CN117048164B - High-weather-resistance photovoltaic backboard base film and preparation method thereof - Google Patents
High-weather-resistance photovoltaic backboard base film and preparation method thereof Download PDFInfo
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- CN117048164B CN117048164B CN202311312151.6A CN202311312151A CN117048164B CN 117048164 B CN117048164 B CN 117048164B CN 202311312151 A CN202311312151 A CN 202311312151A CN 117048164 B CN117048164 B CN 117048164B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B7/02—Physical, chemical or physicochemical properties
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The application relates to the technical field of photovoltaic backboard base films, in particular to a high-weather-resistance photovoltaic backboard base film and a preparation method thereof. The high-weather-resistance photovoltaic back plate base film comprises a central polyester base film and laminated films, wherein the laminated films are arranged on one side or two sides of the central polyester base film; the laminated film is a film in which 50 or more layers are alternately laminated with a layer a containing a thermoplastic resin a as a main component and a layer B containing a thermoplastic resin B having a refractive index different from that of the thermoplastic resin a as a main component; the high weather-resistant photovoltaic backboard base film has the light transmittance of not less than 85% for the light with the wavelength of 380-1100nm and the light transmittance of not more than 10% for the light with the wavelength of less than 380 nm; the thickness of the central polyester base film is 100-300 micrometers, and the thickness of the laminated film is 10-50 micrometers. The structure and the design of the high weather-resistant photovoltaic back plate base film prepared by the method can simultaneously meet the requirements of mechanical and optical properties of the photovoltaic back plate base film, and have excellent weather resistance.
Description
Technical Field
The application relates to the technical field of photovoltaic backboard base films, in particular to a high-weather-resistance photovoltaic backboard base film and a preparation method thereof.
Background
The backsheet of a solar photovoltaic cell, also known as solar cell backsheet film, acts as a direct barrier to protect the cell sheet and the encapsulant, playing a vital role in the safety, long-term reliability and durability of the assembly. With the development of photovoltaic building integration and double-sided photovoltaic power generation assemblies and the like, the solar cell backboard film not only has excellent weather resistance, insulativity, barrier property and other performances, but also needs higher light transmittance and lower haze so as to meet the requirements of the back power generation efficiency of the double-sided photovoltaic power generation assemblies and the indoor lighting of the photovoltaic building integration.
Currently, the main solar cell back sheet film has a structure of fluorine film, PET base film (namely, polyethylene terephthalate) film and fluorine film (TPT for short). From the integral structure of the back plate, the PET base film generally occupies more than two thirds of the thickness of the integral back plate, so the improvement of the weather resistance of the PET base film is greatly beneficial to the weather resistance of the integral photovoltaic back plate base film. In the related art, the weather resistance of the photovoltaic back sheet base film is improved by adding an inorganic ultraviolet absorber or an organic ultraviolet absorber to the PET base film.
However, the above manner has the following problems: in order to achieve higher ultraviolet blocking rate, a higher-concentration inorganic ultraviolet absorbent is generally added, the higher-concentration inorganic ultraviolet absorbent is easy to agglomerate, and the incident light is scattered or reflected to cause the increase of the haze of the film layer and the decrease of the transmittance; the organic ultraviolet absorber gradually decreases the ultraviolet absorption effect with an increase in the ultraviolet absorption dose (dose).
The US3711176a proposes that two resins a and B having different refractive indices (different from each other by 0.05 or more) are melt-co-extruded to form a multilayer film of alternating layers (AB structure) uniformly parallel in the thickness direction, and when the optical thickness of the adjacent two layers is equal to 1/2 of the wavelength of light, light reflection occurs due to the principle of light interference. By controlling the thickness of the film, the reflection band can be realized in the ultraviolet, visible or infrared region. The center position of the reflection peak is determined by the following formula:
formula (VI)1
Wherein n is A ,n B Refractive index d of resin materials A and B A ,d B For the thickness of adjacent A and B layers, m is the order or progression of the reflection peak, n A d A And n B d B Also known as the optical thickness of the a and B layers.
