CN117690988A - Weather-resistant low-water light-transmitting photovoltaic backboard and preparation method thereof - Google Patents
Weather-resistant low-water light-transmitting photovoltaic backboard and preparation method thereof Download PDFInfo
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Abstract
The invention provides a weather-proof low-water light-transmitting photovoltaic backboard and a preparation method thereof, and belongs to the technical field of photovoltaics; the modified fluorine film layer comprises the following components in percentage by mass: 73% -77% of PVDF, 8.5% -10.5% of modified multi-wall carbon nano-tubes, 6% -7.2% of toughening agents, 6.6% -7.8% of silicon-containing modified polyurethane, 0.5% -0.8% of antioxidants and 0.5% -0.8% of lubricants; the preparation method of the modified multi-wall carbon nano tube comprises the following steps: a1, putting the multi-wall carbon nano tube into strong acid, heating to 85-100 ℃, and keeping for 1-3 hours to obtain an acid-washed carbon nano tube; a2, placing the acid-washed carbon nano tube into water, carrying out ultrasonic treatment for 30 minutes, carrying out centrifugal separation, and washing the water to be neutral to obtain a neutral carbon nano tube; and A3, putting the neutral carbon nano tube into a polyethyleneimine water solution, oscillating for 24 hours in a constant-temperature water bath, washing with water, and drying to obtain the nano-tube. The photovoltaic backboard prepared by the invention has excellent illumination weather resistance, low water permeability and excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of photovoltaics, and particularly relates to a weather-resistant low-water light-transmitting photovoltaic backboard and a preparation method thereof.
Background
The photovoltaic backboard is positioned on the back of the solar cell panel, is one of key components of the photovoltaic module, plays a role in protecting the cell and supporting the integral structure, and has important functions of blocking air, blocking water vapor, blocking ultraviolet rays and the like. The photovoltaic back sheet is a multilayer structure, such as a three-layer structure (PVDF/PET/PVDF), wherein the outer protective layer PVDF film has good resistance to environmental attack.
PVDF (polyvinylidene fluoride) is a fluorine-containing polymer, and the fluorine-containing polymer refers to a polymer in which all or part of hydrogen atoms connected with C-C bonds in a high molecular polymer are replaced by fluorine atoms. Because of the lower polarizability, strong electronegativity and smaller van der Waals radius of fluorine atoms, the C-F group-containing fluoropolymers often have many-sided superior properties compared to other conventional polymers. For example, they have very high chemical resistance, barrier properties, high temperature resistance and good electrical properties, and do not absorb moisture, have an extremely low coefficient of friction and are also good in weather resistance. In addition, the properties of the PVDF membrane can be improved by blending other materials or grafting materials with different molecular weights on the surface of the membrane, for example, PVDF is blended with materials such as Polysulfone (PSF), polyacrylonitrile (PAN), polyvinyl alcohol (PVA) and the like, so that the oxidation resistance and weather resistance of the PVDF membrane can be effectively improved.
The Chinese patent with publication number of CN113912885B discloses a PVDF film for a photovoltaic backboard capable of resisting low temperature and a preparation method thereof; the PVDF film prepared by taking PVDF, polymethyl methacrylate, magnetization toughening agent, titanium pigment, antioxidant, ultraviolet absorber and the like as raw materials has good weather resistance, high barrier property, low water permeability, low temperature resistance, excellent mechanical properties in a severe cold environment at-40 ℃ and no cracking. However, titanium dioxide is used as a filler, the average particle size of the titanium dioxide is between 0.2 and 0.3 mu m, and the effect of filling gaps among molecules of a PVDF and polymethyl methacrylate blending material is poor, so that the PVDF film has more water permeation paths and higher water permeability; in addition, the titanium dioxide particles have poor shielding effect on ultraviolet rays and infrared rays, so that the PVDF film has poor illumination weatherability; insufficient compatibility and interfacial binding force of titanium dioxide particles with the PVDF and polymethyl methacrylate blending material can also cause poor mechanical properties of the PVDF film.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides a weather-resistant low-water light-transmitting photovoltaic backboard and a preparation method thereof, and the prepared photovoltaic backboard is excellent in light weather resistance, low in water transmission and excellent in mechanical property.
