Preparation method and application of C60 material containing tetrazole olefinic bond

Abstract

The invention belongs to the technical field of photovoltaic materials, and particularly relates to a preparation method and application of a C60 material containing tetrazole olefinic bonds. The preparation method of the C60 material containing the tetrazole olefinic bond comprises the following steps: (1) mixing tetrazole and halogenated olefin to obtain tetrazolyl halogenated olefin; and (2) mixing halogenated C60 and tetrazolyl halogenated olefin, and carrying out Sonogashira coupling reaction to obtain the C60 material containing the tetrazolyl olefin bond. The beneficial effects of the invention are that the C60 material containing tetrazole olefinic bonds is used as the electron transport layer, and in the P2 and P3 laser scribing process, dynamically broken tetrazole halide can be bonded with Pb ions in perovskite, thereby effectively self-repairing possible damage of laser scribing to the perovskite thin film, and improving the performance of the perovskite thin film. A laser scribing area is well protected; meanwhile, non-radiative recombination of a perovskite electron transmission interface can be effectively reduced, and the efficiency and the stability of a device are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of photovoltaic materials, and in particular relates to a preparation method and application of a C60 material containing a tetrazolyl olefin bond. Background Art

[0002] The perovskite laser scribing process is a key step in the production of large-area perovskite photovoltaic modules. Laser etching is used to separate the perovskite layer into multiple sub-cells, thereby improving the photovoltaic conversion efficiency of large-area modules. However, this process can generate excessive heat, causing thermal damage to the perovskite material and affecting device performance. Laser scribing can also result in uneven etching depths, affecting the uniformity and reliability of the sub-cells.

[0003] To overcome these drawbacks, existing technologies have primarily optimized the laser scribing process. For example, through trajectory tracking, precise positioning, and optimization of laser power, scanning speed, and pulse frequency parameters, these improvements improve the accuracy and uniformity of laser scribing, reduce damage to perovskite subcells during the scribing process, and improve device efficiency and reliability. However, existing technologies typically mitigate potential damage to perovskite thin films and subcells during laser scribing by depositing a protective layer before and after scribing. This approach, however, complicates the fabrication process and negatively impacts the performance of perovskite subcells. Summary of the Invention

[0004] The present application provides a preparation method and application of a C60 material containing a tetrazolyl olefin bond, aiming to solve the damage to the uniformity and reliability of perovskite photovoltaic modules caused by the perovskite laser scribing process, as well as the damage to the perovskite film and sub-cells.

[0005] In a first aspect, the present application provides a method for preparing a C60 material containing a tetrazolyl olefin bond, comprising the following steps:

[0006] (1) mixing tetrazole with a haloolefin to obtain a tetrazolyl haloolefin;

[0007] (2) Mixing halogenated C60 and tetrazolyl haloolefin to carry out a Sonogaoka coupling reaction to obtain the tetrazolyl olefin bonded C60 material.

[0008] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in this application, the structural formula of the halogenated olefin is C n H 2n-1 X, wherein 1≤n≤8, and x is selected from one or more of F, Cl and Br.

[0009] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the molar ratio of the tetrazolyl to the halogenated olefin is 1:(1-10).

[0010] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, in step (1), the mixing temperature is 20-30° C., and the mixing time is 1-3 hours.

[0011] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the molar ratio of the halogenated C60 to the tetrazolyl halogenated olefin is 1:(3-5).

[0012] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the Sonogashira coupling reaction is carried out in the presence of a catalyst.

[0013] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the molar ratio of the halogenated C60 to the catalyst is 1:(0.01-0.05).

[0014] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the catalyst includes a palladium catalyst and copper iodide.

[0015] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the catalyst includes Pd(PPh3)4 and CuI.

[0016] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the mass ratio of Pd(PPh3)4 and CuI is 1:(1-3).

[0017] According to some embodiments of the method for preparing a C60 material containing a tetrazolyl olefin bond described in the present application, the temperature of the Sonogashira coupling reaction is 30-50° C., and the time of the Sonogashira coupling reaction is 30-50 min.

[0018] The second aspect of the present application provides an electron transport layer, comprising a C60 material containing a tetrazolyl olefin bond obtained by the preparation method described in the first aspect of the present application.

[0019] A third aspect of the present application provides a perovskite solar cell, comprising the electron transport layer described in the second aspect of the present application.

[0020] According to some embodiments of the perovskite solar cell described in this application, the thickness of the electron transport layer is 20-80 nm.