The patent CN108136745A adopts the principle, realizes high reflection in the ultraviolet region through the design of a laminated film of two polyester resins, and simultaneously realizes high barrier in the region below 410 nanometers by combining means of adding an ultraviolet absorber and the like, but is unfavorable for optimizing the power generation efficiency due to the fact that the wave band corresponding to the power generation of the solar cell is 380-1100 nanometers and the high barrier is formed in the region of 380-410 nanometers overlapped with the patent. Moreover, the films corresponding to the patent are thin, a thicker central layer is not considered, and the requirements of the mechanical property and the electrical property of the photovoltaic backboard base film cannot be met.
The patent CN104737039B adopts a method of compounding two laminated films, the first laminated film provides at least 50% of reflection of a certain wave band in the range of 300-400 nm, the second laminated film provides at least 50% of reflection of a certain wave band in the range of 430-500 nm, and the second laminated film is not suitable for a transparent photovoltaic backboard because the wave band of the second laminated film is coincident with 380-1100nm required for photovoltaic cell power generation.
Therefore, there is still a lack of a photovoltaic base film on the market at present, and the structure and design of the photovoltaic base film can simultaneously meet the requirements of mechanical and optical properties of the photovoltaic base film, and the photovoltaic base film has excellent weather resistance.
Disclosure of Invention
The structure and the design of the high weather-resistant photovoltaic back plate base film can simultaneously meet the requirements of mechanical and optical properties of the photovoltaic back plate base film, and the high weather-resistant photovoltaic back plate base film has excellent weather resistance.
In a first aspect, the present application provides a high weather-resistant photovoltaic back sheet base film, which adopts the following technical scheme:
the high-weather-resistance photovoltaic back sheet base film comprises a central polyester base film and laminated films, wherein the laminated films are arranged on one side or two sides of the central polyester base film; the laminated film is a film in which 50 or more layers are alternately laminated with a layer a containing a thermoplastic resin a as a main component and a layer B containing a thermoplastic resin B having a refractive index different from that of the thermoplastic resin a as a main component; the high weather-resistant photovoltaic backboard base film has the light transmittance of not less than 85% for the light with the wavelength of 380-1100nm and the light transmittance of less than 10% for the light with the wavelength of less than 380 nm; the thickness of the central polyester base film is 100-300 micrometers, and the thickness of the laminated film is 10-50 micrometers.
By adopting the technical scheme, more than 50 layers are alternately laminated by adopting the layer A and the layer B to obtain a laminated film, and the laminated film and the central polyester base film are compounded to obtain the photovoltaic backboard base film. The main materials of the layer A and the layer B are thermoplastic resins with different refractive indexes, and through the design of laminated films of the two thermoplastic resins, the photovoltaic backboard base film can realize high reflection in the ultraviolet region without adding nano inorganic oxide/organic ultraviolet absorbent, and finally the prepared high-weather-resistance photovoltaic backboard base film has good weather resistance for the light transmittance of less than 10% of 380 nm; the light transmittance of the photovoltaic cell is more than or equal to 85% for the wavelength of 380-1100nm (required by photovoltaic cell power generation), so that the high-weather-resistant photovoltaic backboard base film has higher transmittance, and the photovoltaic cell has higher power generation efficiency; the thicknesses of the central polyester base film and the laminated films at the side edges are designed, and when the thickness of the film layers is in the range, the photovoltaic back sheet base film has good mechanical properties.
The structure and the design of the high-weather-resistance photovoltaic back plate base film can simultaneously meet the requirements of mechanical and optical properties (high transmittance for 380-1100nm wavelength) of the photovoltaic back plate base film, and have excellent weather resistance.
Preferably, the refractive index difference between the thermoplastic resin A and the thermoplastic resin B is more than or equal to 0.03.
Preferably, the refractive index difference between the thermoplastic resin A and the thermoplastic resin B is more than or equal to 0.05.
Preferably, the transmittance of the high weather-resistant photovoltaic backboard base film to light with the wavelength of 380-1100nm is not lower than 92%.
Preferably, the high weather-resistant photovoltaic back sheet base film has a light transmittance of 5% or less for light having a wavelength of less than 380 nm.
Preferably, the central polyester base film and/or the laminate film contains an ultraviolet absorber.
Preferably, the ultraviolet absorber is nano zinc oxide and/or nano titanium dioxide.
Preferably, the polyester base film comprises an inorganic ultraviolet absorbent, and the inorganic ultraviolet absorbent is hyperbranched polyester modified nano zinc oxide.
