CN111641383B - Preparation method and application of amorphous silicon flat-plate type fluorescent solar collector - Google Patents
Preparation method and application of amorphous silicon flat-plate type fluorescent solar collector Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/20—Optical components
- H02S40/22—Light-reflecting or light-concentrating means
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
- C09K11/7751—Vanadates; Chromates; Molybdates; Tungstates
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0543—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the refractive type, e.g. lenses
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Abstract
The invention discloses a preparation method and application of an amorphous silicon flat-plate type fluorescent solar light collector based on long afterglow micron particles, which is characterized in that the preparation method comprises the following steps: compounding the luminescence center powder and the thiol-ene copolymer to obtain an amorphous silicon flat-plate type fluorescent solar collector, wherein an amorphous silicon solar panel with a conductive metal PCB (printed Circuit Board) is adhered to the periphery of the amorphous silicon flat-plate type fluorescent solar collector, a top antireflection layer is arranged on the upper surface of the amorphous silicon flat-plate type fluorescent solar collector, and a bottom metal reflection layer is arranged on the lower surface of the amorphous silicon flat-plate type fluorescent solar collector to obtain a photovoltaic power generation device; the flat-plate type optical waveguide photoelectric conversion device has the advantages of high photoelectric conversion efficiency and long luminescence service life, and can effectively reduce the surface reflection loss of incident light and the transmission loss in the flat-plate type optical waveguide when being applied to the photovoltaic power generation device, thereby obviously improving the optical collection efficiency and the photoelectric conversion efficiency under the condition of weak illumination.
Description
Technical Field
The invention relates to a fluorescent solar light collector, in particular to a preparation method and application of an amorphous silicon flat-plate type fluorescent solar light collector based on long-afterglow micron particles.
Background
The rapid development of the global photovoltaic industry, the market prospect of the amorphous silicon solar cell is good, the technology is mature day by day, and the photoelectric conversion efficiency and the stability of the amorphous silicon solar cell are continuously improved. On one hand, compared with the monocrystalline silicon solar cell, the amorphous silicon solar cell has higher optical absorption coefficient (one order of magnitude higher) in a visible light wave band, so that sunlight can be effectively absorbed by adopting a very thin amorphous silicon film, and the material cost of power generation is greatly reduced; on the other hand, amorphous silicon has a larger forbidden band width than single crystal silicon, and therefore the open circuit voltage of an amorphous silicon solar cell is higher. Also, since amorphous silicon does not have the periodic atomic arrangement required for crystalline silicon, it does not take into account the problem of lattice mismatch between the material and the substrate that must be considered for preparing the crystal. Currently, the best spectral response band of commercial amorphous silicon cells is in the 400-700nm band.
The photoelectric conversion efficiency of the traditional amorphous silicon photovoltaic power generation device is greatly influenced by the sunshine condition, and particularly under the weak light conditions of night or cloudy days, rainy days and the like, the power generation efficiency of the amorphous silicon photovoltaic component is extremely low. In fact, the amorphous silicon photovoltaic device hardly generates electricity under weak illumination conditions such as nights, cloudy days, rainy days and the like, and a grid-connected inverter in the amorphous silicon photovoltaic power generation device is in a standby state and continuously consumes a part of electricity. Therefore, under low-light conditions such as nighttime, cloudy days, and rainy days, the average photoelectric conversion efficiency of a commercial amorphous silicon photovoltaic module is almost 0. On the other hand, under normal sunshine conditions, in order to improve the photoelectric conversion efficiency of the amorphous silicon photovoltaic module, scientists design an amorphous silicon concentrating photovoltaic power generation device based on a fresnel concentrating mirror. At present, commercial photovoltaic light-gathering components generally use a geometric light-gathering principle, and adopt a series of reflectors and convex lens arrays to gather sunlight with a larger area to the surface of an amorphous silicon photovoltaic cell with a small area, so that the number of incident photons in a unit area and the photoelectric conversion efficiency of a photovoltaic device in the unit area are improved to a certain extent. However, current amorphous silicon concentrated photovoltaic power generation devices also face significant technical challenges. On one hand, the light-gathering type amorphous silicon photovoltaic power generation device has obvious thermal effect, so that the average service life of a photovoltaic device is short, and the unit power generation cost is high; on the other hand, because the incident angle of sunlight changes every moment, the focus of the convex lens array in the traditional amorphous silicon photovoltaic collector shifts continuously, in order to ensure that photons in the photovoltaic collector reach a photon collecting area of a solar cell, a set of sun tracking system is required to track the incident sunlight in real time, and the unit power generation cost of the concentrating photovoltaic device is greatly improved by additional driving control devices such as a motor. In a word, the use of a complex cooling system and a very expensive day tracking system greatly increases the unit power generation cost and the laying site area of the traditional concentrating amorphous silicon photovoltaic device.
