CN110512271B - Mesh-woven perovskite and preparation method and application thereof - Google Patents

Mesh-woven perovskite and preparation method and application thereof Download PDF

Info

Publication number
CN110512271B
CN110512271B CN201910624894.4A CN201910624894A CN110512271B CN 110512271 B CN110512271 B CN 110512271B CN 201910624894 A CN201910624894 A CN 201910624894A CN 110512271 B CN110512271 B CN 110512271B
Authority
CN
China
Prior art keywords
perovskite
conductive glass
glass substrate
precursor solution
drying
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
CN201910624894.4A
Other languages
Chinese (zh)
Other versions
CN110512271A (en
Inventor
陈梦诗
肖也
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.)
Guangdong University of Technology
Original Assignee
Guangdong University of 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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201910624894.4A priority Critical patent/CN110512271B/en
Publication of CN110512271A publication Critical patent/CN110512271A/en
Application granted granted Critical
Publication of CN110512271B publication Critical patent/CN110512271B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/12—Halides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • 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

Abstract

The invention belongs to the technical field of perovskite materials, and discloses a meshed perovskite and a preparation method and application thereof. Adding FABr and PbBr into a solvent to prepare a precursor solution of 0.5-3 mol/L, diluting the precursor solution by 10-30 times, dropwise adding the diluted precursor solution onto an FTO conductive glass substrate, dropwise adding toluene, and drying to prepare a perovskite single crystal; and soaking the obtained perovskite single crystal in a cobalt iso-octoate solution for 5-30 min, and then putting the sample into a drying oven for drying to finally obtain the mesh-shaped perovskite. The method adopts an anti-solvent method to prepare perovskite single crystals, and then utilizes a cobalt iso-octoate solution with isopropanol as a solvent to prepare the meshed perovskite. The perovskite material can be applied to the field of solar cells.

