KR20210151647A - Fire extinguishing device for secondary battery, and battery pack containing thereof - Google Patents

Abstract

The present invention relates to a fire extinguishing device for a secondary battery, and a battery pack including the same. The fire extinguishing device for a secondary battery includes a core-shell structure fire extinguishing microcapsule and a polymer composition, and quickly extinguishes a fire by decapsulation of the fire extinguishing microcapsule when a fire occurs, thereby securing safety from currently increasing fire or explosion related to a battery pack.

Description

Fire extinguishing device for secondary battery and battery pack including same {Fire extinguishing device for secondary battery, and battery pack containing thereof}

The present invention relates to a fire extinguishing device for a secondary battery and a battery pack including the same, wherein the secondary battery fire extinguishing device includes a core-shell structure fire extinguishing microcapsule and a polymer composition, and is used for decapsulation of fire extinguishing microcapsules in case of fire. It relates to a technology for quickly extinguishing a fire by means of a technology to secure safety from fires or explosions related to battery packs, which are recently increasing.

Encapsulation is a physico-chemical process in which a liquid, solid, or gas as a core and a shell surrounding the outside of the core are formed. prevent it from working The main purpose of such encapsulation is the controlled external release of the encapsulated core, in which case the encapsulated core generally requires complete isolation from the outside during storage and processing steps.

In addition, the external release of the core according to the encapsulation may vary depending on the intended use. For example, in order to take advantage of the controlled external release of the core that is released from the shell, the core can be encapsulated and used in drugs, pesticides, fragrances and mineral fertilizers. Among the various uses of this encapsulation, in particular, the fire extinguishing agent is released to the outside when the shell is destroyed in case of fire, including fire extinguishing agent in the core, and the technology to extinguish the fire is related to this in the modern society where a lot of electronic products and electrical products are used. It is urgently required to prepare for or extinguish a fire.

Meanwhile, as high-power secondary batteries using non-aqueous electrolytes with high energy density have been commercialized in recent years, research and development in related fields is being actively conducted so that they can be used not only in portable devices but also in medium and large-sized devices such as electric vehicles that require large power. These secondary batteries are drawing attention as a new power source for enhancing energy efficiency while being environmentally friendly in that not only can the use of fossil fuels be dramatically reduced, but also no by-products are generated from the use of energy.

Accordingly, the types of secondary batteries currently widely used include lithium ion batteries, lithium polymer batteries, nickel cadmium batteries, nickel hydride batteries, nickel zinc batteries, and the like. Secondary batteries are also connected to form a battery pack.

In general, a battery pack accommodates a plurality of battery modules composed of a plurality of battery cells in a housing, and connects a plurality of battery modules included in one or more housings in series, parallel, or series-parallel to provide a voltage or current required by a load. is made

Lithium batteries using lithium ions are widely used in these battery packs in terms of performance and efficiency, but lithium batteries have a risk of fire or explosion, so care must be taken in handling them. In particular, when the battery pack is used in a harsh environment with frequent vibrations or shocks, such as a driving state of a hybrid vehicle or an electric vehicle, securing its safety becomes a very important issue. Accordingly, in order to secure safety from fire or explosion when using a battery pack, technologies that require various technologies are being developed.

The present invention was completed after research to develop a technology for quickly extinguishing fires while simultaneously applying various fire extinguishing devices including microcapsules for fire extinguishing in a battery pack for secondary batteries.

Korean Patent Publication No. 10-2009-0026648 (2009.03.13) Korean Patent Publication No. 10-2010012 (2019.08.06)

An object of the present invention is to solve all of the above problems.

An object of the present invention is to prevent or suppress a fire related thereto by variously applying a fire extinguishing device including a microcapsule for fire extinguishing to a battery pack.

An object of the present invention is to provide a wide range of uses of the fire extinguishing device because it is possible to apply the fire extinguishing device regardless of the type or model of the battery pack.

It is an object of the present invention to provide a fire extinguishing device that provides excellent ductility and thermal insulation, thereby preventing a chain explosion of a secondary battery in a battery pack, thereby helping to prevent and extinguish a fire.

In order to achieve the object of the present invention as described above and to realize the characteristic effects of the present invention to be described later, the characteristic configuration of the present invention is as follows.

According to an embodiment of the present invention, it includes microcapsules for digestion and a polymer composition, wherein the microcapsules for digestion have a core-shell structure, and the core contains 80 to 97% by weight of a fire extinguishing agent, and the shell includes There is provided a fire extinguishing device for a secondary battery, characterized in that it comprises at least one selected from a precipitating agent and a coagulant as a non-porous polymer surrounding the core.

