Fire-resistant composite materials for electric vehicle batteries made from liquid coatings and mats or fleece.

Abstract

The present invention relates to a fire-resistant composite material made from a liquid coating and a mat or fleece, a method for manufacturing the fire-resistant composite material, the use of the fire-resistant composite material for electric vehicles, an electric vehicle battery containing the fire-resistant composite material, and a method for manufacturing an electric vehicle battery.

Description

Technical Field

[0001] The present invention relates to a fireproof composite material made from a liquid coating and a mat or fleece that can be used for the battery of an electric vehicle.

Background Art

[0002] In recent years, the number of electric vehicles has been increasing, and the main power source of electric vehicles is the battery. Due to the increase in the energy density of the battery, it is necessary to further improve the fireproof and heat insulation properties of the battery to protect the passengers of the vehicle.

[0003] However, all the fireproof products available for the battery do not have sufficient fireproof performance or heat insulation performance, or there are problems with mechanical stability and electrical insulation, especially when a thermal runaway event occurs.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, a fireproof composite material that shows improvement in fireproof, heat insulation, and mechanical stability is required.

Means for Solving the Problems

[0005] The present invention provides a fireproof composite material made from a liquid coating and a mat or fleece.

[0006] The present invention further provides a fireproof composite material of the present invention, including applying the liquid coating of the present invention onto a substrate; subsequently, placing the mat or fleece of the present invention on the coating; optionally, applying another liquid coating of the present invention onto the mat or fleece; and drying the coating at room temperature or high temperature.

[0007] Furthermore, the present invention provides for the use of the fire-resistant composite material for electric vehicle batteries, preferably for electric vehicle battery housings.

[0008] Furthermore, the present invention provides an electric vehicle battery containing the fire-resistant composite material of the present invention.

[0009] Furthermore, the present invention provides a method for manufacturing an electric vehicle battery, which includes preparing a fire-resistant composite material on an electric vehicle battery lid and / or housing according to the method for manufacturing a fire-resistant composite material of the present invention. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 shows the adhesion of the mat on the coating of the fire-resistant composite material of the present invention. [Figure 2] Figure 2 shows the wettability of the liquid fire-resistant coating applied to the mat in the fire-resistant composite material of the present invention, with Figure 2a corresponding to Example 4 and Figure 2b corresponding to Example 3. [Figure 3] Figure 3 shows a test method used to measure the heat and fire resistance capacity of a fire-resistant composite material over a specified period of time. [Figure 4] Figure 4 shows the results of comparative tests on heat resistance and flame retardancy between the composite material of the present invention and a reference electron-coated steel substrate. [Figure 5] Figure 5 shows photographs of a reference electron-coated steel substrate without coating or mat (Figure 5a) and the fire-resistant composite material of the present invention (Figure 5b) after a thermal runaway test using a 50Ah rectangular cell. [Modes for carrying out the invention]

[0011] The present invention will be described in more detail in the following text. Each aspect described herein can be combined with other aspects unless otherwise explicitly indicated. In particular, any feature shown as preferred or advantageous can be combined with other features shown as preferred or advantageous.

[0012] In the context of this invention, terms used shall be interpreted according to the following definitions unless otherwise specified in the context.

[0013] As used herein, the singular forms "a," "an," and "the" refer to both singular and plural objects unless otherwise explicitly indicated by the context.

[0014] As used herein, the terms “comprising,” “comprises,” and “comprised of” are synonymous with “including,” “includes,” or “containing,” and are comprehensive or open-ended and do not exclude additional unlisted members, elements, or process steps.

[0015] As used herein, the term "consisting of" excludes any unspecified elements, components, members, or methods or processes.

[0016] The terms “preferred,” “preferably,” “desirably,” and “particularly” are frequently used herein to refer to embodiments of the Disclosure that may provide particular benefits under specific circumstances. However, the enumeration of one or more preferred, preferred, desirable, or particular embodiments does not imply that other embodiments are not useful, nor is it intended to exclude those other embodiments from the scope of the Disclosure.

[0017] As used throughout this application, the term "may" is used in a permissive sense, not a mandatory sense, and it means having a possibility.

[0018] The recitation of numerical endpoints includes all numbers and fractions subsumed within the respective ranges, as well as the recited endpoints.

