AU2021102630A4 - Novel high-efficiency composite fire extinguishing agent and preparation thereof - Google Patents
Novel high-efficiency composite fire extinguishing agent and preparation thereof Download PDFInfo
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- fire extinguishing
- extinguishing agent
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- lithium
- ion battery
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- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002131 composite material Substances 0.000 title description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 37
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 33
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 27
- WVSNNWIIMPNRDB-UHFFFAOYSA-N 1,1,1,3,3,4,4,5,5,6,6,6-dodecafluorohexan-2-one Chemical compound FC(F)(F)C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WVSNNWIIMPNRDB-UHFFFAOYSA-N 0.000 claims abstract description 24
- IDBYQQQHBYGLEQ-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorocyclopentane Chemical compound FC1CC(F)(F)C(F)(F)C1(F)F IDBYQQQHBYGLEQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000011257 shell material Substances 0.000 claims abstract description 13
- 239000011162 core material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004299 exfoliation Methods 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920006255 plastic film Polymers 0.000 claims description 6
- -1 polydimethylsiloxane Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- FFWAMIKRUMYSOW-UHFFFAOYSA-M potassium 1,1,2,2,3,3,4-heptafluorooctane-1-sulfonate Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)CCCC.[K+] FFWAMIKRUMYSOW-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 20
- 230000009977 dual effect Effects 0.000 abstract description 5
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003094 microcapsule Substances 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- A62D1/0021—Microcapsules
-
- 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
Landscapes
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
Provided are a high-efficiency fire extinguishing agent and a fire extinguishing process, in
which melamine urea-formaldehyde resin prepolymer is prepared followed by mixing with
montmorillonite, defoaming agent and fire extinguishing materials of perfluorohexanone and
heptafluorocyclopentane to prepare the core-shell high-efficiency fire extinguishing agent,
where melamine urea-formaldehyde resin is used as the shell material, and perfluorohexanone
and heptafluorocyclopentane are used as core materials. The prepared high-efficiency fire
extinguishing agent is loaded on the outer surface of the lithium-ion battery, providing effective
safety protection for the lithium-ion battery and ensuring the fire safety of lithium-ion battery.
In the fire extinguishing process, the high-efficiency fire extinguishing agent is ruptured when
temperature of the lithium ion battery is out of control, and the fire extinguishing materials are
released to play the dual role of fire retardant and fire extinguishing in time, ensuring the fire
extinguishing effect while taking into account the cooling ability. The fire of the lithium-ion
battery can be quickly extinguished and cooled, effectively preventing the re-ignition of the
lithium-ion battery and ensuring the safety of the lithium-ion battery.
Description
This application relates to fire safety, and more particularly to a novel high-efficiency
composite fire extinguishing agent and a preparation thereof.
Recently, lithium-ion batteries have been widely used in portable products, backup power
supplies, electric vehicles and other fields due to their advantages of high energy density and
long cycle life. However, during long-term use and storage, lithium-ion batteries inevitably face
problems such as squeezing, breakdown, temperature shock, overcharging, etc., resulting in
short-circuit and other damage. As a result, combustion or even explosion will be occurred,
resulting in equipment damage, casualties, etc. Therefore, in the large-scale application of
lithium-ion batteries, it is very important to solve the fire safety problem.
To ensure the safety of lithium-ion batteries, in addition to optimizing the internal
materials of the battery to reduce the possibility of fire, it is also necessary to establish an
effective external protection mechanism to judge whether there is a fire by detecting
temperature changes or voltage changes caused by thermal runaway of lithium-ion batteries.
zO Then the fire extinguishing agent is sprayed to extinguish the fire of the lithium-ion battery and
stop the spread of the fire in time. However, lithium-ion battery is a kind of high-energy
material, which has the characteristics of strong burning, fast heat diffusion and strong toxicity.
