Application of benzyl ester hydrochloride in perovskite battery, perovskite precursor solution, perovskite light absorption layer, perovskite battery and preparation method

Abstract

The invention relates to the technical field of perovskite solar cells, and particularly provides application of benzyl ester hydrochloride in a perovskite cell, a perovskite precursor solution, a perovskite light absorption layer, the perovskite cell and a preparation method. The invention aims to solve the problem that the single function of the traditional additive or passivator in the prior art cannot meet the multiple requirements of crystallization control, interface optimization and stability enhancement at the same time. Therefore, the invention provides an application of benzyl ester hydrochloride in preparation of a perovskite solar cell, and the benzyl ester hydrochloride has a structure as shown in a formula (I): # imgabs0 # in the formula (I), R is alkyl. According to the invention, benzyl ester hydrochloride is introduced into preparation of the perovskite cell, so that coordination regulation and control, crystallization optimization and solution stability improvement of the perovskite precursor solution, surface defect passivation and interface contact enhancement of the perovskite film, and synergistic improvement of hydrophobicity and thermal stability are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite solar cells, and specifically provides application of benzyl ester hydrochloride in perovskite cells, a perovskite precursor solution, a perovskite light-absorbing layer, a perovskite cell, and a preparation method. Background Art

[0002] Since 2012, perovskite solar cells (PSCs) have experienced rapid development in the field of solar technology and have demonstrated great application potential. Due to their unique optoelectronic properties, high photoelectric conversion efficiency, and low material cost, PSCs have gradually become a powerful alternative to silicon-based solar cells in the photovoltaic field. However, their commercial development still faces challenges due to the tendency of perovskite precursor solutions to form uneven grains, grain boundary defects, and pores during crystallization, leading to non-radiative recombination and carrier loss. Furthermore, interfacial defects (such as dangling bonds and uncoordinated ions) between the perovskite layer and the electrode or charge transport layer can trigger charge recombination and reduce device efficiency.

[0003] In the prior art, additives and passivators are usually used separately, for example:

[0004] Additives: such as polymers (PEG) and small molecules (such as MACl) improve film quality by regulating the crystallization process, but it is difficult to take into account interface passivation.

[0005] Passivating agents such as PEAI and PDADI reduce defects through surface modification, but have limited effect on improving the stability of the precursor solution.

[0006] In addition, the single function of traditional additives or passivators cannot simultaneously address the multiple requirements of crystallization control, interface optimization, and stability enhancement.

[0007] Accordingly, this field requires a new technical solution to solve the above technical problems. Summary of the Invention

[0008] The present invention aims to solve the above technical problems, that is, to solve the problem that the single function of traditional additives or passivators in the prior art cannot simultaneously meet the multiple requirements of crystallization control, interface optimization and stability enhancement.

[0009] In a first aspect, the present invention provides a use of benzyl ester hydrochloride in a perovskite battery, wherein the benzyl ester hydrochloride has a structure shown in formula (I):

[0010] In formula (I), R is an alkyl group.

[0011] In the preferred technical solution of the above application, R is selected from C1 to C3 alkyl;

[0012] In a more preferred technical solution of the above application, R is -CH3.

[0013] Specifically, the benzyl ester hydrochloride is used as a perovskite precursor solution additive and / or passivating agent in a perovskite cell.

[0014] In a second aspect, the present invention provides a perovskite precursor solution, wherein the perovskite precursor solution includes a perovskite precursor solution additive, and the perovskite precursor solution additive is the benzyl ester hydrochloride described in the application described in the first aspect.

[0015] In the preferred technical solution of the above perovskite precursor solution, the concentration of the benzyl ester hydrochloride in the perovskite precursor solution is 1 to 5 wt %.

[0016] In a third aspect, the present invention provides a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is a perovskite thin film formed from the perovskite precursor solution described in the second aspect.

[0017] In a fourth aspect, the present invention provides a perovskite battery comprising the following two structures:

[0018] The first structure: the perovskite cell includes a perovskite light-absorbing layer, and the perovskite light-absorbing layer is the perovskite light-absorbing layer described in the third aspect above.

[0019] In the preferred technical solution of the above-mentioned perovskite cell, the perovskite cell comprises, from bottom to top, a conductive substrate, a first charge transport layer, a perovskite light absorption layer, a second charge transport layer and a back electrode.

[0020] The second structure: the perovskite battery includes a perovskite light-absorbing layer and a passivation layer; the perovskite light-absorbing layer is the perovskite light-absorbing layer described in the third aspect above, and / or the passivation layer includes the benzyl ester hydrochloride described in the application described in the first aspect above.

[0021] In the preferred technical solution of the above-mentioned perovskite battery, when the passivation layer includes the benzyl ester hydrochloride, the passivation layer is formed by a passivator solution, and the passivator is benzyl ester hydrochloride.

[0022] The concentration of the benzyl ester hydrochloride in the passivating agent solution is 0.3-1.2 mg / mL, preferably 0.6 mg / mL.

[0023] In the preferred technical solution of the above-mentioned perovskite cell, the perovskite solar cell includes, from bottom to top, a conductive substrate, a first charge transport layer, a perovskite light absorption layer, a passivation layer, a second charge transport layer and a back electrode.

