A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module

Abstract

The present invention relates to a method for preparing a double-additive double-layer electron transport layer perovskite solar cell module. The present invention comprises the following steps: S1. applying a high-temperature adhesive tape to a conductive substrate, treating it with ultraviolet ozone, removing the high-temperature adhesive tape, and printing a first electron transport layer on the conductive substrate; S2. preparing a second electron transport layer on the first electron transport layer; S3. applying the high-temperature adhesive tape to the second electron transport layer, treating it with ultraviolet ozone, removing the high-temperature adhesive tape, dripping a perovskite precursor solution, printing to form a film, and annealing to form a perovskite film; S4. applying the high-temperature adhesive tape to the perovskite film, dripping a carbon slurry, printing the carbon slurry to form a low-temperature carbon electrode, and obtaining the double-additive double-layer electron transport layer perovskite solar cell module. The double-additive double-layer electron transport layer perovskite solar cell module prepared by the present invention can significantly reduce the interface defects and leakage current between the electron transport layer and the perovskite active layer, thereby improving the energy conversion efficiency of the module device.

Description

Technical Field

[0001] The present invention belongs to the technical field of solar cells and relates to a method for preparing a double-additive double-layer electron transport layer perovskite solar cell module. Background Art

[0002] Solar energy is a clean, renewable energy source bestowed upon humanity by nature. Its efficient utilization has become a key technology for achieving my country's carbon peak and carbon neutrality goals. Silicon-based solar cells, as the first generation of solar cell technology, currently dominate the photovoltaic market. However, the production and fabrication of silicon-based solar cells requires energy-intensive and costly processes, necessitating the development of new, efficient, and cost-effective solar cell technologies.

[0003] As a third-generation new photovoltaic technology, perovskite solar cells have been rapidly 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. In addition, the preparation of large-area modules has also received great attention and active participation from the business community, making it a new thin-film solar cell technology with great market application potential.

[0004] In the preparation of large-area perovskite solar cell modules with an upright structure, only one electron transport layer is usually used, which can easily cause many interface defects between the electron transport layer and the perovskite active layer, resulting in increased leakage current, thereby affecting the photoelectric conversion efficiency of the entire photovoltaic module.

[0005] Therefore, in order to solve the shortcomings of the existing single-layer electron transport layer technology and improve the photoelectric conversion efficiency of perovskite solar cell modules, it is urgent to develop a new preparation method for perovskite solar cell modules to meet the urgent needs of market applications. Summary of the Invention

[0006] The term "low-temperature carbon electrode" in the present invention refers to a carbon paste that is printed on a device and then heated and cured at a temperature below 150°C.

[0007] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a method for preparing a double-additive double-layer electron transport layer perovskite solar cell module, the method comprising the following steps:

[0008] S1. A high-temperature tape is attached to a conductive substrate. After UV-ozone treatment, the high-temperature tape is removed and a first electron transport layer is printed on the conductive substrate;

[0009] S2. A high-temperature tape is attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape is removed and a second electron transport layer is printed on the first electron transport layer;

[0010] S3. Attaching a high-temperature tape to the second electron transport layer, after UV-ozone treatment, removing the high-temperature tape, adding a perovskite precursor solution dropwise, printing a film, and annealing to form a perovskite film;

[0011] S4. Attaching a high-temperature tape to the perovskite film, adding a carbon slurry, and printing the carbon slurry to form a low-temperature carbon electrode to obtain the double-additive double-layer electron transport layer perovskite solar cell module;

[0012] in,

[0013] The first electron transport layer is TiO2 or SnO2 added with a metal salt, and the mass percentage of the metal salt is 0.1%-10% of the first electron transport layer;

[0014] The second electron transport layer is TiO2 or SnO2 added with a surfactant, and the mass percentage of the surfactant is 0.1%-10% of the second electron transport layer.

[0015] Furthermore, the double-additive double-layer electron transport layer perovskite solar cell module further comprises a hole transport layer between the perovskite film and the low-temperature carbon electrode, and the preparation method of the hole transport layer comprises the following steps:

[0016] The hole transport layer solution is dropped onto the perovskite film and the hole transport layer is prepared by printing.

