Preparation methods of perovskite thin film, perovskite cell and laminated cell
By adding modified materials to the perovskite film to react with PbI2, the problems of low efficiency and poor stability caused by PbI2 residue in perovskite batteries are solved, and the effect of improving the efficiency and stability of perovskite batteries is achieved.
Patent Information
- Application Number
- CN202410717558.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-04
- Publication Date
- 2025-03-28
Smart Images
Figure CN119730678A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the technical field of solar cells, and in particular to a method for preparing a perovskite film, a method for preparing a perovskite cell, and a method for preparing a perovskite cell and a stacked cell. Background Art
[0002] In the prior art, an interface modification layer may be added to the surface of the perovskite film, so as to react with the excess PbI2 remaining in the perovskite film to generate low-dimensional perovskite, thereby forming a stable perovskite cell. When preparing the perovskite film, an inorganic framework may be evaporated on the crystalline silicon velvet surface, but the inorganic framework formed by the above-mentioned method is uneven, and there are often many PbI2 that have not reacted completely. The introduction of the interface modification layer material cannot completely deplete the PbI2. In addition, the remaining interface modification layer material that has not participated in the reaction and the remaining PbI2 may also act as defect centers, aggravating the recombination of electrons and holes at the interface, thereby causing a sharp drop in the efficiency and stability of the perovskite / crystalline silicon stacked solar cell. Summary of the invention
[0003] The present application provides a method for preparing a perovskite film, a method for preparing a perovskite battery, a method for preparing a perovskite battery and a stacked battery, so as to solve the problems of low efficiency and poor stability of perovskite batteries in related technologies.
[0004] According to one aspect of the present application, a method for preparing a perovskite film is provided, comprising the following steps: providing a substrate; forming an inorganic phase on one side of the substrate; forming an organic phase on a side of the inorganic phase facing away from the substrate, wherein the material forming the organic phase contains a modifying material; and removing the substrate to obtain a perovskite film.
[0005] Optionally, after the step of forming the inorganic phase, the preparation method further comprises: performing gradient annealing treatment on the inorganic phase.
[0006] Optionally, the modifying material includes at least one of the following: succinamide, propylene glycol, sodium stearate and polyethylene glycol.
[0007] Optionally, the material of the organic phase includes at least one of the following: methylamine, ethylamine and methylamine.
[0008] According to another aspect of the present application, a method for preparing a perovskite cell is provided, comprising the following steps: providing a substrate, on which a first transparent conductive layer is disposed; forming a hole transport layer on a side of the first transparent conductive layer facing away from the substrate; forming a mixed interface layer on a side of the hole transport layer facing away from the first transparent conductive layer; and forming a perovskite film prepared by the above-mentioned method for preparing a perovskite film on a side of the mixed interface layer facing away from the hole transport layer.
[0009] Optionally, the step of forming the mixed interface layer includes: forming the mixed interface layer on the hole transport layer using a mixed interface solution, wherein the solute of the mixed interface solution is pyridylmethanonecarbazole and its derivatives.
[0010] Optionally, the preparation method further comprises the step of forming a mixed interface solution: mixing a first solution and a second solution having the same concentration, wherein the solute of the first solution is 2-bipyridyl ketone and the solute of the second solution is 2-methoxycarbazole.
[0011] Optionally, the volume ratio of the first solution to the second solution is (65:35) to (85:15).
[0012] Optionally, after the step of forming the perovskite film, the method for preparing the perovskite cell further comprises: sequentially forming an electron transport layer, a second transparent conductive layer and an electrode layer on a side of the perovskite film away from the mixed interface layer.
[0013] According to another aspect of the present application, a perovskite cell is provided, which is prepared by the above-mentioned perovskite cell preparation method.
[0014] According to another aspect of the present application, a method for preparing a stacked cell is provided, including providing a crystalline silicon bottom cell; and using the above-mentioned method for making a perovskite cell to form a perovskite cell on the crystalline silicon bottom cell to obtain a stacked cell.
