CN111233824B - Organic spectrum conversion material, preparation method thereof and luminescent solar concentrator comprising organic spectrum conversion material - Google Patents

Organic spectrum conversion material, preparation method thereof and luminescent solar concentrator comprising organic spectrum conversion material Download PDF

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CN111233824B
CN111233824B CN201811436003.4A CN201811436003A CN111233824B CN 111233824 B CN111233824 B CN 111233824B CN 201811436003 A CN201811436003 A CN 201811436003A CN 111233824 B CN111233824 B CN 111233824B
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CN111233824A (en
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王权
刘琦
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Zishi Energy Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • 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
    • 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
    • H01L31/0549—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising spectrum splitting means, e.g. dichroic mirrors
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/52—PV systems with concentrators

Abstract

The invention provides an organic spectrum conversion material, a preparation method thereof and a luminescent solar concentrator comprising the organic spectrum conversion material. The organic spectrum conversion material comprises triarylammonium-thiophene compound shown in formula (I). The triarylamine group and the thiophene group can form a larger rigid plane and a conjugated structure, and the delocalization of electrons is enhanced, thereby being beneficial to the transition of electrons. When the organic spectrum conversion material is adopted to absorb ultraviolet light below 400nm, the organic spectrum conversion material benefits from the characteristics of the structure of the organic spectrum conversion material, can convert the ultraviolet light into an effective radiation spectrum which can be absorbed by a photovoltaic cell, and has higher Stokes shift (larger than 170nm), thereby realizing the effect of greatly improving the photoelectric conversion efficiency of the photovoltaic cell.
Figure DDA0001883808570000011

Description

Organic spectrum conversion material, preparation method thereof and luminescent solar concentrator comprising organic spectrum conversion material
Technical Field
The invention relates to the field of solar cells, in particular to an organic spectrum conversion material, a preparation method thereof and a luminescent solar concentrator comprising the organic spectrum conversion material.
Background
The operating wavelength of the solar cell is larger than 400nm, that is, ultraviolet light below 400nm cannot be absorbed sufficiently and converted into electric energy. Spectral conversion materials (spectral converter materials) are capable of capturing solar radiation outside the optimal spectral range and converting it into useful radiation, and thus can be used to improve the performance of photovoltaic cells. The use of spectral conversion materials for the manufacture of Luminescent Solar Concentrators (LSCs) facilitates increasing the current in photovoltaic cells.
Luminescent Solar Concentrators (LSCs) are generally made of a transparent material, large plates, mixed with a spectral conversion material, capable of converting the light radiation of the bands not available to the solar cell into radiation emitted by fluorescent molecules. The optical phenomenon of total reflection is then used to "drive" the radiation emitted by the fluorescent molecules into the thin edge of the plate, which is concentrated on the solar cell mounted therein.
As a material for spectrum conversion, it is necessary to satisfy many requirements, of which the following are important: the absorption frequency and the emission frequency must be as different as possible, and the larger the stokes shift (the difference between the peak of the absorption spectrum with the lower frequency and the peak of the emitted radiation is generally expressed in stokes shift and measured in nm) the better, otherwise the radiation emitted by a molecule of the fluorescent compound will be absorbed by or at least partially diffused by the neighboring molecules.
Some existing luminescent solar concentrators adopt quantum dots as spectrum conversion materials, but the yield of the quantum dots is unstable, the manufacturing cost is high, and the preparation and performance of LSC are affected by the problems that the quantum dots are easy to agglomerate, difficult to disperse and the like.
The organic spectrum conversion material can avoid the problems, and the existing documents provide a series of benzothiadiazole compounds as the spectrum transfer material, but the Stokes shift of the organic spectrum conversion material is only 133-160 nm. The organic spectrum conversion material has no obvious effect on improving the performance of the photovoltaic cell because of smaller Stokes shift.
