A multilayer fireproof material for a battery and a method of manufacturing the same

Abstract

The application discloses a multilayer fireproof material for a battery and a manufacturing method thereof, relates to the technical field of fireproof materials, and comprises a fireproof material base and a protective layer wrapped on the outer surface of the fireproof material base; the fireproof material base comprises a first glass fiber cloth layer, a ceramicized silicone rubber layer and a second glass fiber cloth layer from top to bottom; the multilayer fireproof material disclosed by the application has the advantages of remarkable fire-retardant and fireproof effects, good weather resistance and environmental protection performance, sufficient high-temperature flame impact resistance and good mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fireproof materials for batteries, and particularly relates to a multilayer fireproof material for batteries and a preparation method thereof. BACKGROUND

[0002] In recent years, with the rapid advancement of global industrialization and urbanization, the shortage of fossil energy and pollution problems are becoming increasingly serious, and the demand for new energy, especially new energy vehicles, has increased significantly. Therefore, in the face of a huge new energy vehicle market, high requirements are placed on the safety performance of new energy vehicle batteries.

[0003] During use, the heat generation rate of the chemical reaction inside the battery is much higher than the heat dissipation rate, and a large amount of heat accumulates inside the battery, causing the battery temperature to rise rapidly, eventually causing the battery to catch fire or explode, resulting in thermal runaway of the battery. Since thermal runaway usually reacts very quickly and has a very large impact, it poses a serious threat to the personal safety of users. In order to improve the safety of the battery, a fireproof material is usually used to coat the battery. However, the existing battery fireproof materials still have technical defects such as insufficient impact resistance, poor flame retardant and fireproof performance, weather resistance and environmental protection performance, poor flame impact resistance of the material itself, easy collapse of the material during burning, and lack of high-temperature flame impact resistance.

[0004] In order to solve the above problems, Chinese patent document CN109987884B discloses a fireproof material for batteries, a preparation method and use thereof. The fireproof material for batteries of the present application comprises a mica layer and a foamed coating layer, the mica layer comprises mica material and adhesive in a mass ratio of 100:(10-25), and the foamed coating layer comprises resin, foaming agent and flame retardant in a mass ratio of 100:(1-20):(5-15). The preparation method of the present application is simple, the prepared fireproof material for batteries is thin in thickness, light in mass, good in mechanical properties, resistant to deformation at 500 DEG C high temperature, has a flame retardant grade V0, and can effectively protect and delay the safety problems caused by thermal runaway of the battery pack. However, the mica layer of the fireproof material has a large density and is a steel material that is not easy to deform, making it difficult to fully adhere to the battery; the adhesive used is also easy to fall off at high temperatures, thereby losing its effectiveness.

[0005] Therefore, there is still a need in the art for a fireproof material for batteries that has significant flame retardant and fireproof effect, good weather resistance and environmental protection performance, sufficient high-temperature flame impact resistance, and good mechanical properties. SUMMARY

[0006] The application aims to provide a multi-layer fireproof material for batteries, which has significant fireproof effect, good weather resistance, environmental protection, high temperature flame impact resistance and mechanical properties.

[0007] To achieve the above purposes, the application provides a multi-layer fireproof material for batteries, which comprises a fireproof material substrate and a protective layer coated on the outer surface of the fireproof material substrate; the fireproof material substrate comprises, from top to bottom, a first glass fiber cloth layer, a ceramicized silicone rubber layer and a second glass fiber cloth layer; the ceramicized silicone rubber layer is made of the following raw materials by weight: 80-100 parts of silicone rubber, 25-35 parts of ceramic filler, 1-3 parts of structure control agent, 4-6 parts of vulcanizing agent, 8-12 parts of nano filler, 8-15 parts of flame retardant, 3-5 parts of coupling agent, 1-3 parts of 2,4-diamino-6-diallyl amino-1,3,5-triazine, 0.8-1.2 parts of initiator, 5-8 parts of polyether sulfone type hyperbranched epoxy resin with epoxy end groups, and 3-5 parts of 2-(1-propen-2-yl)benzo[D]oxazole.

[0008] Preferably, the silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed in a mass ratio of 1:(1-2); the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; and the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA 120.