Description

Mesh-woven perovskite and preparation method and application thereof
Technical Field
The invention belongs to the technical field of perovskite material preparation, and particularly relates to a meshed perovskite and a preparation method and application thereof.
Background
In recent years, the energy crisis has become an important issue to be solved urgently. The perovskite material has unique performance, so that the perovskite material injects new activity for the preparation of solar cells. Particularly, in the face of the serious challenge of solar energy conversion, the perovskite material can absorb and utilize green energy of sunlight to effectively improve the efficiency of the solar cell, so that the development of the perovskite material with large specific surface area, high stability and wide photoresponse range becomes an important content of current research.
The perovskite is a functional material with excellent optical and electrical properties, and has wide application prospect in the fields of solar cells, light emitting diodes, micro lasers and the like. Metal Halide Perovskite (MHP) materials have developed rapidly in the field of photovoltaics in recent years due to their excellent photovoltaic properties. And FABrBr3The perovskite material is an organic-inorganic perovskite material which is very popular at present, and has a wide application prospect in various fields such as gas sensors, electrode materials, solar cells and the like due to good light absorption capacity. However, with the human pairing of FABrBr3Further research shows that the photocatalyst is also a good photocatalyst, and more people apply the photocatalyst to the field of photocatalysis. The photocatalysis is generated by excitation under the irradiation of ultraviolet light with higher energy, but due to FABrBr3The single crystal has a small specific surface area and few active sites capable of participating in the reaction, so that the photocatalytic efficiency is limited. In addition, the instability and easy recombination of photogenerated electron-hole pairs, which play a key role in the photocatalytic process, limit the FABrBr3And (4) exerting a photocatalytic effect. Therefore, to make better use ofFABrBr3The role in the field of photocatalysis has to be solved in two ways: (1) the specific surface area of the material is increased; (2) reducing the recombination rate of the photo-generated electron-hole pairs.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a preparation method of a mesh-shaped perovskite; the method specifically adopts a solvothermal synthesis method to prepare the single crystal perovskite material, and then prepares the mesh-shaped perovskite.
Still another object of the present invention is to provide a perovskite in a mesh form prepared by the above preparation method.
It is a further object of the present invention to provide a use of the above-described reticulated perovskite.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a reticulated perovskite, comprising the following operative steps: adding FABr and PbBr into a solvent to prepare a precursor solution of 0.5 mol/L-3 mol/L, diluting the precursor solution by 10-30 times, dropwise adding the diluted precursor solution onto an FTO conductive glass substrate, dropwise adding toluene, and drying to prepare perovskite single crystals; and soaking the obtained perovskite single crystal in a cobalt iso-octoate solution for 5-30 min, and then putting the sample into a drying oven for drying to finally obtain the mesh-shaped perovskite.
The FTO conductive glass substrate is cleaned before use: and (3) soaking the FTO conductive glass in the piranha solution, and then adding deionized water to dilute the FTO conductive glass to be neutral to obtain a clean FTO conductive glass substrate.
The soaking time is 8-12 h; the piranha solution is a mixture of concentrated sulfuric acid and 30% hydrogen peroxide.
The solvent is DMF.
The cobalt isooctanoate solution is prepared into a solution with the concentration of 5 mmol-50 mmol by taking isopropanol as a solvent.
Diluting the precursor solution by 10-30 times, dripping 1-30 ul of the diluted precursor solution on an FTO conductive glass substrate, dripping 0.5-1 ml of methylbenzene, and drying in an oven at 20-50 ℃ to prepare the perovskite single crystal.
The drying time is 1-3 h, and the drying temperature is 30-60 ℃.
A reticulated perovskite produced according to the above-described production method.
The above-mentioned reticulated perovskite is used in the field of solar cells.
The invention increases the specific surface area, increases the active sites participating in the reaction, shortens the migration path of current carriers, and reduces the recombination of holes and electrons by preparing the mesh-shaped perovskite, thereby increasing the quantity of the electrons and holes participating in the reaction and improving the reaction rate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts an anti-solvent method, takes DMF as a solvent, adds FABr and PbBr, prepares a reaction precursor solution, prepares perovskite single crystal on FTO, and then soaks the FTO in cobalt isooctanoate solution to obtain the mesh-shaped perovskite.
(2) The synthesized meshed perovskite increases the specific surface area, can effectively prolong the service life of carriers, and improves the performance of materials.
(3) The invention has simple required equipment and preparation process and low cost, and can be directly produced in large batch.
Drawings
Fig. 1 is a surface SEM photograph of the reticulated perovskite prepared in example 1, observed under a scanning electron microscope at 1200 x.
FIG. 2 is a SEM image of the surface of a reticulated perovskite prepared in example 1, as observed under a scanning electron microscope at 3000 times.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The piranha solution used in the following examples was a mixture of concentrated sulfuric acid and 30% hydrogen peroxide.
Example 1
Cleaning of FTO conductive glass substrate: soaking the FTO conductive glass in a piranha solution, and then adding deionized water to dilute the FTO conductive glass to be neutral to obtain a clean FTO conductive glass substrate;
2. adding FABr and PbBr into DMF solvent to prepare reaction precursor solution, and preparing 3mol/L precursor solution;
3. diluting the precursor solution by 30 times by using DMF as a solvent;
4. dripping 30ul of the diluted precursor solution onto a clean FTO conductive glass substrate conductive surface, dripping 0.5ml of toluene onto the FTO conductive glass substrate, and drying in an oven at 50 ℃ to obtain perovskite single crystals;
