CN113571648B - Device and method for preparing flexible perovskite and full perovskite laminated solar cell from reel to reel - Google Patents

Device and method for preparing flexible perovskite and full perovskite laminated solar cell from reel to reel Download PDF

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CN113571648B
CN113571648B CN202110753029.7A CN202110753029A CN113571648B CN 113571648 B CN113571648 B CN 113571648B CN 202110753029 A CN202110753029 A CN 202110753029A CN 113571648 B CN113571648 B CN 113571648B
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perovskite
chamber
vacuumizing
thermal annealing
transport layer
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CN113571648A (en
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袁宁一
钱斌辉
丁建宁
王书博
顾磊磊
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Changzhou University
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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
    • 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
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • 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
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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/10—Photovoltaic [PV]
    • 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
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    • Y02E10/549—Organic PV cells

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Abstract

The invention belongs to the technical field of solar cells, and particularly relates to a device and a method for preparing flexible perovskite and full perovskite laminated solar cells in a roll-to-roll manner, wherein the device comprises an electron transport layer preparation module, a perovskite layer preparation module, a hole transport layer preparation module, an electrode preparation module and an unreeling and winding module which are sequentially arranged; the perovskite layer preparation module comprises a perovskite precursor printing roller, a solvent extraction device, a thermal annealing device and a cooling nitrogen air knife. The preparation method comprises the steps of preparing an electron transport layer, printing a perovskite precursor, vacuumizing, anti-solvent-vacuumizing extraction, thermally annealing perovskite and cooling; preparing a hole transport layer; and (5) preparing an electrode. The roll-to-roll flexible perovskite solar cell prepared by the device can realize vacuum extraction of the flexible substrate, the flexible substrate is uniformly stressed in the solvent extraction process, deformation cannot occur, the product quality is high, and the device is compatible with a full perovskite laminated solar cell.

Description

Device and method for preparing flexible perovskite and full perovskite laminated solar cell from reel to reel
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a device and a method for preparing flexible perovskite and full perovskite laminated solar cells in a roll-to-roll manner.
Background
The small area efficiency of perovskite solar cells has exceeded 25.5%, but almost all published literature uses antisolvent spin coating or two-step spin coating methods. In particular, the anti-solvent method, spin-coating anti-solvent method, which promotes the formation of perovskite thin films, often has uncontrollable factors, and the spin-coating anti-solvent method cannot be scaled up to a size of more than 5 x 5 cm. For perovskite solar cell commercialization, a larger area of perovskite thin film is required.
The existing flexible solar cell has wide prospects due to the advantages of light weight, portability, low cost, excellent performance and the like, can be used for solar backpacks, solar open canopies, solar sailboats and other devices, and can be integrated on windows, roofs, outer walls or inner walls. Patent CN 111710783A discloses a preparation scheme of a large-area perovskite solar cell, which aims at a rigid substrate to realize extraction of perovskite by using a perovskite wet film reduced pressure distillation mode, but the scheme can cause serious deformation of a substrate when placed on a flexible substrate, and cannot be applied to a continuous substrate. Patent CN 111341919A, which extracts perovskite by means of antisolvent soaking, is very prone to over-extraction, and there is uncertainty in the quality of the prepared cells. Patent CN 1084287987A provides a roll coating process that can be applied to flexible substrates, but simply blow-dry thermal annealing after coating with perovskite solution is far from adequate to form high quality films.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a device and a method for preparing flexible perovskite and full perovskite laminated solar cells from reel to reel by starting from a perovskite preparation means, and the process of vacuumizing-antisolvent-vacuumizing extraction is carried out on perovskite on a flexible substrate, so that ligand solvents in perovskite precursor solutions are fully extracted. The method can avoid deformation of the flexible substrate while using vacuum extraction, prepare the perovskite thin film with high quality, and is compatible with the full perovskite laminated solar cell.
