Ceramizable composition, adhesive film, adhesive tape, preparation method and application

Abstract

Disclosed in the present invention are a ceramizable composition, an adhesive film, an adhesive tape, a preparation method and an application. The ceramizable composition with fire prevention and heat insulation, characteriyed in that raw materials of the composition comprise the following components: 15-45 parts by mass of an acrylate oligomer; 5-25 parts by mass of an active diluent; 5-25 parts by mass of a skeleton filler; 15-40 parts by mass of a flux; 10-25 parts by mass of a flame retardant; and 0.4-2 parts by mass of a photo-initiator. The adhesive film has a high peeling force on a substrate and a good flame retardant effect. It can be ceramicized in the event of a fire to ensure its own structural integrity while ensuring that the bonded object maintains a certain bonding strength without peeling. The adhesive can be prepared into a ceramizable adhesive tape with fire protection, which can be sintered to form a hard porous ceramized shell in the event of a fire, and has excellent fire protection and heat insulation performance. They can all be applied in the bonding and fixing of battery cells, fire prevention of battery systems, and fire prevention of cables.

Description

[0001] CERAMIZABLE COMPOSITION, ADHESIVE FILM, ADHESIVE TAPE, PREPARATION METHOD AND APPLICATION

[0002] Technical Field

[0003] The present invention relates to the technical field of adhesive tapes, specifically, to a ceramizable adhesive, an adhesive film, an adhesive tape, a preparation method and an application.

[0004] Background Art

[0005] With the rapid development of electrical equipment, the electronics industry, new energy vehicles, chemical energy storage batteries and other fields, higher requirements are put forward on the safety of batteries thereof. 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 undergo thermal runaway due to various abuses, these fireproof materials can block heat conduction when encountering a high temperature or an open flame, avoiding the occurrence of larger- scale heat spread. In the fields of electrical appliances, electronic equipment, batteries, etc., adhesive tapes are often used to bond devices. Due to the different shapes and structures of devices, the performance requirements for adhesive tapes are also different. The structure and performance of adhesive tapes need to meet multiple requirements. Batteries may experience high temperatures and high heat. When a battery is in a high temperature and high heat state, the flame retardant effect of the adhesive tape in the battery is poor. The adhesive tape is prone to burning under high temperature and high heat conditions, resulting in failure of the bonding performance, which in turn leads to a decrease in the safety performance of the battery. Therefore, battery thermal runaway protection products with highly efficient flame retardation, fire protection and heat insulation performance are an urgent need for the development of high-safety batteries. Summary of the Invention

[0006] An objective of the present invention is to provide a ceramizable adhesive, an adhesive film, an adhesive tape, a preparation method and an 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 bonding of members in high-temperature environments or fire protection in different scenarios.

[0007] In a first aspect, an embodiment of the present invention provides a ceramizable adhesive, comprising:

[0008] 70-100 parts by mass of an acrylate polymer;

[0009] 30-180 parts by mass of a ceramized powder; and

[0010] 30-100 parts by mass of a flame retardant.

[0011] Optionally, the acrylate polymer comprises an acrylate pre-polymer.

[0012] Optionally, the acrylate polymer is formed by polymerization of a monofunctional acrylate monomer, and the acrylate polymer has a viscosity of 200-1500 cPs at a temperature of 25°C.

[0013] Optionally, the ceramizable adhesive further comprises: a cross-linking agent.

[0014] Optionally, the cross-linking agent is a multifunctional acrylate monomer; and / or the crosslinking agent is 0.15-0.3 parts by mass.

[0015] Optionally, the ceramizable adhesive further comprises: a tackifying resin.

[0016] Optionally, the tackifying resin is 10-60 parts by mass; and / or the tackifying resin comprises at least one of terpene phenol, petroleum resin, rosin resin and polyterpene.

[0017] Optionally, the ceramized powder further comprises: a flux and a high temperature resistant filler.

[0018] Optionally, 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 has a softening point of 240-700°C; the flux has a particle size of 5-40 urn; 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 high temperature resistant filler has a particle size of 5-45 urn; and / or the high temperature resistant filler has a melting point greater than 1000°C. Optionally, 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 a powder flame retardant in the flame retardant has a particle size of 1 -20 urn.

[0019] Optionally, the ceramizable adhesive further comprises: a photo-initiator.

[0020] In a second aspect, an embodiment of the present invention provides a ceramizable adhesive film, comprising: the ceramizable adhesive described in the above embodiments.

[0021] Optionally, the ceramizable adhesive film has a peeling force of greater than or equal to 4 N / cm; and / or the ceramizable adhesive film has a thickness of 45 urn to 1000 urn.

