Perovskite material, thin film, solar cell, photovoltaic system, electric equipment and power generation equipment

Abstract

The invention provides a perovskite material, a thin film, a solar cell and an electric device. The perovskite material comprises a perovskite substrate and a dopant, the dopant comprises doped anions, and the doped anions comprise at least one of p-toluenesulfonate and phenylacetate. In the perovskite material, by introducing doped anions, the defects of a perovskite layer or a perovskite thin film can be improved, and the photoelectric conversion efficiency of a perovskite solar cell is improved.

Description

Technical Field

[0001] The present application relates to the technical field of solar cells, and in particular to a perovskite material, a perovskite film, a perovskite solar cell, a photovoltaic system, an electrical device, and a power generation device. Background Art

[0002] The statements herein merely provide background information related to the present application and do not necessarily constitute prior art.

[0003] Perovskite solar cells have good application prospects. In traditional perovskite solar cells, the perovskite layer has many defects, making it difficult to further improve the photoelectric conversion efficiency of perovskite solar cells. Summary of the Invention

[0004] The present application is made in view of the above-mentioned problems, and one of its purposes is to provide a perovskite material that has a high photoelectric conversion efficiency as a light-absorbing layer of a perovskite cell.

[0005] In order to achieve the above-mentioned object, the present application provides a perovskite material, comprising a perovskite substrate and a dopant, wherein the dopant comprises a doping anion, and the doping anion comprises at least one of p-toluenesulfonate and phenylacetate.

[0006] In the above-mentioned perovskite material, the introduction of at least one dopant anion selected from p-toluenesulfonate and phenylacetate can reduce defects in the perovskite layer or perovskite film, thereby improving perovskite crystallization, reducing defect state density, and improving the photoelectric conversion efficiency of perovskite solar cells.

[0007] In some embodiments, the mole percentage of the dopant anion is 0.1% to 20% based on the mole percentage of the perovskite material. When the mole percentage of the dopant anion is within this range, the dopant anion can effectively improve the defects of the perovskite layer while maintaining good intrinsic performance of the perovskite solar cell. Alternatively, the mole percentage of the dopant anion is 1% to 5% based on the mole percentage of the perovskite material.

[0008] In some embodiments, the dopant further comprises a doping cation, wherein the doping cation comprises an organic amine cation, a Cs + , K + and Na + At least one of .

[0009] In some embodiments, the organic amine cation is selected from (NR1R2R3R4) + 、(R1R2N=CR3R4) + 、(R1R2N-C(R5)=NR3R4)+ and (R1R2N-C(NR5R6)=R3R4) + At least one of, wherein R1, R2, R3, R4, R5 and R6 are each independently selected from H, substituted or unsubstituted C1~C20 alkyl, or substituted or unsubstituted aryl.

[0010] In some embodiments, the organic amine cation includes at least one of a methylamine cation, an ethylamine cation, a formamidine cation, a benzylamine cation, and a phenylethylamine cation.

[0011] In some embodiments, the dopant includes at least one of methylamine p-toluenesulfonic acid, formamidine p-toluenesulfonic acid, cesium p-toluenesulfonate, potassium p-toluenesulfonate, sodium p-toluenesulfonate, methylamine phenylacetic acid, formamidine phenylacetic acid, cesium phenylacetate, potassium phenylacetate, and sodium phenylacetate.

[0012] In some embodiments, the perovskite substrate includes at least one anion, wherein the anion includes at least one of a halide anion, a halide-like anion, and a carboxylate ion.

[0013] In some embodiments, the perovskite substrate includes a single anion selected from the group consisting of fluoride, chloride, bromide, and iodide. The perovskite substrate including a single anion can reduce the risk of phase separation during the formation of the perovskite layer and improve the performance of the perovskite layer.

[0014] In some embodiments, the perovskite substrate comprises a material having a chemical formula of ABX3, wherein A comprises a methylamine cation, a formamidinium cation, a Li + 、Na + , K + , Rb + and Cs + At least one of, B includes Pb 2+ 、Sn 2+ 、Zn 2+ 、Ti 2+ 、Sb 2+ 、Bi 2+ 、Ni 2+ 、Fe 2+ 、Co 2+ 、Cu 2+ 、Ga 2+ 、Ge 2+ Mg 2+ , Ca 2+ 、Mn 2+ Cr 2+ and Mo 2+ At least one of, X comprises said anion.

[0015] A perovskite film comprises the perovskite material.

[0016] A perovskite solar cell comprises a first electrode, a perovskite layer, and a second electrode stacked in sequence; the perovskite layer comprises the perovskite material; or the perovskite layer comprises the perovskite thin film. The perovskite layer comprising the perovskite material or the perovskite thin film can reduce defects in the perovskite layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0017] In some embodiments, in the perovskite layer, at least some of the dopant anions are located at the grain boundaries of the perovskite substrate. Anions at the grain boundaries of the perovskite substrate are easily missing, resulting in the generation of dangling bonds and free metal ions. The introduction of dopant anions can replace the missing anions, reduce the generation of dangling bonds and free metal ions, and thus reduce the defects of the perovskite layer or perovskite film. At the same time, the dopant anions can coordinate with the free metal ions during the crystallization process of the perovskite substrate, reducing the deep energy level defects of the perovskite layer or perovskite film, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0018] In some embodiments, the perovskite solar cell further includes a passivation layer, the passivation layer including the dopant; the passivation layer is disposed between the first electrode and the perovskite layer, and / or the passivation layer is disposed between the second electrode and the perovskite layer. By introducing a passivation layer onto the surface of the perovskite layer and including doped anions in the passivation layer, surface defects of the perovskite layer can be improved, further improving the photoelectric conversion efficiency of the perovskite solar cell.

