Perovskite material layer passivation method, perovskite thin film and perovskite solar cell comprising perovskite thin film

Abstract

The invention relates to a passivation method of a perovskite material layer. The passivation method of the perovskite material layer comprises the following steps: placing a prefabricated member in an atmosphere containing a passivation material for passivation; the prefabricated member comprises a perovskite material layer, and at least one surface of the perovskite material layer is in contact with the atmosphere containing the passivation material; the passivation material meets the following conditions: (1) the passivation material is liquid at room temperature; (2) the atmosphere containing the passivation material can be formed through volatilization under the room temperature condition; and (3) the chemical structure contains an organic amine group. According to the passivation method, the defects of the perovskite material layer can be effectively passivated, and the stability of the device is improved. Meanwhile, solution spin coating or extra heating treatment is not needed in the whole process, operation is easy and convenient, and the method is particularly suitable for preparing large-area perovskite solar cells.

Description

Technical Field

[0001] The present application relates to the field of battery technology, and in particular to a passivation method for a perovskite material layer, a perovskite film, and a perovskite solar cell comprising the same. 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 are devices that use the photoelectric conversion mechanism of perovskite crystal materials to convert solar energy into electrical energy. They are the third generation of solar cells and have many advantages, such as high photoelectric conversion efficiency, simple manufacturing process, and low production cost. They have been extensively studied in recent years. Despite this, there is still a long way to go before perovskite solar cells can be commercialized and applied on a large scale. Among them, how to improve the stability of perovskite solar cells and extend the service life of perovskite cells is one of the problems that need to be solved urgently.

[0004] In the traditional method, the perovskite material layer in the perovskite solar cell is passivated to improve stability. However, the traditional passivation methods include solution spin coating or heated vapor phase passivation, which have complex process operations and require additional temperature treatment. In particular, they are difficult to adapt to the preparation of large-area perovskite solar cells, and the preparation process has high energy consumption and difficulty in operation. Summary of the invention

[0005] The present application provides a passivation method for a perovskite material layer, a perovskite film, and a perovskite solar cell comprising the same, which can effectively improve stability, are easy to operate and implement, have low energy consumption, and are suitable for the preparation of large-area perovskite solar cells.

[0006] In a first aspect of the present application, a method for passivating a perovskite material layer is provided, comprising the following steps:

[0007] placing the preform in an atmosphere containing a passivating material for passivation;

[0008] The preform comprises a perovskite material layer, at least one surface of the perovskite material layer is in contact with the atmosphere containing the passivation material;

[0009] The passivation material meets the following conditions:

[0010] (1) Liquid at 20℃~30℃;

[0011] (2) being able to volatilize at 20°C to 30°C to form the atmosphere containing the passivation material;

[0012] (3) The chemical structure contains an organic amine group.

[0013] The above passivation method can react the organic amine groups in the passivation material with the defect sites of the perovskite material layer at room temperature to generate low-latitude perovskite materials, passivate the defects of the perovskite material layer, and improve the stability of the device. At the same time, the whole process does not require solution spin coating or additional heating treatment, and is easy to operate, which is particularly suitable for the preparation of large-area perovskite solar cells. In addition, the above passivation method can also improve the efficiency of the device.

[0014] In some embodiments, the passivation material has a general chemical structure as shown in Formula (I) or Formula (II):

[0015] R 1 [(CH2) a -NH2] b (I)

[0016] R 1 Including C6-C15 aryl, C3-C10 heteroaryl or C3-C10 heterocyclic group, a and b are integers, a≥0, b≥1;

[0017] (R 2 )2NH(II),

[0018] R 2 Including C1~C5 alkyl or -C1~C5 alkyl-SH, or two R 2 Together with the N atom to which it is attached, it forms a heterocyclic ring.

[0019] In some embodiments, R 1 including phenyl, pyridyl, piperidyl, furanyl, thienyl, pyrrolyl, imidazolyl, biphenyl or naphthyl; or

[0020] Two R's 2 Together with the connected N atom, it forms a 3- to 8-membered heterocyclic ring.

[0021] In some of these embodiments, 8≥a≥0, 3≥b≥1.

[0022] In some embodiments, the boiling point of the passivation material is 30°C to 250°C.

[0023] In some embodiments, placing the preform in an atmosphere containing a passivation material for passivation comprises:

[0024] The preform and the passivation material are placed in the same closed space.

[0025] In some embodiments, the deactivation time is ≤ 30 min.

[0026] In some embodiments, the perovskite material layer includes a perovskite material before crystallization or a perovskite material after crystallization.

[0027] In some of the embodiments, the preform is a perovskite solar cell before packaging or an intermediate device in its manufacturing process.

[0028] A second aspect of the present application provides a perovskite film, which is prepared by passivation using the passivation method.

[0029] A third aspect of the present application provides a perovskite solar cell, which includes the perovskite film described in the second aspect.