[0021] The beneficial effects of the present application include: the present application adopts a C60 material containing a tetrazolyl olefin bond as the electron transport layer. During the P2 and P3 laser scribing processes, the dynamically broken tetrazolyl halide can form bonds with the Pb ions in the perovskite, effectively self-repairing the damage that may be caused to the perovskite film by laser scribing, and achieving better protection for the laser-scribed area; at the same time, it can effectively reduce the non-radiative recombination of the perovskite electron transport interface, thereby improving the device efficiency and stability. DETAILED DESCRIPTION

[0022] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0023] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and the features of different embodiments or examples without contradiction.

[0024] The present invention provides a method for preparing a C60 material containing a tetrazolyl olefin bond, comprising the following steps:

[0025] (1) mixing tetrazole with a haloolefin to obtain a tetrazolyl haloolefin;

[0026] (2) Mixing halogenated C60 and tetrazolyl haloolefin to carry out a Sonogashira coupling reaction to obtain the C60 material containing a tetrazolyl olefin bond.

[0027] The tetrazolyl olefin bond in the C60 material containing the tetrazolyl olefin bond described in the present application can be formed and broken by thermal activation, and the dynamic process is a [2+2] cycloaddition reaction between the sulfur atom and the olefin.

[0028] In some embodiments of the present application, the structural formula of the halogenated olefin is C n H 2n-1 X, wherein 1≤n≤8, and x is selected from one or more of F, Cl and Br.

[0029] In some embodiments of the present application, the molar ratio of the tetrazole to the halogenated olefin is 1:(1-10), for example, 1:1, 1:2, 1:3, 1:5, 1:8, 1:10, etc.

[0030] In some embodiments of the present application, in step (1), the mixing temperature is 20-30°C, for example, 20°C, 25°C, 28°C, 30°C, etc., and the mixing time is 1-3h, for example, 1h, 2h, 3h, etc.

[0031] In some embodiments of the present application, the molar ratio of the halogenated C60 to the tetrazolyl halogenated olefin is 1:(3-5), for example, 1:3, 1:4, 1:5, etc.

[0032] In some embodiments of the present application, the Sonogashira coupling reaction is performed in the presence of a catalyst.

[0033] In some embodiments of the present application, the molar ratio of the halogenated C60 to the catalyst is 1:(0.01-0.05), for example, 1:0.01, 1:0.02, 1:0.03, 1:0.05, etc.

[0034] In some embodiments of the present application, the catalyst includes a palladium catalyst and copper iodide.

[0035] In some embodiments of the present application, the catalyst includes Pd(PPh3)4 and CuI.

[0036] In some embodiments of the present application, the mass ratio of Pd(PPh3)4 and CuI is 1:(1-3), for example, 1:1, 1:2, 1:3, etc.

[0037] In some embodiments of the present application, the temperature of the Sonogashira coupling reaction is 30-50°C, for example, 30°C, 35°C, 38°C, 40°C, 45°C, 48°C, 50°C, etc., and the time of the Sonogashira coupling reaction is 30-50min, for example, 30min, 35min, 40min, 43min, 45min, 50min, etc.

[0038] An embodiment of the present application also provides an electron transport layer, comprising a C60 material containing a tetrazolyl olefin bond obtained by the preparation method described in the first aspect of the present application.

[0039] C60 material containing tetrazolyl olefin bonds is used as the electron transport layer. During the P2 and P3 laser scribing processes, the dynamically broken tetrazolyl halide can form bonds with the Pb ions in the perovskite, effectively self-repairing the damage that may be caused to the perovskite film by laser scribing, and achieving better protection for the laser-scribed area; at the same time, it can effectively reduce the non-radiative recombination of the perovskite electron transport interface and improve the efficiency and stability of the device.

[0040] An embodiment of the present application also provides a perovskite solar cell, comprising the electron transport layer described in the second aspect of the present application.

[0041] In some embodiments of the present application, the thickness of the electron transport layer is 20-80 nm; for example, 20 nm, 30 nm, 50 nm, 80 nm, etc.

[0042] In some embodiments of the present application, the perovskite photovoltaic module includes an ultra-white glass substrate, a transparent conductive electrode (mainly transparent metal oxides such as ITO, FTO, AZO, etc.), a hole transport layer (mainly NiOx, self-assembled monolayer (SAM), etc.), the hole transport layer is prepared by a solution method such as spraying, blade coating, or magnetron sputtering, the thickness of the hole transport layer is generally 10-50 nm, a perovskite light absorbing layer, and the chemical formula of the perovskite light absorbing layer is ABX3, wherein A is FA, Cs, MA, etc., B is Pb, Sn, etc., and X is I, Br, Cl, etc., and can be prepared by solution methods such as slit coating and blade coating, with a thickness of usually 300-700nm; the electron transport layer is usually prepared by solution methods such as spraying and blade coating or thermal evaporation, with a thickness of usually 20-80nm; the back electrode is mainly a metal electrode such as Au, Ag, Cu or a transparent metal oxide electrode such as ITO and AZ0, and is prepared by thermal evaporation or reactive sputtering deposition (RPD) and other methods, with a thickness of usually 70-170nm.

