CN116271679A - Liquid fire-fighting medium and preparation method and application thereof - Google Patents
Liquid fire-fighting medium and preparation method and application thereof Download PDFInfo
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- CN116271679A CN116271679A CN202310274626.0A CN202310274626A CN116271679A CN 116271679 A CN116271679 A CN 116271679A CN 202310274626 A CN202310274626 A CN 202310274626A CN 116271679 A CN116271679 A CN 116271679A
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- 238000002360 preparation method Methods 0.000 title abstract description 11
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- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 150000003077 polyols Chemical class 0.000 claims abstract description 27
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical class CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 70
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 30
- 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 description 23
- 238000004146 energy storage Methods 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 229910052744 lithium Inorganic materials 0.000 abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 11
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- 239000002904 solvent Substances 0.000 abstract description 11
- 150000005846 sugar alcohols Polymers 0.000 abstract description 10
- 239000002609 medium Substances 0.000 description 112
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- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
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- 229940083957 1,2-butanediol Drugs 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical group CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000002309 gasification Methods 0.000 description 2
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- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 206010060904 Freezing phenomenon Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- 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
- A62C—FIRE-FIGHTING
- A62C31/00—Delivery of fire-extinguishing material
- A62C31/005—Delivery of fire-extinguishing material using nozzles
-
- 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
- A62D1/0035—Aqueous solutions
-
- 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
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- 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
The invention discloses a liquid fire-fighting medium and a preparation method and application thereof, wherein the liquid fire-fighting medium comprises polyalcohol, perfluorinated hexanone, water and pH regulator; 50-60% of polyol, 8-12% of perfluorinated hexanone and the balance of water, wherein the sum of the volumes of the polyol, the perfluorinated hexanone and the water is 100%; wherein the boiling point of the polyol is greater than or equal to 180 ℃; the pH regulator is used for regulating the pH value of the liquid fire-fighting medium to 8-9. The liquid fire-fighting medium can lead the perfluorinated hexanone into the thermal runaway battery core to enter the material level in a liquid state through the guiding of the low-surface tension solvent so as to prevent the thermal runaway from continuing to react, meanwhile, the weak alkalinity of the medium further inhibits the reaction strength of water and lithium in the battery core, and the thermal failure battery core is only immersed in the fire-fighting process. The invention realizes the extinguishing of the fire source from the root, and no afterburning occurs.
Description
Technical Field
The invention relates to the technical field of fire extinguishment, in particular to a liquid fire extinguishing medium and a preparation method and application thereof.
Background
The lithium ion battery is widely applied to the fields of electric automobiles, energy storage systems and the like due to the characteristics of high working voltage, high energy density, wide working temperature, long cycle life, no memory effect, environmental friendliness and the like. Taking a lithium ion battery energy storage power station as an example, along with the large-scale application of the lithium ion battery energy storage power station, the safety problem of an energy storage system is brought into wide attention, the lithium ion battery is easy to generate heat in the charging and discharging process, the local temperature is extremely easy to be too high to cause spontaneous combustion, and once one or a plurality of battery cores are spontaneous combustion, flame is extremely easy to spread in the whole battery box and even the whole energy storage system, so that serious thermal runaway phenomenon occurs; along with the construction and application of the energy storage power station project, the fire hazard of the energy storage power station project is gradually revealed. How to ensure the fire safety of an energy storage power station and ensure the safe operation of the energy storage power station is a problem to be solved urgently in the energy storage industry. The main fire-fighting means in the related art at present are as follows:
one is gas fire protection, which uses perfluoro-hexanone or heptafluoropropane as fire extinguishing inhibitor, and when the battery box is in fire, the fire is extinguished and inhibited by spraying perfluoro-hexanone or heptafluoropropane. In the closed space, the perfluoro-hexanone or heptafluoropropane with certain concentration has excellent cooling and fire extinguishing effects. However, both the perfluoro-hexanone and the heptafluoropropane belong to gaseous fire extinguishing media, and fire surface flames can only be extinguished in a lithium ion battery thermal runaway fire disaster, and even if the fire surface flames are injected into a sealed battery box, the protection of a battery cell shell is difficult to break through so as to contact a battery thermal runaway source. Secondly, the fire extinguishing nature of the perfluoro-hexanone and the heptafluoropropane is that the temperature of a heat source is reduced through gasification heat absorption and the generated gas is isolated from oxygen to achieve the fire control purpose, but the thermal runaway of the lithium ion battery is that the chemical reaction has low temperature requirements, and the material of the lithium ion battery itself is provided with oxygen element to provide oxygen for the thermal runaway reaction, so that the thermal runaway lithium ion battery is difficult to be hindered from being reburning.
