CN113353972B - Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite - Google Patents

Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite Download PDF

Info

Publication number
CN113353972B
CN113353972B CN202110785994.2A CN202110785994A CN113353972B CN 113353972 B CN113353972 B CN 113353972B CN 202110785994 A CN202110785994 A CN 202110785994A CN 113353972 B CN113353972 B CN 113353972B
Authority
CN
China
Prior art keywords
lead
solution
perovskite
salt
ionic liquid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110785994.2A
Other languages
Chinese (zh)
Other versions
CN113353972A (en
Inventor
卢伟伟
姚开胜
胡浩
程浩艳
刘海涛
程楚
宋克兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Science and Technology
Original Assignee
Henan University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University of Science and Technology filed Critical Henan University of Science and Technology
Priority to CN202110785994.2A priority Critical patent/CN113353972B/en
Publication of CN113353972A publication Critical patent/CN113353972A/en
Application granted granted Critical
Publication of CN113353972B publication Critical patent/CN113353972B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention relates to lead halogen perovskite, a preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite, and belongs to the technical field of photoelectric materials. The preparation method of the lead halogen perovskite comprises the following steps: s1, dissolving cesium salt in a protective atmosphere to obtain a first solution; s2, dissolving lead salt and hydrophilic ionic liquid halogen salt containing sulfhydryl in a protective atmosphere to obtain a second solution; s3, reacting the first solution with the second solution for 5-10S at the temperature of 150-180 ℃ under the protective atmosphere. The invention uses the mercapto-functionalized ionic liquid with stronger binding force to replace oleic acid/oleylamine dual-ligand adopted by the traditional hot injection method, overcomes the problems of unstable perovskite nanocrystalline prepared in polar solvents such as water, poor dispersibility and the like caused by small binding force between the oleic acid/oleylamine ligand and the surface of the perovskite material and easy falling off, and widens the application of the perovskite nanocrystalline in aqueous phase systems.