According to the technical scheme, the device for preparing the flexible perovskite and the full perovskite laminated solar cell in a roll-to-roll manner is adopted. The device comprises an electron transport layer preparation module (1), a perovskite layer preparation module (2), a hole transport layer preparation module (3), an electrode preparation module (4) and an unreeling and reeling module (5) which are sequentially arranged; the unreeling and reeling module (5) comprises a flexible substrate (51), and the flexible substrate (51) sequentially passes through each module; the perovskite layer preparation module (2) comprises a perovskite precursor printing roller (21), a solvent extraction device (22), a thermal annealing device (23) and a cooling nitrogen air knife (24) which are sequentially arranged; the solvent extraction device (22) comprises a vacuumizing device A (221), an antisolvent extraction chamber (222) and a vacuumizing device B (223) which are sequentially arranged, wherein the vacuumizing device A (221) comprises an upper vacuumizing chamber (2211) and a lower vacuumizing chamber (2212), the upper vacuumizing chamber (2211) is connected with a vacuum pump (2213), the upper vacuumizing chamber (2211) is connected with a pressure gauge (2214), the lower vacuumizing chamber (2212) is connected with a vacuum pump (2215), and the lower vacuumizing chamber (2212) is connected with a pressure gauge (2216); introducing antisolvent gas into the antisolvent extraction chamber (222); the vacuumizing device B (223) comprises an upper vacuumizing chamber (2231) and a lower vacuumizing chamber (2232), wherein the upper vacuumizing chamber (2231) is connected with a vacuum pump (2233) and is connected with a pressure gauge (2234) above the upper vacuumizing chamber (2231), and the lower vacuumizing chamber (2232) is connected with a vacuum pump (2235) and is connected with a pressure gauge (2236) below the lower vacuumizing chamber (2232); the thermal annealing device (23) comprises a thermal annealing chamber (231), and a hot plate (232) is arranged inside the thermal annealing chamber (231).
The electron transport layer preparation module (1) comprises an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) which are sequentially arranged, wherein the thermal annealing device (12) comprises a thermal annealing chamber (121), and a hot plate (122) is arranged in the thermal annealing chamber (121).
In the vacuum pumping device A (221), a flexible substrate (51) is clamped between an upper vacuum pumping chamber (2211) and a lower vacuum pumping chamber (2212) to form a closed space, and the first solvent extraction is performed.
The antisolvent gas enters an antisolvent extraction chamber (222) for a second solvent extraction.
The flexible substrate in the vacuumizing device B (223) is clamped between the upper vacuumizing chamber (2231) and the lower vacuumizing chamber (2232) to form a closed space, and the third solvent extraction is performed.
The hole transport layer preparation module (3) comprises a hole transport layer printing roller (31) and a blow-drying nitrogen air knife (32) which are sequentially arranged.
The electrode preparation module (4) comprises an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) which are sequentially arranged, wherein the thermal annealing device (42) comprises a thermal annealing chamber (421), and a hot plate (422) is arranged in the thermal annealing chamber (421).
Unreeling and winding module (5) include flexible substrate (51), unreel roller (52), a plurality of backing roll (53) and wind-up roll (54) that set up along substrate transmission direction.
A method of roll-to-roll preparation of flexible perovskite and all-perovskite stacked solar cells comprising the steps of: preparing an electron transport layer; printing perovskite precursors, vacuumizing, anti-solvent, vacuumizing extraction, thermal annealing and cooling; preparing a hole transport layer; and (5) preparing an electrode. The method comprises the following specific steps:
s1, printing an electron transport layer on a flexible substrate through an electron transport layer printing roller, then annealing in a thermal annealing device, adjusting the temperature of a hot plate, controlling the substrate to anneal at 150 ℃ for 15min, and then cooling by using a cooling nitrogen air knife to obtain a sample 1.
