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WO2017107783A1 - Film de réduction de réflexion autonettoyant et procédé de préparation de celui-ci - Google Patents

Film de réduction de réflexion autonettoyant et procédé de préparation de celui-ci Download PDF

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Publication number
WO2017107783A1
WO2017107783A1 PCT/CN2016/109153 CN2016109153W WO2017107783A1 WO 2017107783 A1 WO2017107783 A1 WO 2017107783A1 CN 2016109153 W CN2016109153 W CN 2016109153W WO 2017107783 A1 WO2017107783 A1 WO 2017107783A1
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Prior art keywords
film
self
cleaning
solar cell
cleaning film
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Ceased
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English (en)
Chinese (zh)
Inventor
李东栋
王敏
马朋莎
陈小源
鲁林峰
殷敏
程伟杰
刘东方
方小红
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Shanghai Advanced Research Institute of CAS
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Shanghai Advanced Research Institute of CAS
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H10F77/413—Optical elements or arrangements directly associated or integrated with the devices, e.g. back reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H10F71/137—Batch treatment of the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/40—Optical elements or arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/70—Surface textures, e.g. pyramid structures
    • H10F77/707—Surface textures, e.g. pyramid structures of the substrates or of layers on substrates, e.g. textured ITO layer on a glass substrate
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of functional films, and in particular relates to an anti-reflection self-cleaning film and a preparation method thereof.
  • Solar photovoltaic power generation is a technology that uses the photoelectric effect of semiconductors to directly convert light energy into electrical energy, and is one of the major new energy technologies.
  • the large-scale promotion of photovoltaic power generation mainly depends on its own efficiency improvement and cost reduction.
  • the efficiency can be improved by researching and optimizing the material of the semiconductor absorption layer, adjusting the material interface and energy band, thereby broadening the absorption spectrum, improving the light absorption efficiency, and suppressing the charge recombination.
  • the micro-nano structure can also be used to regulate the incident photons, suppress the surface and interface reflection, and improve the battery's ability to capture light.
  • anti-reflection strategies include surface texturing and anti-reflection (CN 102851743 A), anti-reflection film such as SiN x or SiO x /SiN x deposited on the surface of the cell (CN 104691040 A, CN 104916710 A), surface plasmon resonance enhanced light absorption (CN 102709402 A) and so on.
  • the battery prepared by the above method ultimately requires a packaging process to slow down the degradation of battery performance.
  • the encapsulated window layer is typically a glass or polymer film. The reflection of light at the air/glass or air/polymer interface reduces the number of photons that reach the absorber layer of the battery to some extent.
  • an antireflection film can be formed on the glass or polymer window layer.
  • a commonly used method in crystalline silicon solar cells is to plate a film of a relatively low refractive index porous SiO 2 on the surface of a glass cover (WO 2013174754 A2).
  • Another method is to cover the surface with a nano-array structure film having a sub-wavelength level. For example, Yu et al.
  • nanostructure anti-reflection film has excellent optical properties
  • its sub-micron structure has poor mechanical properties
  • outdoor sand, rain, and dust and residual debris caused by birds can easily stain the surface of the solar panel and affect the efficiency of the battery assembly.
  • an object of the present invention is to provide an anti-reflection self-cleaning film and a preparation method thereof, which have an excellent anti-reflection effect and strong weather resistance, mechanical strength and self-cleaning.
  • An optical film such as a function, and integrating the anti-reflection self-cleaning film with the window layer of the solar cell module can effectively improve battery efficiency.
  • the present invention provides a method for preparing an anti-reflection self-cleaning film, comprising: processing a three-dimensional graphic structure having a micron size on a transparent flexible film by using an imprint technique and a surface modification technique;
  • the transparent flexible film has the property of anti-reflection self-cleaning.
  • the embossing technique comprises one of ultraviolet embossing, hot embossing, heat curing embossing, and microcontact embossing.
  • the ultraviolet imprint comprises: coating the transparent flexible film with a UV curable adhesive, and then imprinting the cured adhesive with a mold having a microscopic structure pattern, and separating the template from the substrate after being irradiated and cured by the ultraviolet lamp, ie The anti-reflection self-cleaning film is obtained.
  • the material of the mold includes one of nickel, copper, chromium, silicon, quartz, sapphire, PI, and polytetrafluoroethylene.
  • the step of heating the transparent flexible film before the imprinting and the gas plasma treatment, or/and the step of heating the transparent flexible film during the imprinting process improve UV imprint efficiency and imprint quality.
  • the hot stamping has a temperature in the range of 90-300 ° C and a pressure in the range of 0.1-30 MPa.
  • the heat curing embossing comprises: pouring or injecting a liquid polymer onto a mold having a micro-structured pattern by using a casting or injection molding technique, and curing the mold and the polymer by heating or natural curing. Separating to obtain the anti-reflection self-cleaning film.
  • the hot stamping comprises one of flat plate imprinting, roll-to-plate imprinting, and roll-to-roll imprinting.
