CN111697140A

CN111697140A - Preparation method of carbon electrode perovskite solar cell

Info

Publication number: CN111697140A
Application number: CN201911426815.5A
Authority: CN
Inventors: 王九鑫; 梁飞燕; 李秋霞
Original assignee: Xi'an Jiutian Incubator Technology Co ltd
Current assignee: Xi'an Jiutian Incubator Technology Co ltd
Priority date: 2019-12-30
Filing date: 2019-12-30
Publication date: 2020-09-22

Abstract

The invention discloses a preparation method of a carbon electrode perovskite solar cell, and belongs to the technical field of solar cells. The method comprises the following steps: step (1), FTO substrate treatment: carrying out ultrasonic cleaning and drying on the FTO substrate, and then attaching a high-temperature adhesive tape to the treated FTO substrate; step (2), solvent preparation: SnCl with the concentration of 0.1mol/mL is prepared by using tin dichloride solid and absolute ethyl alcohol₂·2H₂O solution; PbI with a concentration of 691.25mg/mol was formulated from N, N-dimethylformamide, dimethyl sulfoxide and lead iodide powder₂A solution; preparing an organic ionic solution by formamidine hydroiodide, methyl amine chloride, methyl amine bromide and isopropanol; by graphite, carbon black, ZrO₂A hydroxyl groupAnd (3) preparing carbon slurry by using propyl cellulose and terpineol. The solar cell prepared by the invention has the structure of FTO substrate/SnO₂The carbon thin film layer has a good blocking effect on water molecules in the air as the top electrode, so that the carbon electrode perovskite solar cell has higher moisture resistance.

Description

Preparation method of carbon electrode perovskite solar cell

Technical Field

The invention relates to the technical field of solar cells, in particular to a preparation method of a carbon electrode perovskite solar cell.

Background

Along with the development of human society, the demand of human beings for energy is increasing, and the most used fossil energy at present belongs to non-renewable energy, so that the fossil energy available on the earth is remained a few times. Meanwhile, since the large use of fossil energy has caused extremely serious environmental problems such as serious atmospheric pollution, global warming, etc., which have raised a significant challenge to the survival of all the living things on the earth.

Solar energy, as a green, clean and renewable energy source, has the advantages of abundant reserves, easy acquisition, low cost and the like, so that the solar energy becomes an excellent alternative energy source. The solar cell is a carrier for directly converting light energy into electric energy, scientists make many advances from the earliest research of silicon cells and use the advances in the space field, but due to the bottleneck of the current development of the silicon cells, the defects of energy consumption of cell preparation, serious environmental pollution of byproducts and the like cannot be solved in time to limit the development of the industry. Therefore, scientists have searched for alternative materials and new structures, and the development time of solar cells developed based on dye-sensitized cells is as short as ten years, but the development speed is very fast. The photoelectric conversion efficiency of the solar cell is 24.2% due to continuous optimization of various aspects of performance and continuous improvement of efficiency in a short time, but the moisture resistance of the solar cell is not good enough.

Disclosure of Invention

In order to enable the solar cell to have better moisture resistance, the embodiment of the invention provides a preparation method of a carbon electrode perovskite solar cell. The method comprises the following steps:

step (1), FTO substrate treatment: carrying out ultrasonic cleaning and drying on the FTO substrate, and then attaching a high-temperature adhesive tape to the treated FTO substrate;

step (2), solvent preparation: SnCl with the concentration of 0.1mol/mL is prepared by using tin dichloride solid and absolute ethyl alcohol₂·2H₂O solution; PbI with a concentration of 691.25mg/mol was formulated from N, N-dimethylformamide, dimethyl sulfoxide and lead iodide powder₂A solution; by passingPreparing organic ionic solution from formamidine hydroiodide, methyl amine chloride, methyl amine bromide and isopropanol; by graphite, carbon black, ZrO₂Preparing carbon slurry from hydroxypropyl cellulose and terpineol;

step (3), preparing a carbon electrode perovskite solar cell by the prepared solvent: putting the treated FTO substrate into a preheated ultraviolet ozone processor for treatment for 20min, and spin-coating the SnCl after treatment₂·2H₂Preparation of SnO from O solution₂A thin film layer; then the SnO is put₂Treating the film layer in an ultraviolet ozone machine for 20min to remove surface groups and increase the surface wettability, and spin-coating the PbI after treatment₂Preparing a perovskite layer from the solution and the organic ion solution; blade-coating the carbon slurry on the perovskite layer to obtain a carbon thin film layer, and finally annealing to obtain the carbon electrode perovskite solar cell;