Flat-Plate fluorescent Solar collectors (Flat-Plate Luminescent Solar collectors) are a new type of Solar photon collectors, known as "optical traps" for Solar cells, and have recently been widely paid attention by the industry and scientific research academia at home and abroad. The currently reported luminescent center materials in flat-plate fluorescent solar collectors generally use semiconductor quantum dots (as described in patent publications 109326672A, 110021676A, 109904270A, etc.). Because of poor stability of part of quantum dots, the quantum dots are easy to decompose under illumination conditions (such as perovskite quantum dots and the like), the photoluminescence quantum yield of part of quantum dots is low, the light collecting efficiency is low (such as carbon quantum dots and the like), the toxicity of part of quantum dots is strong, and the preparation process is complex (such as cadmium sulfide, cadmium telluride, copper indium selenium, lead sulfide and the like). The existing flat plate type light collector using quantum dots as a luminescent center material has the technical problems of low light collecting efficiency, poor working stability, low photon transport efficiency and the like. On the other hand, because the fluorescence lifetime of the quantum dots is short (the fluorescence lifetime of almost all known quantum dot band gap radiation luminescence is less than 1 millisecond), under the weak illumination conditions of night or heavy fog, cloudy days, rainy days and the like, the power generation efficiency of the corresponding solar cell is almost 0 for the existing fluorescent solar light collector based on multiple quantum dots, which severely limits the development of the flat plate type light-collecting photovoltaic device and the improvement of the overall light collecting performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a long-afterglow micron particle-based amorphous silicon flat-plate type fluorescent solar collector with high photoelectric conversion efficiency and long luminescence service life, which can effectively reduce the surface reflection loss of incident light and the transmission loss in a flat-plate type optical waveguide when being applied to a photovoltaic power generation device, thereby obviously improving the optical collection efficiency and the photoelectric conversion efficiency under the condition of weak illumination.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing an amorphous silicon flat plate type fluorescent solar light collector based on long afterglow micron particles comprises the following steps:
(1) Preparation of chromium ion and europium ion co-doped strontium aluminum germanate luminescence center material
High-purity raw materials of strontium oxide, aluminum oxide, germanium oxide, chromium oxide and europium oxide powder are mixed according to the molar ratio of Sr: al: ge: cr: eu =1:1:2:0.05:0-0.20, slowly adding deionized water, absolute ethyl alcohol and tetraethyl orthosilicate according to the volume ratio of 3:6:1 to form a mixed precursor solution; then, dropwise adding a dilute nitric acid solution into the mixed precursor solution until the oxide solid mixed powder is completely dissolved; placing the mixed solution into a water-bath heating reaction kettle, controlling the water-bath heating temperature to be 60-80 ℃ and continuously stirring, and controlling the water-bath heating time to be 24-48 hours until the mixed solution in the reaction kettle forms transparent and uniform gel; taking out the gel, placing the gel in a vacuum drying oven, and controlling the drying temperature to be 100-150 ℃ until the redundant ethanol and deionized water are completely evaporated; then placing the dried gel powder in a vacuum sintering furnace, controlling the sintering temperature to be 1200-1800 ℃, sintering for 4-8 hours, and finally grinding to obtain luminescent center powder with the average particle size of 0.8-1.2 microns;