[0015] Through the technical solution of the present application, a method for preparing a perovskite film is provided, the method comprising: providing a substrate; forming an inorganic phase on one side of the substrate; forming an organic phase on the side of the inorganic phase facing away from the substrate, wherein the material forming the organic phase contains a modifying material; removing the substrate to obtain a perovskite film; the inorganic phase of the perovskite film contains residual PbI2, and the modifying material is added to the organic phase, the modifying material can react with PbI2, and the PbI2 is completely consumed, thereby avoiding the recombination of electrons at the interface of the hole transport layer, and improving the efficiency and stability of the perovskite battery. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:
[0017] Figure 1 It is a schematic diagram of a process for preparing a perovskite film according to an embodiment of the present application;
[0018] Figure 2 It is a schematic diagram of the cross-sectional structure of a substrate after a perovskite film is formed on a substrate in a method for preparing a perovskite film provided in an embodiment of the present application;
[0019] Figure 3 It is a schematic diagram of a process for preparing a perovskite battery provided in an embodiment of the present application;
[0020] Figure 4 is a partial cross-sectional schematic diagram of another perovskite battery provided according to an embodiment of the present application;
[0021] Figure 5 is a schematic diagram of the chemical structural formula of 2-pyridylmethanonecarbazole;
[0022] Figure 6 Schematic diagram of the chemical structure of methoxy-2-pyridylmethanonecarbazole.
[0023] The above drawings include the following reference numerals:
[0024] 10. Base; 11. Substrate; 20. First transparent conductive layer; 30. Hole transport layer; 40. Mixed interface layer; 50. Perovskite film; 51. Inorganic phase; 52. Organic phase; 60. Electron transport layer; 70. Second transparent conductive layer; 80. Electrode layer. DETAILED DESCRIPTION
[0025] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.
[0026] In order to enable those skilled in the art to better understand the solution of the present application, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present application.
[0027] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application and the above-mentioned drawings are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the data used in this way can be interchanged where appropriate, so as to describe the embodiments of the present application described herein. In addition, the terms "including" and "having" and any variations thereof are intended to cover non-exclusive inclusions, for example, a process, method, system, product or device that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods, products or devices.
[0028] In the related art, in order to reduce the PbI2 in the perovskite film, the Keen people will add an interface modification layer on the surface of the perovskite film to improve the stability of the perovskite solar cell, so as to generate a low-dimensional perovskite cell. When preparing the perovskite film, an inorganic framework can be evaporated on the crystalline silicon velvet surface, but the inorganic framework formed by the above-mentioned method is uneven, and there will be a lot of unreacted PbI2. The remaining interface modification layer material that did not participate in the reaction and the remaining PbI2 may also act as defect centers, aggravating the recombination of electrons and holes at the interface, thereby causing a sharp drop in the efficiency and stability of the perovskite / crystalline silicon stacked solar cell.
[0029] Therefore, in order to solve the above problems, a method for preparing a perovskite film is provided in the embodiments of the present application. Figure 1 As shown, the following steps are included:
[0030] Step S1: providing a substrate;
[0031] Step S2: forming an inorganic phase on one side of the substrate;
[0032] Step S3: forming an organic phase on the side of the inorganic phase facing away from the substrate, wherein the solution of the organic phase contains a modifying material; removing the substrate to obtain a perovskite film.
[0033] In the above-mentioned method for preparing perovskite film, a modifying material is added to the organic phase of the perovskite film, and the modifying material reacts with PbI2 and completely consumes PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer and improving the efficiency and stability of the perovskite battery.
[0034] The exemplary embodiments of the method for preparing the perovskite film provided in the present application will be described in more detail below. However, these exemplary embodiments can be implemented in a variety of different forms and should not be interpreted as being limited to the embodiments described herein. It should be understood that these embodiments are provided to make the disclosure of the present application thorough and complete, and to fully convey the concepts of these exemplary embodiments to those of ordinary skill in the art.
