CN114887272A - Hydrated inorganic salt dry powder extinguishing agent and application thereof in inhibiting thermal runaway propagation of lithium ion battery - Google Patents
Hydrated inorganic salt dry powder extinguishing agent and application thereof in inhibiting thermal runaway propagation of lithium ion battery Download PDFInfo
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- CN114887272A CN114887272A CN202210650134.2A CN202210650134A CN114887272A CN 114887272 A CN114887272 A CN 114887272A CN 202210650134 A CN202210650134 A CN 202210650134A CN 114887272 A CN114887272 A CN 114887272A
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- 239000000843 powder Substances 0.000 title claims abstract description 95
- 229910017053 inorganic salt Inorganic materials 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000000945 filler Substances 0.000 claims abstract description 33
- 229920002545 silicone oil Polymers 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 32
- 239000010445 mica Substances 0.000 claims abstract description 32
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 32
- 239000004927 clay Substances 0.000 claims abstract description 27
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 30
- WZUKKIPWIPZMAS-UHFFFAOYSA-K Ammonium alum Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZUKKIPWIPZMAS-UHFFFAOYSA-K 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 claims description 4
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 3
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 claims description 3
- 239000003502 gasoline Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims description 3
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 3
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 230000005764 inhibitory process Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 25
- 238000010586 diagram Methods 0.000 description 10
- 239000007921 spray Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 206010003497 Asphyxia Diseases 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010000369 Accident Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- 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
- A62D1/0007—Solid extinguishing substances
- A62D1/0014—Powders; Granules
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
- A62D1/06—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of fire extinguishing agents, and particularly relates to a hydrated inorganic salt dry powder fire extinguishing agent, a preparation method thereof and application thereof in inhibiting thermal runaway of a lithium ion battery. The invention provides a hydrated inorganic salt dry powder extinguishing agent which comprises: 80-90 parts of hydrated inorganic salt, 5-11 parts of inert filler, 1-3 parts of activated clay and 0.5-2 parts of hydrogen-containing silicone oil, wherein the inert filler comprises one or more of talcum powder, mica powder, fumed silica and graphite powder. The hydrated inorganic salt component of the hydrated inorganic salt dry powder extinguishing agent provided by the invention has low decomposition temperature, better matches the initial temperature range of thermal runaway of the lithium ion battery, has strong heat absorption capacity, and can generate a large amount of gas to dilute the oxygen concentration in the decomposition process, thereby effectively reducing the object temperature and the oxygen concentration in the environment and having effective inhibition effect on the thermal runaway of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of fire extinguishing agents, and particularly relates to a hydrated inorganic salt dry powder fire extinguishing agent and application thereof in inhibiting thermal runaway propagation of a lithium ion battery.
Background
Lithium ion batteries have recently been widely used globally due to their advantages of small size, light weight, high energy density, long life, and the like. However, the safety problem of the lithium ion battery is always a concern, because the lithium ion battery is easy to generate thermal runaway under abuse conditions, when the temperature of the lithium ion battery exceeds a certain range (about 130-. At present, with the popularization of new energy electric vehicles, lithium ion electric bicycles and the like, the thermal runaway and fire accidents of lithium ion batteries are frequent.
However, for lithium ion battery fire, few fire extinguishers can be used, and most of the fire fighters select to use a large amount of water to extinguish the special fire, so that the temperature of the lithium ion battery is reduced when a large amount of water is evaporated, and the thermal runaway propagation of the lithium ion battery is inhibited. However, water is conductive, so that the fire extinguisher is not suitable for ordinary people without protective measures, and due to the limitation that the fire extinguisher is difficult to use in water-deficient areas and extremely cold conditions, other effective fire extinguishers are urgent to dig.
