Photovoltaic glass plate and preparation method thereof

Abstract

The invention discloses a photovoltaic glass plate and a preparation method thereof, and relates to the technical field of glass materials. The photovoltaic glass plate comprises a glass plate substrate and at least one photonic crystal structure layer, and the at least one photonic crystal structure layer is located on the surface of the glass plate substrate and / or in the glass plate substrate. Materials of the photonic crystal structure layer comprise a first material and a second material, the absolute value of the refractive index difference value of the first material and the second material is larger than or equal to 0.1, and the first material comprises at least one of an up-conversion material, a down-conversion material and a perovskite material. When the photovoltaic glass plate is used as a glass cover plate of a solar cell, the light field distribution after sunlight incidence can be changed, the propagation path of sunlight in the solar cell is increased, and the effect of enhancing the photoelectric conversion efficiency of the solar cell is achieved through light diffraction. The photonic crystal structure layer comprises at least one of an up-conversion material, a down-conversion material and a perovskite material, so that the photonic crystal structure layer can convert light in a wave band with relatively low absorption and utilization efficiency of the solar cell into light in a wave band with relatively high absorption and utilization efficiency; and the efficient absorption and utilization of sunlight in a wider wave band range by the solar cell are further enhanced. The photoelectric conversion efficiency of the solar cell is improved through the comprehensive effect of the two aspects.

Description

Technical Field

[0001] The present invention relates to the technical field of glass materials, and in particular to a photovoltaic glass plate and a preparation method thereof. Background Art

[0002] The solar energy photoelectric conversion efficiency of ordinary solar cells is still very low. There are two main reasons for the low photoelectric conversion efficiency of solar cells: the solar photons irradiated on the cell will be lost due to reflection or transmission, and the solar cell does not absorb photons below its bandgap width, and although it can absorb photons above its bandgap width, most of them are dissipated in the form of heat energy, which ultimately does not contribute to the photoelectric conversion efficiency.

[0003] At present, glass has a high light transmittance and is often used as a packaging material for solar cells. However, the function of existing glass is only to serve as a packaging material for solar cells and cannot improve the photoelectric conversion efficiency of solar cells. Summary of the invention

[0004] Based on the above-mentioned deficiencies of the prior art, an object of the present invention is to provide a photovoltaic glass plate and a method for preparing the same, aiming to solve the problem that the existing glass cannot improve the photoelectric conversion efficiency of solar cells.

[0005] The technical solution of the present invention is as follows:

[0006] According to a first aspect of the present invention, there is provided a photovoltaic glass plate, wherein the photovoltaic glass plate comprises a glass plate substrate and at least one photonic crystal structure layer, wherein the at least one photonic crystal structure layer is located on the surface of the glass plate substrate and / or in the glass plate substrate; the material of the photonic crystal structure layer comprises a first material and a second material, the absolute value of the refractive index difference between the first material and the second material is greater than or equal to 0.1, and the first material comprises at least one of an up-conversion material, a down-conversion material and a perovskite material.

[0007] Optionally, the raw material of the glass plate substrate includes at least one of SiO2, Na2CO3, CaCO3, CaMg(CO3)2, NaNO3, KAlSi3O8, Al2O3, B2O3 and ZnO;

[0008] And / or, the second material includes at least one of an oxide material, a polymer material and a metal nanomaterial, and the oxide material includes ZrO2, Y2O3, Pr6O 11 , TiO2, ZnO, Al2O3, Fe2O3 and CeO2, the polymer material includes at least one of polystyrene, polymethyl methacrylate and liquid crystal polymer, and the metal nanomaterial includes at least one of gold nanoparticles and silver nanoparticles.

[0009] Optionally, the mass ratio of the first material to the second material is (1-8):(1-8).

[0010] Optionally, the photovoltaic glass panel further comprises a transparent conductive oxide layer, and the transparent conductive oxide layer is located on the surface of the glass panel substrate; or, when the surface of the glass panel substrate contains a photonic crystal structure layer, the transparent conductive oxide layer is located on the surface of the photonic crystal structure layer.

[0011] Optionally, the photovoltaic glass plate further comprises a porous silicon dioxide layer, and the porous silicon dioxide layer is located on the surface of the glass plate substrate; the at least one photonic crystal structure layer is located at at least one of the following positions (1) to (4):

[0012] (1) a surface of the porous silicon dioxide layer facing away from the glass substrate;

[0013] (2) between the porous silica layer and the glass substrate;

[0014] (3) In the glass substrate;

[0015] (4) The surface of the glass substrate that is away from the porous silica layer.

[0016] Optionally, the photonic crystal structure layer includes randomly arranged photonic crystal structure units or periodically arranged photonic crystal structure units.

[0017] Optionally, the periodically arranged photonic crystal structure units include at least one of a honeycomb-arranged photonic crystal structure unit, a square-arranged photonic crystal structure unit, and a corner moiré superlattice-arranged photonic crystal structure unit.

[0018] Optionally, the photonic crystal structure layer includes at least one photonic crystal structure sub-layer, and the photonic crystal structure sub-layer is composed of arranged single photonic crystal structure units.

