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CN118215377A - Perovskite precursor solution, perovskite battery and preparation method thereof, photovoltaic device - Google Patents

Perovskite precursor solution, perovskite battery and preparation method thereof, photovoltaic device Download PDF

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Publication number
CN118215377A
CN118215377A CN202410269804.5A CN202410269804A CN118215377A CN 118215377 A CN118215377 A CN 118215377A CN 202410269804 A CN202410269804 A CN 202410269804A CN 118215377 A CN118215377 A CN 118215377A
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Prior art keywords
perovskite
precursor solution
organic solvent
perovskite precursor
halide
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徐晨鑫
贺锐
王殿曦
时宇
张学玲
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Trina Solar Co Ltd
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Trina Solar Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)

Abstract

本申请涉及一种钙钛矿前驱体溶液、钙钛矿电池及其制备方法、光伏器件。钙钛矿前驱体溶液包括相互混合的钙钛矿前驱体盐、第一有机溶剂和第二有机溶剂，第一有机溶剂为丙三醇，第二有机溶剂的种类不同于第一有机溶剂，丙三醇的浓度为0.05 mg/mL~0.65 mg/mL。通过对有机溶剂进行改进，而无需采用额外的含有无机离子或金属离子的添加剂，具体地是在钙钛矿前驱体溶液中加入特定种类的第一有机溶剂丙三醇，并控制钙钛矿前驱体溶液中丙三醇的特定浓度，可有效延缓钙钛矿薄膜的成膜速率，避免产生新的缺陷，故而不会在钙钛矿薄膜中额外引入无机离子或金属离子，从而有效提升钙钛矿薄膜的光电转换效率。The present application relates to a perovskite precursor solution, a perovskite cell and a preparation method thereof, and a photovoltaic device. The perovskite precursor solution includes a perovskite precursor salt, a first organic solvent, and a second organic solvent that are mixed with each other, wherein the first organic solvent is propylene glycol, and the type of the second organic solvent is different from the first organic solvent, and the concentration of propylene glycol is 0.05 mg/mL to 0.65 mg/mL. By improving the organic solvent without using additional additives containing inorganic ions or metal ions, specifically, adding a specific type of the first organic solvent propylene glycol to the perovskite precursor solution, and controlling the specific concentration of propylene glycol in the perovskite precursor solution, the film formation rate of the perovskite film can be effectively slowed down to avoid the generation of new defects, so that no additional inorganic ions or metal ions are introduced into the perovskite film, thereby effectively improving the photoelectric conversion efficiency of the perovskite film.

Description

Perovskite precursor solution, perovskite battery, preparation method of perovskite battery and photovoltaic device
Technical Field
The application relates to the technical field of photovoltaics, in particular to a perovskite precursor solution, a perovskite battery, a preparation method of the perovskite battery and a photovoltaic device.
Background
Perovskite solar cells are receiving great attention because of their high photoelectric conversion efficiency and simple solution process. The current authentication photoelectric conversion efficiency of the single junction perovskite solar cell reaches 26.1% at the highest, and is comparable with that of a crystalline silicon solar cell. However, various defects exist in the perovskite thin film prepared by the solution method, and the defects can have adverse effects on the photoelectric performance and stability of the perovskite solar cell. Therefore, the selection of an appropriate modification strategy is critical to enhance the performance of perovskite cells. Currently, common modification means include: optimization of charge transport layers, interfacial engineering, compositional engineering, additive engineering, and the like. In an inert gas atmosphere, additive engineering is a common and effective way to passivate the deep and shallow level defects of the perovskite thin film, thereby enhancing the photoelectric performance of the perovskite cell. However, conventional additives typically introduce additional inorganic or metal ions into the perovskite thin film, which can lead to new defects.
Therefore, there is a need for improvements over the conventional art.
Disclosure of Invention
Based on the above, the application provides a perovskite precursor solution, a perovskite battery, a preparation method thereof and a photovoltaic device, wherein new defects caused by the additional introduction of inorganic ions or metal ions can be avoided, and the photoelectric conversion efficiency is effectively improved.
The technical scheme for solving the technical problems is as follows.
The first aspect of the application provides a perovskite precursor solution, which comprises perovskite precursor salt, a first organic solvent and a second organic solvent which are mixed with each other, wherein the first organic solvent is glycerol, the second organic solvent is different from the first organic solvent in kind, and the concentration of the glycerol is 0.05 mg/mL-0.65 mg/mL.
In some embodiments, the concentration of glycerol in the perovskite precursor solution is 0.2 mg/mL to 0.4 mg/mL.
In some of these embodiments, the perovskite precursor salt comprises a monovalent cation halide and a divalent cation halide in the perovskite precursor solution.
In some of these embodiments, the monovalent cation halide comprises at least one of a monovalent organic cation halide and an alkali metal halide in the perovskite precursor solution.
