Self-cleaning photovoltaic glass and preparation method thereof

Abstract

The present invention provides a method for preparing self-cleaning photovoltaic glass, comprising the following steps: A) forming a titanium dioxide layer on the light-receiving surface of a pretreated substrate; B) forming a monolayer of silicon dioxide on the surface of the titanium dioxide layer; C) etching the titanium dioxide layer to form titanium dioxide micropillars; and D) depositing titanium dioxide nanospheres on the surface of the silicon dioxide layer to obtain the self-cleaning photovoltaic glass. The present application also provides a self-cleaning photovoltaic glass. The present application constructs a titanium dioxide micro-nanostructure on the substrate surface, thereby imparting to the resulting photovoltaic glass strong hydrophobic properties and the ability to photocatalytically decompose small molecules, thereby enhancing the self-cleaning effect of the photovoltaic glass.

Description

Technical Field

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

[0002] Photovoltaic panels typically use ultra-clear glass with high light transmittance as their cover. Under operating conditions, dust, stains, animal feces, and other debris adhere to the glass surface, severely affecting the panel's light absorption efficiency and causing hot spots, which shortens the panel's lifespan and causes significant economic losses. Currently, cleaning the photovoltaic glass surface still relies primarily on manual labor, resulting in high maintenance costs. Summary of the Invention

[0003] The technical problem solved by the present invention is to provide a photovoltaic glass, which can improve the self-cleaning effect of the photovoltaic glass.

[0004] In view of this, the present application provides a method for preparing self-cleaning photovoltaic glass, comprising the following steps:

[0005] A) preparing a titanium dioxide layer on the light-receiving surface of the pretreated substrate;

[0006] B) preparing a single layer of silicon dioxide on the surface of the titanium dioxide layer;

[0007] C) etching the titanium dioxide layer to obtain titanium dioxide micron columns;

[0008] D) depositing titanium dioxide nanospheres on the surface of the silicon dioxide layer to obtain self-cleaning photovoltaic glass.

[0009] Preferably, the substrate is ultra-white glass, FTO with a conductive layer, ITO with a conductive layer or AZO with a conductive layer; the pretreatment is to ultrasonically treat the substrate in deionized water, acetone and ethanol in sequence for 20 to 30 minutes.

[0010] Preferably, in step A), the titanium dioxide layer is prepared by chemical vapor deposition, and the titanium source of the titanium dioxide layer is titanium acetylacetonate, titanium tert-butoxide, methyl titanate or isopropyl titanate.

[0011] Preferably, the chemical vapor deposition method is specifically:

[0012] The titanium source is placed in a low-temperature area of ​​100 to 300°C, and the substrate is placed in a high-temperature area of ​​400 to 800°C. The low-temperature areas are connected by a quartz tube and N2 / O2 mixed gas is introduced for deposition.

[0013] Preferably, in step B), the preparation of the silicon dioxide layer is specifically as follows:

[0014] Silica microspheres with a particle size of 2 to 20 μm are prepared into a suspension;

[0015] A single silicon dioxide layer is prepared on the surface of the titanium dioxide layer by adopting a spin coating method, a dip-coating method, a spray coating method, a blade coating method, a vertical sedimentation self-assembly method or a slit coating method.

[0016] Preferably, the etching adopts oxygen reaction plasma etching method, the oxygen pressure of the oxygen reaction plasma etching method is 10-50 mTorr, the flow rate is 10-100 sccm, the power is 100-1000 W, and the etching depth is the thickness of the titanium dioxide layer.

[0017] Preferably, in step D), the deposition method is atomic layer deposition.

[0018] Preferably, the temperature of the atomic layer deposition method is 250-350° C., the atmosphere is nitrogen, the flow rate is 50-200 sccm, and the pulse time is 0.1-0.3 s.

[0019] The present application also provides self-cleaning photovoltaic glass prepared by the preparation method, which is composed of a substrate, a titanium dioxide micron column layer, a single silicon dioxide layer and a titanium dioxide nanosphere layer stacked in sequence.

[0020] Preferably, the thickness of the titanium dioxide micron column is 500 nm to 10 μm.