[0030] The details of one or more embodiments of the present application are set forth in the following drawings and description. Other features, objects, and advantages of the present application will become apparent from the description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to better describe and illustrate the embodiments or examples of those applications 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 as limiting the scope of any of the disclosed applications, the embodiments or examples currently described, and the best modes of these applications currently understood. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the accompanying drawings:

[0032] Figure 1 A schematic diagram of a passivation process device according to an embodiment of the present application;

[0033] Figure 2 A schematic diagram of a perovskite cell according to an embodiment of the present application; the perovskite cell includes a substrate layer, a first electrode, a first transport layer, a perovskite layer, a second transport layer, and a second electrode;

[0034] Figure 3 A schematic diagram of a perovskite cell according to an embodiment of the present application;

[0035] Figure 4 A schematic diagram of an electrical device using a perovskite battery according to an embodiment of the present application as a power source.

[0036] Explanation of the figure numbers: 100 is a perovskite battery; 110 is a substrate layer; 120 is a first electrode; 130 is a first transmission layer; 140 is a perovskite layer; 150 is a second transmission layer; 160 is a second electrode; P1 is a first notch area; P2 is a second notch area; P3 is a third notch area; 20 is an electrical device. DETAILED DESCRIPTION

[0037] Hereinafter, some embodiments of the passivation method of the perovskite material layer, the perovskite film, and the perovskite solar cell containing the same of the present application are described in detail with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structure are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following descriptions are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims.

[0038] "Scope" disclosed in the present application is limited in the form of lower limit and upper limit, and a given range is limited by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a special range. The scope limited in this way can be including end values ​​or not including end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a scope. For example, if the scope of 60-120 and 80-110 is listed for a specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following scope can be all expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise specified, the numerical range "ab" represents the abbreviation of any real number combination between a and b, wherein a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For example, when a parameter is expressed as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9 and 10.

[0039] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0040] If there is no special explanation, all steps of the present application can be performed sequentially or randomly, preferably 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.

[0041] Unless otherwise specified, the terms "include", "contain" and "comprise" mentioned in this application may be open-ended or closed-ended. For open-ended situations, for example, the terms "include", "contain" and "comprise" may mean that other members, elements or method steps not listed may also be included or comprised, or may only include or comprise the listed members, elements or method steps.

[0042] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". Further, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0043] In this application, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0044] In the present application, "plurality", "multiple" and the like, unless otherwise specified, refer to a number greater than or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0045] In the present application, the terms "first", "second", "third", "fourth", etc. in "the first aspect", "the second aspect", "the third aspect", "the fourth aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0046] In this application, when referring to the unit of a data range, if there is a unit only after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same. For example, 3~5h or 3-5h both mean that the units of the left endpoint "3" and the right endpoint "5" are both h (hours).

[0047] In the present application, the term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom, which may be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. For example, "C6-C15 aromatic group" refers to an aromatic group containing 6 to 15 carbon atoms, and each occurrence may be independently C6 aromatic group, C7 aromatic group, C8 aromatic group, C9 aromatic group, C10 aromatic group, C11 aromatic group, C12 aromatic group, C13 aromatic group, C14 aromatic group, C15 aromatic group. Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene and their derivatives.

[0048] In the present application, the term "heteroaryl" refers to an aromatic group in which at least one carbon atom is replaced by a non-carbon atom, and the non-carbon atom may be an N atom, an O atom, an S atom, etc. For example, "C3-C10 heteroaryl" refers to a heteroaryl group containing 3 to 10 carbon atoms, and each occurrence may be independently a C3 heteroaryl group, a C4 heteroaryl group, a C5 heteroaryl group, a C6 heteroaryl group, a C7 heteroaryl group, a C8 heteroaryl group, a C9 heteroaryl group or a C10 heteroaryl group. Suitable examples include, but are not limited to, furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primidine, quinazoline, and quinazolinone.

[0049] In the present application, "heterocyclyl" means that at least one carbon atom is replaced by a non-carbon atom on the basis of a cycloalkyl group, and the non-carbon atom can be an N atom, an O atom, an S atom, etc., and can be a saturated ring or a partially unsaturated ring. Phrases containing this term, for example, "C3-C10 heterocyclyl" means a heterocyclyl containing 3 to 10 carbon atoms, and each occurrence can be independently C3 heterocyclyl, C4 heterocyclyl, C5 heterocyclyl, C6 heterocyclyl, C7 heterocyclyl, C8 heterocyclyl, C9 heterocyclyl or C10 heterocyclyl. Suitable examples include, but are not limited to: dihydropyridyl, tetrahydropyridyl (piperidyl), tetrahydrothienyl, sulfur-oxidized tetrahydrothienyl, tetrahydrofuranyl, tetrahydroquinolyl, tetrahydroisoquinolyl, dihydroindole.

[0050] In the present application, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. A phrase containing the term, for example, "C1-C5 alkyl" refers to an alkyl containing 1 to 5 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl. Suitable examples include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t- Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3).

[0051] Some examples of the present application provide a passivation method for a perovskite material layer, comprising the following steps:

[0052] placing the preform in an atmosphere containing a passivating material for passivation;

[0053] The preform comprises a perovskite material layer, at least one surface of the perovskite material layer is in contact with the atmosphere containing the passivation material;

[0054] The passivation material meets the following conditions:

[0055] (1) Liquid at 20℃~30℃;

[0056] (2) being able to volatilize at 20°C to 30°C to form the atmosphere containing the passivation material;

[0057] (3) The chemical structure contains an organic amine group.