  • the flat hot stamping comprises: contacting a transparent flexible film with a mold having a micro-structure pattern and applying pressure, and then raising the imprint temperature for a certain time to imprint the anti-reflection self-cleaning film. .
  • the roll-to-plate or roll-to-roll embossing comprises: contacting the transparent flexible film with a mold having a micro-structured pattern at a set pressure, roll speed, temperature, light intensity, and draft angle
  • the anti-reflection self-cleaning film is embossed under conditions.
  • the transparent flexible film comprises a transparent polymer material or a composite film of a transparent polymer material and a transparent inorganic material
  • the transparent polymer material comprises polyethylene terephthalate (PET), Polycarbonate (PC), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), polyurethane (PU), polyvinyl chloride (PVC), polypropylene (PP), one of polybutylene terephthalate (PBT), polyimide (PI), polydimethylsiloxane (PDMS), the transparent inorganic material including SiO 2 , TiO 2 , one of Al 2 O 3 , SiN x , SiC.
  • the microscopic three-dimensional graphic structure comprises a pyramidal shape, a pyramid shape, a pit shape, an inverted pyramid shape, an inverted pyramid shape, a grating shape, a prismatic structure, and an ordered arrangement structure or a random arrangement based on the above shape. structure.
  • the surface modification comprises a hard coat of one or more of SiO 2 , TiO 2 , Al 2 O 3 , SiN x , SiC, WO 3 .
  • the self-cleaning surface of the anti-reflective self-cleaning film is a superhydrophobic surface or a super-hydrophilic surface.
  • the method further comprises the steps of: integrating the anti-reflection self-cleaning film with the window layer of the solar cell module to effectively suppress surface reflection of the window layer and increase the number of photons entering the absorption layer of the battery, thereby improving photoelectric conversion efficiency of the battery.
  • the solar cell module includes one of a rigid crystalline silicon solar cell module, a thin film solar cell module, and a flexible solar cell module.
  • integrating the anti-reflection self-cleaning film with the window layer of the solar cell module includes the steps of: backing plate material, third hot melt adhesive, crystalline silicon solar cell, second hot melt adhesive, solar cell
  • the glass cover plate, the first hot melt adhesive, and the anti-reflection self-cleaning film are stacked one on another from bottom to top, and heated to 85-180 ° C, and a pressure of 0.1-1.0 MPa is applied at both ends thereof to achieve reduction Reflex self-cleaning film and crystalline silicon solar cell bonding.
  • integrating the anti-reflection self-cleaning film with the window layer of the solar cell module comprises the steps of: an anti-reflection self-cleaning film, a fourth hot melt adhesive, a solar cell glass cover, and a third hot melt adhesive , crystalline silicon solar cell, second hot melt adhesive, solar cell glass cover, first hot melt adhesive, anti-reflective self-cleaning film stacked in order from bottom to top, and heated to 85-180 ° C Applying a pressure of 0.1-1.0 MPa at both ends to achieve the bonding of the double-glass crystalline silicon solar cell package and the anti-reflection self-cleaning film.
  • integrating the anti-reflection self-cleaning film with the window layer of the solar cell module includes the steps of: backing plate material, second hot melt adhesive, thin film solar cell, first hot melt adhesive, and anti-reflection
  • the cleaning film is stacked one on another from bottom to top and heated to 85-180 ° C, and a pressure of 0.1-1.0 MPa is applied to both ends thereof to achieve adhesion between the anti-reflection self-cleaning film and the thin film solar cell.
  • the back sheet material is a polyester film having water vapor resistance, oxygen permeation, and good ultraviolet resistance
  • the polyester film side has a resin capable of bonding with a hot melt adhesive.
  • the first hot melt adhesive, and/or the second hot melt adhesive, and/or the third hot melt adhesive, and/or the fourth hot melt adhesive comprise ethylene vinyl acetate Copolymer (EVA) adhesive or film, polyvinyl butyral (PVB) One of an adhesive or a film, a polyolefin (PO) adhesive or a film, a polyurethane (TPU) adhesive or a film.
  • EVA ethylene vinyl acetate Copolymer
  • PVB polyvinyl butyral
  • PO polyolefin
  • TPU polyurethane
  • the anti-reflection self-cleaning film is first prepared and integrated with the window layer of the solar cell module, or the preparation of the anti-reflection self-cleaning film is simultaneously performed with the window layer of the solar cell module.
  • the present invention also provides an anti-reflection self-cleaning film comprising a transparent flexible film and a microscopic-sized three-dimensional graphic structure formed on the transparent flexible film, and the three-dimensional graphic structure has a surface
  • the modification makes the transparent flexible film have anti-reflection self-cleaning properties.
