Preparation method for perovskite cell, perovskite cell and photovoltaic module

Abstract

The present application relates to a preparation method for a perovskite cell, a perovskite cell and a photovoltaic module. The preparation method comprises: manufacturing a perovskite cell, comprising: evaporating a compound having a chemical general formula of BX2 to form a skeleton layer; and spin-coating a compound having a chemical general formula of AX on the skeleton layer, and carrying out annealing and crystallization to form a perovskite layer; and irradiating the perovskite cell by using a light source for light injection, wherein rays of light emitted by the light source comprise rays of light having a wavelength of 300-800 nm, the state of the perovskite cell during light injection is an open circuit condition, and the ambient temperature of the perovskite cell during light injection is 20-40°C.

Description

A method for preparing a perovskite battery, a perovskite battery and a photovoltaic module

[0001] Related applications

[0002] This application claims priority to Chinese patent application No. 202311398416.9, filed on October 25, 2023, entitled “A method for preparing a perovskite cell, a perovskite cell and a photovoltaic module,” the entire text of which is hereby incorporated by reference. Technical Field

[0003] The present application relates to the technical field of perovskite cells, and in particular to a method for preparing a perovskite cell, a perovskite cell, and a photovoltaic module. Background Art

[0004] The common preparation method of the perovskite light-absorbing layer in the perovskite battery is the vacuum deposition-spin coating method. For example, a lead iodide skeleton layer is evaporated on a velvet silicon bottom battery (HJT) by vacuum deposition, and then cations are spin-coated, and the perovskite layer is formed by annealing and crystallization. Due to the ionic characteristics of the perovskite material, it has the characteristics of low defect formation energy. The perovskite layer prepared by this method has a large number of deep energy level defects and shallow energy level defects at the interface with the transport layer. The above defects easily capture electrons or holes at the interface of the perovskite, forming non-radiative recombination centers, resulting in a large number of non-radiative recombination, and reducing the open circuit voltage (V OC ), which leads to low efficiency of perovskite cells.

[0005] Summary of the Invention

[0006] The present application discloses a method for preparing a perovskite cell, a perovskite cell and a photovoltaic module.

[0007] In a first aspect, an embodiment of the present application provides a method for preparing a perovskite battery, comprising:

[0008] Prepare an initial perovskite cell; the steps of preparing the initial perovskite cell include: evaporating a compound with a chemical formula of BX2 to form a skeleton layer; spin-coating a compound with a chemical formula of AX on the skeleton layer, and annealing and crystallizing to form a perovskite layer; wherein B is a metal cation, A is an organic amine cation or an alkali metal cation, and X is a halogen ion or a pseudohalogen anion; and,

[0009] A light source is used to illuminate the initial perovskite cell for light injection; wherein the light emitted by the light source includes light with a wavelength of approximately 300nm to 800nm, the state of the initial perovskite cell during light injection is an open circuit condition, and the ambient temperature of the initial perovskite cell during light injection is approximately 20°C to 40°C.

[0010] In some embodiments, in the step of irradiating the initial perovskite cell with a light source to perform light injection, the light injection time is about 15 minutes to 60 minutes.

[0011] In some embodiments, the step of irradiating the initial perovskite cell with a light source to perform light injection includes:

[0012] The light source irradiates vertically from one side of the initial perovskite cell, and the light emitted by the light source covers the entire initial perovskite cell.

[0013] In some embodiments, the spectrum of the light source is the AM 1.5G standard solar spectrum, and the irradiance is about 1000W / m 2 .

[0014] In some embodiments, in the step of irradiating the initial perovskite cell with a light source to perform light injection, a straight-line distance between the light source and the initial perovskite cell is approximately 80 cm to 120 cm.

[0015] In some embodiments, the ambient temperature of the initial perovskite cell during light injection is approximately 25° C. to 30° C.

[0016] In some embodiments, in the step of irradiating the initial perovskite cell with a light source to perform light injection, the humidity of the environment where the initial perovskite cell is located is about 5% to 10%.

[0017] In some embodiments, the compound of the general chemical formula BX2 includes at least one of lead iodide, lead chloride, lead bromide, cesium iodide, cesium bromide, and cesium chloride.

[0018] In some embodiments, the compound of the general chemical formula AX includes at least one of methylammonium iodide, methylammonium bromide, methylammonium chloride, formamidine iodide, formamidine bromide, and formamidine chloride.

[0019] In some embodiments, before the step of evaporating a compound having a chemical formula of BX2 to form a skeleton layer, the step of preparing an initial perovskite cell further comprises:

[0020] preparing a patterned composite layer on the bottom cell;

[0021] preparing a hole transport layer on the composite layer; and,

[0022] A hole modification layer is prepared on the hole transport layer; wherein the skeleton layer is prepared on the hole modification layer.

[0023] In some embodiments, the bottom cell comprises a HJT cell or a TOPCon cell.

[0024] In some embodiments, the composite layer includes at least one of an indium tin oxide layer and an indium zinc oxide layer.

[0025] In some embodiments, the composite layer has a thickness of about 20 nm to about 30 nm.

[0026] In some embodiments, the hole transport layer includes a nickel oxide layer.

[0027] In some embodiments, the hole transport layer has a thickness of about 20 nm to about 30 nm.

[0028] In some embodiments, the material of the hole modification layer includes at least one of 2PACz and MeO-2PACz.

[0029] In some embodiments, the thickness of the skeleton layer is about 300 nm to 350 nm.

[0030] In some embodiments, the thickness of the perovskite layer is about 450 nm to 550 nm.