[0009] Preferably, the ceramic filler is at least one of wollastonite, mica, boron carbide and hexagonal boron nitride; and the particle size of the ceramic filler is 1200-1600 mesh.

[0010] Preferably, the structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double penta sulfurizing agent; the nano filler is at least one of nano zirconium carbide, nano silicon boride and nano calcium carbonate; the particle size of the nano filler is 10-60 nm; the flame retardant is at least one of antimony trioxide, aluminum hydroxide and magnesium hydroxide; the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570; and the initiator is at least one of tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-amyl peroxyacetate and 1,1-di-tert-butyl peroxy-3,3,5-trimethylcyclohexane.

[0011] Preferably, the polyether sulfone type hyperbranched epoxy resin with epoxy end groups is made according to the method of Example 18 in Chinese patent document CN104311832B.

[0012] Preferably, the first glass fiber cloth layer and the second glass fiber cloth layer are both EC110C type glass fiber cloth, which is four satin, thickness 0.11mm, surface weight 110g / m 2 .

[0013] Preferably, the thickness of the fireproof material substrate is 0.4-2.0mm; the thickness of the protective layer is 0.1-0.4mm.

[0014] Preferably, the protective layer is made of the following raw materials by weight parts: amino-terminated hyperbranched polyimide 20-30 parts, fluorine and epoxy-containing polysiloxane 60-80 parts, solvent 30-40 parts.

[0015] Preferably, the amino-terminated hyperbranched polyimide is made according to the method of Example 1 in Chinese patent document CN107789677B.

[0016] Preferably, the fluorine and epoxy-containing polysiloxane is made according to the method of Example 1 in Chinese patent document CN102250355B.

[0017] Preferably, the solvent is any one of isopropyl alcohol, butanone, butyl acetate.

[0018] Another object of the present application is to provide a manufacturing method of the multi-layer fireproof material for batteries, comprising the following steps:

[0019] Step S1, mix the raw materials of the ceramicized silicone rubber layer by weight parts, put them in a mixer for mixing, get the rubber compound, then calender the rubber compound to form the ceramicized silicone rubber layer;

[0020] Step S2, stack in the order of first glass fiber cloth layer, ceramicized silicone rubber layer, second glass fiber cloth layer from top to bottom, heat and press using a hot plate, and then vulcanize to form the fireproof material substrate;

[0021] Step S3, mix the raw materials of the protective layer uniformly, then coat them on the outer surface of the fireproof material substrate, dry, and then get the multi-layer fireproof material for batteries.

[0022] Preferably, the mixing temperature in step S1 is 30-50℃, and the mixing time is 25-45min.

[0023] Preferably, the vulcanization temperature in step S2 is 160-210℃, and the pressure is 8-12MPa.

[0024] Preferably, the drying in step S3 is at 80-120℃ for 10-20min.

[0025] With the technical scheme, the application has the following advantages:

[0026] (1) The manufacturing method of the multilayer fireproof material for batteries disclosed by the application has low requirements for reaction conditions and equipment, does not need special equipment and modification of the existing production line, has low capital investment and energy consumption, high preparation efficiency and yield, and is suitable for industrial production, and has high popularization and application value.

[0027] (2) The multilayer fireproof material for batteries disclosed by the application comprises a fireproof material substrate and a protective layer coated on the outer surface of the fireproof material substrate, and the fireproof material substrate comprises a first glass fiber cloth layer, a ceramicized silicone rubber layer and a second glass fiber cloth layer from top to bottom. Through the multilayer structure, the mechanical properties, weather resistance and fireproof performance of the material can be effectively improved. Through reasonable selection of the raw materials of each layer, the layers cooperate with each other to avoid delamination, improve the material performance stability, further improve the mechanical properties, weather resistance and fireproof performance, and prolong the service life of the fireproof material product.