Traditional fire extinguishing agents have limited extinguishing effects on the fire of the
lithium-ion battery, which can only extinguish open flames but cannot fundamentally suppress
fires. In addition, the external protection of a series of fire extinguishing devices such as early
warning systems, sprays and storage devices will increase the weight and volume of lithium-ion
batteries during application, which not only affects the application of lithium-ion batteries, but
also is not absolutely reliable in the case of thermal abuse. Therefore, it is very meaningful to
choose a suitable extinguishing agent and design a new type of fire extinguishing device for the
large-scale application of lithium-ion batteries.
Chinese Patent Application No. 109420281A disclosed a microcapsule automatic fire
extinguishing agent, in which a resin shell formed by a reaction of melamine and/or
urea-formaldehyde with formaldehyde was used as a coating material to wrap the main fire
extinguishing material to form a microcapsule. The microcapsules were mixed with auxiliary
materials such as polymer resins, fibers and inorganic fillers to form a fire extinguishing agent
that integrates detection, control, activation and fire extinguishing units. However, the main fire
extinguishing material is not specially designed for the fires of the lithium ion battery. Although
the main fire extinguishing material can prevent and extinguish common electrical fires, the
main fire extinguishing material does not have the double functions of cooling and fire
extinguishing, and the re-ignition of lithium battery fires is difficult to effectively inhibit.
Therefore, it is still necessary to improve the existing fire extinguishing agents for the fire
safety of lithium-ion batteries, and design corresponding protection strategies to ensure the
safety of lithium-ion batteries to solve the above-mentioned problems.
An object of this application is to provide a novel high-efficiency composite fire
extinguishing agent and a preparation thereof to overcome the defects of the prior art. The
melamine urea-formaldehyde resin is taken as a shell material and the perfluorohexanone and
heptafluorocyclopentane are taken as core materials to prepare the high-efficiency fire
zO extinguishing agent with a core-shell structure. The prepared high-efficiency fire extinguishing
agent is loaded on the outer surface of the lithium ion battery to provide effective safety
protection on the lithium ion battery, and the dual functions of inflaming retarding and fire
extinguishing are timely played when the lithium ion battery is out of control due to heat, so as
to guarantee the use safety of the lithium ion battery.
To achieve the above object, this application provides a fire extinguishing process,
comprising:
Si. preparing a melamine urea-formaldehyde resin prepolymer;
S2, preparing a montmorillonite suspension; and mixing the montmorillonite suspension
with a fire extinguishing material, a defoaming agent and the melamine urea-formaldehyde resin prepolymer obtained in step Si according to a preset ratio followed by filtering and drying to obtain a high-efficiency fire extinguishing agent; and S3. loading the high-efficiency fire extinguishing agent obtained in step S2 uniformly on an outer surface of an aluminum-plastic film of a lithium ion battery. In some embodiments, in step S2, the fire extinguishing material is prepared by mixing perfluorohexanone and heptafluorocyclopentane according to a preset proportion. In some embodiments, in step S2, a mass ratio of the perfluorohexanone and the heptafluorocyclopentane is (0.5-2):1. In some embodiments, in step S, the preparation of the melamine urea-formaldehyde resin prepolymer specifically comprises: mixing melamine, urea, formaldehyde solution and water uniformly according to a preset molar ratio followed by adjusting a pH to 8.5-9.0; heating and stirring the mixture to fully react followed by cooling down quickly with ice water; and diluting the mixture to obtain a predetermined concentration of the melamine urea-formaldehyde resin prepolymer. In some embodiments, in step S, a molar ratio of the melamine to urea to the formaldehyde is 1:(1-3):(2-9). In some embodiments, in step Si, a concentration of the melamine urea-formaldehyde resin prepolymer is 1-50wt%. In some embodiments, a particle size of the high-efficiency fire extinguishing agent is zO 50-100 km. In some embodiments, in step S2, a volume ratio of the montmorillonite suspension to the fire extinguishing material to the melamine urea-formaldehyde resin prepolymer is (1-4):1:(2-6); and a concentration of the montmorillonite suspension is 0.1-1wt%. In some embodiments, in step S2, the montmorillonite suspension is obtained by ultrasonic exfoliation of natural montmorillonite in distilled water; and a power of the ultrasonic exfoliation is 10-50 kHZ, and a ultrasonic time is 1-2 h. In some embodiments, in step S2, the defoaming agent can be, but is not limited to, potassium heptafluorooctane sulfonate, sodium dodecylbenzene sulfonate, polydimethylsiloxane, n-octanol and a combination thereof.
