Perovskite solar cell synergist and use method and application thereof

Abstract

The invention discloses a perovskite solar cell synergist and a use method and application thereof. The perovskite solar cell synergist comprises a synergistic solute and an alcohol solvent, the synergistic solute comprises a combination of small organic molecules and an ionic compound, the small organic molecules at least comprise pyridine groups and amino groups, and the ionic compound at least comprises sulfonate ions and iodide ions. The use method comprises the following steps: in the process of preparing the perovskite solar cell, applying the perovskite solar cell synergist to the surface of a perovskite layer, fully infiltrating and drying. According to the synergist disclosed by the invention, crystals on the surface of a perovskite layer enter a reformation state by utilizing the polarity of alcohol, and various effective components in the synergist are respectively combined with surface defects with different charges of the perovskite layer, so that the growth of defect site crystal grains is promoted, and a crystal repairing effect is realized; and a more complete perovskite film surface state is obtained after drying, so that the efficiency and the service life of the perovskite solar cell are improved and prolonged.

Description

Technical Field

[0001] The present invention relates to a battery synergist, in particular to a perovskite solar cell synergist, and a use method and application of the battery synergist in a perovskite solar cell, belonging to the technical field of optoelectronic materials. Background Art

[0002] Improving the efficiency of perovskite solar cells can reduce the cost of unit power generation and save the space for using solar cells. At the same time, the service life of perovskite cells still cannot meet the requirements of commercial applications. At present, the main methods to improve the efficiency and service life of perovskite solar cells include using additives in perovskite raw materials, using more sophisticated machinery for thin film coating, strictly controlling the production atmosphere and temperature, and using more rigorous packaging coverage on the outside of perovskite solar cells.

[0003] In the above methods, the use of additives is often effective only for perovskite raw materials with a specific ratio, and it is difficult to extend it to perovskite solar cells using other perovskite raw material components, and the implementation is difficult. The use of more sophisticated production equipment, stricter process environment, and more rigorous packaging will greatly increase the production cost of perovskite cells, reducing the benefits brought by the improvement of perovskite solar cell efficiency and lifespan. Summary of the invention

[0004] The main purpose of the present invention is to provide a perovskite solar cell enhancer and a method and application thereof to overcome the deficiencies in the prior art.

[0005] In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention includes:

[0006] An embodiment of the present invention provides a perovskite solar cell synergist, which includes a synergist solute and an alcohol solvent, wherein the synergist solute includes a combination of organic small molecules and ionic compounds, the organic small molecules include at least a pyridine group and an amino group, and the ionic compounds include at least a sulfonate ion and an iodide ion.

[0007] In some embodiments, the organic small molecule further comprises at least any one or more of an amine group, an amidine group, and a halogenated hydrocarbon group.

[0008] In some embodiments, the ionic compound further includes at least one or more of chloride ions, bromide ions, and ammonium ions.

[0009] The embodiment of the present invention also provides a method for using the perovskite solar cell synergist, which comprises: in the process of preparing the perovskite solar cell, applying the perovskite solar cell synergist to the surface of the perovskite layer, fully infiltrating it, and drying it.

[0010] The embodiment of the present invention also provides a perovskite solar cell obtained by the aforementioned use method.

[0011] Compared with the prior art, the beneficial effects of the present invention include:

[0012] 1) The perovskite solar cell synergist provided by the present invention utilizes the polarity of alcohol itself to make the surface crystals of the perovskite layer enter a reformed state, and the various active ingredients in the synergist are respectively combined with the surface defects of the perovskite layer with different charges, thereby promoting the growth of grains at the defect sites, achieving a crystal repair effect, and obtaining a more intact perovskite film surface state after drying, thereby substantially improving the efficiency and service life of the perovskite solar cell;

[0013] 2) The effective ingredients contained in the perovskite solar cell synergist provided by the present invention have a binding effect on the basic components of perovskite, and can generally act on perovskite solar cells of various raw material components. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0015] Figure 1 A schematic diagram of the structure, manufacturing sequence and method for using a synergist of a perovskite solar cell in Example 1 of the present invention;

[0016] Figure 2 This is a schematic diagram of the surface changes of the perovskite film before and after the use of a perovskite solar cell synergist in Example 1 of the present invention;

[0017] Figure 3 This is a graph showing the test data of the perovskite battery before and after the use of the synergist in Example 2 of the present invention;

[0018] Figure 4 This is a graph showing the test data results of the perovskite battery before and after the use of the enhancer in Example 3 of the present invention. DETAILED DESCRIPTION

[0019] In view of the problems existing in the above-mentioned prior art, after long-term research and a large number of experiments, the inventor of this case proposed this technical solution, which mainly uses an effective and easy-to-implement method to essentially optimize the film quality of perovskite batteries with various raw material components, that is, to reduce the defects on the surface of the perovskite film and improve the quality of the perovskite crystals on the surface of the film, thereby achieving an improvement in the efficiency and service life of perovskite solar cells.

[0020] The technical solution, its implementation process and principle will be further explained as follows.

[0021] As one aspect of the technical solution of the present invention, a perovskite solar cell synergist is provided, the main components of which include a synergist solute and an alcohol solvent, the synergist solute includes a combination of organic small molecules and ionic compounds, the organic small molecules include at least a pyridine group and an amino group, and the ionic compounds include at least a sulfonate ion and an iodide ion.

[0022] In some preferred embodiments, the main components of the perovskite solar cell synergist include alcohol solvents and organic small molecules or ionic compounds synergistic solutes composed of pyridine, amide, sulfonate, and iodide ions. Organic small molecules and ionic compounds need to be added to the synergist at the same time.

[0023] In some preferred embodiments, the organic small molecule also includes at least one or more of an amine group, an amidine group, a halogenated hydrocarbon group, etc., but is not limited thereto. That is, the organic small molecule must contain an amide group and a pyridine group, and at the same time contains an organic small molecule of one or more of an amine group, an amidine group, and a halogenated hydrocarbon group. The amide and pyridine groups exist in the same synergist organic small molecule, and as electron donor groups, they provide the molecule with a binding site between the perovskite lattice, thereby achieving surface modification of the perovskite film, reducing the defect density of the film, and thus achieving efficiency improvement.

[0024] In some preferred embodiments, the ionic compound also includes at least one or more of chloride ions, bromide ions, ammonium ions, etc., but is not limited thereto. That is, the ionic compound must contain sulfonate ions and iodide ions, and at the same time contain an ionic compound of one or more ions of chloride ions, bromide ions, and ammonium ions. Sulfonate ions, as divalent anions, can effectively bind to uncoordinated lead ions in the perovskite lattice to achieve perovskite surface passivation, and iodide ions, as the main constituent ions of perovskite perovskite, will migrate during the working process of the perovskite battery, destroying the original perovskite structure. The additional iodide ions added to the synergist can exist on the surface of the perovskite film, which can effectively reduce the reduction in the life of the perovskite battery caused by the migration of iodine ions.

[0025] In some preferred embodiments, the molar ratio of the organic small molecule to the ionic compound is 1:1 to 1:2.

[0026] In some preferred embodiments, the concentration of the synergistic solute in the perovskite solar cell synergist is 1 mg / mL to 3 mg / mL, that is, the concentration of the synergistic solute (that is, the total concentration of the synergist including organic small molecules and ionic compounds) should be controlled between 1 mg / mL and 3 mg / mL to ensure its effect.

[0027] In some preferred embodiments, the alcohol solvent may include any one or a combination of two or more of ethanol, isopropanol, methanol, etc., but is not limited thereto.

[0028] As one aspect of the technical solution of the present invention, a method for using a perovskite solar cell synergist is provided, which comprises: in the process of preparing a perovskite solar cell, applying the perovskite solar cell synergist to the surface of a perovskite layer, fully infiltrating it, and drying it.

[0029] The mechanism of action of the perovskite solar cell synergist provided by the present invention is: the self-polarity of alcohol is used to make the surface crystals of the prepared perovskite layer enter a reforming state, and the various effective ingredients in the synergist are respectively combined with the surface defects of the perovskite layer with different charges, promoting the growth of grains at the defect sites, achieving the crystal repair effect, and obtaining a more intact perovskite film surface state after drying, thereby substantially improving the efficiency and service life of the perovskite solar cell. Since the effective ingredients contained in the synergist have a binding effect on the basic components of the perovskite, this effect is independent of the perovskite component ratio, so it can generally act on perovskite solar cells of various raw material components.

[0030] In some preferred embodiments, the method of use specifically comprises the following steps:

[0031] preparing a transmission layer on a transparent electrode substrate;

[0032] preparing a perovskite layer on the transport layer;

[0033] The perovskite solar cell synergist is added dropwise to the surface of the perovskite layer, fully infiltrated, and dried to form a perovskite film (i.e., the synergist treatment of the perovskite film is completed);

[0034] preparing a transport layer on the perovskite film;

[0035] A metal electrode is prepared on the transport layer.

[0036] In some preferred embodiments, the thickness of the perovskite film is 500 nm to 1 μm.

[0037] In some preferred embodiments, the infiltration time is 20 to 45 seconds.

[0038] In some preferred embodiments, the drying includes baking, the baking temperature is 80°C to 120°C, and the drying time is 3min to 10min. In addition to drying, the perovskite film can also be dried by vacuum extraction, long-term natural placement, etc., which has the same effect as hot stage drying, but vacuum extraction is more complicated and more expensive, and long-term natural placement may waste time and affect the subsequent process of perovskite solar cells. Therefore, drying is preferably used.

[0039] In some embodiments, the amount of the perovskite solar cell synergist used per square centimeter of the perovskite layer is 50 μL to 100 μL.

[0040] In some more specific embodiments, the method of use includes: when using a synergist, spraying or dripping a certain volume of the synergist on the surface of the pre-prepared perovskite film to wet it, the specific amount is 50 microliters to 100 microliters of the synergist per square centimeter of film area, after the synergist acts for 20 to 45 seconds, drying the perovskite film on a hot plate at 80°C to 120°C for 3 to 10 minutes.

[0041] As one aspect of the technical solution of the present invention, it relates to a perovskite solar cell obtained by the aforementioned method of use.

[0042] In summary, the perovskite solar cell enhancer of the present invention can promote the growth of defective site grains, achieve a crystal repair effect, and obtain a more intact perovskite film surface state after drying, thereby substantially improving the efficiency and service life of the perovskite solar cell.

[0043] The whole process is described in detail below through several embodiments and drawings, but the scope of the claims of the present invention is not limited by these embodiments. At the same time, the embodiments only provide some conditions for achieving this purpose, but it does not mean that these conditions must be met to achieve this purpose. All variations associated with or derived from the contents disclosed in the present invention are considered to be within the scope of protection of the present invention.

[0044] Example 1

[0045] See also Figure 1 , showing a typical case of using a synergist to improve the efficiency and service life of perovskite solar cells. First, a perovskite solar cell is made using a common method. The main steps include: 1. Coating a transmission layer on a transparent electrode substrate; 2. Coating a perovskite layer and a synergist; 3. Coating a transmission layer; 4. Preparing a metal electrode.

[0046] Specifically, the specific components of the synergist used in this embodiment are: 2-(2-methylaminoethyl)pyridine, ammonium sulfonate, and propylamine hydroiodide in equal molar ratios, the solvent is ethanol, and the concentration of the synergist solution is 2 mg / mL.

[0047] When the enhancer is used, first add 500 microliters of the enhancer to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 30 seconds, the perovskite solar cell is transferred to a hot stage at 100°C and dried for five minutes.

[0048] In this embodiment, perovskite solar cells were prepared using three different raw material ratios of the perovskite layer (Formula A, Formulation B, and Formulation C, respectively). Table 1 shows the changes in efficiency of the perovskite solar cells prepared using the three different raw material ratios before and after the use of the synergist. It was found that the use of the synergist on the perovskite cells with different raw material ratios resulted in an improvement in efficiency.

[0049] Table 1 Changes in the maximum efficiency of perovskite solar cells with 13 formulations before and after the use of enhancers

[0050] Perovskite battery raw material ratio Maximum efficiency without using synergist (%) Maximum efficiency of using synergist (%) Recipe A 21.17 24.56 Recipe B 20.32 23.86 Recipe C 19.37 22.94

[0051] Among them, the perovskite layer formula A: the main ingredients are lead iodide, formamidine hydroiodide, methylamine hydroiodide, formamidine hydrobromide, methylamine hydrobromide, and methylamine hydrochloride, and the solvents are amide solvents and sulfone / sulfoxide solvents.

[0052] Perovskite layer formula B: main ingredients are cesium iodide, rubidium iodide, lead iodide, formamidine hydroiodide, methylamine hydroiodide, formamidine hydrobromide, and methylamine hydrobromide; solvents are amide solvents and sulfone / sulfoxide solvents.

[0053] Perovskite layer formula C: main components are lead iodide, formamidine hydroiodide, methylamine hydroiodide, formamidine hydrobromide, and methylamine hydrobromide; solvents are amide solvents, hydrocarbons, and halogenated hydrocarbon solvents.

[0054] Table 2 shows the improvement of the service life of perovskite solar cells by the synergist by displaying the change in efficiency of the tested perovskite solar cells before and after being placed at room temperature for 1000 hours. It includes the changes in the service life of three types of perovskite solar cells before and after the use of the synergist. It is found that the service life of perovskite cells with different raw material ratios is significantly improved after the synergist is used.

[0055] Table 2 Changes in the service life of 3 kinds of perovskite solar cells before and after using the enhancer

[0056]

[0057] See also Figure 2By taking pictures of the perovskite battery film crystals before and after using the enhancer using a scanning electron microscope, it can be observed that the wrinkles on the crystal surface are reduced and the crystal boundaries are tighter, indicating that the quality of the perovskite film has improved. Better film quality can effectively improve the efficiency and service life of perovskite solar cells.

[0058] Example 2

[0059] The specific ingredients of the synergist used in this example are: 2-(2-methylaminoethyl)pyridine, ammonium sulfonate, propylamine hydroiodide, and 3-bromopropylamine hydrobromide in equal molar ratios, the solvent is isopropanol, and the concentration of the synergist solution is 2 mg / mL.

[0060] When the enhancer is used, first add 500 microliters of the enhancer to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 20 seconds, the perovskite solar cell is transferred to a hot stage at 80°C and dried for 10 minutes.

[0061] Figure 3 The test data chart of the perovskite solar cell prepared by using formula A before and after using the enhancer of this embodiment is shown. It can be seen that the photoelectric conversion performance of the perovskite solar cell is significantly improved after using the enhancer.

[0062] Example 3

[0063] The specific components of the synergist used in this example are: 2-(2-methylaminoethyl)pyridine, ammonium sulfonate, propylamine hydroiodide, and formamidine hydrochloride in equal molar ratios. The solvent is isopropanol and methanol, the solvent volume ratio is 10:1, and the concentration of the synergist solution is 2 mg / mL.

[0064] When the enhancer is used, 450 microliters of the enhancer is first added to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 45 seconds, the perovskite solar cell is transferred to a hot stage at 120°C and dried for 3 minutes.

[0065] Figure 4 The test data chart of the perovskite solar cell prepared by using formula B before and after using the enhancer of this embodiment is shown. It can be seen that the photoelectric conversion performance of the perovskite solar cell is significantly improved after using the enhancer.

[0066] Example 4

[0067] The difference between this embodiment and embodiment 1 is that the molar ratio of the organic small molecule to the ionic compound is 1:2.

[0068] Example 5

[0069] The difference between this embodiment and embodiment 1 is that the concentration of the synergistic solute in the synergist is 1 mg / mL.

[0070] Example 6

[0071] The difference between this embodiment and embodiment 1 is that the concentration of the synergistic solute in the synergist is 3 mg / mL.

[0072] Comparative Example 1 (without ionic compound)

[0073] The specific component of the synergist used in this comparative example is 2-(2-methylaminoethyl)pyridine, the solvent is ethanol, and the concentration of the synergist solution is 2 mg / mL.

[0074] When the enhancer is used, 500 microliters of the enhancer is first added to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 30 seconds, the perovskite solar cell is transferred to a hot stage at 100°C and dried for five minutes.

[0075] As shown in Table 3, the synergist of this comparative example was dripped onto the surface of the perovskite layer prepared by formula A. The maximum efficiency of the perovskite solar cell was improved before and after the use of the synergist, but it was far less significant than that of Example 1, and the service life was slightly reduced before and after the use of the synergist.

[0076] Comparative Example 2 (without small organic molecules)

[0077] The specific components of the synergist used in this comparative example are ammonium sulfonate and propylamine hydroiodide in an equal molar ratio, the solvent is ethanol, and the concentration of the synergist solution is 2 mg / mL.

[0078] When the enhancer is used, 500 microliters of the enhancer is first added to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 30 seconds, the perovskite solar cell is transferred to a hot stage at 100°C and dried for five minutes.

[0079] As shown in Table 3, the synergist of this comparative example was dripped onto the surface of the perovskite layer prepared by formula A. The maximum efficiency of the perovskite solar cell was slightly reduced before and after the use of the synergist, and the service life was improved before and after the use of the synergist.

[0080] Comparative Example 3 (without iodine ion)

[0081] The specific ingredients of the synergist used in this comparative example are 2-(2-methylaminoethyl)pyridine and ammonium sulfonate, the solvent is ethanol, and the concentration of the synergist solution is 2 mg / mL.

[0082] When the enhancer is used, 500 microliters of the enhancer is first added to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 30 seconds, the perovskite solar cell is transferred to a hot stage at 100°C and dried for five minutes.

[0083] As shown in Table 3, the synergist of this comparative example was dripped onto the surface of the perovskite layer prepared by formula A. The maximum efficiency of the perovskite solar cell was slightly improved before and after the use of the synergist, but it was far less significant than that of Example 1, and the service life was reduced before and after the use of the synergist.

[0084] Comparative Example 4 (Solvent is non-alcoholic solvent)

[0085] The specific ingredients of the synergist used in this comparative example are 2-(2-methylaminoethyl)pyridine, ammonium sulfonate, and propylamine hydroiodide in equal molar ratios, the solvent is chlorobenzene, and the concentration of the synergist solution is 2 mg / mL.

[0086] When the enhancer is used, 500 microliters of the enhancer is first added to the surface of the 9 square centimeter perovskite layer to wet it. After the enhancer reacts for 30 seconds, the perovskite solar cell is transferred to a hot stage at 100°C and dried for five minutes.

[0087] As shown in Table 3, the enhancer of this control example was added dropwise to the surface of the perovskite layer prepared by Formula A. The maximum efficiency of the perovskite solar cell did not change significantly before and after the use of the enhancer, and the service life did not change significantly before and after the use of the enhancer.

[0088] See Table 3 for the comparison results of the maximum efficiency and lifespan of the above control examples 1-4 and Example 1 before and after the use of the synergist.

[0089] Table 3 Comparison of the maximum efficiency and life of the synergist before and after use of the control examples 1-4 and the embodiment 1

[0090] Device efficiency The device has the highest efficiency after 1000h Device efficiency maintenance percentage after 1 000h No enhancers used 21.17％ 19.10％ 90.22％ Example 1 24.56％ 24.10％ 98.13％ Comparative Example 1 22.21％ 19.72％ 88.79％ Comparative Example 2 21.11％ 20.22％ 95.78％ Comparative Example 3 23.00％ 20.51％ 89.17％ Comparative Example 4 21.10％ 19.36％ 91.75％

[0091] In addition, the inventors of this case also conducted experiments with other raw materials and conditions listed in this specification in accordance with the above embodiments, and also prepared a perovskite solar cell enhancer with the same effect.

[0092] It should be understood that the above are only specific application examples of the present invention and do not constitute any limitation on the protection scope of the present invention. Any technical solution formed by equivalent transformation or equivalent replacement falls within the protection scope of the present invention.

Claims

1. A perovskite solar cell synergist, characterized in that: include: A synergistic solute and an alcohol solvent, wherein the synergistic solute comprises a combination of an organic small molecule and an ionic compound, wherein the organic small molecule at least comprises a pyridine group and an amino group, and the ionic compound at least comprises a sulfonate ion and an iodide ion.

2. The perovskite solar cell synergist according to claim 1, characterized in that: The organic small molecule further comprises at least any one or more of an amine group, an amidine group, and a halogenated hydrocarbon group.

3. The perovskite solar cell synergist according to claim 1, characterized in that: The ionic compound further includes at least one or more of chloride ion, bromide ion and ammonium ion.

4. The perovskite solar cell synergist according to claim 1, characterized in that: The molar ratio of the organic small molecule to the ionic compound is 1:1 to 1:

2.

5. The perovskite solar cell synergist according to claim 1, characterized in that: The concentration of the synergistic solute in the perovskite solar cell synergist is 1 mg / mL to 3 mg / mL.

6. The perovskite solar cell synergist according to claim 1, characterized in that: The alcohol solvent includes any one of ethanol, isopropanol, and methanol, or a combination of two or more thereof.

7. The method for using the perovskite solar cell synergist according to any one of claims 1 to 6, characterized in that: include: In the process of preparing the perovskite solar cell, the perovskite solar cell synergist is applied to the surface of the perovskite layer, fully infiltrated, and dried.

8. The method of use according to claim 7, characterized in that: include: preparing a transmission layer on a transparent electrode substrate; preparing a perovskite layer on the transport layer; The perovskite solar cell synergist is added dropwise to the surface of the perovskite layer, fully infiltrated, and dried to form a perovskite film; preparing a transport layer on the perovskite film; A metal electrode is prepared on the transport layer.

9. The method of use according to claim 7, characterized in that: The soaking time is 20 to 45 seconds; and / or the drying includes any one of drying, vacuum extraction, and natural placement; the drying temperature is 80°C to 120°C, and the time is 3 minutes to 10 minutes; And / or, the thickness of the perovskite film is 500nm to 1μm; And / or, the amount of the perovskite solar cell enhancer used per square centimeter of the perovskite layer is 50 μL to 100 μL.

10. A perovskite solar cell obtained by the method according to any one of claims 7 to 9.

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