[0021] The present application provides a method for preparing photovoltaic glass, specifically: first, a titanium dioxide layer is prepared on the light-receiving surface of a pretreated substrate, then a single titanium dioxide layer is prepared on the surface of the titanium dioxide layer, and then the titanium dioxide layer is etched to obtain titanium dioxide micron columns, and finally titanium dioxide nanospheres are deposited on the surface of the silicon dioxide layer, thereby constructing a titanium dioxide micro-nano structure, so that the obtained photovoltaic glass has strong hydrophobic properties and has the function of photocatalytic decomposition of small molecules, thereby improving the self-cleaning effect of the photovoltaic glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic diagram of the process for preparing the photovoltaic glass of the present invention. DETAILED DESCRIPTION

[0023] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0024] In view of the problem of the influence of dirt on the surface of photovoltaic glass on the light absorption efficiency and high maintenance cost in the prior art, the present application provides a self-cleaning photovoltaic glass and its preparation method. The self-cleaning photovoltaic glass prepared in the present application constructs a titanium dioxide micro-nano structure, which makes it have strong hydrophobic properties, and ultimately improves the self-cleaning effect of the photovoltaic glass. Specifically, the embodiment of the present invention discloses a method for preparing self-cleaning photovoltaic glass, the flow diagram of which is as follows: Figure 1 As shown, ① is a substrate, ② is a titanium dioxide layer, ③ is a single layer of silicon dioxide, ④ is a titanium dioxide micron column, and ⑤ is a titanium dioxide nanosphere; the preparation method of the self-cleaning photovoltaic glass specifically comprises the following steps:

[0025] A) preparing a titanium dioxide layer on the light-receiving surface of the pretreated substrate;

[0026] B) preparing a single layer of silicon dioxide on the surface of the titanium dioxide layer;

[0027] C) etching the titanium dioxide layer to obtain titanium dioxide micron columns;

[0028] D) depositing titanium dioxide nanospheres on the surface of the silicon dioxide layer to obtain self-cleaning photovoltaic glass.

[0029] In the process of preparing self-cleaning photovoltaic glass, the present application first pre-treats the substrate, that is, the substrate is ultrasonically treated in deionized water, acetone and ethanol for 20 to 30 minutes in sequence; the substrate is a substrate familiar to those skilled in the art, specifically, the substrate is selected from ultra-white glass, FTO with a conductive layer, ITO with a conductive layer or AZO with a conductive layer.

[0030] After the substrate is pretreated, the present application prepares a titanium dioxide layer on the light-receiving surface of the substrate, specifically by chemical vapor deposition. In this process, the titanium source used is selected from titanium metal organic compounds such as isopropyl titanate, titanium acetylacetonate, titanium tert-butoxide, and methyl titanate. The titanium source is placed in a low-temperature zone (100-300°C), and the substrate is placed in a high-temperature zone (400-800°C). The low-temperature zone is connected by a quartz tube, and a N2 / O2 mixed gas is introduced to perform chemical vapor deposition. In the above-mentioned N2 / O2 mixed gas, the volume percentage of O2 is 1-5%. The thickness of the titanium dioxide layer described in the present application is 500nm-10μm, and more specifically, the thickness of the titanium dioxide layer is 1μm-8μm.

[0031] After obtaining the titanium dioxide layer, the present application prepares a single layer of silicon dioxide on its surface. Specifically, polystyrene or silicon dioxide microspheres with a particle size of 20nm to 2μm are prepared into a suspension with a mass fraction of 0.01% to 10%. Then, a single layer of silicon dioxide is prepared on the titanium dioxide layer by spin coating, dip-coating, spray coating, vertical sedimentation self-assembly, or slit coating. The single layer of silicon dioxide acts as a barrier layer for the titanium dioxide layer, preventing the titanium dioxide layer beneath the silicon dioxide layer from being etched during the etching process, thereby forming titanium dioxide nanopillars.

[0032] In the above process, silica microspheres with a diameter of 30 nm to 1 μm are preferably used; the concentration of the suspension is 0.1 to 5 wt%; and the solvent in the suspension is selected from one or both of water and anhydrous ethanol. The spin coating, dip coating, spray coating, vertical sedimentation self-assembly, or slit coating method can be performed according to procedures well known to those skilled in the art and is not particularly limited in this application.

