CN114541041A - Preparation method and application of flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane - Google Patents
Preparation method and application of flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane Download PDFInfo
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- CN114541041A CN114541041A CN202210150268.8A CN202210150268A CN114541041A CN 114541041 A CN114541041 A CN 114541041A CN 202210150268 A CN202210150268 A CN 202210150268A CN 114541041 A CN114541041 A CN 114541041A
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- inorganic perovskite
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- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 46
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 27
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
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- 239000011347 resin Substances 0.000 claims abstract description 11
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- 239000000654 additive Substances 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 12
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- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
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- 150000005309 metal halides Chemical class 0.000 claims description 5
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- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 4
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 4
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 4
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- ODLHGICHYURWBS-LKONHMLTSA-N trappsol cyclo Chemical compound CC(O)COC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](COCC(C)O)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)COCC(O)C)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1COCC(C)O ODLHGICHYURWBS-LKONHMLTSA-N 0.000 claims description 3
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 2
- 239000012769 display material Substances 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002798 polar solvent Substances 0.000 abstract description 5
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- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001523 electrospinning Methods 0.000 description 3
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 3
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- 239000002096 quantum dot Substances 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/26—Materials of the light emitting region
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a preparation method and application of a flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane2Dissolving inorganic halide salt AX in organic solvent to obtain all-inorganic perovskite ABX3Precursor solution, then addingInjecting the precursor solution into a high molecular resin solution to prepare a spinning solution 1; adding cyclodextrin additives and fluorine-containing silane into the spinning solution 1 to prepare a spinning solution 2; and finally, spinning the spinning solution 2 by an electrostatic spinning technology to prepare the large-area fiber membrane. The preparation method has the advantages of easily obtained raw materials, simple operation, good controllability, high repetition rate and the like, and is beneficial to industrial preparation of large-area luminescent fiber membranes. The obtained all-inorganic perovskite luminescent fiber film has high luminous efficiency, extremely high stability in polar solvents such as water and the like, and can stably emit light even in water.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a preparation method and application of a flexible large-area all-inorganic perovskite waterproof luminescent fibrous membrane.
Background
The perovskite material has the excellent characteristics of adjustable band gap, high absorption coefficient, high fluorescence quantum yield, high color purity, high carrier mobility, long carrier diffusion distance and the like, so the perovskite material has attractive application prospects in the aspects of light emitting and displaying illumination devices, solar cells, detection imaging and the like. Among perovskite luminescent materials with different compositions, the all-inorganic perovskite quantum dot has the advantages of high luminous efficiency, easy regulation and control of luminous wavelength, narrow half-peak width and the like, so that the all-inorganic perovskite quantum dot becomes a star material of a luminous and display device. Currently, all-inorganic perovskite materials are mainly prepared by solution methods. However, the inorganic perovskite material or the thin film prepared by the method has more defects, such as the inorganic perovskite material or the thin film is quite easy to degrade in a high humidity environment and other harsh conditions (such as polar solvents), so that the luminescence property and the stability of the material are seriously influenced.
The electrostatic spinning technology is a spinning technology which obtains a fibrous substance by placing fluid under a high-voltage electric field and flowing and deforming the fluid. The technology can be used for preparing various types of nano fibers, and the manufacturing device is simple, the spinning cost is low, so the method has wide application in the technical field of material science. Based on the technical characteristics of electrostatic spinning, the inorganic perovskite is effectively coated in a functional way by combining the electrostatic spinning with a supramolecular inclusion technology, so that the defect that the inorganic perovskite is exposed to a high-humidity condition for a long time or is dissolved and degraded after being soaked in a polar solvent is hopefully improved, and the luminescence property of the inorganic perovskite is more stable. However, no report is available to prepare all-inorganic perovskite materials by using electrospinning technology.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method and application of a flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane.
The second purpose of the invention is to provide the application of the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane prepared by the preparation method of the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane.
