Conductive glass with ultraviolet cut-off function and preparation method thereof

Abstract

The invention discloses conductive glass with an ultraviolet cut-off function and a preparation method thereof, the light transmittance of the conductive glass to UVB wave band light is less than 5.0%, the conductive glass comprises: ultraviolet cut-off glass which selects rare earth doped glass and is used as a matrix of the conductive glass; the ultraviolet cut-off layer is arranged on the ultraviolet cut-off glass in a laminated manner; the conductive layer is arranged on the ultraviolet cut-off layer in a stacked manner; the ultraviolet cut-off glass is prepared from the following components in percentage by mass: 10.0 to 15.0 weight percent of sodium oxide, 2.0 to 6.0 weight percent of magnesium oxide, 8.0 to 12.0 weight percent of calcium oxide, 0.5 to 2.0 weight percent of aluminum oxide, 70.0 to 75.0 weight percent of quartz sand, 0 to 1.0 weight percent of potassium oxide and 0.01 to 0.1 weight percent of rare earth element oxide.

Description

Technical Field

[0001] The invention relates to the technical field of photovoltaic glass, and in particular to a conductive glass with an ultraviolet cutoff function and a preparation method thereof. Background Art

[0002] Perovskite battery components currently have great development prospects, with advantages such as high efficiency and low cost, but the stability of perovskite is still the biggest obstacle to the commercial development of perovskite batteries. Among them, UV aging and degradation is the biggest killer of perovskite stability. Solving the UV resistance of perovskite or ensuring that ultraviolet light is cut off and cannot reach the perovskite layer, while not reducing the long-wavelength light reaching the perovskite layer, can greatly improve the stability of perovskite. TCO conductive glass is an important component of perovskite components. It not only serves as the electrode of perovskite batteries, but also as the cover glass of perovskite components to provide protection. Summary of the invention

[0003] The purpose of the present invention is to address the problem of poor stability caused by ultraviolet aging and degradation of current perovskite cells. The present invention provides a conductive glass with ultraviolet cutoff function, which can prevent ultraviolet light from reaching the perovskite cell layer, thereby avoiding ultraviolet aging and degradation of the perovskite cell and improving the stability of the perovskite.

[0004] To achieve the above object, the present invention is implemented by the following technical solutions:

[0005] The present invention provides a conductive glass with an ultraviolet cut-off function, wherein the transmittance of the conductive glass to UVB band light is less than 5.0%, and the conductive glass comprises:

[0006] Ultraviolet cut-off glass, which uses rare earth-doped glass as a matrix of conductive glass;

[0007] An ultraviolet cut-off layer, which is stacked on the ultraviolet cut-off glass;

[0008] and a conductive layer stacked on the ultraviolet cutoff layer;

[0009] The ultraviolet cut-off glass comprises the following components by mass fraction:

[0010] 10.0-15.0wt% of sodium oxide, 2.0-6.0wt% of magnesium oxide, 8.0-12.0wt% of calcium oxide, 0.5-2.0wt% of aluminum oxide, 70.0-75.0wt% of quartz sand, 0-1.0wt% of potassium oxide and 0.01-0.1wt% of rare earth element oxide.

[0011] Furthermore, a conductive glass with ultraviolet cutoff function: the thickness of the ultraviolet cutoff layer is set to 10.0-50.0 nm.

[0012] Furthermore, a conductive glass with ultraviolet cutoff function: the ultraviolet cutoff layer is selected from a cerium oxide layer, or a rare earth element oxide layer or a transition metal oxide layer with ultraviolet cutoff function.

[0013] Furthermore, a conductive glass with ultraviolet cutoff function: the iron content of the quartz sand is less than 350ppm.

[0014] Furthermore, a conductive glass with ultraviolet cutoff function: the thickness of the conductive layer is set to 180-800nm, and it is selected from FTO, ITO, AZO or doped FTO, ITO or any mixed layer of the above.

[0015] Furthermore, a conductive glass with ultraviolet cutoff function: the rare earth element oxide is selected from rare earth element oxides having absorption effect in the ultraviolet band, and cerium oxide is selected.