[0019] Optionally, the up-conversion material comprises NaYF4:Yb 3+ ,Tm 3+ @TiO2、NaYF4:Yb 3+ ,Er 3+ 、YF3:Yb 3+ ,Er 3 + 、YOF:Yb 3+ ,Er 3+ 、NaYF4:Yb 3+ ,Er 3+ @SiO2@TiO2、NaYF4:Yb 3+ ,Er 3+@TiO2 and NaYF4:Yb 3+ ,Er 3+ At least one of @SiO2@Au;

[0020] The down conversion material comprises at least one of an inorganic down conversion material and an organic fluorescent down conversion material, wherein the inorganic down conversion material comprises SrAlF5:Pr 3+ 、YF3:Pr 3+ 、NaYF4:Pr 3+ 、CaAlF5:Pr 3+ 、NaMgF3:Pr 3+ 、KMgF3:Pr 3 + 、LaZrF7:Pr 3+ 、SrAl 12 O 19 :Pr 3+ 、LiYF4:Gd 3+ 、LiGdF4:Eu 3+ 、GdF3:Eu 3+ 、BaF2:Gd 3+ ,Eu 3+ 、LiGdF4:Er 3+ ,Tb 3+ , Zn2SiO4:Mn, Zn3(PO4)2:Mn, Cd3(PO4)2:Mn, Y2O3:Eu, YVO4:Eu, ZnS:Zn, ZnS:Ag, ZnS:Cu,Ag and ZnS:Cu,Al; the organic fluorescent down conversion material comprises at least one of BUV 395, AF 350, AF 405, BV 421, coumarin and coumarin derivatives;

[0021] The perovskite material includes at least one of an organic and inorganic mixed perovskite and an all-inorganic perovskite.

[0022] A second aspect of the present invention provides a method for preparing the photovoltaic glass panel as described above, wherein the method for preparing the photovoltaic glass panel comprises one of the following methods (1) to (7):

[0023] (1) depositing the first material and the second material on the surface of the glass plate substrate by a deposition method to form a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate;

[0024] (2) forming a photonic crystal structure layer on the surface of the glass plate substrate by micro-nano processing of the first material and the second material, thereby obtaining the photovoltaic glass plate;

[0025] (3) forming a photonic crystal structure layer on a glass plate substrate by self-assembly of the first material and the second material, thereby obtaining the photovoltaic glass plate;

[0026] (4) mixing the first material, the second material, the raw materials of the glass plate substrate and the solvent, and coating them to form a glass plate substrate containing a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate;

[0027] (5) melting the raw material of the glass plate substrate, and then mixing it with the first material and the second material, and forming and heat treating it to form a glass plate substrate containing a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate;

[0028] (6) mixing the first material, the second material, the raw materials of the glass plate substrate and the solvent, and coating them to form a glass plate substrate containing a photonic crystal structure layer; then forming another photonic crystal structure layer on the surface of the glass plate substrate by one of the methods (1) to (3), thereby obtaining the photovoltaic glass plate;

[0029] (7) The raw materials of the glass plate substrate are melted, and then mixed with the first material and the second material, and after molding and heat treatment, a glass plate substrate containing a photonic crystal structure layer is formed; then, another photonic crystal structure layer is formed on the surface of the glass plate substrate by one of methods (1) to (3), thereby obtaining the photovoltaic glass plate.

[0030] Optionally, the deposition method includes a sputtering deposition method or an evaporation deposition method;

[0031] The step of melting the raw material of the glass plate substrate specifically includes: heating and melting the raw material of the glass plate substrate at a temperature of 400-1000° C.;

[0032] The forming process includes float process or calendaring process.

[0033] Beneficial effects: The light transmittance of the photovoltaic glass plate provided by the present invention can be greater than 85%. It can not only be used as a glass cover plate for solar cells, but also the present invention sets a photonic crystal structure layer in the glass plate substrate and / or on the surface of the glass plate substrate, which can change the light field distribution after the incident sunlight, increase the propagation path of sunlight in the solar cell, and use the diffraction of light to enhance the photoelectric conversion efficiency of the solar cell. In addition, since the first material in the photonic crystal structure layer includes at least one of an up-conversion material, a down-conversion material, and a perovskite material, it can convert light in a band with a lower absorption and utilization efficiency of the solar cell into light in a band with a higher absorption and utilization efficiency, further enhancing the efficient absorption and utilization of sunlight in a wider band by the solar cell. The combined effect of the two aspects improves the photoelectric conversion efficiency of the solar cell. Compared with a solar cell using ordinary tempered glass as a glass cover plate, the photoelectric conversion efficiency of the solar cell using the photovoltaic glass provided by the present invention as a cover plate is improved by at least 0.2%. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a schematic diagram of the structure of the first photovoltaic glass panel in an embodiment of the present invention.

[0035] Figure 2 Schematic diagram of the structure of the second photovoltaic glass panel in an embodiment of the present invention.

[0036] Figure 3 Schematic diagram of the structure of the third photovoltaic glass panel in an embodiment of the present invention.

[0037] Figure 4 Schematic diagram of the structure of the fourth photovoltaic glass panel in an embodiment of the present invention.

[0038] Figure 5 Schematic diagram of the structure of the fifth photovoltaic glass panel in an embodiment of the present invention.

[0039] Figure 6 Schematic diagram of the structure of the sixth photovoltaic glass panel in an embodiment of the present invention.

[0040] Figure 7 Schematic diagram of a photonic crystal structure layer containing photonic crystal structure units arranged in a honeycomb pattern.

[0041] Figure 8 Schematic diagram of a photonic crystal structure layer containing photonic crystal structure units arranged in a square shape.

[0042] Fig. 9 Schematic diagram of a photonic crystal structure layer containing a single layer of non-close-packed photonic crystal structure units.

