A perovskite battery and its preparation method

Abstract

The present invention relates to a perovskite cell and a method for preparing the same. The perovskite cell comprises a back electrode, an electron transport layer, an interface passivation layer, a perovskite absorber layer, a hole transport layer, and a conductive substrate layer stacked in sequence; the interface passivation layer and / or the perovskite absorber layer comprises an azulene-based compound. The perovskite cell exhibits excellent photovoltaic power generation efficiency, stability, and high reliability.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite batteries, and in particular to a perovskite battery and a preparation method thereof. Background Art

[0002] As an inexhaustible clean energy source, solar energy holds enormous development potential and a significant market. As a natural nuclear reactor, the sun releases packets of energy called photons. One hour of exposure to these photons generates enough energy to meet Earth's annual global energy needs. When photons strike the surface of a solar cell, electrons in the valence band of the semiconductor material are excited to the conduction band. As these charge carriers flow through the solar cell, a circuit is formed, successfully converting sunlight into useful electrical energy. Since the 1950s, silicon semiconductors have been the primary material used in solar cells. However, due to the complex manufacturing processes, high production costs, and stringent material purity requirements of crystalline silicon, gallium arsenide, cadmium telluride, and copper indium gallium tin cells, perovskite solar cells emerged.

[0003] Perovskite possesses strong light absorption, a broad spectral absorption range, and the ability to absorb the entire visible spectrum. Furthermore, it can be prepared cost-effectively using a solution method under mild conditions. These properties make it an excellent material for solar cells. Over the past decade, the photovoltaic efficiency of perovskite has increased from 3% to 25.7%, approaching the peak efficiency of crystalline silicon cells at 26.7%. Compared to previous generations of photovoltaic conversion materials, perovskite solar cells offer the advantages of high efficiency and low-cost preparation, demonstrating enormous potential for the future.

[0004] CN111628080A discloses a perovskite solar cell and a method for preparing a perovskite absorber layer used in the perovskite solar cell. The disclosed perovskite solar cell includes a substrate, a transparent electrode, an electron transport layer, a perovskite absorber layer, a hole transport layer, and a back electrode. The perovskite absorber layer is a 2D / 3D composite perovskite absorber layer comprising a 2D perovskite material and a 3D perovskite material.

[0005] CN106083695A discloses a series of preparation methods and applications of azulene-containing asymmetric squaryl cyanine small molecules. Azulene and different electron-rich aromatic units are used as donors, and the electron-deficient 1,3-squaryl acid unit is used as an acceptor to form a donor-acceptor-donor asymmetric squaryl cyanine small molecules containing azulene. Such materials all have a low band gap, and the absorption spectrum covers the visible and near-infrared regions (400-900nm), while also having good solubility and film-forming properties. In addition, the introduction of azulene fragments is also beneficial for the material to obtain deep HOMO energy levels and high mobility, which are all very beneficial for the preparation of high-performance organic solar cells.

[0006] Currently, a large number of cation and anion vacancies are easily formed during the crystallization process of perovskites. The electron and hole traps caused by these vacancies in the device reduce the carrier transport efficiency, thereby degrading performance. Furthermore, suppressing the generation of interface defects in perovskite films and reducing the recombination of photogenerated carriers at these interface defects are also key to further improving the performance of perovskite solar cells. Furthermore, while the performance of perovskite solar cells in the laboratory is rapidly improving, the reliability and stability of perovskite materials are hindered by their sensitivity to environmental factors such as water and heat, making their industrial manufacturing and commercialization challenging.

[0007] In summary, it is crucial to develop a perovskite cell with both excellent photovoltaic power generation efficiency and stability. Summary of the Invention

[0008] In view of the deficiencies of the prior art, the object of the present invention is to provide a perovskite cell and a preparation method thereof, wherein the perovskite cell has excellent photovoltaic power generation efficiency and stability and high reliability.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a perovskite cell, comprising a back electrode, an electron transport layer, an interface passivation layer, a perovskite absorption layer, a hole transport layer, and a conductive substrate layer stacked in sequence;

[0011] The interface passivation layer and / or the perovskite absorption layer include an azulene-based compound.

[0012] In the present invention, an azulene-based compound is added to the interface passivation layer and the perovskite absorption layer. Azulene is a special molecule with a large dipole moment (1.08D) and a narrow HOMO-LOMO energy gap. The azulene-based compound forms a high-performance and highly stable perovskite solar cell by enhancing the interaction between bonds, reducing grain boundaries, and passivating surface defects.

