CN114361350A - Preparation method of perovskite solar cell module - Google Patents
Preparation method of perovskite solar cell module Download PDFInfo
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- CN114361350A CN114361350A CN202111538762.3A CN202111538762A CN114361350A CN 114361350 A CN114361350 A CN 114361350A CN 202111538762 A CN202111538762 A CN 202111538762A CN 114361350 A CN114361350 A CN 114361350A
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Abstract
The invention belongs to the technical field of solar cells, and relates to a preparation method of a non-laser-etched large-area perovskite solar cell module. The invention comprises the following steps: s1, attaching a high-temperature adhesive tape to a conductive substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and printing to prepare an electronic transmission layer; s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, dropwise adding a perovskite precursor solution, printing to form a film, and annealing to form a perovskite thin film; and S3, attaching a high-temperature adhesive tape to the perovskite thin film, dropwise adding carbon slurry, and printing to prepare a low-temperature carbon electrode to obtain the perovskite solar module. The perovskite solar cell module prepared by the method has the characteristics of uniform film formation and large film grain size, is prepared in the air, does not need laser etching or adding an anti-solvent, has simple and controllable steps, improves the energy conversion efficiency of module products, and has important significance in the industrialization of solar cells.
Description
Technical Field
The invention belongs to the technical field of solar cells, and relates to a preparation method of a non-laser-etched large-area perovskite solar cell module.
Background
Solar energy is clean and renewable energy given to human beings by nature, and the efficient utilization of solar energy becomes one of the key technologies for realizing the aim of carbon peak-reaching carbon neutralization in China. Silicon-based solar cells currently dominate the photovoltaic market as the first generation of solar cell technology. However, since the production process of silicon-based solar cells requires high energy consumption and high cost processes, the development of new solar cell technologies with high efficiency and low cost is an urgent need in the market.
Since the early development (3.8% photoelectric conversion efficiency) in 2009, perovskite solar cells have been rapidly developed in 12 years due to the characteristics of excellent carrier mobility, high absorption coefficient, low-cost solution processing and the like, and the photoelectric conversion efficiency certified in 2021 is over 25%, and the preparation of large-area modules is also greatly concerned and actively participated in the business industry, and thus, perovskite solar cells become a novel thin-film solar cell technology with great market application potential.
In the fabrication of large area perovskite solar cell modules, the perovskite active layer (P2) and the top electrode (P3) are typically scribed by laser etching, a high power laser (red or green) is required, and the lowermost (P1) transparent conductive layer is very easily etched away, causing failure of the entire module device.
Therefore, in order to overcome the defects in the prior art, improve the yield, reduce the production cost, and improve the photoelectric conversion efficiency of the perovskite solar cell module, it is urgently needed to develop a preparation method of a non-laser-etched perovskite solar cell module to meet the urgent demand of market application.
Disclosure of Invention
The term "high temperature adhesive tape" of the present invention refers to a high temperature single-sided adhesive tape of 3M company.
The term "low-temperature carbon electrode" of the present invention refers to a carbon paste which is printed on a device and then cured by heating at a temperature of less than 150 ℃.
The invention aims to overcome the defects of the prior art and provides a preparation method of a perovskite solar cell module, which comprises the following steps:
s1, attaching a high-temperature adhesive tape to a conductive substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and printing and preparing an electronic transmission layer on the conductive substrate;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, dropwise adding a perovskite precursor solution, printing to form a film, and annealing to form a perovskite thin film;
and S3, attaching a high-temperature adhesive tape to the perovskite thin film, dropwise adding carbon slurry, and printing the carbon slurry to form a low-temperature carbon electrode to obtain the perovskite solar module.
Further, a hole transport layer is further arranged between the perovskite thin film of the perovskite solar cell module and the low-temperature carbon electrode, and the preparation method of the hole transport layer comprises the following steps:
and dropwise adding the hole transport layer solution onto the perovskite thin film, and printing to prepare the hole transport layer.
