Preparation method of carbon electrode meso-perovskite battery, perovskite battery, assembly and power generation system

Abstract

The application discloses a preparation method of a carbon electrode meso-perovskite battery, and a perovskite battery, a component and a power generation system, and comprises the following steps: S1, selecting FTO conductive glass as a transparent conductive substrate or selecting a glass substrate, preparing a transparent conductive film on the glass substrate, and forming the transparent conductive substrate by the glass substrate and the transparent conductive film; S2, preparing a dense electron transport layer on the transparent conductive film; S3, preparing a mesoporous electron transport layer on the dense electron transport layer; S4, preparing a ferroelectric interval insulating layer on the mesoporous electron transport layer by using an inorganic ferroelectric body; S5, preparing a carbon electrode on the ferroelectric interval insulating layer; S6, preparing a perovskite light absorption layer on the carbon electrode; and S7, applying a ferroelectric polarization field to the ferroelectric interval insulating layer in a direction from the perovskite light absorption layer to the glass substrate 1, and the strength of the applied ferroelectric polarization field is greater than that of a ferroelectric coercive field of the ferroelectric interval insulating layer. The application improves the perovskite built-in field, and further improves the open-circuit voltage and photoelectric conversion efficiency of the traditional perovskite battery.

Description

Technical Field

[0001] This invention relates to the field of perovskite battery technology, specifically to a method for preparing a carbon electrode mesoscopic perovskite battery, as well as the perovskite battery, module, and power generation system. Background Technology

[0002] In existing technologies, the electrode fabrication methods for perovskite solar cells typically include the following steps:

[0003] Step S1: Prepare a transparent conductive film on a glass substrate;

[0004] Step S2: Prepare a dense electron transport layer on a transparent conductive film;

[0005] Step S3: Prepare a mesoporous electron transport layer on the dense electron transport layer;

[0006] Step S4: Prepare a ZrO insulating layer on the mesoporous electron transport layer using ZrO;

[0007] Step S5: Fabricate a carbon electrode on the ferroelectric spacer insulating layer;

[0008] Step S6: Prepare a perovskite light-absorbing layer on the carbon electrode;

[0009] The perovskite solar cells prepared by the above method can only prevent direct contact between the carbon electrode and the electron transport layer, thereby preventing leakage and suppressing the recombination of photogenerated electron-hole pairs. However, due to the weak built-in field of perovskite in traditional perovskite solar cells, the open-circuit voltage of traditional perovskite solar cells is low and their photoelectric conversion efficiency is low.

[0010] Therefore, how to improve the built-in field of perovskite, and thus improve the open-circuit voltage and photoelectric conversion efficiency of traditional perovskite solar cells, has become an urgent problem to be solved in the field of perovskite solar cell fabrication technology. Summary of the Invention

[0011] This invention aims to enhance the built-in field of perovskite, thereby improving the open-circuit voltage and photoelectric conversion efficiency of traditional perovskite solar cells. It provides a method for preparing a carbon electrode mesoscopic perovskite solar cell, as well as the perovskite solar cell, module, and power generation system.

[0012] To achieve this objective, the present invention adopts the following technical solution:

[0013] A method for fabricating a carbon electrode mesoscopic perovskite solar cell, as well as the perovskite solar cell, its components, and a power generation system, are provided, including:

[0014] Step S1: Select FTO conductive glass as a transparent conductive substrate or select a glass substrate, and prepare a transparent conductive film on the glass substrate, so that the transparent conductive substrate is composed of the glass substrate and the transparent conductive film;

[0015] Step S2: Prepare a dense electron transport layer on a transparent conductive film;

[0016] Step S3: Prepare a mesoporous electron transport layer on the dense electron transport layer;

[0017] Step S4: Prepare a ferroelectric spacer insulating layer on the mesoporous electron transport layer using inorganic ferroelectric materials;

[0018] Step S5: Fabricate a carbon electrode on the ferroelectric spacer insulating layer;

[0019] Step S6: Prepare a perovskite light-absorbing layer on the carbon electrode;

[0020] Step S7: Apply a ferroelectric polarization field from the perovskite light-absorbing layer toward the glass substrate to the ferroelectric spacer insulating layer. The intensity of the applied ferroelectric polarization field is greater than the ferroelectric coercive field of the ferroelectric spacer insulating layer.

[0021] Preferably, in step S4, the inorganic ferroelectric material is PZT.