Description

Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite
Technical Field
The invention relates to lead halogen perovskite, a preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite, and belongs to the technical field of photoelectric materials.
Background
In recent years, metal halide perovskite nanomaterials typified by lead halide perovskite are a hotspot in the field of current photoelectric material research. The nano material has high light absorption coefficient in a visible light wave band, long carrier diffusion distance, small exciton binding energy, long carrier service life and other excellent photoelectric conversion performances, so that the nano material has great application potential in the fields of solar cells, light emitting diodes, light detectors, laser emitters, photocatalysis and the like.
In the conventional high-temperature injection method for preparing the all-inorganic perovskite nanocrystalline, oleic acid and oleylamine with long chains of 18 carbon atoms are often selected as surface ligands in order to maintain the uniformity of the morphology and the size of the nanocrystalline, and the stability of a lattice structure and an interface. However, since the chemical combination of oleylamine/oleic acid and the surface of the quantum dot is relatively weak, oleic acid or halogen is often carried away by protonated oleylamine when the oleylamine leaves the surface of the quantum dot to ensure charge balance, so that the ligand is easy to fall off in the purification or use process, and the perovskite protection effect is lost. In addition, the existing oleic acid/oleylamine ligand has a nonpolar long carbon chain, so that the dispersibility of the synthesized perovskite nanocrystalline in polar solvents such as water, ethanol and the like is limited. The perovskite nanocrystalline synthesized by the prior art cannot be dispersed in water, and can be converted in a moist environment to gradually lose fluorescence (the fluorescence intensity is reduced or even vanished, and the position of a fluorescence emission peak is changed), so that the wide application of the perovskite nanocrystalline in the fields of photocatalysis, biological markers and the like is greatly limited.
Disclosure of Invention
The invention aims to provide a preparation method of lead halide perovskite with high stability and good dispersibility in water.
A second object of the present invention is to provide a lead-halide perovskite prepared by the above-mentioned preparation method.
The third object of the invention is to provide an application of a hydrophilic ionic liquid halogen salt containing mercapto in preparing lead halogen perovskite.
In order to achieve the above purpose, the technical scheme of the preparation method of the lead halogen perovskite of the invention is as follows:
a method for preparing lead-halogen perovskite, comprising the following steps:
s1, dissolving cesium salt in a protective atmosphere to obtain a first solution;
s2, dissolving lead salt and hydrophilic ionic liquid halogen salt containing sulfhydryl in a protective atmosphere to obtain a second solution;
s3, reacting the first solution with the second solution for 5-10S at the temperature of 150-180 ℃ under the protective atmosphere.
According to the invention, a single ionic liquid ligand is used for replacing a double-ligand system used by a traditional hot injection method, and the mercapto functional ionic liquid with stronger binding force is used for replacing oleic acid/oleylamine double-ligand used by the traditional hot injection method, so that the problems of phase change, structural collapse, decomposition, even dissolution and the like of the prepared perovskite nanocrystalline caused by unstable in a polar solvent such as water due to small binding force between the oleic acid/oleylamine ligand and the surface of a perovskite material are overcome, and the lead perovskite prepared by the invention has excellent environmental stability.
The surface of the lead halogen perovskite prepared by the invention is coated by the ionic liquid, so that the lead halogen perovskite prepared by the invention can show good dispersibility in aqueous solution through the coated hydrophilic ionic liquid, and the application of perovskite nanocrystalline in an aqueous phase system is widened.
The hydrophilic ionic liquid halogen salt containing sulfhydryl group can also be used as a halogen element source, so that the halogen element source and a lead source can be separated, and the problem that CsPbBr is synthesized by adopting a lead-halogen compound as the halogen element source and the lead source simultaneously in the traditional thermal injection method is overcome 3 The toxic lead source is not reacted completely in the process, so that the loss and the waste are caused.
Preferably, in step S3, the reaction time is 5S.
Preferably, the sulfhydryl-containing hydrophilic ionic liquid halogen salt has a structure shown in a formula I,
wherein R is 1 、R 2 Each independently selected from C 1 -C 6 An alkyl group; x is Cl, br or I.
Preferably, said R 1 Is methyl, R 2 Is butyl.
Preferably, the molar ratio of cesium element in the cesium salt to lead element in the lead salt to hydrophilic ionic liquid halogen salt containing sulfhydryl is 1-3.5:1-12:3-15.
Further preferably, the molar ratio of cesium element in the cesium salt to lead element in the lead salt to the hydrophilic ionic liquid halogen salt containing sulfhydryl is 1-2.8:4-11.25:5-12.
Still more preferably, the molar ratio of cesium element in the cesium salt, lead element in the lead salt and hydrophilic ionic liquid halogen salt containing mercapto group is 1-2.8:4-7.5:5-8.