By adopting the technical scheme, the hyperbranched polyester modified nano zinc oxide is added into the polyester base film, and compared with the nano zinc oxide, the hyperbranched polyester modified nano zinc oxide has the following advantages: firstly, the hyperbranched polyester modified nano zinc oxide has good dispersibility in a polyester base film, is not easy to agglomerate, is matched with a laminated film, has good compatibility with the polyester base film, can greatly transmit visible light through the polyester base film, and ensures higher transmittance while further improving the ultraviolet blocking performance of the photovoltaic backboard base film; secondly, the hyperbranched polyester modified nano zinc oxide has better compatibility with the polyester base film, and the long chain segment on the hyperbranched polyester modified nano zinc oxide can be mutually crosslinked with the polyester chain segment of the polyester base film, so that the mechanical property of the polyester base film is improved, and the mechanical property of the photovoltaic backboard base film is further improved.
Preferably, the hyperbranched polyester modified nano zinc oxide is prepared by reacting hyperbranched polyester and nano zinc oxide according to the mass ratio of (5-15): 1, and the particle size of the nano zinc oxide is 40-100nm.
Selecting a laminated film material:
the thermoplastic resin A/B may be selected from polyolefin resins including, but not limited to, polyethylene, polypropylene, poly (1-butene), poly (4-methylpentene), polyisobutylene, polyisoprene, polybutadiene, polyvinylcyclohexane, polystyrene, poly (alpha-methylstyrene), poly (p-methylstyrene), polynorbornene, polycyclopentene, etc.; polyamide-based resins including, but not limited to, nylon 6, nylon 11, nylon 12, nylon 66, and the like; copolymer-based resins of vinyl monomers, including, but not limited to, ethylene/propylene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/norbornene copolymers, ethylene/vinyl acetate copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, vinyl chloride/vinyl acetate copolymers, and the like; acrylic resins including, but not limited to, polyacrylates, polymethacrylates, polymethyl methacrylates, polyacrylamides, polyacrylonitriles, and the like; polyester resins represented by polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene 2, 6-naphthalate, and the like; polyether resins such as polyethylene oxide, polypropylene oxide, and polyalkylene glycol; cellulose ester-based resins including, but not limited to, diacetyl cellulose, triacetyl cellulose, propionyl cellulose, butyryl cellulose, levulinyl cellulose, nitrocellulose; biodegradable polymers such as polylactic acid, polybutyl succinate and the like; polyvinyl chloride, polyvinylidene chloride, 1-polyvinyl alcohol, polyvinyl butyral, polyacetal, polyglycolic acid, polycarbonate, polyketone, polyethersulfone, polyetheretherketone, modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, polyimide, polysiloxane, tetrafluoroethylene resin, trifluoroethylene resin, chlorotrifluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride 1, 1-and the like.
The polymer is preferably a synthetic polymer, more preferably polyolefin, acrylic, polyester, cellulose ester, polyvinyl butyral, polycarbonate, polyether sulfone, polyvinylidene fluoride 1,1-, and particularly preferably one or more of polyethylene, polypropylene, polymethyl methacrylate, polyester, triacetylcellulose, and polyvinylidene fluoride 1, 1.
In addition, these different thermoplastic resins preferably have different thermal characteristics in addition to the refractive index, that is, they have different melting points Tm and glass transition temperatures Tg in Differential Scanning Calorimetry (DSC), and by virtue of the difference in melting points Tm and glass transition temperatures Tg, the orientation state of each layer can be highly controlled in the step of stretching and heat-treating the laminate film; the orientation state can be controlled to a high degree, and thus the refractive index in the plane and the direction perpendicular to the plane of each layer of the thermoplastic resin can be controlled, and the wavelength of the reflected light can be controlled. Therefore, when selecting a material, the thermal characteristics of the material also need to be emphasized, and particularly, the difference between the glass transition temperature and the melting point, which affect the orientation state of the resin in the stretching step, is preferably 0.1 ℃. Among the thermoplastic resins, from the viewpoints of strength, heat resistance, transparency, versatility and bonding force with the central polyester layer, at least one of the thermoplastic resin a and the thermoplastic resin B is preferably made of a polyester-based resin, and more preferably one of them is the same as the central polyester layer material, for example, PET.
