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CN-122008646-A - Ceramic fiber composite resin fireproof flame-retardant material and preparation method and application thereof

CN122008646ACN 122008646 ACN122008646 ACN 122008646ACN-122008646-A

Abstract

The application relates to the technical field of flame-retardant materials, in particular to a ceramic fiber composite resin fireproof flame-retardant material, a preparation method and application thereof. The ceramic fiber composite resin fireproof flame-retardant material comprises a ceramic fiber fireproof layer and a continuous glass fiber RTM layer, wherein the ceramic fiber fireproof layer comprises fireproof ceramic fibers and nano-oxide/modified nano-oxide, and the surface of the ceramic fiber fireproof layer is subjected to plasma activation operation and silane coupling agent treatment. The ceramic fiber composite resin fireproof flame-retardant material has excellent thermal runaway protection effect, and the bonding effect between the ceramic fiber fireproof layer and the continuous glass fiber RTM layer is excellent.

Inventors

  • DING KAI
  • PANG PEIYAN
  • ZHANG YUANHAO

Assignees

  • 浙江葆润应用材料有限公司

Dates

Publication Date
20260512
Application Date
20260126

Claims (10)

  1. 1. A ceramic fiber composite resin fireproof flame-retardant material is characterized by comprising a ceramic fiber fireproof layer and a continuous glass fiber RTM layer, wherein the ceramic fiber fireproof layer comprises fireproof ceramic fibers and nano oxides, and the surface of the ceramic fiber fireproof layer is subjected to plasma activation operation and silane coupling agent treatment.
  2. 2. The ceramic fiber composite resin fireproof flame-retardant material according to claim 1, wherein the ceramic fiber fireproof layer comprises, by mass, 20-40 parts of fireproof ceramic fibers, 2-5 parts of nano oxides, 5-10 parts of organic binders, 20-40 parts of inorganic binders, 15-35 parts of porcelain-forming fillers, 10-30 parts of glass powder and 0.05-0.3 part of flocculating agents.
  3. 3. The ceramic fiber composite resin fireproof flame retardant material according to claim 2, wherein: The nano oxide is treated by a silane coupling agent.
  4. 4. The ceramic fiber composite resin fireproof flame retardant material according to claim 2, wherein: The refractory ceramic fiber is one or more of aluminum silicate fiber, high aluminum silicate fiber, aluminum oxide fiber, polycrystalline mullite fiber, quartz fiber, silicon carbide fiber, zirconia fiber and nitride fiber, and/or The nano oxide is one or more of nano silicon dioxide and nano aluminum oxide, and/or The organic adhesive is one or more of starch, water-based acrylic glue and water-based polyurethane, and/or The inorganic binder is silica sol, and/or The ceramic filler is one or more of wollastonite, diatomite, kaolin, calcium carbonate and mica powder, and/or The glass powder is one or more of sodium-calcium-silicon glass powder and boron oxide glass powder, and/or The flocculant is one or more of polyacrylamide, polyethylenimine, aluminum sulfate, ferric sulfate and polyaluminum chloride, and/or The silane coupling agent is one or more of KH-560 and KH-570.
  5. 5. The ceramic fiber composite resin fireproof flame retardant material according to claim 1, wherein: the thickness ratio of the ceramic fiber fireproof layer to the continuous glass fiber RTM layer is 2 (2-4); the continuous glass fiber RTM layer comprises a continuous glass fiber fabric and an epoxy resin composition, and the number of layers of the continuous glass fiber RTM layer is 1-5; The mass ratio of the continuous glass fiber fabric to the epoxy resin composition is (3-4) to (6-7).
  6. 6. The ceramic fiber composite resin fireproof flame-retardant material according to claim 5, wherein the epoxy resin composition is a flame-retardant low-foam epoxy resin composition, and the flame-retardant low-foam epoxy resin composition comprises, by mass, 80-120 parts of polyphosphoric acid/octadecanedioic acid synergistic modified epoxy resin, 2-4 parts of a dispersing agent and 20-30 parts of a curing agent.
