CN113774436B - Nickel mold, preparation method and application thereof, antireflection film, and preparation method and application thereof - Google Patents
Nickel mold, preparation method and application thereof, antireflection film, and preparation method and application thereof Download PDFInfo
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- CN113774436B CN113774436B CN202111126521.8A CN202111126521A CN113774436B CN 113774436 B CN113774436 B CN 113774436B CN 202111126521 A CN202111126521 A CN 202111126521A CN 113774436 B CN113774436 B CN 113774436B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/10—Moulds; Masks; Masterforms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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Abstract
The invention relates to the technical field of photovoltaic cells, in particular to a nickel die, a preparation method and application thereof, an antireflection film, and a preparation method and application thereof. The invention ensures that the prepared die surface has the microstructure of the three-aperture tower type nano-holes by means of step electrolysis and step etching, thereby realizing the adjustability of the microstructure, reducing the time consumption in the preparation process and improving the light absorption efficiency of the anti-reflection film prepared later.
Description
Technical Field
The invention relates to the technical field of photovoltaic cells, in particular to a nickel die, a preparation method and application thereof, an antireflection film, and a preparation method and application thereof.
Background
With the rapid development of society and economy, the demand for energy is increasing, fossil energy is becoming depleted and pollution to the ecological environment is caused, and sustainable development of society and economy is seriously threatened. Therefore, there is an urgent need to replace it with renewable energy sources. Solar energy has gained widespread attention worldwide as an inexhaustible green renewable energy source. Solar panels are devices that convert solar radiation energy directly or indirectly into electrical energy by absorption of sunlight, either through the photoelectric effect or the photochemical effect. And with the development of technology, the application of solar panels is becoming more and more popular. The solar cell back film is an important component in a solar cell panel, is mainly used for packaging a solar cell, and has the characteristics of insulation (electric breakdown resistance), aging resistance, weather influence resistance, corrosion resistance and the like. However, the light absorption efficiency of the current solar cell back film is not enough to meet the requirements of the photovoltaic industry.
Disclosure of Invention
The invention aims to provide a nickel die, a preparation method and application thereof, an antireflection film, and a preparation method and application thereof. When the anti-reflection film die prepared by the preparation method is used for preparing the anti-reflection film in the follow-up process, the surface of the anti-reflection film can be provided with the three-aperture tower-type nano-pore microstructure, so that the anti-reflection film has higher light absorptivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nickel mold, which comprises the following steps:
taking an aluminum sheet as an anode, taking a carbon rod as a cathode, and performing first electrolysis in a first electrolyte to obtain a first intermediate product; the first intermediate product is an aluminum sheet with an aluminum oxide layer; the aluminum oxide layer in the aluminum sheet with the aluminum oxide layer is of a hole-shaped structure;
placing the first intermediate product in a first etching solution for first etching to obtain an aluminum sheet with a microstructure on the surface;
taking the aluminum sheet with the microstructure on the surface as an anode, taking a carbon rod as a cathode, and performing second electrolysis in a second electrolyte to obtain a second intermediate product; the second intermediate product includes an aluminum sheet having a microstructure on the surface and an aluminum oxide layer on the surface of the aluminum sheet having a microstructure on the surface;
placing the second intermediate product in a second etching solution for second etching to obtain a third intermediate product; the third intermediate product includes an aluminum sheet having a microstructure on a surface thereof and an aluminum oxide layer on a surface of the aluminum sheet having the microstructure on the surface thereof; the pore size of the alumina layer in the third intermediate product is greater than the pore size of the alumina layer in the second intermediate product;
taking the third intermediate product as an anode, taking a carbon rod as a cathode, and performing third electrolysis in a third electrolyte to obtain a fourth intermediate product; the fourth intermediate product comprises two nano-pore alumina layers with different pore diameters;
placing the fourth intermediate product in a third etching solution for third etching to obtain a fifth intermediate product; the fifth intermediate product comprises two nano-pore alumina layers with different pore diameters, and the pore diameter of the alumina layer in the fifth intermediate product is larger than that of the alumina layer in the fourth intermediate product; the second etching liquid and the third etching liquid are phosphoric acid solutions;
taking the fifth intermediate product as an anode, taking a carbon rod as a cathode, and performing fourth electrolysis in a fourth electrolyte to obtain a sixth intermediate product; the sixth intermediate product comprises three nano-pore alumina layers with different pore diameters; the first electrolyte, the second electrolyte, the third electrolyte and the fourth electrolyte are all citric acid solutions;
sequentially preparing a gold layer and a copper layer on the upper surface of the sixth intermediate product to obtain a seventh intermediate product;
placing the seventh intermediate product into fourth etching liquid for fourth etching to obtain an eighth intermediate product; the eighth intermediate product comprises a copper layer and a gold layer, and the surface of the gold layer is a microstructure with three-aperture tower-type nanopores; the first etching liquid and the fourth etching liquid are mixed liquid of chromic acid and phosphoric acid;
and after the nickel layer is electroplated on the gold layer surface of the eighth intermediate product, removing the copper layer and the gold layer to obtain the nickel mold.