The first object of the present invention is achieved by the following technical solutions:
a preparation method of a flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane comprises the following steps:
s1, mixing metal halide BX2And dissolving inorganic halide salt AX powder in organic solvent to obtain inorganic perovskite ABX3Adding the obtained precursor solution into a high-molecular resin solution to prepare a spinning solution 1;
s2, adding cyclodextrin additives and fluorine-containing silane into the spinning solution 1 to prepare a spinning solution 2;
s3, spinning the spinning solution 2 by an electrostatic spinning technology to prepare the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane.
Preferably, the all-inorganic perovskite ABX3In which A is selected from Cs+，Rb+One or a combination of both; b is selected from Pb2+，Cu2+，Ag+,In3+And Sn2+One or more of; x is selected from Cl-，Br-，I-One or more of the above. In particular, the all-inorganic perovskite ABX3In which A is Cs+(ii) a B is Pb2+X is Br-。
In the method, the cyclodextrin and the cyclodextrin derivative have special guest structures, so that very strong chemical interaction can be generated with the perovskite, lattice distortion is reduced, and crystal defects are effectively passivated, so that the non-radiative recombination of the perovskite material is inhibited, the surface of the perovskite is well wrapped, and the luminescence property and the stability of the perovskite nanocrystal are greatly improved. In addition, the perovskite is combined with hydrophobic polymer resin and perfluorosilane, so that invasion of water molecules and oxygen can be further isolated, and the perovskite nanocrystal is more favorably stabilized. Therefore, the fiber membrane prepared by the method has high luminous efficiency, and can stably emit light even in water.
Preferably, the all-inorganic perovskite ABX3The molar concentration of the precursor solution is 0.1-1M. In the precursor solution, a metal halide BX2The molar concentration of the inorganic halide salt AX is the same.
Preferably, the all-inorganic perovskite ABX3The volume ratio of the precursor solution to the polymer resin solution is (50-1000) uL: (1-100) mL.
Preferably, the organic solvent comprises a mixture of one or more of dimethyl sulfoxide (DMSO), N, N Dimethylformamide (DMF), N, N Dimethylacetamide (DMAC), N-methylformamide (NMF-1), N-methylmorpholine (NMF-2) and N-methylpyrrolidone (NMP). Further, the organic solvent takes DMF as a main body, and the ratio of DMF to DMF in the organic solvent to DMF in the other organic solvent is 1: (0-1) in the ratio. Specifically, the organic solvent is DMF.
Preferably, the polymer resin includes Polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), Polyethylene (PE), polypropylene (PP), Polyamide (PA), Polyoxymethylene (POM), high temperature nylon, Polyphenylene Sulfide (PPs).
The polymer resin comprises general resins such as Polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), Polyethylene (PE), polypropylene (PP) and the like; engineering resins such as Polyamide (PA) and Polyoxymethylene (POM); high-temperature nylon, polyphenylene sulfide (PPS) and other characteristic plastics: such as barrier plastics, corrosion resistant plastics, thermoplastic elastomers, rubber, etc.
Specifically, the polymer resin is Polystyrene (PS).
Preferably, the mass concentration of the polymer resin solution is 10-25%. Specifically, the mass concentration of the polymer resin solution is 20%.
Preferably, the solvent for dissolving the polymer resin and the metal halide BX2The organic solvent of the inorganic halide salt AX is the same solvent.
Preferably, the cyclodextrin includes α -cyclodextrin (α -CD), β -cyclodextrin (β -CD), γ -cyclodextrin (γ -CD), 2-hydroxypropyl- β -cyclodextrin, iodobutylether- β -cyclodextrin.
The cyclodextrin includes common cyclodextrin compounds such as alpha-cyclodextrin (alpha-CD), beta-cyclodextrin (beta-CD), gamma-cyclodextrin (gamma-CD) and the like, and can also be cyclodextrin derivatives with inclusion guest molecular structures, such as 2-hydroxypropyl-beta-cyclodextrin, iodobutyl ether-beta-cyclodextrin and the like.
