Photovoltaic device and preparation method thereof, and power utilization device

Abstract

The invention provides a photovoltaic device and a preparation method thereof, and a power utilization device, the photovoltaic device comprises a first electrode layer, a light absorption layer and a second electrode layer which are stacked in sequence, at least one side of the second electrode layer is provided with a protection layer, the protection layer comprises a corrosion inhibitor, and the corrosion inhibitor is arranged in the protection layer. The corrosion inhibitor comprises one or a combination of more of imidazoline quaternary ammonium salt, phytic acid, caprylic acid tributylamine and derivatives thereof.

Description

Photovoltaic device and preparation method thereof, and power-using device Technical Field

[0001] The present application relates to the field of solar photovoltaic technology, and in particular to photovoltaic devices, preparation methods thereof, and electrical devices. Background Art

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

[0003] In recent years, photovoltaic devices, particularly perovskite solar cells, have been the subject of extensive research. Perovskite solar cells, currently the third generation of solar cells, utilize the photoelectric conversion mechanism of perovskite-type crystal materials to convert solar energy into electrical energy. They offer numerous advantages, including high photoelectric conversion efficiency, simple manufacturing processes, and low production costs. Despite this, photovoltaic devices, particularly perovskite solar cells, still suffer from poor stability.

[0004] Summary of the Invention

[0005] In view of the above problems, the present application provides a photovoltaic device and a preparation method thereof, and an electrical device, which can improve the stability of the photovoltaic device.

[0006] In a first aspect, the present application provides a photovoltaic device comprising: a first electrode layer, a light absorbing layer, and a second electrode layer stacked in sequence, wherein a protective layer is provided on at least one side of the second electrode layer, and the protective layer contains a corrosion inhibitor, and the corrosion inhibitor includes a combination of one or more of imidazoline quaternary ammonium salt, phytic acid, tributylamine octanoate, and their derivatives.

[0007] The photovoltaic device provided herein is provided with the aforementioned protective layer. The corrosion inhibitor contained in the protective layer can form a dense film layer through interaction with the second electrode. On the one hand, the protective film layer can block the reaction between the chemical components (such as the perovskite component) in the light-absorbing layer and the second electrode, reducing the decomposition of the chemical components due to the reaction with the second electrode. On the other hand, the film layer can also prevent corrosion of the second electrode caused by water and oxygen in the air, thereby improving the photoelectric conversion efficiency, stability, and service life of the photovoltaic device.

[0008] In some embodiments, the imidazoline quaternary ammonium salt has a structure shown in formula (1),

[0009] In formula (1), R1, R2 and R3 each independently include a hydrogen atom, an unsubstituted C 1-20 or a hydrocarbon group substituted by at least one R4, each R4 comprising a combination of one or more of a thiourea group, an amino group, and a hydroxyl group, R -including one of halogen ions and acid radical ions; optionally, the acid radical ions include HSO4 - , HCOO - , CH3COO - and CN - or a combination of one or more of them.

[0010] When the imidazoline quaternary ammonium salt provided in this application interacts with the metal electrode as the second electrode, it can provide electrons to the empty d orbitals of the metal and accept the d electrons of the metal with the antibonding orbitals. When the imidazoline quaternary ammonium salt approaches the surface of the metal electrode, the π electrons of the π bond on the imidazoline ring will enter the empty d orbitals of the metal, and the anti-π orbital (π*) can also accept the electrons in the d orbitals of the metal to form a feedback bond, thus generating chemisorption and forming a dense protective layer on the surface of the metal. At the same time, the R groups (R1, R2, and R3) on the imidazoline ring can also stretch towards the metal surface to form a hydrophobic protective layer, enhancing the ability of the photovoltaic device to block and isolate water and oxygen in the air, thereby improving the stability and service life of the battery.

[0011] In some embodiments, the imidazoline quaternary ammonium salt includes one or a combination of more of 2-aminoethyl heptadecene imidazoline quaternary ammonium salt, thiourea-based imidazoline quaternary ammonium salt, 2-undecyl imidazoline quaternary ammonium salt, heptadecene amine ethyl imidazoline quaternary ammonium salt, and heptadecene hydroxyethyl imidazoline quaternary ammonium salt, and it can be optionally the thiourea-based imidazoline quaternary ammonium salt.

[0012] For the thiourea-based imidazoline quaternary ammonium salt provided in this application, since the sulfur atom on its thiourea group can form a coordination bond with the empty orbitals of the metal in the metal electrode, the formed protective layer is denser, which is beneficial to further enhancing the inhibitory effect of the protective layer on the decomposition of chemical components and the blocking and isolation effect on water and oxygen in the air, thereby further improving the photoelectric conversion efficiency, stability, and service life of the photovoltaic device.

[0013] In some embodiments, a first protective layer is provided between the light-absorbing layer and the second electrode layer, and the thickness of the first protective layer is 0 < d1 ≤ 5 nm, and it can be optionally 1 nm ≤ d1 ≤ 3 nm.

[0014] When the thickness of the first protective layer is within the above range, it can not only inhibit the decomposition of chemical components in the light-absorbing layer but also not affect the carrier transport.

[0015] In some embodiments, a second protective layer is further provided on the side of the second electrode layer relatively far from the light-absorbing layer, and the thickness of the second protective layer is d2, 0 < d2 ≤ 15 nm, and it can be optionally 1 nm ≤ d2 ≤ 10 nm.

[0016] The thickness of the second protective layer is within the above range, which can effectively block and isolate water and oxygen in the air without affecting the normal performance of the photovoltaic device.

[0017] In some embodiments, at least one of a first charge transport layer and a second charge transport layer is further included, wherein the first charge transport layer is arranged between the first electrode layer and the light absorbing layer, and the second charge transport layer is arranged between the light absorbing layer and the first protective layer.

[0018] In some embodiments, the second electrode layer is a metal electrode layer.

[0019] In some embodiments, the photovoltaic device comprises a perovskite cell.

[0020] In some embodiments, the first electrode layer is a transparent electrode layer, and the light absorbing layer is a perovskite layer.

[0021] In a second aspect, the present application provides a method for preparing a photovoltaic device, comprising: preparing a first electrode layer, a light-absorbing layer, and a second electrode layer; and preparing a protective layer on at least one side of the second electrode layer to obtain the photovoltaic device, wherein the protective layer contains a corrosion inhibitor, and the corrosion inhibitor includes a combination of one or more of imidazoline quaternary ammonium salt, phytic acid, tributylamine octanoate, and their derivatives.

[0022] The method provided herein, by preparing a protective layer comprising a corrosion inhibitor on at least one side of the second electrode layer, can block the reaction between the chemical components (such as the perovskite component) in the light-absorbing layer and the second electrode, reducing the decomposition of the chemical components due to the reaction with the second electrode. It can also inhibit the migration of chemical components (such as halogen ions) in the light-absorbing layer to the second electrode layer, reducing electrochemical corrosion of the second electrode layer, and improving the photoelectric conversion efficiency, stability, and service life of the photovoltaic device. Furthermore, the protective layer can also block corrosion of the second electrode caused by water and oxygen in the air, thereby further improving the service life of the photovoltaic device.