Disclosure of Invention
The invention mainly aims to provide an organic spectrum conversion material, a preparation method thereof and a luminescent solar concentrator comprising the organic spectrum conversion material, so as to solve the problem that the existing organic spectrum conversion material has poor performance of a photovoltaic cell due to small Stokes shift.
In order to achieve the above object, according to one aspect of the present invention, there is provided an organic spectrum-converting material comprising a triarylammonium-thiophene compound represented by formula (i):
Figure BDA0001883808550000021
wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen atom, halogen atom, dicyanovinyl group, - (C ═ O) R', carboxyl group, C 1 ～C 6 Alkyl radical, C 2 ～C 5 Alkenyl radical, C 3 ～C 10 Cycloalkyl or C 6 ～C 10 Aryl, wherein R' is selected from the group consisting of a hydrogen atom, C 1 ～C 6 Alkyl radical, C 2 ～C 5 Alkenyl radical, C 3 ～C 10 Cycloalkyl or C 6 ～C 10 And (4) an aryl group.
Further, R 1 、R 2 And R 3 Each independently selected from a hydrogen atom, a halogen atom, a dicyanovinyl group, - (C ═ O) R', a carboxyl group or C 2 ～C 5 A chain alkyl group.
Further, R 1 is-CHO, R 2 And R 3 Each independently selected from H or-CH ═ C (CN) 2 。
The application also provides a luminescent solar concentrator, which comprises a transparent substrate and the organic spectrum conversion material.
Furthermore, the weight ratio of the transparent base material to the organic spectrum conversion material is 1 (0.01-1).
The application also provides a preparation method of the organic spectrum conversion material, and the preparation method comprises the following steps: s1, under the protection of rare gas, adding the magnesium strip and halogenated thiophene into a first organic solvent to carry out a first reaction to obtain a Grignard reagent of the halogenated thiophene; s2 reacting dihalogenated triarylamine A, PdCl under the protection of rare gas 2 (PPh 3 ) 2 Adding the Grignard reagent of the halogenated thiophene into a second organic solvent to carry out a second reaction to obtain dithiophene aniline B; the halogenated thiophene is selected from one of 2-chlorothiophene, 2-bromothiophene and 2-iodothiophene, and the dihalogenated triarylamine A is selected from one of dichlorotriarylamine, dibromotriarylamine and diiodothiophene; s3, R in organic Spectrum-converting Material 1 、R 2 、R 3 When the compounds are all selected from hydrogen atoms, the dithienylaniline B is the organic spectrum conversion material; when R is 1 、R 2 、R 3 When at least one of the two is not selected from hydrogen atoms, the dithiophene aniline B is used as a first intermediate product to carry out substitution reaction on the dithiophene aniline B, and the organic spectrum conversion material is obtained.
Further, the first organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, DMF and toluene; the second organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, DMF and toluene.
Further, in step S1, the addition amount of the first organic solvent is 10 to 20mL, the addition amount of the halogenated thiophene is 3 to 8mL, the first reaction is a reflux reaction, and the reaction time is 1 to 2 hours per 0.1mol of the magnesium strip.
Further, in step S2, the second reaction is a reflux reaction, and the reaction time is 15-20 hours, with respect to every 0.008mol of halogenated triarylamine a, PdCl 2 (PPh 3 ) 2 The addition amount of (3) is 0.0001-0.0004 mol, the addition amount of the second organic solvent is 20-40 mL, and the addition amount of the Grignard reagent of halogenated thiophene is 0.024-0.030 mol.
Further, after the step of the second reaction and before obtaining the dithienylaniline B, the preparation method also comprises the step of adding a saturated ammonium chloride solution into a system of the second reaction to carry out a first quenching reaction; preferably, after the first quenching reaction is performed and before the dithienylaniline B is obtained, the preparation method further comprises the step of extracting and purifying the dithienylaniline B, and the step of extracting and purifying the dithienylaniline B comprises the following steps: performing first extraction on a product after the first quenching reaction by using chloroform, and then performing first drying treatment on a product obtained by the first extraction by using anhydrous sodium sulfate; performing column chromatography purification on the product subjected to the first drying treatment by using a first eluent to obtain dithiophene aniline B; wherein the first eluent is a mixed solution of n-hexane and dichloromethane in a volume ratio of 3: 1.