Preferably, the solvent of the citric acid solution comprises a mixed solution of water and ethylene glycol;
the mass concentration of the citric acid in the citric acid solution is 1-5%.
Preferably, the temperature of the first electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 1-8 h;
the temperature of the second electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 0.5-4 h;
the temperature of the third electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 0.5-3.5 h;
the temperature of the fourth electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 0.5-3.5 h
Preferably, the mass concentration of chromic acid in the chromic acid and phosphoric acid mixed solution is 0.5-5%;
the mass concentration of phosphoric acid in the chromic acid and phosphoric acid mixed solution is 1-10%;
the temperature of the first etching and the fourth etching are independently 90-100 ℃, and the time is independently 10-50 min.
Preferably, the mass concentration of the phosphoric acid solution is 2-8%;
the temperature of the second etching and the third etching are independently 45-53 ℃, and the time is independently 8-15 min.
The invention also provides a nickel die prepared by the preparation method, and the surface of the die for preparing the anti-reflection film is provided with a microstructure of three-aperture tower type nanopores.
The invention also provides application of the nickel die in preparation of the antireflection film.
The invention also provides a preparation method of the antireflection film, which comprises the following steps:
and imprinting the nickel mold on the surface of the polymer film by adopting a roll-to-roll preparation mode to obtain the antireflection film.
The invention also provides the antireflection film prepared by the preparation method of the technical scheme, and the surface of the antireflection film is provided with a microstructure of three-aperture tower type nanopores.
The invention also provides application of the antireflection film in the photovoltaic field.
The invention provides a preparation method of a nickel mold, which comprises the following steps: taking an aluminum sheet as an anode, taking a carbon rod as a cathode, and performing first electrolysis in a first electrolyte to obtain a first intermediate product; the first intermediate product is an aluminum sheet with an aluminum oxide layer; the aluminum oxide layer in the aluminum sheet with the aluminum oxide layer is of a hole-shaped structure; placing the first intermediate product in a first etching solution for first etching to obtain an aluminum sheet with a microstructure on the surface; taking the aluminum sheet with the microstructure on the surface as an anode, taking a carbon rod as a cathode, and performing second electrolysis in a second electrolyte to obtain a second intermediate product; the second intermediate product includes an aluminum sheet having a microstructure on the surface and an aluminum oxide layer on the surface of the aluminum sheet having a microstructure on the surface; placing the second intermediate product in a second etching solution for second etching to obtain a third intermediate product; the third intermediate product includes an aluminum sheet having a microstructure on a surface thereof and an aluminum oxide layer on a surface of the aluminum sheet having the microstructure on the surface thereof; the pore size of the alumina layer in the third intermediate product is greater than the pore size of the alumina layer in the second intermediate product; taking the third intermediate product as an anode, taking a carbon rod as a cathode, and performing third electrolysis in a third electrolyte to obtain a fourth intermediate product; the fourth intermediate product comprises two nano-pore alumina layers with different pore diameters; placing the fourth intermediate product in a third etching solution for third etching to obtain a fifth intermediate product; the fifth intermediate product comprises two nano-pore alumina layers with different pore diameters, and the pore diameter of the alumina layer in the fifth intermediate product is larger than that of the alumina layer in the fourth intermediate product; the second etching liquid and the third etching liquid are phosphoric acid solutions; taking the fifth intermediate product as an anode, taking a carbon rod as a cathode, and performing fourth electrolysis in a fourth electrolyte to obtain a sixth intermediate product; the sixth intermediate product comprises three nano-pore alumina layers with different pore diameters; the first electrolyte, the second electrolyte, the third electrolyte and the fourth electrolyte are all citric acid solutions; sequentially preparing a gold layer and a copper layer on the upper surface of the sixth intermediate product to obtain a seventh intermediate product; placing the seventh intermediate product into fourth etching liquid for fourth etching to obtain an eighth intermediate product; the eighth intermediate product comprises a copper layer and a gold layer, and the surface of the gold layer is a microstructure with three-aperture tower-type nanopores; the first etching liquid and the fourth etching liquid are mixed liquid of chromic acid and phosphoric acid; and after the nickel layer is electroplated on the gold layer surface of the eighth intermediate product, removing the copper layer and the gold layer to obtain the nickel mold.