[0058] The above passivation method attempts to use a passivation material that is liquid at room temperature (20°C to 30°C) and can volatilize at room temperature to form a material atmosphere to passivate the perovskite material layer. At room temperature, the organic amine groups in the passivation material can react with the defect sites of the perovskite material layer (usually uncoordinated divalent cation (B) groups) to generate low-latitude perovskite materials, passivate the defects of the perovskite material layer, and improve the stability of the device. At the same time, the entire process does not require solution spin coating or additional heating treatment, is easy to operate, and is particularly suitable for the preparation of large-area perovskite solar cells.

[0059] In addition, the above passivation method can also improve the efficiency of the device.

[0060] Without limitation, the passivation material can be used alone or mixed with a solvent to form a solution of a certain concentration, as long as the solvent used has little effect on the volatilization of the passivation material. In some examples, the passivation material is used alone, that is, the atmosphere containing the passivation material is formed only by the volatilization of the passivation material.

[0061] Furthermore, choosing the right material chemical structure can enhance the passivation effect and improve the efficiency and stability of the device.

[0062] In some examples, the passivation material has a general chemical structure as shown in Formula (I):

[0063] R 1 [(CH2) a -NH2] b (I)

[0064] R 1 It includes C6-C15 aromatic groups, C3-C10 heteroaromatic groups or C3-C10 heterocyclic groups, a and b are integers, a≥0, b≥1.

[0065] Furthermore, R 1 These include phenyl, pyridyl, piperidyl, furyl, thienyl, pyrrolyl, imidazolyl, biphenyl or naphthyl.

[0066] Furthermore, 8≥a≥0, 3≥b≥1. Without limitation, the value of a includes, but is not limited to, 0, 1, 2, 3, 4, 5, 6, 7, 8, or any two of the foregoing; the value of b includes, but is not limited to, 1, 2, 3, or any two of the foregoing.

[0067] In some examples, the passivation material has a general chemical structure as shown in Formula (II):

[0068] (R 2 )2NH(II)

[0069] R 2Including C1~C5 alkyl or -C1~C5 alkyl-SH, or two R 2 Together with the N atom to which it is connected, a heterocyclic ring is formed. 2 It can be the same or different.

[0070] In some of these examples, R 2 Including C1~C3 alkyl or -C1~C3 alkyl-SH.

[0071] In some of these examples, the two R 2 Together with the connected N atom, it forms a 3- to 8-membered heterocyclic ring.

[0072] In some examples, the boiling point of the passivation material is 30°C to 250°C.

[0073] Without limitation, the passivation material includes one or more of benzylamine, 4-pyridinemethylamine, 4-piperidinemethylamine, 3-thiophenemethylamine, 2-(1-aminoethyl)naphthalene or mercaptomorpholine.

[0074] Some examples of passivation of a preform by placing it in an atmosphere containing a passivating material include:

[0075] The preform and the passivation material are placed in the same closed space.

[0076] Without limitation, Figure 1 As shown, for example, the preform 100 can be placed in a container 200 with a lid, and the passivation material 300 is coated on the inner side of the lid. As the passivation material volatilizes, an atmosphere 400 is formed and contacts the surface of the perovskite material layer to react, thereby passivating the surface defects of the perovskite material layer.

[0077] In some of the examples, the passivation time is ≤30min. It is understandable that the present application uses a pure passivation material, which can react quickly with the perovskite material layer after volatilization, and the reaction is almost completed when the step of placing the preform in an atmosphere containing the passivation material is completed. Therefore, the lower limit of the passivation time depends on the speed of the operation and is not particularly limited. Further, the passivation time includes but is not limited to: 5s, 10s, 20s, 30s, 50s, 1min, 5min, 10min, 15min, 20min, 25min, 30min or any two of the foregoing. Since the passivation is carried out using the atmosphere of the passivation material, compared with the traditional solution spin coating method, the material molecule concentration is large, the passivation is rapid, and the reaction time is short, which is conducive to improving industrial efficiency.

[0078] In some examples, the perovskite material layer includes a perovskite material before crystallization or a perovskite material after crystallization. The above passivation method has no special requirements for the state of the perovskite material layer, which can be a perovskite material before crystallization (i.e., a perovskite material before annealing, usually in a wet film state) or a perovskite material after crystallization.

[0079] Furthermore, when the perovskite material layer includes a perovskite material before crystallization, during the passivation process, the amino groups in the passivation material coordinate with the perovskite, which can adjust the perovskite crystallization rate, increase the perovskite grain size, and improve the quality of the perovskite film, while passivating grain boundary defects and improving efficiency and stability.

[0080] In some of the examples, the preform is a perovskite solar cell before packaging or an intermediate device in its manufacturing process. It can be understood that the perovskite solar cell before packaging refers to a device after the preparation of each functional layer of the perovskite solar cell, wherein the perovskite material layer is mainly exposed on the side and can be in contact with the atmosphere of the passivation material and passivated. The intermediate device includes the perovskite material layer, which can be a wet film of the perovskite material or a perovskite material layer after annealing.