By applying the technical scheme of the invention, in the triarylamine-thiophene compound with the structure, triarylamine groups and thiophene groups can form a larger rigid plane and a conjugated structure, the delocalization of electrons is enhanced, and the transition of the electrons is facilitated. When the organic spectrum conversion material is used for absorbing ultraviolet light below 400nm, the organic spectrum conversion material is beneficial to the characteristics of the structure of the organic spectrum conversion material, can convert the ultraviolet light into an effective radiation spectrum which can be absorbed by a photovoltaic cell, and has higher Stokes shift (larger than 170nm), so that the effect of greatly improving the photoelectric conversion efficiency of the photovoltaic cell is realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows an infrared spectrum of an organic spectrum converting material obtained in example 1 according to the present invention; and
FIG. 2 shows an infrared spectrum of an organic spectrum converting material obtained in example 2 according to the present invention.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background, the existing organic spectral conversion materials have a problem that the stokes shift is small, resulting in a photovoltaic cell. In order to solve the above technical problems, the present application provides an organic spectrum conversion material comprising a triarylammonium-thiophene compound represented by formula (i):
Figure BDA0001883808550000031
wherein R is 1 、R 2 And R 3 Each independently selected from hydrogen atom, halogen atom, dicyanovinyl group, - (C ═ O) R', carboxyl group, C 1 ～C 6 Alkyl radical, C 2 ～C 5 Alkenyl radical, C 3 ～C 10 Cycloalkyl or C 6 ～C 10 Aryl, wherein R' is selected from the group consisting of a hydrogen atom, C 1 ～C 6 Alkyl radical, C 2 ～C 5 Alkenyl radical, C 3 ～C 10 Cycloalkyl or C 6 ～C 10 And (4) an aryl group.
In the triarylamine-thiophene compound with the structure, triarylamine groups and thiophene groups can form a larger rigid plane and a conjugated structure, and the electron delocalization is enhanced, thereby being beneficial to the transition of electrons. When the organic spectrum conversion material is used for absorbing ultraviolet light below 400nm, the organic spectrum conversion material is beneficial to the characteristics of the structure of the organic spectrum conversion material, can convert the ultraviolet light into an effective radiation spectrum which can be absorbed by a photovoltaic cell, and has higher Stokes shift (larger than 170nm), so that the effect of greatly improving the photoelectric conversion efficiency of the photovoltaic cell is realized.
Preferably, R 1 、R 2 And R 3 Each independently selected from the group consisting of, but not limited to, a hydrogen atom, a halogen atom, a dicyanovinyl group, - (C ═ O) R', a carboxyl group, and C 2 ～C 5 A chain alkyl group.
In order to further improve the photoelectric conversion efficiency of the spectrum conversion material, in the triarylammonium-thiophene compound shown in the formula (I), R 1 is-CHO, R 2 And R 3 Each independently selected from H or-CH ═ C (CN) 2 。
More preferably, R 1 is-CHO, R 2 And R 3 Is H, and has the following structural formula:
Figure BDA0001883808550000041
bis [4- (2-thienyl) phenyl]-4-formylphenylamine.
More preferably, R 1 is-CHO, R 2 And R 3 is-CH ═ C (CN) 2 The structural formula is as follows:
Figure BDA0001883808550000042
bis [4- (5-dicyanovinyl-2-thienyl) phenyl]-4-formylphenylamine.