In order to achieve the above object, in a first aspect, the present invention provides a weather-resistant low-water light-transmitting photovoltaic back sheet, including an EVOH layer, a first adhesive layer, a PET layer, a second adhesive layer, and a modified fluorine film layer, which are sequentially disposed;
the modified fluorine film layer comprises the following raw material components in percentage by mass: 73% -77% of PVDF, 8.5% -10.5% of modified multi-wall carbon nano-tubes, 6% -7.2% of toughening agents, 6.6% -7.8% of silicon-containing modified polyurethane, 0.5% -0.8% of antioxidants and 0.5% -0.8% of lubricants;
the preparation method of the modified multi-wall carbon nano tube comprises the following steps:
a1, putting the multi-wall carbon nano tube into strong acid, heating to 85-100 ℃, and keeping for 1-3 hours to obtain an acid-washed carbon nano tube;
a2, putting the acid-washed carbon nano tube obtained in the step A1 into deionized water, performing ultrasonic treatment in an ultrasonic cleaner for 30 minutes, then performing centrifugal separation by using a centrifugal machine, and repeatedly washing with the deionized water to be neutral to obtain a neutral carbon nano tube;
a3, putting the neutral carbon nano tube obtained in the step A2 into a polyethyleneimine water solution, oscillating for 24 hours in a constant-temperature water bath, washing with deionized water, and drying to obtain the modified multi-wall carbon nano tube.
Further, in A1, the strong acid adopts mixed acid, and the mass ratio of 98% sulfuric acid to 68% nitric acid is 3:1, and mixing.
Further, in A3, the concentration of the aqueous polyethyleneimine solution is 50%.
Further, the preparation method of the silicon-containing modified polyurethane comprises the following steps:
b1, mixing isophorone diisocyanate and hydroxyl-terminated polybutadiene acrylonitrile according to N (NCO)/n (HTBN) =1.6, adding 0.5wt% of dibutyltin dilaurate, adding amino silicone oil according to n (amino silicone oil)/n (HTBN) =0.06, heating to 78 ℃ under the protection of dry nitrogen, and reacting 2 h;
and B2, adding a chain extender methyl propylene glycol according to n (chain extender)/n (HTBN) =0.05, keeping the temperature at 78 ℃ for reaction for 0.5h, slowly heating to 90 ℃ to complete the reaction, and cooling to room temperature to obtain the silicon-containing modified polyurethane.
Further, the toughening agent comprises a styrene toughening agent or a polyolefin toughening agent.
Further, the antioxidant comprises butyl hydroxy anisole and/or 2, 6-di-tert-butyl-p-cresol.
Further, the lubricant includes an alcohol-based lubricant or a silicone-based lubricant.
Further, the preparation method of the modified fluorine film layer comprises the following steps: PVDF, modified multi-wall carbon nano tube, toughening agent, silicon-containing modified polyurethane, antioxidant and lubricant are taken, mixed in a high-speed mixer, added with ultrasound, and subjected to double-screw melt extrusion, cooled and granulated to obtain the modified fluorine film layer constituent material.
Further, the first adhesive layer and the second adhesive layer are both maleic anhydride grafted polyethylene.
In a second aspect, the present invention provides a method for preparing a weather-resistant low-water-transmittance photovoltaic back panel, which is used for preparing the weather-resistant low-water-transmittance photovoltaic back panel, and includes the following steps: and (3) carrying out coextrusion on the constituent materials of the EVOH layer, the first bonding layer, the PET layer, the second bonding layer and the modified fluorine film layer to obtain the photovoltaic backboard.
