CN118215374A - Method for preparing low-temperature titanium oxide and efficiently stabilizing carbon electrode perovskite solar cell by screen printing - Google Patents
Method for preparing low-temperature titanium oxide and efficiently stabilizing carbon electrode perovskite solar cell by screen printing Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000007650 screen-printing Methods 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000000087 stabilizing effect Effects 0.000 title description 3
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 238000000137 annealing Methods 0.000 claims abstract description 30
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004528 spin coating Methods 0.000 claims abstract description 18
- 230000005525 hole transport Effects 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- DDQAGDLHARKUFX-UHFFFAOYSA-N acetic acid;methanamine Chemical compound [NH3+]C.CC([O-])=O DDQAGDLHARKUFX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000007639 printing Methods 0.000 claims description 88
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 29
- 239000001856 Ethyl cellulose Substances 0.000 claims description 17
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims description 17
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 15
- 239000001739 pinus spp. Substances 0.000 claims description 15
- 229940036248 turpentine Drugs 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 8
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940116411 terpineol Drugs 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002159 nanocrystal Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
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- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention relates to a method for preparing low-temperature titanium oxide and a high-efficiency stable carbon electrode perovskite solar cell by screen printing, belonging to the field of optoelectronic materials and devices. The preparation of the perovskite film adopts a screen printing technology to print a precursor solution taking methylamine acetate as a solvent on an FTO conductive substrate taking low-temperature titanium oxide as an electron transmission layer, and the perovskite film is prepared by vacuum annealing, and the whole process is completed in air with the relative humidity of 20% -80%. And spin-coating a Spiro-OMeTAD (aluminum oxide film) on the film as a hole transport layer, and screen-printing a carbon electrode to complete the preparation of the device. The method uses the autonomously prepared printable low-temperature titanium oxide slurry and the autonomously prepared carbon electrode with high conductivity, low cost and excellent interface contact, and the prepared perovskite solar cell is efficient and stable.
Description
Technical Field
The invention relates to a method for preparing a carbon electrode efficient stable perovskite solar cell in air with relative humidity of 20% -80% by screen printing based on methylamine acetate ionic liquid as a precursor solvent, in particular to a simple method for preparing a low-temperature titanium oxide electron transport layer and a perovskite solar cell by screen printing in air with relative humidity of 20% -80%, and belongs to the technical field of optoelectronic materials.
Background
The perovskite solar cell has the characteristics of simple manufacture and low cost, and the photoelectric conversion efficiency of the perovskite solar cell is rapidly improved from 3.8% to 25.7% from 2009. However, perovskite solar cells have poor stability, high production cost and low production efficiency, which limits commercial applications. In order to improve the stability of the perovskite battery, reduce the production cost and improve the production efficiency, scientific researchers propose to use screen printing technology to prepare each functional layer of perovskite and use carbon electrodes to replace expensive metal electrodes, so that the stability of the perovskite tire pressure energy battery is improved, the cost is reduced and the production efficiency is improved.
Conventional perovskite solar cells include electron transporting materials, hole transporting materials, perovskite active materials, and electrode materials. Titanium oxide in oxide is mostly adopted as an electron transport material of a battery, but the commercialization development of the conventional titanium oxide is limited by high-temperature treatment, so that the development of the electron transport material capable of being prepared at a low temperature is particularly critical. The titanium oxide nanocrystalline printable slurry is synthesized, the anatase titanium oxide film with high quality is prepared by screen printing and annealing at low temperature, perovskite is prepared by adopting a screen printing technology, and a carbon electrode is used for replacing a metal electrode to prepare the perovskite solar cell with high efficiency, stability and low cost.
