CN113113542B - Conformable high-transparency luminous solar concentrator and preparation method thereof - Google Patents
Conformable high-transparency luminous solar concentrator and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-transparency luminous solar concentrator capable of being attached and a preparation method thereof, wherein the luminous solar concentrator is of a layered structure, and the layered structure is as follows: (1) The laminated structure sequentially comprises a glass substrate, a perovskite-polyvinylidene fluoride composite film, a polystyrene anti-reflection/blocking layer, an ultraviolet light curing adhesive, a polystyrene anti-reflection/blocking layer, a perovskite-polyvinylidene fluoride composite film and the glass substrate from bottom to top; (2) The layered structure sequentially comprises a glass substrate, a perovskite-polyvinylidene fluoride composite film, a polystyrene anti-reflection/blocking layer and the glass substrate from bottom to top. The preparation method simplifies the preparation of the perovskite luminescent solar concentrator, improves the fluorescence quantum yield of the perovskite-PVDF composite film prepared in situ, improves the transmittance of the perovskite luminescent solar concentrator, and reduces the manufacturing cost of the perovskite luminescent solar concentrator.
Description
Technical Field
The invention relates to a conformable high-transparency luminous solar concentrator and a preparation method thereof, belonging to the field of photovoltaic devices.
Background
The luminous solar concentrator is a large-area photoelectric conversion device, can absorb sunlight incident from the front, and transmits the sunlight to the side through the down-conversion of fluorophores and waveguide media, and finally converts the sunlight into electric energy through a side-coupled photovoltaic device. Luminescent solar concentrators are a complement to conventional photovoltaic devices, providing a viable strategy for meeting the ever-increasing clean, renewable energy demands. In recent years, lead-halogen perovskite has become an excellent candidate for preparing luminescent solar concentrators at its low material cost and high fluorescence quantum yield. Currently, the preparation of perovskite luminescent solar concentrators generally comprises the following steps: (1) pre-synthesis and purification of perovskite luminescent materials; (2) Redispersing the prepared perovskite luminescent material in a polymer monomer; (3) The monomers are polymerized or film coated after introduction of the photoinitiator. The preparation process is relatively complex and needs to be further simplified. In the use process of the conventional luminescent solar concentrator, the original glass window or curtain wall of a building needs to be completely removed, which increases the practical use cost. Therefore, a new strategy is needed to be proposed, which not only simplifies the preparation of the perovskite luminescent solar concentrator, but also can directly convert the original glass window or curtain wall on the building into the luminescent solar concentrator, thereby reducing the use cost of the luminescent solar concentrator.
Disclosure of Invention
The invention aims to provide a high-transparency luminous solar concentrator capable of being attached and a preparation method thereof, so that the preparation of the perovskite luminous solar concentrator is simplified, the fluorescence quantum yield of an in-situ prepared perovskite-polyvinylidene fluoride composite film is improved, the transmittance of the perovskite luminous solar concentrator is improved, and the use cost of the perovskite luminous solar concentrator is reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the utility model provides a but laminating formula high transparent luminous solar concentrator, this luminous solar concentrator is the lamellar structure, the lamellar structure is one of the following:
(1) The laminated structure sequentially comprises a glass substrate, a perovskite-polyvinylidene fluoride composite film, a polystyrene anti-reflection/blocking layer, an ultraviolet light curing adhesive, a polystyrene anti-reflection/blocking layer, a perovskite-polyvinylidene fluoride composite film and the glass substrate from bottom to top;
(2) The layered structure sequentially comprises a glass substrate, a perovskite-polyvinylidene fluoride composite film, a polystyrene anti-reflection/blocking layer and the glass substrate from bottom to top.