A fire-fighting liquid medium is mainly to use water as fire-fighting medium and to achieve the purpose of fire-fighting by directly injecting water into a thermal runaway cell. After water enters, the energy of thermal runaway of the battery core is absorbed and reacts with internal lithium so as to block electrochemical energy runaway reaction; but the negative effects are: the reaction of water and lithium inside the cell is severe, which is unfavorable for water entering the thermal runaway cell, so a large amount of water is often needed to dilute the negative effect of the reaction, but a large amount of water can also cause the short circuit and the fire of the battery module of the energy storage power station to cause secondary damage. Meanwhile, water is easy to freeze at low temperature, and is unfavorable for use in low-temperature environment.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, it is an object of embodiments of the present invention to provide a liquid fire fighting medium.
Another object of the embodiment of the invention is to provide a method for preparing a liquid fire-fighting medium.
It is a further object of embodiments of the present invention to provide for the use of the liquid fire fighting medium described above.
To this end, a first aspect of an embodiment of the present invention provides a liquid fire fighting medium comprising a polyol, perfluoro hexanone, water, and a pH adjustor;
the sum of the volumes of the polyol, the perfluorinated hexanone and the water is 100 percent, wherein the polyol is 50 to 60 percent, the perfluorinated hexanone is 8 to 12 percent and the balance is the water; wherein, the liquid crystal display device comprises a liquid crystal display device,
the boiling point of the polyol is more than or equal to 180 ℃;
the pH regulator is used for regulating the pH value of the liquid fire-fighting medium to 8-9.
According to the liquid fire-fighting medium, the perfluorinated hexanone is led into the thermal runaway battery core to enter the material level in a liquid state through the low-surface tension solvent, so that the thermal runaway continuous reaction is prevented, meanwhile, the weak alkalinity of the liquid fire-fighting medium further inhibits the reaction intensity of water and lithium in the battery core, and the thermal failure battery core is immersed in the fire-fighting process. The embodiment of the invention realizes the root extinguishing of the fire source in the battery core without the occurrence of reburning. In addition, the liquid fire-fighting medium provided by the embodiment of the invention takes the polyalcohol with the boiling point of more than or equal to 180 ℃ as the main solvent, so that the liquid fire-fighting medium has a wider temperature application window.
In some embodiments, the polyol is one or more of ethylene glycol, propylene glycol, glycerol, or butanediol. Preferably, the polyol is ethylene glycol.
In some embodiments, the pH adjuster is NaHCO 3 、KHCO 3 、LiHCO 3 、Na 2 CO 3 、K 2 CO 3 One or more of the following. Preferably, the pH regulator is LiHCO 3 。
In some embodiments, the water is deionized water.
In some embodiments, the polyol is 50 to 55%.
In some embodiments, the pH adjustor is used to adjust the pH of the liquid fire-fighting medium to 8.5 to 9.
The second aspect of the embodiment of the invention also provides a preparation method of the liquid fire-fighting medium, which comprises the following steps: and (3) uniformly mixing the perfluorinated hexanone, the polyol and the water, and then regulating the pH value by using the pH regulator to obtain the liquid fire-fighting medium.
The preparation method of the embodiment of the invention is simple, easy to operate, high in safety of the used components, stable in property of the prepared liquid fire-fighting medium and easy to transport and store.
The third aspect of the embodiment of the invention also provides an application of the liquid fire-fighting medium as a fire extinguishing agent for lithium ion batteries, wherein the liquid fire-fighting medium is the liquid fire-fighting medium or the liquid fire-fighting medium prepared by the method.
In some embodiments of use, the liquid fire-fighting medium is applied to fire protection of a lithium ion battery energy storage system, and is applied to a battery box of the lithium ion battery energy storage system when a thermal runaway phenomenon occurs in a battery cell of the battery box.
In some embodiments of use, the liquid fire-fighting medium is immersed directly inside the cell through an explosion-proof valve that opens before the cell is thermally out of control.
In some embodiments of the use, the injection is stopped after the battery compartment is filled with the liquid fire-fighting medium. Preferably, the liquid fire-fighting medium fills the battery box within 2-4 min.
In some embodiments of use, the liquid fire medium is used at an ambient temperature of-40 to 60 ℃.
In some embodiments of use, the liquid fire medium is used at an ambient temperature of-40 to 0 ℃.