[0081] In addition, without limitation, in some embodiments, the perovskite material contained in the perovskite material layer comprises a perovskite-type metal halide; the chemical formula of the perovskite-type metal halide is ABX3; wherein A is a monovalent cation, B is a divalent cation, and X is a monovalent anion.

[0082] In some embodiments, A includes Cs + , K + , Rb + , monovalent amine cations and monovalent amidine cations. Non-limiting examples of monovalent amine cations include CH3NH3 + (Methylamine, MA + ), ammonium (NH4 + ). Non-limiting examples of monovalent amidinium cations include NH2CH=NH2 + (Formamidine, can be written as FA + ).

[0083] In some embodiments, B includes Pb 2+ Sn 2+ , Fe 2+ , Mn 2+ 、Ni 2+ ,Ge 2+ 、Co 2+ and Sb 2+ One or more of .

[0084] In some embodiments, X comprises I- Br - and Cl - One or more of .

[0085] In some embodiments, X comprises I - Br - One or two of X. - Br - Or a combination thereof. In some embodiments, X is 1 - .

[0086] The present application also provides a perovskite film, which is prepared by passivation using the passivation method described above in the present application.

[0087] The present application also provides a perovskite solar cell, which includes the perovskite film described above in the present application.

[0088] In some embodiments, the present application provides a perovskite solar cell, which includes an electron transport layer, a hole transport layer, and the perovskite film as described above in the present application, wherein the perovskite film is disposed between the electron transport layer and the hole transport layer.

[0089] In some embodiments, the present application provides a perovskite solar cell, which includes a positive electrode, a negative electrode, and a perovskite film as described above in the present application, wherein the perovskite film is disposed between the positive electrode and the negative electrode.

[0090] In some embodiments, the present application provides a perovskite solar cell, which includes a positive electrode, an electron transport layer, a perovskite film as described above in the present application, a hole transport layer, and a negative electrode arranged in sequence. Further, it can be any one of an inverted pin cell and a formal nip cell.

[0091] Without limitation, the perovskite film as described above in the present application may also be referred to as a perovskite layer, which is also a light-absorbing layer in a perovskite cell.

[0092] When the perovskite battery is working, after the light-absorbing layer is exposed to light, the internal electrons gain energy and break free from the light-absorbing layer to form negatively charged electron carriers, and at the same time form positively charged hole carriers, thereby obtaining electron-hole pairs. Free electrons and free holes are transmitted in opposite directions through the corresponding transport layer, so that electrons and holes flow, forming external current, and realizing the conversion of light energy into electrical energy. Further, after the perovskite layer absorbs photons, it is stimulated to generate electron-hole pairs, which further dissociate to form free carriers with opposite charges. The free electrons are transmitted to the positive electrode through the electron transport layer, and the free holes are transmitted to the negative electrode through the hole transport layer. The two free carriers are collected by the corresponding electrodes, further forming photocurrent in the circuit of the perovskite battery.

[0093] The electron transport layer can extract and transport electron carriers and block the passage of free holes.

[0094] The hole transport layer can extract and transport hole carriers and block the passage of free electrons.

[0095] It can be understood that the perovskite battery further comprises two electrodes, one of which is a positive electrode that can collect electron carriers transmitted via the electron transport layer, and the other is a negative electrode that can collect hole carriers transmitted via the hole transport layer.

[0096] In some embodiments, the electron transport layer material 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), metal oxides, silicon oxide (SiO2), strontium titanate (SrTiO3), etc.; wherein the metal elements may include one or more of Mg, Cd, Zn, In, Pb, Sb, Bi, Hg, Ti, Mn, Fe, Sn, Zr, Sr, Ga and Cr.

[0097] In some embodiments, 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), N-(4-aniline)carbazole-spirobifluorene (CzPAF-SBF), polytriarylamine (PTAA), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), nickel oxide (NiO x ), poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS), poly 3-hexylthiophene (P3HT), polythiophene, cuprous thiocyanate (CuSCN), WO3 and other materials can transport holes and block electrons.

[0098] In some embodiments, the perovskite solar cell 100 includes Figure 2 The structure shown includes a substrate layer 110, a first electrode 120, a first transmission layer 130, a perovskite layer 140, a second transmission layer 150 and a second electrode 160 arranged in sequence. Further, the structure layers shown in the figure are stacked in sequence.

[0099] In some embodiments, the perovskite cell comprises Figure 3The structure shown (a vertical cross-sectional structure diagram of the device) includes a substrate layer 110, a first electrode 120, a first transmission layer 130, a perovskite layer 140, a second transmission layer 150, and a second electrode 160, which are stacked in sequence. Among them, P1, P2, and P3 are etching areas arranged across layers, which are used to divide the film layer prepared in a large area into different components, so that it is a series battery structure; wherein P1, P2, and P3 are respectively used to connect the structural layers arranged separately, so that the structural layers between the first electrode and the second electrode form a loop, and the perovskite battery forms a perovskite battery component. P1, P2, and P3 can each independently be a linear etching area, also called an etching line. P1, P2, and P3 can each independently be a laser etching area. The number of P1, P2, and P3 can each independently be one or more. Figure 3 In the figure, P1 penetrates the first transmission layer and the bottom of the first electrode from the surface of the first transmission layer and is connected to the base layer, so that the left and right sides of the divided P1 are not connected to each other (to achieve insulation), and the material in the P1 etching area is consistent with that in the perovskite layer; P2 penetrates the second transmission layer, the perovskite layer, and the first transmission layer from the surface of the second transmission layer and is connected to the surface of the first electrode, and the material in the P2 etching area is consistent with that of the second electrode; P3 penetrates the second electrode, the second transmission layer, the perovskite layer, the first transmission layer from the surface of the second electrode to the surface of the first electrode, and no material is filled in the P3 etching area.