ABC dry powder fire extinguisher and CO 2 The three extinguishers, namely the fire extinguisher and the foam extinguisher, are most civil extinguishers at present, and the main extinguishment mechanisms of the extinguishers are chemical inhibition and suffocation, but the lithium ion battery thermal runaway is mainly caused by smoking or explosion due to internal chemical reaction caused by high temperature, so the chemical inhibition and the suffocation of the three extinguishers have little inhibition on the thermal runaway of the lithium ion battery, and the ABC dry powder extinguishing agent is heated, can generate overhigh decomposition temperature of decomposition and heat absorption and is not matched with the initial thermal runaway temperature of the lithium ion battery; CO 2 2 CO in fire extinguisher 2 The vaporization heat absorption capacity is very limited, and the thermal runaway of the lithium ion battery cannot be effectively inhibited; the foam fire extinguisher has weaker capability of reducing the temperature of an object, so that the three fire extinguishers have proved to have insignificant capability of suppressing the lithium ion battery fire at present.
Disclosure of Invention
The invention aims to provide a hydrated inorganic salt dry powder extinguishing agent, a preparation method thereof and application thereof in inhibiting thermal runaway propagation of a lithium ion battery.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a hydrated inorganic salt dry powder extinguishing agent which comprises the following components in parts by weight:
80-90 parts of hydrated inorganic salt, 5-11 parts of inert filler, 1-3 parts of activated clay and 0.5-2 parts of hydrogen-containing silicone oil; the inert filler comprises one or more of talcum powder, mica powder, fumed silica and graphite powder.
Preferably, when the inert filler comprises talcum powder, mica powder, fumed silica and graphite powder, the inert filler comprises the following components in parts by weight: 1-2 parts of talcum powder, 2-3 parts of mica powder, 1-4 parts of fumed silica and 1-2 parts of graphite powder.
Preferably, the hydrated inorganic salts include one or more of disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate, magnesium sulfate heptahydrate, aluminum potassium sulfate dodecahydrate, sodium thiosulfate pentahydrate, and sodium acetate trihydrate.
Preferably, the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.8 wt%.
The invention provides a preparation method of the hydrated inorganic salt dry powder extinguishing agent in the technical scheme, which comprises the following steps:
mixing hydrated inorganic salt, inert filler, activated clay, hydrogen-containing silicone oil, water and organic dispersant to obtain mixed feed liquid;
and sequentially carrying out solid-liquid separation, drying and crushing on the mixed feed liquid to obtain the hydrated inorganic salt dry powder extinguishing agent.
Preferably, the organic dispersant includes one or more of n-hexane, acetone, benzene, toluene, xylene, chloroform, carbon tetrachloride, petroleum ether, gasoline, kerosene and perchloroethylene.
Preferably, the mixing temperature is 85-95 ℃, and the mixing heat preservation time is 2-5 h.
Preferably, the mass ratio of the organic dispersant to the hydrogen-containing silicone oil is (3-5): 1.
Preferably, the particle size of the activated clay is 40-45 μm; the particle size of the talcum powder is 2.5-3 mu m, the particle size of the mica powder is 130-180 mu m, the particle size of the fumed silica is 10-15 mu m, and the particle size of the graphite powder is 17-23 mu m.
The invention provides application of the hydrated inorganic salt dry powder extinguishing agent in the technical scheme in inhibiting thermal runaway propagation of a lithium ion battery.
The invention provides a hydrated inorganic salt dry powder extinguishing agent which comprises the following components in parts by weight: 80-90 parts of hydrated inorganic salt, 5-11 parts of inert filler, 1-3 parts of activated clay and 0.5-2 parts of hydrogen-containing silicone oil; the inert filler comprises one or more of talcum powder, mica powder, fumed silica and graphite powder. The hydrated inorganic salt component of the hydrated inorganic salt dry powder extinguishing agent has the characteristics of low decomposition temperature and large decomposition enthalpy, is well matched with the initial temperature interval of thermal runaway of a lithium ion battery, has strong heat absorption capacity, and can generate a large amount of gas to dilute the oxygen concentration in the decomposition process; finally, the hydrated inorganic salt, the inert filler, the activated clay and the hydrogen-containing silicone oil are compounded, and the hydrophobicity of the hydrated inorganic salt and the inert filler can be obviously enhanced by the hydrogen-containing silicone oil under the catalytic action of the activated clay, so that the dry powder extinguishing agent provided by the invention is not wet when meeting water, mutual adhesion and agglomeration are not easy to occur, and the fluidity is improved. Therefore, the hydrated inorganic salt dry powder extinguishing agent provided by the invention can effectively reduce the temperature of an object and the oxygen concentration in the environment, and has an effective inhibiting effect on thermal runaway of a lithium ion battery.
