CN114361350A - Preparation method of perovskite solar cell module - Google Patents

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

A kind of preparation method of perovskite solar cell module

technical field

The invention belongs to the technical field of solar cells, and relates to a preparation method of a large-area perovskite solar cell module by non-laser etching.

Background technique

Solar energy is a clean and renewable energy provided by nature to human beings. Efficient use of solar energy has become one of the key technologies for my country to achieve the goal of "carbon peaking and carbon neutrality". Silicon-based solar cells, as the first generation of solar cell technology, currently dominate the photovoltaic market. However, since the production and preparation process of silicon-based solar cells requires high energy consumption and high cost processes, the development of new high-efficiency and low-cost solar cell technologies has become an urgent market demand.

As a third-generation new photovoltaic technology, perovskite solar cells have been developed since their earliest development in 2009 (3.8% photoelectric conversion efficiency), due to their excellent carrier mobility, high absorption coefficient, and low-cost solution processing. After 12 years of rapid development, the certified photoelectric conversion efficiency has exceeded 25% by 2021, and the preparation of large-area modules has also received great attention and active participation from the business community, becoming a new type of thin-film solar cell technology with great market application potential. .

In the preparation of large-area perovskite solar cell modules, the perovskite active layer (P2) and top electrode (P3) are usually scribed by laser etching, which requires a high-power laser (red or green light), Moreover, it is very easy to etch away the lowermost (P1) transparent conductive layer, causing the failure of the entire module device.

Therefore, in order to solve the shortcomings of the existing technology, improve the yield, reduce the production cost and improve the photoelectric conversion efficiency of the perovskite solar cell module, it is urgent to develop a non-laser etching perovskite solar cell module. The preparation method meets the urgent needs of market applications.

SUMMARY OF THE INVENTION

The term "high temperature adhesive tape" in the present invention refers to the high temperature single-sided adhesive tape of 3M Company.

The term "low-temperature carbon electrode" in the present invention refers to a carbon paste formed by heating and curing at a temperature lower than 150° C. after the carbon paste is printed on the device.

The object of the present invention is to overcome the deficiencies of the above-mentioned prior art, and provide a preparation method of a perovskite solar cell module, comprising the following steps:

S1. the high temperature adhesive tape is attached on the conductive substrate, after the ultraviolet ozone treatment, the high temperature adhesive tape is torn off, and the electron transport layer is prepared by printing on the conductive substrate;

S2. Affix the high temperature tape on the electron transport layer, after ultraviolet ozone treatment, remove the high temperature tape, drop the perovskite precursor solution, print to form a film, and anneal to form a perovskite film;

S3. Affix the high-temperature tape on the perovskite film, drop the carbon paste, and print the carbon paste to form a low-temperature carbon electrode to obtain the perovskite solar module.

Further, a hole transport layer is also contained between the perovskite film and the low-temperature carbon electrode of the perovskite solar cell module, and the preparation method of the hole transport layer includes the following steps:

The hole transport layer solution is dropped onto the perovskite thin film, and the hole transport layer is prepared by printing.

Further, in step S2, the perovskite material is ABX ₃ type perovskite, wherein A is selected from at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium; B is selected from lead, at least one of tin, germanium and bismuth; X is selected from at least one of iodine, bromine and chlorine.

Further, the printing method is selected from one of blade coating, spray coating and slit coating.

Further, in step S1, the conductive base includes a substrate and a transparent electrode,

in,

The substrate is selected from one of a flexible substrate and a rigid substrate, and the flexible substrate material is selected from one of polyimide, polyethylene terephthalate and polyethersulfone resin; the rigid substrate The material is 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 one of TiO ₂ and SnO ₂ .

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 200-20000 nm.

Further, the thickness of the hole transport layer is 5-200 nm.

Further, in step S2, the temperature of the annealing is 50-150°C.

Further, the perovskite precursor solution of the present invention is a MAPbI ₃ perovskite precursor solution.

The beneficial effects of the present invention are as follows:

1. The preparation method of the perovskite solar cell module disclosed in the present invention, the whole process is carried out in the air, and the material is subjected to ultraviolet ozone treatment after lamination with high-temperature single-sided tape, and does not need to be prepared in a nitrogen atmosphere, and does not use Laser etching and scribing can realize the patterning of the perovskite active (P2) layer and the top electrode (P3), the preparation conditions are easy to realize, simple and controllable, and the manufacturing cost is saved. The utilization rate of materials is high when the film layer is used, and large-area components can be prepared in batches, and at the same time, it has good stability and high yield, which is conducive to large-scale industrial production;

2. The present invention optimizes the process, the prepared perovskite thin film layer is completed in one step, and does not need to add anti-solvent, the operation is simple, it can crystallize quickly and is conducive to the growth of crystal nucleus, and the film formation is uniform and the grain size is large. The thin film has the advantages of uniform reaction and scalable, and improves the photoelectric conversion efficiency of perovskite solar cells.