5. using isopropanol as a solvent to prepare 50mml of cobalt iso-octoate solution, soaking the obtained perovskite single crystal in the cobalt iso-octoate solution for 30min, and then putting the perovskite single crystal into an oven to dry for 1h at 60 ℃ to obtain the mesh-shaped perovskite.
Fig. 1 is an SEM photograph of the mesh-shaped perovskite prepared in this example. As is clear from fig. 1, the perovskite single crystal surface observed under a scanning electron microscope at 1200 times had a network structure. Fig. 2 is a surface SEM photograph of the mesh-like perovskite prepared in this example. As can be seen from fig. 2, the ordered meshed perovskite was observed under a scanning electron microscope at a magnification of 3000.
Example 2
Cleaning of FTO conductive glass substrate: soaking the FTO conductive glass in a piranha solution, and then adding deionized water to dilute the FTO conductive glass to be neutral to obtain a clean FTO conductive glass substrate;
2. adding FABr and PbBr into DMF solvent to prepare reaction precursor solution, and preparing 1mol/L precursor solution;
3. diluting the precursor solution by 30 times by using DMF as a solvent;
4. dripping 30ul of the diluted precursor solution onto a clean FTO conductive glass substrate conductive surface, dripping 0.5ml of toluene onto the FTO conductive glass substrate, and drying in an oven at 50 ℃ to obtain perovskite single crystals;
5. using isopropanol as a solvent to prepare 50mml of cobalt iso-octoate solution, soaking the obtained perovskite single crystal in the cobalt iso-octoate solution for 30min, and then putting the perovskite single crystal into an oven to dry for 1h at 60 ℃ to obtain the mesh-shaped perovskite. The surface of the perovskite single crystal observed by the obtained product under a scanning electron microscope with the magnification of 1200 times is in a mesh shape.
Example 3
Cleaning of FTO conductive glass substrate: soaking the FTO conductive glass in a piranha solution, and then adding deionized water to dilute the FTO conductive glass to be neutral to obtain a clean FTO conductive glass substrate;
2. adding FABr and PbBr into DMF solvent to prepare reaction precursor solution, and preparing 3mol/L precursor solution;
3. diluting the precursor solution by 10 times by using DMF as a solvent;
4. dripping 30ul of the diluted precursor solution onto a clean FTO conductive glass substrate conductive surface, dripping 0.5ml of toluene onto the FTO conductive glass substrate, and drying in an oven at 50 ℃ to obtain perovskite single crystals;
5. using isopropanol as a solvent to prepare 50mml of cobalt iso-octoate solution, soaking the obtained perovskite single crystal in the cobalt iso-octoate solution for 30min, and then putting the perovskite single crystal into an oven to dry for 1h at 60 ℃ to obtain the mesh-shaped perovskite. The surface of the perovskite single crystal observed by the obtained product under a scanning electron microscope with the magnification of 1200 times is in a mesh shape.
Example 4
Cleaning of FTO conductive glass substrate: soaking the FTO conductive glass in a piranha solution, and then adding deionized water to dilute the FTO conductive glass to be neutral to obtain a clean FTO conductive glass substrate;
2. adding FABr and PbBr into DMF solvent to prepare reaction precursor solution, and preparing 1mol/L precursor solution;
3. diluting the precursor solution by 10 times by using DMF as a solvent;
4. dripping 30ul of the diluted precursor solution onto a clean FTO conductive glass substrate conductive surface, dripping 0.5ml of toluene onto the FTO conductive glass substrate, and drying in an oven at 50 ℃ to obtain perovskite single crystals;
preparing 50mml of precursor solution from cobalt iso-octoate by using isopropanol as a solvent, soaking the obtained perovskite single crystal in the cobalt iso-octoate precursor solution for 30min, and then putting the perovskite single crystal into an oven to dry for 1h at 60 ℃ to obtain the mesh-shaped perovskite. The surface of the perovskite single crystal observed by the obtained product under a scanning electron microscope with the magnification of 1200 times is in a mesh shape.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A method for preparing a reticulated perovskite, characterized in that it comprises the following operative steps: adding FABr and PbBr into a solvent to prepare a precursor solution of 0.5 mol/L-3 mol/L, diluting the precursor solution by 10-30 times, dropwise adding the diluted precursor solution onto an FTO conductive glass substrate, dropwise adding toluene, and drying to prepare perovskite single crystals; and soaking the obtained perovskite single crystal in a cobalt iso-octoate solution for 5-30 min, and then putting the sample into a drying oven for drying to finally obtain the mesh-shaped perovskite.
2. The method of claim 1, wherein: the FTO conductive glass substrate is cleaned before use: and (3) soaking the FTO conductive glass substrate in the piranha solution, and then adding deionized water to dilute the FTO conductive glass substrate to be neutral to obtain a clean FTO conductive glass substrate.
3. The method of claim 2, wherein: the soaking time is 8-12 h; the piranha solution is a mixture of concentrated sulfuric acid and 30% hydrogen peroxide.
4. The method of claim 1, wherein: the solvent is DMF.
5. The method of claim 1, wherein: diluting the precursor solution by 10-30 times, dripping 1-30 ul of the diluted precursor solution on an FTO conductive glass substrate, dripping 0.5-1 ml of methylbenzene, and drying in an oven at 20-50 ℃ to prepare the perovskite single crystal.
6. The method of claim 1, wherein: the drying time is 1-3 h, and the drying temperature is 30-60 ℃.
7. A mesh-like perovskite produced by the production method according to any one of claims 1 to 6.
8. Use of the reticulated perovskite of claim 7 in the field of solar cells.
CN201910624894.4A 2019-07-11 2019-07-11 Mesh-woven perovskite and preparation method and application thereof Active CN110512271B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910624894.4A CN110512271B (en) 2019-07-11 2019-07-11 Mesh-woven perovskite and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910624894.4A CN110512271B (en) 2019-07-11 2019-07-11 Mesh-woven perovskite and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110512271A CN110512271A (en) 2019-11-29
CN110512271B true CN110512271B (en) 2021-09-03