The invention provides a preparation method of the hydrated inorganic salt dry powder extinguishing agent in the technical scheme, which comprises the following steps: mixing hydrated inorganic salt, inert filler, activated clay, hydrogen-containing silicone oil, water and organic dispersant to obtain mixed feed liquid; and sequentially carrying out solid-liquid separation, drying and crushing on the mixed feed liquid to obtain the hydrated inorganic salt dry powder extinguishing agent. The preparation method provided by the invention has the advantages of simple preparation process, rich raw material sources, low cost and the like, has a good inhibition effect on thermal runaway of the lithium ion battery, and has wide application prospect and market potential.
Drawings
FIG. 1 is a DSC spectrum of an aluminum ammonium sulfate dodecahydrate fire extinguishing agent prepared in example 2 of the present invention;
FIG. 2 is a TG spectrum of an aluminum ammonium sulfate dodecahydrate fire extinguishing agent prepared in example 2 of the present invention;
FIG. 3 is a particle size distribution diagram of an aluminum ammonium sulfate dodecahydrate fire extinguishing agent prepared in example 2 of the present invention;
fig. 4 is a schematic diagram of the temperature of the surface of 4 18650 lithium ion batteries when thermal runaway occurs in parallel;
FIG. 5 is a schematic diagram showing the temperature change of the surface of 4 18650 lithium ion batteries in parallel before and after spraying aluminum ammonium sulfate dodecahydrate fire extinguishing agent when thermal runaway spray flame occurs in the No. 1 battery;
FIG. 6 is a schematic diagram showing the temperature changes of the surfaces of 4 18650 lithium ion batteries in parallel, before and after spraying aluminum ammonium sulfate dodecahydrate fire extinguishing agent when thermal runaway spray flame occurs in No. 2 battery;
fig. 7 is a schematic diagram of the temperature change of the surface of 4 18650 lithium ion batteries before and after spraying aluminum ammonium sulfate dodecahydrate fire extinguishing agent when the pressure release valve of battery No. 2 is opened.
Detailed Description
The invention provides a hydrated inorganic salt dry powder extinguishing agent which comprises the following components in parts by weight:
80-90 parts of hydrated inorganic salt, 5-11 parts of inert filler, 1-3 parts of activated clay and 0.5-2 parts of hydrogen-containing silicone oil; the inert filler comprises one or more of talcum powder, mica powder, fumed silica and graphite powder.
In the present invention, all the preparation starting materials/components are commercially available products well known to those skilled in the art unless otherwise specified.
The hydrated inorganic salt dry powder extinguishing agent comprises, by mass, 80-90 parts of hydrated inorganic salt, preferably 85-90 parts of hydrated inorganic salt, and preferably 90 parts of hydrated inorganic salt.
In the invention, the hydrated inorganic salt has the characteristics of low decomposition temperature and large decomposition enthalpy, and can be well matched with the initial temperature interval of thermal runaway of the lithium ion battery.
In the present invention, the hydrated inorganic salt preferably includes one or more of disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate, magnesium sulfate heptahydrate, aluminum potassium sulfate dodecahydrate, sodium thiosulfate pentahydrate, and sodium acetate trihydrate, and preferably includes aluminum ammonium sulfate dodecahydrate and/or aluminum potassium sulfate dodecahydrate.
Based on the mass parts of the hydrated inorganic salt, the hydrated inorganic salt dry powder extinguishing agent provided by the invention comprises 5-11 parts of inert filler, and preferably 6.5-8 parts.
In the present invention, the inert filler includes one or more of talc powder, mica powder, fumed silica and graphite powder, and more preferably includes talc powder, mica powder, fumed silica and graphite powder or mica powder, fumed silica and graphite powder.