The polyester is a polycondensate obtained by polymerizing monomers containing an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and a diol as main components;
aromatic dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 4 '-diphenyl ether dicarboxylic acid and 4,4' -diphenyl sulfone dicarboxylic acid;
aliphatic dicarboxylic acid, which is selected from one or more of adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, 1, 4-cyclohexanedicarboxylic acid and ester derivatives thereof; among them, terephthalic acid and 2, 6-naphthalene dicarboxylic acid exhibiting a high refractive index are preferably used;
glycol, one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, neopentyl glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2-bis (4-hydroxyethoxyphenyl) propane, isosorbide and spiro glycol are selected, wherein ethylene glycol is preferably used;
the polyester resin is selected from one or more of polyethylene terephthalate PET and its copolymer, polyethylene naphthalate PEN and its copolymer, polybutylene terephthalate and its copolymer, polybutylene naphthalate and its copolymer, and polyhexamethylene terephthalate and its copolymer, and polyhexamethylene naphthalate and its copolymer. It should be noted that polymers containing naphthalene dicarboxylic acid groups such as PEN absorb to some extent at 380-400 nm, which affects the light transmittance at this wavelength, and thus polyester materials containing terephthalic acid groups are more preferred than others.
Also to be described is: in general, in addition to the above-mentioned refractive index difference requirements, the thermoplastic resin a and the thermoplastic resin B are required to satisfy the following series of requirements in order to ensure the quality of the final product:
1. the resin selected needs to have good thermal stability;
2. in the production process, the process temperatures of the resins should be relatively close, and particularly, the melt temperatures need to be relatively close when the lamination process is carried out in the molten state of the resins so as to avoid the occurrence of changes of physical properties such as viscosity, elastic modulus and the like caused by heat transfer;
3. at the production process temperature, each resin melt should have close rheological properties to avoid disturbing and damaging the layered structure during the flow process;
4. the ultraviolet is stable or can be protected, and the quality degradation caused by long-term irradiation of ultraviolet rays is mainly avoided when the product is used outdoors for a long time;
5. the selected resin has high transmission and low absorption characteristics to visible light when used alone;
6. the glass transition temperatures should be matched with each other, and thermoplastic resins such as PET, PEN, etc. having birefringence properties need to be biaxially stretched in a post-treatment process to obtain a desired refractive index and mechanical properties, which are usually achieved around the glass transition temperature, so that the glass transition temperature of the matched additional thermoplastic resin should be lower than or equal to this temperature to avoid the occurrence of microcracks during biaxial stretching to cause degradation of quality;
7. the adjacent resin has good interlayer binding force, and the product cannot be split or stripped in the use process;
8. the adjacent resin has low diffusion performance, and the optical performance is not reduced due to material diffusion in the long-term use process of the subsequent product;
9. the resin selected should have matched tensile properties.
In a second aspect, the present application provides a method for preparing a high weather-resistant photovoltaic back sheet base film, which adopts the following technical scheme:
a preparation method of a high weather-resistant photovoltaic backboard base film comprises the following steps:
the central polyester base film and the laminated film are respectively prepared and then are compounded by an adhesive or are formed in one step by a coextrusion mode.
In summary, the present application has the following beneficial effects:
1. the application adopts a laminated film obtained by alternately laminating more than 50 layers of layers A and B, and the laminated film and a central polyester base film are compounded to obtain the photovoltaic backboard base film. The main materials of the layer A and the layer B are thermoplastic resins with different refractive indexes, and the light transmittance of the finally prepared high-weather-resistance photovoltaic backboard base film to the light with the wavelength smaller than 380nm is less than 10%, so that the high-weather-resistance photovoltaic backboard base film has good weather resistance; the light transmittance of the photovoltaic cell is more than or equal to 85% for the wavelength of 380-1100nm (required by photovoltaic cell power generation), so that the high-weather-resistant photovoltaic backboard base film has higher transmittance, and the photovoltaic cell has higher power generation efficiency; the thicknesses of the central polyester base film and the laminated films at the side edges are designed, and when the thickness of the film layers is in the range, the photovoltaic back sheet base film has good mechanical properties.