S2, printing a perovskite layer on the cooled sample 1 through a perovskite precursor printing roller, reducing the pressure inside a chamber to 10-1000Pa through a vacuumizing device A, extracting a solvent through an anti-solvent extraction chamber filled with chlorobenzene anti-solvent gas, fully extracting a ligand solvent through a vacuumizing device B, nucleating perovskite, finally entering a thermal annealing device, annealing for 20min at 100 ℃, and cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing the hole transport layer on the cooled sample 2 through a hole transport layer printing roller, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing an electrode on the sample 3 through an electrode printing roller, solidifying by using a thermal annealing device, and cooling by using a cooling nitrogen air knife to obtain a sample 4.
The obtained sample 3 was used as a flexible substrate (51), and the processes of S1 to S4 were performed again, whereby a full perovskite laminated flexible solar cell was produced.
The invention has the following beneficial effects:
(1) Printing a perovskite wet film, starting mechanical pumps at two sides after the perovskite wet film enters a vacuumizing cavity, synchronously reducing pressure at two sides of a flexible substrate, partially volatilizing a ligand solvent in the wet film, avoiding deformation of the flexible substrate, then inflating the cavity, enabling the perovskite film to enter an antisolvent cavity, further extracting the ligand solvent in the wet film, and finally entering the vacuumizing cavity again to ensure thorough volatilization of the ligand solvent in the wet film.
(2) The ligand solvent is fully extracted by adopting vacuumizing, antisolvent and vacuumizing operation, so that the prepared perovskite film has better compactness and better battery stability;
(3) Can be suitable for preparing perovskite solar cells with different flexible substrates and different types.
(4) The invention can prepare the full perovskite laminated solar cell on the basis of preparing the flexible perovskite solar cell.
Description of the drawings:
in order to more clearly illustrate the technical solution in the embodiments of the present invention, the following description briefly describes the drawings.
FIG. 1 is a schematic diagram of an apparatus for roll-to-roll preparation of flexible perovskite and all perovskite stacked solar cells.
Fig. 2 is a schematic view of the vacuum pumping apparatus a.
Fig. 3 is a schematic view of the vacuum pumping apparatus B.
The attached labels illustrate: 1. an electron transport layer preparation module; 11. an electron transport layer printing roller; 12. a thermal annealing device; 121. a thermal annealing chamber; 122. a hot plate; 13, cooling a nitrogen air knife; 2. a perovskite layer preparation module; 21. perovskite precursor printing rollers; 2. a solvent extraction module; 221. a vacuumizing device A; 2211. an upper vacuum pumping chamber; 2212. a lower vacuumizing chamber; 2213. a vacuum pump; 2214. a pressure gauge; 2215. a vacuum pump; 2216. a pressure gauge; 222. an antisolvent extraction chamber; 223. a vacuum pumping device B; 2231. an upper vacuum pumping chamber; 2232. a lower vacuumizing chamber; 2233. a vacuum pump; 2234. a pressure gauge; 2235. a vacuum pump; 2236. a pressure gauge; 23. a thermal annealing device; 231. a thermal annealing chamber; 232. a hot plate; 24. cooling the nitrogen air knife; 3. a hole transport layer preparation module; 31. a hole transport layer printing roller; 32. blowing nitrogen air knife; 4. an electrode preparation module; 41. an electrode printing roller; 42. a thermal annealing device; 421. a thermal annealing chamber; 422. a hot plate; 43. cooling the nitrogen air knife; 5. unreeling and reeling the module; 51. a flexible substrate; 52. an unreeling roller; 53. a support roller; 54. and (5) a wind-up roller.
FIG. 4 is an X-ray diffraction pattern of perovskite thin films produced by different perovskite layer production methods.
Fig. 5 is a J-V plot of solar cells made by different perovskite layer preparation methods.
Detailed Description
The following description of the technical solution in the embodiments of the present invention is clear and complete.