[0022] In a third aspect, an embodiment of the present invention provides a ceramizable adhesive tape, comprising: a lining layer; and a ceramizable adhesive layer, wherein at least one side of the lining layer is provided with a ceramizable adhesive layer, and the ceramizable adhesive layer comprises the ceramizable adhesive described in the above embodiments.

[0023] Optionally, the lining layer comprises a barrier layer and a reinforcement layer, the barrier layer is provided on one side of the reinforcement layer, and the ceramizable adhesive layer is provided on the other side of the reinforcement layer.

[0024] 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 the barrier layer is a flame retardant material layer.

[0025] Optionally, the reinforcement layer comprises at least one of fibre woven fabric, non-woven fabric, fibre paper, and fibre felt; and / or a part of the barrier layer is embedded in the reinforcement layer.

[0026] Optionally, the reinforcement layer comprises at least one of glass fibres, basalt fibres, ceramic fibres, silicate fibres and high-silica fibres.

[0027] Optionally, the barrier layer has a thickness of 10-100 urn; and / or the reinforcement layer has a thickness of 50-2000 urn; and / or the ceramizable adhesive layer has a thickness of 400-2500 urn; and / or the ceramizable adhesive tape has a thickness of 500-2500 urn.

[0028] In a fourth aspect, an embodiment of the present invention provides a method for preparing a ceramizable adhesive film, comprising: mixing, dispersing and degassing the raw materials in the adhesive described in the above embodiments to obtain a ceramizable adhesive slurry; and coating the ceramizable adhesive slurry on a surface of a release film, and curing the same by using ultraviolet light to obtain the ceramizable adhesive film.

[0029] In a fifth aspect, an embodiment of the present invention provides a method for preparing a ceramizable adhesive tape, comprising: mixing, dispersing and degassing the raw materials in the adhesive described in the above embodiments to obtain a ceramizable adhesive slurry; and coating the ceramizable adhesive slurry on a surface of a lining layer, and curing the same by using ultraviolet light to obtain the ceramizable adhesive tape.

[0030] In a sixth aspect, the adhesive film described in the above embodiments or the adhesive tape described in the above embodiments is applied in the bonding and fixing of a battery cell, fire protection of a battery system or fire protection of a cable.

[0031] The ceramizable adhesive according to the embodiments of the present invention comprises: 70-100 parts by mass of an acrylate polymer; 30-180 parts by mass of a ceramized powder; 30-100 parts by mass of a flame retardant. The acrylate polymer is easily coated, facilitating photo-curing, and the adhesive film and adhesive tape prepared therefrom have good adhesion. The ceramized powder has a skeleton supporting function. When encountering high temperatures and high heat, the flux absorbs heat in order to be in a molten state, softens and deforms, and is connected with the high temperature resistant filler to form a whole, providing sufficient supporting 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 under high temperature and high heat conditions, and the structure of the adhesive tape remains stable. The adhesive tape with the adhesive can be used for batteries to protect the batteries from thermal runaway.

[0032] Brief Description of the Drawings

[0033] FIG. 1 is a schematic diagram of the structure of a ceramizable adhesive tape in an embodiment of the present invention;

[0034] FIG. 2 is a schematic diagram of the structure of a ceramizable adhesive tape in another embodiment of the present invention;

[0035] FIG. 3 is a schematic diagram of a fire protection and heat insulation performance test of the adhesive tape of the present invention; and

[0036] FIG. 4 is a schematic diagram of a peeling force test of an adhesive tape. Reference numerals

[0037] Lining layer 10; barrier layer 11 ; reinforcement layer 12; ceramizable adhesive layer 20.

[0038] Detailed Description of the Embodiments

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art on the basis of the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0040] The terms "first", "second", etc. in the description 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 description and claims means at least one of the connected objects, and the character generally indicates that objects associated with each other are in an "or" relationship.

[0041] With reference to FIGS. 1 to 4, a ceramizable adhesive, an adhesive film, an adhesive tape, a preparation method, and an application provided by the embodiments of the present invention will be described in detail below through specific embodiments and their application scenarios.

[0042] The ceramizable adhesive according to the embodiments of the present invention includes: 70-100 parts by mass of an acrylate polymer; 30-180 parts by mass of a ceramized powder; and 30-100 parts by mass of a flame retardant. In the ceramizable adhesive, the adhesive has good adhesion and can be used as the adhesive layer of the adhesive tape. The acrylate polymer is easily coated on the reinforcement layer of the adhesive tape, facilitating photocuring. The ceramized powder has a skeleton supporting function. When encountering high temperatures and high heat, the flux absorbs heat in order to be in a molten state, softens and deforms, and is connected with the high temperature resistant filler to form a whole, providing sufficient supporting 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 under high temperature and high heat conditions, and the structure of the adhesive tape remains stable. The adhesive tape with the adhesive can be used for batteries to protect the batteries from thermal runaway.