further, the PbI in the step (2)₂The preparation method of the solution comprises the following steps: weighing 691.25mg of lead iodide powder in a No. 1 glass bottle by using an analytical balance, respectively taking 0.9mL of N, N-dimethylformamide and 0.1mL of dimethyl sulfoxide by using a liquid transfer gun according to the volume ratio of 9: 1, injecting the obtained mixture into the No. 1 glass bottle, putting magnetons into the glass bottle, screwing the bottle cap, sticking a label, stirring the obtained product for 1d at 70-85 ℃ on a magnetic rotary heating table, filtering the obtained product by using a 0.22 mu m organic filter tip, and heating the obtained product at 80 ℃ to obtain the PbI₂And (3) solution.

Further, the preparation method of the organic ion solution in the step (2) comprises the following steps: respectively taking 90mg of formamidine hydroiodide with the concentration of 90mg/ml, 6.39mg of methyl ammonium chloride with the concentration of 6.39mg/ml and 9mg of methyl ammonium bromide with the concentration of 9mg/ml in a No. 2 glass bottle by using an analytical balance, then taking the isopropanol in the No. 2 glass bottle by using a liquid transfer gun, putting magnetons in the glass bottle, stirring the glass bottle for one day in a magnetic rotary heating table at normal temperature, and filtering the solution to obtain the organic ion solution.

Further, the preparation method of the carbon slurry in the step (2) comprises the following steps: 6g of the graphite, 1g of the carbon black and 1g of the ZrO were weighed using an analytical balance₂1g of the hydroxypropyl cellulose is evenly poured into a clean container filled with agate beadsAnd (3) mixing 50mL of terpineol in a ball milling tank by using a liquid transfer gun, then putting the mixture into a planetary ball mill for treatment for 1h, scraping carbon slurry by using an iron spoon, putting the carbon slurry into a clean 100mL beaker, and putting the beaker into a vacuum drying oven at 90 ℃ under a vacuum condition for concentration for 20 d.

Further, the carbon electrode perovskite solar cell in the step (3) is prepared by the following specific method: taking a proper amount of SnCl₂·2H₂Dripping O solution at the center of the conductive surface of the FTO substrate, carrying out spin coating at 3000rpm/min for 30s, and annealing at 180 ℃ for 1h after the spin coating is finished, so that the O solution is hydrolyzed to become the SnO₂A thin film layer;

taking a proper amount of PbI by using a liquid-transferring gun₂The SnO is fully paved by solution₂Performing two-stage spin coating process on the thin film layer, spreading the solution at a low rotation speed of 800rpm/min for 5s at the front stage, forming the film at a high speed of 3000rpm/min for 30s at the rear stage, and depositing to obtain PbI₂A film; mixing the PbI₂The film is placed on a hot table to be annealed at 70 ℃ for 1min, the organic ion solution is spin-coated through the two-stage spin coating process after annealing, and then the film is placed on the hot table to be annealed at 150 ℃ for 20min, and finally the perovskite layer is obtained;

and after the perovskite layer is cooled, blade coating the carbon slurry on the perovskite layer by adopting a blade coating method, and annealing for 20min at 100 ℃ after the blade coating is finished to obtain the carbon electrode perovskite solar cell.

The technical scheme provided by the embodiment of the invention has the following beneficial effects: the solar cell prepared by the invention has the structure of FTO substrate/SnO₂The carbon thin film layer has a good blocking effect on water molecules in the air as the top electrode, so that the carbon electrode perovskite solar cell has higher moisture resistance.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic structural diagram of a carbon electrode perovskite solar cell provided by the invention;

FIG. 2 is a schematic view of the structure of an FTO substrate provided by the present invention;

FIG. 3 is a schematic illustration of the encapsulation of a carbon electrode perovskite solar cell provided by the present invention;

FIG. 4 is a diagram of an experimental test for moisture resistance of a carbon electrode perovskite solar cell provided by the invention;

fig. 5 is a schematic diagram of a conclusion of moisture resistance test of a carbon electrode perovskite solar cell provided by the invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Example one