[0019] In some embodiments, the thickness of the passivation layer is 0.1 nm to 10 nm.

[0020] A perovskite solar cell comprises a first electrode, a perovskite layer, and a second electrode stacked in sequence, and also includes a passivation layer; the perovskite layer comprises a perovskite substrate, the passivation layer is disposed between the first electrode and the perovskite layer, and / or the passivation layer is disposed between the second electrode and the perovskite layer; the passivation layer comprises a dopant, the dopant comprising a dopant anion, and the dopant anion comprises at least one of p-toluenesulfonate and phenylacetate. The inclusion of the dopant anion in the passivation layer can improve surface defects of the perovskite layer, further improving the photoelectric conversion efficiency of the perovskite solar cell.

[0021] In some embodiments, the dopant further comprises a doping cation, wherein the doping cation comprises an organic amine cation, a Cs + , K + and Na + At least one of .

[0022] In some embodiments, the thickness of the passivation layer is 0.1 nm to 10 nm.

[0023] A photovoltaic system comprises the perovskite solar cell.

[0024] An electrical device comprises the perovskite solar cell.

[0025] A power generation device comprises the perovskite solar cell. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] To more clearly illustrate the technical solution of this application, the following is a brief introduction to the drawings used in this application. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on the drawings without inventive effort.

[0027] Figure 1 Schematic diagram of the structure of a perovskite solar cell in one embodiment of the present application.

[0028] Figure 2 This is a schematic structural diagram of a perovskite solar cell in another embodiment of the present application.

[0029] Figure 3 This is a schematic structural diagram of a perovskite solar cell in another embodiment of the present application.

[0030] Figure 4 This is a schematic structural diagram of a perovskite solar cell in another embodiment of the present application.

[0031] Figure 5 This is a scanning electron microscope (SEM) image of the perovskite layer in the perovskite solar cell in Example 11 of the present application.

[0032] Figure 6 This is an SEM image of the perovskite layer in the perovskite solar cell in Comparative Example 1 of the present application.

[0033] Description of the marks in the figure:

[0034] 100. Perovskite solar cell; 101. Transparent electrode; 102. Hole transport layer; 103. Perovskite layer; 104. Electron transport layer; 105. Metal electrode;

[0035] 200, perovskite solar cell; 201, transparent electrode; 202, electron transport layer; 203, perovskite layer; 204, hole transport layer; 205, metal electrode;

[0036] 300, perovskite solar cell; 301, transparent electrode; 302, hole transport layer; 303, perovskite layer; 304, electron transport layer; 305, metal electrode; 306, passivation layer;

[0037] 400, perovskite solar cell; 401, transparent electrode; 402, hole transport layer; 403, perovskite layer; 404, electron transport layer; 405, metal electrode; 406, passivation layer.

[0038] In order to better describe and illustrate the embodiments and / or examples of the inventions disclosed herein, reference may be made to one or more of the accompanying drawings. The additional details or examples used to describe the accompanying drawings should not be considered to limit the scope of the disclosed inventions, the presently described embodiments and / or examples, and any of the best modes currently understood for these inventions. DETAILED DESCRIPTION

[0039] Below, some embodiments of the present application are described in detail with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of substantially identical structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0040] The details of one or more embodiments of the present application are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0042] The "range" disclosed in this application is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​listed are 1 and 2, and if the maximum range values ​​listed are 3, 4, and 5, then the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4, and 2 to 5. In this application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, wherein a and b are both real numbers. For example, a numerical range of "0-5" indicates that all real numbers between "0-5" are listed herein, and "0-5" is simply an abbreviation for these numerical combinations. Furthermore, stating that a parameter is an integer ≥ 2 is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0043] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0044] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0045] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, and in some embodiments are performed sequentially. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.

[0046] Unless otherwise specified, the terms "include" and "comprising" used in this application may be open-ended or closed-ended. For example, "include" and "comprising" may mean that other components not listed may also be included or that only the listed components are included.

[0047] Unless otherwise specified, the term "or" is used in this application to be inclusive. For example, the phrase "M or N" means "M, N, or both M and N." More specifically, the condition "M or N" is satisfied by any of the following conditions: M is true or present, and N is false or absent; M is false or absent, and M is true or present; or both M and N are true, or both M and N are present.

[0048] If not otherwise specified, in this application, the term "room temperature" generally refers to 4°C to 30°C, preferably 25±5°C.

[0049] Unless otherwise indicated, the terms used in this application have the commonly understood meanings generally understood by those skilled in the art. Unless otherwise indicated, the numerical values ​​of the various parameters mentioned in this application can be measured using various measurement methods commonly used in the art. For example, the tests can be performed using the methods described in the examples of this application.

[0050] One embodiment of the present application provides a perovskite material. The perovskite material includes a perovskite substrate and a dopant, wherein the dopant includes a dopant anion, and the dopant anion includes at least one of p-toluenesulfonate and phenylacetate. In the perovskite material, the introduction of at least one of p-toluenesulfonate and phenylacetate dopant anions can reduce defects in the perovskite layer or perovskite film, improve perovskite crystallization, and thereby increase the photoelectric conversion efficiency of the perovskite solar cell.