The application also provides a preparation method of the organic spectrum conversion material, and the preparation method comprises the following steps: s1, under the protection of rare gas, adding the magnesium strip and halogenated thiophene into a first organic solvent to carry out a first reaction to obtain a Grignard reagent of the halogenated thiophene; s2, under the protection of rare gas, dihalogenated triarylamine A, PdCl 2 (PPh 3 ) 2 Adding the Grignard reagent of the halogenated thiophene into a second organic solvent to carry out a second reaction to obtain dithiophene aniline B; wherein, the halogenated thiophene is selected from one of 2-chlorothiophene, 2-bromothiophene and 2-iodothiophene, and the dihalogenated triarylamine A is selected from dichloro triarylamine AOne of amine, dibromo triarylamine and diiodothiophene; s3, R in organic spectrum conversion material 1 、R 2 、R 3 When the compounds are all selected from hydrogen atoms, the dithienylaniline B is the organic spectrum conversion material; when R is 1 、R 2 、R 3 When at least one of the two is not selected from hydrogen atoms, the dithiophene aniline B is used as a first intermediate product to carry out substitution reaction on the dithiophene aniline B, and the organic spectrum conversion material is obtained.
According to the technical scheme provided by the application, firstly, a Grignard reagent of halogenated thiophene is prepared, and then dihalogenated triarylamine A and the Grignard reagent of the halogenated thiophene are mixed and reacted to obtain dithiophene aniline B, so that the triarylamine-thiophene system compound which can be used as the most basic compound is obtained. The Grignard reagent containing the thiophene structure is preferably prepared by the method, and then the Grignard reagent reacts with the compound containing the triarylamine, so that on one hand, the operation is simple and convenient, and the Grignard reagent is easy to obtain; on the other hand, the generation of byproducts and the interference thereof are reduced, and the yield of the obtained dithienylaniline B is high. In addition, due to the active characteristic of thiophene groups, dithiophene aniline B can be used as a first intermediate product for further substitution, so that an organic spectrum conversion material with higher performance can be obtained. Of course, the methods for preparing the more various organic spectrum conversion materials include, but are not limited to, the methods provided above, and the organic spectrum conversion materials can also be obtained by preferentially performing substitution of corresponding functional groups on thiophene groups according to actual requirements and then combining the derivatized thiophene groups with reaction of triarylamine-containing compounds.
In a preferred embodiment, the first organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, DMF and toluene; preferably, in step S1, the amount of the first organic solvent added is 10 to 20mL and the amount of the halogenated thiophene added is 3 to 8mL per 0.1mol of magnesium strip. The first organic solvent is selected from the group including, but not limited to, those provided above, but the organic solvent provided above is used to facilitate the more sufficient dissolution of magnesium and the halogenated thiophene to facilitate the reaction when contacting each other. Similarly, the addition ratio of the magnesium strip, the halogenated thiophene and the first organic solvent is not limited to the ratio provided above, but the reaction is carried out according to the ratio provided above, so that the generation of byproducts can be reduced, the structure of thiophene groups can be prevented from being damaged, the yield of the grignard reagent of the halogenated thiophene can be improved, and the performance of the organic hole transport material can be improved.
In a preferred embodiment, in step S1, the first reaction is a reflux reaction, and the reaction time is 1-2 hours; in step S2, the second reaction is a reflux reaction, and the reaction time is 15-20 h. The above mixed reactants are heated and then subjected to a reflux reaction, whereby the recovery rate of the product can be further improved, and the reaction time can be controlled to obtain a higher yield.
In a preferred embodiment, the second organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, DMF and toluene. The second organic solvent is selected from the group including, but not limited to, those provided above, but advantageously employed in the preparation of the halotriarylamine A and PdCl 2 (PPh 3 ) 2 More fully dissolved to facilitate the reaction in contact with each other.
In a preferred embodiment, in step S2, PdCl is added for every 0.008mol of the halogenated triarylamine a 2 (PPh 3 ) 2 The addition amount of the halogenated thiophene is 0.0001-0.0004 mol, the addition amount of the second organic solvent is 20-40 mL, and the addition amount of the halogenated thiophene Grignard reagent is 0.024-0.030 mol. Halogenated triarylamine A, PdCl 2 (PPh 3 ) 2 The ratio of the second organic solvent to be added is not limited to the above-mentioned ratio, but the reaction carried out in the above-mentioned ratio can reduce the production of by-products and improve the yield of dithienylaniline B.