[0013] It should be noted that perovskite solar cell structures are divided into formal and trans structures, and the perovskite cell described in the present invention is applicable to both structures.

[0014] Preferably, the azulenyl compound contains a carboxyl group and / or a carbonyl group and an amino group.

[0015] In this exemplary embodiment, the azulene compound contains carboxyl and / or carbonyl groups as well as amino groups. The carboxyl groups (-COOH) interact with the formamidine materials in the perovskite (hydrogen bonds and ionic bonds), making the perovskite structure more stable. The amino groups can form an intermediate structure with the formamidine materials (e.g., formamidine iodide FAI) in the perovskite, resulting in vertically oriented perovskite crystals with high crystallinity and few grain boundaries. By reducing or even eliminating the grain boundaries between the perovskite grains, the device efficiency and the intrinsic stability of the perovskite absorber layer are improved.

[0016] Preferably, the azulene compound includes any one or a combination of at least two of 2-amino-1,3-dicarboxyazulene, 2-amino-1,3-diethoxycarbonylazulene or 2-aminoazulene, wherein typical but non-limiting combinations include: a combination of 2-amino-1,3-dicarboxyazulene and 2-amino-1,3-diethoxycarbonylazulene, a combination of 2-amino-1,3-diethoxycarbonylazulene and 2-aminoazulene, a combination of 2-amino-1,3-dicarboxyazulene, 2-amino-1,3-diethoxycarbonylazulene and 2-aminoazulene, etc., and further preferred are 2-amino-1,3-dicarboxyazulene and / or 2-amino-1,3-diethoxycarbonylazulene.

[0017] Preferably, the back electrode comprises a gold electrode.

[0018] Preferably, the thickness of the back electrode is 60-100 nm, for example, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, etc.

[0019] Preferably, the electron transport layer includes a carbon layer and a tin layer.

[0020] Preferably, the carbon layer comprises carbon 60.

[0021] Preferably, the tin layer comprises tin dioxide.

[0022] Preferably, the thickness of the carbon layer is 10-30 nm, for example, 12 nm, 14 nm, 16 nm, 18 nm, 20 nm, 22 nm, 24 nm, 26 nm, 28 nm, etc.

[0023] Preferably, the thickness of the tin layer is 3-15 nm, for example, 4 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, etc.

[0024] Preferably, the thickness of the interface passivation layer is 1-10 nm, for example, 4 nm, 6 nm, 8 nm, etc.

[0025] Preferably, the perovskite absorption layer further comprises a lead halide compound.

[0026] Preferably, the lead halide compound comprises MA xFA 1-x PbI3、FA 1-x Cs x PbI3, MAPbI3, (FAPbI3) 1-x (MAPbBr3) x , CsPbI2Br, CsPbI3, CsPbBr3 or Cs 0.05 (FA 1-x MA x ) 0.95 Pb(I 1-y Bry) 3 any one or a combination of at least two, wherein typical but non-limiting combinations include: MA x FA 1-x PbI3 and FA 1-x Cs x Combination of PbI3, MAPbI3, (FAPbI3) 1-x (MAPbBr3) x , CsPbI2Br and CsPbI3, CsPbI2Br, CsPbI3, CsPbBr3 and Cs 0.05 (FA 1-x MA x ) 0.95 Pb(I 1-y Bry)3 combination, etc.;

[0027] The values ​​of x and y are independently 0-1 and are not equal to 0 and 1, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc.

[0028] Preferably, in the perovskite absorption layer, based on the total mass of the lead halide compound as 100%, the mass percentage of the azulene compound is 0.1%-5%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, etc.

[0029] In this exemplary embodiment, based on the total mass of the lead halide compound as 100%, the mass percentage of the azulene compound is 0.1%-5%. The reason for controlling it within this range is to achieve a balance between the efficiency and stability of the device; if the proportion of the azulene compound is too high, excess azulene compound will cause precipitation of excess azulene compound from the perovskite, hindering the crystallization of the perovskite; if the proportion of the azulene compound is too low, it will cause doping failure to produce new grain boundaries, thereby having a negative impact on efficiency and stability.

[0030] Preferably, the thickness of the perovskite absorption layer is 300-500 nm, for example, 320 nm, 340 nm, 360 nm, 380 nm, 400 nm, 420 nm, 440 nm, 460 nm, 480 nm, etc.