[0028] (3) The multilayer fireproof material for batteries disclosed by the application is made of the following raw materials by weight: 80-100 parts of silicone rubber, 25-35 parts of ceramic filler, 1-3 parts of structure control agent, 4-6 parts of vulcanizing agent, 8-12 parts of nano filler, 8-15 parts of flame retardant, 3-5 parts of coupling agent, 1-3 parts of 2,4-diamino-6-diallyl amino-1,3,5-triazine, 0.8-1.2 parts of initiator, 5-8 parts of polyether sulfone type hyperbranched epoxy resin with epoxy end groups, and 3-5 parts of 2-(1-propen-2-yl)benzo[D]oxazole. Through the interaction between the raw materials, the prepared material has excellent fire-retardant and fireproof effect, good weather resistance and environmental protection performance, sufficient high-temperature flame impact resistance, and good mechanical properties; 2,4-diamino-6-diallyl amino-1,3,5-triazine and 2-(1-propen-2-yl)benzo[D]oxazole, which contain unsaturated alkene bonds, can copolymerize and graft with the unsaturated alkene bonds in the silicone rubber under the action of the initiator, and the amino groups on the 2,4-diamino-6-diallyl amino-1,3,5-triazine can also undergo epoxy ring-opening reaction with the epoxy groups on the polyether sulfone type hyperbranched epoxy resin with epoxy end groups, forming an interpenetrating network structure, and introducing organic silicon, triazine, benzoxazole and polyether sulfone structures into the molecular structure of the material. Under the multiple effects of electronic effect, steric effect and conjugation effect, the fire-retardant and fireproof performance, weather resistance, high-temperature flame impact resistance and mechanical properties of the prepared material are further improved.

[0029] (4) The multilayer fireproof material for a battery disclosed in the present application, the protective layer is made of each raw material in parts by weight: amino-terminated hyperbranched polyimide 20-30 parts, fluorine-containing and epoxy-containing polysiloxane 60-80 parts, solvent 30-40 parts. Through the mutual cooperation between raw materials, the high temperature resistance and weather resistance of the material can be improved, and the fire-retardant fireproof effect is improved. DETAILED DESCRIPTION

[0030] The following description is used to disclose the present application so that those skilled in the art can implement the present application. The preferred embodiments in the following description are only as examples, and other obvious modifications can be thought by those skilled in the art.

[0031] Example 1

[0032] A multilayer fireproof material for a battery, comprising a fireproof material substrate and a protective layer coated on the outer surface of the fireproof material substrate; the fireproof material substrate comprises a first glass fiber cloth layer, a ceramicized silicone rubber layer and a second glass fiber cloth layer from top to bottom; the ceramicized silicone rubber layer is made of each raw material in parts by weight: silicone rubber 80 parts, ceramic filler 25 parts, structure control agent 1 part, vulcanizing agent 4 parts, nano filler 8 parts, flame retardant 8 parts, coupling agent 3 parts, 2,4-diamino-6-diallyl amino-1,3,5-triazine 1 part, initiator 0.8 parts, polyether sulfone type hyperbranched epoxy resin with epoxy end group 5 parts, 2-(1-propylene-2-yl) benz [D] oxazole 3 parts.

[0033] The silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed in a mass ratio of 1:1; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA120.

[0034] The ceramic filler is wollastonite; the particle size of the ceramic filler is 1200 mesh; the structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double five vulcanizing agent; the nano filler is nano zirconium carbide; the particle size of the nano filler is 60 nm; the flame retardant is antimony trioxide; the coupling agent is silane coupling agent KH550; the initiator is tert-butyl peroxybenzoate; the polyether sulfone type hyperbranched epoxy resin with epoxy end group is made according to the method in the implementation case 18 of Chinese patent document CN104311832B.

[0035] The first glass fiber cloth layer and the second glass fiber cloth layer are both EC110C type glass fiber cloth, which is four satin, thickness 0.11mm, surface weight 110g / m 2 ; the thickness of the fireproof material substrate is 1.8mm; the thickness of the protective layer is 0.1mm.

[0036] The protective layer is made of the following raw materials in parts by weight: amino-terminated hyperbranched polyimide 20 parts, fluorine and epoxy-containing polysiloxane 60 parts, solvent 30 parts.

[0037] The amino-terminated hyperbranched polyimide is made according to the method of Example 1 in Chinese patent document CN107789677B; the fluorine and epoxy-containing polysiloxane is made according to the method of Example 1 in Chinese patent document CN102250355B; and the solvent is isopropyl alcohol.