  • the transparent flexible film comprises a transparent polymer material or a composite film of a transparent polymer material and a transparent inorganic material
  • the transparent polymer material comprises polyethylene terephthalate (PET), Polycarbonate (PC), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), polyurethane (PU), polyvinyl chloride (PVC), polypropylene (PP), one of polybutylene terephthalate (PBT), polyimide (PI), polydimethylsiloxane (PDMS), the transparent inorganic material including SiO 2 , TiO 2 , one of Al 2 O 3 , SiN x , SiC.
  • the microscopic three-dimensional graphic structure comprises a pyramidal shape, a pyramid shape, a pit shape, an inverted pyramid shape, an inverted pyramid shape, a grating shape, a prismatic structure, and an ordered arrangement structure or a random arrangement based on the above shape. structure.
  • the surface modification comprises a hard coat of one or more of SiO 2 , TiO 2 , Al 2 O 3 , SiN x , SiC, WO 3 .
  • the self-cleaning surface of the anti-reflective self-cleaning film is a superhydrophobic surface or a super-hydrophilic surface.
  • the anti-reflection self-cleaning film is integrated with the window layer of the solar cell module to effectively suppress surface reflection of the window layer and increase the number of photons entering the absorption layer of the battery, thereby improving the photoelectric conversion efficiency of the battery.
  • the solar cell module comprises one of a rigid crystalline silicon solar cell module, a thin film solar cell module, and a flexible solar cell module.
  • the anti-reflection self-cleaning film and the window layer of the solar cell module comprise a backing material stacked in order from bottom to top, a third hot melt adhesive, a crystalline silicon solar cell, and a second hot melt bonding.
  • Agent, solar cell glass cover, first hot melt adhesive, and anti-reflection self-cleaning film comprise a backing material stacked in order from bottom to top, a third hot melt adhesive, a crystalline silicon solar cell, and a second hot melt bonding.
  • Agent, solar cell glass cover, first hot melt adhesive, and anti-reflection self-cleaning film are examples of the window layer of the solar cell module.
  • the anti-reflection self-cleaning film integrates with the window layer of the solar cell module, including an anti-reflection self-cleaning film stacked in order from bottom to top, a fourth hot melt adhesive, a solar cell cover, and a third heat.
  • a flux adhesive, a crystalline silicon solar cell, a second hot melt adhesive, a solar cell glass cover, a first hot melt adhesive, and an anti-reflective self-cleaning film is included in the window layer of the solar cell module.
  • a flux adhesive a crystalline silicon solar cell, a second hot melt adhesive, a solar cell glass cover, a first hot melt adhesive, and an anti-reflective self-cleaning film.
  • the anti-reflection self-cleaning film and the window layer of the solar cell module comprise a backing material stacked in order from bottom to top, a second hot melt adhesive, a thin film solar cell, and a first hot melt adhesive. And anti-reflection self-cleaning film.
  • the backing material is a polyester film having waterproof steam, oxygen permeation, and good ultraviolet resistance.
  • the polyester film side has a resin capable of bonding with a hot melt adhesive.
  • the first hot melt adhesive, and/or the second hot melt adhesive, and/or the third hot melt adhesive, and/or the fourth hot melt adhesive comprise ethylene vinyl acetate Copolymer (EVA) adhesive or film, polyvinyl butyral (PVB) adhesive or film, polyolefin (PO) adhesive or film, polyurethane (TPU) adhesive or film One of them.
  • EVA ethylene vinyl acetate Copolymer
  • PVB polyvinyl butyral
  • PO polyolefin
  • TPU polyurethane
  • the first hot melt adhesive, and/or the second hot melt adhesive, and/or the third hot melt adhesive, and/or the fourth hot melt adhesive comprise ethylene vinyl acetate Copolymer (EVA) adhesive or film, polyvinyl butyral (PVB) adhesive or film, polyolefin (PO) adhesive or film, polyurethane (TPU) adhesive or film One of them.
  • EVA ethylene vinyl acetate Copolymer
  • PVB polyvinyl butyral
  • PO polyolefin
  • TPU polyurethane
  • the anti-reflection self-cleaning film of the present invention and the preparation method thereof have the following beneficial effects:
  • a film having a micron-sized structure can increase the transmittance of the film by multiple reflections and refractions, and can achieve a reversal effect equivalent to that of the conventional nanostructure anti-reflection film.
  • the anti-reflection film having a micron-sized structure is easier to process and has higher mechanical strength than the nanostructure anti-reflection film.
  • the film has a broad spectrum and wide-angle anti-reflection effect. Taking the anti-reflection film and the crystalline silicon solar cell as an example, it is optically simulated at a wavelength of 600 nm.
  • Figure 1 shows the propagation path of light in the presence of a planar film and a microprism antireflection film (period 50 ⁇ m, prism height 25 ⁇ m) at incident angles of 0° and 30°, respectively. It can be seen that the light absorption of the battery at 0° and 30° incident angles is changed from 92.4% and 95.3% to 92.2% and 95.7%, respectively.
  • Fig. 2 is a light absorption characteristic of a battery calculated by taking a microprism film with a period of 50 ⁇ m and different heights as an example. It can be seen that such a film can effectively improve the light absorption of the battery at different incident angles.