Further, in step S2, the perovskite material is ABX3Perovskite type, wherein A is selected from at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium; b is at least one selected from lead, tin, germanium and bismuth; x is at least one selected from iodine, bromine and chlorine.
Further, the printing method is selected from one of knife coating, spray coating and slit coating.
Further, in step S1, the conductive substrate includes a substrate and a transparent electrode,
wherein the content of the first and second substances,
the substrate is selected from one of a flexible substrate and a rigid substrate, and the flexible substrate is made of one of polyimide, polyethylene terephthalate and polyether sulfone resin; the rigid substrate is made of glass;
the transparent electrode is selected from one of Indium Tin Oxide (ITO), fluorine-doped tin oxide (FTO) and aluminum-doped zinc oxide (AZO).
Further, in step S1, the electron transport layer material is selected from TiO2And SnO2One kind of (1).
Further, the material of the hole transport layer is selected from at least one of PTAA, P3HT, CuSCN, Spiro-OMeTAD, and phosphorus.
Further, the thickness of the perovskite thin film is 200-.
Further, the thickness of the hole transport layer is 5-200 nm.
Further, in step S2, the annealing temperature is 50 to 150 ℃.
Further, the perovskite precursor solution is MAPbI3A perovskite precursor solution.
The invention has the following beneficial effects:
1. the preparation method of the perovskite solar cell module disclosed by the invention is carried out in the air in the whole process, the ultraviolet ozone treatment is carried out on the material after the high-temperature single-sided adhesive tape is used for laminating, the preparation is not needed in the nitrogen atmosphere, the patterning of the perovskite active (P2) layer and the top electrode (P3) can be realized without laser etching and scribing, the preparation conditions are easy to realize, simple and controllable, and the manufacturing cost is saved;
2. the method optimizes the process, the prepared perovskite thin film layer is finished in one step, an anti-solvent is not required to be added, the operation is simple and convenient, the rapid crystallization can be realized, the crystal nucleus growth is facilitated, the thin film with uniform film formation and large crystal grain size is obtained, the advantages of uniform reaction, realization of large scale and the like are achieved, and the photoelectric conversion efficiency of the perovskite solar cell is improved.
Drawings
Fig. 1 is a schematic diagram of a perovskite solar cell prepared in example 1 of the present invention.
FIG. 2 is an SEM electron microscope photograph of the perovskite thin film prepared in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are given, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the embodiment of the invention, the preparation method of the perovskite solar cell module is carried out under the air atmosphere condition.
In the examples of the present invention, the ITO glass substrate and the FTO glass substrate were purchased from asahi glass company.
In the embodiment of the invention, the high-temperature adhesive tape is 3M company 7416J, and the width is 2 mm.
In the embodiment of the invention, the ultraviolet ozone treatment instrument is a UV irradiation machine BZS250 GF-TC.
In the embodiment of the invention, the preparation method of the perovskite precursor solution is to mix PbI2And adding a DMF solvent into the MAI to prepare a 1M solution.
In the embodiment of the invention, the solution of the hole transport layer is 20mg/ml of P3HT solution or Spiro-OMeTAD solution.
In the embodiment of the invention, the carbon paste is conductive carbon paste CCI-305LD of Shenzhen Qianji company.
Example 1
A preparation method of a perovskite solar cell module comprises the following steps:
s1, attaching a high-temperature adhesive tape to a 10 cm-by-10 cm ITO glass substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and blade-coating SnO on the treated ITO glass substrate2Preparing an electron transport layer with the thickness of 30 nm;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and dropwise adding MAPbI to the electronic transmission layer3Perovskite precursor solution, blade coating said MAPbI3Forming a film by the perovskite precursor solution, and then annealing for 30min at 100 ℃ to obtain a perovskite thin film with the thickness of 600 nm;
and S3, attaching a high-temperature adhesive tape to the perovskite thin film, dropwise adding carbon slurry, and blade-coating the carbon slurry to prepare a low-temperature carbon electrode with the thickness of 3 microns to obtain the perovskite solar cell module.