[0038] A manufacturing method of the multilayer fireproof material for batteries, comprising the following steps:

[0039] Step S1, mixing raw materials of the ceramicized silicone rubber layer in parts by weight, placing them in a mixer for mixing to obtain a rubber compound, and then calendering the rubber compound to form the ceramicized silicone rubber layer;

[0040] Step S2, stacking in the order of first glass fiber cloth layer, ceramicized silicone rubber layer, and second glass fiber cloth layer from top to bottom, heating and pressing with a hot plate, and vulcanizing to form a fireproof material base;

[0041] Step S3, mixing raw materials of the protective layer uniformly, coating them on the outer surface of the fireproof material base, and drying to obtain the multilayer fireproof material for batteries.

[0042] The mixing temperature in Step S1 is 30℃, and the mixing time is 25min; the vulcanizing temperature in Step S2 is 160℃, and the pressure is 8MPa; and the drying in Step S3 is carried out at 80℃ for 20min.

[0043] Example 2

[0044] A multilayer fireproof material for batteries, comprising a fireproof material base and a protective layer coated on the outer surface of the fireproof material base; the fireproof material base comprises, from top to bottom, a first glass fiber cloth layer, a ceramicized silicone rubber layer, and a second glass fiber cloth layer; the ceramicized silicone rubber layer is made of the following raw materials in parts by weight: silicone rubber 85 parts, ceramic-forming filler 27 parts, structure control agent 1.5 parts, vulcanizing agent 4.5 parts, nanoscale filler 9 parts, flame retardant 10 parts, coupling agent 3.5 parts, 2,4-diamino-6-diallyl amino-1,3,5-triazine 1.5 parts, initiator 0.9 parts, polyether sulfone type hyperbranched epoxy resin with epoxy end groups 6 parts, and 2-(1-propen-2-yl)benzo[D]oxazole 3.5 parts.

[0045] The organic silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed in a mass ratio of 1:1.2; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; and the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA 120.

[0046] The ceramic filler is mica; the particle size of the ceramic filler is 1300 mesh; the structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double five vulcanizing agent; the nano filler is nano boronized silicon; the particle size of the nano filler is 50 nm; the flame retardant is aluminum hydroxide; the coupling agent is silane coupling agent KH560; the initiator is tert-butyl peroxide 3,5,5 trimethyl hexanoate; and the polyether sulfone type hyperbranched epoxy resin with epoxy end groups is prepared according to the method of case 18 in Chinese patent document CN104311832B.

[0047] The first glass fiber cloth layer and the second glass fiber cloth layer are both EC110C type glass fiber cloth, which is four satin, 0.11mm thick, and 110g / m 2 The thickness of the fireproof material substrate is 1.8mm; and the thickness of the protective layer is 0.1mm.

[0048] The protective layer is prepared from the following raw materials in parts by weight: amino-terminated hyperbranched polyimide 23 parts, fluorine-containing and epoxy-containing polysiloxane 65 parts, and solvent 33 parts; the amino-terminated hyperbranched polyimide is prepared according to the method of example 1 in Chinese patent document CN107789677B; the fluorine-containing and epoxy-containing polysiloxane is prepared according to the method of example 1 in Chinese patent document CN102250355B; and the solvent is butanone.

[0049] A method for manufacturing the multilayer fireproof material for batteries, comprising the following steps:

[0050] Step S1, mixing the raw materials of the ceramicized silicone rubber layer according to weight parts, placing them in a mixer for mixing, obtaining a mixed rubber, and then calendering the mixed rubber to form a ceramicized silicone rubber layer;

[0051] Step S2, stacking in the order of first glass fiber cloth layer, ceramicized silicone rubber layer, and second glass fiber cloth layer from top to bottom, heating and pressing using a heating plate, and then vulcanizing to form a fireproof material substrate;

[0052] Step S3, mixing the raw materials of the protective layer uniformly, coating them on the outer surface of the fireproof material substrate, and then drying to obtain the multilayer fireproof material for batteries.

[0053] The temperature of the mixing in step S1 is 35℃, and the mixing time is 30 min; the temperature of the vulcanization forming in step S2 is 180℃, and the pressure is 9 MPa; the drying in step S3 is at 90℃ for 17 min.