[0023] In some embodiments, the imidazoline quaternary ammonium salt has a structure shown in formula (1),

[0024] In formula (1), R1, R2 and R3 each independently include a hydrogen atom, an unsubstituted C 1-20 or a hydrocarbon group substituted by at least one R4, each R4 comprising a combination of one or more of a thiourea group, an amino group, and a hydroxyl group, R - Including one of halogen ions and acid radical ions; optionally, the acid radical ions include HSO4 - HCOO - 、CH3COO - and CN- A combination of one or more of .

[0025] Above-mentioned imidazoline quaternary ammonium salt can interact with the metal electrode as the second electrode, can provide electrons to the empty d orbital of metal, can accept the d electrons of metal with anti-bonding orbital again.When imidazoline quaternary ammonium salt approaches the metal electrode surface, the π bond on the imidazoline ring, just has π electrons to enter the empty d orbital of metal, and anti-π orbital (π*) can accept the electron formation feedback bond in the d orbital of metal again, thereby produces chemical adsorption, and forms a dense protective layer on the surface of metal.Simultaneously, the R base (R1, R2 and R3) on the imidazoline ring can stretch to the metal surface again and form a hydrophobic protective layer, strengthen the blocking isolation ability of photovoltaic device to water oxygen in air, and promote the photoelectric conversion efficiency, stability and the service life of photovoltaic device.

[0026] In some embodiments, the imidazoline quaternary ammonium salt includes a combination of one or more of 2-aminoethyl heptadecenyl imidazoline quaternary ammonium salt, thiourea imidazoline quaternary ammonium salt, 2-undecyl imidazoline quaternary ammonium salt, heptadecenylaminoethyl imidazoline quaternary ammonium salt and heptadecenyl hydroxyethyl imidazoline quaternary ammonium salt, and can be thiourea imidazoline quaternary ammonium salt.

[0027] In some embodiments, the solution for preparing the protective layer contains the corrosion inhibitor, and the mass concentration of the corrosion inhibitor in the solution is 0.1 mg / ml to 10 mg / ml, and optionally 0.5 mg / ml to 5 mg / ml.

[0028] The concentration of the corrosion inhibitor in the solution is within the above range, which is beneficial to further promote the role of the protective layer in photovoltaic devices in improving the photoelectric conversion efficiency, stability and service life of the battery.

[0029] In some embodiments, the solution for preparing the protective layer comprises an organic solvent, and the organic solvent comprises an alcohol organic solvent. Optionally, the alcohol organic solvent comprises at least one of methanol, ethanol, propanol, and isopropanol.

[0030] In a third aspect, the present application provides an electrical device, which includes the photovoltaic device described in the first aspect of the present application or the photovoltaic device prepared by the method described in the second aspect of the present application.

[0031] The electrical device of the present application includes the photovoltaic device provided by the present application, and thus has at least the same advantages as the photovoltaic device.

[0032] 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

[0033] In order to better describe and illustrate the embodiments or examples of the 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 to limit the scope of the disclosed applications, the embodiments or examples currently described, and any of the best modes currently understood for these applications. Moreover, the same reference numerals are used throughout the drawings to represent the same components. In the drawings:

[0034] FIG1 is a schematic structural diagram of a photovoltaic device according to one embodiment of the present application.

[0035] FIG2 is a schematic structural diagram of a photovoltaic device according to an embodiment of the present application.

[0036] FIG3 is a schematic structural diagram of a photovoltaic device according to an embodiment of the present application.

[0037] FIG4 is a schematic structural diagram of a perovskite battery according to an embodiment of the present application.

[0038] FIG5 is a schematic structural diagram of a perovskite battery according to an embodiment of the present application.

[0039] FIG6 is a schematic structural diagram of a perovskite cell according to an embodiment of the present application.

[0040] FIG7 is a schematic diagram of an electrical device using a photovoltaic device as a power source according to an embodiment of the present application.

[0041] Description of reference numerals:

[0042] 11 substrate layer; 12 first electrode layer; 13 first charge transport layer; 14 light absorption layer; 15 second charge transport layer; 16 first protective layer; 17 second electrode layer; 18 second protective layer; 14' perovskite layer. DETAILED DESCRIPTION

[0043] Below, some embodiments of the photovoltaic device, its preparation method, and the electrical device 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 actually identical structures may be omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the 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.

[0044] " scope " disclosed in the present application is limited in the form of lower limit and upper limit, and given range is limited by selecting a lower limit and an upper limit, and selected lower limit and upper limit define the boundary of special scope.The scope that this mode limits can be to include end value or not include end value, and can be combined arbitrarily, and promptly any lower limit can form a scope with any upper limit combination.For example, if the scope of 60-120 and 80-110 is listed for specific parameter, it is understood that the scope of 60-110 and 80-120 is also expected.In addition, if the minimum range value 1 and 2 listed, and if the maximum range value 3,4 and 5 are listed, then the following scope can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.In the present application, unless otherwise specified, numerical range " ab " represents the abbreviation of any real number combination between a and b, and wherein a and b are all 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 merely an abbreviation for a combination of these values. Furthermore, when a parameter is expressed as an integer ≥ 2, this 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. For example, when a parameter is expressed as an integer including "2-10", this is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0045] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0046] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating 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), indicating 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.

[0047] Unless otherwise specified, the terms "include," "contain," and "comprise" used in this application are open-ended or closed-ended. For example, "include," "contain," and "comprise" may indicate that the present invention may also include or contain other members, elements, or method steps not listed, or may indicate that the present invention may include or contain only the listed members, elements, or method steps.

[0048] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B." Furthermore, the condition "A or B" is satisfied by any of the following conditions: 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).

[0049] 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.

[0050] In this application, "a plurality of" or "a plurality of" refers to a number greater than or equal to 2 unless otherwise specified. For example, "one or more" means one or more than or equal to two.

[0051] In this application, the terms "first," "second," "third," and "fourth," etc., in "the first aspect," "the second aspect," "the third aspect," and "the fourth aspect," etc., are used for descriptive purposes only and should not be understood as indicating or implying relative importance or quantity, nor as implicitly indicating the importance or quantity of the technical features indicated. Furthermore, "first," "second," "third," and "fourth," etc., are used only for non-exhaustive enumeration and description purposes and should be understood not to constitute closed-ended limitations on quantity.

[0052] In this application, unless otherwise specified, the term "hydrocarbyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated or unsaturated hydrocarbon containing a primary (normal) carbon atom, a secondary carbon atom, a tertiary carbon atom, a quaternary carbon atom, or a combination thereof. Phrases containing this term, for example, "C1-C20" hydrocarbyl, include but are not limited to C1-C20 saturated alkane groups and C2-C20 unsaturated alkane groups, which may be unsubstituted or substituted with functional groups.

[0053] In this application, unless otherwise specified, the term "halogen ion" refers to F - 、Cl - Br - or I - .