[0100] In some embodiments, the width of P1 is 10-50 μm, for example, 30 μm.

[0101] In some embodiments, the width of P2 is 10-200 μm, for example, 150 μm. Further, the interval between P2 and P1 may be 20-80 μm, for example, 20 μm.

[0102] In some embodiments, the width of P3 is 10-50 μm, for example, 15 μm. Further, the interval between P3 and P2 may be 20-40 μm, for example, 20 μm.

[0103] In some embodiments, P1 in the perovskite cell can penetrate from the surface of the first transport layer to the bottom of the first electrode, and the P1 filling material is consistent with the perovskite layer (e.g. Figure 3 In some other embodiments, P1 in the perovskite cell may also penetrate from the surface of the first electrode to the bottom, and the filling material in P1 is consistent with the first transport layer.

[0104] In some embodiments, one of the "first transport layer" and the "second transport layer" is an electron transport layer, and the other is a hole transport layer. In some embodiments, the first transport layer is an electron transport layer. In some embodiments, the first transport layer is a hole transport layer.

[0105] In some embodiments, one of the "first electrode" and the "second electrode" is a transparent electrode for light incidence. In some embodiments, the first electrode is a transparent electrode.

[0106] In some embodiments, the material of the transparent electrode may be exemplified by, but not limited to, one or more of the following materials: FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), BZO (boron-doped zinc oxide), IZO (indium zinc oxide), IWO (tungsten-doped indium oxide), etc.

[0107] In some embodiments, the second electrode comprises a conductive material, and further, the conductive material may be an organic conductive material, an inorganic conductive material, or a combination thereof. Non-limiting examples of inorganic conductive materials include metal conductive materials, and further, the metal conductive material may include any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), etc., or any suitable mixture of the aforementioned elements. The conductive material may include a conductive oxide, and further, the conductive material may be a conductive oxide; non-limiting examples of conductive oxides may include one or more of FTO, ITO, IWO, AZO, etc.

[0108] In some embodiments, the perovskite cell is any one of an inverted pin cell and a formal nip cell.

[0109] The perovskite cells provided in this application may include formal and trans forms.

[0110] Officially, the perovskite cell includes a transparent electrode and an electron transport layer, a perovskite layer, a hole transport layer and a second electrode layer stacked in sequence on the transparent electrode.

[0111] For the trans type, the perovskite cell comprises a transparent electrode and a hole transport layer, a perovskite layer, an electron transport layer and a second electrode layer sequentially stacked on the transparent electrode, wherein the transparent electrode is used for light incidence.

[0112] In some embodiments, the perovskite cell includes the following structures arranged in sequence: a substrate layer (which may be a glass substrate or a flexible substrate), a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode. The flexible substrate may include one or more materials selected from polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyethylene naphthalate, etc. Optionally, the first electrode is a transparent electrode for light incidence.

[0113] In some embodiments, the perovskite cell comprises the following structures arranged in sequence: a substrate layer (glass substrate or flexible substrate), a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode. Optionally, the first electrode is a transparent electrode for light incidence. The definition of the flexible substrate can be found in the above text.

[0114] The substrate layer involved in the implementation manner or example of the present application may be, but is not limited to, a glass substrate or a flexible substrate.

[0115] In some embodiments, the substrate layer is a flexible substrate layer. Further, the material of the substrate layer may be, for example (but not limited to), an organic polymer material, and further, may be mixed in different proportions with one or more of the following materials: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), etc.

[0116] In some embodiments, Figure 3 The substrate layer 110 in the structure shown is a light-incident glass substrate.

[0117] The specifications of the perovskite cell are not particularly limited and may be, but not limited to, 300 mm×300 mm.

[0118] It can be understood that the structure of the perovskite battery involved in the present application may not be limited to the structural layers listed above. Other functional layers, such as buffer layers, can also be introduced as needed. In some embodiments, the perovskite battery can be provided with a buffer layer with a suitable energy level, which can play a role in reducing energy level barriers, promoting energy level matching, improving carrier extraction efficiency, and at the same time, passivating interface defect states, protecting light absorption layers, inhibiting water molecules, oxygen oxidation and decomposition of batteries, improving photoelectric conversion efficiency, and improving the stability of perovskite batteries. One or more of the above. Depending on the location of the buffer layer, the type of buffer layer 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 absorption layer, and a buffer layer between the electron transport layer and the absorption layer. The materials that can be used for the buffer layer in the perovskite battery may include, but are not limited to: Cu2O, NiO, AZO, TiO2, etc.

[0119] In addition, the present application provides an electrical device, which includes the perovskite battery described above in the present application.