Disclosure of Invention
The invention solves the technical problem that titanium oxide cannot be prepared at low temperature by the existing electron transport material, and provides a method for preparing low-temperature titanium oxide and efficiently stabilizing a carbon electrode perovskite solar cell by screen printing. The invention develops the titanium oxide nanocrystalline printing slurry, and can obtain the high-quality titanium oxide film through a screen printing process and annealing at a low temperature of 150 ℃, thereby avoiding the defect that the traditional titanium oxide needs to be treated at a high temperature of 500 ℃ and reducing the preparation difficulty of an electron transport layer;
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing comprises the following steps:
(1) Preparing titanium oxide nanocrystalline printing slurry, namely dispersing anatase titanium oxide nanocrystalline in ethanol, then respectively adding ethylcellulose and turpentine through alcohol, fully swinging and stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary evaporation to obtain the titanium oxide nanocrystalline printing slurry;
(2) Adding graphite flakes, carbon fibers, carbon black and ethylcellulose into a plastic pot, uniformly mixing, putting the mixture into an oven for drying treatment, cooling, adding zirconia ball milling beads and turpentine through alcohol, putting the mixture into a defoaming mixer for mixing and defoaming, and then stirring and defoaming repeatedly for a plurality of times to obtain a carbon slurry completely prepared;
(3) Dissolving methyl amine iodide and lead iodide in methylamine acetate solvent to prepare MAPbI 3 perovskite precursor solution, heating and stirring at 60 ℃ for dissolving for 6-12 hours;
(4) Screen printing low-temperature titanium oxide as an electron transport layer on the cleaned and ozonated FTO transparent conductive glass sheet; diluting the nanocrystalline titanium oxide printing slurry synthesized in the step (1) with terpineol, uniformly dispersing the slurry by using a stirring deaeration machine, printing the slurry on a treated FTO substrate by using a screen printing process, standing and leveling a titanium oxide wet film, and then annealing for 30 minutes at 150 ℃;
(5) Screen printing the prepared MAPbI 3 perovskite precursor solution on an FTO conductive substrate with an electron transport layer in air with the relative humidity of 20% -80%, and carrying out vacuum annealing at 100 ℃ for 5 minutes to obtain a flat and compact perovskite film;
(6) Spin-coating a hole transport layer Spiro-OMeTAD on the perovskite layer;
(7) And (3) screen printing the carbon paste in the step (2) on the hole transport layer to prepare a carbon electrode.
Preferably, the preparation of the titanium oxide nanocrystalline printing slurry in the step (1) comprises the steps of taking 3g of titanium oxide nanocrystalline, dispersing in 30mL of ethanol, then respectively adding 8.0g of ethanol dispersion liquid with the mass ratio of ethyl cellulose of 30% and 7.0g of turpentine through alcohol, fully swinging and stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary evaporation to obtain the titanium oxide nanocrystalline printing slurry with the solid content of 10%;
Adding 8.0g of graphite sheets, 2.5g of carbon fibers, 3.0g of carbon black and 1.5g of ethyl cellulose into a plastic pot, uniformly mixing, putting the mixture into a 100 ℃ oven for drying treatment for 1h, cooling, adding 15g of ZrO 2 ball-milling beads, 23g of water-removed turpentine through alcohol, putting the mixture into a defoaming mixer for mixing for 10min, defoaming for 20min, and stirring and defoaming for at least 3 times to obtain a complete carbon slurry;
Preferably, the concentration of the MAPbI 3 perovskite precursor solution in the step (1) is 100-800mg/mL.
Preferably, in the step (4), the electron transport layer on the transparent conductive FTO glass is titanium oxide, and the specific steps are as follows:
(1) Screen printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.1MPa, the printing speed is 10cm/s, and the printing interval is 0.5mm;
(2) After the screen printing is finished, the titanium oxide wet film is horizontally kept stand for 30 minutes for leveling, and then is annealed at 150 ℃ for 30 minutes.
Preferably, the film in the step (5) is prepared by adopting a screen printing and vacuum annealing mode in air with the relative humidity of 20% -80%, and the specific steps are as follows:
(1) Screen printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.12MPa, the printing speed is 8cm/s, and the printing interval is 0.4mm;
(2) And (3) standing the perovskite wet film after screen printing for 1 minute for leveling, wherein the vacuum annealing condition is 100 ℃ for 5 minutes.
Preferably, the hole transport layer spin-deposited in the step (6) is a Spiro-ome; the method comprises the following specific steps:
(1) 85.8mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene;
(2) 520mg of lithium bistrifluoromethyl-sulf-fonamide are dissolved in 1mL of acetonitrile solution.