[0054] In this application, unless otherwise specified, the term "amino" refers to a derivative of amino having the structural characteristics of the formula -N(X)2, wherein each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, etc. Non-limiting types of amino groups include -NH2, -N(alkyl)2, -NH(alkyl), -N(cycloalkyl)2, -NH(cycloalkyl), -N(heterocyclyl), -NH(heterocyclyl), -N(aryl), -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclyl), -N(cycloalkyl)(heterocyclyl), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0055] The stability and service life of photovoltaic devices, such as perovskite cells, are affected by a variety of factors. Firstly, the stability of photovoltaic devices is closely related to their metal electrodes. Specifically, the decomposition of the perovskite component is inevitable in photovoltaic devices such as perovskite cells. Decomposition products, such as hydrogen halide and halogen elements, can migrate to and react with the metal electrode, further accelerating the decomposition of the perovskite component and reducing the performance, stability, and service life of the device. Secondly, water and oxygen in the air can also damage the metal electrodes of photovoltaic devices, further shortening the device's stability and service life.

[0056] Based on this, in the first aspect, the present application provides a photovoltaic device comprising: a first electrode layer, a light absorbing layer, and a second electrode layer stacked in sequence, wherein at least one side of the second electrode layer is provided with a protective layer, and the protective layer contains a corrosion inhibitor, and the corrosion inhibitor includes a combination of one or more of imidazoline quaternary ammonium salt, phytic acid, tributylamine octanoate, and their derivatives.

[0057] It can be understood that in the above-mentioned photovoltaic device, a protective layer is provided on at least one side of the second electrode layer, which can be, as shown in Figure 1, a first protective layer 16 is provided on the side of the second electrode layer 17 relatively close to the light absorbing layer 14; or, as shown in Figure 2, a second protective layer 18 is provided on the side of the second electrode layer 17 relatively far from the light absorbing layer 14; or, as shown in Figure 3, a first protective layer 16 and a second protective layer 18 are provided on both sides of the second electrode layer 17.

[0058] The photovoltaic device provided by the present application is provided with the above-mentioned protective layer, and the corrosion inhibitor contained in the protective layer can form a dense film layer through the interaction with the second electrode. On the one hand, the protective film layer can block the reaction between the chemical components (such as perovskite components) in the light-absorbing layer and the second electrode, and reduce the decomposition of the chemical components caused by the reaction with the second electrode. On the other hand, the film layer can also block the corrosion of the second electrode caused by water oxygen in the air, and improve the photoelectric conversion efficiency, stability and service life of the photovoltaic device.

[0059] It can be understood that in the first protective layer and the second protective layer, the types of corrosion inhibitors can be the same or different.

[0060] In some embodiments, the second electrode layer is a metal electrode layer.

[0061] In some embodiments, a first protective layer is provided between the light-absorbing layer and the second electrode layer, and the thickness of the first protective layer is 0 < d1 ≤ 5 nm. For example, d1 can be 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm or within the range composed of any of the above values. Optionally, the thickness of the first protective layer is 1 nm ≤ d1 ≤ 3 nm.

[0062] When the thickness of the first protective layer is within the above range, it can not only inhibit the decomposition of the chemical components (such as perovskite components) in the light-absorbing layer, but also does not affect the transport of carriers.

[0063] In some embodiments, a second protective layer is further provided on the side of the second electrode layer relatively far from the light-absorbing layer, and the thickness of the second protective layer is d2, 0 < d2 ≤ 15 nm. For example, d2 can be 0.5 nm, 1 nm, 3 nm, 5 nm, 7 nm, 9 nm, 11 nm, 13 nm, 15 nm or within the range composed of any of the above values. Optionally, the thickness of the second protective layer is 1 nm ≤ d2 ≤ 10 nm.

[0064] When the thickness of the second protective layer is within the above range, it can not only effectively block and isolate water oxygen in the air, but also does not affect the normal performance of the photovoltaic device.

[0065] In some embodiments, as shown in FIG. 1, the photovoltaic device further includes at least one of a first charge transport layer 13 and a second charge transport layer 15. The first charge transport layer 13 is provided between the first electrode layer 12 and the light-absorbing layer 14, and the second charge transport layer 15 is provided between the light-absorbing layer 14 and the first protective layer 16.

[0066] In some embodiments, the photovoltaic device may include a device containing a metal electrode, such as a perovskite cell, a silicon-based solar cell, and a light-emitting diode. Optionally, the photovoltaic device includes a perovskite cell.

[0067] The following will take perovskite cells as an example to explain photovoltaic devices in detail.

[0068] In some embodiments, when the photovoltaic device is a perovskite cell and a first protective layer is disposed on the side of the second electrode layer relatively close to the light-absorbing layer, the corrosion inhibitor contained in the first protective layer can form a dense film through interaction with the second electrode. This film can block the reaction between the perovskite component in the light-absorbing layer and the second electrode, reducing the decomposition of the perovskite component due to the reaction with the second electrode. It can also inhibit the migration of halogen ions in the light-absorbing layer to the second electrode layer, reducing electrochemical corrosion of the second electrode layer in a halogen environment, thereby improving the photoelectric conversion efficiency, stability, and service life of the photovoltaic device.

[0069] In some embodiments, when the photovoltaic device is a perovskite cell and a second protective layer is disposed on a side of the second electrode layer relatively remote from the light-absorbing layer, the corrosion inhibitor contained in the second protective layer can be adsorbed on the surface of the second electrode through interaction with the second electrode, forming a dense film. This film can prevent corrosion of the second electrode caused by water and oxygen in the air, thereby extending the service life of the photovoltaic device.

[0070] In some embodiments, when the photovoltaic device is a perovskite cell and a first protective layer and a second protective layer are provided on both sides of the second electrode layer, the corrosion inhibitor contained in the first protective layer can form a dense film layer through interaction with the second electrode. This film layer can block the reaction between the perovskite component in the light-absorbing layer and the second electrode, reducing the decomposition of the perovskite component due to the reaction with the second electrode; it can also inhibit the migration of halogen ions in the light-absorbing layer to the second electrode layer, reducing the electrochemical corrosion of the second electrode layer in a halogen environment, and improving the photoelectric conversion efficiency, stability, and service life of the photovoltaic device. At the same time, the corrosion inhibitor contained in the second protective layer can be adsorbed on the surface of the second electrode through interaction with the second electrode, forming a dense film layer. This film layer can block corrosion of the second electrode caused by water and oxygen in the air, thereby further improving the service life of the photovoltaic device.

[0071] In some embodiments, when the photovoltaic device is a perovskite cell, one of the "first electrode layer" and the "second electrode layer" is a transparent electrode layer, and the other is a metal electrode layer.

[0072] In some embodiments, when the photovoltaic device is a perovskite cell, the first electrode layer is a transparent electrode layer, the second electrode layer is a metal electrode layer, and the light absorbing layer is a perovskite layer.

[0073] It can be understood that of the two electrodes of the perovskite battery, one serves as a positive electrode, which can collect electron carriers transmitted via the electron transport layer, and the other serves as a negative electrode, which can collect hole carriers transmitted via the hole transport layer.

[0074] In some embodiments, the transparent electrode layer is an anode layer, which collects holes and can conduct photogenerated carriers. While conducting electricity, it can also filter out ultraviolet light that is destructive to the perovskite layer.