[0043] In some embodiments, the acrylate polymer may include an acrylate pre-polymer.

[0044] A method for preparing the acrylate pre-polymer may include: placing an acrylate monomer and a photo-initiator separately in a four-port detachable flask with a stirrer, a temperature sensor, a nitrogen inlet pipe and a cooling pipe, stirring them, and adjusting a rotational speed to 200-300 rpm until they are evenly mixed; then bubbling with nitrogen for 10-30 minutes to remove dissolved oxygen in the slurry; then applying LIV light from the outside of the flask for polymerization; when the temperature rises by about 6-9°C to reach a moderate viscosity, turning off the light, stopping blowing nitrogen, and introducing oxygen into the flask for 20-30 minutes; and finally preparing the acrylate pre-polymer.

[0045] The acrylate pre-polymer may be prepared by adjusting the preparation parameters as needed, and the acrylate pre-polymer may also be prepared by other preparation methods.

[0046] The acrylate polymer is formed by polymerization of a monofunctional acrylate monomer. The type of the monofunctional acrylate monomer is not specifically limited, as long as the viscosity of the acrylate polymer obtained after polymerization at 25°C is 200-1500 cPs. For example, the monofunctional acrylate monomer may be at least one 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, 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.

[0047] In some embodiments, the ceramizable adhesive may include a cross-linking agent. The cross-linking agent may include at least one of a polyacrylate monomer, a bifunctional acrylate monomer, a tertiary functional acrylate monomer and dimethyl propane tetraacrylate, and the cross-linking agent may facilitate cross-linking of acrylate compounds.

[0048] Optionally, the cross-linking agent may be a multifunctional acrylate monomer.

[0049] Optionally, the cross-linking agent may be 0.15-0.3 parts by mass. In some embodiments, the ceramizable adhesive may include: a tackifying resin. The tackifying resin may be used to increase the adhesion of the adhesive.

[0050] 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 specifically selected according to actual situations.

[0051] 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 and petroleum resin, and the tackifying resin may be rosin resin, which may be specifically selected according to actual situations.

[0052] Optionally, the ceramized powder may include: a flux and a high temperature resistant filler.

[0053] 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 types and contents of which may be specifically selected according to actual situations.

[0054] Optionally, the particle size of the flux may be 5-40 urn. The particle size of the flux may be less than or equal to 38 urn. For example, the particle size of the flux may be 5 urn. The melting point may be 310-380°C. For example, the melting point may be 330°C.

[0055] The softening point of the flux is 240-700°C. For example, the softening point of the flux may be 400-600°C. When encountering high temperatures and high heat, the flux softens and deforms, and then is in a molten state. The molten flux can connect the high temperature resistant filler, so that the adhesive tape can maintain the integrity of the structure under high temperature and high heat conditions and have fire prevention and heat insulation effects.

[0056] The high temperature resistant filler has a skeleton supporting function, and the molten flux can be connected with the high temperature resistant filler to form a whole, providing sufficient supporting 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 under high temperature and high heat conditions, and the structure of the adhesive tape remains stable. The adhesive tape with the adhesive can be used for batteries to protect the batteries from thermal runaway.

[0057] 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, the specific types and contents of which may be selected according to actual situations. Optionally, the particle size of the high temperature resistant filler may be 5-45 urn. 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 easily coated on the reinforcement layer, and it is easy for the particles to protrude from the surface coating. Therefore, the particle size of the high temperature resistant filler may be 5-45 urn.

[0058] 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 having a higher melting point can have better supporting strength under high temperature and high heat conditions, and is not easily 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 the high temperature resistant filler after absorbing heat and melting. As a result, 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 conditions.

[0059] Optionally, the particle size of the high temperature resistant filler may be larger than the particle size of the flux, so that the flux may be dispersed or filled between the particles of the high temperature resistant filler. The flux can connect the high temperature resistant filler after absorbing heat and 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 conditions.

[0060] In some embodiments, the flame retardant may include: 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.