According to an embodiment of the present invention, the fire extinguishing device may be provided in any one form selected from a bar type, a pillar type, a tube type, and a sheet type. In addition, the fire extinguishing device may be provided in a paste type.

According to an embodiment of the present invention, there is provided a battery pack including the fire extinguishing device for a secondary battery.

In this case, the battery pack can be applied to various fields such as electric vehicles, electric bicycles, electric kickboards, golf cars, lawn mowers, power tools, electronic devices, communication devices, energy storage devices, drones and ships.

The fire extinguishing device for a secondary battery according to the present invention is to prevent or suppress a fire related thereto by variously applying it to a battery pack and others.

In the fire extinguishing device for a secondary battery according to the present invention, when a fire occurs in a battery pack, the microcapsules rupture simultaneously within a short time to prevent a fire or to extinguish a fire quickly and efficiently.

The fire extinguishing device for secondary batteries according to the present invention can be widely applied because it is not limited by the type or model of the battery pack, and can be used by inserting or filling the battery pack. Accordingly, it does not require a separate additional space for fire extinguishing in the battery pack, and thus provides an advantage of not requiring separate maintenance or management.

The fire extinguishing device for a secondary battery according to the present invention provides excellent ductility and thermal insulation, thereby preventing a chain explosion of secondary batteries in a battery pack, thereby helping to prevent and extinguish a fire.

1 shows a microcapsule for digestion according to the present invention.
2 shows the structure of a battery pack according to the present invention.
3 shows an example in which the fire extinguishing device for secondary batteries provided in a bar type according to the present invention is applied to a battery pack.
4 is a cross-sectional view showing a fire extinguishing device for a secondary battery provided in a bar type according to the present invention.
5 shows an example in which the fire extinguishing device for secondary batteries provided in a sheet type according to the present invention is applied to a pouch type battery pack.
6 shows an example in which the fire extinguishing device for secondary batteries provided in a paste type according to the present invention is applied to a holder of a battery pack.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention. Accordingly, the embodiments described in this specification and the configurations shown in the drawings are only the most preferred embodiment of the present invention, and do not represent all of the technical spirit of the present invention, so they can be substituted at the time of the present application It should be understood that various equivalents and modifications may exist.

Hereinafter, a fire extinguishing device 30 for a secondary battery including a microcapsule 40 for fire extinguishing and a battery pack 1 including the same will be described with reference to the drawings.

The present invention relates to a fire extinguishing device 30 for secondary batteries including a fire extinguishing microcapsule 40 as shown in FIG. 1 , and when this is applied to the battery pack 1 as shown in FIG. When a fire occurs due to the explosion of (10), the microcapsules 40 are simultaneously ruptured within a short time to prevent a fire or extinguish the fire quickly and efficiently.

The fire extinguishing device 30 for a secondary battery according to the present invention includes a fire extinguishing microcapsule 40 and a polymer composition, and the fire extinguishing microcapsule 40 has a core 41-shell 42 structure, and the core ( 41) contains 80 to 97% by weight of an extinguishing agent, and the shell 42 surrounds the core 41, and it is a non-porous polymer, characterized in that it contains at least one selected from a precipitating agent and a coagulant.

Referring to FIG. 1 , the fire extinguishing microcapsule 40 is formed in the form of a core 41-shell 42 in which an inner core 41 is surrounded by an outer shell 42 .

The fire extinguishing microcapsule 40 encapsulates the core 41 containing the fire extinguishing agent into the shell 42, and when a fire occurs, the fire extinguishing agent leaves the shell 42 within a short time in a narrow temperature range. Encapsulation (decapsulation) can be made to expedite fire suppression. In this case, when a fire extinguishing agent is included in the core 41, the fire extinguishing agent contains 80 to 97% by weight of the microcapsule 40, providing the best fire extinguishing effect in this range, improving the efficiency of fire suppression can do it

The size of the fire extinguishing microcapsule 40 is preferably 1 to 1000 μm, and is vaporized at a specific temperature in case of fire, and may be torn and reacted as if the shell 42 is ruptured by the vaporization energy of the fire extinguishing agent. A very small amount of fire extinguishing agent is ejected in one size of the fire extinguishing microcapsule 40, but a large number of fire extinguishing microcapsules 40 react explosively and simultaneously to eject a sufficient amount of vaporized fire extinguishing agent. can suppress

In addition, when a fire occurs, the extinguishing agent may be vaporized and expanded by heat, but does not react (rupture, leak) due to the durability and airtightness of the shell 42 formed of the non-porous polymer, and a specific temperature higher than that In particular, in case of a fire, the vaporized extinguishing agent acts directly on the ignition point of the fire, causing a chain reaction with the four conditions of combustion: fuel (flammables), oxygen (air), heat (ignition source), chain reaction, and heat (ignition source). It can be cut off to put out the fire.