[0031] In some embodiments, the band gap of the perovskite layer is approximately 1.63 eV to 1.70 eV.

[0032] In some embodiments, after the step of spin-coating a compound having a chemical formula of AX on the skeleton layer and annealing and crystallizing to form a perovskite layer, the step of preparing an initial perovskite cell further comprises:

[0033] preparing a passivation layer on the perovskite layer;

[0034] preparing an electron transport layer on the passivation layer;

[0035] preparing a buffer layer on the electron transport layer;

[0036] preparing a patterned transparent electrode on the buffer layer;

[0037] preparing a positive electrode on the transparent electrode;

[0038] Prepare a back electrode on the back of the bottom cell; and

[0039] An anti-reflection layer is formed on the positive electrode.

[0040] In some embodiments, the passivation layer includes a lithium fluoride layer.

[0041] In some embodiments, the thickness of the passivation layer is about 0.8 nm to 1.2 nm.

[0042] In some embodiments, the material of the electron transport layer includes C60.

[0043] In some embodiments, the thickness of the electron transport layer is about 15 nm to 20 nm.

[0044] In some embodiments, the material of the transparent electrode includes at least one of indium tin oxide and indium zinc oxide.

[0045] In some embodiments, the transparent electrode has a thickness of about 80 nm to 120 nm.

[0046] In some embodiments, the material of the positive electrode includes at least one of silver and copper.

[0047] In some embodiments, the positive electrode has a thickness of about 150 nm to about 300 nm.

[0048] In some embodiments, the material of the back electrode includes at least one of silver and copper.

[0049] In some embodiments, the thickness of the back electrode is about 150 nm to 300 nm.

[0050] In some embodiments, the material of the anti-reflection layer includes at least one of MgF2 and LiF.

[0051] In some embodiments, the anti-reflection layer has a thickness of about 100 nm to 120 nm.

[0052] In a second aspect, an embodiment of the present application provides a perovskite battery, which is prepared by the perovskite battery preparation method as described in the first aspect.

[0053] In a third aspect, an embodiment of the present application provides a photovoltaic module comprising the perovskite cell as described in the second aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the conventional technology, the following briefly introduces the drawings required for use in the embodiments or the conventional technology descriptions. Obviously, the drawings described below are merely embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the disclosed drawings without any creative work.

[0055] FIG1 is a flow chart of a method for preparing a perovskite battery according to one or more embodiments of the present application;

[0056] FIG2 is a flow chart of steps for preparing a perovskite layer in a method for preparing a perovskite cell according to one or more embodiments of the present application;

[0057] FIG3 is another flow chart of steps for manufacturing a perovskite cell in a perovskite cell provided by one or more embodiments of the present application;

[0058] FIG4 is a schematic structural diagram of a perovskite battery according to Example 1 of the present application;

[0059] FIG5 is a dotted line graph of light injection time and power conversion efficiency of Example 1 and Comparative Example 2 of the present application;

[0060] FIG6 is an IV curve diagram of Example 1 and Comparative Example 1 of the present application.

[0061] Reference numerals:

[0062] 100, HJT bottom cell; 200, composite layer; 300, hole transport layer; 310, hole modification layer; 400, perovskite layer; 500, passivation layer; 600, electron transport layer; 700, buffer layer; 800, transparent electrode layer; 900, anti-reflection layer; 810, positive electrode; 110, back electrode. DETAILED DESCRIPTION

[0063] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0064] The technical solution of this application will be described below with reference to embodiments and drawings.

[0065] In the first aspect, as shown in FIG1 and FIG2 , an embodiment of the present application provides a method for preparing a perovskite battery, comprising:

[0066] Preparation of an initial perovskite cell; the steps of preparing the initial perovskite cell include: evaporating a compound with a chemical formula of BX2 to form a skeleton layer; spin-coating a compound with a chemical formula of AX on the skeleton layer, and annealing and crystallizing to form a perovskite layer; wherein B is a metal cation, A is an organic amine cation or an alkali metal cation, and X is a halogen ion or a pseudohalogen anion; and,

[0067] A light source is used to illuminate the initial perovskite cell for light injection. The light emitted by the light source includes light with a wavelength of approximately 300 nm to 800 nm. The initial perovskite cell is in an open circuit state during the light injection. The ambient temperature of the initial perovskite cell during the light injection is approximately 20° C. to 40° C.

[0068] Specifically, the term "open circuit condition" refers to the condition in which the perovskite cell is not connected to any external load. Furthermore, under open circuit conditions, no bias voltage can be applied to the perovskite cell. The term "bias voltage" refers to a voltage added to change the operating state of the perovskite cell, and the term "no bias voltage applied" refers to the absence of such a voltage that would otherwise change the operating state of the perovskite cell.

[0069] In the above preparation method, the perovskite layer can be produced to meet the production line compatibility by combining evaporation deposition with spin coating. On this basis, the light injection operation with special control conditions can be added to solve the impact of the interface defects of the perovskite layer caused by the combination of evaporation deposition and spin coating.

[0070] In traditional technology, when making the perovskite layer of a perovskite battery (especially a perovskite-crystalline silicon stacked battery), a method combining evaporation deposition and spin coating can better adapt to the production line of the perovskite battery, which is conducive to large-scale industrial operations. However, while it has industrial advantages, due to the ionic characteristics of the perovskite material, it has the characteristics of low defect formation energy. The above approach will cause deep energy level defects and shallow energy level defects at the interface between the perovskite layer and the transport layer. These defects can easily capture electrons or holes at the interface of the perovskite, forming non-radiative recombination centers, resulting in a large number of non-radiative recombination, and reducing the open circuit voltage (V OC ), which leads to low efficiency of perovskite cells.