[0017] Furthermore, the metal salt is selected from one of KCl, NaCl, KBr, NaBr, KI and NaI.

[0018] Furthermore, the surfactant is selected from one of MACl, FACl, MABr, FABr, MAI, FAI, guanidine hydrochloride, and biguanide hydrochloride.

[0019] Furthermore, in step S3, the perovskite material is an ABX3 type perovskite, wherein A is selected from at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium; B is selected from at least one of lead, tin, germanium and bismuth; and X is selected from at least one of iodine, bromine and chlorine.

[0020] Furthermore, the printing method is selected from one of blade coating, spray coating and slit coating.

[0021] Furthermore, in step S1, the conductive substrate includes a substrate and a transparent electrode,

[0022] in,

[0023] The substrate is selected from one of a flexible substrate and a rigid substrate,

[0024] The flexible substrate material is selected from one of polyimide, polyethylene terephthalate and polyethersulfone resin; the rigid substrate material is glass;

[0025] The transparent electrode is selected from one of indium tin oxide, fluorine-doped tin oxide and aluminum-doped zinc oxide.

[0026] Furthermore, the material of the hole transport layer is selected from at least one of PTAA, P3HT, CuSCN, Spiro-OMeTAD and phosphorus.

[0027] Furthermore, the thickness of the perovskite film is 200-20000 nm.

[0028] Furthermore, in step S3, the annealing temperature is 50-150°C.

[0029] The beneficial effects of the present invention are as follows:

[0030] 1. The preparation method of the double-additive double-layer electron transport layer perovskite solar cell module disclosed in the present invention is carried out in the air throughout the process. The material is subjected to ultraviolet ozone treatment after lamination using high-temperature single-sided tape. It does not need to be prepared under a nitrogen atmosphere, and patterning of the perovskite active (P2) layer and the top electrode (P3) can be achieved without using laser etching and scribing. The preparation conditions are easy to achieve, simple and controllable, saving manufacturing costs. The scraping printing method adopted in the present invention has a high material utilization rate when preparing the thin film layer, and can realize batch preparation of large-area photovoltaic modules. At the same time, the device has high stability and yield, which is conducive to large-scale industrial production.

[0031] 2. The present invention innovates the original single-layer electron transport layer device structure and adopts a new device structure with a double-additive double-layer electron transport layer. The first electron transport layer has the function of improving the electron transport mobility. Since the surfactant added to the second electron transport layer is cationic, its cations have electrostatic attraction with the anions in the perovskite active layer, which can induce the crystallization of the perovskite film, significantly reducing the interface defects and leakage current between the electron transport layer and the perovskite active layer, and improving the photoelectric conversion efficiency of the perovskite solar cell module.

[0032] 3. The present invention optimizes the process, and the prepared perovskite thin film layer is completed in one step without the addition of anti-solvent. It is easy to operate, can quickly crystallize and is conducive to the growth of crystal nuclei, and obtains a film with uniform film formation and large grain size. It has the advantages of uniform reaction and scalability. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a physical picture of the double-additive double-layer electron transport layer perovskite solar cell prepared in Example 1 of the present invention.

[0034] Figure 2 This is a SEM electron microscope image of the perovskite film prepared in Example 1 of the present invention;

[0035] Among them, H1 is the perovskite thin film layer, H2 is the double-additive double-layer electron transport layer, and H3 is the ITO layer. DETAILED DESCRIPTION

[0036] In order to more clearly illustrate the technical solution of the present invention, the following embodiments are listed, but the present invention is not limited thereto.

[0037] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; the reagents, materials, etc. used in the following examples are all commercially available unless otherwise specified.

[0038] In the embodiment of the present invention, the preparation method of the double-additive double-layer electron transport layer perovskite solar cell module is carried out under air atmosphere conditions.

[0039] In the embodiment of the present invention, the ITO glass substrate and the FTO glass substrate are purchased from Asahi Glass Co., Ltd.

[0040] In the embodiment of the present invention, the high temperature tape is model 7416J from 3M Company, and has a width of 2 mm.

[0041] In the embodiment of the present invention, the ultraviolet ozone treatment instrument is a UV irradiator BZS250GF-TC.

[0042] In an embodiment of the present invention, the perovskite precursor solution is prepared by adding PbI2, MAI and FAI in a molar ratio of 1:0.6:0.4 to DMF and DMSO solvents to prepare a 1M solution.

[0043] In the embodiment of the present invention, the hole transport layer solution is a 20 mg / ml P3HT solution or a Spiro-OMeTAD solution.

[0044] In the embodiment of the present invention, the carbon slurry is the conductive carbon slurry CCI-305LD produced by Shenzhen Qiandai Company.

[0045] In the embodiments of the present invention, the addition amounts are all expressed in mass percentages.

[0046] Example 1

[0047] A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module comprises the following steps:

[0048] S1. A high-temperature tape was attached to a 10cm*10cm ITO glass substrate. After UV-ozone treatment, the high-temperature tape was removed and a first electron transport layer of 40nm thick was prepared by coating SnO2 with 1% NaCl on the treated ITO glass substrate.

[0049] S2. A high-temperature tape was attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape was removed and a second electron transport layer was prepared by scraping SnO2 with 1.5% guanidine hydrochloride added to the first electron transport layer to a thickness of 60 nm.

[0050] S3. Attach the high-temperature tape to the second electron transport layer, remove the high-temperature tape after UV ozone treatment, and drop MA on the second electron transport layer. 0.6 FA 0.4 PbI3 perovskite precursor solution, blade coating the MA 0.6 FA 0.4 The PbI3 perovskite precursor solution was formed into a film, and then annealed at 100°C for 30 minutes to obtain a perovskite film with a thickness of 700 nm;

[0051] S4. Attach a high-temperature tape to the perovskite film, drip carbon slurry, and apply the carbon slurry by scraping to prepare a low-temperature carbon electrode with a thickness of 4 μm, thereby obtaining the double-additive double-layer electron transport layer perovskite solar cell module.

[0052] Figure 1 This is a physical picture of the double-additive double-layer electron transport layer perovskite solar cell prepared in Example 1 of the present invention.

[0053] Figure 2 This is a SEM electron microscope image of a double-additive double-layer electron transport layer perovskite solar cell prepared in Example 1 of the present invention. Figure 2 It can be seen that the perovskite film layer is dense and uniform.

[0054] Example 2

[0055] A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module comprises the following steps:

[0056] S1. A high-temperature tape was attached to a 10cm*10cm ITO glass substrate. After UV-ozone treatment, the high-temperature tape was removed and a first electron transport layer of 30nm thick was prepared by scraping SnO2 with 2% KCl added on the treated ITO glass substrate.

[0057] S2. A high-temperature tape was attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape was removed and a second electron transport layer was prepared by scraping SnO2 with 1.5% guanidine hydrochloride added to the first electron transport layer to a thickness of 60 nm.

[0058] S3. Attach the high-temperature tape to the second electron transport layer, remove the high-temperature tape after UV ozone treatment, and drop MA on the second electron transport layer. 0.6 FA 0.4 PbI3 perovskite precursor solution, blade coating the MA 0.6 FA 0.4 The PbI3 perovskite precursor solution was formed into a film, and then annealed at 100°C for 30 minutes to obtain a perovskite film with a thickness of 700 nm;

[0059] S4. The P3HT hole transport layer solution is added dropwise onto the perovskite thin film layer, and the P3HT hole transport layer solution is scraped to obtain a hole transport layer having a thickness of 50 nm;

[0060] S5. Attach a high-temperature tape to the hole transport layer, drip carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 4 μm to obtain the double-additive double-layer electron transport layer perovskite solar cell module.

[0061] Example 3

[0062] A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module comprises the following steps:

[0063] S1. A high-temperature tape was attached to a 10cm*10cm FTO glass substrate. After UV-ozone treatment, the high-temperature tape was removed and a first electron transport layer of 30nm thick was prepared by scraping SnO2 with 3% NaCl added on the treated FTO glass substrate.

[0064] S2. A high-temperature tape was attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape was removed and a second electron transport layer was prepared by scraping SnO2 with 2% biguanidine hydrochloride added to the first electron transport layer to a thickness of 60 nm.

[0065] S3. Attach the high-temperature tape to the second electron transport layer, remove the high-temperature tape after UV ozone treatment, and drop MA on the second electron transport layer. 0.6 FA 0.4 PbI3 perovskite precursor solution, blade coating the MA 0.6 FA 0.4 The PbI3 perovskite precursor solution was formed into a film, and then annealed at 100°C for 30 minutes to obtain a perovskite film with a thickness of 600 nm;

[0066] S4. Attach a high-temperature tape to the perovskite film, drip carbon slurry, and apply the carbon slurry by scraping to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the double-additive double-layer electron transport layer perovskite solar cell module.

[0067] Example 4

[0068] A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module comprises the following steps:

[0069] S1. A high-temperature tape was attached to a 10cm*10cm FTO glass substrate. After UV-ozone treatment, the high-temperature tape was removed and a first electron transport layer of 30nm thick was prepared by scraping SnO2 with 2% KBr added on the treated FTO glass substrate.

[0070] S2. A high-temperature tape was attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape was removed and a second electron transport layer was prepared by scraping SnO2 with 3% guanidine hydrochloride added to the first electron transport layer to a thickness of 60 nm.

[0071] S3. Attach the high-temperature tape to the second electron transport layer, remove the high-temperature tape after UV ozone treatment, and drop MA on the second electron transport layer. 0.6 FA 0.4 PbI3 perovskite precursor solution, blade coating the MA 0.6 FA 0.4 The PbI3 perovskite precursor solution was formed into a film, and then annealed at 100°C for 30 minutes to obtain a perovskite film with a thickness of 600 nm;

[0072] S4. The P3HT hole transport layer solution is added dropwise onto the perovskite thin film layer, and the P3HT hole transport layer solution is scraped to obtain a hole transport layer having a thickness of 50 nm;

[0073] S5. Attach a high-temperature tape to the hole transport layer, drip carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 4 μm to obtain the double-additive double-layer electron transport layer perovskite solar cell module.

[0074] Example 5

[0075] A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module comprises the following steps:

[0076] S1. A high-temperature tape was attached to a 10cm*10cm ITO glass substrate. After UV-ozone treatment, the high-temperature tape was removed and a first electron transport layer of 30nm thick was prepared by scraping SnO2 with 3% KBr added on the treated ITO glass substrate.

[0077] S2. A high-temperature tape was attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape was removed and a second electron transport layer was prepared by scraping SnO2 with 4% guanidine hydrochloride added to the first electron transport layer to a thickness of 60 nm.

[0078] S3. Attach the high-temperature tape to the second electron transport layer, remove the high-temperature tape after UV ozone treatment, and drop MA on the second electron transport layer. 0.6 FA 0.4 PbI3 perovskite precursor solution, blade coating the MA 0.6 FA 0.4 The PbI3 perovskite precursor solution was formed into a film, and then annealed at 100°C for 30 minutes to obtain a perovskite film with a thickness of 600 nm;

[0079] S4. The Spiro-OMeTAD hole transport layer solution was added dropwise onto the perovskite film layer, and the Spiro-OMeTAD hole transport layer solution was scraped to obtain a hole transport layer having a thickness of 50 nm;

[0080] S5. Attach a high-temperature tape to the hole transport layer, drip carbon slurry, and scrape the carbon slurry to prepare a low-temperature carbon electrode with a thickness of 3 μm to obtain the double-additive double-layer electron transport layer perovskite solar cell module.

[0081] Comparative Example 1

[0082] A method for preparing a perovskite solar cell module. The difference between this comparative example and Example 1 is that the comparative example is prepared in a nitrogen glove box environment, the comparative example electron transport layer is a layer of SnO2 without adding additives, and the remaining materials are consistent with Example 1. The comparative example perovskite thin film layer and carbon electrode are both prepared by spin coating and manual rubbing methods.

[0083] Comparative Example 2

[0084] A method for preparing a perovskite solar cell module. The difference between this comparative example and Example 1 is that the additive for the first electron transport layer in the comparative example is NH4Cl, and the rest of the preparation method is consistent with Example 1.

[0085] Comparative Example 3

[0086] A method for preparing a perovskite solar cell module. The difference between this comparative example and Example 1 is that the additive for the second electron transport layer in the comparative example is NaCO3, and the rest of the preparation method is consistent with Example 1.

[0087] Comparative Example 4

[0088] A method for preparing a perovskite solar cell module. The difference between this comparative example and Example 1 is that the comparative example does not contain a second electron transport layer, but only a first electron transport layer with a metal salt added. The rest of the preparation method is consistent with Example 1.

[0089] Comparative Example 5

[0090] A method for preparing a perovskite solar cell module. The difference between this comparative example and Example 1 is that the comparative example does not contain a first electron transport layer, but only a second electron transport layer with a surfactant added. The rest of the preparation method is consistent with Example 1.

[0091] Test Case

[0092] The performance tests were performed on the perovskite solar cell modules prepared in Examples 1-5 and Comparative Examples 1-5.

[0093] Test method:

[0094] Energy conversion efficiency test: Place the prepared perovskite solar cell module under a standard solar simulator of 1 sun at 25°C, test the IV curve of the device, and then calculate the energy conversion efficiency according to the following formula:

[0095] PCE=Jsc×Voc×FF

[0096] Where Jsc is the short-circuit current, Voc is the open-circuit voltage, and FF is the fill factor.

[0097] Test results: The relevant results are shown in Table 1.

[0098] Table 1 Energy conversion efficiency of Examples 1-5 and Comparative Examples 1-5

[0099]

[0100] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0101] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing a double-additive double-layer electron transport layer perovskite solar cell module, characterized in that: The preparation method of the double-additive double-layer electron transport layer perovskite solar cell module comprises the following steps: S1. A high-temperature tape is attached to a conductive substrate. After UV-ozone treatment, the high-temperature tape is removed and a first electron transport layer is printed on the conductive substrate to prepare the first electron transport layer; S2. A high-temperature tape is attached to the first electron transport layer. After UV-ozone treatment, the high-temperature tape is removed and a second electron transport layer is printed on the first electron transport layer to prepare the second electron transport layer. S3. A high-temperature tape is attached to the second electron transport layer. After UV-ozone treatment, the high-temperature tape is removed, a perovskite precursor solution is added dropwise, a film is printed, and a perovskite film is annealed to form the perovskite film; S4. Affixing a high-temperature tape to the perovskite film, dripping a carbon slurry, and printing the carbon slurry to form a low-temperature carbon electrode to obtain the double-additive double-layer electron transport layer perovskite solar cell module; in, The first electron transport layer is TiO2 or SnO2 added with a metal salt, and the mass percentage of the metal salt is 0.1%-10% of the first electron transport layer; The second electron transport layer is TiO2 or SnO2 added with a surfactant, and the mass percentage of the surfactant is 0.1%-10% of the second electron transport layer; The surfactant is selected from one of MACl, FACl, MABr, FABr, MAI, FAI, guanidine hydrochloride, and biguanidine hydrochloride.

2. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: The double-additive double-layer electron transport layer perovskite solar cell module further comprises a hole transport layer between the perovskite film and the low-temperature carbon electrode. The preparation method of the hole transport layer comprises the following steps: The hole transport layer solution is dropped onto the perovskite film and the hole transport layer is prepared by printing.

3. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: The metal salt is selected from one of KCl, NaCl, KBr, NaBr, KI and NaI.

4. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: In step S3, the perovskite material is an ABX3 type perovskite, wherein A is selected from at least one of methylamine, formamidine, cesium, rubidium, potassium and sodium; B is selected from at least one of lead, tin, germanium and bismuth; and X is selected from at least one of iodine, bromine and chlorine.

5. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: The printing method is selected from one of blade coating, spray coating and slit coating.

6. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: In step S1, the conductive substrate includes 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.

7. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 2, characterized in that: The hole transport layer is made of at least one material selected from PTAA, P3HT, CuSCN, Spiro-OMeTAD, and phosphorus.

8. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: The thickness of the perovskite film is 200-20000 nm.

9. The method for preparing a double-additive double-layer electron transport layer perovskite solar cell module according to claim 1, characterized in that: In step S3, the annealing temperature is 50-150°C.

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