[0033] The present application then etches the titanium dioxide layer, and the etching adopts an oxygen reaction plasma etching method. The oxygen pressure of this method is 10 to 50 mTorr, specifically 20 to 40 mTorr; the flow rate is 10 to 100 sccm, specifically 30 to 80 sccm; the etching power is 100 to 1000 W, specifically 200 to 700 W; the etching depth is 500 nm to 10 μm, specifically 1 μm to 6 μm; the etching depth is to etch away the titanium dioxide layer to form a titanium dioxide micro-nano structure.

[0034] According to the present invention, titanium dioxide nanospheres are finally deposited on the surface of the silicon dioxide layer to obtain photovoltaic glass with a titanium dioxide micro-nanostructure. During this process, the deposition method uses atomic layer deposition (ALD), the ALD temperature is 200-400°C, more specifically 250-350°C, the ALD is performed in a nitrogen atmosphere, the nitrogen flow rate is 50-200 sccm, more specifically 80-120 sccm, and the ALD pulse time is 0.1-0.3 seconds.

[0035] The present application also provides a self-cleaning photovoltaic glass prepared by the above preparation method, which consists of a substrate, a titanium dioxide micron column layer, a single silicon dioxide layer and a titanium dioxide nanosphere layer stacked in sequence.

[0036] In the present application, a titanium dioxide micron column layer and a titanium dioxide nanosphere layer are constructed into a micro-nano structure, which is beneficial to improving the hydrophobicity of photovoltaic glass.

[0037] In order to further understand the present invention, the preparation method of the self-cleaning photovoltaic glass provided by the present invention is described in detail below with reference to the examples. The protection scope of the present invention is not limited by the following examples.

[0038] Example 1

[0039] (1) Cut the FTO transparent conductive glass into 4 cm × 4 cm pieces, place them in deionized water, acetone, and ethanol for ultrasonic cleaning for 20 min respectively, blow dry them with nitrogen, and store them for later use;

[0040] (2) A titanium dioxide layer was prepared on the light-receiving surface of the glass by chemical vapor deposition. The Ti source was isopropyl titanate. The Ti source was placed in a low-temperature zone (180°C) and the substrate was located in a high-temperature zone (400°C). The low-temperature zones were connected by a quartz tube and fed with a N2 / O2 (O2 content 1%) mixed gas. The titanium dioxide layer had a thickness of 2 μm.

[0041] (3) 0.1 g of silica microspheres with a particle size of 50 nm were placed in 125 ml of anhydrous ethanol and ultrasonically dispersed for 1 h to prepare a suspension with a mass fraction of 0.1%. An FTO glass sheet was inserted into the suspension with the conductive surface facing upward and tilted at 45°. The sheet was placed in a constant temperature and humidity chamber at 55°C and RH 45% until the solvent was completely evaporated and then removed for use to obtain a single layer of silica.

[0042] (4) Preparation of titanium dioxide micro-nanostructures: The titanium dioxide layer was etched using oxygen reactive plasma etching with an oxygen pressure of 30 mTorr, a flow rate of 50 sccm, an etching power of 500 W, and an etching depth of 2 μm to obtain titanium dioxide micro-pillars;

[0043] (5) Titanium dioxide nanospheres were prepared on the surface of the silicon dioxide layer by atomic layer deposition at a temperature of 300 °C, in a nitrogen atmosphere, with a flow rate of 100 sccm and a pulse time of 0.1 s to obtain photovoltaic glass with titanium dioxide micro-nanostructure.

[0044] Example 2

[0045] (1) Cut the FTO transparent conductive glass into 4 cm × 4 cm pieces, place them in deionized water, acetone, and ethanol for ultrasonic cleaning for 20 min respectively, blow dry them with nitrogen, and store them for later use;

[0046] (2) A titanium dioxide layer was prepared on the light-receiving surface of the glass by chemical vapor deposition. The Ti source was isopropyl titanate. The Ti source was placed in a low-temperature zone (180°C) and the substrate was located in a high-temperature zone (400°C). The low-temperature zones were connected by a quartz tube and fed with a N2 / O2 (O2 content 1%) mixed gas. The titanium dioxide layer had a thickness of 1 μm.

