CN115521210B - Perovskite material and preparation method and application thereof - Google Patents

Perovskite material and preparation method and application thereof Download PDF

Info

Publication number
CN115521210B
CN115521210B CN202210120021.1A CN202210120021A CN115521210B CN 115521210 B CN115521210 B CN 115521210B CN 202210120021 A CN202210120021 A CN 202210120021A CN 115521210 B CN115521210 B CN 115521210B
Authority
CN
China
Prior art keywords
substance
hydroiodide
perovskite
perovskite material
pbi
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
CN202210120021.1A
Other languages
Chinese (zh)
Other versions
CN115521210A (en
Inventor
董庆锋
毕伟辉
宋益龙
康一飞
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.)
Dong Qingfeng
Jilin University
Original Assignee
Jilin University
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 Jilin University filed Critical Jilin University
Priority to CN202210120021.1A priority Critical patent/CN115521210B/en
Publication of CN115521210A publication Critical patent/CN115521210A/en
Application granted granted Critical
Publication of CN115521210B publication Critical patent/CN115521210B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/04—Mono-, di- or tri-methylamine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/15—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
    • C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a perovskite material and a preparation method and application thereof. The preparation method of the perovskite material comprises the following steps: carrying out solid-phase reaction on the substance m, the substance p and the substance n; substance m is one or more AX; substance p is one or more DX; substance n is one or more BY 2 . The preparation method of the perovskite material is simple, low in equipment requirement, low in energy consumption, environment-friendly, low in raw material cost, high in atomic economy and reaction efficiency and beneficial to industrial production.