The structure and the design of the high-weather-resistance photovoltaic back plate base film can simultaneously meet the requirements of mechanical and optical properties (high transmittance for 380-1100nm wavelength) of the photovoltaic back plate base film, and have excellent weather resistance.
Drawings
Fig. 1 is a schematic structural diagram of a high weatherability photovoltaic backsheet base film in an embodiment of the present application.
Fig. 2 is a process flow diagram of an embodiment of the present application.
Reference numerals illustrate: 1. a laminated film; 2. a central polyester base film.
Detailed Description
Preparation example
Preparation example of hyperbranched polyester modified nano zinc oxide
Preparation example 1
The hyperbranched polyester modified nano zinc oxide is prepared according to the following steps:
adding 5g of nano zinc oxide (with the particle size of 40 nm) and 100g of hydroxyl-terminated hyperbranched polyester (model H303) into 500g of dimethylformamide solvent, heating to 60 ℃, carrying out ultrasonic blending for 40min, heating to 120 ℃, stirring for 24H to obtain a pretreatment liquid, adding 2L of acetone into the pretreatment liquid, stirring to obtain a mixed liquid, carrying out reduced pressure filtration on the mixed liquid, adopting absolute ethyl alcohol to remove unreacted hydroxyl-terminated hyperbranched polyester and redundant solvent, and drying to obtain the hyperbranched polyester modified nano zinc oxide.
Preparation example 2
The hyperbranched polyester modified nano zinc oxide is prepared according to the following steps:
adding 5g of nano zinc oxide (with the particle size of 100 nm) and 100g of hydroxyl-terminated hyperbranched polyester (model H303) into 500g of dimethylformamide solvent, heating to 60 ℃, carrying out ultrasonic blending for 40min, heating to 120 ℃, stirring for 24H to obtain a pretreatment liquid, adding 2L of acetone into the pretreatment liquid, stirring to obtain a mixed liquid, carrying out reduced pressure filtration on the mixed liquid, adopting absolute ethyl alcohol to remove unreacted hydroxyl-terminated hyperbranched polyester and redundant solvent, and drying to obtain the hyperbranched polyester modified nano zinc oxide.
Preparation example 3
The hyperbranched polyester modified nano zinc oxide is prepared according to the following steps:
adding 5g of nano zinc oxide (with the particle size of 80 nm) and 100g of hydroxyl-terminated hyperbranched polyester (model H303) into 500g of dimethylformamide solvent, heating to 60 ℃, carrying out ultrasonic blending for 40min, heating to 120 ℃, stirring for 24H to obtain a pretreatment liquid, adding 2L of acetone into the pretreatment liquid, stirring to obtain a mixed liquid, carrying out reduced pressure filtration on the mixed liquid, adopting absolute ethyl alcohol to remove unreacted hydroxyl-terminated hyperbranched polyester and redundant solvent, and drying to obtain the hyperbranched polyester modified nano zinc oxide.
Examples
Example 1
The high weather-resistant photovoltaic backboard base film is prepared according to the following steps:
9400g of film-grade PET particles with the particle size of about 60 meshes, 500g of hyperbranched polyester modified nano zinc oxide, 50g of 1010 antioxidant and 50g of LS119 light stabilizer prepared in preparation example 1 are mixed, extruded and granulated by a double-screw extruder, and then high weather-resistant photovoltaic backboard master batch is obtained;
according to the process flow chart shown in fig. 2, the pre-crystallized and dried mixture (the mass ratio of the high weather-resistant photovoltaic backboard master batch to the film-grade PET resin is 1:5, wherein the brand of the film-grade PET resin is the ceremony petrochemical FG600, the refractive index is 1.65 after biaxial stretching, the particle size is 60 meshes), is fed into the extruders A1, A2, C1, C2 and D, meanwhile, the PETG resin (refractive index is 1.57) is dried and is fed into the extruders B1 and B2, and the feed blocks S1 and S2 are respectively designed into 251 laminated layer structures, wherein the materials of the layers A and B are PET and PETG respectively. The thickness is designed as follows: the front is 24 layers (12 AB periods) with an optical thickness of 65 nanometers, the back is 26 layers (13 AB periods) with an optical thickness of 95 nanometers, and the middle is 201 layers, and the optical thickness of each layer is increased from 65 nanometers to 95 nanometers in a linear thickness increasing mode. The protective surface layers on two sides are PET, the thickness is 5 micrometers, the film thicknesses of the laminated layers on two sides are 22.5 micrometers respectively, and the thickness of the final high weather-resistant photovoltaic backboard base film reaches 295 micrometers by adjusting the feeding amount of the extruder.