  7. 7. The ceramic fiber composite resin fireproof flame-retardant material according to claim 6, wherein the preparation method of the polyphosphoric acid/octadecanedioic acid synergistic modified epoxy resin comprises the following steps: Firstly, mixing octadecanedioic acid and polyphosphoric acid according to a molar ratio of 1 (0.7-0.9), then adding p-toluenesulfonic acid catalyst accounting for 0.5-2wt% of the total mass of reactants and toluene serving as a water-carrying agent accounting for 30-40% of the total mass of reactants, heating to 120-160 ℃, reacting for 2-4h, continuously refluxing for carrying water, cooling to 70-80 ℃ after the reaction is finished, and taking out an organic phase after liquid separation to obtain the polyphosphoric acid/octadecanedioic acid intermediate; The preparation method of the polyphosphoric acid/octadecanedioic acid synergistic modified epoxy resin comprises the steps of mixing E51 epoxy resin, polypropylene glycol diglycidyl ether and polyphosphoric acid/octadecanedioic acid intermediate in a molar ratio of 10:1 (7-9), heating to 90-100 ℃ under a nitrogen environment, continuously stirring, adding p-toluenesulfonic acid catalyst accounting for 1-2wt% of the total mass, heating to 130-150 ℃, preserving heat, continuously stirring for 2-4h, neutralizing with Na 2 CO 3 solution to pH=6-7, removing toluene by rotary evaporation, and finally cooling and drying to obtain the polyphosphoric acid/octadecanedioic acid synergistic modified epoxy resin.
  8. 8. A preparation method of the ceramic fiber composite resin fireproof flame-retardant material according to any one of claims 1 to 7 is characterized by comprising a ceramic fiber fireproof layer forming step and a ceramic fiber composite resin fireproof flame-retardant material preparation step; the ceramic fiber fireproof layer forming step comprises the following steps: Adding water into a mixing tank; 15-35 parts of porcelain filler and 10-30 parts of glass powder are added, the rotating speed is 300-2000r/min, and the time is 3-6min; adding 2-5 parts of nano oxide or nano oxide treated by a silane coupling agent, wherein the rotating speed is 300-2000r/min, and the time is 2-5min; Adding 20-40 parts of aluminum silicate fiber, and rotating at 300-2000r/min for 2-10min; adding 5-10 parts of organic adhesive, and rotating at 300-2000r/min for 2-6min; Adding 20-40 parts of inorganic adhesive, and rotating at 300-2000r/min for 2-6min; adding 0.05-3 parts of flocculant, rotating at 300-2000r/min for 1-5min; Pouring the prepared slurry into a slurry pool of a forming machine, and placing the slurry pool into a mould for vacuum adsorption, wherein the vacuum degree is between-0.06 MPa and-0.08 MPa, and the time is 0.5-3min; Transferring the molded material into a die of a hot press for hot press drying at 120-180 ℃ for 1-5min to obtain the ceramic fiber fireproof layer.
  9. 9. The method for preparing a ceramic fiber composite resin fireproof flame retardant material according to claim 8, wherein the ceramic fiber composite resin fireproof flame retardant material preparing step comprises: S1, mixing a silane coupling agent, water and acetic acid to prepare a silane hydrolysis agent; S2, performing plasma activation treatment on the surface to be compounded of the ceramic fiber fireproof layer, and then spraying a silane hydrolytic agent on the surface to be compounded by using a spray gun to form a wetting film; S3, placing the ceramic fiber fireproof layer in a room temperature environment for 5-10min; s4, placing the ceramic fiber fireproof layer into an oven, and curing for 15-30min at 100-120 ℃; S5, cutting and spreading the continuous glass fiber fabric, laminating the continuous glass fiber fabric and the ceramic fiber fireproof layer, and then placing the continuous glass fiber fabric in a die for prepressing and forming to obtain a prefabricated member; S6, placing the prefabricated member in a mould, closing the mould, injecting the epoxy resin composition, and performing hot press molding to obtain the ceramic fiber composite resin fireproof flame-retardant material.
  10. 10. The application of the ceramic fiber composite resin fireproof flame-retardant material according to any one of claims 1 to 7 is characterized in that the ceramic fiber composite resin fireproof flame-retardant material is used for protecting an upper cover of an automobile battery or an energy storage battery.

Description

Ceramic fiber composite resin fireproof flame-retardant material and preparation method and application thereof Technical Field The application relates to the technical field of flame-retardant materials, in particular to a ceramic fiber composite resin fireproof flame-retardant material, a preparation method and application thereof. Background The design and performance of the battery top cover as a core component of the battery system directly affect the safety, reliability and service life of the battery. The traditional battery upper cover is mainly made of sheet metal parts, and along with the rapid development of the new energy automobile industry, the light weight requirement of vehicles is continuously increased. Therefore, how to break through the weight limitation of the traditional sheet metal part and replace the sheet metal part by adopting a material with the advantage of lighter weight becomes a core stress point of the research and development work of the upper cover of the current battery. At present, the main scheme of the battery pack upper cover is an RTM upper cover, which stands out by virtue of the excellent balance of light weight characteristics and comprehensive performance. RTM covers are usually manufactured by a Resin Transfer Molding (RTM) process, and the core principle is that resin is injected into a vacuum sealing mold by means of high pressure, so that the resin uniformly infiltrates a fiber preform, and finally the resin is integrally formed into a component with high comprehensive performance. However, it should be noted that the RTM top cover uses epoxy resin as a core substrate, and the decomposition temperature of the epoxy resin is generally below 300 ℃. When the battery core is in thermal runaway to cause high temperature, the epoxy resin is easy to generate decomposition reaction, so that the sealing performance and rigidity of the upper cover are rapidly reduced, and finally the upper cover is difficult to resist internal high-voltage impact to be punched through, and becomes a potential short plate for battery pack safety protection. Disclosure of Invention In order to overcome the defect of insufficient fireproof and flame-retardant performance of the conventional battery pack upper cover, the application provides a ceramic fiber composite resin fireproof and flame-retardant material, and a preparation method and application thereof. In a first aspect, the application provides a ceramic fiber composite resin fireproof flame-retardant material, which adopts the following technical scheme: The ceramic fiber composite resin fireproof flame-retardant material comprises a ceramic fiber fireproof layer and a continuous glass fiber RTM layer, wherein the ceramic fiber fireproof layer comprises fireproof ceramic fibers and nano oxides, and the surface of the ceramic fiber fireproof layer is subjected to plasma activation operation and silane coupling agent treatment. According to the application, the ceramic fiber fireproof layer is compounded on the continuous glass fiber RTM layer, so that the temperature resistance of the composite material is more than 1200 ℃, when the battery core is in thermal runaway, the upper cover of the battery pack prepared by the composite material is not easy to break down by high-temperature combustible substances, the spread of fire can be restrained, the safety of personnel in a vehicle is ensured, and the composite material can be integrally formed, has a simple process and is convenient for mass production. However, in actual production, the applicant finds that, because the ceramic fiber fireproof layer and the continuous glass fiber RTM layer are both composite materials based on fibers, if the ceramic fiber fireproof layer and the continuous glass fiber RTM layer are not processed, the ceramic fiber fireproof layer and the continuous glass fiber RTM layer are directly compounded only by hot pressing, and the combination effect of the ceramic fiber fireproof layer and the continuous glass fiber RTM layer is not ideal, so that the battery pack upper cover prepared from the ceramic fiber fireproof layer and the continuous glass fiber RTM layer often has phenomena of swelling and delamination, and the normal use of the product is seriously affected. In this way, the applicant sequentially carries out plasma activation operation and silane coupling agent treatment on the ceramic fiber fireproof layer, so that the binding force between the ceramic fiber fireproof layer and the continuous glass fiber RTM layer is effectively improved. The plasma activation operation aims at etching and cleaning the surface of the ceramic fiber fireproof layer, introducing hydroxyl and other polar or active groups into the surface of the ceramic fiber fireproof layer, improving the physical and chemical states of the surface of the ceramic fiber fireproof layer, forming active centers on the surface of the ceramic fiber fireproof layer, promoting the subse