[0019] All percentages, parts, ratios, etc. described herein are based on weight, unless otherwise specified.

[0020] Where a quantity, concentration, or other value or other parameter is expressed in the form of a range, preferred range, or preferred upper and lower limits, any range obtained by combining any upper or preferred value with any lower or preferred value should be understood to be specifically disclosed, whether or not the resulting range is explicitly recited in the context.

[0021] As used herein, the term "one-component (1K) composition" refers to a composition in which all the composition components are mixed during storage of the composition, and the properties of the composition, including viscosity, are kept sufficiently consistent throughout the storage period, resulting in a good and useful composition later.

[0022] A "two-component (2K) composition" is understood to be a composition in which the first component / part and the second component / part must be stored in separate containers due to their (high) reactivity. The two components / parts are mixed only immediately before application and then react, usually without additional activation, to form a bond, thereby forming a polymer network. Here, a higher temperature may be applied to promote the crosslinking reaction.

[0023] As used herein, the term "battery" can refer to any of a variety of different battery chemistries and configurations, including, but not limited to, lithium ion (such as lithium iron phosphate, lithium cobalt oxide, and other lithium metal oxides), lithium ion polymer, nickel metal hydride, nickel cadmium, nickel hydrogen, nickel zinc, silver zinc, or other battery types / compositions.

[0024] As used herein, the term "electric vehicle" refers to a fully electric vehicle, also called an EV, a plug-in hybrid vehicle, also called a PHEV, or a hybrid vehicle, also called an HEV, and a hybrid vehicle refers to a vehicle that utilizes multiple propulsion sources, one of which is an electric drive system.

[0025] All references cited herein are hereby incorporated by reference in their entirety.

[0026] Unless otherwise defined, all terms used in the disclosure of the present invention, including technical and scientific terms, have the meanings commonly understood by one of ordinary skill in the art to which this invention belongs. As a further guide, definitions of terms are included to better understand the teachings of the present invention.

[0027] <Fireproof composite material> The present invention relates to a fireproof composite material made from a liquid coating and a mat or fleece.

[0028] Surprisingly, the inventors have found that the fireproof composite material according to the present invention exhibits significant improvements in fire resistance, heat insulation behavior, and / or mechanical stability compared to the prior art.

[0029] Preferably, the thickness of the composite material is 0.2 - 4 mm, more preferably 0.5 - 2 mm. When the thickness of the composite material is within the above range, an optimal balance between the layer thickness required for sufficient fire protection and the minimum layer thickness possible to save installation space for the battery system is achieved according to the battery design.

[0030] Where used herein, all thicknesses are determined by a caliper and / or ultrasonic thickness measuring device.

[0031] <Liquid coating application> As used herein, the term “liquid coating” means a coating whose components, in whole or in part, are liquid at application, preferably at 5 to 80°C, and which can be cured by crosslinking or evaporation of the solvent. The viscosity of the coating is not particularly limited, however, if the coating is epoxy-based, the viscosity is preferably in the range of 15 to 30 Pa·s at 25°C, and if the coating is aqueous, the viscosity is preferably in the range of 10 to 1000 Pa·s at 25°C.

[0032] When used herein, all viscosities are measured using a Brookfield viscometer (spindle 27) at 25°C.

[0033] Preferably, the liquid coating in the present invention is a one-component aqueous material comprising a two-component epoxy-based expandable material and / or an inorganic filler and / or fibers. When the coating is a one-component aqueous material comprising a two-component epoxy-based expandable material and / or an inorganic filler and / or fibers, the compatibility between the coating and the mat or fleece is improved, further enhancing the adhesion and mechanical stability of the fire-resistant composite material according to the present invention.

[0034] In a preferred embodiment of the present invention, the two-component epoxy-based expandable material is: 1) Epoxy resin; and 2) flame retardant compounds, The first component includes, 1) A first amine comprising N,N'-bis(3-aminopropyl)ethylenediamine and 3,3'-oxybis(ethylene-oxy)bis(propylamine), 2) Second amines comprising a polymer of m-phenylenebis(methylamine) and formaldehyde, 1,3-benzenedimethaneamine and phenol; and 3) flame retardant compounds, A second component containing and .

