CN114395342B - Water vapor barrier fireproof flexible back plate and preparation method thereof - Google Patents
Water vapor barrier fireproof flexible back plate and preparation method thereof Download PDFInfo
- Publication number
- CN114395342B CN114395342B CN202210100520.4A CN202210100520A CN114395342B CN 114395342 B CN114395342 B CN 114395342B CN 202210100520 A CN202210100520 A CN 202210100520A CN 114395342 B CN114395342 B CN 114395342B
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- water vapor
- flexible
- vapor barrier
- layer
- barrier
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Abstract
The application relates to the technical field of solar flexible backboard materials, in particular to a water vapor barrier fireproof flexible backboard and a preparation method thereof. A water vapor barrier fireproof flexible backboard comprises a high barrier modified PET substrate, wherein a water vapor barrier fireproof layer is integrally formed on the surface of the high barrier modified PET substrate facing to the air side; the surface of the water vapor barrier fireproof layer, which faces away from the high barrier modified PET substrate, is integrally formed with an anti-aging layer; tiO is formed on the surface of the anti-aging layer facing away from the water vapor barrier fireproof layer 2 A self-cleaning layer; the water vapor barrier fireproof layer and the anti-aging layer are respectively and fixedly connected to the upper surface and the lower surface of the water vapor barrier fireproof layer through a hot press molding process; the surface of the high-barrier modified PET substrate facing the battery side is compounded with a glue layer. The flame retardant coating has the advantages of long service life, high temperature resistance, flame retardance and water vapor barrier property. In addition, the flexible and mechanical strength of the plastic has better flexibility and mechanical strength, and the thickness is controlled to be 0.4-0.5mm, so that the plastic is thinner and lighter.
Description
Technical Field
The application relates to the technical field of solar flexible backboard materials, in particular to a water vapor barrier fireproof flexible backboard and a preparation method thereof.
Background
With the national emphasis on environmental protection, the utilization and development of new energy become a new development and development trend. Solar energy is a clean energy source and is focused by various nationists and researchers. The solar cell panel can convert solar energy into electric energy for utilization, so that the tension of the electric energy can be relieved, and the dependence on fossil fuel power generation is reduced. With the deep popularization and application of solar panels, the research of flexible solar cell modules is particularly necessary. The flexible solar cell module has the advantages of light weight, thin module and flexibility, and can be suitable for more application scenes.
A solar panel in the related art mainly comprises a glass surface layer, an EVA sealing layer, a solar cell, an EVA sealing layer and a solar cell back film, wherein the solar cell is sealed and wrapped by two layers of EVA sealing layers. The solar cell back film is fixedly bonded with the EVA sealing layer facing away from the surface of the solar cell sheet, so that the overall mechanical strength of the solar cell panel is improved, water vapor is prevented from penetrating into the sealing layer, and the service life of the cell sheet is prolonged. Therefore, the quality of the back film of the solar cell can directly influence the service life of the solar cell panel. For example, chinese patent application No. CN201520087689.6 discloses a transparent solar cell back film and components thereof, in which a transparent weather-proof coating is coated on both sides of a transparent base layer, and the transparent weather-proof coating has the advantages of high ultraviolet blocking and low yellowing, so as to improve the service life of the solar cell back film.
In view of the solar cell back film in the related art described above, the applicant found that the following problems exist in this technical solution: the transparent weather-proof coating can keep better high ultraviolet blocking performance in a period of time, but in the long-time use process, the problem of relatively short overall service life caused by poor coating adhesion still occurs, and the popularization and application of the solar cell are severely limited.
Disclosure of Invention
In order to solve the problem that the whole service life is relatively short in the related art and severely limit popularization and application of the solar cell, the application provides a water vapor barrier fireproof flexible back plate and a preparation method thereof.
In a first aspect, the application provides a flexible backplate of steam separation fire prevention, is realized through following technical scheme:
the water vapor barrier fireproof flexible back plate comprises a high barrier modified PET substrate, wherein a water vapor barrier fireproof layer is integrally formed on the surface of the high barrier modified PET substrate facing the air side; an anti-aging layer is integrally formed on the surface of the water vapor barrier fireproof layer, which faces away from the high barrier modified PET substrate; tiO is formed on the surface of the anti-aging layer, which is opposite to the water vapor barrier fireproof layer 2 A self-cleaning layer; the water vapor barrier fireproof layer and the anti-aging layer are respectively and fixedly connected to the upper surface and the lower surface of the water vapor barrier fireproof layer through a hot press molding process; and a glue layer is compounded on the surface of the high-barrier modified PET substrate facing the battery side.
Through adopting above-mentioned technical scheme, high separation modified PET base plate has given this application good steam barrier property and gas barrier property, promotes holistic life, steam and gas barrier property, and life is more than 25 years. The water vapor separation fireproof layer endows the product with good service life, high temperature resistance, flame retardance, fireproof performance and water vapor separation performance, and the product can be used at 180 ℃ and has good high temperature resistance. The anti-aging layer gives the application good chemical stability, weather resistance and aging resistance. In addition, the thickness of the solar cell backboard is controlled to be 0.4-0.5mm, and the solar cell backboard is light and thin, has good flexibility and mechanical strength, is an ideal solar cell backboard material, and is beneficial to popularization and application of the solar cell backboard. In conclusion, the novel high-temperature-resistant flame-retardant plastic has longer service life, better water vapor and gas barrier property, higher high-temperature resistance and flame retardance, light weight, good flexibility and better mechanical strength.
Preferably, the water vapor blocking fireproof layer is a flexible composite mica sheet; the thickness of the flexible composite mica sheet is 0.15-0.25mm; the flexible composite mica sheet is prepared from phlogopite paper and composite organic silica gel water; the thickness of the phlogopite paper is 30-50 microns; the compound organic silica gel water comprises KR-242A silicone resin and FM-0425 modified hydroxyl siloxane; the mass ratio of the KR-242A silicone resin to the FM-0425 modified hydroxyl siloxane is 100:15-20.
Through adopting above-mentioned technical scheme, endowed flexible compound mica sheet good pliability, insulating nature, anti electric breakdown nature, fire resistance and comparatively permanent life, and then guaranteed holistic pliability, insulating nature, anti electric breakdown nature, fire resistance, life of this application.
Preferably, the preparation method of the flexible composite mica sheet comprises the following steps:
step one, preparing compound organosilicon glue;
step two, preparation of phlogopite/composite glue unit paper: the first step of scraping and coating one surface of the phlogopite paper is compounded with the organosilicon glue, and the dosage of the compounded organosilicon glue is 10-12g/m 2 Drying to enable the compound organosilicon glue to be in a gel state;
thirdly, selecting the number of layers of the phlogopite/composite glue unit paper in the second step for superposition according to the thickness requirement of the flexible composite mica sheet, and then compositing the phlogopite paper without the composite silicone glue on the surface of the adjacent phlogopite/composite glue unit paper coated with the composite silicone glue, and preforming by a hot-pressing roller to obtain the flexible composite mica coiled material;
and step four, cutting the flexible composite mica coiled material in the step three to obtain a semi-finished flexible composite mica sheet, carrying out vacuum hot press molding on the semi-finished flexible composite mica sheet, and naturally cooling to obtain the finished flexible composite mica sheet.
By adopting the technical scheme, the preparation method is relatively simple, and is convenient for industrialized mass production of the flexible composite mica sheet. The flexible composite mica sheet produced by the preparation method has good flexibility, insulativity, electric breakdown resistance, flame retardance and longer service life.