[0024] In a fifth aspect, the present invention provides a method for preparing the perovskite cells of the above two structures.

[0025] Specifically, the preparation method of the perovskite battery of the first structure includes:

[0026] providing a conductive substrate;

[0027] A first charge transport layer, a perovskite light absorption layer, a second charge transport layer and a back electrode are sequentially formed on a conductive substrate.

[0028] The preparation method of the perovskite battery of the second structure includes:

[0029] providing a conductive substrate;

[0030] A first charge transport layer, a perovskite light absorption layer, a passivation layer, a second charge transport layer and a back electrode are sequentially formed on a conductive substrate.

[0031] The technical solution of the present invention has at least one or more of the following technical effects:

[0032] 1. The present invention uses the amino group (-NH2), ester group (-COOR), benzyl group (C6H5CH2-) and hydrochloride (Cl - ) synergistically, a single molecule achieves multiple functions, serving as both an additive to the perovskite precursor solution and an interface passivator. This multifunctional synergy not only simplifies the process but also improves device performance in multiple aspects.

[0033] 2. By regulating the coordination of benzyl ester hydrochloride in the perovskite precursor solution, the present invention optimizes the crystallization process of the perovskite film and significantly improves the stability of the solution. Compared with existing technologies, this effectively avoids the film instability caused by solution instability or poor crystallization quality in existing methods, thereby ensuring uniform film and excellent optoelectronic properties.

[0034] 3. By introducing benzyl ester hydrochloride into perovskite solar cells, the present invention effectively passivates surface defects in the perovskite film, improving the film's charge transfer efficiency. This gives the present invention a significant advantage over existing technologies in terms of interface engineering, helping to improve device stability and performance.

[0035] 4. The present invention demonstrates significant improvements in thermal stability and hydrophobicity. Through intramolecular synergy, benzyl ester hydrochloride not only effectively improves the thermal stability of perovskite films but also enhances their hydrophobicity. This dual improvement not only enhances the durability of the material but also effectively extends the life of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The preferred embodiments of the present invention are described below with reference to the accompanying drawings, in which:

[0037] Figure 1 This is a schematic structural diagram of a perovskite battery according to the present invention;

[0038] Figure 2 is a schematic structural diagram of another perovskite battery of the present invention;

[0039] Figure 3 This is a schematic structural diagram of another perovskite battery of the present invention;

[0040] Figure 4 is the XRD pattern of the perovskite film without the addition of LABE-HCl;

[0041] Figure 5 is the XRD pattern of the perovskite film with LABE-HCl added;

[0042] Figure 6 is the SEM morphology of the perovskite film without adding LABE-HCl;

[0043] Figure 7 is the SEM morphology of the perovskite film with LABE-HCl added;

[0044] In the accompanying drawings, the reference numerals are as follows:

[0045] 1 - conductive substrate;

[0046] 2 - first charge transport layer;

[0047] 3——Perovskite light-absorbing layer;

[0048] 4 - second charge transport layer;

[0049] 5——back electrode;

[0050] 6 - passivation layer;

[0051] 7——Barrier layer. DETAILED DESCRIPTION

[0052] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0053] In this application, the term "and / or" describes the relationship between associated objects, indicating that three possible relationships exist. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.

[0054] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0055] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0056] The terms used in the embodiments of the present application are for the purpose of describing specific embodiments only and are not intended to limit the present application. The singular forms "a", "an", "the" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

[0057] The weights of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass described in the examples of this application may be a mass unit known in the chemical industry, such as μg, mg, g, kg, etc.

[0058] The terms "first" and "second" are used solely for descriptive purposes to distinguish objects, such as substances, from one another and should not be understood to indicate or imply relative importance or to implicitly specify the quantity of the technical features being referred to. For example, without departing from the scope of the embodiments of this application, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX. Thus, features defined as "first" or "second" may explicitly or implicitly include one or more of such features.

[0059] The experimental methods in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.

[0060] Based on the problem pointed out in the background art that the single function of conventional additives or passivators in the prior art cannot simultaneously solve the multiple requirements of crystallization control, interface optimization and stability enhancement. The present invention introduces benzyl ester hydrochloride into perovskite cells for the first time, and through the amino group (-NH2), ester group (-COOR), benzyl group (C6H5CH2-) and hydrochloride (Cl - ) to achieve coordination regulation in perovskite precursor solution, crystallization optimization and solution stability improvement, surface defect passivation and interface contact enhancement of perovskite film, as well as synergistic improvement of hydrophobicity and thermal stability.

[0061] Specifically, in a first aspect, the present invention provides a use of benzyl ester hydrochloride in a perovskite battery, wherein the benzyl ester hydrochloride has a structure shown in formula (I):

[0062] In formula (I), R is an alkyl group.

[0063] The benzyl ester hydrochloride of formula (I) contains an amino group (-NH2), an ester group (-COOR), a benzyl group (C6H5CH2-), and a hydrochloride group (Cl-). Through their synergistic interaction, they can achieve multiple functions within a single molecule. This invention applies benzyl ester hydrochloride to the preparation of perovskite solar cells for the first time, enabling coordination regulation in perovskite precursor solutions, crystallization optimization, and improved solution stability. It also enables surface defect passivation and enhanced interfacial contact in perovskite films, as well as synergistic improvements in hydrophobicity and thermal stability.