The embodiment of the invention has the advantages and beneficial effects that:
(1) According to the liquid fire-fighting medium, the perfluorinated hexanone is invaded into the thermal runaway battery cell in a liquid state to radically extinguish fire, and re-burning cannot occur. When the lithium ion battery energy storage system is applied to the lithium ion battery energy storage system, thermal runaway occurs in a single battery box, other electric boxes and the whole system are not affected, and therefore the safety of the whole system is protected to the greatest extent.
(2) According to the embodiment of the invention, the liquid fire-fighting medium is guided to enter the thermal runaway cell through the low-surface tension solvent and then invades the material level, so that the thermal runaway is prevented from continuously reacting.
(3) The liquid fire-fighting medium is alkalescent, so that the reaction strength of the liquid fire-fighting medium with lithium after entering the battery cell can be effectively reduced, and the battery cell with thermal failure only needs to be immersed in the fire-fighting process.
(4) The liquid fire-fighting medium takes glycol as a main solvent, has a wider temperature application window, and can adapt to the application environment of-40 ℃ to 60 ℃.
(5) The liquid fire-fighting medium provided by the embodiment of the invention is more environment-friendly and safer in the fire-fighting process, and has better stability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
fig. 1 is a state diagram of a battery pack for performing a fire extinguishing experiment on a lithium ion battery pack by using a liquid fire-fighting medium according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In this document, the term "and/or" is merely an association relation describing an associated object, meaning that there may be three relations, e.g. a and/or B, which may mean: a exists alone, A and B exist together, and B exists alone.
The term "plurality" herein refers to more than two (including two).
In this context, the term "battery compartment" is used in its ordinary sense in the art, also called "battery pack", and includes a battery module and a case that serves to house and protect the battery module. In addition, the battery box further comprises a battery management system, and the battery management system is in data communication with the fire-fighting linkage control system through detecting the states of all the battery cores in the battery module and performing corresponding control adjustment and strategy implementation on the battery box according to the states of all the battery cores. So as to intensively control the fire fighting device to work through the fire fighting linkage control system. It is understood that the term "battery module" is used in its ordinary sense in the art, and a battery module includes a plurality of cells connected in series or parallel or a series-parallel connection, where a series-parallel connection refers to both series connection and parallel connection of the plurality of cells, and may further include a bus bar for implementing electrical connection between the plurality of cells. It is understood that the term "battery cell" is used in its ordinary meaning in the art, i.e., the battery cell is the smallest unit that constitutes a battery module, and performs the conversion between electrical energy and chemical energy, such as a lithium ion battery according to an embodiment of the present invention.
Where a value is described herein as a range, it is understood that such disclosure includes disclosure of all possible sub-ranges within the range, as well as specific values falling within the range, regardless of whether the specific value or sub-range is explicitly recited.
In this context, the terms "about", "left and right" refer to +/-10% of the recited values.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Embodiments of the present invention aim to solve at least one of the technical problems in the related art to a certain extent, and a first aspect of the embodiments of the present invention proposes a liquid fire-fighting medium comprising polyol, perfluoro-hexanone, water and a pH adjustor;
the sum of the volumes of the polyol, the perfluorinated hexanone and the water is 100%, wherein the polyol is 50-60%, the perfluorinated hexanone is 8-12%, and the balance is water;
wherein the boiling point of the polyol is greater than or equal to 180 ℃;
the pH regulator is used for regulating the pH value of the liquid fire-fighting medium to 8-9.
In the embodiment of the invention, the perfluorinated hexanone is led into the thermal runaway battery core to enter the material level in a liquid state through a low surface tension solvent so as to prevent the thermal runaway from continuing to react, and meanwhile, the weak alkalinity of the liquid fire-fighting medium further inhibits the reaction strength of water and lithium in the battery core, and the thermal failure battery core is immersed in the fire-fighting process. The embodiment of the invention realizes the root extinguishing of the fire source in the battery core without the occurrence of reburning. In addition, the liquid fire-fighting medium provided by the embodiment of the invention takes the polyalcohol with the boiling point of more than or equal to 180 ℃ as the main solvent, so that the liquid fire-fighting medium has a wider temperature application window.
It can be understood that the liquid fire-fighting medium of the embodiment of the invention is different from gaseous fire-fighting medium perfluoro-hexanone or heptafluoropropane, can be directly immersed into the thermal runaway cell through the explosion-proof valve opened before the thermal runaway of the cell, can radically extinguish the fire source in the cell, and can not generate afterburning.
