High-temperature-resistant protective film for amorphous silicon solar cell and preparation method of high-temperature-resistant protective film
By applying a protective film composed of a release film layer, a high-temperature adhesive layer and a PET layer on an amorphous silicon solar cell, the problem of oxidation failure of the amorphous silicon layer at high temperature is solved, and the effect of improving the thermal conductivity and heat resistance of the battery is achieved.
Patent Information
- Application Number
- CN202411380568.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2025-06-03
AI Technical Summary
When amorphous silicon solar cells undergo photovoltaic glass silicon coating reflow soldering at high temperatures, the amorphous silicon layer is prone to oxidation failure, resulting in a degradation of battery performance.
Amorphous silicon solar cell high-temperature protection film consisting of a release film layer, a high-temperature rubber layer and a PET layer are used. The high-temperature rubber layer is an acrylic polymer binder, containing branched copper/silica, and cured by UV light irradiation.
It improves the thermal conductivity and heat resistance of amorphous silicon solar cells at high temperatures, prevents the oxidation of the amorphous silicon layer, and extends the service life of the battery.
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Abstract
Description
Technical Field
[0001] The invention relates to the field of release films, and in particular to a high-temperature resistant protective film for an amorphous silicon solar cell and a preparation method thereof. Background Art
[0002] Existing amorphous silicon solar cells are usually manufactured using methods such as plasma enhanced chemical vapor deposition, reactive sputtering, glow discharge, electron beam evaporation and thermal decomposition silane. The general process of amorphous silicon solar cell production includes the following steps: 1) Use an edge grinding and cleaning machine to remove the edges, oil stains and impurities on the transparent conductive film; 2) Etch lines on the conductive glass using infrared light with a wavelength of 1064 nanometers or acid-base solutions to achieve isolation effects; 3) Then vacuum coat and deposit a PIN structured amorphous silicon layer on the conductive film surface; 4) Then A green light with a wavelength of 532 is used to draw a line on the amorphous silicon layer; 5) Conductive paste, ink characters, etc. are then printed on the surface of the amorphous silicon by screen printing, and then the product is obtained after solder cutting, testing and packaging. The existing soldering process is mainly manual or machine spot welding, which is inefficient. The newly developed process is to apply solder paste to the position where the whole piece needs to be welded by the machine and then bake it at a high temperature of 260°C for 10-15 minutes. The efficiency is very high, but the amorphous silicon layer of this process will oxidize and fail after high temperature, so a layer of high temperature resistant protective film is needed to protect the amorphous silicon layer from oxidation. Summary of the invention
[0003] Technical problem to be solved: The purpose of the present invention is to provide a high temperature resistant protective film for amorphous silicon solar cells to solve the problem of high temperature process protection of the silicon coating of photovoltaic glass of amorphous silicon solar cells during reflow soldering.
[0004] Technical solution: A high temperature resistant protective film for amorphous silicon solar cells, the protective film consisting of a release film layer, a high temperature resistant adhesive layer and a PET layer, the release film layer and the PET layer are compounded by the high temperature resistant adhesive layer, and the high temperature resistant adhesive layer is an acrylic polymer adhesive. Preferably, the acrylic polymer binder is composed of the following components in parts by weight: Acrylic polymer curable precursor 50-140 parts Silane coupling agent 0.1-5 parts Antioxidant 0.1-5 parts Dendritic copper / silicon dioxide 1-5 parts 1-30 parts of heat-resistant additives; Among them, the preparation method of the curable precursor of the acrylic polymer is as follows: 70 - 80 parts of isooctyl acrylate, 2 - 4 parts of isooctyl methacrylate, 13 - 15 parts of 2 - hydroxyethyl acrylate, 2 - 4 parts of acrylic acid, 4 - 6 parts of isobornyl acrylate, 0.01 - 0.02 parts of n - dodecyl mercaptan and 0.1 - 0.2 parts of 1 - hydroxycyclohexyl phenyl ketone are stirred at a rotation speed of 120 rpm, and nitrogen is introduced with a flow rate of 700 - 900 mL / min. After stirring for 40 - 60 min, it is irradiated under a UV lamp until the reaction reaches a viscosity of 2500 cps to stop the reaction and obtain a prepolymer. Then, 0.1 - 0.2 parts of 2,4,6 - trimethylbenzoyl - diphenylphosphine oxide and 0.15 - 0.25 parts of 1,6 - hexanediol diacrylate are added to the prepolymer, and stirred and dispersed evenly to obtain the curable precursor of the acrylic polymer. Preferably, the preparation method of the dendritic copper / silica includes the following steps: S1. After cutting and crushing the straw, washing and drying it, adding it to water, and then performing high - speed shearing to obtain nano - straw fibers with a certain aspect ratio. S2. The straw fibers prepared in step S1 are subjected to steam explosion treatment to obtain dendritic nano - straw fibers. S3. After adding the dendritic straw fibers to ethanol and ultrasonically dispersing them evenly, adding water, stirring evenly, continuing to add tetraethyl orthosilicate under stirring, then adding ammonia water to adjust the pH to 9 - 10, stirring and reacting for 20 - 30 min, filtering, drying, and sintering to obtain dendritic hollow silica. S4. The dendritic hollow silica prepared in step S3 is added to a PVP solution containing copper sulfate, and ultrasonically stirred so that copper sulfate is adsorbed on the surface and in the hollow layer of the dendritic hollow silica, and then a sodium borohydride solution is added to obtain dendritic copper / silica. Preferably, the crushing length of the straw is 0.5 - 1.5 cm, the high - speed shearing rate is 8000 - 12000 rpm, and the high - speed shearing time is 10 - 20 min. Preferably, the explosion pressure of the steam explosion treatment is 1 - 1.5 MPa, and the pressure - maintaining time is 5 - 20 min. Preferably, the concentration of the PVP solution is 1 - 3 wt%, the concentration of copper sulfate in the PVP solution is 1 - 3 wt%, and the mass ratio of copper sulfate to sodium borohydride is 8 - 9:1. Preferably, the mass - to - volume ratio of the dendritic straw fibers, ethanol, water, and tetraethyl orthosilicate is 10 - 20:40 - 50:4.5 - 5.5:4.5 - 5.5. The preparation method of the above - mentioned high - temperature resistant protective film for amorphous silicon solar cells, the preparation method includes the following steps: Mix the components in the acrylate - based polymer binder to obtain a high - temperature resistant binder. The obtained high-temperature resistant binder is coated between the PET layer and the release film, and irradiated with 365 nm UV light for 10 - 20 min to obtain a high-temperature resistant protective film for amorphous silicon solar cells. Beneficial effects: The high-temperature resistant protective film for amorphous silicon solar cells of the present invention has the following advantages: 1. The protective film in the present invention is composed of a release film layer, a high-temperature resistant adhesive layer, and a PET layer. The high-temperature resistant layer contains dendritic copper / silica. The composite material of this structure is a dendritic structure, and adjacent or close dendritic copper / silica are in contact with each other to form a heat conduction path, improving the heat conduction effect of the high-temperature resistant layer; 2. In the present invention, a composite dendritic material is prepared from copper and silica. The silica prepared using straw as a template has a hollow structure in the middle. In order to improve the heat conduction effect of silica, metallic copper is filled in the middle layer and coated on the surface layer of silica, which can further improve the heat resistance performance; 3. In the present invention, straw is used as a template material. During the preparation of the template material, through the action of high-speed shearing, the straw is crushed into nanofibers with a certain aspect ratio, and then steam explosion is used to disperse the nanofibers, making the nanofibers into discrete dendritic shapes. Such a template can be used to prepare dendritic silica. Specific embodiments The present invention will be further described below in conjunction with embodiments. The following embodiments are explanations of the present invention and the present invention is not limited to the following embodiments: Embodiment 1 A preparation method of a high-temperature resistant protective film for amorphous silicon solar cells, the preparation method comprising the following steps: Mix each component in an acrylate polymer binder to obtain a high-temperature resistant binder; Coat the obtained high-temperature resistant binder between the PET layer and the release film, and irradiate with 365 nm UV light