A preparation method of a carbon electrode perovskite solar cell comprises the following steps:

step (2), solvent preparation: SnCl with the concentration of 0.1mol/mL is prepared by using tin dichloride solid and absolute ethyl alcohol₂·2H₂O solution; PbI with a concentration of 691.25mg/mol was formulated from N, N-dimethylformamide, dimethyl sulfoxide and lead iodide powder₂A solution; preparing an organic ionic solution by formamidine hydroiodide, methyl amine chloride, methyl amine bromide and isopropanol; by graphite, carbon black, ZrO₂Preparing carbon slurry from hydroxypropyl cellulose and terpineol;

step (a)3) And preparing the carbon electrode perovskite solar cell by using the prepared solvent: putting the treated FTO substrate into a preheated ultraviolet ozone processor for treatment for 20min, and spin-coating SnCl after treatment₂·2H₂Preparation of SnO from O solution₂A thin film layer; then SnO₂Treating the film layer in an ultraviolet ozone machine for 20min to remove surface groups and increase the surface wettability, and spin-coating PbI after treatment₂Preparing a perovskite layer by using the solution and the organic ion solution; coating carbon slurry on the perovskite layer to obtain a carbon thin film layer, and finally obtaining the carbon electrode perovskite solar cell;

in the present invention, fluorine-doped tin oxide (FTO) is used as the bottom electrode substrate. The FTO substrate is purchased from Liaoning preferred energy technology Co., Ltd, the size of the FTO substrate is 24mm multiplied by 24mm, the conductive film is distributed on the substrate as shown in figure 2 after laser etching, and the blank part is the conductive film.

Example two

step (1): FTO substrate treatment

Firstly, numbering an FTO substrate by using a metal nicking tool, placing the FTO substrate into a culture dish, pouring a proper amount of deionized water into the culture dish to immerse the FTO substrate, wiping off large particles visible to the naked eye on the surface by using a cotton swab, and placing the cleaned FTO substrate into a crystallization dish containing deionized water to immerse;

then, pouring the deionized water in the crystallization dish, pouring the deionized water, cleaning in an ultrasonic cleaning machine for 20min, pouring the deionized water, pouring acetone, cleaning in the ultrasonic cleaning machine for 20min, pouring the acetone into a recovery barrel, rinsing with the deionized water once, pouring the deionized water again, cleaning in the ultrasonic cleaning machine for 20min, pouring the deionized water, pouring isopropanol, and cleaning in the ultrasonic cleaning machine for 20 min;

and finally, pouring isopropanol into a recycling bin, putting the crystallization vessel with the FTO substrate into a drying oven, adjusting the temperature to 80 ℃ for drying, and attaching a high-temperature adhesive tape to the treated FTO substrate.

Step (2): solvent preparation

Firstly, preparing SNCl with the concentration of 0.1mol/mL by using tin dichloride solid and absolute ethyl alcohol₂·2H₂O solution;

secondly, 691.25mg of lead iodide powder is weighed by an analytical balance and put in a No. 1 glass bottle, 0.9mLN, N-dimethylformamide and 0.1mL of dimethyl sulfoxide are respectively taken by a pipette gun with the volume ratio of 9: 1 and then poured into the No. 1 glass bottle, magnetons are put in the glass bottle, the bottle cap is screwed up, a label is pasted, the mixture is stirred for 1d at 70-85 ℃ on a magnetic rotary heating table, filtered by a 0.22 mu m organic filter tip and then heated at 80 ℃ to obtain PbI₂And (3) solution.

Then, 90mg of formamidine hydroiodide with a concentration of 90mg/ml, 6.39mg of methylammonium chloride with a concentration of 6.39mg/ml and 9mg of methylammonium bromide with a concentration of 9mg/ml were taken out from a No. 2 glass bottle by an analytical balance, isopropanol was taken out from the No. 2 glass bottle by a pipette gun, magnetons were put in the glass bottle, and the glass bottle was stirred for one day in a state of a magnetic rotary heating table at normal temperature, and an organic ion solution was obtained after filtration.

Finally, 6g of the graphite, 1g of the carbon black and 1g of the ZrO were weighed using an analytical balance₂And 1g of the hydroxypropyl cellulose is uniformly poured into a clean ball milling tank filled with agate beads, 50mL of terpineol is taken by a liquid transfer gun to be mixed in the ball milling tank, then the mixture is put into a planetary ball mill for treatment for 1 hour, then the carbon slurry is scraped by an iron spoon and put into a clean 100mL beaker, and the beaker is put into a vacuum drying oven at 90 ℃ under vacuum condition for concentration for 20 days.