Specifically, the cyclodextrin is beta-cyclodextrin.
Preferably, the feed-to-liquid ratio of the cyclodextrin additive to the spinning solution 1 is (0.001-10) g: 1-10 mL.
Preferably, the fluorine-containing silane comprises heptadecafluorodecyltrimethoxysilane, polyperfluoroalkylsiloxane, triethoxy-tridecafluoro-N-octylsilane. Of course, the fluorosilane includes other strongly hydrophobic fluorosilane molecules in addition to the strongly hydrophobic fluorosilane listed.
Specifically, the fluorine-containing silane is triethoxy-tridecafluoro-N-octyl silane.
Preferably, the volume ratio of the fluorine-containing silane to the spinning solution 1 is (50-1000) uL: 1-10 mL.
Preferably, the spinning of the spinning solution 2 by the electrospinning technique means that the spinning solution 2 is loaded into an injector, the injector is loaded on a pushing device, a layer of fiber cloth or metal aluminum foil paper is attached to a rotating shaft or a receiving plate, and then the spinning solution 2 is spun by an electrospinning machine.
Further, the rotating speed is 150-.
Furthermore, the specification of the injector is 1, 2.5, 5, 10, 20, 50, 100mL and the like, and the diameter of the needle hole is 0.1-1 mm.
Preferably, the area of the prepared luminescent fiber film can be 5-35 centimeters (width) multiplied by 5-35 (length), and the fiber area is determined by the diameter of the rotating shaft and the size of the receiving flat plate and can be adjusted and controlled as required.
The invention also provides a flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane prepared by the preparation method of the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane.
The second object of the present invention is achieved by the following technical solutions:
the invention also provides application of the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane in preparation of luminescent materials or display materials.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a flexible large-area all-inorganic perovskite waterproof luminescent fibrous membrane, which comprises the steps of firstly using metal halide BX2And dissolving inorganic halide salt AX powder in organic solvent to obtain all-inorganic perovskite ABX3Injecting the precursor solution into a high-molecular resin solution to prepare a spinning solution 1; adding cyclodextrin additives and fluorine-containing silane into the spinning solution 1 to prepare a spinning solution 2; and finally, spinning the spinning solution 2 by an electrostatic spinning technology to prepare the large-area fiber membrane. The preparation method has the advantages of easily obtained raw materials, simple operation, good controllability, high repetition rate and the like, and is beneficial to industrial preparation of large-area luminescent fiber membranes. The obtained all-inorganic perovskite luminescent fiber film has high luminous efficiency, extremely high stability in polar solvents such as water and the like, can stably emit light even in water, and can be applied to the fields of luminescence, photoelectric detection, deep sea detection, rescue and the like.
Drawings
FIG. 1 is a physical size diagram of the all-inorganic perovskite waterproof luminescent fiber membrane of example 1;
FIG. 2 is an SEM image of an all-inorganic perovskite waterproof luminescent fiber membrane of example 1;
FIG. 3 is a fluorescence microscopic view of the all-inorganic perovskite waterproof luminescent fiber membrane of example 1;
FIG. 4 is the fluorescence quantum yield of the all-inorganic perovskite waterproof luminescent fiber membrane of example 1;
FIG. 5 is a water repellency test of the all inorganic perovskite waterproof luminescent fiber membrane of example 1;
FIG. 6 is an electron scanning microscope (SEM) image of an all-inorganic perovskite luminescent fiber membrane of comparative example 1;
FIG. 7 is a fluorescence microscopic view of the all-inorganic perovskite luminescent fiber film of comparative example 1;
fig. 8 is a fluorescence quantum yield of the all-inorganic perovskite luminescent fiber film of comparative example 1.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation method of all-inorganic perovskite waterproof luminescent fiber membrane