[0061] The flame retardant may be an inorganic hydroxide or a phosphorus-containing substance, which can improve the flame retardation of the material. The flame retardant can inhibit the additional heat release caused by the combustion of the acrylate solidified material itself, thereby further improving the heat insulation performance of the fire protection and heatinsulating material and delaying the temperature rise rate of the protected substrate. The flame retardant may include: at least one of aluminum hydroxide, magnesium hydroxide, antimony trioxide, tricresyl phosphate and isopropylated triphenyl phosphate. For example, the flame retardant may be aluminum hydroxide. The flame retardant may include aluminum hydroxide and tricresyl phosphate. The specific type and content of the flame retardant may be selected according to actual situations. The D90 of a powder flame retardant may be 80-120 urn. For example, the D90 of the powder flame retardant may be 100 urn.

[0062] Optionally, the particle size of the powder flame retardant in the flame retardant may be 1 -20 urn. For example, the particle size of the powder flame retardant in the flame retardant may be 1 urn, 10 urn or 20 urn, 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 situations.

[0063] In some embodiments, the ceramizable adhesive may further include: a photo-initiator. The photo-initiator can initiate the reaction between pre-polymer and the cross-linking agent. The photo-initiator may be 1 .35-1 .8 parts by mass.

[0064] In some embodiments, the present invention prepares a ceramizable adhesive film, including: the ceramizable adhesive described in the above embodiments.

[0065] The adhesive film may be matched with any substrate as required. The adhesive film has high peeling force and a good flame retardant effect. In the event of a fire, it may be ceramicized to ensure its own structural integrity while ensuring that the bonded object maintains a certain bonding strength without peeling off. It may be used for bonding and fixing members in high temperature environments.

[0066] In some embodiments, the peel force of the ceramizable adhesive film may be greater than or equal to 4 N / cm.

[0067] For example, the peel force of the ceramizable adhesive film on a stainless steel plate may be greater than or equal to 4 N / cm, making the ceramizable adhesive film have a certain adhesion force, so that the ceramizable adhesive film may be used as both a room temperature adhesive layer and a high temperature resistant adhesive layer.

[0068] Optionally, the thickness of the ceramizable adhesive film may be 45 urn to 1000 urn. For example, the thickness of the ceramizable adhesive film may be 45 urn, 200 urn, 500 urn or 1000 urn, and the ceramizable adhesive film may be selected to have different thicknesses according to different usage scenarios.

[0069] In some embodiments, the present invention further prepares a ceramizable adhesive tape as shown in FIGS. 1 and 2, including: a lining layer 10; and a ceramizable adhesive layer 20, wherein the ceramizable adhesive layer 20 is provided on at least one side of the lining layer 10, and the ceramizable adhesive layer 20 includes the ceramizable adhesive in the above embodiments.

[0070] The ceramizable adhesive tape with fire protection prepared from the adhesive may be sintered to form a hard porous ceramized shell in the event of a fire, and has excellent fire protection and heat insulation performance. The adhesive tape with the adhesive layer can be used in a battery to protect the battery system from thermal runaway.

[0071] 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.

[0072] Optionally, the lining layer 10 may include at least one of glass fibres, basalt fibres, ceramic fibres, silicate fibres, high-silica fibres, mica paper and high-silica cloth. For example, the material of the lining layer 10 may include glass fibres or high-silica fibres.

[0073] In some embodiments, as shown in FIG. 2, the lining layer 10 may include a barrier layer 11 and a reinforcement layer 12, wherein the barrier layer 1 1 is provided on one side of the reinforcement layer 12, and the ceramizable adhesive layer 20 is provided 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 one side of the reinforcement layer 12 to the other side of the reinforcement layer 12 in the slurry coating process.

[0074] 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 1 1 may be a flexible coating to ensure that the adhesive tape has good flexibility, so that it is suitable for bonding members of various shapes. The barrier layer 11 may be an elastic layer, and may have a buffering effect.

[0075] Optionally, the barrier layer may be a flame retardant material layer. The barrier layer may have a flame retardant function, so that the barrier layer may not only be flame retardant, but also prevent the slurry from penetrating.

[0076] Optionally, the thickness of the barrier layer may be 10-100 urn. For example, the thickness of the barrier layer may be 10 urn, 50 urn, 80 urn or 100 urn, and the specific thickness of the barrier layer may be selected according to actual situations.

[0077] In some embodiments, the reinforcement layer 12 may include at least one of fibre woven fabric, non-woven fabric, fibre paper and fibre felt. For example, the reinforcement layer 12 may include at least one of glass fibre, basalt fibre, ceramic fibre, silicate fibre and high-silica fibre. Optionally, the fibre woven fabric may be stacked, and may be specifically selected according to actual needs.

