CN108198944B - Preparation method of microporous perovskite photovoltaic material - Google Patents
Preparation method of microporous perovskite photovoltaic material Download PDFInfo
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- CN108198944B CN108198944B CN201710452509.3A CN201710452509A CN108198944B CN 108198944 B CN108198944 B CN 108198944B CN 201710452509 A CN201710452509 A CN 201710452509A CN 108198944 B CN108198944 B CN 108198944B
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 39
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 21
- 239000000084 colloidal system Substances 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 16
- 238000005273 aeration Methods 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 13
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000012229 microporous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
Classifications
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- 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
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a microporous perovskite photovoltaic material, which comprises the steps of putting n-butyl titanate into absolute ethyl alcohol, assisting with polyvinylpyrrolidone and a foaming agent to obtain titanium dioxide colloid liquid, coating a film on the surface of a base material after concentration, performing a pressure reaction to obtain a titanium dioxide film, then putting the titanium dioxide film into a calcium chloride solution, performing an ammonia aeration reaction to obtain a calcium hydroxide sediment layer, and finally performing a heating and pressure reaction. And soaking the film by adopting an acid solution, and washing the film by using deionized water and absolute ethyl alcohol to obtain the microporous perovskite photovoltaic material. The microporous perovskite photovoltaic material prepared by the invention can be prepared in a perovskite structure under a microporous structure, and the hole transmission efficiency of the light absorption layer is improved while the light current is generated, so that the photoelectric conversion efficiency can be further improved.
Description
Technical Field
The invention belongs to the technical field of photovoltaic materials, and particularly relates to a preparation method of a microporous perovskite photovoltaic material.
Background
The photovoltaic material is a material capable of converting solar energy into electric energy, mainly is a semiconductor material capable of converting solar energy into electric energy through a photovoltaic effect, and comprises monocrystalline silicon, polycrystalline silicon, amorphous silicon, GaAs, InP, CdS, CdTe and the like. The photoelectric conversion rate of the silicon-based material is relatively high, but the manufacturing cost is also high, and the gallium arsenide and other semiconductor materials have the disadvantages of rare raw materials, low preparation efficiency and poor stability, and are greatly limited in practical application.
The perovskite structure material is applied as a photovoltaic material for the first time in 2009, the raw materials of the perovskite structure material are generally cheap lead, halogen and amine salt, the forbidden bandwidth of the material is small, the material has a good application prospect, the photoelectric conversion rate of the perovskite structure material is developed from the initial 3.8% to 15.9% only in less than 5 years, the efficiency of the perovskite structure material is gradually close to that of a silicon-based photovoltaic material, and partial scholars further predict that the photoelectric conversion rate of the perovskite structure material is faster than that of a single crystal silicon photovoltaic material and reaches 30%.
In the preparation of photovoltaic materials, direct internal recombination of hole transport materials and light absorption materials is a better choice, and if the hole transport materials and the light absorption materials can be prepared into a porous material on the premise of not damaging the basic structure of perovskite, recombination with the hole transport materials is undoubtedly an excellent technical scheme. The porous material can be divided into microporous material, mesoporous material and macroporous material according to the pore size, and the smaller the pore size is, the larger the specific surface area of the material is, so that the specific surface area of the microporous material in the porous material is the largest, but the pore size of the microporous material is less than 2nm, and how to connect the hole transmission material with the same nano scale under the small pore size is also a technical problem.
Disclosure of Invention
The invention aims to provide a preparation method of a microporous perovskite photovoltaic material, the microporous perovskite photovoltaic material can be prepared in a perovskite structure under a microporous structure, and the transmission efficiency of a cavity of a light absorption layer is improved while a photocurrent is generated, so that the photoelectric conversion efficiency can be further improved.
