CN116435395A - Color-adjustable flexible photovoltaic module, preparation method, solar cell and application - Google Patents
Color-adjustable flexible photovoltaic module, preparation method, solar cell and application Download PDFInfo
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- CN116435395A CN116435395A CN202310693168.4A CN202310693168A CN116435395A CN 116435395 A CN116435395 A CN 116435395A CN 202310693168 A CN202310693168 A CN 202310693168A CN 116435395 A CN116435395 A CN 116435395A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- 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
- Y02E10/52—PV systems with concentrators
Abstract
The invention belongs to the technical field of color-adjustable flexible photovoltaic modules, and in particular relates to a color-adjustable flexible photovoltaic module, a preparation method, a solar cell and application thereof, wherein the color-adjustable flexible photovoltaic module comprises a cell, a light-receiving surface transparent adhesive film layer, a front plate, a back transparent adhesive film layer, a back plate and a first transparent film layer and a second transparent film layer, wherein the light-receiving surface transparent adhesive film layer and the front plate are sequentially arranged on one side of a light-receiving surface of the cell, the back transparent adhesive film layer and the back plate are sequentially arranged on the back surface of the cell, the first transparent film layer is arranged on the light-receiving surface of the cell and is positioned between the light-receiving surface of the cell and the light-receiving surface transparent adhesive film layer, and the density of one end of the first transparent film layer, which is close to the light-receiving surface of the cell, is less than the density of the other end of the first transparent film layer, and the density difference of the two ends is 0.2-1.8g/cm 3 The average refractive index of the first transparent film layer is 1.8-2.2. The invention can obtain the high-saturation flexible photovoltaic module with adjustable colors and different colors.
Description
Technical Field
The invention belongs to the technical field of color-adjustable flexible photovoltaic modules, and particularly relates to a color-adjustable flexible photovoltaic module, a preparation method, a solar cell and application.
Background
Color photovoltaic modules are an innovative application in the photovoltaic industry, and the prior art generally uses pigments to color or paste patterns thereon, thereby forming color photovoltaic modules. In addition, interference is formed on the surface of the photovoltaic module, so that multicolor display is realized. However, the prior art has certain limitations in practical application, mainly expressed in the following aspects:
1) The color photovoltaic module based on the interference principle is mainly applied to a glass module. Because of the large weight and rigidity of the glass assembly, the application of the glass assembly in the fields of building integrated photovoltaics, vehicles and the like is limited. The difficulty of the interference principle in the application of the color flexible photovoltaic module is that: the flexible photovoltaic module is made of a polymer packaging material, and when a film layer is deposited on the surface of the flexible photovoltaic module, gas can be released at high temperature to directly influence the film coating effect, so that the display of interference colors is influenced. However, the glass does not have the problem, so that the existing interference principle applied to the glass assembly cannot be directly transferred to the flexible photovoltaic assembly.
2) Because the color of the silicon chip is darker, the color of the color photovoltaic module realized by the prior art is also darker, and the saturation is not high. The color photovoltaic module has limited aesthetic degrees, and cannot meet the requirements of users on high beauty and individuation.
3) The existing color flexible photovoltaic module is mainly a whole piece of single color, and lacks diversity and individuation. The user can not select photovoltaic modules with different colors and patterns according to own needs and aesthetic sense, so that the market potential of the color photovoltaic modules is further limited.
4) The preparation process of the color photovoltaic module is complex and the cost is high. The color photovoltaic module is disadvantageous in market competition, and is difficult to popularize and apply on a large scale.
In order to overcome these limitations, it is necessary to study a novel color flexible photovoltaic module, a method for manufacturing the same, a solar cell and an application thereof, and simultaneously, to improve the color saturation and brightness of the color photovoltaic module so as to have a better aesthetic effect.
Disclosure of Invention
The invention aims to overcome the defects of dark color, low saturation and single color of a color-adjustable flexible photovoltaic module in the prior art, and provides the color-adjustable flexible photovoltaic module, a preparation method, a solar cell and application.
In order to achieve the above object, in a first aspect, the present invention provides a color-adjustable flexible photovoltaic module, including a battery piece, a light-receiving surface transparent adhesive film layer and a front plate sequentially disposed on one side of the light-receiving surface of the battery piece, a back transparent adhesive film layer and a back plate sequentially disposed on the back surface of the battery piece, and a first transparent film layer and a second transparent film layer, wherein the first transparent film layer is disposed on the light-receiving surface of the battery piece and between the light-receiving surface of the battery piece and the light-receiving surface transparent adhesive film layer, and the density of one end of the first transparent film layer, which is close to the light-receiving surface of the battery piece, is less than the density of the other end of the first transparent film layer, and the density difference between the two ends is 0.2-1.8g/cm 3 Preferably 0.4-1.8g/cm 3 The second transparent film layer is arranged between the front plate and the light-receiving surface transparent adhesive film layer.
The average refractive index of the first transparent film layer is 1.8-2.2.
In some preferred embodiments of the present invention, the first transparent film layer has an average density of from 2.2 to 7.2g/cm 3 。
In some preferred embodiments of the present invention, the thickness of the first transparent thin film layer is 100 to 180nm.
In some preferred embodiments of the present invention, the first transparent film layer comprises a transparent conductive film layer and/or a non-conductive transparent film layer.
Preferably, the transparent conductive film layer is a doped oxide containing a doping element, the oxide in the doped oxide comprises at least one of indium oxide, zinc oxide and tin oxide, and the doping element comprises at least one of tin, aluminum, fluorine and silver.
More preferably, the first transparent thin film layer is at least one of tin doped indium oxide, zinc aluminum oxide, fluorine doped tin oxide, and silver doped zinc oxide.
Further preferably, the first transparent thin film layer is tin doped indium oxide.
Preferably, the non-conductive transparent film layer includes at least one of silicon nitride, silicon oxide, silicon oxynitride, silicon carbide, and titanium nitride.
Preferably, the average density of the first transparent film layer is 5.5-7.2g/cm 3 The average density of the first transparent film layer is 2.2-3.2g/cm when the first transparent film layer is a non-conductive transparent film layer 3 。
In some preferred embodiments of the present invention, the ratio of the refractive index of the front plate to the average refractive index of the first transparent film layer is 1:1.28-1.5.
The light-receiving surface of the battery piece is made of suede.
In some preferred embodiments of the present invention, the thickness ratio of the front plate, the second transparent film layer, the light-receiving surface transparent adhesive film layer and the battery piece is 1-3:0.0006-0.0025:3-8:1.
in the invention, preferably, a concave-convex structure is arranged on one surface of the second transparent film layer, which is close to the light-receiving surface transparent adhesive film layer.
In some preferred embodiments of the invention, the relief structure provides the second transparent film layer with an overall thickness dimension between 50-500 nm.
In the present invention, the second transparent thin film layer is preferably at least one of titanium dioxide, zirconium dioxide, zinc aluminum oxide and niobium pentoxide.
In some preferred embodiments of the present invention, the ratio of refractive indices of the front plate and the second transparent film layer is 1:1.28-1.93.
More preferably, the refractive index of the second transparent film layer is >1.8.
The second transparent film layer preferably has a density of 3.8-6.9 g/cm 3 Preferably 3.9-6.9 g/cm 3 Between them.
In some preferred embodiments of the present invention, the second transparent film layer is a single transparent film layer with a refractive index >2.0, or is a plurality of transparent film layers, and there is a refractive index difference between adjacent transparent film layers, the absolute value of the refractive index difference is between 0.3 and 1, and the refractive index of each film layer in the plurality of transparent film layers is in non-increasing or non-decreasing change.
In some preferred embodiments of the present invention, the single transparent film layer having a refractive index >2.0 is a titania film layer or a zirconia film layer.
Preferably, the multilayer transparent film layer is a combination of a titanium dioxide film layer and one or more selected from zinc aluminum oxide film layer, indium tin oxide film layer and niobium pentoxide.
Further preferably, in the direction from the front plate to the light-receiving surface transparent film layer, the multilayer transparent film layer is a combined film of a titanium dioxide film layer and a zinc aluminum oxide film layer which are sequentially arranged, or is a combined film of a titanium dioxide film layer, a zinc aluminum oxide film layer and a titanium dioxide film layer which are sequentially arranged.
In some preferred embodiments of the present invention, the thickness of the titanium dioxide film layer in the second transparent film layer is controlled to be 90% -100% of the total thickness of the second transparent film layer when the required saturation level is 50% -55%; when the required saturation is 40% -49%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to be 60% -89% of the total thickness of the second transparent film layer; when the required saturation is 35% -39%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to account for 31% -59% of the total thickness of the second transparent film layer; and when the required saturation is 25% -34%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to be 0% -30% of the total thickness of the second transparent film layer.