Preferably, the cesium salt is Cs 2 CO 3 、Cs(OOCCH 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The molar concentration of cesium in the first solution is 0.1-0.28mol/L.
Preferably, the solvent in the first solution is octanoic acid and N-methyl pyrrolidone; the volume ratio of the octanoic acid to the N-methyl pyrrolidone is 1:10. In formulating the first solution, heat may be applied appropriately to promote dissolution of the cesium salt in the solvent.
Preferably, the molar concentration of the halogen salt of the hydrophilic ionic liquid containing the sulfhydryl group in the second solution is 0.05-0.08mol/L.
Preferably, the lead salt is Pb (OOCCH 3 ) 2 、Pb(acac) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar concentration of the lead element in the second solution is 0.04-0.075mol/L. Pb (OOCCH) 3 ) 2 Is anhydrous lead acetate, pb (acac) 2 Is lead acetylacetonate.
Preferably, the solvent in the second solution is N-methylpyrrolidone. When preparing the second solution, heating may be appropriate to promote dissolution of the lead salt and the hydrophilic ionic liquid halide salt containing a mercapto group in the solvent.
Preferably, in step S3, the volume ratio of the first solution to the second solution is 1:10-15. For example, the volume ratio of the first solution to the second solution in step S3 is 1:10.
Preferably, the protective atmosphere is nitrogen.
Preferably, step S3 further comprises the steps of: after the reaction was completed, the reaction was terminated by rapid cooling using an ice-water bath.
The lead halogen perovskite of the invention has the technical scheme that:
the lead halide perovskite prepared by the preparation method of the lead halide perovskite.
According to the invention, the mercapto-functionalized ionic liquid with stronger binding force is used for replacing oleic acid/oleylamine double ligand adopted by the traditional hot injection method, the prepared lead halogen perovskite has excellent environmental stability, and can show good dispersibility in aqueous solution through the coated hydrophilic ionic liquid, so that the application of perovskite nanocrystalline in an aqueous phase system is widened.
The technical scheme of the application of the hydrophilic ionic liquid halogen salt containing the mercapto group in preparing lead halogen perovskite is as follows:
preparing lead halogen perovskite by taking hydrophilic ionic liquid halogen salt containing sulfhydryl as ligand.
The invention uses hydrophilic ionic liquid halogen salt containing sulfhydryl as ligand to prepare lead halogen perovskite, and the prepared lead halogen perovskite has good stability and good dispersibility in water.
Preferably, the sulfhydryl-containing hydrophilic ionic liquid halogen salt has a structure shown in a formula I,
wherein R is 1 、R 2 Each independently selected from C 1 -C 6 An alkyl group; x is Cl, br or I.
Further preferably, the R 1 Is methyl, R 2 Is butyl.
Drawings
FIG. 1 is CsPbBr prepared in example 1 3 X-ray diffraction (XRD) spectrum profile of the nanocrystals;
FIG. 2 is CsPbBr prepared in example 1 3 Photographs of the dispersion of nanocrystals under natural light;
FIG. 3 is CsPbBr prepared in example 1 3 Fluorescence photograph of the dispersion liquid of the nano-crystal under 365nm ultraviolet irradiation;
FIG. 4 is CsPbBr prepared in example 1 3 Ultraviolet-visible absorption spectrum of the dispersion of nanocrystals;
FIG. 5 is CsPbBr prepared in example 1 3 Fluorescence spectrum of the dispersion liquid of the nano-crystal under 365nm ultraviolet excitation;
FIG. 6 is CsPbBr prepared in example 1 3 A Transmission Electron Microscope (TEM) image of the nanocrystal;
FIG. 7 is CsPbBr prepared in example 1 3 High Resolution Transmission Electron Microscope (HRTEM) images of nanocrystals;
FIG. 8 is CsPbBr prepared in example 1 3 Photo and fluorescence spectrum of the dispersion of nanocrystals under 365nm ultraviolet light after one month.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments. It should be noted that the purpose of this example is to further illustrate the present invention, and not to limit the scope of the present invention.
1. Specific examples of the preparation method of lead-halogen perovskite of the invention are as follows:
example 1
The preparation method of the lead halogen perovskite of the embodiment comprises the following steps:
(1) Preparation of the first solution
0.3258g of Cs 2 CO 3 Into a three-necked flask containing 10mL of octanoic acid and N-methylpyrrolidone in a volume ratio of 1:10, at 1After vacuum treatment at 20℃for 30 minutes, the three-necked flask was then purged with nitrogen and warmed to 150℃and held for 20 minutes to allow Cs to settle 2 CO 3 Complete dissolution gives a first solution. The first solution was kept at a temperature of 150℃for use, and the molar concentration of Cs in the first solution was 0.2mol/L.
(2) Preparation of the second solution
Pb (OOCCH) 0.2602g 3 ) 2 And 0.2512g of ionic liquid [ HSC 4 mim]Br (1- (4-mercaptobutyl) -3-methylimidazole Bromide) was charged into a three-necked flask containing 20mL of N-methylpyrrolidone, and after vacuum treatment at 120℃for 30 minutes, the three-necked flask was purged with nitrogen and heated to 150℃and then kept for 20 minutes to Pb (OOCCH) 3 ) 2 Complete dissolution, yielding a second solution. Maintaining the second solution at 150deg.C for use, wherein the molar concentration of Pb in the second solution is 0.04mol/L, and the ionic liquid [ HSC ] 4 mim]The molar concentration of Br was 0.05mol/L.
(3)CsPbBr 3 Preparation of perovskite nanocrystals
