Perovskite solar cell and preparation method, assembly, system and device thereof

Abstract

This application discloses a perovskite solar cell and its fabrication method, components, system, and apparatus, relating to the field of perovskite solar cell technology. The perovskite solar cell includes a first electrode, a perovskite light-absorbing layer, and a second electrode; wherein a first carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer, or between the perovskite light-absorbing layer and the second electrode; the first carrier transport layer includes an additive, which includes a coordinating group capable of binding to metal cations, the coordinating group including at least one of amino, piperazine, an alkyl group with at least one carbon atom substituted by an oxygen atom, and an alkyl group with at least one carbon atom substituted by a sulfur atom; the perovskite light-absorbing layer includes uncoordinated metal cations. The technical solution of this application improves the upper and lower interfaces of the first carrier transport layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

Description

Technical Field

[0001] This application relates to the field of perovskite solar cell technology, specifically to a perovskite solar cell and its fabrication method, components, system, and device. Background Technology

[0002] Perovskite solar cells are devices that convert light energy into electrical energy through the photoelectric effect or photochemical effect.

[0003] Incorporating a carrier transport layer in perovskite solar cells facilitates carrier migration, thereby improving the photoelectric conversion efficiency. However, with the widespread application of perovskite solar cells, higher demands are being placed on their photoelectric conversion efficiency. Summary of the Invention

[0004] This application is made in view of the above-mentioned problems, and its purpose is to provide a perovskite solar cell and its fabrication method, components, system, and apparatus. The aim is to improve the photoelectric conversion efficiency of perovskite solar cells.

[0005] To achieve the above objectives, in a first aspect, this application provides a perovskite solar cell, comprising a first electrode, a perovskite light-absorbing layer, and a second electrode; wherein a first carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer, or a first carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode; the first carrier transport layer comprises an additive, the additive comprising a coordinating group capable of binding to a metal cation, the coordinating group comprising at least one of amino, piperazine, an alkyl group in which at least one carbon atom is substituted by an oxygen atom, and an alkyl group in which at least one carbon atom is substituted by a sulfur atom; the perovskite light-absorbing layer comprises an uncoordinated metal cation, the uncoordinated metal cation comprising Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them.

[0006] By incorporating an additive containing coordinating groups into the charge carrier transport layer—coordinating groups containing negatively charged atoms such as N and O with lone pairs of electrons—it is possible for these groups to readily combine with uncoordinated metal ions in the perovskite light-absorbing layer through coordination interactions. This reduces the capture and binding of photogenerated charge carriers generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0007] In any embodiment, the additive comprises a compound with the structure shown in Formula I:

[0008] R1-R2-Si-(OR3)3 formula I

[0009] Wherein, R1 includes at least one of amino, piperazine, methoxy, ethoxy, mercapto, methylthio, and ethylthio, R2 includes an alkyl group having 1-5 carbon atoms, and R3 includes an alkyl group having 1-5 carbon atoms.

[0010] The compound shown in Formula I contains negatively charged atoms such as N and O with lone pairs of electrons in R1, which readily combine with metal ions through coordination interactions. This reduces the capture and binding of photogenerated carriers generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first carrier transport layer, and thus improves the photoelectric conversion efficiency of the perovskite solar cell.

[0011] In any embodiment, R1 includes at least one of amino, piperazine, methoxy, mercapto, and methylthio, R2 includes an alkyl group having 1-3 carbon atoms, and R3 includes an alkyl group having 1-3 carbon atoms.

[0012] In any embodiment, the additive comprises at least one of the compounds shown in Formula I-1 to Formula I-6:

[0013]

[0014] In the technical solution of this application, in the structural formulas shown in I-1 to I-6, groups containing negatively charged atoms such as N and O with lone pairs of electrons are used as coordinating groups. At the interface between the first carrier transport layer and the perovskite light-absorbing layer, at least some of the coordinating groups in the additives can combine with at least some of the unpaired metal ions in the perovskite light-absorbing layer through coordination. This reduces the capture and binding of photogenerated carriers generated by the perovskite solar cell under illumination conditions by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first carrier transport layer, and thus improves the photoelectric conversion efficiency of the perovskite solar cell.

[0015] In any embodiment, the molar percentage of the additive in the first carrier transport layer is 0.3% to 1%. At this suitable ratio, it is beneficial to improve the upper and lower interfaces of the first carrier transport layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.

[0016] In any embodiment, the perovskite solar cell further includes a second carrier transport layer; wherein the first carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer, and the second carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode; or, the first carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode, and the second carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer. Therefore, the provision of the second carrier transport layer facilitates better separation of electrons and holes in the photogenerated carriers.

[0017] In any embodiment, the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer. Because unpaired metal ions exist in the perovskite light-absorbing layer, they readily combine with electrons in electron-hole pairs generated by the perovskite solar cell under illumination. By placing additives in the electron transport layer, at the interface between the electron transport layer and the perovskite light-absorbing layer, the coordinating groups in the additives can combine with the unpaired metal ions in the perovskite light-absorbing layer through coordination interactions. This reduces the capture and binding of electrons generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first carrier transport layer, and thus improves the photoelectric conversion efficiency of the perovskite solar cell.