(2) Preparation of amorphous silicon flat-plate type fluorescent solar collector
Placing 10mg of luminescence center powder in 5ml of n-hexane solution with the concentration of 2mg/ml, carrying out ultrasonic oscillation treatment for 5-10min, and continuously stirring until the luminescence center powder is uniformly dispersed in the n-hexane solution; adding a normal hexane mixed solution containing luminescence center powder into the precursor solution, carrying out ultrasonic oscillation treatment for 5-10min, and continuously stirring until the luminescence center powder is uniformly mixed in the precursor solution to obtain a precursor mixed solution; pouring the precursor mixed solution into a glass mold, then placing a glass grinding tool in a vacuum environment for 30-60min, removing bubbles dissolved in the precursor mixed solution, heating the precursor mixed solution in a water bath at 70 ℃ for 30min at constant temperature, then curing by ultraviolet light irradiation, wherein the irradiation power of an ultraviolet light lamp is 100W, the central wavelength is 365nm, the curing time is 10-15s, and finally, after curing and demolding, performing a polishing process to treat the surface and the end face to obtain the amorphous silicon flat plate type fluorescent solar collector based on the long afterglow micron particles.
The precursor solution in the step (2) is prepared by mixing a photoinitiator, an allyl monomer and a thiol monomer according to the weight ratio of 0.05g:4-6ml:4-6ml of the mixture; the mixing ratio of the luminescence center powder to the photoinitiator is 200ul-800ul:0.05g.
The photoinitiator is 1-hydroxycyclohexyl phenyl ketone or photoinitiator-184 (Irgacure-184), the allyl monomer is triallyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triketone, and the thiol monomer is pentaerythritol tetra-3-mercaptopropionate.
The amorphous silicon flat plate type fluorescent solar light collector based on the long afterglow micron particles is applied to the aspect of preparing an amorphous silicon flat plate type light-collecting photovoltaic power generation device.
The amorphous silicon flat plate type light-collecting photovoltaic power generation device comprises an amorphous silicon flat plate type fluorescent solar light collector, commercial amorphous silicon solar panels are adhered to the periphery of the amorphous silicon flat plate type fluorescent solar light collector, top antireflection layers are arranged on the upper surface of the amorphous silicon flat plate type fluorescent solar light collector and the upper surface of the amorphous silicon solar panels, bottom metal reflecting layers are arranged on the lower surface of the amorphous silicon flat plate type fluorescent solar light collector and the lower surface of the amorphous silicon solar panels, and a PCB (printed circuit board) plated with conductive metal and used for supporting the amorphous silicon solar panels is fixedly arranged on the outer side surfaces of the amorphous silicon solar panels.