According to an embodiment of the present invention, the fire extinguishing device 30 for a secondary battery is provided in any one form selected from a bar type, a pillar type, a tube type, and a sheet type. characterized in that

Referring to FIG. 2 , the battery pack 1 has a structure including a plurality of cylindrical secondary batteries 10 and a case 20 for accommodating them in horizontal and vertical directions while forming a predetermined space.

In addition, referring to FIG. 3 , a fire extinguishing device is installed in a predetermined space between the cylindrical secondary batteries 10 inside the case 20 of the battery pack 1 in a bar type, a pillar type or a tube type. It can be inserted by providing it as a mold. Accordingly, by providing excellent ductility and thermal insulation, it is possible to help prevent and extinguish a fire. In particular, it is possible to solve the problem of sequentially exploding neighboring batteries that are inserted between the cylindrical secondary batteries 10 and cause one cylindrical secondary battery 10 to explode.

According to an embodiment of the present invention, in the case of the bar type, pillar type, or tube type, the longitudinal cut surface thereof may be provided as any one selected from a circle or a polygon. The polygon may be provided, for example, in any one of a triangle to a dodecagon, and the length L of one side thereof is 0.1 mm each to 150 mm may be provided.

Cylindrical secondary batteries currently commonly used include 18650 standard (diameter 18 mm, length 65 mm), 21700 standard (diameter 21 mm, length 70 mm), and standard 4680 (diameter 46 mm, length 80 mm). In the case of the cylindrical secondary battery 18650 standard, the radius (R) of the battery may be provided as 9 mm, in the case of the cylindrical secondary battery 21700 standard, the radius (R) of the battery may be provided as 10.5 mm, and the cylindrical secondary battery 4680 In the case of the standard, the radius (R) of the battery may be provided as 23 mm.

Referring to FIG. 4 , when the fire extinguishing device 30 is provided in a bar shape or a pillar shape between the cylindrical secondary batteries 10 , the longitudinal section thereof is an octagonal shape. In this case, the length L of one side may be provided in a range of 0.1 mm to 150 mm.

In addition, the length of the bar (bar) type or pillar (pillar) type may be provided in a range of 10 to 80 mm.

Referring to FIG. 5 , when the fire extinguishing device 30 according to the present invention is provided in a sheet type, it shows that the pouch type secondary battery 10 is applied to a battery pack. In general, in the case of a pouch-type secondary battery, a plurality of secondary battery cells are accommodated while maintaining a constant space inside the battery pack. Accordingly, such a constant space may include a sheet, a film, etc. to reinforce functions such as shock mitigation, heat insulation, insulation, and flame retardancy, if necessary.

Accordingly, in the present invention, by providing a sheet-type fire extinguishing device 30 including the microcapsules 40 , as well as the above-mentioned effects, the fire extinguishing function can be improved by the microcapsules 40 , so the pouch type When a fire occurs in the secondary battery 10 , the microcapsules rupture simultaneously within a short time to prevent a fire or extinguish the fire quickly and efficiently.

According to an embodiment of the present invention, the weight ratio of the microcapsule 40 for digestion and the polymer composition is 1: 0.5 to 1.5. When provided in the above range, it is possible to provide an excellent fire extinguishing effect in a range that does not impair the physical properties of the finally formed fire extinguishing device 30 .

In addition, the microcapsules 40 for digestion in the fire extinguishing device 30 may contain 30 to 80 wt%. Preferably, it may contain 60 to 80% by weight. Therefore, the fire extinguishing device 30 according to the present invention is applied to the battery pack 1 to completely protect the fire extinguishing microcapsules 40 in normal times, and when a fire occurs, the fire extinguishing microcapsules 40 all at once in a short time. It can be detonated, making it possible to effectively extinguish a fire.

According to an embodiment of the present invention, the polymer composition is characterized in that it contains 60 to 100 parts by weight of the monomer and 1 to 30 parts by weight of the additive based on 100 parts by weight of the oligomer.