for 10 min to obtain a high-temperature resistant protective film for amorphous silicon solar cells; The acrylate polymer binder is composed of the following components by weight: 140 parts of a curable precursor of an acrylic polymer 5 parts of a silane coupling agent 5 parts of antioxidant 1010 5 parts of dendritic copper / silica 30 parts of high-temperature resistant additive Sanhe and SD - 1227AX; Among them, the preparation method of the curable precursor of the acrylic polymer is as follows: 70 parts of isooctyl acrylate, 2 parts of isooctyl methacrylate, 13 parts of 2-hydroxyethyl acrylate, 2 parts of acrylic acid, 4 parts of isobornyl acrylate, 0.01 part of n-dodecyl mercaptan and 0.1 part of 1-hydroxycyclohexyl phenyl ketone are stirred at a rotation speed of 120 rpm, and nitrogen is introduced with a flow rate of 700 mL / min. After stirring for 60 min, it is placed under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction and obtain a prepolymer. 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.15 part of 1,6-hexanediol diacrylate are added to the prepolymer and stirred and dispersed evenly to obtain the curable precursor of the acrylic polymer; The preparation method of the dendritic copper / silica includes the following steps: S1. The straw is sheared and then crushed, and the crushing length of the straw is 0.5 - 1.5 cm. After washing and drying, it is added to water, and then high-speed shearing is carried out at a high-speed shearing rate of 8000 rpm for 20 min to obtain nano-straw fibers with a certain aspect ratio; S2. The straw fibers prepared in step S1 are subjected to steam explosion treatment with a blasting pressure of 1.5 MPa and a pressure-holding time of 5 min to obtain dendritic nano-straw fibers; S3. After the dendritic straw fibers are ultrasonically dispersed evenly in ethanol, water is added and stirred evenly. Under the stirring state, tetraethyl orthosilicate is continuously added. The mass-volume ratio of the dendritic straw fibers, ethanol, water, and tetraethyl orthosilicate is 20:50:5.5:5.5. Then ammonia water is added to adjust the pH to 9, and after stirring and reacting for 30 min, it is filtered, dried, and sintered to obtain dendritic hollow silica; S4. The dendritic hollow silica prepared in step S3 is added to a PVP solution containing 3 wt% of copper sulfate, and the concentration of copper sulfate in the PVP solution is 1 wt%. Ultrasonic stirring is carried out to adsorb copper sulfate on the surface and in the hollow layer of the dendritic hollow silica, and then a sodium borohydride solution is added. The mass ratio of copper sulfate to sodium borohydride is 8:1 to obtain dendritic copper / silica. Example 2 A preparation method of a high-temperature resistant protective film for an amorphous silicon solar cell, the preparation method includes the following steps: Each component in the acrylate polymer binder is mixed to obtain a high-temperature resistant binder; The obtained high-temperature resistant binder is coated between the PET layer and the release film and irradiated with 365 nm UV light for 20 min to obtain a high-temperature resistant protective film for an amorphous silicon solar cell; The acrylate polymer binder is composed of the following components by weight: 50 parts of curable precursor of acrylic polymer 0.1 part of silane coupling agent 0.1 part of antioxidant 1010 1 part of dendritic copper / silica 1 part of heat-resistant additive Sanhe SD-1227AX; Among them, the preparation method of the curable precursor of the acrylic polymer is as follows: Stir 80 parts of isooctyl acrylate, 4 parts of isooctyl methacrylate, 15 parts of 2-hydroxyethyl acrylate, 4 parts of acrylic acid, 6 parts of isobornyl acrylate, 0.02 part of n-dodecyl mercaptan and 0.2 part of 1-hydroxycyclohexyl phenyl ketone at a rotation speed of 120 rpm, and introduce nitrogen with a flow rate of 900 mL / min. After stirring for 40 min, place it under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. Add 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.25 part of 1,6-hexanediol diacrylate to the prepolymer, and stir and disperse evenly to obtain the curable precursor of the acrylic polymer; The preparation method of the dendritic copper / silica includes the following steps: S1. Cut and crush the straw, the crushing length of the straw is 0.5 - 1.5 cm. After washing and drying, add it to water, and then carry out high-speed shearing. The high-speed shearing rate is 12000 rpm, and the high-speed shearing time is 10 min to obtain nano-straw fibers with a certain aspect ratio; S2. Carry out steam explosion treatment on the straw fibers prepared in step S1, the explosion pressure is 1 MPa, and the pressure