[0043] Fig.10 Schematic diagram of a photonic crystal structure layer containing two layers of non-close-packed photonic crystal structure units.

[0044] Fig.11 Schematic diagram of a photonic crystal structure layer containing two layers of close-packed photonic crystal structure units.

[0045] Fig.12 Schematic diagram of a photonic crystal structure layer containing three layers of close-packed photonic crystal structure units.

[0046] Fig.13 Schematic diagram of a photonic crystal structure layer containing a rotation moiré superlattice photonic crystal structure unit.

[0047] Fig.14 Schematic diagram of applying photovoltaic glass to solar cells. DETAILED DESCRIPTION

[0048] The present invention provides a photovoltaic glass panel and a method for preparing the same. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0049] Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0050] An embodiment of the present invention provides a photovoltaic glass plate, wherein the photovoltaic glass plate includes a glass plate substrate and at least one photonic crystal structure layer, and the at least one photonic crystal structure layer is located on the surface of the glass plate substrate and / or in the glass plate substrate; the material of the photonic crystal structure layer includes a first material and a second material, the absolute value of the refractive index difference between the first material and the second material is greater than or equal to 0.1, and the first material includes at least one of an up-conversion material, a down-conversion material and a perovskite material.

[0051] In the embodiment of the present invention, the photonic crystal structure layer can be located on the surface of the glass plate substrate (one surface or two surfaces), can be located in the glass plate substrate, can be located on the surface of the glass plate substrate and in the glass plate substrate. The photonic crystal structure layer can be one layer, two layers, three layers, etc.

[0052] Specifically, in some embodiments, Figure 1 As shown, the photovoltaic glass plate 1 includes a glass plate substrate 11 and a photonic crystal structure layer 12 , and the photonic crystal structure layer 12 is located in the glass plate substrate 11 .

[0053] In some embodiments, Figure 2As shown, the photovoltaic glass plate 1 includes a glass plate substrate 11 and a photonic crystal structure layer 12 , and the photonic crystal structure layer 12 is located on the surface of the glass plate substrate 11 .

[0054] In some embodiments, Figure 3 As shown, the photovoltaic glass plate 1 includes a glass plate substrate 11 and two photonic crystal structure layers 12 , and the photonic crystal structure layers 12 on both sides are respectively located on the surface of the glass plate substrate 11 and in the glass plate substrate 11 .

[0055] In some embodiments, Figure 4 As shown, the photovoltaic glass plate 1 includes a glass plate substrate 11 and two photonic crystal structure layers 12 , and the two photonic crystal structure layers 12 are respectively located on the upper surface and the lower surface of the glass plate substrate 11 .

[0056] The light transmittance of the photovoltaic glass plate provided by the present invention can be greater than 85%. It can not only be used as a glass cover plate for solar cells, but also the present invention sets a photonic crystal structure layer in the glass plate substrate and / or on the surface of the glass plate substrate (the first material and the second material with an absolute value of the refractive index difference greater than or equal to 0.1 are used in combination to form a photonic crystal structure layer), which can change the light field distribution after the incident sunlight, increase the propagation path of sunlight in the solar cell, and use the diffraction of light to enhance the photoelectric conversion efficiency of the solar cell. In addition, since the first material in the photonic crystal structure layer includes at least one of an up-conversion material, a down-conversion material, and a perovskite material, it can convert the light in the band with a lower absorption and utilization efficiency of the solar cell into the light in the band with a higher absorption and utilization efficiency, further enhancing the efficient absorption and utilization of sunlight in a wider band range by the solar cell. The two aspects work together to improve the photoelectric conversion efficiency of the solar cell. Compared with a solar cell using ordinary tempered glass as a glass cover plate, the photoelectric conversion efficiency of the solar cell using the photovoltaic glass provided by the present invention as a cover plate is improved by at least 0.2%.

[0057] In some embodiments, the raw material of the glass plate substrate includes at least one of SiO2, Na2CO3, CaCO3, CaMg(CO3)2, NaNO3, KAlSi3O8, Al2O3, B2O3 and ZnO, but is not limited thereto.

[0058] In some embodiments, the raw materials of the glass plate substrate include the following components by mass:

[0059] SiO2 60-75 parts, Na2CO3 10-15 parts, CaCO3 5-10 parts, CaMg(CO3) 25-10 parts, NaNO3 2-5 parts, additives 1-5 parts;

[0060] The auxiliary agent includes a clarifier and / or an oxidant, the clarifier includes sodium sulfate (Na2SO4), and the oxidant includes sodium pyroantimonate (NaSbO3).

[0061] In some embodiments, the photovoltaic glass panel further includes a transparent conductive oxide layer, and the transparent conductive oxide layer is located on the surface of the glass panel substrate; or, when the surface of the glass panel substrate contains a photonic crystal structure layer, the transparent conductive oxide layer is located on the surface of the photonic crystal structure layer. The provision of the transparent conductive oxide layer can make the photovoltaic glass panel also conductive, and it can be applied to thin-film solar cells (such as amorphous silicon thin-film solar cells, etc.). At the same time, when the transparent conductive oxide layer is located on the surface of the photonic crystal structure layer, the photonic crystal structure can also be protected.

[0062] Specifically, in some embodiments, Figure 5 As shown, the photovoltaic glass plate 1 further includes a transparent conductive oxide layer 13, and the transparent conductive oxide layer 13 is located on the surface of the glass plate substrate 11. That is, the photovoltaic glass plate 1 includes a glass plate substrate 11, a photonic crystal structure layer 12 located in the glass plate substrate 11, and a transparent conductive oxide layer 13 located on the surface of the glass plate substrate 11.

