Ceramic adhesive, adhesive film, adhesive tape, preparation method and application

Abstract

The invention discloses an adhesive capable of being ceramized, an adhesive film, an adhesive tape, a preparation method and application. The adhesive capable of being ceramized comprises the following components in parts by mass: 70-100 parts of an acrylate polymer; 30-180 parts by mass of ceramic powder; and 30-100 parts by mass of a flame retardant. The adhesive film has high stripping force on a base material, and the flame-retardant effect is good; and when a fire disaster occurs, ceramic can be realized, so that the structural integrity is ensured, and meanwhile, a bonded object is ensured to keep certain bonding strength and is not stripped. The adhesive can be prepared into a ceramic fireproof adhesive tape, can be sintered to form a hard porous ceramic shell when a fire disaster occurs, and has excellent fireproof and heat-insulating properties. The adhesive can be applied to bonding and fixing of battery cells, battery system fire prevention and cable fire prevention.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesive tapes, and in particular relates to a ceramic adhesive, an adhesive film, an adhesive tape, and a preparation method and application thereof. Background Art

[0002] With the rapid development of electrical equipment, electronics industry, new energy vehicles, chemical energy storage batteries and other fields, higher requirements are put forward for the safety of batteries. At present, fireproof materials are commonly used for thermal runaway protection of battery components and other structures at home and abroad. When electronic and electrical batteries using these fireproof materials experience thermal runaway due to various abuses, these fireproof materials can block heat conduction when encountering high temperature or open flame, avoiding the occurrence of heat spread in a larger range. In the fields of electrical appliances, electronic equipment, batteries, etc., tapes are often used to bond devices. Due to the different shapes and structures of devices, the performance requirements for tapes are also different. The structure and performance of tapes need to meet multiple requirements. Batteries will experience high temperature and high heat. When the battery is in a high temperature and high heat state, the flame retardant effect of the tape in the battery is poor, and the tape is prone to burn under high temperature and high heat, resulting in failure of the bonding performance, which in turn causes the battery's safety performance to decrease. Therefore, battery thermal runaway protection products with high-efficiency flame retardancy, fireproof and heat insulation properties are an urgent need for the development of high-safety batteries. Summary of the invention

[0003] The purpose of the present invention is to provide a ceramic adhesive, adhesive film, adhesive tape, preparation method and application. The adhesive of the present invention has both high temperature resistance and high peeling force. The adhesive film or tape obtained after UV curing of the adhesive can be used in products such as battery components and systems, and sintered under high-temperature combustion conditions to form a ceramic structural layer with a certain bonding force, thereby effectively achieving component bonding in high-temperature environments or fire protection in different scenarios.

[0004] In a first aspect, an embodiment of the present invention provides a ceramizable adhesive, comprising:

[0005] Acrylate polymer 70-100 parts by weight;

[0006] 30-180 parts by mass of ceramic powder; and

[0007] Flame retardant 30-100 parts by mass.

[0008] Optionally, the acrylic polymer includes an acrylic prepolymer.

[0009] Optionally, the acrylic ester polymer is polymerized from monofunctional acrylic ester monomers, and at a temperature of 25° C., the viscosity of the acrylic ester polymer is 200-1500 cPs.

[0010] Optionally, the ceramizable adhesive further comprises:

[0011] Cross-linking agent.

[0012] Optionally, the crosslinking agent is a multifunctional acrylate monomer; and / or

[0013] The cross-linking agent is 0.15-0.3 parts by mass.

[0014] Optionally, the ceramizable adhesive further comprises:

[0015] Tackifying resin.

[0016] Optionally, the tackifying resin is 10-60 parts by mass; and / or

[0017] The tackifying resin includes at least one of terpene phenol, petroleum resin, rosin resin and polyterpene.

[0018] Optionally, the ceramic powder further includes: a flux and a high temperature resistant filler.

[0019] Optionally, the flux includes: at least one of zinc borate, lithium oxide, zinc oxide, phosphate glass powder, borate glass powder, and silicate glass powder; and / or

[0020] The flux softening point is 240-700°C;

[0021] The flux particle size is 5-40um; and / or

[0022] The high temperature resistant filler comprises: at least one of kaolin, mica powder, talc, clay, montmorillonite, bentonite, wollastonite, surface modified wollastonite, magnesium oxide, aluminum oxide, zirconium oxide, silicon dioxide, titanium dioxide, silicon carbide, mullite, feldspar and attapulgite; and / or

[0023] The particle size of the high temperature resistant filler is 5-45um; and / or

[0024] The high temperature resistant filler has a melting point greater than 1000°C.

[0025] Optionally, the flame retardant includes:

[0026] At least one of aluminum hydroxide, magnesium hydroxide, type II ammonium polyphosphate, melamine polyphosphate, melamine cyanurate, alkyl aluminum hypophosphite, tricresyl phosphate, butyl triphenyl phosphate, tri(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, isopropylated triphenyl phosphate and aryl phosphate oligomers; and / or

[0027] The particle size of the powder flame retardant in the flame retardant is 1-20 um.

[0028] Optionally, the ceramizable adhesive further comprises:

[0029] Photoinitiator.

[0030] In a second aspect, an embodiment of the present invention provides a ceramicizable adhesive film, comprising:

[0031] The ceramicizable adhesive described in the above embodiments.

[0032] Optionally, the peel force of the ceramizable adhesive film is greater than or equal to 4 N / cm; and / or

[0033] The thickness of the ceramicizable adhesive film is 45um-1000um.

[0034] In a third aspect, an embodiment of the present invention provides a ceramicizable adhesive tape, comprising:

[0035] Lining; and

[0036] A ceramizable adhesive layer: at least one side of the lining is provided with a ceramizable adhesive layer, and the ceramizable adhesive layer includes the ceramizable adhesive described in the above embodiment.

[0037] Optionally, the lining layer comprises a barrier layer and a reinforcement layer, the barrier layer is arranged on one side of the reinforcement layer, and the ceramicizable adhesive layer is arranged on the other side of the reinforcement layer.

[0038] Optionally, the barrier layer is a flexible coating, wherein the flexible coating comprises at least one of epoxy resin, polyethylene terephthalate, polysiloxane, polyethylene, and polyurethane; and / or

[0039] The barrier layer is a flame retardant material layer.

[0040] Optionally, the reinforcement layer comprises at least one of fiber woven fabric, non-woven fabric, fiber paper, and fiber felt; and / or

[0041] Portions of the barrier layer are embedded in the reinforcement layer.

[0042] Optionally, the reinforcement layer includes at least one of glass fiber, basalt fiber, ceramic fiber, silicate fiber, and high-silica fiber.

[0043] Optionally, the barrier layer has a thickness of 10-100 um; and / or

[0044] The thickness of the reinforcement layer is 50-2000um; and / or

[0045] The thickness of the ceramicizable adhesive layer is 400-2500 um; and / or

[0046] The thickness of the ceramicizable adhesive tape is 500-2500 um.

[0047] In a fourth aspect, an embodiment of the present invention provides a method for preparing a ceramic adhesive film, comprising:

[0048] The raw materials in the adhesive described in the above embodiment are mixed, dispersed and degassed to obtain a ceramic adhesive slurry;

[0049] The ceramicizable adhesive slurry is coated on the surface of the isolation film and cured by ultraviolet light to obtain the ceramicizable adhesive film.

[0050] In a fifth aspect, an embodiment of the present invention provides a method for preparing a ceramicizable adhesive tape, comprising:

[0051] The raw materials in the adhesive described in the above embodiment are mixed, dispersed and degassed to obtain a ceramic adhesive slurry;

[0052] The ceramicizable adhesive slurry is coated on the surface of the lining and cured by ultraviolet light to obtain the ceramicizable adhesive tape.

[0053] In a sixth aspect, the adhesive film described in the above embodiment or the adhesive tape described in the above embodiment is used in the bonding and fixation of battery cells, fire protection of battery systems, and fire protection of cables.

[0054] The ceramic adhesive of the embodiment of the present invention includes: 70-100 parts by mass of acrylic polymer; 30-180 parts by mass of ceramic powder; 30-100 parts by mass of flame retardant. Acrylic polymer is easy to apply and convenient to achieve photocuring, and the adhesive film and adhesive tape prepared therefrom have good adhesion. Ceramic powder has the function of skeleton support. When encountering high temperature and high heat, the flux absorbs heat and is in a molten state, softens and deforms, and is connected to the high temperature resistant filler as a whole, providing sufficient support strength and stability. The flame retardant can improve the flame retardant effect of the material, so that the adhesive tape with the adhesive is not easy to burn at high temperature and high heat, and the structure of the adhesive tape remains stable. The adhesive tape with the adhesive is used for batteries to protect the batteries from thermal runaway. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 A schematic diagram of the structure of a ceramicizable adhesive tape in one embodiment of the present invention;

[0056] Figure 2 A schematic diagram of the structure of a ceramic adhesive tape in another embodiment of the present invention;

[0057] Figure 3 This is a schematic diagram of the fireproof and heat-insulating performance test of the adhesive tape of the present invention;

[0058] Figure 4 A test diagram of the peeling force of the adhesive tape.

[0059] Reference numerals

[0060] Lining layer 10;

[0061] Barrier layer 11;

[0062] Reinforcement layer 12;

[0063] The adhesive layer 20 may be ceramizable. DETAILED DESCRIPTION

[0064] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0065] The terms "first", "second", etc. in the specification and claims of the present invention are used to distinguish similar objects, and are not used to describe a specific order or sequence. It should be understood that the terms used in this way are interchangeable under appropriate circumstances, so that the embodiments of the present invention can be implemented in an order other than those illustrated or described herein. In addition, the term "and / or" in the specification and claims means at least one of the connected objects, and the character " / " generally indicates that the objects associated with each other are in an "or" relationship.

[0066] The following is combined with Figures 1 to 4 As shown, the ceramicizable adhesive, adhesive film, adhesive tape, preparation method and application provided by the embodiments of the present invention are described in detail through specific embodiments and their application scenarios.

[0067] The ceramic adhesive of the embodiment of the present invention includes: 70-100 parts by mass of acrylic polymer; 30-180 parts by mass of ceramic powder; and 30-100 parts by mass of flame retardant. In the ceramic adhesive, the adhesive has good adhesion and can be used as the adhesive layer of the adhesive tape. The acrylic polymer is easy to be coated on the reinforcing layer of the adhesive tape, which is convenient for light curing. The ceramic powder has the function of skeleton support. When encountering high temperature and high heat, the flux absorbs heat and is in a molten state, softens and deforms, and is connected to the high temperature resistant filler as a whole, providing sufficient support strength and stability. The flame retardant can improve the flame retardant effect of the material, so that the adhesive tape with the adhesive is not easy to burn at high temperature and high heat, and the structure of the adhesive tape remains stable. The adhesive tape with the adhesive is used for batteries to protect the batteries from thermal runaway.

[0068] In some embodiments, the acrylic polymer may include an acrylic prepolymer.

[0069] The method for preparing the acrylate prepolymer may include:

[0070] The acrylate monomer and the photoinitiator are placed in a four-mouth detachable flask equipped with a stirrer, a temperature sensor, a nitrogen inlet tube and a cooling tube, respectively, and stirred, and the rotation speed is adjusted to 200-300rpm until the mixture is evenly mixed; thereafter, nitrogen is bubbled for 10-30 minutes to remove the dissolved oxygen in the slurry; UV light is then applied from the outside of the flask for polymerization; when the temperature rises by about 6-9°C and reaches a moderate viscosity, the light is turned off, the blowing of nitrogen is stopped, and oxygen is passed into the flask for 20-30 minutes to finally prepare the acrylate prepolymer.

[0071] The acrylate prepolymer can be prepared by adjusting the preparation parameters as required, and the acrylate prepolymer can also be prepared by other preparation methods.

[0072] The acrylic polymer is polymerized from a monofunctional acrylic monomer. The type of the monofunctional acrylic monomer is not specifically limited, as long as the viscosity of the acrylic polymer obtained after polymerization is 200-1500 cPs at 25°C. For example, the monofunctional acrylic monomer can be selected from: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, and 1,2-dimethylformamide. At least one of undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, octadecyl iso(meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate.

[0073] In some embodiments, the ceramicizable adhesive may include a crosslinking agent, which may include at least one of polyacrylate monomers, bifunctional acrylate monomers, tertiary functional acrylate monomers, and dimethyl propane tetraacrylate, and the crosslinking agent may facilitate crosslinking of acrylate compounds.

[0074] Optionally, the crosslinking agent may be a multifunctional acrylate monomer.

[0075] Optionally, the cross-linking agent may be 0.15-0.3 parts by mass.

[0076] In some embodiments, the ceramizable adhesive may include:

[0077] Tackifying resins. Tackifying resins can be used to increase the adhesion of adhesives.

[0078] Optionally, the tackifying resin may be 10-60 parts by mass. For example, the tackifying resin may be 10 parts by mass, 30 parts by mass or 60 parts by mass, which may be selected according to actual conditions.

[0079] Optionally, the tackifying resin may include at least one of terpene phenol, petroleum resin, rosin resin, and polyterpene. For example, the tackifying resin may include terpene phenol, petroleum resin, and the tackifying resin may be rosin resin, which may be selected according to actual conditions.

[0080] Optionally, the ceramic powder may include: a flux and a high temperature resistant filler.

[0081] Optionally, the flux may include at least one of zinc borate, lithium oxide, zinc oxide, phosphate glass powder, borate glass powder, and silicate glass powder. The specific type and content may be selected according to actual conditions.

[0082] Optionally, the particle size of the flux may be 5-40 um, the particle size of the flux may be less than or equal to 38 um, for example, the particle size of the flux may be 5 um. The melting point may be 310-380°C, for example, the melting point may be 330°C.

[0083] The softening point of the flux is 240-700°C. For example, the softening point of the flux can be 400-600°C. When encountering high temperature and heat, the flux softens and deforms, and then becomes molten. The molten flux can connect the high temperature resistant filler, so that the tape can maintain the integrity of the structure under high temperature and heat and play a role in fireproofing and heat insulation.

[0084] The high temperature resistant filler has the function of skeleton support, the molten flux can be connected with the high temperature resistant filler into a whole, providing sufficient support strength and stability, the flame retardant can improve the flame retardant effect of the material, so that the adhesive tape with the adhesive is not easy to burn at high temperature and high heat, so that the structure of the adhesive tape remains stable, and the adhesive tape with the adhesive is used for batteries to protect the batteries from thermal runaway.

[0085] The high temperature resistant filler may include at least one of kaolin, mica powder, talc, clay, montmorillonite, bentonite, wollastonite, surface modified wollastonite, magnesium oxide, aluminum oxide, zirconium oxide, silicon dioxide, titanium dioxide, silicon carbide, mullite, feldspar, and attapulgite. For example, the high temperature resistant filler may be a mixture of kaolin, mica powder, and wollastonite, and the specific type and content may be selected according to actual conditions.

[0086] Optionally, the particle size of the high temperature resistant filler can be 5-45um. If the particle size of the high temperature resistant filler is too small, the supporting effect is not good. If the particle size of the high temperature resistant filler is too large, it is not easy to be coated on the reinforcement layer, and the particles are easy to protrude from the surface coating. Therefore, the particle size of the high temperature resistant filler can be 5-45um.

[0087] Optionally, the melting point of the high temperature resistant filler may be greater than 1000°C. The melting point of the high temperature resistant filler may be greater than the melting point of the flux. For example, the melting point of the high temperature resistant filler may be greater than 1000°C, and the melting point of the flux may be 400-700°C. The high temperature resistant filler has a higher melting point and can have better supporting strength under high temperature and heat, and is not easy to be damaged and deformed. The melting point of the flux is lower than the melting point of the high temperature resistant filler so that the flux can connect to the high temperature resistant filler after endothermic melting, so that the high temperature resistant filler and the flux are connected into an integral structure, so that the adhesive tape maintains structural stability under high temperature and heat.

[0088] Optionally, the particle size of the high temperature resistant filler can be larger than the particle size of the flux, so that the flux can be dispersed or filled between the particles of the high temperature resistant filler. The flux can connect the high temperature resistant filler after endothermic melting, so that the high temperature resistant filler and the flux are connected into an integral structure, so that the adhesive tape maintains structural stability under high temperature and high heat.

[0089] In some embodiments, the flame retardant may include:

[0090] At least one of aluminum hydroxide, magnesium hydroxide, type II ammonium polyphosphate, melamine polyphosphate, melamine cyanurate, alkyl aluminum hypophosphite, tricresyl phosphate, butyl triphenyl phosphate, tri(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, isopropylated triphenyl phosphate and aryl phosphate oligomers.

[0091] The flame retardant can be an inorganic hydroxide or a phosphorus-containing substance, which can improve the flame retardancy of the material. The flame retardant can inhibit the additional heat release caused by the combustion of the acrylic ester solid material itself, thereby further improving the thermal insulation performance of the fireproof and heat-insulating material and delaying the temperature rise rate of the protected substrate. The flame retardant can include: at least one of aluminum hydroxide, magnesium hydroxide, antimony trioxide, tricresyl phosphate and isopropylated triphenyl phosphate. For example, the flame retardant can be aluminum hydroxide, and the flame retardant can include aluminum hydroxide and tricresyl phosphate. The specific type and content of the flame retardant can be selected according to actual conditions. The D90 of the powder flame retardant can be 80-120um, for example, the D90 of the powder flame retardant can be 100um.

[0092] Optionally, the particle size of the powder flame retardant in the flame retardant may be 1-20um. For example, the particle size of the powder flame retardant in the flame retardant may be 1um, 10um or 20um, and the particle size of the flame retardant may be smaller than the particle size of the high temperature resistant filler. The specific particle size may be selected according to actual conditions.

[0093] In some embodiments, the ceramizable adhesive may further include:

[0094] Photoinitiator. The photoinitiator can initiate the reaction between the prepolymer and the crosslinking agent. The photoinitiator can be 1.35-1.8 parts by mass.

[0095] In some embodiments, the present invention prepares a ceramizable adhesive film, comprising:

[0096] The ceramicizable adhesive described in the above embodiments.

[0097] The adhesive film can be matched with any substrate as required. The adhesive film has high peeling force and good flame retardant effect. In the event of a fire, it can be ceramicized to ensure its own structural integrity while ensuring that the bonded object maintains a certain bonding strength without peeling off. It can be used for bonding and fixing components in high temperature environments.

[0098] In some embodiments, the peel force of the ceramizable adhesive film may be greater than or equal to 4 N / cm.

[0099] For example, the peeling force of the ceramic adhesive film on the stainless steel plate can be greater than or equal to 4N / cm, so that the ceramic adhesive film has a certain adhesion force, so that the ceramic adhesive film can be used as a room temperature adhesive layer and a high temperature resistant adhesive layer at the same time.

[0100] Optionally, the thickness of the ceramic adhesive film may be 45um-1000um. For example, the thickness of the ceramic adhesive film may be 45um, 200um, 500um or 1000um. The ceramic adhesive film may have different thicknesses according to different usage scenarios.

[0101] In some embodiments, the present invention also prepares Figure 1 and Figure 2 The ceramicizable adhesive tape shown comprises:

[0102] Lining layer 10;

[0103] Ceramicizable adhesive layer 20: A ceramicizable adhesive layer 20 is disposed on at least one side of the lining 10. The ceramicizable adhesive layer 20 includes the ceramicizable adhesive in the above-mentioned embodiment.

[0104] The ceramic fireproof adhesive tape prepared with the adhesive can be sintered to form a hard porous ceramic shell when a fire occurs, and has excellent fireproof and heat-insulating properties. The adhesive tape with the adhesive layer is used in a battery to protect the battery system from thermal runaway.

[0105] A release film may be provided on the side of the ceramizable adhesive layer 20 away from the liner 10 , and the release film may be removed during use.

[0106] Optionally, the lining 10 may include at least one of glass fiber, basalt fiber, ceramic fiber, silicate fiber, high silica fiber, mica paper, and high silica cloth. For example, the material of the lining 10 may include glass fiber or high silica fiber.

[0107] In some embodiments, Figure 2 As shown, the liner 10 may include a barrier layer 11 and a reinforcement layer 12, wherein the barrier layer 11 is disposed on one side of the reinforcement layer 12, and the ceramic adhesive layer 20 is disposed on the other side of the reinforcement layer 12. The barrier layer 11 may have a barrier effect, and may prevent the slurry from penetrating from the other side of the reinforcement layer 12 to one side of the reinforcement layer 12 during the slurry coating process.

[0108] Optionally, the barrier layer 11 may be a flexible coating, wherein the flexible coating may include at least one of epoxy resin, polyethylene terephthalate, polysiloxane, polyethylene, and polyurethane. The barrier layer 11 may be a flexible coating to ensure that the adhesive tape has good flexibility, so that it is suitable for laminating components of various shapes. The barrier layer 11 may be an elastic layer, and may have a buffering effect.

[0109] Optionally, the barrier layer may be a flame retardant material layer. The barrier layer may have a flame retardant effect, so that the barrier layer can be both flame retardant and prevent slurry from penetrating.

[0110] Optionally, the thickness of the barrier layer may be 10-100 um. For example, the thickness of the barrier layer may be 10 um, 50 um, 80 um or 100 um, and the specific thickness of the barrier layer may be selected according to actual conditions.

[0111] In some embodiments, the reinforcing layer 12 may include at least one of fiber woven fabric, non-woven fabric, fiber paper, and fiber felt. For example, the reinforcing layer 12 may include at least one of glass fiber, basalt fiber, ceramic fiber, silicate fiber, and high silica fiber. Optionally, the fiber woven fabric may be stacked and may be selected according to actual needs.

[0112] Part of the barrier layer 11 may be embedded in the reinforcement layer 12. The reinforcement layer 12 may be a fiber layer, and the barrier layer material may be infiltrated into the reinforcement layer to form a continuous film layer by at least one of a solution method, a hot melt method, and a coating method, thereby enhancing the bonding strength between the barrier layer 11 and the reinforcement layer 12.

[0113] Optionally, the thickness of the reinforcement layer may be 50-2000 um. For example, the thickness of the reinforcement layer may be 50 um, 500 um, 1000 um or 2000 um, and the specific thickness of the reinforcement layer may be selected according to actual conditions.

[0114] Optionally, the thickness of the ceramizable adhesive layer 20 may be 400-2500 um. For example, the thickness of the ceramizable adhesive layer 20 may be 400 um, 1000 um or 2500 um, and the specific thickness may be selected according to actual conditions.

[0115] Optionally, the thickness of the ceramicizable adhesive tape may be 500-2500 um. For example, the thickness of the ceramicizable adhesive tape may be 500 um, 1000 um or 2500 um, and the specific thickness may be selected according to actual conditions.

[0116] The method for preparing the ceramic adhesive film according to the embodiment of the present invention comprises:

[0117] The raw materials in the adhesive described in the above embodiment are mixed, dispersed and degassed to obtain a ceramic adhesive slurry;

[0118] The ceramicizable adhesive slurry is coated on the surface of the isolation film and cured by ultraviolet light to obtain a ceramicizable adhesive film.

[0119] The method for preparing the ceramicizable adhesive tape according to the embodiment of the present invention comprises:

[0120] The raw materials in the adhesive described in the above embodiment are mixed, dispersed and degassed to obtain a ceramic adhesive slurry;

[0121] The ceramic adhesive slurry is coated on the surface of the lining layer and cured by ultraviolet light to obtain a ceramic adhesive tape. The ceramic adhesive slurry can also be coated on the side of the reinforcing layer in the lining layer away from the barrier layer.

[0122] The adhesive film or the adhesive tape described in the above embodiment can be used for bonding and fixing of battery cells, fire protection of battery systems, and fire protection of cables to provide thermal runaway protection.

[0123] The present invention is further described below by means of some specific embodiments, but the present invention is not limited to these embodiments.

[0124] The separator used in the following examples is a biaxially stretched polyethylene terephthalate film (PET).

[0125] Implementation

[0126] Table 1. Raw materials list

[0127]

[0128]

[0129] Test methods for adhesive tape performance

[0130] 1. 180° peel force test

[0131] like Figure 4 As shown, a 4kg metal stick was used to press a 20mm wide sample onto a plate by rolling and pressing five times at a speed of 10m / min. After pressing, the sample was immediately peeled off at 180° in a tensile testing machine at 23±1°C, 50±5% relative humidity, and a moving speed (peeling speed) of 300mm / min to evaluate the adhesion of the sample to a standard stainless steel plate.

[0132] 2. High temperature adhesion test 1

[0133] The test equipment used in high temperature adhesion test 1 is the same as that used in thermal insulation performance test ( Figure 3 ). The adhesive tape obtained in the embodiments and comparative examples was cut into sheets B of size 120mm×120mm, which were attached to the steel plate A and burned with butane gas fire at above 1200°C for 10 minutes. The power of the gun head (model: ZT-09, manufactured by Iwatani) was 1.85kW to simulate the thermal runaway of new energy vehicle batteries. The bonding performance of the adhesive layer of the fireproof and heat-insulating adhesive tape with the battery pack shell at high temperature. Visually test the state of the sample on the bonded substrate. The state where the sample and the substrate are not peeled off from each other is marked with the symbol "√", the state where the sample is peeled off from no more than half of the substrate is marked with the symbol "Δ", and the state where the sample and the substrate are peeled off from more than half of each other is marked with the symbol "X" for evaluation.

[0134] 3. High temperature adhesion test 2

[0135] Each adhesive tape obtained in the embodiment and the comparative example is cut into a circular sample with a diameter of 50 mm and attached to a stainless steel plate substrate with a size of 100 mm × 100 mm × 0.8 mm coated with an electrophoretic insulating coating, thereby forming a sample of the adhesive tape and the stainless steel substrate. After being burned with a butane gas flame above 1200°C for 10 minutes, the high-temperature bonding and flame propagation isolation performance of the ceramic adhesive tape are simulated under the condition of thermal runaway of the new energy vehicle battery. Then, the state of the sample on the bonded substrate and whether there is an open flame on the side away from the flame gun are visually tested. The state where the sample and the substrate are not peeled off from each other is marked with the symbol "√", the state where the sample is peeled off from no more than half of the substrate is marked with the symbol "Δ", and the state where the sample and the substrate are peeled off from each other for more than half is marked with the symbol "X" for evaluation.

[0136] 4. Thermal insulation performance test

[0137] Combustion test equipment Figure 3 As shown. A 0.8 mm thick steel plate A with KTL coating is used to simulate the battery pack of a car. Adhesive tape sample B (size 200×200 mm) is laminated on steel plate A and burned with butane gas fire above 1200°C for 10 minutes to simulate the thermal insulation performance of the material in the case of thermal runaway. During this period, the temperature of the steel plate on the other side away from the flame, i.e., the "cold side", is tested. K-type thermocouples or B-type thermocouples are used to monitor the temperature of the cold side and hot side, respectively (the temperature of the side of the tape away from the flame is the "cold side"). The lower the temperature of the cold side, the better the thermal insulation performance.

[0138] Synthesis Example 1 (Preparation of Acrylate Prepolymer)

[0139] 100 parts by mass of isooctyl acrylate, 14 parts by mass of hydroxypropyl acrylate, and 0.05 parts by mass of a photoinitiator (trade name: OMNIRAD 184, produced by IGM RESINS) were placed in a four-mouth detachable flask equipped with a stirrer, a temperature sensor, a nitrogen inlet pipe, and a cooling pipe, and stirred. The speed was adjusted to 200-300 rpm until the mixture was uniformly mixed. After that, nitrogen was bubbled for 30 minutes to remove dissolved oxygen in the slurry. Then, 365nm LED UV light (5mW / cm 2 ) to carry out polymerization. Thus, a partially polymerized prepolymer syrup, i.e., an acrylate prepolymer, is prepared.

[0140] Example E1

[0141] 98 parts by mass of acrylate prepolymer (Synthesis Example 1), 0.4 parts by mass of photoinitiator OMNIRAD 184, 1.4 parts by mass of photoinitiator OMNIRAD TPO-L, and 0.2 parts by mass of crosslinking agent 1,6-hexanediol diacrylate were placed in a reactor with a vacuum degassing and temperature control system, and mixed at a speed of 200 to 300 rpm for about 5 minutes to obtain slurry A.

[0142] At a speed of 300 rpm, 100 parts by mass of slurry A, 60 parts by mass of tackifying resin (trade name Plastolyn 240), 180 parts by mass of ceramic powder (wollastonite: low melting point glass powder = 1:1; wollastonite, trade name GH-1250; glass powder, trade name D235), and 60 parts by mass of flame retardant (aluminum hydroxide, trade name HT-205) listed in Table 2 were added in sequence. The dispersion speed was adjusted to 1500-1800 rpm, and the circulating cooling device was turned on to keep the material temperature within 45°C. Disperse for 30-40 minutes, adjust the speed to 300-400 rpm, and turn on the vacuum system for 30-40 minutes to remove bubbles in the slurry to obtain a ceramic adhesive.

[0143] The adhesive was applied to a double-roll laminator with upper and lower isolation films to achieve the designed film thickness and isolate the air. A 365nm LED light was used at 12mW / cm 2 The strength was set at 0.1 and the curing time was 50s to obtain a pressure-sensitive adhesive film.

[0144] The ceramic adhesive film is pressed onto one side of the glass fiber cloth of the fireproof and heat-insulating composite tape with a thickness of 2.0 mm, and the following can be obtained: Figure 1 The adhesive tape having the structure shown in the figure was cut into sheet samples with a shape of 120 mm×120 mm. The peeling force and high temperature bonding force 1 were tested according to the above test method. The test results are shown in Table 2.

[0145] Examples E2-E7

[0146] The preparation methods of Examples E2-E7 are the same as those of Example E1, except for the content of the adhesive component and the thickness of the film layer, which can be specifically seen in Table 2. Corresponding performance tests were performed according to the above test methods, and the test results are shown in Table 2.

[0147] Example E8

[0148] The preparation method of the adhesive tape of Example E8 is the same as that of Example E1, except that the low melting point glass powder used in the adhesive is C4140. The adhesive components are shown in Table 2. The corresponding performance tests are carried out according to the above test methods, and the test results are shown in Table 2.

[0149] Comparative Examples C1-C3

[0150] The preparation methods of Comparative Examples C1-C3 are the same as those of Example E1, except for the content of the adhesive component and the thickness of the film layer, as shown in Table 2. Corresponding performance tests were performed according to the above test methods, and the test results are shown in Table 2.

[0151] Comparative Example C4

[0152] 100 parts by mass of tackifying resin, 75 parts by mass of ceramic powder, and 75 parts by mass of flame retardant were added to 100 parts by mass of ethyl acetate, mixed evenly using a disperser, and the obtained slurry was coated on the isolation film through a doctor blade coating head, and dried in an oven at 120°C for 5 minutes to obtain a film material with a thickness of 60um. The obtained film material did not have initial adhesion and adhesion, and was not evaluated accordingly.

[0153] Example E9

[0154] 73.5 parts by mass of acrylate prepolymer (Synthesis Example 1), 25 parts by mass of tackifying resin, 0.3 parts by mass of photoinitiator OMNIRAD 184, 1.05 parts by mass of photoinitiator OMNIRAD TPO-L, and 0.15 parts by mass of crosslinking agent 1,6-hexanediol diacrylate were placed in a reactor with a vacuum degassing and temperature control system, and mixed at a speed of 200 to 300 rpm for about 5 minutes to obtain slurry B.

[0155] At a speed of 300 rpm, the components listed in Table 3 were added in sequence, 100 parts by mass of slurry B, 75 parts by mass of ceramic powder (wollastonite: low melting point glass powder = 4:1; wollastonite, trade name GH-1250; glass powder, trade name C4051), and 60 parts by mass of flame retardant (ammonium polyphosphate: aluminum hydroxide = 5:1, aluminum hydroxide, trade name HT-205). The dispersion speed was adjusted to 1500-1800 rpm, and the circulating cooling device was turned on to keep the material temperature within 45°C. Disperse for 30-40 minutes, adjust the speed to 300-400 rpm, and turn on the vacuum system for 30-40 minutes to remove bubbles in the slurry to obtain a ceramic adhesive.

[0156] The adhesive was applied to one side of the 0.3 mm glass fiber cloth coated with polysiloxane on one side, and then covered with a release film and passed through a double-roll laminating machine to reach the set thickness. A 365 nm LED lamp was used at 12 mW / cm 2 The strength of the ceramic adhesive tape was cured for 60 seconds to obtain a ceramic adhesive tape with adhesive properties. Figure 2 Adhesive tape of the structure shown in .

[0157] Examples E10 and E11

[0158] The preparation methods of the adhesive tapes of Example E10 and Example E11 are the same as those of Example E9, except for the flux used in the two adhesives. The adhesive components are shown in Table 3. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 3.

[0159] Example E12

[0160] 73.5 parts by mass of acrylate prepolymer (Synthesis Example 1), 25 parts by mass of tackifying resin, 0.3 parts by mass of photoinitiator OMNIRAD 184, 1.05 parts by mass of photoinitiator OMNIRAD TPO-L, and 0.15 parts by mass of crosslinking agent 1,6-hexanediol diacrylate were placed in a reactor with a vacuum degassing and temperature control system, and mixed at a speed of 200 to 300 rpm for about 5 minutes to obtain slurry B.

[0161] At a speed of 300 rpm, the components listed in Table 3 were added in sequence, 100 parts by mass of slurry B, 75 parts by mass of ceramic powder (wollastonite: flux = 4:1; wollastonite, trade name GH-1250), and 60 parts by mass of flame retardant (ammonium polyphosphate: melamine cyanurate = 5:1, melamine cyanurate is abbreviated as MCA, trade name MC25), the dispersion speed was adjusted to 1500-1800 rpm, the circulating cooling device was turned on to keep the material temperature within 45°C, and the dispersion was performed for 30-40 minutes. The speed was adjusted to 300-400 rpm, and the vacuum system was turned on for 30-40 minutes to remove the bubbles in the slurry to obtain a ceramic adhesive.

[0162] The adhesive was applied to one side of the 0.3 mm glass fiber cloth coated with polysiloxane on one side, and then covered with a release film and passed through a double-roll laminating machine to reach the set thickness. A 365 nm LED lamp was used at 12 mW / cm 2 The strength of the ceramic adhesive tape was cured for 60 seconds to obtain a ceramic adhesive tape with adhesive properties. Figure 2 Adhesive tape of the structure shown in .

[0163] Embodiment E13

[0164] The method for preparing the adhesive tape in Example E13 is the same as that in Example E12, except that the thickness of the adhesive tape in this example is 600 um, and the adhesive components are specifically shown in Table 3. Corresponding performance tests were performed according to the above test methods, and the test results are shown in Table 3.

[0165] Comparative Examples C5-C7

[0166] The preparation methods of Comparative Examples C5-C7 are the same as those of Example E9, except for the content of the adhesive component and the thickness of the film layer, as shown in Table 3. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 3.

[0167] Table 2

[0168]

[0169] Table 3

[0170]

[0171]

[0172] It can be seen from the above embodiments and comparative examples that the adhesive tape prepared by the adhesive has a high peeling force on the substrate, has excellent fire resistance and heat insulation, has a good flame retardant effect, can be ceramicized in the event of a fire, can ensure its own structural integrity, and at the same time ensure that the adherend maintains a certain bonding strength and does not peel off.

[0173] The embodiments of the present invention are described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned specific implementation modes, which are merely illustrative rather than restrictive. Under the guidance of the present invention, ordinary technicians in this field can also make many forms without departing from the scope of protection of the present invention and the claims, all of which are within the protection of the present invention.

Claims

1. A ceramic adhesive, It is characterized in that include: Acrylate polymer 70-100 parts by weight; 30-180 parts by weight of ceramic powder; and Flame retardant 30-100 parts by mass.

2. The ceramizable adhesive according to claim 1, It is characterized in that The acrylic polymer includes an acrylic prepolymer.

3. The ceramizable adhesive according to claim 2, It is characterized in that The acrylic ester polymer is polymerized from monofunctional acrylic ester monomers, and at a temperature of 25° C., the viscosity of the acrylic ester polymer is 200-1500 cPs.

4. The ceramizable adhesive according to claim 1, It is characterized in that The ceramizable adhesive further comprises a cross-linking agent.

5. The ceramizable adhesive according to claim 4, It is characterized in that The crosslinking agent is a multifunctional acrylate monomer; and / or The cross-linking agent is 0.15-0.3 parts by mass.

6. The ceramizable adhesive according to claim 1, It is characterized in that The ceramicizable adhesive further comprises: a tackifying resin.

7. The ceramizable adhesive according to claim 6, It is characterized in that The tackifying resin is 10-60 parts by mass; and / or The tackifying resin includes at least one of terpene phenol, petroleum resin, rosin resin and polyterpene.

8. The ceramicizable adhesive according to claim 1, It is characterized in that The ceramic powder also includes: flux and high temperature resistant filler.

9. The ceramizable adhesive according to claim 8, It is characterized in that The flux comprises: at least one of zinc borate, lithium oxide, zinc oxide, phosphate glass powder, borate glass powder, and silicate glass powder; and / or The flux softening point is 240-700°C; and / or The flux particle size is 5-40um; and / or The high temperature resistant filler comprises: at least one of kaolin, mica powder, talc, clay, montmorillonite, bentonite, wollastonite, surface modified wollastonite, magnesium oxide, aluminum oxide, zirconium oxide, silicon dioxide, titanium dioxide, silicon carbide, mullite, feldspar and attapulgite; and / or The particle size of the high temperature resistant filler is 5-45um; and / or The high temperature resistant filler has a melting point greater than 1000°C.

10. The ceramizable adhesive according to claim 1, It is characterized in that The flame retardant comprises: At least one of aluminum hydroxide, magnesium hydroxide, type II ammonium polyphosphate, melamine polyphosphate, melamine cyanurate, alkyl aluminum hypophosphite, tricresyl phosphate, butyl triphenyl phosphate, tri(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, isopropylated triphenyl phosphate and aryl phosphate oligomers; and / or The particle size of the powder flame retardant in the flame retardant is 1-20 um.

11. The ceramicizable adhesive according to claim 1, further comprising: include: Photoinitiator.

12. A ceramicizable adhesive film, It is characterized in that include: The ceramizable adhesive according to any one of claims 1 to 11.

13. The ceramizable adhesive film according to claim 12, It is characterized in that The peel force of the ceramizable adhesive film is greater than or equal to 4 N / cm; and / or The thickness of the ceramicizable adhesive film is 45um-1000um.

14. A ceramicizable adhesive tape, It is characterized in that include: lining; and A ceramizable adhesive layer, wherein at least one side of the lining is provided with a ceramizable adhesive layer, and the ceramizable adhesive layer comprises the ceramizable adhesive according to any one of claims 1 to 11.

15. The ceramizable adhesive tape according to claim 14, It is characterized in that The lining layer comprises a barrier layer and a reinforcement layer, wherein the barrier layer is arranged on one side of the reinforcement layer, and the ceramicizable adhesive layer is arranged on the other side of the reinforcement layer.

16. The ceramizable adhesive tape according to claim 15, It is characterized in that The barrier layer is a flexible coating, wherein the flexible coating comprises at least one of epoxy resin, polyethylene terephthalate, polysiloxane, polyurethane, and polyethylene; and / or The barrier layer is a flame retardant material layer.

17. The ceramizable adhesive tape according to claim 15, It is characterized in that The reinforcing layer comprises at least one of fiber woven fabric, non-woven fabric, fiber paper, and fiber felt; and / or Portions of the barrier layer are embedded in the reinforcement layer.

18. The ceramizable adhesive tape according to claim 17, It is characterized in that The reinforcement layer includes at least one of glass fiber, basalt fiber, ceramic fiber, silicate fiber, and high-silica fiber.

19. The ceramizable adhesive tape according to any one of claims 15 to 18, It is characterized in that The thickness of the barrier layer is 10-100 um; and / or The thickness of the reinforcement layer is 50-2000um; and / or The thickness of the ceramicizable adhesive layer is 400-2500 um; and / or The thickness of the ceramicizable adhesive tape is 500-2500 um.

20. A method for preparing a ceramic adhesive film, It is characterized in that include: Mixing, dispersing and degassing the raw materials in the adhesive according to any one of claims 1 to 11 to obtain a ceramic adhesive slurry; The ceramicizable adhesive slurry is coated on the surface of the isolation film and cured by ultraviolet light to obtain the ceramicizable adhesive film.

21. A method for preparing a ceramic adhesive tape, It is characterized in that include: Mixing, dispersing and degassing the raw materials in the adhesive according to any one of claims 1 to 11 to obtain a ceramic adhesive slurry; The ceramicizable adhesive slurry is coated on the surface of the lining and cured by ultraviolet light to obtain the ceramicizable adhesive tape.

22. Use of the adhesive film according to any one of claims 12 to 13 or the adhesive tape according to any one of claims 14 to 19 in bonding and fixing of battery cells, fire protection of battery systems, and fire protection of cables.

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