(3) Adding 39.0 μl of TBP solution to the Spiro-OMeTAD solution;
(4) Adding 23.0 μl to the Spiro-ome solution;
(5) Stirring the mixed solution for 2 hours at normal temperature;
(6) Spin coating conditions were 3000 rpm for 30s.
Preferably, the components of the carbon electrode screen-printed in the step (7) are carbon black, graphite, carbon fiber and ethylcellulose, and the specific steps are as follows:
(1) Screen printing parameters: the mesh number of the screen is 150, the printing pressure is 0.2MPa, the printing speed is 5cm/s, and the printing interval is 0.6mm;
(2) And (3) screen printing a carbon electrode, standing the carbon electrode for 5 minutes, leveling, and annealing at 100 ℃ for 5 minutes.
Preferably, the method comprises the following steps:
step (1), sequentially adding cleaning agent, ultrapure water and ethanol into the full FTO conductive glass, respectively carrying out ultrasonic treatment for 15 minutes, and drying by nitrogen to obtain a clean FTO substrate;
dissolving methyl amine iodide, formamidine iodide and lead iodide in a methylamine acetate solvent to prepare MAPbI 3 perovskite precursor solution, and heating and stirring at 60 ℃ for dissolving for 6 hours, wherein the concentration is 400mg/mL;
Step (3) 85.8mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene; 520mg of lithium bistrifluoromethyl-sulf-fonamide is dissolved in 1mL of acetonitrile solution; 39. Mu.L of TBP solution was added to the Spiro-OMeTAD solution, and 23. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution;
Stirring the mixed solution for 2 hours at normal temperature; spin coating conditions were 3000 rpm for 30 seconds;
Step (4) taking 3g of titanium oxide nanocrystals, dispersing the titanium oxide nanocrystals in 30mL of ethanol, then respectively adding 8.0g of ethanol dispersion liquid with the mass ratio of ethyl cellulose of 30% and 7.0g of turpentine through alcohol, fully swinging and stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary evaporation to obtain titanium oxide nanocrystal printing slurry with the solid content of 10%;
Step (5), treating the FTO substrate cleaned in the step (1) with ultraviolet and ozone for 10 minutes;
And (6) diluting the nanocrystalline titanium oxide printing raw slurry synthesized in the step (4) to 3% of solid content by terpineol, uniformly dispersing by using a stirring deaeration machine, printing on the FTO substrate treated in the step (5) by using a screen printing process, standing for 30 minutes, leveling, annealing for 30 minutes at 150 ℃, and printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.1MPa, the printing speed is 10cm/s, and the printing interval is 0.5mm;
placing the FTO conductive base printed with the electron transport layer and annealed in the step (6) on a printing table of a screen printer, standing for 1 minute, leveling, and then vacuum annealing for 5 minutes at 100 ℃ to obtain perovskite wet films through screen printing, wherein the printing parameters are as follows: the mesh number of the screen is 400 meshes, the printing pressure is 0.12MPa, the printing speed is 8cm/s, and the printing interval is 0.4mm;
step (8), spin-coating the hole transport material in the step (3) on the perovskite film after annealing in the step (7), spin-coating the Spiro-OMeTAD for 30 seconds by adopting 3000 spin-coating to form a hole transport layer;
Step (9), adding 8.0g of graphite flakes, 2.5g of carbon fibers, 3.0g of carbon black and 1.5g of ethyl cellulose into a plastic pot, uniformly mixing, and then putting the mixture into a 100 ℃ oven for drying treatment for 1h; after cooling, 15g of ZrO 2 ball-milling beads and 23g of water-removing turpentine permeant are added. Mixing in a defoaming mixer for 10min, defoaming for 20min, and stirring and defoaming for at least 3 times to obtain completely prepared carbon slurry;
And (10) carrying out screen printing, standing and leveling on the carbon slurry in the step (9) on the hole transport layer for 5 minutes, and then annealing at 100 ℃ for 5 minutes, wherein the whole device is prepared, and printing parameters are as follows: the screen mesh number is 150, the printing pressure is 0.2MPa, the printing speed is 5cm/s, and the printing interval is 0.6mm.
In order to solve the technical problem of the invention, another technical proposal is that: the low-temperature titanium oxide prepared by the method is high-efficiency and stable in carbon electrode perovskite solar cell.
