CN113697850A - Perovskite nanocrystalline powder capable of being dispersed by polar solvent and large-scale preparation method thereof - Google Patents
Perovskite nanocrystalline powder capable of being dispersed by polar solvent and large-scale preparation method thereof Download PDFInfo
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing lead, with or without oxygen or hydrogen, and containing two or more other elements
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- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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Abstract
The invention relates to perovskite nanocrystalline powder capable of being dispersed by a polar solvent and a large-scale preparation method thereof, belonging to the technical field of photoelectric material preparation and comprising the following steps: A. CsX (X is Cl, Br, I), PbX are proportionally mixed2Adding glycyrrhizic acid into the solvent, and fully dissolving to prepare a precursor solution; B. heating the precursor solution to obtain colorless to light brown liquid; C. rapidly injecting the colorless to light brown liquid into an anti-solvent; D. insoluble substances are extracted, washed by the anti-solvent and dried to obtain the perovskite nanocrystalline powder, so that the problem of CsPbX existing in the prior art is solved3Perovskite can only obtain perovskite nanocrystalline nonpolar sol, so that a large amount of powdery products are difficult to obtain, and even if a solid sample is obtained, the perovskite nanocrystalline sol is difficult to well disperse in a polar solvent.
Description
Technical Field
The invention belongs to the technical field of photoelectric material preparation, and particularly relates to perovskite nanocrystalline powder capable of being dispersed by a polar solvent and a large-scale preparation method thereof.
Background
Lead-halide perovskite APbX3(A＝CH3NH3，Cs，CH(NH2) (ii) a X ═ Cl, Br, I) has achieved remarkable success in the fields of displays, lasers, photodetectors, light emitting diodes, etc., because of their high fluorescence quantum yield, excellent spectral purity and adjustable emission wavelength. In addition, the perovskite nanocrystal is simple to synthesize and low in cost, and has great commercial application prospect.
At present, APbX is restricted3One of the key problems of the commercial application of the nano-crystal is the poor stability of the polar solvent, so that the synthesis and subsequent processing of the material can only be carried out in non-polar solvents which are not friendly to the environment, such as toluene, normal hexane and the like, the cost is high, and the environmental pollution is great. Although some strategies have been developed to enhance APbX by coating or building core-shell structures3Stability of nanocrystals in polar solvents (Angew. chem. int. Ed.2016,55, 8864-8868; chem. Commun.2018,54, 8064-8067; J. Mater. chem.C 2020,8,1413-1420), but APbX3The nanocrystals thus lose their peptization in the solvent and subsequent solution processing is not possible. Therefore, how to increase APbX3The stability of the nanocrystalline solvent and the maintenance of the peptization of the nanocrystalline solvent have important practical significance.
The stability of the lead-halogen perovskite nanocrystalline is always one of the main factors restricting the commercial application of the lead-halogen perovskite nanocrystalline, and the material is easy to remove surface ligands in a polar solvent to cause nanocrystalline aggregation and increase surface defects, thereby losing excellent optical properties. Therefore, the preparation and the test of the perovskite nanocrystalline can only be carried out in nonpolar solvents such as toluene, normal hexane and the like for a long time, which greatly limits the application of the perovskite nanocrystalline in different scenes. In addition, concentration regulation of perovskite nanocrystals is also a difficult problem in traditional preparation methods. Due to weak interaction between the ligand and the perovskite nanocrystal, the dissolution adsorption balance of the surface ligand can be damaged in the process of diluting and concentrating the nanocrystal colloidal solution, so that the perovskite nanocrystal generates subsequent agglomeration, stripping and other phenomena, the optical properties including the luminous efficiency, the luminous wavelength, the half-peak width and the like of a sample are influenced, and the subsequent commercial research of the perovskite nanocrystal is not facilitated. Finally, most of the perovskite nanocrystals prepared by the existing method are stored in the form of colloidal solution, and once the perovskite nanocrystals are prepared into powder materials, the prepared perovskite nanocrystal particles are irreversibly aggregated, the particle size is increased, organic ligands fall off, the colloidal solution with the same property as the original solution can not be obtained any more, and the property is extremely unstable.
