CN109888113A - Calcium titanium ore bed and preparation method thereof, perovskite solar battery - Google Patents
Calcium titanium ore bed and preparation method thereof, perovskite solar battery Download PDFInfo
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- CN109888113A CN109888113A CN201910226035.XA CN201910226035A CN109888113A CN 109888113 A CN109888113 A CN 109888113A CN 201910226035 A CN201910226035 A CN 201910226035A CN 109888113 A CN109888113 A CN 109888113A
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- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000011159 matrix material Substances 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000009835 boiling Methods 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 46
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 230000005540 biological transmission Effects 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000010010 raising Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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- Photovoltaic Devices (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of calcium titanium ore beds and preparation method thereof, perovskite solar battery.Above-mentioned preparation method includes the following steps: that offer matrix and perovskite solution, the boiling point of the perovskite solution are less than or equal to 85 DEG C；And roll-to-roll process is utilized, by perovskite solution coating on matrix, dry later, annealing obtains calcium titanium ore bed.The preparation method of above-mentioned calcium titanium ore bed, using roll-to-roll process, by low-boiling perovskite solution coating on matrix, perovskite crystal fast-growth, in a relatively short period of time fast filming, simple process and process is less, the calcium titanium ore bed film of formation is smooth uniform, and hole is less.The quality of calcium titanium ore bed is not only increased, and reduces the equipment cost of the perovskite solar battery of production large area, is suitable for preparation high efficiency large area perovskite solar cell flexible component.
Description
Technical field
The present invention relates to photovoltaic technology field, more particularly to a kind of calcium titanium ore bed and preparation method thereof, the perovskite sun
It can battery.
Background technique
Perovskite solar battery is widely studied in Scientific Research in University Laboratory in recent years, and since report, efficiency is climbed all the way
It rises.Currently, effective area is 0.09cm2Perovskite battery efficiency already exceed 23%, be expected to substitution conventional crystalline silicon battery at
For the main product of the following solar battery.In addition, the raw material of perovskite solar battery are easy to make, cheap, draw
The concern of numerous Technological research persons and enterpriser are carried out.
Currently, most of to the research of perovskite still tested based on small area, large area calcium titanium is being done in global range
The producer of mine productive experiment is very few, and the major part of large area experiment is rigid basement, and application range is not as good as flexibility
Component is extensive.
Traditional roll-to-roll method for preparing perovskite thin film, the most commonly used is the modes of oven drying in laboratory, make calcium titanium
Mine film quality cannot be guaranteed.
Summary of the invention
Based on this, it is necessary to aiming at the problem that how to improve calcium titanium ore bed quality, provide a kind of calcium titanium ore bed and its preparation
Method, perovskite solar battery.
A kind of preparation method of calcium titanium ore bed, includes the following steps:
Matrix and perovskite solution are provided, the boiling point of the perovskite solution is less than or equal to 85 DEG C；And
Using roll-to-roll process, on the matrix by the perovskite solution coating, dry later, annealing obtains calcium
Titanium ore layer.
The preparation method of above-mentioned calcium titanium ore bed, using roll-to-roll process, by low-boiling perovskite solution coating in matrix
On, perovskite crystal fast-growth, fast filming in a relatively short period of time, simple process and process is less, the perovskite of formation
Layer film is smooth uniform, and hole is less.The quality of calcium titanium ore bed is not only increased, and reduces the perovskite of production large area
The equipment cost of solar battery is suitable for preparation high efficiency large area perovskite solar cell flexible component.
In one of the embodiments, in the operation of the coating, using painting knife by the perovskite solution coating in institute
It states on matrix；
Wherein, the painting knife is 90 μm -95 μm at a distance from described matrix.
The flow by perovskite solution coating on matrix is 220 μ of μ l/s~350 in one of the embodiments,
l/s。
In one of the embodiments, in the operation of the drying, it is dried using air knife；
Wherein, the angle of the air knife and described matrix is 60 ° -75 °.
The gas of the air knife connection is nitrogen, air pressure 0.05MPa-2Mpa in one of the embodiments,.