[0031] Preferably, the hole transport layer comprises a nickel-containing compound.

[0032] Preferably, the nickel-containing compound comprises nickel oxide.

[0033] Preferably, the conductive base layer comprises fluorine-doped tin oxide (FTO) and / or indium tin oxide (ITO).

[0034] In a second aspect, the present invention provides a method for preparing the perovskite battery according to the first aspect, the preparation method comprising the following steps:

[0035] The conductive substrate layer, the hole transport layer, the perovskite absorption layer, the interface passivation layer, the electron transport layer and the back electrode are stacked in sequence to obtain the perovskite battery.

[0036] Preferably, the preparation method comprises the following steps:

[0037] (1) providing a hole transport layer on the surface of the conductive substrate;

[0038] (2) mixing a lead halide compound and an azulene compound and coating the mixture on the surface of the hole transport layer to form a perovskite absorption layer;

[0039] (3) mixing an azulene compound and a solvent, and coating the mixture on the surface of the perovskite absorption layer to form an interface passivation layer;

[0040] (4) An electron transport layer is provided on the interface passivation layer, and a back electrode is provided on the surface of the electron transport layer to obtain the perosite titanium battery.

[0041] Preferably, in step (1), the setting method includes magnetron sputtering.

[0042] Preferably, in step (2), the coating method includes scraping.

[0043] Preferably, the coating further includes a thermal annealing treatment.

[0044] Preferably, the temperature of the thermal annealing treatment is 100-120°C, such as 105°C, 110°C, 115°C, etc.

[0045] Preferably, the thermal annealing treatment time is 10-30 min, for example, 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 24 min, 26 min, 28 min, etc.

[0046] In this exemplary embodiment, when the perovskite absorber layer is prepared, due to the use of an azulene compound containing carboxyl and / or carbonyl groups and amino groups, the interaction (hydrogen bond, ionic bond) between the carboxyl or carbonyl groups and the formamidine material in the perovskite is utilized to make the perovskite structure more stable; the amino group forms an intermediate structure with the formamidine material (such as formamidine iodide FAI), which depletes the free formamidine material in the precursor. This is beneficial for the perovskite film prepared by the one-step solution method. In the initial stage of preparation, the perovskite crystals grow vertically and orderly from the solution surface downward, and finally, during the annealing process (that is, the process of completely volatilizing the solution during high-temperature heating), vertically oriented perovskite crystals with high crystallinity and few grain boundaries are formed. By reducing or even eliminating the grain boundaries between the perovskite grains, the efficiency of the device and the intrinsic stability of the perovskite absorber layer are improved.

[0047] Preferably, in step (3), the coating method includes scraping.

[0048] Preferably, the solvent comprises any one or a combination of at least two of isopropanol, chloroform or ethanol, wherein typical but non-limiting combinations include: a combination of isopropanol and chloroform, a combination of chloroform and ethanol, a combination of isopropanol, chloroform and ethanol, etc.

[0049] Preferably, in step (4), the electron transport layer is provided by vacuum evaporation.

[0050] Preferably, the vacuum degree of the vacuum evaporation is less than 10 -4 Pa, for example 10 -5 Pa, 10 -6 Pa et al.

[0051] Preferably, the arrangement of the electron transport layer specifically includes: -4 Pa (e.g. 10 -5 Pa, 10 - 6 Under conditions of Pa, etc., a carbon layer and a tin layer are sequentially deposited on the surface of the interface passivation layer.

[0052] Preferably, the deposition rate of the carbon layer is For example wait.

[0053] Preferably, the deposition rate of the tin layer is For example wait.

[0054] Preferably, the back electrode is provided by vacuum evaporation.

[0055] Preferably, the vacuum degree of the vacuum evaporation is less than 10 -4Pa, for example 10 -5 Pa, 10 -6 Pa et al.

[0056] Preferably, the evaporation rate is For example wait.

[0057] As a preferred technical solution, the preparation method comprises the following steps:

[0058] (1) providing a hole transport layer on the surface of the conductive substrate layer by magnetron sputtering;

[0059] (2) mixing a lead halide compound and an azulene compound, applying the mixture to the surface of the hole transport layer by scraping, and then thermally annealing the mixture at 100-120° C. for 10-30 minutes to form a perovskite absorption layer;

[0060] (3) mixing an azulene compound and a solvent, and applying the mixture to the surface of the perovskite absorption layer to form an interface passivation layer;

[0061] (4) When the vacuum degree is less than 10 -4 Under the condition of Pa, by vacuum evaporation, the surface of the interface passivation layer is sequentially and The carbon layer and the tin layer are deposited at a rate of 1000 nm to form an electron transport layer;

[0062] At a vacuum degree of less than 10 -4 Pa and evaporation rate are Under the conditions of , a back electrode is evaporated on the surface of the electron transport layer by vacuum evaporation to obtain the perosite titanium battery.