[0054] Example 3

[0055] A multilayer fireproof material for a battery comprises a fireproof material substrate and a protective layer coated on the outer surface of the fireproof material substrate; the fireproof material substrate comprises, from top to bottom, a first glass fiber cloth layer, a ceramicized silicone rubber layer, and a second glass fiber cloth layer; the ceramicized silicone rubber layer is made of the following raw materials in parts by weight: 90 parts of silicone rubber, 30 parts of ceramic filler, 2 parts of structure control agent, 5 parts of vulcanizing agent, 10 parts of nano filler, 12 parts of flame retardant, 4 parts of coupling agent, 2 parts of 2,4-diamino-6-diallyl amino-1,3,5-triazine, 1 part of initiator, 6.5 parts of polyether sulfone type hyperbranched epoxy resin with epoxy end groups, and 4 parts of 2-(1-propen-2-yl)benzo[D]oxazole.

[0056] The silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed at a mass ratio of 1:1.5; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA 120; the ceramic filler is boron carbide; the particle size of the ceramic filler is 1400 mesh; the structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double penta vulcanizing agent; the nano filler is nano calcium carbonate; the particle size of the nano filler is 30 nm; the flame retardant is magnesium hydroxide; the coupling agent is silane coupling agent KH570; the initiator is t-amyl peroxy acetate; and the polyether sulfone type hyperbranched epoxy resin with epoxy end groups is made according to the method in Example 18 of Chinese patent document CN104311832B.

[0057] The first glass fiber cloth layer and the second glass fiber cloth layer are both EC110C type glass fiber cloth, which is four satin, 0.11 mm thick, and 110 g / m 2 ; the thickness of the fireproof material substrate is 1.8 mm; and the thickness of the protective layer is 0.1 mm.

[0058] The protective layer is made of the following raw materials in parts by weight: 25 parts of amino-terminated hyperbranched polyimide, 70 parts of fluorine and epoxy-containing polysiloxane, and 35 parts of solvent; the amino-terminated hyperbranched polyimide is made according to the method in Example 1 of Chinese patent document CN107789677B; the fluorine and epoxy-containing polysiloxane is made according to the method in Example 1 of Chinese patent document CN102250355B; and the solvent is butyl acetate.

[0059] A manufacturing method of the multilayer fireproof material for batteries, comprising the following steps:

[0060] Step S1, mixing each raw material of the ceramicized silicone rubber layer according to weight parts, placing in a mixer for mixing, obtaining a mixed rubber, and then calendering the mixed rubber to form the ceramicized silicone rubber layer;

[0061] Step S2, sequentially laminating from top to bottom in the order of the first glass fiber cloth layer, the ceramicized silicone rubber layer, and the second glass fiber cloth layer, heating and extruding by using a heating plate, and then vulcanizing to form the fireproof material base material;

[0062] Step S3, mixing each raw material of the protective layer uniformly, coating on the outer surface of the fireproof material base material, and drying to obtain the multilayer fireproof material for batteries.

[0063] The mixing temperature in step S1 is 40℃, and the mixing time is 35min; the vulcanizing temperature in step S2 is 190℃, and the pressure is 10MPa; and the drying in step S3 is drying at 100℃ for 15min.

[0064] Example 4

[0065] A multilayer fireproof material for batteries, comprising a fireproof material base material and a protective layer coated on the outer surface of the fireproof material base material; the fireproof material base material sequentially comprises a first glass fiber cloth layer, a ceramicized silicone rubber layer, and a second glass fiber cloth layer from top to bottom; the ceramicized silicone rubber layer is made of each raw material according to weight parts as follows: 95 parts of silicone rubber, 33 parts of porcelain-forming filler, 2.5 parts of structure control agent, 5.5 parts of vulcanizing agent, 11 parts of nano filler, 14 parts of flame retardant, 4.5 parts of coupling agent, 2.5 parts of 2,4-diamino-6-diallyl amino-1,3,5-triazine, 1.1 parts of initiator, 7.5 parts of polyether sulfone type hyperbranched epoxy resin with epoxy end groups, and 4.5 parts of 2-(1-propen-2-yl)benzo[D]oxazole.