In one of the embodiments, in the roll-to-roll process, the transmission speed of described matrix is 80mm/s-120mm/
s。
The solvent of the perovskite solution is 20wt%-33wt%'s by acetonitrile and concentration in one of the embodiments,
Amine aqueous solution mixes；And/or
The volume ratio of the acetonitrile and the amine aqueous solution is 3:1-6:1.
The solute of the amine aqueous solution is selected from least one of methylamine, propylamine and butylamine in one of the embodiments,；
And/or
The solvent of the amine aqueous solution is selected from least one of methanol, ethyl alcohol and tetrahydrofuran.
The present invention also provides a kind of calcium titanium ore bed, the calcium titanium ore bed is obtained using the preparation method of the calcium titanium ore bed
?.
Above-mentioned calcium titanium ore bed is obtained, calcium titanium ore bed film light using the preparation method of calcium titanium ore bed provided by the present invention
Cunning is uniform, and hole is less, better quality.
The present invention also provides a kind of perovskite solar batteries, including calcium titanium ore bed provided by the present invention.
Above-mentioned perovskite solar battery, due to using calcium titanium ore bed provided by the invention, to obtain higher short
Road current density and fill factor, there has also been biggish raisings for the photoelectric conversion efficiency of final battery.In addition, using the present invention
The calcium titanium ore bed of offer reduces the equipment cost of the perovskite solar battery of production large area, and it is big to be suitable for preparation high efficiency
Area perovskite solar cell flexible component.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the calcium titanium ore bed of an embodiment of the present invention；
Fig. 2 is the cross section structure schematic diagram of the perovskite solar battery of an embodiment of the present invention；
Fig. 3 is the volume pair that perovskite solar battery is prepared using low boiling point perovskite solution of an embodiment of the present invention
Winding apparatus Local map；
Fig. 4 is the volume pair that perovskite solar battery is prepared using higher boiling perovskite solution of an embodiment of the present invention
Winding apparatus Local map.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, to specific embodiment party of the invention
Formula is described in detail.In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.But this hair
Bright to be implemented with being much different from other way described herein, those skilled in the art can be without prejudice in the present invention
Similar improvement is done in the case where culvert, therefore the present invention is not limited by the specific embodiments disclosed below.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the listed item of pass.
Referring to Figure 1, the preparation method of a kind of calcium titanium ore bed of an embodiment of the present invention, includes the following steps:
S10, matrix and perovskite solution are provided, the boiling point of perovskite solution is less than or equal to 85 DEG C.
In the present embodiment, matrix is suitable for roll-to-roll process, it can be the substrate for individually preparing calcium titanium ore bed,
It is also possible to the semi-finished product cell base made.
Using low-boiling perovskite solution, solvent volatilization is very fast, so that perovskite crystal fast-growth, when shorter
Interior fast filming, and can anneal at a lower temperature.
Specifically, the process for preparation of perovskite solution are as follows: big bottle is taken, perovskite material is added and solvent is added, ultrasound
Dissolution to get.
Preferably, the solvent of perovskite solution is mixed by acetonitrile with concentration for the amine aqueous solution of 20wt%-33wt%.Second
The volume ratio of nitrile and the amine aqueous solution is 3:1-6:1.The solute of amine aqueous solution is selected from least one of methylamine, propylamine and butylamine.
The solvent of amine aqueous solution is selected from at least one of methanol, ethyl alcohol and tetrahydrofuran.Select the solvent preparation of above-mentioned low boiling point, low viscosity
Perovskite solution improves the quality of forming film of calcium titanium ore bed, is introduced into roll-to-roll production technology, greatly reduces equipment
It is required that reducing production cost.
Preferably, perovskite material is selected from compound representated by following chemical formula: MAxFA1-xPbI3-aBra、MAxFA1- xPbI3-bClb、MAxFA1-xPbBr3-cClc, wherein the equal value 0-3 of x value 0-1, a, b, c；Wherein the chemical structural formula of MA is
CH3NH3 +, the chemical structural formula of FA is CH (NH2)2 +。
It is highly preferred that perovskite material is CH3NH3PBI3Crystal, the concentration of perovskite solution are 0.3M-0.5M.Certainly,
It is understood that perovskite material of the invention does not limit to above compound, it can also be that those skilled in the art think
Suitable other perovskite materials.