The working principle is as follows: when sunlight is incident to the surface of the device, the reflection of the sunlight can be effectively reduced by the structural design of the top antireflection layer, so that more solar photons enter the flat-plate type fluorescent solar collector in the device. The luminescence center in the flat-plate fluorescent solar collector is based on chromium ion and europium ion co-doped strontium aluminum germanate powder, and after sunlight is absorbed, the luminescence center generates characteristic fluorescence emission with the central wavelength of 613nm through a photoluminescence process. Since the refractive index of a slab-type polymer thiol-ene copolymer (OSTE) optical waveguide is about 1.7-1.9, which is much larger than that of air (about 1.0). When the luminescent center material emits characteristic fluorescence, most photons are limited in the flat-plate type fluorescent solar light collector due to the total reflection process of the fluorescence in the transmission process, and after part of emitted photons are transmitted from the lower layer, the photons return to the amorphous silicon again due to the reflection effect of the metal filmThe flat-plate fluorescent solar collector. After a plurality of total emission processes in the amorphous silicon flat type fluorescent solar collector, the surface of the commercial amorphous silicon solar panel is finally reached. Because the luminescent fluorescence of the chromium ion and europium ion co-doped strontium aluminum germanate powder has long service life, when the photovoltaic power generation device is under the condition of weak light irradiation, long afterglow fluorescence is continuously generated and is continuously gathered on the surface of the commercial amorphous silicon solar panel through the total reflection process, so that the stable photoelectron transport efficiency and the relatively high photoelectric conversion efficiency of the solar panel under the condition of weak light irradiation are ensured. On the other hand, the optimal spectral response band of commercial amorphous silicon cells is mainly centered at the 600-700nm band. The spectral response of a solar cell refers to the number of carriers that can be generated on average per photon when light of a certain wavelength is irradiated on the surface of the cell, and reflects the ability of the solar cell to convert the light energy of incident light of different wave bands into electric energy. Eu ions in the flat-plate type fluorescent solar light collecting device are in the same atomic energy level 5 D 0 To 7 F 2 The characteristic emission center wavelength of the amorphous silicon solar cell is 613nm, and the optimal spectral response band of the commercial amorphous silicon solar cell is completely matched.
Compared with the prior art, the invention has the advantages that:
(1) According to the amorphous silicon flat-plate type fluorescent solar light collector based on the long-afterglow micron particles, the chromium ion and europium ion co-doped strontium aluminum germanate is used as a luminescence center, on one hand, photoluminescence conversion efficiency of the traditional quantum dots is greatly improved, on the other hand, large Stokes displacement exists between a characteristic absorption peak and an emission peak of the long-afterglow micron particles, the spectrum reabsorption problem of the traditional quantum dots can be effectively avoided, so that photon transport efficiency of the flat-plate type fluorescent solar light collector is greatly improved, and finally high light collection efficiency is obtained.
(2) According to the invention, metal cations are dispersed by utilizing the hydrolysis process of tetraethyl orthosilicate, and compared with the traditional solid micro-powder high-temperature sintering preparation method, the agglomeration of the metal cations is effectively avoided according to the restrictive crystallization principle, so that the long-afterglow micron particles prepared by the invention have uniform components and sizes and good consistency of luminescence property. In addition, the radius of the strontium ions is about 0.118 nm, which is equivalent to the ion radius of rare earth doped ions (europium ions, the ion radius is between 0.095 nm and 0.117 nm), so that the substitution doping is easy to realize, the synergistic effect between the strontium ions and the europium ions is enhanced, and the device performances such as the fluorescence lifetime and the like are greatly improved.
(3) The chromium ion and europium ion co-doped strontium aluminum germanate and polymer matrix (OSTE) have high intersolubility, the fluorescent life can be greatly prolonged under the synergistic effect of the chromium ion and europium ion co-doped strontium aluminum germanate and the polymer matrix (OSTE), and the long afterglow micron particles can provide continuous photons to be gathered on the surface of an amorphous silicon photovoltaic panel under the continuous weak illumination condition, so that the photoelectric conversion efficiency of the commercial amorphous silicon solar cell under the weak illumination condition is improved.
(4) The photovoltaic power generation device based on the micron-size long-afterglow luminescence center can effectively reduce the surface reflection loss of incident light and the transmission loss in the flat-plate optical waveguide, thereby obviously improving the optical collection efficiency of the flat-plate light-collecting amorphous silicon photovoltaic device under the condition of weak illumination and the photoelectric conversion efficiency of a commercial amorphous silicon solar cell.
(5) The spectrum matching degree is one of the important factors influencing the power generation efficiency of the solar cell, and the accuracy of the power test result is also influenced. The peak value of the optimal spectral response band of the commercial amorphous silicon cell is 600-700nm. The characteristic fluorescence luminescence central peak position in the flat plate type light collecting device designed by the invention is 613nm. The matching degree of the flat-plate type fluorescence light collecting device and the amorphous silicon solar cell is high.
