CN115835660A

CN115835660A - Back electrode material, preparation method and high-performance perovskite solar cell

Info

Publication number: CN115835660A
Application number: CN202211458256.8A
Authority: CN
Inventors: 武文俊; 黄锦海
Original assignee: Shanghai Huinasi Optoelectronic Technology Co ltd
Current assignee: Shanghai Huinasi Optoelectronic Technology Co ltd
Priority date: 2022-11-21
Filing date: 2022-11-21
Publication date: 2023-03-21

Abstract

The invention relates to a back electrode material suitable for a high-performance perovskite solar cell and a preparation method thereof, wherein the back electrode material is based on improvement

The micro-spherical phenolic resin porous carbon material is prepared by taking phenolic resin as a carbon precursor, tetraethyl orthosilicate as a hard mask and cetyl trimethyl ammonium bromide as a structure directing agent and adopting a co-assembly engineering method. The phenolic resin porous carbon material has uniform appearance, high specific surface area and graphitization degree, and can improve the printable mesoscopic perovskite solar cell deviceThe perovskite solar cell has the advantages of charge transfer performance and photoelectric conversion efficiency, simple preparation method, and extremely low preparation cost compared with a metal electrode, and can effectively reduce the cost of the perovskite solar cell.

Description

Back electrode material, preparation method and high-performance perovskite solar cell

Technical Field

The invention belongs to the technical field of solar cells, and particularly relates to a back electrode material and a preparation method thereof, and further relates to a printable mesoscopic perovskite solar cell prepared by applying the back electrode material and a preparation method thereof.

Background

Calcium halideTitanium ore solar cells (PSCs) have attracted worldwide attention due to their advantages of high efficiency and low cost, and are known as the most potential next-generation solar cells. Single junction perovskite solar cells have now improved Photoelectric Conversion Efficiency (PCE) from 3.8% In 2009 to 25.7% In 2022 [ m.kim, j.jeong, h.lu, k.lee Tae, t.eickemeyer Felix, y.liu, w.choi In, j.choi Seung, y.jo, h.b.kim, s.i.mo, y.k.kim, h.lee, g.an Na, s.cho, r.tres wolfgarg, m.zakeruddin Shaik, a.hagfeldt, y.kim Jin, M.

S.Kim Dong,Science2022,375,302]. Conventionally, conventional high-efficiency PSCs generally rely on expensive fabrication materials, such as gold or silver and organic Hole Transport Materials (HTM) such as (N, N-di-p-methoxyphenylamine) -9,90-spirobifluorene (spiro-OMeTAD). Therefore, the commercialization is achieved, and the first task is to reduce the material and process preparation cost of the PSCs. Among many perovskite devices, HTM-free printable mesoscopic PSCs (p-MPSCs) are of great interest because of their simple fabrication process, low cost, and ultra-high stability. Among them, carbon electrode-based non-HTM perovskite solar cells (p-MPSCs) are attracting attention. However, the photoelectric conversion efficiency of the existing p-MPSCs cells still lags behind the conventional halide perovskite solar cells. Accordingly, it is highly desirable to develop superior carbon materials having properties at least comparable to those of conventional PSCs.

Disclosure of Invention

The invention adopts phenolic resin as a carbon precursor, tetraethyl orthosilicate (TEOS) as a hard mask and Cetyl Trimethyl Ammonium Bromide (CTAB) as a structure guiding agent, and is based on the improvement

The strategy adopts a co-assembly engineering method to prepare a microspheric phenolic resin porous carbon material (PFc). The particle size of the phenolic resin porous carbon material is 0.07-1.2 mu m, and the phenolic resin porous carbon material has a unique lemon-like porous structure appearance and high graphitization degree. The printable mesoscopic perovskite solar cell assembled by the phenolic resin porous carbon material provided by the invention has excellent photoelectricityThe chemical property, especially the open circuit voltage can reach 1.03V at most. The feasibility of the mesoporous perovskite solar cell back electrode as a back electrode for preparing high-performance perovskite solar cells applied to the field of printable non-Hole Transport Materials (HTM) mesoscopic perovskite solar cells PSCs (p-MPSCs) is proved. Experimental results show that the phenolic resin porous carbon material provided by the invention is easy to prepare, has lower cost than metal electrodes, and can effectively reduce the cost of perovskite solar cells.