[0064] In some embodiments, R is selected from C1-C3 alkyl.

[0065] For example, in some embodiments, R is -CH3, and the structure of the benzyl ester hydrochloride shown in formula (I) is:

[0066] The above structural formula (I-1) refers to L-alanine benzyl ester hydrochloride (LABE-HCl).

[0067] In some specific embodiments, R is -CH(CH3)2, and the structure of the benzyl ester hydrochloride shown in formula (I) is:

[0068] The above structural formula (I-2) refers to L-valine benzyl ester hydrochloride.

[0069] The above-mentioned L-alanine benzyl ester hydrochloride (LABE-HCl) and L-valine benzyl ester hydrochloride are both existing compounds.

[0070] In some preferred embodiments, R is -CH3, i.e., L-alanine benzyl ester hydrochloride (LABE-HCl).

[0071] Specifically, the benzyl ester hydrochloride is used as a perovskite precursor solution additive and / or passivating agent in perovskite cells.

[0072] In the present invention, by introducing benzyl ester hydrochloride into the perovskite battery, multiple functions are achieved in one molecule, serving as both an additive to the perovskite precursor solution and an interface passivator. This multifunctional synergistic effect not only simplifies the process flow, but also improves device performance in many aspects. When used as an additive to the perovskite precursor solution, benzyl ester hydrochloride can optimize the crystallization process of the perovskite film and significantly improve the stability of the solution by regulating the coordination in the perovskite precursor solution. Compared with the prior art, this can effectively avoid the problem of unstable film performance caused by unstable solution or poor crystallization quality in the existing method, thereby ensuring the uniformity and excellent photoelectric performance of the film. When used as a passivator, it can effectively passivate defects on the surface of the perovskite film and improve the charge transfer efficiency of the film. This makes the present invention have significant advantages over the prior art in terms of interface engineering, which helps to improve the stability and performance of the device.

[0073] Furthermore, the present invention provides a perovskite precursor solution in a second aspect, wherein the perovskite precursor solution includes a perovskite precursor solution additive, and the perovskite precursor solution additive is the benzyl ester hydrochloride described in the application described in the first aspect above.

[0074] In some specific embodiments, the concentration of the benzyl ester hydrochloride in the perovskite precursor solution is 1-5 wt %.

[0075] In a third aspect, the present invention provides a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is a perovskite thin film formed from the perovskite precursor solution described in the second aspect.

[0076] The present invention does not limit the specific method for preparing the perovskite light-absorbing layer, and commonly used methods in the art can be selected.

[0077] In some embodiments, the method for preparing the perovskite light absorbing layer adopts a slit coating method. For example, in some embodiments, the slit coating method has a slit height of 70 μm, a coating speed of 30 mm / s, a liquid output rate of 0.58 μL / s, and a coating time of 20 s.

[0078] In some embodiments, the perovskite light absorbing layer is annealed, and those skilled in the art can select annealing conditions according to actual conditions, for example, annealing at 130° C. for 20 minutes.

[0079] In a fourth aspect, the present invention provides a perovskite battery comprising the following two structures:

[0080] Specifically, the present invention provides a first structure of the above-mentioned perovskite solar cell, in which the perovskite solar cell includes a perovskite light-absorbing layer 3, and the perovskite light-absorbing layer 3 is the perovskite light-absorbing layer described in the third aspect above.

[0081] In some specific embodiments of the first structure described above, the perovskite light-absorbing layer 3 is a perovskite thin film formed by a perovskite precursor solution, the perovskite precursor solution includes a perovskite precursor solution and a perovskite precursor solution additive, and the perovskite precursor solution additive is benzyl hydrochloride.

[0082] In this invention, benzyl ester hydrochloride is used as an additive in the perovskite precursor solution. By regulating the coordination of the perovskite precursor solution, the crystallization process of the perovskite film can be optimized and the stability of the solution can be significantly improved. Compared with existing technologies, this method can effectively avoid the problem of unstable film performance caused by unstable solution or poor crystallization quality in existing methods, thereby ensuring the uniformity of the film and excellent optoelectronic properties.

[0083] In some specific embodiments of the first structure, the concentration of the benzyl ester hydrochloride in the perovskite precursor solution is 1-5 wt %, for example, 1 wt %, 2 wt %, 3 wt %, 4 wt %, 5 wt %, or any value within the range.

[0084] It can be understood that the perovskite cell of the first structure of the present invention includes, in addition to the above-mentioned perovskite light-absorbing layer 3, some functional layers commonly found in perovskite cells in the relevant field, including but not limited to a conductive substrate 1, a first charge transport layer 2, a second charge transport layer 4 and a back electrode 5.

[0085] For example, in some specific implementations of the first structure above, please refer to Figure 1 The perovskite cell includes, from bottom to top, a conductive substrate 1, a first charge transport layer 2, a perovskite light absorption layer 3, a second charge transport layer 4 and a back electrode 5.