In the present invention, the talc powder preferably improves the fluidity of the hydrated inorganic salt dry powder extinguishing agent and reduces the tendency of the dry powder extinguishing agent to agglomerate.
In the present invention, the mica powder is preferably capable of improving the electrical insulation and the fluidity of the dry powder extinguishing agent.
In the present invention, the fumed silica is preferably capable of reducing the tendency of the dry powder extinguishing agent to agglomerate while adjusting the bulk of the dry powder extinguishing agent.
In the present invention, the graphite powder is preferably capable of reducing the caking tendency of the dry powder extinguishing agent while adjusting the bulk density of the dry powder extinguishing agent.
In the present invention, when the inert filler preferably includes talc powder, mica powder, fumed silica, and graphite powder, the inorganic filler preferably includes: 1-2 parts of talcum powder, 2-3 parts of mica powder, 1-4 parts of fumed silica and 1-2 parts of graphite powder.
In the present invention, when the inert filler preferably includes mica powder, fumed silica, and graphite powder, the inorganic filler preferably includes: 2-3 parts of mica powder, 1-4 parts of fumed silica and 1-3 parts of graphite powder.
In the present invention, unit 1 for calculating the mass part of the inert filler is the same as unit 1 for calculating the mass part of the hydrated inorganic salt dry powder extinguishing agent.
Based on the mass parts of the hydrated inorganic salt, the inert filler in the hydrated inorganic salt dry powder extinguishing agent provided by the invention preferably comprises 1-2 parts of talcum powder, and more preferably 1.5 parts or 0 part.
Based on the mass parts of the hydrated inorganic salt, the inert filler in the hydrated inorganic salt dry powder extinguishing agent provided by the invention preferably comprises 2-3 parts of mica powder, and more preferably 2 parts.
Based on the mass parts of the hydrated inorganic salt, in the hydrated inorganic salt dry powder extinguishing agent provided by the invention, the inert filler preferably comprises 1-4 parts of fumed silica, more preferably 1.5-3 parts, and further preferably 2 parts.
Based on the mass parts of the hydrated inorganic salt, the inert filler in the hydrated inorganic salt dry powder extinguishing agent provided by the invention preferably comprises 1-3 parts of graphite powder, and more preferably 1.5 parts or 2.5 parts.
Based on the mass parts of the hydrated inorganic salt, the hydrated inorganic salt dry powder extinguishing agent provided by the invention comprises 1-3 parts of activated clay, preferably 1.5-2.5 parts, and more preferably 2 parts.
Based on the mass parts of the hydrated inorganic salt, the hydrated inorganic salt dry powder extinguishing agent provided by the invention comprises 0.5-2 parts of hydrogen-containing silicone oil, preferably 0.8-1.5 parts, and more preferably 1 part or 1.5 parts.
In the invention, the hydrogen content of the hydrogen-containing silicone oil is preferably 1.5-1.8 wt%, and more preferably 1.55-1.7%.
In the invention, the activated clay is used as a catalyst for polymerization of hydrogen-containing silicone oil, can promote the hydrogen-containing silicone oil to polymerize and cover the surfaces of the dry powder extinguishing agent particles, forms a solid protection layer after polymerization, modifies the surfaces of the particles from hydrophilicity to hydrophobicity, is not wet when meeting water, and is not easy to be bonded and agglomerated.
In the invention, the hydrated inorganic salt dry powder fire extinguishing agent preferably comprises 80-90 parts by mass of hydrated inorganic salt, 1-3 parts by mass of activated clay, 0.5-2 parts by mass of hydrogen-containing silicone oil, 1-2 parts by mass of talcum powder, 2-3 parts by mass of mica powder, 1-4 parts by mass of fumed silica and 1-2 parts by mass of graphite powder, and more preferably comprises 90 parts by mass of hydrated inorganic salt, 1.5 parts by mass of talcum powder, 2 parts by mass of mica powder, 2 parts by mass of fumed silica, 2 parts by mass of activated clay, 1.5 parts by mass of graphite powder and 1 part by mass of hydrogen-containing silicone oil.
