepare the nano graphene doped organic pillared vermiculite dispersion liquid.
2. The method for preparing a nano graphene doped organic pillared vermiculite dispersion according to claim 1, wherein the preparation conditions of step (1) are at least one selected from (i) to (iii):
the quaternary ammonium salt is any one of dodecyl, tetradecyl, hexadecyl and octadecyl trimethyl ammonium bromide;
(ii) the vermiculite is expanded vermiculite;
(III) the mass ratio of the quaternary ammonium salt to the vermiculite is (1-2): (1-3).
3. The method of preparing a nano graphene doped organic pillared vermiculite dispersion according to claim 1, wherein step (1) comprises:
(a) Grinding the vermiculite, sieving, adding into deionized water, and stirring;
(b) Adding the quaternary ammonium salt, stirring once every 15-20 min, reacting for 2-3 h at constant temperature, performing ultrasonic treatment for 20-30 min, aging, separating, washing and drying to obtain the organic pillared vermiculite.
4. The method of preparing a nano graphene doped organic pillared vermiculite dispersion according to claim 1, wherein the reaction conditions of step (2) are at least one selected from (iv) to (vi):
(IV) preparing an organic pillared vermiculite suspension with the solid content of 10-20wt%;
(V) preparing nano graphene dispersion liquid with solid content of 20-25 wt% by taking water, nano graphene and a dispersing agent as raw materials;
the volume ratio of the organic pillared vermiculite suspension to the nano graphene dispersion is (2-3): (1-2).
5. The method for preparing the nano graphene doped organic pillared vermiculite dispersion according to claim 1, wherein the raw materials in the step (3) further comprise a wetting agent and water.
6. The method for preparing the nano graphene doped organic pillared vermiculite dispersion according to claim 1, wherein the dispersing agent is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and hexadecyl ammonium bromide.
7. The method of preparing a nano graphene doped organic pillared vermiculite dispersion according to claim 5, wherein the reaction conditions of step (3) are at least one selected from (vii) to (viii):
(VII) the mass ratio of the composite pillared vermiculite to the foaming agent to the dispersing agent to the wetting agent to the water is (5-10): (1-2): (3-8): (2-6): (74-89);
(VIII) sanding for 10-20 h.
8. The method for preparing the nano graphene doped organic pillared vermiculite dispersion of claim 7, wherein the foaming agent is at least one of dodecyl dimethyl betaine, cocamidopropyl betaine, alkyl glycoside and octylamidopropyl betaine;
the wetting agent is at least one of alkyl monohydric alcohol, alkyl dihydric alcohol, alkyl polyhydric alcohol and alkyl dihydric alcohol polyether derivative.
9. The nano graphene doped organic pillared vermiculite dispersion prepared by the method for preparing the nano graphene doped organic pillared vermiculite dispersion of any one of claims 1 to 8.
10. The application of the nano graphene doped organic pillared vermiculite dispersion liquid in a foam extinguishing agent is characterized in that the nano graphene doped organic pillared vermiculite dispersion liquid is the nano graphene doped organic pillared vermiculite dispersion liquid in claim 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786815A (en) * | 2010-01-19 | 2010-07-28 | 武汉科技大学 | Inorganic intercalated vermiculite insulation refractory material and preparation method thereof |
| US20110256376A1 (en) * | 2007-05-14 | 2011-10-20 | Northwestern University | Composite graphene oxide-polymer laminate and method |
| CN106377862A (en) * | 2016-08-31 | 2017-02-08 | 胡泽军 | Fire extinguishing agent prepared from grapheme and superfine materials |
| CN113440785A (en) * | 2020-03-26 | 2021-09-28 | 上海汇友消防技术有限公司 | Preparation of nano-scale vermiculite dispersion liquid and application of nano-scale vermiculite dispersion liquid in foam extinguishing agent |
| CN113526497A (en) * | 2021-08-11 | 2021-10-22 | 洛阳理工学院 | Preparation method of organic modified vermiculite/graphene composite aerogel |
| CN115970219A (en) * | 2022-12-26 | 2023-04-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of suspended water vermiculite fire extinguishing agent and product thereof |
-
2023
- 2023-12-18 CN CN202311742187.8A patent/CN117797443A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110256376A1 (en) * | 2007-05-14 | 2011-10-20 | Northwestern University | Composite graphene oxide-polymer laminate and method |
| CN101786815A (en) * | 2010-01-19 | 2010-07-28 | 武汉科技大学 | Inorganic intercalated vermiculite insulation refractory material and preparation method thereof |
| CN106377862A (en) * | 2016-08-31 | 2017-02-08 | 胡泽军 | Fire extinguishing agent prepared from grapheme and superfine materials |
| CN113440785A (en) * | 2020-03-26 | 2021-09-28 | 上海汇友消防技术有限公司 | Preparation of nano-scale vermiculite dispersion liquid and application of nano-scale vermiculite dispersion liquid in foam extinguishing agent |
| CN113526497A (en) * | 2021-08-11 | 2021-10-22 | 洛阳理工学院 | Preparation method of organic modified vermiculite/graphene composite aerogel |
| CN115970219A (en) * | 2022-12-26 | 2023-04-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of suspended water vermiculite fire extinguishing agent and product thereof |
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