[0120] In some embodiments, the perovskite battery can be used as a power generation device of an electrical device. The type of the power generation device can include but is not limited to integrated power generation. The location of the power generation device can include but is not limited to the roof, back panel, etc. of a car.

[0121] Furthermore, the above-mentioned electrical devices may include mobile devices, such as mobile phones, laptop computers, etc., electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited thereto.

[0122] Figure 4 The power consumption device 20 is an automobile, and can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.

[0123] As another example, the electric device may be a mobile phone, a tablet computer, a laptop computer, a calculator, etc.

[0124] As another example, the power-consuming device may be a wearable device, such as a watch.

[0125] Below, some embodiments of the present application are described. The embodiments described below are exemplary, are only used to explain the present application, and cannot be construed as limiting the present application. In the embodiments, if the technology or conditions are not indicated, they are carried out according to the description above, or according to the technology or conditions described in the document in this area or according to the product specification. The reagents used or the instruments that do not indicate the manufacturer are conventional products that can be obtained commercially, or can be synthesized in a conventional manner by commercially available products.

[0126] In the following embodiments, "room temperature" refers to 20°C to 30°C, and further, may be 25°C.

[0127] Comparative Example 1

[0128] The perovskite battery prepared in this comparative example adopts a trans-structure, FTO / NiO x / M2P / Perovskite / C60 / BCP / Cu.

[0129] 1.1. Preparation of the first electrode of the component: FTO

[0130] A set of FTO conductive glass with a specification of 300mm×300mm was etched with infrared laser P1, and the width of P1 was about 30μm. The whole piece of glass was divided into 44 sub-cells along the long side. The series resistance of different sub-cells was greater than 10MΩ. 10mm above and below were used as the component welding area;

[0131] The etched conductive glass surface was cleaned twice with acetone and isopropanol in turn, immersed in deionized water for ultrasonic treatment for 10 minutes, dried in a forced air drying oven, and placed in a drying room (with humidity less than 2% RH, relative humidity) to serve as the first electrode.

[0132] 1.2. Preparation of component hole transport layer: NiO x / M2P

[0133] Preparation of NiO by spin coating of nanoparticles on the cleaned conductive glass surface x Layer: Prepare NiO with a concentration of 5 mg / mL x The aqueous solution was spin-coated at 3000 rpm for 40 seconds, and then annealed at 150 ° C for 15 minutes. x The film thickness is about 15nm.

[0134] NiO x The M2P layer was prepared on the surface of the layer by spin coating: an isopropanol solution of M2P with a concentration of 0.3 mg / mL was prepared, and the solution was spin coated at 5000 rpm for 30 s, followed by annealing at 100° C. for 10 minutes. The thickness of the M2P layer was about 15 nm.

[0135] 1.3. Preparation of the main perovskite layer of the module

[0136] The surface of the M2P layer was spin-coated with a 1.25 M FAPbI3 perovskite precursor solution, the solvent was DFM / DMSO = 4 / 1 (v / v), first at 1000 rpm for 10 s, then at 5000 rpm for 30 s, and 150 μL of chlorobenzene antisolvent was added at the 20th second, the wet film thickness was about 500 nm; then annealed at 100°C for 30 minutes and cooled to room temperature.

[0137] 1.4. Preparation of component electron transport layer: C60 / BCP

[0138] The substrate with the perovskite absorption layer prepared was placed in a vacuum thermal evaporation device and evacuated to 4×10 -4 Pa, deposit 30nm C 60 and 7nm BCP (bathocuproine) as the component electron transport layer;

[0139] 1.5. Preparation of the second electrode of the component: Cu

[0140] After the electron transport layer was deposited in the vacuum thermal evaporation device, 20 nm Cu was deposited on the surface and then the vacuum was broken and taken out. P2 was laser etched. The width of P2 was 150 μm and the depth was etched to the FTO layer. The interval between P2 and P1 was 20 μm. Then the substrate was put into the evaporation device again and vacuumed to 4×10 -4 After Pa, a layer of Cu is deposited with a thickness of about 80nm;

[0141] After cooling, the vacuum is broken and P seconds of green laser is used to etch P3. The width of P3 is 15 μm, and the depth is etched to the FTO layer. The interval between P3 and P2 is 20 μm (the positions of the etching lines are P1 / P2 / P3 in sequence);

[0142] Then use infrared edge cleaning on the component, that is, etching 10mm on both sides of the component.

[0143] Comparative Example 2

[0144] The perovskite cell prepared in this comparative example adopts a formal structure, FTO / SnO2 / perovskite / Spiro-MeOTAD / Au.

[0145] 1.1. Preparation of the first electrode of the component: FTO

[0146] A set of FTO conductive glass with a specification of 300mm×300mm was etched with infrared laser P1, and the width of P1 was about 30μm. The whole piece of glass was divided into 44 sub-cells along the long side. The series resistance of different sub-cells was greater than 10MΩ. 10mm above and below were used as the component welding area;

[0147] The etched conductive glass surface was cleaned twice with acetone and isopropanol in turn, immersed in deionized water for ultrasonic treatment for 10 minutes, dried in a forced air drying oven, and placed in a drying room (with humidity less than 2% RH, relative humidity) to serve as the first electrode.