[0071] In order to solve the problem of deep energy level defects and shallow energy level defects at the interface between the perovskite layer and the transport layer caused by evaporation deposition and spin coating methods. The preparation method of the perovskite cell of the present application selects the wavelength conditions of 300nm to 800nm ​​and the open circuit conditions for light injection into the initial perovskite cell. The light within the above conditions is more easily absorbed by the perovskite layer and is less likely to cause ion rearrangement in the perovskite layer. The generated photoelectric field can promote ion migration to fill the interface defects and promote halogen ion migration to fill the halogen vacancy defects at the interface, thereby inhibiting non-radiative recombination, improving the power conversion efficiency (PCE) of the perovskite cell, and increasing the open circuit voltage (V OC ) and fill factor (FF).

[0072] Related technologies use wavelength conditions outside the range of 300nm to 800nm, short-circuit conditions, or applied bias voltages to inject light into perovskite cells. Any of the above conditions may affect the generation of a photogenerated electric field by light injection, resulting in the inability of light injection to effectively promote the migration of halogen ions. When light with a wavelength outside the range of 300nm to 800nm ​​is used for light injection, since the perovskite layer has a light absorption band of 300nm to 800nm, the light absorbed by the perovskite cell may not be able to generate an effective photogenerated electric field. Short-circuit conditions and applied bias voltages change the electric field state inside the cell, which may affect the photogenerated electric field generated by light injection, interfere with the migration of halogen ions caused by light injection, and thus hinder the migration of halogen ions to fill the halogen vacancy defects at the interface.

[0073] This application performs light injection under wavelength conditions of 300nm to 800nm, open circuit conditions, and no bias voltage applied. First, the perovskite layer can absorb light in the wavelength range of 300nm to 800nm, generating an effective photogenerated electric field. Second, under open circuit conditions, no bias voltage can be applied to the perovskite cell. The internal electric field of the perovskite cell is a photogenerated electric field, so the halogen ions promoted by the photogenerated electric field can migrate to fill the halogen vacancy defects at the interface.

[0074] Furthermore, due to the relatively poor thermal stability of the perovskite layer, excessively high temperatures can easily lead to the decomposition of the perovskite layer, reducing device performance. In order to avoid the adverse effects of temperature, this application does not perform light injection under high temperature conditions (>200°C). However, temperature is also one of the factors affecting the migration of halogen ions to fill the halogen vacancy defects at the interface. If the temperature is relatively low, the halogen ions cannot migrate quickly. Therefore, in this application, the ambient temperature of the perovskite cell during light injection is 20°C to 40°C, which can not only avoid the decomposition of the perovskite layer, but also promote the migration of halogen ions to fill the halogen vacancy defects at the interface.

[0075] Solar cells in related technologies require heating to relatively high temperatures (300°C to 650°C) to fully activate hydrogen ions. In contrast, light injection in this application promotes the migration of halogen ions to fill halogen vacancies at the interface, eliminating the need for heating. Temperatures of 20°C to 40°C are sufficient. Clearly, this process is simpler, eliminating the need for heating.

[0076] In some embodiments of the present application, in the step of irradiating the initial perovskite cell with a light source to perform light injection, the light injection time is approximately 15 minutes to 60 minutes, including any value within this time range, such as 15 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, and 60 minutes. As the light injection time increases, the power conversion efficiency of the perovskite cell increases accordingly. After the light injection time reaches 15 minutes, the power conversion efficiency of the perovskite cell gradually approaches saturation. If the light injection time exceeds 60 minutes, the power conversion efficiency of the perovskite cell may decay.

[0077] In some embodiments, the step of irradiating the initial perovskite cell with a light source to perform light injection includes:

[0078] The light source is vertically irradiated from one side of the initial perovskite cell, and the light emitted by the light source covers the entire initial perovskite cell; ensuring that the effective area of ​​the cell is completely in the center of the light source.

[0079] In some embodiments, the spectrum of the light source is the AM 1.5G standard solar spectrum, and the irradiance is about 1000W / m 2 The AM 1.5G standard solar spectrum refers to the standard spectrum of the Earth's surface. AM 1.5G comes from an ASTM (American Society of Testing Materials) standard related to solar energy. Furthermore, the AM 1.5G standard solar spectrum has a wavelength range of 300nm to 1200nm, covering the absorption wavelength range of perovskite cells from 300nm to 800nm.

[0080] In some embodiments, in the step of irradiating the initial perovskite cell with a light source for light injection, the straight-line distance between the light source and the initial perovskite cell is about 80 cm to 120 cm, including any point value within the straight-line distance range, such as 80 cm, 90 cm, 100 cm, 110 cm, and 120 cm. Within this straight-line distance range, the light emitted by the light source is more evenly distributed, and the irradiance can meet 1000 W / m 2 .

[0081] Optionally, the ambient temperature of the initial perovskite cell during light injection is approximately 25°C to 30°C, including any point within this temperature range, such as 25°C, 26°C, 28°C or 30°C, that is, light injection can be completed at room temperature.

[0082] On the other hand, the perovskite layer is sensitive to water vapor, and water vapor intrusion may affect the stability of the perovskite cell. The perovskite layer is exposed to the environment during the light injection process. To avoid excessive water vapor in the test environment affecting the perovskite layer, the humidity of the initial perovskite cell environment is optionally about 5% to 10%, including any value within this humidity range, such as 5%, 8%, and 10%.

