Composite coating body, preparation method and application thereof, and solar cell
阅读说明：本技术 带复合涂层体及其制备方法和应用、太阳能电池 (Composite coating body, preparation method and application thereof, and solar cell ) 是由 董兵海 梁子辉 王世敏 周泽铸 赵丽 万丽 王二静 李静 于 2019-10-16 设计创作，主要内容包括：本发明涉及太阳能电池领域,具体而言,提供了一种带复合涂层体及其制备方法和应用、太阳能电池。该带复合涂层体包括：基材以及形成于基材表面的复合涂层,所述复合涂层包括：纳米二氧化硅层,所述纳米二氧化硅层采用化学气相沉积法形成于基材表面；超疏水二氧化硅层,与所述纳米二氧化硅层相对设置；所述纳米二氧化硅层与超疏水二氧化硅层之间通过硅氧键连接；其中,纳米二氧化硅层和超疏水二氧化硅层各自含有的羟基与硅烷偶联剂的水解产物缩合,形成硅氧键。该带复合涂层体具有结构稳定牢固、疏水性好、耐沾污性能优良和透明度高的优点,在恶劣户外长期使用的情况下,也能够保持良好的超疏水性质和透光率,保证太阳能电池的光电效率不受损失。(The invention relates to the field of solar cells, and particularly provides a composite coating body, a preparation method and application thereof, and a solar cell. The tape composite coating body includes: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises: the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method; the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer; the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond. The composite coating body with the composite coating has the advantages of stable and firm structure, good hydrophobicity, excellent stain resistance and high transparency, and can keep good super-hydrophobic property and light transmittance under the condition of long-term use in severe outdoor environment, so that the photoelectric efficiency of the solar cell is not lost.)
1. A coated composite body, comprising: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises:
the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method;
the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer;
the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond.
2. The composite coated body of claim 1, wherein the substrate comprises glass, silicon, mica, or polymer sheets;
preferably, the glass comprises quartz glass, high borosilicate glass or soda lime glass, preferably quartz glass;
preferably, the polymeric sheet comprises a polyethylene sheet, a polyvinyl chloride sheet, a polypropylene sheet, a polycarbonate sheet, a polymethylmethacrylate sheet or a polyphenylsulfone sheet;
preferably, the thickness of the nano silicon dioxide layer is 200-800 nm; an intermediate connecting layer is formed between the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer, and the thickness of the intermediate connecting layer is 0.5-1 mu m; the thickness of the super-hydrophobic silicon dioxide layer is 200-600 nm;
preferably, the particle size of the silicon dioxide in the nano silicon dioxide layer is 10-20 nm;
preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropylmethyldiethoxysilane.
3. The method of manufacturing a body with a composite coating according to claim 1 or 2, comprising the steps of:
(a) providing a base material, and depositing a nano silicon dioxide layer on the surface of the base material by adopting a chemical vapor deposition method;
(b) providing a hydrolysate of a silane coupling agent;
(c) providing a super-hydrophobic silica suspension;
(d) and sequentially coating the hydrolysate of the silane coupling agent and the super-hydrophobic silica suspension on the surface of the nano silica layer, and curing to obtain the composite coating body.
4. The method of claim 3, wherein the chemical vapor deposition process comprises plasma enhanced chemical vapor deposition, ultra high vacuum chemical vapor deposition, or low temperature chemical vapor deposition, preferably plasma enhanced chemical vapor deposition.
5. The method of claim 3, wherein the source of the chemical vapor deposition reaction gas comprises SiH4Si and N2O；
Preferably, SiH4And N2The volume ratio of O is 1: 0.1 to 5, preferably 1: 0.1 to 2;
preferably, the deposition conditions of the chemical vapor deposition method include at least one of the following conditions:
the deposition temperature is 30-300 ℃, preferably 150-250 ℃, and more preferably 150-180 ℃;
the radio frequency power is 20-200W, preferably 60-80W, and further preferably 65-75W;
the deposition pressure is 10-150Pa, preferably 80-100Pa, and more preferably 85-95 Pa;
the deposition time is 1-10min, preferably 5-10min, and more preferably 6-9 min.