In a second aspect, the present invention provides a method for preparing a color-tunable flexible photovoltaic module, the method comprising the steps of:
s1, depositing a first transparent film layer on a light receiving surface of a battery piece in a magnetron sputtering mode, wherein the process of depositing in the magnetron sputtering mode comprises the following steps: first sputtering is carried out for 3-8min, and then second sputtering is carried out while negative bias is applied to the back surface of the battery piece; wherein, the vacuum degree of the first sputtering is controlled to be lower than that of the second sputtering; the power of the first sputtering is more than or equal to the power of the second sputtering, and the vacuum degree of the second sputtering is 5 multiplied by 10 -1 - 5×10 -2 Pa, the power of the second sputtering is 6-9kw;
s2, depositing a second transparent film layer on one surface of the front plate;
s3, sequentially laying a back plate, a back transparent adhesive film layer, a battery piece deposited with a first transparent film layer, a light-receiving surface transparent adhesive film layer and a front plate deposited with a second transparent film layer, and then laminating, wherein the first transparent film layer is positioned between the light-receiving surface of the battery piece and the light-receiving surface transparent adhesive film layer, and the second transparent film layer is positioned between the front plate and the light-receiving surface transparent adhesive film layer;
the density of one end of the first transparent film layer, which is close to the light receiving surface of the battery piece, after deposition is smaller than that of the other end of the first transparent film layer.
In some preferred embodiments of the present invention, the ratio of the vacuum level of the first sputtering to the vacuum level of the second sputtering is 3 to 10: 1. preferably 5-10:1, the ratio of the power of the first sputtering to the power of the second sputtering is 1-1.8: 1. preferably 1.2-1.8:1.
in some preferred embodiments of the present invention, the negatively biased condition comprises: the applied voltage is 3-8kV, and the applied frequency is 300-500Hz.
In some preferred embodiments of the present invention, the process of depositing the second transparent thin film layer having the concave-convex structure in S2 includes a step of controlling the material, thickness, and position of the desired thin film layer according to the desired color, specifically including any one of the following a-d methods:
a. Stamping one surface of the front plate through an stamping die with a required concave-convex structure to obtain the front plate with the concave-convex structure; then depositing a second transparent film layer on one surface of the concave-convex structure of the front plate;
b. attaching a mask material with a mask pattern on one surface of a front plate, and then depositing film materials with different materials and thicknesses on the surface; removing the mask material after the deposition is completed to obtain a second transparent film layer;
c. depositing film materials with different thicknesses and different materials on one surface of the front plate, performing laser scribing on different areas of the film materials to remove part of the film materials with different thicknesses, and forming patterns with different thicknesses and/or different shapes by laser scribing to obtain a second transparent film layer;
d. providing a mask plate with different spacing areas, keeping unequal distances between the mask plate and one surface of the front plate in the different spacing areas, depositing a second transparent film layer within the distances, and removing the mask plate to obtain the second transparent film layer.
In a third aspect, the present invention provides a color-tunable flexible photovoltaic module, which is prepared by the method for preparing the color-tunable flexible photovoltaic module according to the second aspect. The color-tunable flexible photovoltaic module of the third aspect is the same in structure as the color-tunable flexible photovoltaic module of the first aspect.
In a fourth aspect, the present invention provides a solar cell comprising the color-tunable flexible photovoltaic module of the first or third aspect.
In a fifth aspect, the present invention provides the use of a solar cell of the fourth aspect in a sun protection device and/or a solar device.
The sunshade device of the present invention may comprise, for example, a sunshade device or cover mounted on at least one of a caravan, a camper, a store, a vending machine, a swimming pool.
The solar device according to the present invention may include, for example, a solar power generation apparatus mounted on at least one of a balcony, a garden fence, a wall surface, a window, and an external lane of a garage.
The beneficial effects are that:
the inventors of the present invention found in the course of research that in the process of manufacturing a solar cell, in order to improve light absorption efficiency and photoelectric conversion efficiency: the surface area of the surface of the silicon wafer is increased through texturing, and diffuse reflection is increased, so that reflection is reduced, and the solar cell can absorb light better. The light absorption capacity of the solar cell is increased, so that the photoelectric conversion efficiency of the solar cell is improved. However, texturing greatly reduces light reflection, so the color displayed is a darker black blue. In the prior art, although the heterojunction battery has the ITO film, the step coverage rate (namely, the ratio of the thickness of the film layer A at the step crossing position to the thickness of the film layer B at the flat position) of the ITO film is larger, namely, the film thickness of each position (such as the film layer A area at the vertical position crossing the step and the film layer B area at the horizontal position crossing the flat position) is more uniformly thickened, so that the suede surface of the battery still keeps more complete, obvious diffuse reflection still exists, the reflection of blue light is still less, and the formed color is still darker blue.
According to the technical scheme, particularly, the first transparent film layers with the densities at the two ends from low to high and with proper density difference are arranged on the surfaces of the battery pieces, and the second transparent film layers are matched with the front plate, so that the refractive indexes are properly changed on the film layers to form interference, the absorption of blue light by the battery pieces can be reduced, the bright blue color is formed, the brightness of the battery pieces is obviously improved, the matching among the film layers is facilitated through the structure arrangement of the density change, the interface binding force is facilitated, and the conversion efficiency of the battery is improved. Meanwhile, the color can be adjusted by controlling the film thickness and the material of the second transparent film layer and matching with the first transparent film layer and other characteristics.
In the preferred scheme of the invention, the second transparent film layer with the concave-convex structure is arranged, and different colors are generated by different film thicknesses, so that the film layers with specific structures interfere to form different color colors with high saturation.
The invention particularly prefers a first transparent film layer with specific type and specific thickness of 100-180nm, is more beneficial to forming bright blue, can be beneficial to reducing the absorption of silicon by a body and improves the conversion efficiency of the battery; specifically, the non-blue light emitted by the first transparent film layer at different film thicknesses can be exactly absorbed by the bulk silicon, for example, the absorption of ITO becomes more when the thickness is lower than 100nm, so that the color can be gradually changed into green, yellow or red when the thickness is higher than 180nm, the conductivity of the first transparent film layer (such as ITO) is possibly insufficient when the thickness is lower than 100nm, the dimming based on purple is more complex, the interference color is not easy to color, the absorption of the first transparent film layer (such as ITO) becomes more when the thickness is higher than 180nm, and the light with the wavelength to be absorbed by the bulk silicon is reflected too much, so that the conversion efficiency of the battery piece can be greatly influenced.
The invention provides a preparation method of a flexible photovoltaic module which is beneficial to forming high saturation color, and the probability of increasing the collision of sputtering ions and sputtering the ions in all directions is considered to be the same, so that the receiving angle of a step A area is smaller, the received ions are less, the deposited sputtering material is less, and the film is thinner; the invention forms a first transparent film layer by combining two sputtering processes, reduces diffuse reflection of blue light, leads more blue light to reflect, and is beneficial to forming bright blue on the surface of a battery piece. The sputtering is performed for a certain time under a lower vacuum degree in the first sputtering, namely the probability of collision in all directions is the same, so that the single downward direction is reduced, the step coverage rate is poor, the sputtering is performed more in the area with a large receiving angle, and the sputtering is performed less in the area with a small receiving angle, so that the texture is slightly flattened, the density of the formed end film layer is smaller, and the absorption of blue light by a battery piece is reduced, so that bright blue is formed; and then in the second sputtering, the ion collision is reduced, the downward component of the speed is more straight, and meanwhile, the negative bias is added to attract the ions downward, so that the formed film has larger density, better quality and higher refractive index, is favorable for multi-angle multiple interference and is favorable for forming high-saturation color.
In addition, the first sputtering is performed under a lower vacuum degree, so that the influence of the quantity of gas released by the polymer packaging material of the flexible photovoltaic module on the lower vacuum degree is small, the lower vacuum degree can still maintain a stable level, and the consistency of the corresponding deposited film layer is good, so that the flexible photovoltaic module can be obtained by adopting an interference principle.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of one embodiment of a color-tunable flexible photovoltaic module of the present invention;
FIG. 2 is a schematic structural view of one embodiment of the front sheet and the second transparent film layer of the present invention;
FIG. 3 is a front plate with a concave-convex structure after embossing in embodiment 10 of the present invention;
fig. 4 is a front plate of the relief structure of the present invention after sputtering a second transparent film layer.