[0063] Compared with the prior art, the present invention has the following beneficial effects:

[0064] The perosite titanium battery of the present invention has excellent electrical performance and stability. The initial light conversion efficiency of the perosite titanium battery is above 16.4%. After aging for 1200 hours at 85°C / 85% RH, the light conversion efficiency is above 15.8%. The absolute value of the PCE change rate after aging is within 4.82%. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 is a schematic structural diagram of the perovskite battery described in Example 1;

[0066] Figure 2 is a graph showing the light conversion efficiency of the perovskite cells described in various embodiments and comparative examples;

[0067] Figure 3 3. It is a stability test diagram of the photostability of the perovskite cells described in the embodiments and comparative examples;

[0068] Figure 4 3. It is a test chart of the high humidity and high heat stability of the perovskite battery described in each embodiment and comparative example;

[0069] Among them, 1-back electrode; 2-electron transport layer; 3-interface passivation layer; 4-perovskite absorption layer; 5-hole transport layer; 6-conductive substrate layer. DETAILED DESCRIPTION

[0070] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0071] For example, the structural formula of the 2-amino-1,3-dicarboxyazulene is as follows:

[0072]

[0073] For example, the structural formula of the 2-amino-1,3-diethoxycarbonylazulene is as follows:

[0074]

[0075] Illustratively, the structural formula of the 2-aminoazulene is as follows:

[0076]

[0077] In this exemplary embodiment, the azulene compound can be a commercially available product or can be homemade.

[0078] In the present invention, the synthetic routes of 2-amino-1,3-dicarboxyazulene, 2-amino-1,3-diethoxycarbonylazulene and 2-aminoazulene involved in each embodiment can be as follows:

[0079]

[0080] The specific synthesis process can be described as follows:

[0081] Preparation of 7-oxocyclohepta-1,3,5-triene-4-methylbenzenesulfonate: 5.3 g (43 mmol) of 2-hydroxycyclohepta-2,4,6-trienone and 8.2 g (43 mmol) of 4-methylbenzene-1-sulfonyl chloride were weighed and added sequentially to a previously dried 500 mL round-bottom flask under nitrogen. 60 mL of anhydrous dichloromethane was added and the mixture was thoroughly mixed by magnetic stirring at room temperature. Subsequently, 4.4 g (6 mL, 43 mmol) of triethylamine was added dropwise to the mixed solution using a syringe to produce a yellow viscous solution. An additional 60 mL of dichloromethane was added to provide sufficient stirring volume, and the mixture was stirred at room temperature for 32 hours. After the reaction was completed, 150 mL of deionized water was added to quench the reaction. The reaction mixture was transferred to a 500 mL separatory funnel and extracted three times with 150 mL of dichloromethane. After drying, the solvent was rotary evaporated to obtain a tan solid, compound 1.

[0082] The H-NMR spectrum results of compound 1 are as follows: 1 H NMR (DMSO-d6, 500MHz); δ (ppm) 2.43 (s, 3H), 6.95 (t, 1H), 7.05 (t, 1H), 7.12 (d, 1H), 7.18 (m, 1H), 7.32 (d, 2H), 7.43 (d, 1H), 7.905 (d, 2H).

[0083] Preparation of 2-amino-1,3-diethoxycarbonylazulene: 11.8 g (43 mmol) of compound 1 and 9.7 g of ethyl cyanoacetate were weighed and added sequentially to a previously dried 250 mL round-bottom flask under nitrogen. Simultaneously, 5.8 g (86 mmol) of sodium ethoxide was dissolved in 50 mL of ethanol. The mixture was then placed in an ice bath at 0°C, and the sodium ethoxide solution was slowly added dropwise. The reaction was allowed to proceed in an ice bath for 6 h and then at room temperature for an additional 12 h. The reaction was then quenched by adding 100 mL of deionized water and extracted three times with 100 mL of chloroform. The solvent was then rotary evaporated to yield an orange-yellow crude product. The crude product was purified by silica gel column chromatography using a 1:1 mixture of petroleum ether and dichloromethane as the eluent. The purified product, compound 2, was obtained as a yellow solid, representing 2-amino-1,3-diethoxycarbonylazulene.

