WO2023273879A1 - Device and method for roll-to-roll preparation of flexible perovskite and full-perovskite laminated solar cells - Google Patents

Device and method for roll-to-roll preparation of flexible perovskite and full-perovskite laminated solar cells Download PDF

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WO2023273879A1
WO2023273879A1 PCT/CN2022/098824 CN2022098824W WO2023273879A1 WO 2023273879 A1 WO2023273879 A1 WO 2023273879A1 CN 2022098824 W CN2022098824 W CN 2022098824W WO 2023273879 A1 WO2023273879 A1 WO 2023273879A1
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perovskite
chamber
roll
thermal annealing
transport layer
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PCT/CN2022/098824
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French (fr)
Chinese (zh)
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袁宁一
丁建宁
王书博
李绿洲
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常州大学
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention belongs to the technical field of solar cells, and in particular relates to a roll-to-roll preparation device and method for flexible perovskite and full perovskite laminated solar cells.
  • perovskite solar cells The small-area efficiency of perovskite solar cells has exceeded 25.5%, but almost all published literatures have used anti-solvent spin coating or two-step spin coating methods. Especially for the anti-solvent method, there are often uncontrollable factors in promoting the formation of perovskite films by spin-coating anti-solvent, and the spin-coating anti-solvent method cannot be enlarged to a size above 5*5cm. For the commercialization of perovskite solar cells, larger area perovskite films are required.
  • Patent CN 111710783 A discloses a large-area perovskite solar cell preparation scheme, which uses perovskite wet film vacuum distillation method to achieve perovskite extraction for rigid substrates, but this scheme is placed on flexible substrates On the other hand, the substrate will be severely deformed, and it cannot be applied to continuous substrates.
  • Patent CN 111341919 A which extracts perovskite by anti-solvent immersion, is very prone to over-extraction, and there is uncertainty in the quality of the prepared battery.
  • Patent CN 1084287987 A provides a roller coating process, which can be applied to flexible substrates, but simply drying and thermal annealing after coating perovskite solution is far from enough to form high-quality films.
  • the technical problem to be solved by the present invention is to provide a device and method for preparing flexible perovskite and full perovskite stacked solar cells roll-to-roll starting from the perovskite preparation method.
  • the vacuum-anti-solvent-vacuum extraction process is carried out to fully extract the ligand solvent in the perovskite precursor solution.
  • the technical solution adopted in the present invention is a roll-to-roll device for preparing flexible perovskite and all-perovskite laminated solar cells.
  • 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 unwinding and winding module (5) arranged in sequence;
  • the unwinding and winding module (5) includes a flexible substrate (51), and the flexible substrate (51) passes through each module in turn;
  • the perovskite layer preparation module (2) includes a perovskite precursor printing roll arranged in sequence (21), solvent extraction device (22), thermal annealing device (23), cooling nitrogen air knife (24);
  • described solvent extraction device (22) comprises the vacuum pumping device A (221) that arranges successively, anti-solvent extraction chamber Chamber (222), vacuumizing device B (223), described vacuumizing device A (221) comprises an upper vacuum chamber (2211) and a lower vacuum chamber (2212), and an upper vacuum chamber (2211)
  • the electron transport layer preparation module (1) includes an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) arranged in sequence, wherein the thermal annealing device (12) includes a thermal annealing A chamber (121), a thermal plate (122) is placed inside the thermal annealing chamber (121).
  • the flexible substrate (51) is sandwiched between the upper vacuum chamber (2211) and the lower vacuum chamber (2212) to form a closed space for the first solvent extraction.
  • the anti-solvent gas enters the anti-solvent extraction chamber (222) for a second solvent extraction.
  • the flexible substrate is sandwiched between the upper vacuum chamber (2231) and the lower vacuum chamber (2232) to form a closed space, and the third solvent extraction is performed.
  • the hole transport layer preparation module (3) includes a hole transport layer printing roller (31) and a nitrogen air knife (32) arranged in sequence.
  • the electrode preparation module (4) includes an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) arranged in sequence, wherein the thermal annealing device (42) includes a thermal annealing chamber (421 ), a hot plate (422) is placed inside the thermal annealing chamber (421).
  • the unwinding and winding module (5) includes a flexible substrate (51), an unwinding roller (52), several supporting rollers (53) arranged along the conveying direction of the substrate, and a winding roller (54).
  • a roll-to-roll method for preparing flexible perovskite and full perovskite stacked solar cells comprising the following steps: preparation of an electron transport layer; printing of a perovskite precursor, vacuuming-antisolvent-vacuuming extraction, thermal annealing and Cooling; hole transport layer preparation; electrode preparation. Specific steps are as follows:
  • the cooled sample 1 prints the perovskite layer through the perovskite precursor printing roller, and then uses the vacuum device A to reduce the pressure inside the chamber to 10-1000Pa, and then passes through the anti-solvent extraction chamber filled with chlorobenzene anti-solvent gas Extract the solvent in the chamber, and finally use the vacuum device B to reduce the pressure inside the chamber to 10-1000pa to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device to anneal at 100°C for 20min, and use cooling nitrogen wind The knife was cooled and sample 2 was obtained.
  • the cooled sample 2 was printed with a hole transport layer by a hole transport layer printing roller, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the electrode was printed on the sample 3 by the electrode printing roller, solidified by using a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the obtained sample 3 is used as a flexible substrate (51), and the processes of S1 to S4 are performed again to prepare an all-perovskite stack flexible solar cell.
  • the prepared perovskite film has better compactness and better battery stability
  • the present invention can prepare all-perovskite tandem solar cells on the basis of preparing flexible perovskite solar cells.
  • Figure 1 is a schematic diagram of the roll-to-roll preparation of flexible perovskite and all-perovskite tandem solar cells.
  • FIG. 2 is a schematic diagram of a vacuum device A.
  • FIG. 3 is a schematic diagram of the vacuum device B.
  • Electron transport layer preparation module 11. Electron transport layer printing roller; 12. Thermal annealing device; 121. Thermal annealing chamber; 122. Hot plate; 13 Cooling nitrogen air knife; 2. Perovskite layer Preparation module; 21, perovskite precursor printing roller; 2, solvent extraction module; 221, vacuum device A; 2211, upper vacuum chamber; 2212, lower vacuum chamber; 2213, vacuum pump; 2214, pressure gauge 2215, vacuum pump; 2216, pressure gauge; 222, anti-solvent extraction chamber; 223, vacuum device B; 2231, upper vacuum chamber; 2232, lower vacuum chamber; 2233, vacuum pump; 2234, pressure gauge; 2235. Vacuum pump; 2236. Pressure gauge; 23.
  • Thermal annealing device 231. Thermal annealing chamber; 232. Hot plate; 24. Cooling nitrogen air knife; 3. Hole transport layer preparation module; 31. Hole transport layer printing Roller; 32. Drying nitrogen air knife; 4. Electrode preparation module; 41. Electrode printing roller; 42. Thermal annealing device; 421. Thermal annealing chamber; 422. Hot plate; 43. Cooling nitrogen air knife; 5. Rolling and winding module; 51, flexible substrate; 52, unwinding roller; 53, support roller; 54, winding roller.
  • Fig. 4 is the X-ray diffraction pattern of the perovskite thin film prepared by different perovskite layer preparation methods.
  • Fig. 5 is a J-V curve diagram of solar cells prepared by different perovskite layer preparation methods.
  • the roll-to-roll preparation device for flexible perovskite and all-perovskite laminated solar cells described in this embodiment includes an electron transport layer preparation module (1), a perovskite layer preparation module (2), and a hole transport layer preparation module (2).
  • the unwinding and winding module (5) includes a flexible substrate (51), and the flexible substrate (51) passes through each module;
  • the perovskite layer preparation module (2) includes a perovskite precursor printing roll (21), a solvent extraction device (22), a thermal annealing device (23), and a cooling nitrogen air knife (24) arranged in sequence;
  • the solvent extraction device (22) includes a vacuum device A (221), an anti-solvent extraction chamber (222), and a vacuum device B (223) arranged in sequence, and the vacuum device A (221) includes an upper vacuum chamber chamber (2211) and the lower vacuum chamber (2212), the upper vacuum chamber (2211) is connected with the
  • the vacuum chamber (2212) is connected with the vacuum pump (2215), and is connected with the pressure gauge (2216) below the lower vacuum chamber (2212); the anti-solvent gas is passed into the anti-solvent extraction chamber (222); the
  • the vacuum device B (223) comprises an upper vacuum chamber (2231) and a lower vacuum chamber (2232), the upper vacuum chamber (2231) is connected with a vacuum pump (2233), and the upper vacuum chamber (2231 ) is connected with the pressure gauge (2234) above, the lower vacuum chamber (2232) is connected with the vacuum pump (2235), and is connected with the pressure gauge (2236) below the lower vacuum chamber (2232);
  • the thermal annealing device (23 ) includes a thermal annealing chamber (231), and a thermal plate (232) is placed inside the thermal annealing chamber (231).
  • the flexible substrate is sandwiched between the upper vacuum chamber and the lower vacuum chamber to form a closed space for the first solvent extraction.
  • anti-solvent gas enters the anti-solvent extraction chamber for a second solvent extraction.
  • the flexible substrate in the vacuuming device B is sandwiched between the upper vacuum chamber and the lower vacuum chamber to form a closed space for the third solvent extraction.
  • the electron transport layer preparation module (1) includes an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) arranged in sequence, wherein the thermal annealing device (12) includes a thermal annealing A chamber (121), a thermal plate (122) is placed inside the thermal annealing chamber (121).
  • the hole transport layer preparation module (3) includes a hole transport layer printing roller (31) and a nitrogen air knife (32) arranged in sequence.
  • the electrode preparation module (4) includes an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) arranged in sequence, wherein the thermal annealing device (42) includes a thermal annealing chamber (421 ), a hot plate (422) is placed inside the thermal annealing chamber (421).
  • the unwinding and winding module (5) includes a flexible substrate (51), an unwinding roller (52), several supporting rollers (53) arranged along the conveying direction of the substrate, and a winding roller (54).
  • a roll-to-roll method for preparing flexible perovskite and full perovskite stacked solar cells comprising the following steps: preparation of an electron transport layer; printing of a perovskite precursor, vacuuming-antisolvent-vacuuming extraction, thermal annealing and Cooling; hole transport layer preparation; electrode preparation.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 10 Pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 10pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 10 Pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas
  • the extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 500pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas
  • the extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 500pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas
  • the extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 1000pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 1000pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas
  • the extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 1000pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the cooled sample 1 is printed with a perovskite layer (Cs 0.1 FA 0.9 PbI 2.1 Br 0.9 ) by a perovskite precursor printing roller, and then the pressure inside the chamber is reduced to 500pa by a vacuum device A, and then filled with chlorobenzene
  • the anti-solvent extraction chamber of the gas extracts the solvent (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • sample 3 print the electron transport layer SnO 2 through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device, control the temperature of the hot plate to anneal the substrate at 100°C for 15min, and then use the cooling nitrogen wind The knife was cooled and Sample 4 was obtained.
  • the cooled sample 4 is printed with a perovskite layer (Cs 0.1 FA 0.9 Pb 0.5 Sn 0.5 I 3 ) by a perovskite precursor printing roller, and then the internal pressure of the chamber is reduced to 500 Pa by a vacuum device A, and then filled with The anti-solvent extraction chamber of chlorobenzene gas extracts the solvent (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa by vacuuming device B to fully extract the ligand solvent, so that the perovskite can be formed Finally, enter the thermal annealing device and anneal at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600nm, and then use a cooling nitrogen air knife to cool to obtain sample 5.
  • a perovskite layer Cs 0.1 FA 0.9 Pb 0.5 Sn 0.5 I 3
  • the cooled sample 5 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 6.
  • the carbon electrode was printed on the sample 3 by an electrode printing roller with a thickness of 1 ⁇ m, solidified with a thermal annealing device, and then cooled with a cooling nitrogen air knife to obtain a sample 7.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the pressure inside the chamber to 500pa through the vacuum device to nucleate the perovskite, and finally enters the thermal annealing device Annealed at 100°C for 20 minutes to obtain a perovskite layer thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • MAbI 3 perovskite layer
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the pressure inside the chamber to 500pa through the vacuum device to nucleate the perovskite, and finally enters the thermal annealing device Annealed at 100°C for 20 minutes to obtain a perovskite layer thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
  • the cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 500pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas Extract the solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ) to nucleate the perovskite, and finally enter the thermal annealing device for annealing at 100°C for 20 minutes to obtain a perovskite layer thickness of 600nm, and then use a cooling nitrogen air knife Cool to obtain sample 2.
  • the cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
  • the carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 ⁇ m, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.

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Abstract

A device and a method for roll-to-roll preparation of flexible perovskite and full-perovskite laminated solar cells. 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 unwinding and winding module (5) which are sequentially arranged, wherein 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). The preparation method comprises electron transport layer preparation, perovskite precursor printing, vacuum-anti-solvent-vacuum extraction, thermal annealing of perovskite and cooling of same, hole transport layer preparation and electrode preparation. When the device is used to prepare a roll-to-roll flexible perovskite solar cell, vacuum extraction can be performed on a flexible substrate. In the solvent extraction process, the flexible substrate is subjected to uniform pressure and is not deformed, such that the product has high quality and is compatible with a full-perovskite laminated solar cell.

Description

卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置及方法Device and method for roll-to-roll preparation of flexible perovskite and all-perovskite tandem solar cells 技术领域technical field
本发明属于太阳电池技术领域，具体涉及卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置及方法。The invention belongs to the technical field of solar cells, and in particular relates to a roll-to-roll preparation device and method for flexible perovskite and full perovskite laminated solar cells.
背景技术Background technique
钙钛矿太阳电池的小面积效率已经超过了25.5％，但几乎所有公开报道的文献都使用了反溶剂旋涂或者两步旋涂的方法。特别是反溶剂法，旋涂反溶剂促进钙钛矿薄膜生成往往有着不可控制的因素，并且旋涂反溶剂法无法放大到5*5cm以上的尺寸。对于钙钛矿太阳能电池商业化而言，需要更大面积的钙钛矿薄膜。The small-area efficiency of perovskite solar cells has exceeded 25.5%, but almost all published literatures have used anti-solvent spin coating or two-step spin coating methods. Especially for the anti-solvent method, there are often uncontrollable factors in promoting the formation of perovskite films by spin-coating anti-solvent, and the spin-coating anti-solvent method cannot be enlarged to a size above 5*5cm. For the commercialization of perovskite solar cells, larger area perovskite films are required.
现有柔性太阳能电池因其质量轻、便携、成本低、性能优良等优点而前景广阔，可用于太阳能背包、太阳能敞篷、太阳能帆船等装备上，也可以集成在窗户、屋顶、外墙或内墙上。专利CN 111710783 A公布了一种大面积钙钛矿太阳电池制备方案，针对于钢性衬底使用钙钛矿湿膜减压蒸馏方式实现钙钛矿的萃取，但是此种方案放置于柔性衬底上则会使基材产生严重变形，同时无法应用于连续衬底。通过反溶剂浸泡的方式萃取钙钛矿的专利CN 111341919 A，非常容易发生过度萃取的情况，所制备电池质量存在着不确定性。专利CN 1084287987 A提供了一种辊涂工艺，能够适用于柔性基底，但是在涂布钙钛矿溶液后仅仅进行简单的吹干热退火，远远不足以形成高质量薄膜。Existing flexible solar cells have broad prospects due to their light weight, portability, low cost, and excellent performance. They can be used in solar backpacks, solar convertibles, solar sailboats and other equipment, and can also be integrated in windows, roofs, exterior walls or interior walls. superior. Patent CN 111710783 A discloses a large-area perovskite solar cell preparation scheme, which uses perovskite wet film vacuum distillation method to achieve perovskite extraction for rigid substrates, but this scheme is placed on flexible substrates On the other hand, the substrate will be severely deformed, and it cannot be applied to continuous substrates. Patent CN 111341919 A, which extracts perovskite by anti-solvent immersion, is very prone to over-extraction, and there is uncertainty in the quality of the prepared battery. Patent CN 1084287987 A provides a roller coating process, which can be applied to flexible substrates, but simply drying and thermal annealing after coating perovskite solution is far from enough to form high-quality films.
发明内容Contents of the invention
本发明所要解决的技术问题在于，拟从钙钛矿制备手段出发，提供卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置及方法，对在柔性基底上的 钙钛矿进行抽真空-反溶剂-抽真空萃取的工艺，充分萃取钙钛矿前驱体溶液中的配体溶剂。采用本发明方法能够在使用抽真空萃取的同时，避免柔性基材的变形，制备高质量的钙钛矿薄膜，并且兼容全钙钛矿叠层太阳能电池。The technical problem to be solved by the present invention is to provide a device and method for preparing flexible perovskite and full perovskite stacked solar cells roll-to-roll starting from the perovskite preparation method. The vacuum-anti-solvent-vacuum extraction process is carried out to fully extract the ligand solvent in the perovskite precursor solution. By adopting the method of the invention, the deformation of the flexible substrate can be avoided while vacuum extraction is used, and a high-quality perovskite thin film can be prepared, which is compatible with all perovskite stacked solar cells.
本发明所采用的技术方案，卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置。该装置包含依次设置的电子传输层制备模块(1)，钙钛矿层制备模块(2)，空穴传输层制备模块(3)，电极制备模块(4)以及放卷收卷模块(5)；所述放卷收卷模块(5)包含柔性基材(51)，柔性基材(51)依次经过各个模块；所述钙钛矿层制备模块(2)包含依次设置的钙钛矿前驱体印刷辊(21)、溶剂萃取装置(22)、热退火装置(23)、冷却氮气风刀(24)；所述溶剂萃取装置(22)包含依次设置的抽真空装置A(221)、反溶剂萃取腔室(222)、抽真空装置B(223)，所述抽真空装置A(221)包含上抽真空腔室(2211)和下抽真空腔室(2212)，上抽真空腔室(2211)与真空泵(2213)连接，并在上抽真空腔室(2211)上方与压力表(2214)连接，下抽真空腔室(2212)与真空泵(2215)连接，并在下抽真空腔室(2212)下方与压力表(2216)连接；所述反溶剂萃取腔室(222)中通入反溶剂气体；所述抽真空装置B(223)包含上抽真空腔室(2231)和下抽真空腔室(2232)，上抽真空腔室(2231)与真空泵(2233)连接，并在上抽真空腔室(2231)上方与压力表(2234)连接，下抽真空腔室(2232)与真空泵(2235)连接，并在下抽真空腔室(2232)下方与压力表(2236)连接；所述热退火装置(23)包含有一个热退火腔室(231)，在热退火腔室(231)内部放置有一个热板(232)。The technical solution adopted in the present invention is a roll-to-roll device for preparing flexible perovskite and all-perovskite laminated solar cells. 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 unwinding and winding module (5) arranged in sequence; The unwinding and winding module (5) includes a flexible substrate (51), and the flexible substrate (51) passes through each module in turn; the perovskite layer preparation module (2) includes a perovskite precursor printing roll arranged in sequence (21), solvent extraction device (22), thermal annealing device (23), cooling nitrogen air knife (24); described solvent extraction device (22) comprises the vacuum pumping device A (221) that arranges successively, anti-solvent extraction chamber Chamber (222), vacuumizing device B (223), described vacuumizing device A (221) comprises an upper vacuum chamber (2211) and a lower vacuum chamber (2212), and an upper vacuum chamber (2211) and The vacuum pump (2213) is connected, and is connected with the pressure gauge (2214) above the upper vacuum chamber (2211), and the lower vacuum chamber (2212) is connected with the vacuum pump (2215), and is connected below the lower vacuum chamber (2212) Connect with pressure gauge (2216); In described antisolvent extraction chamber (222), pass into antisolvent gas; Described vacuumizing device B (223) comprises upper vacuum chamber (2231) and lower vacuum chamber ( 2232), the upper vacuum chamber (2231) is connected with the vacuum pump (2233), and is connected with the pressure gauge (2234) above the upper vacuum chamber (2231), and the lower vacuum chamber (2232) is connected with the vacuum pump (2235) connected, and connected with the pressure gauge (2236) below the lower vacuum chamber (2232); the thermal annealing device (23) includes a thermal annealing chamber (231), and a A hot plate (232).
电子传输层制备模块(1)包含有依次设置的电子传输层印刷辊(11)、热退火装置(12)及冷却氮气风刀(13)，其中，热退火装置(12)包含有一个热退火腔室(121)，在热退火腔室(121)内部放置有一个热板(122)。The electron transport layer preparation module (1) includes an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) arranged in sequence, wherein the thermal annealing device (12) includes a thermal annealing A chamber (121), a thermal plate (122) is placed inside the thermal annealing chamber (121).
抽真空装置A(221)中，柔性基材(51)夹于上抽真空腔室(2211)和下抽真空腔室(2212)之间形成密闭空间，进行第一次溶剂萃取。In the vacuuming device A (221), the flexible substrate (51) is sandwiched between the upper vacuum chamber (2211) and the lower vacuum chamber (2212) to form a closed space for the first solvent extraction.
反溶剂气体进入反溶剂萃取腔室(222)中，进行第二次溶剂萃取。The anti-solvent gas enters the anti-solvent extraction chamber (222) for a second solvent extraction.
抽真空装置B(223)中柔性基材夹于上抽真空腔室(2231)和下抽真空腔室(2232)之间形成密闭空间，进行第三次溶剂萃取。In the vacuum device B (223), the flexible substrate is sandwiched between the upper vacuum chamber (2231) and the lower vacuum chamber (2232) to form a closed space, and the third solvent extraction is performed.
空穴传输层制备模块(3)包含有依次设置的空穴传输层印刷辊(31)、吹干氮气风刀(32)。The hole transport layer preparation module (3) includes a hole transport layer printing roller (31) and a nitrogen air knife (32) arranged in sequence.
电极制备模块(4)包含有依次设置的电极印刷辊(41)、热退火装置(42)和冷却氮气风刀(43)，其中，热退火装置(42)包含有一个热退火腔室(421)，在热退火腔室(421)内部放置有一个热板(422)。The electrode preparation module (4) includes an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) arranged in sequence, wherein the thermal annealing device (42) includes a thermal annealing chamber (421 ), a hot plate (422) is placed inside the thermal annealing chamber (421).
放卷收卷模块(5)包含有柔性基材(51)、放卷辊(52)、若干沿基材传输方向设置的支撑辊(53)以及收卷辊(54)。The unwinding and winding module (5) includes a flexible substrate (51), an unwinding roller (52), several supporting rollers (53) arranged along the conveying direction of the substrate, and a winding roller (54).
卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的方法，包括以下步骤：电子传输层制备；钙钛矿前驱体印刷、抽真空-反溶剂-抽真空萃取、热退火并进行冷却；空穴传输层制备；电极制备。具体步骤如下：A roll-to-roll method for preparing flexible perovskite and full perovskite stacked solar cells, comprising the following steps: preparation of an electron transport layer; printing of a perovskite precursor, vacuuming-antisolvent-vacuuming extraction, thermal annealing and Cooling; hole transport layer preparation; electrode preparation. Specific steps are as follows:
S1、将柔性基材通过电子传输层印刷辊印刷电子传输层，然后在热退火装置内进行退火，调整热板温度，控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。S1. Print the electron transport layer on the flexible substrate through the electron transport layer printing roller, and then anneal in the thermal annealing device, adjust the temperature of the hot plate, control the annealing of the substrate at 150°C for 15 minutes, and then use the cooling nitrogen air knife to cool to obtain the sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层，然后通过抽真空装置A使腔室内部压强降为10-1000pa，再通过充满氯苯反溶剂气体的反溶剂萃取腔室萃取溶剂、最后通过抽真空装置B使腔室内部压强降为10-1000pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，并使用冷却氮气风刀冷却，得到样品2。S2. The cooled sample 1 prints the perovskite layer through the perovskite precursor printing roller, and then uses the vacuum device A to reduce the pressure inside the chamber to 10-1000Pa, and then passes through the anti-solvent extraction chamber filled with chlorobenzene anti-solvent gas Extract the solvent in the chamber, and finally use the vacuum device B to reduce the pressure inside the chamber to 10-1000pa to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device to anneal at 100°C for 20min, and use cooling nitrogen wind The knife was cooled and sample 2 was obtained.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer by a hole transport layer printing roller, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷电极，使用热退火装置进行固化后，使用冷却氮气风刀进行冷却，得到样品4。S4. The electrode was printed on the sample 3 by the electrode printing roller, solidified by using a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
将得到的样品3作为柔性基材(51)，再次进行S1至S4的工艺，可以制备全钙钛矿叠层柔性太阳能电池。The obtained sample 3 is used as a flexible substrate (51), and the processes of S1 to S4 are performed again to prepare an all-perovskite stack flexible solar cell.
本发明具有以下有益效果：The present invention has the following beneficial effects:
(1)印刷钙钛矿湿膜，待其进入抽真空腔室后，两侧抽机械泵同时启动，柔性基底两侧的压强同步降低，湿膜中的配体溶剂部分挥发，避免柔性基底变形，之后腔体充气，钙钛矿膜随后进入反溶剂腔室，进一步萃取湿膜中的配体溶剂，最后再次进入抽真空腔室，保证湿膜中的配体溶剂彻底挥发。(1) Print the perovskite wet film, after it enters the vacuum chamber, the mechanical pumps on both sides are started at the same time, the pressure on both sides of the flexible substrate is simultaneously reduced, and the ligand solvent in the wet film is partially volatilized to avoid deformation of the flexible substrate , after the cavity is inflated, the perovskite film then enters the anti-solvent chamber to further extract the ligand solvent in the wet film, and finally enters the vacuum chamber again to ensure that the ligand solvent in the wet film is completely volatilized.
(2)采用抽真空、反溶剂、抽真空操作充分萃取配体溶剂，制备的钙钛矿薄膜致密性更好，电池稳定性更佳；(2) Using vacuuming, anti-solvent, and vacuuming to fully extract the ligand solvent, the prepared perovskite film has better compactness and better battery stability;
(3)能够适用于不同柔性基底、不同类型的钙钛矿太阳能电池制备。(3) It can be applied to the preparation of different flexible substrates and different types of perovskite solar cells.
(4)本发明能够在制备柔性钙钛矿太阳能电池的基础上，兼顾制备全钙钛矿叠层太阳能电池。(4) The present invention can prepare all-perovskite tandem solar cells on the basis of preparing flexible perovskite solar cells.
附图说明：Description of drawings:
为了更清楚地说明本发明实施例中的技术方案，下面对附图作简单地介绍。In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings are briefly introduced below.
图1为卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置示意图。Figure 1 is a schematic diagram of the roll-to-roll preparation of flexible perovskite and all-perovskite tandem solar cells.
图2为抽真空装置A的示意图。FIG. 2 is a schematic diagram of a vacuum device A.
图3为抽真空装置B的示意图。FIG. 3 is a schematic diagram of the vacuum device B.
图附标记说明：1、电子传输层制备模块；11、电子传输层印刷辊；12、热退火装置；121、热退火腔室；122、热板；13冷却氮气风刀；2、钙钛矿层制 备模块；21、钙钛矿前驱体印刷辊；2、溶剂萃取模块；221、抽真空装置A；2211、上抽真空腔室；2212、下抽真空腔室；2213、真空泵；2214、压力表；2215、真空泵；2216、压力表；222、反溶剂萃取腔室；223、抽真空装置B；2231、上抽真空腔室；2232、下抽真空腔室；2233、真空泵；2234、压力表；2235、真空泵；2236、压力表；23、热退火装置；231、热退火腔室；232、热板；24、冷却氮气风刀；3、空穴传输层制备模块；31、空穴传输层印刷辊；32、吹干氮气风刀；4、电极制备模块；41、电极印刷辊；42、热退火装置；421、热退火腔室；422、热板；43、冷却氮气风刀；5、放卷收卷模块；51、柔性基材；52、放卷辊；53、支撑辊；54、收卷辊。Explanation of symbols attached to the figure: 1. Electron transport layer preparation module; 11. Electron transport layer printing roller; 12. Thermal annealing device; 121. Thermal annealing chamber; 122. Hot plate; 13 Cooling nitrogen air knife; 2. Perovskite layer Preparation module; 21, perovskite precursor printing roller; 2, solvent extraction module; 221, vacuum device A; 2211, upper vacuum chamber; 2212, lower vacuum chamber; 2213, vacuum pump; 2214, pressure gauge 2215, vacuum pump; 2216, pressure gauge; 222, anti-solvent extraction chamber; 223, vacuum device B; 2231, upper vacuum chamber; 2232, lower vacuum chamber; 2233, vacuum pump; 2234, pressure gauge; 2235. Vacuum pump; 2236. Pressure gauge; 23. Thermal annealing device; 231. Thermal annealing chamber; 232. Hot plate; 24. Cooling nitrogen air knife; 3. Hole transport layer preparation module; 31. Hole transport layer printing Roller; 32. Drying nitrogen air knife; 4. Electrode preparation module; 41. Electrode printing roller; 42. Thermal annealing device; 421. Thermal annealing chamber; 422. Hot plate; 43. Cooling nitrogen air knife; 5. Rolling and winding module; 51, flexible substrate; 52, unwinding roller; 53, support roller; 54, winding roller.
图4为不同钙钛矿层制备方法制得的钙钛矿薄膜X射线衍射图。Fig. 4 is the X-ray diffraction pattern of the perovskite thin film prepared by different perovskite layer preparation methods.
图5为不同钙钛矿层制备方法制得的太阳能电池的J-V曲线图。Fig. 5 is a J-V curve diagram of solar cells prepared by different perovskite layer preparation methods.
具体实施方式detailed description
下面对本发明实施例中的技术方案进行清楚、完整地描述。The technical solutions in the embodiments of the present invention are clearly and completely described below.
实施例1Example 1
本实施例所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置包含依次设置的电子传输层制备模块(1)，钙钛矿层制备模块(2)，空穴传输层制备模块(3)，电极制备模块(4)以及放卷收卷模块(5)；所述放卷收卷模块(5)包含柔性基材(51)，柔性基材(51)依次经过各个模块；所述钙钛矿层制备模块(2)包含依次设置的钙钛矿前驱体印刷辊(21)、溶剂萃取装置(22)、热退火装置(23)、冷却氮气风刀(24)；所述溶剂萃取装置(22)包含依次设置的抽真空装置A(221)、反溶剂萃取腔室(222)、抽真空装置B(223)，所述抽真空装置A(221)包含上抽真空腔室(2211)和下抽真空腔室(2212)，上抽真空腔室(2211)与真空泵(2213)连接，并在上抽真空腔室(2211)上方与 压力表(2214)连接，下抽真空腔室(2212)与真空泵(2215)连接，并在下抽真空腔室(2212)下方与压力表(2216)连接；所述反溶剂萃取腔室(222)中通入反溶剂气体；所述抽真空装置B(223)包含上抽真空腔室(2231)和下抽真空腔室(2232)，上抽真空腔室(2231)与真空泵(2233)连接，并在上抽真空腔室(2231)上方与压力表(2234)连接，下抽真空腔室(2232)与真空泵(2235)连接，并在下抽真空腔室(2232)下方与压力表(2236)连接；所述热退火装置(23)包含有一个热退火腔室(231)，在热退火腔室(231)内部放置有一个热板(232)。The roll-to-roll preparation device for flexible perovskite and all-perovskite laminated solar cells described in this embodiment includes an electron transport layer preparation module (1), a perovskite layer preparation module (2), and a hole transport layer preparation module (2). A layer preparation module (3), an electrode preparation module (4) and an unwinding and winding module (5); the unwinding and winding module (5) includes a flexible substrate (51), and the flexible substrate (51) passes through each module; the perovskite layer preparation module (2) includes a perovskite precursor printing roll (21), a solvent extraction device (22), a thermal annealing device (23), and a cooling nitrogen air knife (24) arranged in sequence; The solvent extraction device (22) includes a vacuum device A (221), an anti-solvent extraction chamber (222), and a vacuum device B (223) arranged in sequence, and the vacuum device A (221) includes an upper vacuum chamber chamber (2211) and the lower vacuum chamber (2212), the upper vacuum chamber (2211) is connected with the vacuum pump (2213), and is connected with the pressure gauge (2214) above the upper vacuum chamber (2211), and the lower vacuum chamber (2211) is connected with the pressure gauge (2214). The vacuum chamber (2212) is connected with the vacuum pump (2215), and is connected with the pressure gauge (2216) below the lower vacuum chamber (2212); the anti-solvent gas is passed into the anti-solvent extraction chamber (222); the The vacuum device B (223) comprises an upper vacuum chamber (2231) and a lower vacuum chamber (2232), the upper vacuum chamber (2231) is connected with a vacuum pump (2233), and the upper vacuum chamber (2231 ) is connected with the pressure gauge (2234) above, the lower vacuum chamber (2232) is connected with the vacuum pump (2235), and is connected with the pressure gauge (2236) below the lower vacuum chamber (2232); the thermal annealing device (23 ) includes a thermal annealing chamber (231), and a thermal plate (232) is placed inside the thermal annealing chamber (231).
在实际应用中，抽真空装置A中，柔性基材夹于上抽真空腔室和下抽真空腔室之间形成密闭空间，进行第一次溶剂萃取。In practical application, in the vacuuming device A, the flexible substrate is sandwiched between the upper vacuum chamber and the lower vacuum chamber to form a closed space for the first solvent extraction.
在实际应用中，反溶剂气体进入反溶剂萃取腔室中，进行第二次溶剂萃取。In practical applications, anti-solvent gas enters the anti-solvent extraction chamber for a second solvent extraction.
在实际应用中，抽真空装置B中柔性基材夹于上抽真空腔室和下抽真空腔室之间形成密闭空间，进行第三次溶剂萃取。In practical application, the flexible substrate in the vacuuming device B is sandwiched between the upper vacuum chamber and the lower vacuum chamber to form a closed space for the third solvent extraction.
电子传输层制备模块(1)包含有依次设置的电子传输层印刷辊(11)、热退火装置(12)及冷却氮气风刀(13)，其中，热退火装置(12)包含有一个热退火腔室(121)，在热退火腔室(121)内部放置有一个热板(122)。The electron transport layer preparation module (1) includes an electron transport layer printing roller (11), a thermal annealing device (12) and a cooling nitrogen air knife (13) arranged in sequence, wherein the thermal annealing device (12) includes a thermal annealing A chamber (121), a thermal plate (122) is placed inside the thermal annealing chamber (121).
空穴传输层制备模块(3)包含有依次设置的空穴传输层印刷辊(31)、吹干氮气风刀(32)。The hole transport layer preparation module (3) includes a hole transport layer printing roller (31) and a nitrogen air knife (32) arranged in sequence.
电极制备模块(4)包含有依次设置的电极印刷辊(41)、热退火装置(42)和冷却氮气风刀(43)，其中，热退火装置(42)包含有一个热退火腔室(421)，在热退火腔室(421)内部放置有一个热板(422)。The electrode preparation module (4) includes an electrode printing roller (41), a thermal annealing device (42) and a cooling nitrogen air knife (43) arranged in sequence, wherein the thermal annealing device (42) includes a thermal annealing chamber (421 ), a hot plate (422) is placed inside the thermal annealing chamber (421).
放卷收卷模块(5)包含有柔性基材(51)、放卷辊(52)、若干沿基材传输方向设置的支撑辊(53)以及收卷辊(54)。The unwinding and winding module (5) includes a flexible substrate (51), an unwinding roller (52), several supporting rollers (53) arranged along the conveying direction of the substrate, and a winding roller (54).
卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的方法，包括以下步骤：电子传输层制备；钙钛矿前驱体印刷、抽真空-反溶剂-抽真空萃取、热退火并进行冷却；空穴传输层制备；电极制备。A roll-to-roll method for preparing flexible perovskite and full perovskite stacked solar cells, comprising the following steps: preparation of an electron transport layer; printing of a perovskite precursor, vacuuming-antisolvent-vacuuming extraction, thermal annealing and Cooling; hole transport layer preparation; electrode preparation.
S1、将柔性基材(51)PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate (51) PET through the electron transport layer printing roller with a thickness of 30nm, and then perform annealing in a thermal annealing device, and control the annealing of the substrate at 150°C for 15 minutes by adjusting the temperature of the hot plate. Then use cooling nitrogen air knife to cool to obtain Sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置A使腔室内部压强降为10pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔室内部压强降为10pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 10 Pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 10pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
实施例2Example 2
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置A使腔室内部压强降为10pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔 室内部压强降为500pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 10 Pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas The extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
实施例3Example 3
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置A使腔室内部压强降为500pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔室内部压强降为500pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 500pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas The extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
实施例4Example 4
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为 30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置A使腔室内部压强降为500pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔室内部压强降为1000pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 500pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas The extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 1000pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
实施例5Example 5
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置A使腔室内部压强降为1000pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔室内部压强降为1000pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 1000pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas The extraction solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 1000pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device in the Annealed at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD， 厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
实施例6Example 6
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(Cs 0.1FA 0.9PbI 2.1Br 0.9)，然后通过抽真空装置A使腔室内部压强降为500pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔室内部压强降为500pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火30min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 is printed with a perovskite layer (Cs 0.1 FA 0.9 PbI 2.1 Br 0.9 ) by a perovskite precursor printing roller, and then the pressure inside the chamber is reduced to 500pa by a vacuum device A, and then filled with chlorobenzene The anti-solvent extraction chamber of the gas extracts the solvent (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa through the vacuum device B to fully extract the ligand solvent to nucleate the perovskite. Finally, enter the thermal annealing device and anneal at 100°C for 30 minutes to obtain a perovskite layer thickness of 600nm, and then use cooling nitrogen air knife to cool to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在100℃退火15min，随后使用冷却氮气风刀冷却，得到样品4。 S4. For sample 3, print the electron transport layer SnO 2 through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device, control the temperature of the hot plate to anneal the substrate at 100°C for 15min, and then use the cooling nitrogen wind The knife was cooled and Sample 4 was obtained.
S5、冷却后的样品4通过钙钛矿前驱体印刷辊印刷钙钛矿层(Cs 0.1FA 0.9Pb 0.5Sn 0.5I 3)，然后通过抽真空装置A使腔室内部压强降为500pa，再通过充满氯苯气体的反溶剂萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，最后通过抽真空装置B使腔室内部压强降为500pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm， 随后使用冷却氮气风刀冷却，得到样品5。 S5. The cooled sample 4 is printed with a perovskite layer (Cs 0.1 FA 0.9 Pb 0.5 Sn 0.5 I 3 ) by a perovskite precursor printing roller, and then the internal pressure of the chamber is reduced to 500 Pa by a vacuum device A, and then filled with The anti-solvent extraction chamber of chlorobenzene gas extracts the solvent (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ), and finally the pressure inside the chamber is reduced to 500pa by vacuuming device B to fully extract the ligand solvent, so that the perovskite can be formed Finally, enter the thermal annealing device and anneal at 100°C for 20 minutes to obtain a perovskite layer with a thickness of 600nm, and then use a cooling nitrogen air knife to cool to obtain sample 5.
S6、冷却后的样品5通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品6。S6. The cooled sample 5 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 6.
S7、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品7。S7. The carbon electrode was printed on the sample 3 by an electrode printing roller with a thickness of 1 μm, solidified with a thermal annealing device, and then cooled with a cooling nitrogen air knife to obtain a sample 7.