[0047] (3) 0.1 g of silica microspheres with a particle size of 50 nm were placed in 125 ml of anhydrous ethanol and ultrasonically dispersed for 1 h to prepare a suspension with a mass fraction of 0.1%. An FTO glass slide was inserted into the suspension with the conductive surface facing up and tilted at 45°. The suspension was placed in a constant temperature and humidity chamber at 55°C and RH 45% until the solvent was completely evaporated and then removed for use to obtain a single layer of silica.

[0048] (4) Preparation of titanium dioxide micro-nanostructures: The titanium dioxide layer was etched by oxygen reactive plasma etching with an oxygen pressure of 30 mTorr, a flow rate of 50 sccm, an etching power of 500 W, and an etching depth of 1 μm to obtain titanium dioxide micro-pillars;

[0049] (5) Titanium dioxide nanospheres were prepared on the surface of the silicon dioxide layer by atomic layer deposition at a temperature of 300 °C, in a nitrogen atmosphere, with a flow rate of 100 sccm and a pulse time of 0.1 s to obtain photovoltaic glass with titanium dioxide micro-nanostructure.

[0050] Example 3

[0051] (1) Cut the FTO transparent conductive glass into 4 cm × 4 cm pieces, place them in deionized water, acetone, and ethanol for ultrasonic cleaning for 20 min respectively, blow dry them with nitrogen, and store them for later use;

[0052] (2) A titanium dioxide layer was prepared on the light-receiving surface of the glass by chemical vapor deposition. The Ti source was isopropyl titanate. The Ti source was placed in a low-temperature zone (180°C) and the substrate was located in a high-temperature zone (400°C). The low-temperature zones were connected by a quartz tube and fed with a N2 / O2 (O2 content 1%) mixed gas. The titanium dioxide layer had a thickness of 2 μm.

[0053] (3) 0.1 g of silica microspheres with a particle size of 100 nm were placed in 125 ml of anhydrous ethanol and ultrasonically dispersed for 1 h to form a suspension with a mass fraction of 0.1%. An FTO glass sheet was inserted into the suspension with the conductive surface facing upward and tilted at 45°. The sheet was placed in a constant temperature and humidity chamber at 55°C and RH 45% until the solvent was completely evaporated and then removed for use to obtain a single layer of silica.

[0054] (4) Preparation of titanium dioxide micro-nanostructures: The titanium dioxide layer was etched using oxygen reactive plasma etching with an oxygen pressure of 30 mTorr, a flow rate of 50 sccm, an etching power of 500 W, and an etching depth of 2 μm to obtain titanium dioxide micro-pillars;

[0055] (5) Titanium dioxide nanospheres were prepared on the surface of the silicon dioxide layer by atomic layer deposition at a temperature of 300 °C, in a nitrogen atmosphere, with a flow rate of 100 sccm and a pulse time of 0.1 s to obtain photovoltaic glass with titanium dioxide micro-nanostructure.

[0056] Comparative Example 1

[0057] (1) Cut the FTO transparent conductive glass into 4 cm × 4 cm pieces, place them in deionized water, acetone, and ethanol for ultrasonic cleaning for 20 min respectively, blow dry them with nitrogen, and store them for later use;

[0058] (2) A titanium dioxide layer was prepared on the light-receiving surface of the glass by chemical vapor deposition. The Ti source was isopropyl titanate. The Ti source was placed in a low-temperature zone (180°C) and the substrate was located in a high-temperature zone (400°C). The low-temperature zones were connected by a quartz tube and fed with a N2 / O2 (O2 content 1%) mixed gas. The titanium dioxide layer had a thickness of 2 μm.

[0059] (3) 0.1 g of silica microspheres with a particle size of 50 nm were placed in 125 ml of anhydrous ethanol and ultrasonically dispersed for 1 h to prepare a suspension with a mass fraction of 0.1%. An FTO glass slide was inserted into the suspension with the conductive surface facing up and tilted at 45°. The suspension was placed in a constant temperature and humidity chamber at 55°C and RH 45% until the solvent was completely evaporated and then removed for use to obtain a single layer of silica.

[0060] (4) Preparation of titanium dioxide micro-nanostructure: The titanium dioxide layer was etched by oxygen reactive plasma etching with an oxygen pressure of 30 mTorr, a flow rate of 50 sccm, an etching power of 500 W, and an etching depth of 2 μm to obtain photovoltaic glass with titanium dioxide micro-nanostructure.