It can be appreciated that the liquid fire-fighting medium of the embodiment of the invention is different from the water medium, and the surface tension of the medium is far lower than that of water, so that the liquid fire-fighting medium is beneficial to the fire fighting by invading the material level inside the battery cell. The liquid medium can inhibit the reaction intensity of the liquid fire-fighting medium and lithium in the battery cell, and the liquid fire-fighting medium only needs to submerge the battery cell with heat failure relative to the water medium. In the liquid fire-fighting medium, the gaseous fire-fighting medium, namely the perfluorinated hexanone, is introduced into the failure cell through the liquid characteristic to perform fire-fighting, and other fire-extinguishing substances and additives are allocated to strengthen the overall fire-extinguishing capability of the liquid medium.
In the present invention, the solvent includes a polyhydric alcohol and water, and the polyhydric alcohol is the main solvent, and the inventors found that: in the embodiment of the invention, the ratio of the polyhydric alcohol in the liquid fire-fighting medium is 50-60%, under the ratio, the freezing point of the liquid fire-fighting medium can be detected below-40 ℃, thereby meeting the application scene of more than 99%, simultaneously, under the addition, the surface tension of water is reduced, so that the liquid fire-fighting medium is easier to be injected into the battery core and invaded into a material level for fire fighting, and meanwhile, the boiling point and specific heat capacity of the water are improved, and the fire extinguishing capability is enhanced. Non-limiting examples are: the polyol may be 50%, 52%, 55%, 56%, 58%, 60%, etc.
The inventors found that: in the embodiment of the invention, when the proportion of the perfluorinated hexanone in the liquid fire-fighting medium is less than 8%, the temperature reduction rate is low during fire fighting, and the fire-fighting effect is not achieved; when the proportion of the perfluorinated hexanone is more than 12%, the cooling rate can not be effectively improved, and the overall cost is increased; comprehensively considering that the proportion of the perfluorinated hexanone is 8-12%; non-limiting examples are: the content of the perfluoro-hexanone is 8%, 9%, 10%, 11%, 12% and the like.
The inventors found that: when the pH value of the liquid fire-fighting medium is lower than 8, the reaction inhibition strength of water and lithium metal in the battery is low, the reaction is severe, and the safety is influenced; when the pH value of the liquid fire-fighting medium is more than 9, on one hand, the ageing of the fire-fighting system is accelerated, and on the other hand, the high alkaline environment is easy to produce dirt, and comprehensively considered, the pH value of the liquid fire-fighting medium is adjusted to be 8-9 through the pH regulator. Non-limiting examples are: the pH regulator is used for regulating the pH of the liquid fire-fighting medium to 8, 8.2, 8.5, 8.6, 8.8, 9, etc.
In the invention, the main solvent is the polyhydric alcohol with the boiling point of more than or equal to 180 ℃, and the main reasons are as follows: the lithium ion battery has the explosion-proof valve opening stage before thermal runaway, and the temperature of the explosion-proof valve opening is generally 130-160 ℃, and the boiling point of the polyhydric alcohol in the formula is controlled to be more than or equal to 180 ℃ in the application, so that potential safety hazards formed by gasification when alcohols with lower selected temperature are effectively avoided.
In some embodiments, the polyol is one or more of ethylene glycol, propylene glycol, glycerol, or butanediol. Preferably, the polyol is ethylene glycol. It can be understood that the ethylene glycol has better miscibility compared with other alcohols, so that the fire-fighting effect is further improved, and the application range is wider and the ethylene glycol is more available.
In some embodiments, the pH adjuster is NaHCO 3 、KHCO 3 、LiHCO 3 、Na 2 CO 3 、K 2 CO 3 One or more of the following. Preferably, the pH adjustor is LiHCO 3 . When the pH regulator is LiHCO 3 On the one hand LiHCO 3 The lithium ion battery is slightly alkaline, and can inhibit the reaction of water and lithium in the battery through the alkalinity, and on the other hand, the concentration of lithium ions is increased, so that the reaction of water and lithium in the battery is inhibited to generate lithium ions. The combined action of the alkali inhibition and the concentration inhibition effectively inhibits the reaction intensity of water and lithium in the battery.
In some embodiments, the water is deionized water.
In some embodiments, the liquid fire medium has 50-55% polyol, 8-12% perfluorohexanone, and 33-42% water.
In some embodiments, a pH adjustor is used to adjust the pH of the liquid fire-fighting medium to between 8.5 and 9. The inventors found that: under the condition that the pH is 8.5-9, the alkali inhibition can be better, the aging of the fire-fighting system is basically negligible, the generation probability of dirt is reduced, and the safety and the reliability of the whole fire-fighting system are further ensured.