[0063] In some embodiments, Figure 6 As shown, the photovoltaic glass panel 1 further includes a transparent conductive oxide layer 13, and the transparent conductive oxide layer 13 is located on the surface of the photonic crystal structure layer 12. That is, the photovoltaic glass panel 1 includes a glass panel substrate 11, a photonic crystal structure layer 12 located on the surface of the glass panel substrate 11, and a transparent conductive oxide layer 13 located on the surface of the photonic crystal structure layer 12.

[0064] In some embodiments, the transparent conductive oxide includes at least one of aluminum-doped zinc oxide, fluorine-doped tin oxide, and indium tin oxide, but is not limited thereto.

[0065] In some embodiments, the photovoltaic glass panel further comprises a porous silicon dioxide layer, wherein the porous silicon dioxide layer (composed of porous silicon dioxide) is located on the surface of the glass panel substrate; and the at least one photonic crystal structure layer is located at at least one of the following positions (1) to (4):

[0066] (1) a surface of the porous silicon dioxide layer facing away from the glass substrate;

[0067] (2) between the porous silica layer and the glass substrate;

[0068] (3) In the glass substrate;

[0069] (4) The surface of the glass substrate that is away from the porous silica layer.

[0070] In this embodiment, the provision of the porous silicon dioxide layer can significantly reduce light reflection and improve the high temperature resistance of the photovoltaic glass.

[0071] In some embodiments, the thickness of the photovoltaic glass panel is 1 to 5 mm, for example, it can be 1 mm, 2 mm, 3 mm, 4 mm or 5 mm, etc.; the thickness of the photonic crystal structure layer is 20 nm to 1000 μm, for example, it can be 20 nm, 50 nm, 100 nm, 200 nm, 500 nm, 800 nm, 1 μm, 5 μm, 10 μm, 100 μm, 200 μm, 500 μm, 800 μm or 1000 μm, etc.

[0072] In some embodiments, the photonic crystal structure layer includes randomly arranged photonic crystal structure units or periodically arranged photonic crystal structure units.

[0073] In some embodiments, the periodically arranged photonic crystal structure units include honeycomb-arranged photonic crystal structure units (eg Figure 7 As shown, Figures 7 to 13 A small ball in the middle can be represented as a photonic crystal structure unit), a square-arranged photonic crystal structure unit (such as Figure 8 As shown), photonic crystal structure units arranged in a corner moiré superlattice structure (such as Fig.13 In this way, the periodically arranged photonic crystal structure units can produce a bandgap effect on light waves, thereby achieving control over the propagation direction of light. This makes the photonic crystal structure have higher optical performance, lower transmittance, higher absorptivity and scattering for specific light.

[0074] In some embodiments, the photonic crystal structure layer includes at least one photonic crystal structure sublayer, and the photonic crystal structure sublayer is composed of a single photonic crystal structure unit. When the photonic crystal structure layer includes one photonic crystal structure sublayer, Figures 7 to 9 As shown, it may include a single layer of closely packed photonic crystal structural units (such as Figure 7 and Figure 8 ), which also includes a single layer of non-close-packed photonic crystal structural units (such as Fig. 9 When the photonic crystal structure layer includes multiple layers of photonic crystal structure sublayers, it may include two layers of non-close-packed photonic crystal structure units (such as Fig.10 As shown), it may also include two layers of closely packed photonic crystal structural units (such as Fig.11 As shown), it may also include three layers of closely packed photonic crystal structural units (such as Fig.12As shown), it can also include a photonic crystal structure unit (such as Fig.13 shown).

[0075] In some embodiments, the single photonic crystal structure unit is spherical. The particle size of each photonic crystal structure unit is 20nm to 1μm, for example, it can be 20nm, 50nm, 100nm, 150nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1μm. Such a suitable particle size range can improve the light absorption rate and scattering characteristics of the photonic crystal structure layer.

[0076] In some embodiments, the mass ratio of the first material to the second material is (1-8):(1-8). In some embodiments, the mass ratio of the first material to the second material is (1-2):(1-8) or (1-8):(1-2). For example, the mass ratio of the first material to the second material is 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1 or 8:1, etc.

[0077] In some embodiments, the second material includes at least one of an oxide material, a polymer material, and a metal nanomaterial, and the oxide material includes ZrO2, Y2O3, Pr6O 11 , TiO2, ZnO, Al2O3, Fe2O3 and CeO2, but not limited thereto; the polymer material includes at least one of polystyrene, polymethyl methacrylate and liquid crystal polymer (such as cyanate liquid crystal polymer), but not limited thereto; the metal nanomaterial includes at least one of gold nanoparticles and silver nanoparticles, but not limited thereto.

[0078] In some embodiments, the upconversion material includes but is not limited to NaYF4:Yb 3+ ,Tm 3+ @TiO2 (For its preparation method, please refer to β-NaYF4:Yb 3+ ,Tm 3+ @TiO2 core-shell nanoparticles incorporated into themesoporous layer for high efficiency perovskite solar cells, Liang, Jiwei, "Electrochimica Acta"), NaYF4:Yb 3+ ,Er 3+ 、YF3:Yb 3+,Er 3+ 、YOF:Yb 3+ ,Er 3+ 、NaYF4:Yb 3+ ,Er 3+ @SiO2@TiO2 (the preparation method is shown in Performance optimization in dye-sensitized solar cells with beta-NaYF4:Yb 3+ ,Er 3+ @SiO2@TiO2 mesoporous microspheres as multi-functional photoanodes, Zhu, Yihua, "Electrochimica Acta") and NaYF4:Yb 3+ ,Er 3+ @SiO2@Au (For its preparation method, please refer to Multifunctional NaYF4:Yb 3+ ,Er 3+ @SiO2@Au heterogeneous nanocomposites for upconversion luminescence,temperature sensing and photothermal conversion, DLi, "Rsc Advances").