Description of the reference numerals
1. The battery piece, 2, first transparent film layer, 3, light-receiving surface transparent adhesive film layer, 4, second transparent film layer, 401, concave-convex structure, 5, front plate, 6, back transparent adhesive film layer, 7, backplate.
Detailed Description
In the present disclosure, the terms "first," "second," and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying a number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. Wherein the terms "optional" and "optionally" mean either comprising or not comprising (or may not be present).
In a first aspect, the invention provides a color-adjustable flexible photovoltaic module, which comprises a battery piece, a light-receiving surface transparent adhesive film layer, a front plate, a back transparent adhesive film layer, a back plate, a first transparent film layer and a second transparent film layer, wherein the light-receiving surface transparent adhesive film layer and the front plate are sequentially arranged on one side of a light-receiving surface of the battery piece, and the back transparent adhesive film layer and the back plate are sequentially arranged on the back surface of the battery piece. The first transparent film layer is arranged on the light receiving surface of the battery piece and is positioned between the light receiving surface of the battery piece and the transparent adhesive film layer of the light receiving surface, the density of one end of the first transparent film layer, which is close to the light receiving surface of the battery piece, is less than the density of the other end of the first transparent film layer, and the density difference of the two ends is 0.2-1.8g/cm 3 Preferably 0.4-1.8g/cm 3 The second transparent film layer is arranged between the front plate and the light-receiving surface transparent adhesive film layer.
The invention adopts the first transparent film layer with proper density difference at two ends, can promote the change of the battery piece from dark blue to bright blue, and can promote the saturation promotion of the flexible photovoltaic module while promoting the color regulation of the flexible photovoltaic module by matching the refractive index difference between the second transparent film layer and the front plate as well as between the front plate and each transparent film layer and the structure difference and thickness difference of different positions of the adjustable second transparent film layer. Under the same conditions, if the density difference between the two ends of the first transparent film layer is smaller or the densities of the two ends are the same, the battery piece is still dark blue, so that the flexible photovoltaic module cannot display high-saturation color and cannot realize colorful color adjustment; if the density difference between the two ends of the first transparent film layer is too large, the low-density transparent film layer near one end of the light receiving surface of the battery piece is too small in density, sparse in structure and unstable in structure, and the quality of the film layer is too poor, so that the performance of the solar battery is directly affected.
In the invention, preferably, a concave-convex structure is arranged on one surface of the second transparent film layer, which is close to the light-receiving surface transparent adhesive film layer. In the scheme, the density change of the first transparent film layer is particularly adjusted to be matched with the concave-convex structure of the second transparent film layer, so that interference is generated on the surface of the flexible photovoltaic module, and different colors are displayed. Meanwhile, the concave-convex structure enables second transparent film layers with different film thicknesses to be arranged at different positions, a three-dimensional structure is displayed, interfaces are more, and the flexible photovoltaic module with adjustable colors of various colors is realized.
In some preferred embodiments of the present invention, the first transparent film layer comprises a transparent conductive film layer and/or a non-conductive transparent film layer. The invention adopts the transparent conductive film layer as the first transparent film layer under the condition that the front side of the solar cell is provided with the electrode, and adopts the non-conductive transparent film layer or/and the transparent conductive film layer under the condition that the front side of the solar cell is not provided with the electrode.
Preferably, the transparent conductive film layer is a doped oxide containing a doping element, the oxide in the doped oxide comprises at least one of indium oxide, zinc oxide and tin oxide, and the doping element comprises at least one of tin, aluminum, fluorine and silver. The amounts of the doping elements of the invention are all carried out according to the prior art, and the effect of the invention can be realized as long as the transparent conductive film layer is made of the corresponding material.
In some preferred embodiments of the present invention, the first transparent thin film layer is at least one of tin doped indium oxide (ITO), zinc aluminum oxide (AZO), fluorine doped tin oxide (FTO), silver doped zinc oxide (AGZO).
More preferably, the first transparent thin film layer is tin doped indium oxide. In the preferred scheme, the ITO film is more beneficial to changing the color of the battery piece from dark black to brighter blue, mainly because the ITO film has the characteristics of high light transmittance and high refractive index, and can change the light propagation characteristic, so that part of light waves interfere on the surface of the film, and the reflection and transmission of blue light are increased. Meanwhile, the ITO film reduces the transmission of other color lights to a certain extent, so that the battery piece presents bright blue, and the battery piece is more beneficial to being matched with the second transparent film layer to obtain high-saturation color.
Preferably, the non-conductive transparent film layer includes at least one of silicon nitride, silicon oxide, silicon oxynitride, silicon carbide, and titanium nitride.
The average refractive index of the first transparent film layer is 1.8-2.2.
In some preferred embodiments of the present invention, the ratio of the refractive index of the front plate to the average refractive index of the first transparent film layer is 1:1.28-1.5. Under this preferred scheme, set up the ratio of suitable refracting index, the diffuse reflection to the blue light is reduced to the first transparent thin film layer of adjustment that can be better, more does benefit to and shows bright blue at the battery piece surface, more does benefit to flexible photovoltaic module's mixing of colors and saturation.
In some preferred embodiments of the present invention, the first transparent film layer has an average density of from 2.2 to 7.2g/cm 3 。
Further preferably, the average density of the first transparent film layer is 5.5-7.2g/cm 3 The average density of the first transparent film layer is 2.2-3.2g/cm when the first transparent film layer is a non-conductive transparent film layer 3 。
The metering mode of the average refractive index of the first transparent film layer is as follows: average refractive index=d1/d×n1+d2/d×n2, d=d1+d2, where d1 is the first end film layer thickness of the first transparent film layer (i.e., the film obtained by the first sputtering), d2 is the second end film layer thickness of the other end of the first transparent film layer (i.e., the film obtained by the second sputtering), d is the total thickness of the first transparent film layer, n1 is the refractive index of the first end film layer, and n2 is the refractive index of the second end film layer. The average density is the same, that is, average density=d1/(d1+d2) ×m1+d2/(d1+d2) ×m2, m1 is the density of the film obtained by the first sputtering, and m2 is the density of the film obtained by the second sputtering.
In some preferred embodiments of the present invention, the thickness of the first transparent thin film layer is 100 to 180nm. Under the preferred scheme, the surface of the battery piece is more favorable for obtaining bright blue.
The light-receiving surface of the battery piece is made of suede. The invention can reduce diffuse reflection of blue light caused by texturing, is more beneficial to displaying bright blue on the surface of the battery piece, and is more beneficial to color mixing and saturation of the flexible photovoltaic module.
In some preferred embodiments of the present invention, the thickness ratio of the front plate, the second transparent film layer, the light-receiving surface transparent adhesive film layer and the battery piece is 1-3:0.0006-0.0025:3-8:1. it is understood that, since the second transparent film layer has a concave-convex structure, the film thicknesses of the second transparent film layer are different, and the film thicknesses of the second transparent film layer at different positions are all within the range of the thickness ratio. Under the preferred scheme, the interference among all layers of structures can be better adjusted by setting the ratio of proper thickness, so that the simultaneous adjustment of various interference colors, saturation and brightness is more facilitated, and the display of more colorful colors is realized.
The thicknesses of the back transparent adhesive film layer and the back plate can be carried out according to the existing range, the invention is not limited to the range, and the thickness ratio of the back transparent adhesive film layer to the back plate to the battery piece is 1-6:1-3:1.
It should be noted that, in the color-adjustable flexible photovoltaic module of the present invention, the front plate, the light-receiving surface transparent adhesive film layer, the back transparent adhesive film layer and the back plate may be any of the existing corresponding materials. The front plate is a flexible front plate, for example, EFTE, PVDF, etc., and the refractive index is generally about 1.4. The transparent adhesive film layer on the light receiving surface may be, for example, EVA, POE, silica gel, etc., and its refractive index is generally about 1.4. The back transparent adhesive film layer may be, for example, EVA, POE, silica gel, etc., and its refractive index is generally about 1.4. The back-sheet is a flexible back-sheet, which may be, for example, EFTE, PVDF, etc., and has a refractive index of typically about 1.4. The battery plate of the invention is a battery plate with a metal electrode.
In some preferred embodiments of the present invention, the relief structure is such that the second transparent film layer as a whole also forms a relief structure, with interface differences at different locations, the second transparent film layer as a whole having a thickness dimension between 50-500 nm. Under this preferred scheme, set up the second transparent thin film layer of suitable thinness, can adjust the light and form the light reflection of different wavelength to at flexible photovoltaic module surface after the emergence is interfered, more do benefit to the bright-colored colour of realizing multiple high saturation and show the flexible photovoltaic module of colour adjustable simultaneously.