In some of these embodiments, the monovalent cation halide in the perovskite precursor solution satisfies at least one of the following characteristics:
(1) The monovalent organic cations in the monovalent organic cation halide comprise at least one of an organic amine ion and a formamidine ion;
(2) The monovalent organic cations in the monovalent organic cation halide comprise at least one of CH3NH3 +、CH3(CH2)nNH3 +、HC(NH2)2 + and C 6H5(CH2)n·NH3 +; wherein n is an integer of 1 to 3;
(3) The alkali metal ions in the alkali metal halide include at least one of Li +、Na+、K+、Rb+ and Cs +;
(4) The halide ions in the monovalent organic cationic halide and the halide ions in the alkali metal halide each independently comprise at least one of F -、Cl-、Br- and I -.
In some of these embodiments, the monovalent cation halide comprises at least one of formamidine iodide, formamidine bromide, formamidine chloride, methylamine bromide, and methylamine chloride in the perovskite precursor solution.
In some of these embodiments, the divalent cation halide satisfies at least one of the following characteristics in the perovskite precursor solution:
(1) The divalent cations in the divalent cation halide include at least one of Pb 2+ and Sn 2+;
(2) The halide ions in the divalent cation halide include at least one of F -、Cl-、Br- and I -.
In some of these embodiments, the divalent cation halide comprises at least one of lead iodide, tin iodide, lead bromide, and tin bromide in the perovskite precursor solution.
In some embodiments, the concentration of the monovalent cation halide and the divalent cation halide in the perovskite precursor solution are each independently 0.5 mol/L to 5 mol/L.
In some of these embodiments, the second organic solvent comprises at least one of N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and γ -butyrolactone in the perovskite precursor solution.
In some of these embodiments, in the perovskite precursor solution, the second organic solvent satisfies at least one of the following characteristics:
(1) The second organic solvent comprises N, N-dimethylformamide and dimethyl sulfoxide;
(2) The volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 1 (2-10).
The third aspect of the application provides a perovskite thin film prepared by adopting the perovskite precursor solution provided by the first aspect of the application.
The third aspect of the application provides a method for preparing a perovskite thin film, comprising the following steps:
Preparing a perovskite precursor solution provided by the first aspect of the application into a wet film;
And annealing the wet film to obtain the perovskite film.
A fourth aspect of the present application provides a perovskite battery comprising a first electrode, a second electrode, and a perovskite thin film provided in the second aspect of the present application or a perovskite thin film produced by a production method provided in the third aspect of the present application, which are stacked.
The fifth aspect of the present application provides a method for producing a perovskite battery, comprising the steps of:
Setting perovskite precursor solution on the first electrode, and forming a perovskite film on the first electrode after annealing treatment; the perovskite precursor solution comprises perovskite precursor salt, a first organic solvent and a second organic solvent which are mixed with each other, wherein the first organic solvent is glycerol, the second organic solvent is different from the first organic solvent in kind, and the concentration of the glycerol is 0.05 mg/mL-0.7 mg/mL;
and forming a second electrode on the surface of one side of the perovskite thin film far away from the first electrode.
The sixth aspect of the application provides a photovoltaic device comprising a perovskite cell as provided in the fourth aspect of the application or a perovskite cell as produced by a method of production as provided in the fifth aspect of the application.
Compared with the prior art, the perovskite precursor solution has the following beneficial effects:
According to the perovskite precursor solution, the organic solvent is improved without adopting an additive containing inorganic ions or metal ions, specifically, the first organic solvent glycerol of a specific type is added into the perovskite precursor solution, the specific concentration of the glycerol in the perovskite precursor solution is controlled, the viscosity of the perovskite precursor solution can be increased, the volatilization speed of the solvent in the perovskite precursor solution is reduced, the solvent can not react with the perovskite precursor salt, the film forming speed of the perovskite film is effectively delayed, new defects are avoided, and the inorganic ions or the metal ions can not be additionally introduced into the perovskite film, so that the photoelectric conversion efficiency of the perovskite film is effectively improved.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The meaning of "a plurality of" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present invention may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present invention are scaled up or down within the scope of the disclosure of the embodiments of the present invention. Specifically, the weight described in the specification of the embodiment of the invention can be mass units known in the chemical industry field such as mu g, mg, g, kg.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
The perovskite precursor solution comprises perovskite precursor salt, glycerol and a second organic solvent, wherein the concentration of the glycerol is 0.05 mg/mL-0.65 mg/mL.
According to the perovskite precursor solution, the organic solvent is improved without adopting an additive containing inorganic ions or metal ions, specifically, the first organic solvent glycerol of a specific type is added into the perovskite precursor solution, the specific concentration of the glycerol in the perovskite precursor solution is controlled, the viscosity of the perovskite precursor solution can be increased, the volatilization speed of the solvent in the perovskite precursor solution is reduced, the solvent can not react with the perovskite precursor salt, the film forming speed of the perovskite film is effectively delayed, new defects are avoided, and the inorganic ions or the metal ions can not be additionally introduced into the perovskite film, so that the photoelectric conversion efficiency of the perovskite film is effectively improved.
