CN113637197A - Efficient rare earth complex luminescent film and preparation method and application thereof - Google Patents
Efficient rare earth complex luminescent film and preparation method and application thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000010408 film Substances 0.000 claims abstract description 84
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000010409 thin film Substances 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 12
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 claims description 9
- 238000004806 packaging method and process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
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- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 4
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910016644 EuCl3 Inorganic materials 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 40
- 229910052710 silicon Inorganic materials 0.000 abstract description 40
- 239000010703 silicon Substances 0.000 abstract description 40
- 230000003287 optical effect Effects 0.000 abstract description 4
- -1 tetraphenylphosphine cation Chemical class 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 46
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 21
- 230000008878 coupling Effects 0.000 description 18
- 238000010168 coupling process Methods 0.000 description 18
- 238000005859 coupling reaction Methods 0.000 description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- GMQVFHZSXKJCIV-UHFFFAOYSA-N 2,2,2-trifluoro-n-(2,2,2-trifluoroacetyl)acetamide Chemical compound FC(F)(F)C(=O)NC(=O)C(F)(F)F GMQVFHZSXKJCIV-UHFFFAOYSA-N 0.000 description 11
- 238000009833 condensation Methods 0.000 description 9
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 2
- 238000001857 fluorescence decay curve Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- 229920013660 Cellon Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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Abstract
The invention relates to a high-efficiency rare earth complex luminescent film, a preparation method and application thereof. The composition of the film isA heteromedium Ln-quaternary-beta-diketone-tetraphenylphosphine cation complex and a macromolecular matrix; wherein, the mass of the doping medium is 0.01-90% of that of the polymer matrix film; the doping medium Ln (beta-diketone)4The structural formula of the-phosphonium salt counter cation complex is as follows. Ln (beta-diketone) developed by the invention4The tetraphenylphosphine cation complex luminescent thin film has excellent optical performance, and the good performance can improve the photoelectric conversion efficiency of the silicon-based solar cell. Meanwhile, the light-emitting film can also effectively protect the degradation problem of EVA caused by ultraviolet irradiation.
Description
Technical Field
The invention belongs to the field of rare earth luminescent material application, and relates to a preparation method of a rare earth quaternary complex luminescent film with high-efficiency luminescence and application of the rare earth quaternary complex luminescent film in a solar cell.
Background
With the rapid development of the economy in the world, the traditional fossil energy is no longer stable, and all countries in the world are dedicated to developing various renewable new energy sources by new technologies. Among various renewable energy sources, solar energy has become the most important renewable energy source due to the years' progress in abundant sunlight and technologies for capturing light energy. For many years, solar photovoltaic cells have become the primary means of utilizing solar energy because they are not only renewable, but also safe and pollution free. The silicon-based solar cells of various types have already been applied to large-scale marketization, but the current situation of the solar photovoltaic industry in China still has a large gap compared with the situation in abroad, and the main reasons are that the cost of upstream products is relatively high, the technology lags behind, and the efficiency of the photovoltaic cells is low. In addition, the existing photovoltaic cells occupy large-scale land areas when being installed outdoors, and whether sunlight can be sufficiently irradiated is also considered, so that most photovoltaic products are applied to remote areas, and the development of the photovoltaic products is limited. Therefore, from the technical point of view, it is a key research direction in the energy technology field to improve the photoelectric conversion efficiency of the existing silicon-based solar cell, increase the generated power, and solve the problem of the regional limitation of the cell.
The forbidden band width of the silicon-based solar cell is 1000nm, and the silicon-based solar cell is mismatched with a standard solar radiation spectrum (globeamm 1.5) to a certain extent, particularly in an ultraviolet light wave band, the utilization rate of the silicon solar cell to ultraviolet light is not high due to obvious spectrum mismatch, and the silicon solar cell loses in the form of lattice thermal vibration, so that the silicon solar cell has lower external quantum efficiency in an ultraviolet light region. In addition, ultraviolet light causes aging and yellowing phenomena to a certain extent for EVA used by a traditional encapsulated solar cell module, which finally causes the situations of cell efficiency reduction, life decay and the like in the use process of the cell. Therefore, converting the short wavelength light of the sunlight into the 500-900nm wavelength light by a certain means is an effective means for improving the conversion efficiency of the cell.