In some embodiments, this application also provides the high-efficiency fire extinguishing
agent, and the high-efficiency fire extinguishing agent is prepared according to a method
* provided in steps S1-S2 in thefire extinguishing process. The high-efficiency fire extinguishing
agent includes the melamine urea-formaldehyde resin as a shell material and the fire
extinguishing materials as a core material; and the fire extinguishing materials include
perfluorohexanone and heptafluorocyclopentane.
This application has the following beneficial effects.
(1) This application prepares a core-shell structured high-efficiency fire extinguishing
agent by using melamine urea-formaldehyde resin as the shell material and perfluorohexanone
and heptafluorocyclopentane as the core materials. The liquid fire extinguishing agent is
changed to solid microcapsules, which breaks through the traditional external protection
mechanism and realizes the micro-precision control of flame retardant materials and fire
extinguishing agents. At the same time, the prepared high-efficiency fire extinguishing agent is
loaded on the outer surface of the aluminum-plastic film of the lithium ion battery to provide
effective safety protection for the lithium ion battery, and the dual functions of inflaming
retarding and fire extinguishing are timely played when the lithium ion battery is out of control
due to heat, so as to guarantee the use safety of the lithium ion battery.
(2) In this application, a composite fire extinguishing material for lithium-ion batteries is
prepared by mixing perfluorohexanone and heptafluorocyclopentane in a certain ratio, which is
zO used as a core material for high-efficiency fire extinguishing agents. It can not only effectively
extinguish the open flame of lithium ion batteries by using the excellent fire extinguishing
performance of perfluorohexanone, but also can achieve excellent cooling effects by using the
vaporization and heat absorption of heptafluorocyclopentane. In addition, the ratio of
perfluorohexanone and heptafluorocyclopentane was regulated to make the core material has a
suitable boiling point, a higher heat of vaporization and a specific heat, thereby ensuring the fire
extinguishing effect while taking into account the cooling ability. The fire of the lithium ion
battery can be quickly extinguished and cooled under the action of the composite fire
extinguishing material, effectively preventing the re-ignition of the lithium ion battery.
(3) Based on the characteristics of low boiling point and high vapor pressure of
perfluorohexanone used in fire extinguishing materials, melamine, urea and formaldehyde are used as raw materials in this application to prepare melamine urea-formaldehyde resin as shell material. The shell material has the advantages of high crosslinking density, good compactness,
' high mechanical strength, etc., and its flame retardant effect can also effectively prevent the fire
from spreading when a fire of the lithium ion battery occurs. The shell material is easy to crack
5 during use, so that the wrapped fire extinguishing agent is released to extinguish the early fire
source, realizing the dual function of flame retardant and fire extinguishing. At the same time,
the montmorillonite is added to modify the melamine urea-formaldehyde resin shell material to
improve the surface roughness of the fire extinguishing agent, thereby further improving its
thermal conductivity and stability, and making the core material of the liquid fire extinguishing
0 agent can be stably stored under the coating of the melamine urea-formaldehyde resin shell
material. This application can also effectively remove the gas foam in the reaction solution by
adding a defoaming agent, thereby ensuring that the wall material is complete after the fire
extinguishing agent is formed, and there is no foam in the liquid fire extinguishing agent
wrapped inside, which further improves the stability and fire extinguishing effect of the
5 high-efficiency fire extinguishing agent.
(4) In this application, the prepared high-efficiency fire extinguishing agent is directly
loaded on the surface of the lithium ion battery, which can effectively break through the
traditional external protection mechanism, and can easily and effectively establish safety
protection for the lithium ion battery without affecting the use of the lithium ion battery. When
zO the internal heat of the lithium ion battery is out of control and reaches a certain temperature,
the high-efficiency fire extinguishing agent loaded on the surface of the lithium ion battery
automatically ruptures, thereby releasing the fire extinguishing material, quickly blocking the
thermal runaway process of the lithium ion battery, and extinguishing the early fire source to
prevent the fire from spreading. At the same time, the cooling effect on the lithium-ion battery
can be achieved to avoid re-ignition, so as to ensure the safety of the lithium-ion battery.