[0086] In some embodiments, the perovskite cell of the first structure described above further includes a modification layer, which includes but is not limited to a passivation layer. For example, a passivation layer can be prepared on the surface of the perovskite light-absorbing layer 3. The present invention does not limit the preparation of the above-mentioned functional layer, and it can be designed according to actual needs.

[0087] Furthermore, the present invention also provides a second structure of the above-mentioned perovskite battery, in which the perovskite battery includes a perovskite light-absorbing layer 3 and a passivation layer 6; the perovskite light-absorbing layer 3 is the perovskite light-absorbing layer described in the third aspect above, and / or the passivation layer 6 includes the benzyl ester hydrochloride described in the application described in the first aspect above.

[0088] It should be noted that in the present invention, when the structure of the perovskite cell includes at least a perovskite light-absorbing layer 3 and a passivation layer 6, benzyl hydrochloride can be added to the perovskite light-absorbing layer 3; benzyl hydrochloride can also be added to the passivation layer 6; or benzyl hydrochloride can be added to both the perovskite light-absorbing layer 3 and the passivation layer 6.

[0089] As a preferred embodiment, the present invention chooses to add benzyl ester hydrochloride to both the perovskite light absorbing layer 3 and the passivation layer 6 .

[0090] The present invention introduces benzyl ester hydrochloride into the perovskite battery and uses it as both an additive to the perovskite precursor solution and a passivating agent, thereby realizing multiple functions within a single molecule. This multifunctional synergistic effect not only simplifies the process flow, but also improves device performance in multiple aspects, enabling coordination regulation in the perovskite precursor solution, crystallization optimization, and improved solution stability, passivation of surface defects in the perovskite film, enhanced interface contact, and synergistic improvement of hydrophobicity and thermal stability.

[0091] In some specific embodiments of the second structure, the perovskite light-absorbing layer 3 is a perovskite thin film formed from a perovskite precursor solution, the perovskite precursor solution includes a perovskite precursor solution additive, and the perovskite precursor solution additive is the benzyl ester hydrochloride;

[0092] And / or, the passivation layer 6 is formed by a passivation agent solution, and the passivation agent is benzyl ester hydrochloride.

[0093] In some specific embodiments of the second structure described above, the concentration of the benzyl ester hydrochloride in the perovskite precursor solution is 1 to 5 wt%; for example, it can be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or any value within the range.

[0094] And / or, the concentration of the benzyl ester hydrochloride in the passivating agent solution is 0.3 to 1.2 mg / mL, for example, 0.3 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1.2 mg / mL, or any value within the range.

[0095] In some preferred embodiments, the concentration of the benzyl ester hydrochloride in the passivating agent solution is 0.6 mg / mL.

[0096] In some specific embodiments of the above two structures, the perovskite precursor solution further includes a perovskite precursor and an organic solvent.

[0097] Specifically, the general formula of the perovskite precursor is ABX3, wherein: A is cesium (Cs + ), formamidinyl (FA + ) in one or more; and / or, B is one or more metal atoms, preferably B is one or more lead, tin; and / or, X is one or more halogen atoms, preferably X is Cl - Br - , I - One or more of .

[0098] In some embodiments, the perovskite precursor is FA 0.9 Cs 0.1 PbI3.

[0099] The organic solvent is one or more of dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), acetonitrile, N-methylpyrrolidone, 2-methoxyethanol or γ-butyrolactone.

[0100] In some embodiments, the organic solvent is a mixed solvent of DMF and DMSO.

[0101] In some embodiments, the volume ratio of DMF to DMSO in the mixed solvent of DMF and DMSO is 4:1.

[0102] In the present invention, the perovskite precursor solution can be prepared by a method well known to those skilled in the art, except that a perovskite precursor solution additive, benzyl ester hydrochloride, is added.

[0103] For example, the perovskite precursor solution can be prepared by dissolving a perovskite precursor and a perovskite precursor solution additive in an organic solvent; or by dissolving a perovskite precursor in an organic solvent and then adding the perovskite precursor solution additive to the resulting solution.

[0104] The passivating agent solution is prepared from the benzyl ester hydrochloride and a solvent.

[0105] In some specific embodiments, the solvent is isopropyl alcohol.

[0106] It can be understood that the perovskite cell of the second structure of the present invention includes, in addition to the above-mentioned perovskite light-absorbing layer 3, some functional layers commonly found in perovskite cells in the relevant field, including but not limited to a conductive substrate 1, a first charge transport layer 2, a second charge transport layer 4 and a back electrode 5.

[0107] For example, in some specific implementations of the second structure above, please refer to Figure 2 The perovskite cell comprises, from bottom to top, a conductive substrate 1, a first charge transport layer 2, a perovskite light absorption layer 3, a passivation layer 6, a second charge transport layer 4, and a back electrode 5. This type of perovskite cell, based on the first structure described above, further includes a passivation layer 6, which is disposed between the perovskite light absorption layer 3 and the second charge transport layer 4.

[0108] In some preferred embodiments of the above two structures, the benzyl ester hydrochloride is L-alanine benzyl ester hydrochloride (LABE-HCl).

[0109] It can be understood that for the above two structures of perovskite cells, according to the different materials of the first charge transport layer 2 and the second charge transport layer 4 in the structure, the perovskite solar cells can be divided into inverse perovskite cells and regular perovskite cells.