In this case, the oligomer and the monomer may include one or more selected from polyacrylic, epoxy, urethane, and silicone, and the polyacrylic resin is a photocurable resin under light conditions, for example, UV, visible light, electron beam (EB). ), LED, etc. may be curing in progress. Preferably, ultraviolet (UV) light may be provided, and in this case, it is eco-friendly as non-VOCs (Volatile Organic Compounds) because no solvent is used. In addition, the polymer may be provided with a weight average molecular weight of 100 to 1,000,000. Meanwhile, when the oligomer and the monomer are polyacrylic, the polymer composition may further include a photoinitiator.

The oligomer is a component that determines the physical properties of the cured resin, and it is characterized in that it includes at least one selected from polyacrylic, epoxy, urethane, and silicone. Preferably, polyacrylic oligomers may be used, and more specifically, polyacrylates, epoxy acrylates, urethane acrylates, polyester acrylates, silicone acrylates, polyether acrylates, and the like may be used. Accordingly, it is possible to provide a thermal or mechanical shock absorption effect, to control the elasticity of the oligomer, and to control excellent viscosity and flowability.

The monomer is used as a diluent and can also serve as a crosslinking agent. The monomer may include at least one selected from polyacrylic, epoxy, urethane, and silicone.

In the case of polyacrylic, polyacrylate, epoxy acrylate, urethane acrylate, polyester acrylate, silicone acrylate and polyether acrylate may be included.

When a polyacrylic system is provided, for example, methyl acrylate, ethyl acrylate, hexyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, butyl cyclohexyl acrylate, isooctyl acrylate, isononyl acrylate, Isobornyl acrylate, isodecyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclic trimethylol formal acrylate, phenoxy polyethylene glycol acrylate, lauryl acrylate , benzyl acrylate, epoxyethyl acrylate, phenoxyethyl acrylate, hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, pentaerythritol tetraacrylate, tetraethylene glycol diacrylate, and di(trimethylolpropane) tetraacrylate, and the like.

Epoxy systems are linear polymeric epoxides, for example diglycidyl ethers of polyoxyalkylene glycols may be provided, and polymeric epoxides with backbone epoxy groups may be provided, for example polybutadiene polyepoxy. and can be provided as a polymer epoxide having pendant epoxy groups, for example, a glycidyl methacrylate polymer or copolymer.

The urethane-based urethane is mainly obtained by including a diol component and a diisocyanate component. If necessary, a UV-curable urethane monomer further containing an acrylate may be provided. The diol may be an alkylene oxide-based polyol or silicone-based polyol such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol. In the case of the above diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene 1,6-diisocyanate, isophorone diisocyanate, para-toluenesulfonyl isocyanate, dicyclomethane 4,4-di Isocyanate, diphenylmethane 4,4-diisocyanate, 2,4-diisocyanate, 2,2-diisocyanate, dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate and 2-methyl Any one or more selected from pentamethylene 1,5-diisocyanate may be provided.

The silicone type is provided including polyorganosiloxane, and for example, polydimethyl siloxane resin and hydrogen silane may be provided alone or as a mixture.

In the case of a photoinitiator, a polymerization reaction is initiated by absorbing light energy to generate radical ions, cations, and the like. The photoinitiator is provided with at least one selected from an acylphosphine oxide-based compound, an α-hydroxyketone-based compound, a phenyl glyoxylate-based compound, and a benzoin ether-based compound. A photoinitiator that can be cured using UV or LED UV lamp is suitable, for example, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Diphenyl (2,4, 6-Trimethylbenzonyl)phosphine oxide) may be provided, but is not limited thereto.

The additive may further include at least one selected from an antifoaming agent, a flame retardant, a solid fire extinguishing agent, and an oxidizing agent.

An antifoaming agent is added to prevent a decrease in surface tension by a third material other than air and liquid, and to remove air and air bubbles during manufacturing.

For example, a silicone-based antifoaming agent may be provided, and in this case, it is prepared by emulsifying a silicone oil compound in which a fine powder inorganic filler such as silica, titanium dioxide, aluminum oxide is dispersed in silicone oil. In order to improve the stability of the silicone oil compound by appropriately adjusting the amount of emulsifier used during the emulsification process, a method of hydrophilicizing and dispersing the silicone oil compound can be applied.

The flame retardant is added to improve the combustion resistance, and it is possible to prevent the polymer composition from burning and lowering the extinguishing performance when an excessive fire occurs, and is mainly used for safety requirements so as not to cause a bigger fire. By adding an organic compound containing bromine (Br), chlorine (Cl), etc., it reacts with radicals in the combustion process to stop combustion. Halogen-based, phosphorus-based, nitrogen-based or inorganic flame retardants may be mainly used.