In conclusion, the preparation method and the application of the amorphous silicon flat plate type fluorescent solar collector based on the long afterglow micron particles have the advantages that the size of the prepared chromium ion and europium ion co-doped strontium aluminum germanate luminescence center particles is in the micron order, and the fluorescence life is as long as several hours or even longer; further, the synergy of the chromium ion and europium ion co-doped strontium aluminum germanate luminescence center and a high refractive index polymer matrix (OSTE) greatly improves the light collection efficiency, so that the further prepared flat-plate type light collection photovoltaic power generation device has a larger optical absorption cross section and higher photoluminescence fluorescence conversion efficiency, is green and environment-friendly, has low cost, has high light collection efficiency, can continuously generate power under the conditions of weak illumination such as night or cloudy days and rainy days, and greatly widens the working time of the traditional flat-plate type light collection photovoltaic device.
Drawings
FIG. 1 shows Cr: eu molar ratio =0.05: (0.05,0.10,0.15,0.20) based on photoluminescence intensity spectra of chromium and europium ion co-doped strontium aluminum germanate luminescence centers;
fig. 2 is a change rule of the luminous intensity of the OSTE panel based on the chromium ion and europium ion co-doped strontium aluminum germanate fluorescent powder with time;
FIG. 3 is a physical diagram of a flat fluorescent solar collector based on long afterglow microparticles prepared in the present invention under AM1.5 illumination;
fig. 4 is a schematic structural diagram of a light-harvesting amorphous silicon photovoltaic cell power generation device based on chromium ion and europium ion co-doped strontium aluminum germanate in an embodiment of the present invention, where the drawings are labeled as follows: the solar cell comprises a 1-amorphous silicon flat plate type fluorescent solar collector, a 2-amorphous silicon solar cell panel, a 3-top antireflection layer, a 4-bottom metal reflecting layer and a 5-PCB.
Detailed Description
The invention is described in further detail below with reference to the following examples of the drawings.
Detailed description of the preferred embodiment
A preparation method of an amorphous silicon flat plate type fluorescent solar light collector 1 based on long afterglow micron particles comprises the following steps:
(1) Preparation of chromium ion and europium ion co-doped strontium aluminum germanate luminescence center material
High-purity raw materials of strontium oxide, aluminum oxide, germanium oxide, chromium oxide and europium oxide powder are mixed according to the mol ratio of Sr: al: ge: cr: eu =1:1:2:0.05:0-0.20, slowly adding deionized water, absolute ethyl alcohol and tetraethyl orthosilicate according to the volume ratio of 3:6:1 to form a mixed precursor solution; then, dropwise adding a dilute nitric acid solution into the mixed precursor solution until the oxide solid mixed powder is completely dissolved; placing the mixed solution into a water-bath heating reaction kettle, controlling the water-bath heating temperature to be 60-80 ℃, continuously stirring, and controlling the water-bath heating time to be 24-48 hours until the mixed solution in the reaction kettle forms transparent and uniform gel; taking out the gel, placing the gel in a vacuum drying oven, and controlling the drying temperature to be 100-150 ℃ until the redundant ethanol and deionized water are completely evaporated; then placing the dried gel powder in a vacuum sintering furnace, controlling the sintering temperature to be 1200-1800 ℃, sintering for 4-8 hours, and finally grinding to obtain luminescent center powder with the average particle size of 0.8-1.2 microns;
FIG. 1 shows Cr: eu molar ratio =0.05: (0.05,0.10,0.15,0.20), based on photoluminescence intensity spectrum of luminescent centers of chromium ions and europium ions co-doped strontium aluminum germanate at different wavelengths. Wherein, sr: al: ge: the molar ratio of Cr is fixed at 1:1:2:0.05. as the Eu concentration is gradually increased, the characteristic luminescence intensity of Eu ion at 613nm is gradually increased from 0 to 0.15, which means that the density of luminescence centers is gradually increased, and thus the photoluminescence intensity is gradually increased. When the Eu content is continuously increased and the characteristic luminescence of Eu ions at 613nm is slightly weakened from 0.15-0.2, the concentration quenching effect of rare earth europium ions is dominant at the moment;