The preparation method comprises the following steps:

1) Adding a certain amount of aminophenol, formaldehyde, cetyl Trimethyl Ammonium Bromide (CTAB), tetraethyl orthosilicate (TEOS) and a solvent into a reaction vessel in a certain sequence at a certain temperature, stirring for a period of time at a certain temperature, and then putting the mixture into a reaction kettle to react for a period of time at a certain temperature;

2) After the reaction is finished, removing the solvent by using reduced pressure suction filtration, then placing the solid intermediate in an oven to be dried at a certain temperature to obtain brown solid powder, then placing the brown solid powder in a tubular furnace to be carbonized at a certain temperature;

3) And after carbonization, washing the solid product with a certain amount of sodium hydroxide solution with certain solubility, then washing with water until the filtrate is neutral, and drying the solid product to obtain the phenolic resin porous carbon material.

The certain temperature in the step 1) is 15-60 ℃; the certain sequence is that the solvent is put firstly, then CTAB and aminophenol are put in, then ammonia water is added, formaldehyde is added, and finally TEOS is added; the mass ratio of aminophenol to CTAB is preferably 1: (2-6); the mass ratio of the ammonia water to the CTAB is 1 (2-6); the mass ratio of formaldehyde to CTAB is preferably 1: (2-6); the mass ratio of TEOS to CTAB is preferably 1: (1-5); the solvent used is a mixed solvent of alcohols (methanol, ethanol, butanol, etc.) and water, and the mass ratio of the alcohols to the water in the mixed solvent is not limited.

The reaction temperature of the hydrothermal reaction in the step 1) is 15-100 ℃.

The temperature of the oven used for drying the solid intermediate in the step 2) is 30-100 ℃, and the time is 10-60 minutes; the carbonization reaction is carried out in a tubular furnace, and the temperature of the tubular furnace is 500-1200 ℃.

The concentration of the sodium hydroxide used in the step 3) is 0.5-3M; the dosage is 10-30 mL.

The invention has the beneficial technical effects that: the invention takes phenolic resin as a carbon precursor, tetraethyl orthosilicate (TEOS) as a hard mask and Cetyl Trimethyl Ammonium Bromide (CTAB) as a structure guiding agent, and is based on the improvement

The strategy is to prepare the phenolic resin porous carbon material (PFc) by adopting a co-assembly engineering method. By controlling the alcohol/water ratio and the calcining temperature, the novel PFc carbon material with uniform appearance, high graphitization degree and large specific surface area is obtained. And applied to printable HTM-free mesoscopic PSCs (p-MPSCs). Due to the high specific surface area, the contact property of the perovskite and the carbon material is improved, and the charge transmission performance of the device is improved together with the high graphitization degree. The uniformity of the appearance reduces the defect state density of the electrode, and the photoelectric conversion efficiency can reach 17.73 percent. Especially, the open circuit voltage can reach 1.03V without any passivation treatment. The fill factor is also close to 80%. In addition, the target matter of the phenolic resin porous carbon microsphere is controllable in particle size of 0.07-1.2 microns, and good in dispersibility.

Drawings

Fig. 1 is a Scanning Electron Microscope (SEM) photograph of the battery 2.

Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the cell 3.

Fig. 3 is a Scanning Electron Microscope (SEM) photograph of the battery 4.

Fig. 4 is a Scanning Electron Microscope (SEM) photograph of the battery 5.

Fig. 5 is a schematic view of a mesoscopic perovskite solar cell.