maintaining time is 20 min to obtain dendritic nano-straw fibers; S3. After adding the dendritic straw fibers to ethanol and ultrasonic dispersing evenly, add water, stir evenly, and continue to add tetraethyl orthosilicate under stirring. The mass-volume ratio of the dendritic straw fibers, ethanol, water and tetraethyl orthosilicate is 10:40:4.5:4.5. Then add ammonia water to adjust the pH to 10, stir and react for 30 min, filter and dry, and sinter to obtain dendritic hollow silica; S4. Add the dendritic hollow silica prepared in step S3 to a PVP solution containing 1 wt% of copper sulfate, the concentration of copper sulfate in the PVP solution is 1 wt%, and ultrasonically stir to adsorb copper sulfate on the surface and in the hollow layer of the dendritic hollow silica. Then add sodium borohydride solution, and the mass ratio of copper sulfate to sodium borohydride is 9:1 to obtain dendritic copper / silica. Example 3 A preparation method of a high-temperature resistant protective film for an amorphous silicon solar cell, the preparation method includes the following steps: Mix the components in the acrylate polymer binder to obtain a high-temperature resistant binder; Coat the obtained high-temperature resistant binder between the PET layer and the release film, and irradiate with 365 nm UV light for 10 min to obtain a high-temperature resistant protective film for an amorphous silicon solar cell; The acrylate polymer binder is composed of the following components by weight: 80 parts of curable precursor of acrylic polymer 1 part of silane coupling agent 0.5 part of antioxidant 1010 3 parts of dendritic copper / silica 5 parts of heat-resistant additive Sanhe SD-1227AX; Among them, the preparation method of the curable precursor of acrylic polymer is as follows: 72 parts of isooctyl acrylate, 3 parts of isooctyl methacrylate, 13 parts of 2-hydroxyethyl acrylate, 2.4 parts of acrylic acid, 4.5 parts of isobornyl acrylate, 0.02 part of n-dodecyl mercaptan and 0.1 part of 1-hydroxycyclohexyl phenyl ketone are stirred at a rotation speed of 120 rpm, and nitrogen is introduced, and the flow rate is 750 mL / min. After stirring for 55 min, it is placed under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.15 part of 1,6-hexanediol diacrylate are added to the prepolymer, and stirred and dispersed evenly to obtain the curable precursor of acrylic polymer; The preparation method of the dendritic copper / silica includes the following steps: S1. Cut and crush the straw, the crushing length of the straw is 0.5 - 1.5 cm. After washing and drying, add it to water, and then carry out high-speed shearing. The high-speed shearing rate is 9000, and the high-speed shearing time is 18 min to obtain nano-straw fibers with a certain aspect ratio; S2. Carry out steam explosion treatment on the straw fibers prepared in step S1, the explosion pressure is 1.4 MPa, and the pressure maintaining time is 15 min to obtain dendritic nano-straw fibers; S3. After ultrasonically dispersing the dendritic straw fibers evenly in ethanol, add water, stir evenly, and continue to add tetraethyl orthosilicate under stirring. The mass-volume ratio of dendritic straw fibers, ethanol, water and tetraethyl orthosilicate is 13:43:4.8:4.8. Then add ammonia water to adjust the pH to 9, stir and react for 20 min, filter and dry, and sinter to obtain dendritic hollow silica; S4. Add the dendritic hollow silica prepared in step S3 to a PVP solution containing 1.5 wt% of copper sulfate, and the concentration of copper sulfate in the PVP solution is 2.5 wt%. Ultrasonically stir to adsorb copper sulfate on the surface and in the hollow layer of the dendritic hollow silica, and then add sodium borohydride solution. The mass ratio of copper sulfate to sodium borohydride is 9:1 to obtain dendritic copper / silica. , Example 4 A preparation method of a high-temperature resistant protective film for amorphous silicon solar cells, the preparation method includes the following steps: Mix the components in the acrylate polymer binder to obtain a high-temperature resistant binder; Coat the obtained high-temperature resistant binder between the PET layer and the release film, and irradiate with 365 nm UV light for 20 min to obtain a high-temperature resistant protective film for amorphous silicon solar cells; The acrylate polymer binder is composed of the following components by weight: 120 parts of a curable precursor of an acrylic polymer 2 parts of a silane coupling agent 2 parts of antioxidant 1010 5 parts of dendritic copper / silica 10 parts of heat-resistant additive Sanhe SD-1227AX; Among them, the preparation method of the curable precursor of the acrylic polymer is as follows: Mix 78 parts of isooctyl