[0016] The present invention also provides a method for preparing conductive glass with ultraviolet cutoff function, the method comprising the following steps:

[0017] S1. According to the mass fraction of the raw materials of the ultraviolet cutoff glass, accurately weigh sodium oxide, magnesium oxide, calcium oxide, aluminum oxide, quartz sand, potassium oxide and rare earth element oxides, and mix them evenly to form a batch;

[0018] S2, melting the batch material to form molten glass;

[0019] S3, sending the glass liquid into a glass forming pool, cooling it, and then rolling it into shape, annealing it, and cooling it to obtain UV cutoff glass;

[0020] S4, strengthening the ultraviolet cutoff glass;

[0021] S5. Forming an ultraviolet cutoff layer and a conductive layer in sequence on the surface of the strengthened ultraviolet cutoff glass, thereby obtaining a conductive glass with ultraviolet cutoff function.

[0022] Furthermore, a method for preparing a conductive glass with UV cutoff function: step S2, preheating a platinum crucible with a kiln to 1300-1400°C, then adding a batch material and heating it to 1500-1600°C in 60-90 minutes, keeping it warm for 200-240 minutes, and obtaining glass liquid.

[0023] Furthermore, a method for preparing a conductive glass with a UV cutoff function: in step S3, the annealing temperature is 450-650° C., the cooling rate is 1-3° C. / min, and the glass is cooled to room temperature.

[0024] Furthermore, a method for preparing a conductive glass with a UV cutoff function: Step S5, using a PVD process to sequentially sputter a UV cutoff layer and a conductive layer on the surface of the strengthened UV cutoff glass.

[0025] Beneficial effects of the present invention:

[0026] In view of the problem that ultraviolet aging degradation is the biggest factor affecting the stability of perovskite, the present application doped an appropriate amount of rare earth metal oxide in the glass matrix, which can play a role of ultraviolet cutoff, can assist in intercepting the ultraviolet band to prevent it from entering the perovskite battery layer, thereby improving the stability of the perovskite. At the same time, the present application also sputtered a layer of cerium oxide ultraviolet cutoff film on the surface of the glass matrix, which can enhance the effect of ultraviolet cutoff to avoid excessive addition of rare earth metal oxide in the glass matrix causing the glass to produce color, thereby affecting the transmittance of available light in the perovskite battery layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0028] Figure 1 A schematic structural diagram of a conductive glass with ultraviolet cutoff function provided in Example 1 of the present invention;

[0029] Figure 2 A schematic diagram of the structure of the conductive glass provided for Comparative Example 1;

[0030] Figure 3 The light transmittance test results of the conductive glass of Example 1 and Comparative Example 1 are shown.

[0031] Markings in the figure: 1-UV cutoff glass, 2-UV cutoff layer, 3-conductive layer, 4-glass substrate. DETAILED DESCRIPTION

[0032] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] Example 1

[0034] like Figure 1 As shown, this embodiment 1 provides a conductive glass with ultraviolet cutoff function, wherein the transmittance of the conductive glass to UVB band light is less than 5.0%, and the conductive glass comprises:

[0035] Ultraviolet cutoff glass 1, which is a substrate of conductive glass and has a thickness of 2.0 mm. The ultraviolet cutoff glass 1 is made of rare earth-doped glass;

[0036] The ultraviolet cutoff layer 2 is stacked on the ultraviolet cutoff glass 1 and is made of cerium oxide with a thickness of 30.0 nm;

[0037] and a conductive layer 3, which is stacked on the ultraviolet cutoff layer 2 and is made of an ITO conductive layer with a thickness of 195.0 nm;

[0038] The above-mentioned ultraviolet cut-off glass includes the following components in mass fraction:

[0039] 13.5wt% sodium oxide, 3.0wt% magnesium oxide, 9.5wt% calcium oxide, 1.0wt% aluminum oxide, 72.5wt% quartz sand, 0.45wt% potassium oxide and 0.05wt% rare earth element oxide (cerium oxide is selected), the iron content in the quartz sand is less than 350ppm, and the rare earth element oxide is selected from rare earth element oxides with absorption effect in the ultraviolet band, specifically cerium oxide is selected.