Example 1
The device for preparing flexible perovskite and full perovskite laminated solar cell from roll to roll in the embodiment comprises an electron transport layer preparation module (1), a perovskite layer preparation module (2), a hole transport layer preparation module (3), an electrode preparation module (4) and an unreeling and reeling module (5) which are sequentially arranged; the unreeling and reeling module (5) comprises a flexible substrate (51), and the flexible substrate (51) sequentially passes through each module; the perovskite layer preparation module (2) comprises a perovskite precursor printing roller (21), a solvent extraction device (22), a thermal annealing device (23) and a cooling nitrogen air knife (24) which are sequentially arranged; the solvent extraction device (22) comprises a vacuumizing device A (221), an antisolvent extraction chamber (222) and a vacuumizing device B (223) which are sequentially arranged, wherein the vacuumizing device A (221) comprises an upper vacuumizing chamber (2211) and a lower vacuumizing chamber (2212), the upper vacuumizing chamber (2211) is connected with a vacuum pump (2213), the upper vacuumizing chamber (2211) is connected with a pressure gauge (2214), the lower vacuumizing chamber (2212) is connected with a vacuum pump (2215), and the lower vacuumizing chamber (2212) is connected with a pressure gauge (2216); introducing antisolvent gas into the antisolvent extraction chamber (222); the vacuumizing device B (223) comprises an upper vacuumizing chamber (2231) and a lower vacuumizing chamber (2232), wherein the upper vacuumizing chamber (2231) is connected with a vacuum pump (2233) and is connected with a pressure gauge (2234) above the upper vacuumizing chamber (2231), and the lower vacuumizing chamber (2232) is connected with a vacuum pump (2235) and is connected with a pressure gauge (2236) below the lower vacuumizing chamber (2232); the thermal annealing device (23) comprises a thermal annealing chamber (231), and a hot plate (232) is arranged inside the thermal annealing chamber (231).
In practical application, in the vacuum-pumping device A, the flexible substrate is clamped between the upper vacuum-pumping chamber and the lower vacuum-pumping chamber to form a closed space, and the first solvent extraction is performed.
In practice, the antisolvent gas enters the antisolvent extraction chamber for a second solvent extraction.
In practical application, the flexible substrate in the vacuumizing device B is clamped between the upper vacuumizing chamber and the lower vacuumizing chamber to form a closed space, and the third solvent extraction is performed.
The electron transport layer preparation module (1) comprises an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) which are sequentially arranged, wherein the thermal annealing device (12) comprises a thermal annealing chamber (121), and a hot plate (122) is arranged in the thermal annealing chamber (121).
The hole transport layer preparation module (3) comprises a hole transport layer printing roller (31) and a blow-drying nitrogen air knife (32) which are sequentially arranged.
The electrode preparation module (4) comprises an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) which are sequentially arranged, wherein the thermal annealing device (42) comprises a thermal annealing chamber (421), and a hot plate (422) is arranged in the thermal annealing chamber (421).
Unreeling and winding module (5) include flexible substrate (51), unreel roller (52), a plurality of backing roll (53) and wind-up roll (54) that set up along substrate transmission direction.
A method of roll-to-roll preparation of flexible perovskite and all-perovskite stacked solar cells comprising the steps of: preparing an electron transport layer; printing perovskite precursors, vacuumizing, anti-solvent, vacuumizing extraction, thermal annealing and cooling; preparing a hole transport layer; and (5) preparing an electrode.