In a preferred embodiment, after the second reaction step and before obtaining the dithienylaniline B, the preparation method further comprises a step of adding a saturated ammonium chloride solution to the system of the second reaction to perform a first quenching reaction; preferably, after the first quenching reaction is performed and before the dithienylaniline B is obtained, the preparation method further comprises the step of extracting and purifying the dithienylaniline B, and the step of extracting and purifying the dithienylaniline B comprises the following steps: performing first extraction on a product after the first quenching reaction by using chloroform, and then performing first drying treatment on a product obtained by the first extraction by using anhydrous sodium sulfate; performing column chromatography purification on the product subjected to the first drying treatment by using a first eluent to obtain dithiophene aniline B; wherein the first eluent is a mixed solution of n-hexane and dichloromethane in a volume ratio of 3: 1. After the reflux reaction is carried out for a period of time, the second reaction can be stopped by quenching reaction, the preparation process is simplified, and the extraction and purification steps further improve the purity of the dithienylaniline B and avoid the adverse effect of other chemical combination components on the performance of the dithienylaniline B used as the organic spectrum conversion material; moreover, when the dithienylaniline B is used as a first intermediate product to prepare other organic spectral conversion materials, the dithienylaniline B with higher purity can reduce the generation of byproducts and improve the yield of the target organic spectral conversion material.
For a better understanding of the present application, a further aspect of the present application also provides a luminescent solar concentrator comprising a transparent substrate and the above-mentioned organic spectrum converting material.
In the triarylamine-thiophene compound with the structure, triarylamine groups and thiophene groups can form a larger conjugated structure, so that the energy system of the whole compound is lower, and the transition of electrons is facilitated. When the organic spectrum conversion material is used for absorbing ultraviolet light below 400nm, the organic spectrum conversion material can convert the ultraviolet light into an effective radiation spectrum which can be absorbed by a photovoltaic cell and has higher Stokes shift (more than 170nm) by virtue of the characteristics of the structure of the organic spectrum conversion material. The application of the organic spectrum conversion material with the structure and the transparent base material in the preparation of the luminescent solar concentrator is beneficial to improving the proportion of the spectrum which can be absorbed by the photovoltaic cell in the spectrum emitted by the concentrator, thereby being beneficial to increasing the current in the photovoltaic cell.
In the above luminescent solar concentrator, the weight ratio of the transparent substrate to the organic spectrum conversion material may be in a ratio commonly used in the art. In a preferred embodiment, the weight ratio of the transparent substrate to the organic spectrum conversion material is 1 (0.01-1). Limiting the weight ratio of the transparent substrate to the organic spectrum conversion material within the above range is beneficial to further improving the photoelectric conversion efficiency of the luminescent solar concentrator, and is further beneficial to improving the current in the photovoltaic cell.
In the above luminescent solar concentrator, the transparent substrate is not limited to a specific kind, and a substrate commonly used in the art, such as a polymer substrate and/or a glass substrate, may be used.
Preferably, the polymeric substrate includes, but is not limited to, one or more of the group consisting of polymethylmethacrylate, epoxy resin, silicone resin, polyalkylene terephthalate, polycarbonate, polystyrene, and polypropylene.
Preferably, the glassy substrate includes, but is not limited to, silica and/or polymethyl methacrylate (PMMA).
