CN111478659A - Preparation method and application of polycrystalline silicon flat plate type fluorescent solar light collector based on long afterglow micron particles - Google Patents
Preparation method and application of polycrystalline silicon flat plate type fluorescent solar light collector based on long afterglow micron particles Download PDFInfo
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- CN111478659A CN111478659A CN202010300820.8A CN202010300820A CN111478659A CN 111478659 A CN111478659 A CN 111478659A CN 202010300820 A CN202010300820 A CN 202010300820A CN 111478659 A CN111478659 A CN 111478659A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
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- 239000002243 precursor Substances 0.000 claims description 27
- -1 terbium ion Chemical class 0.000 claims description 27
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims description 3
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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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
-
- 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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- 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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- 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
- H01L31/0543—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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- 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
- H01L31/0547—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention discloses a preparation method and application of a flat-plate type fluorescent solar 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 a polycrystalline silicon flat-plate type fluorescent solar collector, wherein a polycrystalline silicon solar cell panel with a conductive metal PCB (printed Circuit Board) is adhered to the periphery of the polycrystalline silicon flat-plate type fluorescent solar collector, a top antireflection layer is arranged on the upper surface of the polycrystalline silicon flat-plate type fluorescent solar collector, and a bottom metal reflecting layer is arranged on the lower surface of the polycrystalline 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 a flat-plate type fluorescent solar light collector based on long-afterglow micro-particles.
Background
The polycrystalline silicon solar cell has the advantages of rich production raw materials, low cost, high conversion efficiency, good stability and the like, is favored by the photovoltaic market, and currently occupies the main share of the solar cell market. The conversion efficiency of the polycrystalline silicon solar cell is generally between 17% and 18%, and is slightly lower than that of a monocrystalline silicon solar cell, but compared with the monocrystalline silicon solar cell, the polycrystalline silicon solar cell does not have the problem of obvious efficiency decline, is easy to prepare on a cheap substrate material, has the cost far lower than that of the monocrystalline silicon solar cell, and has the efficiency higher than that of an amorphous silicon thin film solar cell. The optimal spectral response band of commercial polysilicon cells is mainly centered at the 500-600nm band.
The photoelectric conversion efficiency of the traditional polycrystalline silicon photovoltaic power generation device is greatly influenced by the sunshine condition, and particularly under the weak illumination conditions of night or cloudy days, rainy days and the like, the power generation efficiency of a polycrystalline silicon photovoltaic module is extremely low. In fact, because the polycrystalline silicon photovoltaic device hardly generates electricity under weak illumination conditions such as nights, cloudy days, rainy days and the like, a grid-connected inverter in the polycrystalline silicon photovoltaic device is in a standby state, and a part of electric quantity is continuously consumed. Therefore, under low-light conditions such as nighttime, cloudy days, rainy days, and the like, the average photoelectric conversion efficiency of commercial polycrystalline silicon photovoltaic modules is almost 0. On the other hand, under normal sunshine conditions, in order to improve the photoelectric conversion efficiency of the polycrystalline silicon photovoltaic module, scientists design a polycrystalline 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 on the surface of a small-area polycrystalline silicon photovoltaic cell, 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 polysilicon concentrated photovoltaic power generation devices also face significant technical challenges. On one hand, the concentrating polycrystalline 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 polycrystalline 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 an extra motor and other drive control devices greatly improve the unit power generation cost of the concentrating photovoltaic device. 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 polycrystalline silicon photovoltaic device.
The Flat-Plate fluorescent Solar collector (Flat-Plate L fluorescent Solar collectors) is a novel Solar photon collector, is known as a "light catcher" of Solar cells, and has recently received wide attention from the industry and scientific research academies at home and abroad, the luminescent center materials in the Flat-Plate fluorescent Solar collectors reported at present generally adopt semiconductor quantum dots (as disclosed in patent publications: 109326672A, 110021676A, 109904270a and the like), are easily decomposed under the illumination condition (such as perovskite quantum dots and the like), have low photoluminescence quantum yield of partial quantum dots, low light collection efficiency (such as carbon quantum dots and the like), have strong toxicity of partial quantum dots, have complex preparation process (such as cadmium telluride, cadmium sulfide, copper indium selenium, lead sulfide and the like), and the conventional Flat-Plate collector using the quantum dots as the luminescent center materials has the technical problems of low quantum efficiency, poor work stability, low photon transport efficiency and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a flat polysilicon fluorescent solar collector based on long-afterglow microparticles, which has high photoelectric conversion efficiency and long luminescence life, and can effectively reduce the surface reflection loss of incident light and the transmission loss in a flat 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 preparation method of a flat-plate type fluorescent solar collector based on long-afterglow micron particles comprises the following steps:
(1) preparation of chromium ion and terbium ion co-doped zinc aluminum germanate luminescence center material
High-purity raw materials of zinc oxide, aluminum oxide, germanium oxide, chromium oxide and terbium oxide powder are mixed according to the molar ratio of Zn: al: ge: cr: tb = 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 box, 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 polycrystalline silicon flat-plate type fluorescent solar light 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 long afterglow micron particle-based polycrystalline silicon flat-plate type fluorescent solar collector.