[0035] In the present invention, when the above two-component epoxy-based expandable material is used as a coating, it can be applied to 2D components (such as battery lids) by flat streaming, which means that there is no overspray and no aerosol formation, thus eliminating the need for masking. Furthermore, the thickness of the initial layer can be reduced, saving installation space and providing excellent thermal protection due to the expansion reaction.

[0036] In another preferred embodiment of the present invention, the one-component aqueous material comprising an inorganic filler and / or fibers is a non-reactive aqueous dispersion comprising an acrylic binder, glass fibers, and a flame retardant component.

[0037] In the present invention, when a one-component aqueous material containing the above-mentioned inorganic filler and / or fibers is used as a coating, water is used as an environmentally friendly and health-friendly solvent, the one-component material is advantageous in terms of equipment procurement, does not produce flames or smoke when exposed to heat / flame, does not cause chemical reactions within the battery system, and, depending on the design, does not block ventilation channels because thermal protection is formed by the thickness of the initially applied layer.

[0038] The two-component epoxy-based expandable material of the present invention comprises an epoxy resin. The epoxy resin is present as the first component of the composition.

[0039] Preferably, the epoxy resin is an epoxy resin based on bisphenol A and epichlorohydrin, bisphenol-A diglycidyl ether epoxy resin; bisphenol-F diglycidyl ether epoxy resin; cresol novolac epoxy resin, C4-28 alkylene diglycidyl ether, C2-28 alkylene and / or alkenylene-diglycidyl ester; C2-28 alkylene, monophenol and polyphenol glycidyl ether; trimethylolpropane, pyrocatechol, resorcinol, hydroquinone, 4,4',4''-trihydroxyphenylmethane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxydiphenyldimethyl Polyglycidyl ethers of tris(4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenylmethylmethane, 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxydiphenylsulfone, or tris(4-hydroxyphenyl)methane; methylenebis(naphthalene)-diol, -triol or -tetrol, 2,7,2',7'-tetraglycidyloxynaphthalenemethane and / or 1,1,2,2-tetrakis(4-glycidyloxyphenyl)ethane, cresol novolac epoxy resins, sorbitol glycidyl ethers, and mixtures thereof, more preferably the epoxy resin is based on bisphenol A and epichlorohydrin.

[0040] The above epoxy resins are preferred, and in particular, epoxy resins based on bisphenol A and epichlorohydrin are preferred because they are flame-resistant when exposed to flame testing.

[0041] Suitable commercially available epoxy resins for use in the present invention include, but are not limited to, Olin's DER331.

[0042] The two-component epoxy-based expandable material according to the present invention may contain epoxy resin in an amount of 30 to 60% by weight, preferably 35 to 50% by weight, and more preferably 38 to 42% by weight, of the total weight of the first component of the composition.

[0043] The above range is preferred because it can provide optimal heat resistance, flame retardancy, and rheological behavior for the composition.

[0044] The two-component epoxy-based expandable material according to the present invention comprises a combination of a first amine and a second amine. The first and second amines are present in the second component of the composition.

[0045] In one embodiment, the first amine comprises a mixture of N,N'-bis(3-aminopropyl)ethylenediamine and 3,3'-oxybis(ethylene-oxy)bis(propylamine), and the second amine comprises a mixture of m-phenylenebis(methylamine) and a polymer of formaldehyde, 1,3-benzenedimethaneamine, and phenol.

[0046] In one embodiment, the first amine consists of a mixture of N,N'-bis(3-aminopropyl)ethylenediamine and 3,3'-oxybis(ethylene-oxy)bis(propylamine), and the second amine consists of a mixture of m-phenylenebis(methylamine) and a polymer of formaldehyde, 1,3-benzenedimethaneamine, and phenol.

[0047] In another embodiment, the first amine is poly(propylene glycol)bis(2-aminopropyl ether) (CAS 9046-10-0), and the second amine is 5-amino-1,3,3-trimethylcyclohexanemethylamine (CAS 2855-16-2).

[0048] A mixture of the first and second amines described above is selected and used because it exhibits good flame resistance when exposed to flame testing. Furthermore, the applicant has found that the combined use of the first and second amines results in control of the crosslinking rate and an increase in the crosslinking rate.

[0049] In the two-component epoxy-based expandable material according to the present invention, the first amine and the second amine may be present in a ratio of 60:40 to 99:1.