Fig. 1 is a flow chart of a fire extinguishing process according to an embodiment of the
disclosure.
Fig. 2 is a schematic diagram of a covering position of a high-efficiency fire extinguishing agent in a lithium-ion battery soft pack in afire extinguishing process according to an embodiment of the disclosure. Fig. 3 is an X-ray energy spectrum of a high-efficiency fire extinguishing agent prepared in a fire extinguishing process according to an embodiment of the disclosure. Fig. 4 schematically shows a fire extinguishing effect of a high-efficiency fire extinguishing agent prepared in Embodiment 1 on a fire of a lithium ion battery. Fig. 5 is an application test of a lithium ion battery treated by afire extinguishing process prepared in Embodiment 1.
DETAILED DESCRIPTION OF EMBODIMENTS In order to render the objects, technical solutions and beneficial effects of the invention clearer, the invention will be described below in detail in conjunction with embodiments. It should be noted that only the structure and/or processing steps closely related to the solution of the invention are shown in the accompanying drawings, and other details not relevant to the present invention are omitted to avoid obscuring the invention due to unnecessary details. In addition, it should be further noted that the terms "comprises" "includes" or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article or apparatus that comprises a list of elements does not include only those elements but zo may include other elements not expressly listed or inherent to such process, method, article, or apparatus. A fire extinguishing process was provided in this application, which included the following specific steps. Si. A melamine urea-formaldehyde resin prepolymer was prepared. S2, A montmorillonite suspension was prepared. The montmorillonite suspension was mixed with a fire extinguishing material, a defoaming agent and the melamine urea-formaldehyde resin prepolymer obtained in step S Iaccording to a preset ratio followed by filtering and drying to obtain a high-efficiency fire extinguishing agent. S3. The high-efficiency fire extinguishing agent obtained in step S2 was loaded uniformly on an outer surface of an aluminum-plastic film of a lithium ion battery.
In step Si, the preparation of the melamine urea-formaldehyde resin prepolymer
specifically included the following steps.
The melamine, urea, formaldehyde solution and water were mixed uniformly according to
a preset molar ratio followed by adjusting a pH to 8.5-9.0. The mixture was heated and stirred
to fully react followed by cooling down quickly with ice water. The mixture was diluted to
obtain a predetermined concentration of the melamine urea-formaldehyde resin prepolymer. A
molar ratio of the melamine to urea to formaldehyde was 1:(1-3):(2-9). A concentration of the
prepared melamine urea-formaldehyde resin prepolymer was 1-50wt%.
In step S2, the montmorillonite suspension was obtained by ultrasonic exfoliation of
natural montmorillonite in distilled water. A power of the ultrasonic exfoliation was 10-50 kHZ,
and a ultrasonic time was 1-2 h. Thefire extinguishing material was prepared by mixing
perfluorohexanone and heptafluorocyclopentane according to a preset proportion, and a mass
ratio of the perfluorohexanone and the heptafluorocyclopentane was (0.5-2):1. A volume ratio
of the montmorillonite suspension to the fire extinguishing material to the melamine
urea-formaldehyde resin prepolymer was (1-4):1:(2-6), and a concentration of the
montmorillonite suspension was 0.1-1wt%. A particle size of the high-efficiency fire
extinguishing agent was 50-100 m. The defoaming agent can be, but was not limited to,
potassium heptafluorooctane sulfonate, sodium dodecylbenzene sulfonate, polydimethylsiloxane, n-octanol and a combination thereof.
The high-efficiency fire extinguishing agent and the fire extinguishing process provided in
this application are further described with reference to the following embodiments.
Embodiment 1
As shown in Fig. 1, provided herein were a high-efficiency fire extinguishing agent and a
fire extinguishing process, which has the following specific steps.