Description

Perovskite material and preparation method and application thereof
Technical Field
The invention relates to the fields of material science and technology and photoelectric application, in particular to a perovskite material and a preparation method and application thereof.
Background
Perovskite materials are widely used in semiconductor photoelectric devices, such as solar cells, photodetectors, light emitting diodes, high-energy ray scintillators, field effect transistors, memristors, and the like, due to their advantages of controllable direct band gap, high electron mobility, high absorption coefficient, long carrier lifetime, and the like. Compared with the traditional silicon-based semiconductor material, the perovskite material has low production cost, wide raw material sources and low production cost; furthermore, the material has excellent photoelectric properties such as low defect density, high carrier mobility, ultra-long carrier diffusion distance, high defect tolerance, and the like.
At present, the development of the organic metal halide perovskite in the field of solar cells is very rapid, the photoelectric conversion efficiency of the prepared solar cells is rapidly developed and reaches a very high level, and the photoelectric conversion efficiency is rapidly improved to 25.5% from 3.8% in 2009 to 2020.
The preparation method of the film in the current device is mainly a solution method or a deposition method, and the purity of the obtained material is high, but the two methods have the advantages of complex process conditions, high equipment requirement, high energy consumption, and great environmental pollution caused by the solvent, and are not environment-friendly.
Literature (Prochowicz D, yadav P, saliba M, et al, mechanosynthesis of pure phase mixed-cation MA x FA1 x PbI 3 hybrid perovskites:photovoltaic performance and electrochemical properties[J].Sustainable Energy&Fuels,2017,1.) discloses the use of methylamine hydroiodide (MAI), formamidine hydroiodide (FAI) and lead iodide (PbI) 2 ) A method for solid phase synthesis of perovskite. Although the method has simple process, the raw material cost is higher and the reaction efficiency is lower.
Therefore, there is a need to provide a preparation method of perovskite materials with simple process, green and environment-friendly properties, low raw material cost and high reaction efficiency.
Disclosure of Invention
The invention aims to provide a perovskite material, a preparation method and application thereof, and a solar cell. The preparation method of the perovskite material is simple, low in equipment requirement, low in energy consumption, environment-friendly, low in raw material cost, high in atomic economy and reaction efficiency and beneficial to industrial production.
The inventor shows through experiments that: selection of raw materials AX and BY 2 At this time, AX+2DX+BY may occur 2 ＝ABX 3 +2DY or 2AX+2DX+BY 2 ＝A 2 BX 4 Solid phase reaction of +2DY; wherein ABX 3 And A 2 BX 4 Is a perovskite material which is a target product. When the byproduct DY is an ionic liquid, the method is environment-friendly and can be further recycled. The perovskite material with higher purity and better thermal stability can be prepared by the specially selected raw materials and the preparation method, and the perovskite material has higher conversion efficiency when being used in a solar cell.
In order to achieve the above object, the present invention provides the following technical solutions:
one of the technical schemes provided by the invention is as follows: a method of preparing a perovskite material comprising the steps of: carrying out solid-phase reaction on the substance m, the substance p and the substance n;
the substance m is one or more AX; the substance p is one or more DX; the substance n is one or more BY 2 ；
Wherein A is independently Cs + Or an organic amine cation;
the D is independently an organic amine cation, NH 4 + 、K + Or Na (or) + ；
The X is independently a halide;
the B is independently Pb 2+ 、Sn 2+ 、Ge 2+ 、Cu 2+ 、Mn 2+ 、Fe 2+ 、Bi 3+ 、Tb 3+ Or Zn 2+ ；
The Y is independently CH 3 COO - 、C 2 O 4 2- 、CF 3 COO - 、CH 3 CHOHCOO - 、HCOO - 、CF 3 SO 3 - 、BF 4 - Or PF (physical pattern) 6 - 。
In the present invention, (the amount of substance of the substance m+the amount of substance of the substance p): (the amount of the substance n) may be (1 to 8): 1, a step of; preferably (2 to 5): 1, a step of; more preferably (3 to 4): 1.
the molar ratio of the substance m, the substance p, and the substance n may be (1 to 4): (1-4): 1, a step of; preferably 1:2:1 or 2:2:1.
In the present invention, the substance m is preferably one or two kinds of AX.
Wherein, when the substance m is two kinds of AX, the mass ratio of the two kinds of AX can be (0.1-10): 1, preferably (0.2 to 2): 1 or (8-9): 1.
the substance p is preferably one or two DX.
Wherein, when the substance p is two kinds of DX, the mass ratio of the two kinds of DX may be (0.1 to 10): 1, more preferably (0.2 to 2): 1 or (8-9): 1.
the substance n is preferably one or two BY 2 。
In the present invention, the organic amine cation is preferably CH 3 NH 3 + 、HC(NH 2 ) 2 + 、CH 3 CH 2 NH 3 + 、CH 3 (CH 2 ) 2 NH 3 + 、CH 3 (CH 2 ) 3 NH 3 + 、CF 3 CH 2 NH 3 + 、(CH 3 ) 2 NH 2 + 、C(NH 2 ) 3 + Or (b)For example CH 3 NH 3 + 、(CH 3 ) 2 NH 2 + 、CH 3 NH 3 + Or HC (NH) 2 ) 2 + 。
The D is preferably NH 4 + 、K + Or Na (or) + 。
The halide ions may be conventional in the art, preferably I - 、Br - Or Cl - The method comprises the steps of carrying out a first treatment on the surface of the For example I - Or Br (Br) - 。
Said B is independently preferably Pb 2+ 、Sn 2+ 、Ge 2+ Or Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the More preferably Pb 2+ Or Sn (Sn) 2+ 。
The Y is independently preferably HCOO - Or CH (CH) 3 COO - The method comprises the steps of carrying out a first treatment on the surface of the More preferably CH 3 COO - 。