Fig. 1 is a schematic diagram of a perovskite solar cell prepared in example 1 of the present invention.
Fig. 2 is an SEM electron microscope picture of the perovskite thin film prepared in example 1 of the present invention, and it can be seen from fig. 2 that the perovskite thin film prepared in the present invention has a uniform film formation and a large size.
Example 2
A preparation method of a perovskite solar cell module comprises the following steps:
s1, attaching a high-temperature adhesive tape to a 10 cm-by-10 cm ITO glass substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and blade-coating SnO on the treated ITO flexible substrate2Preparing an electron transport layer with the thickness of 30 nm;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and dropwise adding MAPbI to the electronic transmission layer3Perovskite precursor solution, blade coating said MAPbI3Forming a film by the perovskite precursor solution, and then annealing for 30min at 100 ℃ to obtain a perovskite thin film with the thickness of 600 nm;
s3, dropwise adding a P3HT hole transport layer solution onto the perovskite thin film layer, and blade-coating the P3HT hole transport layer solution to obtain a hole transport layer with the thickness of 50 nm;
and S4, attaching a high-temperature adhesive tape to the hole transport layer, dropwise adding carbon slurry, and blade-coating the carbon slurry to prepare a low-temperature carbon electrode with the thickness of 3 microns to obtain the perovskite solar cell module.
Example 3
A preparation method of a perovskite solar cell module comprises the following steps:
s1, sticking a high-temperature adhesive tape on a 10 cm-10 cm FTO glass substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and carrying out blade coating on SnO2Preparing an electron transport layer with the thickness of 30 nm;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and dropwise adding MAPbI to the electronic transmission layer3Perovskite precursor solution, blade coating said MAPbI3Film formation from perovskite precursor solutionThen annealing at 100 ℃ for 30min to obtain a perovskite thin film with the thickness of 600 nm;
and S3, attaching a high-temperature adhesive tape to the perovskite thin film, dropwise adding carbon slurry, and blade-coating the carbon slurry to prepare a low-temperature carbon electrode with the thickness of 3 microns to obtain the perovskite solar cell module.
Example 4
A preparation method of a perovskite solar cell module comprises the following steps:
s1, sticking a high-temperature adhesive tape on a 10 cm-10 cm FTO glass substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and carrying out blade coating on SnO2Preparing an electron transport layer with the thickness of 30 nm;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and dropwise adding MAPbI to the electronic transmission layer3Perovskite precursor solution, blade coating said MAPbI3Forming a film by the perovskite precursor solution, and then annealing for 30min at 100 ℃ to obtain a perovskite thin film with the thickness of 600 nm;
s3, dropwise adding a P3HT hole transport layer solution onto the perovskite thin film layer, and blade-coating the P3HT hole transport layer solution to obtain a hole transport layer with the thickness of 50 nm;
and S4, attaching a high-temperature adhesive tape to the hole transport layer, dropwise adding carbon slurry, and blade-coating the carbon slurry to prepare a low-temperature carbon electrode with the thickness of 3 microns to obtain the perovskite solar cell module.
Example 5
A preparation method of a perovskite solar cell module comprises the following steps:
s1, sticking a high-temperature adhesive tape on a 10 cm-by-10 cm ITO glass substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and carrying out blade coating on SnO2Preparing an electron transport layer with the thickness of 30 nm;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and dropwise adding MAPbI to the electronic transmission layer3Perovskite precursor solution, blade coating said MAPbI3Forming a film by the perovskite precursor solution, then annealing for 30min at 100 ℃,obtaining the perovskite thin film with the thickness of 600 nm;
s3, dropwise adding a Spiro-OMeTAD hole transport layer solution onto the perovskite thin film layer, and blade-coating the Spiro-OMeTAD hole transport layer solution to obtain a hole transport layer with the thickness of 50 nm;
and S4, attaching a high-temperature adhesive tape to the hole transport layer, dropwise adding carbon slurry, and blade-coating the carbon slurry to prepare a low-temperature carbon electrode with the thickness of 3 microns to obtain the perovskite solar cell module.