The cause is as follows:
1. structural properties of the material itself: perovskite ABX3A site cations in the ionic crystal structure are easy to dissolve in a polar solvent to cause structural damage, so that the material is difficult to disperse in the polar solvent;
2. concentration regulation and control: in the process of diluting and concentrating the perovskite colloidal solution, the dissolution adsorption balance of the surface ligand is damaged, and the nano-crystals are agglomerated or peeled off, so that the optical property of the colloidal solution is changed;
3. perovskite nanocrystalline powder sample: the conventional ligand can only obtain perovskite nanocrystalline sol generally, and even a solid sample obtained by anti-solvent precipitation has poor redispersion effect due to the defects of few precipitated samples, ligand falling, particle size change and the like.
Disclosure of Invention
The invention aims to provide perovskite nanocrystalline powder capable of being dispersed by a polar solvent and a large-scale preparation method thereof, and solves the problems that in the prior art, perovskite can only be obtained to obtain perovskite nanocrystalline sol, a large amount of powdery products are difficult to obtain, even a solid sample is obtained, the perovskite nanocrystalline powder is difficult to be well dispersed in the polar solvent, and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a large-scale preparation method of perovskite nanocrystalline powder capable of being dispersed by polar solvent comprises the following steps:
A. proportionally mixing CsX and PbX2Adding glycyrrhizic acid into solvent, and fully dissolving to prepare precursor solution, wherein X comprises one or more of Cl, Br and I;
B. heating the precursor solution to obtain colorless to light brown liquid;
C. injecting the colorless to light brown liquid into an anti-solvent and stirring;
D. and (3) extracting insoluble substances, washing with the anti-solvent, and drying to obtain the perovskite nanocrystalline powder.
In the research, glycyrrhizic acid has an aglycone structure, has a large hydrophobic group and two glucuronic acids as hydrophilic groups, and the existence of carboxyl and large steric hindrance enable glycyrrhizic acid to be used as a capping ligand to improve the problem that the perovskite nanocrystal is poor in stability in a polar solvent. In addition, glycyrrhizic acid exhibits a ph-dependent dissolution behavior in solution and tends to aggregate into nanomicelles in neutral solution. The unique molecular structure and dissolution behavior show that glycyrrhizic acid can be used as passivated CsPbX3The ligand of (2) can also prevent CsPbX3Is degraded by polar solvents.
The previous work of the invention proposes that the CsPbBr passivated by glycyrrhizic acid is synthesized by an ultrasonic method with the assistance of water3Nanocrystals, although this method also achieved CsPbBr3The nano-crystal is dispersed in an ethanol phase, but the quantum yield of the prepared nano-crystal is low (38%), the concentration of a colloidal solution is dilute, large-scale production cannot be realized, the redispersibility effect of the prepared sample is poor, the prepared sample cannot be prepared into a powder sample, and the washing, purification, storage and transportation are not facilitated.
A large number of experiments show that the perovskite nanocrystalline powder can be obtained by using glycyrrhizic acid as a ligand to prepare a precursor solution, heating the precursor solution and injecting the precursor solution into an anti-solvent, and the perovskite nanocrystalline powder can be further dispersed in a polar solution to obtain the perovskite nanocrystalline polar sol with the quantum yield of more than 80%. The polar sol can keep consistent optical properties with the original powder sample, can be purified and washed for multiple times, and the powder product is favorable for storage and transportation, so that the polar sol has wider application prospect.
In step C, the solution should be injected into the anti-solvent at a relatively high rate, otherwise the particles of the perovskite nanocrystals to be produced are not uniform in size.
Preferably, the solution comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the anti-solvent comprises one or more of toluene, o-xylene, m-xylene or p-xylene.
Preferably, in step A, the CsX and the PbX are used2And the glycyrrhizic acid is added according to the molar ratio of 0.8-1.2: 0.8-1.2: 0.01-100 parts by weight of a solvent.
Preferably, in the step B, the precursor solution is heated until the solution is clear, and the colorless to light brown liquid is obtained after the solution is kept for 1-60 min.
Preferably, in step C, the volume ratio of the colorless to pale brown liquid to the antisolvent is 1: 10 to 10000.
Preferably, in step D, insoluble matter is extracted by filtration or centrifugation.