[0078] A part of the barrier layer 11 may be embedded in the reinforcement layer 12. The reinforcement layer 12 may be a fibre 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 1 1 and the reinforcement layer 12. Optionally, the thickness of the reinforcement layer may be 50-2000 urn. For example, the thickness of the reinforcement layer may be 50 urn, 500 urn, 1000 urn or 2000 urn, and the specific thickness of the reinforcement layer may be selected according to actual situations.

[0079] Optionally, the thickness of the ceramizable adhesive layer 20 may be 400-2500 urn. For example, the thickness of the ceramizable adhesive layer 20 may be 400 urn, 1000 urn or 2500 urn, and the specific thickness may be selected according to actual situations.

[0080] Optionally, the thickness of the ceramizable adhesive tape may be 500-2500 urn. For example, the thickness of the ceramizable adhesive tape may be 500 urn, 1000 urn or 2500 urn, and the specific thickness may be selected according to actual situations.

[0081] A method for preparing a ceramizable adhesive film according to an embodiment of the present invention includes: mixing, dispersing and degassing the raw materials in the adhesive described in the above embodiments to obtain a ceramizable adhesive slurry; and coating the ceramizable adhesive slurry on a surface of a release film, and curing the same by using ultraviolet light to obtain the ceramizable adhesive film.

[0082] A method for preparing a ceramizable adhesive tape according to an embodiment of the present invention includes: mixing, dispersing and degassing the raw materials in the adhesive described in the above embodiments to obtain a ceramizable adhesive slurry; and coating the ceramizable adhesive slurry on a surface of a lining layer, and curing the same by using ultraviolet light to obtain the ceramizable adhesive tape. The ceramizable adhesive slurry may also be coated on the side of the reinforcement layer in the lining layer away from the barrier layer.

[0083] The adhesive film or the adhesive tape described in the above embodiments may be used for the bonding and fixing of battery cells, fire protection of battery systems and fire protection of cables to provide thermal runaway protection.

[0084] The present invention will be further described below by means of some specific examples, but the present invention is not limited to these examples.

[0085] The release film used in the following examples is a biaxially stretched polyethylene terephthalate film (PET). Implementations

[0086] Table 1 . List of raw materials Test methods for adhesive tape performance

[0087] 1. 180° peel force test

[0088] As shown in FIG. 4, a 20 mm-wide sample was pressed onto a plate using a 4 kg metal stick at a speed of 10 m / min by means of five reciprocating rolling presses. Immediately after pressing, the sample was peeled off at 180° in a tensile testing machine under the conditions of 23±1 °C, 50±5% relative humidity, and a moving speed (peeling speed) of 300 mm / min to evaluate the adhesion of the sample to a standard stainless steel plate.

[0089] 2. High temperature adhesion test 1

[0090] A test device used in high temperature adhesion test 1 is the same as that in the heat insulation performance test (FIG. 3). The adhesive tapes obtained in the examples and the comparative examples were cut into sheets B with a size of 120 mm x 120 mm. The sheet was attached to a steel plate A and burned by a butane gas fire above 1200°C for 10 minutes. The power of a gun head (model: ZT-09, manufactured by Iwatani) was 1.85 kW. The bonding performance of the adhesive layer of the fire protection and heat insulation adhesive tape with the battery pack shell at a high temperature was simulated in the case of thermal runaway of a new energy vehicle battery. The state of the sample on a bonded substrate was visually tested. A state where the sample and the substrate were not peeled off from each other was marked with the symbol the state where the sample was peeled off from no more than half of the substrate was marked with a symbol "A", and a state where the sample and the substrate were peeled off from more than half of each other was marked with the symbol "X" for evaluation.

[0091] 3. High temperature adhesion test 2

[0092] Each adhesive tape obtained in the examples and the comparative examples was cut into a circular sample with a diameter of 50 mm, and the sample was attached to a stainless steel plate substrate with a size of 100 mmx100 mmx0.8 mm coated with an electrophoretic insulating coating, thereby forming a sample with the adhesive tape and the stainless steel substrate. After the sample was burned by a butane gas flame above 1200°C for 10 minutes, the high-temperature bonding and flame propagation isolation performance of the ceramizable adhesive tape was simulated in the case of thermal runaway of a new energy vehicle battery. Then, the state of the sample on a bonded substrate and whether there is an open flame on the side away from the flame gun were visually tested. A state where the sample and the substrate were not peeled off from each other was marked with the symbol the state where the sample was peeled off from no more than half of the substrate was marked with a symbol "A", and a state where the sample and the substrate were peeled off from more than half of each other was marked with the symbol "X" for evaluation.