A preparation method of a conformable high-transparency luminous solar concentrator comprises the following steps:
(1) Preparing a perovskite-polyvinylidene fluoride composite film: mixing perovskite precursor liquid containing long-chain ligand with polyvinylidene fluoride (PVDF) in N, N-Dimethylformamide (DMF) to prepare viscous perovskite-polyvinylidene fluoride slurry; the prepared perovskite-polyvinylidene fluoride slurry is coated on a glass substrate in a scraping way to form a uniform liquid film; placing the glass substrate with the liquid film into a vacuum oven for drying, then taking out the glass substrate with the perovskite-polyvinylidene fluoride composite film, and cutting for later use;
(2) Preparation of polystyrene antireflective/barrier layer: dissolving Polystyrene (PS) in toluene to prepare viscous polystyrene-toluene slurry; spreading polystyrene-toluene slurry on the perovskite-polyvinylidene fluoride composite film obtained in the step (1), and then airing to obtain a glass substrate with the perovskite-polyvinylidene fluoride composite film and a polystyrene anti-reflection/barrier layer;
(3) Preparing a luminescent solar concentrator: and (3) laminating and curing the two glass substrates with the perovskite-polyvinylidene fluoride composite film and the polystyrene anti-reflection/blocking layer obtained in the step (2) face to face by using an ultraviolet light curing adhesive, or laminating the glass substrate with the perovskite-polyvinylidene fluoride composite film and the polystyrene anti-reflection/blocking layer obtained in the step (2) with another glass substrate.
In the step (1), the perovskite precursor liquid is prepared from lead iodide (PbI) 2 ) Methyl iodinated amine (MAI) and phenethyl iodinated amine (PEAI) according to PbI 2 :MAI:PEAI＝1:[(n-1)/n]Is prepared by dissolving (2/N) in N, N-Dimethylformamide (DMF), wherein the value of N is 1-5 and PbI 2 Is 0.08mmol/mL; when preparing perovskite-polyvinylidene fluoride slurry, perovskite precursor liquid, polyvinylidene fluoride and N, N-dimethylformamide are mixed according to the proportion of 2mL:0.84g:5mL of the mixture was mixed and the mixture was stirred well in a water bath at 70℃to allow sufficient dissolution of the polyvinylidene fluoride.
In the step (1), a liquid film is prepared by a knife coating mode, the knife coating height is 50 mu m, and the drying is carried out in a vacuum low-pressure environment at 40 ℃.
In the step (2), polystyrene (PS) is dissolved in toluene, and the obtained mixture is fully stirred in a water bath at 70 ℃ so that the polystyrene is fully dissolved, and the concentration of the polystyrene is 0.33g/mL.
In the step (2), the polystyrene anti-reflection/blocking layer is prepared by a knife coating method, the knife coating height is 120 mu m, and after the knife coating is finished, the liquid film is placed in air for drying for 2 hours, so that toluene is completely volatilized.
In the step (3), the ultraviolet light curing adhesive has light transmittance, and after the bonding, the ultraviolet light curing adhesive is irradiated by using an ultraviolet lamp of 320-400 nm until the ultraviolet light curing adhesive is completely cured.
The beneficial effects are that: compared with the prior art, the attachable high-transparency luminous solar concentrator and the preparation method thereof provided by the invention have the following advantages:
(1) The operation is simple, the material utilization rate is high, the dependency on equipment is small, and the preparation period is short;
(2) The air/humidity stability of the film is good;
(3) The luminescent layer is clamped between two glass substrates to form a sandwich structure, and the sandwich structure is beneficial to protecting the luminescent layer from being scratched;
(4) The in-situ preparation of the ligand-assisted perovskite-polyvinylidene fluoride composite film simplifies the luminescent layer, avoids the preparation, purification and redispersion processes of perovskite materials, greatly simplifies the preparation of the luminescent layer, and improves the utilization rate of materials;
(5) Compared with a composite film without the ligand, the perovskite-polyvinylidene fluoride composite film prepared by introducing the ligand into the perovskite precursor liquid has obviously improved fluorescence quantum yield;
(6) The PS anti-reflection/blocking layer greatly improves the transmittance of the device and inhibits the damage and photoluminescence quenching of the luminescent layer caused by the ultraviolet light curing adhesive;
(7) The luminous layer prepared in situ is favorable for preparing the attachable high-transparency luminous solar concentrator, and is hopeful to directly refit the original common glass window or curtain wall of a building into the luminous solar concentrator, thereby saving the cost in actual use.