S20, using roll-to-roll process, it is dry later, anneal by perovskite solution coating on matrix, obtain perovskite
Layer.
Roll-to-roll process refers on flexible or elastic film, by continuous coiled mode, production flexibility equipment
Technology.
Preferably, in the operation of coating, using apply knife by perovskite solution coating on matrix.Wherein, the height of knife is applied
With at a distance from matrix be 90 μm -95 μm.When painting knife is greater than 95 μm at a distance from matrix, the probability for being coated with rupture of membranes is larger, and works as
It when distance is less than 90 μm, easily causes and hits knife, be unfavorable for keeping the safety in production.The present invention utilizes painting cutter painting cloth perovskite solution, technique
Simple and process is less, and calcium titanium ore bed film obtained is smooth uniform, there is no hole, is suitable for preparation large area calcium titanium
Mine solar battery.
Preferably, the flow by perovskite solution coating on matrix is 220 μ l/s-350 μ l/s, and the distance of coating is
635mm.When flow is lower than 220 μ l/s, the cell photoelectric transfer efficiency being prepared can decline, when flow is lower than 180 μ l/s
When, when coating, can be easy rupture of membranes；And when the flow of coating is higher than 350 μ l/s, film is blocked up, and cell photoelectric transfer efficiency can be more
It is low.
Here coating distance is easy for the range of our operations, due to be it is roll-to-roll, when experiment need not entire volume all apply,
It is desirable it is wherein a bit of test just, so being set to 635mm, the time for also being understood as continuing to be coated with out liquid is 2s, be exactly
The length of roll-to-roll upper fluid film.
Preferably, it in dry operation, is dried using air knife.Wherein, the angle of air knife and matrix is 60 ° -75 °
(angle of air knife and matrix transmission direction).When the angle of air knife and matrix is less than 60 °, the film quality naked eyes of calcium titanium ore bed
It can be seen that it is worse than film quality when angle is 60 ° -75 °, and film quality is worse when the angle of air knife and matrix is greater than 75 °.
So the angle that above-mentioned air knife and matrix is arranged is conducive to evenly drying of the perovskite solution on matrix, guarantee calcium titanium ore bed
Quality of forming film.
Preferably, the gas of air knife connection is nitrogen, air pressure 0.05MPa-2Mpa.When the nitrogen pressure of air knife connection is small
When 0.05Mpa, air-flow is smaller to guide calcium titanium ore bed effectively to form a film, and when the nitrogen pressure of air knife connection is greater than 2Mpa
When, it will affect quality of forming film.Therefore, using nitrogen and above-mentioned pressure is set, it can be to avoid because water can be contained using air
It influences, is conducive to the fast-growth of perovskite crystal, in a relatively short period of time fast filming.
Preferably, in roll-to-roll process, the transmission speed of matrix is 80mm/s-120mm/s.When the transmission speed of matrix is big
In 120mm/s, continuous film can not be formed, film can rupture；And when the transmission speed of matrix is lower than 80mm/s, film mistake
Thickness will affect battery conversion efficiency.Therefore, above-mentioned transmission speed is set and is conducive to continuous film forming, improves the quality of calcium titanium ore bed.
Preferably, the temperature of annealing is 80 DEG C -100 DEG C.The calcium titanium ore bed compactness obtained in this way is more preferable.
Preferably, the time of annealing is 10min-15min.Be conducive to the growth of perovskite crystal in this way, so that film matter
Amount is more preferable, and hole is less, and the effect of perovskite battery is more excellent.