Or in the invention, the hydrated inorganic salt dry powder fire extinguishing agent provided by the invention preferably comprises 90 parts of hydrated inorganic salt, 2 parts of mica powder, 2 parts of fumed silica, 2 parts of activated clay, 2.5 parts of graphite powder and 1.5 parts of hydrogen-containing silicone oil in parts by mass.
The invention provides a preparation method of the hydrated inorganic salt dry powder extinguishing agent in the technical scheme, which comprises the following steps:
mixing hydrated inorganic salt, inert filler, activated clay, hydrogen-containing silicone oil, water and organic dispersant to obtain mixed feed liquid;
and sequentially carrying out solid-liquid separation, drying and crushing on the mixed feed liquid to obtain the hydrated inorganic salt dry powder extinguishing agent.
The method comprises the steps of mixing hydrated inorganic salt, inert filler, activated clay, hydrogen-containing silicone oil, water and an organic dispersant to obtain mixed feed liquid, wherein the inert filler comprises one or more of talcum powder, mica powder, fumed silica and graphite powder.
In the present invention, the particle size of the activated clay is 40 to 45 μm, and more preferably 44 μm.
In the invention, when the inert filler comprises talcum powder, mica powder, fumed silica and graphite powder, the particle size of the talcum powder is preferably 2.5-3 μm, and more preferably 2.7 μm. The particle size of the mica powder is preferably 130-180 mu m, and more preferably 150 mu m. The particle size of the fumed silica is preferably 10-15 μm, and more preferably 13 μm. The particle size of the graphite powder is preferably 17-23 μm, and more preferably 17.65-20 μm.
In the present invention, the organic dispersant preferably includes one or more of n-hexane, acetone, benzene, toluene, xylene, chloroform, carbon tetrachloride, petroleum ether, gasoline, kerosene and perchloroethylene.
In the invention, the mass ratio of the organic dispersant to the hydrogen-containing silicone oil is preferably (3-5): 1, and more preferably 4: 1.
In the present invention, the order of mixing is preferably: mixing the hydrated inorganic salt, the inert filler, the activated clay and the hydrogen-containing silicone oil to obtain a base material; and mixing the base material, water and the organic dispersant to obtain mixed feed liquid.
In the invention, the mixing temperature is preferably 85-95 ℃, and more preferably 90 ℃.
In the invention, the mixing heat preservation time is preferably 2-5 h, and more preferably 3 h.
After the mixed feed liquid is obtained, the mixed feed liquid is subjected to solid-liquid separation, drying and crushing in sequence to obtain the hydrated inorganic salt dry powder extinguishing agent.
In the present invention, the solid-liquid separation is preferably suction filtration.
In the present invention, the drying is preferably performed in a blower.
In the present invention, the temperature of the drying is preferably 50 ℃.
In the present invention, the pulverization is preferably carried out in a pulverizer.
In the present invention, the time for the pulverization is preferably 2 min.
In the invention, the crushed material is obtained after crushing, and the crushed material is preferably screened to obtain the hydrated inorganic salt dry powder extinguishing agent.
The invention provides an application of the hydrated inorganic salt dry powder extinguishing agent in the technical scheme in inhibiting the thermal runaway propagation of the lithium ion battery.
In the invention, the hydrated inorganic salt dry powder extinguishing agent is sprayed on the surface of the lithium ion battery with thermal runaway and is used for cooling and extinguishing the lithium ion battery.
In order to further illustrate the present invention, the following detailed description of the hydrated inorganic salt dry powder fire extinguishing agent provided by the present invention is made with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
The invention provides a dry powder extinguishing agent taking ammonium aluminum sulfate dodecahydrate as a main material, which comprises the following components in percentage by mass: 90 percent of aluminum ammonium sulfate dodecahydrate, 2 percent of mica powder, 2 percent of fumed silica, 2 percent of activated clay, 2.5 percent of graphite powder and 1.5 percent of hydrogen-containing silicone oil, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.65 percent. Wherein the particle size of the activated clay is 44 μm, the particle size of the mica powder is 150 μm, the particle size of the fumed silica is 13 μm, and the particle size of the graphite powder is 20 μm.