[0075] In some embodiments, the transparent electrode layer may include at least one of 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).

[0076] In some embodiments, the transparent electrode layer has a thickness of 200 nm to 1000 nm. For example, the transparent conductive layer may have a thickness of 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range thereof.

[0077] In some embodiments, the metal electrode layer is a cathode layer, which has the function of collecting free electrons.

[0078] In some embodiments, the metal electrode layer is generally an organic or inorganic or organic-inorganic hybrid conductive material, including at least one of indium tin oxide (ITO), lanthanide metal-doped indium oxide, boron-doped zinc oxide (BZO), aluminum zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), indium tungsten oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and alloys thereof, graphite, graphene, and carbon nanotubes; optionally, Ag, Cu, C, Au, Al, ITO, AZO, BZO, or IZO, and further optionally, Cu, Ag, Au, or a combination thereof.

[0079] In some embodiments, the thickness of the metal electrode layer is 20 nm to 200 nm. For example, the thickness of the back electrode layer can be 20 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, or any range thereof.

[0080] In some embodiments, when the corrosion inhibitor includes an imidazoline quaternary ammonium salt, the imidazoline quaternary ammonium salt has a structure shown in formula (1),

[0081] In formula (1), R1, R2 and R3 are each independently a hydrogen atom, an unsubstituted C 1-20 A hydrocarbon group or a hydrocarbon group substituted by at least one R4, each R4 includes: a combination of one or more of a thiourea group, an amino group and a hydroxyl group, and R includes one of a halogen ion and an acid radical ion; optionally, the acid radical ion includes HSO4 - HCOO - 、CH3COO - and CN - A combination of one or more of .

[0082] It is understood that the above “unsubstituted C 1-20 "Hydrocarbon" refers to C 1-20 The hydrogen atoms in the hydrocarbon group are not replaced by other functional groups, that is, the hydrocarbon group does not contain other substituted functional groups except carbon atoms and hydrogen atoms; "hydrocarbon group substituted by at least one R4" refers to C 1-20 In the hydrocarbon group, at least one hydrogen atom is replaced by other functional groups.

[0083] It is understood that the above-mentioned "thiourea group" refers to "Hydroxyl" refers to "-OH"; "amino" can be a primary amino group (-NH2) or a secondary amino group (>NH).

[0084] The above-mentioned imidazoline quaternary ammonium salt provided by the present application, when interacting with the metal electrode as the second electrode, can provide electrons to the empty d orbital of the metal, and can also accept the d electrons of the metal with the anti-bonding orbital. When the imidazoline quaternary ammonium salt approaches the surface of the metal electrode, the π bond on the imidazoline ring will have π electrons enter the empty d orbital of the metal, and the anti-π orbital (π*) can accept the electrons in the d orbital of the metal to form a feedback bond, thereby generating a chemical adsorption effect and forming a dense protective layer on the surface of the metal. At the same time, the R groups (R1, R2 and R3) on the imidazoline ring can stretch to the metal surface to form a hydrophobic protective layer, thereby enhancing the barrier isolation ability of the perovskite battery to water and oxygen in the air. In addition, the N + The strong adsorption effect on metal surfaces makes it difficult for hydrogen ions from the hydrogen halide contained in the perovskite layer to migrate to the metal surface when quaternary ammonium cations adsorb on the negatively charged metal surface. This reduces the reaction rate between the hydrohalic acid and the metal electrode at the cathode of the perovskite cell, thereby improving the cell's photoelectric conversion efficiency. Furthermore, the strong adsorption of imidazoline quaternary ammonium salt corrosion inhibitors on metal surfaces can reduce the problem of metal electrodes in perovskite cells easily falling off during use.

[0085] In some embodiments, the imidazoline quaternary ammonium salt includes a combination of one or more of 2-aminoethyl heptadecenyl imidazoline quaternary ammonium salt, thiourea imidazoline quaternary ammonium salt, 2-undecyl imidazoline quaternary ammonium salt, heptadecenylaminoethyl imidazoline quaternary ammonium salt and heptadecenyl hydroxyethyl imidazoline quaternary ammonium salt, and can be thiourea imidazoline quaternary ammonium salt.

[0086] The above-mentioned thiourea-based imidazoline quaternary ammonium salt provided in the present application, because the sulfur atom on its thiourea group can form a coordination bond with the empty metal orbital in the metal electrode, thereby making the formed protective layer denser, which is beneficial to further enhance the inhibitory effect of the protective layer on the migration of halogen ions and the blocking and isolation effect on water and oxygen in the air, thereby further improving the photoelectric conversion efficiency, stability and service life of the perovskite battery.

[0087] In some embodiments, when the corrosion inhibitor includes phytic acid, the structure of the phytic acid is shown in the following formula (2):

[0088] As can be seen from formula (2), the phytic acid molecule has 24 oxygen atoms, 9 hydroxyl groups, and 6 phosphate groups that can complex with metals, and contains dissociable hydrogen ions. Therefore, phytic acid is a metal multidentate chelating agent. It can complex with the metal in the metal electrode layer, easily forming multiple chelate rings. The resulting complex is highly stable. The phytate ion has a strong complexing ability for the metal, and the formed complex can form a protective film on the surface of the metal electrode layer, thereby inhibiting metal corrosion. In addition, due to the large number of polar groups in the phytic acid molecule, it is easier to provide electrons, which enhances its chemical adsorption and can further improve its corrosion inhibition effect, thereby further enhancing its protective effect on the metal electrode layer, and thus improving the photoelectric conversion efficiency and stability of the perovskite battery.

[0089] In some embodiments, when the corrosion inhibitor includes tributylamine octanoate and its derivatives, the molecular formula of tributylamine octanoate is shown in the following formula (3):

[0090] Tributylamine octanoate and its derivatives are vapor-phase corrosion inhibitors that can first hydrolyze or dissociate in a humid environment (such as a water-oxygen environment) to separate groups with corrosion-inhibiting effects (such as hydroxyl groups), which then adhere to the surface of the metal electrode layer to inhibit corrosion and inhibit the corrosion of the metal electrode layer by water and oxygen in the air, thereby improving the photoelectric conversion efficiency and stability of the perovskite battery.

[0091] In some embodiments, as shown in FIG4 , the perovskite cell may include a substrate layer 11 , a first electrode layer 12 , a first charge transport layer 13 , a perovskite layer 14 ′, a second charge transport layer 15 , a first protective layer 16 and a second electrode layer 17 stacked in sequence.

[0092] In some embodiments, as shown in FIG5 , the perovskite cell may include a substrate layer 11 , a first electrode layer 12 , a first charge transport layer 13 , a perovskite layer 14 ′, a second charge transport layer 15 , a second electrode layer 17 and a second protective layer 18 stacked in sequence.

[0093] In some embodiments, as shown in FIG6 , the perovskite cell may include a substrate layer 11 , a first electrode layer 12 , a first charge transport layer 13 , a perovskite layer 14 ′, a second charge transport layer 15 , a first protective layer 16 , a second electrode layer 17 and a second protective layer 18 , which are stacked in sequence.