By way of example, embodiments of the present invention provide a liquid fire fighting medium comprising ethylene glycol, perfluoro hexanone, water, and LiHCO 3 ；
According to the volume percentage, the ethylene glycol accounts for 50-60 percent, the perfluorinated hexanone accounts for 8-12 percent, and the balance is water;
LiHCO 3 is used for adjusting the pH value of the liquid fire-fighting medium to 8-9.
In the example, ethylene glycol is used as a main solvent of a liquid fire-fighting medium, and perfluoro-hexanone is mixed into ethylene glycol to form ethylene glycol-perfluoro-hexanone emulsion, and the ethylene glycol-perfluoro-hexanone emulsion has an ethylene glycol guiding flow function and can release perfluoro-hexanone when heated, and can be gasified rapidly and cooled for first-round fire fighting; the glycol-perfluoro hexanone emulsion is matched with weak alkaline water for strengthening the fire-fighting function of the fire-fighting medium. The water is dissolved in the ethylene glycol to reduce the surface tension, so that the liquid fire-fighting medium can conveniently invade the internal material of the thermal runaway battery cell to carry out fire-fighting, the weak alkaline water enters the internal part of the battery cell and then carries out chemical reaction with internal lithium, the weak alkaline water can inhibit the chemical reaction intensity, the fire-fighting function is further enhanced, the reaction of the weak alkaline water and the internal lithium of the battery cell replaces the original thermal runaway reaction after the weak alkaline water enters the internal part of the battery cell, and the generated heat can be gasified and taken away by the perfluoro-hexanone.
The second aspect of the embodiment of the invention also provides a preparation method of the liquid fire-fighting medium, which comprises the following steps: and (3) uniformly mixing the perfluorinated hexanone, the polyalcohol and the water, and then regulating the pH value by using the pH regulator to obtain the liquid fire-fighting medium.
The preparation method of the embodiment of the invention is simple, easy to operate, high in safety of the used components, stable in property of the prepared liquid fire-fighting medium and easy to transport and store.
The preparation process of the embodiment of the invention can be carried out at normal temperature (25 ℃ +/-5 ℃).
The third aspect of the embodiment of the invention also provides an application of the liquid fire-fighting medium as a fire extinguishing agent for lithium ion batteries, wherein the liquid fire-fighting medium is the liquid fire-fighting medium or the liquid fire-fighting medium prepared by the method.
In some embodiments of the use, the liquid fire-fighting medium is applied to fire protection of a lithium ion battery energy storage system, and when a thermal runaway phenomenon occurs in an electrical cell in a battery box of the lithium ion battery energy storage system, the liquid fire-fighting medium is applied to the battery box.
In some embodiments of use, the liquid fire-fighting medium is immersed directly inside the cell through an explosion-proof valve that opens before thermal runaway of the cell.
In some embodiments of the use, the injection is stopped after the battery compartment is filled with the liquid fire-fighting medium. Preferably, the liquid fire-fighting medium fills the battery box within 2-4 min. Non-limiting examples are: the battery box is filled for a period of about 2 minutes, about 2.5 minutes, about 3 minutes, about 3.5 minutes, about 4 minutes, etc.
In some embodiments of use, the liquid fire medium is used at an ambient temperature of-40 ℃ to 60 ℃. Non-limiting examples are: the application environment temperature can be-40 to-20 ℃, 20 to 0 ℃, 10 to 0 ℃, 0 to 30 ℃, 20 to 60 ℃ and the like.
In some embodiments of use, the liquid fire medium is used at an ambient temperature of-40 ℃ to 0 ℃.
The following are non-limiting examples and comparative examples of the present invention.
Example 1
A liquid fire fighting medium, comprising: ethylene glycol, perfluoro hexanone, deionized water and a pH regulator;
according to the volume percentage, the glycol is 55 percent, the perfluorinated hexanone is 10 percent, and the water is 35 percent;
the pH regulator is NaHCO 3 For adjusting the pH of the liquid fire-fighting medium to 8.5.
The preparation method of the liquid fire-fighting medium comprises the following steps: uniformly mixing perfluoro-hexanone, polyalcohol and deionized water, and using NaHCO 3 Adjusting pH to 8.5.
Example 2
Unlike example 1, ethylene glycol was replaced with 1, 2-propanediol, and example 1 was otherwise repeated.