[0148] 1.2. Preparation of component hole transport layer: SnO2

[0149] The SnO2 layer was prepared on the cleaned conductive glass surface by spin coating of nanoparticles: an aqueous solution of SnO2 with a concentration of 2.26 mg / mL was prepared, spin coated at 4000 rpm for 30 seconds, and then annealed at 150°C for 15 minutes. The SnO2 layer had a thickness of about 15 nm.

[0150] 1.3. Preparation of the main perovskite layer of the module

[0151] The SnO2 layer was subjected to spin coating of a 1.25 M FAPbI3 perovskite precursor solution with a solvent of DMF / DMSO = 4 / 1 (v / v). The solution was first spun at 1000 rpm for 10 s and then at 5000 rpm for 30 s. At the 20th s, 150 μL of chlorobenzene antisolvent was added. The wet film thickness was about 500 nm. The layer was then annealed at 100°C for 30 minutes and cooled to room temperature.

[0152] 1.4. Preparation of component electron transport layer: Spiro-MeTAD

[0153] 72.3 mg of Spiro-MeTAD powder was dissolved in 1 mL of chlorobenzene. After complete dissolution, 28.5 mL of TBP and 17.5 mL of bis(trifluoromethane)sulfonamide lithium salt solution (520 mg / mL acetonitrile solution) were added thereto, and stirred for 10 minutes to obtain a Spiro-MeTAD solution, which was spin-coated at 3000 rpm for 30 seconds with a thickness of about 70 nm.

[0154] 1.5. Preparation of the second electrode of the component: Au

[0155] After the electron transport layer was deposited in the vacuum thermal evaporation device, 20 nm Au was deposited on the surface and then the vacuum was broken and taken out. P2 was laser etched. The width of P2 was 150 μm and the depth was etched to the FTO layer. The interval between P2 and P1 was 20 μm. Then the substrate was put into the evaporation device again and vacuumed to 4×10 -4 After Pa, a layer of Au is continuously deposited with a thickness of about 80 nm;

[0156] After cooling, the vacuum is broken and P seconds of green laser is used to etch P3. The width of P3 is 15 μm, and the depth is etched to the FTO layer. The interval between P3 and P2 is 20 μm (the positions of the etching lines are P1 / P2 / P3 in sequence);

[0157] Then use infrared edge cleaning on the component, that is, etching 10mm on both sides of the component.

[0158] Comparative Example 3

[0159] The perovskite battery prepared in this comparative example adopts a trans-structure, FTO / NiO x / M2P / Perovskite / C60 / BCP / Cu, the preparation method is the same as that of Comparative Example 1, the main difference being that the spin coating method is used to perform passivation after the annealing step in the preparation of the component perovskite main layer.

[0160] 1.3. Preparation of the main perovskite layer of the module

[0161] The surface of the M2P layer was spin-coated with a 1.25M FAPbI3 perovskite precursor solution, the solvent was DMF / DMSO=4 / 1 (v / v), first at 1000rpm for 10s, then at 5000rpm for 30s, and 150μL of chlorobenzene antisolvent was added at the 20th second, and the wet film thickness was about 500nm; then annealed at 100°C for 30 minutes and cooled to room temperature; the passivator solution was continued to be spin-coated on the cooled perovskite layer, the passivator solution was formed by dissolving benzylamine in isopropanol solvent, the passivator solution concentration was 0.1mg / mL, and it was spin-coated at 5000rpm for 30s.

[0162] Example 1a

[0163] The perovskite battery prepared in this example adopts a trans-structure, FTO / NiO x / M2P / Perovskite / C60 / BCP / Cu, the preparation method is the same as that of Comparative Example 1, the main difference being that passivation is performed before annealing in the preparation of the component perovskite main layer.

[0164] 1.3. Preparation of the main perovskite layer of the module

[0165] A 1.25M FAPbI3 perovskite precursor solution was spin-coated on the surface of the M2P layer. The solvent was DMF / DMSO=4 / 1 (v / v). The solution was first spin-coated at 1000 rpm for 10 s and then at 5000 rpm for 30 s. 150 μL of chlorobenzene antisolvent was added at the 20th second. The wet film thickness was about 500 nm. The preform with the wet film was placed in a container with a lid, and 15 uL of benzylamine (passivation material) was applied to the inside of the lid. The solution was sealed and passivated for 1 min, then annealed at 100°C for 30 min and cooled to room temperature.

[0166] Example 1b to Example 1f

[0167] The preparation methods of the perovskite cells prepared in Examples 1b to 1f are the same as those in Example 1a, the main difference being that the type of passivation material is changed.

[0168] Example 2

[0169] The perovskite battery prepared in this example adopts a trans-structure, FTO / NiO x / M2P / Perovskite / C60 / BCP / Cu, the preparation method is the same as that of Comparative Example 1, the main difference being that the passivation is performed after the annealing step in the preparation of the component perovskite main layer.

[0170] 1.3. Preparation of the main perovskite layer of the module

[0171] The surface of the M2P layer was spin-coated with a 1.25M FAPbI3 perovskite precursor solution, the solvent being DMF / DMSO=4 / 1 (v / v), first at 1000rpm for 10s, then at 5000rpm for 30s, and 150μL of chlorobenzene antisolvent was added at the 20th second, with a wet film thickness of about 500nm; then annealed at 100°C for 30 minutes and cooled to room temperature; the cooled preform was placed in a container with a lid, and benzylamine (passivation material) was applied to the inside of the lid, and the lid was sealed and passivated for 10 minutes.