[0083] In some embodiments, the compound of the general chemical formula BX2 includes at least one of lead iodide, lead chloride, lead bromide, cesium iodide, cesium bromide, and cesium chloride.

[0084] In some embodiments, the compound of the general chemical formula AX comprises at least one of methylammonium iodide, methylammonium bromide, methylammonium chloride, formamidine iodide, formamidine bromide, and formamidine chloride.

[0085] In some embodiments, as shown in FIG3 , before the step of evaporating a compound having a chemical formula of BX2 to form a skeleton layer, the steps of preparing the initial perovskite cell further include:

[0086] preparing a patterned composite layer on the bottom cell;

[0087] preparing a hole transport layer on the composite layer; and,

[0088] A hole modification layer is prepared on the hole transport layer; wherein the skeleton layer is prepared on the hole modification layer.

[0089] In some embodiments, as shown in FIG3 , after the step of spin-coating a compound having a chemical formula AX on the skeleton layer and annealing and crystallizing to form a perovskite layer, the steps of making the initial perovskite cell further include:

[0090] forming a passivation layer on the perovskite layer;

[0091] preparing an electron transport layer on the passivation layer;

[0092] preparing a buffer layer on the electron transport layer;

[0093] preparing a patterned transparent electrode on the buffer layer;

[0094] preparing a positive electrode on the transparent electrode;

[0095] Prepare a back electrode on the back of the bottom cell; and

[0096] An antireflection layer is formed on the positive electrode.

[0097] The present application performs light injection after the step of preparing the initial perovskite cell. Alternatively, light injection can be performed after the step of preparing the anti-reflection layer on the positive electrode, or after the step of preparing the back electrode on the back of the bottom cell, as long as the initial perovskite cell prepared in the step of preparing the initial perovskite cell can generate an effective photogenerated electric field. It is understood that in the above-mentioned steps of preparing the initial perovskite cell, the step of preparing the anti-reflection layer on the positive electrode can be omitted.

[0098] In some embodiments, the step of preparing a patterned composite layer on the bottom cell includes:

[0099] A patterned composite layer is prepared on the bottom cell using magnetron sputtering (PVD). The material of the composite layer includes at least one of indium tin oxide (ITO) and indium zinc oxide (IZO), and is required to have high mobility and transmittance, with a thickness of about 20nm to 30nm.

[0100] In some embodiments, the step of preparing a hole transport layer on the composite layer comprises:

[0101] A hole transport layer is prepared on the composite layer. The preparation method of the hole transport layer can be PVD, and the material of the hole transport layer can be nickel oxide (NiO x ), with a thickness of about 20nm to 30nm.

[0102] In some embodiments, the step of preparing a hole modification layer on the hole transport layer comprises:

[0103] A hole modification layer is prepared on the hole transport layer. The hole modification layer comprises at least one of 2PACz and MeO-2PACz. 2PACz refers to (2-(9H-carbazol-9-yl)ethyl)phosphonic acid, and MeO-2PACz refers to [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid. The concentration is approximately 0.8 mg / mL to 1 mg / mL. For example, the hole modification layer can be prepared using a spin coating process at a rotation speed of approximately 3000 to 5000 rpm, an annealing temperature of approximately 80°C to 120°C, and an annealing time of approximately 10 to 15 minutes.

[0104] In some embodiments, the step of evaporating a compound having a general chemical formula of BX2 to form a skeleton layer comprises:

[0105] On the hole modification layer, a skeleton layer is vacuum deposited with a thickness of about 300nm to 350nm. For example, a dual-source co-evaporation process is used to evaporate the PbI2 skeleton layer. The material of the evaporation source 2 can be PbI2, and the material of the evaporation source 1 can be CsBr. The evaporation rate ratio is 5:1 to 10:1, and the vacuum degree is required to be less than 1×10 -3Pa; a three-source co-evaporation process can also be used. The material of the evaporation source three can be one of PbX2 (X = Br, Cl) and CsX (X = I, Cl), and the evaporation rate is about

[0106] In some embodiments, the step of spin-coating a compound having a general chemical formula AX on the skeleton layer and then annealing and crystallizing the compound to form a perovskite layer comprises:

[0107] A cationic solution is spin-coated onto the skeleton layer. The cationic materials include at least two or more of FAI, FABr, MABr, and MACl, and the solvent is at least one of anhydrous ethanol and isopropanol. The cationic ratio and concentration can be adjusted appropriately, with the FAI concentration being approximately 0.3M to 0.6M, the FABr concentration being approximately 0.05M to 0.2M, the MABr concentration being approximately 0.1M to 0.2M, and the MACl concentration being approximately 0.05M to 0.15M. The spin-coating speed is approximately 3000-6000 rpm, and the spin-coating time is approximately 25-35 seconds. The spin-coating environment requires a humidity of less than 10% and a temperature of approximately 22°C to 28°C. After spin-coating, the substrate is annealed at a humidity of approximately 5% to 40%, at a temperature of approximately 100°C to 170°C, and for approximately 15-30 minutes. The spin-coated cationic solution reacts with lead iodide and is annealed and crystallized to form a perovskite layer. The thickness of the perovskite layer is about 450nm to 550nm, and the band gap is about 1.63eV to 1.70eV.

