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CN-121991686-A - Core-shell structure light conversion agent, photovoltaic glass light conversion coating liquid and preparation method thereof

CN121991686ACN 121991686 ACN121991686 ACN 121991686ACN-121991686-A

Abstract

The invention discloses a core-shell structure light conversion agent, photovoltaic glass light conversion coating liquid and a preparation method thereof, and belongs to the technical field of photovoltaic packaging. The core-shell structured light conversion agent comprises a core layer and a shell layer, wherein the core layer comprises a light conversion agent luminescent molecular material, the shell layer comprises a silicon dioxide material, the particle size of the core-shell structured light conversion agent is 20-200 nm, and the thickness of the shell layer is 10-50% of the particle size of the core-shell structured light conversion agent. According to the invention, by designing the core-shell structure with the inorganic silica shell layer, the light conversion agent molecules are effectively packaged, so that the ultraviolet stability of the light conversion film layer is improved while the high light transmittance is maintained, and the service life of the film coating layer in an outdoor environment is prolonged.

Inventors

  • AN YU
  • YANG NING
  • CHEN LANFEN
  • LUO YONGJIAN

Assignees

  • 长三角太阳能光伏技术创新中心
  • 麦加芯彩新材料科技(上海)股份有限公司

Dates

Publication Date
20260508
Application Date
20251223

Claims (10)