[0051] In some embodiments, the mole percentage of the doped anion is 0.1% to 20% based on the mole percentage of the perovskite material. When the mole percentage of the doped anion is within this range, the effect of the doped anion on improving the defects of the perovskite layer can be better exerted, while the perovskite solar cell maintains good intrinsic performance. Optionally, the mole percentage of the doped anion can be 0.1%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, and any value within the range consisting of any two of the above values. Optionally, the mole percentage of the doped anion is 1% to 5% based on the mole percentage of the perovskite material.

[0052] In some embodiments, the dopant further comprises a doping cation, and the doping cation comprises an organic amine cation, Cs + , K + and Na + At least one of. Optionally, the organic amine cation is selected from (NR1R2R3R4) + 、(R1R2N=CR3R4) + 、(R1R2N-C(R5)=NR3R4)+ and (R1R2N-C(NR5R6)=R3R4) + At least one of, wherein R1, R2, R3, R4, R5 and R6 are each independently selected from H, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl. Further optionally, the organic amine cation includes an alkylamine cation, a formamidinium cation (HC(NH2)2 + ), benzylamine cation and phenylethylamine cation. Further optionally, the alkylamine cation includes methylamine cation (CH3NH3 + ), ethylamine cation (CH3CH2NH3 + )wait.

[0053] It is understood that the doping cations and the doping anions are paired. It is also understood that in the dopant, the total charge carried by the doping cations is equal to the total charge carried by the doping anions.

[0054] In some embodiments, the dopant comprises at least one of the following: an organic amine, p-toluenesulfonic acid, cesium p-toluenesulfonate (TsOCs), potassium p-toluenesulfonate (TsOK), sodium p-toluenesulfonate (TsONa), an organic amine, phenylacetic acid, cesium phenylacetate, potassium phenylacetate, and sodium phenylacetate. Alternatively, the organic amine, p-toluenesulfonic acid, comprises methylamine p-toluenesulfonic acid (TsOMA) and / or formamidine p-toluenesulfonic acid (TsOFA). The organic amine, phenylacetic acid, comprises methylamine phenylacetic acid and / or formamidine phenylacetic acid.

[0055] It is understandable that the types and contents of the doped anions and doped cations in the present application can be tested by infrared spectroscopy, elemental analysis, etc.

[0056] It is understood that when preparing the perovskite material, materials including doping anions and doping cations may be added to the precursor solution of the perovskite substrate to make the perovskite material include doping anions and doping cations.

[0057] In some embodiments, the perovskite substrate includes at least one anion, wherein the anion includes at least one of a halogen anion, a halogen-like anion, and a carboxylate ion. Optionally, the halogen anion includes a fluoride ion, a chloride ion, a bromide ion, or an iodide ion; the halogen-like anion includes a CN - 、SCN - 、SeCN - 、OCN - 、SCSN3 - or N3 -Further optionally, the perovskite substrate includes a single anion, and the anion is selected from any one of fluoride, chloride, bromide, and iodide. The perovskite substrate including a single anion can reduce the risk of phase separation during the formation of the perovskite layer and improve the performance of the perovskite layer.

[0058] In some embodiments, the perovskite substrate comprises a material having the chemical formula ABX3, wherein A comprises a methylamine cation, a formamidinium cation, a Li + 、Na + , K + , Rb + and Cs + At least one of, B includes Pb 2+ 、Sn 2+ 、Zn 2+ 、Ti 2+ 、Sb 2+ 、Bi 2+ 、Ni 2+ 、Fe 2+ 、Co 2+ 、Cu 2+ 、Ga 2+ 、Ge 2+ Mg 2+ , Ca 2+ 、Mn 2+ Cr 2+ and Mo 2+ At least one of the above anions, X includes the above anions. That is, X includes at least one of a halogen anion, a quasi-halogen anion, and a carboxylate ion. Optionally, A is a methylamine cation and / or a formamidinium cation. B is Pb 2+ and / or Sn 2+ .X includes F - 、Cl - Br - , I - and at least one of carboxylate ions.

[0059] In some embodiments, X includes a single type of halogen anion. X including a single type of halogen anion can reduce the risk of phase separation of different halogens during the formation of the perovskite layer and improve the performance of the perovskite layer. However, when a single type of halogen anion is used, the perovskite material is more difficult to crystallize during the formation process and the defect density is high. In this case, the introduction of doping anions including at least one of p-toluenesulfonate and phenylacetate into the single halogen perovskite material can improve the stability of the BX framework, improve the crystallization quality of the perovskite material, and help improve the crystallization performance of the perovskite material with a single type of halogen anion, and promote the formation of a perovskite layer or perovskite film with better performance. For example, when the B ion is Pb 2+ , X is 1 -When doping anions, on the one hand, they can react with free Pb during the crystallization of perovskite materials. 2+ On the other hand, doping with anions can improve the stability of the lead iodide framework, improve the crystallization quality of the perovskite material, and promote the performance of the perovskite layer or perovskite film. - or Cl - or Br - or I - .

[0060] Another embodiment of the present application provides a perovskite film, which includes the above-mentioned perovskite material.