[0022] Preferably, the ferroelectric spacer insulating layer is prepared by the following steps:

[0023] Step L1: Grind PZT powder to obtain PZT nanocrystals;

[0024] Step L2: Add PZT nanocrystals to deionized water and stir to obtain PZT hydrosol;

[0025] Step L3: Apply PZT hydrosol to the mesoporous electron transport layer, and anneal the PZT hydrosol coated on the mesoporous electron transport layer to form a ferroelectric spacer insulating layer.

[0026] Preferably, the transparent conductive film is made of one of the following materials: ITO (tin-doped indium oxide), FTO (fluorine-doped tin oxide), IWO (tungsten-doped indium oxide), and ICO (cerium-doped indium oxide).

[0027] Preferably, the dense electron transport layer is composed of at least one of PCBM, TiO2, ZnO, SnO2, H-PDI, and F-PDI.

[0028] Preferably, the constituent material of the mesoporous electron transport layer is at least one of PCBM, TiO2, ZnO, SnO2, H-PDI, and F-PDI.

[0029] Preferably, the perovskite light-absorbing layer is composed of an organic-inorganic hybrid perovskite with the general formula ABX3; wherein A is at least one of CH3NH3+ (MA+), CH(CH2)2+ (FA+), and Cs+, B is one of Pb2+, Sn2+, and Ge2+, and X is at least one of Cl-, Br-, and I-.

[0030] The present invention also provides a perovskite solar cell, which is prepared by the preparation method described above.

[0031] The present invention also provides a perovskite solar cell module, which is composed of a plurality of perovskite solar cells prepared by the above-described preparation method and electrically connected together.

[0032] The present invention also provides a solar power generation system comprising a plurality of electrically connected perovskite cell modules as described above.

[0033] The present invention has the following beneficial effects:

[0034] By using inorganic ferroelectric materials to prepare ferroelectric spacer insulation layers and applying ferroelectric polarization fields to the ferroelectric spacer insulation layers, the ferroelectric domains inside the ferroelectric spacer insulation layers are oriented and arranged, thereby forming a directional polarization electric field inside the ferroelectric spacer insulation layers. The perovskite is then passivated by the ferroelectric polarization, thereby enhancing the built-in field of the perovskite.

[0035] The enhancement of the built-in field in perovskites produces two beneficial effects:

[0036] 1. On the one hand: The built-in field of the enhanced perovskite material intensifies the splitting of the quasi-Fermi level of electrons and holes in the perovskite pin junction, which further improves the open-circuit voltage of the battery.

[0037] 2. On the other hand: The built-in field of the enhanced perovskite material causes band bending at the interface of the heterojunction formed by the perovskite light absorption layer 7 and the dense electron transport layer 3, thereby increasing the rate of separation and extraction of photogenerated carriers at the heterojunction interface.

[0038] The enhancement of the built-in field within the perovskite cell increases the open-circuit voltage and improves the separation and extraction rate of charge carriers, thus solving the problem of low photoelectric conversion efficiency in perovskite cells prepared in the prior art. Attached Figure Description

[0039] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments of the present invention will be briefly described below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0040] Figure 1 This is a schematic diagram of a carbon electrode mesoscopic perovskite solar cell structure prepared by the preparation method provided in this invention.

[0041] Figure 2 This is a schematic diagram of a large-area carbon electrode mesoscopic perovskite solar cell structure prepared by the preparation method provided in this invention.

[0042] Figure 3 This is an experimental comparison of the open-circuit voltage and carrier separation and extraction rate of a carbon electrode mesoscopic perovskite solar cell when the ferroelectric spacer insulating layer is prepared using PZT, PbTiO3, BaTiO3, BiFeO3 or zirconium oxide.

[0043] Reference numerals: 1. Glass substrate; 2. Transparent conductive film; 3. Dense electron transport layer; 4. Mesoporous electron transport layer; 5. Ferroelectric spacer insulating layer; 6. Carbon electrode; 7. Perovskite light absorption layer; 8. Laser scribing groove. Detailed Implementation

[0044] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0045] The accompanying drawings are for illustrative purposes only and are schematic diagrams, not actual images. They should not be construed as limiting the scope of this patent. To better illustrate the embodiments of the present invention, some parts in the drawings may be omitted, enlarged, or reduced, and do not represent the actual dimensions of the product. It is understandable to those skilled in the art that some well-known structures and their descriptions may be omitted in the drawings.