[0093] 4. Test of heat insulation performance A combustion test device is shown in FIG. 3. A 0.8 mm-thick steel plate A with a KTL coating was used to simulate a battery pack of a car. An adhesive tape sample B (size: 200x200 mm) is laminated on a steel plate A and burned by a butane gas fire above 1200°C for 10 minutes to simulate the heat insulation performance of the material under thermal runaway conditions. During this process, the temperature of the steel plate on the other side away from the flame, i.e., a "cold side", is tested. The temperature of the cold side (the temperature of the side of the adhesive tape away from the flame is the "cold side") and the temperature of a hot side were monitored by a k-type thermocouple or a b-type thermocouple, respectively. The lower the temperature on the cold side, the better the heat insulation performance.

[0094] Synthesis Example 1 (Preparation of Acrylate Pre-polymer)

[0095] 100 parts by mass of isooctyl acrylate, 14 parts by mass of hydroxypropyl acrylate, and 0.05 parts by mass of a photo-initiator (trade name: OMNIRAD 184, produced by IGM RESINS) were separately placed in a four-port detachable flask with a stirrer, a temperature sensor, a nitrogen inlet pipe and a cooling pipe, and stirred, and a rotational 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, 365 nm LED LIV light (5 mW / cm2) was applied from the outside of the flask to polymerize. Thus, a partially polymerized pre-polymerized slurry, i.e., an acrylate pre-polymer, was prepared.

[0096] Example E1

[0097] 98 parts by mass of an acrylate pre-polymer (Synthesis Example 1 ), 0.4 parts by mass of a photo-initiator, OMNIRAD 184, 1.4 parts by mass of a photo-initiator, OMNIRAD TPO-L, and 0.2 parts by mass of a cross-linking agent 1 ,6-hexanediol diacrylate, were placed in a reaction kettle with a vacuum degassing and temperature control system, and mixed at a rotational speed of 200-300 rpm for about 5 minutes to obtain a slurry A.

[0098] At a rotational speed of 300 rpm, 100 parts by mass of the slurry A, 60 parts by mass of a tackifying resin (trade name: Plastolyn 240), 180 parts by mass of ceramized 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 a flame retardant (aluminum hydroxide, trade name: HT-205) listed in Table 2 were added in sequence. A dispersion speed was adjusted to 1500-1800 rpm, and a circulating cooling device was turned on to keep the material temperature at 45°C. The mixture was dispersed for 30-40 minutes, the rotational speed was adjusted to 300-400 rpm, and the vacuum system was turned on for 30-40 minutes to remove bubbles in the slurry to obtain a ceramizable adhesive. The adhesive was coated on a double-roll laminating machine with upper and lower release films to achieve a designed film thickness and isolate the air. A 365 nm LED lamp was used at an intensity of 12 mW / cm2and cured for 50 seconds to obtain a pressure-sensitive adhesive film.

[0099] The ceramizable adhesive film was pressed onto one side of the glass fibre cloth of the fire protection and heat insulation composite tape with a thickness of 2.0 mm so that an adhesive tape with a structure as shown in FIG. 1 could be obtained. The obtained adhesive tape was cut into sheet samples with a shape of 120 mmx120 mm. The peel strength and high temperature adhesion 1 were tested according to the above test methods. The test results are shown in Table 2.

[0100] Examples E2-E7

[0101] The preparation methods of Examples E2-E7 are the same as that of Example E1 , except for the content of the adhesive components and the thickness of the film layer, which may be specifically shown in Table 2. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 2.

[0102] Example E8

[0103] A method for preparing an adhesive tape in Example E8 is the same as that in Example E1 , except that the low melting point glass powder used in the adhesive is C4140. See Table 2 for details of the adhesive components. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 2.

[0104] Comparative Examples C1 -C3

[0105] The preparation methods of Comparative Examples C1 -C3 are the same as that of Example E1 , except for the content of the adhesive components and the thickness of the film layer, which may be specifically shown in Table 2. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 2.

[0106] Comparative Example C4

[0107] 100 parts by mass of a tackifying resin, 75 parts by mass of a ceramized powder, and 75 parts by mass of a flame retardant were added to 100 parts by mass of ethyl acetate, and mixed evenly using a disperser. The obtained slurry was coated on a release 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 60 urn. The obtained film material did not have initial adhesion and adhesiveness, and was not evaluated accordingly. Example E9

[0108] 73.5 parts by mass of an acrylate pre-polymer (Synthesis Example 1 ), 25 parts by mass of a tackifying resin, 0.3 parts by mass of a photo-initiator, OMNIRAD 184, 1 .05 parts by mass of a photo-initiator, OMNIRAD TPO-L, and 0.15 parts by mass of a cross-linking agent, 1 ,6- hexanediol diacrylate, were placed in a reaction kettle with a vacuum degassing and temperature control system, and mixed at a rotational speed of 200-300 rpm for about 5 minutes to obtain a slurry B.