The preparation method of the dry powder extinguishing agent with ammonium aluminum sulfate dodecahydrate as the main material comprises the following steps:
uniformly mixing 90 mass percent of ammonium aluminum sulfate dodecahydrate, 2 mass percent of mica powder, 2 mass percent of fumed silica, 2 mass percent of activated clay, 2.5 mass percent of graphite powder and 1.5 mass percent of hydrogen-containing silicone oil to prepare a base material;
adding a mixed liquid of water and a dispersing agent (acetone) into the base material, wherein the mass of the dispersing agent is 4 times that of hydrogen-containing silicone oil, and stirring for 3 hours at 90 ℃ to obtain a mixed material liquid;
filtering the mixed material liquid, and drying in a 50 ℃ blast drying oven to obtain a dried material;
putting the dried material into a pulverizer to pulverize for 2min to obtain a pulverized material;
and vibrating and sieving the crushed materials to obtain the aluminum ammonium sulfate dodecahydrate hydrated inorganic salt dry powder extinguishing agent.
Example 2
The invention provides a dry powder extinguishing agent taking ammonium aluminum sulfate dodecahydrate as a main material, which comprises the following components in percentage by mass: 90 percent of ammonium aluminum sulfate dodecahydrate, 1.5 percent of talcum powder, 2 percent of mica powder, 2 percent of fumed silica, 2 percent of activated clay, 1.5 percent of graphite powder and 1 percent of hydrogen-containing silicone oil, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.65 percent. Wherein the particle size of the activated clay is 44 μm, the particle size of the talcum powder is 2.7 μm, the particle size of the mica powder is 150 μm, the particle size of the fumed silica is 13 μm, and the particle size of the graphite powder is 20 μm.
The preparation method of the dry powder extinguishing agent with ammonium aluminum sulfate dodecahydrate as the main material comprises the following steps:
uniformly mixing 90 mass percent of ammonium aluminum sulfate dodecahydrate, 2 mass percent of mica powder, 2 mass percent of fumed silica, 2 mass percent of activated clay, 2.5 mass percent of graphite powder and 1.5 mass percent of hydrogen-containing silicone oil to prepare a base material;
adding a mixed liquid of water and a dispersing agent (acetone) into the base material, wherein the mass of the dispersing agent is 4 times that of hydrogen-containing silicone oil, and stirring for 3 hours at 90 ℃ to obtain a mixed material liquid;
filtering the mixed material liquid, and drying in a 50 ℃ blast drying oven to obtain a dried material;
and (3) putting the dried material into a grinder to be ground for 2min to obtain a ground material.
And vibrating and sieving the crushed materials to obtain the aluminum ammonium sulfate dodecahydrate hydrated inorganic salt dry powder extinguishing agent.
The unidirectional Differential Scanning Calorimetry (DSC), thermogravimetry curve (TG) and particle size distribution diagram of the ammonium aluminum sulfate dodecahydrate inorganic salt dry powder extinguishing agent prepared in the embodiment 2 are shown in figures 1-3, and shown in figures 1 and 2, the inorganic salt dry powder extinguishing agent prepared in the embodiment has a weight loss peak under a lower temperature condition, and has high thermal decomposition speed, low decomposition temperature and strong heat absorption capacity. As shown in FIG. 3, the inorganic salt dry powder fire extinguishing agent prepared by the present example has a uniform particle size distribution and a small particle size.
Application example
In the application example, a heating rod and 4 18650 type cylindrical batteries (corresponding to No. 1-4 lithium ion batteries) are arranged side by side, the lithium ion batteries are induced to be out of control thermally by the heating rod, thermal runaway spray flames are generated in the No. 1 batteries respectively, a certain amount of aluminum ammonium sulfate dodecahydrate fire extinguishing agent material is sprayed under three different thermal runaway conditions that the No. 2 batteries generate the thermal runaway spray flames and the No. 2 batteries open pressure release valves, the surface temperature of the batteries is recorded in real time through a thermocouple, and the thermal runaway conditions of the batteries are observed.