Example 3
Unlike example 1, the ethylene glycol was replaced with glycerol, the glycerol was 60%, the deionized water was 30%, and the same as in example 1 was used.
Example 4
Unlike example 1, ethylene glycol was replaced with 1, 2-butanediol, 1, 2-butanediol was 50%, water was 40%, and the same as in example 1 was repeated.
Example 5
Unlike example 1, the perfluorinated hexanone was 8% and deionized water was 37%; otherwise, the same as in example 1 was conducted.
Example 6
Unlike example 1, the perfluorinated hexanone was 12% and deionized water was 33%; otherwise, the same as in example 1 was conducted.
Example 7
Unlike example 1, naHCO is used 3 The procedure of example 1 was followed except that the pH of the liquid fire-fighting medium was adjusted to 8.
Example 8
Unlike example 1, naHCO is used 3 The procedure of example 1 was followed except that the pH of the liquid fire-fighting medium was adjusted to 9.
Example 9
Unlike example 1, the NaHCO therein 3 Replaced by KHCO 3 Otherwise, the same as in example 1 was conducted.
Example 10
Unlike example 1, the NaHCO therein 3 Replaced by LiHCO 3 Otherwise, the same as in example 1 was conducted.
Comparative example 1:
deionized water is used as a fire-fighting medium.
Comparative example 2
The perfluoro-hexanone is used as a fire-fighting medium.
Comparative example 3
Unlike example 1, ethylene glycol was 70%, deionized water was 20%, and the same as in example 1 was used.
Comparative example 4
Unlike example 1, ethylene glycol was 30% and deionized water was 60%, otherwise the same as in example 1.
Comparative example 5
Unlike example 1, the amount of perfluorohexanone was 6%, and the amount of deionized water was 39%, as in example 1.
Comparative example 6
Unlike example 1, the perfluorohexanone was 14% and deionized water was 31%, otherwise the same as in example 1.
Comparative example 7
Unlike example 1, naHCO is used 3 For adjusting the pH of the liquid fire-fighting medium to 7.5.
Comparative example 8
Unlike example 1, na was used 2 CO 3 For adjusting the pH of the liquid fire-fighting medium to 9.5.
The formulations of the liquid fire fighting media of examples 1-10 and comparative examples 1-8 are shown in Table 1;
table 1 liquid fire fighting media formulation
Fire extinguishing test of liquid fire-fighting medium
(1) Preparation of a Battery pack
(1) Charging a plurality of battery cores for experiments to a full-charge state at normal temperature; (2) integrating the fully charged battery cells together but not in series-parallel connection, and then placing the battery cells into a battery pack; (3) mounting temperature and voltage probes on a thermal runaway experiment battery cell, and connecting the anode and the cathode of the battery cell with an overcharging device; (4) an ignition device is arranged on the battery pack to ensure that the thermal runaway battery core burns and the fire-fighting medium injection port is connected with the fire-fighting pipeline; (5) and the connection of the experimental device is checked, so that the control is ensured to be normal.
(2) The experiment was started:
(1) turning on related devices (camera, daily data recorder, etc.); (2) starting charging (overcharge mode trigger 160A/7.3V); (3) the battery core spray valve smokes to generate combustible gas; (4) the battery thermal runaway signal is detected, and the audible and visual alarm is automatically started; (5) continuously charging, and starting an electric ignition device; (6) the ignition is successful, and the charging is stopped; (7) the battery pack is continuously burnt for about 3min; (8) the fire fighting device automatically starts fire fighting spraying action, liquid fire fighting medium is injected, (9) the liquid fire fighting medium is fully filled with a battery pack (fully immersed) for about 3min, and spraying is automatically stopped; and standing to observe the battery pack, and recording key experimental phenomena and time nodes. 1) Storing the monitoring data of the upper computer; 2) Storing the experimental process photos and videos; 3) And saving the data of the data acquisition equipment. Standing for 12 hours, and observing whether the battery pack is reburning.
(3) Fig. 1 shows a state diagram of a battery pack for performing a fire extinguishing experiment on a lithium ion battery pack by using a liquid fire-fighting medium according to an embodiment of the invention. In the experimental process, a large amount of gas is sprayed out after the explosion-proof valve of the thermal runaway battery cell is opened, glass is observed to be fogged and disappear rapidly, then the ignition device is started, the fire-fighting device is started after ignition and combustion are carried out for about 3min, the liquid fire-fighting medium fills the battery pack and enters the thermal runaway battery cell, a large amount of white fog appears when entering the inside, and meanwhile 'pyrolling' sound is accompanied.