[0084] The H-NMR spectrum results of compound 2 are as follows: 1 H NMR (DMSO-d6, 500MHz): δ (ppm) 1.49 (t, 6H), 4.47 (q, 4H), 7.44 (t, 1H), 7.55 (t, 2H), 7.81 (s, 2H), 9.16 (d, 2H).

[0085] Preparation of 2-amino-1,3-dicarboxazulene: Dissolve 2g of potassium hydroxide in 50mL of a 4:1 ethanol / water mixture, stirring to dissolve. Add 5g of compound 2 and heat under reflux for 6h. After the reaction is complete, cool to room temperature and add 6M HCl dropwise to the solution, immediately forming an orange precipitate. Filter and wash three times with deionized water to obtain compound 3, 2-amino-1,3-dicarboxazulene.

[0086] The mass spectrometry results of compound 3 are as follows: MS: Theoretical value: C 12 H9NO4[M+1]:231.05, test value:231.93.

[0087] Preparation of 2-aminoazulene:

[0088] The H NMR and MS results of compound 4 are as follows:

[0089] 1 H NMR (DMSO-d6, 500 MHz): δ (ppm) 6.52 (s, 2H), 6.54 (s, 2H), 6.98 (m, 3H), 7.66 (d, 2H). 13C NMR (DMSO-d6, 500 MHz): δ (ppm) 159.88, 142.37, 127.47, 125.99, 124.31, 103.06. MS: Calculated: C 10 H9N(M+1):143.07,test value:143.05.

[0090] Example 1

[0091] This embodiment provides a perovskite battery, the structural diagram of which is shown in FIG. Figure 1 As shown, the perovskite cell includes a back electrode 1 (with a thickness of 80 nm), an electron transport layer 2 (a carbon layer with a thickness of 20 nm and a tin layer with a thickness of 10 nm), an interface passivation layer 3 (with a thickness of 2 nm), a perovskite absorption layer 4 (with a thickness of 400 nm), a hole transport layer 5 (with a thickness of 15 nm) and a conductive base layer 6 (with a thickness of 500 nm) stacked in sequence.

[0092] The perovskite battery is prepared by the following preparation method, which includes the following steps:

[0093] (1) Magnetron sputtering of nickel oxide on the surface of the conductive substrate (FTO glass) to form a hole transport layer;

[0094] (2) Set the 1.5M MA 0.7 FA 0.3 PbI3 and 2-amino-1,3-dicarboxyazulene were mixed, wherein MA 0.7 FA 0.3The total mass of PbI3 is 100%, and the mass concentration of 2-amino-1,3-dicarboxyazulene is 1%. It is coated on the surface of the hole transport layer and then thermally annealed at 110°C for 20 minutes to form a perovskite absorption layer.

[0095] (3) dissolving 2-amino-1,3-dicarboxyazulene in isopropanol to form a solution with a concentration of 0.5 mg / mL, and applying the solution on the surface of the perovskite absorption layer to form an interface passivation layer;

[0096] (4) When the vacuum degree is less than 10 -4 Under the condition of Pa, by vacuum evaporation, the surface of the interface passivation layer is sequentially and The rate of deposition of C 60 and SnO2, forming an electron transport layer containing a carbon layer and a tin layer;

[0097] At a vacuum degree of less than 10 -4 Pa and evaporation rate are Under the conditions of , a back electrode is evaporated on the surface of the electron transport layer by vacuum evaporation to obtain the perosite titanium battery.

[0098] Example 2

[0099] The difference between this embodiment and embodiment 1 is that in step (2), the mass concentration of 2-amino-1,3-dicarboxyazulene is 3%, and in step (3), the amount of 2-amino-1,3-dicarboxyazulene added is 1 mg / mL. The rest is the same as in embodiment 1.

[0100] Example 3

[0101] This embodiment provides a perovskite cell, which includes a back electrode (with a thickness of 100 nm), an electron transport layer (a carbon layer with a thickness of 10 nm and a tin layer with a thickness of 3 nm), an interface passivation layer (with a thickness of 8 nm), a perovskite absorption layer (with a thickness of 400 nm), a hole transport layer (with a thickness of 15 nm) and a conductive base layer (with a thickness of 500 nm) stacked in sequence.