2.0mL of the first solution (150 ℃ C.) was withdrawn using a syringe, rapidly injected into the second solution prepared in step (2) at 150 ℃ C., and after 5 seconds the reaction flask was quickly immersed in an ice-water bath to quench the reaction. The reaction mixture is subjected to centrifugal dispersion (the rotating speed is 8000 revolutions per minute, and the centrifugation is carried out for 15 minutes) and then the supernatant is removed, then the precipitate is washed twice by ethyl acetate and ethanol with the volume ratio of 1:3, and the washed precipitate is dried for 2 hours in a vacuum environment at 50 ℃ to obtain CsPbBr 3 Perovskite nanocrystals. CsPbBr 3 Dispersing perovskite nanocrystalline into secondary deionized water (resistivity of 1.5 mu S/cm, pH of 7.0) to obtain CsPbBr 3 Perovskite nanocrystalline dispersion, csPbBr 3 CsPbBr in perovskite nanocrystalline dispersion 3 The mass fraction of perovskite nanocrystals was 2.0%.
Example 2
The preparation method of the lead halogen perovskite of the embodiment comprises the following steps:
(1) Preparation of the first solution
Will 0.1920g Cs (OOCCH 3 ) Is added into a three-neck flask containing 10mL of octanoic acid and N-methyl pyrrolidone in volume ratio of 1:10, vacuum-treated at 120 ℃ for 30 minutes, then the three-neck flask is filled with nitrogen and heated to 150 ℃ and kept for 20 minutes to ensure Cs (OOCCH 3 ) Complete dissolution gives a first solution. The first solution was kept at a temperature of 150℃for use, and the molar concentration of Cs in the first solution was 0.1mol/L.
(2) Preparation of the second solution
0.4054g of Pb (acac) 2 And 0.3014g of ionic liquid [ HSC 4 mim]Br (1- (4-mercaptobutyl) -3-methylimidazole Bromide) was charged into a three-necked flask containing 20mL of N-methylpyrrolidone, after vacuum treatment at 120℃for 30 minutes, the three-necked flask was purged with nitrogen and heated to 150℃and then kept for 20 minutes to Pb (acac) 2 Complete dissolution, yielding a second solution. Maintaining the second solution at 150deg.C for use, wherein the molar concentration of Pb in the second solution is 0.05mol/L, and the ionic liquid [ HSC ] 4 mim]The molar concentration of Br was 0.06mol/L.
(3)CsPbBr 3 Preparation of perovskite nanocrystals
2.0mL of the first solution (150 ℃ C.) was withdrawn using a syringe, rapidly injected into the second solution prepared in step (2) at 150 ℃ C., and after 5 seconds the reaction flask was quickly immersed in an ice-water bath to quench the reaction. The reaction mixture is subjected to centrifugal dispersion (the rotating speed is 8000 revolutions per minute, and the centrifugation is carried out for 15 minutes) and then the supernatant is removed, then the precipitate is washed twice by ethyl acetate and ethanol with the volume ratio of 1:3, and the washed precipitate is dried for 2 hours in a vacuum environment at 50 ℃ to obtain CsPbBr 3 Perovskite nanocrystals. CsPbBr 3 Dispersing perovskite nanocrystalline into secondary deionized water (resistivity of 1.5 mu S/cm, pH of 7.0) to obtain CsPbBr 3 Perovskite nanocrystalline dispersion, csPbBr 3 CsPbBr in perovskite nanocrystalline dispersion 3 The mass fraction of perovskite nanocrystalline is 1.6%.
Example 3
The preparation method of the lead halogen perovskite of the embodiment comprises the following steps:
(1) Preparation of the first solution
0.4561g of Cs 2 CO 3 Adding into a three-neck flask containing 10mL of octanoic acid and N-methyl pyrrolidone in volume ratio of 1:10, vacuum treating at 140 ℃ for 40 min, introducing nitrogen into the three-neck flask, heating to 180 ℃, and continuously maintaining for 30 min to ensure Cs 2 CO 3 Complete dissolution gives a first solution. The first solution was kept at a temperature of 150℃for use, and the molar concentration of Cs in the first solution was 0.28mol/L.
(2) Preparation of the second solution
0.6081g of Pb (acac) 2 And 0.4019g of ionic liquid [ HSC 4 mim]Br (1- (4-mercaptobutyl) -3-methylimidazole Bromide) was charged into a three-necked flask containing 20mL of N-methylpyrrolidone, after vacuum treatment at 140℃for 40 minutes, the three-necked flask was purged with nitrogen and warmed to 180℃and then kept for 30 minutes to Pb (acac) 2 Complete dissolution, yielding a second solution. Maintaining the second solution at 180deg.C for use, wherein the molar concentration of Pb in the second solution is 0.075mol/L, and the ionic liquid [ HSC ] 4 mim]The molar concentration of Br was 0.08mol/L.
(3)CsPbBr 3 Preparation of perovskite nanocrystals
2.0mL of the first solution (150 ℃ C.) was withdrawn using a syringe, rapidly injected into the second solution prepared in step (2) at 180 ℃ C., and after 5 seconds the reaction flask was quickly immersed in an ice-water bath to quench the reaction. The reaction mixture is subjected to centrifugal dispersion (the rotating speed is 8000 revolutions per minute, and the centrifugation is carried out for 15 minutes) and then the supernatant is removed, then the precipitate is washed twice by ethyl acetate and ethanol with the volume ratio of 1:3, and the washed precipitate is dried for 2 hours in a vacuum environment at 50 ℃ to obtain CsPbBr 3 Perovskite nanocrystals. CsPbBr 3 Dispersing perovskite nanocrystalline into secondary deionized water (resistivity of 1.5 mu S/cm, pH of 7.0) to obtain CsPbBr 3 Perovskite nanocrystalline dispersion, csPbBr 3 CsPbBr in perovskite nanocrystalline dispersion 3 The mass fraction of perovskite nanocrystalline is 1.5%.
2. Specific examples of the lead-halide perovskite of the present invention are as follows;
the lead-halide perovskite may be obtained by the preparation method of the lead-halide perovskite according to examples 1 to 3, and will not be described here.