[0094] In some embodiments, one of the "first charge transport layer" and the "second charge transport layer" is an electron transport layer and the other is a hole transport layer. In some embodiments, the first charge transport layer is an electron transport layer. In some embodiments, the first charge transport layer is a hole transport layer.

[0095] The electron transport layer can extract and transport electron carriers and block the passage of free holes.

[0096] The hole transport layer can extract and transport hole carriers and block the passage of free electrons.

[0097] In some embodiments, the perovskite cell is any one of an inverted pin cell and a formal nip cell.

[0098] The perovskite cells provided in this application may include formal and trans types.

[0099] In some embodiments, the first charge transport layer comprises an electron transport layer, and the second charge transport layer comprises a hole transport layer, and the perovskite cell corresponds to a formal (nip) perovskite cell.

[0100] In some embodiments, the first charge transport layer comprises a hole transport layer and the second charge transport layer comprises an electron transport layer, and the perovskite cell corresponds to an inverted (pin) perovskite cell.

[0101] In some embodiments, the first charge transport layer has a thickness of 10 nm to 100 nm. For example, the first charge transport layer has a thickness of 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or any range thereof.

[0102] In some embodiments, the second charge transport layer has a thickness of 10 nm to 100 nm. For example, the second charge transport layer has a thickness of 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or any range thereof.

[0103] In some embodiments, the material of the electron transport layer may include 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 with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT- OMeTPA), N-(4-phenylamino)carbazole-spirobifluorene (CzPAF-SBF), [6,6]-phenyl-C61-butyric acid isomethyl ester (PCBM), polythiophene, metal oxides, silicon oxide (SiO2), tin oxide (SnO2), strontium titanate (SrTiO3), cuprous thiocyanate (CuSCN), etc.; wherein the metal element can include one of Mg, Ni, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr, Sr, Ga, and Cr to obtain a plurality of them.

[0104] In some embodiments, the material of the hole transport layer may include at least one of the following materials and their derivatives: 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro- OMeTAD), polytriarylamine (PTAA), NiOx, poly 3,4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT:PSS), Me-4PACz, MeO-2PACz, WO3, BTPA series hole transport materials, poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA), 2,2',7,7'-tetrakis [N,N-di (4-methoxyphenyl) amino] -9,9'-spirobifluorene (Spiro-OMeTAD), poly-3-hexylthiophene (P3HT), triphenylamine with triptycene as the core (H101), 3,4-ethylenedioxythiophene-methoxytriphenylamine (EDOT-OMeTPA), N-(4-phenylamino) carbazole-spirobifluorene (CzPAF-SBF), polythiophene, molybdenum oxide (MoO3), cuprous iodide (CuI), cuprous oxide (CuO), etc.

[0105] In some embodiments, the perovskite layer has a thickness of 400 nm to 1000 nm. For example, the perovskite layer can have a thickness of 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, or any range thereof. Alternatively, the perovskite layer has a thickness of 500 nm to 900 nm.

[0106] In some embodiments, the perovskite layer has a band gap of 1.20 eV to 2.30 eV.

[0107] In some embodiments, the perovskite 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.

[0108] In some embodiments, A includes Cs + , K + , Rb + , one or more of monovalent amine cations and monovalent amidino 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 + ).

[0109] 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 .

[0110] In some embodiments, X comprises I - Br - and Cl - One or more of .

[0111] In some embodiments, X comprises I - Br - One or two of X can be 1 - Br - Or a combination thereof. In some embodiments, X is 1 - .

[0112] As the light-absorbing layer in the perovskite battery, when the perovskite battery is working, after the perovskite layer is exposed to light, the internal electrons gain energy and break free from the constraints of the perovskite layer to form negatively charged electron carriers, while also forming positively charged hole carriers, thereby obtaining electron-hole pairs. The free electrons and free holes are transmitted in opposite directions through the corresponding transport layer, causing the electrons and holes to flow, forming an external current and realizing the conversion of light energy into electrical energy. Furthermore, 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 a photocurrent in the perovskite battery circuit.

[0113] In some embodiments, the substrate layer serves as a support for the battery, and its light transmittance and strength need to meet the requirements of the perovskite battery. The substrate layer may be, but is not limited to, a glass substrate or a flexible substrate.

[0114] In some embodiments, the substrate layer is a flexible substrate layer. Furthermore, the substrate layer may be made of, for example (but not limited to), an organic polymer material, and may be made of one or more of the following materials mixed in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), and the like.

[0115] In some embodiments, the thickness of the base layer is 0.5 mm to 5 mm. For example, the thickness of the base layer can be 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, or any range thereof.

[0116] In this application, the thickness of each layer in a photovoltaic device has a meaning commonly known in the art and can be measured using methods known in the art, for example, using a step profiler test method.

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

[0118] It is understood that the structure of the perovskite cell involved in this application may not be limited to the structural layers listed above. Other functional layers, such as buffer layers, may also be introduced as needed. In some embodiments, the perovskite cell may be provided with a buffer layer with a suitable energy level, which may play one or more roles in reducing the energy level barrier, promoting energy level matching, improving carrier extraction efficiency, passivating interface defect states, protecting the light absorption layer, inhibiting water molecules and oxygen from oxidative decomposition of the cell, improving photoelectric conversion efficiency, and improving the stability of the perovskite cell. Depending on the location of the buffer layer, the types of buffer layers may include four types: 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. Materials that can be used for the buffer layer in the perovskite cell may include, but are not limited to: Cu2O, NiO, AZO, TiO2, etc.

[0119] In a second aspect, the present application provides a method for preparing the photovoltaic device described in the first aspect of the present application, which may include the following steps:

[0120] S10, preparing a first electrode layer, a light absorbing layer, and a second electrode layer; and

[0121] S20. Preparing a protective layer on at least one side of the second electrode layer to obtain the photovoltaic device, wherein the protective layer contains a corrosion inhibitor, and the corrosion inhibitor includes a combination of one or more of imidazoline quaternary ammonium salt, phytic acid, tributylamine octanoate, and derivatives thereof.

[0122] The above-mentioned method provided by the present application, by preparing a protective layer containing a corrosion inhibitor on at least one side of the second electrode layer, can block the reaction between the chemical components (such as perovskite components) in the light-absorbing layer and the second electrode, reducing the decomposition of the chemical components (such as perovskite components) due to the reaction between the second electrode; at the same time, it can also inhibit the migration of chemical components (such as halogen ions) in the light-absorbing layer to the second electrode layer, reducing the electrochemical corrosion of the second electrode layer, and improving the photoelectric conversion efficiency, stability and service life of the photovoltaic device. In addition, the protective layer can also prevent corrosion of the second electrode caused by water and oxygen in the air, thereby further improving the service life of the photovoltaic device.

[0123] In some embodiments, when the corrosion inhibitor includes an imidazoline quaternary ammonium salt, the imidazoline quaternary ammonium salt has a structure shown in formula (1),

[0124] In formula (1), R1, R2 and R3 are each independently a hydrogen atom, an unsubstituted C 1-20 or a hydrocarbon group substituted by at least one R4, each R4 independently comprising: a combination of one or more of a thiourea group, an amino group, and a hydroxyl group, R - Includes one of halogen ions and acid radical ions.