[0050] The reaction rate depends on the content of the second amine, so a ratio of 60:40 to 99:1 is preferred. If the ratio of the second amine is too high, the reaction will be too fast, which may adversely affect the application process.

[0051] A suitable commercially available first amine for use in the present invention is, but is not limited to, Ancamine 2432 manufactured by Evonik. Furthermore, a suitable commercially available second amine for use in the present invention is, but is not limited to, Ancamine 2914UF manufactured by Evonik.

[0052] In the two-component epoxy-based expandable material according to the present invention, the first amine and the second amine may be present in the second component of the composition in an amount of 30 to 50% by weight, preferably 38 to 48% by weight, and more preferably 43 to 47% by weight, based on the total weight of the second component of the composition.

[0053] The above range is preferable because, based on the amount of epoxy resin in the first component, it can result in a complete reaction that does not contain any unreacted epoxy resin in the composition.

[0054] The one-component aqueous material according to the present invention contains a (meth)acrylic resin. Preferably, the resin is an acrylic resin.

[0055] The (meth)acrylic resin used in the present invention may be linear or branched, and may be composed of copolymerized alkyl-functional (meth)acrylic monomers, acid-functional (meth)acrylic monomers, or tertiary amine-functional (meth)acrylic monomers, or may contain other functional groups. Branching in the (meth)acrylic resin can be induced by copolymerizing polyfunctional comonomers and / or by using polyfunctional chain transfer agents and / or polyfunctional initiators.

[0056] Suitable comonomers used to form the (meth)acrylic resin of the present invention include, but are not limited to, C1-C12 esters of methacrylic acid and acrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl(lauryl) methacrylate, or the corresponding acrylate. Mixtures of compatible (meth)acrylate monomers can also be used. Methacrylic and acrylic comonomers based on esters of methacrylic acid and acrylic acid with poly(ethylene glycol) and / or poly(propylene glycol and / or glycol ether) may also be used. Other additional vinyl monomers that may be used include vinyl esters (e.g., vinyl acetate and vinyl propionate); vinyl ethers; esters of crotonic acid, maleic acid, fumaric acid, and itaconic acid; styrene; alkylstyrene; acrylonitrile; butadiene; and their comonomers. The specific monomer selected depends primarily on the end use for which the adhesive is intended.

[0057] Suitable acid-functional comonomers used in forming the (meth)acrylic resin of the present invention include, but are not limited to, methacrylic acid and acrylic acid.

[0058] Suitable hydroxyl-functionalized comonomers that can be incorporated to form the (meth)acrylic resin of the present invention include, but are not limited to, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxybutyl methacrylate or the corresponding acrylates.

[0059] Suitable amine-functionalized comonomers used to form the (meth)acrylic resin of the present invention include, but are not limited to, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or the corresponding acrylate.

[0060] (Meth)acrylic resins can be prepared by free radical polymerization, and their molecular weight (Mn) is controlled using chain transfer agents, such as thiols (e.g., dodecyl mercaptans) or catalytic chain transfer based on transition metal complexes. Branched (meth)acrylic resins are prepared by copolymerizing polyfunctional monomers and / or using polyfunctional chain transfer agents and / or polyfunctional initiators.

[0061] Suitable commercially available acrylic resins for use in the present invention include, but are not limited to, Acronal DS 3502 manufactured by BASF.

[0062] The one-component aqueous material according to the present invention may contain 6 to 30% by weight, preferably 8 to 25% by weight, and more preferably 10 to 20% by weight of acrylic resin, based on the total weight of the first component of the composition.

[0063] The above range is preferred because it can provide optimal heat resistance, flame retardancy, and rheological behavior for the composition.

[0064] The one-component aqueous material according to the present invention contains glass fibers.

[0065] Suitable commercially available glass fibers for use in the present invention include, but are not limited to, 4.5 mm Faser glass manufactured by Saint-Gobain Vetrotex.

[0066] The one-component aqueous material according to the present invention may contain glass fibers in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 1.5% by weight, of the total weight of the composition.

[0067] The one-component aqueous material according to the present invention contains water.

[0068] The one-component aqueous material according to the present invention may contain 15 to 45% by weight, more preferably 20 to 40% by weight, and even more preferably 25 to 35% by weight of water, based on the total weight of the composition.

[0069] The two-component epoxy-based expandable material and the one-component aqueous material according to the present invention contain a flame-retardant compound.