[0061] Another embodiment of the present application provides a perovskite solar cell. The perovskite solar cell comprises a first electrode, a perovskite layer, and a second electrode stacked in sequence. The perovskite layer comprises the aforementioned perovskite material; or, the perovskite layer comprises the aforementioned perovskite thin film. In this embodiment, the perovskite layer comprising the aforementioned perovskite material or the aforementioned perovskite thin film can reduce defects in the perovskite layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0062] In some embodiments, at least a portion of the doped anions in the perovskite layer are located at the grain boundaries of the perovskite substrate. Anions at the grain boundaries of the perovskite substrate are easily missing, resulting in the formation of dangling bonds and free metal ions. The introduction of doped anions can replace the missing anions, reducing the formation of dangling bonds and free metal ions, thereby reducing defects in the perovskite layer or perovskite film. Furthermore, the doped anions can coordinate with the free metal ions during the crystallization process of the perovskite substrate, reducing deep energy level defects in the perovskite layer or perovskite film, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0063] In some embodiments, the perovskite material includes lead ions and iodide ions. During the crystallization process of the perovskite material, the doped anions can coordinate with the free lead ions, reducing deep energy level defects. Furthermore, the doped anions can stabilize the lead iodide framework formed during the perovskite crystallization process, improving the crystal quality and thereby increasing the photoelectric conversion efficiency of the perovskite solar cell.

[0064] In some embodiments, the perovskite solar cell further comprises a passivation layer, and the passivation layer comprises a dopant. A passivation layer is provided between the first electrode and the perovskite layer, and / or a passivation layer is provided between the second electrode and the perovskite layer. By introducing a passivation layer on the surface of the perovskite layer and making the passivation layer include doped anions, the defects on the surface of the perovskite layer can be improved, and the photoelectric conversion efficiency of the perovskite cell can be further improved. Optionally, the passivation layer is in direct contact with the perovskite layer. Optionally, the dopant comprises a doped anion, and the doped anion comprises at least one of p-toluenesulfonate and phenylacetate. Further optionally, the dopant further comprises a doped cation, and the doped cation comprises an organic amine cation, Cs + , K + and Na + At least one of .

[0065] In some embodiments, the thickness of the passivation layer is 0.1 nm to 10 nm. For example, the thickness of the passivation layer can be 0.1 nm, 0.3 nm, 0.5 nm, 0.8 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, or any value within a range consisting of any two of the above values.

[0066] It is understood that the perovskite solar cell also includes a charge extraction layer, which is located between the first electrode and the perovskite layer, or between the second electrode and the perovskite layer. The charge extraction layer is used to extract and transfer electron-hole pairs generated by the perovskite layer absorbing photon energy of sunlight to the first electrode and the second electrode respectively. The passivation layer is located between the charge extraction layer and the perovskite layer. Optionally, the charge extraction layer includes a hole transport layer or an electron transport layer.

[0067] In some embodiments, the perovskite solar cell further comprises a hole transport layer, and the hole transport layer is located between the first electrode and the perovskite layer, or the hole transport layer is located between the second electrode and the perovskite layer. Optionally, the passivation layer is located between the hole transport layer and the perovskite layer. Further optionally, the material of the hole transport layer may include but is not limited to one or more of the following materials and their derivatives: 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), polytriarylamine (PTAA), nickel oxide (NiO x ), poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT:PSS), WO3 and other materials can transport holes and block electrons.

[0068] In some embodiments, the perovskite solar cell further comprises an electron transport layer, which is located between the first electrode and the perovskite layer, or the electron transport layer is located between the second electrode and the perovskite layer. Optionally, the passivation layer is located between the electron transport layer and the perovskite layer. Further optionally, the material of the electron transport layer may include, but is not limited to, one or more of the following materials and their derivatives: imide compounds, quinone compounds, fullerenes and their derivatives, methoxytriphenylamine-fluoroformamidine (OMeTPA-FA), calcium titanate (CaTiO3), lithium fluoride (LiF), calcium fluoride (CaF2), poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT:PSS), poly 3-hexylthiophene (P3HT), triphenylamine (H101) with triptycene as the core, 3,4 -ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), polythiophene, metal oxides, silicon oxide (SiO2), strontium titanate (SrTiO3), cuprous thiocyanate (CuSCN), etc.; wherein the metal element may include one or more of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr. Further optionally, the material of the electron transport layer includes [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), fullerenes and their derivatives, as well as tin dioxide (SnO2), zinc oxide (ZnO), etc.

[0069] It is understood that the first electrode can be a transparent electrode, and the second electrode can be a metal electrode, a metal-nonmetal hybrid electrode, or a transparent electrode. Generally, placing the first electrode on the light-entering side can produce a formal perovskite solar cell or an inverted perovskite solar cell. Optionally, the transparent electrode is made of at least one material selected from fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), and indium tungsten oxide (IWO). Optionally, the first electrode has a thickness of 100 nm to 1000 nm, and further optionally, the transparent electrode has a thickness of 300 nm to 800 nm. Optionally, the metal electrode is made of at least one material selected from Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and alloys thereof. In the metal-nonmetal hybrid electrode, the metal material is selected from at least one of Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W, and alloys thereof, and the non-metallic material is selected from C. Optionally, the thickness of the metal electrode or the metal-nonmetal mixed electrode is 20 nm to 200 nm. Optionally, the thickness of the second electrode is 60 nm to 100 nm. Further optionally, the thickness of the second electrode is 70 nm to 90 nm.

[0070] It is understood that perovskite solar cells also include a substrate. A transparent electrode is formed on the substrate. Substrates include glass substrates and flexible substrates. Flexible substrate materials include, but are not limited to, organic polymer materials. Furthermore, the flexible substrate material can be a mixture of one or more of the following materials, including but not limited to, polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), and the like, in varying proportions.