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
(1) Preparation of organic spectrum conversion material:
Figure BDA0001883808550000071
2.528g of polished magnesium strips are weighed and placed in a three-neck flask, 15mL of distilled tetrahydrofuran THF is added, nitrogen is introduced for protection, 5mL of 2-bromothiophene is dripped into a constant pressure funnel for carrying out a first reflux reaction, and the reaction is stopped after the reflux is carried out for 1h, so that the Grignard reagent of the 2-bromothiophene is obtained. 4.027g of dibromotriphenylamine and 0.135g of PdCl are weighed out 2 (PPh 3 ) 2 Adding 30mL of THF into a three-neck flask, adding a Grignard reagent of 2-bromothiophene while stirring, heating for carrying out a second reflux reaction for 16 hours under the protection of nitrogen, adding saturated ammonium chloride for quenching reaction, then extracting a product obtained after quenching with chloroform, drying the product obtained after extraction with anhydrous sodium acetate, and carrying out column chromatography purification on the dried product with an eluent consisting of n-hexane and dichloromethane (the volume ratio is 3:1) to obtain 3.48g of a yellowish green needle crystal compound (1), namely the yield is that75.4% of dithienylaniline.
Weighing 0.573g dithienylaniline (compound 1) and placing the dithienylaniline into a three-neck flask, adding 10mL 1-dichloroethane and 2mL DMMF, stirring in an ice bath for 0.5h under the protection of nitrogen, then dropwise adding 2mL phosphorus oxychloride by using a constant pressure funnel, heating for carrying out a third reflux reaction for 15h, then cooling and pouring into ice water, adding 100mL saturated sodium acetate solution for carrying out a quenching reaction, then extracting the quenched product by using 50mL dichloromethane, simultaneously washing an organic layer for a plurality of times by using water, then drying the extracted product by using anhydrous sodium sulfate, finally purifying the dried product by using dichloromethane and ethyl acetate eluent (the volume ratio is 20:1) by column chromatography, separating to obtain 0.53g orange yellow solid product (2), namely bis [4- (2-thienyl) phenyl ] -4-formylphenylamine, the yield thereof was 73.3%. The infrared spectrum is shown in figure 1.
(2) Preparing a luminescent solar concentrator:
6g of polymethyl methacrylate PMMA and 76.5mg of bis [4- (2-thienyl) phenyl ] -4-formylphenylamine (formula Ia) are dissolved in 30mL of 1, 2-dichlorobenzene. Subsequently, the resulting solution was uniformly deposited on a polymethyl methacrylate Plate (PMMA) (size 90 mm. times.90 mm. times.6 mm) using a knife type film coater, and the solvent was exposed to air at room temperature (25 ℃) to evaporate for 24 hours. The luminescent solar concentrator 1 is obtained.
Example 2
(1) Preparation of organic spectrum conversion material:
Figure BDA0001883808550000072
weighing 0.573g dithienylaniline (1) into a three-neck flask, adding 10mL of 1-dichloroethane and 2mL of DMMF, stirring in an ice bath for 0.5h under the protection of nitrogen, then dropwise adding 6mL of phosphorus oxychloride into a constant pressure funnel, heating for carrying out a third reflux reaction for 15h, then cooling and pouring into ice water, adding 100mL of saturated sodium acetate solution for carrying out a quenching reaction, then extracting the quenched product with 50mL of dichloromethane, simultaneously washing an organic layer for a plurality of times with water, then drying the extracted product with anhydrous sodium sulfate, finally purifying the dried product by column chromatography by using dichloromethane and ethyl acetate eluent with the volume ratio of 25:1, and separating to obtain 0.67g orange yellow solid product (3), namely bis [4- (5-formyl-2-thienyl) phenyl ] -4-formylphenylamine (3), the yield was 80.3%.
0.25g of bis [4- (5-formyl-2-thienyl) phenyl ] -4-formylphenylamine (3) and 50mL of malononitrile were weighed and placed in a round-bottom flask, and then 15mL of dichloromethane was added thereto and dissolved by stirring, 20mL of triethylamine was added thereto and reacted at room temperature for 2 hours, and then petroleum ether was added thereto and subjected to precipitation reaction to obtain a red-black solid precipitate, which was purified by column chromatography using dichloromethane to obtain 0.18g of a blood-red solid product (4), i.e., bis [4- (5-dicyanovinyl-2-thienyl) phenyl ] -4-formylphenylamine, in a yield of 42.5%. The infrared spectrum is shown in figure 2.