The rare earth complex is a luminescent material capable of converting ultraviolet light into visible light or near infrared light, and has the advantages of large molar extinction coefficient of organic ligands, high luminous efficiency, large Stokes displacement, long luminous life and the like, so that the rare earth complex has wide application prospects in the fields of illumination, display, energy, biology and the like. The rare earth complex applied to the silicon-based solar cell needs to meet the following points: 1) broadband absorption after 300nm in the ultraviolet region and higher quantum efficiency; 2) can be incorporated into a polymer matrix and maintain better transparency; 3) better light stability.
Disclosure of Invention
The invention aims to realize the application of a rare earth complex on a silicon-based solar cell, and provides a preparation method of a high-efficiency rare earth complex luminescent film and an application mode of the high-efficiency rare earth complex luminescent film on the solar cell. According to the invention, a series of Ln-quaternary-beta-diketone complexes functionalized by tetraphenylphosphine counter cations are mixed with various types of polymer matrixes, namely polymethyl methacrylate (PMMA), polyvinyl butyral (PVB) and ethylene-vinyl acetate copolymer (EVA) to prepare corresponding rare earth complex luminescent films and apply the rare earth complex luminescent films to silicon-based solar cells. The thin film and the silicon-based solar cell have two coupling modes: the other method is that the ready-made EVA luminous film is directly encapsulated with the silicon-based solar cell module; and the other method is that the prepared luminescent film precursor solution is placed on the surface of acrylic glass or photovoltaic glass in a dripping or spin coating mode, and then the silicon-based solar cell is coupled with the side surface of the glass to prepare the solar concentrator.
The technical scheme of the invention is as follows:
an efficient rare earth complex luminescent film comprises a doping medium Ln-quaternary-beta-diketone-tetraphenylphosphine cation complex and a macromolecular substrate; wherein, the mass of the doping medium is 0.01-90% of that of the polymer matrix film;
the doping medium Ln (beta-diketone)4The structural formula of the phosphonium salt counter cation complex is as follows, wherein, a beta-diketone ligand and a rare earth element form an anion part of the complex, and a tetraphenylphosphine counter cation with positive charge is taken as a cation part;
wherein R is1Or R2Same or different H, CH respectively3、CF3Benzene, thiophene or naphthalene.
The rare earth element Ln is specifically as follows: one or more of Sm, Eu, Tm, Yb, Tb, Gd and Er.
The polymer matrix is EVA, PMMA or PVB.
When the polymer matrix is EVA, the doping proportion of the doping medium in the polymer matrix is 0.01-1%; when the polymer matrix is PMMA, the doping proportion of the doping medium in the polymer matrix is 1-90%; when the polymer matrix is PVB, the doping medium is doped in the polymer matrix in a proportion of 1-5%.
The thickness range of the luminescent film is 50-400 μm.
The organic beta-diketone ligand is preferably:
the preparation method of the high-efficiency rare earth complex luminescent film comprises the following steps:
(1) adding an equimolar amount of sodium hydroxide ethanol solution into an ethanol solution of a beta-diketone ligand, reacting for 5-20 minutes at room temperature, and then adding EuCl3Carrying out reflux reaction on the solution at 55-65 ℃, adding an aqueous solution of tetraphenylphosphonium chloride after 30-120 minutes, continuing the reaction for 30-180 minutes, finally adding water for extraction to obtain white precipitate, and washing and drying the white precipitate to obtain a rare earth complex; wherein the material ratio is that the mol ratio of beta-diketone ligand: eucl3: tetraphenylphosphonium chloride 4: 1: 1; the concentration of the sodium hydroxide ethanol solution is 0.05-1 mol/L; eucl3The concentration of the solution is 0.05-0.1 mol/L; the aqueous solution of tetraphenylphosphonium chloride is 5ml of water, and 0.2-0.8 g of tetraphenylphosphonium chloride is added into the water.
(2) According to the doping proportion, under the condition of room temperature to 80 ℃, adding the solution of the rare earth complex into the polymer matrix solution, cooling to room temperature after the dissolution is finished, coating the solution on a substrate, and curing to form a film at the room temperature to 110 ℃; the thickness of the film is about 50-400 μm.
The solvent for dissolving the polymer matrix is: EVA corresponds to a toluene solvent, PMMA corresponds to a DMF solvent, and PVB corresponds to an acetone solvent. Theoretically, the polymer matrix can be dissolved, and 1g of the polymer matrix is dissolved by 10-20 ml of a corresponding solvent.
The substrate is acrylic glass or photovoltaic glass.