Si. Preparation of melamine urea-formaldehyde resin prepolymer
7.76 g of melamine, 7.40 g of urea, 29.98 g of formaldehyde solution (with a concentration
of 37wt%) and 30 g of distilled water were added into a three-necked flask followed by
adjusting a pH to 8.5-9.0 with anhydrous sodium carbonate. Then the three-necked flask was
heated in a water bath, and the temperature of the water bath was gradually increased from
30°C to 70°C at a rate of 2.5°C/min. After stirring for 1 h, the temperature of the mixture decreased rapidly to below 40°C with ice water. Then the mixture was diluted with 375 g of distilled water to obtain a melamine urea-formaldehyde resin (MUF) prepolymer with a concentration of 10 wt%.
S2. Preparation of high-efficiency fire extinguishing agent 0.06 g of natural montmorillonite powder was added to 32 mL of distilled water followed by exfoliating in an ultrasonic bath at 20 kHZ for 1.5 h to obtain a transparent, slightly milky white montmorillonite suspension. Then the montmorillonite suspension was mixed with 5 mL of perfluorohexanone, 5 mL of heptafluorocyclopentane, 0.3 g potassium heptafluorooctane sulfonate and 50 mL of 1Owt% MUF prepolymer prepared in step Si followed by stirring at 500 r/min for 6 h. The resulting solution was placed at least 6 h followed byfiltering and drying, and a high-efficiency fire extinguishing agent with an average particle size of 80 m was obtained. S3.Protection of lithium ion battery The high-efficiency fire extinguishing agent obtained in step S2 was uniformly coated on the outer surface of the middle of the aluminum-plastic film of the lithium ion soft package battery (3.7 V, 2000 mA), and the covering position of the high-efficiency fire extinguishing agent was shown in Fig. 2. In order to analyze the composition of the fire extinguishing agent prepared in this zA embodiment, the energy spectrum test was performed on the fire extinguishing agent before and after the rupture, and the results were shown in Fig. 3. The upper part of the Fig. 3 showed the element distribution of the complete fire extinguishing agent, and the lower part showed the element distribution of the ruptured fire extinguishing agent. The specific element weights were shown in Table 1. Table 1 Comparison of the weight of different elements in the complete fire extinguishing agent and the ruptured fire extinguishing agent C N 0 F
Complete fire extinguishing agent 26.67 18.12 7.94 47.27
Ruptured fire extinguishing agent 40.54 36.20 14.17 9.09
As shown in Fig. 3 and Table 1, it can be seen that the C, N and 0 elements in the complete fire extinguishing agent were evenly distributed in the entire microcapsule structure, ' but the F element was concentrated in the middle of the fire extinguishing agent, which proved that the fire extinguishing materials of perfluorohexanone and heptafluoride Cyclopentane were 5 encapsulated in a microcapsule structure. When the fire extinguishing agent ruptured and released the fire extinguishing material, the content of F element was significantly reduced and presented a more uniform distribution state, which indicated that the fire extinguishing material was fully released. The fire extinguishing ability of the high-efficiency fire extinguishing agent prepared in 0 this embodiment on lithium ion battery fires was tested according to the method shown in Fig. 5. Firstly, a heating rod was used to simulate thermal runaway, and six 32650 batteries (23.12 whx3.6 V) were ignited in an explosion-proof box, and 500 g of the high-efficiency fire extinguishing agent prepared in this embodiment was gradually sprayed after the batteries was fired. The fire can be extinguished after spraying the fire extinguishing agent for 10 s, and the 5 fire extinguishing agent was sprayed continuously for 20 s to further cool the battery. The internal reaction of the battery gradually stopped, and the surface temperature and internal temperature of the battery dropped to room temperature, and the battery did not burn again. The results showed that the high-efficiency fire extinguishing agent prepared in this embodiment had a better fire extinguishing effect on the fires of the lithium ion battery, which can achieve a zO cooling effect and effectively prevent re-ignition. To study the fire extinguishing effect of the fire extinguishing process provided herein, a fire extinguishing test was performed on the lithium-ion soft package battery loaded with high-efficiency fire extinguishing agent obtained in step S3. As shown in Fig. 5, the lithium-ion soft package battery was ignited and the fire began to spread rapidly. When the fire reached the part covered by the high-efficiency extinguishing agent, the fire quickly weakened and the open flame was completely extinguished after 15s, and the surface temperature of the battery dropped to room temperature. The shell of the high-efficiency fire extinguishing agent was destroyed after the temperature rises, and thefire extinguishing materials of perfluorohexanone and heptafluorocyclopentane were released, which can quickly extinguish the fire of the lithium-ion battery and perform a cooling effect. Further observations showed that the battery had no re-ignition phenomenon, indicating that the fire extinguishing process provided herein can quickly extinguish an open flame of a lithium ion battery, and the temperature of the lithium ion battery can quickly drop from 800°C to 30°C within 15 s, reaching a significant cooling effect and effectively avoiding the re-ignition of the battery.