The preparation method comprises the following steps:
(1) weighing 0.1M CsBr and 0.1M PbBr2Dissolving in 1mL of DMF, and stirring thoroughly (4-8 hr) to obtain all-inorganic perovskite ABX3Precursor solution;
(2) preparing a PS (polystyrene)/DMF (N, N-dimethylformamide) resin solution with the mass fraction of 20%, and then adding 750uL of precursor solution into 5mL of PS resin solution to prepare a spinning solution 1;
(3) adding 0.01g of beta-cyclodextrin (one of cyclodextrin) and 150uL of triethoxy-tridecafluoro-N-octylsilane (one of fluorine-containing silane) into 1mL of spinning solution 1, and stirring for 60 minutes to prepare spinning solution 2;
(4) the spinning solution 2 is filled into an injector, then the injector is filled into a pushing device, a layer of fiber cloth or metal aluminum foil paper is pasted on a rotating shaft or a receiving plate, the spinning solution 2 is spun by an electrostatic spinning machine, wherein the rotating speed is 500 r/min, the pushing speed of the spinning solution is 1 ml/h, the initial distance between a needle head and the rotating shaft is 8 cm, the diameter of the needle head hole is 0.5 mm, the voltage is 10kV, the temperature is 25 ℃, and ventilation is kept during spinning. Finally preparing the large-area all-inorganic perovskite waterproof luminescent fibrous membrane with the size of 15 multiplied by 25cm2As shown in fig. 1.
And observing the prepared all-inorganic perovskite waterproof luminescent fiber membrane by using a Scanning Electron Microscope (SEM) and a fluorescence microscope, and detecting the fluorescence quantum yield of the all-inorganic perovskite waterproof luminescent fiber membrane.
As can be seen from the SEM image of fig. 2, the film prepared by adding cyclodextrin and fluorine-containing silane has smooth fibers and no pores, and can sufficiently protect the perovskite, so that external water molecules and oxygen cannot directly contact the perovskite, and the film can stably emit light even in water or polar solvent. As can be seen from the fluorescence microscopic image of FIG. 3, the fibers were uniformly distributed and the diameter size was uniform, a dense film was formed, and a fluorescence yield of 49.7% was obtained (as shown in FIG. 4).
In addition, fig. 5 is a picture of the green light emitted by the large-area luminescent fiber prepared in this example under the irradiation of ultraviolet light (365nm, 2 w). It can be seen that even in the case of dropping water droplets on the surface thereof, green light can be emitted under the irradiation of ultraviolet light. Therefore, the large-area waterproof luminescent fiber has good waterproof performance and stable luminescent property, can be applied to the fields of luminescence, photoelectric detection, deep sea detection, rescue and the like, for example, the large-area waterproof luminescent fiber is used as waterproof fabric to prepare search and rescue clothes and is applied to signal display of maritime rescue.
Comparative example 1 preparation method of all-inorganic perovskite luminescent fiber membrane
The preparation method comprises the following steps:
(1) weighing 0.1M CsBr and 0.1M PbBr2Dissolving in 1mL of DMF, and stirring thoroughly (4-8 hr) to obtain all-inorganic perovskite ABX3Precursor solution;
(2) preparing a PS/DMF resin solution with the mass fraction of 20%, and then adding 750uL of precursor solution into 5mL of PS resin solution to prepare a spinning solution 1;
(3) the spinning solution 2 is filled into an injector, then the injector is filled into a pushing device, a layer of fiber cloth or metal aluminum foil paper is pasted on a rotating shaft or a receiving plate, the spinning solution 1 is spun by an electrostatic spinning machine, wherein the rotating speed is 500 r/min, the pushing speed of the spinning solution is 1 ml/h, the initial distance between a needle head and the rotating shaft is 8 cm, the diameter of the needle head hole is 0.5 mm, the voltage is 10kV, the temperature is 25 ℃, and ventilation is kept during spinning. Finally, preparing the all-inorganic perovskite luminescent fiber membrane.