  • the improvement of light absorption capacity is further reflected in the improvement of photoelectric conversion efficiency of various types of solar cells.
  • the film is coated on the surface of various solar cell modules (such as rigid single-sided crystalline silicon solar cell modules, crystalline silicon double-glass components, thin-film solar cells, and flexible solar cell modules of various material systems), which can effectively improve the battery.
  • various solar cell modules such as rigid single-sided crystalline silicon solar cell modules, crystalline silicon double-glass components, thin-film solar cells, and flexible solar cell modules of various material systems
  • the micron structure can effectively increase the contact angle between the film and water.
  • the optimized microstructure film has a contact angle with water of more than 150° and a rolling angle of up to 10°.
  • the water droplets can form a sphere on the surface, which is easy to roll off. Contaminants with good self-cleaning ability.
  • the modification of the inorganic hard coating on the surface of the micro-structure can improve the mechanical strength of the film.
  • semiconductor materials such as TiO 2 , ZnO, In 2 O 3 , WO 3 and the like can also have the effect of removing surface static electricity, blocking ultraviolet light transmission, and reducing the photo-induced attenuation of the solar cell.
  • the film is transformed into a super-hydrophilic property, and combined with photocatalysis, degrades the surface organic contamination to achieve a self-cleaning effect.
  • 1a to 1d show the propagation paths of parallel light (600 nm) in the presence of planar films and microprism films (period 50 ⁇ m, prism height 25 ⁇ m) at incident angles of 0° and 30°, respectively, where a is incident.
  • the angle is 0°, 1 represents a structured anti-reflection self-cleaning film, 2 represents a silicon wafer, 3 represents an aluminum back-reflection layer;
  • Figure b shows a light incident angle of 0°, and 1 represents an unstructured polymer film (material and anti-reflection) The self-cleaning film is the same), 2 represents the silicon wafer, 3 represents the aluminum back-reflection layer;
  • Figure c shows the light incident angle of 30°, 1 represents the structured anti-reflection self-cleaning film, 2 represents the silicon wafer, and 3 represents the aluminum back-reflection layer;
  • d is the light incident angle of 30°, 1 represents an unstructured polymer film (the material is the same as the anti-reflection self-cleaning film), 2 represents a silicon wafer, and 3 represents an aluminum back-reflecting layer.
  • Figure 2 shows a flat film and a 50 ⁇ m period, different height (20, 25, 30 ⁇ m) microprism antireflection film attached to silicon in the range of 0-45° from the normal angle of the 600 nm parallel light to the cell surface.
  • Figure 3 shows the superhydrophobic character of the antireflection film with a contact angle of 156° with water and a roll angle of 10°.
  • Figure 4 shows a schematic diagram of the integration of an anti-reflection self-cleaning film with a crystalline silicon cell ( Figure a) and a dual-glass crystalline silicon cell ( Figure b) flexible thin film solar cell ( Figure c).
  • FIG. 5a to 5h are respectively a schematic diagram showing the periodic arrangement of several typical structures of the anti-reflection self-cleaning film of the present invention, wherein a is a grating structure; FIG. b is a pyramid structure; and FIG. Conical structure; Figure e is a columnar structure; Figure f is an inverted pyramid structure; Figure g is an inverted triangular pyramid structure; Figure h is a hexagonal pit structure.
  • Figure 6 shows the surface of the battery having the anti-reflection self-cleaning film (AR) and the anti-reflection film of the present invention at different angles (0°, 30°, 45°, 60°) from the normal of the surface of the battery.
  • the IV (current-voltage) curve of the amorphous silicon thin film solar cell under the condition of (Flat), 30, 45, and 60 represent the incident light tilt angles of 30°, 45°, and 60°, respectively.
  • Table 1 shows the anti-reflection self-cleaning film (AR) and the anti-reflection film of the present invention on the surface of the battery under different angles (0°, 30°, 45°, 60°) of the sunlight and the normal of the surface of the battery.
  • the embodiment provides a method for preparing an anti-reflection self-cleaning film, comprising: processing a microscopic three-dimensional graphic structure on a transparent flexible film by using an imprint technique and a surface modification technology, so that the transparent flexible film has anti-reflection Clean performance.
  • the embossing technique includes one of ultraviolet embossing, hot embossing, heat curing embossing, and microcontact embossing, wherein the thermal embossing includes flat embossing, roll-to-plate embossing, and One of the roll-to-roll embossing.
  • the UV imprinting comprises: coating a UV-curable adhesive on a transparent flexible film, and then imprinting the cured adhesive with a mold having a micro-structured pattern, and separating the template from the substrate after being irradiated and cured by the ultraviolet lamp, ie, The anti-reflection self-cleaning film is obtained.
  • the material of the mold includes one of nickel, copper, chromium, silicon, quartz, sapphire, PI, and polytetrafluoroethylene.