[0102] The perovskite battery is prepared by the following preparation method, which includes the following steps:

[0103] (1) Magnetron sputtering of nickel oxide on the surface of the conductive substrate (FTO glass) to form a hole transport layer;

[0104] (2) Set the 1.5M MA 0.7 FA 0.3 PbI3 and 2-amino-1,3-dicarboxyazulene were mixed, wherein MA 0.7 FA 0.3The total mass of PbI3 is 100%, and the mass concentration of 2-amino-1,3-dicarboxyazulene is 0.1%. It is coated on the surface of the hole transport layer and then thermally annealed at 100°C for 30 minutes to form a perovskite absorption layer;

[0105] (3) dissolving 2-amino-1,3-diethoxycarbonylazulene in isopropanol to form a solution with a concentration of 0.5 mg / mL, and applying the solution on the surface of the perovskite absorption layer to form an interface passivation layer;

[0106] (4) When the vacuum degree is less than 10 -4 Under the condition of Pa, by vacuum evaporation, the surface of the interface passivation layer is sequentially and The rate of deposition of C 60 and SnO2, forming an electron transport layer containing a carbon layer and a tin layer;

[0107] At a vacuum degree of less than 10 -4 Pa and evaporation rate are Under the conditions of , a back electrode is evaporated on the surface of the electron transport layer by vacuum evaporation to obtain the perosite titanium battery.

[0108] Example 4

[0109] This embodiment provides a perovskite cell, which includes a back electrode (with a thickness of 100 nm), an electron transport layer (a carbon layer with a thickness of 30 nm and a tin layer with a thickness of 15 nm), an interface passivation layer (with a thickness of 10 nm), a perovskite absorption layer (with a thickness of 400 nm), a hole transport layer (with a thickness of 15 nm) and a conductive base layer (with a thickness of 500 nm) stacked in sequence.

[0110] The perovskite battery is prepared by the following preparation method, which includes the following steps:

[0111] (1) Magnetron sputtering of nickel oxide on the surface of the conductive substrate (FTO glass) to form a hole transport layer;

[0112] (2) Set the 1.5M MA 0.7 FA 0.3 PbI3 and 2-amino-1,3-diethoxycarbonylazulene were mixed, wherein MA 0.7 FA 0.3 The total mass of PbI3 is 100%, and the mass concentration of 2-amino-1,3-dicarboxyazulene is 5%. It is coated on the surface of the hole transport layer and then thermally annealed at 120°C for 10 minutes to form a perovskite absorption layer.

[0113] (3) dissolving 2-amino-1,3-dicarboxyazulene in isopropanol to form a solution with a concentration of 0.5 mg / mL, and applying the solution on the surface of the perovskite absorption layer to form an interface passivation layer;

[0114] (4) When the vacuum degree is less than 10 -4 Under the condition of Pa, by vacuum evaporation, the surface of the interface passivation layer is sequentially and The rate of deposition of C 60 and SnO2, forming an electron transport layer containing a carbon layer and a tin layer;

[0115] At a vacuum degree of less than 10 -4 Pa and evaporation rate are Under the conditions of , a back electrode is evaporated on the surface of the electron transport layer by vacuum evaporation to obtain the perosite titanium battery.

[0116] Example 5

[0117] The difference between this embodiment and embodiment 1 is that the 2-amino-1,3-dicarboxyazulene in the perovskite absorber layer is replaced with azulene of equal mass, and the rest is the same as embodiment 1.

[0118] Example 6

[0119] The difference between this embodiment and embodiment 1 is that the 2-amino-1,3-dicarboxyazulene in the perovskite absorption layer is replaced with 2-aminoazulene of equal mass, and the rest is the same as embodiment 1.

[0120] Comparative Example 1

[0121] The difference between this comparative example and Example 1 is that the perovskite absorption layer does not include 2-amino-1,3-dicarboxyazulene and has no interface passivation layer, and the rest is the same as Example 1.

[0122] Comparative Example 2

[0123] The difference between this comparative example and Example 1 is that the perovskite cell does not include an interface passivation layer, and the rest is the same as Example 1.

[0124] Performance Testing

[0125] The perosite titanium batteries described in Examples 1-6 and Comparative Examples 1-2 were tested as follows:

[0126] (1) Photovoltaic conversion efficiency (PCE): The photovoltaic conversion efficiency of the perovskite titanium battery during the aging process was tested.