FIG. 6 is an I-V curve of a solar cell 16 having a carbon electrode made of phenolic resin porous carbon microspheres, in which the open-circuit voltage (unit/V) is plotted on the abscissa and the short-circuit current density (unit/mA.cm) is plotted on the ordinate ^-3 )。

Detailed Description

The invention provides a preparation method of phenolic resin porous carbon microspheres and application of the phenolic resin porous carbon microspheres in preparation of carbon electrodes of perovskite solar cells.

The phenolic resin porous carbon microsphere provided by the invention not only has a good specific surface area, but also can effectively reduce non-radiative recombination. Compared with the existing back electrode, the phenolic resin porous carbon microsphere provided by the invention has the advantages of high graphitization degree, low defect state density, high open circuit voltage and the like.

The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the invention. The examples given do not therefore limit the scope of protection of the invention. In all the following examples, the room temperature is 20 ℃ to 25 ℃ and the raw materials and reagents used are commercially available.

Example 1

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and an aqueous alcohol solution (alcohol/water = 0/7). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 800 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 2

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and an aqueous alcohol solution (alcohol/water = 1/6). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 800 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 3

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and aqueous alcohol (alcohol/water = 3/4). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 800 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 4

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and aqueous alcohol (alcohol/water = 4/3). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 800 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 5

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and aqueous alcohol (alcohol/water = 6/1). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 800 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 6

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and aqueous alcohol (alcohol/water = 7/0). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 800 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 7

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and aqueous alcohol (alcohol/water = 6/1). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent is removed by suction filtration with water, and the mixture is dried in an oven at 70 ℃ for about 20min to obtain tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 900 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Example 8

In a 250mL round bottom flask was added 3.25g CTAB, 1.1g 3-aminophenol and aqueous alcohol (alcohol/water = 6/1). After stirring to clear, 1.54mL of formaldehyde was added and the solution was allowed to become cloudy. Immediately after becoming cloudy, 5.5mL TEOS was added and stirred for 24h. After the reaction, the mixture is put into a hydrothermal kettle and then put into an oven at 80 ℃ for reaction for 24 hours. After the reaction, the solvent was removed by suction filtration with water, and the residue was dried in an oven at 70 ℃ for about 20min to obtain a tan solid powder. And putting the reacted solid into a tubular furnace to react for 3 hours at 1000 ℃. The carbonized solid was put into a 30mL sample bottle, and 30mL of 1M sodium hydroxide solution was added thereto, followed by stirring at 60 ℃ for 24 hours. And after the reaction, water is used for suction filtration to be neutral, and the mixture is added into a 70 ℃ oven to be dried for about 1h, so that the PFc porous carbon material is obtained.

Morphology characterization of carbon Material morphology carbon material morphology was characterized by Field emission Scanning Electron Microscopy (FESEM, hitachi S-4800, japan). The surface morphology difference of the carbon material of the invention is observed by using a field emission scanning electron microscope.

FIG. 1 is an SEM photograph of example 2, FIG. 2 is an SEM photograph of example 3, and FIG. 3 is an SEM photograph of example 4, and shows that FIG. 4 is an SEM photograph of example 5, and shows that a carbon material having a uniform particle size and containing a large number of pores is prepared to give a uniformly dispersed mesoporous material, and a porous carbon structure is capable of promoting downward penetration of a perovskite precursor solution until m-TiO is formed ₂ And ZrO ₂ And reducing internal defects of the device.

Example 9

1. Perovskite solar cell assembly

1) Etching and cleaning of FTO conductive glass

And (2) etching the conductive glass by using zinc powder and hydrochloric acid according to requirements, then washing the FTO conductive glass by using water containing detergent, clear water, acetone and ethanol in sequence, and drying for later use.

2) Preparation of a Titania dense layer

Placing the cleaned conductive surface of the conductive glass on a heating table to preheat to 450 ℃, uniformly spraying the diluted precursor solution of the dense layer (isopropanol solution of diisopropyl di (acetylacetonate) titanate) on the conductive glass by using a spray gun taking carrier gas as air, and preserving heat for 30min at 450 ℃ after the spraying is finished. And naturally cooling to room temperature to obtain the titanium dioxide compact layer.