Example 2
The difference between the high weather-resistant photovoltaic back sheet base film and the example 1 is that: the ultraviolet absorber is different, and the hyperbranched polyester modified nano zinc oxide prepared in preparation example 1 is replaced by the hyperbranched polyester modified nano zinc oxide prepared in preparation example 2.
Example 3
The difference between the high weather-resistant photovoltaic back sheet base film and the example 1 is that: the ultraviolet absorber is different, and the hyperbranched polyester modified nano zinc oxide prepared in preparation example 1 is replaced by the hyperbranched polyester modified nano zinc oxide prepared in preparation example 3.
Comparative example
Comparative example 1
The high weather-resistant photovoltaic backboard base film is prepared according to the following steps:
9100g of film-grade PET particles with the particle size of about 60 meshes, 800g of nano zinc oxide, 50g of 1010 antioxidant and 50g of LS119 light stabilizer are mixed, extruded and granulated by a double-screw extruder, and the high weather-resistant photovoltaic backboard master batch is obtained.
And mixing the high weather-resistant photovoltaic backboard master batch with film-grade PET resin according to a ratio of 1:5, feeding the mixture to an experimental extruder for casting to obtain a cast sheet, and carrying out biaxial stretching by using a small-sized stretcher to obtain a film sample with the thickness of 295 microns.
Comparative example 2
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 1 is that: the weight of the film grade PET particles in this comparative example was 9400g and the weight of the nano zinc oxide was 500g.
Comparative example 3
The high weather-resistant photovoltaic backboard base film is prepared according to the following steps:
according to the process flow diagram shown in fig. 2, the pre-crystallized and dried film grade PET resin is fed to the extruders A1, A2, C1, C2, D, while PETG resin (refractive index 1.57) is dried and fed to the extruders B1, B2, the feed blocks S1 and S2 being respectively designed with 251 laminate layer structure, wherein the a and B layer materials are PET and PETG, respectively. The thickness is designed as follows: the front is 24 layers (12 AB periods), each layer has an optical thickness of 65 nanometers, the back is 26 layers (13 AB periods), each layer has an optical thickness of 95 nanometers, the middle is 201 layers, and the optical thickness of each layer increases from 65 nanometers to 95 nanometers in a linear thickness increasing manner. The protective surface layers on two sides are PET, the thickness is 5 micrometers, the film thicknesses of the laminated layers on two sides are 22.5 micrometers respectively, and the thickness of the final high weather-resistant photovoltaic backboard base film reaches 295 micrometers by adjusting the feeding amount of the extruder.
Comparative example 4
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the film-grade PET resin is different, the comparative example adopts a mixture (the high weather-resistant photovoltaic backboard master batch and the film-grade PET resin are compounded according to the mass ratio of 1:5) to replace the pure film-grade PET resin, and the preparation method of the high weather-resistant photovoltaic backboard master batch in the comparative example comprises the following steps:
9400g of film-grade PET particles with the particle size of about 60 meshes, 500g of UV360 ultraviolet absorber, 50g of 1010 antioxidant and 50g of LS119 light stabilizer are mixed, extruded and granulated by a double-screw extruder, and the high weather-resistant photovoltaic backboard master batch is obtained.
Comparative example 5
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the film-grade PET resin is different, the comparative example adopts a mixture (the high weather-resistant photovoltaic backboard master batch and the film-grade PET resin are compounded according to the mass ratio of 1:5) to replace the pure film-grade PET resin, and the preparation method of the high weather-resistant photovoltaic backboard master batch in the comparative example comprises the following steps:
9300g of film-grade PET particles with the particle size of about 60 meshes, 150g of rutile type nano titanium dioxide (particle size: 40 nm), 450g of UV3638 ultraviolet absorbent (bisbenzoxazinone ultraviolet absorbent), 50g of 1330 antioxidant and 50g of LS119 light stabilizer are mixed, and extruded and granulated by a double-screw extruder to obtain the high weather-resistant photovoltaic backboard master batch.