The technical purpose of the invention is realized by the following technical scheme: a preparation method of a microporous perovskite photovoltaic material comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding polyvinylpyrrolidone, carrying out sealed ultrasonic reaction for 30-60min, and naturally cooling to obtain titanium dioxide colloid liquid;
step 2, adding a foaming agent into the titanium dioxide colloid liquid, sealing and stirring, and then carrying out reduced pressure distillation reaction to obtain a concentrated precursor liquid;
step 3, spraying the concentrated precursor solution on a substrate, and then carrying out sealed pressurized reaction for 1-2h to obtain a titanium dioxide film;
step 4, putting the base material with the titanium dioxide film into a calcium chloride solution, and then carrying out ammonia gas aeration reaction for 3-5h to obtain a calcium hydroxide deposition layer;
step 5, putting the base material with the deposition layer into a reaction kettle, pressurizing, heating and reacting for 3-5 hours to obtain a microporous film material;
and step 6, adding the film material into an acid solution, soaking for 10-15min, then washing with deionized water and absolute ethyl alcohol for multiple times, and airing to obtain the microporous perovskite photovoltaic material.
The molar weight ratio of the n-butyl titanate to the absolute ethyl alcohol in the step 1 is 2:15-19, the molar weight of the polyvinylpyrrolidone is 1.9-2.5 times of that of the n-butyl titanate, the n-butyl titanate and the polyvinylpyrrolidone are used as main raw materials in the step, the high molecular property of the polyvinylpyrrolidone is utilized, a good dispersion effect is achieved, and the polyvinylpyrrolidone directly acts on the surface of the titanium dioxide to form colloidal particles; the step fully utilizes the performance of the polyvinylpyrrolidone and effectively acts on the n-butyl titanate; the purpose of using anhydrous ethanol is mainly to consider the following: (1) the polyvinylpyrrolidone has good dissolving effect in absolute ethyl alcohol to form slightly viscous solution; (2) the n-butyl titanate can have good solubility in the absolute ethyl alcohol, and meanwhile, the absolute ethyl alcohol can ensure the dissolving effect and prevent the hydrolysis of the n-butyl titanate due to the formation of precipitates in water through hydrolysis.
The ultrasonic frequency in the sealed ultrasonic reaction in the step 1 is 1.5-2.5kHz, the ultrasonic pressure is 1.5-2.2MPa, the reaction is processed in an ultrasonic mode in the step, the titanium dioxide can be formed by opening n-butyl titanate, the surface of the titanium dioxide is wrapped, and the polyvinylpyrrolidone can be dispersed by the low-frequency ultrasonic, so that the uniform effect of the solution is ensured, and the viscosity is increased.
The foaming agent in the step 2 is 4, 4-oxo-bis-benzenesulfonylhydrazide, the molar weight of the 4, 4-oxo-bis-benzenesulfonylhydrazide is 10-15% of n-butyl titanate, the sealing and stirring speed is 1500r/min, the reduced pressure distillation temperature is 60-80 ℃, and the volume after the reduced pressure distillation is 40-60% of the original volume; uniformly distributing a foaming agent in the colloidal fluid in a sealing and stirring manner; and simultaneously, removing the absolute ethyl alcohol and the n-butyl alcohol by adopting a reduced pressure distillation mode.
The spraying amount in the step 3 is 10-15mL/cm2The pressure of the sealing and pressurizing reaction is 10-15MPa, the temperature of the sealing and pressurizing reaction is 90-100 ℃, the step adopts a spraying mode to form a uniform titanium dioxide colloid film on the surface of the base material, and polyvinylpyrrolidone and absolute ethyl alcohol molecules in the film are slowly released in the sealing and pressurizing process to obtain the compact and uniform titanium dioxide film.
The concentration of the calcium chloride solution in the step 4 is 0.1-0.3mol/L, the molar weight of the calcium chloride is 1.5-1.8 times of that of the n-butyl titanate, the ammonia amount is 2.1-2.5 times of that of the n-butyl titanate, and the ammonia gas aeration flow rate is 100-200 mL/min; the step is to put the base material into calcium chloride solution, and form calcium hydroxide to deposit on the surface of titanium dioxide in the reaction process of calcium chloride and ammonia gas, so as to obtain a calcium hydroxide deposition layer.