[0071] It is understood that perovskite solar cells include formal perovskite solar cells and inverse perovskite solar cells. For formal perovskite solar cells, the formal perovskite solar cell includes a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode layer stacked in sequence. For inverse perovskite solar cells, the inverse perovskite solar cell includes a first electrode layer, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode layer stacked in sequence.

[0072] It is understood that the perovskite solar cell can be a tandem cell comprising a formal perovskite solar cell or an inverted perovskite solar cell. Optionally, the tandem cell can be a two-junction tandem cell, a three-junction tandem cell, a four-junction tandem cell, etc., and those skilled in the art can select the number of tandem cells according to actual needs. Optionally, the tandem cell can be a full perovskite tandem cell, a perovskite-crystalline silicon tandem cell, or a perovskite-heterojunction tandem cell, and the stacking method can be adjusted according to actual needs, such as two-terminal tandem cell, multi-terminal tandem cell, etc.

[0073] It is understandable that other functional layers, such as a buffer layer, can be introduced into the perovskite solar cell as required.

[0074] In some embodiments, a perovskite solar cell may be provided with a buffer layer of suitable energy level, which may play one or more of the following roles: reducing energy level barriers, promoting energy level matching, improving carrier extraction efficiency, passivating interface defect states, protecting the light absorption layer, inhibiting the oxidative decomposition of water molecules and oxygen in the cell, improving photoelectric conversion efficiency, and improving the stability of the perovskite solar cell. Depending on the location of the buffer layer, the types of buffer layers may include a buffer layer between the hole transport layer and the anode, a buffer layer between the electron transport layer and the cathode, a buffer layer between the hole transport layer and the perovskite layer, and a buffer layer between the electron transport layer and the perovskite layer. Materials that can be used for the buffer layer in perovskite solar cells may include, but are not limited to, Cu2O, NiO, AZO, TiO2, etc.

[0075] See also Figure 1 , which shows an inverted perovskite solar cell 100. The perovskite solar cell 100 includes a transparent electrode 101, a hole transport layer 102, a perovskite layer 103, an electron transport layer 104, and a metal electrode 105, which are stacked in sequence. The perovskite layer 103 includes a perovskite substrate and dopant anions, wherein the dopant anions include at least one of p-toluenesulfonate and phenylacetate.

[0076] See also Figure 2 , which shows a formal perovskite solar cell 200. The perovskite solar cell 200 includes a transparent electrode 201, an electron transport layer 202, a perovskite layer 203, a hole transport layer 204, and a metal electrode 205, which are stacked in sequence. The perovskite layer 203 includes a perovskite substrate and dopant anions, wherein the dopant anions include at least one of p-toluenesulfonate and phenylacetate.

[0077] See also Figure 3, which shows a perovskite solar cell 300. The perovskite solar cell 300 includes a transparent electrode 301, a hole transport layer 302, a perovskite layer 303, a passivation layer 306, an electron transport layer 304, and a metal electrode 305, which are stacked in sequence. The perovskite layer 103 includes a perovskite substrate and a dopant, wherein the dopant includes a dopant anion, and the dopant anion includes at least one of p-toluenesulfonate and phenylacetate. The passivation layer 306 includes a dopant, wherein the dopant includes a dopant anion, and the dopant anion includes at least one of p-toluenesulfonate and phenylacetate. By introducing dopant anions into the perovskite layer 303 and the passivation layer 306, defects inside and on the surface of the perovskite layer can be improved, thereby improving the photoelectric conversion efficiency of the perovskite cell.

[0078] Another embodiment of the present application provides a perovskite solar cell. The perovskite solar cell includes a first electrode, a perovskite layer, and a second electrode stacked in sequence, and also includes a passivation layer. The perovskite layer includes a perovskite substrate, and the passivation layer is disposed between the first electrode and the perovskite layer, and / or the passivation layer is disposed between the second electrode and the perovskite layer. The passivation layer includes a dopant, the dopant including a dopant anion, and the dopant anion includes at least one of p-toluenesulfonate and phenylacetate. The inclusion of the dopant anion in the passivation layer can improve surface defects in the perovskite layer and further improve the photoelectric conversion efficiency of the perovskite cell. Optionally, the passivation layer is in direct contact with the perovskite layer. Optionally, in this embodiment, the perovskite layer does not include the aforementioned dopant.

[0079] In some embodiments, the dopant in the passivation layer further comprises a dopant cation, and the dopant cation comprises an organic amine cation, a Cs + , K + and Na + It is understood that the doping cations and the doping anions in the passivation layer can be paired, and the charge number carried by the doping cations is equal to the charge number carried by the doping anions.

[0080] It is understood that when preparing the passivation layer, dopants including dopant anions and dopant cations may be added to the precursor solution of the passivation layer to make the passivation layer include dopant anions and dopant cations.

[0081] See also Figure 4, which shows a perovskite solar cell 400. The perovskite solar cell 400 comprises a transparent electrode 401, a hole transport layer 402, a perovskite layer 403, a passivation layer 406, an electron transport layer 404, and a metal electrode 405, stacked in sequence. The perovskite layer 403 comprises a perovskite substrate, and the passivation layer 406 comprises dopant anions, including at least one of p-toluenesulfonate and phenylacetate. By introducing dopant anions into the passivation layer 406, surface defects in the perovskite layer can be improved, thereby enhancing the photoelectric conversion efficiency of the perovskite cell. Optionally, the passivation layer has a thickness of 0.1 nm to 10 nm.