The preparation method of above-mentioned calcium titanium ore bed, using roll-to-roll process, by low-boiling perovskite by the way of coating
Solution coating is dry by air knife on matrix, perovskite crystal fast-growth, in a relatively short period of time fast filming, technique
Simple and process is less, and the calcium titanium ore bed film of formation is smooth uniform, and hole is less.The quality of calcium titanium ore bed is not only increased,
And the equipment cost of the perovskite solar battery of production large area is reduced, it is suitable for preparation high efficiency large area perovskite
Solar cell flexible component.
The present invention also provides a kind of calcium titanium ore beds, are obtained using the preparation method of calcium titanium ore bed provided by the present invention.
Above-mentioned calcium titanium ore bed is obtained, calcium titanium ore bed film light using the preparation method of calcium titanium ore bed provided by the present invention
Cunning is uniform, and hole is less, better quality.
The present invention also provides a kind of perovskite solar batteries, including calcium titanium ore bed provided by the present invention.
Specifically, referring to fig. 2, the perovskite solar battery 100 of an embodiment of the present invention is saturating including what is stacked gradually
Bright conductive substrates 110, hole transmission layer 120, calcium titanium ore bed 130, electron transfer layer 140 and back electrode 150.
Wherein, electrically conducting transparent substrate 110 includes that transparent base layer and the electrically conducting transparent being attached on transparent base layer are thin
Film layer.
Preferably, transparent base layer with a thickness of 0.3mm-1.5mm, material PET.Transparent conductive film layer with a thickness of
150nm~500nm, material ITO, ZTO, AZO, IWO, silver nanowires transparent electrode etc..Transparent conductive film layer can pass through
Physical vaporous deposition, vapor deposition or sputtering are formed on transparent base layer.
Preferably, hole transmission layer 120 is that nickel oxide is prepared by way of magnetron sputtering with a thickness of 5nm-50nm,
Main function is to be electrically separated by what calcium titanium ore bed generated and transmit export.
Preferably, the electron transfer layer 140 deposited on calcium titanium ore bed 130 is that PCBM passes through with a thickness of 5nm-100nm
The mode of coating is prepared.
Preferably, back electrode 150 is that ITO is obtained with a thickness of 100nm-500nm using vacuum deposition.
Above-mentioned perovskite solar battery, due to using calcium titanium ore bed provided by the invention, to obtain higher short
Road current density and fill factor, there has also been biggish raisings for the photoelectric conversion efficiency of final battery.In addition, using the present invention
The calcium titanium ore bed of offer reduces the equipment cost of the perovskite solar battery of production large area, and it is big to be suitable for preparation high efficiency
Area perovskite solar cell flexible component.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The preparation of calcium titanium ore bed: taking big bottle, and 92.25g perovskite CH is added3NH3PBI3Crystal, and 240mL acetonitrile is added
With the 33wt% methylethylolamine solution of 60mL, ultrasonic dissolution is configured to the perovskite solution 300ml of 0.5M, and the color of solution is
It is light yellow to get perovskite solution.
As shown in figure 3, the transmission speed for adjusting matrix is 90mm/s in roll-to-roll equipment 200, knife 210 will be applied and adjusted
It is 70 ° (angle with transmission direction) to the angle at 90 μm of matrix, adjusting air knife 220 and matrix, adjusts the stream of coating
Amount is 260 μ l/s；By above-mentioned perovskite solution coating on matrix, the distance of coating is 635mm；The liquid film being coated with passes through wind
After knife 220 (nitrogen pressure 0.5Mpa) is dry, the color of matrix becomes black by yellow completely；By matrix from roll-to-roll equipment
It is removed in 200, is placed on 100 DEG C of substrate and heats 10min, obtain the calcium titanium ore bed with a thickness of 300nm.
Embodiment 2
The preparation of calcium titanium ore bed: taking big bottle, and 92.25g perovskite CH is added3NH3PBI3Crystal, and 240mL acetonitrile is added
With the 33wt% methylethylolamine solution of 60mL, ultrasonic dissolution is configured to the perovskite solution 300ml of 0.5M, and the color of solution is
It is light yellow to get perovskite solution.