[0043] Example 1

[0044] A method for preparing a C60 material containing a tetrazolyl olefin bond comprises the following steps:

[0045] (1) Tetrazolyl haloolefins C3H5Cl in a molar ratio of 1:5 were mixed at 20°C for 1.5 hours to obtain tetrazolyl haloolefins;

[0046] (2) A halogenated C60 and a tetrazolyl haloolefin in a molar ratio of 1:3 are mixed, and a Sonogashira coupling reaction is carried out in the presence of catalysts Pd(PPh3)4 and CuI, wherein the molar ratio of the halogenated C60 and the catalyst is 1:0.01, the mass ratio of Pd(PPh3)4 and CuI is 1:1, the temperature of the Sonogashira coupling reaction is 30°C, and the reaction is carried out at this temperature for 30 minutes to obtain the C60 material containing the tetrazolyl olefin bond.

[0047] Example 2

[0048] The preparation method of the C60 material containing a tetrazolyl olefin bond described in Example 2 is different from that of Example 1 only in that the molar ratio of tetrazolyl to halogenated olefin in the preparation process of the C60 material containing a tetrazolyl olefin bond described in Example 2 is 1:3.

[0049] The specific steps include:

[0050] (1) Tetrazolyl haloolefins C3H5Cl in a molar ratio of 1:3 were mixed at 20°C for 1.5 hours to obtain tetrazolyl haloolefins;

[0051] (2) A halogenated C60 and a tetrazolyl haloolefin in a molar ratio of 1:3 are mixed, and a Sonogashira coupling reaction is carried out in the presence of catalysts Pd(PPh3)4 and CuI, wherein the molar ratio of the halogenated C60 and the catalyst is 1:0.01, the mass ratio of Pd(PPh3)4 and CuI is 1:1, the temperature of the Sonogashira coupling reaction is 30°C, and the reaction is carried out at this temperature for 30 minutes to obtain the C60 material containing the tetrazolyl olefin bond.

[0052] Example 3

[0053] The preparation method of the C60 material containing a tetrazolyl olefin bond described in Example 3 is different from that of Example 1 only in that the molar ratio of tetrazolyl to halogenated olefin in the preparation process of the C60 material containing a tetrazolyl olefin bond described in Example 3 is 1:10.

[0054] The specific steps include:

[0055] (1) Tetrazolyl haloolefins C3H5Cl in a molar ratio of 1:10 were mixed at 20°C for 1.5 hours to obtain tetrazolyl haloolefins;

[0056] (2) A halogenated C60 and a tetrazolyl haloolefin in a molar ratio of 1:3 are mixed, and a Sonogashira coupling reaction is carried out in the presence of catalysts Pd(PPh3)4 and CuI, wherein the molar ratio of the halogenated C60 and the catalyst is 1:0.01, the mass ratio of Pd(PPh3)4 and CuI is 1:1, the temperature of the Sonogashira coupling reaction is 30°C, and the reaction is carried out at this temperature for 30 minutes to obtain the C60 material containing the tetrazolyl olefin bond.

[0057] Example 4

[0058] The preparation method of the C60 material containing a tetrazolyl olefin bond described in Example 4 is different from that of Example 1 only in that the molar ratio of halogenated C60 and tetrazolyl halogenated olefin in the preparation process of the C60 material containing a tetrazolyl olefin bond described in Example 4 is 1:5.

[0059] The specific steps include:

[0060] (1) Tetrazolyl haloolefins C3H5Cl in a molar ratio of 1:5 were mixed at 20°C for 1.5 hours to obtain tetrazolyl haloolefins;

[0061] (2) A halogenated C60 and a tetrazolyl haloolefin in a molar ratio of 1:5 are mixed, and a Sonogashira coupling reaction is carried out in the presence of catalysts Pd(PPh3)4 and CuI, wherein the molar ratio of the halogenated C60 and the catalyst is 1:0.01, the mass ratio of Pd(PPh3)4 and CuI is 1:1, the temperature of the Sonogashira coupling reaction is 30°C, and the reaction is carried out at this temperature for 30 minutes to obtain the C60 material containing the tetrazolyl olefin bond.

