Perovskite material and solar cell

Abstract

The application relates to the technical field of solar cells, in particular to a perovskite material and a solar cell, the perovskite material is A2B + B 3+ X6; wherein A is a monovalent cation, B + is a monovalent metal cation, B 3+ is a trivalent metal cation, and X is a halogen element; the mass ratio of the amino benzene sulfonic acid to A2B + B 3+ X6 is 1:100-250, and the solar cell prepared by using the disclosed perovskite material as a perovskite layer has good photoelectric performance.

Description

Technical Field

[0001] This invention relates to the field of solar cell technology, specifically to a perovskite material and a solar cell. Background Technology

[0002] With the rapid development of the global economy, human demand for energy far exceeds the Earth's supply capacity. Traditional fossil fuels (oil, natural gas, etc.) are non-renewable resources; not only are they non-renewable, but they also have a significant impact on the environment. Recently, traditional fossil fuels have faced a crisis, and environmental pollution has intensified. Breaking free from dependence on traditional fossil fuels and developing renewable energy is the inevitable path for the future development of human society. Renewable energy includes wind power, hydropower, solar power, geothermal energy, and tidal energy. Among these, solar energy has the largest resource volume and the widest distribution, and can be considered inexhaustible.

[0003] Perovskite solar cells are a typical example of high-efficiency, low-cost new solar cells. Since their discovery in 2009, perovskite solar cells have attracted widespread attention due to their excellent light absorption, superior charge transport rate, high photoelectric conversion efficiency, simple process, and huge development potential.

[0004] The most representative organic-inorganic hybrid perovskite material is CH3NH3PbI3, which currently boasts a certified photoelectric conversion efficiency approaching 24%. However, organic-inorganic hybrid perovskite materials suffer from two significant drawbacks:

[0005] (1) Performance is easily affected by conditions such as temperature, humidity and light;

[0006] (2) The presence of Pb in the ingredients leads to their toxicity and environmental unfriendliness.

[0007] Therefore, inorganic lead-free double perovskite materials with higher stability have begun to attract attention and research. The photoelectric conversion efficiency of pure inorganic lead-free double perovskite materials is relatively low and cannot compare with existing organic-inorganic hybrid perovskite materials. Therefore, improving the photoelectric conversion efficiency of inorganic lead-free double perovskite materials has become a current research focus. Summary of the Invention

[0008] Purpose of the invention: In view of the above-mentioned technical problems, the present invention proposes a perovskite material and a solar cell.

[0009] The technical solution adopted is as follows:

[0010] A perovskite material, wherein the perovskite material is A2B modified with aminobenzenesulfonic acid. Ⅰ + B Ⅱ 3+ X6;

[0011] Where A is a monovalent cation, B Ⅰ + B is a monovalent metal cation. Ⅱ 3+ X is a trivalent metal cation, and X is a halogen element.

[0012] Aminobenzenesulfonic acid and A2B Ⅰ + B Ⅱ 3+ The mass ratio of X6 is 1:100-250.

[0013] Furthermore, A is Li + Na + K + 、Rb + Cs + [(CH3)4N] + [CH3NH3] + [CH2NH=CH] + Any one of them, preferably Cs + .

[0014] Furthermore, B Ⅰ + Cu + Ag + Au + Any one or more combinations thereof, preferably Ag + .

[0015] Furthermore, B Ⅱ 3+ For As 3+ Bi 3+ ,Rh 3+ Sb 3+ Cr 3+ Co 3+ Ga 3+ Fe 3+ Ru 3+ Y 3+ Any one or more combinations thereof, preferably Bi 3+ and Ga 3+ , the Bi 3+ and Ga 3+ The molar ratio is 1-7:1-7.

[0016] Furthermore, aminobenzenesulfonic acid and A2B Ⅰ + B Ⅱ 3+ The mass ratio of X6 is 1:125.

[0017] The present invention also provides a solar cell comprising an FTO layer, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode layer, wherein the perovskite layer comprises the aforementioned perovskite material.

[0018] Furthermore, the electron transport layer comprises a 1-aminopropyl-3-methylimidazolium bromide ionic liquid.

[0019] Furthermore, the hole transport layer comprises Cu x O / graphene oxide composite hole transport material.

[0020] Furthermore, the method for fabricating the solar cell is as follows:

[0021] S1: Add 1-aminopropyl-3-methylimidazolium bromide ionic liquid to isopropanol and stir to obtain an electron transport liquid. Then, spin-coating is used to generate the electron transport layer on the FTO layer.

[0022] S2: Using one or more of DMF, DMSO, and GBL as solvents, AX and B Ⅰ + X, B Ⅱ 3+ X3 is added to the solvent and stirred until it is completely dissolved. Then aminobenzenesulfonic acid is added and stirring is continued to obtain perovskite solution. The perovskite solution is then spin-coated on the surface of the electron transport layer. After spin-coating, the perovskite layer is obtained by annealing at 120-180℃ for 10-30 minutes.

[0023] S3: Add copper acetate to water and stir to dissolve it. Then add graphene oxide and sonicate to disperse it evenly. Then add sodium hydroxide solution and glucose. After heating and stirring for a period of time, separate the solid, wash it repeatedly with water and ethanol and dry it. Then disperse the obtained solid evenly in isopropanol to obtain the hole transport liquid. Take the hole transport liquid and spin-coat it on the surface of the perovskite layer. After spin-coating, anneal at 80-120℃ for 10-30 min to obtain the hole transport layer.

[0024] S4: Finally, a metal electrode layer is generated on the hole transport layer to obtain the solar cell.

[0025] Furthermore, the mass ratio of copper acetate to graphene oxide is 1:0.025-0.05.

[0026] The beneficial effects of this invention are:

[0027] This invention provides a perovskite material, Ga 3+The doping of Cu makes carrier transitions in the Cs2AgBiBr6 crystal structure easier, significantly reducing exciton energy and facilitating exciton transitions. This is beneficial for capturing sunlight, making it more suitable as a light-absorbing material and improving photoelectric properties. Aminobenzenesulfonic acid modification optimizes the interfacial contact between the perovskite layer and the electron / hole transport layer, improving energy level matching and carrier transport capacity. Furthermore, the introduction of aminobenzenesulfonic acid can increase the crystallinity of the perovskite material, reduce the number of pinholes on the perovskite layer surface, and improve film formation performance. Using 1-aminopropyl-3-methylimidazolium bromide ionic liquid as the electron transport layer facilitates better interfacial contact between the perovskite layer and the electron transport layer. x O / graphene oxide composite hole transport material, as a hole transport layer, has better conductivity, and the structure formed by the three components is beneficial to improving the photoelectric performance of solar cells. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of the solar cells prepared in the embodiments and comparative examples of the present invention;

[0029] Figure 2 This is a SEM image of the perovskite layer prepared in Example 1 of the present invention. Detailed Implementation

[0030] Unless otherwise specified in the examples, the conditions were performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products. Techniques not mentioned in this invention refer to existing technologies. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0031] Example 1:

[0032] A solar cell includes an FTO layer, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode layer;

[0033] The perovskite layer is Cs2AgBi modified with p-aminobenzenesulfonic acid. 0.25 Ga 1.75 Br6;

[0034] The electron transport layer is a 1-aminopropyl-3-methylimidazolium bromide ionic liquid.

[0035] Hole transport layer is Cu x O / graphene oxide composite hole transport material;

[0036] The metal electrode layer is an Ag electrode;

[0037] The above-mentioned solar cell is prepared by the following method:

[0038] The FTO glass was ultrasonically cleaned sequentially with HJ-B311 detergent, water, and ethanol, followed by ozone ionization treatment for 30 min to further remove residual organic residues. It was then dried with a nitrogen gun. 0.25 g of 1-aminopropyl-3-methylimidazolium bromide ionic liquid was added to 12.4 mL of isopropanol and stirred for 30 min to obtain an electron transport liquid. 80 μL of this electron transport liquid was dropped onto the FTO glass surface and spin-coated at 3000 rpm for 40 s. The surface was then heated at 70°C for 10 min to generate an electron transport layer approximately 60 nm thick. CsBr, AgBr, BiBr3, and GaBr3 were weighed according to the molar ratio in the chemical formula. DMF and GBL were mixed at a volume ratio of 7:1 to obtain a solvent. CsBr, AgBr, BiBr3, and GaBr3 were added to the solvent and stirred until completely dissolved to obtain a 0.5 M precursor solution. Then, p-aminobenzenesulfonic acid was added. The aminobenzenesulfonic acid reacted with Cs2AgBi... 0.25 Ga 1.75 The mass ratio of Br6 was 1:125. After stirring, a perovskite solution was obtained. 100 μL of the perovskite solution was spin-coated onto the surface of the electron transport layer at 5000 rpm for 40 s. After spin-coating, the layer was annealed at 150℃ for 15 min to obtain a perovskite layer with a thickness of approximately 100 nm. 15 mmol of copper acetate was added to 20 mL of water and stirred until dissolved. Then, graphene oxide was added, with a copper acetate to graphene oxide mass ratio of 1:0.025. The mixture was ultrasonically vibrated for 30 min to ensure uniform dispersion. Then, 10 mL of 9M sodium hydroxide solution and 0.6 g of glucose were added. The mixture was heated to 70℃ and stirred for 90 min. After centrifugation, the solid was separated, washed repeatedly with water and ethanol, and dried. 260 mg of the obtained solid was then uniformly dispersed in 15 mL of isopropanol to obtain the hole transport fluid. 80 μL of the hole transport fluid was spin-coated onto the surface of the perovskite layer at 5000 rpm for 40 s. After spin coating, the layer was annealed at 100℃ for 30 min to obtain a hole transport layer with a thickness of approximately 65 nm. The resulting semi-finished product and silver particles were then placed in a high-vacuum resistance evaporation coating machine at a vacuum degree of 9 × 10⁻⁶. - 4 The solar cell can be obtained by starting the evaporation of Ag electrodes at Pa and depositing a thickness of 100 nm.

[0039] Example 2:

[0040] A solar cell includes an FTO layer, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode layer;

[0041] The perovskite layer is Cs2AgBi modified with p-aminobenzenesulfonic acid. 0.25 Ga 1.75 Br6;

[0042] The electron transport layer is a 1-aminopropyl-3-methylimidazolium bromide ionic liquid.

[0043] Hole transport layer is Cu x O / graphene oxide composite hole transport material;

[0044] The metal electrode layer is an Ag electrode;

[0045] The above-mentioned solar cell is prepared by the following method:

[0046] The FTO glass was ultrasonically cleaned sequentially with HJ-B311 detergent, water, and ethanol, followed by ozone ionization treatment for 30 min to further remove residual organic residues. It was then dried with a nitrogen gun. 0.25 g of 1-aminopropyl-3-methylimidazolium bromide ionic liquid was added to 12.4 mL of isopropanol and stirred for 30 min to obtain an electron transport liquid. 80 μL of this electron transport liquid was dropped onto the FTO glass surface and spin-coated at 3000 rpm for 40 s. The surface was then heated at 70°C for 10 min to generate an electron transport layer approximately 60 nm thick. CsBr, AgBr, BiBr3, and GaBr3 were weighed according to the molar ratio in the chemical formula. DMF and GBL were mixed at a volume ratio of 7:1 to obtain a solvent. CsBr, AgBr, BiBr3, and GaBr3 were added to the solvent and stirred until completely dissolved to obtain a 0.5 M precursor solution. Then, p-aminobenzenesulfonic acid was added. The aminobenzenesulfonic acid reacted with Cs2AgBi... 0.25 Ga 1.75 The mass ratio of Br6 was 1:125. After stirring, a perovskite solution was obtained. 100 μL of the perovskite solution was spin-coated onto the surface of the electron transport layer at 5000 rpm for 40 s. After spin-coating, the layer was annealed at 130℃ for 20 min to obtain a perovskite layer with a thickness of approximately 100 nm. 15 mmol of copper acetate was added to 20 mL of water and stirred until dissolved. Then, graphene oxide was added, with a mass ratio of copper acetate to graphene oxide of 1:0.03. The mixture was ultrasonically vibrated for 30 min to ensure uniform dispersion. Then, 10 mL of 9M sodium hydroxide solution and 0.6 g of glucose were added. The mixture was heated to 70℃ and stirred for 90 min. After centrifugation, the solid was separated, washed repeatedly with water and ethanol, and dried. 260 mg of the obtained solid was then uniformly dispersed in 15 mL of isopropanol to obtain the hole transport fluid. 80 μL of the hole transport fluid was spin-coated onto the surface of the perovskite layer at 5000 rpm for 40 s. After spin coating, the layer was annealed at 120℃ for 10 min to obtain a hole transport layer with a thickness of approximately 65 nm. The resulting semi-finished product and silver particles were then placed in a high-vacuum resistance evaporation coating machine at a vacuum degree of 9 × 10⁻⁶. - 4 The solar cell can be obtained by starting the evaporation of Ag electrodes at Pa and depositing a thickness of 100 nm.

[0047] Example 3:

[0048] A solar cell includes an FTO layer, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode layer;

[0049] The perovskite layer is Cs2AgBi modified with p-aminobenzenesulfonic acid. 0.25 Ga 1.75 Br6;

[0050] The electron transport layer is a 1-aminopropyl-3-methylimidazolium bromide ionic liquid.

[0051] Hole transport layer is Cu x O / graphene oxide composite hole transport material;

[0052] The metal electrode layer is an Ag electrode;

[0053] The above-mentioned solar cell is prepared by the following method:

[0054] The FTO glass was ultrasonically cleaned sequentially with HJ-B311 detergent, water, and ethanol, followed by ozone ionization treatment for 30 min to further remove residual organic residues. It was then dried with a nitrogen gun. 0.25 g of 1-aminopropyl-3-methylimidazolium bromide ionic liquid was added to 12.4 mL of isopropanol and stirred for 30 min to obtain an electron transport liquid. 80 μL of this electron transport liquid was dropped onto the FTO glass surface and spin-coated at 3000 rpm for 40 s. The surface was then heated at 70°C for 10 min to generate an electron transport layer approximately 60 nm thick. CsBr, AgBr, BiBr3, and GaBr3 were weighed according to the molar ratio in the chemical formula. DMF and GBL were mixed at a volume ratio of 7:1 to obtain a solvent. CsBr, AgBr, BiBr3, and GaBr3 were added to the solvent and stirred until completely dissolved to obtain a 0.5 M precursor solution. Then, p-aminobenzenesulfonic acid was added. The aminobenzenesulfonic acid reacted with Cs2AgBi... 0.25 Ga 1.75The mass ratio of Br6 was 1:125. After stirring, a perovskite solution was obtained. 100 μL of the perovskite solution was spin-coated onto the surface of the electron transport layer at 5000 rpm for 40 s. After spin-coating, the layer was annealed at 180℃ for 30 min to obtain a perovskite layer with a thickness of approximately 100 nm. 15 mmol of copper acetate was added to 20 mL of water and stirred until dissolved. Then, graphene oxide was added, with a mass ratio of copper acetate to graphene oxide of 1:0.05. The mixture was ultrasonically vibrated for 30 min to ensure uniform dispersion. Then, 10 mL of 9M sodium hydroxide solution and 0.6 g of glucose were added. The mixture was heated to 70℃ and stirred for 90 min. After centrifugation, the solid was separated, washed repeatedly with water and ethanol, and dried. 260 mg of the obtained solid was then uniformly dispersed in 15 mL of isopropanol to obtain the hole transport fluid. 80 μL of the hole transport fluid was spin-coated onto the surface of the perovskite layer at 5000 rpm for 40 s. After spin coating, the layer was annealed at 120℃ for 30 min to obtain a hole transport layer with a thickness of approximately 65 nm. The resulting semi-finished product and silver particles were then placed in a high-vacuum resistance evaporation coating machine at a vacuum degree of 9 × 10⁻⁶. - 4 The solar cell can be obtained by starting the evaporation of Ag electrodes at Pa and depositing a thickness of 100 nm.

[0055] Example 4:

[0056] It is basically the same as Example 1, except that m-aminobenzenesulfonic acid is used instead of p-aminobenzenesulfonic acid.

[0057] Example 5:

[0058] It is basically the same as Example 1, except that o-aminobenzenesulfonic acid is used instead of p-aminobenzenesulfonic acid.

[0059] Comparative Example 1: Basically the same as Example 1, except that the perovskite layer is Cs2AgBi. 0.25 Ga 1.75 Br6, without modification by p-aminobenzenesulfonic acid.

[0060] Comparative Example 2: Basically the same as Example 1, except that the perovskite layer is Cs2AgBiBr6 modified with p-aminobenzenesulfonic acid.

[0061] Comparative Example 3: Basically the same as Example 1, except that the hole transport layer is Cu. x O-hole transport material, without graphene oxide.

[0062] Performance testing: at AM1.5, 100mW / cm 2 Under illumination, the performance of the solar cells prepared in each embodiment and comparative example was tested using a solar simulator. The test results are shown in Table 1.

[0063]

[0064] As shown in Table 1 above, the solar cells prepared using the perovskite material disclosed in this invention as the perovskite layer have excellent photoelectric performance.

[0065] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A solar cell, characterized in that, It includes an FTO layer, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode layer, wherein the perovskite layer comprises a perovskite material; The perovskite material is A2B modified with aminobenzenesulfonic acid. Ⅰ + B Ⅱ 3+ X6; Where X represents a halogen element; Aminobenzenesulfonic acid and A2B Ⅰ + B Ⅱ 3+ The mass ratio of X6 is 1:100-250; A is Cs + B Ⅰ + For Ag + ; B Ⅱ 3+ for Bi 3+ and Ga 3+ , the Bi 3+ and Ga 3+ The molar ratio is 1-7:1-7; The electron transport layer comprises a 1-aminopropyl-3-methylimidazolium bromide ionic liquid; The hole transport layer includes Cu x O / graphene oxide composite hole transport material.

2. The solar cell as described in claim 1, characterized in that, Aminobenzenesulfonic acid and A2B Ⅰ + B Ⅱ 3+ The mass ratio of X6 is 1:

125.

3. The solar cell as described in claim 1, characterized in that, The method for preparing the solar cell is as follows: S1: Add 1-aminopropyl-3-methylimidazolium bromide ionic liquid to isopropanol and stir to obtain an electron transport liquid. Then, spin-coating is used to generate the electron transport layer on the FTO layer. S2: Using one or more of DMF, DMSO, and GBL as solvents, AX and B Ⅰ + X, B Ⅱ 3+ X3 is added to the solvent and stirred until it is completely dissolved. Then aminobenzenesulfonic acid is added and stirring is continued to obtain perovskite solution. The perovskite solution is then spin-coated on the surface of the electron transport layer. After spin-coating, the perovskite layer is obtained by annealing at 120-180℃ for 10-30 minutes. S3: Add copper acetate to water and stir to dissolve it. Then add graphene oxide and sonicate to disperse it evenly. Then add sodium hydroxide solution and glucose. After heating and stirring for a period of time, separate the solid, wash it repeatedly with water and ethanol and dry it. Then disperse the obtained solid evenly in isopropanol to obtain the hole transport liquid. Take the hole transport liquid and spin-coat it on the surface of the perovskite layer. After spin-coating, anneal at 80-120℃ for 10-30 min to obtain the hole transport layer. S4: Finally, a metal electrode layer is generated on the hole transport layer to obtain the solar cell.

4. The solar cell as described in claim 3, characterized in that, The mass ratio of copper acetate to graphene oxide is 1:0.025-0.05.

Images