[0046] In the accompanying drawings of the embodiments of the present invention, the same or similar reference numerals correspond to the same or similar components. In the description of the present invention, it should be understood that if terms such as "upper," "lower," "left," "right," "inner," and "outer" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, they are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, the terms used to describe positional relationships in the drawings are only for illustrative purposes and should not be construed as limiting the present patent. For those skilled in the art, the specific meaning of the above terms can be understood according to the specific circumstances.

[0047] In the description of this invention, unless otherwise explicitly specified and limited, the term "connection" or similar designation indicating a connection between components should be interpreted broadly. For example, it can refer to a fixed connection, a detachable connection, or an integral part; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can refer to the internal communication between two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0048] Example 1:

[0049] This invention provides a method for preparing a carbon electrode mesoscopic perovskite solar cell, as well as the perovskite solar cell, its module, and a power generation system. Figure 1 , 2 As shown, it includes:

[0050] Step S1: Select a glass substrate 1, and prepare a transparent conductive film 2 on the glass substrate 1. The transparent conductive film and the glass substrate 1 together form a transparent conductive substrate.

[0051] Alternatively, high-transmittance FTO conductive glass can be used directly as a transparent conductive substrate.

[0052] The transparent conductive substrate is then cleaned. First, the FTO substrate surface is wiped with ethanol-soaked lint-free paper. Then, it is ultrasonically cleaned with cleaning agent, deionized water, acetone, and ethanol in sequence for 15-20 minutes. After that, it is dried in a ventilated oven and treated with O3UV for 20 minutes. The cleaning of the transparent conductive substrate is then completed.

[0053] Step S2: Prepare a dense electron transport layer 3 on the transparent conductive film 2;

[0054] TiO2 was selected as the raw material for the dense electron transport layer 3. An appropriate amount of deionized water was frozen into ice for later use. Under a fume hood, TiCl4 was evenly dropped onto the ice using a pipette, and a small amount of deionized water was quickly added. The mixture was stirred at 70°C for 1 hour. The prepared FTO substrate was coated with high-temperature tape and placed in a petri dish, then immersed in the above precursor solution. After reacting at 70°C for 1 hour, the dense TiO2 layer was deposited on the FTO. The TiO2 film was blown with N2 and dried at 70°C for 1 hour to obtain the dense electron transport layer 3.

[0055] Step S3: Prepare a mesoporous electron transport layer 4 on the dense electron transport layer 3;

[0056] TiO2 was selected as the raw material for the mesoporous electron transport layer 4. Purchased TiO2 slurry was mixed with terpineol in a certain proportion to obtain a TiO2 slurry mixture. The TiO2 slurry mixture was then screen-printed onto the dense layer 3. After standing for 30 minutes to allow the bubbles in the TiO2 slurry mixture to disappear, it was dried on a heating stage at 70°C. Subsequently, it was placed on a high-temperature heating stage and heated to 500°C and held for 20 minutes, then naturally cooled to room temperature to obtain the mesoporous electron transport layer 4.

[0057] Step S4: A ferroelectric spacer insulating layer 5 is prepared on the mesoporous electron transport layer 4 using inorganic ferroelectric materials;

[0058] PZT is selected as the inorganic ferroelectric material because it has high remanent polarization, good ferroelectricity, and low preparation cost. Therefore, PZT is preferred for the preparation of the ferroelectric spacer insulating layer 5.

[0059] Step L1: PZT powder is synthesized by hydrothermal method and then ground into PZT nanocrystals using a ball mill;

[0060] Step L2: Add PZT nanocrystals to deionized water and stir for 2 hours to make PZT hydrosol;

[0061] Step L3: PZT hydrosol is coated onto the mesoporous electron transport layer 4 using the slot-die coating method, and then annealed at 350°C to form the ferroelectric spacer insulating layer 5.

[0062] Step S5: Prepare a carbon electrode 6 on the ferroelectric spacer insulating layer 5;

[0063] Carbon paste was printed on the PZT ferroelectric spacer insulation layer 5 using screen printing. After standing for 10 minutes, it was dried on a heating table at 70°C. Then, it was placed on a high-temperature heating table and heated to 400°C for sintering. After holding at that temperature for 30 minutes, it was naturally cooled to room temperature.