[0035] First, if Figure 2 As shown, the above step S1 is performed: providing a substrate 11 .
[0036] Specifically, the substrate 11 may be a semiconductor substrate, such as any one of silicon, gallium arsenide and silicon nitride substrates, but is not limited to the above types. Those skilled in the art may also reasonably select the type of substrate for preparing the perovskite film according to actual needs.
[0037] After the step of providing the substrate, as Figure 2 As shown, the above step S2 is performed: an inorganic phase 51 is formed on one side of the substrate 11 .
[0038] Specifically, the perovskite film used in the present application can be a methyl lead iodide perovskite layer, and the material of the inorganic phase 51 in the formed methyl lead iodide perovskite layer can be PbI2. After the formation of the inorganic phase 51, there will still be a lot of unreacted PbI2. The remaining PbI2 may also act as a defect center, aggravating the recombination of electrons and holes at the interface, thereby causing the efficiency and stability of the perovskite / crystalline silicon stacked solar cell to drop sharply. In the subsequent preparation of the organic phase 52, the modifying material is added to completely consume the PbI2, thereby improving the efficiency and stability of the perovskite cell.
[0039] After the step of forming an inorganic phase on one side of the substrate, as Figure 2 As shown, the above step S3 is performed: an organic phase 52 is formed on the side of the inorganic phase 51 away from the substrate 11 , and the material forming the organic phase 52 contains a modifying material; the substrate 11 is removed to obtain a perovskite film 50 .
[0040] Specifically, the modifying material is mixed with the organic phase material, and the mixed material is used to form the organic phase 52 on the surface of the inorganic phase 51 facing away from the substrate 11 , and then the substrate 11 is removed to form a complete perovskite film 50 .
[0041] Through the technical solution of the above-mentioned method for preparing the perovskite film of the present application, a method for preparing the perovskite film is provided, the method comprising: providing a substrate; forming an inorganic phase on one side of the substrate; forming an organic phase on the side of the inorganic phase away from the substrate, wherein the material forming the organic phase has a modifying material; removing the substrate to obtain the perovskite film 50; there is residual PbI2 in the inorganic phase of the above-mentioned perovskite film, and the modifying material is added to the above-mentioned organic phase, and the modifying material can react with PbI2 to completely consume the PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer, and improving the efficiency and stability of the perovskite battery.
[0042] In some optional embodiments, after the step of forming the inorganic phase, the preparation method further comprises: performing gradient annealing treatment on the inorganic phase.
[0043] In the above optional embodiment, the process for forming the inorganic phase can be any one or more of vacuum evaporation, chemical vapor deposition and physical vapor deposition. Those skilled in the art can reasonably select the method for forming the above inorganic phase and the above organic phase according to actual conditions, and this application does not make specific limitations.
[0044] In the above optional embodiment, the above gradient annealing includes a first annealing and a second annealing, wherein the temperature of the first annealing is 90°C to 110°C, the first annealing time is 3 to 5 minutes, and the temperature of the second annealing is 160°C to 200°C, and the second annealing time is 4 to 7 minutes; by gradually lowering the temperature during the annealing process, the inorganic framework (inorganic phase) forms a more uniform crystalline structure, reduces defects and impurities, improves the quality and stability of the perovskite film, and also improves the combination effect of PbI2 and the organic phase, making the reaction of PbI2 and the organic phase more complete, thereby improving the efficiency and stability of the perovskite solar cell.
[0045] In some optional embodiments, the above-mentioned modifying material includes at least one of the following: succinamide, propylene glycol, sodium stearate and polyethylene glycol.
[0046] In the above optional embodiments, the modifying material may be any one or more of succinamide, propylene glycol, sodium stearate and polyethylene glycol. The above modifying materials may help improve the contact and diffusion between PbI2 and the organic phase, thereby promoting the complete reaction of PbI2. Those skilled in the art may reasonably select the type of modifying material according to actual conditions, and this application does not make any specific limitation.