[0018] In any embodiment, the electron transport layer material includes at least one of [6,6]-phenyl C61 butyrate, [6,6]-phenyl C71 butyrate, and copper hydroxide; the hole transport layer material includes at least one of nickel oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly-3-hexylthiophene, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polythiophene, molybdenum oxide, cuprous iodide, cuprous oxide, molybdenum oxide, vanadium oxide, tungsten oxide, molybdenum sulfide, and carbazole phosphate. Of course, the material is not limited to the above-mentioned bulk materials, and those skilled in the art can adjust them according to actual needs.

[0019] In any embodiment, the perovskite solar cell further includes an atomic layer deposition protective layer disposed between the electron transport layer and the second electrode; wherein the atomic layer deposition protective layer is made of a metal oxide, and at least some of the metal ions in the atomic layer deposition protective layer are capable of forming chemical bonds with at least some of the oxygen atoms in the additive.

[0020] The inclusion of an atomic layer deposition (ALD) protective layer helps suppress ion migration, further improving the photoelectric conversion efficiency of perovskite solar cells. When preparing the ALD protective layer using ALD technology, highly reactive precursors are typically employed. For example, in depositing a SnOx protective layer, tetra(dimethylamino)tin can be used as the precursor. The oxygen atoms in the additives, such as those in compounds with the structure shown in Formula I that are bonded to silicon, can form chemical bonds with the tin in tetra(dimethylamino)tin. This provides active sites for the ALD reaction. Furthermore, the additives in the electron transport layer reduce the reaction between tetra(dimethylamino)tin and the perovskite light-absorbing layer (e.g., perovskite light-absorbing layer) through pinholes, thus preventing degradation of the perovskite light-absorbing layer.

[0021] In any embodiment, the metal oxide includes at least one of tin oxide, zinc oxide, titanium oxide, indium oxide, tungsten oxide, cerium oxide, and zirconium oxide. A protective layer using these materials helps to suppress ion migration.

[0022] In any embodiment, the perovskite light-absorbing layer comprises a compound with the chemical formula ABX3, wherein A comprises CH3(NH2)2. + CH(NH2)2 + CH3NH2 + Li + Na + K + 、Rb + Cs + At least one of them, B includes Pb 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them, X includes Cl - ,Br - I - SCN - CNO - OCN - OSCN- SH - OH - CP - CN - SeCN - N3 - NO2 - At least one of the following. The metal ions in the aforementioned perovskite light-absorbing layer material are uncoordinated, for example, Pb. 2+ The additives can readily combine with electrons in electron-hole pairs generated by perovskite solar cells under illumination. The coordinating groups in the additives can also combine with unpaired metal ions in the perovskite light-absorbing layer through coordination, improving the upper and lower interfaces of the first carrier transport layer and thus improving the photoelectric conversion efficiency of the perovskite solar cell.

[0023] Secondly, this application provides a method for preparing a perovskite solar cell, comprising:

[0024] Provide the first electrode;

[0025] A perovskite light-absorbing layer is prepared on the surface of the first electrode;

[0026] A first carrier transport layer is prepared on the surface of the perovskite light-absorbing layer;

[0027] A second electrode is fabricated on the surface of the first carrier transport layer to obtain the perovskite solar cell;

[0028] The first carrier transport layer includes an additive, which comprises a coordinating group capable of binding to a metal cation. The coordinating group includes at least one of the following: amino, piperazine, an alkyl group with at least one carbon atom substituted by an oxygen atom, or an alkyl group with at least one carbon atom substituted by a sulfur atom. The perovskite light-absorbing layer includes uncoordinated metal cations, including Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them.

[0029] The above preparation method is simple and easy to implement, which is conducive to industrial application.

[0030] In any embodiment, the first carrier transport layer is an electron transport layer, and the step of fabricating a second electrode on the surface of the first carrier transport layer includes:

[0031] An atomic layer deposition protective layer was prepared on the surface of the first carrier transport layer using atomic layer deposition technology;

[0032] A second electrode is prepared on the surface of the atomic layer deposition protective layer;

[0033] The atomic layer deposition protective layer is made of metal oxide, and at least some of the metal ions in the atomic layer deposition protective layer can form chemical bonds with at least some of the oxygen atoms in the additive.

[0034] The protective layer helps suppress ion migration and further improves the photoelectric conversion efficiency of perovskite solar cells.

[0035] When preparing the protective layer using atomic layer deposition (ALD), a highly reactive precursor is typically employed. For example, in depositing a SnOx protective layer, tetra(dimethylamino)tin can be used as the precursor. The oxygen atoms in the additive, such as those in compounds with the structure shown in Formula I that are bonded to silicon, can form chemical bonds with the tin in tetra(dimethylamino)tin. This provides active sites for the ALD reaction. Furthermore, the additives in the electron transport layer reduce the reaction between tetra(dimethylamino)tin and the perovskite light-absorbing layer (e.g., perovskite light-absorbing layer) through pinholes, thus preventing degradation of the perovskite light-absorbing layer.