In some preferred embodiments of the present invention, the ratio of refractive indices of the front plate and the second transparent film layer is 1:1.28-1.93. Under the preferred scheme, the ratio of proper refractive indexes is set, a larger refractive index difference interval can be provided, and interference is more facilitated to develop on the surface of the flexible photovoltaic module.
More preferably, the refractive index of the second transparent film layer is >1.8. In the scheme, the difference between the refractive indexes of the second transparent film layer and the front plate is proper and large, so that interference is facilitated to develop on the surface of the flexible photovoltaic module.
In some preferred embodiments of the present invention, the second transparent film layer has a density of 3.8 to 6.9 g/cm 3 Preferably 3.9-6.9 g/cm 3 Between them. According to the invention, under the preferred scheme, the second transparent film layer with proper density is arranged, so that the suede structure on the surface of the battery piece can be adjusted by using the film layer with lower density to reduce diffuse reflection, and meanwhile, the high refractive index is realized by using the second transparent film layer with high density, so that the display of obvious blue color on the surface of the battery piece is facilitated.
In the present invention, the second transparent thin film layer is preferably at least one of titanium dioxide, zirconium dioxide, zinc aluminum oxide and niobium pentoxide. The second transparent film layer of the present invention may be a single component or may be a plurality of components, where each component may be stacked in a direction perpendicular to the surface of the front plate, or may be sequentially arranged in a direction parallel to the surface of the front plate, or may be a single component or different components at different heights in a direction parallel to the surface of the front plate (the second transparent film layer 4 shown in fig. 2 includes a two-layer structure in which a first layer near the surface of the front plate 5 is a single component, and an upward second layer is sequentially arranged in a plurality of different components and forms the concave-convex structure 401). The refractive index and density of each film layer in the second transparent film layer are determined according to the deposition method and conditions, film thickness and substrate, and the required refractive index and density can be adjusted and obtained according to the requirements. The invention is that The refractive index of the titanium dioxide film can be 1.8-2.7, and the density is 3.9-4.25 g/cm 3 . The zirconium dioxide film has refractive index of 2.0-2.2 and density of 5.6-6.0 g/cm 3 . The refractive index of the zinc aluminum oxide film is 1.8-2.2, and the density is 5.3-6.9 g/cm 3 。Nb 2 O 5 The density of the film is about 4.6-4.9 g/cm 3 The refractive index is 1.9-2.4 at 550 nm.
In some preferred embodiments of the present invention, the second transparent film layer is a single transparent film layer with a refractive index >2.0, or is a plurality of transparent film layers, and there is a refractive index difference between adjacent transparent film layers, the absolute value of the refractive index difference is between 0.3 and 1, and the refractive index of each film layer in the plurality of transparent film layers is in non-increasing or non-decreasing change. Under the preferred scheme, the multi-layer transparent film layer is provided with the second transparent film layer with refractive indexes changing in a certain difference value and being non-progressive or non-progressive, so that interference can be better formed on the surface of the component, and the display of multiple colors is facilitated. Wherein, the refractive index of the transparent multilayer film layer is not increased or decreased, which means that the refractive index cannot be increased or decreased continuously, and the refractive index needs to be changed alternately in high/low/high or low/high/low. While incremental or decremental changes do not interfere.
The second transparent film layer of the invention can use different structures and materials according to the requirements and application situations of specific positions. The second transparent film layer of the present invention may be, for example, titanium dioxide (TiO 2 ) At least one of zinc aluminum oxide (AZO) and tin-doped indium oxide (ITO). These film materials have high refractive index, good conductivity and transparency, and contribute to the formation of a rich color effect. In some preferred embodiments of the invention, the refractive index>The single-layer transparent film layer of 2.0 is a titanium dioxide film layer or a zirconium dioxide film layer.
In the present invention, the multilayer transparent film layer is preferably a combination of a titanium dioxide film layer and one or more selected from zinc aluminum oxide film layer, indium tin oxide film layer and niobium pentoxide. Namely, one or more selected from zinc aluminum oxide film layer, indium tin oxide film layer and niobium pentoxide are further arranged on the basis of the titanium dioxide-containing film layer. It should be noted that the same film layer may be provided as a plurality of layers at one layer or at different positions, for example, as a titanium dioxide film layer, a zinc aluminum oxide film layer, a sandwich type film layer of a titanium dioxide film layer.
Further preferably, in the direction from the front plate to the light-receiving surface transparent film layer, the multilayer transparent film layer is a combined film of a titanium dioxide film layer and a zinc aluminum oxide film layer which are sequentially arranged, or is a combined film of a titanium dioxide film layer, a zinc aluminum oxide film layer and a titanium dioxide film layer which are sequentially arranged. The latter three-layer combined film can increase the combination of the thickness of each film layer compared with the two-layer combined film, and is more beneficial to calling out more various colors for color development.
In some preferred embodiments of the present invention, the thickness of the titanium dioxide film layer in the second transparent film layer is controlled to be 90% -100% of the total thickness of the second transparent film layer when the required saturation level is 50% -55%; when the required saturation is 40% -49%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to be 60% -89% of the total thickness of the second transparent film layer; when the required saturation is 35% -39%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to account for 31% -59% of the total thickness of the second transparent film layer; and when the required saturation is 25% -34%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to be 0% -30% of the total thickness of the second transparent film layer. It is understood that the thickness of the titanium oxide film layer refers to the total thickness of the titanium oxide film layer. In a preferred embodiment of the invention, tiO 2 The thickness ratio is proper, the saturation of the color can be adjusted according to different requirements, and the vividness of the color can be easily adjusted under the condition of obtaining the required color system.
In a second aspect, the present invention provides a method for preparing a color-adjustable flexible photovoltaic module, where the color-adjustable flexible photovoltaic module is the color-adjustable flexible photovoltaic module in the first aspect.
The preparation method comprises the following steps:
s1, depositing a first transparent film layer on a light receiving surface of a battery piece in a magnetron sputtering mode;
s2, depositing a second transparent film layer on one surface of the front plate;
s3, sequentially laying a back plate, a back transparent adhesive film layer, a battery piece deposited with a first transparent film layer, a light-receiving surface transparent adhesive film layer and a front plate deposited with a second transparent film layer, and then laminating, wherein the first transparent film layer is positioned between the light-receiving surface of the battery piece and the light-receiving surface transparent adhesive film layer, and the second transparent film layer is positioned between the front plate and the light-receiving surface transparent adhesive film layer.
The density of one end of the first transparent film layer, which is close to the light receiving surface of the battery piece, after deposition is smaller than that of the other end of the first transparent film layer.
In the invention S1, the process of depositing by magnetron sputtering includes: first sputtering is carried out for 3-8min, and then second sputtering is carried out while negative bias is applied to the back surface of the battery piece; wherein, the vacuum degree of the first sputtering is controlled to be lower than that of the second sputtering; the power of the first sputtering is more than or equal to the power of the second sputtering, and the vacuum degree of the second sputtering is 5 multiplied by 10 -1 - 5×10 -2 Pa, the power of the second sputtering is 6-9kw.
The first sputtering method adopts a specific and proper time range, can obviously reduce diffuse reflection of blue light, and is beneficial to obtaining bright blue on the surface of the battery piece. Under the same conditions, if the first sputtering time is too long, the suede pits can cover more, the suede structure becomes too flat, and the density and quality of the deposited film are poor; the time is too short, the concave points of the suede cover less, the effect of filling the suede is insufficient, the diffuse reflection of the suede to blue light is insufficient, less blue light reflection is caused, and the blue brightness of the surface of the battery piece is darker.
The second sputtering time can be determined according to the thickness difference between the required total thickness and the first sputtering, and the time range is controlled according to the deposition speed, for example, the second sputtering time can be about 8-18min.
Other conditions in the magnetron sputtering deposition are carried out according to the conditions of a conventional method, for example, the target material is ITO, the sputtering voltage can be 200-300V, and the mixed gas of oxygen and argon is introduced, wherein the oxygen content is 1-5 vol%.
In some preferred embodiments of the present invention, the ratio of the vacuum level of the first sputtering to the vacuum level of the second sputtering is 3 to 10: 1. preferably 5-10:1, the ratio of the power of the first sputtering to the power of the second sputtering is 1-1.8: 1. preferably 1.2-1.8:1. under the preferred scheme, the first sputtering conditions which are suitable for large are set, so that the number of sputtered ions can be increased, the number of collisions among the sputtered ions can be increased more favorably, further, the sputtered ions are deposited in the contact angle area, the surface texture of the battery is reduced from the surface, the battery is smoother, and diffuse reflection of blue light is reduced more favorably.