3. Specific examples of the application of the sulfhydryl-containing hydrophilic ionic liquid halogen salt in preparing lead halogen perovskite are as follows:
example 4
This example uses ionic liquid [ HSC ] 4 mim]Br (1- (4-mercaptobutyl) -3-methylimidazole Bromide) as ligand, cs 2 CO 3 Adding the solution to Pb-containing (OOCCH 3 ) 2 And [ HSC 4 mim]Performing a hot injection reaction in a solution of Br to prepare CsPbBr of example 1 3 Perovskite nanocrystals; wherein Cs 2 CO 3 The temperature of the solution is 150 ℃, nitrogen is used as a protective atmosphere, the solvent of the solution is octanoic acid and N-methyl pyrrolidone (the volume ratio of octanoic acid to N-methyl pyrrolidone is 1:10), and the molar concentration of Cs in the solution is 0.2mol/L; pb (OOCCH) 3 ) 2 And [ HSC 4 mim]The temperature of Br solution is 150 ℃, nitrogen is taken as protective atmosphere, the solvent of solution is N-methylpyrrolidone, the molar concentration of Pb in solution is 0.04mol/L, and the ionic liquid [ HSC ] 4 mim]The molar concentration of Br is 0.05mol/L; the time for the hot injection reaction was 5s.
Example 5
This example uses ionic liquid [ HSC ] 4 mim]Br (1- (4-mercaptobutyl) -3-methylimidazole Bromide) as ligand, cs (OOCCH) 3 ) The solution was added to Pb (acac) 2 And [ HSC 4 mim]Performing a hot injection reaction in a solution of Br to prepare CsPbBr of example 2 3 Perovskite nanocrystals; wherein Cs (OOCCH 3 ) The temperature of the solution is 150 ℃, nitrogen is used as a protective atmosphere, the solvent of the solution is octanoic acid and N-methyl pyrrolidone (the volume ratio of octanoic acid to N-methyl pyrrolidone is 1:10), and the molar concentration of Cs in the solution is 0.1mol/L; pb (acac) 2 And [ HSC 4 mim]The temperature of Br solution is 150 ℃, nitrogen is taken as protective atmosphere, the solvent of solution is N-methylpyrrolidone, the molar concentration of Pb in solution is 0.05mol/L, and the ionic liquid [ HSC ] 4 mim]The molar concentration of Br is 0.06mol/L; the time for the hot injection reaction was 5s.
Example 6
This example uses ionic liquid [ HSC ] 4 mim]Br (1- (4-mercaptobutyl) -3-methylimidazole Bromide) as ligand, cs 2 CO 3 The solution was added to Pb (acac) 2 And [ HSC 4 mim]Performing a hot injection reaction in a solution of Br to prepare CsPbBr of example 3 3 Perovskite nanocrystals; wherein Cs 2 CO 3 The temperature of the solution is 150 ℃, nitrogen is used as a protective atmosphere, the solvent of the solution is octanoic acid and N-methyl pyrrolidone (the volume ratio of octanoic acid to N-methyl pyrrolidone is 1:10), and the molar concentration of Cs in the solution is 0.28mol/L; pb (acac) 2 And [ HSC 4 mim]The temperature of Br solution is 180 ℃, nitrogen is taken as protective atmosphere, the solvent of solution is N-methylpyrrolidone, the molar concentration of Pb in solution is 0.075mol/L, and the ionic liquid [ HSC ] 4 mim]The molar concentration of Br is 0.08mol/L; the time for the hot injection reaction was 5s.
Experimental example 1 (XRD) characterization
CsPbBr prepared in example 1 by X-ray diffraction (XRD) 3 The perovskite nanocrystalline is characterized, and the result is shown in figure 1, PDF- #75-0412 in figure 1 is CsPbBr 3 As can be seen from fig. 1, the XRD diffraction peaks and CsPbBr of the sample 3 The XRD standard card of the cubic phase is consistent, which shows that the prepared sample is CsPbBr with cubic phase 3 Perovskite nanocrystals.
Experimental example 2 optical test
CsPbBr prepared in example 1 was observed under irradiation of natural light and 365nm ultraviolet light, respectively 3 The results of the perovskite nanocrystalline dispersion are shown in fig. 2 and 3. As can be seen from FIGS. 2 and 3, csPbBr prepared in example 1 3 The perovskite nanocrystalline dispersion was yellow, and under irradiation of ultraviolet lamp, csPbBr prepared in example 1 3 The perovskite nanocrystalline dispersion emits bright green fluorescence. CsPbBr prepared for further analysis 3 For CsPbBr prepared in example 1 3 Ultraviolet-visible absorption spectrum of perovskite nanocrystalline dispersion and use thereof inFluorescence spectra under 365nm ultraviolet excitation were tested and the results are shown in fig. 4 and 5. As can be seen from FIGS. 4 and 5, csPbBr prepared in example 1 3 The absorption peak and the emission peak of the perovskite nanocrystalline dispersion are located at 506nm and 517nm, respectively.
Experimental example 3 characterization of morphology
CsPbBr prepared in example 1 was subjected to Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) 3 Perovskite nanocrystals were characterized and the results are shown in fig. 6 and 7. As can be seen from FIG. 6, csPbBr prepared in example 1 3 The grain size of the perovskite nanocrystalline is about 12 nm. As can be seen from FIG. 7, csPbBr prepared in example 1 3 The interplanar spacing of the perovskite nanocrystals was 0.29nm, matching the (100) crystal plane of the perovskite nanocrystals of the cubic phase.
Experimental example 4 stability
CsPbBr prepared in example 1 3 After the perovskite nanocrystalline dispersion was left in a dark environment at room temperature for one month, it was observed under 365nm ultraviolet irradiation, and then the fluorescence spectrum under 365nm ultraviolet excitation was tested, and the result is shown in fig. 8. As can be seen from FIG. 8, csPbBr prepared in example 1 3 After the perovskite nanocrystalline dispersion is placed for one month, bright green light can still be emitted, the emission peak is still located at 517nm, and the fluorescence intensity is only reduced by 5%, which indicates that CsPbBr prepared in example 1 3 The perovskite nanocrystalline has good dispersibility and stability in water.