[0110] Specifically, when the first charge transport layer 2 and the second charge transport layer 4 are respectively a hole transport layer and an electron transport layer, the structure is an inverse perovskite cell.

[0111] For example, in some embodiments, the perovskite cell includes, from bottom to top, a conductive substrate 1, a hole transport layer, a perovskite light absorbing layer 3, an electron transport layer, and a back electrode 5. The perovskite cell of this embodiment is an inverted perovskite cell.

[0112] When the first charge transport layer 2 and the second charge transport layer 4 are respectively an electron transport layer and a hole transport layer, the structure is a formal perovskite cell.

[0113] For example, in some embodiments, the perovskite cell includes, from bottom to top, a conductive substrate 1, an electron transport layer, a perovskite light absorbing layer 3, a hole transport layer, and a back electrode 5. The perovskite cell of this embodiment is a formal perovskite cell.

[0114] In some embodiments, the material of the electron transport layer includes but is not limited to C 60 , SnO2, PCBM, TiO2, ZnO, Spiro-OMeTAD, PTAA or one or more combinations thereof.

[0115] The present invention does not limit the specific method for preparing the electron transport layer, and commonly used methods in the art can be selected.

[0116] In some embodiments, the method for preparing the electron transport layer is a thermal evaporation method.

[0117] In some specific embodiments, the material of the hole transport layer is a SAM (self-assembled monomolecule) layer, including but not limited to 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), and 2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz).

[0118] The present invention does not limit the specific method for preparing the hole transport layer, and commonly used methods in the art can be selected.

[0119] In some embodiments, the hole transport layer is prepared by slit coating, for example, in some embodiments, the slit height is 60 μm, the coating speed is 20 mm / s, the liquid output rate is 0.5 μL / s, and the coating time is 20 s.

[0120] In some embodiments, the hole transport layer is annealed, and the annealing conditions can be selected by those skilled in the art according to actual conditions, for example, annealing at 100° C. for 10 minutes.

[0121] In some embodiments, the conductive substrate 1 includes a flexible substrate or a rigid substrate.

[0122] The flexible substrate includes but is not limited to polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone resin (PES) or polyimide (PI).

[0123] The rigid substrate includes ITO (indium tin oxide) transparent conductive glass, FTO (fluorine-doped tin oxide) transparent conductive glass, IWO (tungsten-doped indium oxide) transparent conductive glass or AZO (aluminum-doped zinc oxide) transparent conductive glass.

[0124] In some embodiments, the conductive substrate 1 is sequentially cleaned with a solution of detergent and deionized water, deionized water, and anhydrous ethanol, ultrasonically cleaned, blown dry with nitrogen, and then treated with ultraviolet ozone for 15 minutes, and cooled for use.

[0125] In some embodiments, the material of the back electrode 5 is Ag electrode, Au electrode, Cu electrode, ITO, FTO, IZO, etc.

[0126] In the present invention, the back electrode can be prepared by materials and methods well known to those skilled in the art, and the present invention does not limit the specific method for preparing the back electrode.

[0127] In some embodiments, the back electrode is prepared by thermal evaporation.

[0128] It is understood that in the above two structures of perovskite cells, other functional layers commonly used in the art may be provided between the second charge transport layer 4 and the back electrode 5. For example, a blocking layer 7 may be provided between the second charge transport layer 4 and the back electrode 5.

[0129] For example, in some embodiments, see Figure 3 The perovskite cell includes, from bottom to top, a conductive substrate 1, a first charge transport layer 2, a perovskite light absorption layer 3, a passivation layer 6, a second charge transport layer 4, a blocking layer 7 and a back electrode 5.

[0130] In a fifth aspect, the present invention provides a method for preparing the perovskite cells of the above two structures.

[0131] Specifically, the preparation method of the perovskite battery of the first structure includes:

[0132] Providing a conductive substrate 1;

[0133] A first charge transport layer 2 , a perovskite light absorption layer 3 , a second charge transport layer 4 and a back electrode 5 are sequentially formed on a conductive substrate 1 .

[0134] The preparation method of the perovskite battery of the second structure includes:

[0135] Providing a conductive substrate 1;

[0136] A first charge transport layer 2 , a perovskite light absorption layer 3 , a passivation layer 6 , a second charge transport layer 4 and a back electrode 5 are sequentially formed on a conductive substrate 1 .

[0137] It should be noted that the preparation of each layer in the perovskite cell of the present invention can be obtained by methods well known to those skilled in the art.

[0138] The application of the benzyl ester hydrochloride in the perovskite battery and the perovskite battery of the present invention are described in detail below through several specific examples.

[0139] Example 1

[0140] This embodiment provides an inverse perovskite cell, which comprises, from bottom to top, a conductive substrate 1, a first charge transport layer 2, a perovskite light absorbing layer 3, a second charge transport layer 4, a blocking layer 7 and a back electrode 5; wherein: the conductive substrate 1 is FTO; the first charge transport layer 2 is a hole transport layer, the material of which is Me-4PACz; the perovskite light absorbing layer 3 is FA including LABE-HCl 0.9 Cs 0.1The perovskite film is formed by PbI3 solution; the second charge transport layer 4 is an electron transport layer, and its material is C 60 film; the barrier layer 7 is a SnO2 thin film; and the back electrode 5 is a copper electrode.