Comparative example 6
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the film-grade PET resin is different, the comparative example adopts a mixture (the high weather-resistant photovoltaic backboard master batch and the film-grade PET resin are compounded according to the mass ratio of 1:10) to replace the pure film-grade PET resin, and the preparation method of the high weather-resistant photovoltaic backboard master batch in the comparative example comprises the following steps:
8900g of film-grade PET particles with the particle size of about 60 meshes, 1000g of UV3638 ultraviolet absorber, 50g of 1330 antioxidant and 50g of LS119 light stabilizer are mixed to obtain the high weather-resistant photovoltaic backboard master batch.
Comparative example 7
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the PETG resin of this comparative example had a refractive index of 1.60, unlike comparative example 3.
Comparative example 8
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the PETG resin of this example, unlike comparative example 3, has a refractive index of 1.62.
Comparative example 9
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the thickness of the center polyester base film of this comparative example was 100 μm and the thickness of the laminate film was 50 μm.
Comparative example 10
The difference between the high weather-resistant photovoltaic back sheet base film and comparative example 3 is that: the thickness of the center polyester base film of this comparative example was 300 μm and the thickness of the laminate film was 10. Mu.m.
Comparative example 11
The difference from comparative example 4 is that: the ultraviolet absorber is different, and the comparative example replaces the UV360 ultraviolet absorber with nano zinc oxide.
Performance test
Referring to GB/T2410-2008, the light transmittance of the photovoltaic backboard base film prepared in the examples and the comparative examples is tested by using a spectrometer, and specific test items are as follows:
1. transmittance of 380-1100 nm;
2. the light transmittance with the wavelength smaller than 380nm (the barrier effect of the base film on ultraviolet rays is represented by the light transmittance, the lower the light transmittance is, the better the barrier effect of the base film on ultraviolet rays is shown);
3. light transmittance (under the environment condition of 85 ℃ and 85% humidity) with wavelength less than 380nm after 3000 hours of humidity and heat aging resistance;
4. after 3000 hours of UV aging, the light transmittance of the glass fiber is less than 380nm (using a UV light accelerated aging tester (365 nm,70 ℃ C., 1.5W/m) 2 ））；
The tensile strength of the photovoltaic back sheet base films prepared in examples and comparative examples was tested with reference to GB/T1040-2006 to characterize the mechanical properties of the photovoltaic back sheet base films.
The specific detection results are shown in the following table 1:
TABLE 1 photovoltaic backsheet base film Performance test
As can be seen from Table 1, the transmittance of the photovoltaic backboard base film prepared in the embodiment of the application to the light with the wavelength of 380-1100nm is more than or equal to 95.3%, the transmittance to the light with the wavelength of less than 380nm is less than or equal to 0.3%, and the tensile strength is more than or equal to 116.1MPa.
As can be seen in combination with examples 1-3 and comparative example 2 and in combination with table 1, the photovoltaic backsheet base film produced in comparative example 2 has a significantly higher transmittance at wavelengths less than 380nm than examples 1-3, probably because: comparative example 2 in comparison with examples 1 to 3, comparative example 2 did not employ A, B laminated film structure nor did it increase the amount of nano zinc oxide.
As can be seen in combination with examples 1-3 and comparative example 1 and in combination with table 1, the transmittance of the photovoltaic back sheet base film produced in comparative example 1 to light having a wavelength of 380 to 1100nm is much lower than that of examples 1-3, probably because: comparative example 1 compared with examples 1-3, comparative example 1 did not adopt a A, B laminated film structure, but only adopted a way of increasing the amount of nano zinc oxide to reduce the transmittance of light with a wavelength of less than 380nm, and too high an amount of nano zinc oxide would result in the reduction of the transmittance of the photovoltaic back sheet base film to light with a wavelength of 380-1100nm, thereby affecting the power generation efficiency of the photovoltaic cell.
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 present application.