Preferably, the water vapor barrier fireproof layer is a flexible mica die casting sheet; the thickness of the flexible mica die casting sheet is 0.20-0.30mm; the flexible mica die casting sheet is prepared from the following raw materials in parts by weight: 120-140 parts of organic solvent, 20-40 parts of synthetic fluorophlogopite, 60-80 parts of phlogopite, 0.5-1.5 parts of organic titanium surface modifier, 4-8 parts of modified aramid fiber, 0.2-1 part of nano titanium dioxide, 0.1-0.3 part of nano zinc oxide whisker, 0.2-1 part of nano cerium oxide and 32-40 parts of organic silicon resin; the organic silicon resin comprises KR-242A silicon resin and FM-0425 modified hydroxyl siloxane; the mass ratio of the KR-242A silicone resin to the FM-0425 modified hydroxyl siloxane is 100:15-20; an electric conductive coating is formed on the outer wall of the modified aramid fiber; the electric conductive coating is prepared from the following raw materials: graphene, carbon nanotubes, nano titanium dioxide, a surface modifier, a film forming additive, polyurethane emulsion, a pH regulator, a defoaming agent and an organosilicon base material wetting agent.
Through adopting above-mentioned technical scheme, endowed flexible compound mica sheet good pliability, insulating nature, anti electric breakdown nature, fire resistance and comparatively permanent life's the surface tear resistance performance of flexible compound mica sheet is excellent simultaneously, and steam separation flame retardant coating is difficult for taking place to peel off with high separation modified PET base plate, ageing resistance layer, can guarantee holistic pliability, insulating nature, anti electric breakdown nature, fire resistance, life of this application further.
Preferably, the preparation method of the flexible mica die casting sheet comprises the following steps:
step one, preparing modified aramid fibers;
step two, weighing the synthesized fluorophlogopite and phlogopite according to the proportion, and carrying out ultrasonic treatment and dispersion treatment on the synthesized fluorophlogopite and phlogopite and the accurately-metered organic titanium surface modifier to obtain surface modified mixed mica powder;
step three, uniformly mixing the modified mica mixture in the step two with modified aramid fiber, nano titanium dioxide, nano zinc oxide whisker, nano cerium oxide and an organic solvent, adding organic silicon resin, and uniformly stirring to obtain mica slurry;
injecting the mica slurry into a forming die, placing the forming die between two polar plates of a capacitor, enabling the electric field direction of the capacitor and the height direction of the forming die to be in the same direction, performing electric field treatment for 20-40min, performing heating treatment on the forming die after performing electric field treatment for 10min, removing organic solvents in the mica slurry, performing heating treatment on the forming die for 5-10min after performing electric field treatment, and performing hot press forming to obtain a finished flexible mica coiled material;
And fifthly, cutting the finished flexible mica coiled material to obtain a finished flexible mica sheet, and performing vacuum hot press molding on the finished flexible mica sheet to obtain the finished flexible composite mica sheet.
Through adopting above-mentioned technical scheme, can carry out the flexible compound mica sheet of batch production, though production cost is higher than the flexible compound mica sheet of phlogopite paper pressfitting production relatively, but the flexible compound mica sheet of this method preparation has better anti surface peel strength, steam separation flame retardant coating is difficult for taking place to peel off with high separation modified PET base plate, ageing resistance layer, can further guarantee holistic pliability, insulating nature, anti electric breakdown nature, fire resistance, life of this application, the flexible compound mica sheet of this method preparation has better stability in use and security, life is more lasting, be suitable for as high-end solar energy backplate material.
Preferably, the high-barrier modified PET substrate is prepared from the following raw materials in percentage by mass: 4-6% of TPEE compound, 10-15% of PEN resin, 10-15% of LCP resin, 0.6-1.2% of ultraviolet absorber, 0.5-1% of nano titanium dioxide, 0.5-1% of polyvinyl alcohol, 0.5-0.8% of KH550 siloxane coupling agent and the balance of PET resin; the PEE compound is one or a plurality of combinations of Hytrel HTR8068, hytrel G4774, hytrel G4778, hytrel G5564 and Hytrel G5526; the content of the HytrelHTR8068 accounts for 60-70% of the total mass of the TPEE compound; the ultraviolet absorbent is one or a combination of more of poly succinic acid (4-hydroxy-2, 6-tetramethyl 1-piperidinol) ester, 2-hydroxy-4-n-octoxybenzophenone and 2- (2-hydroxy-3, 5-tert-butylphenyl) -5-chlorobenzotriazole.
Through adopting above-mentioned technical scheme, endowed high separation modified PET base plate good steam barrier property, gas barrier property and mechanical properties, and then can guarantee holistic life, steam and the gas barrier property of this application.
Preferably, the preparation method of the high-barrier modified PET substrate comprises the following steps:
step one, placing PEN resin, PET resin, LCP resin and TPEE compound at 80-90 ℃ and drying for 2-4 hours for later use;
uniformly mixing the PEN resin, the PET resin, the LCP resin, the TPEE compound, the ultraviolet absorbent, the nano titanium dioxide, the KH550 siloxane coupling agent and the polyvinyl alcohol which are dried in the first step, extruding, granulating, water-cooling and granulating to obtain modified PET granules with the granularity of 1.5-2.2 mm;
step three, the modified PET granules in the step two are placed at 80-90 ℃ and dried for 2-4 hours, and the moisture content is lower than 0.5 percent and stored for standby;
extruding, casting to form a film, and naturally cooling to obtain the high-barrier modified PET coiled material;
and fifthly, cutting Gao Zuge modified PET coiled material, performing heat treatment for 25-40min, controlling the heat treatment temperature to 68-72 ℃, and cooling and rolling to obtain the finished high-barrier modified PET substrate.
By adopting the technical scheme, the preparation method is relatively simple, the high-barrier modified PET substrate is convenient for industrialized mass production, each performance of the high-barrier modified PET substrate in the same batch is stable, the product quality control is relatively simple, the production cost of the high-barrier modified PET substrate is reduced, and the high-barrier modified PET substrate has more competitive advantages in commerce.
Preferably, the anti-aging layer is a fluororesin film; the fluorine resin film is one of an ETFE resin film, a PTFE resin film, a PVDF resin film and a THV resin film; the fluororesin film faces away from the TiO 2 The self-cleaning layer is formed with an adhesion promoting layer by low temperature plasma treatment.
By adopting the technical scheme, tiO 2 The self-cleaning layer gives the application a better self-cleaning effect; the fluororesin film has better chemical stability, weather resistance and ageing resistance, and can ensure the whole service life of the application. The tackifying layer formed by the fluororesin film can effectively strengthen the fluororesin film and waterThe bonding strength and bonding stability of the vapor barrier fire-resistant layer further ensure the service life of the application.
In a second aspect, the preparation method of the water vapor barrier fireproof flexible back plate provided by the application is realized through the following technical scheme:
A preparation method of a water vapor barrier fireproof flexible back plate comprises the following steps:
preparing a water vapor barrier fireproof layer material, a high-barrier modified PET substrate and a fluororesin film;
coating the water surface of the water vapor barrier fireproof layer with compound organic silica gel water, wherein the dosage of the compound organic silica gel water is controlled to be 10-12g/m 2 Preheating and solidifying to enable the compound organosilicon glue to be in a gel state;
step three, rolling an anti-aging layer on the upper surface of the water vapor barrier fireproof layer, rolling a high-barrier modified PET substrate on the lower surface of the water vapor barrier fireproof layer, and rolling for 200-250N to obtain a pre-composite sheet;
step four, performing vacuum hot-pressing treatment on the pre-composite sheet in the step three to obtain a semi-finished flexible composite sheet;
step five, spraying self-cleaning paint on the surface of the anti-aging layer of the semi-finished flexible composite sheet to form TiO (titanium dioxide) by curing 2 A self-cleaning layer;
step six, the semi-finished flexible composite sheet is back to TiO 2 And coating an adhesive on the surface of the self-cleaning layer to form a glue layer, thus obtaining the finished water vapor barrier fireproof flexible back plate.
Through adopting above-mentioned technical scheme, the preparation method of this application is simple relatively, and the flexible backplate of finished product steam separation fire prevention is obtained in the industrialization batch production of being convenient for, and the flexible backplate each item performance stability of finished product steam separation fire prevention of same batch, the control work of product is simple relatively, does benefit to the manufacturing cost who reduces the flexible backplate of finished product steam separation fire prevention, and then makes this application have more competitive advantage in the business.
Preferably, the vacuum hot pressing treatment in the fourth step is divided into five steps of vacuum hot pressing treatment, wherein the hot pressing condition in the first step of vacuum hot pressing forming is that the temperature of a pressing plate is 80-100 ℃, the pressure is 0.4-0.6Mpa, and the duration is 30-40s; the second step of vacuum hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 140-150 ℃, the pressure is 0.8-1.0Mpa, and the duration time is 30-40s; the third step of vacuum hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 160-165 ℃, the pressure is 1.5-1.8Mpa, and the duration is 60-80s; the fourth step is that the hot pressing condition in the vacuum hot pressing forming is that the temperature of the pressing plate is 130-140 ℃, the pressure is 0.8-1.0Mpa, the duration is 30-40s, the fifth step is that the hot pressing condition in the vacuum hot pressing forming is that the temperature of the pressing plate is 100-110 ℃, the pressure is 0.6-0.8Mpa, the duration is 30-40s, the cooling is carried out to room temperature, the semi-finished flexible composite sheet after the five steps of vacuum hot pressing treatment is carried out heat treatment, the heat treatment is carried out for 100-120s at 60-65 ℃, the heat treatment is carried out for 300-500s at 75-80 ℃, the heat treatment is carried out for 200-250s at 120-125 ℃, the heat preservation is carried out for 180-300s at 60-80 ℃, the temperature is reduced to 40-45 ℃ at the speed of 0.8-1.2 ℃ for 5-10min, and the semi-finished flexible composite sheet is cooled to room temperature in a furnace.
Through adopting above-mentioned technical scheme, can guarantee the flexible backplate quality of steam separation fire prevention of production, and the article accuse work of product is simple relatively, does benefit to the manufacturing cost who reduces the flexible backplate of finished product steam separation fire prevention, and then makes this application more have competitive advantage in the business.
In summary, the present application has the following advantages:
1. the waterproof plastic has the advantages of better flexibility, mechanical strength, service life, high temperature resistance, flame retardance, waterproofness and water vapor barrier property, thickness control of 0.4-0.5mm, thinness and convenience in transportation and assembly.
2. The preparation method is relatively simple, and the finished product water vapor barrier fireproof flexible back plate is conveniently obtained through industrial batch production.
3. The product control work of the product control device is relatively simple, and is beneficial to reducing the production cost of the finished product water vapor barrier fireproof flexible back plate, so that the product control device has more competitive advantage in commerce.
Drawings
Fig. 1 is a schematic view of the overall structure in embodiment 1 in the present application.
In the figure, 1, a high-barrier modified PET substrate; 2. a water vapor barrier flame retardant layer; 3. anti-agingA layer; 30. TiO (titanium dioxide) 2 A self-cleaning layer; 31. an adhesion promoting layer; 4. and a glue layer.
Detailed Description
The present application is described in further detail below with reference to the drawings and examples.
Preparation example
Preparation example 1
The flexible composite mica sheet is prepared by vacuum hot pressing of phlogopite paper and composite organic silica gel water. Wherein, the phlogopite paper is made of 50 micrometer thick phlogopite paper. The compound organic silicon glue is self-prepared organic silicon gel. The preparation method of the compound organic silicon glue comprises the steps of weighing 100g of KR-242A silicone resin, 18g of FM-0425 modified hydroxy siloxane (JNC in Japan) and 0.02g of diethylenetriamine, placing the materials in a three-necked flask, heating the materials in a water bath to 68-70 ℃ for 150s to react, cooling the materials with ice water to below 4 ℃, adding 120g of methanol, stirring the materials at 200rpm for 5min, adding 0.06g of diethylenetriamine, and stirring the materials at 60rpm for 100s to obtain the compound organic silicon glue.
The preparation method of the flexible composite mica sheet comprises the following steps:
step one, preparing compound organosilicon glue: 100g of KR-242A silicone resin, 18g of FM-0425 modified hydroxy siloxane (JNC in Japan) and 0.02g of diethylenetriamine are weighed and placed in a three-necked flask, water bath is heated to 68-70 ℃ for 150s reaction, ice water is cooled to below 4 ℃, 120g of methanol is added and stirred at 200rpm for 5min, then 0.06g of diethylenetriamine is added and stirred at 60rpm for 100s to obtain compound organosilicon glue;
step two, preparation of phlogopite/composite glue unit paper: and (2) a compound organic silicon glue in the first step of scraping and coating one surface of the phlogopite paper, wherein the dosage of the compound organic silicon glue is 10g/m 2 Drying in oven at 60-65deg.C for 30min to remove formaldehyde in the compound organosilicon glue to make the compound organosilicon gel adhere to one surface of phlogopite paper in gel state;
step three, selecting two pieces of phlogopite/composite glue unit paper in the step two for superposition, bonding the surface of the phlogopite/composite glue unit paper, which is not coated with the compound organosilicon glue, with the surface of the adjacent phlogopite/composite glue unit paper, then selecting a phlogopite paper, which is not attached with the organosilicon glue, to be composited on the surface of the adjacent phlogopite/composite glue unit paper, which is coated with the compound organosilicon glue, carrying out six hot press shaping treatment, wherein the surface temperature of a hot press roller in the six hot press shaping treatment is respectively 60 ℃, 80 ℃, 85 ℃, 75 ℃, 60 ℃ and the gap of the hot press roller in the six hot press shaping treatment is adjusted to 0.168mm, and carrying out hot press shaping to obtain the flexible composite mica coiled material;
And step four, cutting the flexible composite mica coiled material in the step three to obtain a semi-finished flexible composite mica sheet, loading the semi-finished flexible composite mica sheet into a hot pressing mold, feeding the semi-finished flexible composite mica sheet into a vacuum hot pressing tank for vacuum hot pressing forming treatment, controlling the hot pressing temperature to be 230 ℃, controlling the hot pressing time to be 30min, and naturally cooling to obtain the finished flexible composite mica sheet with the thickness of 0.165-0.168 mm.
Preparation example 2
Preparation 2 differs from preparation 1 in that: the compounded silicone glue does not contain FM-0425 modified hydroxyl siloxane and is pure KR-242A silicone resin glue.
Preparation example 3
Preparation 3 differs from preparation 1 in that: the preparation method of the compound organic silicon glue comprises the steps of weighing 100g of KR-242A silicone resin, 5g of FM-0425 modified hydroxyl siloxane and 0.02g of diethylenetriamine, placing the materials into a three-necked flask, heating the materials in a water bath to 68-70 ℃ for 150s reaction, cooling the ice water to below 4 ℃, adding 110g of methanol, stirring the mixture at 200rpm for 5min, adding 0.06g of diethylenetriamine, and stirring the mixture at 60rpm for 100s to obtain the compound organic silicon glue.
Preparation example 4
The flexible mica die casting sheet is prepared from the following raw materials in parts by weight: 120 parts of methanol, 25 parts of synthetic fluorophlogopite, 75 parts of phlogopite, 1.5 parts of isopropyl tri (dioctyl pyrophosphoryl oxy) titanate (CAS: 67691-13-8) serving as an organic titanium surface modifier, 6 parts of modified aramid fiber, 1 part of nano titanium dioxide, 0.2 part of nano zinc oxide whisker, 0.3 part of nano cerium oxide and 35 parts of organic silicon resin. The outer wall of the modified aramid fiber is sprayed with an electrically conductive coating and cured to form an electrically conductive coating.
The electric guiding paint is prepared from the following raw materials: 5 parts of nano graphite powder with the average particle size of 100nm (Shanghai super-Wei nano technology Co., ltd.), 3 parts of carbon nano tube with the inner diameter of 10-20nm and the tube length of 10-15um (Shanghai maoshan nano technology Co., ltd.), 1 part of nano titanium dioxide, 1 part of KH550 siloxane coupling agent, 2 parts of propylene glycol butyl ether, 80 parts of aqueous polyurethane emulsion, 1.5 parts of multifunctional auxiliary agent AMP-95, 1.2 parts of modified polysiloxane emulsion defoamer X8803 and 2.5 parts of Di high TEGO Tain 4000 base material wetting agent.
A method of preparing an electrically conductive coating comprising the steps of:
weighing 10g of graphene, 6g of carbon nano tube and 2g of KH550 siloxane coupling agent, stirring, mixing and dispersing for 10min to obtain a surface modified conductive material;
step two, 160g of aqueous polyurethane emulsion is added with 4g of propylene glycol butyl ether, 2.4g of modified polysiloxane emulsion defoamer X8803, 5g of DigaTEGO Twain 4000 base material wetting agent and the surface modified conductive material in step one, dispersed for 20min at 500rpm, then 3g of multifunctional auxiliary agent AMP-95 is added to adjust the pH value to 7.0-7.5, and dispersed for 5min at 500rpm, thus obtaining the conductive coating.
The preparation method of the organic silicon resin comprises the steps of weighing 100g of KR-242A silicon resin, 18g of FM-0425 modified hydroxyl siloxane and 0.02g of diethylenetriamine, placing the materials into a three-necked flask, heating the materials in a water bath to 68-70 ℃ for 150s reaction, cooling the materials to below 4 ℃, adding 120g of methanol, stirring the materials at 200rpm for 5min, adding 0.06g of diethylenetriamine, and stirring the materials at 60rpm for 100s to obtain the organic silicon glue.
The preparation method of the modified aramid fiber comprises the following steps:
step one, selecting single fiber with the length of 76mm and the single fiber with the length of 2.5D as the raw material aramid fiber
Chopped para-aramid yarn to be purchased +.>
The chopped para-aramid yarn is placed inIn 5% sodium hydroxide solution, controlling the temperature of the sodium hydroxide solution at 80 ℃, placing the chopped para-aramid filaments after soaking for 30min into 1.5g/L cocoyl glucoside aqueous solution, soaking for 10min, then transferring into deionized water solution, performing ultrasonic treatment, taking out the chopped para-aramid filaments at 40 ℃ for drying for 4h at the ultrasonic frequency of 48KHz for 5min for later use;
step two, carrying out low-temperature plasma surface treatment on the chopped para-aramid yarn in the step one, wherein the treatment temperature is 4 ℃, the gas medium is air, and the treatment time is controlled to be 30min;
step three, spraying the prepared electrically conductive coating on the surface of the chopped para-aramid fiber yarn in the step two, curing at 80 ℃, then spraying the electrically conductive coating, and curing at 80 ℃ to obtain the modified aramid fiber;
cutting the modified aramid fiber prepared in the third step, wherein the length of the cut modified aramid fiber is controlled to be 0.2+/-0.02 mm, so as to obtain the modified aramid fiber;
Step five, weighing 50g of modified aramid fiber, soaking in 100ml of 0.5g/L KH550 siloxane coupling agent water solution for 20min, taking out the modified aramid fiber, transferring the modified aramid fiber into an oven, and drying at a low temperature of 20 ℃ to remove water to obtain the finished modified aramid fiber.
The preparation method of the flexible mica die casting sheet comprises the following steps:
step one, preparing modified Kevlar fibers;
step two, adding 7.5g of isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate and 150g of deionized water into 125g of synthetic fluorophlogopite and 375g of phlogopite, stirring at 150rpm for 5min, and then carrying out ultrasonic treatment dispersion treatment with the ultrasonic frequency of 44kHz for 15min to obtain surface modified mixed mica powder;
adding 30g of the prepared finished modified aramid fiber, 5g of nano titanium dioxide, 1g of nano zinc oxide whisker, 1.5g of nano cerium oxide and 600g of methanol into the modified mica mixture in the second step, mixing and dispersing for 20min at 240rpm, adding 175g of organic silicon resin, and stirring for 10min at 120rpm to obtain mica slurry;
step four, the mica slurry prepared in the step three is injected into a forming die, the forming die is prepared from an insulating material-PTFE resin, in the preparation process, the forming die is fixedly placed between two electrode plates of a parallel plate capacitor, the electric field direction formed by the parallel plate capacitor and the height direction of the forming die are arranged in the same direction and are perpendicular to a horizontal plane, the voltage of the capacitor is controlled at 36V, the distance between the parallel plate capacitors is 30cm, the electric field treatment time is 30min, the forming die is heated after the electric field treatment is carried out for 10min, the temperature is heated to 80 ℃, the forming die is heated for 10min after the electric field treatment is completed, the heating temperature is maintained at 80 ℃, and methanol in the mica slurry is removed, so that a semi-finished flexible mica sheet is obtained;
Step five, performing four-step hot-press forming on the semi-finished flexible mica sheet, wherein the hot-press condition in the first step of hot-press forming is that the temperature of a pressing plate is 60 ℃, the pressure is 0.5Mpa, and the duration is 30s; the second hot press forming is carried out under the condition that the temperature of the pressing plate is 120 ℃, the pressure is 0.8Mpa, the duration is 60s, and the third hot press forming is carried out under the condition that the temperature of the pressing plate is 165 ℃, the pressure is 1.2Mpa, and the duration is 150s; the fourth step of hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 100 ℃, the pressure is 0.8Mpa, and the duration is 60s, so that the finished flexible mica coiled material is obtained;
cutting the finished flexible mica coiled material, carrying out vacuum hot-press forming on the cut sheet, loading the semi-finished flexible composite mica sheet into a hot-press die, sending the semi-finished flexible composite mica sheet into a vacuum hot-press tank for vacuum hot-press forming treatment, controlling the hot-press temperature at 230 ℃, controlling the hot-press time at 30min, and naturally cooling to obtain the finished flexible composite mica sheet with the thickness of 0.21 mm+/-0.01 mm.
Preparation example 5
Preparation 5 differs from preparation 4 in that: the organic silicon glue does not contain FM-0425 modified hydroxyl siloxane and is pure KR-242A silicon resin glue.
Preparation example 6
Preparation 6 differs from preparation 4 in that: the preparation method of the organic silicon glue comprises the steps of weighing 100g of KR-242A silicone resin, 5g of FM-0425 modified hydroxyl siloxane and 0.02g of diethylenetriamine, placing the materials into a three-necked flask, heating the materials in a water bath to 68-70 ℃ for 150s reaction, cooling the ice water to below 4 ℃, adding 110g of methanol, stirring the mixture at 200rpm for 5min, adding 0.06g of diethylenetriamine, and stirring the mixture at 60rpm for 100s to obtain the compound organic silicon glue.
Preparation example 7
The high-barrier modified PET substrate is prepared from the following raw materials in percentage by mass: 3.2% Hytrel HTR8068, 1.8% Hytrel G5564, 15% PEN resin, 15% LCP resin, 0.5% poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, 0.3% 2- (2-hydroxy-3, 5-tert-butylphenyl) -5-chlorobenzotriazole, 0.3% 2-hydroxy-4-n-octoxybenzophenone, 1% nano titanium dioxide, 0.6% polyvinyl alcohol, 0.8% KH550 siloxane coupling agent, the balance PET resin.
The preparation method of the high-barrier modified PET substrate comprises the following steps:
step one, weighing 150G of PEN resin, 615G of PET resin, 150G of LCP resin, 32G of Hytrel HTR8068 and 18G of Hytrel G5564, and drying for 4 hours at 80 ℃ for later use;
placing 150G of PEN resin, 615G of PET resin, 150G of LCP resin, 32G of Hytrel HTR8068 and 18G of Hytrel G5564 which are dried in the first step into a high-speed dispersion kettle, adding 10G of nano titanium dioxide, 8G of KH550 siloxane coupling agent and 6G of polyvinyl alcohol, mixing and dispersing for 20min at 500rpm, putting into a double-screw extruder for extrusion granulation, wherein the extrusion temperature is divided into seven temperature areas, namely 260 ℃ and 270 ℃,275 ℃,285 ℃,284 ℃,284 ℃ and 285 ℃ respectively, the die temperature is 285 ℃, the plasticizing temperature is 298.4 ℃, water-cooling, and granulating to obtain modified PET granules with the granularity of 1.5-2.2 mm;
Step three, the modified PET granules in the step two are sent into a baking oven, the temperature is controlled at 80 ℃, and the drying is carried out for 4 hours, so that the moisture of the modified PET granules is lower than 0.5%, and the modified PET granules are stored for standby;
step four, adding the modified PET granules dried in the step three into a double-screw extruder, extruding and casting to form a film, biaxially stretching the cast film, wherein the stretching ratio is 1.0, the temperature of a cooling roller is 80 ℃, and naturally cooling to obtain a high-barrier modified PET coiled material;
and fifthly, cutting the high-barrier modified PET coiled material into a high-barrier modified PET sheet, performing heat treatment for 30min, controlling the heat treatment temperature at 72 ℃, naturally cooling and rolling to obtain a finished high-barrier modified PET substrate with the thickness of 180+/-2 micrometers.
Preparation example 8
Preparation 8 differs from preparation 7 in that:
the high-barrier modified PET substrate is prepared from the following raw materials in percentage by mass: 0.5% of poly (4-hydroxy-2, 6-tetramethyl-1-piperidineethanol) succinate, 0.3% of 2- (2-hydroxy-3, 5-tert-butylphenyl) -5-chlorobenzotriazole, 0.3% of 2-hydroxy-4-n-octoxybenzophenone, 1% of nano titanium dioxide, 0.6% of polyvinyl alcohol, 0.8% of KH550 siloxane coupling agent and the balance of PET resin.
Examples
Example 1
Referring to fig. 1, a water vapor barrier fireproof flexible back plate disclosed in the application is composed of a high barrier modified PET substrate 1, a water vapor barrier fireproof layer 2, an anti-aging layer 3 and a glue layer 4. The high-barrier modified PET substrate 1 is integrally formed on the lower surface of the water vapor barrier fireproof layer in a hot-press mode, namely the water vapor barrier fireproof layer 2 is integrally formed on the surface of the high-barrier modified PET substrate 1 facing the air side in a hot-press mode. The anti-aging layer 3 is integrally formed on the upper surface of the water vapor barrier fireproof layer in a hot-pressing mode, namely the water vapor barrier fireproof layer 2 is integrally formed on the surface of the high-barrier modified PET substrate 1 facing the battery side in a hot-pressing mode. The glue layer 4 is adhered to the surface of the high-barrier modified PET substrate 1 facing away from the water vapor barrier fireproof layer 2.
In this embodiment, the high-barrier modified PET substrate 1 was the final high-barrier modified PET substrate in preparation example 7. The water vapor barrier fire-resistant layer 2 is a finished flexible composite mica sheet in preparation example 1. The ageing resistant layer 3 is formed of a THV resin film having a thickness of 60.+ -.5. Mu.m. The glue layer 4 is EVA hot melt glue film.
A preparation method of a water vapor barrier fireproof flexible back plate comprises the following steps:
step one, preparing a water vapor barrier fireproof layer material, a high barrier modified PET substrate and a fluororesin film:
The preparation of the water vapor barrier flame retardant layer material is described in preparation example 1;
preparation of high barrier modified PET substrate see preparation example 7;
the fluorine resin film is a THV resin film with the size of 60+/-5 microns, the THV resin film is cut into THV resin films with the same size as the high-barrier modified PET substrate, one surface of the THV resin film is subjected to low-temperature plasma treatment at the temperature of 0-4 ℃, the gas medium is oxygen, and the treatment time is controlled to be 10 minutes for standby;
step two, coating the upper and lower surfaces of the finished flexible composite mica sheet in preparation example 1 with the composite organosilicon glue in preparation example 1, wherein the dosage of the composite organosilicon glue is controlled to be 10g/m 2 Curing for 10min at 80 ℃, and preheating and curing to enable the compound organosilicon glue to be in a gel state;
step three, the upper surface of the finished flexible composite mica sheet is pressed by hot-pressing to form an anti-aging layer 3, meanwhile, the lower surface of the finished flexible composite mica sheet is pressed by hot-pressing to form a water vapor barrier fireproof layer 2 by pressing the high-barrier modified PET substrate in preparation example 7, the lower surface of the high-barrier modified PET substrate 1 is pressed by pressing the lower surface of the high-barrier fireproof layer 2, the pressing temperature of the hot-pressing roller is 250N, and the surface temperature of the hot-pressing roller is 120 ℃, so that a pre-composite sheet is obtained;
step four, carrying out vacuum hot-pressing treatment on the pre-composite sheet in the step three, loading the pre-composite sheet into a hot-pressing mold, sending the pre-composite sheet into a vacuum hot-pressing tank for vacuum hot-pressing forming treatment, controlling the hot-pressing temperature to be 230 ℃, controlling the hot-pressing time to be 30min, and naturally cooling to obtain a semi-finished flexible composite sheet;
Step five, the surface of the THV resin film sheet of the semi-finished flexible composite sheet is coated with a nano coating self-cleaning paint (model IOTA ST2 of Anhui Ai Yaoda silicone oil Co., ltd.) in a scraping way, and is solidified to form a TiO2 self-cleaning layer 30;
step six, the semi-finished flexible composite sheet is back to TiO 2 And pressing the EVA hot melt adhesive film on the surface of the self-cleaning layer 30 to form a glue layer 4, thus obtaining the finished water vapor barrier fireproof flexible back plate.
Example 2
Example 2 differs from example 1 in that: the water vapor barrier fire-resistant layer 2 is a finished flexible composite mica sheet in preparation example 4.
Example 3
Example 3 differs from example 1 in that:
fourthly, performing vacuum hot pressing treatment and heat treatment on the pre-composite sheet in the third step:
the vacuum hot-pressing treatment is divided into five steps, wherein the hot-pressing condition in the first step of vacuum hot-pressing forming is that the temperature of a pressing plate is 80 ℃, the pressure is 0.6Mpa, and the duration time is 30s; the second step of vacuum hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 145 ℃, the pressure is 1.0Mpa, and the duration time is 40s; the third step of vacuum hot press molding, wherein the hot press condition is that the temperature of a pressing plate is 165 ℃, the pressure is 1.6Mpa, and the duration is 80s; the fourth step of vacuum hot press forming, wherein the hot press condition is that the temperature of the pressing plate is 140 ℃, the pressure is 1.0Mpa, the duration time is 40s, the fifth step of vacuum hot press forming, wherein the hot press condition is that the temperature of the pressing plate is 100 ℃, the pressure is 0.8Mpa, the duration time is 40s, and the cooling is carried out to room temperature;
And (3) performing heat treatment on the semi-finished flexible composite sheet subjected to the five-step vacuum hot-pressing treatment, performing heat treatment at 65 ℃ for 120 seconds, heating to 78 ℃ at a heating rate of 0.8 ℃, performing heat treatment at 500 seconds, heating to 125 ℃ at a heating rate of 0.8 ℃, performing heat treatment for 240 seconds, performing cooling to 75 ℃ at a cooling rate of 1.2 ℃ for 200 seconds, performing cooling to 40 ℃ at a speed of 1.2 ℃, performing heat preservation for 6 minutes, and opening the furnace to cool to room temperature.
Example 4
Example 4 differs from example 2 in that:
fourthly, performing vacuum hot pressing treatment and heat treatment on the pre-composite sheet in the third step:
the vacuum hot-pressing treatment is divided into five steps, wherein the hot-pressing condition in the first step of vacuum hot-pressing forming is that the temperature of a pressing plate is 80 ℃, the pressure is 0.6Mpa, and the duration time is 30s; the second step of vacuum hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 145 ℃, the pressure is 1.0Mpa, and the duration time is 40s; the third step of vacuum hot press molding, wherein the hot press condition is that the temperature of a pressing plate is 165 ℃, the pressure is 1.6Mpa, and the duration is 80s; the fourth step of vacuum hot press forming, wherein the hot press condition is that the temperature of the pressing plate is 140 ℃, the pressure is 1.0Mpa, the duration time is 40s, the fifth step of vacuum hot press forming, wherein the hot press condition is that the temperature of the pressing plate is 100 ℃, the pressure is 0.8Mpa, the duration time is 40s, and the cooling is carried out to room temperature;
And (3) performing heat treatment on the semi-finished flexible composite sheet subjected to the five-step vacuum hot-pressing treatment, performing heat treatment at 65 ℃ for 120 seconds, heating to 78 ℃ at a heating rate of 0.8 ℃, performing heat treatment at 500 seconds, heating to 125 ℃ at a heating rate of 0.8 ℃, performing heat treatment for 240 seconds, performing cooling to 75 ℃ at a cooling rate of 1.2 ℃ for 200 seconds, performing cooling to 40 ℃ at a speed of 1.2 ℃, performing heat preservation for 6 minutes, and opening the furnace to cool to room temperature.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: the water vapor barrier fire-resistant layer 2 is a finished flexible composite mica sheet in preparation example 2.
Comparative example 2
Comparative example 2 differs from example 1 in that: the water vapor barrier fire-resistant layer 2 is a finished flexible composite mica sheet in preparation example 3.
Comparative example 3
Comparative example 3 differs from example 1 in that: the water vapor barrier fire-resistant layer 2 is a finished flexible composite mica sheet in preparation example 5.
Comparative example 4
Comparative example 4 differs from example 1 in that: the water vapor barrier fire-resistant layer 2 is a finished flexible composite mica sheet in preparation example 6.
Comparative example 5
Comparative example 5 differs from comparative example 1 in that: the high-barrier modified PET substrate 1 was the final high-barrier modified PET substrate in preparation example 8.
Comparative example 6
Comparative example 6 differs from comparative example 2 in that: the high-barrier modified PET substrate 1 was the final high-barrier modified PET substrate in preparation example 8.
Comparative example 7
Comparative example 7 differs from comparative example 3 in that: the high-barrier modified PET substrate 1 was the final high-barrier modified PET substrate in preparation example 8.
Comparative example 8
Comparative example 8 differs from comparative example 4 in that: the high-barrier modified PET substrate 1 was the final high-barrier modified PET substrate in preparation example 8.
Comparative example 9
Comparative example 9 differs from example 1 in that: the high-barrier modified PET substrate 1 is not compounded with the water vapor barrier fireproof layer 2, and the thickness is controlled to be 350-355 microns.
Performance test
Detection method/test method
1. And (3) glue content testing: the finished flexible composite mica sheets in preparation examples 1-6 were tested according to GB/T5019.2-2009 item 8.4.5, "organic silicone adhesive without reinforced material (insoluble adhesive)".
2. Electrical strength test: GB/T5019.2-2009 mica product test method, 22 nd "electrical strength" test the finished flexible composite mica sheet in preparation examples 1-6.
3. Water vapor transmission test: the test was carried out according to ISO 2528-1995 Standard for gravimetric determination of moisture permeability of sheet Material. The finished high barrier modified PET substrates of preparation examples 7-8 were tested for water vapor transmission.
4. Oxygen transmission amount: the test is carried out according to GB/T19789-2005 Coulomb meter test method for packaging material plastic film and sheet oxidative permeability test. The oxygen transmission rate test was performed on the finished high barrier modified PET substrates in preparation examples 7-8.
5. Wet leakage test: the finished water vapor barrier fire resistant flexible backsheet in examples 1-4 and comparative examples 1-9 were subjected to wet leakage testing. Test description: in the testing process, the finished product water vapor barrier fireproof flexible backboard is immersed in a container containing the required solution, and all surfaces of the finished product water vapor barrier fireproof flexible backboard are covered. The insulation resistance was measured after 2 minutes at 1500 v. The test specification was 800 x 400mm.
6. Exposure test: the finished product water vapor barrier fireproof flexible back plates in examples 1-4 and comparative examples 1-9 are placed outdoors (test time is 12-14 points, southern wind is 1 level, initial environmental temperature is 33.2 ℃ and end environmental temperature is 35.2 ℃), the temperatures of the front side and the back side of the finished product water vapor barrier fireproof flexible back plate are tested every 30min, the temperature difference values of the two sides of the finished product water vapor barrier fireproof flexible back plate are recorded, and the average value of the four temperature difference values is taken as an average temperature difference to reflect the anti-insolation performance of the application.
7. Fire protection test: the final water vapor barrier fire-resistant flexible backsheets of examples 1-4 and comparative examples 1-9 were fire tested. Test conditions: the temperature is 25 ℃, the level of the south wind is 1, and the humidity is 36 percent. The component placement mode is as follows: horizontally placed on an iron frame, and the back surface is suspended. Pretreatment of a combustion block: the dried fuel pieces were soaked in alcohol for 2min. Size of the fuel block: 100 x 200mm. Combustion time: 30min. Combustion region: the surface of the finished product water vapor blocking fireproof flexible back plate facing away from the battery side.
8. Average thickness test: the final moisture barrier fire-resistant flexible back sheets of examples 1-4 and comparative examples 1-9 were tested for thickness using a che-CA thickness gauge, taking five test points, respectively, at the upper left corner, lower left corner, upper right corner, lower right corner, and center. X is X D = (d1+d2+d3+d4+d5)/5, where D1 is the thickness at the upper left corner, D2 is the thickness at the lower left corner, D3 is the thickness at the upper right corner, D4 is the thickness at the lower right corner, and D5 is the thickness at the center.
Data analysis
Table 1 shows the test parameters of the finished flexible composite mica sheets of preparation examples 1-6
| Glue content% | Electrical Strength (kv/mm) | |
| Preparation example 1 | 26.5 | 24.5 |
| Preparation example 2 | 26.4 | 24.3 |
| Preparation example 3 | 26.6 | 23.8 |
| Preparation example 4 | 24.6 | 26.8 |
| Preparation example 5 | 24.6 | 26.3 |
| Preparation example 6 | 24.5 | 26.5 |
Table 2 is the test parameters of the finished high barrier modified PET substrate in preparation examples 7-8
Table 3 shows the final moisture barrier fire-resistant flexible backsheet test parameters for examples 1-4 and comparative examples 1-9
Table 4 is the fire test parameters for the finished moisture barrier fire resistant flexible backsheet of examples 1-4 and comparative examples 1-9
As can be seen by combining preparation example 1-and combining table 1, the finished flexible composite mica sheet has better electrical strength and better insulation protection effect. In addition, the flexibility requirement of the finished flexible composite mica sheet in the application is that the glue content is between 24 and 27 percent, and the electrical strength is reduced to a certain extent, but the flexible composite mica sheet still has good insulation protection effect, has good flame retardant and fireproof performance, and can effectively ensure the integral use safety of the application.
As can be seen from the combination of preparation examples 7 to 8 and table 2, the gas barrier property and the water vapor barrier property of the finished product high-barrier modified PET substrate in preparation example 7 in the present application are better than those of the finished product high-barrier modified PET substrate in preparation example 8, so that the finished product high-barrier modified PET substrate prepared by adopting the processing technology of combining the finished product high-barrier modified PET substrate formulation with the finished product high-barrier modified PET substrate in the present application has good gas barrier property and water vapor barrier property, and the whole good gas barrier property and water vapor barrier property in the present application are given.
As can be seen by combining examples 1-4 and comparative examples 1-9 and by combining table 3, the thickness of the finished water vapor barrier fire-resistant flexible backsheet prepared in this application is controlled to be 0.4-0.5mm, and is relatively thin and lightweight.
As can be seen by combining examples 1-4 and comparative examples 1-9 and combining table 3, the resistance of the finished water vapor barrier fireproof flexible back plate with 800 x 400mm under 1500V compression in a wet leakage test is above 50gΩ, and meets the requirements of the wet leakage test (MQT 15) in IEC 61215-2-2016, so that the finished water vapor barrier fireproof flexible back plate prepared by the method has better wet leakage resistance and gives the whole application safety.
It can be seen from the combination of examples 1 to 4 and comparative examples 1 to 9 and the combination of table 3 that the resistance of the finished water vapor barrier fireproof flexible back sheet in examples 1 to 4 is 50gΩ or more, and the resistance of the finished water vapor barrier fireproof flexible back sheet in comparative example 9 is about 14.6gΩ, so that the moisture barrier fireproof layer can effectively improve the moisture leakage resistance of the present application. In combination with the table 1, the moisture blocking fireproof layer is provided with the moisture leakage resistance, the insulation protection performance, the flame retardance and the fireproof performance, the high temperature resistance and the mechanical strength of the application are effectively improved, and the overall better use safety and longer service life of the application are provided.
As can be seen by combining examples 1-4 and comparative examples 1-9 and combining table 3, the parameters in the exposure test of the present application show that the temperature difference between the front and back sides is above 7 ℃ in the environment with higher outdoor temperature in summer, so that the present application has better anti-exposure performance, and gives the present application overall better service life and use safety.
It can be seen by combining examples 1-4 and comparative examples 1-9 and combining Table 4 that the present application has better fire safety, giving the present application overall better service life and safety in use.
As can be seen from the combination of examples 1-4 and comparative examples 1-9 and table 4, the fire performance of the finished water vapor barrier fire-resistant flexible backsheet in examples 1-4 is better than that of the finished water vapor barrier fire-resistant flexible backsheet in comparative example 9, and therefore, the provision of the water vapor barrier fire-resistant layer can effectively improve the overall fire safety of the present application.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (7)
1. The utility model provides a flexible backplate of steam separation fire prevention which characterized in that: the high-barrier modified PET (polyethylene terephthalate) comprises a high-barrier modified PET substrate (1), wherein a water vapor barrier fireproof layer (2) is integrally formed on the surface of the high-barrier modified PET substrate (1) facing the air side; the back of the water vapor barrier fireproof layer (2)An anti-aging layer (3) is integrally formed on the surface of the high-barrier modified PET substrate (1); the surface of the anti-aging layer (3) facing away from the water vapor barrier fireproof layer (2) is provided with TiO 2 A self-cleaning layer (30); the water vapor barrier fireproof layer (2) is integrally formed on the surface of the high barrier modified PET substrate (1) facing the air side in a hot pressing mode; the anti-aging layer (3) is integrally formed on the upper surface of the water vapor barrier fireproof layer (2) through hot pressing;
a glue layer (4) is compounded on the surface of the high-barrier modified PET substrate (1) facing the battery side; the water vapor blocking fireproof layer (2) is a flexible composite mica sheet; the thickness of the flexible composite mica sheet is 0.15-0.25mm; the flexible composite mica sheet is prepared from phlogopite paper and composite organic silica gel water; the thickness of the phlogopite paper is 30-50 microns; the compound organic silica gel water comprises KR-242A silicone resin and FM-0425 modified hydroxyl siloxane; the mass ratio of the KR-242A silicone resin to the FM-0425 modified hydroxyl siloxane is 100:15-20;
Or the water vapor barrier fireproof layer (2) is a flexible mica die casting sheet; the thickness of the flexible mica die casting sheet is 0.20-0.30mm; the flexible mica die casting sheet is prepared from the following raw materials in parts by weight: 120-140 parts of organic solvent, 20-40 parts of synthetic fluorophlogopite, 60-80 parts of phlogopite, 0.5-1.5 parts of organic titanium surface modifier, 4-8 parts of modified aramid fiber, 0.2-1 part of nano titanium dioxide, 0.1-0.3 part of nano zinc oxide whisker, 0.2-1 part of nano cerium oxide and 32-40 parts of organic silicon resin; the organic silicon resin comprises KR-242A silicon resin and FM-0425 modified hydroxyl siloxane; the mass ratio of the KR-242A silicone resin to the FM-0425 modified hydroxyl siloxane is 100:15-20; an electric conductive coating is formed on the outer wall of the modified aramid fiber; the electric conductive coating is prepared from the following raw materials: graphene, carbon nanotubes, nano titanium dioxide, a surface modifier, a film forming additive, polyurethane emulsion, a pH regulator, a defoaming agent and an organosilicon base material wetting agent;
the high-barrier modified PET substrate (1) is prepared from the following raw materials in percentage by mass: 4-6% of TPEE compound, 10-15% of PEN resin, 10-15% of LCP resin, 0.6-1.2% of ultraviolet absorber, 0.5-1% of nano titanium dioxide, 0.5-1% of polyvinyl alcohol, 0.5-0.8% of KH550 siloxane coupling agent and the balance of PET resin; the PEE compound is one or a plurality of combinations of Hytrel HTR8068, hytrel G4774, hytrel G4778, hytrel G5564 and Hytrel G5526; the content of the Hytrel HTR8068 accounts for 60-70% of the total mass of the TPEE compound; the ultraviolet absorbent is one or a combination of more of poly succinic acid (4-hydroxy-2, 6-tetramethyl 1-piperidinol) ester, 2-hydroxy-4-n-octoxybenzophenone and 2- (2-hydroxy-3, 5-tert-butylphenyl) -5-chlorobenzotriazole.