[0109] At a rotational speed of 300 rpm, 100 parts by mass of the slurry B, 75 parts by mass of ceramized 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 a flame retardant (ammonium polyphosphate:aluminum hydroxide = 5:1 , aluminum hydroxide, trade name: HT- 205) listed in Table 3 were added in sequence. A dispersion speed was adjusted to 1500-1800 rpm, and a circulating cooling device was turned on to keep the material temperature at 45°C. The mixture was dispersed for 30-40 minutes, the rotational speed was adjusted to 300-400 rpm, and the vacuum system was turned on for 30-40 minutes to remove bubbles in the slurry to obtain a ceramizable adhesive.

[0110] The adhesive was coated on one side of the 0.3 mm glass fibre cloth coated with polysiloxane on one side, and then covered with a release film and passed through a doubleroll laminating machine to reach a set thickness. A 365 nm LED lamp was used, and, at the intensity of 12 mW / cm2, curing was carried out for 60 s to obtain a ceramizable adhesive tape with adhesiveness. An adhesive tape with a structure as shown in FIG. 2 was obtained.

[0111] Examples E10 and E11

[0112] The methods for preparing adhesive tapes in Examples E10 and E11 are the same as that in Example E9, except for the flux used in the two adhesives. See Table 3 for details of the adhesive components. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 3.

[0113] Example E12

[0114] 73.5 parts by mass of an acrylate pre-polymer (Synthesis Example 1 ), 25 parts by mass of a tackifying resin, 0.3 parts by mass of a photo-initiator, OMNIRAD 184, 1 .05 parts by mass of a photo-initiator, OMNIRAD TPO-L, and 0.15 parts by mass of a cross-linking agent, 1 ,6- hexanediol diacrylate, were placed in a reaction kettle with a vacuum degassing and temperature control system, and mixed at a rotational speed of 200-300 rpm for about 5 minutes to obtain a slurry B. At a rotational speed of about 300 rpm, 100 parts by mass of the slurry B, 75 parts by mass of ceramized powder (wollastonite:flux = 4:1 ; wollastonite, trade name: GH-1250), and 60 parts by mass of a flame retardant (ammonium polyphosphate:melamine cyanurate = 5:1 , melamine cyanurate being simply referred to as MCA, trade name: MC25) listed in Table 3 were added in sequence. A dispersion speed was adjusted to 1500-1800 rpm, and a circulating cooling device was turned on to keep the material temperature at 45°C. The mixture was dispersed for 30-40 minutes, the rotational speed was adjusted to 300-400 rpm, and the vacuum system was turned on for 30-40 minutes to remove bubbles in the slurry to obtain a ceramizable adhesive.

[0115] The adhesive was coated on one side of the 0.3 mm glass fibre cloth coated with polysiloxane on one side, and then covered with a release film and passed through a double-roll laminating machine to reach a set thickness. A 365 nm LED lamp was used, and, at the intensity of 12 mW / cm2, curing was carried out for 60 s to obtain a ceramizable adhesive tape with adhesiveness. An adhesive tape with a structure as shown in FIG. 2 was obtained.

[0116] Example E13

[0117] A method for preparing an 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 urn. See Table 3 for details of the adhesive components. The corresponding performance tests were carried out according to the above test methods, and the test results are shown in Table 3.

[0118] Comparative Examples C5-C7

[0119] The preparation methods of Comparative Examples C5-C7 are the same as that of Example E9, except for the content of the adhesive components and the thickness of the film layer, which may be specifically 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.

[0120] Table 2

[0121] Table 3

[0122] It can be seen from the above embodiments and comparative examples that the adhesive tape prepared from the adhesive has a high peeling force on the substrate, has excellent fire protection and heat insulation and has a 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.

[0123] The embodiments of the present invention have been described above with reference to the drawings, but the present invention is not limited to the above-mentioned specific implementations, which are merely illustrative rather than restrictive. In light of the present invention, those of ordinary skill in the art 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

AMENDED CLAIMS received by the International Bureau on 28th March 2025 (28.03.25)1 . Ceramizable adhesive, characterized by comprising:70-100 parts by mass of an acrylate polymer;30-180 parts by mass of a ceram ized powder; and30-100 parts by mass of a flame retardant.