[0066] The organic silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed in a mass ratio of 1:1.8; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA 120; the ceramic-forming filler is hexagonal boron nitride; the particle size of the ceramic-forming filler is 1500 mesh; the structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double five vulcanizing agent; the nano-scale filler is a mixture of nano-zirconium carbide, nano-silicon boride and nano-calcium carbonate mixed in a mass ratio of 1:1:3; the average particle size of the nano-scale filler is 20 nm; the flame retardant is a mixture of antimony trioxide, aluminum hydroxide and magnesium hydroxide mixed in a mass ratio of 2:1:5; the coupling agent is a mixture of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570 mixed in a mass ratio of 1:1:3; the initiator is a mixture of tert-butyl benzene peroxide, tert-butyl 3,5,5-trimethylhexanoate peroxide, tert-amyl acetate peroxide and 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane mixed in a mass ratio of 2:2:3:1; the polyether sulfone type hyperbranched epoxy resin with epoxy group as the end group is prepared according to the method of case 18 in Chinese patent document CN104311832B.

[0067] The first glass fiber cloth layer and the second glass fiber cloth layer are both EC110C type glass fiber cloth, which is four satin, 0.11mm thick, 110g / m 2 The thickness of the fireproof material substrate is 1.8mm; the thickness of the protective layer is 0.1mm.

[0068] The protective layer is made of the following raw materials in parts by weight: amino-terminated hyperbranched polyimide 28 parts, fluorine-containing and epoxy-containing polysiloxane 75 parts, solvent 38 parts; the amino-terminated hyperbranched polyimide is prepared according to the method of example 1 in Chinese patent document CN107789677B; the fluorine-containing and epoxy-containing polysiloxane is prepared according to the method of example 1 in Chinese patent document CN102250355B; the solvent is isopropyl alcohol.

[0069] A manufacturing method of the multilayer fireproof material for the battery, comprising the following steps:

[0070] Step S1, mixing the raw materials of the ceramicized silicone rubber layer according to the weight parts, placing them in a mixer for mixing to obtain a rubber compound, and then calendering the rubber compound to form the ceramicized silicone rubber layer;

[0071] Step S2, laminating in the order of first glass fiber cloth layer, ceramicized silicone rubber layer, second glass fiber cloth layer from top to bottom, heating and pressing by using hot plate, and then vulcanizing and forming to obtain the fireproof material base;

[0072] Step S3, mixing the raw materials of the protective layer uniformly, coating on the outer surface of the fireproof material base, and drying to obtain the multilayer fireproof material for battery.

[0073] The temperature of mixing in step S1 is 45℃, and the mixing time is 40min; the temperature of vulcanizing and forming in step S2 is 200℃, and the pressure is 11MPa; the drying in step S3 is drying at 110℃ for 13min.

[0074] Example 5

[0075] A multilayer fireproof material for battery comprises a fireproof material base and a protective layer coated on the outer surface of the fireproof material base; the fireproof material base comprises in order from top to bottom a first glass fiber cloth layer, a ceramicized silicone rubber layer, and a second glass fiber cloth layer; the ceramicized silicone rubber layer is made of the following raw materials by weight: 100 parts of silicone rubber, 35 parts of ceramic filler, 3 parts of structure control agent, 6 parts of vulcanizing agent, 12 parts of nano filler, 15 parts of flame retardant, 5 parts of coupling agent, 3 parts of 2,4-diamino-6-diallyl amino-1,3,5-triazine, 1.2 parts of initiator, 8 parts of polyether sulfone type hyperbranched epoxy resin with epoxy end groups, and 5 parts of 2-(1-propen-2-yl)benzo[D]oxazole.

[0076] The silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed in a mass ratio of 1:2; the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA120; the ceramic filler is wollastonite; the particle size of the ceramic filler is 1600 mesh; the structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double five vulcanizing agent; the nano filler is nano zirconium carbide; the particle size of the nano filler is 10nm; the flame retardant is antimony trioxide; the coupling agent is silane coupling agent KH560; the initiator is 1,1-di-tert-butyl peroxy-3,3,5-trimethylcyclohexane; and the polyether sulfone type hyperbranched epoxy resin with epoxy end groups is made according to the method in the implementation case 18 of Chinese patent document CN104311832B.

