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CN-122010421-A - High-transmittance multilayer antireflection coated photovoltaic glass and preparation method thereof

CN122010421ACN 122010421 ACN122010421 ACN 122010421ACN-122010421-A

Abstract

The invention discloses high-transmittance multilayer antireflection coated photovoltaic glass and a preparation method thereof, and belongs to the technical field of photovoltaic modules. The photovoltaic glass comprises a glass substrate, a multilayer anti-reflection film positioned on the surface of the glass substrate, and at least comprises a hollow SiO 2 @TiO 2 core-shell layer, an MgF 2 nano-pillar array layer positioned on the outer side of the hollow SiO 2 @TiO 2 core-shell layer, an SiO 2 aerogel layer positioned on the outer side of the MgF 2 nano-pillar array layer, a first SiO 2 layer and a TiO 2 -SiO 2 nano-composite layer positioned between the glass substrate and the hollow SiO 2 @TiO 2 core-shell layer. The photovoltaic glass provided by the invention has the advantages of high transmittance and low reflectivity in a wide spectrum range, excellent weather resistance, mechanical strength and self-cleaning performance, mature preparation process, low cost and easiness in industrialization.

Inventors

  • CHEN MENGYUN
  • GAO FENG
  • QIAN XUHAO
  • SHEN ZHIMIN
  • TAO LONGZHONG
  • ZHAO DIANDONG
  • YANG YANG
  • ZHAO RUQIANG
  • YANG SHUAI

Assignees

  • 江苏海博瑞光伏科技有限公司

Dates

Publication Date
20260512
Application Date
20260113

Claims (12)

  1. 1. The high-transmittance multilayer antireflection coated photovoltaic glass is characterized by comprising a glass substrate and a multilayer antireflection film positioned on the surface of the glass substrate, wherein the multilayer antireflection film at least comprises: The hollow SiO 2 @TiO 2 core-shell layer comprises a hollow SiO 2 nanosphere and a TiO 2 shell layer coated on the surface of the hollow SiO 2 nanosphere; The MgF 2 nano-pillar array layer is positioned on the outer side of the hollow SiO 2 @TiO 2 core-shell layer and has a nano-pillar porous structure.
  2. 2. The photovoltaic glass of claim 1, wherein the multilayer antireflective film further comprises a SiO 2 aerogel layer located outside the MgF 2 nanopillar array layer.
  3. 3. The photovoltaic glass of claim 1 or 2, wherein the multilayer antireflective film further comprises: A first SiO 2 layer between the glass substrate and the hollow SiO 2 @TiO 2 core-shell layer; A TiO 2 -SiO 2 nanocomposite layer between the first SiO 2 layer and the hollow SiO 2 @TiO 2 core shell layer.
  4. 4. The photovoltaic glass according to claim 1, wherein the hollow SiO 2 @TiO 2 core-shell layer has a thickness of 60-80nm and a refractive index of 1.26+ -0.02, and the MgF 2 nano-pillar array layer has a thickness of 80-100nm and a refractive index of 1.18+ -0.02.
  5. 5. The photovoltaic glass of claim 2, wherein the SiO 2 aerogel layer has a thickness of 120-150nm and a refractive index of 1.08±0.02.
  6. 6. The photovoltaic glass according to claim 3, wherein the first SiO 2 layer has a thickness of 20-30nm and a refractive index of 1.44+ -0.02, and the TiO 2 -SiO 2 nanocomposite layer has a thickness of 40-60nm and a refractive index of 1.36+ -0.02.
  7. 7. The photovoltaic glass according to claim 1, wherein the hollow SiO 2 nanospheres have a diameter of 50-60nm, the thickness of the TiO 2 shell is 10-15nm, and the hollow spheres occupy 55-65% by volume.
  8. 8. A method of producing the photovoltaic glass according to any one of claims 1 to 7, comprising the steps of: S1, preprocessing a glass substrate; S2, preparing a hollow SiO 2 @TiO 2 core-shell layer, namely preparing a monodisperse hollow SiO 2 nanosphere template, carrying out surface amination treatment on the hollow SiO 2 nanospheres, coating the hollow SiO 2 nanospheres into a film by a sol-gel method, and then depositing a TiO 2 shell layer on the surfaces of the hollow SiO 2 nanospheres by magnetron sputtering; S3, preparing an MgF 2 nano-pillar array layer, namely preparing the MgF 2 film with the nano-pillar porous structure by adopting an inclined magnetron sputtering method and using an MgF 2 ceramic target through adjusting the sputtering angle, the working air pressure and the substrate temperature in an argon atmosphere.
  9. 9. The method according to claim 8, wherein the pretreatment in step S1 comprises sequentially ultrasonic cleaning the glass substrate with acetone, ethanol and deionized water for 15 minutes each, and then plasma treating under argon atmosphere at a power of 200W for 5 minutes.
  10. 10. The preparation method of the hollow SiO 2 nanospheres according to claim 8, wherein in the step S2, the preparation method comprises the steps of preparing a monodisperse SiO 2 nanosphere template with the diameter of 50-60nm, and forming a hollow structure with the shell thickness of 10-15nm through a selective etching process; the coating mode of the sol-gel method comprises slit coating, roller coating, spraying or spin coating, wherein a radio frequency magnetron sputtering system is adopted for the double-target magnetron sputtering, the sputtering power ratio of TiO 2 /SiO 2 is regulated to be 1.2-1.5:1, the substrate rotation speed is 10-15rpm, a real-time ellipsometer is used for monitoring the refractive index, and the volume ratio of hollow spheres is controlled to be 55-65%.
  11. 11. The method according to claim 8, wherein in step S3, the sputtering angle of the oblique magnetron sputtering is 70 °, the working air pressure is 0.3Pa, and the substrate temperature is 250 ℃.
  12. 12. The method of claim 8, further comprising, after step S1 and before step S2: Depositing a compact SiO 2 layer on the surface of the glass substrate by a magnetron sputtering method, wherein the thickness is 20-30nm, the sputtering power is 500-600W, the atmosphere is a mixed gas of argon gas 20sccm and oxygen gas 5sccm, the vacuum degree is less than or equal to 5X 10 -3 Pa, the working air pressure is 0.3Pa, and the substrate temperature is 250 ℃; Preparing a TiO 2 -SiO 2 nano composite layer by a sol-gel method, wherein the thickness is 40-60nm, tetrabutyl titanate and tetraethoxysilane are used as precursors, and the molar ratio is 3:1 to 1:1 in a gradient manner; After step S3, the method further comprises the step of preparing an SiO 2 aerogel layer with the thickness of 120-150nm by a sol-gel method and combining with supercritical drying.