[0079] In some embodiments, the down conversion material comprises at least one of an inorganic down conversion material and an organic fluorescent down conversion material, wherein the inorganic down conversion material comprises SrAlF5:Pr 3+ (This material is Pr 3+ doped SrAlF5, the meaning of similarly expressed materials in the present invention is analogous), YF3:Pr 3+ 、NaYF4:Pr 3+ 、CaAlF5:Pr 3+ 、NaMgF3:Pr 3+ 、KMgF3:Pr 3+ 、LaZrF7:Pr 3+ 、SrAl 12 O 19 :Pr 3+ 、LiYF4:Gd 3+ 、LiGdF4:Eu 3+ 、GdF3:Eu 3+ 、BaF2:Gd 3+ ,Eu 3+ 、LiGdF4:Er3+ , Tb 3+ at least one of Zn2SiO4:Mn, Zn3(PO4)2:Mn, Cd3(PO4)2:Mn, Y2O3:Eu, YVO4:Eu, ZnS:Zn, ZnS:Ag, ZnS:Cu,Ag, and ZnS:Cu,Al; the organic fluorescence down-conversion material includes at least one of BUV 395 (i.e., Brilliant Ultra Violet 395, available from ThermoFisher scientific), AF350 (i.e., Alexa Fluor 350, available from Duofluorescent Biotechnology), AF 405 (i.e., Alexa Fluor 405, available from Duofluorescent Biotechnology), BV 421 (i.e., Brilliant Ultra Violet 421, available from ThermoFisher scientific), coumarin, and coumarin derivatives.

[0080] In some embodiments, the perovskite material includes at least one of organic-inorganic hybrid perovskite and all-inorganic perovskite. The organic-inorganic hybrid perovskite material includes at least one of CH3NH3PbBr3, CH3NH3PbI3, CH3NH3PbI 3- x Br x (0 < x < 3); the all-inorganic perovskite material includes at least one of perovskite sulfide (e.g., CsPbS3), perovskite selenide (e.g., CsPbSe3), perovskite lead ferrite (e.g., PbFeO3), perovskite bismuth ferrite (e.g., BiFeO3), and perovskite oxide (e.g., CaTiO3).

[0081] The embodiments of the present invention also provide a method for preparing the photovoltaic glass plate as described above. Among them, the method for preparing the photovoltaic glass plate includes one of the following methods (1) to (7):

[0082] (1) Depositing the first material and the second material on the surface of the glass plate substrate by a deposition method to form a photonic crystal structure layer, and then obtaining the photovoltaic glass plate;

[0083] (2) Forming a photonic crystal structure layer on the surface of the glass plate substrate by micro-nano processing of the first material and the second material, and then obtaining the photovoltaic glass plate;

[0084] (3) Forming a photonic crystal structure layer on the glass plate substrate by self-assembly of the first material and the second material, and then obtaining the photovoltaic glass plate;

[0085] (4) mixing the first material, the second material, the raw materials of the glass plate substrate and the solvent, and coating them to form a glass plate substrate containing a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate;

[0086] (5) melting the raw material of the glass plate substrate, and then mixing it with the first material and the second material (adding oxides, nitrides, etc.), forming and heat treating the raw material to form a glass plate substrate containing a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate;

[0087] (6) mixing the first material, the second material, the raw materials of the glass plate substrate and the solvent, and coating them to form a glass plate substrate containing a photonic crystal structure layer; then forming another photonic crystal structure layer on the surface of the glass plate substrate by one of the methods (1) to (3), thereby obtaining the photovoltaic glass plate;

[0088] (7) The raw materials of the glass plate substrate are melted, and then mixed with the first material and the second material, and after molding and heat treatment, a glass plate substrate containing a photonic crystal structure layer is formed; then, another photonic crystal structure layer is formed on the surface of the glass plate substrate by one of methods (1) to (3), thereby obtaining the photovoltaic glass plate.

[0089] The selection of the first material and the second material is as described above.

[0090] The preparation method provided by the present invention is simple, and the prepared photovoltaic glass plate has high light transmittance. As a glass cover plate of a solar cell, it can increase the propagation path of sunlight in the solar cell, enhance the solar cell's absorption of sunlight, and increase the photoelectric conversion efficiency of the solar cell.

[0091] In method (1), in some embodiments, the deposition method includes sputtering deposition and evaporation deposition, and the sputtering deposition can be magnetron sputtering deposition, etc. Specifically, the first material and the second material can be heated to an evaporation temperature to evaporate them into atoms or molecules, and then deposited on the surface of the glass plate substrate; or the first material and the second material can be bombarded with high-energy particles or plasma to sputter them onto the surface of the glass plate substrate; or the ion trajectory during the sputtering process can be controlled by a magnetic field to achieve directional deposition of the first material and the second material.