6. The method of claim 3, wherein step (b) comprises: under the alkaline condition, the silane coupling agent is subjected to hydrolysis reaction in an aqueous solution of alcohol to obtain a hydrolysate of the silane coupling agent;
preferably, step (b) comprises: firstly, uniformly mixing a silane coupling agent with an aqueous solution of alcohol, and then uniformly mixing the silane coupling agent with an alkaline substance to obtain a hydrolysate of the silane coupling agent;
preferably, the time of the hydrolysis reaction is 10-60min, preferably 20-40 min;
preferably, the alcohol comprises a C1-C4 alcohol;
preferably, the C1-C4 alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol, propylene glycol, or glycerol;
preferably, the mass ratio of alcohol to water in the aqueous alcohol solution is 1: 0.01 to 5, preferably 1: 0.05 to 1;
preferably, the alkaline substance includes an organic alkaline substance and/or an inorganic alkaline substance;
preferably, the organic basic substance includes an organic amine;
preferably, the organic amine comprises an aliphatic amine;
preferably, the fatty amine comprises at least one of decylamine, dodecylamine, hexadecylamine, or octadecylamine;
preferably, the inorganic alkaline substance comprises ammonia and/or sodium carbonate.
7. The method of preparing a composite coated body according to claim 3, wherein step (c) comprises: carrying out surface grafting reaction on the silica gel obtained by the sol-gel method and a low surface energy modifier to obtain a super-hydrophobic silica suspension;
preferably, a silicon source, a catalyst and a solvent are mixed, and silica gel is obtained after sol-gel reaction;
preferably, the silicon source comprises a silicate;
preferably, the silicate comprises at least one of methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, or butyl orthosilicate;
preferably, the solvent comprises an aqueous solution of an alcohol;
preferably, the catalyst comprises ammonia, hydrochloric acid, acetic acid or carbon dioxide;
preferably, the low surface energy modifying agent comprises at least one of hexamethyldisilazane, trimethylmethoxysilane, or triethylethoxysilane.
8. The method of preparing the composite coated body according to any one of claims 3 to 7, wherein the coating comprises blade coating, spray coating or spin coating;
preferably, the curing temperature is 20-200 ℃, preferably 50-100 ℃; and/or the curing time is 1-60min, preferably 10-30 min.
9. Use of the composite coated body according to claim 1 or 2 or the composite coated body obtained by the method for producing a composite coated body according to any one of claims 3 to 8 for producing a solar cell.
10. A solar cell comprising the composite coated body according to claim 1 or 2 or the composite coated body obtained by the method for producing a composite coated body according to any one of claims 3 to 8.
Technical Field
The invention relates to the field of solar cells, in particular to a composite coating body, a preparation method and application thereof and a solar cell.
Background
With the increasing population and the increasing demand for energy, green and renewable energy sources have great significance for the sustainable development of society. Solar cells have become a research hotspot in the field of renewable energy sources as a clean, low-cost energy device.
However, the power generation efficiency of a solar photovoltaic module used for power generation is generally affected by many environmental factors, such as available solar radiation, wind speed, wind direction, ambient temperature, humidity, and atmospheric dust. Particularly in desert regions, due to frequent occurrence of sand storms, the dust on the surface of the solar module is accumulated too much, and finally the power generation efficiency of the solar cell is remarkably reduced.
Dust on the surface of the solar photovoltaic module reduces the transmittance of the glass cover and prevents incident light photons from reaching the working part of the solar cell, thereby reducing the output power. A number of studies report the effect of dust deposition on solar panel efficiency: adinoyi et al report that if a solar photovoltaic module is not clean for more than 6 months, its photoelectric conversion efficiency will decrease by 50%; also, in the same manner as above,hee et al found that for bare glass samples, the transmission rate decreased despite heavy rain on singapore lasting several months. After 33 days, the transmittance of the common glass slide is reduced from 90.7 percent to 87.6 percent; paudyal et al reported that the dust deposition density on the surface of the solar cell panel was from 0.1047g/m for 5 months outdoor exposure2Raised to 9.6711g/m2Resulting in a solar panel efficiency of only 29.76%. Therefore, how to improve the long-term contamination resistance of the solar cell panel is the key to ensure the conversion efficiency of the solar cell.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first object of the present invention is to provide a composite coating with a high bonding strength, in which a nano-silica layer is firmly bonded to a substrate, and the layers in the composite coating are bonded to each other by chemical bonds, so that the composite coating is not easily separated from the surface of the substrate, and has super-strong hydrophobicity, contamination resistance and good light transmittance, thereby preventing the photoelectric conversion efficiency of a solar cell from being reduced after the composite coating with a high bonding strength is used for a long time.