Halogen-based flame retardants include decabromodiphenyl oxide (DBDPO, Decabromodiphenyl oxide), decabromodiphenyl ethane (DBDPE, Decabromodiphenyl ethane), hexabromocyclododecane (HBCD, Hexabromocyclododecane), tetrabromobisphenol-A (TBBA, Tetrabromobisphenol). -A), tetrabromobisphenol A bis 2,3-dibromopropyl ether (BDDP, Tetrabromobisphenol A Bis (2,3-dibromopropyl ether)) may be provided, but is not limited thereto.

The phosphorus-based flame retardant may be selected from red, phosphoric acid ester-based or phosphate, phosphonate, phosphinate, phosphine oxide, and phosphazene.

Nitrogen-based flame retardants include melamine, melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkyl An amine phosphate (alkyl amine phosphate), piperazine acid polyphosphate (piperazine acid polyphosphate), ammonium phosphinate, etc. may be provided, but is not limited thereto.

Inorganic flame retardants are metal-based inorganic oxides, such as antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate carbonate, antimony metal, antimony trichloride, antimony pentachloride, barium metaborate, zirconium oxide, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, etc. may be provided, but is not limited thereto.

Solid extinguishing agent means potassium oxide. For example, potassium nitrate (KNO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), etc. may be provided, and preferably potassium nitrate may be provided. They are pyrolyzed at a high temperature of 400°C or higher to generate potassium radicals in an enclosed space. The generated potassium radical reacts with OH radicals generated in the process of the combustion reaction of the fire target material to break the chain reaction, thereby providing fire extinguishing action. In particular, the higher the temperature, the smaller the particle size of potassium radicals, and the better the extinguishing performance. Therefore, when perfect fire-fighting is not achieved by the microcapsule for fire extinguishing, secondary fire extinguishing can be carried out by means of a solid fire extinguishing agent and an oxidizing agent, and they can effectively suppress the fire even in more extreme conditions. In addition, the size of the solid extinguishing agent is 1 to 150㎛.

For oxidizing agents provided with solid extinguishing agents, potassium perchlorate, potassium nitrite, potassium dichromate, potassium citrate, potassium bicarbonate, potassium sulfate, sodium nitrate, sodium bicarbonate, ammonium nitrate, ammonium perchlorate, barium nitrate, cesium nitrate, potassium cyanide, At least one selected from sodium cyanide, 1,2-diformylhydrazine and cyanoguanidine may be provided, but is not limited thereto.

In addition, the additional content of the oxidizing agent for potassium nitrate is preferably 1 to 10% by weight based on the total weight of the solid extinguishing agent and the oxidizing agent. By adding an oxidizing agent, it can help improve the efficiency of potassium radical generation within the fire extinguishing system, and can help improve fire extinguishing performance.

On the other hand, the fire extinguishing agent contained in the core 41 of the microcapsule 40 for fire extinguishing can be used as a material with excellent fire extinguishing performance, the main component of which is a fire extinguishing agent that is not limited in production and use by the Montreal Protocol.