[0125] Optionally, the acid ions include HSO4 - HCOO - 、CH3COO - and CN - A combination of one or more of .

[0126] Above-mentioned imidazoline quaternary ammonium salt can interact with the metal electrode as the second electrode, can provide electrons to the empty d orbital of metal, can accept the d electrons of metal with anti-bonding orbital again.When imidazoline quaternary ammonium salt approaches the metal electrode surface, the π bond on the imidazoline ring, just has π electrons to enter the empty d orbital of metal, and anti-π orbital (π*) can accept the electron formation feedback bond in the d orbital of metal again, thereby produces chemical adsorption, and forms a dense protective layer on the surface of metal.Simultaneously, the R base (R1, R2 and R3) on the imidazoline ring can stretch to the metal surface again and form a hydrophobic protective layer, strengthen the blocking isolation ability of photovoltaic device to water oxygen in air, and promote the photoelectric conversion efficiency, stability and the service life of photovoltaic device.

[0127] In some embodiments, the imidazoline quaternary ammonium salt includes a combination of one or more of 2-aminoethyl heptadecenyl imidazoline quaternary ammonium salt, thiourea imidazoline quaternary ammonium salt, 2-undecyl imidazoline quaternary ammonium salt, heptadecenylaminoethyl imidazoline quaternary ammonium salt and heptadecenyl hydroxyethyl imidazoline quaternary ammonium salt, and can be thiourea imidazoline quaternary ammonium salt.

[0128] In some embodiments, when the corrosion inhibitor includes phytic acid, the structure of the phytic acid is shown in the following formula (2):

[0129] As shown in formula (2), the phytic acid molecule has 24 oxygen atoms, 9 hydroxyl groups, and 6 phosphate groups that can complex with metals, and contains dissociable hydrogen ions. Therefore, phytic acid is a metal multidentate chelating agent. It can complex with the metal in the metal electrode layer, easily forming multiple chelate rings. The resulting complex is highly stable. The phytate ion has a strong complexing ability for the metal, and the formed complex can form a protective film on the surface of the metal electrode layer, thereby inhibiting metal corrosion. In addition, due to the large number of polar groups in the phytic acid molecule, it is easier to provide electrons, which enhances its chemical adsorption and further improves its corrosion inhibition effect, thereby further enhancing the protective effect on the metal electrode layer, and thus improving the photoelectric conversion efficiency and stability of the photovoltaic device.

[0130] In some embodiments, when the corrosion inhibitor includes tributylamine octanoate and its derivatives, the molecular formula of tributylamine octanoate is shown in the following formula (3):

[0131] Tributylamine octanoate and its derivatives are vapor-phase corrosion inhibitors that can first hydrolyze or dissociate in a humid environment (such as a water-oxygen environment) to separate groups with corrosion-inhibiting effects (such as hydroxyl groups), which then adhere to the surface of the metal electrode layer to inhibit corrosion and suppress the corrosion of the metal electrode layer by water and oxygen in the air, thereby improving the photoelectric conversion efficiency and stability of photovoltaic devices.

[0132] In some embodiments, the solution used to prepare the protective layer contains the corrosion inhibitor, and the mass concentration of the corrosion inhibitor in the solution is 0.1 mg / ml to 10 mg / ml. For example, the concentration of the corrosion inhibitor in the solution can be 0.1 mg / ml, 0.3 mg / ml, 0.5 mg / ml, 0.7 mg / ml, 1 mg / ml, 3 mg / ml, 5 mg / ml, 7 mg / ml, 9 mg / ml, 10 mg / ml, or within a range consisting of any of the above values. Alternatively, the mass concentration of the corrosion inhibitor in the solution is 0.5 mg / ml to 5 mg / ml.

[0133] The concentration of the corrosion inhibitor in the solution is within the above range, which is beneficial to further promote the role of the protective layer in photovoltaic devices in improving the photoelectric conversion efficiency, stability and service life of the battery.

[0134] In some embodiments, the solution used to prepare the protective layer comprises an organic solvent, and the organic solvent comprises an alcohol organic solvent. Alternatively, the alcohol organic solvent comprises methanol, ethanol, propanol, isopropanol, or a combination thereof.

[0135] In some embodiments, when the photovoltaic device is a perovskite cell, the method for preparing the perovskite cell may further include the following steps:

[0136] S100, etching and cleaning the transparent conductive glass substrate, and drying it for later use;

[0137] S200, preparing a first charge transport layer on a transparent conductive glass substrate;

[0138] S300, preparing a perovskite layer on the first charge transport layer;

[0139] S400, preparing a second charge transport layer on the perovskite layer;

[0140] S500, preparing a first protective layer on the second charge transport layer;

[0141] S600, preparing a metal electrode layer on the first protective layer;

[0142] S700 , protecting the metal electrode test site, preparing a second protective layer on the metal electrode layer, and obtaining a perovskite battery.

[0143] It is understandable that the serial numbers of the above steps are merely an exemplary description of the method for preparing a perovskite cell and do not necessarily limit the order of the steps.

[0144] In a third aspect, the present application provides an electrical device, which includes the photovoltaic device described in the first aspect of the present application or the photovoltaic device manufactured by the method described in the second aspect of the present application.

[0145] In some embodiments, the photovoltaic device can be used as a power generation device for an electrical device. The type of power generation device can include, but is not limited to, an integrated power generation device. The location of the power generation device can include, but is not limited to, the roof or back panel of a vehicle.

[0146] 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.

[0147] Figure 7 shows an example of an electric device, which is a car, and can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.

[0148] As another example, the electric device may be a mobile phone, a tablet computer, a laptop computer, a calculator, etc.

[0149] As another example, the power-consuming device may be a wearable device, such as a watch.

[0150] Example

[0151] Below, some embodiments of the present application are described. The embodiment described below is exemplary, is only used to explain the present application, and cannot be construed as limiting the present application. In the embodiment, if no technology or conditions are indicated, it is 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. Reagents used or instruments that are not indicated by the manufacturer are conventional products that can be obtained commercially, or can be synthesized in a conventional manner by commercially available products.

[0152] In the following embodiments, "room temperature" refers to 20°C to 30°C, and further, may be 25°C.

[0153] Example 1

[0154] The formal perovskite cell includes a stacked transparent conductive glass substrate, an electron transport layer, a perovskite layer, a hole transport layer, a first protective layer, a metal electrode layer, and a second protective layer. The preparation method is as follows:

[0155] (1) Preparation of transparent conductive glass substrate: Specifications: 2.0 × 2.0 cm 2The FTO glass was prepared, and 0.35 cm of FTO was removed from both ends by laser etching to expose the glass substrate; the etched FTO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropyl alcohol, and then blown dry with nitrogen for use as a transparent conductive glass substrate.