The invention ensures that the prepared die surface has the microstructure of the three-aperture tower type nano-holes by means of step electrolysis and step etching, thereby realizing the adjustability of the microstructure, reducing the time consumption in the preparation process and improving the light absorption efficiency of the anti-reflection film prepared later.
Drawings
FIG. 1 is an SEM image of an aluminum sheet with three alumina layers having different pore diameters prepared in example 1;
fig. 2 is a light reflectance of the solar cell panel prepared in test example 1.
Detailed Description
The invention provides a preparation method of a nickel mold, which comprises the following steps:
taking an aluminum sheet as an anode, taking a carbon rod as a cathode, and performing first electrolysis in a first electrolyte to obtain a first intermediate product; the first intermediate product is an aluminum sheet with an aluminum oxide layer; the aluminum oxide layer in the aluminum sheet with the aluminum oxide layer is of a hole-shaped structure;
placing the aluminum sheet with the aluminum oxide layer into a first etching solution for first etching to obtain an aluminum sheet with a microstructure on the surface;
taking the aluminum sheet with the microstructure on the surface as an anode, taking a carbon rod as a cathode, and performing second electrolysis in a second electrolyte to obtain a second intermediate product; the second intermediate product includes an aluminum sheet having a microstructure on the surface and an aluminum oxide layer on the surface of the aluminum sheet having a microstructure on the surface;
placing the second intermediate product in a second etching solution for second etching to obtain a third intermediate product; the third intermediate product includes an aluminum sheet having a microstructure on a surface thereof and an aluminum oxide layer on a surface of the aluminum sheet having the microstructure on the surface thereof; the pore size of the alumina layer in the third intermediate product is greater than the pore size of the alumina layer in the second intermediate product;
taking the third intermediate product as an anode, taking a carbon rod as a cathode, and performing third electrolysis in a third electrolyte to obtain a fourth intermediate product; the fourth intermediate product comprises two nano-pore alumina layers with different pore diameters;
placing the fourth intermediate product in a third etching solution for third etching to obtain a fifth intermediate product; the fifth intermediate product comprises two nano-pore alumina layers with different pore diameters, and the pore diameter of the alumina layer in the fifth intermediate product is larger than that of the alumina layer in the fourth intermediate product; the second etching liquid and the third etching liquid are phosphoric acid solutions;
taking the fifth intermediate product as an anode, taking a carbon rod as a cathode, and performing fourth electrolysis in a fourth electrolyte to obtain a sixth intermediate product; the sixth intermediate product comprises three nano-pore alumina layers with different pore diameters; the first electrolyte, the second electrolyte, the third electrolyte and the fourth electrolyte are all citric acid solutions;
sequentially preparing a gold layer and a copper layer on the upper surface of the sixth intermediate product to obtain a seventh intermediate product;
placing the seventh intermediate product into fourth etching liquid for fourth etching to obtain an eighth intermediate product; the eighth intermediate product comprises a copper layer and a gold layer, and the surface of the gold layer is a microstructure with three-aperture tower-type nanopores; the first etching liquid and the fourth etching liquid are mixed liquid of chromic acid and phosphoric acid;
and after the nickel layer is electroplated on the gold layer surface of the eighth intermediate product, removing the copper layer and the gold layer to obtain the nickel mold.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
According to the invention, an aluminum sheet is used as an anode, a carbon rod is used as a cathode, and first electrolysis is performed in a first electrolyte to obtain a first intermediate product; the first intermediate product is an aluminum sheet with an aluminum oxide layer; the aluminum oxide layer in the aluminum sheet with the aluminum oxide layer is in a hole-shaped structure.
In the invention, the aluminum sheet is preferably a high purity aluminum sheet, and the purity of the high purity aluminum sheet is preferably not less than 95wt%. The invention does not have any special limitation on the size of the aluminum sheet, and the size of the aluminum sheet is selected according to actual needs. In a specific embodiment of the invention, the aluminum sheet is specifically 30cm by 13cm.
In the invention, the first electrolyte is a citric acid solution; the solvent of the citric acid solution preferably comprises a mixed solution of water and ethylene glycol; the volume ratio of water to glycol in the water and glycol mixture is preferably 1:1. In the present invention, the mass concentration of citric acid in the citric acid solution is preferably 1 to 5%, more preferably 1.5 to 3%, and most preferably 1.5%.
In the present invention, a direct current voltage is preferably applied during the first electrolysis; the temperature of the first electrolysis is preferably-5 to 10 ℃, more preferably-5 to 5 ℃, and most preferably 1 to 3 ℃; the voltage is preferably 50 to 300V, more preferably 100 to 200V, and most preferably 160 to 180V; the time is preferably 1 to 8 hours, more preferably 3 to 8 hours, and most preferably 4 to 8 hours.