  • the step of heating the transparent flexible film before the imprinting and the gas plasma treatment, or/and the step of heating the transparent flexible film during the imprinting process improve UV imprint efficiency and imprint quality.
  • the hot stamping has a temperature in the range of 90-300 ° C and a pressure in the range of 0.1-30 MPa.
  • the heat curing embossing comprises: casting or injecting a liquid polymer onto a mold having a micro-structure pattern by using a casting or injection molding technique, and curing the mold and the polymer by heating or natural curing. Separating to obtain the anti-reflection self-cleaning film.
  • the flat hot stamping comprises: contacting a transparent flexible film with a mold having a micro-structure pattern and applying pressure, and then raising the imprint temperature for a certain time to imprint the anti-reflection self-cleaning film.
  • the roll-to-plate or roll-to-roll embossing comprises: contacting the transparent flexible film with a mold having a micro-structured pattern at a set pressure, roll speed, temperature, light intensity, and draft angle
  • the anti-reflection self-cleaning film is embossed under conditions.
  • the transparent flexible film comprises a transparent polymer material or a composite film of a transparent polymer material and a transparent inorganic material
  • the transparent polymer material comprises polyethylene terephthalate (PET), Polycarbonate (PC), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), polyurethane (PU), polyvinyl chloride (PVC), polypropylene (PP), one of polybutylene terephthalate (PBT), polyimide (PI), polydimethylsiloxane (PDMS), the transparent inorganic material including SiO 2 , TiO 2 , one of Al 2 O 3 , SiN x , SiC.
  • the microscopic three-dimensional graphic structure includes a cylindrical shape (as shown in FIG. 5e), a tapered shape (as shown in FIG. 5d), and a pyramid shape (as shown in FIG. 5b). ), a pit shape (as shown in Figure 5h), an inverted triangular pyramid (as shown in Figure 5g), an inverted cone, an inverted pyramid (as shown in Figure 5f), a grating (as shown in Figure 5a), A prismatic (as shown in Figure 5c) structure and an ordered or random array of structures derived from the above shapes.
  • the surface modification includes a hard coat layer of one or more of SiO 2 , TiO 2 , Al 2 O 3 , SiN x , SiC, WO 3 .
  • the self-cleaning surface of the anti-reflective self-cleaning film is a superhydrophobic surface or a super-hydrophilic surface.
  • the method further includes the steps of: integrating the anti-reflection self-cleaning film with the window layer of the solar cell module to effectively suppress surface reflection of the window layer, increase the number of photons entering the absorption layer of the battery, thereby improving photoelectric conversion efficiency of the battery.
  • the solar cell module includes one of a rigid crystalline silicon solar cell module, a thin film solar cell module, and a flexible solar cell module.
  • integrating the anti-reflection self-cleaning film with the window layer of the solar cell module includes the steps of: backing plate material, third hot melt adhesive, crystalline silicon solar cell, second hot melt adhesive, solar cell
  • the glass cover plate, the first hot melt adhesive, and the anti-reflection self-cleaning film are stacked one on another from bottom to top, and heated to 85-180 ° C, and a pressure of 0.1-1.0 MPa is applied at both ends thereof to achieve reduction Reflex self-cleaning film and crystalline silicon solar cell bonding.
  • integrating the anti-reflection self-cleaning film with the window layer of the solar cell module includes the steps of: anti-reflective self-cleaning film, fourth hot melt adhesive, solar cell glass cover, third hot melt adhesive , crystalline silicon solar cell, second hot melt adhesive, solar cell glass cover, first hot melt adhesive, anti-reflective self-cleaning film stacked in order from bottom to top, and heated to 85-180 ° C Applying a pressure of 0.1-1.0 MPa at both ends to achieve the bonding of the double-glass crystalline silicon solar cell package and the anti-reflection self-cleaning film.
  • integrating the anti-reflection self-cleaning film with the window layer of the solar cell module includes the steps of: backing plate material, second hot melt adhesive, thin film solar cell, first hot melt adhesive, and anti-reflection
  • the cleaning film is stacked one on another from bottom to top and heated to 85-180 ° C, and a pressure of 0.1-1.0 MPa is applied to both ends thereof to achieve adhesion between the anti-reflection self-cleaning film and the thin film solar cell.
  • the back sheet material is a polyester film having water vapor resistance, oxygen permeation, and good ultraviolet resistance
  • the polyester film side has a resin capable of bonding with a hot melt adhesive.
  • the first hot melt adhesive, and/or the second hot melt adhesive, and/or the third hot melt adhesive, and/or the fourth hot melt adhesive comprise ethylene vinyl acetate.
  • the anti-reflection self-cleaning film is first prepared and integrated with the window layer of the solar cell module, or the preparation of the anti-reflection self-cleaning film is performed simultaneously with the window layer of the solar cell module.
  • the embodiment further provides an anti-reflection self-cleaning film comprising a transparent flexible film and a microscopic three-dimensional graphic structure formed on the transparent flexible film, and the three-dimensional graphic structure has The surface modification makes the transparent flexible film have anti-reflection self-cleaning properties.