[0108] In some embodiments, the step of preparing a passivation layer on the perovskite layer includes:

[0109] A passivation layer is prepared on the perovskite light-absorbing layer by a vacuum deposition process; the material of the passivation layer can be LiF, with a thickness of about 0.8nm to 1.2nm and an evaporation rate of about

[0110] In some embodiments, the step of preparing an electron transport layer on the passivation layer includes:

[0111] On the passivation layer, the electron transport layer 600 is evaporated; the electron transport layer material can be C60, with a thickness of about 15nm to 20nm, and an evaporation rate of about

[0112] In some embodiments, the step of preparing a buffer layer on the electron transport layer includes:

[0113] A buffer layer is prepared on the electron transport layer by atomic layer deposition (ALD). The material of the buffer layer may be tin dioxide (SnO2), and the thickness of the buffer layer is about 20nm to 30nm.

[0114] In some embodiments, the step of preparing a patterned transparent electrode on the buffer layer includes:

[0115] On the buffer layer, a patterned transparent electrode is prepared by magnetron sputtering (PVD). The transparent electrode material includes at least one of ITO and IZO, and has a thickness of about 80nm to 120nm.

[0116] In some embodiments, the step of preparing a positive electrode on the transparent electrode includes:

[0117] The positive electrode is deposited on the transparent electrode. The positive electrode is a patterned metal electrode, the material of which includes at least one of silver (Ag) and copper (Cu), with a thickness of about 150nm to 300nm and an evaporation rate of about

[0118] In some embodiments, the step of preparing a back electrode on the back side of the bottom cell includes:

[0119] The back electrode is deposited on the back of the HJT bottom cell. The back electrode is similar to the positive electrode, and the material includes at least one of silver (Ag) and copper (Cu), with a thickness of about 150nm to 300nm and an evaporation rate of about

[0120] In some embodiments, the step of preparing an anti-reflection layer on the positive electrode includes:

[0121] An anti-reflection layer is prepared on the positive electrode. The anti-reflection layer is also deposited by evaporation process. The material includes MgF2 or LiF. The thickness is about 100nm to 120nm. The evaporation rate is about The refractive index n is approximately 1.4.

[0122] It should be noted that the perovskite cell in the embodiments of the present application can be a pin-type trans structure or a nip-type formal structure. Generally, the top cell in a tandem cell can be a pin-type trans structure. On the other hand, the perovskite cell in the embodiments of the present application can be a tandem cell or a single-junction perovskite cell.

[0123] In some embodiments, the bottom cell includes a HJT cell or a TOPCon cell.

[0124] In some embodiments, the composite layer includes at least one of an indium tin oxide layer and an indium zinc oxide layer.

[0125] In some embodiments, the composite layer has a thickness of about 20 nm to about 30 nm, including any value within this thickness range, such as 20 nm, 25 nm, and 30 nm.

[0126] In some embodiments, the hole transport layer includes a nickel oxide layer.

[0127] In some embodiments, the hole transport layer is approximately 20 nm to 30 nm, including any value within this thickness range, such as 20 nm, 25 nm, and 30 nm.

[0128] In some embodiments, the material of the hole modification layer includes at least one of 2PACz and MeO-2PACz.

[0129] In some embodiments, the thickness of the skeleton layer is approximately 300 nm to 350 nm, including any value within the thickness range, such as 300 nm, 310 nm, 320 nm, and 350 nm.

[0130] In some embodiments, the thickness of the perovskite layer is approximately 450 nm to 550 nm, including any value within this thickness range, such as 450 nm, 480 nm, 500 nm, 520 nm, and 550 nm.

[0131] In some embodiments, the band gap of the perovskite layer is approximately 1.63 eV to 1.70 eV, including any value within the band gap range, such as 1.63 eV, 1.68 eV, and 1.70 eV.

[0132] In some embodiments, the passivation layer includes a lithium fluoride layer.

[0133] In some embodiments, the thickness of the passivation layer is approximately 0.8 nm to 1.2 nm, including any value within this thickness range, such as 0.8 nm, 1.0 nm, and 1.2 nm.

[0134] In some embodiments, the material of the electron transport layer includes C60.

[0135] In some embodiments, the thickness of the electron transport layer is about 15 nm to 20 nm, including any value within this thickness range, such as 15 nm, 18 nm, and 20 nm.

[0136] In some embodiments, the material of the transparent electrode includes at least one of indium tin oxide and indium zinc oxide.

[0137] In some embodiments, the transparent electrode has a thickness of about 80 nm to about 120 nm, including any value within the thickness range, such as 80 nm, 100 nm, and 120 nm.

[0138] In some embodiments, the material of the positive electrode includes at least one of silver and copper.

[0139] In some embodiments, the thickness of the positive electrode is approximately 150 nm to 300 nm, including any value within this thickness range, such as 150 nm, 200 nm, 250 nm, and 300 nm.

[0140] In some embodiments, the material of the back electrode includes at least one of silver and copper.

[0141] In some embodiments, the thickness of the back electrode is approximately 150 nm to 300 nm, including any value within the thickness range, such as 150 nm, 200 nm, 250 nm, and 300 nm.

[0142] In some embodiments, the material of the anti-reflection layer includes at least one of MgF2 and LiF.

[0143] In some embodiments, the thickness of the anti-reflection layer is about 100 nm to 120 nm, including any value within this thickness range, such as 80 nm, 100 nm, and 120 nm.

[0144] In a second aspect, an embodiment of the present application provides a perovskite battery, which is prepared by the perovskite battery preparation method as described in the first aspect.

[0145] In a third aspect, an embodiment of the present application provides a photovoltaic module comprising the perovskite cell as described in the second aspect.