S1, printing an electron transport layer SnO on a flexible substrate (51) PET through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) Then the pressure in the chamber was reduced to 10pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) Finally, the internal pressure of the chamber is increased by the vacuumizing device BAnd (3) fully extracting ligand solvent by reducing the pressure to 10pa to nucleate perovskite, finally entering a thermal annealing device to anneal for 20min at 100 ℃ to obtain a perovskite layer with thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Example 2
S1, printing an electron transport layer SnO on a flexible substrate PET through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) Then the pressure in the chamber was reduced to 10pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) And finally, sufficiently extracting the ligand solvent by reducing the pressure in the chamber to 500pa through a vacuumizing device B, nucleating perovskite, finally, entering a thermal annealing device, annealing for 20min at 100 ℃ to obtain a perovskite layer with the thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Example 3
S1, printing electron transfer of a flexible substrate PET through an electron transfer layer printing rollerLayer-transported SnO 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) Then the pressure in the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) And finally, sufficiently extracting the ligand solvent by reducing the pressure in the chamber to 500pa through a vacuumizing device B, nucleating perovskite, finally, entering a thermal annealing device, annealing for 20min at 100 ℃ to obtain a perovskite layer with the thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Example 4
S1, printing an electron transport layer SnO on a flexible substrate PET through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) Then the pressure in the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) Finally, the pressure in the chamber is reduced to 1000Pa through a vacuumizing device B to fully extract ligand solvent, perovskite is nucleated, and finally the perovskite is annealed for 20min at 100 ℃ in a thermal annealing device to obtain a perovskite layer with thickness of 600nm, and then the perovskite layer is cooled by a cooling nitrogen air knife to obtain a sampleProduct 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Example 5
S1, printing an electron transport layer SnO on a flexible substrate PET through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) Then the pressure in the chamber was reduced to 1000Pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (the concentration of chlorobenzene in the chamber was 1 ml/cm) 3 ) And finally, sufficiently extracting the ligand solvent by reducing the pressure in the chamber to 1000Pa through a vacuumizing device B, nucleating perovskite, finally, entering a thermal annealing device, annealing for 20min at 100 ℃ to obtain a perovskite layer with the thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Example 6
S1, printing an electron transport layer SnO on a flexible substrate PET through an electron transport layer printing roller 2 The thickness is 30nm, then annealing is carried out in a thermal annealing device, the temperature of a hot plate is adjusted to control the base material to be annealed at 150 ℃ for 15min, and then cooling is carried out by using a cooling nitrogen air knife, thus obtaining a sample1。
S2, printing a perovskite layer (Cs) on the cooled sample 1 through a perovskite precursor printing roller 0.1 FA 0.9 PbI 2.1 Br 0.9 ) Then the pressure in the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) And finally, sufficiently extracting the ligand solvent by reducing the pressure in the chamber to 500pa through a vacuumizing device B, nucleating perovskite, finally, entering a thermal annealing device, annealing for 30min at 100 ℃ to obtain a perovskite layer with the thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
S4, printing an electron transport layer SnO on the sample 3 through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 100℃for 15 minutes by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 4.
S5, printing a perovskite layer (Cs) on the cooled sample 4 through a perovskite precursor printing roller 0.1 FA 0.9 Pb 0.5 Sn 0.5 I 3 ) Then the pressure in the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) And finally, the pressure in the chamber is reduced to 500pa through a vacuumizing device B to fully extract ligand solvent, perovskite is nucleated, and finally, the perovskite is annealed for 20min at 100 ℃ in a thermal annealing device to obtain the perovskite with the thickness of 600nm, and then, a cooling nitrogen air knife is used for cooling to obtain a sample 5.
And S6, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 5, and drying by using a drying nitrogen air knife to obtain a sample 6.
And S7, printing a carbon electrode with the thickness of 1 mu m on the sample 3 through an electrode printing roller, solidifying the sample by using a thermal annealing device, and cooling the sample by using a cooling nitrogen air knife to obtain a sample 7.
Comparative example 1
S1, printing an electron transport layer SnO on a flexible substrate PET through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) And then the pressure in the chamber is reduced to 500pa by a vacuumizing device, perovskite is nucleated, and finally the perovskite is annealed for 20min at 100 ℃ in a thermal annealing device, so that the thickness of the perovskite layer is 600nm, and then a cooling nitrogen air knife is used for cooling, so that a sample 2 is obtained.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Comparative example 2
S1, printing an electron transport layer SnO on a flexible substrate PET through an electron transport layer printing roller 2 The thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 150 ℃ for 15min by adjusting the temperature of a hot plate, followed by cooling with a cooling nitrogen air knife, to obtain sample 1.