Recording the number (number) of the thermal runaway batteries, the highest surface temperature (DEG C) of the thermal runaway batteries, the surface temperature (DEG C) of the thermal runaway batteries after the liquid fire-fighting medium starts to be injected for 1min, the surface temperature (DEG C) of the thermal runaway batteries when the liquid fire-fighting medium is immersed in a battery box, the reburning performance of 12h and the like in the experimental process. The results are shown in Table 2.
After the experiment, the battery box material object is disassembled, the battery core after the experiment in the figure 1 is shown, and the explosion-proof valves of other battery cores (adjacent battery cores No. 2 and No. 3) are not operated except that the explosion-proof valve of the No. 1 battery core is opened, and the appearance is normal.
Table 2 liquid fire fighting Medium Performance and Experimental Effect of examples 1-10 and comparative examples 1-8
As can be seen from the data of examples 1 to 10, the liquid fire-fighting medium of the embodiment of the invention can realize rapid cooling, and the surface temperature of the thermal runaway battery is 40.2 to 52.9 ℃ when the liquid fire-fighting medium is immersed in the battery box for about 3min; and standing and observing the experimental sample for 12 hours, wherein the battery pack is not reburnt and does not thermally diffuse. And disassembling the battery pack object after the experiment. Except that the 1# cell explosion-proof valve is opened, other cell explosion-proof valves are not operated and have normal appearance, so that the fire-fighting experiment achieves a plurality of targets of extinguishing open fire, quickly cooling, blocking/insulating, continuously inhibiting, inerting explosion suppression and the like on a thermal runaway battery after the injection of the liquid fire-fighting medium in a simulated open fire combustion scene of the lithium iron phosphate battery, and the experiment proves that the liquid fire-fighting medium has a strong fire-fighting function. The liquid fire-fighting medium of the embodiment of the invention is not frozen at the temperature of minus 40 ℃, has a wider temperature application window, and can adapt to the application environment of minus 40 ℃ to 60 ℃.
As can be seen from the comparison of examples 1, 5 and 6 and comparative examples 5 and 6, when the content of the perfluorinated hexanone in the liquid fire-fighting medium is lower than 8%, the temperature reduction speed is low during fire fighting, the fire-fighting capacity is affected, and when the content is higher than 12%, the influence on the fire-fighting capacity is not obviously improved. In the range of examples 8 to 12% of the present invention, the rate of cooling increases as the content of perfluorohexanone increases.
As can be seen from the comparison of examples 1 to 10 with comparative example 1, compared with the aqueous medium, examples 1 to 10 of the present invention have a wider temperature application window, a faster cooling rate, and the "pyridine" sound in examples 1 to 10 of the present invention is far lower than the "pyridine" sound degree of comparative example 1, as found by monitoring the "pyridine" emitted from the thermal runaway cell during the experiment; the liquid fire-fighting medium of the embodiments 1 to 10 can effectively inhibit the reaction strength of water and lithium in the battery cell, and improve the safety of the whole fire-fighting system.
As can be seen from the comparison of examples 1 to 10 and comparative example 2, the pure perfluoro-hexanone in comparative example 2 can be used as a fire-fighting medium to rapidly cool the battery box and the thermal runaway cell, but after the perfluoro-hexanone volatilizes in the later stage of fire-fighting, the electrochemical reaction in the thermal runaway cell can be continued, so that the phenomenon of afterburning occurs.
As can be seen from comparison of the embodiment 1, the comparative examples 3 and 4, the temperature lowering performance of the fire-fighting medium can be improved to a certain extent when the water ratio is large, but the effect is limited, but when the water content is more than or equal to 60%, the freezing phenomenon is generated in the environment of-20 ℃, the application range of the liquid fire-fighting medium is affected, meanwhile, the freezing point of the liquid fire-fighting medium is affected due to the excessively high ethylene glycol ratio, and the cost is considered, so that the ethylene glycol ratio is controlled to be 50-60% and the water ratio is controlled to be 28-42% in the embodiment of the invention.
The comparison of the experimental phenomena of fire fighting in examples 1, 7 and 8 and comparative examples 7 and 8 shows that the 'pyrolyl' sound emitted from the thermal runaway cell in the experimental process is reduced along with the increase of the pH value of the liquid fire fighting medium, and the analysis is that the more obvious the inhibition effect on the reaction intensity of water and lithium in the thermal runaway cell is along with the enhancement of the alkalinity of the liquid fire fighting medium, but the more the pH value exceeds 9, the ageing of a fire fighting system is accelerated, meanwhile, the dirt is easy to generate in the high alkaline environment, and the pH is controlled to be 8-9 comprehensively considered.