It is understood that the concentration of glycerol refers to the mass of glycerol/(the total volume of the first organic solvent after mixing with the second organic solvent); it is further understood that the concentration of glycerol, including but not limited to 0.05 mg/mL、0.08 mg/mL、0.1 mg/mL、0.15 mg/mL、0.2 mg/mL、0.25 mg/mL、0.3 mg/mL、0.35 mg/mL、0.4 mg/mL、0.45 mg/mL、0.5 mg/mL、0.55 mg/mL、0.6 mg/mL、0.65 mg/mL;, may be within the range that any two of these points constitute as endpoints in some examples, as follows.
In some examples, the concentration of glycerol in the perovskite precursor solution is 0.2 mg/mL to 0.6 mg/mL.
In some examples, the concentration of glycerol in the perovskite precursor solution is 0.2 mg/mL to 0.4 mg/mL.
In some of these examples, the perovskite precursor solution includes a monovalent cation halide and a divalent cation halide.
In some examples, the monovalent cation halide comprises at least one of a monovalent organic cation halide and an alkali metal halide in the perovskite precursor solution.
In some examples, the monovalent organic cations in the monovalent organic cation halide in the perovskite precursor solution include at least one of an organic amine ion and a formamidine ion.
In some examples, the monovalent organic cations in the monovalent organic cation halide in the perovskite precursor solution include at least one of CH3NH3 +（MA+）、CH3(CH2)nNH3 +、HC(NH2)2 +（FA+） and C 6H5(CH2)n·NH3 +; wherein n is an integer of 1 to 3.
It is understood that CH 3(CH2)nNH3 + includes CH3CH2NH3 +、CH3(CH2)2NH3 +、CH3(CH2)3NH3 +,C6H5(CH2)n·NH3 + includes C6H5CH2NH3 +、C6H5(CH2)2NH3 +、C6H5(CH2)3NH3 +.
In some of these examples, the halide ion in the monovalent organic cationic halide in the perovskite precursor solution includes at least one of F -、Cl-、Br- and I -.
In some examples, the monovalent cation halide in the perovskite precursor solution includes at least one of formamidine iodide (FAI), formamidine bromide (FABr), formamidine chloride (FACl), methylamine iodide (MAI), methylamine bromide (MABr), and methylamine chloride (MACl).
In some of these examples, the alkali metal ions in the metal halide in the perovskite precursor solution include at least one of Li +、Na+、K+、Rb+ and Cs +.
In some of these examples, the halide ions in the alkali metal halide in the perovskite precursor solution include at least one of F -、Cl-、Br- and I -.
In some of these examples, the metal halide includes at least one of cesium bromide (CsBr) and cesium iodide (CsI) in the perovskite precursor solution.
In some of these examples, the divalent cation in the divalent cation halide comprises at least one of Pb 2+ and Sn 2+ in the perovskite precursor solution.
In some of these examples, the halide ions in the divalent cation halide comprise at least one of F -、Cl-、Br- and I - in the perovskite precursor solution.
In some of these examples, the divalent cation halide includes at least one of lead iodide (PbI 2), tin iodide, lead bromide, and tin bromide in the perovskite precursor solution.
In some examples, the concentration of monovalent cation halides and divalent cation halides in the perovskite precursor solution are each independently 0.5 mol/L to 5 mol/L.
It is understood that the concentrations of monovalent and divalent cationic halides independently include, but are not limited to, 0.5 mol/L, 1 mol/L, 1.5 mol/L, 1.8 mol/L, 2 mol/L, 3 mol/L, 4 mol/L, 5 mol/L, respectively.
In some examples, the perovskite precursor solution, the second organic solvent comprises at least one of N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and γ -butyrolactone.
In some examples, the perovskite precursor solution, the second organic solvent includes N, N-dimethylformamide and dimethylsulfoxide.
In some examples, the volume ratio of dimethyl sulfoxide to N, N-dimethylformamide in the perovskite precursor solution is 1 (2-10).
It is understood that the volume ratio of dimethyl sulfoxide to N, N-dimethylformamide includes, but is not limited to, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10.
An embodiment of the present application provides a method for preparing a perovskite precursor solution, including the steps of:
Mixing a perovskite precursor salt, a first organic solvent and a second organic solvent to obtain a perovskite precursor solution; the first organic solvent is glycerol, the second organic solvent is different from the first organic solvent, and the concentration of the glycerol is 0.05 mg/mL-0.7 mg/mL.
According to the preparation method of the perovskite precursor solution, the specific type of first organic solvent glycerol is added into the perovskite precursor salt, and the specific concentration of the glycerol in the perovskite precursor solution is controlled, so that the film forming rate of the perovskite film can be effectively delayed, new defects are avoided, inorganic ions or metal ions are not additionally introduced into the perovskite film, and the photoelectric conversion efficiency of the perovskite film can be effectively improved.
It is understood that the perovskite precursor solution provided by the application can be prepared by the perovskite precursor solution preparation method provided by the application.
In some examples, the perovskite precursor solution is prepared by mixing a first organic solvent and a second organic solvent and then adding a perovskite precursor salt.
In some examples, the perovskite precursor solution is prepared by mixing glycerol and N, N-dimethylformamide, then adding dimethyl sulfoxide, and then adding the perovskite precursor salt.