Embodiments 2-9 and Comparative Embodiments 1-3
Embodiments 2-9 and Comparative Embodiments 1-3 respectively provided a
high-efficiency fire extinguishing agent and fire extinguishing process. Compared with
Embodiments 1, the difference was that some preparation parameters in steps Sl and S2 were
adjusted. The corresponding parameters of each Embodiment and Comparative Embodiment
were shown in Table 2, and the remaining steps and parameters were the same as those of
Embodiment 1.
Table 2 Related process parameters of Embodiments 2-9 and Comparative Embodiments 1- 3
Step Sl Step S2 Embodiments/ Mass ratio of Volume ratio of montmorillonite Comparative Molar ratio of melamine to urea perfluorohexanone to suspension to fire extinguishing Embodiments to formaldehyde heptafluorocyclopentane material to prepolymer
Embodiments 2 1:1:2 1:1 3:1:5
Embodiments 3 1:3:9 1:1 3:1:5
Embodiments 4 1:2:6 0.5:1 3:1:5
Embodiments 5 1:2:6 2:1 3:1:5
Embodiments 6 1:2:6 1:1 1:1:5
Embodiments 7 1:2:6 1:1 4:1:5
Embodiments 8 1:2:6 1:1 3:1:2
Embodiments 9 1:2:6 1:1 3:1:6
Comparative 1:2:6 1:0 3:1:5 Embodiments 1
Comparative 1:2:6 0:1 3:1:5 Embodiments 2
Comparative 1:2:6 1:1 0:1:5
The corresponding fire extinguishing agents were prepared according to the process
parameters provided in Embodiments 2-9 and Comparative Embodiments 1-3, and were loaded
on the outer surface of the aluminum plastic film of the lithium ion battery according to the
method of step S3 in Embodiment 1. Then the fire extinguishing effect of the fire extinguishing
agents provided in Embodiments 2-9 and Comparative Embodiments 1-3 were tested.
The processes provided in Embodiments 2-9 can effectively protect lithium-ion batteries,
and had good fire extinguishing effects on the fires of lithium-ion battery. The core material of
the fire extinguishing agent provided in Comparative Embodiment 1 was only
heptafluorocyclopentane, and the core material of the fire extinguishing agent provided in
Comparative Embodiment 2 was only perfluorohexanone.
Compared with the microcapsule fire extinguishing agent prepared in each Embodiment
that contained heptafluorocyclopentane and perfluorohexanone as the core material, the single
fire extinguishing agent component in Comparative Embodiments 1 and 2 was difficult to
achieve the fire extinguishing and cooling effects at the same time, leading to the problem of
poor fire extinguishing effect and easy re-ignition. In Comparative Embodiment 3, montmorillonite was not added during the preparation of the microcapsule fire extinguishing
agent. Compared with the other embodiments, the prepared microcapsules were relatively
inferior in stability, and were easily damaged during storage, resulting in weakened fire
extinguishing effect in practical applications. Therefore, the high-efficiency fire extinguishing
agent and fire extinguishing process provided in this application designed a composite fire
extinguishing agent suitable for lithium-ion batteries, which was encapsulated by melamine
urea-formaldehyde resin and then modified with montmorillonite, so as to obtain the
high-efficiency fire extinguishing agent with excellent fire extinguishing effects and high
stability that can provide an effective external protection mechanism for lithium-ion batteries.