Drawings
FIG. 1 is a PLQY comparison of several samples of example 1;
FIG. 2 is an atomic force microscope image and multi-line scanning results of the composite film obtained in example 2, wherein (a) is an atomic force microscope image and multi-line scanning results of a < n > = 3 perovskite-polyvinylidene fluoride composite film without a scratch-coated polystyrene anti-reflection/barrier layer; (b) Atomic force microscope images and multi-line scanning result graphs of < n > =3 perovskite-polyvinylidene fluoride composite films for doctor-blading polystyrene anti-reflection/barrier layers;
FIG. 3 is a graph showing the transmittance of a perovskite-polyvinylidene fluoride composite film of < n > = 3 before and after doctor blading a polystyrene antireflective/barrier layer in example 2;
FIG. 4 is a graph of current density versus voltage for perovskite luminescent solar concentrators of different PEAI content as described in example 3;
FIG. 5 is a graph comparing optical efficiency of perovskite luminescent solar concentrators of different PEAI content in example 3;
FIG. 6 is a schematic diagram of one embodiment of a conformable highly transparent luminescent solar concentrator of the present invention.
Detailed Description
The invention will be further explained with reference to examples and figures.
Example 1
(1) Preparing perovskite precursor liquid: pbI of lead iodide 2 Methyl iodinated amine MAI and phenethyl iodinated amine PEAI according to PbI 2 :MAI:PEAI＝1:[(n-1)/n](2/N) in N, N-dimethylformamide DMF, wherein N has values of 1,2,3,4 and 5, and the corresponding samples are respectively recorded as<n>=1, 2,3,4 and 5. In addition, lead iodide PbI 2 With methyl iodinated amine MAI according to PbI 2 MAI=1:1 in N, N-dimethylformamide DMF, the corresponding sample was designated Pristine, and the PEAI-free sample was used for comparison with other PEAI-containing samples. PbI 2 The concentration of (C) was 0.08mmol/mL.
(2) Perovskite-polyvinylidene fluoride slurry preparation: 2mL of the perovskite precursor solution of step (1) and 0.84g of polyvinylidene fluoride PVDF were added to 5mL of N, N-dimethylformamide DMF. The mixture was stirred thoroughly in a 70 ℃ water bath to allow for sufficient dissolution of PVDF.
(3) Perovskite-polyvinylidene fluoride composite film preparation: dropping the perovskite-polyvinylidene fluoride slurry in the step (2) on a glass substrate, and carrying out blade coating by using a four-corner film scraper, wherein the blade coating height parameter is set to be 50 mu m. Then, the sample is put into a vacuum oven, and the drying process is carried out in a vacuum low-pressure environment at 40 ℃. After the film turns brown, the sample is taken out of the vacuum oven, dried to room temperature and cut for later use, and then PLQY test is performed.
Fig. 1 is a PLQY comparison of six samples, as shown by the lower PLQY for the < n > = 1 samples without MAI compared to the film samples without pei incorporation. < n > = PLQY of 2,3,4,5 samples were raised by 2.1, 10.2,7.2,5.8 times, respectively. Thus, the introduction of an appropriate amount of PEAI provides a significant improvement in PLQY of the film.
Example 2
(1) Preparing perovskite precursor liquid: pbI of lead iodide 2 Methyl iodinated amine MAI and phenethyl iodinated amine PEAI according to PbI 2 MAI/PEAI=1:0.67:0.67 in N, N-dimethylformamide DMF, sample was recorded as<n>＝3。PbI 2 The concentration of (C) was 0.08mmol/mL.
(2) Perovskite-polyvinylidene fluoride slurry preparation: 2mL of the perovskite precursor solution of step (1) and 0.84g of polyvinylidene fluoride PVDF were added to 5mL of N, N-dimethylformamide DMF. The mixture was stirred thoroughly in a 70 ℃ water bath to allow for sufficient dissolution of PVDF.
(3) Perovskite-polyvinylidene fluoride composite film preparation: and (3) dripping the perovskite-polyvinylidene fluoride slurry in the step (2) on a glass substrate, and carrying out blade coating by using a four-corner film scraper, wherein the blade coating height parameter is 50 mu m. Then, the sample is put into a vacuum oven, and the drying process is carried out in a vacuum low-pressure environment at 40 ℃. And after the film turns brown, taking out the sample from the vacuum oven, airing to normal temperature, cutting for later use, and carrying out atomic force microscope and transmittance characterization on the sample.
(4) Preparation of polystyrene anti-reflection/blocking layer: 2g of polystyrene PS was dissolved in 6mL of toluene and the mixture was stirred well in a 70℃water bath to allow for adequate dissolution of polystyrene PS. And (3) dripping polystyrene-toluene slurry on the perovskite-polyvinylidene fluoride composite film in the step (3), and carrying out blade coating by using a four-corner film scraper, wherein the blade coating height parameter is set to be 120 mu m. After the blade coating was completed, the liquid film was dried in air for 2 hours to evaporate toluene completely. And (3) carrying out atomic force microscope and transmittance characterization on the sample, and comparing the characterization results in the step (3).