[0127] (2) Stability: The photoelectric conversion efficiency of the perovskite titanium battery was tested and characterized by aging under light stability (maximum output power under simulated sunlight) and high humidity and high heat stability (85°C, 85% RH) conditions. The difference between the photoelectric conversion efficiency of the perovskite titanium battery with an aging time of 1200 h and the photoelectric conversion efficiency of the perovskite titanium battery in the initial state was statistically calculated.

[0128] The test results are summarized in Table 1 and Figure 2-4 middle.

[0129] Table 1

[0130]

[0131] Analysis of the data in Table 1 shows that the light conversion efficiency of the permite titanium battery described in the present invention is above 16.4% in the initial state. After aging for 1200 hours under 85°C / 85% RH conditions, the light conversion efficiency is above 15.8%, and the absolute value of the PCE change rate after aging is within 4.82%. The permite titanium battery described in the present invention has excellent electrical performance and stability.

[0132] Analysis of Comparative Examples 1-2 and Example 1 shows that the performance of Comparative Examples 1-2 is not as good as that of Example 1, which proves that the perovskite titanium battery with a perovskite absorption layer and an interface passivation layer containing an azulene compound has better performance. The example even achieves a positive increase in light conversion efficiency after aging.

[0133] analyze Figure 2 It can be seen that the light conversion efficiency of the perosite titanium battery in the initial state of Comparative Examples 1-2 is not as good as that of the embodiments.

[0134] analyze Figure 3 and Figure 4 It can be seen that the light conversion efficiency of the perovskite titanium battery described in each embodiment changes slightly with the extension of aging time, and the stability is relatively high; while the light conversion efficiency of the perovskite titanium battery described in Comparative Examples 1-2 changes greatly with the extension of aging time, and the stability is relatively poor.

[0135] Analysis of Examples 5-6 and Example 1 shows that the performance of Examples 5-6 is not as good as that of Example 1, which proves that the perovskite titanium battery with an azulene compound containing carboxyl and / or carbonyl and amino groups has better performance.

[0136] The applicant states that the present invention is intended to illustrate the detailed methods of the present invention through the above-described embodiments, but the present invention is not limited to the above-described detailed methods, that is, it does not mean that the present invention must rely on the above-described detailed methods in order to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for various raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., are all within the scope of protection and disclosure of the present invention.

Claims

1. A perovskite battery, characterized in that: The perovskite cell comprises a back electrode, an electron transport layer, an interface passivation layer, a perovskite absorption layer, a hole transport layer and a conductive substrate layer stacked in sequence; The interfacial passivation layer and / or the perovskite absorption layer include an azulene-based compound; The preparation method of the perovskite battery comprises the following steps: (1) providing a hole transport layer on the surface of the conductive substrate; (2) mixing a lead halide compound and an azulene compound and coating the mixture on the surface of the hole transport layer to form a perovskite absorption layer; (3) mixing an azulene compound and a solvent, and coating the mixture on the surface of the perovskite absorption layer to form an interface passivation layer; (4) An electron transport layer is provided on the interface passivation layer, and a back electrode is provided on the surface of the electron transport layer to obtain the perovskite battery.

2. The perovskite battery according to claim 1, characterized in that The azulenyl compound contains a carboxyl group and / or a carbonyl group and an amino group.

3. The perovskite battery according to claim 2, characterized in that The azulene compound includes any one of 2-amino-1,3-dicarboxyazulene, 2-amino-1,3-diethoxycarbonylazulene or 2-aminoazulene, or a combination of at least two thereof.

4. The perovskite battery according to claim 1, characterized in that The back electrode includes a gold electrode.

5. The perovskite battery according to claim 1, characterized in that The thickness of the back electrode is 60-100 nm.

6. The perovskite cell according to claim 1, characterized in that The electron transport layer includes a carbon layer and a tin layer.