[0146] The technical solutions of the present application will be described below in conjunction with the examples and drawings. It should be understood that these examples are intended only to illustrate the present application and are not intended to limit the scope of the present application. For experimental methods in the following examples where specific conditions are not specified, reference should be made to the guidance provided in this application, or to experimental manuals or conventional conditions in the art, or to conditions recommended by the manufacturer, or to experimental methods known in the art.

[0147] Example 1

[0148] As shown in Figure 4, the perovskite cell prepared in this embodiment is composed of, from bottom to top, an HJT bottom cell 100, a composite layer 200, a hole transport layer 300, a hole modification layer 310, a perovskite layer 400, a passivation layer 500, an electron transport layer 600, a buffer layer 700, a transparent electrode layer 800, and an anti-reflection layer 900. Each layer is conformally grown along a pyramid shape. The front of the perovskite cell is provided with a positive electrode 810 and the back of the perovskite cell is provided with a back electrode 110. The positive electrode 810 penetrates the anti-reflection layer 900 and is connected to the transparent electrode layer 800. The back electrode 110 is connected to the HJT bottom cell 100.

[0149] The preparation method of the perovskite battery comprises the following steps:

[0150] Step 1: A patterned composite layer 200 is prepared on the HJT bottom cell 100 by magnetron sputtering (PVD). The material of the composite layer 200 is indium tin oxide (ITO) with a thickness of 25 nm.

[0151] Step 2: Prepare a hole transport layer 300 on the composite layer 200. The preparation method of the hole transport layer 300 is PVD. The material of the hole transport layer 300 is nickel oxide (NiO x ), with a thickness of 25 nm;

[0152] Step 3: A hole modification layer 310 is formed on the hole transport layer 300. The hole modification layer 310 is formed by spin coating with a spin speed of 4000 rpm, an annealing temperature of 100°C, and an annealing time of 12 min.

[0153] Step 4-1: On the hole modification layer 310, a skeleton layer is vacuum deposited. The thickness of the skeleton layer is required to be 300nm to 350nm. The PbI2 skeleton layer is evaporated using a dual-source co-evaporation process. The material of the evaporation source 2 is PbI2 and the material of the evaporation source 1 is CsBr. The evaporation rate ratio is 5:1 to 10:1. The vacuum degree is required to be less than 1×10 -3 Pa; a three-source co-evaporation process can also be used. The materials of the evaporation source three are PbI2 and CsBr, and the evaporation rate is

[0154] Step 4-2: On the skeleton layer, a cationic solution is spin-coated, wherein the cationic material comprises at least two or more of FAI, FABr, MABr, and MACl, and the solvent is anhydrous ethanol or isopropanol; the cationic ratio and concentration can be adjusted appropriately, wherein the FAI concentration is 0.4M, the FABr concentration is 0.1M, the MABr concentration is 0.15M, and the MACl concentration is 0.1M; the spin-coating speed is 4000 rpm, the spin-coating time is 30s, and the spin-coating environment requires a humidity of less than 10% and a temperature of 25°C; after the spin-coating is completed, annealing is performed at a humidity of 5%-40%, an annealing temperature of 140°C, and an annealing time of 20min; the despinned cationic solution reacts with lead iodide, and annealing and crystallization form a perovskite layer 400, the perovskite layer 400 having a thickness of 500nm and a band gap of 1.63eV to 1.70eV;

[0155] Step 5: Prepare a passivation layer 500 on the perovskite light absorbing layer by vacuum deposition process; the passivation layer material is LiF, with a thickness of 1nm and an evaporation rate of

[0156] Step 6: On the passivation layer, evaporate the electron transport layer 600; the material of the electron transport layer 600 is C60, the thickness is 18nm, and the evaporation rate is

[0157] Step 7: A buffer layer 700 is formed on the electron transport layer 600 by atomic deposition (ALD); the material of the buffer layer 700 is tin dioxide (SnO 2 ), and the thickness of the buffer layer 700 is 25 nm;

[0158] Step 8: On the buffer layer 700, a patterned transparent electrode 800 is prepared by magnetron sputtering (PVD); the material of the transparent electrode 800 can be ITO or IZO, with a thickness of 100 nm;

[0159] Step 9-1: Evaporate the positive electrode 810 on the transparent electrode; the positive electrode 810 is a patterned metal electrode made of silver (Ag) with a thickness of 200nm and an evaporation rate of

[0160] Step 9-2: After completing the above steps, evaporate the back electrode 110 on the back of the HJT bottom cell; the material of the back electrode 110 is silver (Ag), with a thickness of 200nm and an evaporation rate of

[0161] Step 10: Prepare an anti-reflection layer on the positive electrode. The anti-reflection layer also adopts the evaporation process. The material can be MgF2 with a thickness of 110nm and an evaporation rate of The refractive index n value is about 1.4, and a perovskite-silicon tandem cell is produced;

[0162] Step 11: Inject light into the perovskite cell obtained above. The light source spectrum requires standard sunlight AM1.5G, with a wavelength range of 300nm to 1200nm and 1000W / m 2 ; Light injection temperature control requirements: stage temperature 25°C, humidity 5%; the state of the perovskite cell during light injection is open circuit condition; during light injection, the light is vertically irradiated from the top side of the perovskite cell, covering the entire perovskite cell, ensuring that the effective area of ​​the perovskite cell is completely in the center of light; the vertical height distance between the light source and the perovskite cell is 100cm; the light injection time is 3min, 6min, 9min, 12min, 15min, 18min, 21min, 24min, 27min, 30min.