[0047] In some optional embodiments, the material of the organic phase includes at least one of the following: methylamine, ethylamine and methylamine.
[0048] In the above optional embodiment, the material of the organic phase can be any one or more of methylamine (MA), ethylamine (EA) and methylamine (FA), wherein the above materials can react with PbI2 to form a perovskite crystal structure, and help to improve the photoelectric conversion efficiency and stability of the perovskite film, but will not completely react PbI2. For example, methylamine (MA) can completely react with residual PbI2 with the help of modifying materials to form MAI, and then MAI and PbI2 form a perovskite film together. Those skilled in the art can reasonably select the type of organic phase material according to actual conditions, and this application does not make specific limitations.
[0049] According to another embodiment of the present application, a method for preparing a perovskite battery is also provided. Figure 3 As shown, the following steps are included:
[0050] Step S4: providing a substrate, on which a first transparent conductive layer is disposed;
[0051] Step S5: forming a hole transport layer on the side of the first transparent conductive layer away from the substrate;
[0052] Step S6: forming a mixed interface layer on the side of the hole transport layer away from the first transparent conductive layer;
[0053] Step S7: forming a perovskite thin film prepared by the above-mentioned perovskite thin film preparation method on a side of the above-mentioned mixed interface layer away from the above-mentioned hole transport layer.
[0054] The perovskite film in the above-mentioned perovskite cell is prepared by the above-mentioned perovskite film preparation method, which improves the efficiency and stability of the perovskite cell. The inorganic phase of the above-mentioned perovskite film has residual PbI2, and a modifying material is added to the above-mentioned organic phase. The modifying material can react with PbI2 to completely consume PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer, thereby improving the crystallization quality and photoelectric performance of the perovskite film of the perovskite cell, thereby improving the efficiency and stability of the perovskite cell.
[0055] The following is a more detailed description of exemplary embodiments of the method for preparing a perovskite cell provided in accordance with the present application. However, these exemplary embodiments may be implemented in a variety of different forms and should not be construed as being limited to the embodiments described herein. It should be understood that these embodiments are provided to make the disclosure of the present application thorough and complete, and to fully convey the concepts of these exemplary embodiments to those of ordinary skill in the art.
[0056] First, if Figure 4 As shown, step S4 is performed: providing a substrate 10 , on which a first transparent conductive layer 20 is disposed.
[0057] Specifically, the above-mentioned substrate 10 can also be other types of photovoltaic cell structures, such as crystalline silicon cells. The above-mentioned preparation method of the embodiment of the present application is adopted to form a stacked photovoltaic cell by forming a perovskite cell on the different types of photovoltaic cell structures; the first transparent conductive layer 20 has the function of carrying other materials and collecting photoelectrons, and is a transparent electrode with high visible light transmittance and low resistivity. The material of the first transparent conductive layer 20 can be any one or more of indium tin oxide, zinc oxide and tin oxide, but is not limited to the above types. Those skilled in the art can also reasonably select the material types of the substrate and the first transparent conductive layer according to actual needs, and the present application does not make specific limitations.
[0058] After the step of providing a substrate, Figure 4 As shown, step S5 is performed: a hole transport layer 30 is formed on the side of the first transparent conductive layer 20 away from the substrate 10 .
[0059] Specifically, Figure 4As shown, the material forming the hole transport layer 30 can be Spiro-OMeTAD (2,2',7,7'-tetramethyl-9,9'-bis(3,3'-dimethyl-2,1'-benzothiadiazole-4,4'-diyl)-9H-anthraquinone dimethanol), PTAA (poly(terephthalate)), PEDOT:PSS (a mixture of poly(3,4-ethylenedioxythiophene) and polystyrene sulfonic acid) and NiO x (nickel oxide), and those skilled in the art can also reasonably select the material type of the hole transport layer according to actual needs, and this application does not make any specific limitation.