S2, printing a perovskite layer (MAPbI) on the cooled sample 1 through a perovskite precursor printing roller 3 ) Then the pressure in the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the antisolvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm) 3 ) And (3) nucleating perovskite, finally, entering a thermal annealing device, and annealing for 20min at 100 ℃ to obtain a perovskite layer with a thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
And S3, printing a hole transport layer Spiro-oMeTAD with a thickness of 400nm by using a hole transport layer printing roller for the cooled sample 2, and drying by using a drying nitrogen air knife to obtain a sample 3.
And S4, printing a carbon electrode on the sample 3 through an electrode printing roller, wherein the thickness of the carbon electrode is 1 mu m, solidifying the carbon electrode by using a thermal annealing device, and cooling the carbon electrode by using a cooling nitrogen air knife to obtain a sample 4.
Table 1 photovoltaic properties of perovskite solar cells prepared in examples and comparative examples
It should be noted that modifications and improvements can be made by those skilled in the art without departing from the inventive concept, and these are all within the scope of the present invention.

Claims (7)

1. A method for preparing flexible perovskite and full perovskite laminated solar cell from roll to roll, characterized in that the method comprises the following steps:
s1, printing an electron transport layer on a flexible substrate (51) through an electron transport layer printing roller (11), then entering a thermal annealing device (12) for annealing, adjusting the temperature of a hot plate (122), controlling the annealing temperature of the substrate to be 150 ℃ for 15min, and then cooling by using a cooling nitrogen air knife (13) to obtain a sample 1;
s2, printing a perovskite layer on the cooled sample 1 through a perovskite precursor printing roller (21), reducing the pressure inside a chamber to 10-1000pa through a vacuumizing device A (221), extracting a solvent through a antisolvent extraction chamber (222) filled with chlorobenzene antisolvent gas, reducing the pressure inside the chamber to 10-1000pa through a vacuumizing device B (223), fully extracting a ligand solvent, nucleating perovskite, finally entering a thermal annealing device (23), annealing for 20min at 100 ℃, and cooling by using a cooling nitrogen air knife (24), so as to obtain a sample 2;
in the vacuum-pumping device A (221), the flexible substrate (51) is clamped between the upper vacuum-pumping chamber (2211) and the lower vacuum-pumping chamber(2212) Forming a closed space between the two, and performing first solvent extraction to reduce the pressure in the chamber to 10-500pa; the antisolvent gas enters an antisolvent extraction chamber (222) in which the chlorobenzene concentration is 1ml/cm 3 Performing a second solvent extraction; in the vacuumizing device B (223), the flexible substrate is clamped between the upper vacuumizing chamber (2231) and the lower vacuumizing chamber (2232) to form a closed space, and the third solvent extraction is carried out to reduce the pressure in the chamber to 500-1000pa;
s3, printing a hole transport layer on the cooled sample 2 through a hole transport layer printing roller (31), and drying by using a drying nitrogen air knife (32) to obtain a sample 3;
s4, printing an electrode on the sample 3 through an electrode printing roller (41), solidifying by using a thermal annealing device (42), and cooling by using a cooling nitrogen air knife (431) to obtain a sample 4 large-area flexible perovskite solar cell;
the device adopted by the method comprises an electron transport layer preparation module (1), a perovskite layer preparation module (2), a hole transport layer preparation module (3), an electrode preparation module (4) and an unreeling and reeling module (5) which are sequentially arranged; the unreeling and reeling module (5) comprises a flexible substrate (51), and the flexible substrate (51) sequentially passes through each module; the perovskite layer preparation module (2) comprises a perovskite precursor printing roller (21), a solvent extraction device (22), a thermal annealing device (23) and a cooling nitrogen air knife (24) which are sequentially arranged; the