The second objective of the invention is to provide a preparation method of the composite coating body, the method has scientific process, the composite coating body obtained by the method has stable structure, the composite coating is not easy to separate from the surface of the base material, and has super-strong hydrophobicity, stain resistance and good light transmission, and the composite coating body can not reduce the photoelectric conversion efficiency of the solar cell after long-term use.
The third purpose of the invention is to provide the application of the composite coating in the preparation of the solar cell.
A fourth object of the present invention is to provide a solar cell.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a coated composite body comprising: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises:
the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method;
the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer;
the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond.
As a further preferred technical solution, the substrate comprises glass, silicon wafer, mica sheet or polymer sheet;
preferably, the glass comprises quartz glass, high borosilicate glass or soda lime glass, preferably quartz glass;
preferably, the polymeric sheet comprises a polyethylene sheet, a polyvinyl chloride sheet, a polypropylene sheet, a polycarbonate sheet, a polymethylmethacrylate sheet or a polyphenylsulfone sheet;
preferably, the thickness of the nano silicon dioxide layer is 200-800 nm; an intermediate connecting layer is formed between the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer, and the thickness of the intermediate connecting layer is 0.5-1 mu m; the thickness of the super-hydrophobic silicon dioxide layer is 200-600 nm;
preferably, the particle size of the silicon dioxide in the nano silicon dioxide layer is 10-20 nm;
preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropylmethyldiethoxysilane.
In a second aspect, the present invention provides a method for producing a body with a composite coating layer, including the steps of:
(a) providing a base material, and depositing a nano silicon dioxide layer on the surface of the base material by adopting a chemical vapor deposition method;
(b) providing a hydrolysate of a silane coupling agent;
(c) providing a super-hydrophobic silica suspension;
(d) and sequentially coating the hydrolysate of the silane coupling agent and the super-hydrophobic silica suspension on the surface of the nano silica layer, and curing to obtain the composite coating body.
In a further preferred embodiment, the chemical vapor deposition method includes a plasma enhanced chemical vapor deposition method, an ultra-high vacuum chemical vapor deposition method, or a low temperature chemical vapor deposition method, and is preferably a plasma enhanced chemical vapor deposition method.
As a further preferred embodiment, the reaction gas source for chemical vapor deposition comprises SiH4And N2O；
Preferably, SiH4And N2The volume ratio of O is 1: 0.1 to 5, preferably 1: 0.1 to 2;
preferably, the deposition conditions of the chemical vapor deposition method include at least one of the following conditions:
the deposition temperature is 30-300 ℃, preferably 150-250 ℃, and more preferably 150-180 ℃;
the radio frequency power is 20-200W, preferably 60-80W, and further preferably 65-75W;
the deposition pressure is 10-150Pa, preferably 80-100Pa, and more preferably 85-95 Pa;
the deposition time is 1-10min, preferably 5-10min, and more preferably 6-9 min.
As a further preferred embodiment, the step (b) comprises: under the alkaline condition, the silane coupling agent is subjected to hydrolysis reaction in an aqueous solution of alcohol to obtain a hydrolysate of the silane coupling agent;
preferably, step (b) comprises: firstly, uniformly mixing a silane coupling agent with an aqueous solution of alcohol, and then uniformly mixing the silane coupling agent with an alkaline substance to obtain a hydrolysate of the silane coupling agent;
preferably, the time of the hydrolysis reaction is 10-60min, preferably 20-40 min;
preferably, the alcohol comprises a C1-C4 alcohol;
preferably, the C1-C4 alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol, propylene glycol, or glycerol;
preferably, the mass ratio of alcohol to water in the aqueous alcohol solution is 1: 0.01 to 5, preferably 1: 0.05 to 1;
preferably, the alkaline substance includes an organic alkaline substance and/or an inorganic alkaline substance;
preferably, the organic basic substance includes an organic amine;
preferably, the organic amine comprises an aliphatic amine;
preferably, the fatty amine comprises at least one of decylamine, dodecylamine, hexadecylamine, or octadecylamine;
preferably, the inorganic alkaline substance comprises ammonia and/or sodium carbonate.