The temperature of the pressurizing and heating reaction in the step 5 is 150-200 ℃, the pressurizing pressure is 20-25MPa, the step adopts a heating and pressurizing mode to ensure the reaction between titanium dioxide and calcium hydroxide, and the titanium dioxide and the calcium hydroxide form a perovskite film through the water loss of the calcium hydroxide; meanwhile, in the heating and pressurizing reaction process, the foaming agent is decomposed to form a gas state under the condition, and micropores are formed on the surface in the gas-state discharge process, so that the distribution is good.
The acid solution in the step 6 is hydrochloric acid, nitric acid or sulfuric acid, the concentration of the acid solution is 0.01-0.05mol/L, and the airing temperature is 80-100 ℃; the calcium hydroxide on the upper surface of the film material is converted into calcium salt through soaking in the acid solution, so that the calcium salt is dissolved into the solution, the film material forming the perovskite does not react with low-concentration acid based on the firmness of the spatial structure of the film material, the purpose of removing impurities is achieved, and the film material is cleaned for multiple times to remove residual surface impurities.
According to the technical scheme, n-butyl titanate is placed into absolute ethyl alcohol, polyvinylpyrrolidone and a foaming agent are used as auxiliary materials to obtain titanium dioxide colloid liquid, the titanium dioxide colloid liquid is coated on the surface of a base material after being concentrated, a titanium dioxide film is obtained through pressurization reaction, then the titanium dioxide film is placed into a calcium chloride solution, a calcium hydroxide deposition layer is obtained after ammonia gas aeration reaction, and finally heating and pressurization reaction are carried out. And soaking the film by adopting an acid solution, and washing the film by using deionized water and absolute ethyl alcohol to obtain the microporous perovskite photovoltaic material.
In conclusion, the invention has the following beneficial effects:
the preparation method is simple and feasible, and has strong practicality and universality. The prepared microporous perovskite photovoltaic material can be prepared in a perovskite structure under a microporous structure, so that the hole transmission efficiency of a light absorption layer is improved while photocurrent is generated, and the photoelectric conversion efficiency can be further improved; the preparation method provided by the invention is suitable for industrial production and has no environmental protection problem.
Detailed Description
Example 1
A preparation method of a microporous perovskite photovoltaic material comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding polyvinylpyrrolidone, carrying out sealed ultrasonic reaction for 30min, and naturally cooling to obtain titanium dioxide colloid liquid;
step 2, adding a foaming agent into the titanium dioxide colloid liquid, sealing and stirring, and then carrying out reduced pressure distillation reaction to obtain a concentrated precursor liquid;
step 3, spraying the concentrated precursor solution on a substrate, and then carrying out sealed pressurization reaction for 1h to obtain a titanium dioxide film;
step 4, putting the base material with the titanium dioxide film into a calcium chloride solution, and then carrying out ammonia aeration reaction for 3 hours to obtain a calcium hydroxide deposition layer;
step 5, putting the base material with the deposition layer into a reaction kettle, and performing pressurization and heating reaction for 3 hours to obtain a microporous film material;
and step 6, adding the film material into an acid solution, soaking for 10min, then washing with deionized water and absolute ethyl alcohol for multiple times, and airing to obtain the microporous perovskite photovoltaic material.
The molar weight ratio of the n-butyl titanate to the absolute ethyl alcohol in the step 1 is 2:15, and the molar weight of the polyvinylpyrrolidone is 1.9 times that of the n-butyl titanate.
The ultrasonic frequency in the sealed ultrasonic reaction in the step 1 is 1.5kHz, and the ultrasonic pressure is 1.5 MPa.
The foaming agent in the step 2 is 4, 4-oxybis-benzenesulfonyl hydrazide, the molar weight of the 4, 4-oxybis-benzenesulfonyl hydrazide is 10% of n-butyl titanate, the sealing and stirring speed is 1000r/min, the reduced pressure distillation temperature is 60 ℃, and the volume after reduced pressure distillation is 40% of the original volume.