In the present invention, the AX is preferably one or more of cesium iodide, methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide and guanidine hydroiodide; more preferred are methylamine hydroiodide and dimethylamine hydroiodide, or formamidine hydroiodide and methylamine hydroiodide.
The DX is preferably one or more of methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide, guanidine hydroiodide, sodium iodide, potassium bromide and ammonium iodide; more preferred are sodium iodide, potassium bromide, ammonium iodide, methylamine hydroiodide and dimethylamine hydroiodide, or formamidine hydroiodide and methylamine hydroiodide.
Wherein, when the AX or the DX is methyl amine hydroiodidate and dimethylamine hydroiodidate, the mass ratio of the methyl amine hydroiodidate to the dimethylamine hydroiodidate can be (8-9): 1, a step of; preferably 8.27:1.
when AX or DX is formamidine hydroiodate and methylamine hydroiodate, the mass ratio of formamidine hydroiodate to methylamine hydroiodate may be (0.2 to 2): 1, a step of; preferably 1.08: 1. 0.36: 1. 0.72:1 or 1.62:1.
the BY 2 Preferably lead acetate and/or tin acetate.
The BY 2 May carry crystallization water or adsorption water.
In the present invention, the molecular formula of the perovskite material is preferably ABX 3 And/or A 2 BX 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein said A, said X and said B are as previously described. The ABX 3 Can be MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 . The A is 2 BX 4 Can be BA 2 PbI 4 Or PEA (PEA) 2 PbI 4 。
In the present invention, the solid phase reaction may be conventional in the art, such as milling.
Wherein, the grinding method can be manual grinding or mechanical grinding. The manually ground container may be a mortar. The diameter of the mortar may be conventional in the art, for example, 10 to 20cm. The mechanically milled vessel may be a ball mill.
The temperature of the milling may be conventional in the art, for example 20 to 30 ℃, preferably 25 ℃.
The ambient conditions of the milling may be conventional in the art, such as air, a vacuum environment, or an inert atmosphere.
The method for judging the end of grinding can be conventional in the art, and generally can be when the color of the raw materials and the reactant of the solid phase reaction is changed significantly. For example, when AX, DX and BY 2 When the reaction products are white, the color of the reaction products is changed from white to orange or black through grinding, and grinding is finished. The grinding time can be 10-60 min; preferably 30 to 60 minutes; for example 35min, 40min, 45min or 50min.
In the present invention, after the solid phase reaction, optionally, a washing and/or drying step may be further included.
The washing method can be conventional in the art, such as filtration washing or centrifugal washing; for separating by-products from reactants of a solid phase reaction. The filter wash may be conventional in the art, and generally refers to the washing of AX and BY 2 Placing the reactant in a funnel, and adding a washing liquid; the funnel is preferably a buchner funnel or a sand core funnel. The centrifugal washing may be conventional in the art. The rotational speed of the centrifugal washing may be conventional in the art, e.gSuch as 3000 to 6000rpm, preferably 4000rpm. The time for each centrifugal washing may be 5 to 15 minutes, preferably 10 minutes.
The washing liquid of the washing may be conventional in the art, preferably an organic solvent. The organic solvent can be one or more of methanol, ethanol, isopropanol, acetonitrile, anisole, tetrahydrofuran, acetone, n-butanol, tertiary butanol, sec-butanol, ethyl acetate, cyclohexane and toluene; preferably acetonitrile, isopropanol or ethyl acetate.
The number of washes may be conventional in the art, for example 1 to 4 times; preferably 3 times.
The volume of the washing liquid may be conventional in the art, for example, the volume of the washing liquid per 1g of the reactant may be 2 to 5mL, preferably 3mL or 4mL, per one washing. For example, when the mass of the reactant is 6g, the volume of the acidic solution is 12 to 30mL.
The solid and liquid can be collected separately after the washing.
In the present invention, when the step of washing and drying is included after the solid phase reaction, the drying may be drying the solid collected after the washing to obtain the perovskite material.
And after the solid phase reaction, and without the step of washing, drying the reactant after the solid phase reaction, wherein DY is volatilized to obtain the perovskite material.
Wherein the drying method may be conventional in the art.
The ambient conditions of the drying may be conventional in the art, such as air, vacuum environment, or inert atmosphere; preferably a vacuum environment.
The temperature of the drying may be conventional in the art, for example 20-100 ℃; preferably 50 to 80 ℃; more preferably 60 ℃.
The drying time may be conventional in the art, for example, 4 to 12 hours; preferably 8h.
The drying apparatus may be conventional in the art, such as a vacuum oven.
The dried perovskite material may be conventional in the art, preferably stored in a sealed condition. The sealed storage conditions may be stored in an inert atmosphere, preferably a nitrogen atmosphere.
In the present invention, it is preferable that the washing is further comprised of a step of distilling or extracting the liquid collected after the washing for recovering by-products and washing liquid.
The distillation method may be a distillation concentration method conventional in the art.
The apparatus for the distillation may be conventional in the art, such as a rotary evaporator.
The temperature of the distillation may be conventional in the art, for example 30-50 ℃; preferably 35 to 45 ℃.
The method of extraction may be conventional in the art.