As a further preferred embodiment, the step (c) comprises: carrying out surface grafting reaction on the silica gel obtained by the sol-gel method and a low surface energy modifier to obtain a super-hydrophobic silica suspension;
preferably, a silicon source, a catalyst and a solvent are mixed, and silica gel is obtained after sol-gel reaction;
preferably, the silicon source comprises a silicate;
preferably, the silicate comprises at least one of methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, or butyl orthosilicate;
preferably, the solvent comprises an aqueous solution of an alcohol;
preferably, the catalyst comprises ammonia, hydrochloric acid, acetic acid or carbon dioxide;
preferably, the low surface energy modifying agent comprises at least one of hexamethyldisilazane, trimethylmethoxysilane, or triethylethoxysilane.
As a further preferred technical solution, the coating comprises blade coating, spray coating or spin coating;
preferably, the curing temperature is 20-200 ℃, preferably 50-100 ℃; and/or the curing time is 1-60min, preferably 10-30 min.
In a third aspect, the present invention provides a use of the above-described coated composite body or the coated composite body obtained by the above-described method for producing a coated composite body in the production of a solar cell.
In a fourth aspect, the present invention provides a solar cell including the above-described composite coated body or the composite coated body with tape obtained by the above-described method for producing a composite coated body with tape.
Compared with the prior art, the invention has the beneficial effects that:
the composite coating body comprises a base material and a composite coating formed on the surface of the base material, wherein a nano silicon dioxide layer in the composite coating is formed on the surface of the base material by adopting a chemical vapor deposition method, the chemical vapor deposition method is good in film forming quality, and a plated film is thin, and the nano silicon dioxide layer is formed independently, so that the nano silicon dioxide layer can be firmly combined with the base material; in addition, the surface of the nano silicon dioxide layer formed by the chemical vapor deposition method has a large number of active hydroxyl groups, which is beneficial to being connected with the active hydroxyl groups in the hydrolysate of the silane coupling agent to form silicon-oxygen bonds, so that the connection strength of the nano silicon dioxide layer and the hydrolysate of the silane coupling agent is improved; active hydroxyl in the hydrolysis condensation product of the silane coupling agent can be connected with active hydroxyl in the super-hydrophobic silica layer to form a silicon-oxygen bond, so that the connection strength between the super-hydrophobic silica layer and the hydrolysis product of the silane coupling agent (the two ends of the hydrolysis product both contain hydroxyl) is improved (the hydrolysis product of the silane coupling agent is condensed with the nano silica layer and the super-hydrophobic silica layer to form an intermediate connection layer).
Therefore, in the composite coating body with the specific structure, the composite coating can be firmly connected with the substrate, and the layers of the composite coating are connected through chemical bonds, so that the connection strength is high, the composite coating is not easy to separate from the surface of the substrate, and the structure of the composite coating body with the specific structure is stable. In addition, due to the existence of the super-hydrophobic silica layer, the super-hydrophobic silica layer has super hydrophobicity and stain resistance, and the hydrolysate of the silane coupling agent has high transparency, so that the super-hydrophobic silica layer can ensure good light transmission.
Therefore, the composite coating body with the super-hydrophobic property and the light transmittance can be kept well even if the composite coating body with the super-hydrophobic property is applied to packaging of the surface of a solar cell and used outdoors for a long time, and the photoelectric efficiency of the solar cell is guaranteed not to be lost.
Drawings
FIG. 1 is a schematic view of the structure of a composite coated body obtained in example 28;
FIG. 2 is a light transmission UV (ultraviolet and visible spectrum) spectrum of a blank glass, an intermediate bonding layer and the resulting composite coated body of example 28;
fig. 3 is a graph comparing the photoelectric conversion efficiency of the composite coated body-packaged solar cell and the bare glass-packaged solar cell obtained in example 28 during outdoor use for 60 days.
Icon: 1-a substrate; 2-composite coating; 201-a nano-silica layer; 202-a superhydrophobic silicon dioxide layer; 203-intermediate connection layer.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.
According to an aspect of the present invention, there is provided a coated composite body comprising: the composite coating comprises a substrate and a composite coating formed on the surface of the substrate, wherein the composite coating comprises:
the nano silicon dioxide layer is formed on the surface of the base material by adopting a chemical vapor deposition method;
the super-hydrophobic silicon dioxide layer is arranged opposite to the nano silicon dioxide layer;
the nano silicon dioxide layer is connected with the super-hydrophobic silicon dioxide layer through a silicon-oxygen bond; wherein, the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer respectively contain hydroxyl and are condensed with a hydrolysate of a silane coupling agent to form a silicon-oxygen bond.