[0141] The preparation method of the above-mentioned inverse perovskite battery specifically includes the following steps:

[0142] Step 1: Place the FTO glass with a size of 10×10 cm after laser scribing P1 in a cleaning rack and ultrasonically clean it in an ultrasonic machine using a solution with a volume ratio of detergent to deionized water = 1:20, deionized water, and anhydrous ethanol for 20 minutes, then blow dry with nitrogen for later use;

[0143] Step 2: Weigh 12 mg of Me-4PACz ([4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphoric acid) and add 20 ml of anhydrous ethanol solvent in a glove box. Dissolve the mixture for 4 hours to obtain a Me-4PACz solution.

[0144] Step 3: Weigh 11064.2 mg of PbI2, 3714.6 mg of FAI, and 623.5 mg of CsI. Then, add 16 ml of DMF and 4 ml of DMSO solvent in the glove box, and add 2% LABE-HCl as an additive to prepare 20 ml of 1.2 M molar concentration of FAI. 0.9 Cs 0.1 PbI3 precursor solution;

[0145] Step 4: The FTO glass cleaned in step 1 was subjected to UV ozone treatment for 15 minutes to serve as a conductive substrate 1; the Me-4PACz solution prepared in step 2 was coated on the surface of the conductive substrate 1 by a slit coating method. After coating, the solution was annealed at 100° C. for 10 minutes to obtain a hole transport layer, wherein the slit height was 60 μm, the coating speed was 20 mm / s, the liquid discharge rate was 0.5 μL / s, and the coating time was 20 seconds;

[0146] Step 5: The surface of the hole transport layer obtained in step 4 is coated with the FA prepared in step 3 by a slit coating method. 0.9 Cs 0.1 After coating, the PbI3 precursor solution was annealed at 130°C for 20 minutes to obtain a perovskite film, namely the perovskite light-absorbing layer 3, wherein the slit height was 70 μm, the coating speed was 30 mm / s, the liquid discharge rate was 0.58 μL / s, and the coating time was 20 seconds;

[0147] Step 6: Place the conductive substrate 1 coated with the perovskite light absorbing layer 3 into a sealed box, and thermally evaporate 15 nm of C on the surface of the perovskite light absorbing layer 3. 60membrane, serving as an electron transport layer;

[0148] Step 7: On the surface of the electron transport layer, a SnO2 thin film is deposited by atomic layer deposition as a barrier layer 7, wherein tetrakis(dimethylamino)tin and ozone are used as the tin source and oxygen source, respectively. The deposition temperature is 100°C, and the deposition sequence is tin source-nitrogen purge-oxygen source-nitrogen purge. The deposition time is 5s-2s-5s-5s, and the final thickness is 20nm.

[0149] Step 8: After laser scribbling P2, the conductive substrate 1 is again evaporated with a thermal evaporation device to deposit a 100nm thick Cu electrode as the back electrode 5; finally, laser scribe P3 and perform local edge cleaning to obtain an effective area of 49cm 2 FA 0.9 Cs 0.1 PbI3 inverse perovskite battery.

[0150] Example 2

[0151] The other conditions of this embodiment are the same as those of embodiment 1. The only difference is that the FA 0.9 Cs 0.1 The concentration of LABE-HCl additive in the PbI3 precursor solution was 1%.

[0152] Example 3

[0153] The other conditions of this embodiment are the same as those of embodiment 1. The only difference is that the FA 0.9 Cs 0.1 The concentration of LABE-HCl additive in the PbI3 precursor solution is 3%.

[0154] Example 4

[0155] The other conditions of this embodiment are the same as those of embodiment 1. The only difference is that the FA 0.9 Cs 0.1 The concentration of LABE-HCl additive in the PbI3 precursor solution is 5%.

[0156] Example 5

[0157] The other conditions of this embodiment are the same as those of embodiment 1, except that this embodiment further includes a passivation layer 6 between the perovskite light absorbing layer 3 and the electron transport layer. The structure of the inverted perovskite cell is as follows: Figure 2 shown.

[0158] The preparation method of the above-mentioned inverse perovskite battery is as follows: first, a passivation layer 6 is prepared on the surface of the perovskite functional layer 3 by a slit coating method, and then an electron transport layer is deposited on the surface of the passivation layer 6 by thermal evaporation. The passivation layer 6 is formed by a passivator solution, and the passivation solution is prepared by dissolving LABE-HCl in isopropanol, and its concentration is 0.6 mg / mL, that is, 0.6 mg / mL@IPA; when the passivation layer 6 is prepared by the slit coating method, the slit height is 60 μm, the coating speed is 20 mm / s, the liquid discharge rate is 0.5 μL / s, and the coating time is 20 s.

[0159] Example 6

[0160] Other conditions in this example are the same as those in Example 5, except that the concentration of the passivating agent solution in this example is 0.3 mg / mL.

[0161] Example 7

[0162] Other conditions of this embodiment are the same as those of embodiment 5, except that the concentration of the passivating agent solution in this embodiment is 1.2 mg / mL.