In the present invention, the first intermediate product is an aluminum sheet with an aluminum oxide layer; the aluminum oxide layer in the aluminum sheet with the aluminum oxide layer is of a hole-shaped structure; the distance between two adjacent nano holes in the alumina layer is preferably 2-2.5 times the corresponding value of the voltage of the first electrolysis, namely, when the voltage of the first electrolysis is 50-300V, the distance between two adjacent nano holes in the alumina layer is 125-750 nm.
After a first intermediate product is obtained, the first intermediate product is placed in a first etching solution to carry out first etching, and an aluminum sheet with a microstructure on the surface is obtained.
In the invention, the first etching liquid is a mixed liquid of chromic acid and phosphoric acid; the mass concentration of chromic acid in the chromic acid and phosphoric acid mixed solution is preferably 0.5 to 5%, more preferably 1 to 4%, most preferably 1.5 to 2.5%; the mass concentration of phosphoric acid in the mixed solution of chromic acid and phosphoric acid is preferably 1 to 10%, more preferably 1.5 to 5%.
In the present invention, the temperature of the first etching is preferably 90 ℃ to 100 ℃, more preferably 96 ℃ to 100 ℃; the time is preferably 10 to 50 minutes, more preferably 20 to 30 minutes.
After an aluminum sheet with a microstructure on the surface is obtained, the aluminum sheet with the microstructure on the surface is used as an anode, a carbon rod is used as a cathode, and second electrolysis is carried out in a second electrolyte to obtain a second intermediate product; the second intermediate product includes an aluminum sheet having a microstructure on the surface and an aluminum oxide layer on the surface of the aluminum sheet having a microstructure on the surface.
In the invention, the second electrolyte is a citric acid solution; the solvent of the citric acid solution preferably comprises a mixed solution of water and ethylene glycol; the volume ratio of water to glycol in the water and glycol mixture is preferably 1:1. In the present invention, the mass concentration of citric acid in the citric acid solution is preferably 1 to 5%, more preferably 1.5 to 3%, and most preferably 1.5%.
In the present invention, a direct current voltage is preferably applied during the second electrolysis; the temperature of the first electrolysis is preferably-5 to 10 ℃, more preferably-5 to 5 ℃, and most preferably 1 to 3 ℃; the voltage is preferably 50 to 300V, more preferably 100 to 200V, and most preferably 160 to 180V; the time is preferably 0.5 to 4 hours, more preferably 1 to 3 hours.
After a second intermediate product is obtained, placing the second intermediate product in a second etching solution for second etching to obtain a third intermediate product; the third intermediate product includes an aluminum sheet having a microstructure on a surface thereof and an aluminum oxide layer on a surface of the aluminum sheet having the microstructure on the surface thereof; the pore size of the alumina layer in the third intermediate product is greater than the pore size of the alumina layer in the second intermediate product.
In the invention, the second etching solution is phosphoric acid solution; the mass concentration of the phosphoric acid solution is preferably 2 to 8%, more preferably 3 to 6%. In the present invention, the temperature of the second etching is preferably 45 to 53 ℃, more preferably 53 ℃; the time is preferably 8 to 15min, most preferably 10 to 12min; the etching rate is preferably 8 to 15nm/min.
In the present invention, the second etching is used for etching the alumina layer, so that the aperture of the alumina layer is further increased.
After the second etching is completed, the method also preferably comprises the steps of cleaning and drying sequentially. In the invention, the cleaning is preferably performed by deionized water; the drying is preferably performed by drying with nitrogen.
After a third intermediate product is obtained, the third intermediate product is taken as an anode, a carbon rod is taken as a cathode, and third electrolysis is carried out in a third electrolyte to obtain a fourth intermediate product; the fourth intermediate product comprises two nano-pore alumina layers with different pore diameters.
In the invention, the third electrolyte is a citric acid solution; the solvent of the citric acid solution preferably comprises a mixed solution of water and ethylene glycol; the volume ratio of water to glycol in the water and glycol mixture is preferably 1:1. In the present invention, the mass concentration of citric acid in the citric acid solution is preferably 1 to 5%, more preferably 1.5 to 3%, and most preferably 1.5%.
In the present invention, a direct current voltage is preferably applied during the third electrolysis; the temperature of the first electrolysis is preferably-5 to 10 ℃, more preferably-5 to 5 ℃, and most preferably 1 to 3 ℃; the voltage is preferably 50 to 300V, more preferably 100 to 200V, and most preferably 160 to 180V; the time is preferably 0.5 to 3.5 hours, more preferably 1 to 3 hours.
In the invention, the third electrolysis further converts the aluminum sheet on the inner side of the aluminum oxide layer into the aluminum oxide layer with a pore structure, and forms a double-layer aluminum oxide layer with different pore diameters from outside to inside, and the pore diameters from outside to inside are reduced.