7. The perovskite cell according to claim 6, characterized in that The carbon layer includes C60.

8. The perovskite cell according to claim 6, characterized in that The tin layer includes tin dioxide.

9. The perovskite cell according to claim 6, characterized in that The thickness of the carbon layer is 10-30 nm.

10. The perovskite cell according to claim 6, characterized in that: The thickness of the tin layer is 3-15 nm.

11. The perovskite cell according to claim 1, wherein The thickness of the interface passivation layer is 1-10 nm.

12. The perovskite battery according to claim 1, characterized in that The perovskite absorption layer further includes a lead halide compound; The lead halide compound includes MA x FA 1-x PbI3、FA 1-x Cs x PbI3, MAPbI3, (FAPbI3) 1-x (MAPbBr3) x , CsPbI2Br, CsPbI3, CsPbBr3 or Cs 0.05 (FA 1-x MA x ) 0.95 Pb(I 1-y Bry) Any one or a combination of at least two of 3; The values ​​of x and y are independently 0-1 and are not equal to 0 and 1.

13. The perovskite cell according to claim 12, characterized in that: In the perovskite absorption layer, based on the total mass of the lead halide compound being 100%, the mass percentage of the azulene compound is 0.1%-5%.

14. The perovskite cell according to claim 1, wherein: The thickness of the perovskite absorption layer is 300-500 nm.

15. The perovskite cell according to claim 1, characterized in that The hole transport layer includes a nickel-containing compound.

16. The perovskite cell according to claim 15, characterized in that The nickel-containing compound includes nickel oxide.

17. The perovskite cell according to claim 1, characterized in that The conductive base layer includes fluorine-doped tin oxide and / or indium tin oxide.

18. A method for preparing a perovskite battery according to any one of claims 1 to 17, characterized in that: The preparation method comprises the following steps: (1) providing a hole transport layer on the surface of the conductive substrate; (2) mixing a lead halide compound and an azulene compound and coating the mixture on the surface of the hole transport layer to form a perovskite absorption layer; (3) mixing an azulene compound and a solvent, and coating the mixture on the surface of the perovskite absorption layer to form an interface passivation layer; (4) An electron transport layer is provided on the interface passivation layer, and a back electrode is provided on the surface of the electron transport layer to obtain the perovskite battery.

19. The preparation method according to claim 18, characterized in that In step (1), the setting method includes magnetron sputtering.

20. The preparation method according to claim 18, characterized in that In step (2), the coating method includes scraping.

21. The preparation method according to claim 18, characterized in that Step (2) also includes thermal annealing treatment after the coating.

22. The preparation method according to claim 21, characterized in that The temperature of the thermal annealing treatment is 100-120°C.

23. The preparation method according to claim 21, characterized in that The thermal annealing treatment time is 10-30 minutes.

24. The preparation method according to claim 18, characterized in that In step (3), the coating method includes scraping.

25. The preparation method according to claim 18, characterized in that The solvent includes any one of isopropyl alcohol, chloroform or ethanol, or a combination of at least two of them.

26. The preparation method according to claim 18, characterized in that In step (4), the electron transport layer is provided by vacuum evaporation.

27. The preparation method according to claim 26, characterized in that The vacuum degree of the vacuum evaporation is less than 10 -4 Pa.

28. The preparation method according to claim 18, characterized in that The electron transport layer is specifically provided by: -4 Pa, a carbon layer and a tin layer are sequentially deposited on the surface of the interface passivation layer.

29. The preparation method according to claim 28, characterized in that The deposition rate of the carbon layer is 30. The preparation method according to claim 28, characterized in that The deposition rate of the tin layer is 31. The preparation method according to claim 18, characterized in that The back electrode is provided by vacuum evaporation.

32. The preparation method according to claim 31, characterized in that The vacuum degree of the vacuum evaporation is less than 10 -4 Pa.

33. The preparation method according to claim 31, characterized in that The evaporation rate of the vacuum evaporation is 34. The preparation method according to claim 18, characterized in that The preparation method comprises the following steps: (1) providing a hole transport layer on the surface of the conductive substrate layer by magnetron sputtering; (2) mixing a lead halide compound and an azulene compound, applying the mixture to the surface of the hole transport layer by scraping, and then thermally annealing the mixture at 100-120° C. for 10-30 minutes to form a perovskite absorption layer; (3) mixing an azulene compound and a solvent, and applying the mixture to the surface of the perovskite absorption layer to form an interface passivation layer; (4) When the vacuum degree is less than 10 -4 Under the condition of Pa, by vacuum evaporation, the surface of the interface passivation layer is sequentially and The carbon layer and the tin layer are deposited at a rate of 1000 nm to form an electron transport layer; At a vacuum degree of less than 10 -4 Pa and evaporation rate are Under the conditions of , a back electrode is evaporated on the surface of the electron transport layer by vacuum evaporation to obtain the perovskite battery.

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