[0060] After the step of forming the hole transport layer, Figure 4 As shown, step S6 is performed: forming a mixed interface layer 40 on the side of the hole transport layer 30 away from the first transparent conductive layer 20 .
[0061] Specifically, Figure 4 As shown, a mixed interface solution is coated on one side of the hole transport layer 30 to obtain a mixed interface layer 40. The mixed interface layer 40 can enhance the compatibility between the perovskite material and the electrolyte, improve the stability and durability of the perovskite battery, and add the mixed interface layer 40 between the hole transport layer 30 and the perovskite film 50 to improve the crystallization quality of the perovskite film. The mixed interface solution can be a plurality of isopropanol solution, 2PACz solution and MeO-2PACz solution, which is not specifically limited in this application.
[0062] After the step of forming the mixed interface layer, as Figure 4 As shown, step S7 is performed: a perovskite film 50 prepared by the above-mentioned perovskite film preparation method is formed on the side of the above-mentioned mixed interface layer 40 away from the above-mentioned hole transport layer 30.
[0063] Specifically, the perovskite film 50 obtained by the preparation method of the perovskite film is placed on the side of the mixed interface layer 40 away from the above-mentioned hole transport layer 30. The inorganic phase of the above-mentioned perovskite film 50 has residual PbI2. A modifying material is added to the above-mentioned organic phase. The modifying material can react with PbI2 to completely consume PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer 30, and improving the efficiency and stability of the perovskite battery.
[0064] In some optional embodiments, the step of forming the mixed interface layer comprises: forming the mixed interface layer on the hole transport layer using a mixed interface solution, wherein the solute of the mixed interface solution is pyridylmethanonecarbazole and its derivatives.
[0065] In the above optional implementation, the solute of the mixed interface solution is pyridylmethanonecarbazole and its derivatives, the solvent can be isopropanol, the mixed interface solution is spin-coated on the hole transport layer by a spin coating process, and annealed in air to obtain a mixed interface layer.
[0066] In the above optional implementation manner, the solvent of the mixed interface solution is not limited to the above-mentioned isopropanol, and this application does not make any specific limitation.
[0067] In some optional embodiments, such as Figure 5 and Figure 6 As shown, the preparation method further includes the step of forming the mixed interface solution: mixing a first solution and a second solution having the same concentration, wherein the solute of the first solution is 2-bipyridyl ketone and the solute of the second solution is 2-methoxycarbazole.
[0068] In the above optional embodiment, 2-bipyridyl ketone solution and 2-methoxycarbazole solution of the same concentration are mixed, and then mixed with isopropanol of the same concentration. 2-bipyridyl ketone solution and 2-methoxycarbazole solution of the same concentration are used as the solution of the mixed interface layer. The organic substances in the above two solutions will be evenly distributed on the interface of the perovskite battery, thereby improving the electron transfer efficiency and reducing the possibility of electron recombination.
[0069] In the above optional implementation, if Figure 5 As shown, Figure 5 Is the chemical structural formula of 2-bipyridyl ketone; Figure 6 As shown, Figure 6 It is the chemical structural formula of 2-methoxycarbazole.
[0070] In some optional embodiments, the volume ratio of the first solution to the second solution is (65:35) to (85:15).
[0071] In the above optional embodiment, the 2-bipyridyl ketone solution and the 2-methoxycarbazole solution of the same concentration are mixed within the above volume ratio range, so that the mixed interface layer formed by the 2-bipyridyl ketone solution and the 2-methoxycarbazole solution can be made denser and the defects of the mixed interface layer can be reduced.
[0072] In some optional embodiments, such as Figure 3 and Figure 4 As shown, after the step of forming the above-mentioned perovskite film 50, the preparation method of the above-mentioned perovskite battery also includes: step S8: forming an electron transport layer 60, a second transparent conductive layer 70 and an electrode layer 80 in sequence on the side of the above-mentioned perovskite film 50 away from the above-mentioned mixed interface layer 40.