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 0.05 g: 4-6 ml: 4-6ml of the mixture; the mixing ratio of the luminescence center powder to the photoinitiator is 200ul-800 ul: 0.05 g.
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 polycrystalline silicon flat plate type fluorescent solar light collector based on the long afterglow micron particles is applied to the preparation of a polycrystalline silicon flat plate type light-collecting photovoltaic power generation device.
The flat type polycrystalline silicon light-collecting photovoltaic power generation device comprises a flat type polycrystalline silicon fluorescent solar collector, commercial polycrystalline silicon solar panels are adhered to the periphery of the flat type polycrystalline silicon fluorescent solar collector, top antireflection layers are arranged on the upper surface of the flat type polycrystalline silicon fluorescent solar collector and the upper surface of each polycrystalline silicon solar panel, bottom metal reflecting layers are arranged on the lower surface of the flat type polycrystalline silicon fluorescent solar collector and the lower surface of each polycrystalline silicon solar panel, and a PCB (printed circuit board) which is used for supporting the polycrystalline silicon solar panels and is plated with conductive metal is fixedly arranged on the outer side surfaces of the polycrystalline silicon solar panels.
The working principle is as follows: when the sunlight is incident toWhen the surface of the device is used, the reflection of sunlight can be effectively reduced by the structural design of the top anti-reflection 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 light collector is based on chromium ion and terbium ion co-doped zinc aluminum germanate powder, and after sunlight is absorbed, characteristic fluorescence emission with the central wavelength of 547nm is generated 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 polycrystalline silicon flat-plate type fluorescent solar light collector again due to the reflection effect of the metal film. After a plurality of total emission processes in the polycrystalline silicon flat plate type fluorescent solar collector, the surface of the commercial polycrystalline silicon solar panel is finally achieved. Because the luminescent fluorescence of the chromium ion and terbium ion co-doped zinc 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 polycrystalline 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 the commercial polysilicon cell is in the visible light band, and is mainly concentrated in the 500-600nm 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. Tb ions in flat-plate fluorescent solar light collector are in atomic-like energy level5D4To7F5Has a characteristic emission center wavelength of 547nm, and completely matches the optimal spectral response band of commercial polycrystalline silicon solar cells.
Compared with the prior art, the invention has the advantages that:
(1) according to the flat-plate type polycrystalline silicon fluorescent solar light collector based on the long-afterglow micron particles, the chromium ion and terbium ion co-doped zinc aluminum germanate is used as a luminescence center, on one hand, the photoluminescence conversion efficiency of the traditional quantum dots is greatly improved, on the other hand, large Stokes displacement exists between the characteristic absorption peak and the emission peak of the long-afterglow micron particles, the spectrum reabsorption problem of the traditional quantum dots can be effectively avoided, so that the 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 are uniform in component and size and good in consistency of luminous performance. In addition, the radius of zinc ions is about 0.074 nm, which is equivalent to the ion radius of rare earth doped ions (terbium ions, the ion radius is between 0.076 nm and 0.092 nm), so that substitution doping is easy to realize, the synergistic effect between the zinc ions and the rare earth doped ions is enhanced, and the device performances such as the fluorescence life and the like are greatly improved.
(2) The chromium ion and terbium ion co-doped zinc aluminum germanate and polymer matrix (OSTE) have high intersolubility, the fluorescent life can be greatly prolonged under the synergistic action of the chromium ion and terbium ion co-doped zinc aluminum germanate and the polymer matrix (OSTE), and the long afterglow micron particles can provide continuous photons to be gathered on the surface of the polycrystalline silicon photovoltaic panel under the continuous weak illumination condition, so that the photoelectric conversion efficiency of the commercial polycrystalline silicon solar cell under the weak illumination condition is improved.