In order to solve the technical problem of the invention, another technical proposal is that: the low-temperature titanium oxide and the high-efficiency stable carbon electrode perovskite solar cell are applied to the field of photoelectricity.
The invention has the beneficial effects that:
(1) The invention develops the titanium oxide nanocrystalline printing slurry, and can obtain the high-quality titanium oxide film through a screen printing process and low-temperature annealing, thereby avoiding the defect that the traditional titanium oxide needs to be treated at a high temperature of 500 ℃, and reducing the preparation difficulty of an electron transport layer;
(2) All the functional layers (except the hole transport layer) of the invention are prepared in the air by using a screen printing process, so that the preparation efficiency of the device is improved, the carbon electrode is used for replacing the metal electrode, the preparation cost of the device is reduced, the photoelectric performance of the large-area device is excellent, and the commercialization prospect is wide.
(3) The invention adopts screen printing low-temperature titanium oxide as an electron transport layer, and the optimal concrete method comprises the following steps: 3g of titanium oxide nanocrystalline is taken and dispersed in 30mL of ethanol, then 8.0g of ethanol dispersion liquid with the mass ratio of ethyl cellulose of 30% and 7.0g of turpentine through alcohol are respectively added, after full swing stirring, the mixture is dispersed by an ultrasonic crushing machine, and the titanium oxide nanocrystalline printing slurry with the solid content of 10% is obtained after decompression rotary evaporation; diluting the synthesized nanocrystalline titanium oxide printing raw slurry to 3% of solid content by terpineol, uniformly dispersing by using a stirring deaeration machine, printing on a processed FTO substrate by using a screen printing process, standing for 30 minutes, leveling, annealing for 30 minutes at 150 ℃, and printing parameters: the screen mesh number is 400 mesh, the printing pressure is 0.1MPa, the printing speed is 10cm/s, and the printing interval is 0.5mm. The titanium oxide used as an electron transport layer in the traditional method needs to be calcined at a high temperature of 500 ℃, and the titanium oxide film with high quality can be obtained only by annealing at 150 ℃. As is clear from comparative examples 1-2, the wet film of titanium oxide was left to stand for 30 minutes and was annealed at 150℃for 30 minutes as an optimal parameter.
Drawings
FIG. 1 is a cross-sectional view of a perovskite device of the present invention;
FIG. 2 is a J-V plot of a perovskite solar cell of the invention prepared based on screen printing low temperature titanium oxide;
FIG. 3 is a J-V plot of a large area (1 cm 2) perovskite solar cell prepared based on screen printed low temperature titanium oxide according to the invention;
FIG. 4 is a schematic structural view of a perovskite device of the present invention;
Detailed Description
Example 1
Step 1), sequentially adding cleaning agent, ultrapure water and ethanol into the full FTO conductive glass, respectively carrying out ultrasonic treatment for 15 minutes, and drying by nitrogen to obtain a clean FTO substrate;
Step 2) dissolving 102.6mg of methyl amine iodide and 297.4mg of lead iodide in a methylamine acetate solvent to prepare a new MAPbI 3 perovskite precursor solution, and heating, stirring and dissolving at 60 ℃ for 6 hours, wherein the concentration is 400mg/mL;
Step 3) 85.8mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene; 520mg of lithium bistrifluoromethyl-sulf-fonamide is dissolved in 1mL of acetonitrile solution; 39. Mu.L of TBP solution was added to the Spiro-OMeTAD solution, and 23. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution;
Stirring the mixed solution for 2 hours at normal temperature; spin coating conditions were 3000 rpm for 30 seconds;
Step 4) taking 3g of titanium oxide nanocrystalline, dispersing in 30mL of ethanol, and then respectively adding 8.0g of ethanol dispersion liquid with ethyl cellulose accounting for 30% and 7.0g of turpentine permeant. After full swing stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary steaming to obtain titanium oxide nanocrystalline printing slurry with the solid content of 10%;
Step 5) ultraviolet ozone treatment is carried out on the FTO substrate cleaned in the step 1) for 10 minutes.