[0036] Thirdly, this application provides a method for preparing a perovskite solar cell, comprising:

[0037] Provide the first electrode;

[0038] A first carrier transport layer is prepared on the surface of the first electrode;

[0039] A perovskite light-absorbing layer is prepared on the surface of the first carrier transport layer;

[0040] A second electrode is fabricated on the surface of the perovskite light-absorbing layer to obtain the perovskite solar cell;

[0041] The first carrier transport layer includes an additive, which comprises a coordinating group capable of binding to a metal cation. The coordinating group includes at least one of amino, piperazine, an alkyl group with at least one carbon atom substituted by an oxygen atom, or an alkyl group with at least one carbon atom substituted by a sulfur atom. The perovskite light-absorbing layer includes uncoordinated metal cations, including Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+Fe 2+ Co 2 + Ni 2+ At least one of them.

[0042] The above preparation method is simple and easy to implement, which is conducive to industrial application.

[0043] Fourthly, this application provides a photovoltaic module, including the perovskite solar cell of the first aspect of this application.

[0044] Fifthly, this application provides a photovoltaic power generation system including a plurality of electrically connected photovoltaic modules as described in the fourth aspect.

[0045] Sixthly, this application provides an electrical device including a plurality of electrically connected photovoltaic power generation systems according to the fifth aspect of this application. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of the structure of the photovoltaic module in the embodiments of this application.

[0047] Figure 2 The images show fluorescence spectral data of the FTO / NiOx / PVK / PCBM structures in Examples 1 to 6 and Comparative Example 1 of this application.

[0048] Explanation of reference numerals in the attached figures:

[0049] 100 perovskite solar cells; 1000 photovoltaic modules; 1100 cell strings; 1200 front glass; 1300 front encapsulating film; 1400 back encapsulating film; 1500 back glass. Detailed Implementation

[0050] The following detailed description, with appropriate reference to the accompanying drawings, discloses embodiments of the perovskite solar cells, their fabrication methods, components, systems, and apparatus as described in this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0051] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0052] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0053] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0054] Unless otherwise specified, all steps in this 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 it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0055] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0056] Incorporating a carrier transport layer in a perovskite solar cell facilitates carrier migration, thereby improving the photoelectric conversion efficiency. When sunlight illuminates the perovskite light-absorbing layer of a perovskite solar cell, photogenerated carriers are generated, including electrons and holes. Electrons move from the perovskite light-absorbing layer to the carrier transport layer. However, due to the presence of uncoordinated metal cations, such as Pb, in the perovskite light-absorbing layer… 2+ Defects lead to Pb 2+ It easily traps electrons, leading to carrier loss, a decrease in open-circuit voltage, and a reduction in photoelectric conversion efficiency.

[0057] Based on this, in a first aspect, this application provides a perovskite solar cell, comprising a first electrode, a perovskite light-absorbing layer, and a second electrode; wherein a first carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer, or a first carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode; the first carrier transport layer comprises an additive, the additive comprising a coordinating group capable of binding to a metal cation, the coordinating group comprising at least one of amino, piperazine, an alkyl group in which at least one carbon atom is substituted by an oxygen atom, and an alkyl group in which at least one carbon atom is substituted by a sulfur atom; the perovskite light-absorbing layer comprises an uncoordinated metal cation, the uncoordinated metal cation comprising Pb 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them.

[0058] In this paper, whether the coordinating groups can bind to at least some of the metal ions in the perovskite light-absorbing layer through coordination can also be qualitatively or quantitatively determined using instruments and methods known in the art to assess the perovskite light-absorbing layer and the first carrier transport layer. For example, the layers in a perovskite solar cell can be disassembled, retaining the connection state of the perovskite light-absorbing layer and the first carrier transport layer. Then, the infrared spectra of the perovskite light-absorbing layer and the first carrier transport layer of this application can be tested using an IS10 Fourier transform infrared spectrometer from Nicolet Corporation, according to the general rules of infrared spectroscopy analysis method in GB / T6040-2002.

[0059] The working principle of a perovskite solar cell is as follows: When sunlight shines on the perovskite light-absorbing layer in the perovskite solar cell, the perovskite absorbs the light and generates photogenerated charge carriers. Under the action of the built-in electric field, these charge carriers are separated into electrons and holes. The electrons are driven to move towards the electrode, such as the first electrode, and are collected by the first electrode. The holes are driven to move towards the other electrode, such as the second electrode, and are collected by the second electrode. When the electrons and holes are collected at the electrode, they form a current, thereby generating electrical energy.

[0060] By incorporating an additive containing coordinating groups in the charge carrier transport layer—coordinating groups containing negatively charged atoms such as N and O with lone pairs of electrons—it is possible for these groups to readily combine with uncoordinated metal ions in the perovskite light-absorbing layer through coordination interactions. This reduces the capture and binding of photogenerated charge carriers generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first charge carrier transport layer, and consequently improves the photoelectric conversion efficiency of the perovskite solar cell.

[0061] It should be noted that, as an example, in this embodiment, the first electrode, the perovskite light-absorbing layer, and the second electrode can be arranged along the incident light direction.