In some preferred embodiments of the present invention, the negatively biased condition comprises: the applied voltage is 3-8kw, and the applied frequency is 300-500Hz. Under the preferred scheme, the sputtering ion is better attracted to vertically downwards by setting a proper negative bias condition, and the formation of a high-density, high-quality and high-refractive-index film layer is better facilitated.
In S2, the front sheet of the present invention is preferably a panel having good transparency, weather resistance and flexibility in order to achieve long-term stability and flexible application of the color-tunable flexible photovoltaic module.
In the invention, the second transparent film layer can be deposited by setting different film thicknesses or film materials at different positions through the conventional deposition methods such as magnetron sputtering, chemical vapor deposition or solution treatment and the like and the technologies such as mask, etching and the like, so that the second transparent film layer with or without the concave-convex structure can be obtained, and color patterns with various colors can be formed. In the deposition process, the film thickness and the refractive index can be controlled by adjusting deposition parameters (such as deposition rate, temperature and the like), and under the condition that the film thickness and the refractive index are determined, a person skilled in the art can select corresponding deposition parameters through the prior art, which is the prior art, and the inventive labor is not required, and the detailed description is omitted.
The process of depositing the second transparent film layer with the concave-convex structure in the S2 can control the material, thickness and position of the required film layer according to the required color, so that the film layer at different positions has different structures or different thicknesses, and different colors are displayed at different positions, thereby realizing simultaneous display of multiple colors.
In a first preferred embodiment of the present invention, the process of depositing the second transparent thin film layer having the concave-convex structure in S2 includes: a. stamping one surface of the front plate through an stamping die with a required concave-convex structure to obtain the front plate with the concave-convex structure; and then depositing a second transparent film layer on one surface of the concave-convex structure of the front plate (deposition such as magnetron sputtering, chemical vapor deposition or solution treatment). In this scheme, by embossing the multi-layered concave-convex structure on the front plate, concave-convex structures with different depths and shapes are formed, and when the second transparent thin film layer is deposited on the surface of such front plate, the film thickness will change due to the existence of the concave-convex structure. This change in film thickness causes interference on the surface, thereby realizing a three-dimensional color pattern. Meanwhile, by combining stamping marks with different depths, a richer three-dimensional color effect can be realized on the same battery piece. According to the scheme, multilayer embossing and different embossing marks are combined on the front plate, so that the stereoscopic color pattern effect of the color-adjustable flexible photovoltaic module is achieved. This approach enhances both the aesthetics of the assembly and its personalized features. Meanwhile, the preparation process is simple, easy to implement and has good practical value. It also includes the following specific advantages:
Aesthetic properties: through multi-level embossing and different embossing marks, rich three-dimensional color patterns can be realized, the visual effect of the color photovoltaic module is improved, and the requirements of consumers on attractiveness are met;
individualizing: the multi-layer imprinting and the imprinting marks with different shapes can form unique color patterns, so that more personalized choices are provided for users, and the added value of products is increased;
is simple and easy to implement: the preparation process of the technical scheme is simple, does not need complex equipment and operation, and is convenient for engineering popularization and application;
the application is wide: the flexible photovoltaic module with adjustable stereoscopic colors can be applied to the fields of building integrated photovoltaics, household photovoltaic systems, mobile energy equipment and the like, and has wide market prospect.
In the above-described first preferred embodiment of the present invention, the conditions for embossing include heating and applying pressure as long as embossing can be achieved to obtain a front plate having a concave-convex structure, for example, the conditions for embossing include: the heating temperature is 80-120 ℃, and the applied pressure is 25-105 Pa. The heating time depends on the depth of the imprint.
In a second preferred embodiment of the present invention, the process of depositing the second transparent thin film layer having the concave-convex structure in S2 includes: b. attaching a mask material with a mask pattern on one surface of a front plate, and then depositing film materials with different materials and thicknesses on the surface; and removing the mask material after the deposition is completed to obtain a second transparent film layer. In the scheme, a plurality of film structures of the second transparent film layer can be realized through multiple masks, and particularly, the second transparent film layer with different film structures and thicknesses can be formed on the front plate by using multiple mask processes; after each masking, a required film layer can be formed on the covering area of the masking by etching, sputtering or other methods, which is more beneficial to the manufacture of the second transparent film layer with various film layer structures and thicknesses.
In the second preferred embodiment of the present invention, the mask pattern may be set according to the desired color effect and pattern requirement, and the mask material may be made of photoresist, metal film, etc. so as to have good shielding performance and precise pattern shape. It should be noted that, the set mask pattern is manufactured on the mask material by photolithography, electron beam etching, and the like, so that the precision and the edge definition of the mask pattern need to be ensured to meet the preparation requirements. When a mask material with a mask pattern is attached to a front plate, no bubbles or pollutants are required to be ensured between the mask material and the front plate, so that a good shielding effect is ensured; there is also a need to ensure that the deposited second transparent film layer and front plate are not damaged during removal of the masking material. In the deposition process, the area of the shielding part of the mask material is not deposited, the original film thickness in the shielding part is not affected, and a film layer structure and a film layer thickness which are different from those of the area without the mask material are formed. Of course, in the preparation, the person skilled in the art can check the color effect and pattern of the obtained second transparent film layer, and optimize the preparation parameters according to the test result to achieve better color effect and pattern quality.
In a third preferred embodiment of the present invention, the process of depositing the second transparent thin film layer having the concave-convex structure in S2 includes: c. depositing film materials with different thicknesses and different materials on one surface of the front plate, performing laser scribing on different areas of the film materials to remove part of the film materials with different thicknesses, and forming patterns with different thicknesses and/or different shapes by laser scribing to obtain a second transparent film layer. In the scheme, the laser scribing realizes multiple colors and patterns, and the laser scribing technology can accurately remove part of thickness of film materials on the transparent film, so that different second transparent film layers are formed in different areas. The laser scribing can scribe complex pattern shapes to realize color patterns with various colors, and the laser scribing technology can realize complex pattern shapes such as characters, graphics, gradual change colors and the like, so that the color-adjustable flexible photovoltaic module can not only display various colors, but also display unique color patterns according to design requirements, and the aesthetic property and uniqueness of a product are enhanced. The laser scribing can realize high-precision and high-resolution film scribing, and the thickness variation of the second transparent film layer in different areas can be realized by adjusting laser energy and scribing parameters, which can cause light to interfere in the areas to different degrees, thereby realizing the color effect of multiple colors. The skilled artisan can select the conditions for laser scribing according to the desired thickness of the second transparent film layer, which is known in the art and does not require any inventive effort, and is not described in detail herein.
The second and third technical schemes can realize the display of the color-adjustable flexible photovoltaic modules with different colors on the same battery piece, have higher color saturation and brightness, and meet the requirements of users on beauty and individuation. Meanwhile, the flexible photovoltaic module with adjustable color is more suitable for the fields of building integrated photovoltaics, vehicles and the like.
In a fourth preferred embodiment of the present invention, the process of depositing the second transparent thin film layer having the concave-convex structure in S2 includes: d. providing a mask plate with different spacing areas, keeping different spacing distances between the mask plate and one surface of the front plate, depositing (such as by magnetron sputtering, chemical vapor deposition or solution treatment) a second transparent film layer within the distance, and removing the mask plate to obtain the second transparent film layer. In the scheme, the mask plate and the front plate to be plated are arranged at different distances, the thickness of the film layer can be changed in the deposition process, so that interference is generated on the surface of the flexible photovoltaic module with adjustable color, and the dazzling effect is realized. The change of the distance can influence the morphology and thickness distribution of the deposited film, so that the difference of the colors and the glossiness of different areas is caused, a unique dazzling effect is formed, and therefore the dazzling color-adjustable flexible photovoltaic module is realized. The scheme has higher flexibility, can adjust interval distribution according to actual demands, and realizes the glare effect of different degrees.
In the fourth preferred embodiment of the present invention, the pitch distribution on the mask is designed according to the desired glare effect on the mask to form different pitch regions, and the pitch variation can be achieved by adjusting the support structure between the mask and the front plate. When the mask plate is removed, a second transparent film layer with different thickness is formed on the front plate, and a dazzling effect is displayed.