And 6) diluting the nanocrystalline titanium oxide printing raw slurry synthesized in the step 4) to 3% of solid content by terpineol, uniformly dispersing by using a stirring deaeration machine, printing on the FTO substrate treated in the step 4) by using a screen printing process, standing for 30 minutes, leveling, annealing for 30 minutes at 150 ℃, and printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.1MPa, the printing speed is 10cm/s, and the printing interval is 0.5mm;
Step 7) placing the FTO conductive base printed with the electron transport layer and annealed in the step 6) on a printing table of a screen printer, standing for 1 minute, leveling, and then vacuum annealing at 100 ℃ for 5 minutes, wherein printing parameters are as follows: the mesh number of the screen is 400 meshes, the printing pressure is 0.12MPa, the printing speed is 8cm/s, and the printing interval is 0.4mm;
Step 8) spin-coating the hole transport material in the step 3) on the perovskite film after annealing in the step 7), and spin-coating the Spiro-OMeTAD for 30 seconds by adopting 3000 spin-coating to form a hole transport layer;
Step 9) adding 8.0g of graphite flake, 2.5g of carbon fiber, 3.0g of carbon black and 1.5g of ethyl cellulose into a plastic pot, uniformly mixing, and then putting the mixture into a 100 ℃ oven for drying for 1h. After cooling, 15g of ZrO 2 ball-milling beads and 23g of water-removing turpentine permeant are added. Mixing in a defoaming mixer for 10min, defoaming for 20min, and stirring and defoaming for at least 3 times to obtain completely prepared carbon slurry;
Step 10) carrying out screen printing and standing on the carbon slurry in the step 9) on the hole transport layer for 5 minutes, and then carrying out annealing at 100 ℃ for 5 minutes after leveling, wherein the whole device is prepared, and printing parameters are as follows: the mesh number of the screen is 150, the printing pressure is 0.2MPa, the printing speed is 5cm/s, and the printing interval is 0.6mm;
Step 11) under standard test conditions (AM 1.5G illumination), the energy conversion efficiency of the optimal battery device prepared in this example is 17.19% respectively as shown in fig. 2, the open circuit voltage is 1.07V, the short circuit current is 21.32mA/cm 2, the filling factor is 75.29%, and the effective area of the device is 0.05cm 2. As shown in fig. 3, the device efficiency was 16.07% with an effective area of 1cm 2.
Comparative example 1
The wet titanium oxide films were annealed at 100, 110, 120, 130, 140℃and 160℃for 30 minutes, respectively, and other experimental procedures were the same as in example 1, and Table 1 shows the parameters of the photoelectric properties of the perovskite solar cell under the corresponding conditions. When the annealing temperature is too low, terpineol is not completely removed, the quality of the titanium oxide film is poor, and the photoelectric performance of the device is not good; when the annealing temperature is too high, terpineol evaporates too fast, which affects the growth of the titanium oxide film and is also detrimental to the photoelectric performance of the device.
TABLE 1
Comparative example 2
The mesh numbers adopted in the printing of the titanium oxide are 150 mesh, 250325 mesh and 500 mesh respectively, other experimental steps are the same as those of the example 1, and table 2 shows the photoelectric performance parameters of the perovskite solar cell under corresponding conditions. When the mesh number of the screen is low, the blanking amount is large, and the thickness of the titanium oxide is too thick, so that the transmission of charges is influenced, and the photoelectric performance of the device is further reduced; when the mesh number is too high, the blanking amount is smaller, the titanium oxide film is not continuous and compact enough, the charge extraction and transmission are affected, and the photoelectric performance of the device is reduced.
TABLE 2
The invention is not limited to the specific technical scheme described in the above embodiments, and all technical schemes formed by adopting equivalent substitution are the protection scope of the invention.