For example, the extinguishing agent is fluorine carbon, fluorine chlorine carbon, fluorine bromine carbon-based halogen carbon, fluorine iodine carbon-based halogen carbon, 2-iodine-1,1,1,2,3,3,3- Heptafluoropropane (HFC-227ea) and Iodofluorocarbon (FIC-217I1 or FIC-13I1), 1,1,1,2,2-Pentafluoroethane (CF ₃ CF ₂ H, HFC-125), 1,1,1,2,3 ,3,3-Heptafluoropropane(CF ₃ CHFCF ₃ ), Chlorotetrafluoroethane(CHClFCF ₃ ), fluorine-based ketone compound, dodecafluoro-2-methylpentan-3-one(FK-5-1-12, CF ₃ CF ₂ C( O)CF(CF ₃ ) ₂ )), 1-chloro-1,2,2,2-tetrafluoroethane(C ₂ HClF ₄ ), 2-chloro-1,1,1,2-tetrafluoroethane(CHClFCF ₃ , HCFC- 124), decafluorocyclohexanone (perfluorocyclohexanone), CF ₃ CF ₂ C(O)CF(CF ₃ ) ₂ (-1,1,1,2,4,4,5,5, 5-nonafluoro-2-trifluoromethyl-butan- _{3one), (CF 3} ) ₂ CFC(O)CF(CF ₃ ) ₂ (-1,1,1,2,4,5,5, 5,6,6,6-octafluoro-2,4-bis(trifluoromethyl)pentan-3-one), CF ₃ CF ₂ C(O)CF ₂ CF ₂ CF ₃ , CF ₃ C(O) )CF(CF ₃ ) ₂ , 1,1,1,3,3,4,4,5,5,6,6,7,7,8,8,8-hexadodecafluorooctan-2-one (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ C(O)CF ₃ ), 1,1,1,3,4,4,4-heptafluoro-3-trifluoromethylbutan-2-one (CF ₃ C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,4,4,5,5-octafluoro-2-trifluoromethylpentan-3-one (HCF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-trifluoromethylhexan-3-one (CF ₃ CF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ), 1-Chloro-1,1,3,4,4,4-hexafluoro-3-trifluoromethyl-butane-2- On((CF ₃ ) ₂ CFC(O)CF ₂ CL), 1,1,1,2,2,4,4,5,5,6,6,6-dodecafluorohexan-3-one ( CF ₃ CF ₂ C(O)CF ₂ CF ₂ CF ₃ ), 1,1,1,5,5,5-hexafluoropentane-2-4-dione (CF ₃ C(O)CH ₂ C(O) )CF ₃ ), 1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hexane-3,4-dione ((CF ₃ ) ₂ CFC (O)C(O)C(O)CF(CF ₃ ) ₂ ), 1,1,1,2,2,3,3,5,5,6,6,7,7,7-tetradecafluoro Roheptan-4-one (CF ₃ CF ₂ CF ₂ C(O)CF ₂ CF ₂ CF ₃ ), 1,1,1,3,3,4,4,4-octafluorobutal-2-one ( CF ₃ C(O)CF ₂ CF ₃ ), 1,1,2,2,4,5,5,5-octafluoro-1-trifluoromethoxy-4-trifluoromethylpentan-3-one (CF ₃ OCF ₂ CF ₂ C(O)CF(CF ₃ ) ₂ ) and 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro- It is characterized in that at least one selected from 2-trifluoromethylheptan-3-one (CF ₃ CF ₂ CF ₂ CF ₂ C(O)CF(CF ₃ ) _{2 ).}

In addition, as an extinguishing agent, one of the formula C _x H _y O _z Hal _k (where x, y, z, k are natural numbers, and Hal is Br, I, F) can be used, for example, 3M's Novec 1230 (Novec 1230) may be used, but is not limited thereto.

In addition, the extinguishing agent is provided in a liquid phase at room temperature, phase change to a gaseous phase at a temperature of 30 ℃ to 100 ℃. Preferably, by changing the weather at 30° C. to 60° C., when a fire occurs, the capsule ruptures to suppress the fire.

In addition, the manufacture of the microcapsule 40 for fire extinguishing is a hydrophobic organic solvent containing a fire extinguishing agent and a polymerization reaction at the interface with an aqueous surfactant to form a shell 42, and aging the shell 42 to produce a fire extinguishing agent. While maintaining liquidity, only the shell 42 is solidified. Agitated to form capsules, then microcapsules 40 are precipitated and the liquid is removed. Thereafter, the microcapsules 40 are washed with an aqueous solution, and then selected and dried at a low temperature. Therefore, the final content of the extinguishing agent is 80 to 97%.

According to an embodiment of the present invention, the shell 42 is a non-porous polymer and may include at least one selected from a precipitating agent and a coagulant. In this case, based on 100 parts by weight of the non-porous polymer, 1 to 10 parts by weight of the precipitating agent or coagulant may be included.

The shell 42 surrounds the outside of the fire extinguishing agent, which is the core 41, and serves to contain the fire extinguishing agent, and maintains weather resistance and airtightness to protect the fire extinguishing agent from leaking into the atmosphere by the external environment at normal times or up to a specific temperature. should be However, at 30° C. to 100° C., the shell 42 may be ruptured due to the phase change from liquid to gaseous phase of the extinguishing agent and softening of the shell 42 at high temperature. In this case, the shell 42 thickness may be provided in the range of 50 to 2000 nm.

In addition, in order to perform a role by a temperature reaction, the shell 42 is preferably made of a non-porous polymer. For example, polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, polyvinyl It may be provided including one or more selected from alcohol, phenol formaldehyde resin, and resorcinol formaldehyde resin, but is not limited thereto.

According to an embodiment of the present invention, the precipitating agent included in the non-porous polymer may be provided with at least one selected from potassium acetate, sodium citrate, sodium chloride, ammonium chloride, sodium iodide, potassium iodide, copper sulfate and sodium thiocyanate. And, the coagulant may be provided at least one selected from aluminum sulfate, zinc hydroxide, iron hydroxide and iron chloride, but is not limited thereto.