(2) Preparing a luminescent solar concentrator:
6g of polymethyl methacrylate PMMA and 80.5mg of bis [4- (5-dicyanovinyl-2-thienyl) phenyl ] -4-formylphenylamine (formula Ib) are dissolved in 30mL of 1, 2-dichlorobenzene. Subsequently, the resulting solution was uniformly deposited on a polymethylmethacrylate Plate (PMMA) (size 90 mm. times.90 mm. times.6 mm) using a knife-type film coater, and the solvent was evaporated in a small air flow at room temperature (25 ℃ C.) for 24 hours. The luminescent solar concentrator 2 is obtained.
Example 3
24g of polymethyl methacrylate PMMA and 320mg of bis [4- (5-dicyanovinyl-2-thienyl) phenyl ] -4-formylphenylamine (formula Ib) are dissolved in 150mL of 1, 2-dichlorobenzene. Subsequently, the resulting solution was uniformly deposited on a polymethylmethacrylate Plate (PMMA) (size 90 mm. times.90 mm. times.6 mm) using a knife-type film coater, and the solvent was evaporated in a small air flow at room temperature (25 ℃ C.) for 24 hours. The luminescent solar concentrator 3 is obtained.
Example 4
The differences from example 1 are: r 1 Is a halogen atom, R 2 Is a dicyanovinyl group, R 3 Is a carboxyl group.
Accordingly, a luminescent solar concentrator 4 is available.
Example 5
The differences from example 1 are: r 1 Is butyl, R 2 Is ethyl, R 3 Is cyclopropyl.
Accordingly, a luminescent solar concentrator 5 is available.
Example 6
The differences from example 1 are: r 1 Is H, R 2 Is methyl, R 3 Is methyl.
Accordingly, a luminescent solar concentrator 6 is available.
And (3) performance testing:
the performance of the luminescent solar concentrator was tested using a Shimadzu RF5301PC fluorescence spectrophotometer (Shimadzu, japan) with the following instrument parameters: the spectral type: an Emission; excitation wave wavelength: 370 nm; test emission wavelength range: 400 nm-800 nm; wave intensity recording range: determined by the intensity of the emission spectrum; scanning speed: super; grating width: EX 5; EM 5, and other parameters are software default parameters.
Respectively dissolving luminescent solar condenser in chloroform to obtain 1 × 10 solution -5 The difference between the fluorescence emission peak and the excitation peak is measured as the Stokes shift in nm using a fluorescence spectrophotometer for the solution in mol/L. The results of the tests are shown in Table 1.
TABLE 1
Stoke shift, nm
Example 1 178nm
Examples2 185nm
Example 3 185nm
Example 4 165nm
Example 5 160nm
Example 6 166nm
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the organic spectrum conversion material provided by the application is favorable for greatly improving the Stokes shift of the spectrum conversion material, and further can obviously improve the comprehensive performance of the photovoltaic cell.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. An application of an organic spectrum conversion material on a luminescent solar concentrator is characterized in that the luminescent solar concentrator comprises a transparent substrate and an organic spectrum conversion material, wherein the organic spectrum conversion material comprises a triarylamine-thiophene compound shown in a formula (I):
Figure FDA0003709689710000011
wherein R is 1 is-CHO and R 2 And R 3 Simultaneously is-CH ═ C (CN) 2 (ii) a Or R 1 Is a halogen atom, R 2 Is a dicyanovinyl group and R 3 Is a carboxyl group; or R 1 Is butyl, R 2 Is ethyl and R 3 Is cyclopropyl; or R 1 Is H and R 2 And R 3 And is simultaneously methyl;
the weight ratio of the transparent base material to the organic spectrum conversion material is 1 (0.01-1).
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