[0082] In some embodiments, the band gap of the perovskite layer is 1.2 eV to 2.3 eV, and / or the thickness of the perovskite layer is 400 nm to 1000 nm.

[0083] Another embodiment of the present application provides a photovoltaic system, which includes the above-mentioned perovskite solar cell.

[0084] Another embodiment of the present application provides an electrical device. The electrical device includes the aforementioned perovskite solar cell. Alternatively, the electrical device may include, but is not limited to, mobile devices such as mobile phones and laptops, electric vehicles, electric trains, ships, satellites, and power generation systems.

[0085] Another embodiment of the present application provides a power generation device. The power generation device includes the aforementioned perovskite solar cell. Optionally, the power generation device may include, but is not limited to, integrated power generation. The power generation device may be located, but is not limited to, on the roof or backplane of a vehicle.

[0086] In order to make the technical problems, technical solutions and beneficial effects solved by this application clearer, the application will be further described in detail below with reference to the embodiments and drawings. Obviously, the described embodiments are only a part of the embodiments of this application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is in no way intended to limit the present application and its applications. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0087] If no specific techniques or conditions are specified in the examples, the experiments were carried out according to the techniques or conditions described in the literature in the field or according to the product instructions. All reagents or instruments used without specifying the manufacturer are commercially available conventional products.

[0088] Example 1

[0089] The preparation method of the perovskite solar cell in this embodiment is as follows:

[0090] S101: Preparation of FTO conductive glass electrodes: FTO glass with a specification of 2.0 cm × 2.0 cm is removed by laser etching at both ends of 0.35 cm of FTO to expose the glass substrate; the etched FTO conductive glass is ultrasonically cleaned several times with water, acetone, and isopropyl alcohol in sequence, and then blown dry with nitrogen for later use.

[0091] S102: Preparation of hole transport layer: FTO was treated with UV ozone, and then NiOx with a thickness of about 30 nm was magnetron sputtered, and annealed at 300°C for 60 min to obtain a hole transport layer.

[0092] S103: Preparation of the Perovskite Layer: A one-step method was used to prepare the perovskite layer. Methylamine p-toluenesulfonic acid was added to the perovskite precursor solution at a molar ratio of 1% to the perovskite material. Once completely dissolved, the perovskite precursor solution was spin-coated on the hole transport layer at 4000 rpm for 40 seconds. Approximately 10 seconds after the start of spin coating, 300 μL of anisole antisolvent was added dropwise. The layer was then annealed at 120°C for 60 minutes to obtain a 500 nm thick perovskite layer. The perovskite substrate was FAPbI3.

[0093] S104: Preparation of electron transport layer: Vapor-depositing a C60 electron transport layer with a thickness of 30 nm on the surface of the perovskite layer.

[0094] S105: Preparation of metal electrode: vapor-depositing an 80 nm thick Ag electrode on the surface of the electron transport layer.

[0095] Example 2 to Example 8

[0096] Compared with Example 1, the difference between Examples 2 to 8 is that in S103, the molar percentage of methylamine p-toluenesulfonic acid is different.

[0097] Example 9

[0098] Compared with Example 1, the difference of this example is that in S103, methylamine p-toluenesulfonic acid is replaced by sodium phenylacetate.

[0099] Example 10

[0100] The preparation method of the perovskite solar cell in this embodiment is as follows:

[0101] S101: Preparation of FTO conductive glass electrodes: FTO glass with a specification of 2.0 cm × 2.0 cm is removed by laser etching at both ends of 0.35 cm of FTO to expose the glass substrate; the etched FTO conductive glass is ultrasonically cleaned several times with water, acetone, and isopropyl alcohol in sequence, and then blown dry with nitrogen for later use.

[0102] S102: Preparation of hole transport layer: FTO was treated with UV ozone, and then NiOx with a thickness of about 30 nm was magnetron sputtered, and annealed at 300°C for 60 min to obtain a hole transport layer.

[0103] S103: Preparation of the Perovskite Layer: A one-step process was used to prepare the perovskite layer. A perovskite precursor solution was spin-coated onto the hole transport layer at 4000 rpm for 40 seconds. Approximately 10 seconds after the start of spin coating, 300 μL of anisole antisolvent was added dropwise. The layer was then annealed at 120°C for 60 minutes to obtain a 500 nm thick perovskite layer. The perovskite material was FAPbI3.

[0104] S104: Preparation of passivation layer: Prepare an isopropanol solution of potassium p-toluenesulfonate with a concentration of 3 mg / ml. After it is completely dissolved, spin-coat the isopropanol solution of potassium p-toluenesulfonate on the surface of the prepared perovskite layer at a speed of 3000 rpm for 30 seconds, and then anneal at 100°C for 5 minutes to obtain a passivation layer with a thickness of 5 nm.

[0105] S105: Preparation of electron transport layer: vapor-depositing a C60 electron transport layer with a thickness of 30 nm on the surface of the passivation layer.

[0106] S106: Preparation of metal electrode: vapor-depositing an 80 nm thick Ag electrode on the surface of the electron transport layer.

[0107] Example 11

[0108] The preparation method of the perovskite solar cell in this embodiment is as follows:

[0109] S101: Preparation of FTO conductive glass electrodes: FTO glass with a specification of 2.0 cm × 2.0 cm is removed by laser etching at both ends of 0.35 cm of FTO to expose the glass substrate; the etched FTO conductive glass is ultrasonically cleaned several times with water, acetone, and isopropyl alcohol in sequence, and then blown dry with nitrogen for later use.