[0040] The method for preparing the conductive glass with ultraviolet cutoff function provided in the above embodiment 1 comprises the following specific steps:

[0041] S1. According to the mass fraction of the raw materials of the ultraviolet cutoff glass, 13.5wt% of sodium oxide, 3.0wt% of magnesium oxide, 9.5wt% of calcium oxide, 1.0wt% of aluminum oxide, 72.5wt% of quartz sand, 0.45wt% of potassium oxide and 0.05wt% of rare earth element oxide (cerium oxide) are accurately weighed, and these raw materials are uniformly mixed in a mixer to form a batch;

[0042] S2, preheating the platinum crucible to 1350° C. with the kiln, then adding the above-mentioned batch materials, raising the kiln temperature to 1550° C. in 70 minutes, and keeping the temperature for 240 minutes to obtain glass liquid;

[0043] S3, sending the above-mentioned glass liquid into a glass forming pool, cooling the glass liquid to make it have a viscosity suitable for calendering, and then calendering, and then annealing at 550° C. for 8 minutes in an annealing furnace, and then cooling to room temperature at a cooling rate of 3° C. / min to obtain a UV cutoff glass with a thickness of 2.0 mm;

[0044] S4, physically strengthening (tempering) the obtained UV cutoff glass;

[0045] S5. On the surface of the strengthened UV cutoff glass, a UV cutoff layer 2 with a thickness of 30.0 nm and a conductive layer 3 with a thickness of 195.0 nm are sequentially sputtered by PVD, thereby obtaining a conductive glass with UV cutoff function.

[0046] Example 2

[0047] Embodiment 2 provides a conductive glass with ultraviolet cutoff function, wherein the transmittance of the conductive glass to UVB band light is less than 5.0%, and the conductive glass comprises:

[0048] Ultraviolet cutoff glass 1, which is a substrate of conductive glass and has a thickness of 2.0 mm. The ultraviolet cutoff glass 1 is made of rare earth-doped glass;

[0049] The ultraviolet cutoff layer 2 is stacked on the ultraviolet cutoff glass 1 and is made of a rare earth element oxide layer with ultraviolet cutoff function, and has a thickness of 15.0 nm;

[0050] and a conductive layer 3, which is stacked on the ultraviolet cutoff layer 2 and adopts a FTO conductive layer with a thickness of 500.0 nm;

[0051] The above-mentioned ultraviolet cut-off glass includes the following components in mass fraction:

[0052] 10.2wt% sodium oxide, 5.0wt% magnesium oxide, 8.2wt% calcium oxide, 0.5wt% aluminum oxide, 75.0wt% quartz sand, 1.0wt% potassium oxide and 0.1wt% rare earth element oxide, the iron content in the quartz sand is less than 350ppm, and the rare earth element oxide is selected from rare earth element oxides with absorption effect in the ultraviolet band, specifically cerium oxide.

[0053] The method for preparing the conductive glass with ultraviolet cutoff function provided in the above-mentioned embodiment 2 comprises the following specific steps:

[0054] S1. According to the mass fraction of the raw materials of the UV cutoff glass, 10.2wt% of sodium oxide, 5.0wt% of magnesium oxide, 8.2wt% of calcium oxide, 0.5wt% of aluminum oxide, 75.0wt% of quartz sand, 1.0wt% of potassium oxide and 0.1wt% of rare earth element oxide are accurately weighed, and these raw materials are uniformly mixed in a mixer to form a batch;

[0055] S2, preheating the platinum crucible to 1300° C. with the kiln, then adding the above-mentioned batch material, raising the kiln temperature to 1500° C. in 60 minutes, and keeping the temperature for 220 minutes to obtain glass liquid;

[0056] S3, sending the above-mentioned glass liquid into a glass forming pool, cooling the glass liquid to make it have a viscosity suitable for calendering, and then calendering, and then annealing at 450° C. for 10 minutes in an annealing furnace, and then cooling to room temperature at a cooling rate of 2° C. / min to obtain a UV cutoff glass with a thickness of 2.0 mm;

[0057] S4, physically strengthening (tempering) the obtained UV cutoff glass;

[0058] S5. On the surface of the strengthened UV cutoff glass, a UV cutoff layer 2 with a thickness of 15.0 nm and a conductive layer 3 with a thickness of 500.0 nm are sequentially sputtered by PVD, thereby obtaining a conductive glass with UV cutoff function.

[0059] Example 3

[0060] Embodiment 3 provides a conductive glass with ultraviolet cutoff function, wherein the transmittance of the conductive glass to UVB band light is less than 5.0%, and the conductive glass comprises:

[0061] Ultraviolet cutoff glass 1, which is a substrate of conductive glass and has a thickness of 2.0 mm. The ultraviolet cutoff glass 1 is made of rare earth-doped glass;

[0062] The ultraviolet cutoff layer 2 is stacked on the ultraviolet cutoff glass 1 and is a transition metal oxide layer with a thickness of 45.0 nm;

[0063] and a conductive layer 3, which is stacked on the ultraviolet cutoff layer 2 and is made of AZO conductive layer with a thickness of 750.0 nm;

[0064] The above-mentioned ultraviolet cut-off glass includes the following components in mass fraction:

[0065] 14.5wt% sodium oxide, 2.0wt% magnesium oxide, 11.5wt% calcium oxide, 1.89wt% aluminum oxide, 70.0wt% quartz sand, 0.1wt% potassium oxide and 0.01wt% rare earth element oxide, the iron content in the quartz sand is less than 350ppm, and the rare earth element oxide is selected from rare earth element oxides with absorption effect in the ultraviolet band, specifically cerium oxide.