[0062] In some embodiments, the additive includes a compound with the structure shown in Formula I:

[0063] R1-R2-Si-(OR3)3 formula I

[0064] Wherein, R1 includes at least one of amino, piperazine, methoxy, ethoxy, mercapto, methylthio, and ethylthio, R2 includes an alkyl group having 1-5 carbon atoms, and R3 includes an alkyl group having 1-5 carbon atoms.

[0065] In this article, "amino" refers to -NH2.

[0066] In this article, "piperazinyl" refers to the group formed by the carbonyl group of piperazine (C4H). 10 A group derived from N2 by removing one hydrogen atom, where the removed hydrogen atom can be a hydrogen atom bonded to N.

[0067] In this article, "methoxy" refers to CH3O- 。

[0068] In this article, "ethoxy" refers to CH3CH2O- 。

[0069] In this article, "methylthio" refers to CH3S-.

[0070] In this article, "ethioyl" refers to CH3CH2S-.

[0071] In this article, "thiol group" refers to SH-.

[0072] In this document, "alkyl group having 1-5 carbon atoms" refers to a straight-chain or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, without any unsaturation, having 1 to 5 carbon atoms, and attached to the rest of the molecule by single bonds. Suitable examples include, but are not limited to: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, isopentyl, neopentyl, and tert-pentyl.

[0073] The compound shown in Formula I contains negatively charged atoms such as N and O with lone pairs of electrons in R1, which readily combine with metal ions through coordination interactions. This reduces the capture and binding of photogenerated carriers generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first carrier transport layer, and thus improves the photoelectric conversion efficiency of the perovskite solar cell.

[0074] In some embodiments, R1 includes at least one of amino, piperazine, methoxy, mercapto, and methylthio, R2 includes an alkyl group having 1-3 carbon atoms, and R3 includes an alkyl group having 1-3 carbon atoms.

[0075] In some embodiments, the additive includes at least one of the compounds represented by Formulas I-1 to I-6:

[0076]

[0077] In the technical solution of this application, in the structural formulas shown in I-1 to I-6, groups containing negatively charged atoms such as N and O with lone pairs of electrons are used as coordinating groups. At the interface between the first charge carrier transport layer and the perovskite light-absorbing layer, at least some of the coordinating groups in the additives can combine with at least some of the metal ions in the perovskite light-absorbing layer through coordination. This reduces the capture and binding of photogenerated charge carriers generated by the perovskite solar cell under illumination conditions by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first charge carrier transport layer, and thus improves the photoelectric conversion efficiency of the perovskite solar cell.

[0078] In some embodiments, the molar percentage of the additive in the first carrier transport layer is 0.3% to 1%. At this suitable ratio, it is beneficial to improve the upper and lower interfaces of the first carrier transport layer, thereby improving the photoelectric conversion efficiency of the perovskite solar cell. The molar percentage of the additive in the first carrier transport layer can be any two values ​​within the range of 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or more.

[0079] It should be noted that the molar percentage of the additive in the first carrier transport layer can be obtained by measuring the atomic percentage of Si in the additive using EDS.

[0080] In some embodiments, the perovskite solar cell further includes a second carrier transport layer; wherein, the first carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer, and the second carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode; or, the first carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode, and the second carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer. Therefore, the provision of the second carrier transport layer facilitates better separation of electrons and holes in the photogenerated carriers.

[0081] In some embodiments, the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer. Because unpaired metal ions exist in the perovskite light-absorbing layer, they readily combine with electrons in electron-hole pairs generated by the perovskite solar cell under illumination. By placing additives in the electron transport layer, at the interface between the electron transport layer and the perovskite light-absorbing layer, the coordinating groups in the additives can combine with the unpaired metal ions in the perovskite light-absorbing layer through coordination interactions. This reduces the capture and binding of electrons generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, improves the upper and lower interfaces of the first carrier transport layer, and thus improves the photoelectric conversion efficiency of the perovskite solar cell.

[0082] In some embodiments, the electron transport layer material includes at least one of [6,6]-phenyl C61 butyrate, [6,6]-phenyl C71 butyrate, and copper hydroxide; the bulk material of the hole transport layer includes at least one of nickel oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly-3-hexylthiophene, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polythiophene, molybdenum oxide, cuprous iodide, cuprous oxide, molybdenum oxide, vanadium oxide, tungsten oxide, molybdenum sulfide, and carbazole phosphate. Of course, the materials are not limited to those described above, and those skilled in the art can adjust them according to actual needs.

[0083] In some embodiments, the perovskite solar cell further includes an atomic layer deposition protective layer disposed between the electron transport layer and the second electrode; wherein the atomic layer deposition protective layer is made of a metal oxide, and at least some of the metal ions in the atomic layer deposition protective layer are capable of forming chemical bonds with at least some of the oxygen atoms in the additive.