[0070] The flame retardant compound may be present in the first component of the composition and / or the second component of a two-component composition, and may be the same or different in the first and second components of the composition.

[0071] The flame-retardant compounds are, independently, aluminum trihydroxylate, aluminum hydroxide, mica, calcium carbonate, arsenic oxide, expanded graphite, calcium sulfate, cyanuric acid derivatives, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tris-(isopropylated phenyl) phosphate, trixylyl phosphate, tritolyl phosphate, 2-ethylhexyl diphenyl phosphate, decyl diphenyl phosphate, tris-(2-chloroethyl) phosphate, tris-(2-chloropropyl) phosphate, tris-(2,3-di The phosphate is selected from the group consisting of bromopropyl phosphate, tetrakis-(2-chloro)-ethylene diphosphate, dimethylmethyl phosphonate, diethyl ethyl phosphonate, chloroparaffin, hexabromobenzene, brominated diphenyl ether, dibromoneopentyl glycol, monopentaerythritol, dipentaerythritol, coated red phosphorus, and mixtures thereof, and is preferably selected from cresyl diphenyl phosphate, calcium carbonate, mica, aluminum trihydroxylate, aluminum hydroxide ammonium polyphosphate, and mixtures thereof.

[0072] The above preferred flame-retardant compounds are preferable because they allow the composition of the present invention to be applied as a thin, lightweight protective coating layer that reduces temperature propagation and provides flame retardancy and heat insulation.

[0073] Suitable commercially available flame retardant compounds for use in the present invention include, but are not limited to, Omya BLH manufactured by Omya and Disflamoll DPK manufactured by Lanxess.

[0074] In the two-component epoxy-based expandable material according to the present invention, the first component may contain a flame retardant compound in an amount of 35 to 65% by weight, preferably 45 to 60% by weight, and more preferably 51 to 57% by weight, based on the total weight of the first component of the composition.

[0075] In the two-component epoxy-based expandable material according to the present invention, the second component may contain a flame retardant compound in an amount of 20 to 65% by weight, preferably 50 to 60% by weight, and more preferably 51 to 57% by weight, of the total weight of the second component of the composition.

[0076] A one-component aqueous material according to the present invention may contain a flame retardant compound in an amount of 30 to 65% by weight, preferably 35 to 60% by weight, and more preferably 38 to 55% by weight, of the total weight of the composition.

[0077] The above range provides the composition with good viscosity and good mixing properties. In particular, if the amount of flame retardant compound is too low, it may adversely affect the heat transfer properties, and the composition may flow freely, making mixing difficult. On the other hand, if the amount is too high, it may adversely affect the application process.

[0078] The two-component epoxy-based expandable material or the one-component aqueous material according to the present invention may further contain a rheology modifier.

[0079] The rheological modifier may be present in the first component of the composition and / or the second component of a two-component composition, and may be the same or different in the first and second components of the composition.

[0080] The rheological modifier is preferably selected from the group consisting of fumed silica, fused silica, amorphous silica, hydrated silica, mineral nanosilicate clay, and mixtures thereof, and more preferably the rheological modifier is fumed silica.

[0081] Fumed silica is a particularly preferred rheological modifier because its presence can increase the viscosity of the composition during the application process (spraying). Examples of such fumed silica include polydimethylsiloxane-treated silica and hexamethyldisilazane-treated silica.

[0082] Suitable commercially available rheological modifiers for use in the present invention include, but are not limited to, CAB-O-SIL ND-TS, TS610, TS710, and TS720 from Cabot, and AEROSIL R805, R8200, 300, and 200 from Degussa.

[0083] A two-component, room-temperature curable, heat-resistant and flame-retardant composition according to the present invention may contain a rheology modifier in the first component of the composition in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, and more preferably 0.3 to 1.5% by weight of the total weight of the first component, and / or, a rheology modifier may contain in the second component of the composition in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, and more preferably 0.3 to 1.5% by weight of the total weight of the second component.

[0084] The one-component aqueous material according to the present invention may contain a rheological modifier in an amount of 0.1 to 5% by weight, preferably 0.2 to 5% by weight, and more preferably 0.2 to 3% by weight, of the total weight of the first component of the composition.

[0085] The above range has been found to be ideal for providing a good viscosity profile for the first and second components without increasing viscosity.