Description

High-transmittance multilayer antireflection coated photovoltaic glass and preparation method thereof Technical Field The invention relates to the technical field of photovoltaic modules, in particular to a high-transmittance multilayer antireflection coated photovoltaic glass and a preparation method thereof. Background There is strong coupling relation between the conversion efficiency of the photovoltaic module and the transmissivity of the glass cover plate, and the optical performance of the glass cover plate directly influences the photoelectric conversion efficiency of the solar cell. In outdoor use environment, the optical performance of the glass cover plate is seriously reduced due to the deposition of dust, pollutants and the like, and the reflectivity of the glass surface is further increased under severe weather conditions such as rain and fog and the like, so that the conversion efficiency of the photovoltaic module is obviously attenuated. In order to reduce the influence of environmental factors on the efficiency of the assembly and improve the overall conversion efficiency of the photovoltaic assembly, developing high-transmittance and low-reflection photovoltaic glass is an urgent need of the industry. Conventional photovoltaic glass often employs a single layer anti-reflective coating to reduce surface reflection. For example, a single layer film using silicon dioxide (SiO 2) or magnesium fluoride (MgF 2) as an antireflection material can improve the transmittance of glass to some extent and exhibit hydrophobic properties under the action of hydroxyl groups (-OH) due to good thermal stability and relatively low refractive index of SiO 2. However, single-layer SiO 2 films have relatively poor mechanical properties due to van der waals forces and the porous structure of the film, and their reflectivity in the uv and near ir bands is still high, typically above 4%, resulting in significant loss of optical energy in these bands. In addition, the single-layer antireflection film is difficult to realize ultra-low reflectivity in a wide spectral range of 380-1100nm, and has certain limitation on optical performance. In order to improve the optical properties of the single-layer film, researchers have developed a multi-layer antireflection film structure. For example, with a two-layer film design of silica in combination with titanium dioxide (TiO 2), the antireflection band can be widened to some extent by utilizing the large refractive index difference between the two materials. However, such multilayer film structures face a number of technical challenges in practical applications. On one hand, the optical performance of the film is affected by the low porosity of the solid nanoparticle structure, on the other hand, when the interlayer refractive index gradient of the multilayer film is not well matched, the interface reflection loss is increased, and meanwhile, the overall durability is affected by insufficient adhesive force between the film layers. Particularly, after long-term use in a high-temperature and high-humidity environment, the multilayer film is easy to peel off, the transmittance attenuation is remarkable, and the outdoor service life requirement of the photovoltaic module for more than 25 years is difficult to meet. Further increasing the number of film layers, for example, using more than five complex film systems, theoretically more excellent optical performance can be achieved by finer refractive index gradient designs. However, the preparation process of the complex multilayer film system is generally complicated, the production cost is high, and large-scale production is difficult to realize. In the preparation process of the multilayer film, interface element diffusion is easy to cause by interlayer heat treatment, and solvent residues can cause defects such as microcracks, so that the problems further limit the practical application of the complex film system in the field of photovoltaic glass. Meanwhile, the existing multilayer film design is often focused on optimization of optical performance, and comprehensive consideration in the aspects of mechanical strength, weather resistance, anti-pollution capability and the like is insufficient, so that the actual application effect is difficult to achieve expectations. Therefore, how to ensure excellent optical performance, and simultaneously, excellent mechanical strength, long-term environmental durability and good process economy becomes a comprehensive technical problem to be solved in the photovoltaic glass antireflection film technology. Disclosure of Invention Based on the problems existing in the background technology, the invention provides the multilayer anti-reflection coated photovoltaic glass for the solar cell cover plate, which obviously improves the light transmittance and reduces the reflectivity and simultaneously enhances the weather resistance and the mechanical strength by optimizing the coating process,