[0092] Specifically, the process parameters used in the magnetron sputtering deposition are:

[0093] Vacuum degree is 10 -5 ~10 -3 Pa, sputtering power is 50-500W, sputtering gas pressure is 0.1-10Pa, deposition time is 10-600s, and substrate temperature is 20-500℃.

[0094] In method (2), in some embodiments, the step of forming a photonic crystal structure layer on the surface of the glass plate substrate by micro-nano processing (for example, photolithography, nanoimprinting or two-photon printing, etc.) of the first material and the second material to obtain the photovoltaic glass plate specifically includes:

[0095] The first material and the second material are mixed and applied to a glass substrate by spin coating or spray coating (such as inkjet coating) to form a film, and then photoetched to form a photonic crystal structure layer on the glass substrate.

[0096] Furthermore, method (2) specifically comprises the following steps:

[0097] Adding the first material and the second material into a polyvinyl alcohol (PVA) aqueous solution for ultrasonic dispersion to obtain a dispersion;

[0098] The dispersion is spin-coated or spray-coated on the glass plate substrate, and after drying (for example, drying in a dryer at 80° C.), laser etching is performed using a mask (depending on the shape of the mask, a photonic crystal structure layer containing different photonic crystal structure unit arrangements is obtained) (process parameters are: power of 10 to 50 W, laser pulse width of 1 to 10 nanoseconds, laser pulse frequency of 1 to 1000 Hz, defocus of 0.01 to 0.1 mm, and auxiliary gas of argon or helium) to form a photonic crystal structure layer on the glass plate substrate.

[0099] In method (3), in some embodiments, the step of forming a photonic crystal structure layer on the glass plate body by self-assembly of the first material and the second material specifically includes:

[0100] The first material, the second material and the surfactant are added to a polyvinyl alcohol (PVA) aqueous solution for ultrasonic dispersion to obtain a dispersion; wherein the surfactant includes at least one of anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants; the anionic surfactant includes at least one of alkylbenzene sulfonates (such as ammonium dodecylbenzenesulfonate), α-olefin sulfonates, and alkyl sulfonates; the cationic surfactant includes at least one of hexadecyltrimethylammonium chloride and octadecyldimethylbenzylammonium chloride; the amphoteric surfactant includes at least one of dodecylaminopropionic acid, sulfobetaine and phosphate betaine; the nonionic surfactant includes at least one of glycerol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene fatty alcohol ethers and fatty acid sorbitan;

[0101] The dispersion is coated on the glass substrate, and after drying, a proper amount of charge is applied using an electrostatic voltage of 15-25 kV for 5-10 min to automatically assemble the first material and the second material into a specific structure, thereby forming a photonic crystal structure layer on the glass substrate.

[0102] Of course, the dispersion can also be coated on the glass substrate, and projected through a DLP (digital light processing) chip, exposed and developed, and then multi-layer photocuring is performed to form a photonic crystal structure layer on the glass substrate.

[0103] In method (4) and method (6), in some embodiments, the solvent includes water, but is not limited thereto.

[0104] In method (5) and method (7), in some embodiments, the step of melting the raw material of the glass plate substrate specifically includes: heating and melting the raw material of the glass plate substrate at a temperature of 400-1000°C.

[0105] In method (5) and method (7), in some embodiments, the forming process includes a float process or a calendering process. Specifically, the process parameters of the calendering process are: a rolling temperature of 250 to 300° C., a rolling speed of 5 to 8 m / min, and a stretching speed of 5 to 8 m / min.

[0106] In some embodiments, the heat treatment includes annealing or quenching, which can eliminate stress, phase separation or crystallization inside the glass and modify the structural state of the glass. Specifically, the process parameters of the annealing are: temperature of 500-700°C and holding time of 2-8 hours.

[0107] The process parameters of the quenching treatment are: temperature of 200-500° C. and holding time of 10-60 minutes.

[0108] In some embodiments, the photovoltaic glass panel includes a glass panel substrate, a porous silicon dioxide layer located on the surface of the glass panel substrate, and a photonic crystal structure layer located on the surface of the porous silicon dioxide layer. In this case, the method for preparing the photovoltaic glass panel includes the following steps:

[0109] Forming a porous silicon dioxide layer on the surface of the glass substrate by a sol method or a gel method at a temperature below 300°C;

[0110] By using the above method, a photonic crystal structure layer is formed on the porous silicon dioxide layer to obtain the photovoltaic glass plate.

[0111] The present invention will be further described below by means of specific examples.

[0112] Example 1

[0113] This embodiment provides a photovoltaic glass plate and a method for preparing the same. Figure 2 As shown, the photovoltaic glass plate 1 includes a glass plate substrate 11 and a photonic crystal structure layer 12 located on the surface of the glass plate substrate 11 (the structure of the photonic crystal structure layer is as shown in FIG. Figure 8 As shown), the thickness of the glass substrate is 1 mm, and the material of the photonic crystal structure layer is NaYF4:Yb 3+ ,Er 3+ (Yb 3+ The molar number accounts for 2% of the molar number of NaYF4, Er 3+ The molar number of NaYF4 accounts for 3% of the molar number of NaYF4. The preparation method thereof can be found in "NaYF4:Yb 3+ / Er 3+ Upconversion temperature sensing properties under 1550nm excitation, Journal of Huzhou Normal University") and TiO2, and NaYF4:Yb 3+ ,Er 3+ The mass ratio of TiO2 is 1:1, and the thickness of the photonic crystal structure layer is 500nm (that is, the particle size of each photonic crystal structure unit is 500nm).