[0163] Example 8

[0164] The other conditions of this embodiment are the same as those of embodiment 5. The only difference is that the FA 0.9 Cs 0.1 The PbI3 precursor solution does not contain LABE-HCl additive.

[0165] Example 9

[0166] The other conditions of this example are the same as those of Example 5, except that the passivating agent solution of this example is a mixed solution of PEAI and MAI, which is prepared by preparing a 1 mg / mL PEAI and 0.5 mg / mL MAI solution in isopropanol, heating and stirring at 70° C. for 2 hours, and then filtering.

[0167] Example 10

[0168] The other conditions of this embodiment are the same as those of embodiment 1. The only difference is that the FA 0.9 Cs 0.1 The additive in the PbI3 precursor solution is L-valine benzyl ester hydrochloride.

[0169] Example 11

[0170] The other conditions of this embodiment are the same as those of embodiment 5. The difference is that the FA 0.9 Cs 0.1The additive in the PbI3 precursor solution is L-valine benzyl ester hydrochloride, and the passivating agent solution is prepared by dissolving L-valine benzyl ester hydrochloride in isopropanol, with a concentration of 0.6 mg / mL.

[0171] Example 12

[0172] The other conditions of this embodiment are the same as those of embodiment 11. The difference is that the FA 0.9 Cs 0.1 The PbI3 precursor solution does not contain L-valine benzyl ester hydrochloride additive.

[0173] Example 13

[0174] This embodiment provides a formal perovskite battery. The difference from embodiment 1 is that the first charge transport layer 2 is an electron transport layer, and its material is C 60 film; the second charge transport layer 4 is a hole transport layer, whose material is Me-4PACz.

[0175] The preparation method of the formal perovskite battery specifically includes the following steps:

[0176] Step 1, same as Example 1;

[0177] Step 2, same as Example 1;

[0178] Step 3, same as Example 1;

[0179] Step 4: The FTO glass cleaned in step 1 is subjected to UV-ozone treatment for 15 minutes to serve as a conductive substrate 1; the conductive substrate 1 after UV-ozone treatment is placed in a sealed box, and a 15 nm C layer is deposited on the surface of the conductive substrate 1 by thermal evaporation. 60 membrane, serving as an electron transport layer;

[0180] Step 5: preparing a perovskite light absorbing layer 3 on the surface of the electron transport layer obtained in step 4, and the specific operation is the same as that in Example 1;

[0181] Step 6: On the surface of the perovskite light-absorbing layer 3, a hole transport layer is prepared by a slit coating method. The specific operation is the same as the preparation of the hole transport layer in Example 1;

[0182] Step 7: preparing a barrier layer 7 on the surface of the hole transport layer, and the specific operation is the same as that in Example 1;

[0183] Step 8: Same as in Example 1, the final effective area is 49 cm 2 FA 0.9 Cs 0.1 PbI3 formal perovskite battery.

[0184] Comparative Example 1

[0185] The other conditions of this comparative example are the same as those of Example 1, except that the FA 0.9 Cs 0.1 The PbI3 precursor solution does not contain LABE-HCl additive.

[0186] Comparative Example 2

[0187] The other conditions of this comparative example are the same as those of Example 13, except that the FA 0.9 Cs 0.1 The PbI3 precursor solution does not contain LABE-HCl additive.

[0188] Test Example 1

[0189] This test example tests the photoelectric performance of the perovskite cells prepared in each embodiment and comparative example, specifically including the short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF) and photoelectric conversion efficiency (PCE).

[0190] Test conditions: The perovskite cells prepared in each embodiment and comparative example were placed under a solar simulator (Abet Sun3000) at 100 mW / cm 2 The photoelectric conversion efficiency was tested under standard light irradiation, with a bias voltage of 22V to 0.2V and an effective area of 49cm 2 .

[0191] The results are shown in Table 1:

[0192] Table 1 Photoelectric properties of perovskite cells prepared in Examples and Comparative Examples

[0193] As can be seen from Table 1, compared with the perovskite cell without the additive LABE-HCl prepared in Comparative Example 1, the photovoltaic parameters of the LABE-HCl perovskite cells prepared in Examples 1-4 are all improved, especially the fill factor and open circuit voltage are significantly improved, indicating that the addition of the LABE-HCl additive is beneficial to the growth of perovskite grains and effectively reduces non-radiative recombination defects, thereby greatly improving the device performance.

[0194] Furthermore, by comparing Examples 1-4 with Example 5, it was found that when the same material LABE-HCl was used to passivate the surface of the perovskite film, the device performance was further improved, and the fill factor was as high as 81.27%, indicating that the additive is an effective multifunctional material that not only significantly helps the crystallization of the thin film, but also can passivate defects at the interface to further improve the interface contact and enhance the carrier transport capability.

[0195] By comparing Examples 5-7, it was found that when the concentration of benzyl ester hydrochloride (LABE-HCl) in the passivating agent solution was 0.6 mg / mL, the performance of the device was better.