Claims (7)

1. A method for preparing lead-halogen perovskite, which is characterized by comprising the following steps:
s1, dissolving cesium salt in a protective atmosphere to obtain a first solution;
s2, dissolving lead salt and hydrophilic ionic liquid halogen salt containing sulfhydryl in a protective atmosphere to obtain a second solution;
s3, reacting the first solution with the second solution for 5-10S at the temperature of 150-180 ℃ under the protective atmosphere;
the molar ratio of cesium element in the cesium salt to lead element in the lead salt to hydrophilic ionic liquid halogen salt containing sulfhydryl is 1-3.5:1-12:3-15;
the sulfhydryl-containing hydrophilic ionic liquid halogen salt has a structure shown in a formula I,
wherein R is 1 、R 2 Each independently selected from C 1 -C 6 An alkyl group; x is Cl, br or I.
2. A method of preparing a lead-halide perovskite according to claim 1, wherein R 1 Is methyl, R 2 Is butyl.
3. A method of preparing a lead-halide perovskite according to claim 1 or claim 2, wherein the cesium salt is Cs 2 CO 3 、Cs(OOCCH 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The molar concentration of cesium in the first solution is 0.1-0.28mol/L.
4. The method of preparing lead-halide perovskite according to claim 1 or 2, wherein the molar concentration of the hydrophilic ionic liquid halide salt containing mercapto groups in the second solution is 0.05-0.08mol/L.
5. The method 7 for preparing lead-halide perovskite according to claim 1 or 2, wherein the lead salt is Pb (OOCCH) 3 ) 2 、Pb(acac) 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar concentration of the lead element in the second solution is 0.04-0.075mol/L.
6. The method of preparing lead-halide perovskite according to claim 1 or claim 2, wherein in step S3, the volume ratio of the first solution to the second solution is 1:10-15.
7. A lead-halide perovskite produced by the production process of the lead-halide perovskite according to any one of claims 1 to 6.
CN202110785994.2A 2021-07-12 2021-07-12 Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite Active CN113353972B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110785994.2A CN113353972B (en) 2021-07-12 2021-07-12 Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110785994.2A CN113353972B (en) 2021-07-12 2021-07-12 Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite

Publications (2)

Publication Number Publication Date
CN113353972A CN113353972A (en) 2021-09-07
CN113353972B true CN113353972B (en) 2024-03-26

Family

ID=77539220

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110785994.2A Active CN113353972B (en) 2021-07-12 2021-07-12 Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite

Country Status (1)

Country Link
CN (1) CN113353972B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113881432B (en) * 2021-10-27 2023-06-06 河南科技大学 Ligand modified CsPbBr 3 Preparation method of quantum dot material
CN114057221B (en) * 2021-12-20 2023-06-13 中国科学院长春光学精密机械与物理研究所 Method for preparing flower-like lead halide cesium perovskite structure nanowire

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106062983A (en) * 2013-12-17 2016-10-26 埃西斯创新有限公司 Photovoltaic device comprising a metal halide perovskite and a passivating agent
CN109742236A (en) * 2018-12-13 2019-05-10 东莞理工学院 A kind of perovskite solar battery of ionic liquid enhanced sensitivity and preparation method thereof
WO2019218449A1 (en) * 2018-05-14 2019-11-21 武汉华星光电半导体显示技术有限公司 Preparation method for perovskite quantum dot and perovskite quantum dot solution
CN111162140A (en) * 2019-12-19 2020-05-15 中国海洋大学 Ionic liquid interface modification CsPbBr3Perovskite solar cell preparation method and application
CN111740017A (en) * 2020-08-06 2020-10-02 江西省科学院能源研究所 Method for preparing perovskite solar cell light absorption layer film
CN111777096A (en) * 2020-04-28 2020-10-16 深圳瀚光科技有限公司 Preparation method of water-soluble perovskite nanocrystal, water-soluble perovskite nanocrystal and application
CN111933802A (en) * 2020-08-18 2020-11-13 昆山协鑫光电材料有限公司 Application of ionic liquid in preparation of perovskite photosensitive layer and perovskite solar cell
CN112251221A (en) * 2020-11-10 2021-01-22 上海比英半导体科技有限公司 Method for preparing cesium-lead halogen perovskite quantum dots based on in-situ mercaptosilane passivation
CN112687795A (en) * 2019-10-18 2021-04-20 杭州纤纳光电科技有限公司 Porous film, preparation method thereof and solar cell module using porous film
CN113004319A (en) * 2021-02-02 2021-06-22 中山大学 Dimension-reducing perovskite and preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2566914T3 (en) * 2012-05-18 2016-04-18 Isis Innovation Limited Photovoltaic device comprising perovskites
CN109504379A (en) * 2018-10-25 2019-03-22 武汉华星光电半导体显示技术有限公司 The gorgeous perovskite quantum dot preparation method of inorganic halide lead and display device