  • the transparent flexible film comprises a transparent polymer material or a composite film of a transparent polymer material and a transparent inorganic material
  • the transparent polymer material comprises polyethylene terephthalate (PET), Polycarbonate (PC), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkoxy vinyl ether copolymer (PFA), polyurethane (PU), polyvinyl chloride (PVC), polypropylene (PP), one of polybutylene terephthalate (PBT), polyimide (PI), polydimethylsiloxane (PDMS), the transparent inorganic material including SiO 2 , TiO 2 , one of Al 2 O 3 , SiN x , SiC.
  • the micro-dimensional three-dimensional graphic structure comprises a pyramid, a pyramid, a pit, an inverted cone, an inverted pyramid, a grating, a prismatic structure, and an ordered arrangement derived from the above shape or randomly arranged. structure.
  • the surface modification includes a hard coat layer of one or more of SiO 2 , TiO 2 , Al 2 O 3 , SiN x , SiC, WO 3 .
  • the self-cleaning surface of the anti-reflective self-cleaning film is a superhydrophobic surface or a super-hydrophilic surface.
  • the anti-reflection self-cleaning film is integrated with the window layer of the solar cell module to effectively suppress surface reflection of the window layer and increase the number of photons entering the absorption layer of the battery, thereby improving the photoelectric conversion efficiency of the battery.
  • the solar cell module includes one of a rigid crystalline silicon solar cell module, a thin film solar cell module, and a flexible solar cell module.
  • the anti-reflection self-cleaning film integrates with the window layer of the solar cell module, including a back sheet material stacked in order from bottom to top, a third hot melt adhesive, a crystalline silicon solar cell, and a second hot melt bonding.
  • the anti-reflection self-cleaning film integrates with the window layer of the solar cell module, including an anti-reflection self-cleaning film stacked in order from bottom to top, a fourth hot melt adhesive, a solar cell cover, and a third heat.
  • a flux adhesive, a crystalline silicon solar cell, a second hot melt adhesive, a solar cell glass cover, a first hot melt adhesive, and an anti-reflective self-cleaning film is included in the window layer of the solar cell module.
  • the anti-reflection self-cleaning film integrates with the window layer of the solar cell module, including a back sheet material stacked in order from bottom to top, a second hot melt adhesive, a thin film solar cell, and a first hot melt adhesive. And anti-reflection self-cleaning film.
  • the backing material is a polyester film having water vapor resistance, oxygen permeation, and good ultraviolet resistance.
  • the polyester film side has a resin capable of bonding with a hot melt adhesive.
  • the first hot melt adhesive, and/or the second hot melt adhesive, and/or the third hot melt adhesive, and/or the fourth hot melt adhesive comprise ethylene vinyl acetate.
  • the first hot melt adhesive, and/or the second hot melt adhesive, and/or the third hot melt adhesive, and/or the fourth hot melt adhesive comprise ethylene vinyl acetate.
  • an anti-reflection self-cleaning film is prepared by ultraviolet nanoimprinting, and the preparation process is as follows:
  • Step 1) the UV embossing adhesive was applied to a clean PET substrate, and the embossing adhesive was 100 ⁇ m thick.
  • Step 2) covering the sample in the step 1) with a pre-processed PDMS template having a micro-pit structure (pit depth 10 ⁇ m, diameter 10 ⁇ m, period 15 ⁇ m), applying a uniform pressure of 0.2 MPa, and irradiating with ultraviolet light.
  • Photograph power is 100mW/cm 2
  • irradiation time is 200s.
  • Step 3 after the UV embossing adhesive is cured, the stencil is separated from the substrate, that is, a micron-sized columnar structure is formed on the substrate, and the obtained film has anti-reflection and super-hydrophobic properties. Its water contact angle is 156° (as shown in Figure 3) and the roll angle is 10°.
  • a backing material (a polyester film having a waterproof vapor property, the structure is a three-layer film composite material, wherein the lower film is a fluoride-containing resin; the upper film is capable of sticking with a hot melt adhesive
  • the resin is a resin with insulating properties, wherein an aluminum film is added between the upper film and the lower film of the polyester film, a third hot melt adhesive, a crystalline silicon solar cell, and a second hot melt.
  • the adhesive, the solar cell glass cover, the first hot melt adhesive, and the ETFE anti-reflection self-cleaning film are stacked one on another from bottom to top.
  • the above sample was heated to 140 ° C, and a pressure of 0.3 MPa was applied to both ends thereof to realize bonding of the crystalline silicon solar cell package and the anti-reflection self-cleaning film.
  • the structure is schematically shown in Fig. 4a.
  • the embodiment provides a preparation method of a method for preparing an anti-reflection self-cleaning film, wherein in the embodiment, the anti-reflection self-cleaning film prepared by the two-step hot pressing method is prepared as follows:
  • Step 1) the clean ETFE film is embossed by means of roll-to-roll or roll-to-plate hot pressing, the hot pressing temperature is 120 ° C, and the surface of the roll is zigzag (saw period is 50 ⁇ m, height is 30 ⁇ m).