The solvent of the rare earth complex solution is water, ethanol, methanol, dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide, diethyl ether or N-hexane; the concentration of the solution is 0.01-90%;
the stable rare earth complex luminescent film is applied as follows: the adhesive for packaging the cell assembly in the solar cell is coated on the surface of acrylic glass or photovoltaic glass to obtain the solar concentrator.
The invention has the substantive characteristics that:
(1) the invention relates to a series of Ln (beta-diketone) functionalized by tetraphenylphosphine counter cation4The tetraphenylphosphine cation complex is mixed with various types of polymer matrixes, such as polymethyl methacrylate (PMMA), polyvinyl butyral (PVB) and ethylene-vinyl acetate copolymer (EVA), so that complex luminescent films with different optical properties and stable properties can be obtained.
(2) The prepared film and the silicon-based solar cell have two coupling modes: directly encapsulating the prepared rare earth complex luminescent EVA film with a silicon-based solar cell module; due to the light conversion effect of the complex, the damage of ultraviolet rays in sunlight to the EVA film and the silicon-based cell piece can be weakened, the weak response problem of the cell in an ultraviolet region is improved, and the photoelectric conversion efficiency is further improved. And (II) placing the prepared luminescent film precursor solution on the surface of acrylic glass or photovoltaic glass in a dripping or spin coating mode, and coupling the silicon-based solar cell to the side surface of the glass to prepare the solar concentrator. The structure of the solar condenser can be applied to urban photovoltaic buildings, the floor area of a photovoltaic cell is reduced, and the photovoltaic cost is effectively saved.
The invention has the beneficial effects that:
(1) the rare earth complex in the film can convert ultraviolet light in sunlight into visible light, and the characteristic can effectively improve the external quantum efficiency of the silicon-based solar cell by about 1.22%, so that the photoelectric conversion efficiency of the cell is improved.
(2) The film precursor solution can be applied to a solar condenser after being subjected to drop coating or spin coating to form a film, so that the land area of a photovoltaic cell can be effectively reduced, and a good idea is provided for future photovoltaic industry construction.
Drawings
FIG. 1 shows Eu (TTA) in example 14Single crystal schematic of TPP.
FIG. 2 shows Eu (TTA) in example 14Excitation spectrum of TPP-EVA.
FIG. 3 shows Eu (TTA) in example 14Emission spectrum of TPP-EVA.
FIG. 4 shows Eu (TTA) in example 14Life spectrum of TPP-EVA.
FIG. 5 shows the blank EVA and Eu (TTA) in example 1 and comparative example 14And a transmission rate spectrogram of the TPP-EVA film from ultraviolet to visible light region.
FIG. 6 shows Eu (TTA) in example 1 and comparative example 14And the TPP-EVA film and the blank EVA film are covered on the external quantum efficiency graph of the silicon-based solar cell.
FIG. 7 shows Eu (TTA) in example 1 and comparative example 14And covering the TPP-EVA film and the blank EVA film on the J-V curve chart of the silicon-based solar cell.
FIG. 8 shows Eu (TTA) in example 84The I-V curve of the TPP-PMMA concentrator and concentrator edge coupled solar cell, wherein fig. 8a is the I-V curve of the solar concentrator, and fig. 8b is the I-V curve of the solar cell coupled to the concentrator edge.
Detailed Description
In order to illustrate the present invention more clearly, the following examples are given without any limitation to the scope of the invention.
Example 1
1) Dissolving 4mmol of TTA in 5ml of ethanol, adding 4mmol of 0.1mol/L NaOH absolute ethanol solution, deprotonating the TTA ligand, condensing and refluxing at 60 deg.C, and adding 1mmol of 0.1mol/L EuCl3An ethanol solution, reacting for two hours, adding 2ml of 0.5mol/L tetraphenylphosphonium chloride aqueous solution, reacting for two hours, cooling to room temperature,adding a large amount of distilled water to obtain a precipitate, and washing and drying the precipitate, wherein the mark is Eu (TTA)4TPP;
2) Mixing Eu (TTA) in the step 1)4TPP complex 2.5mg dissolved in 20ml dichloromethane solvent;
3) adding 5g of EVA into 50ml of toluene solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; the doping proportion of the mixed medium in the polymer matrix is 0.05 percent
4) Dropping the solution obtained in the step 3) into a culture dish with the diameter of 17cm, and heating the solution on a flat plate at the temperature of 100 ℃ to solidify the solution into a film, which is recorded as Eu (TTA)4The TPP-EVA film has a thickness of about 50-400 μm. According to the photovoltaic glass, the bottom plate, the silicon-based solar cell and the Eu (TTA)4The TPP-EVA film and the photovoltaic glass are sequentially stacked and adhered together by a vacuum lamination method to obtain Eu (TTA)4And the TPP-EVA film is used as the adhesive of the solar cell.