Claims (10)
1. A method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing is characterized by comprising the following steps:
(1) Preparing titanium oxide nanocrystalline printing slurry, namely dispersing anatase titanium oxide nanocrystalline in ethanol, then respectively adding ethylcellulose and turpentine through alcohol, fully swinging and stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary evaporation to obtain the titanium oxide nanocrystalline printing slurry;
(2) Adding graphite flakes, carbon fibers, carbon black and ethylcellulose into a plastic pot, uniformly mixing, putting the mixture into an oven for drying treatment, cooling, adding zirconia ball milling beads and turpentine through alcohol, putting the mixture into a defoaming mixer for mixing and defoaming, and then stirring and defoaming repeatedly for a plurality of times to obtain a carbon slurry completely prepared;
(3) Dissolving methyl amine iodide and lead iodide in methylamine acetate solvent to prepare MAPbI 3 perovskite precursor solution, heating and stirring at 60 ℃ for dissolving for 6-12 hours;
(4) Screen printing low-temperature titanium oxide as an electron transport layer on the cleaned and ozonated FTO transparent conductive glass sheet; diluting the nanocrystalline titanium oxide printing slurry synthesized in the step (1) with terpineol, uniformly dispersing the slurry by using a stirring deaeration machine, printing the slurry on a treated FTO substrate by using a screen printing process, standing and leveling a titanium oxide wet film, and then annealing for 30 minutes at 150 ℃;
(5) Screen printing the prepared MAPbI 3 perovskite precursor solution on an FTO conductive substrate with an electron transport layer in air with the relative humidity of 20% -80%, and carrying out vacuum annealing at 100 ℃ for 5 minutes to obtain a flat and compact perovskite film;
(6) Spin-coating a hole transport layer Spiro-OMeTAD on the perovskite layer;
(7) And (3) screen printing the carbon paste in the step (2) on the hole transport layer to prepare a carbon electrode.
2. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of:
The preparation of the titanium oxide nanocrystalline printing slurry in the step (1) comprises the steps of dispersing 3g of titanium oxide nanocrystalline in 30mL of ethanol, then respectively adding 8.0g of ethanol dispersion liquid with the mass ratio of ethyl cellulose of 30% and 7.0g of turpentine through alcohol, fully swinging and stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary steaming to obtain the titanium oxide nanocrystalline printing slurry with the solid content of 10%;
And (2) adding 8.0g of graphite flakes, 2.5g of carbon fibers, 3.0g of carbon black and 1.5g of ethyl cellulose into a plastic pot, uniformly mixing, putting the mixture into a 100 ℃ oven for drying treatment for 1h, cooling, adding 15g of ZrO 2 ball-milling beads, 23g of water-removed turpentine through alcohol, putting the mixture into a defoaming mixer for mixing for 10min, defoaming for 20min, and stirring and defoaming for at least 3 times to obtain the complete carbon slurry.
3. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of: the concentration of the MAPbI 3 perovskite precursor solution in the step (1) is 100-800mg/mL.
4. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of: the electron transport layer on the transparent conductive FTO glass in the step (4) is titanium oxide, and the specific steps are as follows:
(1) Screen printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.1MPa, the printing speed is 10cm/s, and the printing interval is 0.5mm;
(2) After the screen printing is finished, the titanium oxide wet film is horizontally kept stand for 30 minutes for leveling, and then is annealed at 150 ℃ for 30 minutes.
5. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of: the film preparation in the step (5) adopts a screen printing and vacuum annealing mode in air with the relative humidity of 20% -80%, and the specific steps are as follows:
(1) Screen printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.12MPa, the printing speed is 8cm/s, and the printing interval is 0.4mm;
(2) And (3) standing the perovskite wet film after screen printing for 1 minute for leveling, wherein the vacuum annealing condition is 100 ℃ for 5 minutes.
6. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of: the hole transport layer deposited by spin coating in the step (6) is Spiro-OMeTAD; the method comprises the following specific steps:
(1) 85.8mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene;
(2) 520mg of lithium bistrifluoromethyl-sulf-fonamide are dissolved in 1mL of acetonitrile solution.
(3) Adding 39.0 μl of TBP solution to the Spiro-OMeTAD solution;
(4) Adding 23.0 μl to the Spiro-ome solution;
(5) Stirring the mixed solution for 2 hours at normal temperature;
(6) Spin coating conditions were 3000 rpm for 30s.
7. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of: the screen-printed carbon electrode in the step (7) comprises carbon black, graphite, carbon fiber and ethylcellulose, and the specific steps are as follows:
(1) Screen printing parameters: the mesh number of the screen is 150, the printing pressure is 0.2MPa, the printing speed is 5cm/s, and the printing interval is 0.6mm;
(2) And (3) screen printing a carbon electrode, standing the carbon electrode for 5 minutes, leveling, and annealing at 100 ℃ for 5 minutes.