[0110] S102: Preparation of hole transport layer: FTO was treated with UV ozone, and then NiOx with a thickness of about 30 nm was magnetron sputtered, and annealed at 300°C for 60 min to obtain a hole transport layer.

[0111] S103: Preparation of the Perovskite Layer: A one-step method was used to prepare the perovskite layer. Methylamine p-toluenesulfonic acid was added to the perovskite precursor solution at a molar ratio of 1% to the perovskite material. Once completely dissolved, the perovskite precursor solution was spin-coated on the hole transport layer at 4000 rpm for 40 seconds. Approximately 10 seconds after the start of spin coating, 300 μL of anisole antisolvent was added dropwise. The layer was then annealed at 120°C for 60 minutes to obtain a 500 nm thick perovskite layer. The perovskite substrate was FAPbI3.

[0112] S104: Preparation of passivation layer: Prepare an isopropanol solution of potassium p-toluenesulfonate with a concentration of 3 mg / ml. After it is completely dissolved, spin-coat the isopropanol solution of potassium p-toluenesulfonate on the surface of the prepared perovskite layer at a speed of 3000 rpm for 30 seconds, and then anneal at 100°C for 5 minutes to obtain a passivation layer with a thickness of 5 nm.

[0113] S105: Preparation of electron transport layer: vapor-depositing a C60 electron transport layer with a thickness of 30 nm on the surface of the passivation layer.

[0114] S106: Preparation of metal electrode: vapor-depositing an 80 nm thick Ag electrode on the surface of the electron transport layer.

[0115] Example 12

[0116] Compared with Example 1, the difference of this example is that methylamine p-toluenesulfonic acid is replaced by formamidine p-toluenesulfonic acid.

[0117] Example 13

[0118] Compared with Example 1, the difference of this example is that methylamine p-toluenesulfonic acid is replaced by cesium p-toluenesulfonate.

[0119] Example 14

[0120] Compared with Example 1, the difference of this comparative example is that methylamine p-toluenesulfonic acid is replaced by 1-methylimidazole p-toluenesulfonic acid.

[0121] Example 15

[0122] Compared with Example 1, the difference of this embodiment is that the perovskite substrate is FAPbI 2.85 Br 0.15 .

[0123] Comparative Example 1

[0124] The preparation method of the perovskite solar cell in this comparative example is:

[0125] S101: Preparation of FTO conductive glass electrodes: FTO glass with a specification of 2.0 cm × 2.0 cm is removed by laser etching at both ends of 0.35 cm of FTO to expose the glass substrate; the etched FTO conductive glass is ultrasonically cleaned several times with water, acetone, and isopropyl alcohol in sequence, and then blown dry with nitrogen for later use.

[0126] S102: Preparation of hole transport layer: FTO was treated with UV ozone, and then NiOx with a thickness of about 30 nm was magnetron sputtered, and annealed at 300°C for 60 min to obtain a hole transport layer.

[0127] S103: Preparation of the Perovskite Layer: A one-step process was used to prepare the perovskite light-absorbing layer. A perovskite precursor solution was spin-coated onto the hole transport layer at 4000 rpm for 40 seconds. Approximately 10 seconds after the start of spin coating, 300 μL of anisole antisolvent was added dropwise. The layer was then annealed at 120°C for 60 minutes to obtain a 500 nm thick perovskite layer. The perovskite material was FAPbI3.

[0128] S104: Preparation of electron transport layer: Vapor-depositing a C60 electron transport layer with a thickness of 30 nm on the surface of the perovskite layer.

[0129] S106: Preparation of metal electrode: vapor-depositing an 80 nm thick Ag electrode on the surface of the electron transport layer.

[0130] Test Case

[0131] (1) The performance of the perovskite solar cells obtained in the examples and comparative examples was tested. The testing method was as follows:

[0132] Using Keithley 2400SMU, AM 1.5G solar irradiation at 100 mW / cm 2 The battery performance is tested under a light source, and the photoelectric conversion efficiency is calculated as follows:

[0133] PCE=Pout / Popt

[0134] =Voc×Jsc×(Vmpp×Jmpp) / (Voc×Jsc)

[0135] =Voc×Jsc×FF

[0136] Where Pout, Popt, Vmpp, Jmpp, Voc, and Jsc are the battery operating output power, incident light power, battery maximum power point voltage, battery maximum power point current, open circuit voltage, and short circuit current, respectively. The test results are shown in Table 1.

[0137] (2) The morphology of the perovskite layer of the perovskite solar cell in Example 11 and Comparative Example 1 was analyzed using SEM. The SEM image of the perovskite layer in Example 11 is as follows: Figure 5 As shown, the SEM image of the perovskite layer of Comparative Example 1 is as follows Figure 6 As shown. Figure 5 and Figure 6 It can be seen that the defects of the perovskite layer in the perovskite solar cell in Example 11 are significantly less than those in Comparative Example 1. Combined with Table 1, it can be seen that the photoelectric conversion efficiency of the perovskite solar cell in Example 11 is significantly higher than that in Comparative Example 1.

[0138] Table 1

[0139]

[0140] Note: In Table 1, “ / ” indicates not included.

[0141] It can be seen from Table 1 that when the perovskite layer and / or the passivation layer contain doped anions, the perovskite solar cell exhibits higher photoelectric conversion efficiency.