The existing hydrophobic coating is mainly formed by adding a hydrophobic material with low surface energy into a coating and then coating the coating on the surface of an object, for example, by adopting a dip-dyeing method and the like. However, the coating formed by the method has the characteristics of poor adhesion and unstable super-hydrophobic property. The inventor finds out through research that: on the one hand, conventional coating methods such as dip dyeing dry the resulting coating to a substrate have poor adhesion; on the other hand, the hydrophobic material is mixed with other components of the coating, the binding force is poor, and a stable hydrophobic surface cannot be fully formed on the surface of the hydrophobic material; on the other hand, the existing multi-component coating containing hydrophobic materials is obviously incapable of forming a coating layer by a chemical vapor deposition method.
In view of the above, the present invention provides a composite coating body with the above structure, which has the advantages of stable and firm structure, good hydrophobicity, excellent stain resistance, and high transparency, and the long-term service performance is not deteriorated, so that the composite coating body with the above structure is applied to the packaging of the surface of a solar cell, and can maintain good super-hydrophobic property and light transmittance even under the long-term use in severe outdoor environment, thereby ensuring that the photoelectric efficiency of the solar cell is not lost.
It should be noted that:
the "nano-silica layer" mentioned above means a coating layer mainly composed of nano-scale silica, and the nano-scale silica means silica having a particle diameter ranging from 1 to 100 nm.
The super-hydrophobic silica layer is a coating formed by surface-modified silica, the surface-modified silica has super-strong hydrophobicity, the contact angle of water on the surface of the silica exceeds 140 degrees, and the sliding angle of the silica is less than 10 degrees.
In a preferred embodiment, the substrate comprises glass, silicon wafer, mica sheet or polymer sheet. The polymer sheet means a sheet material made of a polymer. The light transmission of the glass, the mica sheet and the polymer sheet is high, and the silicon wafer has high photoelectric conversion efficiency. The above substrate has good transparency and is not easily deformed or damaged during deposition.
Preferably, the glass comprises quartz glass, high borosilicate glass or soda lime glass, preferably quartz glass. The quartz glass has high spectral transmission, can transmit ultraviolet rays and infrared rays, and cannot be damaged by radiation rays.
Preferably, the polymer sheet comprises a polyethylene sheet, a polyvinyl chloride sheet, a polypropylene sheet, a polycarbonate sheet, a polymethylmethacrylate sheet or a polyphenylsulfone sheet. Polyethylene sheet refers to a sheet material made of polyethylene. The polyvinyl chloride sheet is a sheet material made of polyvinyl chloride. The polypropylene sheet refers to a sheet material made of polypropylene. Polycarbonate sheet refers to a sheet material made of polycarbonate. The polymethyl methacrylate sheet refers to a sheet material made of polymethyl methacrylate. The polyphenylene sulfone sheet is a sheet material made of polyphenylene sulfone.
Preferably, the thickness of the nano silicon dioxide layer is 200-800 nm; an intermediate connecting layer is formed between the nano silicon dioxide layer and the super-hydrophobic silicon dioxide layer, and the thickness of the intermediate connecting layer is 0.5-1 mu m; the thickness of the super-hydrophobic silicon dioxide layer is 200-600 nm. The thickness of the aforementioned nanosilica layer is typically, but not limited to, 200, 300, 400, 500, 600, 700 or 800 nm; the thickness of the above-mentioned intermediate tie layer is typically, but not limited to, 0.5, 0.6, 0.7, 0.8, 0.9 or 1 μm; the thickness of the aforementioned superhydrophobic silicon dioxide layer is typically, but not limited to, 200, 300, 400, 500, or 600 nm. When the thicknesses of the nano silicon dioxide layer, the middle connecting layer and the super-hydrophobic silicon dioxide layer are in the ranges, the mechanical property and the light transmittance of the nano silicon dioxide layer are optimal.
Preferably, the particle size of the silicon dioxide in the nano silicon dioxide layer is 10-20 nm. The above particle size is typically, but not limited to, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 nm. When the particle size of the silicon dioxide is in the range, the mechanical property of the nano silicon dioxide layer is higher, and the cracking phenomenon is not easy to occur after long-term use, so that the service life of the composite coating is longer.
Preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyl) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, or gamma-aminopropylmethyldiethoxysilane. The above silane coupling agents include, but are not limited to, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (2, 3-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, a combination of gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane, a combination of gamma- (2, 3-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane, a combination of gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane, or a combination of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-aminopropylmethyldiethoxysilane, and the like.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned composite coated body, comprising the steps of:
(a) providing a base material, and depositing a nano silicon dioxide layer on the surface of the base material by adopting a chemical vapor deposition method;
(b) providing a hydrolysate of a silane coupling agent;
(c) providing a super-hydrophobic silica suspension;
(d) and sequentially coating the hydrolysate of the silane coupling agent and the super-hydrophobic silica suspension on the surface of the nano silica layer, and curing to obtain the composite coating body.
The method has the advantages that the process is scientific and reasonable, the obtained composite coating body with the composite coating layer is stable in structure, the composite coating layer is not easy to separate from the surface of the base material, the composite coating layer has super-strong hydrophobicity, stain resistance and good light transmission, and the photoelectric conversion efficiency of the solar cell cannot be reduced after the composite coating body with the composite coating layer is used for a long time.
The "basic substance" refers to a substance having an ability to donate electrons or an ability to accept protons. The alkaline substance can be divided into organic base and inorganic base according to the material characteristics; the proton-absorbing material can be divided into monobasic alkali, binary alkali, ternary alkali, polybasic alkali and the like according to the quantity of protons accepted by the material; the alkaline substances can be classified into strong alkali and weak alkali according to their alkalinity.
In a preferred embodiment, the chemical vapor deposition method comprises plasma enhanced chemical vapor deposition, ultra high vacuum chemical vapor deposition or low temperature chemical vapor deposition, preferably plasma enhanced chemical vapor deposition. The ultra-high vacuum chemical vapor deposition method is below 10 deg.C-6Chemical vapor deposition in a pressure atmosphere of Pa. The Plasma Enhanced Chemical Vapor Deposition (PECVD) method has the advantages of low basic Deposition temperature, high Deposition rate, good film forming quality, less pinholes and difficult cracking.
In a preferred embodiment, the reactant gas source for chemical vapor deposition comprises SiH4And N2O。
Preferably, SiH4And N2The volume ratio of O is 1: 0.1 to 5, preferably 1: 0.1-2. The above volume ratio is typically, but not limited to, 1: 0.1, 1: 0.5, 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5. when the volume ratio of the two is within the above range, the surface of the obtained nano silica layer is relatively flat, and the molar ratio of Si to O is closer to the theoretical value.
In a preferred embodiment, the deposition conditions of the chemical vapor deposition process include at least one of the following conditions:
the deposition temperature is 30-300 deg.C, preferably 150-250 deg.C, and more preferably 150-180 deg.C. The deposition temperature is typically, but not limited to, 30, 50, 100, 150, 200, 250, or 300 ℃. When the deposition temperature is within the above range, the reaction for generating silicon dioxide is favorably and smoothly carried out, the deposition speed is high, and the reaction is difficult to realize or the bonding force between the coating and the substrate is poor due to the excessively high or excessively low deposition temperature.
The radio frequency power is 20-200W, preferably 60-80W, and more preferably 65-75W. The rf power is typically, but not limited to, 20, 40, 60, 80, 100, 120, 140, 160, 180, or 200W. When the radio frequency power is within the range, the thickness of the obtained nano silicon dioxide layer is more reasonable, and the number of active hydroxyl groups on the surface of the nano silicon dioxide layer is more, so that the number of binding points with the active hydroxyl groups of the hydrolysate of the silane coupling agent is more, and the connection strength between the two layers is higher. If the radio frequency power is too low, the thickness of the nano silicon dioxide layer is too small, and the number of active groups on the surface is too small, so that the strength of the nano silicon dioxide layer is not improved; if the radio frequency power is too high, the thickness of the nano silicon dioxide layer is too large, so that the whole thickness of the composite coating is too large, and light cannot penetrate through the composite coating easily.
The deposition pressure is 10 to 150Pa, preferably 80 to 100Pa, and more preferably 85 to 95 Pa. The deposition pressure is typically, but not limited to, 10, 20, 40, 60, 80, 100, 120, 140, or 150 Pa. The deposition pressure may also be referred to as the working pressure or the reaction pressure. When the deposition pressure is within the above range, the deposition rate is high and the continuity of the resulting film is strong. If the deposition pressure is too low, the film has poor continuity and low deposition rate; if the deposition pressure is too high, the particle size of the silicon dioxide in the nano silicon dioxide layer is too large, which may affect the light transmittance.