(2) Preparation of amorphous silicon flat-plate type fluorescent solar light collector 1
Placing 10mg of luminescence center powder in 5ml of n-hexane solution with the concentration of 2mg/ml, carrying out ultrasonic oscillation treatment for 5-10min, and continuously stirring until the luminescence center powder is uniformly dispersed in the n-hexane solution; adding a normal hexane mixed solution containing luminescence center powder into the precursor solution, carrying out ultrasonic oscillation treatment for 5-10min, and continuously stirring until the luminescence center powder is uniformly mixed in the precursor solution to obtain a precursor mixed solution; pouring the precursor mixed solution into a glass mold, then placing a glass grinding tool in a vacuum environment for 30-60min, removing bubbles dissolved in the precursor mixed solution, heating the precursor mixed solution in a water bath at 70 ℃ for 30min at constant temperature, then curing by adopting ultraviolet light irradiation, wherein the irradiation power of an ultraviolet light lamp is 100W, the central wavelength is 365nm, the irradiation time is 10-15s, and finally, performing a polishing process after curing and demolding to obtain the amorphous silicon flat plate type afterglow solar light collector 1 based on long micron particles. Wherein the precursor solution is prepared by mixing a photoinitiator, an allyl monomer and a thiol monomer according to the weight ratio of 0.05g:4-6ml:4-6ml of the raw materials are mixed together; the mixing ratio of the luminous center powder to the photoinitiator is 200ul-800ul:0.05g.
In this embodiment, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone or photoinitiator-184 (Irgacure-184), the allyl monomer is triallyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, and the thiol monomer is pentaerythritol tetra-3-mercaptopropionate.
The polymer matrix is selected from thiol-ene copolymers (OSTE). Compared with common polymer matrix materials such as polymethyl methacrylate (PMMA) or Polydimethylsiloxane (PDMS), the dispersion of the long-afterglow phosphor material such as the thiol-ene copolymer (OSTE) with chromium ions and europium ions co-doped with strontium aluminum germanate is the best. The thiol-ene copolymer (OSTE) is used as a luminescent center material matrix with micron scale, so that the problems of characteristic fluorescence quenching or low photon transport efficiency and the like caused by luminescent center clusters can be effectively avoided.
Fig. 2 shows the fluorescence lifetime of the luminescence center based on co-doping of chromium ions and europium ions with strontium aluminum germanate. The black line circle is the change rule of the luminous intensity of the chromium ion and europium ion co-doped strontium aluminum germanate fluorescent powder along with time after the fluorescent powder is irradiated by standard AM1.5 sun light for 10 minutes; the gray line square is the change rule of the luminous intensity of an OSTE flat plate based on chromium ion and europium ion co-doped strontium aluminum germanate fluorescent powder, namely an amorphous silicon flat plate type fluorescent solar light collector 1 based on long afterglow micron particles along with time after the gray line square is irradiated by standard AM1.5 sun for 10 minutes. As can be seen from FIG. 2, the fluorescent powder in the OSTE matrix has a longer fluorescence lifetime.
FIG. 3 is a physical diagram of the long afterglow micron particle based amorphous silicon flat fluorescent solar collector 1 prepared in the present invention under the irradiation of AM 1.5. According to experimental measurement, the amorphous silicon flat plate type fluorescent solar light collector 1 based on the long afterglow micron particles with the size of 10cm × 0.5cm has the highest light collecting efficiency of 9.5 percent under the standard AM1.5 sun light. On the one hand, the luminescence stability of the luminescence center material is increased due to the passivation of the OSTE host. Germanium ions replace aluminum ions to occupy the position of a distorted octahedron, due to charge imbalance, defects in an OSTE matrix capture electrons together with chromium ions, and the fluorescence life is further prolonged through non-radiative recombination energy co-transfer and other mechanisms; on the other hand, the OSTE matrix provides a larger optical absorption cross-section compared to other crystal field environments, resulting in a slight increase in the photoluminescence efficiency.