  • the pressure between the two rolls is 10 MPa, and the temperature and pressure of the instrument reach the set value.
  • Step 2 the clean ETFE film is preheated on a hot plate at 50 ° C for 15 s, and rolled at a speed of 7 m / min to obtain a self-cleaning film, as shown in Fig. 5c.
  • Step 3 the anti-reflection self-cleaning film prepared in step 2) (specifically, ETFE anti-reflection hydrophobic film), fourth hot melt adhesive, solar cell glass cover, third hot melt adhesive, crystalline silicon
  • the solar cell, the second hot melt adhesive, the solar cell glass cover, the first hot melt adhesive, and the ETFE anti-reflection self-cleaning film are stacked one on another from bottom to top.
  • the above sample was heated to 150 ° C, and a pressure of 0.3 MPa was applied to both ends thereof to realize bonding of the double-glass silicon solar cell package and the anti-reflection self-cleaning film.
  • the structure is schematically shown in Fig. 4b.
  • the embodiment provides a preparation method of a method for preparing an anti-reflection self-cleaning film, wherein in the embodiment, the anti-reflection self-cleaning film prepared by the two-step hot pressing method is prepared as follows:
  • Step 1) the clean ETFE film is embossed by means of roll-to-roll or roll-to-plate hot pressing, the hot pressing temperature is 120 ° C, and the surface of the roll is zigzag (saw period is 50 ⁇ m, height is 25 ⁇ m).
  • the pressure between the two rolls is 10 MPa, and the temperature and pressure of the instrument reach the set value.
  • Step 2) the clean ETFE is preheated on a hot plate at 50 ° C for 15 s, and the roll is pressed at a speed of 7 m/min to obtain a self-cleaning film, as shown in Fig. 5c.
  • a backing material (a polyester film having a waterproof vapor property, the structure is a three-layer film composite material, wherein the lower film is a fluoride-containing resin; the upper film is capable of sticking with a hot melt adhesive Resin; the middle film is a resin with insulating properties, wherein an aluminum film is added between the upper film and the lower film of the polyester film), the second hot melt adhesive, and the flexible amorphous silicon film solar cell (surface layer) It is a transparent conductive oxide and a metal electrode), a first hot melt adhesive, and an ETFE anti-reflection self-cleaning film are stacked one on another from bottom to top.
  • the above sample was heated to 150 ° C, and a pressure of 0.3 MPa was applied to both ends thereof to realize bonding of the flexible amorphous silicon solar cell package and the anti-reflection self-cleaning film.
  • the structure is shown in FIG. 4c.
  • the embodiment provides a preparation method of a method for preparing an anti-reflection self-cleaning film, wherein in the embodiment, the anti-reflection self-cleaning film prepared by one-step hot pressing method is prepared as follows:
  • a back sheet material (a polyester film having water vapor resistance properties, the structure is a three-layer film composite material, wherein the lower layer film is a fluoride-containing resin; the upper layer film is capable of sticking with a hot melt adhesive Resin; the middle film is a resin with insulating properties, wherein an aluminum film is added between the upper film and the lower film of the polyester film), the second hot melt adhesive, and the flexible amorphous silicon film solar cell (surface layer)
  • It is a transparent conductive oxide and metal electrode), a first hot melt adhesive, a flat ETFE film, and a flexible nickel (or polyvinylidene fluoride (PVDF), etc.) having a zigzag structure (saw period of 50 ⁇ m, height of 25 ⁇ m)
  • the molds are stacked one after the other from bottom to top.
  • the sample is heated to 150 ° C, and a pressure of 0.3 MPa is applied to both ends thereof to realize surface bonding of the flexible amorphous silicon solar cell and adhesion of the anti-reflection self-cleaning film in one step.
  • Step 3) spraying a solution containing a material such as SiO 2 , TiO 2 , Al 2 O 3 , SiN x , SiC or the like on the surface of the film to improve the mechanical strength of the film, adjusting the contact angle of the film with water, and adjusting the incidence to the film.
  • a material such as SiO 2 , TiO 2 , Al 2 O 3 , SiN x , SiC or the like
  • the embodiment provides a preparation method of a method for preparing an anti-reflection self-cleaning film, wherein the anti-reflection self-cleaning film prepared by the heat curing method is prepared as follows:
  • Step 1) weigh 100 g of PDMS, add 10 g of curing agent, and stir both.
  • the bubbles in the PDMS were removed under a certain degree of vacuum, poured onto a template having a pyramidal structure on the surface, and after standing and leveling, placed in an oven at 60 ° C for 3 hours, and after being cured, the PDMS was separated from the template. That is, the anti-reflection self-cleaning film is obtained.
  • Step 2 the surface of the film is coated with a SiO 2 coating by a vacuum sputtering method to increase the mechanical strength of the film and adjust the contact angle of the film with water.