acrylate, 3.6 parts of isooctyl methacrylate, 13 parts of 2-hydroxyethyl acrylate, 3.5 parts of acrylic acid, 5.5 parts of isobornyl acrylate, 0.01 part of n-dodecyl mercaptan and 0.2 part of 1-hydroxycyclohexyl phenyl ketone, stir at a rotation speed of 120 rpm, and introduce nitrogen with a flow rate of 850 mL / min. After stirring for 45 min, place it under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. Add 0.2 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.25 part of 1,6-hexanediol diacrylate to the prepolymer, and stir and disperse evenly to obtain a curable precursor of an acrylic polymer; The preparation method of the dendritic copper / silica includes the following steps: S1. Cut and crush the straw, the crushing length of the straw is 0.5 - 1.5 cm. After washing and drying, add it to water, and then carry out high-speed shearing at a high-speed shearing rate of 11000 rpm for 13 min to obtain nano-straw fibers with a certain aspect ratio; S2. Carry out steam explosion treatment on the straw fibers prepared in step S1, with a blasting pressure of 1.2 MPa and a pressure maintaining time of 10 min to obtain dendritic nano-straw fibers; S3. After ultrasonic dispersion of the dendritic straw fibers in ethanol, add water, stir evenly, and continue to add tetraethyl orthosilicate under stirring. The mass-volume ratio of dendritic straw fibers, ethanol, water and tetraethyl orthosilicate is 17:47:5.2:5.2. Then add ammonia water to adjust the pH to 10, stir and react for 30 min, filter, dry, and sinter to obtain dendritic hollow silica; S4. Add the dendritic hollow silica prepared in step S3 to a PVP solution containing 2.5 wt% copper sulfate, where the concentration of copper sulfate in the PVP solution is 1.5 wt%. Stir ultrasonically to adsorb copper sulfate on the surface and in the hollow layer of the dendritic hollow silica, and then add a sodium borohydride solution. The mass ratio of copper sulfate to sodium borohydride is 8:1 to obtain dendritic copper / silica. Example 5 A method for preparing a high-temperature resistant protective film for an amorphous silicon solar cell, the preparation method comprising the following steps: Mix the components in the acrylate polymer binder to obtain a high-temperature resistant binder; Coat the obtained high-temperature resistant binder between the PET layer and the release film, and irradiate with 365 nm UV light for 15 min to obtain a high-temperature resistant protective film for an amorphous silicon solar cell; The acrylate polymer binder is composed of the following components by weight: 100 parts of a curable precursor of an acrylic polymer 1.5 parts of a silane coupling agent 1 part of antioxidant 1010 5 parts of dendritic copper / silica 10 parts of high-temperature resistant additive Sanhe and SD-1227AX; Among them, the preparation method of the curable precursor of the acrylic polymer is: Stir 75 parts of isooctyl acrylate, 3 parts of isooctyl methacrylate, 14 parts of 2-hydroxyethyl acrylate, 3 parts of acrylic acid, 5 parts of isobornyl acrylate, 0.01 part of n-dodecyl mercaptan and 0.1 part of 1-hydroxycyclohexyl phenyl ketone at a rotation speed of 120 rpm, and introduce nitrogen with a flow rate of 800 mL / min. After stirring for 50 min, place it under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. Add 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.25 part of 1,6-hexanediol diacrylate to the prepolymer, and stir and disperse evenly to obtain a curable precursor of an acrylic polymer; The preparation method of the dendritic copper / silica comprises the following steps: S1. Cut and crush the straw. The crushed length of the straw is 0.5 - 1.5 cm. After washing and drying, add it to water, and then perform high-speed shearing. The high-speed shearing rate is 10000 rpm, and the high-speed shearing time is 15 min to obtain nano-straw fibers with a certain aspect ratio; S2. Perform steam explosion treatment on the straw fibers prepared in step S1. The explosion pressure is 1.5 MPa and the pressure maintaining time is 10 min to obtain dendritic nano-straw fibers; S3. After adding dendritic straw fiber into ethanol and ultrasonically dispersing it evenly, add water, stir evenly, and then continue to add tetraethyl orthosilicate under stirring. The mass-volume ratio of dendritic straw fiber, ethanol, water, and tetraethyl orthosilicate is 15:45:5:5. Then add ammonia water to adjust the pH to 10, stir and react for 25 min, filter, dry, and sinter to obtain dendritic hollow silica; S4. Add the dendritic hollow silica prepared in step S3 into a PVP solution containing 2 wt% of copper sulfate, where the concentration of copper sulfate in the PVP solution is 2 wt%. Ultrasonically stir to