In the present invention, the preparation method of the perovskite material preferably comprises the following steps: carrying out solid phase reaction on a substance m, a substance p and a substance n to obtain a reactant; washing the reactant, and collecting solid and liquid respectively; drying the solid to obtain a perovskite material; the liquid is distilled, and the washing liquid and the byproducts are respectively collected.
In the invention, the perovskite material can be one or more of one-dimensional perovskite, two-dimensional perovskite and three-dimensional perovskite; such as a two-dimensional perovskite or a three-dimensional perovskite.
The particle size of the perovskite material may be conventional in the art, preferably 3 to 6mm, for example 4 to 5mm.
The second technical scheme provided by the invention is as follows: a method of purifying a perovskite material comprising the steps of:
heating the supersaturated solution of the perovskite material in sections to obtain a perovskite single crystal material;
the sectional heating comprises a first heating section, a second heating section and a third heating section; the temperature difference between the first heating section and the second heating section is 10-50 ℃; the temperature difference between the second heating section and the third heating section is 10-50 ℃.
In the present invention, the perovskite material is preferably prepared by the preparation method of the perovskite material.
In the present invention, the perovskite material may be conventional in the art, such as MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 、TFEAPbI 3 、BA 2 PbI 4 Or PEA (PEA) 2 PbI 4 。
In the present invention, the supersaturated solution of the perovskite material may be generally obtained by mixing the perovskite material with a purification solvent. The purification solvent may be one or more of aqueous hydroiodic acid, aqueous hydrobromic acid, N-dimethylformamide, dimethyl sulfoxide and γ -butyrolactone, as is conventional in the art.
In the present invention, the temperature of the supersaturated solution of perovskite material may be conventional in the art, typically below the boiling point of the purification solvent; for example 40 to 140 ℃.
In the present invention, it is preferable that the supersaturated solution of the perovskite material is transported upward through a transport pipe and then subjected to staged heating.
Wherein the diameter of the delivery conduit may be determined according to the volume of the solution as is conventional in the art. For example, when the solution volume of the perovskite material is 1L, the diameter of the conveying pipeline is 1-10 cm; preferably 5cm.
The conveying speed can be 5-30 mL/min; preferably 10 to 20mL/min.
In the present invention, the temperatures of the first heating section, the second heating section, and the third heating section are preferably sequentially reduced or sequentially increased. For example, the temperatures of the first heating section, the second heating section, and the third heating section are 90 ℃, 60 ℃, 30 ℃, respectively; alternatively, 100 ℃, 80 ℃, 60 ℃; alternatively, 90 ℃,100 ℃, 110 ℃; alternatively, 45 ℃, 55 ℃, 65 ℃.
Wherein when the purification solvent is an aqueous solution of hydroiodic acid or hydrobromic acid, the pH of the supersaturated solution of perovskite material is 7 or less, and the temperatures of the first heating stage, the second heating stage and the third heating stage are preferably sequentially reduced.
In the present invention, it is preferable that the step of collecting the perovskite single-crystal material is further included after the step of heating the supersaturated solution of the perovskite material in stages.
In the invention, preferably, the purification device adopted by the purification method comprises a feeding area, a seed crystal area, a heating unit, a sectional temperature control crystal growth area, a crystal collecting area and a feed liquid circulating and returning area;
the feeding zone is connected with the seed crystal zone and is used for adding a solution of perovskite materials into the seed crystal zone;
the heating unit is used for heating the solution of the perovskite material in the seed crystal zone;
the sectional temperature control crystal growth area comprises a feed liquid transport power component and a transport pipeline; the feed liquid conveying power component is arranged in the conveying pipeline; one end of the conveying pipeline is positioned in the seed crystal area, and the other end of the conveying pipeline is connected with the crystal collecting area;
the conveying pipeline sequentially comprises a feed liquid conveying power component, a first heating element, a second heating element and a third heating element along the solution flowing direction of the perovskite material; the conveying pipeline is used for circulating and heating the solution of the perovskite material input from the seed crystal zone;
one end of the feed liquid circulating and returning area is connected with the crystal collecting area and is used for receiving the residual feed liquid after the perovskite single crystal material is collected by the crystal collecting area; the other end is connected with the seed crystal area and is used for conveying the residual feed liquid to the seed crystal area. The perovskite material and the purifying solvent can be fully utilized, and the perovskite single crystal material can be grown through multiple cycles.
The third technical scheme provided by the invention is as follows: a perovskite single crystal material is prepared by the purification method of the perovskite material.
In the invention, the molecular formula of the perovskite single crystal material is preferablyIs ABX 3 And/or A 2 BX 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein said A, said X and said B are as previously described.
The ABX 3 Preferably MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 . The A is 2 BX 4 Preferably BA 2 PbI 4 Or PEA (PEA) 2 PbI 4 。