After a fourth intermediate product is obtained, placing the fourth intermediate product into a third etching solution for third etching to obtain a fifth intermediate product; the fifth intermediate product comprises two nano-pore alumina layers with different pore diameters, and the pore diameter of the alumina layer in the fifth intermediate product is larger than that of the alumina layer in the fourth intermediate product; the second etching liquid and the third etching liquid are phosphoric acid solutions.
In the invention, the third etching solution is phosphoric acid solution; the mass concentration of the phosphoric acid solution is preferably 2 to 8%, more preferably 3 to 6%. In the present invention, the temperature of the third etching is preferably 45 to 53 ℃, more preferably 53 ℃; the time is preferably 8 to 15min, most preferably 10 to 12min; the etching rate is preferably 8 to 15nm/min.
In the present invention, the third etching is used for etching the alumina layer, so that the aperture of the alumina layer is further increased.
After the third etching is completed, the method also preferably comprises the steps of cleaning and drying sequentially. In the invention, the cleaning is preferably performed by deionized water; the drying is preferably performed by drying with nitrogen.
After a fifth intermediate product is obtained, the invention takes the fifth intermediate product as an anode and takes a carbon rod as a cathode, and fourth electrolysis is carried out in fourth electrolyte to obtain a sixth intermediate product; the sixth intermediate product comprises three nano-pore alumina layers with different pore diameters; the first electrolyte, the second electrolyte, the third electrolyte and the fourth electrolyte are all citric acid solutions.
In the invention, the fourth electrolyte is a citric acid solution; the solvent of the citric acid solution preferably comprises a mixed solution of water and ethylene glycol; the volume ratio of water to glycol in the water and glycol mixture is preferably 1:1. In the present invention, the mass concentration of citric acid in the citric acid solution is preferably 1 to 5%, more preferably 1.5 to 3%, and most preferably 1.5%.
In the present invention, a direct current voltage is preferably applied during the fourth electrolysis; the temperature of the fourth electrolysis is preferably-5 to 10 ℃, more preferably-5 to 5 ℃, and most preferably 1 to 3 ℃; the voltage is preferably 50 to 300V, more preferably 100 to 200V, and most preferably 160 to 180V; the time is preferably 0.5 to 3.5 hours, more preferably 1 to 3 hours.
In the invention, the fourth electrolysis has the same effect as the third electrolysis, namely, the aluminum in the inner layer is further converted into the alumina with a porous structure, so that three nano-pore alumina layers with different pore diameters are obtained.
After a sixth intermediate product is obtained, a gold layer and a copper layer are sequentially prepared on the upper surface of the sixth intermediate product to obtain a seventh intermediate product.
In the invention, the preparation method of the gold layer is preferably evaporation; the evaporation rate is preferably 0.5 to 3nm/s.
In the present invention, the thickness of the gold layer is preferably 60 to 200nm.
In the present invention, the gold layer provides a conductive electrode for the subsequent electroplated copper and nickel layers.
In the present invention, the preparation method of the copper layer is preferably electroplating; the plating solution for the plating preferably comprises 30 to 125g/L of copper sulfate and 100 to 300g/L of H 2 SO 4 And 0.01 to 0.5g/L HCl.In the present invention, the plating is preferably performed at room temperature; the plating preferably applies a direct voltage; the voltage of the plating is preferably 2 to 6V.
In the present invention, the thickness of the copper layer is preferably 40 to 200 μm.
After a seventh intermediate product is obtained, placing the seventh intermediate product into a fourth etching solution for fourth etching to obtain an eighth intermediate product; the eighth intermediate product comprises a copper layer and a gold layer, and the surface of the gold layer is a microstructure with three-aperture tower-type nanopores.
In the invention, the fourth etching liquid is a mixed liquid of chromic acid and phosphoric acid; the mass concentration of chromic acid in the chromic acid and phosphoric acid mixed solution is preferably 0.5 to 5%, more preferably 1 to 4%, most preferably 1.5 to 2.5% of the mass concentration of chromic acid; the mass concentration of phosphoric acid in the mixed solution of chromic acid and phosphoric acid is preferably 1 to 10%, more preferably 1.5 to 5%.
In the present invention, the temperature of the fourth etching is preferably 90 ℃ to 100 ℃, more preferably 96 ℃ to 100 ℃; the time is preferably 10 to 50 minutes, more preferably 20 to 30 minutes.
Before the fourth etching, in order to ensure that the fourth etching liquid can etch the middle aluminum oxide layer, a scraper is preferably used for scraping the covered gold layer and the copper layer from the side surface of the aluminum sheet covered with the gold layer and the copper layer, so that the fourth etching liquid can etch the exposed aluminum oxide layer from the side surface until the whole oxide layer is completely etched.