Description of drawings

FIG. 1 is a physical diagram of the perovskite solar cell prepared in Example 1 of the present invention.

FIG. 2 is a SEM electron microscope picture of the perovskite thin film prepared in Example 1 of the present invention.

Detailed ways

In order to illustrate the technical solutions of the present invention more clearly, the following examples are given, but the present invention is not limited thereto.

The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

In the embodiments of the present invention, the preparation methods of the perovskite solar cell modules are all carried out under the condition of air atmosphere.

In the embodiment of the present invention, the ITO glass substrate and the FTO glass substrate were purchased from Asahi Glass Company.

In the embodiment of the present invention, the model of the high-temperature adhesive tape is 7416J of 3M company, and the width is 2 mm.

In the embodiment of the present invention, the ultraviolet ozone treatment instrument is a UV irradiation machine BZS250GF-TC.

In the embodiment of the present invention, the preparation method of the perovskite precursor solution is to add PbI ₂ and MAI to the DMF solvent to configure a 1M solution.

In the embodiment of the present invention, the hole transport layer solution is a 20 mg/ml P3HT solution or a Spiro-OMeTAD solution.

In the embodiment of the present invention, the carbon paste is a conductive carbon paste CCI-305LD from Shenzhen Chiyo Company.

Example 1

A preparation method of a perovskite solar cell module, comprising the following steps:

S1. Stick the high temperature tape on the ITO glass substrate of 10cm*10cm, after the ultraviolet ozone treatment, remove the high temperature tape, and scrape _SnO on the treated ITO glass substrate to prepare an electron transport layer with a thickness of 30nm;

S2. Affix the high temperature tape on the electron transport layer, remove the high temperature tape after ultraviolet ozone treatment, drip the MAPbI ₃ perovskite precursor solution on the electron transport layer, and scrape the MAPbI ₃ perovskite The ore precursor solution was formed into a film, and then annealed at 100 °C for 30 min to obtain a perovskite film with a thickness of 600 nm;

S3. Affix the high-temperature tape on the perovskite film, drop the carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the perovskite solar cell module.

FIG. 1 is a physical diagram of the perovskite solar cell prepared in Example 1 of the present invention.

FIG. 2 is a SEM electron microscope picture of the perovskite film prepared in Example 1 of the present invention. According to FIG. 2, it can be seen that the perovskite film prepared by the present invention is uniform in film formation and large in size.

Example 2

A preparation method of a perovskite solar cell module, comprising the following steps:

S1. Stick the high temperature tape on the ITO glass substrate of 10cm*10cm, after the ultraviolet ozone treatment, remove the high temperature tape, and scrape the treated ITO flexible substrate with _SnO to prepare an electron transport layer with a thickness of 30nm;

S2. Affix the high temperature tape on the electron transport layer, remove the high temperature tape after ultraviolet ozone treatment, drip the MAPbI ₃ perovskite precursor solution on the electron transport layer, and scrape the MAPbI ₃ perovskite The ore precursor solution was formed into a film, and then annealed at 100 °C for 30 min to obtain a perovskite film with a thickness of 600 nm;

S3. dropping the P3HT hole transport layer solution onto the perovskite thin film layer, and scraping the P3HT hole transport layer solution to obtain a hole transport layer with a thickness of 50 nm;

S4. Attach a high-temperature tape to the hole transport layer, drop a carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the perovskite solar cell module.

Example 3

A preparation method of a perovskite solar cell module, comprising the following steps:

S1. Stick the high temperature tape on the FTO glass substrate of 10cm*10cm, after ultraviolet ozone treatment, remove the high temperature tape, and scrape SnO ₂ to prepare an electron transport layer with a thickness of 30nm;

S2. Affix the high temperature tape on the electron transport layer, remove the high temperature tape after ultraviolet ozone treatment, drip the MAPbI ₃ perovskite precursor solution on the electron transport layer, and scrape the MAPbI ₃ perovskite The ore precursor solution was formed into a film, and then annealed at 100 °C for 30 min to obtain a perovskite film with a thickness of 600 nm;

S3. Affix the high-temperature tape on the perovskite film, drop the carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the perovskite solar cell module.

Example 4

A preparation method of a perovskite solar cell module, comprising the following steps:

S1. Stick the high temperature tape on the FTO glass substrate of 10cm*10cm, after ultraviolet ozone treatment, remove the high temperature tape, and scrape SnO ₂ to prepare an electron transport layer with a thickness of 30nm;

S2. Affix the high temperature tape on the electron transport layer, remove the high temperature tape after ultraviolet ozone treatment, drip the MAPbI ₃ perovskite precursor solution on the electron transport layer, and scrape the MAPbI ₃ perovskite The ore precursor solution was formed into a film, and then annealed at 100 °C for 30 min to obtain a perovskite film with a thickness of 600 nm;

S3. dropping the P3HT hole transport layer solution onto the perovskite thin film layer, and scraping the P3HT hole transport layer solution to obtain a hole transport layer with a thickness of 50 nm;

S4. Attach a high-temperature tape to the hole transport layer, drop a carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the perovskite solar cell module.