And (3) observing the prepared all-inorganic perovskite luminescent fiber membrane by using an electron scanning microscope (SEM) and a fluorescence microscope, and detecting the fluorescence quantum yield of the all-inorganic perovskite luminescent fiber membrane.
As can be seen from the SEM image of fig. 6, the film prepared without adding cyclodextrin and fluorine-containing silane has coarse fibers and is porous, and cannot resist the intrusion of water molecules and air, and thus cannot provide good protection for the perovskite. As can be seen from the fluorescence microscopic image of fig. 7, the fiber diameter is large and non-uniform, the gap between fibers is large, and the crystal aggregation is severe, there are distinct spherical resin particles, the luminescence property is poor, and only 0.04% fluorescence luminescence yield is obtained (as shown in fig. 8).
As can be seen by combining example 1 with comparative example 1, ABX is an all-inorganic perovskite3The composite material is added with a stabilizer (cyclodextrin and derivatives thereof) and a hydrophobic agent (perfluorosilane) and the like, can efficiently and stably emit light, has waterproof performance (as shown in figure 5), can be applied to the fields of luminescence, photoelectric detection, deep sea detection, rescue and the like, for example, search and rescue clothes prepared by being used as waterproof fabrics and applicationDisplaying the signal of rescue at sea.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of a flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane is characterized by comprising the following steps:
s1, mixing metal halide BX2And dissolving inorganic halide salt AX powder in organic solvent to obtain inorganic perovskite ABX3Adding the obtained precursor solution into a high-molecular resin solution to prepare a spinning solution 1;
s2, adding cyclodextrin additives and fluorine-containing silane into the spinning solution 1 to prepare a spinning solution 2;
s3, spinning the spinning solution 2 by an electrostatic spinning technology to prepare the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane.
2. The method for preparing the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 1, wherein the all-inorganic perovskite ABX is3In which A is selected from Cs+，Rb+One or a combination of both; b is selected from Pb2+，Cu2+，Ag+,In3+And Sn2+One or more combinations of; x is selected from Cl-，Br-，I-One or more of the above.
3. The method for preparing the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 1, wherein the organic solvent comprises one or more of dimethyl sulfoxide, N, N dimethylformamide, N, N dimethylacetamide, N-methylformamide, N-methylmorpholine and N-methylpyrrolidone.
4. The method for preparing the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 1, wherein the polymer resin comprises polystyrene, acrylonitrile-butadiene-styrene copolymer, polyethylene, polypropylene, polyamide, polyoxymethylene, high temperature nylon, polyphenylene sulfide.
5. The preparation method of the flexible large-area all-inorganic perovskite waterproof luminescent fibrous membrane as claimed in claim 1, wherein the cyclodextrin comprises α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, iodobutyl ether- β -cyclodextrin.
6. The method for preparing the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 1, wherein the fluorine-containing silane comprises heptadecafluorodecyltrimethoxysilane, polyperfluoroalkylsiloxane, triethoxy-tridecafluoro-N-octylsilane.
7. The method for preparing the flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 1, wherein the step of spinning the spinning solution 2 by the electrostatic spinning technology is that the spinning solution 2 is filled into an injector, the injector is further filled into a pushing device, a layer of fiber cloth or metal aluminum foil paper is attached to a rotating shaft or a receiving plate, and then the spinning solution 2 is spun by an electrostatic spinning machine.
8. The method for preparing a flexible large-area all-inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 7, wherein the spinning speed is 150-1000 rpm, the spinning solution pushing speed is 0.1-20 ml/h, the initial distance between the needle and the rotating shaft is 1-2 cm, the voltage is 8-30 kV, and the temperature is 15-60 ℃.
9. The flexible large-area all-inorganic perovskite waterproof luminescent fibrous membrane prepared by the preparation method of the flexible large-area all-inorganic perovskite waterproof luminescent fibrous membrane as claimed in any one of claims 1 to 8.
10. Use of the flexible large area all inorganic perovskite waterproof luminescent fiber membrane as claimed in claim 9 in the preparation of luminescent materials or display materials.
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