After the eighth intermediate product is obtained, the nickel mold is obtained by removing the copper layer and the gold layer after electroplating the nickel layer on the gold layer surface of the eighth intermediate product.
In the present invention, the plating solution used for the nickel plating layer preferably comprises 150 to 200g/L of sodium sulfate, 2 to 5g/L of nickel chloride, 10 to 25g/L of boric acid and 1 to 3g/L of saccharin.
In the present invention, the temperature of the nickel plating layer is preferably 40 to 60 ℃, and the nickel plating layer is preferably applied with a direct current voltage; the voltage of the electroplated nickel layer is preferably 2-6V.
In the present invention, nitric acid is preferably used for removing the copper layer; in the present invention, the concentration of the nitric acid is preferably 0.2 to 1mol/L.
In the present invention, the gold layer is preferably removed by using KI and I 2 Is a mixed solution of (a) and (b); in the present invention, the KI and I 2 The mass concentration of KI in the mixed solution of (2) is preferably 3-15%; the KI and I 2 I in the mixed solution of (a) 2 The mass concentration of (2) is preferably 0.01% to 1%.
In the present invention, the thickness of the nickel mold is preferably 100 μm, and the microstructure of the surface of the nickel mold is preferably a three-layer nanopore tower structure.
The invention also provides a nickel die prepared by the preparation method, and the surface of the die for preparing the anti-reflection film is provided with a microstructure of three-aperture tower type nanopores.
The invention also provides application of the nickel die in preparation of the antireflection film.
The invention also provides a preparation method of the antireflection film, which comprises the following steps:
and imprinting the nickel mold on the surface of the polymer film by adopting a roll-to-roll preparation mode to obtain the antireflection film.
The kind of the polymer film is not particularly limited, and polymer films used for solar cell panel packaging materials are well known to those skilled in the art. In a specific embodiment of the invention, the polymer film is specifically a poly perfluoroethylene propylene (FEP) film or a Polydimethylsiloxane (PDMS) film.
The size of the polymer film is not particularly limited, and the size of the polymer film used in the solar panel packaging material, which is well known to those skilled in the art, may be used. In a specific embodiment of the present invention, the polymer film has a width of 10 to 18cm and a thickness of 20 to 100 μm.
In the present invention, the pressure of the imprinting is preferably 0.2 to 0.35MPa and the temperature is preferably 200 to 250 ℃.
In the present invention, the specific process of imprinting is preferably: mounting a nickel die on a roll-to-roll and pattern embossing roller thereon, and heating the roller to 200-250 ℃; and the polymer film passes through the middle of the pattern embossing roller and the counter-pressure roller from the film supply roller and is fixed on the traction stretching roller, and the pressure of 0.2-0.35 MPa is directly provided on the pattern embossing roller and the counter-pressure roller, so that the nano-pore structure of the nickel die can be completely embossed on the surface of the polymer film, and the antireflection film is obtained.
The invention also provides the antireflection film prepared by the preparation method of the technical scheme, and the surface of the antireflection film is provided with a microstructure of three-aperture tower type nanopores.
The invention also provides application of the antireflection film in the photovoltaic field. The method of the present invention is not particularly limited, and may be carried out by a process well known to those skilled in the art.
The nickel mold, the method and application for preparing the same, the antireflection film, the method and application for preparing the same, provided by the invention, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
The preparation process is as shown in fig. 1:
using a 30cm multiplied by 13cm aluminum sheet (purity is more than or equal to 95 wt%) as an anode, using a carbon rod as a cathode, and carrying out electrolysis in a citric acid solution (solvent is a mixed solution of water and ethylene glycol with a volume ratio of 1:1) with a mass concentration of 1.5%, wherein the electrolysis voltage is 160V direct current voltage, the temperature is 1 ℃ and the time is 12 hours, so as to obtain the aluminum sheet with an aluminum oxide layer (the interval between two adjacent holes of the aluminum oxide layer is 400 nm);