[0196] By comparing Examples 8 and 9 with Example 5, it was found that when the device structure includes a perovskite absorption layer 3 and a passivation layer 6, when only the perovskite absorption layer 3 contains benzyl ester hydrochloride (LABE-HCl) or only the passivation layer 6 contains benzyl ester hydrochloride (LABE-HCl), the performance of the device is not as good as the performance of the device in which both the perovskite absorption layer 3 and the passivation layer 6 contain benzyl ester hydrochloride (LABE-HCl).

[0197] Similarly, Examples 10-13 and Comparative Example 2 further verify that L-valine benzyl ester hydrochloride with a similar structure can also have a similar effect on the device, and can also achieve good results in the formal structure, indicating that this type of additive has a good range of application and is not limited to different device structures.

[0198] By comparing Example 10 with Example 1, Example 11 with Example 5, and Example 12 with Example 8, it can be found that when the device structure and other conditions are the same, when the benzyl ester hydrochloride is L-alanine benzyl ester hydrochloride (LABE-HCl), the performance of the device is better than that of the device when the benzyl ester hydrochloride is L-valine benzyl ester hydrochloride.

[0199] In order to more clearly understand the effect of LABE-HCl on the crystallization quality of perovskite films, XRD and SEM tests were performed on the perovskite films of Example 1 and Comparative Example 1, respectively. Figure 4-7 As shown. Figure 4 and Figure 5 It can be seen that compared with the perovskite film without adding LABE-HCl ( Figure 4 ), perovskite film after adding LABE-HCl ( Figure 5 ) crystal orientation is greatly improved, the (110) crystal plane oriented perovskite grains grow better, and the relative diffraction intensity of the XRD diffraction peak is also significantly improved.

[0200] In addition, the SEM surface morphology ( Figure 6 and Figure 7 ) It can also be clearly observed that the perovskite film after adding LABE-HCl ( Figure 7 ) The grain growth is more dense and uniform, and the grain size is greatly improved.

[0201] Thus far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it will be readily understood by those skilled in the art that the scope of protection of the present invention is obviously not limited to these specific embodiments. Without departing from the principles of the present invention, those skilled in the art may make equivalent changes or substitutions to the relevant technical features, and the technical solutions after such changes or substitutions will fall within the scope of protection of the present invention.

Claims

1. Application of benzyl ester hydrochloride in the preparation of perovskite batteries, characterized in that: The benzyl ester hydrochloride has a structure shown in formula (I): In formula (I), R is an alkyl group.

2. The use according to claim 1, characterized in that R is selected from C1-C3 alkyl; Preferably, R is -CH3.

3. The use according to claim 1 or 2, characterized in that The benzyl ester hydrochloride is used as a perovskite precursor solution additive and / or passivating agent in the preparation of perovskite cells.

4. A perovskite precursor solution, characterized in that The perovskite precursor solution includes a perovskite precursor solution additive, and the perovskite precursor solution additive is the benzyl ester hydrochloride described in any one of claims 1 to 3.

5. The perovskite precursor solution according to claim 4, characterized in that The concentration of the benzyl ester hydrochloride in the perovskite precursor solution is 1 to 5 wt%.

6. A perovskite light-absorbing layer, characterized in that: The perovskite light-absorbing layer is a perovskite thin film formed from the perovskite precursor solution according to claim 4 or 5.

7. A perovskite battery, characterized in that: It comprises a perovskite light absorbing layer (3), wherein the perovskite light absorbing layer (3) is the perovskite light absorbing layer according to claim 6.

8. The perovskite cell according to claim 7, characterized in that The perovskite cell comprises, from bottom to top, a conductive substrate (1), a first charge transport layer (2), a perovskite light absorption layer (3), a second charge transport layer (4) and a back electrode (5).

9. A perovskite battery, characterized in that: The invention comprises a perovskite light-absorbing layer (3) and a passivation layer (6); the perovskite light-absorbing layer (3) is the perovskite light-absorbing layer according to claim 6, and / or the passivation layer (6) comprises the benzyl ester hydrochloride according to any one of claims 1 to 3.

10. The perovskite cell according to claim 9, characterized in that When the passivation layer (6) includes the benzyl ester hydrochloride, the passivation layer (6) is formed by a passivator solution, and the passivator is benzyl ester hydrochloride.

11. The perovskite cell according to claim 10, characterized in that The concentration of the benzyl ester hydrochloride in the passivating agent solution is 0.3-1.2 mg / mL, preferably 0.6 mg / mL.

12. The perovskite cell according to any one of claims 9 to 11, characterized in that: The perovskite cell comprises, from bottom to top, a conductive substrate (1), a first charge transport layer (2), a perovskite light absorption layer (3), a passivation layer (6), a second charge transport layer (4) and a back electrode (5).

13. The method for preparing a perovskite battery according to claim 7 or 8, characterized in that: include: Providing a conductive substrate (1); A first charge transport layer (2), a perovskite light absorption layer (3), a second charge transport layer (4) and a back electrode (5) are sequentially formed on a conductive substrate (1).

14. The method for preparing a perovskite battery according to any one of claims 9 to 12, characterized in that: include: Providing a conductive substrate (1); A first charge transport layer (2), a perovskite light absorption layer (3), a passivation layer (6), a second charge transport layer (4) and a back electrode (5) are sequentially formed on a conductive substrate (1).

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