8. The method for preparing low-temperature titanium oxide and high-efficiency stable carbon electrode perovskite solar cell by screen printing according to claim 1, wherein the method comprises the following steps of: the method comprises the following steps:
step (1), sequentially adding cleaning agent, ultrapure water and ethanol into the full FTO conductive glass, respectively carrying out ultrasonic treatment for 15 minutes, and drying by nitrogen to obtain a clean FTO substrate;
dissolving methyl amine iodide, formamidine iodide and lead iodide in a methylamine acetate solvent to prepare MAPbI 3 perovskite precursor solution, and heating and stirring at 60 ℃ for dissolving for 6 hours, wherein the concentration is 400mg/mL;
Step (3) 85.8mg of Spiro-OMeTAD was dissolved in 1mL of chlorobenzene; 520mg of lithium bistrifluoromethyl-sulf-fonamide is dissolved in 1mL of acetonitrile solution; 39. Mu.L of TBP solution was added to the Spiro-OMeTAD solution, and 23. Mu.L of lithium salt solution was added to the Spiro-OMeTAD solution;
Stirring the mixed solution for 2 hours at normal temperature; spin coating conditions were 3000 rpm for 30 seconds;
Step (4) taking 3g of titanium oxide nanocrystals, dispersing the titanium oxide nanocrystals in 30mL of ethanol, then respectively adding 8.0g of ethanol dispersion liquid with the mass ratio of ethyl cellulose of 30% and 7.0g of turpentine through alcohol, fully swinging and stirring, dispersing by using an ultrasonic crushing machine, and performing reduced pressure rotary evaporation to obtain titanium oxide nanocrystal printing slurry with the solid content of 10%;
Step (5), treating the FTO substrate cleaned in the step (1) with ultraviolet and ozone for 10 minutes;
And (6) diluting the nanocrystalline titanium oxide printing raw slurry synthesized in the step (4) to 3% of solid content by terpineol, uniformly dispersing by using a stirring deaeration machine, printing on the FTO substrate treated in the step (5) by using a screen printing process, standing for 30 minutes, leveling, annealing for 30 minutes at 150 ℃, and printing parameters: the mesh number of the screen is 400 meshes, the printing pressure is 0.1MPa, the printing speed is 10cm/s, and the printing interval is 0.5mm;
placing the FTO conductive base printed with the electron transport layer and annealed in the step (6) on a printing table of a screen printer, standing for 1 minute, leveling, and then vacuum annealing for 5 minutes at 100 ℃ to obtain perovskite wet films through screen printing, wherein the printing parameters are as follows: the mesh number of the screen is 400 meshes, the printing pressure is 0.12MPa, the printing speed is 8cm/s, and the printing interval is 0.4mm;
step (8), spin-coating the hole transport material in the step (3) on the perovskite film after annealing in the step (7), spin-coating the Spiro-OMeTAD for 30 seconds by adopting 3000 spin-coating to form a hole transport layer;
Step (9), adding 8.0g of graphite flakes, 2.5g of carbon fibers, 3.0g of carbon black and 1.5g of ethyl cellulose into a plastic pot, uniformly mixing, and then putting the mixture into a 100 ℃ oven for drying treatment for 1h; after cooling, 15g of ZrO 2 ball-milling beads and 23g of water-removing turpentine permeant are added. Mixing in a defoaming mixer for 10min, defoaming for 20min, and stirring and defoaming for at least 3 times to obtain completely prepared carbon slurry;
And (10) carrying out screen printing, standing and leveling on the carbon slurry in the step (9) on the hole transport layer for 5 minutes, and then annealing at 100 ℃ for 5 minutes, wherein the whole device is prepared, and printing parameters are as follows: the screen mesh number is 150, the printing pressure is 0.2MPa, the printing speed is 5cm/s, and the printing interval is 0.6mm.
9. A low temperature titania and highly efficient stable carbon electrode perovskite solar cell prepared according to the method of any one of claims 1-8.
10. The use of low temperature titania and highly stable carbon electrode perovskite solar cells according to claim 9 in the photovoltaic field.
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