3) Preparation of mesoporous titanium dioxide layer

And printing the titanium dioxide slurry on the titanium dioxide compact layer by using a screen printer, standing for 60min, and calcining for 1h in a muffle furnace at 500 ℃. Naturally cooling to room temperature, and preparing the titanium dioxide mesoporous layer on the device.

4) Preparation of mesoporous layer of zirconium dioxide and mesoporous layer of carbon

Printing the self-made zirconium dioxide slurry on the titanium dioxide mesoporous layer by using a screen printer, standing for 10min, and drying on a heating table preheated to 70 ℃. Then, the porous carbon material prepared in example 1 was printed on the zirconia mesoporous layer by a screen printer, and after the printing was completed, the conductive glass was transferred to a muffle furnace and calcined at 500 ℃ for 1 hour. Naturally cooling to room temperature, and then dropwise adding a perovskite precursor solution (a N, N-dimethylformamide solution of lead iodide and iodomethylamine with certain concentration) on the device.

5) Filling and growing of perovskites

4.5 microliter of perovskite precursor solution is dripped on the carbon mesoporous layer of the device, after the solution is uniformly diffused, the conductive glass is transferred into a 60 ℃ oven for annealing, and after 2.5 hours, the solvent is completely volatilized.

2. Testing of perovskite solar cell performance

The working area of the cell is 0.0875cm through one hole ² The light intensity was adjusted to 100mW/cm using an AM1.5 solar simulator (model 91160, newport, USA) as the incident light source ² The highest photoelectric conversion efficiency was measured to be 17.73%, and the short-circuit current was 21.54mA cm ^-2 The open circuit voltage was 1.03V and the fill factor was 79.93%. The details are shown in Table 1.

Examples 10 to 16

The perovskite solar cell assembly and testing procedure is the same as example 9, except that the carbon slurry of step 4) is the carbon slurry of example 2-example 8 instead of example 1, respectively. The device performance parameters of the obtained devices are shown in table 1.

TABLE 1 Performance data of the devices

Battery with a battery cell	Carbon layer	Efficiency (%)	Short-circuit current (mA cm) ^-2 )	Open circuit voltage (V)	Filling factor (%)
						Battery 9	Example 1	16.58	23.15	0.93	77.00
Battery 10	Example 2	17.55	24.24	0.95	76.21
						Battery 11	Example 3	15.16	21.60	0.96	73.15
Battery 12	Example 4	17.63	23.19	0.97	78.40
						Battery 13	Example 5	17.58	24.79	1.01	70.22
Battery 14	Example 6	16.78	22.19	0.99	76.38
						Battery 15	Example 7	15.86	21.72	0.98	74.55
Battery 16	Example 8	17.73	21.54	1.03	79.93

As shown in Table 1 and FIG. 6, the test results show that the photoelectric conversion efficiency of the phenolic resin porous carbon material (PFc) provided by the invention is 15-18%, and the short-circuit current is 20.72-23.50 mAcm ^-2 The open circuit voltage is 0.890-1.030V, the filling factor is 0.59-0.80, and the photoelectric conversion performance is excellent. Change in alcohol/Water ratio in conjunction with SEM pictures (FIGS. 1-4)The morphology of the carbon material can be obviously influenced, so that the distribution condition of the perovskite precursor solution in the battery and the infiltration performance of the carbon material on the perovskite precursor are influenced, and the uniformity of the morphology is good. The compactness of the perovskite lead to the reduction of the filling amount of the perovskite to a certain extent, so that the short-circuit current density is reduced to 21.54mAcm ^-2 The uniformity of the topographies reduces the defect state density, resulting in open circuit voltages up to 1.03V, and photoelectric conversion efficiencies up to 17.73% under the experimental conditions described in the examples of the present invention.