  • Step 3 the film is attached to the surface of the solar cell, and the battery efficiency is greatly improved at different inclination angles.
  • the photoelectric conversion efficiency of the battery is increased by 4.6%; the sunlight is tilted by 30° (the angle between the sunlight and the normal of the battery surface is 30°)
  • the photoelectric conversion efficiency of the battery is increased by 6.7%; when the sunlight is tilted by 45° (the angle between the sunlight and the normal of the battery surface is 45°), the photoelectric conversion efficiency of the battery is increased by 5.8%, and the sunlight is inclined by 60°. (The angle between the sunlight and the normal of the battery surface is 60°), the photoelectric conversion efficiency of the battery is increased by 14.2%, as shown in Figure 6 and Table 1.
  • the anti-reflection self-cleaning film of the present invention and the preparation method thereof have the following beneficial effects:
  • a film having a micron-sized structure can increase the transmittance of the film by multiple reflections and refractions, and can achieve a reversal effect equivalent to that of the conventional nanostructure anti-reflection film.
  • the anti-reflection film having a micron-sized structure is easier to process and has higher mechanical strength.
  • the film has a broad spectrum and wide-angle anti-reflection effect. Taking the anti-reflection film and the crystalline silicon solar cell as an example, it is optically simulated at a wavelength of 600 nm. Fig. 1a to Fig.
  • FIG. 1d show the propagation paths of light in the presence of a planar film and a microprism antireflection film (period 50 ⁇ m, prism height 25 ⁇ m) at incident angles of 0° and 30°, respectively. It can be seen that the light absorption of the battery at 0° and 30° incident angles is changed from 92.4% and 95.3% to 92.2% and 95.7%, respectively.
  • Fig. 2 shows the light absorption characteristics of the battery calculated by taking the microprism film of different heights at intervals of 50 ⁇ m as an example. It can be seen that such a film can effectively improve the light absorption of the battery at different incident angles.
  • the improvement of light absorption capacity is further reflected in the improvement of photoelectric conversion efficiency of various types of solar cells.
  • the film is coated on the surface of various solar cell modules (such as rigid single-sided crystalline silicon solar cell modules, crystalline silicon double-glass components, thin-film solar cells, and flexible solar cell modules of various material systems), which can effectively improve the battery.
  • various solar cell modules such as rigid single-sided crystalline silicon solar cell modules, crystalline silicon double-glass components, thin-film solar cells, and flexible solar cell modules of various material systems
  • the micron structure can effectively increase the contact angle between the film and water.
  • the optimized microstructure film has a contact angle with water of more than 150° and a rolling angle of up to 10°.
  • the water droplets can form a sphere on the surface, which is easy to roll off. Contaminants with good self-cleaning ability.
  • the modification of the inorganic hard coating on the surface of the micro-structure can improve the mechanical strength of the film.
  • semiconductor materials such as TiO 2 , ZnO, In 2 O 3 , WO 3 and the like can also have the effect of removing surface static electricity, blocking ultraviolet light transmission, and reducing the photo-induced attenuation of the solar cell.
  • the film is transformed into a super-hydrophilic property, and combined with photocatalysis, degrades the surface organic contamination to achieve a self-cleaning effect.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

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Abstract

La présente invention concerne un film de réduction de réflexion autonettoyant et un procédé de préparation de celui-ci. Le procédé de préparation comprend : l'utilisation d'une technologie d'impression et d'une technologie de modification de surface pour traiter le film flexible transparent et pour produire une structure à motif tridimensionnel à échelle micrométrique, pour obtenir le film flexible transparent avec des performances de réduction de réflexion et des performances d'autonettoyage, et l'intégration du film de réduction de réflexion autonettoyant et d'une couche de fenêtre d'un élément de cellule solaire, de sorte que le reflet sur la surface de la couche de fenêtre puisse être inhibé efficacement, et qu'une quantité de photons qui entrent dans une couche d'absorption d'une cellule puisse être augmentée, ce qui permet d'améliorer l'efficacité de conversion photoélectrique de la cellule, l'amélioration de l'efficacité de la cellule étant particulièrement notable lorsque la lumière du soleil entre selon un angle incliné. Le film autonettoyant et antireflet selon la présente invention peut être choisi pour être un film ultra hydrophobe ou un film ultra hydrophile. Le film ultra hydrophobe a un angle de contact avec l'eau relativement élevé. Lorsque le film ultra hydrophobe est incliné, les gouttes d'eau tombent facilement et emportent des polluants sur la surface, ce qui permet d'implémenter un effet autonettoyant. Le film ultra hydrophile est combiné à un effet catalytique de la lumière, de sorte que des contaminants organiques sur la surface puissent être dégradés, ce qui permet également d'obtenir un effet autonettoyant.
PCT/CN2016/109153 2015-12-25 2016-12-09 Film de réduction de réflexion autonettoyant et procédé de préparation de celui-ci Ceased WO2017107783A1 (fr)

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