[0073] In the above optional implementation, if Figure 4 As shown, an electron transport layer 60, a second transparent conductive layer 70 and an electrode layer 80 are sequentially prepared on the surface of the side of the perovskite film 50 facing away from the substrate 10 to obtain a complete perovskite battery, wherein the material of the electron transport layer 60 may be any one or more of SnO2, ZnO, TiO2, PCBM (phenyl-C61-butyric acid methyl ester) and C60, the material of the second transparent conductive layer 70 is consistent with the material of the first transparent conductive layer 20, and the material of the electrode layer 80 may be any one or more of Au, Ag, Cu and Al. Those skilled in the art may reasonably select the materials of the electron transport layer, the second transparent conductive layer and the electrode layer according to actual conditions, and this application does not make specific limitations.
[0074] According to another embodiment of the present application, a perovskite battery is provided, which is prepared by the preparation method of the perovskite battery in the above embodiment.
[0075] The perovskite cell obtained by the preparation method of the perovskite cell of the present application has residual PbI2 in the inorganic phase of the perovskite film. A modifying material is added to the above-mentioned organic phase, and the modifying material can react with PbI2 to completely consume PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer and improving the efficiency and stability of the perovskite cell.
[0076] According to another embodiment of the present application, a method for manufacturing a stacked cell is also provided. The stacked cell includes providing a crystalline silicon bottom cell; using the above-mentioned method for manufacturing a perovskite cell, a perovskite top cell is formed on the crystalline silicon bottom cell to obtain a stacked cell.
[0077] In the above optional implementation manner, the crystalline silicon bottom cell can be a single crystal silicon cell, a polycrystalline silicon cell and a thin film silicon cell. Technical personnel in this field can reasonably select the type of silicon crystal bottom cell according to actual conditions, and this application does not make specific limitations. The main material of the single crystal silicon cell is high-purity single crystal silicon, which has high conversion efficiency and stability. The polycrystalline silicon cell uses polycrystalline silicon material. The thin film silicon cell adopts thin film technology to make polycrystalline silicon material into thin sheets, which can achieve a lighter and more flexible design with relatively low cost.
[0078] The stacked battery obtained by the manufacturing method of the stacked battery of the present application has residual PbI2 in the inorganic phase of the perovskite film of the perovskite top battery. A modifying material is added to the above-mentioned organic phase, and the modifying material can react with PbI2 to completely consume PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer and improving the efficiency and stability of the perovskite battery.
[0079] The preparation method of the above-mentioned perovskite battery and the perovskite battery of the present application will be specifically described below in combination with specific embodiments and comparative examples.
[0080] Example 1
[0081] This embodiment provides a method for preparing a perovskite battery, comprising the following steps:
[0082] 1. Providing a substrate, on which a first transparent conductive layer is disposed, wherein the substrate is made of silicon with a thickness of 100 nm, and the first transparent conductive layer is made of ITO with a thickness of 300 nm;
[0083] 2. Forming a hole transport layer on the side of the first transparent conductive layer away from the substrate, the material of the hole transport layer is PTAA, and the thickness is 300nm;
[0084] 3. Forming a mixed interface layer on the side of the hole transport layer away from the substrate, the material of the mixed interface layer is a mixed solution prepared by 2-bipyridyl ketone solution and 2-methoxycarbazole solution in a volume ratio of (75:25), and the thickness is 200 nm;
[0085] 4. An inorganic phase and an organic phase of a perovskite film are sequentially formed on the side of the mixed interface layer away from the substrate. The organic phase material of the perovskite film contains a modifying material. The formed inorganic phase is first annealed at a temperature of 90°C to 110°C for 3 to 5 minutes, and then a second annealing is performed at a temperature of 160°C to 200°C for 4 to 7 minutes. The inorganic phase material of the perovskite film is PbI2 with a thickness of 100nm, the organic phase material is MA with a thickness of 100nm, and the modifying material is SA.