[0064] Step S6: Prepare a perovskite light-absorbing layer 7 on the carbon electrode 6;

[0065] The preferred organic-inorganic hybrid perovskite material FA0.91Cs0.09PbI3, which is free of MA+, is used as the light-absorbing layer of this perovskite solar cell. First, the FA0.91Cs0.09PbI3 precursor solution was prepared by adding PbI2, FAI, and CsI in a chemical ratio of 1:0.91:0.09 to a DMF / DMSO mixture with a volume ratio of 4.75:1 until the solution concentration reached 1.25 mol / L. Then, MaCl was added to the solution until its concentration reached 23 mol% to stabilize the perovskite phase. Next, the perovskite precursor solution was filled. The non-filled areas of the cell were covered with high-temperature tape, and the perovskite precursor solution was filled into the cell using a pipette. Annealing at 160℃ for 10-15 minutes completed the preparation of the perovskite light-absorbing layer 7.

[0066] Step S7: Polarize the ferroelectric spacer insulation layer 5;

[0067] Ferroelectric materials are polarized by applying an electric field to them. Since the constant current source method of applying an electric field is simple, fast and low in equipment cost, the constant current source method is used to apply an electric field to the ferroelectric spacer insulation layer.

[0068] A positive ferroelectric polarization field perpendicular to the surface of the perovskite cell is applied to the ferroelectric spacer insulating layer 5 by means of a constant current voltage source, pointing from the perovskite light absorption layer 7 to the transparent conductive substrate. The applied electric field is greater than the ferroelectric coercive field of PZT, which polarizes the ferroelectric spacer insulating layer 5.

[0069] Example 2:

[0070] The difference between Example 2 and Example 1 is that in Example 1, PZT was used as the inorganic ferroelectric material in step S4, while in Example 2, any one of PbTiO3, BaTiO3, or BiFeO3 was used as the inorganic ferroelectric material in step S4. Among them, BaTiO3 has weaker ferroelectricity and its field passivation effect is not as good as that of PZT; although BiFeO3 has strong ferroelectric polarization, it is very difficult to prepare pure phase BiFeO3, so the ferroelectric polarization measured in BiFeO3 ceramics is usually very weak, and therefore the field passivation effect of BiFeO3 is also very weak; PbTiO3 has stronger ferroelectricity than BaTiO3 or BiFeO3, and its field passivation effect is not much different from that of PZT. Figure 3 Experimental comparative data on the open-circuit voltage and carrier separation and extraction rate of carbon electrode mesoscopic perovskite solar cells when PZT, PbTiO3, BaTiO3, BiFeO3 or zirconium oxide are selected to prepare the ferroelectric spacer insulating layer.

[0071] Example 3:

[0072] The difference between Example 3 and Example 1 lies in step S7. The characteristic of S7 in Example 3 is as follows:

[0073] Step S7: Polarize the ferroelectric spacer insulation layer 5;

[0074] Ferroelectric materials are polarized by applying an electric field to them. Since the polarization effect achieved by applying an electric field to ferroelectric materials using PFM is better, it is time-consuming and requires a large investment in equipment. Therefore, when higher polarization effect is required, the process of applying an electric field to the ferroelectric spacer insulation layer is carried out using PFM.

[0075] A positive ferroelectric polarization field perpendicular to the surface of the perovskite cell is applied to the ferroelectric spacer insulating layer 5 by means of PFM, pointing from the perovskite light-absorbing layer 7 to the transparent conductive substrate. The applied external electric field is greater than the ferroelectric coercive field of PZT, so that the ferroelectric spacer insulating layer 5 is polarized.

[0076] Example 4:

[0077] The difference between Example 4 and Example 2 lies in step S7. The characteristic of S7 in Example 2 is as follows:

[0078] Ferroelectric materials are polarized by applying an electric field to them. Since the polarization effect achieved by applying an electric field to ferroelectric materials using PFM is better, it is time-consuming and requires a large investment in equipment. Therefore, when higher polarization effect is required, the process of applying an electric field to the ferroelectric spacer insulation layer is carried out using PFM.

[0079] A positive ferroelectric polarization field perpendicular to the surface of the perovskite cell is applied to the ferroelectric spacer insulating layer 5 by means of PFM, pointing from the perovskite light-absorbing layer 7 to the transparent conductive substrate. The applied external electric field is greater than the ferroelectric coercive field of PZT, so that the ferroelectric spacer insulating layer 5 is polarized.