The perovskite single crystal material can be one or more of one-dimensional perovskite, two-dimensional perovskite and three-dimensional perovskite; preferably a two-dimensional perovskite or a three-dimensional perovskite.
The particle size of the perovskite single crystal material may be conventional in the art, preferably in the range 1 to 10mm, more preferably 3 to 6mm, for example 4 to 5mm.
The technical scheme provided by the invention is as follows: use of a perovskite single crystal material as hereinbefore described in solar cells.
The technical scheme provided by the invention is as follows: a solar cell comprising a perovskite single crystal material as hereinbefore described.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The preparation method provided by the invention has the advantages of simplicity, low equipment requirement, low energy consumption, environmental protection, low raw material cost, high atom economy and high reaction efficiency, and is beneficial to industrial production.
(2) The preparation method provided by the invention can recycle the washing liquid and byproducts, and is economical and environment-friendly.
(3) The perovskite material has low defect density, higher purity and better thermal stability; the method is used in the solar cell, and the conversion efficiency is high.
Drawings
FIG. 1 is a photograph of perovskite powder in example 1;
FIG. 2 is a photograph (grid scale 1 mm) of a perovskite single crystal in example 15;
FIG. 3 is a Scanning Electron Microscope (SEM) image of perovskite powder of example 1;
FIG. 4 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 3;
FIG. 5 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 1 and the perovskite single crystal of example 15;
FIG. 6 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 2 and the perovskite single crystal of example 16;
FIG. 7 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 20;
FIG. 8 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 19;
FIG. 9 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 4 and the perovskite single crystal of example 18;
FIG. 10 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 24;
FIG. 11 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 21;
FIG. 12 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 22;
FIG. 13 shows a 400MHz nuclear magnetic hydrogen spectrum of perovskite powder as described in example 6 1 H NMR)；
FIG. 14-a is a 400MHz nuclear magnetic hydrogen spectrum of perovskite powder of example 4 1 H NMR)；
FIG. 14-b is a graph comparing nuclear magnetic resonance spectra of perovskite powder of example 4 and perovskite single crystal material of example 18;
FIG. 15 shows a 400MHz nuclear magnetic hydrogen spectrum of perovskite powder as described in example 8 1 H NMR)；
FIG. 16 shows a 400MHz nuclear magnetic hydrogen spectrum of perovskite powder as described in example 7 1 H NMR)；
FIG. 17 shows a 400MHz nuclear magnetic hydrogen spectrum of perovskite powder as described in example 3 1 H NMR)；
FIG. 18 shows a 400MHz nuclear magnetic hydrogen spectrum of perovskite powder as described in example 1 1 H NMR)；
FIG. 19 is a TGA plot of perovskite powder in example 4 and perovskite single crystal material in example 18;
FIG. 20 is a schematic view of an apparatus used for the purification method of perovskite materials in examples 15 to 28.
Description of the reference numerals
Feeding zone 1
Seed region 2
Sectional temperature controlled crystal growth zone 3
Feed liquid transport power part 31
First heating element 32
Second heating element 33
Third heating element 34
Delivery pipe 35
Crystal collection zone 4
Screen 41
Feed liquid circulation return zone 5
Heating unit 6
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Examples 1 to 14 preparation of perovskite materials
Grinding raw materials of perovskite materials to obtain reactants; wherein the grinding container is a mortar, and the diameter of the mortar in examples 1-11 is 10cm; the diameter of the mortar in examples 12 to 14 was 20cm;
placing the reactant in a Buchner funnel, filtering and washing the reactant for 3 times, adding a washing liquid to submerge the reactant, and collecting solids and liquid respectively;
sequentially drying the solid to obtain the perovskite material
Wherein the raw materials of the perovskite material are shown in the following table 1; the process conditions are shown in table 2 below; the reaction equations and the mass of perovskite material are shown in table 3 below; the recovered organic solvent and byproducts are shown in table 4 below.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
Examples 15 to 28 purification of perovskite materials
The perovskite materials prepared in examples 1 to 14 were purified, and as shown in FIG. 20, the purification apparatus comprises a feed zone 1, a seed crystal zone 2, a heating unit 6, a sectional temperature-controlled crystal growth zone 3, a crystal collection zone 4 and a feed liquid recycling zone 5;
the feeding zone 1 is connected with the seed crystal zone 2 and is used for adding a solution of perovskite materials into the seed crystal zone 2;
the heating unit 6 is used for heating the solution of the perovskite material in the seed region 2;
the sectional temperature control crystal growth area 3 comprises a feed liquid conveying power part 31 and a conveying pipeline 35; the feed liquid transporting power part 31 is a propeller and is arranged in the conveying pipeline 35; one end of the conveying pipeline 35 is positioned in the seed crystal region 2, and the other end of the conveying pipeline is connected with the crystal collecting region 4;
the crystal collection zone 4 comprises a screen 41;
the volume of the solution of perovskite material of 2 in the seed zone was 1L, and the diameter of the delivery pipe 35 was 5cm;
the conveying pipe 35 includes a feed liquid transporting power part 31, a first heating element 32, a second heating element 33, and a third heating element 34 in this order along the solution flow direction of the perovskite material; the delivery conduit 35 is used to circulate and heat the solution of perovskite material fed from the seed zone 2;