[0086] 5. An electron transport layer, a second transparent conductive layer and an electrode layer are formed in sequence on the side of the perovskite film facing away from the substrate. The electron transport layer is made of ZnO with a thickness of 300 nm, the second transparent conductive layer is made of ITO with a thickness of 300 nm, and the electrode layer is made of Ag with a thickness of 300 nm.
[0087] Comparative Example 1
[0088] This embodiment provides a method for preparing a perovskite battery, comprising the following steps:
[0089] 1. Providing a substrate, on which a first transparent conductive layer is disposed, wherein the substrate is made of silicon with a thickness of 100 nm, and the first transparent conductive layer is made of ITO with a thickness of 300 nm;
[0090] 2. Forming a hole transport layer on the side of the first transparent conductive layer away from the substrate, the material of the hole transport layer is PTAA, and the thickness is 300nm;
[0091] 3. Forming a mixed interface layer on the side of the hole transport layer away from the substrate, the material of the mixed interface layer is a mixed solution prepared by 2-bipyridyl ketone solution and 2-methoxycarbazole solution in a volume ratio of (75:25), and the thickness is 200 nm;
[0092] 4. The inorganic phase and the organic phase of the perovskite film are sequentially formed on the side of the mixed interface layer away from the substrate. The formed inorganic phase is first annealed at a temperature of 90°C to 110°C for 3 to 5 minutes, and then a second annealing is performed at a temperature of 160°C to 200°C for 4 to 7 minutes. The inorganic phase material of the perovskite film is PbI2 with a thickness of 100nm, and the organic phase material is MA with a thickness of 100nm.
[0093] 5. An electron transport layer, a second transparent conductive layer and an electrode layer are formed in sequence on the side of the perovskite film facing away from the substrate. The electron transport layer is made of ZnO with a thickness of 300 nm, the second transparent conductive layer is made of ITO with a thickness of 300 nm, and the electrode layer is made of Ag with a thickness of 300 nm.
[0094] Comparative Example 2
[0095] This embodiment provides a method for preparing a perovskite battery, comprising the following steps:
[0096] 1. Providing a substrate, on which a first transparent conductive layer is disposed, wherein the substrate is made of silicon with a thickness of 100 nm, and the first transparent conductive layer is made of ITO with a thickness of 300 nm;
[0097] 2. Forming a hole transport layer on the side of the first transparent conductive layer away from the substrate, the material of the hole transport layer is PTAA, and the thickness is 300nm;
[0098] 3. Forming a mixed interface layer on the side of the hole transport layer away from the substrate, the material of the mixed interface layer is a mixed solution prepared by 2-bipyridyl ketone solution and 2-methoxycarbazole solution in a volume ratio of (75:25), and the thickness is 200 nm;
[0099] 4. An inorganic phase and an organic phase of a perovskite film are sequentially formed on the side of the mixed interface layer away from the substrate. The organic phase material of the perovskite film contains a modifying material. The formed inorganic phase is first annealed at a temperature of 90°C to 110°C for 3 to 5 minutes, and then a second annealing is performed at a temperature of 160°C to 200°C for 4 to 7 minutes. The inorganic phase material of the perovskite film is PbI2 with a thickness of 100 nm, the organic phase material is MA with a thickness of 100 nm, and the modifying material is propylene glycol.
[0100] 5. An electron transport layer, a second transparent conductive layer and an electrode layer are formed in sequence on the side of the perovskite film facing away from the substrate. The electron transport layer is made of ZnO with a thickness of 300 nm, the second transparent conductive layer is made of ITO with a thickness of 300 nm, and the electrode layer is made of Ag with a thickness of 300 nm.