The perovskite nanocrystalline powder obtained by the large-scale preparation method of the perovskite nanocrystalline powder capable of being dispersed by the polar solvent has the chemical expression CsPbX3。
The perovskite nanocrystalline colloidal solution containing the perovskite nanocrystalline powder is characterized in that the perovskite nanocrystalline powder is added into a polar dispersing agent to obtain the perovskite nanocrystalline colloidal solution.
Preferably, the polar dispersant comprises an alkyl alcohol CnH2n+1OH (n is 2-8), cyclohexanol, benzyl alcohol, 1, 4-dioxane, tetrahydrofuran, and acetonitrile.
Compared with the prior art, the implementation of the invention has the following beneficial effects:
1. the method can prepare a large amount of powder perovskite nanocrystalline materials, the quantum yield exceeds 80%, and technical support is provided for large-scale production and commercialization of perovskite.
2. The powder perovskite nanocrystalline material prepared by the method can be dispersed in a polar solvent, and has a good dispersion effect.
3. According to the method, perovskite nano crystals with different amounts are weighed and dispersed in a polar solvent to obtain a perovskite sol sample with a specified concentration.
4. The method can obtain perovskite nanocrystalline powder capable of covering fluorescence emission in a visible light range of 420-650 nm.
5. The powder perovskite nanocrystalline material prepared by the method has good redispersibility effect, can keep stable properties after being repeatedly washed and purified, and the powder product is favorable for storage and transportation, so that the powder perovskite nanocrystalline material has wider application prospect.
Drawings
FIG. 1 shows CsPbBr3XRD pattern and standard cards of perovskite powders.
FIG. 2 shows CsPbBr at various concentrations3Normalized photoluminescence spectra of anhydrous ethanolic sols.
Fig. 3 is a normalized photoluminescence spectrum of the perovskite nanocrystalline powder and purified and dispersed, and the insets are an absorption spectrum and a photoluminescence spectrum of each sample.
FIG. 4 shows CsPbX3Absorption spectrum and photoluminescence spectrum of the powder sample.
FIG. 5 shows the structural formula of glycyrrhizic acid.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
0.05mmol CsBr and 0.05mmol PbBr were added to the sample bottle in sequence2Dissolving 100mg glycyrrhizic acid (structure shown in figure 5) and 2mL N, N-dimethylformamide with ultrasound, heating the solution at 120 deg.C for 5min, cooling to room temperature, rapidly injecting into vigorously stirred 200mL toluene, centrifuging, washing the solid with toluene, and vacuum drying the solid at room temperature to obtain about 0.1g CsPbBr3A perovskite powder. The powder can be dispersed in polar solvents such as alkyl alcohol, cyclohexanol, benzyl alcohol, 1, 4-dioxane, tetrahydrofuran, acetonitrile and the like to prepare a colloidal solution with the concentration of 0-50 g/L.
Example 2
To a sample bottle were added 0.05mmol CsBr and 0.05mmol PbCl in that order2100mg glycyrrhizic acid, 1.3mL of N, N-dimethylformamide and 0.7mL of dimethyl sulfoxide,ultrasonic dissolving, heating the above solution at 120 deg.C for 5min, cooling to room temperature, rapidly injecting into vigorously stirred 200mL toluene, centrifuging, washing the solid with toluene, and vacuum drying the solid at room temperature to obtain about 0.1g CsPbCl2Br perovskite powder.
Example 3
0.05mmol CsBr and 0.05mmol PbI were added to the sample bottle in sequence2、0.05mmol CsI、0.05mmol PbBr2Ultrasonic dissolving glycyrrhizic acid 200mg, N-dimethylformamide 2mL and acetonitrile 2mL, rapidly injecting the above solution into vigorously stirred toluene 400mL, centrifuging, washing the solid with toluene, and vacuum drying the solid at room temperature to obtain CsPbBr 0.2g1.5I1.5A perovskite powder.
Effect example 1
CsPbBr prepared in example 13The XRD pattern and standard card of the perovskite powder are shown in fig. 1.