  1. 1. A core-shell structured light conversion agent is characterized by comprising a core layer and a shell layer, The nuclear layer comprises a light conversion agent luminescent molecular material; The shell layer comprises a silica material; the particle size of the core-shell structured light conversion agent is 20-200 nm; the thickness of the shell layer is 10-50% of the particle size of the core-shell structure light conversion agent.
  2. 2. The core-shell structured light conversion agent according to claim 1, wherein the core-shell structured light conversion agent can absorb 300-400 nm ultraviolet light and emit 400-800 nm visible light, and the fluorescence quantum yield of the core-shell structured light conversion agent is 70-100%.
  3. 3. The core-shell structured light conversion agent according to claim 1, wherein the light conversion agent luminescent molecular material comprises at least one of an organic fluorescent material, a rare earth doped inorganic luminescent material, a rare earth organic ligand luminescent material, and a quantum dot luminescent material.
  4. 4. The core-shell structured light conversion agent according to claim 3, wherein the organic fluorescent material comprises at least one of benzotriazole fluorescent material, coumarin fluorescent material, perylene diimide fluorescent material, rhodamine fluorescent material, pyrene fluorescent material, benzothiazole fluorescent material, triphenylamine fluorescent material, carbazole fluorescent material, benzophenone fluorescent material, salicylate fluorescent material, substituted acrylonitrile fluorescent material, and triazine organic fluorescent material; The rare earth doped phosphor comprises at least one of rare earth doped silicate, rare earth doped borate, rare earth doped tungstate, rare earth doped vanadate, rare earth doped chloroaluminate, rare earth doped nitride, rare earth doped oxynitride, rare earth doped phosphate; preferably, the rare earth ions of the rare earth doped phosphor comprise at least one of Eu 2+ 、Eu 3+ 、Ce 3+ 、Tb 3+ 、Sm 3+ 、Dy 3+ 、Po 3 + 、Pr 3+ 、Tm 3+ 、Er 3+ or Yb 3+ 、Ho 3+ ; the organic ligand of the rare earth organic ligand luminescent material comprises at least one of 2-thiophenoyltrifluoroacetone, acetylacetone, dibenzoylmethane and 1, 10-phenanthroline; Preferably, the rare earth ions of the rare earth organic ligand luminescent material comprise at least one of Eu 2+ 、Eu 3+ 、Ce 3+ 、Tb 3+ 、Sm 3+ 、Dy 3+ 、Po 3 + 、Pr 3+ 、Tm 3+ 、Er 3+ 、Yb 3+ 、Ho 3+ ; the quantum dot light-emitting material comprises at least one of CdSe、CdSe/ZnS、CdTe/CdS、InP/ZnS、CsPbBr 3 、CsPb(Br/I) 3 、MAPbBr 3 、ZnS、CuGaS 2 /ZnS、ZnS:Mn 2+ 、 graphene quantum dots, carbon quantum dots, inP/ZnS and InP/ZnSe, pbS, pbSe, znO, cdS.
  5. 5. A method for preparing the core-shell structured light conversion agent according to any one of claims 1 to 4, comprising the steps of: s1, preparing a light conversion agent luminescent molecular material solution, adding absolute ethyl alcohol, stirring and mixing, adding aromatic silane and a catalyst, and stirring and reacting to obtain a preassembled shell material; S2, adding a silane solution into the preassembled shell material, then adding a catalyst, performing ultrasonic treatment, and stirring for reaction; And S3, after the reaction is finished, centrifuging the reaction solution, collecting the precipitate, washing and drying to obtain the core-shell structured light conversion agent.
  6. 6. The method according to claim 5, wherein in the step S1, the concentration of the light-converting agent luminescent molecular material solution is 1 mmol/L-30 mmol/L; the volume ratio of the light conversion agent luminescent molecular material solution to the absolute ethyl alcohol is 1:5-1:60; the stirring and mixing speed is 100-1000 r/min, and the time is 5-15 min; the volume ratio of the aromatic silane to the light-converting agent luminescent molecular material solution is 1:1-1:10; the volume ratio of the catalyst to the light-converting agent luminescent molecular material solution is 1:1-1:10; the rotation speed of the stirring reaction is 100-1000 r/min, and the time is 12-48 h.
  7. 7. The method according to claim 5, wherein in step S2, the silane solution is obtained by dissolving silane in ethanol; In the silane solution, the volume ratio of the silane to the ethanol is 1:3-1:20; The silane comprises at least one of aromatic silane and aliphatic silane; Preferably, the aromatic silane comprises at least one of phenyltriethoxysilane, phenyltrimethoxysilane, pyrenyl triethoxysilane, pyrenyl trimethoxysilane, anthryl triethoxysilane, anthryl trimethoxysilane, 4-biphenyltriethoxysilane, 1-naphthyl triethoxysilane, 1-naphthyl trimethoxysilane; Preferably, the aliphatic silane comprises at least one of tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane; Preferably, the silane consists of an aromatic silane and an aliphatic silane; more preferably, the volume ratio of the aliphatic silane to the aromatic silane is 1:4-4:1; In the step S1, the volume ratio of the light-converting agent luminescent molecular material solution to the silane solution is 1:3-1:30; the volume ratio of the catalyst to the silane solution is 1:10-1:100; The amplitude of the ultrasonic wave is 50-99%, the temperature of the ultrasonic wave is-20-10 ℃, and the time of the ultrasonic wave is 0.5-3 h; The stirring reaction time is 12-48 h; in the step S3, the drying temperature is 60-150 ℃ and the drying time is 12-48 h.
  8. 8. The photovoltaic glass light conversion coating solution is characterized by comprising, by mass, 5.1-35 parts of core-shell structure light conversion agent suspension, 5-30 parts of silane, 50-80 parts of solvent II, 1-10 parts of silane coupling agent, 0.1-3 parts of dispersing agent, 0.1-3 parts of curing agent, 0.1-2 parts of light stabilizer and 0.1-2 parts of antioxidant; The core-shell structure light conversion agent suspension is obtained by dissolving 0.1-5 parts of core-shell structure light conversion agent in 5-30 parts of solvent I and performing ultrasonic dispersion; preferably, the ultrasonic power is 150-600W, and the ultrasonic time is 15-60 min; The core-shell structure light conversion agent is the core-shell structure light conversion agent prepared by any one of claims 1 to 4 or the preparation method of any one of claims 5 to 7.
  9. 9. The photovoltaic glass transition light plating solution according to claim 8, wherein the silane comprises at least one of tetraethoxysilane, tetramethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane; The solvent II comprises at least one of deionized water, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethyl acetate, ethylene glycol monomethyl ether, propylene glycol methyl ether and n-hexane; The silane coupling agent comprises at least one of gamma-glycidol ether oxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-mercaptopropyl triethoxy silane and gamma-isocyanatopropyl triethoxy silane, and the dispersing agent comprises at least one of sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, polyethylene glycol octyl phenyl ether, span, tween, polyether modified siloxane and polyvinylpyrrolidone; The curing agent comprises at least one of a siloxane curing agent, an isocyanate curing agent and a platinum catalyzed hydrosilylation curing agent; The light stabilizer comprises at least one of UV123, UV292, UV770, UV3853, UV4050, UV622, UV944 and UV 79; the antioxidants include at least one of MIANOX, MIANOX, 1076, MIANOX AO-80, MIANOX445, MIANOX565, MIANOX 1222.
  10. 10. A method for preparing the photovoltaic glass light conversion coating liquid according to any one of claims 8 to 9, which comprises the following steps: (1) Mixing and stirring the silane, the solvent II and the silane coupling agent according to the formula amount, adjusting the pH to 4-8, adding the dispersing agent, the curing agent, the light stabilizer and the antioxidant according to the formula amount, and stirring and mixing; (2) Adding the core-shell structure light conversion agent suspension, and carrying out ultrasonic and stirring to obtain the photovoltaic glass light conversion coating liquid; in the step (2), the ultrasonic power is 150-600W, the ultrasonic time is 10-60 min, the stirring rotating speed is 500-3000 rpm, and the time is 0.5-4 h.