The application has the following beneficial effects:
EVOH is a high-barrier material, not only has excellent processability, but also has excellent blocking effect on gases, solvents and the like, and has good strength, elastic modulus and bending property; PET is a thermoplastic polymer of the polyester family, whose mechanical properties and chemical stability are mainly derived from its molecular structure; PVDF has excellent weather resistance, wear resistance, high temperature resistance and other performances; the three materials are compounded through the adhesive to form the photovoltaic backboard with the multilayer structure, so that the advantages of all materials can be fully exerted;
the modified fluorine film layer is prepared from PVDF, and the raw material components comprise a modified multi-wall carbon nano tube and silicon-containing modified polyurethane, wherein the modified multi-wall carbon nano tube is prepared from the multi-wall carbon nano tube through strong acid washing and polyethyleneimine modification, the surface property of the multi-wall carbon nano tube is changed through strong acid washing, the compatibility of the multi-wall carbon nano tube and a hot melt polymer is improved, and the dispersibility of the multi-wall carbon nano tube in a polymer matrix is improved; the multi-wall carbon nano tube has extremely high surface energy, excessive carbon nano tube is easy to agglomerate, and even the excessive generation or uneven distribution of beta-phase crystal forms of PVDF can be promoted, and the promotion effect can be counteracted by modifying polyethyleneimine; both are beneficial to the modified multi-wall carbon nano tube to better fill the gaps among molecules of the material and reduce the permeation path, thereby effectively reducing the water vapor transmittance of the material; moreover, experiments prove that the effects of the two are superior to those of common superposition;
meanwhile, the surface of the multi-wall carbon nano tube treated by strong acid can be endowed with active groups such as carboxyl, hydroxyl and the like, and the active groups can directly improve the interfacial binding force with a polymer matrix, so that the tensile strength is enhanced; the beta crystal form formed by the molecular chains in a regular arrangement mode can lead to the decrease of the mechanical property (tensile strength) of the material, and the offset effect brought by the modification of the polyethyleneimine can offset the decrease trend of the mechanical property, and the phase change plays a role in enhancing the mechanical property; moreover, experiments prove that the effects of the two are superior to those of common superposition;
polyurethane has strong polarity, can be firmly combined with most materials, and further enhances the capability of preventing moisture penetration; after the polyurethane is modified by silicon, a silicon-containing chain segment with low surface energy is introduced into a polyurethane molecular chain, so that the hydrophobicity can be enhanced, and the water vapor permeability can be reduced.
Drawings
FIG. 1 is a schematic diagram of a weatherable low water light transmission photovoltaic backsheet of the present invention;
1. an EVOH layer; 2. a first adhesive layer; 3. a PET layer; 4. a second adhesive layer; 5. and (3) modifying the fluorine film layer.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials of the examples and comparative examples herein are commercially available in general unless otherwise specified.
Example 1
The embodiment provides a weather-proof low-water light-transmitting photovoltaic backboard, which comprises an EVOH layer 1, a first bonding layer 2, a PET layer 3, a second bonding layer 4 and a modified fluorine film layer 5 which are sequentially arranged. The EVOH layer 1 is formed of EVOH, the PET layer 3 is formed of PET chips, and the first adhesive layer 2 and the second adhesive layer 4 are formed of maleic anhydride grafted polyethylene.
The modified fluorine film layer 5 comprises the following raw material components in percentage by mass: 73% of PVDF, 10.4% of modified multi-wall carbon nano-tubes, 7.2% of toughening agent, 7.8% of silicon-containing modified polyurethane, 0.8% of antioxidant and 0.8% of lubricant.
Wherein, the toughening agent adopts styrene toughening agent SEBS.
The antioxidant is prepared by mixing butyl hydroxy anisole and 2, 6-di-tert-butyl-p-cresol according to a mass ratio of 1:1.2.
The lubricant is silicone lubricant.
The preparation method of the modified multi-wall carbon nano tube comprises the following steps:
a1, putting the multi-wall carbon nano tube into strong acid, wherein the mass ratio of the multi-wall carbon nano tube to the strong acid is 1:3; the strong acid adopts mixed acid, and the concentration (mass fraction) of the mixed acid is 98 percent sulfuric acid and the concentration (mass fraction) of the mixed acid is 68 percent nitric acid according to the mass ratio of 3:1, mixing to obtain the product; heating to 90 deg.c and maintaining for 2 hr to obtain pickled carbon nanotube.
A2, putting the acid-washed carbon nano tube obtained in the step A1 into deionized water, performing ultrasonic treatment in an ultrasonic cleaner for 30 minutes, then performing centrifugal separation by using a centrifugal machine, and repeatedly washing with the deionized water to be neutral to obtain a neutral carbon nano tube;
a3, putting the neutral carbon nano tube obtained in the step A2 into a 50% concentration (mass fraction) polyethyleneimine water solution, oscillating for 24 hours in a constant-temperature water bath (30 ℃), washing with deionized water to remove unreacted polyethyleneimine, and finally drying in a vacuum drying oven to obtain the modified multi-wall carbon nano tube.