[0114] The method for preparing a photovoltaic glass panel comprises the following steps:

[0115] By mass, 70 parts of SiO2, 12 parts of Na2CO3, 8 parts of CaCO3, 7 parts of CaMg(CO3)2, 2 parts of NaNO3 and 3 parts of sodium sulfate were crushed, dried and iron-removed;

[0116] Put the raw materials into a tank kiln or a crucible kiln and heat them at 1600℃ to form a uniform, bubble-free melt that meets the molding requirements;

[0117] The melt was rolled into a glass sheet substrate with a thickness of 1 mm by a rolling method (rolling temperature of 250° C., rolling speed of 6 m / min, and stretching speed of 5 m / min);

[0118] 1g of NaYF4:Yb 3+ ,Er 3+ and 1 g of TiO2 were added into 100 g of polyvinyl alcohol (PVA) aqueous solution (PVA mass content was 80%) for ultrasonic dispersion to obtain a dispersion;

[0119] The dispersion is spin-coated on the glass substrate, dried (for example, placed in a dryer at 80°C), and then a mask (with the same shape as the glass substrate) is used. Figure 8Corresponding) is laser etched (process parameters are power 15W; laser pulse width is 3 nanoseconds; laser pulse frequency is 300 Hz; defocus amount is 0.06 mm; auxiliary gas is argon) to form a photonic crystal structure layer to obtain a photovoltaic glass panel.

[0120] like Fig.14 As shown, the photovoltaic glass plate 1 in Example 1 is set on the monocrystalline silicon solar cell 2 as a glass cover, which can increase the propagation path of sunlight in the solar cell and play a role in diffraction and splitting. The photoelectric conversion efficiency of the formed solar cell module is 25.75%. The photoelectric conversion efficiency of the formed solar cell module is 25.5% when ordinary tempered glass (without a photonic crystal structure layer) is used as the glass cover of the monocrystalline silicon solar cell.

[0121] Example 2

[0122] This embodiment provides a photovoltaic glass plate and a preparation method thereof, which is different from the embodiment 1 in that the material of the photonic crystal structure layer includes a first material and a second material in a mass ratio of 1:1, wherein the first material is NaYF4:Yb 3+ ,Er 3+ (its preparation method and specific information are the same as those in Example 1) and ZnS:Cu,Al (wherein the molar ratio of Cu to Zn is 0.0003:1, and the molar ratio of Cu to Al is 0.5:1. For its specific preparation method, see “Preparation of ZnS:Cu,Al Nano X-ray Luminescent Powder by Hydrothermal Method and Its Spectral Characteristics, Xin Mei et al., Journal of Chemistry of Universities”), the second material is ZnO;

[0123] 0.5 g of NaYF4:Yb 3+ ,Er 3+ 0.5 g of ZnS:Cu,Al and 1 g of ZnO were added to 100 g of polyvinyl alcohol (PVA) aqueous solution (PVA mass content was 80%) and ultrasonically dispersed to obtain a dispersion.

[0124] The photovoltaic glass plate in Example 2 is used as the glass cover of the monocrystalline silicon solar cell, and the photoelectric conversion efficiency of the solar cell module formed is 25.8%; the ordinary tempered glass is used as the glass cover of the monocrystalline silicon solar cell, and the photoelectric conversion efficiency of the solar cell module formed is 25.5%.

[0125] In summary, the present invention provides a photovoltaic glass plate and a preparation method thereof. The light transmittance of the photovoltaic glass plate provided by the present invention can be greater than 85%. It can not only be used as a glass cover plate for solar cells, but also the present invention sets a photonic crystal structure layer in the glass plate substrate and / or on the surface of the glass plate substrate, which can change the light field distribution after the incident sunlight, increase the propagation path of sunlight in the solar cell, and use the diffraction of light to enhance the photoelectric conversion efficiency of the solar cell. In addition, since the first material in the photonic crystal structure layer includes at least one of an up-conversion material, a down-conversion material, and a perovskite material, it can convert the light in the band with a lower absorption and utilization efficiency of the solar cell into the light in the band with a higher absorption and utilization efficiency, further enhancing the efficient absorption and utilization of sunlight in a wider band range by the solar cell. The two aspects work together to improve the photoelectric conversion efficiency of the solar cell. Compared with a solar cell using ordinary tempered glass as a glass cover plate, the photoelectric conversion efficiency of the solar cell using the photovoltaic glass provided by the present invention as a cover plate is improved by at least 0.2%.

[0126] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A photovoltaic glass panel, characterized in that: The photovoltaic glass panel includes a glass panel substrate and at least one photonic crystal structure layer, wherein the at least one photonic crystal structure layer is located on the surface of the glass panel substrate and / or in the glass panel substrate; the material of the photonic crystal structure layer includes a first material and a second material, the absolute value of the refractive index difference between the first material and the second material is greater than or equal to 0.1, and the first material includes at least one of an up-conversion material, a down-conversion material and a perovskite material.

2. The photovoltaic glass panel according to claim 1, characterized in that: The raw material of the glass plate substrate includes at least one of SiO2, Na2CO3, CaCO3, CaMg(CO3)2, NaNO3, KAlSi3O8, Al2O3, B2O3 and ZnO; And / or, the second material includes at least one of an oxide material, a polymer material and a metal nanomaterial, and the oxide material includes ZrO2, Y2O3, Pr6O 11 , TiO2, ZnO, Al2O3, Fe2O3 and CeO2, the polymer material includes at least one of polystyrene, polymethyl methacrylate and liquid crystal polymer, and the metal nanomaterial includes at least one of gold nanoparticles and silver nanoparticles.