[0142] Furthermore, when the doped anions are p-toluenesulfonate and phenylacetate, the perovskite solar cells exhibit higher photoelectric conversion efficiency.

[0143] Furthermore, when the molar percentage of anions doped in the perovskite layer is 0.1%~20%, the perovskite solar cell exhibits higher photoelectric conversion efficiency.

[0144] 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.

[0145] 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 present invention. It should be noted that a person skilled in the art could make various modifications and improvements without departing from the spirit of the present application, all of which 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 perovskite material, characterized in that: The invention comprises a perovskite substrate and a dopant, wherein the dopant comprises a doping anion, and the doping anion comprises at least one of p-toluenesulfonate and phenylacetate.

2. The perovskite material according to claim 1, characterized in that The molar percentage of the doping anion is 0.1% to 20% based on the molar percentage of the perovskite material.

3. The perovskite material according to claim 1 or 2, characterized in that The molar percentage of the doping anion is 1% to 5% based on the molar percentage of the perovskite material.

4. The perovskite material according to any one of claims 1 to 3, characterized in that The dopant also includes doping cations, and the doping cations include organic amine cations, Cs + , K + and Na + At least one of .

5. The perovskite material according to claim 4, characterized in that The organic amine cation is selected from (NR1R2R3R4) + 、(R1R2N=CR3R4) + 、(R1R2N-C(R5)=NR3R4) + and (R1R2N-C(NR5R6)=R3R4) + At least one of, wherein R1, R2, R3, R4, R5 and R6 are each independently selected from H, substituted or unsubstituted C1~C20 alkyl, or substituted or unsubstituted aryl.

6. The perovskite material according to claim 5, characterized in that The organic amine cation includes at least one of a methylamine cation, an ethylamine cation, a formamidine cation, a benzylamine cation, and a phenylethylamine cation.

7. The perovskite material according to any one of claims 1 to 6, characterized in that The dopant includes at least one of methylamine p-toluenesulfonic acid, formamidine p-toluenesulfonic acid, cesium p-toluenesulfonate, potassium p-toluenesulfonate, sodium p-toluenesulfonate, methylamine phenylacetic acid, formamidine phenylacetic acid, cesium phenylacetate, potassium phenylacetate and sodium phenylacetate.

8. The perovskite material according to any one of claims 1 to 7, characterized in that The perovskite substrate includes at least one anion, wherein the anion includes at least one of a halogen anion, a halogen-like anion, and a carboxylate ion.

9. The perovskite material according to claim 8, characterized in that The perovskite matrix includes a single anion, and the anion is selected from any one of fluoride ion, chloride ion, bromide ion and iodide ion.

10. The perovskite material according to any one of claims 8 to 9, characterized in that The perovskite substrate includes a material with a chemical formula of ABX3, wherein A includes a methylamine cation, a formamidinium cation, Li + 、Na + , K + , Rb + and Cs + At least one of, B includes Pb 2+ 、Sn 2+ 、Zn 2+ 、Ti 2+ 、Sb 2+ 、Bi 2+ 、Ni 2+ 、Fe 2+ 、Co 2+ 、Cu 2+ 、Ga 2+ 、Ge 2+ Mg 2+ , Ca 2+ 、Mn 2+ Cr 2+ and Mo 2+ At least one of, X comprises said anion.

11. A perovskite film, characterized in that: The perovskite material comprises the perovskite material according to any one of claims 1 to 10.

12. A perovskite solar cell, characterized in that: It includes a first electrode, a perovskite layer and a second electrode stacked in sequence; The perovskite layer comprises the perovskite material according to any one of claims 1 to 10; or The perovskite layer includes the perovskite thin film according to claim 11.

13. The perovskite solar cell according to claim 12, characterized in that In the perovskite layer, at least a portion of the doped anions are located at the grain boundaries of the perovskite substrate.

14. The perovskite solar cell according to claim 12 or 13, characterized in that: The perovskite solar cell further includes a passivation layer, which includes the dopant; the passivation layer is provided between the first electrode and the perovskite layer, and / or the passivation layer is provided between the second electrode and the perovskite layer.

15. The perovskite solar cell according to claim 14, characterized in that The thickness of the passivation layer is 0.1 nm to 10 nm.

16. A perovskite solar cell, characterized in that: The invention comprises a first electrode, a perovskite layer, and a second electrode stacked in sequence, and also comprises a passivation layer; the perovskite layer comprises a perovskite substrate, the passivation layer is provided between the first electrode and the perovskite layer, and / or the passivation layer is provided between the second electrode and the perovskite layer; the passivation layer comprises a dopant, the dopant comprises a doping anion, and the doping anion comprises at least one of p-toluenesulfonate and phenylacetate.

17. The perovskite solar cell according to claim 16, characterized in that The dopant also includes doping cations, and the doping cations include organic amine cations, Cs + , K + and Na + At least one of .

18. The perovskite solar cell according to claim 16 or 17, characterized in that The thickness of the passivation layer is 0.1 nm to 10 nm.

19. A photovoltaic system, characterized in that: A perovskite solar cell comprising the perovskite solar cell according to any one of claims 12 to 18.

20. An electrical device, characterized in that: A perovskite solar cell comprising the perovskite solar cell according to any one of claims 12 to 18.

21. A power generation device, characterized in that: A perovskite solar cell comprising the perovskite solar cell according to any one of claims 12 to 18.

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