[0066] The method for preparing the conductive glass with ultraviolet cutoff function provided in the above-mentioned embodiment 3 comprises the following specific steps:

[0067] S1. According to the mass fraction of the raw materials of the ultraviolet cutoff glass, 14.5wt% of sodium oxide, 2.0wt% of magnesium oxide, 11.5wt% of calcium oxide, 1.89wt% of aluminum oxide, 70.0wt% of quartz sand, 0.1wt% of potassium oxide and 0.01wt% of rare earth element oxide are accurately weighed, and these raw materials are uniformly mixed in a mixer to form a batch;

[0068] S2, preheating the platinum crucible to 1400° C. with the kiln, then adding the above-mentioned batch materials, raising the kiln temperature to 1600° C. in 90 minutes, and keeping the temperature for 200 minutes to obtain glass liquid;

[0069] S3, sending the above-mentioned glass liquid into a glass forming pool, cooling the glass liquid to make it have a viscosity suitable for calendering, and then calendering, and then annealing at 650° C. for 6 minutes in an annealing furnace, and then cooling to room temperature at a cooling rate of 2° C. / min to obtain a UV cutoff glass with a thickness of 2.0 mm;

[0070] S4, chemically strengthening the obtained UV cutoff glass;

[0071] S5. On the surface of the strengthened UV cutoff glass, a UV cutoff layer 2 with a thickness of 45.0 nm and a conductive layer 3 with a thickness of 750.0 nm are sequentially sputtered by PVD, thereby obtaining a conductive glass with UV cutoff function.

[0072] Comparative Example 1

[0073] like Figure 2 As shown, the difference between Comparative Example 1 and Example 1 is that the glass substrate 4 of Comparative Example 1 is not doped with rare earth element oxide and no ultraviolet cutoff layer is provided on the glass substrate 4, and the rest is the same as Example 1.

[0074] Comparative Example 2

[0075] The difference between Comparative Example 2 and Example 1 is that in Comparative Example 2, all the cerium oxide contained in the ultraviolet cutoff layer 2 of Example 1 is doped into the glass matrix without setting the ultraviolet cutoff layer 2, that is, the doping amount of cerium oxide in the glass matrix of Comparative Example 2 is the sum of the doping amount of rare earth element oxide (cerium oxide) in the glass matrix of Example 1 + the amount of cerium oxide contained in the ultraviolet cutoff layer 2, that is, the total amount of cerium oxide contained in the conductive glass of Comparative Example 2 is the same as that in Example 1, but Comparative Document 2 dopes all the cerium oxide into the glass matrix, while in Example 1, a part of the rare earth oxide (cerium oxide) is doped into the glass matrix, and the other part of the cerium oxide is deposited on the surface of the glass matrix in the form of a thin film.

[0076] test:

[0077] (1) The transmittance of the conductive glass of Example 1 and Comparative Example 1 was tested, and the results are as follows: Figure 3 As shown by Figure 3 It can be seen that the transmittance of the conductive glass of Example 1 for light with a wavelength below 320nm does not exceed 5.0%, and its average transmittance in the 280-320nm band (UVB band) is about 2.22%, and its average transmittance in the perovskite battery layer usable light region (>320nm) is about 86.31%; while the transmittance of the conductive glass of Comparative Example 1 for light with a wavelength below 320nm is significantly higher than that of the present application, and its average transmittance in the 280-320nm band (UVB band) is about 36.38%, and its average transmittance in the perovskite battery layer usable light region (>320nm) is about 86.35%; thus, it can be explained that the conductive glass with ultraviolet cutoff function designed by the present invention has a low transmittance for UVB band light, which can greatly reduce the ultraviolet light reaching the perovskite battery layer, thereby avoiding the ultraviolet aging and degradation problem of the perovskite layer, and improving the stability of the perovskite layer; at the same time, Figure 3 It can also be seen that the conductive glass with ultraviolet cutoff function designed by the present invention does not reduce the transmittance of available light that can be absorbed and utilized by the perovskite battery layer, that is, the conductive glass of the present invention can reduce the transmittance of UVB band light without reducing the transmittance of available light of the perovskite battery, so that the perovskite battery assembly assembled using the conductive glass of the present invention has the dual advantages of high power generation and high stability.