This application provides a high-efficiency fire extinguishing agent and a fire
extinguishing process, in which melamine urea-formaldehyde resin prepolymer was prepared
followed by mixing with montmorillonite, defoaming agent and fire extinguishing materials of
perfluorohexanone and heptafluorocyclopentane to prepare the core-shell high-efficiency fire extinguishing agent, where melamine urea-formaldehyde resin was used as the shell material, and perfluorohexanone and heptafluorocyclopentane were used as core materials. The prepared high-efficiency fire extinguishing agent was loaded on the outer surface of the lithium-ion battery, which provided effective safety protection for the lithium-ion battery. In the fire extinguishing process, the high-efficiency fire extinguishing agent was ruptured when temperature of the lithium ion battery was out of control, and thefire extinguishing materials were released to play the dual role offire retardant and fire extinguishing in time, ensuring the fire extinguishing effect while taking into account the cooling ability. The fire of the lithium-ion battery can be quickly extinguished and cooled, effectively preventing the re-ignition of the lithium-ion battery and ensuring the safety of the lithium-ion battery.
The above embodiments are merely illustrative of the disclosure, and are not intended to
limit the disclosure. Any changes, equivalent modifications and improvements made by those
skilled in the art without departing from the spirit of the present disclosure, or
directly/indirectly apply the present disclosure in other related technical fields, shall fall within
the scope of the present disclosure.
Claims (10)
1. A fire extinguishing process, comprising: Si. preparing a melamine urea-formaldehyde resin prepolymer; S2, preparing a montmorillonite suspension; and mixing the montmorillonite suspension with a fire extinguishing material, a defoaming agent and the melamine urea-formaldehyde resin prepolymer obtained in step Si according to a preset ratio followed by filtering and drying to obtain a high-efficiency fire extinguishing agent; and S3. loading the high-efficiency fire extinguishing agent obtained in step S2 uniformly on an outer surface of an aluminum-plastic film of a lithium ion battery.
2. The fire extinguishing process according to claim 1, characterized in that in step S2, the fire extinguishing material is prepared by mixing perfluorohexanone and heptafluorocyclopentane according to a preset proportion.
3. The fire extinguishing process according to claim 2, characterized in that in step S2, a mass ratio of the perfluorohexanone and the heptafluorocyclopentane is (0.5-2):1.
4. The fire extinguishing process according to claim 1, characterized in that in step Si, the preparation of the melamine urea-formaldehyde resin prepolymer specifically comprises: mixing melamine, urea, formaldehyde solution and water uniformly according to a preset molar ratio followed by adjusting a pH to 8.5-9.0; heating and stirring the mixture to fully react followed by cooling down quickly with ice water; and diluting the mixture to obtain a predetermined concentration of the melamine urea-formaldehyde resin prepolymer.
5. The fire extinguishing process according to claim 4, characterized in that in step Si, a molar ratio of the melamine to urea to the formaldehyde is 1:(1-3):(2-9); and a concentration of the melamine urea-formaldehyde resin prepolymer is 1-50wt%.
6. The fire extinguishing process according to any one of claims 1 and 4, characterized in
that a particle size of the high-efficiency fire extinguishing agent is 50-100 [m.
7. The fire extinguishing process according to claim 1, characterized in that in step S2, a
volume ratio of the montmorillonite suspension to the fire extinguishing material to the
melamine urea-formaldehyde resin prepolymer is (1-4):1:(2-6); and a concentration of the
montmorillonite suspension is 0.1-1wt%.
8. The fire extinguishing process according to claim 1, characterized in that in step S2, the
montmorillonite suspension is obtained by ultrasonic exfoliation of natural montmorillonite in
distilled water; and a power of the ultrasonic exfoliation is 10-50 kHZ, and a ultrasonic time is
1-2 h.