[0172] Example 3

[0173] The perovskite battery prepared in this example adopts a trans-structure, FTO / NiO x / M2P / Perovskite / C60 / BCP / Cu, the preparation method is the same as that of Comparative Example 1, the main difference being that passivation is performed after the preparation of the perovskite battery is completed (i.e., the step of "preparation of the second electrode of the component" in Comparative Example 1 is completed, but the final packaging is not performed).

[0174] The prepared perovskite battery was placed in a container with a lid, and benzylamine (passivation material) was applied to the inner side of the lid, and the lid was sealed and passivated for 30 minutes.

[0175] The main parameters of each embodiment and comparative example are summarized in Table 1 below.

[0176] Test example:

[0177] 1. Photoelectric conversion efficiency test:

[0178] In standard simulated sunlight (AM 1.5G, 100mW / cm 2 ) to test the battery performance and obtain the IV curve. According to the IV curve and the data fed back by the test equipment, the short-circuit current Jsc (unit mA / cm2), open-circuit voltage Voc (unit V), maximum light output current Jmpp (unit mA) and maximum light output voltage Vmpp (unit V) can be obtained. The fill factor FF of the battery is calculated by the formula FF = Jsc × Voc / (Jmpp × Vmpp), in %. The photoelectric conversion efficiency PCE of the battery is calculated by the formula PCE = Jsc × Voc × FF / Pw, in %; Pw represents the input power, in mW.

[0179] 2. Stability test:

[0180] In standard simulated sunlight (AM 1.5G, 100mW / cm 2 ) Steady-state output of the battery at the maximum power point voltage under continuous irradiation and heating at 65°C. Note: The percentage of the device PCE remaining at the initial PCE after 500h.

[0181] The test results are shown in Table 1 below:

[0182] Table 1

[0183]

[0184]

[0185] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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.

[0186] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples. Within the scope of the technical solution of the present application, the embodiments that have the same structure as the technical idea and play the same effect are all included in the technical scope of the present application. The above-mentioned embodiments only express several embodiments of the present application, and the description is relatively detailed, but it cannot be understood as a limitation on the scope of the patent. In addition, without departing from the scope of the subject matter of the present application, various deformations that can be thought of by those skilled in the art and other methods of combining and constructing some of the constituent elements in the embodiments are also included in the scope of the present application. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several deformations and improvements can be made, which all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the attached claims, and the description and drawings can be used to explain the content of the claims.

Claims

1. A passivation method for a perovskite material layer, characterized in that: The steps include: placing the preform in an atmosphere containing a passivating material for passivation; The preform comprises a perovskite material layer, at least one surface of the perovskite material layer is in contact with the atmosphere containing the passivation material; The passivation material meets the following conditions: (1) Liquid at 20℃~30℃; (2) being able to volatilize at 20°C to 30°C to form the atmosphere containing the passivation material; (3) The chemical structure contains an organic amine group.

2. The passivation method of the perovskite material layer according to claim 1, characterized in that: The passivation material has a general chemical structure as shown in the following formula (I) or formula (II): R 1 [(CH2) a -NH2] b (I), R 1 Including C6-C15 aryl, C3-C10 heteroaryl or C3-C10 heterocyclic group, a and b are integers, a≥0, b≥1; (R 2 )2NH(II), R 2 Including C1~C5 alkyl or -C1~C5 alkyl-SH, or two R 2 Together with the N atom to which it is attached, it forms a heterocyclic ring.

3. The passivation method of the perovskite material layer according to claim 2, characterized in that: R 1 including phenyl, pyridyl, piperidyl, furanyl, thienyl, pyrrolyl, imidazolyl, biphenyl or naphthyl; or Two R's 2 Together with the connected N atom, it forms a 3- to 8-membered heterocyclic ring.

4. The passivation method of the perovskite material layer according to claim 2, characterized in that: 8≥a≥0, 3≥b≥1.

5. The passivation method of the perovskite material layer according to any one of claims 1 to 4, characterized in that: The boiling point of the passivation material is 30°C to 250°C.

6. The passivation method of the perovskite material layer according to any one of claims 1 to 5, characterized in that: The passivation of the preform by placing it in an atmosphere containing a passivating material includes: The preform and the passivation material are placed in the same closed space.

7. The passivation method of the perovskite material layer according to any one of claims 1 to 6, characterized in that: The passivation time is ≤30min.

8. The passivation method of the perovskite material layer according to any one of claims 1 to 7, characterized in that: The perovskite material layer includes a perovskite material before crystallization or a perovskite material after crystallization.

9. The passivation method of the perovskite material layer according to any one of claims 1 to 8, characterized in that: The prefabricated component is a perovskite solar cell before packaging or an intermediate device in its manufacturing process.

10. A perovskite film, characterized in that: The passivation product is prepared by the passivation method described in any one of claims 1 to 9.

11. A perovskite solar cell, characterized in that: It comprises the perovskite thin film according to claim 10.

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