[0156] (2) Preparation of electron transport layer: The transparent conductive glass substrate was treated with UV ozone, and then a SnO2 colloidal solution was spin-coated on the transparent conductive glass substrate at a rate of 4000 rpm / s and annealed on a hot plate at 150°C for 10 minutes to serve as the electron transport layer.

[0157] (3) Preparation of perovskite layer: The perovskite layer was prepared by a one-step method. The perovskite precursor solution was spin-coated on the electron transport layer at a speed of 3000-5000 rpm for 20-40 s. 300-600 μL of anti-solvent was added about 10 s after the start of spin coating. The film was then placed on a hot plate and annealed at 100-120 °C for 60 min to obtain a perovskite layer with a thickness of 500 nm.

[0158] The perovskite precursor solution is obtained by dissolving 116.91 mg of cesium iodide, 94.19 mg of methylamine chloride, 1440.94 mg of formamidine iodine, 4356.54 mg of lead iodide, 66.06 mg of lead bromide and 111.97 mg of methylamine bromide in 6 mL of a mixed solvent of DMF and DMSO, wherein the volume ratio of DMF to DMSO is 4:1, and the anti-solvent is anisole.

[0159] (4) Preparation of hole transport layer: Prepare 72 mg / ml chlorobenzene solution of Spiro-OMeTAD, a hole transport material, and stir to completely dissolve it. Take 100 μL and spin-coat it on the surface of the perovskite layer at a speed of 4000 rpm to obtain a hole transport layer with a thickness of about 170 nm.

[0160] (5) Preparation of the first protective layer: A 0.5 mg / ml isopropyl alcohol solution of thiourea imidazoline quaternary ammonium salt was prepared and stirred to completely dissolve, and then spin-coated on the surface of the hole transport layer at a speed of 4000 rpm to obtain a first protective layer with a thickness of 3 nm.

[0161] (6) Preparation of metal electrode layer: Place the film with the first protective layer into the evaporation apparatus and wait until the evaporation vacuum reaches 5×10 -4 Pa, and 80nm of Cu metal electrode was evaporated at a rate of 0.1A / s.

[0162] (7) Preparation of the second protective layer: Pre-protect the metal electrode test site, then prepare an isopropanol solution of thiourea imidazoline quaternary ammonium salt with a concentration of 5 mg / ml, stir to completely dissolve it, and then spin-coat it on the metal electrode surface at a speed of 4000 rpm to obtain a second protective layer with a thickness of 10 nm, and obtain a formal perovskite cell.

[0163] Example 2

[0164] The inverse perovskite cell includes a stacked transparent conductive glass substrate, a hole transport layer, a perovskite layer, an electron transport layer, a first protective layer, a metal electrode layer, and a second protective layer. The preparation method is as follows:

[0165] (1) Preparation of transparent conductive glass substrate: Specifications: 2.0 × 2.0 cm 2 The FTO glass was removed by laser etching at both ends of 0.35 cm of FTO to expose the glass substrate; the etched FTO conductive glass was ultrasonically cleaned several times with water, acetone, and isopropyl alcohol in sequence, and then blown dry with nitrogen for use as a transparent conductive glass substrate.

[0166] (2) Preparation of hole transport layer: The transparent conductive glass substrate was treated with UV ozone, and then NiOx with a thickness of about 20 to 50 nm was magnetron sputtered and annealed at 300°C for 60 min to obtain a hole transport layer.

[0167] (3) Preparation of perovskite layer: The perovskite light absorption layer was prepared by a one-step method. The perovskite precursor solution was spin-coated on the hole transport layer at a speed of 3000-5000 rpm for 20-40 seconds. 300-600 μL of anti-solvent was added about 10 seconds after the start of spin coating. The film was then placed on a hot plate and annealed at 100-120°C for 60 minutes to obtain a perovskite layer with a thickness of 500 nm.

[0168] The perovskite precursor solution is obtained by dissolving 116.91 mg of cesium iodide, 94.19 mg of methylamine chloride, 1440.94 mg of formamidine iodine, 4356.54 mg of lead iodide, 66.06 mg of lead bromide and 111.97 mg of methylamine bromide in 6 mL of a mixed solvent of DMF and DMSO, wherein the volume ratio of DMF to DMSO is 4:1, and the anti-solvent is anisole.

[0169] (4) Preparation of electron transport layer: Place the film with the perovskite layer into the evaporation apparatus and wait until the evaporation vacuum reaches 5×10 -4 Pa below, 30nm electron transport layer C was evaporated at a rate of 0.05A / s 60 .

[0170] (5) Preparation of the first protective layer: A 0.5 mg / ml isopropanol solution of thiourea imidazoline quaternary ammonium salt was prepared and stirred to completely dissolve, and then spin-coated on the surface of the electron transport layer at a speed of 4000 rpm to obtain a first protective layer with a thickness of 3 nm.

[0171] (6) Preparation of metal electrode layer: Place the film with the first protective layer into the evaporation apparatus and wait until the evaporation vacuum reaches 5×10 -4 Pa, and 80nm of Cu metal electrode was evaporated at a rate of 0.1A / s.

[0172] (7) Preparation of the second protective layer: Pre-protect the metal electrode test site, then prepare an isopropanol solution of thiourea imidazoline quaternary ammonium salt with a concentration of 5 mg / ml, stir to completely dissolve it, and then spin-coat it on the metal electrode surface at a speed of 4000 rpm to obtain a second protective layer with a thickness of 10 nm, thereby obtaining an inverse perovskite battery.

[0173] Examples 3 to 26

[0174] The same technical solution as in Example 1 is adopted, except for the relevant parameters of the first protective layer and the second protective layer in the perovskite battery, which can be found in Table 1.

[0175] Comparative Example 1

[0176] A technical solution substantially the same as that of Example 1 is adopted, except that steps (5) and (7) are omitted, i.e., no protective layer is provided in the perovskite cell.

[0177] Comparative Example 2

[0178] A technical solution substantially the same as that of Example 2 is adopted, except that steps (5) and (7) are omitted, i.e., no protective layer is provided in the perovskite cell.

[0179] Comparative Example 3

[0180] The same technical scheme as that of Example 1 was adopted, except that in steps (5) and (7), benzotriazole of equal mass was used to replace thiourea imidazoline quaternary ammonium salt.

[0181] Comparative Example 4

[0182] The same technical scheme as Example 24 was adopted, except that in steps (5) and (7), thiourea-based imidazoline quaternary ammonium salt was replaced by benzotriazole of equal mass.

[0183] Comparative Example 5

[0184] The same technical scheme as Example 25 is adopted, except that in steps (5) and (7), thiourea-based imidazoline quaternary ammonium salt is replaced by an equal mass of benzotriazole.

[0185] Table 1

[0186] In addition, the perovskite cells obtained in the above Examples 1 to 26 and Comparative Examples 1 to 5 were subjected to relevant performance tests, and the test results are shown in Table 2 below.

[0187] Test section

[0188] (1) Photoelectric conversion efficiency test

[0189] At room temperature and pressure, the sunlight simulation light source is AM1.5G standard light source (AM 1.5G, 100mW / cm 2 ), a four-channel digital source meter (Keithley 2440) was used to measure the volt-ampere characteristic curve of the component under light illumination to obtain the open circuit voltage Voc, short circuit current density Jsc, and fill factor FF (Fill Factor) of the component, thereby obtaining the photoelectric conversion efficiency PCE (Efficiency) of the component.