Family

ID=68622612

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910624894.4A Active CN110512271B (en) 2019-07-11 2019-07-11 Mesh-woven perovskite and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110512271B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106356456A (en) * 2016-10-17 2017-01-25 北京科技大学 Solar cell based on high-quality perovskite heterojunctions and preparation method thereof
CN109545970A (en) * 2018-12-24 2019-03-29 南京工业大学 A kind of method and perovskite solar battery improving perovskite solar battery efficiency and stability
CN109768163A (en) * 2018-12-07 2019-05-17 南京邮电大学 A kind of TiO2/ CdS perovskite solar battery and preparation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10077507B2 (en) * 2015-11-30 2018-09-18 Wisconsin Alumni Research Foundation Solution growth of single-crystal perovskite structures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106356456A (en) * 2016-10-17 2017-01-25 北京科技大学 Solar cell based on high-quality perovskite heterojunctions and preparation method thereof
CN109768163A (en) * 2018-12-07 2019-05-17 南京邮电大学 A kind of TiO2/ CdS perovskite solar battery and preparation method
CN109545970A (en) * 2018-12-24 2019-03-29 南京工业大学 A kind of method and perovskite solar battery improving perovskite solar battery efficiency and stability

Also Published As

Publication number Publication date
CN110512271A (en) 2019-11-29

Similar Documents

Publication Publication Date Title
CN109402656B (en) Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode
CN107570190B (en) Preparation method of carbon-doped carbon nitride film electrode
CN113136602A (en) Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode
CN110655656A (en) Cobalt metal organic framework material and preparation method and application thereof
CN111364080B (en) C for photo-anodexNy/BiVO4Material, preparation method and application thereof
CN112958116B (en) Bi2O2.33-CdS composite photocatalyst and preparation process thereof
CN114481192B (en) Cd doped titanium dioxide/indium zinc sulfide photo-anode and preparation method thereof
CN109665598A (en) Carbonate radical photocatalysis waste water for generating electricity method
CN106637285B (en) Cu2The TiO 2 nanotubes modified optoelectronic pole of O quantum dot and its preparation and application
CN110665525A (en) Perovskite of composite carbon nitride photocatalytic material and preparation method and application thereof
CN113293404B (en) Heterojunction photo-anode material and preparation method and application thereof
CN111215070B (en) Preparation method of iron oxide photoelectric catalyst with exposed high-activity surface
WO2021103478A1 (en) Preparation method for bismuth acid copper film
CN110512271B (en) Mesh-woven perovskite and preparation method and application thereof
CN111793808A (en) Method for industrially producing high-efficiency catalytic electrode for hydrogen production by water electrolysis
CN109402661B (en) MIL-100(Fe)/TiO2Preparation method and application of composite photoelectrode
CN108855193B (en) TaN/BiVO4Heterojunction composite material and preparation method and application thereof
CN107268020A (en) A kind of Ta3N5The preparation method and Ta of film3N5The application of film
CN114849689B (en) Heterojunction type composite photocatalytic material and preparation method thereof
CN114369942B (en) Carbon fiber/titanium dioxide photoelectric composite material and preparation method and application thereof
CN110747506A (en) Transition metal doped InxGa1-xN nano column and preparation method and application thereof
CN113832479B (en) Fe 2 O 3 (Ti)@NH 2 -MIL-101 (Fe) composite photoelectric catalyst and preparation method thereof
CN113774418B (en) Preparation of three-dimensional conductive framework and application of three-dimensional conductive framework in iron oxide photo-anode
CN110359058B (en) Preparation method of lead zirconate titanate modified hematite nanorod array photoanode
CN111359632A (en) Photocatalytic material for modifying three-dimensional copper sulfide by silver particles grown in situ on copper mesh, preparation method and application

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