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106062983A (en) * 2013-12-17 2016-10-26 埃西斯创新有限公司 Photovoltaic device comprising a metal halide perovskite and a passivating agent
WO2019218449A1 (en) * 2018-05-14 2019-11-21 武汉华星光电半导体显示技术有限公司 Preparation method for perovskite quantum dot and perovskite quantum dot solution
CN109742236A (en) * 2018-12-13 2019-05-10 东莞理工学院 A kind of perovskite solar battery of ionic liquid enhanced sensitivity and preparation method thereof
CN112687795A (en) * 2019-10-18 2021-04-20 杭州纤纳光电科技有限公司 Porous film, preparation method thereof and solar cell module using porous film
CN111162140A (en) * 2019-12-19 2020-05-15 中国海洋大学 Ionic liquid interface modification CsPbBr3Perovskite solar cell preparation method and application
CN111777096A (en) * 2020-04-28 2020-10-16 深圳瀚光科技有限公司 Preparation method of water-soluble perovskite nanocrystal, water-soluble perovskite nanocrystal and application
CN111740017A (en) * 2020-08-06 2020-10-02 江西省科学院能源研究所 Method for preparing perovskite solar cell light absorption layer film
CN111933802A (en) * 2020-08-18 2020-11-13 昆山协鑫光电材料有限公司 Application of ionic liquid in preparation of perovskite photosensitive layer and perovskite solar cell
CN112251221A (en) * 2020-11-10 2021-01-22 上海比英半导体科技有限公司 Method for preparing cesium-lead halogen perovskite quantum dots based on in-situ mercaptosilane passivation
CN113004319A (en) * 2021-02-02 2021-06-22 中山大学 Dimension-reducing perovskite and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A facile, environmentally friendly synthesis of strong photo-emissive methylammonium lead bromide perovskite nanocrystals enabled by ionic liquids;Minh Tam Hoang et al.;Green Chemistry;第22卷(第11期);3433-3440 *
Ionic Liquid-Assisted Improvements in the Thermal Stability of CH3NH3PbI3 Perovskite Photovoltaics;Jinglun Du et al.;Physica Status Solidi-Rapid Research Letters;第12卷(第8期);文献号1800130 *
Passivation of defects in inverted perovskite solar cells using an imidazolium-based ionic liquid;Chuanyao Luo et al.;Sustainable Energy & Fuels;第4卷(第8期);3971-3978 *

Also Published As

Publication number Publication date
CN113353972A (en) 2021-09-07

Similar Documents

Publication Publication Date Title
Chen et al. Non-injection gram-scale synthesis of cesium lead halide perovskite quantum dots with controllable size and composition
Panda et al. Bright white‐light emitting manganese and copper co‐doped ZnSe quantum dots
Haydous et al. The impact of ligands on the synthesis and application of metal halide perovskite nanocrystals
Long et al. High-throughput and tunable synthesis of colloidal CsPbX 3 perovskite nanocrystals in a heterogeneous system by microwave irradiation
CN113353972B (en) Lead halogen perovskite, preparation method thereof and application of ionic liquid halogen salt in preparation of lead halogen perovskite
Aldeek et al. Enhanced photostability from CdSe (S)/ZnO core/shell quantum dots and their use in biolabeling
US6869544B2 (en) Process for producing nanoscale yttrium aluminum garnet (YAG) fluorescent powders
CN101234779A (en) Method for preparing copper-indium-sulfur semi-conductor nano particles
Das et al. Optical downconversion in rare earth (Tb3+ and Yb3+) doped CdS nanocrystals
CN112358875B (en) Water-stable all-inorganic lead-halogen perovskite luminescent material and preparation method thereof
CN103450904A (en) Doped semiconductor nanocrystalline quantum dots having core-shell structure and preparation method thereof
CN110205110B (en) Preparation method of pore confinement-shell isolation double-protection perovskite nano particles
CN110255607B (en) High stability cross CsPbBr3Preparation method of perovskite nanocrystalline and product prepared by preparation method
CN111253942A (en) Up-conversion nano luminescent material with perovskite structure and preparation method and application thereof
Tian et al. Facile synthesis of Ag2Se quantum dots and their application in Dye/Ag2Se co-sensitized solar cells
Tomar et al. Optical properties of Silica capped Mn doped ZnS quantum dots
Yang et al. Highly luminescent Zn–Cu–In–S/ZnS core/gradient shell quantum dots prepared from indium sulfide by cation exchange for cell labeling and polymer composites
Jha et al. Investigation of emission behaviour of perovskite nanocrystals using nano to microspheres of TiO 2
CN107955610B (en) Size-adjustable up-conversion NaYF4Method for preparing nanocrystalline
Yang et al. Synthesis, characterization and optical studies on Sm 2+-doped CdSe nanocrystals: A blueshift and fixed emission with high quantum yields
CN1673095A (en) Prepn process of nano CdSe crystal
CN114058362A (en) Core-shell structure nanocrystalline material and its application in O2Application in gas detection
Panda et al. PVDF-directed synthesis, stability and anion exchange of cesium lead bromide nanocrystals
Zhao et al. Aqueous synthesis of CdSe and CdSe/CdS quantum dots with controllable introduction of Se and S sources
Zhu et al. Structure and composition evaluation of heavily Ge-doped ZnO nanocrystal films

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant