CN113571648A - Device and method for preparing flexible perovskite and all-perovskite laminated solar cell in roll-to-roll mode - Google Patents

Device and method for preparing flexible perovskite and all-perovskite laminated solar cell in roll-to-roll mode Download PDF

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CN113571648A
CN113571648A CN202110753029.7A CN202110753029A CN113571648A CN 113571648 A CN113571648 A CN 113571648A CN 202110753029 A CN202110753029 A CN 202110753029A CN 113571648 A CN113571648 A CN 113571648A
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perovskite
chamber
roll
transport layer
thermal annealing
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CN113571648B (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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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • 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
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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 a flexible perovskite and full perovskite laminated solar cell in a roll-to-roll mode, 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 reeling 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, extracting, thermally annealing perovskite and cooling; preparing a hole transport layer; and (4) preparing an electrode. Adopt the device preparation roll-to-roll flexible perovskite solar cell, can realize the evacuation extraction to flexible substrate, it is even that flexible substrate receives pressure at solvent extraction in-process, can not take place to warp, product quality is high to compatible full perovskite tandem solar cell.

Description

Device and method for preparing flexible perovskite and all-perovskite laminated solar cell in roll-to-roll mode
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 mode.
Background
The small area efficiency of perovskite solar cells has exceeded 25.5%, but almost all published literature uses either an anti-solvent spin coating or a two-step spin coating process. In particular, spin-on anti-solvent methods tend to have uncontrollable factors that promote perovskite thin film formation and cannot scale up to sizes of 5 x 5cm or more. For perovskite solar cell commercialization, larger areas of perovskite thin films are required.
The existing flexible solar cell has wide prospect due to the advantages of light weight, portability, low cost, excellent performance and the like, can be used on equipment such as a solar backpack, a solar open, a solar sailboat and the like, and can also be integrated on a window, a roof, an outer wall or an inner wall. Patent CN 111710783 a discloses a preparation scheme of a large-area perovskite solar cell, which aims at extracting perovskite on a rigid substrate by using a perovskite wet film reduced pressure distillation method, but the scheme placed on a flexible substrate can cause the base material to be seriously deformed, and cannot be applied to a continuous substrate. The patent CN 111341919A for extracting perovskite by means of anti-solvent soaking is very easy to cause over-extraction, and the quality of the prepared battery has uncertainty. Patent CN 1084287987 a provides a roll coating process that can be applied to flexible substrates, but is far from sufficient to form high quality thin films by simply blow-drying thermal annealing after applying the perovskite solution.
Disclosure of Invention
The invention aims to solve the technical problem that a device and a method for preparing flexible perovskite and full perovskite laminated solar cells in a roll-to-roll mode are provided based on a perovskite preparation method, and the perovskite on a flexible substrate is subjected to a process of vacuumizing, anti-solvent and vacuumizing extraction, so that ligand solvent in a perovskite precursor solution is fully extracted. The method can avoid the deformation of the flexible substrate while using the vacuum extraction, prepare the high-quality perovskite thin film and is compatible with the full perovskite tandem solar cell.
The technical scheme adopted by the invention is a device for preparing flexible perovskite and all-perovskite laminated solar cells in a roll-to-roll mode. 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 base material (51), and the flexible base material (51) sequentially passes through the modules; 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 an evacuating device A (221), an anti-solvent extraction chamber (222) and an evacuating device B (223) which are sequentially arranged, wherein the evacuating device A (221) comprises an upper evacuating chamber (2211) and a lower evacuating chamber (2212), the upper evacuating chamber (2211) is connected with a vacuum pump (2213) and is connected with a pressure gauge (2214) above the upper evacuating chamber (2211), the lower evacuating chamber (2212) is connected with a vacuum pump (2215) and is connected with a pressure gauge (2216) below the lower evacuating chamber (2212); introducing anti-solvent gas into the anti-solvent 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 placed inside the thermal annealing chamber (121).
In the vacuum extractor A (221), the flexible base material (51) is sandwiched between the upper vacuum-extracting chamber (2211) and the lower vacuum-extracting chamber (2212) to form a closed space, and the first solvent extraction is performed.
The anti-solvent gas enters an anti-solvent extraction chamber (222) for a second solvent extraction.
In the vacuum extractor B (223), the flexible substrate is clamped between the upper vacuum-extracting chamber (2231) and the lower vacuum-extracting chamber (2232) to form a closed space, and the solvent extraction is carried out for the third time.
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), wherein the thermal annealing device (42) comprises a thermal annealing chamber (421), and a hot plate (422) is placed inside the thermal annealing chamber (421).
The unreeling and reeling module (5) comprises a flexible base material (51), an unreeling roller (52), a plurality of supporting rollers (53) arranged along the base material transmission direction and a reeling roller (54).
The method for preparing the flexible perovskite and all-perovskite laminated solar cell in a roll-to-roll mode comprises the following steps: preparing an electron transport layer; printing a perovskite precursor, vacuumizing, anti-solvent, vacuumizing, extracting, thermally annealing and cooling; preparing a hole transport layer; and (4) preparing an electrode. The method comprises the following specific steps:
s1, printing the electron transfer layer on the flexible base material through an electron transfer layer printing roller, annealing in a thermal annealing device, adjusting the temperature of a hot plate, controlling the base material to anneal at 150 ℃ for 15min, and 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 the chamber to 10-1000pa through a vacuumizing device A, extracting the solvent in the chamber through an anti-solvent filled with chlorobenzene anti-solvent gas, reducing the pressure inside the chamber to 10-1000pa through a vacuumizing device B, fully extracting the ligand solvent to nucleate perovskite, annealing at 100 ℃ for 20min in a thermal annealing device, 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 the hole transport layer by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with an electrode by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife to obtain sample 4.
The resulting sample 3 was used as a flexible substrate (51), and the processes of S1 to S4 were performed again, whereby a full perovskite tandem flexible solar cell was prepared.
The invention has the following beneficial effects:
(1) printing a perovskite wet film, after the perovskite wet film enters an evacuation chamber, simultaneously starting a mechanical pump at two sides, synchronously reducing the pressure at two sides of a flexible substrate, partially volatilizing a ligand solvent in the wet film, avoiding the deformation of the flexible substrate, inflating a cavity, then entering an anti-solvent chamber by the perovskite film, further extracting the ligand solvent in the wet film, and finally entering the evacuation chamber again to ensure that the ligand solvent in the wet film is thoroughly volatilized.
(2) The ligand solvent is fully extracted by adopting the operations of vacuumizing, anti-solvent and vacuumizing, so that the prepared perovskite film has better compactness and better battery stability;
(3) the method can be suitable for preparing perovskite solar cells with different flexible substrates and different types.
(4) The invention can prepare the all-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 briefly describes the accompanying drawings.
Fig. 1 is a schematic diagram of an apparatus for roll-to-roll preparation of flexible perovskite and all-perovskite tandem solar cells.
Fig. 2 is a schematic view of the evacuation device a.
Fig. 3 is a schematic view of the evacuation device B.
The figures are labeled as follows: 1. an electronic transmission 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 the nitrogen air knife; 2. a perovskite layer preparation module; 21. a perovskite precursor printing roller; 2. a solvent extraction module; 221. a vacuumizing device A; 2211. an upper vacuum pumping chamber; 2212. a lower evacuated chamber; 2213. a vacuum pump; 2214. a pressure gauge; 2215. a vacuum pump; 2216. a pressure gauge; 222. an anti-solvent extraction chamber; 223. a vacuumizing device B; 2231. an upper vacuum pumping chamber; 2232. a lower evacuated 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. drying the 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. an unreeling and reeling module; 51. a flexible substrate; 52. unwinding rollers; 53. a support roller; 54. and (7) winding the roller.
FIG. 4 is an X-ray diffraction pattern of perovskite thin films prepared by different perovskite layer preparation methods.
FIG. 5 is a J-V plot of solar cells made by different perovskite layer fabrication methods.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
Example 1
The device for preparing the flexible perovskite and all-perovskite laminated solar cell in a roll-to-roll mode 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 base material (51), and the flexible base material (51) sequentially passes through the modules; 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 an evacuating device A (221), an anti-solvent extraction chamber (222) and an evacuating device B (223) which are sequentially arranged, wherein the evacuating device A (221) comprises an upper evacuating chamber (2211) and a lower evacuating chamber (2212), the upper evacuating chamber (2211) is connected with a vacuum pump (2213) and is connected with a pressure gauge (2214) above the upper evacuating chamber (2211), the lower evacuating chamber (2212) is connected with a vacuum pump (2215) and is connected with a pressure gauge (2216) below the lower evacuating chamber (2212); introducing anti-solvent gas into the anti-solvent 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 extractor a, the flexible substrate is sandwiched between the upper vacuum-extracting chamber and the lower vacuum-extracting chamber to form a closed space, and the first solvent extraction is performed.
In practical applications, the anti-solvent gas enters the anti-solvent extraction chamber for a second solvent extraction.
In practical application, the flexible substrate in the vacuum extractor B is clamped between the upper vacuum-pumping chamber and the lower vacuum-pumping chamber to form a closed space for the third solvent extraction.
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 placed inside 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), wherein the thermal annealing device (42) comprises a thermal annealing chamber (421), and a hot plate (422) is placed inside the thermal annealing chamber (421).
The unreeling and reeling module (5) comprises a flexible base material (51), an unreeling roller (52), a plurality of supporting rollers (53) arranged along the base material transmission direction and a reeling roller (54).
The method for preparing the flexible perovskite and all-perovskite laminated solar cell in a roll-to-roll mode comprises the following steps: preparing an electron transport layer; printing a perovskite precursor, vacuumizing, anti-solvent, vacuumizing, extracting, thermally annealing and cooling; preparing a hole transport layer; and (4) preparing an electrode.
S1, printing the electron transport layer SnO on the flexible base material (51) PET through an electron transport layer printing roller2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) Then, the pressure inside the chamber was reduced to 10pa by the vacuum extractor A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (the concentration of chlorobenzene in the chamber was 1 ml/cm)3) And finally, reducing the pressure inside the chamber to 10pa by using a vacuumizing device B to fully extract the ligand solvent so as to nucleate the perovskite, finally, annealing for 20min at 100 ℃ in a thermal annealing device to obtain the thickness of the perovskite layer of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Example 2
S1, printing the electron transport layer SnO on the flexible base material PET through an electron transport layer printing roller2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) Then, the pressure inside the chamber was reduced to 10pa by the vacuum extractor A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (the concentration of chlorobenzene in the chamber was 1 ml/cm)3) Finally, the pressure in the chamber is reduced to 500p by a vacuum pumping device Ba, fully extracting a ligand solvent to nucleate perovskite, finally annealing for 20min at 100 ℃ in a thermal annealing device 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.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Example 3
S1, printing the electron transport layer SnO on the flexible base material PET through an electron transport layer printing roller2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) Then, the pressure inside the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm)3) And finally, reducing the pressure inside the chamber to 500pa by using a vacuumizing device B to fully extract the ligand solvent so as to nucleate the perovskite, finally, annealing for 20min at 100 ℃ in a thermal annealing device to obtain the thickness of the perovskite layer of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Example 4
S1, printing the electron transfer layer S on the flexible base material PET through the electron transfer layer printing rollernO2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) Then, the pressure inside the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm)3) And finally, reducing the pressure inside the chamber to 1000pa by using a vacuumizing device B to fully extract the ligand solvent so as to nucleate the perovskite, finally, annealing for 20min at 100 ℃ in a thermal annealing device to obtain the thickness of the perovskite layer of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Example 5
S1, printing the electron transport layer SnO on the flexible base material PET through an electron transport layer printing roller2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) Then, the pressure inside the chamber was reduced to 1000Pa by the evacuation device A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (the concentration of chlorobenzene in the chamber was 1 ml/cm)3) And finally, reducing the pressure inside the chamber to 1000pa by using a vacuumizing device B to fully extract the ligand solvent so as to nucleate the perovskite, finally, annealing for 20min at 100 ℃ in a thermal annealing device to obtain the thickness of the perovskite layer of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Example 6
S1, printing the electron transport layer SnO on the flexible base material PET through an electron transport layer printing roller2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, sample 1 after cooling was printed with a perovskite precursor printing roll to form a perovskite layer (Cs)0.1FA0.9PbI2.1Br0.9) Then, the pressure inside the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm)3) And finally, reducing the pressure inside the chamber to 500pa by using a vacuumizing device B to fully extract the ligand solvent so as to nucleate the perovskite, finally annealing the perovskite in a thermal annealing device at 100 ℃ for 30min to obtain the thickness of the perovskite layer of 600nm, and then cooling the perovskite layer by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4 printing of an electron transport layer SnO on the sample 3 by an electron transport layer printing roll2And the thickness was 30nm, and then annealing was performed in a thermal annealing apparatus, and the substrate was annealed at 100 ℃ for 15min by adjusting the temperature of the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 4.
S5, sample 4 after cooling was printed with a perovskite precursor printing roll to form a perovskite layer (Cs)0.1FA0.9Pb0.5Sn0.5I3) Then by pumpingThe vacuum device A reduced the pressure inside the chamber to 500pa, and the solvent was extracted from the chamber by an anti-solvent filled with chlorobenzene gas (the concentration of chlorobenzene in the chamber was 1 ml/cm)3) And finally, reducing the pressure inside the chamber to 500pa by using a vacuumizing device B to fully extract the ligand solvent so as to nucleate the perovskite, finally, annealing for 20min at 100 ℃ in a thermal annealing device to obtain the thickness of the perovskite layer of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 5.
S6, printing the cooled sample 5 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 6.
S7, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 7.
Comparative example 1
S1, printing the electron transport layer SnO on the flexible base material PET through an electron transport layer printing roller2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) And then reducing the pressure inside the chamber to 500pa by a vacuumizing device to nucleate the perovskite, finally annealing for 20min at 100 ℃ in a thermal annealing device to obtain the thickness of the perovskite layer to be 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Comparative example 2
S1, printing roll marks on the flexible base material PET through an electron transport layerBrush electron transport layer SnO2And 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 the hot plate, followed by cooling using a cooling nitrogen air knife, to obtain sample 1.
S2, cooled sample 1, perovskite layer (MAPbI) printing by perovskite precursor printing roller3) Then, the pressure inside the chamber was reduced to 500pa by the vacuum extractor A, and the solvent was extracted by the anti-solvent extraction chamber filled with chlorobenzene gas (chlorobenzene concentration in the chamber was 1 ml/cm)3) And nucleating the perovskite, finally annealing for 20min at 100 ℃ in a thermal annealing device to obtain the perovskite layer with the thickness of 600nm, and then cooling by using a cooling nitrogen air knife to obtain a sample 2.
S3, printing the cooled sample 2 with a hole transport layer Spiro-oMeTAD through a hole transport layer printing roller, wherein the thickness is 400nm, and drying the sample by using a drying nitrogen air knife to obtain a sample 3.
S4, sample 3 was printed with a carbon electrode having a thickness of 1 μm by an electrode printing roll, solidified by a thermal annealing apparatus, and then cooled by a cooling nitrogen air knife, to obtain sample 4.
Table 1 photovoltaic performance of perovskite solar cells prepared in examples and comparative examples
Figure BDA0003145782500000121
It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications belong to the protection scope of the present invention.

Claims (9)

1. The device for preparing the flexible perovskite and all-perovskite laminated solar cell in a roll-to-roll manner is characterized by comprising 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 base material (51), and the flexible base material (51) sequentially passes through the modules; 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 an evacuating device A (221), an anti-solvent extraction chamber (222) and an evacuating device B (223) which are sequentially arranged, wherein the evacuating device A (221) comprises an upper evacuating chamber (2211) and a lower evacuating chamber (2212), the upper evacuating chamber (2211) is connected with a vacuum pump (2213) and is connected with a pressure gauge (2214) above the upper evacuating chamber (2211), the lower evacuating chamber (2212) is connected with a vacuum pump (2215) and is connected with a pressure gauge (2216) below the lower evacuating chamber (2212); introducing anti-solvent gas into the anti-solvent 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 apparatus for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to 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 placed inside the thermal annealing chamber (121).
3. The apparatus for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to 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 apparatus for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to 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), wherein the thermal annealing device (42) comprises a thermal annealing chamber (421), and a hot plate (422) is placed inside the thermal annealing chamber (421).
5. The apparatus for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to claim 1, wherein: unreel rolling module (5) and include flexible substrate (51), unreel roller (52), back-up roll (53) and wind-up roll (54) that set up along substrate direction of transfer.
6. The method for preparing the flexible perovskite and all-perovskite laminated solar cell in a roll-to-roll mode is characterized by comprising the following steps:
s1, printing the electron transport layer on the flexible base material (51) through an electron transport layer printing roller (11), then annealing in a thermal annealing device (12), adjusting the temperature of a hot plate (122), controlling the base material to anneal at 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 the chamber to 10-1000pa through a vacuumizing device A (221), extracting the solvent through an anti-solvent extraction chamber (222) filled with chlorobenzene anti-solvent gas, reducing the pressure inside the chamber to 10-1000pa through a vacuumizing device B (223) to fully extract the ligand solvent, nucleating the perovskite, annealing at 100 ℃ for 20min in a thermal annealing device (23), and cooling by using a cooling nitrogen air knife (24) to obtain a sample 2.
S3, printing the hole transport layer on the cooled sample 2 through a hole transport layer printing roller (31), and drying the hole transport layer by using a drying nitrogen air knife (32) to obtain a sample 3.
And S4, printing an electrode on the sample 3 through an electrode printing roller (41), solidifying the electrode by using a thermal annealing device (42), and cooling the electrode by using a cooling nitrogen air knife (431) to obtain the large-area flexible perovskite solar cell of the sample 4.
7. The method for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to claim 6, wherein: the flexible substrate (51) is a PET, PEN, flexible perovskite film.
8. The method for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to claim 6, wherein: in the vacuum extractor A (221), a flexible base material (51) is clamped between an upper vacuum-extracting chamber (2211) and a lower vacuum-extracting chamber (2212) to form a closed space, and first solvent extraction is carried out; the anti-solvent gas enters an anti-solvent extraction chamber (222) for second solvent extraction; in the vacuum extractor B (223), the flexible base material is sandwiched between the upper vacuum-extracting chamber (2231) and the lower vacuum-extracting chamber (2232) to form a closed space, and the solvent extraction is performed for the third time.
9. The method for roll-to-roll fabrication of flexible perovskite and all-perovskite tandem solar cells according to claim 6, wherein: the obtained sample 3 was used as a flexible substrate (51), and the processes from S1 to S4 were performed again to prepare an all-perovskite laminated flexible solar cell.
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