Description

Core-shell structure light conversion agent, photovoltaic glass light conversion coating liquid and preparation method thereof Technical Field The invention relates to the technical field of photovoltaic packaging, in particular to a core-shell structure light conversion agent, photovoltaic glass light conversion coating liquid and a preparation method thereof. Background About 5% of the energy in the sunlight is distributed in the ultraviolet region (300-400 nm), the photon energy in the wave band is high, free radical reaction and chemical bond breakage in the packaging material are easily caused, and the ageing and yellowing of the packaging adhesive film of the photovoltaic module are caused, so that the light transmittance of the module is reduced, and the output power is attenuated. In addition, ultraviolet irradiation is one of the key factors affecting the long-term stability of crystalline silicon solar cells, perovskite/crystalline silicon tandem solar cells. In the field of photovoltaic packaging and film coating materials, in order to improve the comprehensive utilization rate of solar spectrum and the ultraviolet reliability of components, students and enterprises at home and abroad have tried to convert high-energy ultraviolet photons into low-energy visible photons through a spectrum conversion method so as to improve the absorption and utilization rate of batteries to short-wave band light and inhibit ultraviolet aging. The development of the photovoltaic glass light conversion coating liquid becomes an important direction, and the core of the development is that a spectrum conversion material, namely a light conversion agent, such as organic fluorescent material, rare earth doped inorganic luminescent material, rare earth organic ligand luminescent material, quantum dot luminescent material and the like, is introduced into a photovoltaic glass coating liquid system. The current common process method is to directly mix the light conversion agent molecules into the photovoltaic glass coating liquid to prepare a stable homogeneous liquid system, and then to coat the surface of the ultra-white glass by spraying, roller coating, dip coating and other processes, and then to form a solid film with spectrum conversion function by curing and film forming. However, the light conversion agent has limited stability, and is directly used on the photovoltaic glass film coating, and effective protection is lacking. The light conversion material is easy to be influenced by ultraviolet light and water oxygen to be photo-bleached or chemically degraded to be invalid, so that the further improvement and the practical application of the performance of the photovoltaic glass light conversion coating liquid are restricted. Therefore, development of a light conversion material with high stability is needed to improve the ultraviolet light utilization rate and reliability of the photovoltaic module. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a core-shell structure light conversion agent, photovoltaic glass light conversion coating liquid and a preparation method thereof. According to the invention, by designing the core-shell structure with the inorganic silica shell layer, the light conversion agent molecules are effectively packaged, so that the ultraviolet stability of the light conversion film layer is improved while the high light transmittance is maintained, and the service life of the film coating layer in an outdoor environment is prolonged. The technical scheme of the invention is as follows: The first aspect of the invention provides a core-shell structured light conversion agent, comprising a core layer and a shell layer, The nuclear layer comprises a light conversion agent luminescent molecular material; The shell layer comprises a silica material; the particle size of the core-shell structured light conversion agent is 20-200 nm; the thickness of the shell layer is 10-50% of the particle size of the core-shell structure light conversion agent. Preferably, the core-shell structure light conversion agent can absorb 300-400 nm ultraviolet light and emit 400-800 nm visible light, and the fluorescence quantum yield of the core-shell structure light conversion agent is 70-100%. Preferably, the light conversion agent luminescent molecular material comprises at least one of an organic fluorescent material, a rare earth doped inorganic luminescent material, a rare earth organic ligand luminescent material and a quantum dot luminescent material. Preferably, the organic fluorescent material comprises at least one of benzotriazole fluorescent material, coumarin fluorescent material, perylene diimide fluorescent material, rhodamine fluorescent material, pyrene fluorescent material, benzothiazole fluorescent material, triphenylamine fluorescent material, carbazole fluorescent material, benzophenone fluorescent material, salicylate fluorescent material, substituted acrylon