[0062] Example 5

[0063] A perovskite solar cell comprises a stacked glass substrate layer, a transparent conductive electrode layer, a hole transport layer, a perovskite light absorption layer, an electron transport layer prepared from the C60 material containing tetrazolyl olefin bonds described in Example 1, and a back electrode.

[0064] Example 6

[0065] The only difference between Example 6 and Example 5 is that the C60 material containing a tetrazolyl olefin bond described in Example 2 is used instead of the C60 material containing a tetrazolyl olefin bond described in Example 1, and the remaining operations are the same as those in Example 5.

[0066] Example 7

[0067] The only difference between Example 7 and Example 5 is that the C60 material containing a tetrazolyl olefin bond described in Example 3 is used instead of the C60 material containing a tetrazolyl olefin bond described in Example 1, and the remaining operations are the same as those in Example 5.

[0068] Example 8

[0069] The only difference between Example 8 and Example 5 is that the C60 material containing a tetrazolyl olefin bond described in Example 4 is used instead of the C60 material containing a tetrazolyl olefin bond described in Example 1, and the remaining operations are the same as those in Example 5.

[0070] Performance research of perovskite solar cells described in this application:

[0071] The perovskite solar cells described in Examples 5-8 of the present application were packaged and kept in an air environment. The photoelectric conversion efficiency was tested at regular intervals. The results are shown in Table 1.

[0072] Table 1

[0073] 0 hours 36 hours 120 hours 360 hours 720 hours Example 5 13.50％ 13.46％ 13.35％ 13.21％ 13.07％ Example 6 12.60％ 12.53％ 12.38％ 12.29％ 12.17％ Example 7 10.09％ 10.03％ 9.85％ 9.73％ 9.38％ Example 8 11.80％ 11.69％ 11.53％ 11.38％ 11.26％

[0074] It can be seen from Table 1 that the perovskite solar cell described in this application has good stability.

[0075] Although the above embodiments have been shown and described, it is understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. Changes, modifications, substitutions and variations of the above embodiments by those skilled in the art are all within the scope of protection of the present invention.

Claims

1. A method for preparing a C60 material containing a tetrazolyl olefin bond, characterized in that: The following steps are involved: (1) mixing tetrazole with a haloolefin to obtain a tetrazolyl haloolefin; (2) Mixing halogenated C60 and tetrazolyl haloolefin to carry out a Sonogashira coupling reaction to obtain the C60 material containing a tetrazolyl olefin bond.

2. The method for preparing the C60 material containing a tetrazolyl olefin bond according to claim 1, wherein: The structural formula of the halogenated olefin is C n H 2n-1 X, wherein 1≤n≤8, and x is selected from one or more of F, Cl, and Br; And / or, the molar ratio of the tetrazole to the halogenated olefin is 1:(1-10).

3. The method for preparing the C60 material containing a tetrazolyl olefin bond according to claim 1, wherein: In step (1), the mixing temperature is 20-30° C., and the mixing time is 1-3 h.

4. The method for preparing the C60 material containing a tetrazolyl olefin bond according to claim 1, wherein: The molar ratio of the halogenated C60 to the tetrazolyl halogenated olefin is 1:(3-5).

5. The method for preparing the C60 material containing tetrazolyl olefin bonds according to claim 1, wherein: The Sonogashira coupling reaction is carried out in the presence of a catalyst; Preferably, the molar ratio of the halogenated C60 to the catalyst is 1:(0.01-0.05).

6. The method for preparing the C60 material containing a tetrazolyl olefin bond according to claim 5, characterized in that: The catalyst includes a palladium catalyst and copper iodide.

7. The method for preparing the C60 material containing a tetrazolyl olefin bond according to claim 5, characterized in that: The catalyst comprises Pd(PPh3)4 and CuI. Preferably, the mass ratio of Pd(PPh3)4 to CuI is 1:(1-3).

8. The method for preparing the C60 material containing tetrazolyl olefin bonds according to claim 1, characterized in that: The temperature of the Sonogashira coupling reaction is 30-50° C., and the time of the Sonogashira coupling reaction is 30-50 min.

9. An electron transport layer, characterized in that The invention comprises a C60 material containing a tetrazolyl olefin bond obtained by the preparation method according to any one of claims 1 to 8.

10. A perovskite solar cell, characterized in that: comprising the electron transport layer according to claim 9; Preferably, the thickness of the electron transport layer is 20-80 nm.