Fig. 2a shows AFM image and multi-line scanning result of < n > =3 perovskite-polyvinylidene fluoride composite film without polystyrene anti-reflection/blocking layer, with high surface roughness and gully-like undulation on the film surface. Fig. 2b shows an AFM image of a < n > =3 perovskite-polyvinylidene fluoride composite film containing a polystyrene anti-reflection/blocking layer and a multi-line scanning result, wherein original gully-like undulations on the surface of the film layer are filled, the roughness is obviously reduced, and the scattering is effectively inhibited.
Fig. 3 is a transmittance comparison of < n > =3 perovskite-polyvinylidene fluoride composite films before and after knife coating of a polystyrene antireflective/barrier layer. The transmittance of the < n > =3 perovskite-polyvinylidene fluoride composite film containing the polystyrene anti-reflection/blocking layer is obviously improved.
Example 3
(1) Preparing perovskite precursor liquid: pbI of lead iodide 2 Methyl iodinated amine MAI and phenethyl iodinated amine PEAI according to PbI 2 :MAI:PEAI＝1:[(n-1)/n]The molar ratio of (2/N) is dissolved in N, N-dimethylformamide DMF, wherein the value of N is as follows: 1,2,3,4 and 5, the corresponding samples are respectively designated as<n>=1, 2,3,4 and 5. In addition, lead iodide PbI 2 With methyl iodinated amine MAI according to PbI 2 MAI=1:1 in N, N-dimethylformamide DMF, the corresponding sample was designated Pristine, and the PEAI-free sample was used for comparison with other PEAI-containing samples. PbI 2 The concentration of (C) was 0.08mmol/mL.
(2) Perovskite-polyvinylidene fluoride slurry preparation: 2mL of the perovskite precursor solution of step (1) and 0.84g of polyvinylidene fluoride PVDF were added to 5mL of N, N-dimethylformamide DMF. The mixture was stirred thoroughly in a 70 ℃ water bath to allow for sufficient dissolution of PVDF.
(3) Perovskite-polyvinylidene fluoride composite film preparation: dropping the perovskite-polyvinylidene fluoride PVDF slurry obtained in the step (2) on a glass substrate, and carrying out blade coating by using a four-corner film scraper, wherein the blade coating height parameter is set to be 50 mu m. Then, the sample is put into a vacuum oven, and the drying process is carried out in a vacuum low-pressure environment at 40 ℃. After the film turns brown, the sample is taken out of the vacuum oven, dried to normal temperature and cut for later use.
(4) Preparation of polystyrene anti-reflection/blocking layer: 2g of polystyrene PS was dissolved in 6mL of toluene and the mixture was stirred well in a 70℃water bath to allow for adequate dissolution of the olefin PS. And (3) dripping a polystyrene-toluene solution on the perovskite-polyvinylidene fluoride composite film in the step (3), and carrying out blade coating by using a four-corner film scraper, wherein the blade coating height parameter is set to be 120 mu m. After the blade coating was completed, the liquid film was dried in air for 2 hours to evaporate toluene completely.
(5) Perovskite luminescent solar concentrator preparation: and (3) bonding the two perovskite-polyvinylidene fluoride composite films by using an ultraviolet light curing adhesive, wherein the glass substrate is arranged on the outer side. And irradiating by using a 365nm ultraviolet lamp to cure the ultraviolet curing adhesive. And then, coupling a silicon solar cell at the side of the luminescent solar concentrator to test the current density-voltage and optical efficiency.
Fig. 4 is a current density-voltage curve of perovskite luminescent solar concentrators of different PEAI content, samples with < n > =1 had lower short circuit current density due to lower PLQY, while samples with < n > =2, 3,4 and 5 obtained a significant improvement over samples without PEAI incorporation.