the first, second and third heating elements 32, 33 and 34 divide the transport conduit 35 into a first, second and third temperature zone; for heating the solution of perovskite material fed from the seed zone 2;
one end of the feed liquid circulation return area 5 is connected with the crystal collecting area 4 and is used for receiving the residual feed liquid after the perovskite single crystal material is collected by the crystal collecting area 4; the other end is connected with the seed crystal zone 2 and is used for conveying the residual feed liquid to the seed crystal zone.
The purification method comprises the following steps:
(1) Mixing the perovskite materials prepared in examples 1 to 14 with a purification solvent to obtain a supersaturated solution of the perovskite material; and heating it; the kinds of the purification solvents and the heating temperatures are shown in Table 5;
(2) Conveying the supersaturated solution of the perovskite material heated in the step (1) upwards, and then heating in sections; the sectional heating comprises a first heating section, a second heating section and a third heating section; the temperatures of the first heating section, the second heating section, and the third heating section, and the conveying speeds are shown in table 5.
(3) Collecting the perovskite single crystal material; and distilling the liquid by adopting a rotary evaporator, and respectively collecting the washing liquid and byproducts.
TABLE 5
Note that: the upward transport speed was 1L in total of the solutions in step (1).
Effect examples
(1) Photograph of a person
The photo of the perovskite powder obtained in example 1 is shown in fig. 1, and it can be seen that the perovskite powder has a black color.
A photograph of the perovskite single crystal in example 15 is shown in FIG. 2, in which the scale of the grid is 1mm. From the above, the perovskite single crystal material has a particle size ranging from 1 to 10mm and is mainly distributed in a range from 3 to 6mm.
(2) Scanning electron microscope image
The scanning electron microscope image of the perovskite powder in example 1 is shown in FIG. 3, and it can be seen that the prepared perovskite powder has a relatively regular crystal morphology, and the particle size is mainly distributed around 50 μm.
(3) X-ray diffraction pattern
And carrying out X-ray diffraction pattern test on the perovskite material or perovskite single crystal material prepared in the implementation.
Wherein the X-ray diffraction pattern (XRD) of the perovskite powder of example 3 is shown in fig. 4;
an X-ray diffraction pattern (XRD) of the perovskite powder of example 1 is shown in fig. 5 a, and an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 15 is shown in fig. 5 b;
the X-ray diffraction pattern (XRD) of the perovskite powder of example 2 is shown in fig. 6 c, and the X-ray diffraction pattern (XRD) of the perovskite single crystal of example 16 is shown in fig. 6 d;
the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 20 is shown in fig. 7;
the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 19 is shown in fig. 8;
the X-ray diffraction pattern (XRD) of the perovskite powder in example 4 is shown in fig. 9 e, and the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 18 is shown in fig. 9 f;
the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 24 is shown in fig. 10;
the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 21 is shown in fig. 11;
the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 22 is shown in fig. 12.
As can be seen from fig. 5, 6 and 9, the full width at half maximum FWHM of the diffraction peak of the powder XRD after purification is significantly smaller than that before purification, the intensity of the diffraction peak is greater, and the impurity peak before purification is also disappeared, which proves that the quality and purity of the purified crystal are better.
(4) 400MHz nuclear magnetic hydrogen spectrum 1 H NMR)
The perovskite material prepared by the implementation is subjected to 400MHz nuclear magnetic hydrogen spectrum 1 H NMR) testing.
Wherein the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder of example 6 is shown in FIG. 13; as can be seen from fig. 13, chemical shifts δ1=2.38 ppm and δ2=7.48 ppm in the nuclear magnetic hydrogen spectrum of the perovskite single crystal correspond to methylamine cation-CH, respectively 3 and-NH 3 The chemical shifts δ3=7.85 ppm, δ4=8.66 ppm and δ5=9.01 ppm of hydrogen on the catalyst correspond to-CH-, -NH of formamidine cation respectively 2 and-NH 2+ Hydrogen on the above, FA: ma=1:3 can be calculated from the integrated area;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 4 is shown in FIG. 14-a;
the nuclear magnetic resonance spectrum of the perovskite powder in example 4 is shown as g in fig. 14-b, and the nuclear magnetic resonance spectrum of the perovskite single crystal material in example 18 is shown as h in fig. 14-b;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 8 is shown in FIG. 15;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder of example 7 is shown in FIG. 16;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 3 is shown in FIG. 17;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 1 is shown in FIG. 18.
(5) Thermal stability test
As shown in fig. 19, j is the TGA profile of the perovskite powder in example 4, and k is the TGA profile of the perovskite single crystal material in example 18. As can be seen from the graph, the initial decomposition amount of the perovskite powder in example 4 reached 1%, and the temperature was 295 ℃; after purification, the temperature reached 335 ℃ when the initial decomposition amount of the perovskite single crystal material in example 18 reached 1%, indicating good thermal stability.