The preparation method of the silicon-containing modified polyurethane comprises the following steps:
b1, mixing isophorone diisocyanate and hydroxyl-terminated polybutadiene acrylonitrile according to N (NCO)/n (HTBN) =1.6, adding 0.5wt% of dibutyltin dilaurate, adding amino silicone oil according to n (amino silicone oil)/n (HTBN) =0.06, heating to 78 ℃ under the protection of dry nitrogen, and reacting 2 h;
and B2, adding a chain extender methyl propylene glycol according to n (chain extender)/n (HTBN) =0.05, keeping the temperature at 78 ℃ for reaction for 0.5h, slowly heating to 90 ℃ to complete the reaction, and cooling to room temperature to obtain the silicon-containing modified polyurethane.
The preparation method of the modified fluorine film layer comprises the following steps: mixing PVDF, modified multiwall carbon nanotube, toughening agent, silicon-containing modified polyurethane, antioxidant and lubricant in a high-speed mixer, adding ultrasound (in the specific implementation, the ultrasound equipment is required to be connected with the high-speed mixer; specifically, an ultrasonic generator is arranged on the high-speed mixer, and is linked with a control system of the high-speed mixer, and when the high-speed mixer is started, the ultrasonic generator is also started at the same time), and carrying out double-screw melt extrusion, cooling and granulating to obtain a constituent material of the modified fluorine film layer; and (5) continuously carrying out film forming by extending to obtain the modified fluorine film layer.
The preparation method of the weather-resistant low-water light-transmitting photovoltaic backboard comprises the following steps: and (3) carrying out coextrusion on the structural materials of the EVOH, the maleic anhydride grafted polyethylene, the PET slice, the maleic anhydride grafted polyethylene and the modified fluorine film layer to obtain the photovoltaic backboard. The photovoltaic back sheet has a five-layer structure, and comprises an EVOH layer with the thickness of 40 mu m, a first bonding layer with the thickness of 30 mu m, a PET layer with the thickness of 250 mu m, a second bonding layer with the thickness of 30 mu m and a modified fluorine film layer with the thickness of 20 mu m in sequence.
When the photovoltaic module is used, the photovoltaic module comprises a battery piece, an encapsulation adhesive film and a weather-proof low-water light-transmitting photovoltaic backboard, and the EVOH layer of the weather-proof low-water light-transmitting photovoltaic backboard is contacted and bonded with the encapsulation adhesive film.
Example 2
This embodiment differs from embodiment 1 only in that: the modified fluorine film comprises the following raw material components in percentage by mass: 74% of PVDF, 10% of modified multi-wall carbon nano-tubes, 7% of toughening agent, 7.6% of silicon-containing modified polyurethane, 0.6% of antioxidant and 0.8% of lubricant.
Example 3
This embodiment differs from embodiment 1 only in that: the modified fluorine film comprises the following raw material components in percentage by mass: 75% of PVDF, 10% of modified multi-wall carbon nano-tubes, 6.8% of toughening agent, 7% of silicon-containing modified polyurethane, 0.6% of antioxidant and 0.6% of lubricant.
Example 4
This embodiment differs from embodiment 1 only in that: the modified fluorine film comprises the following raw material components in percentage by mass: 76% of PVDF, 9% of modified multi-wall carbon nano-tubes, 7% of toughening agent, 6.8% of silicon-containing modified polyurethane, 0.7% of antioxidant and 0.5% of lubricant.
Example 5
This embodiment differs from embodiment 1 only in that: the modified fluorine film comprises the following raw material components in percentage by mass: 77% of PVDF, 8.5% of modified multi-wall carbon nano-tubes, 6.2% of toughening agent, 7.2% of silicon-containing modified polyurethane, 0.5% of antioxidant and 0.6% of lubricant.
Example 6
This embodiment differs from embodiment 1 only in that: the toughening agent adopts polyolefin toughening agent EPDM.
Example 7
This embodiment differs from embodiment 1 only in that: the antioxidant is butyl hydroxy anisole.
Example 8
This embodiment differs from embodiment 1 only in that: the antioxidant is 2, 6-di-tert-butyl-p-cresol.
Example 9
This embodiment differs from embodiment 1 only in that: in the preparation of the modified multi-wall carbon nano tube, the strong acid adopts sulfuric acid with the concentration (mass fraction) of 98 percent.
Example 10
This embodiment differs from embodiment 1 only in that: in the preparation of the modified multi-wall carbon nano tube, the strong acid adopts 68% nitric acid in concentration (mass fraction).
Comparative example 1
This comparative example differs from example 3 only in that: and deleting the lubricant from the raw material components of the modified fluorine film layer.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: 75.6% of PVDF, 10% of modified multi-wall carbon nano-tubes, 6.8% of toughening agent, 7% of silicon-containing modified polyurethane and 0.6% of antioxidant.
Comparative example 2
This comparative example differs from example 3 only in that: and deleting the toughening agent from the raw material components of the modified fluorine film layer.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: 81.8% of PVDF, 10% of modified multi-wall carbon nano-tubes, 7% of silicon-containing modified polyurethane, 0.6% of antioxidant and 0.6% of lubricant.
Comparative example 3
This comparative example differs from example 3 only in that: the modified multi-wall carbon nano tube is prepared by pickling the multi-wall carbon nano tube with strong acid.
Specifically, the preparation method of the modified multi-wall carbon nano tube comprises the following steps:
a1, putting the multi-wall carbon nano tube into strong acid, wherein the mass ratio of the multi-wall carbon nano tube to the strong acid is 1:3; the strong acid adopts mixed acid, and the concentration (mass fraction) of the mixed acid is 98 percent sulfuric acid and the concentration (mass fraction) of the mixed acid is 68 percent nitric acid according to the mass ratio of 3:1, mixing to obtain the product; heating to 90 deg.c and maintaining for 2 hr to obtain pickled carbon nanotube.
And A2, putting the acid-washed carbon nano tube obtained in the step A1 into deionized water, performing ultrasonic treatment for 30 minutes in an ultrasonic cleaner, performing centrifugal separation by using a centrifugal machine, repeatedly washing to be neutral by using the deionized water, and finally drying in a vacuum drying oven to obtain the modified multi-wall carbon nano tube.
Comparative example 4
This comparative example differs from example 3 only in that: the modified multi-wall carbon nano tube is prepared by reacting the multi-wall carbon nano tube with 50% polyethyleneimine water solution.
Specifically, the preparation method of the modified multi-wall carbon nano tube comprises the following steps:
adding the multi-wall carbon nano tube into a polyethyleneimine water solution with the concentration (mass fraction) of 50%, oscillating for 24 hours in a constant-temperature water bath (30 ℃), then washing with deionized water to remove unreacted polyethyleneimine, and finally drying in a vacuum drying oven to obtain the modified multi-wall carbon nano tube.
Comparative example 5
This comparative example differs from example 3 only in that: in the raw material components of the modified fluorine film layer, the multiwall carbon nanotube is not modified.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: 75% of PVDF, 10% of multi-wall carbon nano-tubes, 6.8% of toughening agent, 7% of silicon-containing modified polyurethane, 0.6% of antioxidant and 0.6% of lubricant.
Comparative example 6
This comparative example differs from example 3 only in that: in the raw material components of the modified fluorine film layer, polyurethane is not modified.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: 75% of PVDF, 10% of modified multi-wall carbon nano-tubes, 6.8% of toughening agent, 7% of polyurethane, 0.6% of antioxidant and 0.6% of lubricant.
Comparative example 7
This comparative example differs from example 3 only in that: in the raw material components of the modified fluorine film layer, the multi-wall carbon nano tube is not modified, and the polyurethane is not modified.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: 75% of PVDF, 10% of multi-wall carbon nano-tubes, 6.8% of toughening agent, 7% of polyurethane, 0.6% of antioxidant and 0.6% of lubricant.
Comparative example 8
This comparative example differs from example 3 only in that: the modified multi-wall carbon nanotubes are replaced by modified single-wall carbon nanotubes.
Specifically, the preparation method of the modified single-walled carbon nanotube comprises the following steps:
a1, putting the single-walled carbon nanotubes into strong acid, wherein the mass ratio of the single-walled carbon nanotubes to the strong acid is 1:3; the strong acid adopts mixed acid, and the concentration (mass fraction) of the mixed acid is 98 percent sulfuric acid and the concentration (mass fraction) of the mixed acid is 68 percent nitric acid according to the mass ratio of 3:1, mixing to obtain the product; heating to 90 deg.c and maintaining for 2 hr to obtain pickled carbon nanotube.
A2, putting the acid-washed carbon nano tube obtained in the step A1 into deionized water, performing ultrasonic treatment in an ultrasonic cleaner for 30 minutes, then performing centrifugal separation by using a centrifugal machine, and repeatedly washing with the deionized water to be neutral to obtain a neutral carbon nano tube;
a3, putting the neutral carbon nano tube obtained in the step A2 into a 50% concentration (mass fraction) polyethyleneimine water solution, oscillating for 24 hours in a constant-temperature water bath (30 ℃), washing with deionized water to remove unreacted polyethyleneimine, and finally drying in a vacuum drying oven to obtain the modified single-walled carbon nano tube.
Comparative example 9
This comparative example differs from example 3 only in that: the modified multi-wall carbon nano tube is replaced by titanium dioxide. In particular to R-996 rutile type titanium dioxide.
Comparative example 10
This comparative example differs from example 3 only in that: and deleting the modified multi-wall carbon nano tube from the raw material components of the modified fluorine film layer.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: PVDF85%, toughening agent 6.8%, silicon-containing modified polyurethane 7%, antioxidant 0.6% and lubricant 0.6%.
Comparative example 11
This comparative example differs from example 3 only in that: the silicon-containing modified polyurethane is deleted from the raw material components of the modified fluorine film layer.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: PVDF82%, modified multi-wall carbon nano tube 10%, flexibilizer 6.8%, antioxidant 0.6% and lubricant 0.6%.
Comparative example 12
This comparative example differs from example 3 only in that: and deleting the modified multi-wall carbon nano tube and the silicon-containing modified polyurethane from the raw material components of the modified fluorine film layer.
Specifically, the modified fluorine film layer comprises the following raw material components in percentage by mass: PVDF92%, toughening agent 6.8%, antioxidant 0.6% and lubricant 0.6%.
Comparative example 13
This comparative example differs from example 3 only in that: the fluorine film layer is not modified, and the raw material component is single PVDF.
Specifically, a weather-proof low-water light-transmitting photovoltaic backboard comprises an EVOH layer, a first bonding layer, a PET layer, a second bonding layer and a fluorine film layer which are sequentially arranged.
The preparation method of the fluorine film layer comprises the following steps: placing PVDF in a high-speed mixer, adding ultrasound (in particular, an ultrasonic device is required to be connected with the high-speed mixer in the specific implementation, specifically, an ultrasonic generator is arranged on the high-speed mixer, the ultrasonic generator is linked with a control system of the high-speed mixer, and the ultrasonic generator is started simultaneously when the high-speed mixer is started), and obtaining a structural material of a fluorine film layer through double-screw melt extrusion, cooling and granulating; and (5) continuously carrying out film forming by extending to obtain the fluorine film layer.
The preparation method of the weather-resistant low-water light-transmitting photovoltaic backboard comprises the following steps: and (3) carrying out coextrusion on the structural materials of the EVOH, the maleic anhydride grafted polyethylene, the PET slice, the maleic anhydride grafted polyethylene and the fluorine film layer to obtain the photovoltaic backboard. The photovoltaic back sheet has a five-layer structure, and comprises an EVOH layer with the thickness of 40 mu m, a first bonding layer with the thickness of 30 mu m, a PET layer with the thickness of 250 mu m, a second bonding layer with the thickness of 30 mu m and a fluorine film layer with the thickness of 20 mu m in sequence.
Comparative example 14
This comparative example differs from example 3 only in that: in the preparation process of the constituent materials of the modified fluorine film layer, ultrasound is not externally added.
Specifically, the preparation method of the modified fluorine film layer comprises the following steps: PVDF, modified multi-wall carbon nano tubes, a toughening agent, silicon-containing modified polyurethane, an antioxidant and a lubricant are taken and placed into a high-speed mixer to be mixed, and the materials are melted and extruded through double screws, cooled and granulated to obtain a component material of a modified fluorine film layer; and (5) continuously carrying out film forming by extending to obtain the modified fluorine film layer.