[0084] Improving the lifespan of perovskite solar cells is also a goal pursued by the industry. For example, the instability of the perovskite material itself and its weak resistance to various external environments determine the lifespan of the device. Encapsulation can solve problems such as water and oxygen in the external environment. However, the problem of ion migration inside perovskite cells affected by light and heat is unavoidable. Currently, ion migration can be suppressed by setting a protective layer. When preparing the protective layer, atomic layer deposition (ALD) is usually used, which uses a highly reactive organometallic source as the deposit precursor. However, when the first carrier transport layer (such as the electron transport layer) is not dense enough, the highly reactive organometallic source can penetrate the electron transport layer and react directly with the perovskite, leading to the degradation of the perovskite layer. Therefore, the interface between the upper and lower layers of the first carrier transport layer is a key factor affecting the degree of nonradiative recombination and the quality of ALD deposition, thus requiring improvement of the interface between the upper and lower layers of the electron transport layer.

[0085] It is evident that when preparing the protective layer using atomic layer deposition (ALD), a highly reactive precursor is typically employed. For instance, in depositing a SnOx protective layer, tetra(dimethylamino)tin can be used as the precursor. The oxygen atoms in the additive, such as those in the compound shown in Formula I, which are bonded to silicon, can form chemical bonds with the tin in tetra(dimethylamino)tin. This provides active sites for the ALD reaction. Furthermore, the additive in the first carrier transport layer reduces the reaction between tetra(dimethylamino)tin and the perovskite light-absorbing layer (e.g., perovskite perovskite light-absorbing layer) through the pinholes, thus preventing degradation of the perovskite light-absorbing layer.

[0086] It should be noted that whether at least some of the metal ions in the atomic layer deposition protective layer form chemical bonds with the oxygen atoms in the additive can be qualitatively or quantitatively determined using instruments and methods known in the art for the protective layer and the first carrier transport layer. For example, the layers in a perovskite solar cell can be disassembled, retaining the connection state of the protective layer and the first carrier transport layer. Then, the infrared spectra of the protective layer and the first carrier transport layer of this application can be tested using an IS10 Fourier transform infrared spectrometer from Nicolet Corporation, according to the General Rules for Infrared Spectroscopy Analysis in GB / T6040-2002.

[0087] In some embodiments, the metal oxide includes at least one of tin oxide, zinc oxide, titanium oxide, indium oxide, tungsten oxide, cerium oxide, and zirconium oxide. A protective layer using these materials helps to suppress ion migration.

[0088] In some embodiments, the perovskite light-absorbing layer comprises a compound with the chemical formula ABX3, wherein A comprises CH3(NH2)2. + CH(NH2)2 + CH3NH2+ Li + Na + K + 、Rb + Cs + At least one of them, B includes Pb 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them, X includes Cl - ,Br - I - SCN - CNO - OCN - OSCN - SH - OH - CP - CN - SeCN - N3 - NO2 - At least one of the following. The metal ions in the aforementioned perovskite light-absorbing layer material are uncoordinated, for example, Pb. 2+ The additives can readily combine with electrons in electron-hole pairs generated by perovskite solar cells under illumination. The coordinating groups in the additives can also combine with unpaired metal ions in the perovskite light-absorbing layer through coordination, improving the upper and lower interfaces of the first carrier transport layer and thus improving the photoelectric conversion efficiency of the perovskite solar cell.

[0089] Secondly, this application provides a method for preparing a perovskite solar cell, comprising:

[0090] Provide the first electrode;

[0091] A perovskite light-absorbing layer is prepared on the surface of the first electrode;

[0092] A first carrier transport layer is prepared on the surface of the perovskite light-absorbing layer;

[0093] A second electrode is fabricated on the surface of the first carrier transport layer to obtain the perovskite solar cell;

[0094] The first carrier transport layer includes an additive, which comprises a coordinating group capable of binding to a metal cation. The coordinating group includes at least one of the following: amino, piperazine, an alkyl group with at least one carbon atom substituted by an oxygen atom, or an alkyl group with at least one carbon atom substituted by a sulfur atom. The perovskite light-absorbing layer includes uncoordinated metal cations, including Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them.

[0095] The above preparation method is simple and easy to implement, which is conducive to industrial application.

[0096] In some embodiments, the first carrier transport layer is an electron transport layer, and the step of fabricating a second electrode on the surface of the first carrier transport layer includes:

[0097] An atomic layer deposition protective layer was prepared on the surface of the first carrier transport layer using atomic layer deposition technology;

[0098] A second electrode is prepared on the surface of the atomic layer deposition protective layer;

[0099] The atomic layer deposition protective layer is made of metal oxide, and at least some of the metal ions in the atomic layer deposition protective layer can form chemical bonds with at least some of the oxygen atoms in the additive.

[0100] The protective layer helps suppress ion migration and further improves the photoelectric conversion efficiency of perovskite solar cells.

[0101] When preparing the protective layer using atomic layer deposition (ALD), a highly reactive precursor is typically employed. For example, in depositing a SnOx protective layer, tetra(dimethylamino)tin can be used as the precursor. The oxygen atoms in the additive, such as those in compounds with the structure shown in Formula I that are bonded to silicon, can form chemical bonds with the tin in tetra(dimethylamino)tin. This provides active sites for the ALD reaction. Furthermore, the additive in the first carrier transport layer can reduce the reaction between tetra(dimethylamino)tin and the perovskite light-absorbing layer (e.g., perovskite perovskite light-absorbing layer) through pinholes, thus preventing degradation of the perovskite light-absorbing layer.