Comparative example
The preparation method of the perovskite solar cell module is the same as that of the device structure and materials of each layer in example 1, and the difference is as follows: comparative examples were prepared in a nitrogen glove box environment, with the electron transport layer, perovskite thin film layer and carbon electrode all prepared by spin coating and hand wire wiping.
Test example
Performance testing of perovskite solar cell modules prepared in examples 1 to 5 and comparative example
The test method comprises the following steps:
and (3) testing energy conversion efficiency: the prepared perovskite solar cell module is placed under a standard solar simulator of 1 sun, the I-V curve of the device is tested at 25 ℃, then the energy conversion efficiency is calculated according to the following formula,
PCE＝Jsc Voc FF
where Jsc is the short circuit current, Voc is the open circuit voltage, and FF is the fill factor.
And (3) testing results: the correlation results obtained are shown in table 1.
TABLE 1
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a perovskite solar cell module is characterized by comprising the following steps:
s1, attaching a high-temperature adhesive tape to a conductive substrate, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, and printing and preparing an electronic transmission layer on the conductive substrate;
s2, attaching a high-temperature adhesive tape to the electronic transmission layer, tearing off the high-temperature adhesive tape after ultraviolet ozone treatment, dropwise adding a perovskite precursor solution, printing to form a film, and annealing to form a perovskite thin film;
and S3, attaching a high-temperature adhesive tape to the perovskite thin film, dropwise adding carbon slurry, and printing the carbon slurry to form a low-temperature carbon electrode to obtain the perovskite solar module.
2. The method for producing a perovskite solar cell module according to claim 1, wherein a hole transport layer is further provided between the perovskite thin film and the low-temperature carbon electrode of the perovskite solar cell module, and the method for producing a hole transport layer comprises the steps of:
and dropwise adding the hole transport layer solution onto the perovskite thin film, and printing to prepare the hole transport layer.
3. The perovskite solar cell of claim 1The method for manufacturing a battery module is characterized in that in step S2, the perovskite material is ABX3Perovskite type, wherein A is selected from at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium; b is at least one selected from lead, tin, germanium and bismuth; x is at least one selected from iodine, bromine and chlorine.
4. The method of manufacturing the perovskite solar cell module as claimed in claim 1, wherein the printing method is selected from one of blade coating, spray coating and slit coating.
5. The method for producing a perovskite solar cell module as claimed in claim 1, wherein the conductive substrate comprises a substrate and a transparent electrode in step S1,
wherein the content of the first and second substances,
the substrate is selected from one of a flexible substrate and a rigid substrate,
the flexible substrate material is selected from one of polyimide, polyethylene terephthalate and polyether sulfone resin; the rigid substrate is made of glass;
the transparent electrode is selected from one of indium tin oxide, fluorine-doped tin oxide and aluminum-doped zinc oxide.
6. The method for producing the perovskite solar cell module as claimed in claim 1, wherein the electron transport layer material is selected from TiO 12And SnO2One kind of (1).
7. The method for producing the perovskite solar cell module according to claim 2, wherein the material of the hole transport layer is at least one selected from PTAA, P3HT, CuSCN, Spiro-OMeTAD, and phosphorus.
8. The method for preparing the perovskite solar cell module as defined in claim 1, wherein the thickness of the perovskite thin film is 200-.
9. The method for producing a perovskite solar cell module according to claim 2, wherein the thickness of the hole transport layer is 5 to 200 nm.
10. The method for producing the perovskite solar cell module as claimed in claim 1, wherein the annealing temperature is 50 to 150 ℃ in step S2.
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