[0163] Example 2

[0164] The difference between this embodiment and embodiment 1 is that the light injection time is 60 minutes, and the other steps are consistent with embodiment 1.

[0165] Example 3

[0166] The difference between this embodiment and embodiment 1 is that the light injection time is 66 minutes, and the other steps are consistent with embodiment 1.

[0167] Example 4

[0168] The perovskite cell provided in this embodiment is different from the perovskite cell provided in Example 1 only in that the perovskite cell prepared in this embodiment comprises, from bottom to top, a glass substrate, a composite layer, a hole transport layer, a hole modification layer, a perovskite layer, a passivation layer, an electron transport layer, a BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) buffer layer and an anti-reflection layer.

[0169] The method for preparing a perovskite battery provided in this embodiment differs from the method for preparing a perovskite battery provided in Example 1 only in the following steps:

[0170] Step 1: Prepare a patterned composite layer on a glass substrate using magnetron sputtering (PVD);

[0171] Step 7: preparing a buffer layer on the electron transport layer by atomic layer deposition (ALD); the material of the buffer layer is BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline);

[0172] Step 9-1: Vapor depositing a positive electrode on the buffer layer;

[0173] Furthermore, step 8 and step 9-2 are not performed.

[0174] Comparative Example 1

[0175] The difference between this comparative example and Example 1 is that the light injection in step 11 is not performed on the prepared perovskite cell, and the remaining steps are consistent with those in Example 1.

[0176] Comparative Example 2

[0177] The difference between this comparative example and Example 1 is that during light injection in step 11, the state of the perovskite battery is a short-circuit condition, the light injection time is 3 min, 6 min, 9 min, 12 min, and 15 min, and the remaining steps are consistent with Example 1.

[0178] Performance test was conducted using a Wavelabs solar simulator, test conditions: AM1.5, 1000W / m 2 The test environment temperature was 25°C. Before testing, the sunlight intensity simulated by the light source was calibrated using a standard silicon cell. The test results are shown in Table 1, Figures 5, and 6.

[0179] Table 1 shows the performance parameters of the perovskite cells of Examples 1-3 and Comparative Examples 1 and 2, and FIG5 is a dotted line graph of the light injection time and power conversion efficiency of Example 1 and Comparative Example 2 of the present application.

[0180] As shown in Table 1 and FIG5 , the power conversion efficiency (PCE) of the perovskite cell of Example 1 increases significantly with the increase of light injection time, and the power conversion efficiency gradually approaches saturation after the light injection time reaches 15 minutes.

[0181] As shown in Table 1, the light injection time of Example 3 is 66 minutes, which is longer than that of Example 2, but the power conversion efficiency is lower. It can be seen that when the light injection time exceeds a certain time, increasing the light injection time will lead to a decrease in power conversion efficiency.

[0182] Referring to Table 1, in Comparative Example 2, light injection was performed under short-circuit conditions. As the light injection time increased, the maximum and minimum values ​​of the power conversion efficiency of the perovskite cell differed by only 0.1%, showing essentially no significant change. In Example 1, however, as the light injection time increased, the maximum and minimum values ​​of the power conversion efficiency of the perovskite cell differed by 1.35%, showing a significant change. This indicates that when light injection is performed under open-circuit conditions, the photogenerated electric field can promote ion migration to fill interface defects, inhibit non-radiative recombination, and improve the efficiency of the perovskite cell.

[0183] FIG6 is an IV curve diagram of Example 1 and Comparative Example 1 of the present application; wherein the horizontal axis is voltage (Voltage), the unit is volt (V); the vertical axis is current density (Current density), the unit is mA / cm 2 As shown in Figure 6 and Table 1, compared with Comparative Example 1, the perovskite cell treated by the light injection step has a higher power conversion efficiency (PCE) and open circuit voltage (V OC ) and fill factor (FF) are significantly improved.

[0184] Table 1: Performance parameters of perovskite cells in Examples 1-3 and Comparative Examples 1 and 2

[0185] The above is a detailed introduction to the preparation method of a perovskite battery, a perovskite battery and a photovoltaic module disclosed in the embodiments of the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the preparation method of a perovskite battery, a perovskite battery and a photovoltaic module and their core ideas of the present application: At the same time, for general technical personnel in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

[0186] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0187] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present application, and these modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. A method for preparing a perovskite battery, comprising: Making initial perovskite cells; The steps of making the initial perovskite cell include: evaporating a compound with a chemical formula of BX2 to form a skeleton layer; spin coating a compound with a chemical formula of AX on the skeleton layer, and annealing and crystallizing to form a perovskite layer; wherein B is a metal cation, A is an organic amine cation or an alkali metal cation, and X is a halogen ion or a pseudohalogen anion; and, A light source is used to illuminate the initial perovskite cell for light injection; wherein the light emitted by the light source includes light with a wavelength of about 300nm to 800nm, the state of the initial perovskite cell during light injection is an open circuit condition, and the ambient temperature of the initial perovskite cell during light injection is about 20°C to 40°C.

2. The method for preparing a perovskite cell according to claim 1, wherein in the step of using a light source to irradiate the initial perovskite cell for light injection, the light injection time is about 15 minutes to 60 minutes.

3. The method for preparing a perovskite cell according to claim 1 or 2, wherein the step of using a light source to irradiate the initial perovskite cell for light injection comprises: The light source irradiates vertically from one side of the initial perovskite cell, and the light emitted by the light source covers the entire perovskite cell.