Claims (10)

1. A method for preparing a perovskite material, comprising the steps of: carrying out solid-phase reaction on the substance m, the substance p and the substance n;
the substance m is one or more AX; the substance p is one or more DX; the substance n is one or more BY 2 ；
Wherein, A is an organic amine cation; the organic amine cation is CH 3 NH 3 + 、HC(NH 2 ) 2 + 、CH 3 CH 2 NH 3 + 、CH 3 (CH 2 ) 2 NH 3 + 、CH 3 (CH 2 ) 3 NH 3 + 、CF 3 CH 2 NH 3 + 、(CH 3 ) 2 NH 2 + 、C(NH 2 ) 3 + Or (b)；
The D is NH 4 + 、K + Or Na (or) + ；
X is halide;
the B is Pb 2+ ；
The Y is CH 3 COO - 、CF 3 COO - 、CH 3 CHOHCOO - 、HCOO - 、CF 3 SO 3 - 、BF 4 - Or PF (physical pattern) 6 - 。
2. A method of producing a perovskite material as claimed in claim 1, wherein (the amount of substance m + the amount of substance p): (the amount of the substance n is (1 to 8): 1, a step of;
and/or the molar ratio of the substance m, the substance p and the substance n is (1-4): (1-4): 1, a step of;
the substance m is one or two AX;
and/or the substance p is one or two DX;
and/or the substance n is one or two BY 2 ；
And/or the organic amine cation is CH 3 NH 3 + 、(CH 3 ) 2 NH 2 + 、CH 3 NH 3 + Or HC (NH) 2 ) 2 + ；
And/or the halide is I - 、Br - Or Cl - ；
And/or, the Y is HCOO - Or CH (CH) 3 COO - 。
3. A method of producing a perovskite material as claimed in claim 2, wherein (the amount of substance m + the amount of substance p): (the amount of the substance n is (2-5): 1, a step of;
and/or the molar ratio of the substance m, the substance p and the substance n is 1:2:1 or 2:2:1;
and/or, when the substance m is two kinds of AX, the mass ratio of the two kinds of AX is (0.1-10): 1, a step of;
and/or, when the substance p is two DX, the mass ratio of the two DX is (0.1-10): 1, a step of;
and/or the halide is I - Or Br (Br) - ；
And/or, the Y is CH 3 COO - 。
4. A method of producing a perovskite material as claimed in claim 3, wherein (the amount of substance m + the amount of substance p): (the amount of the substance n is 3 to 4): 1, a step of;
and/or, when the substance m is two kinds of AX, the mass ratio of the two kinds of AX is (0.2-2): 1 or (8-9): 1, a step of;
and/or, when the substance p is two DX, the mass ratio of the two DX is (0.2-2): 1 or (8-9): 1.
5. the method of preparing a perovskite material according to claim 2, wherein AX is one or more of methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide, and guanidine hydroiodide;
and/or, the DX is one or more of sodium iodide, potassium bromide, and ammonium iodide;
and/or, the BY 2 Is lead acetate;
and/or the molecular formula of the perovskite material is ABX 3 And/or A 2 BX 4 。
6. The method of producing a perovskite material according to claim 5, wherein AX is methylamine hydroiodide and dimethylamine hydroiodide, or formamidine hydroiodide and methylamine hydroiodide;
and/or, the DX is sodium iodide, potassium bromide or ammonium iodide;
and/or, when the AX is methyl amine hydroiodide and dimethylamine hydroiodide, the mass ratio of the methyl amine hydroiodide to the dimethylamine hydroiodide is (8-9): 1, a step of;
and/or, when the AX is formamidine hydroiodinate and methylamine hydroiodinate, the mass ratio of the formamidine hydroiodinate to the methylamine hydroiodinate is (0.2-2): 1, a step of;
and/or, the BY 2 With water of crystallization or adsorbed water;
and/or, the ABX 3 For MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 ；
And/or, the A 2 BX 4 Is BA 2 PbI 4 Or PEA (PEA) 2 PbI 4 。
7. The method of producing a perovskite material according to claim 6, wherein when AX is methyl amine hydroiodide and dimethylamine hydroiodide, the mass ratio of methyl amine hydroiodide to dimethylamine hydroiodide is 8.27:1, a step of;
and/or, when AX is formamidine hydroiodidate and methylamine hydroiodidate, the mass ratio of formamidine hydroiodidate to methylamine hydroiodidate is 1.08: 1. 0.36: 1. 0.72:1 or 1.62:1.
8. the method for producing a perovskite material according to any one of claims 1 to 7, wherein the solid phase reaction is milling;
and/or, after the solid phase reaction, further comprising a step of washing and/or drying;
and/or the perovskite material is one or more of one-dimensional perovskite, two-dimensional perovskite and three-dimensional perovskite.
9. The method for producing a perovskite material according to claim 8, wherein the temperature of grinding is 20 to 30 ℃;
and/or, after the washing, further comprising a step of distilling or extracting the liquid collected after the washing;
and/or the perovskite material is a two-dimensional perovskite or a three-dimensional perovskite;
and/or the particle size of the perovskite material is 3-6 mm.
10. The method of preparing a perovskite material of claim 9 wherein the temperature of milling is 25 ℃;
and/or, the preparation method of the perovskite material comprises the following steps: carrying out solid phase reaction on a substance m, a substance p and a substance n to obtain a reactant; washing the reactant, and collecting solid and liquid respectively; drying the solid to obtain a perovskite material; distilling the liquid, and respectively collecting a washing liquid and byproducts;
and/or the particle size of the perovskite material is 4-5 mm.
CN202210120021.1A 2022-01-27 2022-01-27 Perovskite material and preparation method and application thereof Active CN115521210B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210120021.1A CN115521210B (en) 2022-01-27 2022-01-27 Perovskite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210120021.1A CN115521210B (en) 2022-01-27 2022-01-27 Perovskite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN115521210A CN115521210A (en) 2022-12-27
CN115521210B true CN115521210B (en) 2023-11-24