2. The water vapor barrier fire resistant flexible backsheet of claim 1, wherein: the preparation method of the flexible composite mica sheet comprises the following steps:
step one, preparing compound organosilicon glue;
step two, preparation of phlogopite/composite glue unit paper: the first step of scraping and coating one surface of the phlogopite paper is compounded with the organosilicon glue, and the dosage of the compounded organosilicon glue is 10-12g/m 2 Drying to enable the compound organosilicon glue to be in a gel state;
thirdly, selecting the number of layers of the phlogopite/composite glue unit paper in the second step for superposition according to the thickness requirement of the flexible composite mica sheet, and then compositing the phlogopite paper without the composite silicone glue on the surface of the adjacent phlogopite/composite glue unit paper coated with the composite silicone glue, and preforming by a hot-pressing roller to obtain the flexible composite mica coiled material;
and step four, cutting the flexible composite mica coiled material in the step three to obtain a semi-finished flexible composite mica sheet, carrying out vacuum hot press molding on the semi-finished flexible composite mica sheet, and naturally cooling to obtain the finished flexible composite mica sheet.
3. The water vapor barrier fire resistant flexible backsheet of claim 1, wherein: the preparation method of the flexible mica die casting sheet comprises the following steps:
Step one, preparing modified aramid fibers;
step two, weighing the synthesized fluorophlogopite and phlogopite according to the proportion, and carrying out ultrasonic treatment and dispersion treatment on the synthesized fluorophlogopite and phlogopite and the accurately-metered organic titanium surface modifier to obtain surface modified mixed mica powder;
step three, uniformly mixing the modified mica mixture in the step two with modified aramid fiber, nano titanium dioxide, nano zinc oxide whisker, nano cerium oxide and an organic solvent, adding organic silicon resin, and uniformly stirring to obtain mica slurry;
injecting the mica slurry into a forming die, placing the forming die between two polar plates of a capacitor, enabling the electric field direction of the capacitor and the height direction of the forming die to be in the same direction, performing electric field treatment for 20-40min, performing heating treatment on the forming die after performing electric field treatment for 10min, removing organic solvents in the mica slurry, performing heating treatment on the forming die for 5-10min after performing electric field treatment, and performing hot press forming to obtain a finished flexible mica coiled material;
and fifthly, cutting the finished flexible mica coiled material to obtain a finished flexible mica sheet, and performing vacuum hot press molding on the finished flexible mica sheet to obtain the finished flexible composite mica sheet.
4. The water vapor barrier fire resistant flexible backsheet of claim 1, wherein: the preparation method of the high-barrier modified PET substrate (1) comprises the following steps:
Step one, placing PEN resin, PET resin, LCP resin and TPEE compound at 80-90 ℃ and drying for 2-4 hours for later use;
uniformly mixing the PEN resin, the PET resin, the LCP resin, the TPEE compound, the ultraviolet absorbent, the nano titanium dioxide, the KH550 siloxane coupling agent and the polyvinyl alcohol which are dried in the first step, extruding, granulating, water-cooling and granulating to obtain modified PET granules with the granularity of 1.5-2.2 mm;
step three, the modified PET granules in the step two are placed at 80-90 ℃ and dried for 2-4 hours, and the moisture content is lower than 0.5 percent and stored for standby;
extruding, casting to form a film, and naturally cooling to obtain the high-barrier modified PET coiled material;
and fifthly, cutting Gao Zuge modified PET coiled material, performing heat treatment for 25-40min, controlling the heat treatment temperature to 68-72 ℃, and cooling and rolling to obtain the finished high-barrier modified PET substrate.
5. The water vapor barrier fire resistant flexible backsheet of claim 1, wherein: the anti-aging layer (3) is a fluororesin film; the fluorine resin film is one of an ETFE resin film, a PTFE resin film, a PVDF resin film and a THV resin film; the fluororesin film faces away from the TiO 2 The self-cleaning layer (30) is formed with an adhesion-promoting layer (31) by low-temperature plasma treatment on the surface.
6. A method for preparing a water vapor barrier fire resistant flexible backsheet as defined in any one of claims 1 to 5, wherein: the method comprises the following steps:
preparing a water vapor barrier fireproof layer material, a high-barrier modified PET substrate and a fluororesin film;
coating the water surface of the water vapor barrier fireproof layer (2) with compound organic silica gel, wherein the water consumption of the compound organic silica gel is controlled to be 10-12g/m 2 Preheating and solidifying to enable the compound organosilicon glue to be in a gel state;
step three, rolling an anti-aging layer (3) on the upper surface of the water vapor barrier fireproof layer (2), rolling a high-barrier modified PET substrate (1) on the lower surface of the water vapor barrier fireproof layer (2), and rolling for 200-250N to obtain a pre-composite sheet;
step four, performing vacuum hot-pressing treatment on the pre-composite sheet in the step three to obtain a semi-finished flexible composite sheet;
step five, spraying self-cleaning paint on the surface of the anti-aging layer (3) of the semi-finished flexible composite sheet to form TiO (titanium dioxide) 2 A self-cleaning layer (30);
step six, the semi-finished flexible composite sheet is back to TiO 2 And (3) coating an adhesive on the surface of the self-cleaning layer (30) to form a glue layer (4) so as to obtain the finished water vapor barrier fireproof flexible back plate.
7. The method for preparing the water vapor barrier fireproof flexible back plate according to claim 6, wherein the method comprises the following steps: the vacuum hot-pressing treatment in the fourth step is divided into five steps of vacuum hot-pressing treatment, wherein the hot-pressing condition in the first step of vacuum hot-pressing forming is that the temperature of a pressing plate is 80-100 ℃, the pressure is 0.4-0.6Mpa, and the duration is 30-40s; the second step of vacuum hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 140-150 ℃, the pressure is 0.8-1.0Mpa, and the duration time is 30-40s; the third step of vacuum hot press forming, wherein the hot press condition is that the temperature of a pressing plate is 160-165 ℃, the pressure is 1.5-1.8Mpa, and the duration is 60-80s; the fourth step is that the hot pressing condition in the vacuum hot pressing forming is that the temperature of the pressing plate is 130-140 ℃, the pressure is 0.8-1.0Mpa, the duration is 30-40s, the fifth step is that the hot pressing condition in the vacuum hot pressing forming is that the temperature of the pressing plate is 100-110 ℃, the pressure is 0.6-0.8Mpa, the duration is 30-40s, the cooling is carried out to room temperature, the semi-finished flexible composite sheet after the five steps of vacuum hot pressing treatment is carried out heat treatment, the heat treatment is carried out for 100-120s at 60-65 ℃, the heat treatment is carried out for 300-500s at 75-80 ℃, the heat treatment is carried out for 200-250s at 120-125 ℃, the heat preservation is carried out for 180-300s at 60-80 ℃, the temperature is reduced to 40-45 ℃ at the speed of 0.8-1.2 ℃ for 5-10min, and the semi-finished flexible composite sheet is cooled to room temperature in a furnace.
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| CN102054878B (en) * | 2009-10-27 | 2013-02-06 | 苏州中来光伏新材股份有限公司 | High barrier ultraviolet ray aging resistant solar cell back film and processing technique thereof |
| JP2011254038A (en) * | 2010-06-04 | 2011-12-15 | Kaneka Corp | Backseat for solar cell and solar cell module |
| US20120312366A1 (en) * | 2010-12-22 | 2012-12-13 | E. I. Du Pont De Nemours And Company | Fire resistant back-sheet for photovoltaic module |
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