4. The method for preparing a perovskite cell according to any one of claims 1 to 3, wherein the spectrum of the light source is the AM 1.5G standard solar spectrum, and the irradiance is about 1000 W / m 2 .

5. The method for preparing a perovskite cell according to any one of claims 1 to 4, wherein in the step of irradiating the initial perovskite cell with a light source to perform light injection, a straight-line distance between the light source and the initial perovskite cell is about 80 cm to 120 cm.

6. The method for preparing a perovskite cell according to any one of claims 1 to 5, wherein the ambient temperature of the initial perovskite cell during light injection is about 25°C to 30°C.

7. The method for preparing a perovskite cell according to any one of claims 1 to 6, wherein in the step of irradiating the initial perovskite cell with a light source to perform light injection, the humidity of the environment where the initial perovskite cell is located is about 5% to 10%.

8. According to the method for preparing a perovskite battery according to any one of claims 1 to 7, the compound with the general chemical formula BX2 includes at least one of lead iodide, lead chloride, lead bromide, cesium iodide, cesium bromide and cesium chloride.

9. The method for preparing a perovskite battery according to any one of claims 1 to 8, wherein the compound with the general chemical formula AX comprises at least one of methylammonium iodide, methylammonium bromide, methylammonium chloride, formamidine iodide, formamidine bromide and formamidine chloride.

10. The method for preparing a perovskite cell according to any one of claims 1 to 9, before the step of evaporating a compound with a chemical formula of BX2 to form a skeleton layer, the step of making an initial perovskite cell further comprises: preparing a patterned composite layer on the bottom cell; preparing a hole transport layer on the composite layer; as well as, A hole modification layer is prepared on the hole transport layer; wherein the skeleton layer is made on the hole modification layer. 11 . The method for preparing a perovskite cell according to claim 10 , wherein the composite layer comprises at least one of an indium tin oxide layer and an indium zinc oxide layer. 12 . The method for preparing a perovskite battery according to claim 10 or 11 , wherein the thickness of the composite layer is about 20 nm to 30 nm.

13. According to the method for preparing a perovskite battery according to any one of claims 10 to 12, the hole transport layer comprises a nickel oxide layer.

14. The method for preparing a perovskite battery according to any one of claims 10 to 13, wherein the thickness of the hole transport layer is about 20 nm to 30 nm. 15 . The method for preparing a perovskite cell according to claim 10 , wherein the material of the hole modification layer comprises at least one of 2PACz and MeO-2PACz.

16. The method for preparing a perovskite battery according to any one of claims 10 to 15, wherein the thickness of the skeleton layer is about 300 nm to 350 nm.

17. The method for preparing a perovskite battery according to any one of claims 10 to 16, wherein the thickness of the perovskite layer is about 450 nm to 550 nm.

18. The method for preparing a perovskite battery according to any one of claims 10 to 17, wherein the band gap of the perovskite layer is about 1.63 eV to 1.70 eV.

19. The method for preparing a perovskite battery according to any one of claims 10 to 18, wherein the bottom battery comprises a HJT battery or a TOPCon battery.

20. The method for preparing a perovskite cell according to any one of claims 10 to 19, wherein after the step of spin coating a compound having a chemical formula of AX on the skeleton layer and annealing and crystallizing to form a perovskite layer, the step of making an initial perovskite cell further comprises: preparing a passivation layer on the perovskite layer; preparing an electron transport layer on the passivation layer; preparing a buffer layer on the electron transport layer; preparing a patterned transparent electrode on the buffer layer; preparing a positive electrode on the transparent electrode; preparing a back electrode on the back side of the bottom cell; as well as, An anti-reflection layer is prepared on the positive electrode.

21. The method for preparing a perovskite battery according to claim 20, wherein the passivation layer comprises a lithium fluoride layer.

22. The method for preparing a perovskite battery according to claim 20 or 21, wherein the thickness of the passivation layer is about 0.8 nm to 1.2 nm.

23. The method for preparing a perovskite battery according to any one of claims 20 to 22, wherein the material of the electron transport layer comprises C60.

24. The method for preparing a perovskite battery according to any one of claims 20 to 23, wherein the thickness of the electron transport layer is about 15 nm to 20 nm.

25. The method for preparing a perovskite cell according to any one of claims 20 to 24, wherein the material of the transparent electrode comprises at least one of indium tin oxide and indium zinc oxide.

26. The method for preparing a perovskite battery according to any one of claims 20 to 25, wherein the thickness of the transparent electrode is about 80 nm to 120 nm.

27. The method for preparing a perovskite battery according to any one of claims 20 to 26, wherein the material of the positive electrode comprises at least one of silver and copper.

28. The method for preparing a perovskite battery according to any one of claims 20 to 27, wherein the thickness of the positive electrode is about 150 nm to 300 nm.

29. The method for preparing a perovskite cell according to any one of claims 20 to 28, wherein the material of the back electrode comprises at least one of silver and copper.

30. The method for preparing a perovskite battery according to any one of claims 20 to 29, wherein the thickness of the back electrode is about 150 nm to 300 nm.

31. The method for preparing a perovskite cell according to any one of claims 20 to 30, wherein the material of the anti-reflection layer comprises at least one of MgF2 and LiF.

32. According to the method for preparing a perovskite cell according to any one of claims 20 to 31, the thickness of the anti-reflection layer is about 100 nm to 120 nm.

33. A perovskite battery, wherein the perovskite battery is prepared by the method for preparing a perovskite battery according to any one of claims 1 to 32.

34. A photovoltaic module comprising the perovskite cell according to claim 33.

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