An embodiment of the application provides a perovskite thin film, which is prepared from the perovskite precursor solution.
The perovskite thin film provided by the application has higher photoelectric conversion efficiency.
In some of these examples, the perovskite thin film has a thickness of 400 nm to 600: 600 nm.
It is understood that the thickness of the perovskite thin film includes, but is not limited to, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm.
An embodiment of the application provides a preparation method of a perovskite thin film, which comprises the following steps:
preparing a wet film from the perovskite precursor solution;
and (5) annealing the wet film to obtain the perovskite film.
The perovskite film preparation method provided by the application is prepared by adopting the perovskite precursor solution, the film forming rate is relatively slow, and the photoelectric conversion efficiency of the perovskite film can be effectively improved.
In some examples, in the preparation method of the perovskite thin film, the annealing treatment temperature is 120-180 ℃ and the annealing treatment time is 10-20 min.
It is understood that the annealing temperatures include, but are not limited to, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ for times including, but not limited to, 10 min, 12 min, 15min, 18 min, 20 min.
It is to be understood that the present application is not limited to the manner in which the wet film is formed, including, but not limited to, spin coating, spray coating, knife coating, or the like.
In some examples, the perovskite thin film is prepared by spin coating to form a wet film.
In some examples, the perovskite thin film is prepared at a spin coating rate of 1200 r/min to 4000 r/min.
It is understood that the rate of spin coating includes, but is not limited to 1200 r/min、1500 r/min、1800 r/min、2000 r/min、2500 r/min、2800 r/min、3000 r/min、3200 r/min、3500 r/min、3800 r/min、4000 r/min.
In some examples, the method for preparing the perovskite thin film comprises sequentially performing first spin coating and second spin coating, wherein the first spin coating is performed at a speed of 1200 r/min-1500 r/min, and the second spin coating is performed at a speed of 3500 r/min-4000 r/min.
In some examples, in the preparation method of the perovskite thin film, the time of the first spin coating is 15 s-20 s, and the time of the second spin coating is 30 s-40 s.
It is understood that the first spin-coating times include, but are not limited to, 15 s, 16 s, 17 s, 18 s, 19 s, 20 s, and the second spin-coating times include, but are not limited to, 30 s, 31 s, 32 s, 33 s, 34 s, 35 s, 36 s, 37 s, 38 s, 39 s, 40 s.
In some examples, the method for preparing a perovskite thin film further includes a step of dropping an antisolvent in the second spin coating step.
In some examples, the anti-solvent includes at least one of diethyl ether, chlorobenzene, anisole, and ethyl acetate.
An embodiment of the present application provides a perovskite battery including a first electrode, a second electrode, and the perovskite thin film.
In some of these examples, the perovskite battery further includes a hole transport layer and an electron transport layer, one of the hole transport layer and the electron transport layer being disposed between the first electrode and the perovskite thin film, and the other of the hole transport layer and the electron transport layer being disposed between the perovskite thin film and the second electrode.
It is understood that when the hole transport layer is disposed between the first electrode and the perovskite thin film, the electron transport layer is disposed between the perovskite thin film and the second electrode; when the electron transport layer is arranged between the first electrode and the perovskite thin film, the hole transport layer is arranged between the perovskite thin film and the second electrode. That is, in some examples, in a perovskite battery, the perovskite battery includes a first electrode, a hole transport layer, a perovskite thin film, an electron transport layer, and a second electrode that are stacked in this order; in other examples, the perovskite battery includes a first electrode, an electron transport layer, a perovskite thin film, a hole transport layer, and a second electrode that are stacked in this order.
In some of these examples, the electron transport layer comprises at least one of C60, PCBM, tiO 2, and SnO 2 in a perovskite cell.
In some of these examples, the electron transport layer comprises a dense electron transport layer comprising an organic titanium source and a mesoporous electron transport layer comprising an inorganic titanium source, arranged in a stack.
By arranging the compact electron transport layer and the mesoporous electron transport layer, the perovskite thin film is formed, and the electric leakage phenomenon is effectively avoided.
In some examples, the perovskite battery comprises a first electrode, a dense electron transport layer, a mesoporous electron transport layer, a perovskite thin film, a hole transport layer and a second electrode which are sequentially stacked.
In some of these examples, the organic titanium source comprises titanium diisopropoxide bis acetylacetonate in the perovskite cell.
In some of these examples, the inorganic titanium source comprises at least one of titanium dioxide and titanium tetrachloride in the perovskite cell.
In some examples, the thickness of the dense electron transport layer is 10 nm to 20 nm and the thickness of the mesoporous electron transport layer is 100 nm to 200 nm in the perovskite cell.
In some of these examples, the hole transport layer comprises a Spiro-ome tad in a perovskite cell.
In some of these examples, the hole transport layer has a thickness of 150 nm to 300 nm in the perovskite cell.
In some of these examples, in the perovskite cell, one of the first electrode and the second electrode is a transparent conductive electrode, and the other is one of a transparent conductive electrode and a metal electrode;
In some of these examples, the perovskite cell has at least one of the first electrode and the second electrode being a transparent conductive electrode.