[0086] The two-component epoxy-based expandable material or the one-component aqueous material according to the present invention may further contain a pigment.

[0087] The pigment may be present in the first component of the composition and / or the second component of a two-component composition, and may be the same or different in the first and second components of the composition.

[0088] The pigment is preferably selected from the group consisting of titanium dioxide, carbon black, graphite, iron oxide, and mixtures thereof.

[0089] The two-component epoxy-based expandable material according to the present invention may contain a pigment in the first component of the composition in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 1.5% by weight of the total weight of the first component, and / or may contain a pigment in the second component of the composition in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 1.5% by weight of the total weight of the second component.

[0090] The one-component aqueous material according to the present invention may contain a pigment in an amount of 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 1.5% by weight, of the total weight of the composition.

[0091] The two-component epoxy-based expandable material according to the present invention is prepared by first mixing all the components of the first component in one container, then mixing all the components of the second component in another container, and then mixing the first and second components together just before use.

[0092] In the two-component epoxy-based expandable material according to the present invention, the first component and the second component are mixed in a ratio of 1.9:1.1 to 2.1:0.9, preferably in a ratio of 2:1.

[0093] The above range is based on the amount of epoxy resin in the first component and the total amount of amine in the second component, and is preferable because it can result in a complete reaction in which no unreacted epoxy resin is present in the final composition.

[0094] A one-component aqueous material according to the present invention is prepared by mixing all the components together.

[0095] <Mat or fleece> As used herein, the term “mat or fleece” means a thermally stable mat or fleece in the art. In the present invention, the mat or fleece may have various types of surfaces composed of glass fibers.

[0096] Preferably, the mat or fleece is a glass fiber mat or glass fiber fleece. In the present invention, using a glass fiber mat or glass fiber fleece as the mat or fleece further improves the heat resistance, electrical nonconductivity, and cost-effectiveness of the fire-resistant composite material according to the present invention.

[0097] Preferably, the thickness of the mat or fleece is 0.2 to 1 mm, and more preferably 0.2 to 0.7 mm. When the thickness of the mat or fleece is within the above range, an optimal balance is achieved between the layer thickness required for sufficient protection and the minimum possible layer thickness to save installation space for the battery system.

[0098] In a preferred embodiment, the fiber diameter of the mat or fleece is 5 μm to 20 μm, preferably 8 μm, 10 μm, and / or 13 μm. When the fiber diameter of the mat or fleece is within the above range, the manufacturing of the mat or fleece has sufficient stability.

[0099] In another preferred embodiment of the present invention, the fiber length of the mat or fleece is 5 mm to 30 mm. When the fiber length of the mat or fleece is within this range, the manufacturing of the mat or fleece has sufficient stability.

[0100] Examples of commercially available mats or fleeces suitable for use in the present invention include, but are not limited to, Johns Manville.

[0101] In yet another preferred embodiment of the present invention, the mat or fleece comprises a binder and / or a coating. The binder may be any conventional binder in the art, preferably a urea-formaldehyde resin and polymer dispersion. The coating may be any conventional coating in the art, preferably aluminum hydroxide and / or sulfate. In the present invention, the use of a urea-formaldehyde resin and polymer dispersion, and / or aluminum hydroxide and / or sulfate further improves heat resistance, electrical nonconductivity, cost-effectiveness, and / or affinity between the components of the fire-resistant composite of the present invention.

[0102] In a preferred embodiment of the present invention, the mat or fleece is embedded in the coating and / or positioned on the surface of the coating.

[0103] The present invention further relates to a method for manufacturing the fire-resistant composite material of the present invention, The present invention provides a method comprising: applying a liquid coating of the present invention onto a substrate; subsequently placing a mat or fleece according to the present invention on the coating; optionally applying another liquid coating of the present invention to the mat or fleece; and drying the coating at room temperature or a high temperature, preferably 25 to 90°C. Preferably, the substrate used in the present invention may be an electronically coated steel or aluminum substrate, and more preferably an electronically coated steel substrate.

[0104] In a preferred embodiment of the present invention, when a two-component epoxy-based expandable material is used as the liquid coating in the present invention, the two components are mixed in a preferred ratio of 2:1 to obtain the coating before application.