As shown in figure 3, the transmission speed for adjusting matrix is 120mm/s in roll-to-roll equipment 200, knife 210 will be applied and adjusted
It is 60 ° (angle with transmission direction) to the angle at 90 μm of matrix, adjusting air knife 220 and matrix, adjusts the stream of coating
Amount is 350 μ l/s；By above-mentioned perovskite solution coating on matrix, the distance of coating is 635mm；The liquid film being coated with passes through wind
After knife 220 (nitrogen pressure 2Mpa) is dry, the color of matrix becomes black by yellow completely；By matrix from roll-to-roll equipment
It is removed in 200, is placed on 100 DEG C of substrate and heats 10min, obtain the calcium titanium ore bed with a thickness of 320nm.
Embodiment 3
1, the flexible PET for being covered with ITO is net with being dried with nitrogen.
2, one layer of NIO the preparation of hole transmission layer: is plated on the flexible PET for being covered with ITO using magnetron sputteringX, thickness
For 30nm.
3, the preparation of calcium titanium ore bed: with embodiment 1.
4, the chlorobenzene solution of PCBM the preparation of electron transfer layer PCBM: is coated with by coating machine.
5, transparent electrode ITO, thickness the preparation of back electrode: are prepared with vacuum-deposited mode on the electron transport layer
200nm。
Embodiment 4
1, the flexible PET for being covered with ITO is net with being dried with nitrogen.
2, one layer of NIO the preparation of hole transmission layer: is plated on the flexible PET for being covered with ITO using magnetron sputteringX, thickness
For 30nm.
3, the preparation of calcium titanium ore bed: with embodiment 2.
4, the chlorobenzene solution of PCBM the preparation of electron transfer layer PCBM: is coated with by coating machine.
5, transparent electrode ITO, thickness the preparation of back electrode: are prepared with vacuum-deposited mode on the electron transport layer
200nm。
Comparative example 1
1, the flexible PET for being covered with ITO is net with being dried with nitrogen.
2, one layer of NIO the preparation of hole transmission layer: is plated on the flexible PET for being covered with ITO using magnetron sputteringX, thickness
For 30nm.
3, the preparation of calcium titanium ore bed: taking big bottle, and 92.25g perovskite CH is added3NH3PBI3Crystal, and be added
300mLDMF solution, ultrasonic dissolution are configured to the perovskite solution 300ml of 0.5M, and the color of solution is yellow to get perovskite
Solution.
As shown in figure 4, the transmission speed for the matrix that regulating step 2 obtains is 90mm/s in roll-to-roll equipment 300, it will
It applies knife 310 to be adjusted at 90 μm of matrix, the flow for adjusting coating is 260 μ l/s；By above-mentioned perovskite solution coating in base
On body, the distance of coating is 635mm；For the liquid film being coated with after baking oven 320 is dry, the color of matrix becomes ash by yellow
Color；Matrix is removed from roll-to-roll equipment 300, is placed on 100 DEG C of substrate and heats 10min, matrix color is become from grey
Black obtains the calcium titanium ore bed with a thickness of 300nm.
4, the chlorobenzene solution of PCBM the preparation of electron transfer layer PCBM: is coated with by coating machine.
5, transparent electrode ITO, thickness the preparation of back electrode: are prepared with vacuum-deposited mode on the electron transport layer
200nm。
Comparative example 2
With embodiment 3, difference is the preparation method of the perovskite solar battery of this comparative example 2, adjusts the stream of coating
Amount is 180 μ l/s.
Comparative example 3
With embodiment 3, difference is the preparation method of the perovskite solar battery of this comparative example 3, adjusts the stream of coating
Amount is 380 μ l/s.
Comparative example 4
With embodiment 3, difference is the preparation method of the perovskite solar battery of this comparative example 4, adjusts the biography of matrix
Dynamic speed is 75mm/s.
Comparative example 5
With embodiment 3, difference is the preparation method of the perovskite solar battery of this comparative example 5, adjusts air knife and base
The angle of body is 50 °.
Comparative example 6
With embodiment 3, difference is the preparation method of the perovskite solar battery of this comparative example 6, adjusts air knife and base
The angle of body is 90 °.