adsorb copper sulfate on the surface and in the hollow layer of the dendritic hollow silica, and then add a sodium borohydride solution. The mass ratio of copper sulfate to sodium borohydride is 8.5:1 to obtain dendritic copper / silica. Comparative Example 1 A preparation method of a high-temperature resistant protective film for an amorphous silicon solar cell, the preparation method comprising the following steps: Mix the components in the acrylate polymer binder to obtain a high-temperature resistant binder; Coat the obtained high-temperature resistant binder between a PET layer and a release film, and irradiate with 365 nm UV light for 15 min to obtain a high-temperature resistant protective film for an amorphous silicon solar cell; The acrylate polymer binder is composed of the following components by weight: 100 parts of a curable precursor of an acrylic polymer 1.5 parts of a silane coupling agent 1 part of antioxidant 1010 5 parts of silica 10 parts of heat-resistant additive Sanhe and SD-1227AX; Among them, the preparation method of the curable precursor of the acrylic polymer is: Stir 75 parts of isooctyl acrylate, 3 parts of isooctyl methacrylate, 14 parts of 2-hydroxyethyl acrylate, 3 parts of acrylic acid, 5 parts of isobornyl acrylate, 0.01 part of n-dodecyl mercaptan, and 0.1 part of 1-hydroxycyclohexyl phenyl ketone at a rotation speed of 120 rpm, and introduce nitrogen with a flow rate of 800 mL / min. After stirring for 50 min, place it under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. Add 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.25 part of 1,6-hexanediol diacrylate to the prepolymer, and stir and disperse evenly to obtain a curable precursor of an acrylic polymer. Comparative Example 2 A preparation method of a high-temperature resistant protective film for an amorphous silicon solar cell, the preparation method comprising the following steps: Mix the components in the acrylate polymer binder to obtain a high-temperature resistant binder; The obtained high-temperature resistant binder is coated between the PET layer and the release film, and irradiated with 365 nm UV light for 15 min to obtain a high-temperature resistant protective film for amorphous silicon solar cells; The acrylate polymer binder is composed of the following components by weight: 100 parts of acrylate polymer curable precursor 1.5 parts of silane coupling agent 1 part of antioxidant 1010 5 parts of copper / silica 10 parts of temperature-resistant additive Sanhe SD-1227AX; Among them, the preparation method of the acrylate polymer curable precursor is as follows: 75 parts of isooctyl acrylate, 3 parts of isooctyl methacrylate, 14 parts of hydroxyethyl acrylate, 3 parts of acrylic acid, 5 parts of isobornyl acrylate, 0.01 part of n-dodecyl mercaptan and 0.1 part of 1-hydroxycyclohexyl phenyl ketone are stirred at a rotation speed of 120 rpm, and nitrogen is introduced, and its flow rate is 800 mL / min. After stirring for 50 min, it is placed under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.25 part of 1,6-hexanediol diacrylate are added to the prepolymer, and stirred and dispersed evenly to obtain the acrylate polymer curable precursor; The preparation method of the copper / silica includes the following steps: S1. Cut and crush the straw, the length of the crushed straw is 0.5-1.5 cm. After washing and drying, add it to water, and then carry out high-speed shearing. The high-speed shearing rate is 10000 rpm, and the high-speed shearing time is 15 min to obtain nano-straw fibers with a certain aspect ratio; S2. After adding the straw fibers to ethanol and ultrasonic dispersing evenly, add water, stir evenly, and continue to add tetraethyl orthosilicate under stirring. The mass-volume ratio of dendritic straw fibers, ethanol, water and tetraethyl orthosilicate is 15:45:5:5, then add ammonia water to adjust the pH to 10, stir and react for 25 min, filter and dry, and sinter to obtain dendritic hollow silica; S3. Add the hollow silica prepared in step S2 to a PVP solution containing 2 wt% of copper sulfate, and the concentration of copper sulfate in the PVP solution is 2 wt%. Ultrasonic stirring is used to adsorb copper sulfate on the surface and in the hollow layer of the hollow silica, and then a sodium borohydride solution is added. The mass ratio of copper sulfate to sodium borohydride is 8.5:1 to obtain copper / silica. Comparative Example 3 A preparation method of a high-temperature resistant protective film for amorphous silicon solar cells, the preparation method includes the following steps: Mix the components in the acrylate polymer binder to obtain a high-temperature resistant binder; The obtained high-temperature resistant binder