9. The high-efficiency fire extinguishing agent and the fire extinguishing process
according to any one of claims 8, characterized in that in step S2, the defoaming agent can be,
but is not limited to, potassium heptafluorooctane sulfonate, sodium dodecylbenzene sulfonate,
polydimethylsiloxane, n-octanol and a combination thereof.
10. The high-efficiency fire extinguishing agent, characterized in that the high-efficiency
fire extinguishing agent is prepared according to a method provided in steps Si-S2 in the fire
extinguishing process according to any one of claims 1-9, and includes the melamine
urea-formaldehyde resin as a shell material and the fire extinguishing materials as a core
material; and the fire extinguishing materials include perfluorohexanone and
heptafluorocyclopentane.
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| CN202110302290.5A CN113181589B (en) | 2021-03-22 | 2021-03-22 | High-efficiency fire extinguishing agent and fire safety extinguishing process |
| CN202110302290.5 | 2021-03-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113533419A (en) * | 2021-07-09 | 2021-10-22 | 中国科学技术大学 | Preparation, filling and discharging integrated device for gas-solid composite fire extinguishing agent |
| CN116850522A (en) * | 2023-05-26 | 2023-10-10 | 广东黑卫防火技术有限公司 | Solid aerogel perfluorinated hexanone fire extinguishing sheet, preparation method thereof, magnetic fire extinguishing patch and energy storage device |
| WO2023241316A1 (en) * | 2022-06-15 | 2023-12-21 | 浙江铭诺新材料科技有限公司 | Perfluorohexanone microcapsule fire extinguishing material and preparation method therefor |
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| CN113948767B (en) * | 2021-10-19 | 2024-01-30 | 广东瑞科美电源技术有限公司 | Preparation method of safe lithium battery electrolyte containing microcapsule and lithium battery |
| CN113948817B (en) * | 2021-10-19 | 2024-01-30 | 广东瑞科美电源技术有限公司 | Preparation method of composite diaphragm for lithium battery and lithium battery using same |
| CN114678632A (en) * | 2022-03-15 | 2022-06-28 | 浙江锂盾新能源材料有限公司 | Cooling fire-extinguishing type flame-retardant lithium ion battery aluminum plastic film and battery |
| CN114618111B (en) * | 2022-03-28 | 2023-05-26 | 中国人民警察大学 | Perfluoro-hexanone fire-extinguishing microcapsule and preparation method thereof |
| CN115671641B (en) * | 2022-10-27 | 2023-10-20 | 国网浙江省电力有限公司湖州供电公司 | High-vaporization heat porous fire extinguishing medium applied to electrochemical energy storage system and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3721857B2 (en) * | 1999-06-04 | 2005-11-30 | 株式会社日立製作所 | Nonflammable electrolyte and lithium secondary battery using the same |
| CN107213576A (en) * | 2017-07-17 | 2017-09-29 | 九江中船化学科技有限公司 | A kind of clean efficient gas extinguishing agent composition |
| CN110639157B (en) * | 2019-09-24 | 2021-01-29 | 九江中船化学科技有限公司 | Efficient composite fire extinguishing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113533419A (en) * | 2021-07-09 | 2021-10-22 | 中国科学技术大学 | Preparation, filling and discharging integrated device for gas-solid composite fire extinguishing agent |
| CN113533419B (en) * | 2021-07-09 | 2022-07-15 | 中国科学技术大学 | Preparation, filling and discharging integrated device for gas-solid composite fire extinguishing agent |
| WO2023241316A1 (en) * | 2022-06-15 | 2023-12-21 | 浙江铭诺新材料科技有限公司 | Perfluorohexanone microcapsule fire extinguishing material and preparation method therefor |
| CN116850522A (en) * | 2023-05-26 | 2023-10-10 | 广东黑卫防火技术有限公司 | Solid aerogel perfluorinated hexanone fire extinguishing sheet, preparation method thereof, magnetic fire extinguishing patch and energy storage device |
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| CN113181589B (en) | 2022-02-08 |
| CN113181589A (en) | 2021-07-30 |
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