The spraying amount in the step 3 is 10mL/cm2The pressure of the sealing pressurization reaction is 10MPa, and the temperature of the sealing pressurization reaction is 90 ℃.
The concentration of the calcium chloride solution in the step 4 is 0.1mol/L, the molar weight of the calcium chloride is 1.5 times of that of the n-butyl titanate, the ammonia amount is 2.1 times of that of the n-butyl titanate, and the ammonia aeration flow rate is 100 mL/min.
The temperature of the pressurization and warming reaction in the step 5 is 150 ℃, and the pressurization pressure is 20 MPa.
The acid solution in the step 6 is hydrochloric acid, the concentration of the acid solution is 0.01mol/L, and the airing temperature is 80-DEG C.
Example 2
A preparation method of a microporous perovskite photovoltaic material comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding polyvinylpyrrolidone, carrying out sealed ultrasonic reaction for 60min, and naturally cooling to obtain titanium dioxide colloid liquid;
step 2, adding a foaming agent into the titanium dioxide colloid liquid, sealing and stirring, and then carrying out reduced pressure distillation reaction to obtain a concentrated precursor liquid;
step 3, spraying the concentrated precursor solution on a substrate, and then carrying out sealed pressurization reaction for 2 hours to obtain a titanium dioxide film;
step 4, putting the base material with the titanium dioxide film into a calcium chloride solution, and then carrying out ammonia aeration reaction for 5 hours to obtain a calcium hydroxide deposition layer;
step 5, putting the base material with the deposition layer into a reaction kettle, and carrying out pressurization and heating reaction for 5 hours to obtain a microporous film material;
and step 6, adding the film material into an acid solution, soaking for 15min, then washing with deionized water and absolute ethyl alcohol for multiple times, and airing to obtain the microporous perovskite photovoltaic material.
The molar weight ratio of the n-butyl titanate to the absolute ethyl alcohol in the step 1 is 2:19, and the molar weight of the polyvinylpyrrolidone is 2.5 times that of the n-butyl titanate.
The ultrasonic frequency in the sealed ultrasonic reaction in the step 1 is 2.5kHz, and the ultrasonic pressure is 2.2 MPa.
The foaming agent in the step 2 is 4, 4-oxybis-benzenesulfonyl hydrazide, the molar weight of the 4, 4-oxybis-benzenesulfonyl hydrazide is 15% of n-butyl titanate, the sealing and stirring speed is 1500r/min, the reduced pressure distillation temperature is 80 ℃, and the volume after reduced pressure distillation is 60% of the original volume.
The spraying amount in the step 3 is 15mL/cm2The pressure of the sealing pressurization reaction is 15MPa, and the temperature of the sealing pressurization reaction is 100 ℃.
The concentration of the calcium chloride solution in the step 4 is 0.3mol/L, the molar weight of the calcium chloride is 1.8 times that of the n-butyl titanate, the ammonia amount is 2.5 times that of the n-butyl titanate, and the ammonia aeration flow rate is 200 mL/min.
The temperature of the pressurization and warming reaction in the step 5 is 200 ℃, and the pressurization pressure is 25 MPa.
The acid solution in the step 6 is hydrochloric acid, nitric acid or sulfuric acid, the concentration of the acid solution is 0.05mol/L, and the airing temperature is 100 ℃.
Example 3
A preparation method of a microporous perovskite photovoltaic material comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding polyvinylpyrrolidone, carrying out sealed ultrasonic reaction for 40min, and naturally cooling to obtain titanium dioxide colloid liquid;
step 2, adding a foaming agent into the titanium dioxide colloid liquid, sealing and stirring, and then carrying out reduced pressure distillation reaction to obtain a concentrated precursor liquid;
step 3, spraying the concentrated precursor solution on a substrate, and then carrying out sealed pressurization reaction for 1h to obtain a titanium dioxide film;
step 4, putting the base material with the titanium dioxide film into a calcium chloride solution, and then carrying out ammonia gas aeration reaction for 3-5h to obtain a calcium hydroxide deposition layer;
step 5, putting the base material with the deposition layer into a reaction kettle, and performing pressurization and heating reaction for 4 hours to obtain a microporous film material;
and step 6, adding the film material into an acid solution, soaking for 12min, then washing with deionized water and absolute ethyl alcohol for multiple times, and airing to obtain the microporous perovskite photovoltaic material.