is coated between the PET layer and the release film, and irradiated with 365 nm UV light for 15 min to obtain a high-temperature resistant protective film for amorphous silicon solar cells; The acrylate polymer binder is composed of the following components by weight: 100 parts of a curable precursor of an acrylic polymer 1.5 parts of a silane coupling agent 1 part of antioxidant 1010 5 parts of dendritic copper / silica 10 parts of heat-resistant additive Sanhe SD-1227AX; Among them, the preparation method of the curable precursor of the acrylic polymer is as follows: 75 parts of isooctyl acrylate, 3 parts of isooctyl methacrylate, 14 parts of 2-hydroxyethyl acrylate, 3 parts of acrylic acid, 5 parts of isobornyl acrylate, 0.01 part of n-dodecyl mercaptan and 0.1 part of 1-hydroxycyclohexyl phenyl ketone are stirred at a rotation speed of 120 rpm, and nitrogen is introduced with a flow rate of 800 mL / min. After stirring for 50 min, it is placed under a UV lamp for irradiation reaction until the viscosity reaches 2500 cps to stop the reaction to obtain a prepolymer. 0.1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.25 part of 1,6-hexanediol diacrylate are added to the prepolymer, and stirred and dispersed evenly to obtain a curable precursor of an acrylic polymer; The preparation method of the dendritic copper / silica includes the following steps: S1. The straw is cut and then crushed. The length of the crushed straw is 0.5 - 1.5 cm. After washing and drying, it is added to water, and then subjected to high-speed shearing at a high-speed shearing rate of 10000 rpm for 15 min to obtain nano-straw fibers with a certain aspect ratio; S2. The straw fibers prepared in step S1 are subjected to steam explosion treatment at a blasting pressure of 1.5 MPa and a pressure-holding time of 10 min to obtain dendritic nano-straw fibers; S3. After the dendritic straw fibers are ultrasonically dispersed evenly in ethanol, water is added and stirred evenly. Under stirring, tetraethyl orthosilicate is continuously added. The mass-volume ratio of dendritic straw fibers, ethanol, water and tetraethyl orthosilicate is 15:45:5:5. Then ammonia water is added to adjust the pH to 10. After stirring and reacting for 25 min, it is filtered, dried and sintered to obtain dendritic hollow silica. Performance test: Adhesion test: The 60 μm thick sample is cut into 25 mm wide, the release film is removed and adhered to a sus standard test steel plate. The end of each strip is clamped in the tensile fixture of a tensile machine (AND tensile machine) and peeled at a speed of 300 mm / min, and 5 groups of data are tested; High-temperature glass adhesion (260°C for 10 min): Cut a 60-μm-thick sample into strips 25 mm wide, remove the release film, attach it to a glass substrate, place it at 260°C for 10 min, clamp the end of each strip to the tensile fixture of a tensile testing machine (AND tensile testing machine), and peel it at a speed of 300 mm / min. Test 5 groups of data; Crosslinking degree: Cut a 60-μm-thick sample into strips 50 mm * 50 mm wide, weigh it to get a. Immerse the sample in ethyl acetate solvent for 72 h, then take it out and bake it in an oven at 150°C for 30 min to get b. Then completely remove the adhesive layer from the PET substrate and weigh the PET substrate to get c. Crosslinking degree = (b - c) / (a - c) * 100; High-temperature holding force: The high-temperature static shear test is carried out at 80°C with a 1000-g hanging weight (according to test method AFERA5012). Cut a pressure-sensitive adhesive film strip 13 mm wide and 25 mm long longitudinally from the sample, and place the sample on a clean steel test plate. Then place the opposite side of the test sample on an aluminum plate with holes for fixing the weight with a light finger pressure. Roll a standard FINAT test roller (weighing 6.8 kg) twice in each direction at a speed of about 10 mm / s to obtain close contact between the pressure-sensitive adhesive substance and the substrate surface (test). After applying the pressure-sensitive adhesive film strip (sample) to the test plate, before testing, allow the test plate to have a pressure-holding time of 72 h at room temperature (23°C + / - 2°C, 50% relative humidity + / - 5%). Place the test panel in a shear holding device. At 80°C, after a 10-min pressure-holding time, hang a 1000-g load in the hole of the aluminum test plate; start the timer, record the result in minutes until failure, and the result is the average of two shear measurements ("10000+" recorded time indicates that when the test is stopped, the strip does not fail after 10000 min). Obviously, the above embodiments are only examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.