In some of these examples, the perovskite cell has one of the first electrode and the second electrode being a transparent conductive electrode and the other being one of a transparent conductive electrode and a metal electrode.
It will be appreciated that in a perovskite cell, the first electrode and the second electrode may be transparent conductive electrodes at the same time; the first electrode may be a transparent conductive electrode, and the second electrode may be a metal electrode; the first electrode may be a metal electrode, and the second electrode may be a transparent conductive electrode.
In some of these examples, the perovskite cell, the metal electrode comprises at least one of gold (Au), silver (Ag), and copper (Cu).
In some of these examples, the transparent conductive electrode includes at least one of Indium Tin Oxide (ITO), fluorine doped indium tin oxide (FTO), indium Zinc Oxide (IZO), tungsten doped indium oxide (IWO), and aluminum doped zinc oxide (AZO) in the perovskite cell.
In some examples, the thickness of the first electrode and the second electrode are each independently 20 nm to 200 nm in the perovskite battery.
It is understood that the thicknesses of the first and second electrodes independently include, but are not limited to, 20 nm, 50nm, 80 nm, 100 nm, 120 nm, 150 nm, 180 nm, 200nm, respectively.
The perovskite battery provided by the application comprises the perovskite thin film, so that the perovskite battery has at least the same advantages as the perovskite thin film.
An embodiment of the present application provides a method for manufacturing a perovskite battery, including the steps of:
Setting perovskite precursor solution on a first electrode, and forming a perovskite film on the first electrode after annealing treatment; the perovskite precursor solution comprises perovskite precursor salt, a first organic solvent and a second organic solvent which are mixed with each other, wherein the first organic solvent is glycerol, the second organic solvent is different from the first organic solvent in kind, and the concentration of the glycerol is 0.05 mg/mL-0.7 mg/mL;
a second electrode is formed on a surface of the perovskite thin film remote from the first electrode.
It is understood that the features of the above-described method for producing a perovskite thin film are applicable to the steps for producing a perovskite thin film in the method for producing a perovskite battery provided by the present application.
It is further understood that the perovskite precursor solution is provided on the conductive side surface of the first electrode.
In some examples, the method for preparing a perovskite battery further comprises:
One of the hole transport layer and the electron transport layer is provided between the first electrode and the perovskite thin film, and the other of the hole transport layer and the electron transport layer is provided between the perovskite thin film and the second electrode.
It is understood that the electron transport layer may be disposed between the first electrode and the perovskite thin film or may be disposed between the perovskite thin film and the second electrode.
That is, in some examples, the step of disposing the electron transport layer includes:
the first mixed solution is arranged on the first electrode, and a compact electron transport layer is formed after first annealing treatment; the first mixed solution comprises an organic titanium source and a third organic solvent;
The second mixed solution is arranged on the surface of the compact electron transport layer far away from the first electrode, and a mesoporous electron transport layer is formed after the second annealing treatment; the second mixed solution comprises an inorganic titanium source and a fourth organic solvent.
In some examples, the third organic solvent comprises n-butanol.
In some examples, in the preparation method of the perovskite battery, the volume ratio of the organic titanium source to the third organic solvent is 1 (14-18).
In some of these examples, the fourth organic solvent comprises ethanol.
In some examples, in the preparation method of the perovskite battery, the mass ratio of the inorganic titanium source to the fourth organic solvent is 1 (6-8).
In some examples, in the preparation method of the perovskite battery, the temperature of the first annealing treatment is 100-130 ℃ and the time is 10-12 min.
In some examples, in the preparation method of the perovskite battery, the temperature of the second annealing treatment is 400-500 ℃ and the time is 120-150 min.
It can be understood that the third annealing treatment is the annealing treatment in the preparation method of the perovskite thin film, and the temperature of the third annealing treatment is 120-180 ℃ and the time is 10-20 min.
In some examples, the perovskite battery is prepared by a method that a first mixed solution is arranged on the surface of the conductive side of the first electrode by a dynamic spin coating method, and a second mixed solution is arranged on the surface of the dense electron transport layer away from the first electrode by a static spin coating method.
In some examples, in the preparation method of the perovskite battery, the spin coating rate of the dynamic spin coating method is 1800 rpm/min-2200 rpm/min, and the time is 30 s-50 s.
In some examples, in the preparation method of the perovskite battery, the spin coating rate of the static spin coating method is 4500 rpm/min-5500 rpm/min, and the time is 5 s-15 s.
It is understood that the formation modes of the hole transport layer, the second electrode layer, and the like are not limited, and the formation modes commonly used in the art may include, but are not limited to, one of a magnetron sputtering method, a spin coating method, a slit coating method, and an evaporation method.
In some examples, the method for preparing a perovskite battery further comprises a step of preprocessing the transparent conductive electrode before forming the film layer on the surface of the transparent conductive electrode.
In some examples, the step of preprocessing includes:
and cleaning, drying and ultraviolet ozone treatment are sequentially carried out on the transparent conductive electrode.