Detailed description of the invention
A flat plate type light collecting photovoltaic power generation device is disclosed, as shown in FIG. 4, and comprises an amorphous silicon flat plate type fluorescent solar light collector 1 based on long afterglow micron particles prepared in the first embodiment, wherein amorphous silicon solar panels 2 are adhered around the amorphous silicon flat plate type fluorescent solar light collector 1, a top antireflection layer 3 is arranged on the upper surface of the amorphous silicon flat plate type fluorescent solar light collector 1 and the upper surface of the amorphous silicon solar panels 2, a bottom metal reflecting layer 4 is arranged on the lower surface of the amorphous silicon flat plate type fluorescent solar light collector 1 and the lower surface of the amorphous silicon solar panels 2, and a PCB 5 plated with conductive metal and used for supporting the amorphous silicon solar panels 2 is fixedly arranged on the outer side surfaces of the amorphous silicon solar panels 2.
In the specific embodiment, the top anti-reflection layer 3 adopts polystyrene spheres with the diameter of 100-300nm as a mask, and the top anti-reflection layer 3 is obtained by adopting a plasma etching technology and a nano-imprinting process; the bottom metal reflecting layer 4 is deposited with a metal film with the thickness of 400nm-1um by adopting the traditional thermal evaporation, electron beam evaporation or magnetron sputtering method; the metal film is any one of an aluminum film, a gold film, and a silver film. Installation of the amorphous silicon solar panel 2: and finally, the amorphous silicon solar panel 2 and the PCB 5 are integrally arranged around the flat-plate type fluorescent solar collector to obtain the flat-plate type light-collecting photovoltaic power generation device based on the chromium ion and europium ion co-doped strontium aluminum germanate under the weak illumination condition.
According to the flat-plate light-collecting photovoltaic power generation device based on the chromium ion and europium ion co-doped strontium aluminum germanate under the weak illumination condition, the long-afterglow luminescent material is introduced to serve as a luminescent center, so that the photoelectric conversion efficiency of the traditional flat-plate light-collecting photovoltaic power generation device under the weak illumination condition can be effectively improved. Meanwhile, the design of the surface top antireflection layer 3 can effectively reduce the surface reflection loss of photons in the incident solar spectrum and increase the number of incident photons in unit area. Through the design of the bottom metal reflecting layer 4, the escape rate of photons can be effectively reduced, and the light collecting efficiency of the prototype device is improved by more than 5%. The device structure is shown in fig. 4. More importantly, in a flat-plate type photovoltaic light-collecting device, micron-sized long afterglow chromium ions and europium ions are co-doped with strontium aluminum germanate powder to replace the existing reported quantum dots, so that the light-collecting efficiency under the condition of continuous weak illumination can be greatly improved. Meanwhile, under normal illumination conditions, due to the synergistic effect of the luminescent center material (long afterglow chromium ions and europium ions co-doped strontium aluminum germanate) and the polymer matrix (OSTE), the light collection efficiency is greatly improved.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (5)
1. A method for preparing an amorphous silicon flat plate type fluorescent solar light collector based on long afterglow micron particles is characterized by comprising the following steps:
(1) Preparation of chromium ion and europium ion co-doped strontium aluminum germanate luminescence center material