[0102] Thirdly, this application provides a method for preparing a perovskite solar cell, comprising:

[0103] Provide the first electrode;

[0104] A first carrier transport layer is prepared on the surface of the first electrode;

[0105] A perovskite light-absorbing layer is prepared on the surface of the first carrier transport layer;

[0106] A second electrode is fabricated on the surface of the perovskite light-absorbing layer to obtain the perovskite solar cell;

[0107] The first carrier transport layer includes an additive, which comprises a coordinating group capable of binding to a metal cation. The coordinating group includes at least one of amino, piperazine, an alkyl group with at least one carbon atom substituted by an oxygen atom, or an alkyl group with at least one carbon atom substituted by a sulfur atom. The perovskite light-absorbing layer includes uncoordinated metal cations, including Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2 + Ni 2+ At least one of them.

[0108] The above preparation method is simple and easy to implement, which is conducive to industrial application.

[0109] Please see Figure 1 Fourthly, embodiments of this application also provide a photovoltaic module 1000, which includes the perovskite solar cell 100 provided by any of the above solutions.

[0110] Photovoltaic module 1000 refers to a perovskite solar cell module, that is, an overall module comprising multiple perovskite solar cells 100. This includes several cell strings 1100, each cell string 1100 comprising multiple perovskite solar cells 100 connected in series via connectors such as solder ribbons.

[0111] In the photovoltaic module 1000, in addition to the cell string 1100, it also includes front glass 1200, front encapsulating film 1300, back encapsulating film 1400, back glass 1500, etc. As an example, the photovoltaic module 1000 includes front glass 1200, front encapsulating film 1300, cell string 1100, back encapsulating film 1400 and back glass 1500 stacked sequentially along the thickness direction.

[0112] Fifthly, embodiments of this application also provide a photovoltaic power generation system, which includes a plurality of electrically connected photovoltaic modules. "A plurality of" refers to two or more integers.

[0113] A photovoltaic (PV) power generation system is a power generation system that directly converts solar radiation energy into electrical energy using the photovoltaic effect. It is divided into stand-alone PV systems and grid-connected PV systems. A stand-alone PV system consists of a solar photovoltaic array composed of photovoltaic modules, a battery bank, a charging controller, a power electronic converter (inverter), and loads. A grid-connected PV system consists of a photovoltaic array, a high-frequency DC / DC boost circuit, a power electronic converter (inverter), and a system monitoring section.

[0114] Sixthly, embodiments of this application also provide an electrical device, which includes the photovoltaic power generation system provided in the above solutions, and the photovoltaic power generation system is used to provide electrical energy to the electrical device. The electrical device can take many forms, such as electric vehicles, ships, spacecraft, solar water heaters, solar energy, etc.

[0115] The power supply for electrical devices can be provided solely by photovoltaic modules, or by a combination of photovoltaic modules and energy storage batteries, meaning the electrical equipment is equipped with both photovoltaic modules and energy storage batteries. Energy storage batteries are not limited to primary and secondary batteries; for example, but not limited to, lithium-ion and sodium-ion secondary batteries.

[0116] Example

[0117] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0118] Example 1

[0119] This embodiment provides a perovskite solar cell. The structure of the perovskite solar cell includes a first electrode, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a protective layer, and a second electrode arranged sequentially along the incident light direction. Its fabrication method includes the following steps:

[0120] Fabrication of the first electrode: Dimensions are 2.0*2.0cm. 2 The FTO glass was laser-etched to remove 0.35 cm of FTO from each end, exposing the glass substrate. The etched FTO conductive glass was then ultrasonically cleaned several times with water, acetone, and isopropanol, and then dried with nitrogen for later use.

[0121] Fabrication of the hole transport layer: FTO conductive glass was treated with ultraviolet ozone, and then NiO with a thickness of approximately 25 nm was sputtered by magnetron sputtering. 1.2 Annealing at 300℃ for 60 minutes yields the hole transport layer.

[0122] Preparation of the perovskite light-absorbing layer: A perovskite precursor solution, consisting of a 1.2 mol / L FAPbI3 solution, was spin-coated onto the hole transport layer at a speed of 3000-5000 rpm. The FAPbI3 solution contained DMF and DMSO in a volume ratio of 8:1. The spin-coating time was 20 s. Approximately 10 s after the start of spin-coating, 300 μL of the anti-solvent chlorobenzene was added dropwise. The film was then placed on a hot plate and annealed at 100 °C for 60 min to obtain a perovskite layer with a thickness of 500 nm.

[0123] Preparation of the electron transport layer: NH2-(CH2)3-Si-(OCH3)3 was added to a chlorobenzene solution with a concentration of 20 mg / mL PCBM to obtain a mixture, with the molar ratio of PCBM to NH2-(CH2)3-Si-(OCH3)3 in the mixture being 100:0.5. The mixture was then spin-coated onto the upper surface of the prepared perovskite light-absorbing layer at 2000 rpm for 30 s to obtain the electron transport layer. PCBM refers to methyl [6,6]-phenyl C61 butyrate.

[0124] Preparation of the protective layer by atomic layer deposition: 10 nm SnO was deposited on the PCBM using an ALD device. 1.84 Protective layer. TDMASn is used as the Sn source and H2O as the oxygen source. The reaction temperature is 100℃, and the deposition cycle is 80 cycles.