It is understood that the cleaning agent used for the cleaning includes, but is not limited to, at least one of water, acetone, isopropyl alcohol, ethanol, glass cleaning agent, and the like.
It can be appreciated that the perovskite battery can be prepared by the preparation method of the perovskite battery provided by the application, and the perovskite battery can also be prepared by the preparation method of the perovskite battery provided by the application.
An embodiment of the application provides a photovoltaic device comprising the perovskite battery or the perovskite battery prepared by the preparation method.
The photovoltaic module comprises the perovskite battery provided by the application, and therefore has at least the same advantages as the perovskite battery.
The present application will be described in further detail with reference to the following specific embodiments, but the embodiments of the present application are not limited thereto.
The transparent conductive layers used in the following examples and comparative examples were pretreated, including: sequentially carrying out ultrasonic cleaning by deionized water, glass cleaning agent, isopropanol, ethanol and deionized water, wherein the cleaning time is 20 min each time, then drying in an oven to remove impurities and moisture on the surface of the FTO, and finally carrying out ultraviolet ozone treatment on the FTO glass.
Example 1
(1) And dynamically spin-coating (2000 rpm/min,40 s) a first mixed solution containing titanium diisopropoxy diacetylacetonate and n-butanol in a volume ratio of 1:16 onto the transparent conductive layer, placing the transparent conductive layer in a drying oven at 120 ℃ after spin-coating, and drying 10 min to form a compact electron transport layer, wherein the thickness of the compact electron transport layer is about 10-20 nm.
(2) And (3) carrying out static spin coating (5000 rpm/min,10 s) on a second solution containing titanium dioxide and ethanol in a mass ratio of 1:8 on the compact electron transport layer, and then placing the compact electron transport layer on a flat heating table and heating at 500 ℃ for 1h to form a mesoporous titanium dioxide electron transport layer, wherein the thickness of the mesoporous titanium dioxide electron transport layer is about 100-200 nm.
(3) Dissolving glycerol into DMF solvent, adding DMSO and stirring uniformly to obtain mixed solvent; in the mixed solvent, the concentration of glycerol is 0.08 mg/mL, and the volume ratio of DMSO to DMF is 1:4; FAI, pbI 2 and MACl are added into a mixed solvent according to the mol ratio of 1:1:0.4 to obtain perovskite precursor solutions, wherein the concentration of FAI and PbI 2 in the perovskite precursor solutions is 1.8 mol/L respectively.
(4) Spin-coating the perovskite precursor solution prepared in the step (3) onto the surface of the mesoporous titanium dioxide electron transport layer formed in the step (2) far away from the compact electron transport layer in two steps, wherein the two steps of spin-coating comprise: the spin coating rate in the first step is 1500 r/min, 18s; the spin coating rate in the second step is 3500 r/min,35s; after the second spin-coating step 15 s, 1 mL of the antisolvent diethyl ether was added dropwise. After spin coating, the perovskite film is formed by heating 15 min at 150 ℃ and the thickness is about 550 a nm a.
(5) And (3) carrying out static spin coating (4000 rpm/min,30 s) on the surface of the perovskite film, oxidizing 12: 12 h in dry air to form a hole transport layer, wherein the thickness is about 180: 180 nm, and scraping out the conductive area by using a knife.
(6) The Au electrode was evaporated by vacuum evaporation to a thickness of about 80 nm a.
Example 2
Substantially the same as in example 1, except that in step (3) of example 2, the concentration of glycerol in the mixed solvent was 0.2 mg/mL.
Example 3
Substantially the same as in example 1, except that in step (3) of example 3, the concentration of glycerol in the mixed solvent was 0.4 mg/mL.
Example 4
Substantially the same as in example 1, except that in step (3) of example 4, the concentration of glycerol in the mixed solvent was 0.6 mg/mL.
Comparative example 1
Substantially the same as in example 1, except that no glycerol was added to the mixed solvent in step (3) of comparative example 1.
Comparative example 2
Substantially the same as in example 1, except that in step (3) of comparative example 2, the concentration of glycerin in the mixed solvent was 0.8 mg/mL.
Comparative example 3
Substantially the same as in example 1, except that in step (3) of comparative example 3, the concentration of glycerin in the mixed solvent was 0.7 mg/mL.
Comparative example 4
Substantially the same as in example 1, except that in step (3) of comparative example 4, the concentration of glycerol in the mixed solvent was 0.01 mg/mL.
Comparative example 5
Substantially the same as in example 1, except that in step (3) of comparative example 5, glycerol in the mixed solvent was replaced with glycerol p-aminobenzoate at an equal concentration.
Comparative example 6
Substantially the same as in example 1, except that in step (3) of comparative example 6, glycerol in the mixed solvent was replaced with isopropyl alcohol at an equal concentration.
Comparative example 7
Substantially the same as in example 1, except that in step (3) of comparative example 7, glycerol in the mixed solvent was replaced with ethylene glycol of equal concentration.
The perovskite batteries prepared in each example and comparative example were tested for performance in terms of open circuit voltage, short circuit current density, fill factor, and energy conversion efficiency using an I-V curve under the following test conditions: AM 1.5G standard solar spectrum, irradiance is 1000W/m 2.