Comparative example 15
This comparative example differs from example 3 only in that: a weather-resistant low-water light-transmitting photovoltaic backboard comprises an EVOH layer, a bonding layer and a modified fluorine film layer which are sequentially arranged.
Comparative example 16
This comparative example differs from example 3 only in that: a weather-resistant low-water light-transmitting photovoltaic backboard comprises a PET layer, a bonding layer and a modified fluorine film layer which are sequentially arranged.
Test example 1
Test object: examples 1-10 and comparative examples 1-16.
The test is based on: CQC3308-2013.
Test item: see table 1:
test results: see table 2:
analysis of results: as can be seen from the data of examples 1-10 in combination with Table 2, the weather-resistant low-water-permeability photovoltaic backboard prepared by the invention has all indexes (heat shrinkage, water vapor transmittance, tensile strength and elongation at break) reaching standards and excellent performance; among them, example 3 is the most preferred example.
As can be seen from the data of examples 3, comparative examples 8 to 10 and comparative examples 11 to 14 in combination with table 2, the participation of the modified multi-walled carbon nanotubes in the preparation of the modified fluorine film layer is advantageous for reducing the heat shrinkage rate of the modified fluorine film layer; in addition, the multi-wall carbon nano tube transposition single-wall carbon nano tube or the modified multi-wall carbon nano tube is directly replaced by titanium dioxide, which is not beneficial to the reduction of the heat shrinkage rate; the operation means of the additional ultrasound is also beneficial to reducing the heat shrinkage rate, probably because the additional ultrasound is beneficial to the dispersion of the modified multi-wall carbon nano tube in the film forming material, thereby playing an auxiliary role.
As can be seen from the data of the table 2 in the embodiment 3 and the comparative examples 3-14, the multi-walled carbon nanotubes are subjected to two treatment means of strong acid washing and polyethyleneimine modification, the modified multi-walled carbon nanotubes are prepared to participate in the preparation of the modified fluorine film layer, the water vapor transmittance of the finally prepared photovoltaic backboard can be effectively reduced, and the two treatment means are synergistic, so that the effect is better than that of the common superposition of the two treatment means; at the same time, the participation of the silicon-containing modified polyurethane can also produce the effect of reducing the water vapor transmittance, and in this aspect, a certain synergistic effect exists between the silicon-containing modified polyurethane and the modified multi-wall carbon nano tube.
As can be seen from the data of examples 3, comparative examples 3-5, comparative examples 7-10 and comparative examples 12-14 in combination with Table 2, the preparation of modified multi-walled carbon nanotubes by performing two treatment means of strong acid washing and polyethyleneimine modification can effectively enhance the mechanical properties (tensile strength) of the finally prepared photovoltaic back panel, and the synergistic effect between the two treatment means is superior to that of the common superposition of the two treatment means.
As can be seen from the data of examples 3, comparative examples 6-7 and comparative examples 11-14 in combination with table 2, the participation of the silicon-containing modified polyurethane can improve the elongation at break of the prepared modified fluorine film layer, and further improve the elongation at break of the finally prepared photovoltaic back sheet.
Test example 2
Test object: example 3, comparative examples 3-5, 9 and 10.
The test is based on: irradiating the photovoltaic backboard with 300kWh ultraviolet light, and measuring yellowing delta b before and after ultraviolet light irradiation; Δb was measured according to the methods of GB/T3979-2008 and GB/T7921-2008.
Test item: and (5) light weatherability.