The deposition time is 1-10min, preferably 5-10min, and more preferably 6-9 min. Deposition times are typically, but not limited to, 1, 2,3, 4, 5, 6, 7, 8, 9, or 10 min. The influence of the deposition time on the nano silicon dioxide layer is similar to the influence of the radio frequency power on the nano silicon dioxide layer, and when the deposition time is within the range, the thickness of the obtained nano silicon dioxide layer is more reasonable. The thickness of the nano silicon dioxide layer is too large due to too long time, the thickness of the nano silicon dioxide layer is too small due to too short time, and the two conditions are not favorable for forming a good nano silicon dioxide layer.
In a preferred embodiment, step (b) comprises: under alkaline conditions, the silane coupling agent is subjected to hydrolysis reaction in an alcohol aqueous solution to obtain a hydrolysate of the silane coupling agent. The "alkaline condition" mentioned above means a condition of pH more than 7.
Preferably, step (b) comprises: firstly, uniformly mixing a silane coupling agent and an alcohol aqueous solution, and then uniformly mixing the silane coupling agent and an alkaline substance to obtain a hydrolysate of the silane coupling agent. According to the preferred embodiment, the hydrolysate of the silane coupling agent is obtained by mixing the silane coupling agent with the aqueous solution of the alcohol and then mixing the silane coupling agent with the alkaline substance, so that the hydrolytic condensation of the silane coupling agent is quicker and more thorough, and the active hydroxyl in the hydrolysate of the silane coupling agent is more, thereby being beneficial to further improving the connection strength between layers in the composite coating.
Optionally, the mixing means comprises stirring and/or ultrasonic dispersion.
Preferably, the mixing reaction time is 10-60min, preferably 20-40 min. The above mixing reaction time is typically, but not limited to, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 min. When the mixing reaction time is within the above range, the silane coupling agent can be completely hydrolyzed and condensed, and active hydroxyl groups in the silane coupling agent can be completely released, which is beneficial to improving the utilization rate of the silane coupling agent and the connecting force between the silane coupling agent and the rest layers.
Preferably, the alcohol comprises a C1-C4 alcohol. The C1-C4 alcohol refers to an alcohol having 1, 2,3 or 4 carbon atoms. The alcohol has reasonable carbon chain length, excessive carbon number, overlong carbon chain and increased boiling point, and is not beneficial to the volatilization of later alcohol solvent; meanwhile, when the number of carbon atoms is increased, the alcohol becomes solid and unusable.
Preferably, the C1-C4 alcohol comprises at least one of methanol, ethanol, isopropanol, n-butanol, propylene glycol, or glycerol. The C1-C4 alcohols include, but are not limited to, ethanol, isopropanol, methanol, n-butanol, propylene glycol, glycerol, a combination of ethanol and isopropanol, a combination of methanol and n-butanol, a combination of propylene glycol and glycerol, a combination of ethanol, isopropanol, and methanol, or a combination of n-butanol, propylene glycol, and glycerol, and the like.
Preferably, the mass ratio of alcohol to water in the aqueous alcohol solution is 1: 0.01 to 5, preferably 1: 0.05-1. The above mass ratio is typically, but not limited to, 1: 0.01, 1: 0.5, 1: 1. 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, 1: 4. 1: 4.5 or 1: 5. the alcohol has better compatibility as a solvent, and the addition of water can promote the hydrolysis process, and when the mass ratio of the alcohol to the water is in the range, the reaction is more favorably carried out.
Preferably, the basic substance includes an organic basic substance and/or an inorganic basic substance. The alkaline substance includes an organic alkaline substance, an inorganic alkaline substance, or a combination of an organic alkaline substance and an inorganic alkaline substance. The organic alkaline substance refers to a substance that is alkaline in organic substances. The inorganic alkaline substance refers to a substance that is alkaline in inorganic substances.
Preferably, the organic basic substance includes an organic amine.
Preferably, the organic amine comprises an aliphatic amine.
Preferably, the fatty amine comprises at least one of decylamine, dodecylamine, hexadecylamine, or octadecylamine. Such fatty amines include, but are not limited to, decylamine, dodecylamine, hexadecylamine, octadecylamine, a combination of decylamine and dodecylamine, a combination of hexadecylamine and octadecylamine, a combination of decylamine, dodecylamine, and hexadecylamine, or a combination of dodecylamine, hexadecylamine, and octadecylamine, and the like.
Preferably, the inorganic alkaline substance comprises ammonia and/or sodium carbonate. The inorganic alkaline substance includes but is not limited to ammonia, sodium carbonate, or a combination of ammonia and sodium carbonate, etc.