The situation of inhibition of the ammonium aluminum sulfate dodecahydrate inorganic salt hydrate dry powder extinguishing agent prepared in the embodiment 2 after thermal runaway on three conditions of the lithium ion battery is shown in fig. 5-7. Fig. 4 is a schematic diagram of the temperature of the surface of 4 18650 lithium ion batteries when thermal runaway occurs in parallel; FIG. 5 is a schematic diagram showing the temperature change of the surface of 4 18650 lithium ion batteries in parallel before and after spraying aluminum ammonium sulfate dodecahydrate fire extinguishing agent when thermal runaway spray flame occurs in the No. 1 battery; FIG. 6 is a schematic diagram showing the temperature changes of the surfaces of 4 18650 lithium ion batteries in parallel, before and after spraying aluminum ammonium sulfate dodecahydrate fire extinguishing agent when thermal runaway spray flame occurs in No. 2 battery; fig. 7 is a schematic diagram of the temperature change of the surface of 4 18650 lithium ion batteries before and after spraying aluminum ammonium sulfate dodecahydrate fire extinguishing agent when the pressure release valve of battery No. 2 is opened. As shown in fig. 4 to 7, the aluminum ammonium sulfate dodecahydrate fire extinguishing agent prepared in embodiment 2 of the present invention can achieve an effect of inhibiting thermal runaway of a lithium ion battery.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A hydrated inorganic salt dry powder fire extinguishing agent is characterized by comprising the following components in parts by mass:
80-90 parts of hydrated inorganic salt, 5-11 parts of inert filler, 1-3 parts of activated clay and 0.5-2 parts of hydrogen-containing silicone oil; the inert filler comprises one or more of talcum powder, mica powder, fumed silica and graphite powder.
2. A hydrated inorganic salt dry powder extinguishing agent according to claim 1, wherein when the inert filler comprises talc, mica powder, fumed silica and graphite powder, the inert filler comprises the following components in parts by weight: 1-2 parts of talcum powder, 2-3 parts of mica powder, 1-4 parts of fumed silica and 1-2 parts of graphite powder.
3. A hydrated inorganic salt dry powder extinguishing agent according to claim 1 or 2, wherein the hydrated inorganic salt comprises one or more of disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate, magnesium sulfate heptahydrate, aluminum potassium sulfate dodecahydrate, sodium thiosulfate pentahydrate, and sodium acetate trihydrate.
4. The dry powder extinguishing agent of hydrated inorganic salt as claimed in claim 1 or 2, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.5-1.8 wt%.
5. The preparation method of the hydrated inorganic salt dry powder extinguishing agent as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing hydrated inorganic salt, inert filler, activated clay, hydrogen-containing silicone oil, water and organic dispersant to obtain mixed feed liquid;
and sequentially carrying out solid-liquid separation, drying and crushing on the mixed feed liquid to obtain the hydrated inorganic salt dry powder extinguishing agent.
6. The method of claim 5, wherein the organic dispersant comprises one or more of n-hexane, acetone, benzene, toluene, xylene, chloroform, carbon tetrachloride, petroleum ether, gasoline, kerosene, and perchloroethylene.
7. The preparation method according to claim 5, wherein the mixing temperature is 85-95 ℃, and the mixing holding time is 2-5 h.
8. The preparation method according to claim 5 or 6, wherein the mass ratio of the organic dispersant to the hydrogen-containing silicone oil is (3-5): 1.
9. The method according to claim 5, wherein the activated clay has a particle size of 40 to 45 μm; the particle size of the talcum powder is 2.5-3 mu m, the particle size of the mica powder is 130-180 mu m, the particle size of the fumed silica is 10-15 mu m, and the particle size of the graphite powder is 17-23 mu m.
10. The application of the hydrated inorganic salt dry powder extinguishing agent as defined in any one of claims 1 to 4 in inhibiting thermal runaway propagation of lithium ion batteries.
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Inventor after: Ling Ziye Inventor after: Zhou Sili Inventor after: Fang Xiaoming Inventor after: Zhang Zhengguo Inventor before: Zhou Sili Inventor before: Ling Ziye Inventor before: Fang Xiaoming Inventor before: Zhang Zhengguo |