[0080] When it is necessary to prepare a large-area carbon electrode mesoscopic perovskite solar cell, any one of Examples 1, 2, 3 and 4 is selected. After step S1 in this example, laser scribing is performed on the transparent conductive film 2 of the transparent conductive substrate to form a laser scribing groove 8. Then, starting from S2 in this example, the process is carried out sequentially to obtain multiple carbon electrode mesoscopic perovskite solar cell units separated by the laser scribing groove 8. Adjacent carbon electrode mesoscopic perovskite solar cell units are connected in series through carbon electrodes to form a large-area perovskite solar cell module.

[0081] The present invention also provides a perovskite solar cell, which is prepared by the preparation method described above.

[0082] The present invention also provides a perovskite solar cell module, characterized in that it is composed of a plurality of perovskite solar cells prepared by the above-described preparation method and electrically connected.

[0083] The present invention also provides a solar power generation system comprising a plurality of electrically connected perovskite cell modules as described above.

[0084] It should be stated that the above-described specific embodiments are merely preferred embodiments of the present invention and the technical principles employed. Those skilled in the art should understand that various modifications, equivalent substitutions, and variations can be made to the present invention. However, such variations, as long as they do not depart from the spirit of the present invention, should be within the scope of protection of the present invention. Furthermore, some terminology used in this specification and claims is not limiting, but merely for ease of description.

Claims

1. A method for preparing a carbon electrode mesoscopic perovskite solar cell, characterized in that, include: Step S1: Select FTO conductive glass as a transparent conductive substrate or select glass substrate 1, and prepare transparent conductive film 2 on glass substrate 1, so that glass substrate 1 and transparent conductive film 2 form a transparent conductive substrate; Step S2: Prepare a dense electron transport layer 3 on the transparent conductive film 2; Step S3: Prepare a mesoporous electron transport layer 4 on the dense electron transport layer 3; Step S4: A ferroelectric spacer insulating layer 5 is prepared on the mesoporous electron transport layer 4 using an inorganic ferroelectric material, PZT. The ferroelectric spacer insulating layer 5 is prepared through the following steps. Step L1: Grind PZT powder to obtain PZT nanocrystals; Step L2: Add PZT nanocrystals to deionized water and stir to obtain PZT hydrosol; Step L3: PZT hydrosol is coated onto the mesoporous electron transport layer 4, and the PZT hydrosol coated on the mesoporous electron transport layer 4 is annealed to form a ferroelectric spacer insulating layer 5. Step S5: Prepare a carbon electrode 6 on the ferroelectric spacer insulating layer 5; Step S6: Prepare a perovskite light-absorbing layer 7 on the carbon electrode 6; Step S7: Apply a ferroelectric polarization field from the perovskite light-absorbing layer 7 to the glass substrate 1 to the ferroelectric spacer insulating layer 5. The intensity of the applied ferroelectric polarization field is greater than the ferroelectric coercive field of the ferroelectric spacer insulating layer 5.

2. The method for preparing a carbon electrode mesoscopic perovskite solar cell according to claim 1, characterized in that, The transparent conductive film 2 is made of one of the following materials: ITO (tin-doped indium oxide), FTO (fluorine-doped tin oxide), IWO (tungsten-doped indium oxide), and ICO (cerium-doped indium oxide).

3. The method for preparing a carbon electrode mesoscopic perovskite solar cell according to claim 1, characterized in that, The dense electron transport layer 3 is composed of at least one of PCBM, TiO2, ZnO, SnO2, H-PDI, and F-PDI.

4. The method for preparing a carbon electrode mesoscopic perovskite solar cell according to claim 1, characterized in that, The mesoporous electron transport layer 4 is composed of at least one of PCBM, TiO2, ZnO, SnO2, H-PDI, and F-PDI.

5. The method for preparing a carbon electrode mesoscopic perovskite solar cell according to claim 1, characterized in that, The perovskite light-absorbing layer 5 is composed of an organic-inorganic hybrid perovskite with the general formula ABX3; wherein A is at least one of CH3NH3+ (MA+), CH(CH2)2+ (FA+), and Cs+, B is one of Pb2+, Sn2+, and Ge2+, and X is at least one of Cl-, Br-, and I-.

6. A perovskite solar cell, characterized in that, It is prepared using the preparation method described in claims 1-5.

7. A perovskite solar cell module, characterized in that, It is composed of several perovskite solar cells electrically connected by the preparation methods described in claims 1-5.

8. A perovskite battery power generation system, characterized in that, The perovskite solar cell module as described in claim 7 includes several electrically connected components.

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