The molar weight ratio of the n-butyl titanate to the absolute ethyl alcohol in the step 1 is 2:16, and the molar weight of the polyvinylpyrrolidone is 2.1 times that of the n-butyl titanate.
The ultrasonic frequency in the sealed ultrasonic reaction in the step 1 is 1.8kHz, and the ultrasonic pressure is 1.7 MPa.
The foaming agent in the step 2 is 4, 4-oxybis-benzenesulfonyl hydrazide, the molar weight of the 4, 4-oxybis-benzenesulfonyl hydrazide is 12% of n-butyl titanate, the sealing and stirring speed is 1200r/min, the reduced pressure distillation temperature is 65 ℃, and the volume after the reduced pressure distillation is 50% of the original volume.
The spraying amount in the step 3 is 12mL/cm2The pressure of the sealing pressurization reaction is 12MPa, and the temperature of the sealing pressurization reaction is 95 ℃.
The concentration of the calcium chloride solution in the step 4 is 0.2mol/L, the molar weight of the calcium chloride is 1.6 times that of the n-butyl titanate, the ammonia amount is 2.3 times that of the n-butyl titanate, and the ammonia aeration flow rate is 150 mL/min.
The temperature of the pressurization and warming reaction in the step 5 is 180 ℃, and the pressurization pressure is 22 MPa.
The acid solution in the step 6 is nitric acid, the concentration of the acid solution is 0.03mol/L, and the airing temperature is 85 ℃.
Example 4
A preparation method of a microporous perovskite photovoltaic material comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding polyvinylpyrrolidone, carrying out sealed ultrasonic reaction for 50min, and naturally cooling to obtain titanium dioxide colloid liquid;
step 2, adding a foaming agent into the titanium dioxide colloid liquid, sealing and stirring, and then carrying out reduced pressure distillation reaction to obtain a concentrated precursor liquid;
step 3, spraying the concentrated precursor solution on a substrate, and then carrying out sealed pressurization reaction for 2 hours to obtain a titanium dioxide film;
step 4, putting the base material with the titanium dioxide film into a calcium chloride solution, and then carrying out ammonia aeration reaction for 5 hours to obtain a calcium hydroxide deposition layer;
step 5, putting the base material with the deposition layer into a reaction kettle, and performing pressurization and heating reaction for 3 hours to obtain a microporous film material;
and step 6, adding the film material into an acid solution, soaking for 14min, then washing with deionized water and absolute ethyl alcohol for multiple times, and airing to obtain the microporous perovskite photovoltaic material.
The molar weight ratio of the n-butyl titanate to the absolute ethyl alcohol in the step 1 is 2:18, and the molar weight of the polyvinylpyrrolidone is 2.3 times that of the n-butyl titanate.
The ultrasonic frequency in the sealed ultrasonic reaction in the step 1 is 2.3kHz, and the ultrasonic pressure is 2.1 MPa.
The foaming agent in the step 2 is 4, 4-oxybis-benzenesulfonyl hydrazide, the molar weight of the 4, 4-oxybis-benzenesulfonyl hydrazide is 14% of n-butyl titanate, the sealing and stirring speed is 1400r/min, the reduced pressure distillation temperature is 75 ℃, and the volume after reduced pressure distillation is 55% of the original volume.
The spraying amount in the step 3 is 14mL/cm2The pressure of the sealing pressurization reaction is 14MPa, and the temperature of the sealing pressurization reaction is 98 ℃.
The concentration of the calcium chloride solution in the step 4 is 0.3mol/L, the molar weight of the calcium chloride is 1.7 times that of the n-butyl titanate, the ammonia amount is 2.4 times that of the n-butyl titanate, and the ammonia aeration flow rate is 150 mL/min.