Comparison of the fire extinguishing experiments of example 1 and example 10 shows that the temperature reduction speed during fire fighting is not greatly different, but the "pyrolliding" sound emitted in the thermal runaway cell of example 10 is lower than that of example 1 in the experimental process, and the analysis reasons are probably as follows: liHCO on the one hand 3 The lithium ion battery is slightly alkaline, and can inhibit the reaction of water and lithium in the battery through the alkalinity, and on the other hand, the concentration of lithium ions is increased, so that the reaction of water and lithium in the battery is inhibited to generate lithium ions. The combined action of the alkali inhibition and the concentration inhibition effectively inhibits the reaction intensity of water and lithium in the battery.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A liquid fire fighting medium comprising polyol, perfluoro hexanone, water and pH adjuster;
the sum of the volumes of the polyol, the perfluorinated hexanone and the water is 100 percent, wherein the polyol is 50 to 60 percent, the perfluorinated hexanone is 8 to 12 percent and the balance is the water;
the boiling point of the polyol is more than or equal to 180 ℃;
the pH regulator is used for regulating the pH value of the liquid fire-fighting medium to 8-9.
2. A liquid fire fighting medium according to claim 1, wherein said polyol is one or more of ethylene glycol, propylene glycol, glycerol or butanediol.
3. A liquid fire fighting medium according to claim 2, wherein said polyol is ethylene glycol.
4. A liquid fire fighting medium according to claim 1, wherein said pH modifier is NaHCO 3 、KHCO 3 、LiHCO 3 、Na 2 CO 3 、K 2 CO 3 One or more of the following.
5. The liquid fire fighting medium of claim 4 wherein said pH adjuster is LiHCO 3 。
6. A liquid fire fighting medium according to any of claims 1 to 5, wherein said polyol is 50 to 55%.
7. A liquid fire fighting medium according to any of claims 1 to 5, characterized in that the pH adjuster is used to adjust the pH of the liquid fire fighting medium to 8.5 to 9.
8. A method of preparing the liquid fire fighting medium of any one of claims 1 to 7, comprising the steps of: and (3) uniformly mixing the perfluorinated hexanone, the polyol and the water, and then regulating the pH value by using the pH regulator to obtain the liquid fire-fighting medium.
9. Use of a liquid fire-fighting medium as a fire extinguishing agent for lithium ion batteries, characterized in that the liquid fire-fighting medium is a liquid fire-fighting medium according to any one of claims 1 to 7 or the liquid fire-fighting medium prepared by the method according to claim 8.
10. The use of a liquid fire-fighting medium according to claim 9 as a fire extinguishing agent for lithium ion batteries, wherein the liquid fire-fighting medium is applied to fire protection of a lithium ion battery energy storage system, and when a thermal runaway phenomenon occurs in a battery cell in a battery box of the lithium ion battery energy storage system, the liquid fire-fighting medium is applied to the battery box; wherein:
the liquid fire-fighting medium is directly immersed into the battery cell through an explosion-proof valve which is opened before the battery cell is in thermal runaway;
and/or stopping injection after the battery box is filled with the liquid fire-fighting medium;
and/or stopping injection after the battery box is filled with the liquid fire-fighting medium within 2-4 min;
and/or the application environment temperature of the liquid fire-fighting medium is-40-60 ℃.
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| US20040118576A1 (en) * | 2002-08-14 | 2004-06-24 | Masahiro Kato | Fire extinguishing agent and fire extinguisher |
| CN109847237A (en) * | 2018-12-18 | 2019-06-07 | 湖南省湘电试研技术有限公司 | A kind of halogenated hydrocarbon gas fire extinguishing system with safe additive |
| CN110368631A (en) * | 2019-08-02 | 2019-10-25 | 厦门一泰消防科技开发有限公司 | A kind of lithium ion battery extinguishing chemical and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040118576A1 (en) * | 2002-08-14 | 2004-06-24 | Masahiro Kato | Fire extinguishing agent and fire extinguisher |
| CN109847237A (en) * | 2018-12-18 | 2019-06-07 | 湖南省湘电试研技术有限公司 | A kind of halogenated hydrocarbon gas fire extinguishing system with safe additive |
| CN110368631A (en) * | 2019-08-02 | 2019-10-25 | 厦门一泰消防科技开发有限公司 | A kind of lithium ion battery extinguishing chemical and preparation method thereof |
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