Claims

1. A back electrode material suitable for high-performance perovskite solar cells is characterized in that phenolic resin is used as a carbon precursor, tetraethyl orthosilicate is used as a hard mask, cetyl trimethyl ammonium bromide is used as a structure directing agent, and the back electrode material is based on improvement

The strategy is that the microspherical phenolic resin porous carbon material with the grain size of 0.07-1.2 mu m is prepared by adopting a co-assembly engineering method.

2. A method of preparing a back electrode material as claimed in claim 1, comprising the steps of:

1) Adding a proper amount of cetyl trimethyl ammonium bromide and aminophenol into a low-carbon alcohol solvent, stirring until the solution is clear, adding a certain amount of formaldehyde, immediately adding a certain amount of tetraethyl orthosilicate after the solution becomes turbid, reacting for a period of time under the stirring condition, and then carrying out hydrothermal reaction for a period of time at a certain temperature;

2) After the reaction is finished, separating the solid intermediate from the liquid product, drying the solid intermediate, and then carbonizing the dried solid intermediate at a certain temperature;

3) And after carbonization, washing the obtained solid product with an appropriate amount of sodium hydroxide solution with a certain concentration in an alkali manner, then washing the solid product with water until the filtrate is neutral, and drying the solid product to obtain the phenolic resin porous carbon material.

3. The method for preparing the back electrode material according to claim 2, wherein the mass ratio of the aminophenol to the cetyltrimethylammonium bromide is 1: 2-6; the addition amount of the formaldehyde is the same as the mass of the aminophenol; the addition amount of the tetraethyl orthosilicate is the mass ratio of the tetraethyl orthosilicate to the hexadecyl trimethyl ammonium bromide of 1 to (1-5).

4. The method for preparing a back electrode material according to claim 2, wherein the lower alcohol solvent is an aqueous methanol solution, an aqueous ethanol solution or an aqueous butanol solution at any ratio.

5. The method for preparing a back electrode material according to claim 2, wherein the reaction temperature of the hydrothermal reaction is 60 to 100 ℃.

6. The method of claim 2, wherein the carbonizing is performed in a tube furnace at 500 to 1200 ℃.

7. The method of claim 2, wherein the concentration of the sodium hydroxide solution is 0.5 to 3M.

8. A high performance perovskite solar cell wherein the back electrode is a carbon electrode, characterized in that said carbon electrode is prepared using the back electrode material of claim 1.

9. The method of fabricating the perovskite solar cell as claimed in claim 8, comprising the steps of:

1) Etching and cleaning the conductive glass: etching the conductive glass by using zinc powder and hydrochloric acid, then cleaning and blow-drying for later use;

2) Spraying a titanium dioxide compact layer: placing the cleaned conductive surface of the conductive glass on a heating table in an upward mode, preheating to 450 ℃, uniformly spraying a precursor solution of the dense layer on the conductive surface of the conductive glass, preserving heat for a period of time at 450 ℃ after spraying is finished, and naturally cooling to room temperature;

3) Printing a titanium dioxide mesoporous layer: printing titanium dioxide slurry on a titanium dioxide compact layer, standing for a period of time, transferring the titanium dioxide slurry to high-temperature equipment, calcining for a period of time at 500 ℃, and naturally cooling to room temperature;

4) Printing a zirconium dioxide mesoporous layer: printing the zirconium dioxide slurry on a titanium dioxide mesoporous layer, standing for a period of time, drying on a heating table, and naturally cooling to room temperature;

5) Printing a carbon mesoporous layer: printing a proper amount of the phenolic resin porous carbon material of claim 1 on a zirconium dioxide mesoporous layer, transferring the printed material to high-temperature equipment, calcining the material at 500 ℃ for a period of time, and naturally cooling the calcined material to room temperature;

6) Filling and growing of perovskite: dropwise adding a certain amount of perovskite precursor solution to the surface of the uppermost carbon mesoporous layer of the conductive glass, and after the solution is uniformly diffused, annealing at 60 ℃ until the solvent is completely volatilized to obtain the printable mesoscopic perovskite solar cell.