[0061] Comparative Example 2

[0062] (1) Cut the FTO transparent conductive glass into 4 cm × 4 cm pieces, place them in deionized water, acetone, and ethanol for ultrasonic cleaning for 20 min respectively, blow dry them with nitrogen, and store them for later use;

[0063] (2) A titanium dioxide layer was prepared on the light-receiving surface of the glass by chemical vapor deposition. The Ti source was isopropyl titanate. The Ti source was placed in a low-temperature zone (180°C) and the substrate was located in a high-temperature zone (400°C). The low-temperature zones were connected by a quartz tube and a N2 / O2 (O2 content 1%) mixed gas was introduced. The thickness of the electron transport layer was 2 μm, and photovoltaic glass with a titanium dioxide layer was obtained.

[0064] Examples 1, 2, and 3 list the contact angle results for different micro-nanostructure parameters. Comparative Examples 1 and 2 are used as comparative experiments. Comparative Example 1 does not have titanium dioxide nanospheres, and the titanium dioxide layer of Comparative Example 2 does not have micro-nanostructures. The results are shown in Table 1.

[0065] Table 1 Contact angle data of photovoltaic glass prepared in Examples and Comparative Examples

[0066] Group Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Contact angle / ° 152.4 142.5 148.4 105.3 82.5

[0067] The table lists the contact angles of Examples 1, 2, and 3 and Comparative Examples 1 and 2. As shown in Table 1, Example 1 having a titanium dioxide micro-nano structure has stronger hydrophobicity, that is, a better self-cleaning effect.

[0068] The above embodiments are only intended to help understand the method and core concept of the present invention. It should be noted that, without departing from the principles of the present invention, a number of improvements and modifications may be made to the present invention by those skilled in the art, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

[0069] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing self-cleaning photovoltaic glass, comprising the following steps: A) preparing a titanium dioxide layer on the light-receiving surface of the pretreated substrate; B) preparing a suspension of silica microspheres having a particle size of 2 to 20 μm; A single layer of silicon dioxide is prepared on the surface of the titanium dioxide layer by using a spin coating method, a dip-coating method, a spray coating method, a doctor blade method, a vertical sedimentation self-assembly method or a slit coating method; C) etching the titanium dioxide layer to obtain titanium dioxide micrometer columns; the etching is performed using an oxygen reactive plasma etching method; D) depositing titanium dioxide nanospheres on the surface of the silicon dioxide layer to obtain self-cleaning photovoltaic glass; the deposition method is atomic layer deposition.

2. The preparation method according to claim 1, characterized in that The substrate is ultra-white glass, FTO with a conductive layer, ITO with a conductive layer or AZO with a conductive layer; the pretreatment is to sequentially ultrasonically treat the substrate in deionized water, acetone and ethanol for 20 to 30 minutes.

3. The preparation method according to claim 1, characterized in that In step A), the titanium dioxide layer is prepared by chemical vapor deposition, and the titanium source of the titanium dioxide layer is titanium acetylacetonate, titanium tert-butoxide, methyl titanate or isopropyl titanate.

4. The preparation method according to claim 3, characterized in that The chemical vapor deposition method is specifically: The titanium source is placed in a low-temperature area of ​​100 to 300°C, and the substrate is placed in a high-temperature area of ​​400 to 800°C. The low-temperature areas are connected by a quartz tube and N2 / O2 mixed gas is introduced for deposition.

5. The preparation method according to claim 1, characterized in that The oxygen pressure of the oxygen reactive plasma etching method is 10-50 mTorr, the flow rate is 10-100 sccm, the power is 100-1000 W, and the etching depth is the thickness of the titanium dioxide layer.

6. The preparation method according to claim 1, characterized in that The temperature of the atomic layer deposition method is 250-350° C., the atmosphere is nitrogen, the flow rate is 50-200 sccm, and the pulse time is 0.1-0.3 s.

7. The self-cleaning photovoltaic glass prepared by the preparation method according to any one of claims 1 to 6, comprising a substrate, a titanium dioxide micron column layer, a single silicon dioxide layer and a titanium dioxide nanosphere layer stacked in sequence.

8. The self-cleaning photovoltaic glass according to claim 7, characterized in that: The thickness of the titanium dioxide micron column is 500nm-10μm.

Images