Example 5

A preparation method of a perovskite solar cell module, comprising the following steps:

S1. Stick the high temperature tape on the ITO glass substrate of 10cm*10cm, after ultraviolet ozone treatment, remove the high temperature tape, and scrape _SnO2 to prepare an electron transport layer with a thickness of 30nm;

S2. Affix the high temperature tape on the electron transport layer, remove the high temperature tape after ultraviolet ozone treatment, drip the MAPbI ₃ perovskite precursor solution on the electron transport layer, and scrape the MAPbI ₃ perovskite The ore precursor solution was formed into a film, and then annealed at 100 °C for 30 min to obtain a perovskite film with a thickness of 600 nm;

S3. drop the Spiro-OMeTAD hole transport layer solution onto the perovskite thin film layer, and scrape the Spiro-OMeTAD hole transport layer solution to obtain a hole transport layer with a thickness of 50 nm;

S4. Affix a high-temperature tape on the hole transport layer, drop a carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the perovskite solar cell module.

Comparative ratio

A preparation method of a perovskite solar cell module, this comparative example is the same as the device structure and the materials of each layer in Example 1, the difference is: the comparative example is prepared in a nitrogen glove box environment, and its electron transport layer, perovskite Mineral film layers and carbon electrodes were prepared by spin coating and manual wiping.

test case

Performance testing of the perovskite solar cell modules prepared in Examples 1-5 and Comparative Examples

testing method:

Energy conversion efficiency test: place the prepared perovskite solar cell module under a standard solar simulator of 1 sun at 25°C, test the I-V curve of the device, and then calculate the energy conversion efficiency 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.

Test results: The relevant results obtained are shown in Table 1.

Table 1

It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, but that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments are to be regarded in all respects as illustrative and not restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, which are therefore intended to fall within the scope of the appended claims. All changes within the meaning and range of the equivalents of , are included in the present invention.

In addition, it should be understood that although this specification is described in terms of embodiments, not each embodiment only includes an independent technical solution, and this description in the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole , the technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by those skilled in the art.

Claims (10)

1. a preparation method of perovskite solar cell module, is characterized in that, the preparation method of described perovskite solar cell module comprises the following steps: S1. the high temperature adhesive tape is attached on the conductive substrate, after the ultraviolet ozone treatment, the high temperature adhesive tape is torn off, and the electron transport layer is prepared by printing on the conductive substrate; S2. Affix the high temperature tape on the electron transport layer, after ultraviolet ozone treatment, remove the high temperature tape, drop the perovskite precursor solution, print to form a film, and anneal to form a perovskite film; S3. Affix the high-temperature tape on the perovskite film, drop the carbon paste, and print the carbon paste to form a low-temperature carbon electrode to obtain the perovskite solar module. 2. The preparation method of the perovskite solar cell module according to claim 1, wherein the perovskite film of the perovskite solar cell module and the low-temperature carbon electrode also contain a hole transport layer, The preparation method of the hole transport layer comprises the following steps: The hole transport layer solution is dropped onto the perovskite thin film, and the hole transport layer is prepared by printing. 3. The method for preparing a perovskite solar cell module according to claim 1, wherein in step S2, the perovskite material is ABX ₃ type perovskite, wherein A is selected from methylamine, methylamine At least one of amidine, cesium, rubidium, potassium and sodium; B is selected from at least one of lead, tin, germanium and bismuth; X is selected from at least one of iodine, bromine and chlorine. 4. The preparation method of the perovskite solar cell module according to claim 1, wherein the printing method is selected from one of blade coating, spray coating and slit coating. 5. The method for preparing a perovskite solar cell module according to claim 1, wherein in step S1, the conductive substrate comprises a substrate and a transparent electrode, in, 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 polyethersulfone resin; the rigid substrate material is 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 preparing a perovskite solar cell module according to claim 1 , wherein in step S1 , the electron transport layer material is selected from one of TiO ₂ and SnO ₂ . 7 . 7 . The method for preparing a perovskite solar cell module according to claim 2 , wherein the material of the hole transport layer is selected from at least one of PTAA, P3HT, CuSCN, Spiro-OMeTAD and phosphorus. 8 . 8 . The method for preparing a perovskite solar cell module according to claim 1 , wherein the thickness of the perovskite film is 200-20000 nm. 9 . 9 . The method for preparing a perovskite solar cell module according to claim 2 , wherein the hole transport layer has a thickness of 5-200 nm. 10 . 10 . The method for preparing a perovskite solar cell module according to claim 1 , wherein, in step S2 , the temperature of the annealing is 50-150° C. 11 .

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