The lamination in the present invention S3 may be, for example, a hot pressing or other bonding process, which is known in the art and will not be described here. The lamination in the present invention S3 preferably includes: laminating a light-receiving surface of the battery piece, a transparent adhesive film layer of the light-receiving surface and a front plate deposited with a second transparent film layer, and then laminating a back plate, a transparent adhesive film layer of the back surface and the back surface of the battery piece.
In a third aspect, the present invention provides a color-tunable flexible photovoltaic module, which is prepared by the method for preparing the color-tunable flexible photovoltaic module according to the second aspect. The color-tunable flexible photovoltaic module of the third aspect is the same in structure as the color-tunable flexible photovoltaic module of the first aspect.
In a fourth aspect, the present invention provides a solar cell comprising the color-tunable flexible photovoltaic module of the first or third aspect.
In a fifth aspect, the present invention provides the use of a solar cell of the fourth aspect in a sun protection device and/or a solar device. The solar cell of the invention can be applied to any scene requiring a solar cell.
The sunshade device of the present invention may comprise, for example, a sunshade device or cover mounted on at least one of a caravan, a camper, a store, a vending machine, a swimming pool.
The solar device according to the present invention may include, for example, a solar power generation apparatus mounted on at least one of a balcony, a garden fence, a wall surface, a window, and an external lane of a garage.
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
Example 1
A color-adjustable flexible photovoltaic module is shown in fig. 1, and comprises a battery piece 1 with a light receiving surface being a textured surface, a first transparent film layer 2 (conductive film layer, ITO) arranged on the light receiving surface of the battery piece 1, a light receiving surface transparent film layer 3 (EVA material) and a front plate 5 (EFTE material) which are sequentially arranged on one side of the light receiving surface of the battery piece 1, a second transparent film layer 4 arranged on the front plate 5 and positioned between the front plate 5 and the light receiving surface transparent film layer 3, and a back transparent film layer 6 (EVA material) and a back plate 7 (EFTE material) which are sequentially arranged on the back surface of the battery piece 1. The density of one end of the first transparent film layer 2 near the light receiving surface of the battery piece 1 is smaller than that of the other end of the first transparent film layer 2, and the density difference of the two ends of the first transparent film layer 2 is 0.4g/cm 3 Average density of 7.00g/cm 3 The front plate 5 has a refractive index of 1.4 and the first transparent film layer 2 has an average refractive index of 2.00.
The ratio of the refractive index of the front plate 5 to the refractive index of the second transparent film layer 4 is 1:1.43. the density of the second transparent film layer 4 is 3.9-5 g/cm 3 Between them. In the direction from the front plate 5 to the light-receiving surface transparent adhesive film layer 3, the second transparent film layer 4 is a multilayer transparent film layer, the multilayer transparent film layer is a combined film of a titanium dioxide film layer and a zinc aluminum oxide film layer which are sequentially arranged, and the thickness of the titanium dioxide film layer accounts for 90% of the total thickness of the titanium dioxide film layer and the zinc aluminum oxide film layer.
The thickness ratio of the front plate 5, the second transparent film layer 4, the light-receiving surface transparent adhesive film layer 3 and the battery piece 1 is 1:0.001:4.1:1. the thickness ratio of the back transparent adhesive film layer 6, the back plate 7 and the battery piece 1 is 4:1:1. the thickness of the battery sheet 1 was 120. Mu.m.
The preparation process is as follows:
1) The battery sheet 1 is prepared, and ETFE panels are prepared as the front plate 5 and the back plate 7.
2) An ITO thin film having a high refractive index is deposited on the light receiving surface of the battery sheet 1. Specifically, the method for depositing by adopting the magnetron sputtering mode comprises the following steps: firstly, performing first sputtering for 5min, then performing second sputtering while applying negative bias (5 KV,400 Hz) on the back surface of the battery piece 1, and subtracting the thickness of the first sputtering from the required total thickness according to the second sputtering time to obtain a required second sputtering thickness, wherein the specific second sputtering thickness is 15min; wherein the conditions for controlling the first sputtering include a vacuum degree: 10 -1 Pa; sputtering power: 10kw. The vacuum degree of the second sputtering is 10 -2 Pa, the power of the second sputtering is 7kw, and the sputtering process is negatively biased. The whole sputtering process is that the target material is ITO, the sputtering voltage is 260V, and the mixed gas of oxygen and argon is introduced, wherein the oxygen content is 1.6 volume percent, and the thickness of the ITO film is 150nm.
3) A material having a second transparent thin film layer 4 with a refractive index >2.0 is prepared.
4) The ETFE panel is taken as a front plate 5, a second transparent film layer 4 is deposited on one surface of the front plate, the second transparent film layer 4 is a combined film of a titanium dioxide film layer and a zinc aluminum oxide film layer, and the specific deposition process and method for depositing the second transparent film layer 4 on the ETFE panel are as follows: 1) Titanium dioxide film layer: sputtering power 7KW, sputtering voltage: 420V, vacuum degree 10 -2 Pa, sputtering thickness is 55nm; 2) Zinc-aluminum oxide film layer: sputtering power 7KW, sputtering voltage: 420V, vacuum degree 10 -2 Pa, sputtering thickness 22nm.
5) The back plate 7, the back transparent adhesive film layer 6, the battery piece 1 deposited with the first transparent film layer 2, the light-receiving surface transparent adhesive film layer 3 and the front plate 5 deposited with the second transparent film layer 4 are sequentially laid, and then lamination is carried out, wherein the first transparent film layer 2 is positioned between the light-receiving surface of the battery piece 1 and the light-receiving surface transparent adhesive film layer 3, and the second transparent film layer 4 is positioned between the front plate 5 and the light-receiving surface transparent adhesive film layer 3, so that tight lamination between all layers is ensured, and the color-adjustable flexible photovoltaic module with a three-dimensional color pattern effect is formed.
Example 2
The method of step 4) is different from that of the method of embodiment 1, the change of the film structure is increased through a mask, different film layers are formed in different areas, three structures are sequentially arranged, the first structure is a titanium dioxide film layer and a zinc aluminum oxide film layer, the second structure is a titanium dioxide film layer only, and the third structure is a zinc aluminum oxide film layer only, so that yellow, yellowish and grey white are sequentially presented, and the pattern colors of the flexible photovoltaic module with adjustable colors are enriched. The method comprises the following specific steps: attaching a mask material with a mask pattern on one surface of a front plate, and then depositing film materials with different materials and thicknesses on the surface; and removing the mask material after the deposition is completed to obtain a second transparent film layer.
Example 3
The process is performed with reference to example 1, except that the first transparent thin film layer is zinc aluminum oxide.
Example 4
With reference to example 1, the difference is that the second transparent film layer has a density of 3.8mg/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The deposition conditions were different from those of example 1 in that the sputtering powers of the titanium oxide film layer and the zinc aluminum oxide film layer were 5KW, and the vacuum degrees were 10 -1 Pa。
Example 5
The process was conducted with reference to example 1, except that the thickness of the titanium oxide film layer in the second transparent film layer was 30%.
Example 6
The process is performed with reference to example 1, and the difference is that the second transparent film layer is a multilayer transparent film layer, specifically a composite film of a titanium dioxide film layer, a zinc oxide aluminum film layer and a titanium dioxide film layer, which are sequentially arranged, and the total thickness of the titanium dioxide film layer is equal to that of example 1 and is equally divided into an upper layer and a lower layer.
Example 7
With reference to example 1, the difference is that the vacuum degree of the first sputtering is changed so that the ratio of the vacuum degree of the first sputtering to the vacuum degree of the second sputtering is 3:1, which makes the structure of the first transparent film layer be a first sputtered ITO film layer with higher step coverage rate and a second sputtered ITO film layer with high step coverage rate, the average refractive index of the first transparent film layer is 2.05, and the density difference between two ends of the first transparent film layer is 0.3g/cm 3 Average density of 7.05mg/cm 3 . The texture of the cell surface is still sharp.
Example 8
With reference to example 1, the difference is that the power of the first sputtering is changed so that the ratio of the power of the first sputtering to the power of the second sputtering is 1:1, the structure of the first transparent film layer is that the first sputtered sputtering ions have fewer collision times, the difference of the number of the ions received in the area with large receiving angle and the small area is smaller, the coverage rate of the formed ITO film layer is higher, the deposition thickness is thinner, the coverage of the lower part of the suede is smaller, the average refractive index of the first transparent film layer is 2.1, and the density difference of the two ends of the first transparent film layer is 0.2g/cm 3 Average density of 7.1mg/cm 3 . The texture of the cell surface is still sharp.