The temperature of the pressurization and warming reaction in the step 5 is 180 ℃, and the pressurization pressure is 23 MPa.
The acid solution in the step 6 is hydrochloric acid, nitric acid or sulfuric acid, the concentration of the acid solution is 0.04mol/L, and the airing temperature is 95 ℃.
The above description is only an embodiment of the present invention, and not intended to limit the present invention, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a microporous perovskite photovoltaic material is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding tetrabutyl titanate into absolute ethyl alcohol, then adding polyvinylpyrrolidone, carrying out sealed ultrasonic reaction for 30-60min, and naturally cooling to obtain titanium dioxide colloid liquid;
step 2, adding a foaming agent into the titanium dioxide colloid liquid, sealing and stirring, and then carrying out reduced pressure distillation reaction to obtain a concentrated precursor liquid;
step 3, spraying the concentrated precursor solution on a substrate, and then carrying out sealed pressurized reaction for 1-2h to obtain a titanium dioxide film;
step 4, putting the base material with the titanium dioxide film into a calcium chloride solution, and then carrying out ammonia gas aeration reaction for 3-5h to obtain a calcium hydroxide deposition layer;
step 5, putting the base material with the deposition layer into a reaction kettle, pressurizing, heating and reacting for 3-5 hours to obtain a microporous film material;
and step 6, adding the film material into an acid solution, soaking for 10-15min, then washing with deionized water and absolute ethyl alcohol for multiple times, and airing to obtain the microporous perovskite photovoltaic material.
2. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the molar weight ratio of the n-butyl titanate to the absolute ethyl alcohol in the step 1 is 2:15-19, and the molar weight of the polyvinylpyrrolidone is 1.9-2.5 times that of the n-butyl titanate.
3. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the ultrasonic frequency in the sealed ultrasonic reaction in the step 1 is 1.5-2.5kHz, and the ultrasonic pressure is 1.5-2.2 MPa.
4. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the foaming agent in the step 2 is 4, 4-oxo-bis-benzenesulfonylhydrazide, the molar weight of the 4, 4-oxo-bis-benzenesulfonylhydrazide is 10-15% of n-butyl titanate, the sealing and stirring speed is 1500r/min, the reduced pressure distillation temperature is 60-80 ℃, and the volume after the reduced pressure distillation is 40-60% of the original volume.
5. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the spraying amount in the step 3 is 10-15mL/cm2The pressure of the sealing pressurization reaction is 10-15MPa, and the temperature of the sealing pressurization reaction is 90-100 ℃.
6. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the concentration of the calcium chloride solution in the step 4 is 0.1-0.3mol/L, the molar weight of the calcium chloride is 1.5-1.8 times of that of the n-butyl titanate, the ammonia amount is 2.1-2.5 times of that of the n-butyl titanate, and the ammonia gas aeration flow rate is 100-200 mL/min.
7. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the temperature of the pressurization and heating reaction in the step 5 is 150-200 ℃, and the pressurization pressure is 20-25 MPa.
8. The method of preparing a microporous perovskite photovoltaic material as claimed in claim 1, wherein: the acid solution in the step 6 is hydrochloric acid, nitric acid or sulfuric acid, the concentration of the acid solution is 0.01-0.05mol/L, and the airing temperature is 80-100 ℃.
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| WO2016203724A1 (en) * | 2015-06-15 | 2016-12-22 | Sony Semiconductor Solutions Corporation | Solid state imaging element and method for manufacturing solid state imaging element, photoelectric conversion element, imaging device, and electronic device |
| CN106430295A (en) * | 2016-09-12 | 2017-02-22 | 天津城建大学 | Micro-nano hierarchy BaTiO3 crystal and preparation method thereof |
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| CN105609645A (en) * | 2015-12-22 | 2016-05-25 | 成都新柯力化工科技有限公司 | Photovoltaic material with microporous perovskite structure and preparation method of photovoltaic material |
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