Fig. 5 is a comparison of optical efficiency of perovskite luminescent solar concentrators of different PEAI content. Similar to the results reflected in fig. 4, the optical efficiency was lower for the samples with < n > =1 because PLQY was lower, while the optical efficiency was significantly improved for the samples with < n > =2, 3,4, and 5 compared to the samples without PEAI incorporation. Where < n > =3 samples obtained an optical efficiency of 2.8% at a geometry factor of 5.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (7)
1. The utility model provides a but laminating formula high transparent luminous solar concentrator which characterized in that: the luminescent solar concentrator is of a layered structure, and the layered structure is one of the following:
(1) The laminated structure sequentially comprises a glass substrate, a perovskite-polyvinylidene fluoride composite film, a polystyrene anti-reflection/blocking layer, an ultraviolet light curing adhesive, a polystyrene anti-reflection/blocking layer, a perovskite-polyvinylidene fluoride composite film and the glass substrate from bottom to top;
(2) The layered structure sequentially comprises a glass substrate, a perovskite-polyvinylidene fluoride composite film, a polystyrene anti-reflection/blocking layer and the glass substrate from bottom to top.
2. The method for manufacturing a conformable highly transparent luminescent solar concentrator according to claim 1, wherein: the method comprises the following steps:
(1) Preparing a perovskite-polyvinylidene fluoride composite film: mixing perovskite precursor liquid containing long-chain ligand with polyvinylidene fluoride in N, N-dimethylformamide to prepare viscous perovskite-polyvinylidene fluoride slurry; the prepared perovskite-polyvinylidene fluoride slurry is coated on a glass substrate in a scraping way to form a uniform liquid film; placing the glass substrate with the liquid film into a vacuum oven for drying, then taking out the glass substrate with the perovskite-polyvinylidene fluoride composite film, and cutting for later use;
(2) Preparation of polystyrene antireflective/barrier layer: dissolving polystyrene in toluene to prepare viscous polystyrene-toluene slurry; spreading polystyrene-toluene slurry on the perovskite-polyvinylidene fluoride composite film obtained in the step (1), and then airing to obtain a glass substrate with the perovskite-polyvinylidene fluoride composite film and a polystyrene anti-reflection/barrier layer;
(3) Preparing a luminescent solar concentrator: and (3) laminating and curing the two glass substrates with the perovskite-polyvinylidene fluoride composite film and the polystyrene anti-reflection/blocking layer obtained in the step (2) face to face by using an ultraviolet light curing adhesive, or laminating the glass substrate with the perovskite-polyvinylidene fluoride composite film and the polystyrene anti-reflection/blocking layer obtained in the step (2) with another glass substrate.
3. Conformable highly transparent light emitting according to claim 2The preparation method of the solar concentrator is characterized by comprising the following steps of: in the step (1), the perovskite precursor liquid is prepared from lead iodide, methyl iodized amine and phenethyl iodized amine according to PbI 2 :MAI:PEAI＝1:[(n-1)/n]The (2/N) molar ratio is dissolved in N, N-dimethylformamide, wherein, the value range of N is 1-5, pbI 2 Is 0.08mmol/mL; when preparing perovskite-polyvinylidene fluoride slurry, perovskite precursor liquid, polyvinylidene fluoride and N, N-dimethylformamide are mixed according to the proportion of 2mL:0.84g:5mL of the mixture was mixed and the mixture was stirred well in a water bath at 70℃to allow sufficient dissolution of the polyvinylidene fluoride.
4. The method for manufacturing a conformable highly transparent luminescent solar concentrator according to claim 2, wherein: in the step (1), a liquid film is prepared by a knife coating mode, the knife coating height is 50 mu m, and the drying is carried out in a vacuum low-pressure environment at 40 ℃.
5. The method for manufacturing a conformable highly transparent luminescent solar concentrator according to claim 2, wherein: in the step (2), polystyrene is dissolved in toluene, and the obtained mixture is fully stirred in a water bath at 70 ℃ to fully dissolve the polystyrene, wherein the concentration of the polystyrene is 0.33g/mL.
6. The method for manufacturing a conformable highly transparent luminescent solar concentrator according to claim 2, wherein: in the step (2), the polystyrene anti-reflection/blocking layer is prepared by a knife coating method, the knife coating height is 120 mu m, and after the knife coating is finished, the liquid film is placed in air for drying for 2 hours, so that toluene is completely volatilized.
7. The method for manufacturing a conformable highly transparent luminescent solar concentrator according to claim 2, wherein: in the step (3), the ultraviolet light curing adhesive has light transmittance, and after the bonding, the ultraviolet light curing adhesive is irradiated by using an ultraviolet lamp of 320-400 nm until the ultraviolet light curing adhesive is completely cured.
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