Example 9
With reference to example 1, the difference is that the first transparent film layer is a non-conductive transparent film layer: silicon nitride, its preparation technology adopts the magnetron sputtering mode to deposit, includes: firstly, performing first sputtering for 5min, then performing second sputtering while applying negative bias (5 KV,400 Hz) on the back surface of the battery piece, and subtracting the thickness of the first sputtering from the required total thickness according to the second sputtering time to obtain a required second sputtering thickness, wherein the second sputtering thickness is specifically 5min; wherein the conditions for controlling the first sputtering include a vacuum degree: 10 -1 Pa; sputtering power: 10kw. The vacuum degree of the second sputtering is 10 -2 Pa, the power of the second sputtering is 7kw, the sputtering processNegatively biased. The whole sputtering process is to sputter a silicon target with a sputtering voltage of 370V, and introducing a mixture gas of nitrogen and argon, wherein the nitrogen content is 3 vol%, and the thickness of the silicon nitride film is about 80nm. The average refractive index of the first transparent film layer is 2, and the density difference of the two ends of the first transparent film layer is 0.6g/cm 3 Average density of 2.5mg/cm 3 。
Example 10
The process according to embodiment 1 is different in that the second transparent film layer 4 has a concave-convex structure 401 on a surface thereof adjacent to the light receiving surface transparent film layer 3. The concave-convex structure 401 makes the second transparent film layer 4 integrally form a concave-convex structure, and interface differences exist at different positions. The thickness ratio of the front plate 5, the second transparent film layer 4, the light-receiving surface transparent adhesive film layer 3 and the battery piece 1 is 1:0.001-0.002:4.1:1.
The corresponding specific preparation process comprises the following steps: after 3) preparing a material having a second transparent film layer 4 with a refractive index >2.0, performing
4) An imprinting mold with a multi-layer structure is designed, and the imprinting mold comprises concave-convex structures 401 with different depths and shapes.
5) The ETFE panel was placed as a front plate 5 in an embossing apparatus, and a multi-layered concave-convex structure 401 was formed on the surface thereof by heating to 100 ℃ and applying a pressure of 80Pa, as shown in fig. 3. At this point, the ETFE panel may exhibit embossed marks of varying depth and shape.
6) The ETFE panel with the multilayer concave-convex structure 401 is used for depositing the second transparent film layer 4, as shown in fig. 4, the second transparent film layer 4 is a combined film of a titanium dioxide film layer and a zinc aluminum oxide film layer, and a specific deposition process and a specific method for depositing the second transparent film layer 4 on the ETFE panel are as follows: 1) Titanium dioxide film layer: sputtering power 7KW, sputtering voltage: 420V, vacuum degree 10 -2 Pa, sputtering thickness is 55nm; 2) Zinc-aluminum oxide film layer: sputtering power 7KW, sputtering voltage: 420V, vacuum degree 10 -2 Pa, sputtering thickness 22nm. Due to the concave-convex structure 401 on the surface of the second transparent film layer 4, the interface of the film layer can be changed, thereby realizing a three-dimensional color pattern and presenting a similar laser effect of a plurality of colors with different brightness and different saturation.
7) The back plate 7, the back transparent adhesive film layer 6, the battery piece 1 deposited with the first transparent film layer 2, the light-receiving surface transparent adhesive film layer 3 and the front plate 5 deposited with the second transparent film layer 4 are sequentially laid, and then lamination is carried out, wherein the first transparent film layer 2 is positioned between the light-receiving surface of the battery piece 1 and the light-receiving surface transparent adhesive film layer 3, and the second transparent film layer 4 is positioned between the front plate 5 and the light-receiving surface transparent adhesive film layer 3, so that tight lamination between all layers is ensured, and the color-adjustable flexible photovoltaic module with a three-dimensional color pattern effect is formed.
According to the technical scheme, multi-level embossing and different embossing marks are combined on the ETFE, so that the three-dimensional color pattern effect of the color-adjustable flexible photovoltaic module is achieved. This approach enhances both the aesthetics of the assembly and its personalized features. Meanwhile, the preparation process is simple, easy to implement and has good practical value.
The present embodiment also includes the following advantages:
aesthetic properties: through multi-level impression and the different impression traces of combination, can realize abundant three-dimensional color pattern, improve the visual effect of color photovoltaic module, satisfy the consumer demand to aesthetic property.
Individualizing: the multi-layer embossing and the embossing traces with different shapes can form unique color patterns, so that more personalized choices are provided for users, and the added value of products is increased.
Is simple and easy to implement: the preparation process of the technical scheme is simple, does not need complex equipment and operation, and is convenient for engineering popularization and application.
The application is wide: the three-dimensional color photovoltaic module can be applied to the fields of building integrated photovoltaics, household photovoltaic systems, mobile energy equipment and the like, and has wide market prospect.
Comparative example 1
With reference to example 1, the difference is that the vacuum degree and sputtering power of the first sputtering are changed so as to be the same as those of the second sputtering, respectively, which makes the structure of the first transparent thin film layer be that the first sputtered ITO film and the second sputtered ITO film are both ITO films of high step coverage, and the densities of the two layers areAlmost identical to the refractive index, and no density difference and refractive index difference (the density difference is substantially 0), the refractive index of the first transparent film layer is 2.2, and the density of the first transparent film layer is 7.2mg/cm 3 。
Comparative example 2
With reference to example 1, the difference is that the vacuum degree of the first sputtering is changed so as to be the same as that of the second sputtering, which makes the structure of the first transparent thin film layer be a first sputtered higher step coverage ITO film layer and a second sputtered high step coverage ITO film layer; the density difference of the two ITO film layers is smaller, the refractive index difference is also smaller, and the density difference of the two ends of the first transparent film layer is 0.1g/cm 3 Average density of 7.15mg/cm 3 The average refractive index of the first transparent film layer was 2.15. The texture of the cell surface is still sharp.
Comparative example 3
With reference to example 1, the difference is that the average refractive index of the first transparent film layer is 1.6, and the density difference between both ends of the first transparent film layer is 0.2g/cm 3 Average density of 6.5mg/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The deposition conditions differ from those of example 1 in that the second sputtering was not negatively biased and the sputtering vacuum was 10 -1 Pa。
Test case
The photovoltaic modules obtained in the above examples and comparative examples and the battery sheet on which the first transparent thin film layer was deposited were respectively subjected to performance tests, and the results are shown in table 1.
TABLE 1
From the above results, it can be seen that, compared with the comparative example, the embodiment of the present invention can improve the color of the battery sheet on which the first transparent thin film layer is deposited from dark blue to bright blue, and make the flexible photovoltaic module exhibit yellow or multiple colors, and the saturation of the flexible photovoltaic module is superior to that of the comparative example, while keeping the generated power substantially unchanged. In contrast, in the case of the comparative example, the first transparent thin film layer has a small or no density difference, and thus a bright (i.e., high saturation) yellow flexible photovoltaic module cannot be obtained.
Further, according to embodiments 1 and 3 of the present invention, the preferred ITO of the present invention is adopted as the preferred solution of the first transparent thin film layer, which is more beneficial to enhancing the saturation of the flexible photovoltaic module and enhancing the saturation of the color of the battery sheet deposited with the first transparent thin film layer compared to zinc aluminum oxide.
Further, according to the embodiment 1 and the embodiments 4 to 5 of the present invention, the embodiment 1 scheme of the preferred density and the thickness ratio of the titanium dioxide film layer of the second transparent film layer of the present invention is more beneficial to enhancing the saturation of the flexible photovoltaic module, and also maintains higher power generation.
Further, according to embodiments 1 and 6 of the present invention, the second transparent film layer of the present invention is preferably a multi-layer structure according to embodiment 6, which is more beneficial to enhancing the saturation of the flexible photovoltaic module.
Further, according to embodiment 1 and embodiments 7 to 8 of the present invention, the embodiment 1 scheme of the first transparent thin film layer with a suitable density difference is adopted, which is more beneficial to significantly improving the saturation of the flexible photovoltaic module and improving the saturation of the color of the battery sheet deposited with the first transparent thin film layer.