Effect example 2
CsPbBr prepared in example 13The perovskite powder is dispersed in absolute ethyl alcohol to be respectively prepared into colloidal solutions with the concentration of 0.5-5.0 g/L, and the normalized photoluminescence spectrum of the colloidal solutions is shown in figure 2. As can be seen from FIG. 2, the concentration is adjusted within the range of 0.5-5.0 g/L, and the luminescence spectrum is only red-shifted by about 10nm, which proves that the perovskite powder prepared by the invention has stable property after being prepared into a colloidal solution.
Effect example 3
CsPbBr prepared in example 13The perovskite powder is dispersed in absolute ethyl alcohol to prepare a colloidal solution with the concentration of 1 g/L. For purification experiments, toluene (the volume ratio of ethanol to toluene is 1:20) is added into the colloidal solution, the solution is centrifuged at 10000r/min for 20min, so that precipitate washed by toluene can be obtained, and the precipitate is re-dispersed in fresh absolute ethanol to obtain a sample which is re-dispersed after being washed for 1 time. In the same way, redispersed samples after 2 and 3 washes were obtained. FIG. 3 shows absorption spectra and photoluminescence spectra of perovskite powder samples and samples before and after perovskite ethanol sol purification experiments, and the normalized luminescence spectra of the samples are shown in the figure, and the central wavelength and half-peak width of the samples are almost unchanged, which proves thatThe prepared colloidal solution of the perovskite powder has stable property.
Effect example 4
The absorption spectrum and photoluminescence spectrum of the perovskite powders prepared in comparative examples 1 to 3, as shown in FIG. 4, cover the fluorescence emission in the visible light range of 420-650 nm.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, therefore, the present invention is not limited by the appended claims.
Claims (10)
1. A large-scale preparation method of perovskite nanocrystalline powder capable of being dispersed by polar solvent is characterized by comprising the following steps:
A. proportionally mixing CsX and PbX2Adding glycyrrhizic acid into solvent, and fully dissolving to prepare precursor solution, wherein X comprises one or more of Cl, Br and I;
B. heating the precursor solution to obtain colorless to light brown liquid;
C. injecting the colorless to light brown liquid into an anti-solvent and stirring;
D. and (3) extracting insoluble substances, washing with the anti-solvent, and drying to obtain the perovskite nanocrystalline powder.
2. The method for large scale production of a polar solvent dispersible perovskite nanocrystal powder of claim 1, wherein the solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, N-methylpyrrolidone.
3. The method for large scale production of polar solvent dispersible perovskite nanocrystalline powder of claim 1, wherein the anti-solvent comprises one or more of toluene, o-xylene, m-xylene, or p-xylene.
4. The polarizable electrode according to claim 1A method for preparing solvent dispersed perovskite nanocrystal powder on a large scale, which is characterized in that in the step A, CsX and PbX are carried out2And the glycyrrhizic acid is added according to the molar ratio of 0.8-1.2: 0.8-1.2: 0.01-100 parts by weight of a solvent.
5. The method for mass production of the polar solvent dispersible perovskite nanocrystal powder of claim 1, wherein in step B, the precursor solution is heated until the solution is clear and kept for 1-60 min to obtain the colorless to light brown liquid.
6. The method for mass-producing a polar-solvent-dispersible perovskite nanocrystal powder as claimed in claim 1, wherein in step C, the volume ratio of the colorless to pale brown liquid to the anti-solvent is 1: 10 to 10000.
7. The method for mass-producing a polar-solvent-dispersible perovskite nanocrystal powder as claimed in claim 1, wherein in the step D, the insoluble matter is extracted by filtration or centrifugation and dried by vacuum drying.
8. The perovskite nanocrystalline powder obtained by the large-scale preparation method of the polar solvent dispersible perovskite nanocrystalline powder according to claim 1, wherein the chemical expression of the perovskite nanocrystalline powder is CsPbX3。
9. A perovskite nanocrystalline colloidal solution containing the perovskite nanocrystalline powder according to claim 8, wherein the perovskite nanocrystalline powder is added to a polar dispersant to obtain the perovskite nanocrystalline colloidal solution.
10. The perovskite nanocrystalline colloidal solution containing the perovskite nanocrystalline powder according to claim 8, wherein the polar dispersant comprises one or more of alkyl alcohol, cyclohexanol, benzyl alcohol, 1, 4-dioxane, tetrahydrofuran, and acetonitrile.
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