对照例1Comparative example 1
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置使腔室内部压强降为500pa，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the pressure inside the chamber to 500pa through the vacuum device to nucleate the perovskite, and finally enters the thermal annealing device Annealed at 100°C for 20 minutes to obtain a perovskite layer thickness of 600 nm, and then cooled with a nitrogen air knife to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
对照例2Comparative example 2
S1、将柔性基材PET通过电子传输层印刷辊印刷电子传输层SnO 2，厚度为30nm，然后在热退火装置内进行退火，通过调整热板温度控制基材在150℃退火15min，随后使用冷却氮气风刀冷却，得到样品1。 S1. Print the electron transport layer SnO 2 on the flexible substrate PET through the electron transport layer printing roller, with a thickness of 30nm, and then anneal in the thermal annealing device. The substrate is annealed at 150°C for 15 minutes by adjusting the temperature of the hot plate, and then use cooling Nitrogen air knife cooling to obtain sample 1.
S2、冷却后的样品1通过钙钛矿前驱体印刷辊印刷钙钛矿层(MAPbI 3)，然后通过抽真空装置A使腔室内部压强降为500pa，再通过充满氯苯气体的反溶剂 萃取腔室萃取溶剂(腔室中氯苯浓度为1ml/cm 3)，使钙钛矿成核，最后进入热退火装置在100℃下退火20min，得到钙钛矿层厚度为600nm，随后使用冷却氮气风刀冷却，得到样品2。 S2. The cooled sample 1 prints the perovskite layer (MAPbI 3 ) through the perovskite precursor printing roller, and then reduces the internal pressure of the chamber to 500pa through the vacuum device A, and then passes through the anti-solvent extraction chamber filled with chlorobenzene gas Extract the solvent in the chamber (the concentration of chlorobenzene in the chamber is 1ml/cm 3 ) to nucleate the perovskite, and finally enter the thermal annealing device for annealing at 100°C for 20 minutes to obtain a perovskite layer thickness of 600nm, and then use a cooling nitrogen air knife Cool to obtain sample 2.
S3、冷却后的样品2通过空穴传输层印刷辊印刷空穴传输层Spiro-oMeTAD，厚度为400nm，并使用吹干氮气风刀进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer Spiro-oMeTAD by a hole transport layer printing roller with a thickness of 400 nm, and dried with a blown nitrogen air knife to obtain a sample 3.
S4、对样品3通过电极印刷辊印刷碳电极，厚度为1μm，使用热退火装置进行固化后使用冷却氮气风刀进行冷却，得到样品4。S4. The carbon electrode was printed on the sample 3 by the electrode printing roller with a thickness of 1 μm, solidified by a thermal annealing device, and then cooled by a cooling nitrogen air knife to obtain a sample 4.
表1实施例和对照例制备得到的钙钛矿太阳能电池的光伏性能The photovoltaic performance of the perovskite solar cell prepared by the embodiment and comparative example of table 1
Figure PCTCN2022098824-appb-000001
Figure PCTCN2022098824-appb-000001
应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the inventive concept of the present invention, and these all belong to the protection scope of the present invention.

Claims (9)

  1. 卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置，其特征在于，所述装置包含依次设置的电子传输层制备模块(1)，钙钛矿层制备模块(2)，空穴传输层制备模块(3)，电极制备模块(4)以及放卷收卷模块(5)；所述放卷收卷模块(5)包含柔性基材(51)，柔性基材(51)依次经过各个模块；所述钙钛矿层制备模块(2)包含依次设置的钙钛矿前驱体印刷辊(21)、溶剂萃取装置(22)、热退火装置(23)、冷却氮气风刀(24)；所述溶剂萃取装置(22)包含依次设置的抽真空装置A(221)、反溶剂萃取腔室(222)、抽真空装置B(223)，所述抽真空装置A(221)包含上抽真空腔室(2211)和下抽真空腔室(2212)，上抽真空腔室(2211)与真空泵(2213)连接，并在上抽真空腔室(2211)上方与压力表(2214)连接，下抽真空腔室(2212)与真空泵(2215)连接，并在下抽真空腔室(2212)下方与压力表(2216)连接；所述反溶剂萃取腔室(222)中通入反溶剂气体；所述抽真空装置B(223)包含上抽真空腔室(2231)和下抽真空腔室(2232)，上抽真空腔室(2231)与真空泵(2233)连接，并在上抽真空腔室(2231)上方与压力表(2234)连接，下抽真空腔室(2232)与真空泵(2235)连接，并在下抽真空腔室(2232)下方与压力表(2236)连接；所述热退火装置(23)包含有一个热退火腔室(231)，在热退火腔室(231)内部放置有一个热板(232)。A roll-to-roll device for preparing flexible perovskite and all-perovskite laminated solar cells, characterized in that the device includes an electron transport layer preparation module (1), a perovskite layer preparation module (2), and an empty A hole transport layer preparation module (3), an electrode preparation module (4) and an unwinding and winding module (5); the unwinding and winding module (5) includes a flexible substrate (51), and the flexible substrate (51) is sequentially After each module; the perovskite layer preparation module (2) comprises a perovskite precursor printing roll (21), a solvent extraction device (22), a thermal annealing device (23), a cooling nitrogen air knife (24) arranged in sequence ; The solvent extraction unit (22) comprises a vacuum unit A (221), an anti-solvent extraction chamber (222), and a vacuum unit B (223) arranged in sequence, and the vacuum unit A (221) comprises an upper pump The vacuum chamber (2211) and the lower vacuum chamber (2212), the upper vacuum chamber (2211) is connected with the vacuum pump (2213), and connected with the pressure gauge (2214) above the upper vacuum chamber (2211), The lower vacuum chamber (2212) is connected to the vacuum pump (2215), and is connected to the pressure gauge (2216) below the lower vacuum chamber (2212); the anti-solvent gas is introduced into the anti-solvent extraction chamber (222); Described vacuumizing device B (223) comprises upper vacuum chamber (2231) and lower vacuum chamber (2232), and upper vacuum chamber (2231) is connected with vacuum pump (2233), and on upper vacuum chamber The top of (2231) is connected with pressure gauge (2234), the lower vacuum chamber (2232) is connected with vacuum pump (2235), and is connected with pressure gauge (2236) below the lower vacuum chamber (2232); the thermal annealing device (23) includes a thermal annealing chamber (231), and a thermal plate (232) is placed inside the thermal annealing chamber (231).