According to an embodiment of the present invention, the fire extinguishing device 30 for a secondary battery is characterized in that it is of a paste type. When provided as a paste-type fire extinguishing device 30, the fire extinguishing microcapsule 40 and a polymer composition are included, and the fire extinguishing microcapsule 40 has a core 41-shell 42 structure, and the core (41) contains 80 to 97% by weight of the extinguishing agent, the shell 42 is a non-porous polymer surrounding the core 41, characterized in that it contains any one or more selected from a precipitating agent and a coagulant.

Specific details are applied in the same manner as described above, but in the case of a polymer composition, there may be differences.

The polymer composition applied in this case is a paste resin, and acrylonitrile, styrene-acrylonitrile, methyl methacrylate-butadiene-styrene, butadiene, acrylic, urethane, epoxy, phenoxy, polyamide, olefin, polyester, silicone One or more selected from resins may be provided. While the paste resin acts as a matrix, the type is not particularly limited and a general thermoplastic resin may be used.

In addition, at least one selected from a flame retardant, a tackifier, an inorganic filler, and a catalyst may be added to the paste resin as an additive, if necessary.

In the case of a flame retardant, a solid fire extinguishing agent and an oxidizing agent, it is the same as described above, and in the case of a tackifier, it is provided to improve the adhesive force of the area where the paste contacts and seals, and an organoalkoxysilane-based tackifier may be provided.

For example, an organoalkoxysilane containing an amino group may be provided, for example, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and an organoalkoxysilane containing an epoxy group. As a silane, for example, γ-glycidoxypropyltrimethoxysilane may be provided, and as an organoalkoxysilane comprising a mercapto group, for example, γ-mercaptopropyltrimethoxysilane, However, the present invention is not limited thereto.

The inorganic filler is, for example, powdered silica, calcium carbonate, calcium sulfate, barium sulfate, barium carbonate, strontium carbonate, magnesium carbonate, strontianite, iron oxide, aluminum oxide, magnesium hydroxide, aluminum trihydroxide, diatomaceous earth, talc, wollastonite. , alumina, gypsum, clay, kaolin, barite, venomite, or silicate may be provided. Preferably, it is economical to provide calcium carbonate, which can serve to prevent the paste from flowing out during application.

The catalyst may be, for example, an imidazole compound, a phosphine compound, a phosphonium salt, or the like, preferably a phosphine compound, for example, triphenylphosphine. Accordingly, the curing rate may be accelerated, and it may help to improve adhesion.

In the case of the paste type, as shown in FIG. 2 , in order to freely provide the extinguishing material in a predetermined empty space between the cylindrical secondary cells 10 of the battery pack 1 , in the present invention, it is not in a predetermined shape but in the form of a paste. It is also possible to provide, so that the filling is possible without being affected by the structure, and in the event of a fire, it is possible to effectively extinguish the fire by bursting the microcapsule 40 for fire extinguishing. In this case, it does not have any effect on the battery performance or arrangement, and when abnormal heat or fire of the battery pack 1 occurs, it can be actively suppressed at an early stage.

In the case of FIG. 6 , in order to fix the cylindrical secondary battery 10 inside the battery pack 1 , it is shown that the holder 50 is used to fix it. In this case, the fire extinguishing device 30 may be provided in the form of a paste in the area in contact with the holder 50 , and the fire extinguishing device 30 is filled with paste and sealed in the empty space generated when the holder 50 comes in contact can be provided.

According to an embodiment of the present invention, the secondary battery may be provided in any one selected from a cylindrical shape, a prismatic shape, a pouch type, and a sticker type. Therefore, regardless of the type or model of the battery pack 1, and not affected by the space or structure, the fire extinguishing device can be widely used, and there is an advantage that it can be used in various ways.

In addition, since the fire extinguishing device 30 according to the present invention does not require a separate space for fire extinguishing in the battery pack 1, separate maintenance or management is not required. Of course, it provides convenience to use because it only needs to fill in the empty space.

The shell 42 of the fire extinguishing microcapsule 40 included in the fire extinguishing device 30 is softened by external heat, and the fire extinguishing agent is explosively ejected from the fire extinguishing microcapsule 40 by the vaporization energy of the fire extinguishing agent. can be Therefore, when a fire occurs, the fire can be quickly suppressed by the extinguishing agent in the microcapsule 40 for extinguishing at a specific temperature or higher.