[0105] The application of the liquid coating and the mixing of the two components can be carried out by any conventional method using any conventional apparatus in the art, if any. Preferably, the liquid coating is applied by a doctor blade method, spray coating, or flat streaming. In a preferred embodiment of the present invention, when a two-component epoxy-based expandable material is used as the liquid coating, a mixer for mixing the two components may be incorporated into the apparatus for applying the liquid coating, depending on the degree of automation.

[0106] The present invention also relates to the use of the fire-resistant composite material of the present invention for electric vehicle batteries, preferably for electric vehicle battery housings.

[0107] Furthermore, the present invention relates to an electric vehicle battery containing the fire-resistant composite material of the present invention.

[0108] The present invention also relates to a method for manufacturing an electric vehicle battery, comprising preparing a fire-resistant composite material on a battery lid and / or housing for an electric vehicle according to the method for manufacturing a fire-resistant composite material of the present invention. [Examples]

[0109] 1. Preparation of fire-resistant composite materials The fire-resistant composite material of Example 1 according to the present invention was prepared as follows. All the components of the first component listed in Table 1 below were mixed in one container (Flacktec plastic container) and mixed in a Flacktec speed mixer to obtain the first component. At the same time, all the components of the second component listed in Table 1 below were mixed in another container (Flacktec plastic container) and mixed in a Flacktec speed mixer to obtain the second component.

[0110] [Table 1]

[0111] The first and second components were combined in a 2:1 ratio and mixed to obtain a liquid coating. Next, 40 mL of the coating was applied to an electronically coated steel plate measuring 250 mm × 190 mm using a doctor blade. Subsequently, a fiberglass mat (610 μm thick, 10 μm fiber diameter, 8 mm fiber length, available from Johns Manville) cut to the size of the area to be protected (150 mm × 105 mm) was placed on top of the coating. Finally, the resulting composite was cured overnight at room temperature.

[0112] The fire-resistant composite material of Example 2 according to the present invention was prepared as follows. All the components listed in Table 2 below were mixed in a single container (Flacktec plastic container) and then mixed in a Flacktec speed mixer to obtain a liquid coating.

[0113] [Table 2]

[0114] A 50 mL liquid coating was applied by bar coating onto an electronically coated steel plate measuring 250 mm x 190 mm. Then, a fiberglass mat (610 μm thick, 10 μm fiber diameter, 8 mm fiber length, available from Johns Manville) cut to the size of the area to be protected (150 mm x 105 mm) was placed on top of the coating. Finally, the resulting composite material was dried overnight at room temperature.

[0115] The fire-resistant composite materials of Examples 3 and 4 according to the present invention were prepared in the same manner as in Examples 1 and 2, except that a different liquid coating was applied to the composite material in the same manner as before laying the mat, before curing the composite material. That is, the fire-resistant composite materials of Examples 3 and 4 were prepared by applying a liquid coating to an electronically coated steel plate, placing a glass fiber mat on the coating, applying the same liquid coating in the same manner as described above, and then curing the resulting composite material.

[0116] 2. Characteristic testing of fire-resistant composite materials 2.1 Adhesion Test of Mat to Coating Both the fire-resistant composite materials of Examples 1 and 2 were tested according to the three-point bending test in accordance with ISO 178 for plastic substrates and ISO 7438 for metal substrates. The results show that both passed these tests. For example, as shown in Figure 1, the fire-resistant composite material of Example 2 exhibited good adhesion of the mat to the coating.

[0117] 2.2 Testing the feasibility of coating mats To test whether the mat could be coated with the coating (i.e., whether the fire-resistant coating applied in liquid form to the mat had sufficient wettability), both fire-resistant composites from Examples 3 and 4 were visually observed. As shown in Figure 2a (photograph of the fire-resistant composite from Example 4) and Figure 2b (photograph of the fire-resistant composite from Example 3), these photographs show that both have good wettability for the liquid-applied fire-resistant coating on the mat.

[0118] 2.3 Thermal protection capability and adhesion test when in contact with flame (flame test) The heat transfer prevention properties of the fire-resistant composites of Examples 3 and 4 were tested by comparing them with a reference electronically coated steel without coatings or mats. After exposing the composites to a temperature of 1000°C for 10 minutes, the temperature (T2) of the fire test object should be less than 300°C.