In a preferred embodiment, step (c) comprises: reacting the silica gel obtained by the sol-gel method with a low surface energy modifier to obtain a silica suspension. The silica gel obtained by the sol-gel method has strong size controllability, and is beneficial to improving the light transmittance of the super-hydrophobic silica layer. The above-mentioned "low surface energy modifier" means a silane coupling agent having a functional group with a low chemical surface energy on the surface, such as hexamethyldisilazane, trimethylmethoxysilane, etc.
Preferably, the silicon source comprises a silicate. "silicate ester" refers to esters which, upon hydrolysis, yield silicic acid (or silica) and various organic alcohols.
Preferably, the silicate comprises at least one of methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, or butyl orthosilicate. Such silicates include, but are not limited to, methyl orthosilicate, tetraethyl orthosilicate, tetrapropyl silicate, butyl orthosilicate, a combination of methyl orthosilicate and tetraethyl orthosilicate, a combination of tetrapropyl silicate and butyl orthosilicate, or a combination of methyl orthosilicate, tetraethyl orthosilicate, and tetrapropyl silicate, and the like.
Tetraethyl orthosilicate is also called ethyl silicate, tetraethyl orthosilicate, tetraethyl silicate or tetraethoxysilane and has the chemical formula C8H20O4Si。
Preferably, the solvent comprises an aqueous solution of an alcohol.
Preferably, the catalyst comprises ammonia, hydrochloric acid, acetic acid or carbon dioxide.
Preferably, the low surface energy modifying agent comprises at least one of hexamethyldisilazane, trimethylmethoxysilane, or triethylethoxysilane. Such low surface energy modifiers include, but are not limited to, hexamethyldisilazane, trimethylmethoxysilane, triethylethoxysilane, a combination of hexamethyldisilazane and trimethylmethoxysilane, a combination of trimethylmethoxysilane and triethylethoxysilane, a combination of hexamethyldisilazane and triethylethoxysilane, or a combination of hexamethyldisilazane, trimethylmethoxysilane and triethylethoxysilane, and the like.
In a preferred embodiment, the coating comprises knife coating, spray coating or spin coating.
Preferably, the curing temperature is 20-200 ℃, preferably 50-100 ℃; and/or the curing time is 1-60min, preferably 10-30 min. The above curing temperature is typically, but not limited to, 20, 50, 80, 100, 120, 150, 170, or 200 ℃; the above curing time is typically, but not limited to, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 min. In the curing temperature and the curing time, the hydrolysate of the silane coupling agent and the silica suspension can be completely cured, and the layers of the composite coating are tightly connected and have strong firmness. If the curing temperature is too low or the curing time is too short, the curing is incomplete, the connection among layers is unstable, and the layers are easy to fall off; if the curing temperature is too high or the curing time is too long, the time cost and energy cost of curing are increased, and unnecessary cracks are easily generated in the coating at high temperature, which affects the functionality of the coating.
The light transmittance of the composite coating body is up to 96%, the static water contact angle on the surface of the composite coating body is 153 degrees, the composite coating body has excellent water resistance and sand impact resistance, and the composite coating body still keeps excellent super-hydrophobic self-cleaning performance after being soaked in extreme conditions such as strong acid, strong alkali, salt water and the like. The photovoltaic efficiency of the solar cell is tested after the composite coated body is applied to the surface of the solar cell and stored outdoors for 2 months, and the result shows that the efficiency of the solar cell with the composite coated body is kept at 14.21 percent, while the efficiency of the solar cell without the coating is only 13.01 percent.
According to another aspect of the present invention, there is provided a use of the above-described body with a composite coating for producing a solar cell. The composite coating body with the function of improving the stain resistance of the solar cell can be effectively improved when the composite coating body is applied to the preparation of the solar cell, and the high photoelectric efficiency of the solar cell can be still kept under the condition of long-term outdoor use.
According to another aspect of the present invention, there is provided a solar cell including the above ribbon composite coating body. The solar cell comprises the composite coating body, so that the solar cell has the advantages of good stain resistance and high photoelectric conversion efficiency after long-term use.
It should be noted that, the specific application mode of the composite coated body in the preparation of the solar cell and the specific position (connection relationship with other components or assemblies) in the solar cell are not particularly limited, and the common methods in the art can be adopted.
The present invention will be described in further detail with reference to examples and comparative examples.