solvent extraction device (22) comprises a vacuumizing device A (221), an antisolvent extraction chamber (222) and a vacuumizing device B (223) which are sequentially arranged, wherein the vacuumizing device A (221) comprises an upper vacuumizing chamber (2211) and a lower vacuumizing chamber (2212), the upper vacuumizing chamber (2211) is connected with a vacuum pump (2213), the upper vacuumizing chamber (2211) is connected with a pressure gauge (2214), the lower vacuumizing chamber (2212) is connected with a vacuum pump (2215), and the lower vacuumizing chamber (2212) is connected with a pressure gauge (2216); introducing antisolvent gas into the antisolvent extraction chamber (222); the vacuumizing device B (223) comprises an upper vacuumizing chamber (2231) and a lower vacuumizing chamber (2232), wherein the upper vacuumizing chamber (2231) is connected with a vacuum pump (2233) and is connected with a pressure gauge (2234) above the upper vacuumizing chamber (2231), and the lower vacuumizing chamber (2232) is connected with a vacuum pump (2235) and is connected with a pressure gauge (2236) below the lower vacuumizing chamber (2232); the thermal annealing device (23) comprises a thermal annealing chamber (231), and a hot plate (232) is arranged inside the thermal annealing chamber (231).
2. The roll-to-roll apparatus for preparing flexible perovskite and all-perovskite stacked solar cell as defined in claim 1 wherein: the electron transport layer preparation module (1) comprises an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) which are sequentially arranged, wherein the thermal annealing device (12) comprises a thermal annealing chamber (121), and a hot plate (122) is arranged in the thermal annealing chamber (121).
3. The roll-to-roll apparatus for preparing flexible perovskite and all-perovskite stacked solar cell as defined in claim 1 wherein: the hole transport layer preparation module (3) comprises a hole transport layer printing roller (31) and a blow-drying nitrogen air knife (32) which are sequentially arranged.
4. The roll-to-roll apparatus for preparing flexible perovskite and all-perovskite stacked solar cell as defined in claim 1 wherein: the electrode preparation module (4) comprises an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) which are sequentially arranged, wherein the thermal annealing device (42) comprises a thermal annealing chamber (421), and a hot plate (422) is arranged in the thermal annealing chamber (421).
5. The roll-to-roll apparatus for preparing flexible perovskite and all-perovskite stacked solar cell as defined in claim 1 wherein: unreeling and reeling module (5) include flexible substrate (51), unreel roller (52), support roller (53) and wind-up roll (54) that set up along substrate transmission direction.
6. The roll-to-roll apparatus for preparing flexible perovskite and all-perovskite stacked solar cell as defined in claim 1 wherein: the flexible substrate (51) is PET, PEN, flexible perovskite film.
7. The roll-to-roll apparatus for preparing flexible perovskite and all-perovskite stacked solar cell as defined in claim 1 wherein: the obtained sample 3 was used as a flexible substrate (51), and the processes of S1 to S4 were performed again to prepare a full perovskite laminated flexible solar cell.
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CN107275495A (en) * 2017-06-28 2017-10-20 南方科技大学 Method for preparing perovskite solar cell module through roll-to-roll printing
CN108807675A (en) * 2018-05-07 2018-11-13 南京邮电大学 A kind of preparation method of solar battery of surface passivation perovskite thin film
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CN111341919A (en) * 2020-03-06 2020-06-26 江苏集萃分子工程研究院有限公司 Continuous preparation process and device for preparing perovskite thin film in roll-to-roll mode by one-step method
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CN107275495A (en) * 2017-06-28 2017-10-20 南方科技大学 Method for preparing perovskite solar cell module through roll-to-roll printing
CN108807675A (en) * 2018-05-07 2018-11-13 南京邮电大学 A kind of preparation method of solar battery of surface passivation perovskite thin film
CN110349886A (en) * 2019-06-19 2019-10-18 江苏大学 Large-area perovskite solar cell preparation device and preparation method

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