The experimental test results are shown in Table 1. Wherein PCE represents photoelectric conversion efficiency in%, voc represents open circuit voltage in V, jsc represents short circuit current density in mA/cm 2, and FF represents fill factor in%.
TABLE 1
Wherein, the glycerol concentration in table 1 refers to the concentration of glycerol in the mixed solution of step (3).
As can be seen from table 1, the perovskite batteries prepared in examples have better overall performance in terms of open circuit voltage, short circuit current density, fill factor, and energy conversion efficiency than the comparative examples. Wherein, the glycerol concentration in the comparative examples 2 and 3 is too high, which plays a role in inhibiting the performance of the battery, so that the PCE is not as good as that of the comparative example 1 without glycerol; the comparative example 4 has too low concentration of the glycerol and has little effect of improving the performance of the battery; comparative examples 5 to 7, glycerol in the mixed solvent was replaced with glycerol paraaminobenzoate, isopropanol and ethylene glycol in equal concentrations, respectively, and the test results showed that glycerol paraaminobenzoate, isopropanol and ethylene glycol had limited improvement effect on battery performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent of the application should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.

Claims (16)

1.一种钙钛矿前驱体溶液，其特征在于，包括相互混合的钙钛矿前驱体盐、第一有机溶剂和第二有机溶剂，所述第一有机溶剂为丙三醇，所述第二有机溶剂的种类不同于所述第一有机溶剂，所述丙三醇的浓度为0.05 mg/mL~0.65 mg/mL。1. A perovskite precursor solution, characterized in that it comprises a perovskite precursor salt, a first organic solvent and a second organic solvent mixed with each other, wherein the first organic solvent is glycerol, the type of the second organic solvent is different from that of the first organic solvent, and the concentration of the glycerol is 0.05 mg/mL~0.65 mg/mL. 2.如权利要求1所述的钙钛矿前驱体溶液，其特征在于，所述丙三醇的浓度为0.2 mg/mL~0.4 mg/mL。2. The perovskite precursor solution according to claim 1, wherein the concentration of glycerol is 0.2 mg/mL to 0.4 mg/mL. 3.如权利要求1~2任一项所述的钙钛矿前驱体溶液，其特征在于，所述钙钛矿前驱体盐包括一价阳离子卤化物和二价阳离子卤化物。3. The perovskite precursor solution according to any one of claims 1 to 2, characterized in that the perovskite precursor salt comprises a monovalent cation halide and a divalent cation halide. 4.如权利要求3所述的钙钛矿前驱体溶液，其特征在于，所述一价阳离子卤化物包括一价有机阳离子卤化物和碱金属卤化物中的至少一种。4 . The perovskite precursor solution according to claim 3 , wherein the monovalent cation halide comprises at least one of a monovalent organic cation halide and an alkali metal halide. 5.如权利要求4所述的钙钛矿前驱体溶液，其特征在于，所述一价阳离子卤化物满足如下特征中的至少一个：5. The perovskite precursor solution according to claim 4, wherein the monovalent cation halide satisfies at least one of the following characteristics: （1）所述一价有机阳离子卤化物中的一价有机阳离子包括有机胺离子和甲脒离子中的至少一种；(1) The monovalent organic cation in the monovalent organic cation halide comprises at least one of an organic amine ion and a formamidine ion; （2）所述一价有机阳离子卤化物中的一价有机阳离子包括CH3NH3 +、CH3(CH2)nNH3 +、HC(NH2)2 +和C6H5(CH2)n·NH3 +中的至少一种；其中，n为1~3的整数；(2) The monovalent organic cation in the monovalent organic cation halide includes at least one of CH 3 NH 3 + , CH 3 (CH 2 ) n NH 3 + , HC(NH 2 ) 2 + and C 6 H 5 (CH 2 ) n ·NH 3 + ; wherein n is an integer of 1 to 3; （3）所述碱金属卤化物中的碱金属离子包括Li+、Na+、K+、Rb+和Cs+中的至少一种；(3) The alkali metal ion in the alkali metal halide includes at least one of Li + , Na + , K + , Rb + and Cs + ; （4）所述一价有机阳离子卤化物中的卤离子和所述碱金属卤化物中的卤离子分别独立地包括F-、Cl-、Br-和I-中的至少一种。(4) The halide ions in the monovalent organic cation halide and the halide ions in the alkali metal halide each independently include at least one of F − , Cl − , Br − and I − . 6.如权利要求3所述的钙钛矿前驱体溶液，其特征在于，所述一价阳离子卤化物包括碘化甲脒、溴化甲脒、氯化甲脒、溴化甲胺和氯化甲胺中的至少一种。6. The perovskite precursor solution according to claim 3, wherein the monovalent cation halide comprises at least one of formamidine iodide, formamidine bromide, formamidine chloride, methylammonium bromide and methylammonium chloride. 