[0078] It was measured that the transmittance of the conductive glass of Comparative Example 2 in the available light area was significantly lower than that of Example 1. The reason for this is that in Comparative Example 2, since all the cerium oxide was doped into the glass matrix, excessive addition of rare earth metal oxides into the glass matrix caused the glass to produce color, thereby affecting the transmittance of available light of the perovskite cell, thereby affecting the power generation power of the perovskite cell assembly.

[0079] The above are preferred embodiments of the present invention and are only used to explain the present invention, not to limit the present invention. Any obvious changes or modifications derived from the technical solution of the present invention are still within the protection scope of the present invention.

Claims

1. A conductive glass with ultraviolet cutoff function, characterized in that: The transmittance of the conductive glass to UVB band light is less than 5.0%, and the conductive glass comprises: Ultraviolet cutoff glass (1), which is made of rare earth doped glass and serves as a matrix of the conductive glass; An ultraviolet cutoff layer (2) is stacked on the ultraviolet cutoff glass (1); and a conductive layer (3) stacked on the ultraviolet cutoff layer (2); The ultraviolet cut-off glass comprises the following components in mass fraction: 10.0-15.0wt% of sodium oxide, 2.0-6.0wt% of magnesium oxide, 8.0-12.0wt% of calcium oxide, 0.5-2.0wt% of aluminum oxide, 70.0-75.0wt% of quartz sand, 0-1.0wt% of potassium oxide and 0.01-0.1wt% of rare earth element oxide.

2. The conductive glass with ultraviolet cutoff function according to claim 1, characterized in that: The thickness of the ultraviolet cutoff layer (2) is set to 10.0-50.0 nm.

3. The conductive glass with ultraviolet cutoff function according to claim 1 or 2, characterized in that: The ultraviolet cutoff layer (2) is selected from a cerium oxide layer, or a rare earth element oxide layer or a transition metal oxide layer having an ultraviolet cutoff function.

4. The conductive glass with ultraviolet cutoff function according to claim 1, characterized in that: The iron content of the quartz sand is less than 350ppm.

5. The conductive glass with ultraviolet cutoff function according to claim 1, characterized in that: The thickness of the conductive layer (3) is set to 180-800 nm, and it is made of FTO, ITO, AZO, or doped FTO, ITO, or any mixed layer of the above.

6. The conductive glass with ultraviolet cutoff function according to claim 1, characterized in that: The rare earth element oxide is selected from rare earth element oxides having absorption effect in the ultraviolet band, and cerium oxide is selected from them.

7. The method for preparing a conductive glass with ultraviolet cutoff function according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: S1. According to the mass fraction of the raw materials of the ultraviolet cutoff glass, accurately weigh sodium oxide, magnesium oxide, calcium oxide, aluminum oxide, quartz sand, potassium oxide and rare earth element oxides, and mix them evenly to form a batch; S2, melting the batch material to form molten glass; S3, sending the glass liquid into a glass forming pool, cooling it, and then rolling it into shape, annealing it, and cooling it to obtain UV cutoff glass; S4, strengthening the ultraviolet cutoff glass; S5. An ultraviolet cutoff layer (2) and a conductive layer (3) are sequentially formed on the surface of the strengthened ultraviolet cutoff glass, thereby obtaining conductive glass with ultraviolet cutoff function.

8. The method for preparing a conductive glass with ultraviolet cutoff function according to claim 7, characterized in that: Step S2, preheating the platinum crucible to 1300-1400° C. with the kiln, then adding the batch material, and heating to 1500-1600° C. in 60-90 minutes, keeping the temperature for 200-240 minutes, to obtain glass liquid.

9. The method for preparing a conductive glass with ultraviolet cutoff function according to claim 7, characterized in that: In step S3, the annealing temperature is 450-650° C., the cooling rate is 1-3° C. / min, and the material is cooled to room temperature.

10. The method for preparing a conductive glass with ultraviolet cutoff function according to claim 7, characterized in that: Step S5: using a PVD process to sequentially sputter a layer of ultraviolet cutoff layer (2) and a conductive layer (3) on the surface of the strengthened ultraviolet cutoff glass.

Images