  2. 根据权利要求1所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置，其特征在于：电子传输层制备模块(1)包含有依次设置的电子传输层印刷辊(11)、热退火装置(12)及冷却氮气风刀(13)，其中，热退火装置(12)包含有一个热退火腔室(121)，在热退火腔室(121)内部放置有一个热板(122)。The device for preparing flexible perovskite and all-perovskite stacked solar cells roll-to-roll according to claim 1, characterized in that: the electron transport layer preparation module (1) includes electron transport layer printing rollers ( 11), thermal annealing device (12) and cooling nitrogen air knife (13), wherein, thermal annealing device (12) comprises a thermal annealing chamber (121), is placed with a thermal annealing chamber (121) inside board (122).
  3. 根据权利要求1所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电 池的装置，其特征在于：空穴传输层制备模块(3)包含有依次设置的空穴传输层印刷辊(31)、吹干氮气风刀(32)。The device for preparing flexible perovskite and all-perovskite laminated solar cells roll-to-roll according to claim 1, characterized in that: the hole transport layer preparation module (3) includes sequentially arranged hole transport layer printing Roller (31), dry nitrogen air knife (32).
  4. 根据权利要求1所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置，其特征在于：电极制备模块(4)包含有依次设置的电极印刷辊(41)、热退火装置(42)和冷却氮气风刀(43)，其中，热退火装置(42)包含有一个热退火腔室(421)，在热退火腔室(421)内部放置有一个热板(422)。The roll-to-roll device for preparing flexible perovskite and all-perovskite stacked solar cells according to claim 1, characterized in that: the electrode preparation module (4) includes electrode printing rollers (41) arranged in sequence, thermal Annealing device (42) and cooling nitrogen air knife (43), wherein, thermal annealing device (42) comprises a thermal annealing chamber (421), is placed with a hot plate (422) inside thermal annealing chamber (421) .
  5. 根据权利要求1所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的装置，其特征在于：放卷收卷模块(5)包含有柔性基材(51)、放卷辊(52)、沿基材传输方向设置的支撑辊(53)以及收卷辊(54)。The device for preparing flexible perovskite and all-perovskite laminated solar cells roll-to-roll according to claim 1, characterized in that: the unwinding and winding module (5) includes a flexible substrate (51), an unwinding A roller (52), a support roller (53) arranged along the conveying direction of the substrate, and a take-up roller (54).
  6. 卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的方法，其特征在于，所述方法步骤如下：A roll-to-roll method for preparing flexible perovskite and all-perovskite laminated solar cells, characterized in that the steps of the method are as follows:
    S1、将柔性基材(51)通过电子传输层印刷辊(11)印刷电子传输层，然后进入热退火装置(12)内进行退火，调整热板(122)温度，控制基材150℃退火15min，随后使用冷却氮气风刀(13)冷却，得到样品1。S1. Pass the flexible substrate (51) through the electron transport layer printing roller (11) to print the electron transport layer, and then enter the thermal annealing device (12) for annealing, adjust the temperature of the hot plate (122), and control the annealing of the substrate at 150°C for 15 minutes , followed by cooling with a nitrogen air knife (13) to obtain Sample 1.
    S2、冷却后的样品1通过钙钛矿前驱体印刷辊(21)印刷钙钛矿层，然后通过抽真空装置A(221)使腔室内部压强降为10-1000pa，再通过充满氯苯反溶剂气体的反溶剂萃取腔室(222)萃取溶剂、最后通过抽真空装置B(223)使腔室内部压强降为10-1000pa充分萃取配体溶剂，使钙钛矿成核，最后进入热退火装置(23)在100℃下退火20min，并使用冷却氮气风刀(24)冷却，得到样品2。S2. The cooled sample 1 prints the perovskite layer through the perovskite precursor printing roller (21), and then reduces the internal pressure of the chamber to 10-1000pa through the vacuum device A (221), and then fills it with chlorobenzene anti-solvent The gas anti-solvent extraction chamber (222) extracts the solvent, and finally the pressure inside the chamber is reduced to 10-1000 Pa through the vacuum device B (223) to fully extract the ligand solvent to nucleate the perovskite, and finally enter the thermal annealing device (23) Anneal at 100° C. for 20 min, and cool with nitrogen air knife ( 24 ), to obtain sample 2.
    S3、冷却后的样品2通过空穴传输层印刷辊(31)印刷空穴传输层，并使用吹干氮气风刀(32)进行吹干，得到样品3。S3. The cooled sample 2 was printed with a hole transport layer by a hole transport layer printing roller (31), and dried with a blown nitrogen air knife (32), to obtain a sample 3.
    S4、对样品3通过电极印刷辊(41)印刷电极，使用热退火装置(42)进 行固化后使用冷却氮气风刀(431)进行冷却，得到样品4大面积柔性钙钛矿太阳能电池。S4. Print electrodes on sample 3 by electrode printing roller (41), use thermal annealing device (42) to solidify, and then use cooling nitrogen air knife (431) to cool to obtain sample 4 large-area flexible perovskite solar cells.
  7. 根据权利要求6所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的方法，其特征在于：柔性基材(51)为PET、PEN、柔性钙钛矿膜。The roll-to-roll method for preparing flexible perovskite and all-perovskite laminated solar cells according to claim 6, characterized in that: the flexible substrate (51) is PET, PEN, flexible perovskite film.
  8. 根据权利要求6所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的方法，其特征在于：抽真空装置A(221)中，柔性基材(51)夹于上抽真空腔室(2211)和下抽真空腔室(2212)之间形成密闭空间，进行第一次溶剂萃取；反溶剂气体进入反溶剂萃取腔室(222)中，进行进行第二次溶剂萃取；抽真空装置B(223)中，柔性基材夹于上抽真空腔室(2231)和下抽真空腔室(2232)之间形成密闭空间，进行第三次溶剂萃取。The roll-to-roll method for preparing flexible perovskite and all-perovskite stacked solar cells according to claim 6, characterized in that: in the vacuum device A (221), the flexible substrate (51) is sandwiched by the upper pump A closed space is formed between the vacuum chamber (2211) and the lower vacuum chamber (2212) for the first solvent extraction; the anti-solvent gas enters the anti-solvent extraction chamber (222) for the second solvent extraction; In the vacuum device B (223), the flexible substrate is sandwiched between the upper vacuum chamber (2231) and the lower vacuum chamber (2232) to form a closed space for the third solvent extraction.
  9. 根据权利要求6所述的卷对卷制备柔性钙钛矿以及全钙钛矿叠层太阳电池的方法，其特征在于：将得到的样品3作为柔性基材(51)，再次进行S1至S4的工艺，制备全钙钛矿叠层柔性太阳能电池。The roll-to-roll method for preparing flexible perovskite and all-perovskite stacked solar cells according to claim 6, characterized in that: the obtained sample 3 is used as a flexible substrate (51), and steps S1 to S4 are performed again process to prepare all-perovskite stacked flexible solar cells.
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