And (3): preparation of carbon electrode perovskite solar cell by prepared solvent

Firstly, taking a proper amount of SnCl₂·2H₂Dripping O solution at the center of the conductive surface of the FTO substrate, performing spin coating at 3000rpm/min for 30s, and annealing at 180 ℃ for 1h after the spin coating is finished to hydrolyze the O solution into SnO₂A thin film layer;

then, a proper amount of PbI is taken out by a liquid-transfering gun₂SnO is fully spread in solution₂Performing two-stage spin coating process on the thin film layer, spreading the solution at a low rotation speed of 800rpm/min for 5s at the front stage, forming the film at a high speed of 3000rpm/min for 30s at the rear stage, and depositing to obtain PbI₂A film; will PbI₂The film is put on a hot bench and annealed at 70 ℃ for 1min, after annealing, spin-coating an organic ion solution by a two-stage spin coating process, and then putting the solution on a hot bench for annealing at 150 ℃ for 20min to finally obtain a perovskite layer;

and finally, after the perovskite layer is cooled, blade coating carbon slurry on the perovskite layer by adopting a blade coating method, and annealing for 20min at 100 ℃ after the coating is finished to obtain the carbon electrode perovskite solar cell.

It should be noted that, the worker tests the moisture resistance of the carbon electrode perovskite solar cell, and here 10 groups of the carbon electrode perovskite solar cells are packaged differently by PMMA, and the packaging schematic diagram is shown in fig. 3, and the moisture resistance test is performed in an incubator with relative humidity of 60%, 70%, and 85%, temperature of 50 ℃, and 60 ℃. It can be seen from fig. 4 that, store in the dampproofing case after this carbon electrode perovskite solar cell of 10 groups that prepare encapsulates, the functional layer is black, perovskite layer does not almost decompose this moment, put this carbon electrode perovskite solar cell of 10 groups into constant temperature and humidity incasement, when the incasement humidometer reaches stable set value, this carbon electrode perovskite solar cell that will heat to a little more than 50 ℃ puts into, do so for this carbon electrode perovskite solar cell put into the case after the temperature itself can be a little more than the incasement temperature, can not lead to meeting heat to make a large amount of steam adhere to and form liquid water on the surface and lead to the perovskite layer directly to take place to decompose.

After lh had been placed in the chamber, it was clearly seen that the functional layer positions in 10 groups of the carbon electrode perovskite solar cells remained black, indicating that the perovskite layer was not decomposed or decomposed to a very low degree. After being left in the cabinet for 2 hours, the cabinet was observed to have substantially no change, at which time the relative humidity in the cabinet was raised to 70% and the temperature was maintained at 50 ℃. After 1h, as is apparent from fig. 4, the functional layers of the perovskite solar cell with 10 groups of carbon electrodes are still black, and no decomposition still occurs. The relative humidity in the box is improved to 85%, and after 30min of observation, the functional layer is still black, and the decomposition degree of the perovskite layer is still very small. And keeping the relative humidity in the box constant at 85%, slowly raising the temperature from 50 ℃ to 60 ℃, and observing that the functional layers in 10 groups of carbon electrode perovskite solar cells obviously turn light in color and slowly turn yellow after 5 min. The perovskite layer in the functional layer is decomposed, and the black perovskite layer is converted into yellow lead iodide. After 30min, the decomposition of the perovskite layer is very obvious, and the decomposition of the perovskite layer of the carbon electrode perovskite solar cell packaged differently is obviously uneven.

10 groups of the carbon electrode perovskite solar cells packaged differently are numbered 3-12, and the numbers 3-12 in the schematic diagram in fig. 3 correspond to the numbers 3-12 in fig. 4. Analysis was performed on figure 4: comparing No. 3 with No. 4, the color of No. 3 is obviously lighter than that of No. 4, but both colors are obviously lighter than the initial color of the test, namely, the perovskite layer is decomposed, but the obvious decomposition degree of No. 3 without the exposed side surface of the perovskite layer is higher and faster. The comparison of No. 5, No. 6 and No. 7 is carried out, wherein the color of No. 5 is lighter, the color of No. 7 is darker relative to that of No. 5, and the color of No. 6 is darkest. The decomposition of all three perovskite layers occurs, and the decomposition degree and speed of No. 5 which exposes two perovskite layers and is not encapsulated are higher and faster. Comparing No. 8 with No. 9, the color of No. 8 is obviously lighter than that of No. 9, and compared with the decomposition of the perovskite layers before the test, the decomposition of the perovskite layer No. 9 of the perovskite layer on one exposed side is more thorough. Comparing nos. 10 and 12, No. 12 was lighter in color than No. 10, and the decomposition occurred in both perovskite layers, with the decomposition degree of the perovskite layer No. 10 in which only the carbon thin film layer was exposed being significantly lower.