[0101] The performance of the perovskite battery prepared by the preparation method of the perovskite battery in the above-mentioned Example 1, Comparative Example 1 and Comparative Example 2 was tested, and the test results are as follows:
[0102] Table 1
[0103]
[0104]
[0105] From the experimental data in the above table, it can be seen that in Example 1, SA is used as a modifying material, and the filling factor and photoelectric conversion efficiency are better than those of Comparative Examples 1 and 2. That is, the addition of SA as a modifying material in the organic phase of the perovskite film can react with PbI2 in the inorganic phase to completely consume PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer and improving the efficiency and stability of the perovskite battery. From the above description, it can be seen that the above-mentioned embodiments of the present application achieve the following technical effects:
[0106] The preparation method of the above-mentioned perovskite film of the embodiment of the present application is adopted. By having residual PbI2 in the inorganic phase of the perovskite film, a modifying material is added to the above-mentioned organic phase. The modifying material can react with PbI2 to completely consume PbI2, thereby avoiding the recombination of electrons at the interface of the hole transport layer and improving the efficiency and stability of the perovskite battery.
[0107] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or device. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the process, method, commodity or device including the elements.
[0108] The above are only embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included within the scope of the claims of the present application.
Claims
1. A method for preparing a perovskite film, characterized in that: The following steps are involved: providing a substrate; forming an inorganic phase on one side of the substrate; forming an organic phase on a side of the inorganic phase facing away from the substrate, wherein the material forming the organic phase contains a modifying material; The substrate is removed to obtain the perovskite film.
2. The method for preparing a perovskite thin film according to claim 1, characterized in that: After the step of forming the inorganic phase, the preparation method further comprises: The inorganic phase is subjected to a gradient annealing treatment.
3. The method for preparing a perovskite thin film according to claim 1, characterized in that: The modifying material comprises at least one of the following: succinamide, propylene glycol, sodium stearate and polyethylene glycol.
4. The method for preparing a perovskite thin film according to claim 1, characterized in that: The material of the organic phase includes at least one of the following: methylamine, ethylamine and methylamine.
5. A method for preparing a perovskite battery, characterized in that: The following steps are involved: Providing a substrate, on which a first transparent conductive layer is disposed; forming a hole transport layer on a side of the first transparent conductive layer away from the substrate; forming a mixed interface layer on a side of the hole transport layer away from the first transparent conductive layer; A perovskite thin film prepared by the method for preparing a perovskite thin film according to any one of claims 1 to 4 is formed on a side of the mixed interface layer away from the hole transport layer.
6. The method for preparing a perovskite battery according to claim 5, characterized in that: The steps of forming the mixed interface layer include: The mixed interface layer is formed on the hole transport layer by using a mixed interface solution, and the solute of the mixed interface solution is pyridylmethanonecarbazole and its derivatives.
7. The method for preparing a perovskite battery according to claim 6, characterized in that: The preparation method further comprises the step of forming the mixed interface solution: A first solution and a second solution having the same concentration are mixed, wherein the solute of the first solution is 2-bipyridyl ketone and the solute of the second solution is 2-methoxycarbazole.
8. The method for preparing a perovskite battery according to claim 7, characterized in that: The volume ratio of the first solution to the second solution is (65:35) to (85:15).
9. The method for preparing a perovskite battery according to claim 5, characterized in that: After the step of forming the perovskite film, the method for preparing the perovskite cell further comprises: An electron transport layer, a second transparent conductive layer and an electrode layer are sequentially formed on a side of the perovskite film away from the mixed interface layer.
10. A perovskite battery, characterized in that: The perovskite battery is prepared by the preparation method of any one of claims 5 to 9.
11. A method for preparing a laminated battery, characterized in that: include: Provide crystalline silicon bottom cells; The method for preparing a perovskite cell according to any one of claims 5 to 9 is adopted to form a perovskite cell on the crystalline silicon bottom cell to obtain the stacked cell.