High-purity raw materials of strontium oxide, aluminum oxide, germanium oxide, chromium oxide and europium oxide powder are mixed according to the molar ratio of Sr: al: ge: cr: eu =1:1:2:0.05:0-0.20, slowly adding deionized water, absolute ethyl alcohol and tetraethyl orthosilicate according to the volume ratio of 3:6:1 to form a mixed precursor solution; then, dropwise adding a dilute nitric acid solution into the mixed precursor solution until the oxide solid mixed powder is completely dissolved; placing the mixed solution into a water-bath heating reaction kettle, controlling the water-bath heating temperature to be 60-80 ℃ and continuously stirring, and controlling the water-bath heating time to be 24-48 hours until the mixed solution in the reaction kettle forms transparent and uniform gel; taking out the gel, placing the gel in a vacuum drying oven, and controlling the drying temperature to be 100-150 ℃ until the redundant ethanol and deionized water are completely evaporated; then placing the dried gel powder in a vacuum sintering furnace, controlling the sintering temperature to be 1200-1800 ℃, sintering for 4-8 hours, and finally grinding to obtain luminescent center powder with the average particle size of 0.8-1.2 microns;
(2) Preparation of amorphous silicon flat-plate type fluorescent solar collector
Placing 10mg of luminescence center powder in 5ml of n-hexane solution with the concentration of 2mg/ml, carrying out ultrasonic oscillation treatment for 5-10min, and continuously stirring until the luminescence center powder is uniformly dispersed in the n-hexane solution; adding a normal hexane mixed solution containing luminescence center powder into the precursor solution, carrying out ultrasonic oscillation treatment for 5-10min, and continuously stirring until the luminescence center powder is uniformly mixed in the precursor solution to obtain a precursor mixed solution; pouring the precursor mixed solution into a glass mold, then placing a glass grinding tool in a vacuum environment for 30-60min, removing bubbles dissolved in the precursor mixed solution, then heating the precursor mixed solution in a water bath at 70 ℃ for 30min at constant temperature, then curing by adopting ultraviolet light irradiation, wherein the irradiation power of an ultraviolet light lamp is 100W, the central wavelength is 365nm, the irradiation time is 10-15s, and finally, after curing and demolding, performing a polishing process to obtain the amorphous silicon flat afterglow fluorescent solar collector based on the long micrometer particles.
2. The method for preparing the amorphous silicon flat plate type fluorescent solar light collector based on the long afterglow micron particles as claimed in claim 1, wherein the method comprises the following steps: the precursor solution in the step (2) is prepared by mixing a photoinitiator, an allyl monomer and a thiol monomer according to the weight ratio of 0.05g:4-6ml:4-6ml of the mixture; the mixing ratio of the luminescence center powder to the photoinitiator is 200ul-800ul:0.05g.
3. The method for preparing the amorphous silicon flat plate type fluorescent solar light collector based on the long afterglow micron particles as claimed in claim 2, characterized in that: the photoinitiator is 1-hydroxycyclohexyl phenyl ketone or photoinitiator-184 (Irgacure-184), the allyl monomer is triallyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triketone, and the thiol monomer is pentaerythritol tetra-3-mercaptopropionate.
4. Use of the long afterglow micron particle based amorphous silicon flat plate type fluorescent solar collector of any one of claims 1-3 in the preparation of amorphous silicon flat plate type light collecting photovoltaic power generation devices.
5. The use of the long persistence microparticle based amorphous silicon slab fluorescence solar collector as claimed in claim 4, wherein: the amorphous silicon flat plate type light-collecting photovoltaic power generation device comprises an amorphous silicon flat plate type fluorescent solar collector, wherein an amorphous silicon solar panel is adhered to the periphery of the amorphous silicon flat plate type fluorescent solar collector, a top antireflection layer is arranged on the upper surface of the amorphous silicon flat plate type fluorescent solar collector and the upper surface of the amorphous silicon solar panel, a bottom metal reflection layer is arranged on the lower surface of the amorphous silicon flat plate type fluorescent solar collector and the lower surface of the amorphous silicon solar panel, and a PCB (printed circuit board) plated with conductive metal and used for supporting the amorphous silicon solar panel is fixedly arranged on the outer side surface of the amorphous silicon solar panel.
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