3. The photovoltaic glass panel according to claim 1, characterized in that: The mass ratio of the first material to the second material is (1-8):(1-8).

4. The photovoltaic glass panel according to claim 1, characterized in that: The photovoltaic glass plate further comprises a transparent conductive oxide layer, which is located on the surface of the glass plate substrate; or, when the surface of the glass plate substrate contains a photonic crystal structure layer, the transparent conductive oxide layer is located on the surface of the photonic crystal structure layer.

5. The photovoltaic glass panel according to claim 1, characterized in that: The photovoltaic glass plate further comprises a porous silicon dioxide layer, and the porous silicon dioxide layer is located on the surface of the glass plate substrate; the at least one photonic crystal structure layer is located at at least one of the following positions (1) to (4): (1) a surface of the porous silicon dioxide layer facing away from the glass substrate; (2) between the porous silica layer and the glass substrate; (3) In the glass substrate; (4) The surface of the glass substrate that is away from the porous silica layer.

6. The photovoltaic glass panel according to any one of claims 1 to 5, characterized in that: The photonic crystal structure layer includes randomly arranged photonic crystal structure units or periodically arranged photonic crystal structure units.

7. The photovoltaic glass panel according to claim 6, characterized in that: The periodically arranged photonic crystal structure units include at least one of a honeycomb-arranged photonic crystal structure unit, a square-arranged photonic crystal structure unit, and a corner moiré superlattice-arranged photonic crystal structure unit.

8. The photovoltaic glass panel according to claim 6, characterized in that: The photonic crystal structure layer includes at least one photonic crystal structure sublayer, and the photonic crystal structure sublayer is formed by arranging single photonic crystal structure units.

9. The photovoltaic glass panel according to claim 1, characterized in that: The up-conversion material includes NaYF4:Yb 3+ ,Tm 3 + @TiO2、NaYF4:Yb 3+ ,Er 3+ 、YF3:Yb 3+ ,Er 3+ 、YOF:Yb 3+ ,Er 3+ 、NaYF4:Yb 3+ ,Er 3+ @SiO2@TiO2、NaYF4:Yb 3+ ,Er 3+ @TiO2 and NaYF4:Yb 3+ ,Er 3+ At least one of @SiO2@Au; The down conversion material comprises at least one of an inorganic down conversion material and an organic fluorescent down conversion material, wherein the inorganic down conversion material comprises SrAlF5:Pr 3+ 、YF3:Pr 3+ 、NaYF4:Pr 3+ 、CaAlF5:Pr 3+ 、NaMgF3:Pr 3+ 、KMgF3:Pr 3+ 、LaZrF7:Pr 3+ 、SrAl 12 O 19 :Pr 3+ 、LiYF4:Gd 3+ 、LiGdF4:Eu 3+ 、GdF3:Eu 3+ 、BaF2:Gd 3+ ,Eu 3+ 、LiGdF4:Er 3 + ,Tb 3+ , Zn2SiO4:Mn, Zn3(PO4)2:Mn, Cd3(PO4)2:Mn, Y2O3:Eu, YVO4:Eu, ZnS:Zn, ZnS:Ag, ZnS:Cu,Ag and ZnS:Cu,Al; the organic fluorescent down conversion material includes at least one of BUV 395, AF 350, AF 405, BV421, coumarin and coumarin derivatives; The perovskite material includes at least one of an organic and inorganic mixed perovskite material and an all-inorganic perovskite material.

10. A method for preparing the photovoltaic glass panel according to claim 1, characterized in that: The method for preparing the photovoltaic glass panel comprises one of the following methods (1) to (7): (1) depositing the first material and the second material on the surface of the glass plate substrate by a deposition method to form a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate; (2) forming a photonic crystal structure layer on the surface of the glass plate substrate by micro-nano processing of the first material and the second material, thereby obtaining the photovoltaic glass plate; (3) forming a photonic crystal structure layer on a glass plate substrate by self-assembly of the first material and the second material, thereby obtaining the photovoltaic glass plate; (4) mixing the first material, the second material, the raw materials of the glass plate substrate and the solvent, and coating them to form a glass plate substrate containing a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate; (5) melting the raw material of the glass plate substrate, and then mixing it with the first material and the second material, and forming and heat treating it to form a glass plate substrate containing a photonic crystal structure layer, thereby obtaining the photovoltaic glass plate; (6) mixing the first material, the second material, the raw materials of the glass plate substrate and the solvent, and coating them to form a glass plate substrate containing a photonic crystal structure layer; then forming another photonic crystal structure layer on the surface of the glass plate substrate by one of the methods (1) to (3), thereby obtaining the photovoltaic glass plate; (7) The raw materials of the glass plate substrate are melted, and then mixed with the first material and the second material, and after molding and heat treatment, a glass plate substrate containing a photonic crystal structure layer is formed; then, another photonic crystal structure layer is formed on the surface of the glass plate substrate by one of methods (1) to (3), thereby obtaining the photovoltaic glass plate.

11. The preparation method according to claim 10, characterized in that: The deposition method includes sputtering deposition or evaporation deposition; The step of melting the raw material of the glass plate substrate specifically includes: heating and melting the raw material of the glass plate substrate at a temperature of 400-1000° C.; The forming process includes float process or calendaring process.

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