Performance test:
The perovskite solar battery that embodiment 3-4 and comparative example 1-6 are obtained is in AM1.5,100mW/cm2Etalon optical power
Irradiation under be tested for the property.Test result is as shown in table 1:
The performance test data of 1 perovskite solar battery of table
It is found by the test data of comparative example 3 and comparative example 1, embodiment 3 is prepared into using low boiling point solvent
The perovskite solar battery arrived has higher short-circuit current density, fill factor and photoelectric conversion efficiency.
It is found by comparative example 3 and the test data of comparative example 2-3, when the flow of coating is lower than 180 μ l/s, electricity
The photoelectric conversion efficiency in pond decreases, and rupture of membranes is easy when coating；When the flow of coating is higher than 350 μ l/s, film mistake
Thickness, photoelectric conversion efficiency only have 3.18%.
It is found by the test data of comparative example 3 and comparative example 4, when the transmission speed of matrix is lower than 80mm/s,
Film is blocked up, and photoelectric conversion efficiency only has 3.45%.
It is found by comparative example 3 and the test data of comparative example 5-6, when the angle of air knife and matrix is less than 60 °,
Photoelectric conversion efficiency is declined, and the visible film quality being worse than when angle is 60 ° -75 ° of film quality naked eyes；Work as air knife
When being greater than 75 ° with the angle of matrix, battery efficiency is lower, and film quality is worse.
In conclusion perovskite thin film of the present invention using the dry preparation of low boiling point solvent, roll-to-roll process and air knife
Better quality, film is smooth uniform, so that higher short-circuit current density and fill factor have been obtained, the photoelectricity of resulting devices
There has also been biggish raisings for transfer efficiency.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of calcium titanium ore bed, which comprises the steps of:
Matrix and perovskite solution are provided, the boiling point of the perovskite solution is less than or equal to 85 DEG C；And
Using roll-to-roll process, on the matrix by the perovskite solution coating, dry later, annealing obtains perovskite
Layer.
2. the preparation method of calcium titanium ore bed according to claim 1, which is characterized in that in the operation of the coating, use
Apply knife by the perovskite solution coating on the matrix；
Wherein, the painting knife is 90 μm -95 μm at a distance from described matrix.
3. the preparation method of calcium titanium ore bed according to claim 1 or 2, which is characterized in that described to apply perovskite solution
Flow of the cloth on matrix is 220 μ of μ l/s~350 l/s.
4. the preparation method of calcium titanium ore bed according to claim 1, which is characterized in that in the operation of the drying, use
Air knife is dried；
Wherein, the angle of the air knife and described matrix is 60 ° -75 °.
5. the preparation method of calcium titanium ore bed according to claim 4, which is characterized in that the gas of the air knife connection is nitrogen
Gas, air pressure 0.05MPa-2Mpa.
6. the preparation method of calcium titanium ore bed according to claim 1, which is characterized in that described in the roll-to-roll process
The transmission speed of matrix is 80mm/s-120mm/s.
7. the preparation method of calcium titanium ore bed according to claim 1, which is characterized in that the solvent of the perovskite solution by
Acetonitrile is mixed with the amine aqueous solution that concentration is 20wt%-33wt%；And/or
The volume ratio of the acetonitrile and the amine aqueous solution is 3:1-6:1.
8. the preparation method of calcium titanium ore bed according to claim 1, which is characterized in that the solute of the amine aqueous solution is selected from first
At least one of amine, propylamine and butylamine；And/or
The solvent of the amine aqueous solution is selected from least one of methanol, ethyl alcohol and tetrahydrofuran.
9. a kind of calcium titanium ore bed, which is characterized in that the calcium titanium ore bed uses the described in any item calcium titanium ore beds of claim 1-8
Preparation method obtain.
10. a kind of perovskite solar battery, which is characterized in that including calcium titanium ore bed as claimed in claim 9.
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| CN112510155A (en) * | 2020-10-19 | 2021-03-16 | 桂林电子科技大学 | Preparation method of all-printed carbon-based mesoscopic perovskite solar cell with low-boiling-point reagent as solvent |
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