Claims
1. A high temperature resistant protective film for amorphous silicon solar cells, characterized in that: The protective film is composed of a release film layer, a high temperature resistant adhesive layer and a PET layer. The release film layer and the PET layer are compounded by the high temperature resistant adhesive layer. The high temperature resistant adhesive layer is an acrylic polymer adhesive.
2. The amorphous silicon solar cell high temperature resistant protective film according to claim 1, characterized in that: The acrylic polymer binder is composed of the following components in parts by weight: Acrylic polymer curable precursor 50-140 parts Silane coupling agent 0.1-5 parts Antioxidant 0.1-5 parts Dendritic copper / silicon dioxide 1-5 parts 1-30 parts of heat-resistant additives; The preparation method of the acrylic polymer curable precursor is as follows: 70-80 parts of isooctyl acrylate, 2-4 parts of isooctyl methacrylate, 13-15 parts of hydroxyethyl acrylate, 2-4 parts of acrylic acid, 4-6 parts of isobornyl acrylate, 0.01-0.02 parts of n-dodecyl mercaptan and 0.1-0.2 parts of 1-hydroxycyclohexyl phenyl ketone are stirred at a rotation speed of 120 rpm, and nitrogen is introduced at a flow rate of 700-900 mL / min. After stirring for 40-60 minutes, the mixture is placed under a UV lamp for irradiation and the reaction is stopped until the viscosity reaches 2500 cps to obtain a prepolymer, and 0.1-0.2 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0.15-0.25 parts of 1,6-hexanediol diacrylate are added to the prepolymer, and the mixture is stirred and dispersed uniformly to obtain an acrylic polymer curable precursor.
3. The amorphous silicon solar cell high temperature resistant protective film according to claim 2, characterized in that: The preparation method of the dendritic copper / silicon dioxide comprises the following steps: S1. The straw is sheared and crushed, washed and dried, added to water, and then sheared at high speed to obtain a certain aspect ratio of the straw fiber; S2. The straw fiber prepared in step S1 is subjected to steam explosion treatment to obtain branched nano-straw fibers; S3. After adding the branched straw fiber to ethanol and ultrasonically dispersing it uniformly, water was added, stirred uniformly, and then ethyl orthosilicate was added under stirring, and then ammonia was added to adjust the pH to 9-10, stirred for 20-30 minutes, filtered and dried, and sintered to obtain branched hollow silica; S4. Add the dendritic hollow silica prepared in step S3 to the PVP solution containing copper sulfate, and ultrasonically stir to allow the copper sulfate to be adsorbed on the surface and hollow layer of the dendritic hollow silica, and then add sodium borohydride solution to obtain dendritic copper / silica.
4. The amorphous silicon solar cell high temperature resistant protective film according to claim 3, characterized in that: The straw crushing length is 0.5-1.5 cm, the high-speed shearing rate is 8000-12000 rpm, and the high-speed shearing time is 10-20 min.
5. The amorphous silicon solar cell high temperature resistant protective film according to claim 3, characterized in that: The explosion pressure of the steam explosion treatment is 1-1.5 MPa, and the pressure maintenance time is 5-20 min.
6. The amorphous silicon solar cell high temperature resistant protective film according to claim 3, characterized in that: The concentration of the PVP solution is 1-3wt%, the concentration of copper sulfate in the PVP solution is 1-3wt%, and the mass ratio of copper sulfate to sodium borohydride is 8-9:
1.
7. The amorphous silicon solar cell high temperature resistant protective film according to claim 3, characterized in that: The mass volume ratio of the branched straw fiber, ethanol, water and tetraethyl orthosilicate is 10-20:40-50:4.5-5.5:4.5-5.
5.
8. The method for preparing the high temperature resistant protective film for amorphous silicon solar cells according to claim 2, characterized in that: The preparation method comprises the following steps: Mixing the components of the acrylic polymer adhesive to obtain a high temperature resistant adhesive; The obtained high temperature resistant adhesive is coated between the PET layer and the release film, and irradiated with 365nm UV light for 10-20min to obtain an amorphous silicon solar cell high temperature resistant protective film.