Meanwhile, according to an embodiment of the present invention, a battery pack 1 including a fire extinguishing device 30 for a secondary battery is provided. In this case, the battery pack 1 can be applied in various ways, such as electric vehicles, electric bicycles, electric kickboards, golf cars, mowers, power tools, electronic devices, communication devices, energy storage devices, drones and ships, and is provided in various forms. As a result, it can be applied directly to accessories and objects to prevent fire.

In addition, the insulating effect may be provided by utilizing it in a region requiring insulation. Accordingly, it also provides excellent electrical resistance such as surface resistance and volume resistance.

In the above description of the present invention with reference to the accompanying drawings, a specific shape and direction have been mainly described, but the present invention can be variously modified and changed by those skilled in the art, and these modifications and changes are included in the scope of the present invention. should be interpreted as

1: battery pack
10: secondary battery
20: case
30: fire extinguishing system
40: microcapsules for digestion
41: core
42: shell
50: holder
L: length of one side (L)
R: radius of cylindrical secondary battery

Claims (17)

A fire extinguishing device for a secondary battery comprising a microcapsule for fire extinguishing and a polymer composition.
According to claim 1,
When the secondary battery has a cylindrical shape, the fire extinguishing device is a bar type, a pillar type, or a tube type,
When the secondary battery is prismatic, the fire extinguishing device is a bar type, a pillar type, a tube type, or a sheet type,
When the secondary battery is a pouch type, the fire extinguishing device is a tube type or a sheet type,
When the secondary battery is a sticker type, the fire extinguishing device for a secondary battery, characterized in that the sheet type (sheet) type.
3. The method of claim 2,
The bar (bar) type or pillar (pillar) type fire extinguishing device for secondary batteries, characterized in that the length is 10 mm to 80 mm.
3. The method of claim 2,
In the case of the bar type, pillar type or tube type, the fire extinguishing device for secondary batteries, characterized in that the longitudinal cut surface is any one selected from a circle or a polygon.
5. The method of claim 4,
The polygon is any one of a triangle to a dodecagon, and the length (L) of one side is 0.1 mm to 150 mm.
According to claim 1,
The microcapsule for digestion has a core-shell structure,
The core contains 80 to 97% by weight of an extinguishing agent,
The shell is a non-porous polymer surrounding the core, and fire extinguishing device for a secondary battery, characterized in that it comprises at least one selected from a precipitating agent and a coagulant.
7. The method of claim 6,
The fire extinguishing agent for a secondary battery, characterized in that the phase change to the gas phase at a temperature of 30 ℃ to 60 ℃ fire extinguishing agent.
7. The method of claim 6,
The shell is a polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-methacrylate copolymer resin, polyvinyl alcohol A fire extinguishing device for a secondary battery, characterized in that at least one selected from , phenol formaldehyde resin, and resorcinol formaldehyde resin.
According to claim 1,
The fire extinguishing device for secondary batteries, characterized in that the weight ratio of the microcapsules for fire extinguishing and the polymer composition is 1: 0.5 to 1.5.
According to claim 1,
The polymer composition is a fire extinguishing device for a secondary battery, characterized in that it contains 60 to 100 parts by weight of a monomer and 1 to 30 parts by weight of an additive based on 100 parts by weight of the oligomer.
11. The method of claim 10,
The oligomers and monomers are
A fire extinguishing device for a secondary battery, comprising at least one selected from polyacrylic, epoxy, urethane, and silicone.
12. The method of claim 11,
When the oligomer and the monomer are polyacrylic, the polymer composition further comprises a photoinitiator.
13. The method of claim 12,
The photoinitiator is a secondary battery fire extinguishing device, characterized in that at least one selected from an acylphosphine oxide-based compound, an α-hydroxyketone-based compound, a phenyl glyoxylate-based compound, and a benzoin ether-based compound.
13. The method of claim 12,
The content of the photoinitiator is a secondary battery fire extinguishing device, characterized in that 1 to 30 parts by weight based on 100 parts by weight of the oligomer.
10. The method of claim 9,
The additive is a fire extinguishing device for a secondary battery, characterized in that it further comprises at least one selected from an antifoaming agent, a flame retardant, a solid fire extinguishing agent, and an oxidizing agent.
A battery pack comprising the fire extinguishing device for a secondary battery according to claim 1 .
17. The method of claim 16,
The battery pack is a battery pack, characterized in that it is applied to any one selected from an electric vehicle, an electric bicycle, an electric kickboard, a golf car, a lawnmower, a power tool, an electronic device, a communication device, an energy storage device, a drone, and a ship.

Images