[0190] “Normal temperature and pressure” means: normal pressure refers to a temperature of 25°C and a pressure of one atmosphere; normal temperature refers to 20°C to 30°C, and can further be 25°C.

[0191] (2) Stability test

[0192] The perovskite cell was placed at 25°C and 100 mW / cm 2 The cell is continuously exposed to a light source and its photoelectric conversion efficiency is tracked as it changes with aging time. The time required for the photoelectric conversion efficiency to decay to 80% of the initial efficiency is recorded as T80. The size of this parameter represents the stability of the perovskite cell.

[0193] Table 2

[0194] In Tables 1 and 2 above, by comparing Example 1 and Examples 3 to 26 with Comparative Example 1, and by comparing Example 2 with Comparative Example 2, it can be seen that the photoelectric conversion efficiency and stability of the perovskite cells in Comparative Example 1 and Comparative Example 2 without a protective layer are significantly lower than those of the corresponding examples, indicating that the provision of a protective layer can improve the photoelectric conversion efficiency and stability of the cell, thereby increasing the service life of the cell.

[0195] Comparing Examples 1 to 22 and Examples 25 to 26 with Comparative Example 3, comparing Example 23 with Comparative Example 4, and comparing Example 24 with Comparative Example 5, it can be seen that when benzotriazole is used instead of the corrosion inhibitor in the present application to prepare the protective layer, the photoelectric conversion efficiency and stability of the obtained perovskite battery are lower than those of the corresponding examples, indicating that the protective layer containing the corrosion inhibitor provided in the present application can further improve the photoelectric conversion efficiency and stability of the battery, thereby improving the service life of the battery.

[0196] 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.

[0197] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and within the scope of the technical solution of the present application, embodiments that have substantially the same structure as the technical idea and exert 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 their descriptions are relatively detailed, but they cannot be understood as limiting the scope of the patent. In addition, without departing from the scope of the subject matter of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of constructing by combining 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 modifications and improvements can be made, which all fall within the scope of protection of the present application. Therefore, the scope of protection of the present application shall be based on the attached claims, and the description and drawings may be used to explain the content of the claims.

Claims

1. A photovoltaic device, include: A first electrode layer, a light absorbing layer, and a second electrode layer are stacked in sequence, wherein at least one side of the second electrode layer is provided with a protective layer, the protective layer contains a corrosion inhibitor, and the corrosion inhibitor includes a combination of one or more of imidazoline quaternary ammonium salt, phytic acid, tributylamine octanoate and its derivatives.

2. The photovoltaic device according to claim 1, in, The imidazoline quaternary ammonium salt has a structure shown in formula (1), In formula (1), R 1 , R 2 and R 3 Each independently includes hydrogen atoms, unsubstituted C 1-20 or at least one R 4 Substituted hydrocarbon groups, each R 4 A combination of one or more of a thiourea group, an amine group and a hydroxyl group, R - including one of a halogen ion and an acid radical ion; Optionally, the acid ion includes HSO 4 - HCOO - , CH 3 COO - and CN - A combination of one or more of .

3. The photovoltaic device according to claim 1 or 2, in, The imidazoline quaternary ammonium salt includes one or more combinations of 2-aminoethyl heptadecenyl imidazoline quaternary ammonium salt, thiourea imidazoline quaternary ammonium salt, 2-undecyl imidazoline quaternary ammonium salt, heptadecenylaminoethyl imidazoline quaternary ammonium salt and heptadecenyl hydroxyethyl imidazoline quaternary ammonium salt, and can be thiourea imidazoline quaternary ammonium salt.

4. The photovoltaic device according to any one of claims 1 to 3, in, A first protective layer is provided between the light absorbing layer and the second electrode layer, and the thickness of the first protective layer is 0 <d 1 ≤5nm, optional 1nm≤d 1 ≤3nm.

5. The photovoltaic device according to any one of claims 1 to 4, in, A second protective layer is provided on the side of the second electrode layer relatively far from the light absorbing layer, and the thickness of the second protective layer is d 2 , 0 <d 2 ≤15nm, optional 1nm≤d 2 ≤10nm.

6. The photovoltaic device according to claim 4 or 5, in, It also includes at least one of a first charge transport layer and a second charge transport layer, wherein the first charge transport layer is arranged between the first electrode layer and the light absorbing layer, and the second charge transport layer is arranged between the light absorbing layer and the first protective layer.

7. The photovoltaic device according to any one of claims 1 to 6, in, The second electrode layer is a metal electrode layer.

8. The photovoltaic device according to any one of claims 1 to 7, in, The photovoltaic device includes a perovskite cell.

9. The photovoltaic device according to claim 8, in, The first electrode layer is a transparent electrode layer, and the light absorbing layer is a perovskite layer.

10. A method for preparing a photovoltaic device, include: preparing a first electrode layer, a light absorbing layer, and a second electrode layer; and A protective layer is prepared on at least one side of the second electrode layer to obtain the photovoltaic device, wherein the protective layer contains a corrosion inhibitor, and the corrosion inhibitor includes a combination of one or more of imidazoline quaternary ammonium salt, phytic acid, tributylamine octanoate and derivatives thereof.

11. The method according to claim 10, in, The imidazoline quaternary ammonium salt has a structure shown in formula (1), In formula (1), R 1 , R 2 and R 3 Each independently includes hydrogen atoms, unsubstituted C 1-20 or at least one R 4 Substituted hydrocarbon groups, each R 4 A combination of one or more of a thiourea group, an amine group and a hydroxyl group, R - including one of a halogen ion and an acid radical ion; Optionally, the acid ion includes HSO 4 - HCOO - , CH 3 COO - and CN - A combination of one or more of .

12. The method according to claim 10 or 11, in, The imidazoline quaternary ammonium salt includes a combination of one or more of 2-aminoethyl heptadecenyl imidazoline quaternary ammonium salt, thiourea imidazoline quaternary ammonium salt, 2-undecyl imidazoline quaternary ammonium salt, heptadecenylaminoethyl imidazoline quaternary ammonium salt, and heptadecenyl hydroxyethyl imidazoline quaternary ammonium salt, and can be thiourea imidazoline quaternary ammonium salt.

13. The method according to any one of claims 10 to 12, in, The solution for preparing the protective layer contains the corrosion inhibitor, and the mass concentration of the corrosion inhibitor in the solution is 0.1 mg / ml to 10 mg / ml, and can be optionally 0.5 mg / ml to 5 mg / ml.

14. The method according to any one of claims 10 to 13, in, The solution for preparing the protective layer comprises an organic solvent, wherein the organic solvent comprises an alcohol organic solvent. Optionally, the alcohol organic solvent includes at least one of methanol, ethanol, propanol and isopropanol.

15. An electrical device, comprising the photovoltaic device according to any one of claims 1 to 9 or the photovoltaic device prepared by the method according to any one of claims 10 to 14.

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