According to the comparison, and as shown in fig. 5, the channels through which water permeates in the air are divided into three types, namely, the side channels only with the exposed perovskite layer, the side channels only with the exposed carbon film layer, and the carbon film layer surface channels covered on the four sides and the surface of the carbon film layer. The rate and extent of water penetration in these three types of channels varies significantly. From the comparison of No. 3 and No. 4, the comparison of No. 5, No. 6 and No. 7, and the comparison of No. 8 and No. 9, the permeation speed and the permeation degree of water in the side channel with the exposed perovskite layer are higher than those of the side channel with the exposed carbon film layer. From the comparison of

numbers

10, 11 and 12, the carbon film layer has a certain barrier effect on water molecules in the air. From the comparison of No. 5, No. 6 and No. 10, the surface carbon film layer channel is the channel with the worst water penetration in the three types of channels and is also the channel with the strongest waterproof capability.

It is worth to say that the solar cell prepared in the invention has the structure of FTO substrate/SnO₂The carbon thin film layer has a good blocking effect on water molecules in the air as the top electrode, so that the carbon electrode perovskite solar cell has higher moisture resistance.

The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A method for preparing a carbon electrode perovskite solar cell, the method comprising:

step (3), preparing a carbon electrode perovskite solar cell by the prepared solvent: putting the treated FTO substrate into a preheated ultraviolet ozone processor for treatment for 20min, and spin-coating the SnCl after treatment₂·2H₂Preparation of SnO from O solution₂A thin film layer; then the SnO is put₂Treating the thin film layer in an ultraviolet ozone machine for 20min to remove surface groups and simultaneously removing surface groupsThe surface wettability is increased, and the PbI is spin-coated after the treatment₂Preparing a perovskite layer from the solution and the organic ion solution; and blade-coating the carbon slurry on the perovskite layer to obtain a carbon thin film layer, and finally annealing to obtain the carbon electrode perovskite solar cell.

2. The method for preparing a carbon electrode perovskite solar cell as claimed in claim 1, wherein the PbI in the step (2)₂The preparation method of the solution comprises the following steps: weighing 691.25mg of lead iodide powder in a No. 1 glass bottle by using an analytical balance, respectively taking 0.9mL of N, N-dimethylformamide and 0.1mL of dimethyl sulfoxide by using a liquid transfer gun according to the volume ratio of 9: 1, injecting the obtained mixture into the No. 1 glass bottle, putting magnetons into the glass bottle, screwing the bottle cap, sticking a label, stirring the obtained product for 1d at 70-85 ℃ on a magnetic rotary heating table, filtering the obtained product by using a 0.22 mu m organic filter tip, and heating the obtained product at 80 ℃ to obtain the PbI₂And (3) solution.

3. The method for preparing a carbon electrode perovskite solar cell according to claim 1, wherein the preparation method of the organic ion solution in the step (2) is as follows: respectively taking 90mg of formamidine hydroiodide with the concentration of 90mg/ml, 6.39mg of methyl ammonium chloride with the concentration of 6.39mg/ml and 9mg of methyl ammonium bromide with the concentration of 9mg/ml in a No. 2 glass bottle by using an analytical balance, then taking the isopropanol in the No. 2 glass bottle by using a liquid transfer gun, putting magnetons in the glass bottle, stirring the glass bottle for one day in a magnetic rotary heating table at normal temperature, and filtering the solution to obtain the organic ion solution.

4. The method for preparing a carbon electrode perovskite solar cell according to claim 1, wherein the carbon slurry in the step (2) is prepared by: 6g of the graphite, 1g of the carbon black and 1g of the ZrO were weighed using an analytical balance₂Uniformly pouring 1g of the hydroxypropyl cellulose into a clean ball milling tank filled with agate beads, mixing 50mL of terpineol in the ball milling tank by using a liquid transfer gun, then putting the mixture into a planetary ball mill for treatment for 1h, scraping off carbon slurry by using an iron spoon, and putting the carbon slurry into 100mL of clean carbon slurryPutting the beaker into a vacuum drying oven at 90 ℃ under vacuum condition for concentrating for 20 days.

5. The method for preparing the carbon electrode perovskite solar cell according to claim 1, wherein the carbon electrode perovskite solar cell in the step (3) is prepared by a specific method comprising the following steps: taking a proper amount of SnCl₂·2H₂Dripping O solution at the center of the conductive surface of the FTO substrate, carrying out spin coating at 3000rpm/min for 30s, and annealing at 180 ℃ for 1h after the spin coating is finished, so that the O solution is hydrolyzed to become the SnO₂A thin film layer;