Test results: see table 3:
analysis of results: as can be seen from the data of example 3 and comparative examples 3-5, 9 and 10 in combination with table 3, the participation of the multiwall carbon nanotubes as a raw material is beneficial to improving the light weatherability of the prepared photovoltaic back sheet; the multi-wall carbon nano tube is subjected to strong acid washing and polyethyleneimine water modification, so that the lifting effect can be enhanced. This is probably because the nano particles (multi-walled carbon nanotubes) can efficiently and long-effectively shield ultraviolet rays, thereby improving the light weatherability; the surface property and the surface energy of the multi-wall carbon nano tube can be changed by the treatment means of strong acid washing and polyethyleneimine water modification, so that the multi-wall carbon nano tube is not easy to migrate in the material, and can adsorb and prevent migration of organic molecules, thereby playing a role in enhancing the lifting effect.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. The weather-resistant low-water light-transmitting photovoltaic backboard is characterized by comprising an EVOH layer (1), a first bonding layer (2), a PET layer (3), a second bonding layer (4) and a modified fluorine film layer (5) which are sequentially arranged;
the modified fluorine film layer (5) comprises the following raw material components in percentage by mass: 73% -77% of PVDF, 8.5% -10.5% of modified multi-wall carbon nano-tubes, 6% -7.2% of toughening agents, 6.6% -7.8% of silicon-containing modified polyurethane, 0.5% -0.8% of antioxidants and 0.5% -0.8% of lubricants;
the preparation method of the modified multi-wall carbon nano tube comprises the following steps:
a1, putting the multi-wall carbon nano tube into strong acid, heating to 85-100 ℃, and keeping for 1-3 hours to obtain an acid-washed carbon nano tube;
a2, putting the acid-washed carbon nano tube obtained in the step A1 into deionized water, performing ultrasonic treatment in an ultrasonic cleaner for 30 minutes, then performing centrifugal separation by using a centrifugal machine, and repeatedly washing with the deionized water to be neutral to obtain a neutral carbon nano tube;
a3, putting the neutral carbon nano tube obtained in the step A2 into a polyethyleneimine water solution, oscillating for 24 hours in a constant-temperature water bath, washing with deionized water, and drying to obtain the modified multi-wall carbon nano tube.
2. The weather-resistant low-water light-transmitting photovoltaic back sheet according to claim 1, wherein in A1, the strong acid adopts mixed acid, and the strong acid is prepared from 98% sulfuric acid and 68% nitric acid according to a mass ratio of 3:1, and mixing.
3. The weatherable low water light transmitting photovoltaic backsheet of claim 1, wherein in A3 the concentration of the aqueous polyethyleneimine solution is 50%.
4. The weatherable low water light transmitting photovoltaic backsheet according to claim 1, wherein the silicon-containing modified polyurethane is prepared by the following method:
b1, mixing isophorone diisocyanate and hydroxyl-terminated polybutadiene acrylonitrile according to N (NCO)/n (HTBN) =1.6, adding 0.5wt% of dibutyltin dilaurate, adding amino silicone oil according to n (amino silicone oil)/n (HTBN) =0.06, heating to 78 ℃ under the protection of dry nitrogen, and reacting 2 h;
and B2, adding a chain extender methyl propylene glycol according to n (chain extender)/n (HTBN) =0.05, keeping the temperature at 78 ℃ for reaction for 0.5h, slowly heating to 90 ℃ to complete the reaction, and cooling to room temperature to obtain the silicon-containing modified polyurethane.
5. The weatherable low water light transmitting photovoltaic backsheet of claim 1, wherein the toughening agent comprises a styrenic toughening agent or a polyolefin toughening agent.
6. The weatherable low water light transmitting photovoltaic backsheet of claim 1, wherein the antioxidant comprises butyl hydroxyanisole and/or 2, 6-di-tert-butyl-p-cresol.
7. The weatherable low water light transmitting photovoltaic backsheet of claim 1, wherein the lubricant comprises an alcohol lubricant or a silicone based lubricant.
8. The weatherable low water light transmission photovoltaic backsheet according to any one of claims 1 to 7, wherein the modified fluorine film layer is prepared by the following method: PVDF, modified multi-wall carbon nano tube, toughening agent, silicon-containing modified polyurethane, antioxidant and lubricant are taken, mixed in a high-speed mixer, added with ultrasound, and subjected to double-screw melt extrusion, cooled and granulated to obtain the modified fluorine film layer constituent material.
9. The weatherable low water light transmitting photovoltaic backsheet of claim 1, wherein the first tie layer and the second tie layer are both maleic anhydride grafted polyethylene.
10. A method for preparing a weatherable low water transmission photovoltaic backsheet according to any one of claims 1 to 9, comprising the steps of: and (3) carrying out coextrusion on the constituent materials of the EVOH layer, the first bonding layer, the PET layer, the second bonding layer and the modified fluorine film layer to obtain the photovoltaic backboard.
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