carrying out first etching on the aluminum sheet with the aluminum oxide layer in a mixed solution of chromic acid and phosphoric acid (the mass concentration of chromic acid is 1.5 percent, and the mass concentration of phosphoric acid is 6 percent), wherein the temperature of the first etching is 100 ℃, the time is 30 minutes, and the aluminum oxide layer is removed to obtain the aluminum sheet with the aluminum oxide layer removed;
the aluminum sheet with the alumina layer removed is taken as an anode, a carbon rod is taken as a cathode, electrolysis is carried out in a citric acid solution with the mass concentration of 1.5% (the solvent is a mixed solution of water and glycol with the volume ratio of 1:1), the electrolysis voltage is 160V direct current voltage, the temperature is 1 ℃ and the time is 2 hours, after the alumina layer with a high-quality pore structure is obtained, the alumina layer is placed in a phosphoric acid solution with the mass concentration of 5%, the alumina layer is etched for 10 minutes at the temperature of 53 ℃ (the etching rate is 10 nm/min), then deionized water is used for washing, and nitrogen is used for drying, so that the aluminum sheet with the reamed nano alumina layer is obtained;
the aluminum sheet with the reamed nano aluminum oxide layer is taken as an anode, a carbon rod is taken as a cathode, and electrolysis is carried out in a citric acid solution (a mixed solution of water and glycol with a volume ratio of 1:1) with a mass concentration of 1.5%, wherein the electrolysis voltage is 160V direct current voltage, the temperature is 1 ℃ and the time is 1.5h, so that the aluminum sheet with two layers of aluminum oxide layers with different apertures is obtained;
placing the aluminum sheet with the two alumina layers with different apertures into a phosphoric acid solution with the mass concentration of 5%, etching for 10min at the temperature of 53 ℃ (the etching rate is 10 nm/min), then washing with deionized water, blow-drying with nitrogen, taking the aluminum sheet as an anode, taking a carbon rod as a cathode, and carrying out electrolysis in a citric acid solution with the mass concentration of 1.5% (the solvent is a mixed solution of water and ethylene glycol with the volume ratio of 1:1), wherein the electrolysis voltage is 160V direct current voltage, the temperature is 1 ℃ and the time is 1.5h, so as to obtain the aluminum sheet with the three alumina layers with different apertures;
plating a 100nm thick gold layer on the surface of the aluminum oxide layer of the aluminum sheet with three aluminum oxide layers with different apertures, plating a copper layer in a copper plating electrolyte (comprising 75g/L copper sulfate, 188g/L sulfuric acid and 0.06g/L hydrochloric acid) after the vapor plating speed is 3nm/s, wherein the plating is performed at room temperature by adopting a direct current voltage of 3V; sequentially preparing a gold layer and a copper layer;
scraping the covered gold layer and copper layer from the side surface of the aluminum sheet covered with the gold layer and copper layer by adopting a scraper, and then etching in a mixed solution of chromic acid and phosphoric acid (the mass concentration of chromic acid is 1.5 percent and the mass concentration of phosphoric acid is 6 percent), wherein the etching temperature is 100 ℃, the etching time is 30 minutes, and removing the aluminum oxide layer to obtain the copper foil with the gold layer;
electroplating a nickel layer on the surface of the gold layer of the copper foil with the gold layer, wherein the electroplating solution adopted by the nickel layer comprises 200g/L sodium sulfate, 5g/L nickel chloride, 25g/L boric acid and 3g/L saccharin; the temperature of the electroplated nickel layer is 50 ℃, and a direct current voltage of 3V is applied;
then the copper layer is removed by adopting nitric acid with the concentration of 0.5mol/L in sequence, and KI and I are adopted 2 Is 15% of the mixed solution (KI; I) 2 The gold layer was removed to obtain a nickel mold (thickness: 100 μm);
mounting the nickel mold on a roll-to-roll and pattern embossing roller thereon, and heating the roller to 250 ℃; the FEP film passes through the middle of the pattern embossing roller and the counter-pressing roller from the film supply roller and is fixed on the traction stretching roller, and pressure of 0.35MPa is directly provided on the pattern embossing roller and the counter-pressing roller, so that the nano-pore structure of the nickel mold can be completely embossed on the surface of the FEP film, and the antireflection film is obtained;
SEM test is carried out on the aluminum sheet with three alumina layers with different pore diameters, and the test result is shown in figure 1. As can be seen from figure 1, the three-layer nano-pore tower-shaped structure with different pore diameters from top to bottom is prepared. The size of the nanopores is about 400nm, 200nm and 100nm in order from top to bottom. The spacing between holes is about 500-600 nm.