[0125] Preparation of the second electrode: Place the substrate with the protective layer into the evaporation apparatus, and wait for the evaporation vacuum to reach 5*10. -4 Below Pa, an 80 nm metal back electrode Ag was deposited by vapor deposition at a rate of 0.1 A / s.

[0126] Examples 2-8 and Comparative Example 1 of this application were prepared using all the preparation steps of Example 1. The differences between Examples 2-8 and Comparative Example 1 and Example 1 are shown in Table 1.

[0127] Performance testing:

[0128] The perovskite solar cells of Examples 1 to 8 and Comparative Example 1 were tested as follows:

[0129] (1) Under normal temperature and pressure, a standard light source with AM1.5G was used to simulate sunlight, which conforms to the national standard IEC61215. The intensity of the light was corrected by using a crystalline silicon perovskite solar cell to achieve a solar intensity. The current-voltage characteristic curve of the perovskite solar cell under the illumination of the light source was measured using a four-channel digital source meter (Keithley 2440). The open-circuit voltage Voc, short-circuit current density Jsc, fill factor FF, and power conversion efficiency PCE of the perovskite solar cell were obtained.

[0130] The energy conversion efficiency is calculated as follows: PCE = Pout / Popt

[0131] =Voc×Jsc×(Vmpp×Jmpp) / (Voc×Jsc)

[0132] =Voc×Jsc×FF

[0133] Wherein, Pout, Popp, Vmpp, and Jmpp are the battery's operating output power, incident light power, battery's maximum power point voltage, and maximum power point current, respectively.

[0134] (2) Testing of data related to the number of charge carriers

[0135] Fluorescence spectroscopy (PL) testing: Fluorescence spectroscopy data were obtained using a PL fluorescence spectrometer with an excitation wavelength of 405 nm. The test objects were the FTO / NiOx / PVK / PCBM structures from Examples 1-6 and Comparative Example 1. The FTO / NiOx / PVK / PCBM structure refers to the structure obtained by sequentially fabricating a first electrode, a hole transport layer, a perovskite light-absorbing layer, and an electron transport layer according to the preparation methods of Examples 1-6 and Comparative Example 1. No second electrode was fabricated on this FTO / NiOx / PVK / PCBM structure. During the test, the incident light direction was FTO→PCBM.

[0136] See test results Figure 2 , Figure 2 The parabolic curves from top to bottom correspond to the test results of Comparative Example 1, Example 6, Example 4, Example 2, Example 5, Example 1, and Example 3. It can be seen that Comparative Example 1 has the highest PL fluorescence intensity, while the PL fluorescence intensity of Examples 6, 4, 2, 5, 1, and 3 gradually decreases. A lower PL fluorescence intensity indicates a faster carrier transfer rate and fewer perovskite defects after passivation.

[0137]

[0138] As can be seen from the results in Table 1, compared with Comparative Example 1, Examples 1-8 of this application, which use additives in the carrier transport layer (electron transport layer), have higher photoelectric conversion efficiency. This indicates that the coordinating groups in the total additives of this application can combine with at least some of the metal ions in the perovskite light-absorbing layer through coordination, thereby reducing the capture and binding of photogenerated carriers generated by the perovskite solar cell under illumination by unpaired metal ions in the perovskite light-absorbing layer, improving the upper and lower interfaces of the first carrier transport layer, and thus improving the photoelectric conversion efficiency of the perovskite solar cell.

[0139] As can be seen from Examples 1-8, the photoelectric conversion efficiency of perovskite solar cells can be further improved by adjusting the molar ratio between the additives, the bulk material, and the additives.

[0140] From Table 1 and Figure 2 As can be seen from the results of Examples 5 and 6, Example 5 has a higher photoelectric conversion efficiency, indicating that the coordination effect between the methylthio group and lead ions in Example 5 is stronger than that of the thio group in Example 6.

[0141] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A perovskite solar cell, characterized in that, It includes a first electrode, a perovskite light-absorbing layer, and a second electrode; Wherein, a first carrier transport layer is provided between the first electrode and the perovskite light-absorbing layer, or a first carrier transport layer is provided between the perovskite light-absorbing layer and the second electrode; The first carrier transport layer includes an additive, the additive including a coordinating group capable of binding to a metal cation, the coordinating group including at least one of amino, piperazine, alkyl with at least one carbon atom replaced by an oxygen atom, and alkyl with at least one carbon atom replaced by a sulfur atom; The perovskite light-absorbing layer includes uncoordinated metal cations; the uncoordinated metal cations include at least one of Pb 2+ , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Ge 2+ , Fe 2+ , Co 2+ , Ni 2+ .

2. The perovskite solar cell according to claim 1, characterized in that, The additive includes compounds with the structure shown in Formula I: R1-R2-Si-(OR3)3 formula I Wherein, R1 includes at least one of amino, piperazine, methoxy, ethoxy, mercapto, methylthio, and ethylthio, R2 includes an alkyl group having 1-5 carbon atoms, and R3 includes an alkyl group having 1-5 carbon atoms.