[0119] The basic principle of the heat transfer test method is shown in Figure 3. T2 is the temperature to be measured and is shown in the graph against time. For example, the graph shows the temperature change over time for the fire-resistant composite material of Example 4 and a reference electronically coated steel without coating and mat. The test results are shown in Figure 5. The fire-resistant composite material of the present invention performed best in this test and can maintain a temperature (T2) well below 300°C for at least 10 minutes.

[0120] 2.4 Testing the mechanical stability of composite materials during explosion (pyrotechnic test) The fire-resistant composites of Examples 1 and 2, along with a reference electron-coated steel substrate without coating and matting, were tested according to a heat transfer test using a 50 Ah rectangular cell. The results showed that the fire-resistant composite of the present invention protected the electron-coated steel substrate. In particular, as shown in Figure 5, compared to the reference electron-coated steel substrate, the electron coating in the fire-resistant composite of the present invention remained undamaged at low temperatures, providing continued corrosion protection. Figure 5a shows a photograph of the reference electron-coated steel substrate without coating and matting, and Figure 5b shows a photograph of the fire-resistant composite of Example 2 after a thermal runaway test using a 50 Ah rectangular cell.

[0121] From the above results, it can be seen that the fire-resistant composite material of the present invention exhibits improvements in fire resistance, heat shielding behavior, and mechanical stability.

Claims

1. Fire-resistant composite materials made from liquid coatings and mats or fleece.

2. The fire-resistant composite material according to claim 1, wherein the liquid coating is a two-component epoxy-based expandable material and / or a one-component aqueous material containing an inorganic filler and / or fibers.

3. The aforementioned two-component epoxy-based expandable material is 1) Epoxy resin; and 2) flame retardant compound, The first component includes, 1) A first amine comprising N,N'-bis(3-aminopropyl)ethylenediamine and 3,3'-oxybis(ethylene-oxy)bis(propylamine), 2) Second amines comprising m-phenylenebis(methylamine) and formaldehyde, 1,3-benzenedimethaneamine and phenol polymers; and 3) flame retardant compound, A fire-resistant composite material according to claim 2, comprising a second component including .

4. The fire-resistant composite material according to claim 2, wherein the one-component aqueous material comprising the inorganic filler and / or fibers is a non-reactive aqueous dispersion comprising an acrylic binder, glass fibers, and a flame-retardant component.

5. The fire-resistant composite material according to any one of claims 1 to 4, wherein the mat or fleece is a glass fiber mat or fleece, and / or the thickness of the mat or fleece is 0.2 to 1 mm, preferably 0.2 to 0.7 mm.

6. The fire-resistant composite material according to any one of claims 1 to 5, wherein the fiber diameter of the mat or fleece is 5 μm to 20 μm, preferably 8 μm, 10 μm and / or 13 μm, and / or the fiber length of the mat or fleece is 5 mm to 30 mm.

7. The fire-resistant composite material according to any one of claims 1 to 6, wherein the mat or fleece preferably comprises a binder which is a urea-formaldehyde resin and a polymer dispersion, and / or a coating which is preferably aluminum hydroxide and / or a sulfate.

8. The fire-resistant composite material according to any one of claims 1 to 7, wherein the thickness of the composite material is 0.2 to 4 mm, preferably 0.5 to 2 mm.

9. The fire-resistant composite material according to any one of claims 1 to 8, wherein the mat or fleece is embedded in the coating and / or disposed on the surface of the coating.

10. A method for manufacturing a fire-resistant composite material according to any one of claims 1 to 9, A method comprising: applying a liquid coating according to any one of claims 1 to 9 onto a substrate, preferably by a doctor blade method, spray coating or flat streaming; subsequently placing a mat or fleece according to any one of claims 1 to 9 onto the coating; optionally applying another liquid coating according to any one of claims 1 to 9 onto the mat or fleece; and drying the coating at room temperature or a high temperature, preferably 25 to 90°C.

11. Use of the fire-resistant composite material according to any one of claims 1 to 9 for an electric vehicle battery, preferably for an electric vehicle battery housing.

12. A battery for an electric vehicle comprising the fire-resistant composite material described in any one of claims 1 to 9.

13. A method for manufacturing an electric vehicle battery according to claim 12, comprising preparing a fire-resistant composite material on an electric vehicle battery lid and / or housing by the method of claim 10.

Images