Family

ID=84694498

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210120021.1A Active CN115521210B (en) 2022-01-27 2022-01-27 Perovskite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN115521210B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702869A (en) * 2016-01-25 2016-06-22 上海科技大学 Mixed cation perovskite and preparation method therefor
CN106748812A (en) * 2016-11-30 2017-05-31 天津市职业大学 A kind of new method for preparing perovskite solar cell lead halide methylamine
CN109338465A (en) * 2018-11-30 2019-02-15 暨南大学 A kind of perovskite monocrystal material and the preparation method and application thereof
CN109336768A (en) * 2018-09-27 2019-02-15 深圳大学 A kind of preparation method of perovskite powder
CN110305019A (en) * 2019-08-15 2019-10-08 暨南大学 A kind of two-dimensional layer perovskite crystal and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105702869A (en) * 2016-01-25 2016-06-22 上海科技大学 Mixed cation perovskite and preparation method therefor
CN106748812A (en) * 2016-11-30 2017-05-31 天津市职业大学 A kind of new method for preparing perovskite solar cell lead halide methylamine
CN109336768A (en) * 2018-09-27 2019-02-15 深圳大学 A kind of preparation method of perovskite powder
CN109338465A (en) * 2018-11-30 2019-02-15 暨南大学 A kind of perovskite monocrystal material and the preparation method and application thereof
CN110305019A (en) * 2019-08-15 2019-10-08 暨南大学 A kind of two-dimensional layer perovskite crystal and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Influence of Additives on the In Situ Crystallization Dynamics of Methyl Ammonium Lead Halide Perovskites;Edwin Pineda De La O等;ACS Appl. Energy Mater.(第4期);1398−1409 *

Also Published As

Publication number Publication date
CN115521210A (en) 2022-12-27

Similar Documents

Publication Publication Date Title
TWI382095B (en) Method for manufacturing multi-element metal chalcogenide synthesis
CN101665696B (en) Preparation method of Eu3+ doped yttrium lanthanum oxide fluorescent powder and transparent scintillating ceramic
CN101870458B (en) Preparation methods of multi-element metal chalcogen compound, target and coating material
CN106757371A (en) A kind of organo-mineral complexing perovskite monocrystalline induced conversion method and device based on methylamine atmosphere
EP3050850B1 (en) Methods for producing a rare earth oxysulfide, ceramic scintillator, scintillator array and radiation detector
CN114836818B (en) Cs (cell lines) 5 Cu 3 Cl 6 I 2 Preparation method of perovskite scintillation crystal
CN114316952B (en) Double-layer DJ lead-iodine perovskite constructed by aromatic amine, and preparation method and application thereof
CN115521210B (en) Perovskite material and preparation method and application thereof
CN113104890A (en) Cs (volatile organic Compounds)4CuSb2Cl12Layered halide double perovskite material and preparation method and application thereof
CN110526824B (en) Beta-ray scintillator based on manganese-doped two-dimensional halogen perovskite and preparation method thereof
CN111647167A (en) Novel metal organic framework material Zn-MOF, and synthesis method and application thereof
CN106748812A (en) A kind of new method for preparing perovskite solar cell lead halide methylamine
CN114988464A (en) Method and device for recycling lead salt from perovskite battery
CN115448357A (en) Method for synthesizing lead-halogen perovskite by recycling lead ions in aqueous solution
CN113684021B (en) Rare earth near-infrared fluorescent powder, and preparation method and application thereof
WO2022217238A1 (en) Methods for purifying perovskite precursors and improved perovskites manufactured therefrom
CN101962181B (en) Preparation of lithium hexafluorophosphate by rheological phase reaction method
CN103214029A (en) Preparation method of wurtzite CuInS2 nanodisk
CN102659084A (en) Preparation method of zinc selenide nanometer powder
CN112028943A (en) Platinum luminescent compound based on pyridine imidazole derivative and preparation method thereof
CN109589998B (en) Novel ZnO/Se/SiO2Preparation method of composite material and application of composite material in preparation of phthalide
CN112028942B (en) Pt (II) photoluminescent compound based on pyridoimidazole derivative and preparation method thereof
US20240188407A1 (en) Methods for purifying perovskite precursors and improved perovskites manufactured therefrom
TWI810867B (en) Method for recovering valuable material from perovskite solar cell
CN106565573A (en) Preparation method of 2-(dimethylamino) tellurium

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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20240426

Address after: 130012 No. 2699 Qianjin Street, Changchun hi tech Development Zone, Jilin

Patentee after: Jilin University

Country or region after: China

Patentee after: Dong Qingfeng

Address before: 130012 No. 2699 Qianjin Street, Changchun hi tech Development Zone, Jilin

Patentee before: Jilin University

Country or region before: China