2. Ceramizable adhesive according to Claim 1 , characterized in that the acrylate polymer comprises an acrylate pre-polymer, whereby preferably the acrylate polymer is formed by polymerization of a monofunctional acrylate monomer, and the acrylate polymer has a viscosity of 200-1500 cPs at a temperature of 25°C.

3. Ceramizable adhesive according to Claim 1 , further comprising: a cross-linking agent, whereby preferably the cross-linking agent is a multifunctional acrylate monomer; and / or preferably the cross-linking agent is 0.15-0.3 parts by mass.

4. Ceramizable adhesive according to Claim 1 , further comprising: a tackifying resin, whereby preferably the tackifying resin is 10-60 parts by mass; and / or preferably the tackifying resin comprises at least one of terpene phenol, petroleum resin, rosin resin and polyterpene.

5. Ceramizable adhesive according to Claim 1 , characterized in that the ceramized powder further comprises: a flux and a high temperature resistant filler.

6. Ceramizable adhesive according to Claim 5, 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 has a softening point of 240-700°C; and / or the flux has a particle size of 5-40 urn;6. Ceramizable adhesive according to Claim 5 or Claim 6, characterized in that the high temperature resistant filler comprises at least one of kaolin, mica powder, talc, clay, montmorillonite, bentonite, wollastonite, surface modified wollastonite, magnesium oxide, aluminium oxide, zirconium oxide, silicon dioxide, titanium dioxide, silicon carbide, mullite, feldspar, and attapulgite; and / or the high temperature resistant filler has a particle size of 5- 45 urn; and / or the high temperature resistant filler has a melting point greater than 1000°C.

7. Ceramizable adhesive according to Claim 1 , characterized in that the flame retardant comprises at least one of aluminium hydroxide, magnesium hydroxide, type II ammonium polyphosphate, melamine polyphosphate, melamine cyanurate, alkyl aluminium hypophosphite, tricresyl phosphate, butyl triphenyl phosphate, tri(2-ethylhexyl)phosphate, 2-ethylhexyl diphenyl phosphate, isopropylated triphenyl phosphate and aryl phosphate oligomers; and / or a powder flame retardant in the flame retardant has a particle size of 1 - 20 pm.

8. Ceramizable adhesive according to Claim 1 , further comprising a photo-initiator.

9. Ceramizable adhesive film, characterized by comprising the ceramizable adhesive according to any one of Claims 1 to 8.

10. Ceramizable adhesive film according to Claim 9, characterized in that the ceramizable adhesive film has a peeling force of greater than or equal to 4 N / cm; and / or the ceramizable adhesive film has a thickness of 45 urn to 1000 urn.11 . Ceramizable adhesive tape, characterized by comprising a lining layer; and a ceramizable adhesive layer, wherein at least one side of the lining layer is provided with a ceramizable adhesive layer, and the ceramizable adhesive layer comprises the ceramizable adhesive according to any one of Claims 1 to 8.

12. Ceramizable adhesive tape according to Claim 11 , characterized in that the lining layer comprises a barrier layer and a reinforcement layer, the barrier layer is provided on one side of the reinforcement layer, and the ceramizable adhesive layer is provided on the other side of the reinforcement layer.

13. Ceramizable adhesive tape according to Claim 12, 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.

14. Ceramizable adhesive tape according to Claim 12, characterized in that the reinforcement layer comprises at least one of fibre woven fabric, non-woven fabric, fibre paper, and fibre felt; and / or a part of the barrier layer is embedded in the reinforcement layer.

15. Ceramizable adhesive tape according to Claim 14, characterized in that the reinforcement layer comprises at least one of glass fibres, basalt fibres, ceramic fibres, silicate fibres, and high-silica fibres.

16. Ceramizable adhesive tape according to any one of Claims 12 to 15, characterized in that the barrier layer has a thickness of 10-100 urn; and / or the reinforcement layer has a thickness of 50-2000 urn; and / or the ceramizable adhesive layer has a thickness of 400-2500 urn; and / or the ceramizable adhesive tape has a thickness of 500-2500 urn.

17. Method for preparing a ceramizable adhesive film, characterized by comprising: mixing, dispersing and degassing the raw materials in the adhesive according to any one of Claims 1 to 8 to obtain a ceramizable adhesive slurry; and coating the ceramizable adhesive slurry on a surface of a release film, and curing the same by using ultraviolet light to obtain the ceramizable adhesive film.

18. Application of the adhesive film according to any one of Claims 9-10 or the adhesive tape according to any one of Claims 10-16 in the bonding and fixing of a battery cell, fire protection of a battery system or fire protection of a cable.

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