7.如权利要求3所述的钙钛矿前驱体溶液，其特征在于，所述二价阳离子卤化物满足如下特征中的至少一个：7. The perovskite precursor solution according to claim 3, wherein the divalent cation halide satisfies at least one of the following characteristics: （1）所述二价阳离子卤化物中的二价阳离子包括Pb2+和Sn2+中的至少一种；(1) The divalent cation in the divalent cation halide includes at least one of Pb 2+ and Sn 2+ ; （2）所述二价阳离子卤化物中的卤离子包括F-、Cl-、Br-和I-中的至少一种。(2) The halide ion in the divalent cation halide includes at least one of F - , Cl - , Br - and I - . 8.如权利要求3所述的钙钛矿前驱体溶液，其特征在于，所述二价阳离子卤化物包括碘化铅、碘化锡、溴化铅和溴化锡中的至少一种。8. The perovskite precursor solution of claim 3, wherein the divalent cation halide comprises at least one of lead iodide, tin iodide, lead bromide and tin bromide. 9.如权利要求3所述的钙钛矿前驱体溶液，其特征在于，所述一价阳离子卤化物和所述二价阳离子卤化物的浓度分别独立地为0.5 mol/L~5 mol/L。9. The perovskite precursor solution according to claim 3, wherein the concentrations of the monovalent cation halide and the divalent cation halide are independently 0.5 mol/L to 5 mol/L. 10.如权利要求1~2、4~9任一项所述的钙钛矿前驱体溶液，其特征在于，所述第二有机溶剂包括N,N-二甲基甲酰胺、二甲基亚砜、N-甲基吡咯烷酮和γ-丁内酯中的至少一种。10. The perovskite precursor solution according to any one of claims 1 to 2 and 4 to 9, characterized in that the second organic solvent comprises at least one of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and γ-butyrolactone. 11.如权利要求1~2、4~9任一项所述的钙钛矿前驱体溶液，其特征在于，所述第二有机溶剂满足如下特征中的至少一个：11. The perovskite precursor solution according to any one of claims 1 to 2 and 4 to 9, wherein the second organic solvent satisfies at least one of the following characteristics: （1）所述第二有机溶剂包括N,N-二甲基甲酰胺和二甲基亚砜；(1) The second organic solvent includes N,N-dimethylformamide and dimethyl sulfoxide; （2）所述N,N-二甲基甲酰胺与所述二甲基亚砜的体积比为1:(2~10)。(2) The volume ratio of the N,N-dimethylformamide to the dimethyl sulfoxide is 1:(2-10). 12.一种钙钛矿薄膜，其特征在于，采用如权利要求1~11任一项所述的钙钛矿前驱体溶液制得。12. A perovskite film, characterized in that it is prepared using the perovskite precursor solution according to any one of claims 1 to 11. 13.一种钙钛矿薄膜的制备方法，其特征在于，包括以下步骤：13. A method for preparing a perovskite film, characterized in that it comprises the following steps: 将如权利要求1~11任一项所述的钙钛矿前驱体溶液制成湿膜；Forming a wet film from the perovskite precursor solution according to any one of claims 1 to 11; 将所述湿膜进行退火处理，得到所述钙钛矿薄膜。The wet film is annealed to obtain the perovskite film. 14.一种钙钛矿电池，其特征在于，包括层叠设置的第一电极、第二电极及如权利要求12所述的钙钛矿薄膜或如权利要求13所述的制备方法制备的钙钛矿薄膜。14. A perovskite battery, characterized by comprising a first electrode, a second electrode and the perovskite film according to claim 12 or a perovskite film prepared by the preparation method according to claim 13, which are stacked. 15.一种钙钛矿电池的制备方法，其特征在于，包括以下步骤：15. A method for preparing a perovskite battery, characterized in that it comprises the following steps: 将钙钛矿前驱体溶液设于第一电极上，经退火处理后在所述第一电极上形成钙钛矿薄膜；所述钙钛矿前驱体溶液包括相互混合的钙钛矿前驱体盐、第一有机溶剂和第二有机溶剂，所述第一有机溶剂为丙三醇，所述第二有机溶剂的种类不同于所述第一有机溶剂，所述丙三醇的浓度为0.05 mg/mL~0.7 mg/mL；Placing a perovskite precursor solution on a first electrode, and forming a perovskite film on the first electrode after annealing; the perovskite precursor solution comprises a perovskite precursor salt, a first organic solvent and a second organic solvent mixed with each other, the first organic solvent is glycerol, the type of the second organic solvent is different from that of the first organic solvent, and the concentration of the glycerol is 0.05 mg/mL to 0.7 mg/mL; 在所述钙钛矿薄膜远离所述第一电极的表面形成第二电极。A second electrode is formed on a surface of the perovskite film away from the first electrode. 16.一种光伏器件，其特征在于，包括如权利要求14所述的钙钛矿电池或如权利要求15所述的制备方法制得的钙钛矿电池。16. A photovoltaic device, characterized in that it comprises the perovskite cell according to claim 14 or the perovskite cell prepared by the preparation method according to claim 15.
CN202410269804.5A 2024-03-11 2024-03-11 Perovskite precursor solution, perovskite battery and preparation method thereof, photovoltaic device Pending CN118215377A (en)

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