[0077] The first glass fiber cloth layer and the second glass fiber cloth layer are both EC110C type glass fiber cloth, which is four satin, 0.11mm in thickness, and 110g / m 2The thickness of the fireproof material substrate is 1.8 mm; and the thickness of the protective layer is 0.1 mm.

[0078] The protective layer is made of the following raw materials by weight parts: amino-terminated hyperbranched polyimide 30 parts, fluorine-containing and epoxy-containing polysiloxane 80 parts, and solvent 40 parts; the amino-terminated hyperbranched polyimide is made according to the method of Example 1 in Chinese patent document CN107789677B; the fluorine-containing and epoxy-containing polysiloxane is made according to the method of Example 1 in Chinese patent document CN102250355B; and the solvent is butyl acetate.

[0079] A manufacturing method of the multilayer fireproof material for batteries, comprising the following steps:

[0080] Step S1, mixing raw materials of the ceramicized silicone rubber layer by weight parts, placing in a mixer for mixing, obtaining a rubber compound, and then calendering the rubber compound to form the ceramicized silicone rubber layer;

[0081] Step S2, sequentially laminating from top to bottom in the order of the first glass fiber cloth layer, the ceramicized silicone rubber layer, and the second glass fiber cloth layer, heating and pressing by using a hot plate, and vulcanizing to form the fireproof material substrate;

[0082] Step S3, uniformly mixing raw materials of the protective layer, coating on the outer surface of the fireproof material substrate, and drying to obtain the multilayer fireproof material for batteries.

[0083] In step S1, the mixing temperature is 50℃, and the mixing time is 45 min; in step S2, the vulcanizing temperature is 210℃, and the pressure is 12 MPa; and in step S3, the drying is performed at 120℃ for 10 min.

[0084] Comparative Example 1

[0085] The present application provides a kind of multilayer fireproof material for batteries, which is similar to Example 1, except that no epoxy-terminated polyether sulfone type hyperbranched epoxy resin is added.

[0086] Comparative Example 2

[0087] The present application provides a kind of multilayer fireproof material for batteries, which is similar to Example 1, except that no 2-(1-propylene-2-yl) benz [D] oxazole and 2,4-diamino-6-diallyl amino-1,3,5-triazine are added.

[0088] In order to further illustrate the beneficial technical effects of the multilayer fireproof material for batteries made by each embodiment of the present application, the multilayer fireproof material for batteries made by each example is tested for relevant performance, and the test results are shown in Table 1, and the test methods are as follows:

[0089] (1) Flame resistance: tested according to UL-94.

[0090] (2) High temperature impact resistance: the material was burned by 1300℃ oxygen acetylene flame, and the time for the whole material to be burned through was recorded, the gas pressure was about 0.4 MPa.

[0091] (3) Weather resistance: each product was placed in the following three conditions: ① 85℃ x 85% RH for 1500 hours, ② 130℃ for 1300 hours, ③ between -40℃ and 85℃, 600 cycles were completed at a temperature gradient of 5℃ / min, and in each cycle, it was stopped at the highest and lowest temperature for 15 min respectively; the material changes were observed, if the material had no bubbles, no deformation, no cracks and no falling off under the three conditions, it was passed, otherwise it was not passed.

[0092] Table 1 Performance test results of the multilayer fireproof material for battery

[0093] Sample Flame retardancy (class) High temperature resistance (min) Weather resistance Example 1 V-0 > 63 min Pass Example 2 V-0 > 66 min Pass Example 3 V-0 > 68 min Pass Example 4 V-0 > 70 min Pass Example 5 V-0 > 73 min Pass Comparative Example 1 V-1 < 53 min Fail Comparative Example 2 V-1 < 47 min Fail

[0094] From Table 1, it can be seen that the multilayer fireproof material for battery disclosed in the embodiments of the present application has more excellent flame resistance, high temperature impact resistance and weather resistance compared with the comparative product, and the addition of the polyether sulfone type hyperbranched epoxy resin with epoxy group, 2-(1-propen-2-yl)benzo[D]oxazole and 2,4-diamino-6-diallyl amino-1,3,5-triazine is beneficial to improving the above-mentioned properties.

[0095] The above shows and describes the basic principles, main features and advantages of the present application. It should be understood by those skilled in the art that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection claimed by the present application is defined by the appended claims and their equivalents.