FIG. 1 shows Eu (TTA)4TPP complex is dissolved in ethanol solution, single crystal is obtained by slowly volatilizing ethanol solvent, and the single crystal structure schematic diagram is obtained by analyzing the crystal structure by utilizing single crystal X-ray diffraction. It can be seen from the figure that each Eu3+Chelated by eight oxygen atoms of four TTA ligands, with one TPP counter cation located in the outer sphere. Thus demonstrating the corresponding chemical structure we synthesized.
Comparative example 1
Preparation of a blank EVA film for comparison: 5g of EVA is dissolved in 50ml of toluene, the solution is dropped into a culture dish with the diameter of 17cm, and the culture dish is placed on a flat plate with the temperature of 100 ℃ to be heated and solidified into a film.
FIGS. 2, 3 and 4 show Eu (TTA)4Excitation, emission spectrum and fluorescence attenuation curve of the TPP-EVA luminous film. It can be obviously observed that the film has a broadband absorption from 270-;fitting the fluorescence decay curve with a first order exponential function gave a fluorescence lifetime of 526 ms. The emission spectrum and the fluorescence decay curve show that the preparation of the film retains the narrow-band emission and long fluorescence lifetime properties of the complex.
FIG. 5 shows blank EVA and Eu (TTA)4The data of the TPP-EVA luminous film transmittance spectrogram show that the average value of the transmittance of the luminous film in a visible light region is 92 percent and almost keeps the same with that of a blank EVA film, which indicates that the TPP-EVA luminous film can well meet the transmittance requirement in the application of solar cells.
FIG. 6 shows Eu (TTA) measured by a Quantum efficiency test System of U.S. photovoltaic measurement, Inc. QEX104The TPP-EVA luminous film and the blank EVA film are covered on the external quantum efficiency graph of the silicon-based solar cell, and Eu (TTA)4The TPP-EVA luminescent film shows a remarkable enhancement of external quantum efficiency in the ultraviolet region of 300-480nm, which is about 1.22%. The wavelength band outside 380nm is almost identical to that of the blank EVA film, thus demonstrating that the light conversion material in the film successfully converts uv light into visible light and for absorption by silicon-based solar cells.
In FIGS. 5 and 6, we have demonstrated that the doping of the complex in the EVA film can realize photoresponse in the ultraviolet region and no influence on the visible region, which ensures that Eu (TTA)4The premise that the photoelectric conversion efficiency of the cell can not be improved by TPP-EVA.
FIG. 7 shows Eu (TTA) measured by using an I-V characteristics test system of PVIV type by Newport corporation4And covering the TPP-EVA film and the blank EVA film on the J-V curve of the silicon-based solar cell. It can be found that Eu (TTA)4Performance of TPP-EVA film coated cells is improved, JSCIncreased from 34.63 to 37.7mA/cm2The corresponding absolute value of the photoelectric conversion efficiency is improved by 0.14 percent. This result demonstrates that the down-conversion luminescent material does contribute to the improvement of the photoelectric conversion efficiency of the silicon-based solar cell.
Example 2
1) Dissolving 4mmol NTA in 5ml ethanol solution, adding 4mmol NaOH anhydrous ethanol solution, and preparing NTAThe resulting phosphor was deprotonated and the remaining experimental runs were the same as in example 1, step 1), dried and reported as Eu (NTA)4TPP; 2) mixing Eu (NTA) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the film obtained in the same manner as in step 3) or 4) of example 1 was designated Eu (NTA)4TPP-EVA film. And packaging the assemblies such as the thin film, the silicon-based solar cell, the bottom plate, the photovoltaic glass and the like by using a vacuum lamination method.
Example 3
1)4mmol of HFA in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the HFA ligand, the procedure is as in 1) of example 1, and the phosphor obtained is dried and is designated Eu (HFA)4TPP; 2) eu (HFA) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) 4) the film obtained in the same manner as in step 3) or 4) of example 1 was designated Eu (HFA)4TPP-EVA film. And packaging the assemblies such as the thin film, the silicon-based solar cell, the bottom plate, the photovoltaic glass and the like by using a vacuum lamination method.
Example 4
1)4mmol of TFAC was dissolved in 5ml of ethanol, 4mmol of NaOH in absolute ethanol was added to deprotonate the TFAC ligand, and the rest of the experiment was performed as in step 1 of example 1), and the resulting phosphor was dried and designated Eu (TFAC)4TPP; 2) the Eu (TFAC) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the film obtained in the same manner as in step 3) or 4) of example 1 was designated Eu (TFAC)4TPP-EVA film. And packaging the assemblies such as the thin film, the silicon-based solar cell, the bottom plate, the photovoltaic glass and the like by using a vacuum lamination method.
Example 5
1)4mmol BTFA in 5ml ethanol solution, 4mmol NaOH in absolute ethanol was added to deprotonate BTFA ligand, and the rest of the experiment was performed as in step 1) of example 1, and the resulting phosphor was dried and designated Eu (BTFA)4TPP; 2) mixing Eu (BTFA) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the steps are the same as the step 3) in the example 1,4) The resulting film was designated Eu (BTFA)4TPP-EVA film. And packaging the assemblies such as the thin film, the silicon-based solar cell, the bottom plate, the photovoltaic glass and the like by using a vacuum lamination method.
Example 6
1)4mmol of DBM in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the ligands of DBM, the rest of the experiment is carried out as in step 1 of example 1), and the phosphor obtained is dried and designated Eu (DBM)4TPP; 2) mixing Eu (DBM) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the film obtained in the same manner as in step 3) or 4) of example 1 was designated Eu (DBM)4TPP-EVA film. And packaging the assemblies such as the thin film, the silicon-based solar cell, the bottom plate, the photovoltaic glass and the like by using a vacuum lamination method.
Example 7
1)4mmol of DNM in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the DNM ligand, the remainder of the experiment is as in step 1) of example 1, and the phosphor obtained is dried and designated Eu (DNM)4TPP; 2) eu (DNM) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the film obtained in the same manner as in step 3) or 4) of example 1 was designated Eu (DNM)4TPP-EVA film. And packaging the assemblies such as the thin film, the silicon-based solar cell, the bottom plate, the photovoltaic glass and the like by using a vacuum lamination method.
Example 8
Step 1), 2) are the same as step 1), 2) in example 1; 3) adding 5g of PMMA into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, heating the glass on a flat plate at the temperature of 60 ℃ to be cured to form a film, coupling a silicon-based solar cell to the side surface, and recording the coupling as Eu (TTA)4TPP-PMMA condenser.
Fig. 8a is an I-V curve of the solar concentrator, and fig. 8b is an I-V curve of the solar cell coupled to the edge of the concentrator, and the calculated optical conversion efficiency is 0.3% according to the efficiency calculation formula. Compared with other complexes, the device has ideal optical conversion efficiency compared with other complexes due to the larger doping amount of the complexes.
Example 9
1)4mmol of NTA in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the NTA ligands, the rest of the experiment is carried out as in step 1) of example 1, and the resulting phosphor is dried and designated Eu (NTA)4TPP; 2) mixing Eu (NTA) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the same procedure as in step 3) and 4) of example 8, and the condenser obtained is recorded as Eu (NTA)4TPP-PMMA condenser.
Example 10
1)4mmol of HFA in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the HFA ligand, the procedure is as in 1) of example 1, and the phosphor obtained is dried and is designated Eu (HFA)4TPP; 2) eu (HFA) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the same procedure as in step 3) and 4) of example 8, the condenser obtained is marked Eu (HFA)4TPP-PMMA condenser.
Example 11
1)4mmol of TFAC was dissolved in 5ml of ethanol, 4mmol of NaOH in absolute ethanol was added to deprotonate the TFAC ligand, and the rest of the experiment was performed as in step 1 of example 1), and the resulting phosphor was dried and designated Eu (TFAC)4TPP; 2) the Eu (TFAC) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the same procedure as in step 3) and 4) of example 8, and the resultant condenser is recorded as Eu (TFAC)4TPP-PMMA condenser.
Example 12
1)4mmol of BTFA in 5ml of ethanol solution, 4mmol of NaOH in absolute ethanol are added to deprotonate the BTFA ligand, and the procedure is as in step 1) of example 1,the resulting phosphor was dried and designated Eu (BTFA)4TPP; 2) mixing Eu (BTFA) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the same procedure as in step 3) and 4) of example 8, the condenser obtained is marked as Eu (BTFA)4TPP-PMMA condenser.
Example 13
1)4mmol of DBM in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the ligands of DBM, the rest of the experiment is carried out as in step 1 of example 1), and the phosphor obtained is dried and designated Eu (DBM)4TPP; 2) mixing Eu (DBM) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the same procedure as in step 3) and 4) of example 8, the resultant condenser is denoted as Eu (DBM)4TPP-PMMA condenser.
Example 14
1)4mmol of DNM in 5ml of ethanol, 4mmol of NaOH in absolute ethanol are added to deprotonate the DNM ligand, the remainder of the experiment is as in step 1 of example 1), and the phosphor obtained is dried and designated Eu (DNM)4TPP; 2) eu (DNM) in the step 1)4TPP complex 0.05mmol dissolved in 20ml dichloromethane solvent; 3) and 4) the same procedure as in step 3) and 4) of example 8 was repeated to obtain a condenser denoted as Eu (DNM)4TPP-PMMA condenser.
Example 15
Step 1), 2) are the same as step 1), 2) in example 1; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, heating the glass on a flat plate at the temperature of 60 ℃ to be cured to form a film, coupling a silicon-based solar cell to the side surface, and recording the coupling as Eu (TTA)4TPP-PVB concentrator.
Example 16
Step 1), 2) are the same as step 1), 2) in example 2; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on acrylic glassPlacing the glass surface or the photovoltaic glass surface on a flat plate at 60 ℃, heating the glass surface or the photovoltaic glass surface to be cured to form a film, coupling the silicon-based solar cell to the side surface, and recording the coupling as Eu (NTA)4TPP-PVB concentrator.
Example 17
Step 1), 2) are the same as step 1), 2) in example 3; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, heating the glass on a flat plate at the temperature of 60 ℃ to be cured to form a film, coupling a silicon-based solar cell on the side surface, and recording the coupling result as Eu (HFA)4TPP-PVB concentrator.
Example 18
Step 1), step 2) are the same as step 1), step 2) in example 4; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, heating the glass on a flat plate at the temperature of 60 ℃ to be cured to form a film, coupling a silicon-based solar cell on the side surface, and recording the coupling as Eu (TFAC)4TPP-PVB concentrator.
Example 19
Step 1), step 2) are the same as step 1), step 2) in example 5; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, heating the glass on a flat plate at the temperature of 60 ℃ to be cured to form a film, coupling a silicon-based solar cell to the side surface, and recording the coupling as Eu (BTFA)4TPP-PVB concentrator.
Example 20
Step 1), step 2) are the same as step 1), step 2) in example 6; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, placing the glass on a flat plate at the temperature of 60 ℃ for heating and curing to form a film, and coupling a silicon-based solar cellOn the side, mark Eu (DBM)4TPP-PVB concentrator.
Example 21
Step 1), step 2) are the same as step 1), step 2) in example 7; 3) adding 5g of PVB into 50ml of N, N dimethylformamide solution, carrying out condensation reflux at the temperature of 80 ℃, adding the solution obtained in the step 2) after the solution is cooled, and carrying out ultrasonic stirring; 4) dripping the solution obtained in the step 3) on the surface of acrylic glass or photovoltaic glass, placing the acrylic glass or photovoltaic glass on a flat plate at the temperature of 60 ℃, heating the acrylic glass or photovoltaic glass to be cured to form a film, coupling a silicon-based solar cell to the side surface, and recording the coupling as Eu (DNM)4TPP-PVB concentrator.
The invention is not the best known technology.
Claims (10)
1. An efficient rare earth complex luminescent film is characterized in that the film consists of a doping medium Ln-quaternary-beta-diketone-tetraphenylphosphine cation complex and a polymer matrix; wherein, the mass of the doping medium is 0.01-90% of that of the polymer matrix film;
the doping medium Ln (beta-diketone)4The structural formula of the phosphonium salt counter cation complex is shown in the specification, wherein a beta-diketone ligand and a rare earth element form an anion part of the complex, and a tetraphenylphosphine counter cation with positive charge is a cation part;
wherein R is1Or R2Same or different H, CH respectively3、CF3Benzene, thiophene or naphthalene.
2. A highly efficient rare earth complex luminescent thin film as claimed in claim 1, wherein said rare earth element Ln is specifically: one or more of Sm, Eu, Tm, Yb, Tb, Gd and Er.
3. The efficient rare earth complex luminescent film according to claim 1, wherein the polymer matrix is EVA, PMMA or PVB.
4. The highly efficient rare earth complex luminescent film as claimed in claim 1, wherein when the polymer matrix is EVA, the doping ratio of the doping medium in the polymer matrix is 0.01% -1%; when the polymer matrix is PMMA, the doping proportion of the doping medium in the polymer matrix is 1-90%; when the polymer matrix is PVB, the doping medium is doped in the polymer matrix in a proportion of 1-5%.
5. A highly efficient rare earth complex luminescent film as set forth in claim 1, wherein the thickness of said luminescent film is in the range of 50 μm to 400 μm.
7. the method of claim 1, wherein the method comprises the steps of:
(1) adding an equimolar amount of sodium hydroxide ethanol solution into an ethanol solution of a beta-diketone ligand, reacting for 5-20 minutes at room temperature, and then adding EuCl3Carrying out reflux reaction on the solution at 55-65 ℃, adding an aqueous solution of tetraphenylphosphonium chloride after 30-120 minutes, continuing the reaction for 30-180 minutes, finally adding water for extraction to obtain white precipitate, and washing and drying the white precipitate to obtain a rare earth complex; wherein the material ratio is that the mol ratio of beta-diketone ligand: eucl3: tetraphenylphosphonium chloride 4: 1: 1; the concentration of the sodium hydroxide ethanol solution is 0.05-1 mol/L; eucl3The concentration of the solution is 0.05-0.1 mol/L; the aqueous solution of tetraphenylphosphonium chloride is prepared by adding 0.2-0.8 g of tetraphenylphosphonium chloride to 5ml of water.
(2) According to the doping proportion, under the condition of room temperature to 80 ℃, the solution of the rare earth complex is added into the polymer matrix solution, after the dissolution is finished, the solution is cooled to the room temperature, and the solution is coated on a substrate and solidified to form a film at the room temperature to 110 ℃.
8. The method according to claim 1, wherein the substrate is acrylic glass or photovoltaic glass.
9. The method according to claim 1, wherein the solvent of the rare earth complex solution is water, ethanol, methanol, dichloromethane, chloroform, tetrahydrofuran, N-dimethylformamide, diethyl ether or N-hexane; the concentration of the solution is 0.01-90%.
10. The application of the highly efficient rare earth complex luminescent thin film as claimed in claim 1, wherein the adhesive for packaging a cell module in a solar cell is coated on the surface of acrylic glass or photovoltaic glass to obtain a solar concentrator.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5158703A (en) * | 1991-04-03 | 1992-10-27 | Mitsui Toatsu Chemicals Inc. | Resin composition for ultraviolet luminescent screen |
CN105131488A (en) * | 2015-08-26 | 2015-12-09 | 重庆理工大学 | Visible light excited europium complex fluorescent film and preparation method therefor and application thereof |
WO2016152524A1 (en) * | 2015-03-20 | 2016-09-29 | 株式会社クレハ | Europium complex salt and use thereof |
CN109721918A (en) * | 2019-01-07 | 2019-05-07 | 河北工业大学 | A kind of flexible rare-earth transparent luminous film and preparation method thereof applied to silica-based solar cell |
-
2021
- 2021-07-15 CN CN202110800965.9A patent/CN113637197A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5158703A (en) * | 1991-04-03 | 1992-10-27 | Mitsui Toatsu Chemicals Inc. | Resin composition for ultraviolet luminescent screen |
WO2016152524A1 (en) * | 2015-03-20 | 2016-09-29 | 株式会社クレハ | Europium complex salt and use thereof |
CN105131488A (en) * | 2015-08-26 | 2015-12-09 | 重庆理工大学 | Visible light excited europium complex fluorescent film and preparation method therefor and application thereof |
CN109721918A (en) * | 2019-01-07 | 2019-05-07 | 河北工业大学 | A kind of flexible rare-earth transparent luminous film and preparation method thereof applied to silica-based solar cell |
Non-Patent Citations (1)
Title |
---|
J. MEZYK等: "Diffusion-mediated resonant energy transfer in lanthanide-based polymer white-light-emitting diodes", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》, vol. 11, 16 September 2009 (2009-09-16), pages 10152 - 10156 * |
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