3. The perovskite solar cell according to claim 2, characterized in that, R1 includes at least one of amino, piperazine, methoxy, mercapto, and methylthio, R2 includes an alkyl group having 1-3 carbon atoms, and R3 includes an alkyl group having 1-3 carbon atoms.

4. The perovskite solar cell according to any one of claims 1 to 3, characterized in that, The additive comprises at least one of the compounds shown in Formula I-1 to Formula I-6:

5. The perovskite solar cell according to any one of claims 1 to 4, characterized in that, The molar percentage of the additive in the first carrier transport layer is 0.3% to 1%.

6. The perovskite solar cell according to any one of claims 1 to 5, characterized in that, The perovskite solar cell further includes a second carrier transport layer; Wherein, the first carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer, and the second carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode. Alternatively, the first carrier transport layer is disposed between the perovskite light-absorbing layer and the second electrode, and the second carrier transport layer is disposed between the first electrode and the perovskite light-absorbing layer.

7. The perovskite solar cell according to claim 6, characterized in that, The first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer.

8. The perovskite solar cell according to claim 7, characterized in that, The electron transport layer is made of at least one of [6,6]-phenyl C61-butyrate methyl ester, [6,6]-phenyl C71-butyrate methyl ester, and copper hydroxide; and / or, The hole transport layer material includes at least one of the following: nickel oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly-3-hexylthiophene, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, polythiophene, molybdenum oxide, cuprous iodide, cuprous oxide, molybdenum oxide, vanadium oxide, tungsten oxide, molybdenum sulfide, and carbazole phosphate.

9. The perovskite solar cell according to claim 7 or 8, characterized in that, The perovskite solar cell further includes an atomic layer deposition protective layer disposed between the electron transport layer and the second electrode; The atomic layer deposition protective layer is made of metal oxide, and at least some of the metal ions in the atomic layer deposition protective layer can form chemical bonds with at least some of the oxygen atoms in the additive.

10. The perovskite solar cell according to claim 9, characterized in that, The metal oxide includes at least one of tin oxide, zinc oxide, titanium oxide, indium oxide, tungsten oxide, cerium oxide, and zirconium oxide.

11. The perovskite solar cell according to any one of claims 1 to 10, characterized in that, The perovskite light-absorbing layer comprises a compound with the chemical formula ABX3, wherein A includes CH3(NH2)2. + CH(NH2)2 + CH3NH2 + Li + Na + K + 、Rb + Cs + At least one of them, B includes Pb 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them, X includes Cl - ,Br - I - SCN - CNO - OCN - OSCN - SH - OH - CP - CN - SeCN - N3 - NO2 - At least one of them.

12. A method for fabricating a perovskite solar cell, characterized in that, include: Provide the first electrode; A perovskite light-absorbing layer is prepared on the surface of the first electrode; A first carrier transport layer is prepared on the surface of the perovskite light-absorbing layer; A second electrode is fabricated on the surface of the first carrier transport layer to obtain the perovskite solar cell; The first carrier transport layer includes an additive, which comprises a coordinating group capable of binding to a metal cation. The coordinating group includes at least one of the following: amino, piperazine, an alkyl group with at least one carbon atom substituted by an oxygen atom, or an alkyl group with at least one carbon atom substituted by a sulfur atom. The perovskite light-absorbing layer includes uncoordinated metal cations, including Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them.

13. The preparation method according to claim 12, characterized in that, The first carrier transport layer is an electron transport layer, and the step of fabricating a second electrode on the surface of the first carrier transport layer includes: An atomic layer deposition protective layer was prepared on the surface of the first carrier transport layer using atomic layer deposition technology; A second electrode is prepared on the surface of the atomic layer deposition protective layer; The atomic layer deposition protective layer is made of metal oxide, and at least some of the metal ions in the atomic layer deposition protective layer can form chemical bonds with at least some of the oxygen atoms in the additive.

14. A method for fabricating a perovskite solar cell, characterized in that, include: Provide the first electrode; A first carrier transport layer is prepared on the surface of the first electrode; A perovskite light-absorbing layer is prepared on the surface of the first carrier transport layer; A second electrode is fabricated on the surface of the perovskite light-absorbing layer to obtain the perovskite solar cell; The first carrier transport layer comprises a bulk material and an additive. The additive includes a coordinating group capable of binding to metal cations, and the coordinating group includes at least one of amino, piperazine, alkyl groups with at least one carbon atom substituted by an oxygen atom, and alkyl groups with at least one carbon atom substituted by a sulfur atom. The perovskite perovskite light-absorbing layer includes uncoordinated metal cations, and the uncoordinated metal cations include Pb. 2+ Be 2+ Mg 2+ Ca 2+ 、Sr 2+ Ba 2+ Zn 2+ 、Ge 2+ Fe 2+ Co 2+ Ni 2+ At least one of them.

15. A photovoltaic module, characterized in that, Including the perovskite solar cell as described in any one of claims 1-11.

16. A photovoltaic power generation system, characterized in that, A photovoltaic module as described in claim 15, comprising several electrically connected components.

17. An electrical device, characterized in that, The photovoltaic power generation system as described in claim 16 includes several electrically connected components.

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