Claims

1. A multi-layer fireproof material for a battery, characterized by, The fireproof material base material and the protective layer coated on the outer surface of the fireproof material base material; the fireproof material base material comprises a first glass fiber cloth layer, a ceramicized silicone rubber layer and a second glass fiber cloth layer from top to bottom; the ceramicized silicone rubber layer is made of the following raw materials by weight: 80-100 parts of silicone rubber, 25-35 parts of ceramic filler, 1-3 parts of structure control agent, 4-6 parts of vulcanizing agent, 8-12 parts of nano filler, 8-15 parts of flame retardant, 3-5 parts of coupling agent, 1-3 parts of 2,4-diamino-6-diallyl amino-1,3,5-triazine, 0.8-1.2 parts of initiator, 5-8 parts of polyether sulfone type hyperbranched epoxy resin with epoxy group as end group, and 3-5 parts of 2-(1-propenyl-2-yl)benzo[D]oxazole; the protective layer is made of the following raw materials by weight: 20-30 parts of amino-terminated hyperbranched polyimide, 60-80 parts of fluorine-containing and epoxy-containing polysiloxane, and 30-40 parts of solvent; the solvent is any one of isopropyl alcohol, butanone and butyl acetate.

2. The multi-layer fire protective material for a battery according to claim 1, characterized by, The silicone rubber is a mixture of methyl vinyl silicone rubber and methyl phenyl vinyl silicone rubber mixed in a mass ratio of 1:(1-2); the methyl vinyl silicone rubber is methyl vinyl silicone rubber 110-2; and the methyl phenyl vinyl silicone rubber is methyl phenyl vinyl silicone rubber IOTA 120.

3. The multi-layer fire protective material for a battery according to claim 1, wherein The ceramic filler is at least one of wollastonite, mica, boron carbide and hexagonal boron nitride; and the particle size of the ceramic filler is 1200-1600 mesh.

4. The multi-layer fire protective material for a battery according to claim 1, wherein The structure control agent is small molecule hydroxyl silicone oil XH209; the vulcanizing agent is double five vulcanizing agent; the nano filler is at least one of nano zirconium carbide, nano silicon boride and nano calcium carbonate; the particle size of the nano filler is 10-60 nm; the flame retardant is at least one of antimony trioxide, aluminum hydroxide and magnesium hydroxide; the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570; and the initiator is at least one of tert-butyl peroxy benzoate, tert-butyl peroxy 3,5,5-trimethyl hexanoate, tert-amyl peroxy acetate and 1,1-di-tert-butyl peroxy-3,3,5-trimethyl cyclohexane.

5. The multi-layer fire protective material for a battery according to claim 1, wherein The first and second glass fiber cloth layers are each EC110C glass fiber cloth, which is four-satin, 0.11 mm in thickness, and 110 g / m2 in areal weight 2 .

6. The multi-layer fire protective material for a battery of claim 1, wherein, The thickness of the fireproof material base material is 0.4-2.0 mm; and the thickness of the protective layer is 0.1-0.4 mm.

7. A method for producing a multilayer fireproof material for a battery according to any one of claims 1 to 6, characterized by, The method comprises the following steps: Step S1, mixing the raw materials of the ceramicized silicone rubber layer by weight, placing them in a mixer for mixing to obtain a mixed rubber, and then calendering the mixed rubber to form the ceramicized silicone rubber layer; Step S2, stacking the first glass fiber cloth layer, the ceramicized silicone rubber layer and the second glass fiber cloth layer in this order from top to bottom, heating and pressing with a heating plate, and then vulcanizing to form the fireproof material base material; Step S3, uniformly mixing the raw materials of the protective layer, coating them on the outer surface of the fireproof material base material, and then drying to obtain the multilayer fireproof material for batteries.

8. The method for producing a multilayer fireproof material for a battery according to claim 7, wherein The temperature of the mixing in step S1 is 30-50℃, and the mixing time is 25-45 min; the temperature of the vulcanization forming in step S2 is 160-210℃, and the pressure is 8-12 MPa.

9. The method of claim 7, wherein the method further comprises: The drying in step S3 is at 80-120℃ for 10-20 min.