Further, according to the embodiments 1, 2 and 10 of the present invention, the second transparent thin film layer schemes with different materials and different film thicknesses and different structures are provided, so that the color flexible photovoltaic module can be obtained while giving consideration to high saturation.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (22)
1. The color-adjustable flexible photovoltaic module comprises a battery piece, and light-receiving surface transparent layers sequentially arranged on one side of the light-receiving surface of the battery pieceThe solar cell comprises a solar cell body, a transparent film layer, a front plate, a back transparent film layer, a back plate and a first transparent film layer, wherein the back transparent film layer and the back plate are sequentially arranged on the back of the solar cell body, the transparent film layer is arranged on a light receiving surface of the solar cell body and between the light receiving surface of the solar cell body and the transparent film layer of the light receiving surface, the density of one end of the first transparent film layer, which is close to the light receiving surface of the solar cell body, is less than the density of the other end of the first transparent film layer, and the density difference of the two ends is 0.2-1.8g/cm 3 The average refractive index of the first transparent film layer is 1.8-2.2; the second transparent film layer is arranged between the front plate and the light-receiving surface transparent adhesive film layer.
2. The color tunable flexible photovoltaic module according to claim 1, wherein the first transparent film layer has an average density of 2.2-7.2g/cm 3 ；
And/or the thickness of the first transparent film layer is 100-180nm.
3. The color tunable flexible photovoltaic module of claim 1, wherein the first transparent thin film layer comprises a transparent conductive thin film layer and/or a non-conductive transparent thin film layer, the transparent conductive thin film layer is a doped oxide containing a doping element, the oxide in the doped oxide comprises at least one of indium oxide, zinc oxide, tin oxide, the doping element comprises at least one of tin, aluminum, fluorine, silver, and the non-conductive transparent thin film layer comprises at least one of silicon nitride, silicon oxide, silicon oxynitride, silicon carbide, titanium nitride.
4. The color tunable flexible photovoltaic module according to claim 3, wherein the first transparent thin film layer is at least one of tin doped indium oxide, zinc aluminum oxide, fluorine doped tin oxide, silver doped zinc oxide.
5. The color tunable flexible photovoltaic module according to claim 3, wherein the first transparent film layer is transparent conductive The average density of the film layer is 5.5-7.2g/cm 3 The average density of the first transparent film layer is 2.2-3.2g/cm when the first transparent film layer is a non-conductive transparent film layer 3 。
6. The color tunable flexible photovoltaic assembly of claim 1, wherein the ratio of the refractive index of the front sheet to the average refractive index of the first transparent film layer is 1:1.28-1.5.
7. The color-tunable flexible photovoltaic module of claim 1, wherein the battery cell light-receiving surface is textured.
8. The color-tunable flexible photovoltaic module of claim 1, wherein the thickness ratio of the front plate, the second transparent film layer, the light-receiving surface transparent adhesive film layer, and the battery piece is 1-3:0.0006-0.0025:3-8:1.
9. the color-tunable flexible photovoltaic module of claim 1, wherein a side of the second transparent film layer adjacent to the light-receiving transparent film layer has a relief structure.
10. The color tunable flexible photovoltaic module of claim 9, wherein the relief structure provides an overall thickness dimension of the second transparent thin film layer between 50-500 nm; and/or the second transparent film layer is at least one of titanium dioxide, zirconium dioxide, zinc aluminum oxide and niobium pentoxide.
11. The color tunable flexible photovoltaic assembly of claim 1, wherein the ratio of refractive indices of the front sheet and the second transparent film layer is 1:1.28-1.93, the refractive index of the second transparent film layer >1.8; and/or
The density of the second transparent film layer is 3.8-6.9 g/cm 3 Between them.
12. The color tunable flexible photovoltaic module of claim 11, wherein the second transparent thin film layer is a single transparent thin film layer with a refractive index >2.0, or is a plurality of transparent thin film layers, and there is a refractive index difference between adjacent transparent thin film layers, the absolute value of the refractive index difference is between 0.3 and 1, and the refractive index of each of the plurality of transparent thin film layers is changed in a non-increasing or non-decreasing manner.
13. The color tunable flexible photovoltaic module of claim 12, wherein the single-layer transparent film with refractive index >2.0 is a titanium dioxide film or a zirconium dioxide film; the multilayer transparent film layer is a combination of a titanium dioxide film layer and one or more selected from zinc aluminum oxide film layer, indium tin oxide film layer and niobium pentoxide.
14. The color-tunable flexible photovoltaic module according to claim 13, wherein the multilayer transparent film layer is a combination film of a titanium dioxide film layer and a zinc aluminum oxide film layer that are sequentially arranged, or a combination film of a titanium dioxide film layer, a zinc aluminum oxide film layer, and a titanium dioxide film layer that are sequentially arranged, in a direction from the front plate to the light-receiving surface transparent film layer.
15. The color tunable flexible photovoltaic module according to claim 13, wherein the thickness of the titanium dioxide film layer in the second transparent film layer is controlled to be 90% -100% of the total thickness of the second transparent film layer when the required saturation is 50% -55%;
when the required saturation is 40% -49%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to be 60% -89% of the total thickness of the second transparent film layer;
when the required saturation is 35% -39%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to account for 31% -59% of the total thickness of the second transparent film layer;
and when the required saturation is 25% -34%, controlling the thickness of the titanium dioxide film layer in the second transparent film layer to be 0% -30% of the total thickness of the second transparent film layer.
16. The preparation method of the color-adjustable flexible photovoltaic module is characterized by comprising the following steps of:
s1, depositing a first transparent film layer on a light receiving surface of a battery piece in a magnetron sputtering mode, wherein the process of depositing in the magnetron sputtering mode comprises the following steps: first sputtering is carried out for 3-8min, and then second sputtering is carried out while negative bias is applied to the back surface of the battery piece; wherein, the vacuum degree of the first sputtering is controlled to be lower than that of the second sputtering; the power of the first sputtering is more than or equal to the power of the second sputtering, and the vacuum degree of the second sputtering is 5 multiplied by 10 -1 - 5×10 -2 Pa, the power of the second sputtering is 6-9kw;
s2, depositing a second transparent film layer on one surface of the front plate;
s3, sequentially laying a back plate, a back transparent adhesive film layer, a battery piece deposited with a first transparent film layer, a light-receiving surface transparent adhesive film layer and a front plate deposited with a second transparent film layer, and then laminating, wherein the first transparent film layer is positioned between the light-receiving surface of the battery piece and the light-receiving surface transparent adhesive film layer, and the second transparent film layer is positioned between the front plate and the light-receiving surface transparent adhesive film layer;
the density of one end of the first transparent film layer, which is close to the light receiving surface of the battery piece, after deposition is smaller than that of the other end of the first transparent film layer.
17. The method of claim 16, wherein the ratio of the vacuum level of the first sputtering to the vacuum level of the second sputtering is 3-10:1, the ratio of the power of the first sputtering to the power of the second sputtering is 1-1.8:1, a step of;
and/or, the negatively biased condition comprises: the applied voltage is 3-8kV, and the applied frequency is 300-500Hz.
18. The method of claim 16, wherein the step of depositing the second transparent film layer having the concave-convex structure in S2 includes a step of controlling the material, thickness, and position of the film layer according to the desired color, and specifically includes any one of the following a-d methods:
a. Stamping one surface of the front plate through an stamping die with a required concave-convex structure to obtain the front plate with the concave-convex structure; then depositing a second transparent film layer on one surface of the concave-convex structure of the front plate;
b. attaching a mask material with a mask pattern on one surface of a front plate, and then depositing film materials with different materials and thicknesses on the surface; removing the mask material after the deposition is completed to obtain a second transparent film layer;
c. depositing film materials with different thicknesses and different materials on one surface of the front plate, performing laser scribing on different areas of the film materials to remove part of the film materials with different thicknesses, and forming patterns with different thicknesses and/or different shapes by laser scribing to obtain a second transparent film layer;
d. providing a mask plate with different spacing areas, keeping unequal distances between the mask plate and one surface of the front plate in the different spacing areas, depositing a second transparent film layer within the distances, and removing the mask plate to obtain the second transparent film layer.
19. A color-tunable flexible photovoltaic module prepared by the method of any one of claims 16-18.
20. A solar cell comprising the color-tunable flexible photovoltaic module of any of claims 1-15, 19.
21. Use of a solar cell according to claim 20 in a sun protection device and/or a solar device.
22. The use of a solar cell according to claim 21 in a sun protection device comprising a sun protection device or cover mounted on at least one of a caravan, a camper, a store, a vending machine, a swimming pool, and/or a solar device comprising a solar power generation device mounted on at least one of a terrace, a balcony, a garden fence, a wall, a window, a garage external lane.
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| CN114242799A (en) * | 2021-09-25 | 2022-03-25 | 中建材蚌埠玻璃工业设计研究院有限公司 | Colored cover plate glass for solar cell |
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