(3) The photovoltaic power generation device based on the micron-sized 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 polycrystalline silicon photovoltaic device under the condition of weak illumination and the photoelectric conversion efficiency of a commercial polycrystalline silicon solar cell.
(4) 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 polysilicon cell is 500-600 nm. The characteristic fluorescence luminescence central peak position in the flat plate type light collecting device designed by the invention is 547 nm. The matching degree of the flat-plate type fluorescence light collecting device and the polycrystalline silicon solar cell is high.
In conclusion, the preparation method and the application of the flat-plate type fluorescent solar collector based on the polysilicon with the long afterglow micron particles have the advantages that the size of the prepared luminescent center particles of the chromium ion and terbium ion co-doped zinc aluminum germanate is in the micron order, and the fluorescent service life of the luminescent center particles is as long as several hours or even longer; further, the synergistic effect of the chromium ion and terbium ion co-doped zinc aluminum germanate luminescence center and a high-refractive-index polymer matrix (OSTE) greatly improves the light collecting efficiency, so that the further prepared flat-plate type light collecting photovoltaic power generation device has a larger optical absorption section and higher photoluminescence fluorescence conversion efficiency, is green and environment-friendly, has low cost, has high light collecting efficiency, can continuously generate power under the conditions of weak illumination such as night, cloudy days and rainy days, and greatly widens the working time of the traditional flat-plate type light collecting photovoltaic device.
Drawings
FIG. 1 shows Cr: tb molar ratio = 0.05: (0.05, 0.10, 0.15, 0.20), based on the photoluminescence intensity spectrum of the luminescent centers of chromium ion and terbium ion co-doped zinc aluminum germanate;
FIG. 2 is a change rule of the luminous intensity of an OSTE panel based on chromium ion and terbium ion co-doped zinc aluminum germanate fluorescent powder along 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-collecting polycrystalline silicon photovoltaic cell power generation device based on co-doping of chromium ions and terbium ions with zinc aluminum germanate in the embodiment of the present invention, wherein the drawings are respectively labeled as follows: the solar collector comprises a 1-polycrystalline silicon flat plate type fluorescent solar collector, a 2-polycrystalline silicon solar 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 accompanying examples.
Detailed description of the preferred embodiment
A preparation method of a polysilicon flat plate type fluorescent solar light collector 1 based on long afterglow micron particles comprises the following steps:
(1) preparation of chromium ion and terbium ion co-doped zinc aluminum germanate luminescence center material
High-purity raw materials of zinc oxide, aluminum oxide, germanium oxide, chromium oxide and terbium oxide powder are mixed according to the molar ratio of Zn: al: ge: cr: tb = 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 box, 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: tb molar ratio = 0.05: (0.05, 0.10, 0.15, 0.20), based on photoluminescence intensity spectra of luminescent centers of chromium ion and terbium ion co-doped zinc aluminum germanate at different wavelengths. Wherein, Zn: al: ge: the molar ratio of Cr is fixed at 1: 1: 2: 0.05. as the Tb content is gradually increased, from 0-0.15, the characteristic luminescence intensity of Tb ions at 547nm is gradually increased, which means that the density of luminescence centers is continuously increased, so that the photoluminescence intensity is gradually increased. When the Tb content is continuously increased and the characteristic luminescence of Tb ions at the position of 547nm is slightly weakened from 0.15-0.2, the concentration quenching effect of the rare earth terbium ions is mainly achieved;
(2) preparation of polysilicon flat plate type fluorescent solar 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 long-micrometer-particle-based polycrystalline silicon flat-plate type fluorescent afterglow solar light collector 1. Wherein the precursor solution is prepared by mixing a photoinitiator, an allyl monomer and a thiol monomer according to the weight ratio of 0.05 g: 4-6 ml: 4-6ml of the mixture; the mixing ratio of the luminous center powder to the photoinitiator is 200ul-800 ul: 0.05 g.
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 long-afterglow phosphor material with the chromium ion and terbium ion co-doped zinc aluminum germanate in the thiol-ene copolymer (OSTE) has the best dispersibility. 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 a luminescence center based on co-doping of chromium ions and terbium ions with zinc aluminum germanate. The black line is the change rule of the luminous intensity of the chromium ion and terbium ion co-doped zinc aluminum germanate fluorescent powder along with time after the standard AM1.5 sun illumination for 10 minutes; the gray line is the change rule of the luminous intensity of an OSTE flat plate based on chromium ion and terbium ion co-doped zinc aluminum germanate fluorescent powder, namely the polycrystalline silicon flat plate type fluorescent solar light collector 1 based on long afterglow micron particles along with the time after the gray line is irradiated by standard AM1.5 sun light 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 polysilicon flat plate type fluorescent solar collector 1 based on long afterglow micron particles prepared in the invention under the irradiation of AM 1.5. According to experimental measurement, the plate type fluorescent solar light collector 1 based on the polysilicon with the size of 10cm by 0.5cm and based on the long afterglow micron particles has the highest light collecting efficiency of 8.5 percent under the standard AM1.5 sunlight. 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, the defects in an OSTE matrix and chromium ions capture electrons together, and the fluorescence life is further prolonged through mechanisms such as non-radiative recombination energy co-transfer and the like; 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 shown in figure 4 and comprises a flat plate type polycrystalline silicon fluorescent solar collector 1 based on long-afterglow micron particles prepared in the first embodiment, a polycrystalline silicon solar panel 2 is adhered to the periphery of the flat plate type polycrystalline silicon fluorescent solar collector 1, a top antireflection layer 3 is arranged on the upper surface of the flat plate type polycrystalline silicon fluorescent solar collector 1 and the upper surface of the polycrystalline silicon solar panel 2, a bottom metal reflecting layer 4 is arranged on the lower surface of the flat plate type polycrystalline silicon fluorescent solar collector 1 and the lower surface of the polycrystalline silicon solar panel 2, and a PCB 5 which is used for supporting the polycrystalline silicon solar panel 2 and is plated with conductive metal is fixedly arranged on the outer side face of the polycrystalline silicon solar panel 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 polycrystalline silicon solar panel 2: and cutting the polycrystalline silicon solar panel 2 into strips by using a laser scribing machine, fixing the strips on the PCB 5 plated with the conductive metal, and finally integrally placing the polycrystalline silicon solar panel 2 and the PCB 5 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 terbium ion co-doped zinc aluminum germanate under the weak illumination condition.
According to the flat-plate light-collecting photovoltaic power generation device based on the chromium ion and terbium ion co-doped zinc 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 photovoltaic light-collecting device, long afterglow chromium ions and terbium ions with micron sizes are co-doped with zinc aluminum germanate powder to replace the quantum dots reported in the prior art, so that the light-collecting efficiency under the condition of continuous weak illumination can be greatly improved. Meanwhile, under the normal illumination condition, due to the synergistic effect of the luminescent center material (long afterglow chromium ions and terbium ions co-doped zinc 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 preparation method of a flat-plate type fluorescent solar collector based on long-afterglow micron particles is characterized by comprising the following steps:
(1) preparation of chromium ion and terbium ion co-doped zinc aluminum germanate luminescence center material
High-purity raw materials of zinc oxide, aluminum oxide, germanium oxide, chromium oxide and terbium oxide powder are mixed according to the molar ratio of Zn: al: ge: cr: tb = 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 box, 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 polycrystalline silicon flat-plate type fluorescent solar light 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 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 polycrystalline silicon flat plate type fluorescent afterglow solar collector based on long micron particles.
2. The method for preparing a flat-plate fluorescent solar collector based on polysilicon with long afterglow micron particles as claimed in claim 1, wherein: 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 0.05 g: 4-6 ml: 4-6ml of the mixture; the mixing ratio of the luminescence center powder to the photoinitiator is 200ul-800 ul: 0.05 g.
3. The method for preparing a polysilicon flat plate type fluorescent solar light collector based on long afterglow micron particles as claimed in claim 2, wherein the method comprises the following steps: 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.
4. Use of the long persistence microparticle based flat plate fluorescent solar collector of any of claims 1-3 in the preparation of flat plate collection photovoltaic devices.
5. The use of the long persistence microparticle based polysilicon slab fluorescence solar collector of claim 4, wherein: the flat type polycrystalline silicon light-collecting photovoltaic power generation device comprises a flat type polycrystalline silicon fluorescent solar collector, polycrystalline silicon solar panels are adhered to the periphery of the flat type polycrystalline silicon fluorescent solar collector, top antireflection layers are arranged on the upper surface of the flat type polycrystalline silicon fluorescent solar collector and the upper surface of each polycrystalline silicon solar panel, bottom metal reflecting layers are arranged on the lower surface of the flat type polycrystalline silicon fluorescent solar collector and the lower surface of each polycrystalline silicon solar panel, and a PCB (printed circuit board) which is used for supporting the polycrystalline silicon solar panels and is plated with conductive metal is fixedly arranged on the outer side surfaces of the polycrystalline silicon solar panels.
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