Test case
The testing process comprises the following steps: in order to investigate the effect of the anti-reflection film on the solar cell performance. The cell performance of the AR film and the standard control group was tested under the light conditions of AM 1.5. As shown in FIG. 2, after the AR antireflection film was used, the short-circuit current of the battery increased from 14.69mA/cm2 to 15.03mA/cm2. The energy conversion efficiency can be increased from pce=6.00% to pce=6.34%, by nearly 5.7%. It is worth noting that the measured results were measured at a normal angle of 89 °. In addition, the AR antireflection film has a self-cleaning function and a wide-angle antireflection function. The solar cell used herein is Cs-based 0.05 FA 0.83 MA 0.12 PbBr 0.333 I 2.667 PerovskiteSolar cells prepared from the materials;
as shown in fig. 2, the anti-reflection film can effectively reduce the reflection of less incident light, so that the energy conversion efficiency of the solar cell is improved by about 5.7%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the nickel mold is characterized by comprising the following steps of:
taking an aluminum sheet as an anode, taking a carbon rod as a cathode, and performing first electrolysis in a first electrolyte to obtain a first intermediate product; the first intermediate product is an aluminum sheet with an aluminum oxide layer; the aluminum oxide layer in the aluminum sheet with the aluminum oxide layer is of a hole-shaped structure;
placing the first intermediate product in a first etching solution for first etching to obtain an aluminum sheet with a microstructure on the surface;
taking the aluminum sheet with the microstructure on the surface as an anode, taking a carbon rod as a cathode, and performing second electrolysis in a second electrolyte to obtain a second intermediate product; the second intermediate product includes an aluminum sheet having a microstructure on the surface and an aluminum oxide layer on the surface of the aluminum sheet having a microstructure on the surface;
placing the second intermediate product in a second etching solution for second etching to obtain a third intermediate product; the third intermediate product includes an aluminum sheet having a microstructure on a surface thereof and an aluminum oxide layer on a surface of the aluminum sheet having the microstructure on the surface thereof; the pore size of the alumina layer in the third intermediate product is greater than the pore size of the alumina layer in the second intermediate product;
taking the third intermediate product as an anode, taking a carbon rod as a cathode, and performing third electrolysis in a third electrolyte to obtain a fourth intermediate product; the fourth intermediate product comprises two nano-pore alumina layers with different pore diameters;
placing the fourth intermediate product in a third etching solution for third etching to obtain a fifth intermediate product; the fifth intermediate product comprises two nano-pore alumina layers with different pore diameters, and the pore diameter of the alumina layer in the fifth intermediate product is larger than that of the alumina layer in the fourth intermediate product; the second etching liquid and the third etching liquid are phosphoric acid solutions;
taking the fifth intermediate product as an anode, taking a carbon rod as a cathode, and performing fourth electrolysis in a fourth electrolyte to obtain a sixth intermediate product; the sixth intermediate product comprises three nano-pore alumina layers with different pore diameters; the first electrolyte, the second electrolyte, the third electrolyte and the fourth electrolyte are all citric acid solutions;
sequentially preparing a gold layer and a copper layer on the upper surface of the sixth intermediate product to obtain a seventh intermediate product;
placing the seventh intermediate product into fourth etching liquid for fourth etching to obtain an eighth intermediate product; the eighth intermediate product comprises a copper layer and a gold layer, and the surface of the gold layer is a microstructure with three-aperture tower-type nanopores; the first etching liquid and the fourth etching liquid are mixed liquid of chromic acid and phosphoric acid;
after electroplating a nickel layer on the gold layer surface of the eighth intermediate product, removing the copper layer and the gold layer to obtain the nickel mold;
the temperature of the first electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 1-8 h;
the temperature of the second electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 0.5-4 h;
the temperature of the third electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 0.5-3.5 h;
the temperature of the fourth electrolysis is-5-10 ℃, the voltage is 50-300V, and the time is 0.5-3.5 h;
the mass concentration of chromic acid in the chromic acid and phosphoric acid mixed solution is 0.5-5%;
the mass concentration of phosphoric acid in the chromic acid and phosphoric acid mixed solution is 1-10%;
the temperature of the first etching and the fourth etching are independently 90-100 ℃, and the time is independently 10-50 min;
the mass concentration of the phosphoric acid solution is 2-8%;
the temperature of the second etching and the third etching are independently 45-53 ℃, and the time is independently 8-15 min.
2. The method according to claim 1, wherein the solvent of the citric acid solution comprises a mixture of water and ethylene glycol;
the mass concentration of the citric acid in the citric acid solution is 1-5%.
3. The nickel mold prepared by the preparation method of claim 1 or 2, wherein the surface of the mold for preparing the antireflection film has a microstructure of three-aperture tower-type nanopores.
4. Use of the nickel mold of claim 3 for the preparation of an antireflection film.
5. The preparation method of the antireflection film is characterized by comprising the following steps of:
embossing a nickel mold on the surface of the polymer film by adopting a roll-to-roll preparation mode to obtain the antireflection film;
the nickel mold is the nickel mold of claim 3.
6. The antireflection film prepared by the preparation method of claim 5, wherein the surface of the antireflection film has a three-aperture tower-type nano-pore microstructure.
7. Use of the antireflection film of claim 6 in the photovoltaic field.
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| JP5029773B1 (en) * | 2011-08-18 | 2012-09-19 | 大日本印刷株式会社 | Mold for manufacturing antireflection film, method for manufacturing mold for manufacturing antireflection film |
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