Claims (4)
1. A high weather-resistant photovoltaic backboard base film is characterized in that: the high weather-resistant photovoltaic backboard base film comprises a laminated film, a central polyester base film and a laminated film which are sequentially arranged, wherein the laminated film is formed by alternately laminating layers A and B, two sides of the laminated film are protective surface layers, the protective surface layers are made of PET, and the thickness of the protective surface layers is 5 microns; the thickness of the laminated film is 22.5 micrometers, and the thickness of the high weather-resistant photovoltaic backboard base film is 295 micrometers; the high weather-resistant photovoltaic backboard base film has the light transmittance of not less than 85% for the light with the wavelength of 380-1100nm and the light transmittance of less than 10% for the light with the wavelength of less than 380 nm; the central polyester base film comprises an inorganic ultraviolet absorbent, wherein the inorganic ultraviolet absorbent is hyperbranched polyester modified nano zinc oxide, and the hyperbranched polyester modified nano zinc oxide is prepared according to the following steps:
adding 5g of nano zinc oxide and 100g of hydroxyl-terminated hyperbranched polyester into 500g of dimethylformamide solvent, heating to 60 ℃, carrying out ultrasonic blending, then heating to 120 ℃, stirring to obtain a pretreatment liquid, adding 2L of acetone into the pretreatment liquid, stirring to obtain a mixed liquid, carrying out reduced pressure filtration on the mixed liquid, removing unreacted hydroxyl-terminated hyperbranched polyester and redundant solvent, and drying to obtain hyperbranched polyester modified nano zinc oxide;
wherein the particle size of the nano zinc oxide is 40-100nm, and the model of the hydroxyl-terminated hyperbranched polyester is H303;
the laminated film is prepared according to the following steps:
9400g of film-grade PET resin with the particle size of 60 meshes, 500g of hyperbranched polyester modified nano zinc oxide, 50g of 1010 antioxidant and 50g of LS119 light stabilizer are mixed, extruded and granulated by a double-screw extruder, and the high weather-resistant photovoltaic backboard master batch is obtained; compounding high weather-resistant photovoltaic backboard master batch and film-grade PET resin according to a mass ratio of 1:5 to obtain a mixture, pre-crystallizing and drying the mixture, wherein the brand of the film-grade PET resin is ceremony petrochemical FG600, the refractive index of the film-grade PET resin is 1.65, the particle size of particles is 60 meshes after biaxial stretching, the film-grade PET resin is fed to an extruder, meanwhile, the PETG resin with the refractive index of 1.57 is fed to the extruder, the material of the layer A is the mixture of the high weather-resistant photovoltaic backboard master batch and the film-grade PET resin, and the material of the layer B is PETG;
the thickness of the laminated film is designed as follows: the front is 12 AB periods, the optical thickness of each layer A or B is 65nm, the rear is 13 AB periods, the optical thickness of each layer A or B is 95nm, the middle is 201 layers, and the optical thickness of each layer is increased from 65nm to 95nm in a mode of linearly increasing the thickness.
2. The high weatherability photovoltaic backsheet base film of claim 1 wherein: the high weather-resistant photovoltaic backboard base film has the light transmittance of not less than 92% for 380-1100nm wavelength.
3. The high weatherability photovoltaic backsheet base film of claim 1 wherein: the high weather-resistant photovoltaic backboard base film has the light transmittance of less than 5% for the wavelength of less than 380 nm.
4. A method for preparing a highly weatherable photovoltaic backsheet film according to any one of claims 1 to 3, comprising the steps of:
the central polyester base film and the laminated film are respectively prepared and then are compounded by an adhesive or are formed in one step by a coextrusion mode.
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| CN204506045U (en) * | 2014-11-27 | 2015-07-29 | 苏州赛伍应用技术有限公司 | A kind of PET film of three-decker and consisting of solar cell backboard |
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| US20190348555A1 (en) * | 2018-05-08 | 2019-11-14 | Beijing Hanergy Solar Power Investment Co., Ltd. | Solar module |
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| CN102529258A (en) * | 2010-10-20 | 2012-07-04 | 苏州尚善新材料科技有限公司 | Improved solar cell assembly back plate and manufacturing method thereof |
| CN204506045U (en) * | 2014-11-27 | 2015-07-29 | 苏州赛伍应用技术有限公司 | A kind of PET film of three-decker and consisting of solar cell backboard |
| CN108136745A (en) * | 2015-12-08 | 2018-06-08 | 东丽株式会社 | Stack membrane |
| CN112071930A (en) * | 2020-09-17 | 2020-12-11 | 山东金晶科技股份有限公司 | Blue cover plate glass for building integrated photovoltaic and preparation method thereof |
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