Fullerene derivative, perovskite solar cell containing fullerene derivative, and preparation method and application of perovskite solar cell

Abstract

The invention provides a fullerene derivative, a perovskite solar cell containing the fullerene derivative and a preparation method and application of the fullerene derivative, and belongs to the technical field of perovskite solar cells, the fullerene derivative has a structure as shown in the following formula I. The perovskite solar cell comprises a first electrode layer, a second electrode layer, a third electrode layer and a fourth electrode layer which are sequentially stacked, the perovskite solar cell comprises a first electrode layer, a first current carrier transmission layer, a perovskite layer, a second current carrier transmission layer, a first current carrier barrier layer and a second electrode layer, the second current carrier transmission layer comprises a fullerene layer and a fullerene derivative layer, and the fullerene derivative layer is located between the fullerene layer and the first current carrier barrier layer. The fullerene derivative layer is formed by the fullerene derivative. The performance and the stability of the solar cell using the fullerene derivative are remarkably improved, and the cost of the cell is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cells, and relates to a fullerene derivative, a perovskite solar cell containing the fullerene derivative, and a preparation method and application thereof. Background Art

[0002] Perovskite solar cells have attracted much attention due to their high efficiency, low cost and diverse applications. Despite their outstanding performance and cost-effectiveness, perovskite solar cells still face an important challenge, namely the poor adhesion of the functional layer on the perovskite surface, especially between C60 and tin oxide, which is particularly evident during the area enlargement of perovskite cells. The adhesion problem of the functional layer on the perovskite surface has led to serious performance degradation in practical applications, especially in enlarged applications. Specifically, the unstable adhesion of the functional layer can lead to delamination problems, thereby compromising the performance and life of the solar cell. This problem is one of the bottlenecks of perovskite solar cell technology, limiting its widespread adoption in various application fields.

[0003] Functional layers play a key role in solar cells, not only for transporting charge carriers, but also for protecting perovskite films from the external environment. However, these functional layers are often exposed to complex environmental conditions, such as high temperature, high humidity, and ultraviolet radiation, which can weaken their adhesion to perovskite films.

[0004] Unstable adhesion of the functional layer can lead to delamination, which in turn causes degradation of the performance of the solar cell. Delamination not only affects the energy conversion efficiency of the solar cell, but also causes damage to the functional layer, reducing the life of the solar cell. This poses a major problem for applications that expect long-term reliability of solar cells, such as solar power plants and embedded power systems.

[0005] Although there are some existing technologies that attempt to improve the adhesion of the functional layer, they fail to provide durability, environmental stability, and mechanical stability. The shortcomings of the existing technologies mainly include the following aspects:

[0006] Surface pretreatment: such as plasma treatment, UV irradiation and other methods to improve its adhesion. However, these treatments are usually temporary and cannot withstand complex environmental conditions such as high temperature or high humidity.

[0007] Coating technology: Applying adhesion layers is another common method to improve adhesion. However, these coatings are often insufficient to maintain stability, especially under prolonged exposure to UV radiation.

[0008] Use of adhesives: In some cases, adhesives are used to enhance the adhesion of the functional layers to the perovskite film. However, such approaches are generally not suitable for large-scale production because they may introduce instabilities.

[0009] Mechanical stability: In some applications, solar cells need to withstand mechanical stress, such as vibration, impact or bending. Existing technologies fail to provide sufficient mechanical stability, resulting in functional layers easily falling off.

[0010] Persistence: The effects of existing technology improvements are often short-lived, with the adhesion of the functional layers gradually weakening over time. This means that the performance of the solar cell degrades over time, reducing its reliability and lifetime.

[0011] These deficiencies hinder the widespread application of solar cell technology, especially in large-scale production and practical applications. In view of this problem, the present invention aims to provide a new method to enhance the adhesion between the functional layer and the perovskite film and solve the deficiencies of the prior art.

[0012] In summary, the functional layer adhesion problem is an important bottleneck in perovskite solar cell technology, which directly affects the performance, reliability and life of solar cells. Existing technologies have attempted to improve adhesion but have failed to provide stability, environmental stability and mechanical stability. This problem restricts the widespread application of solar cell technology, especially in large-scale production and practical applications. Summary of the invention

[0013] In view of the deficiencies in the prior art, the object of the present invention is to provide a fullerene derivative, a perovskite solar cell containing the same, and a preparation method and application thereof.

[0014] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0015] In one aspect, the present invention provides a fullerene derivative having a structure as shown in the following formula I:

[0016]

[0017] Formula I

[0018] wherein A represents fullerene and n is an integer from 0 to 20 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20).

[0019] Preferably, A is C60 or C70.

[0020] Preferably, n is 12-18.

[0021] The fullerene derivative of the present invention is simple to synthesize and has improved carrier transmission efficiency.

[0022] In another aspect, the present invention provides a method for preparing the fullerene derivative as described above, the preparation method comprising the following steps:

[0023] (1) The compound represented by formula II reacts with the acyl chloride compound represented by formula III to obtain the compound represented by formula IV. The reaction formula is as follows:

[0024] ;

[0025] (2) The compound represented by formula IV reacts with fullerene to obtain the compound represented by formula V. The reaction formula is as follows:

[0026] ;

[0027] (3) The compound represented by formula V is reacted with bromotrimethylsilane, and then subjected to a hydrolysis reaction to obtain the compound represented by formula I. The reaction formula is as follows:

[0028] ;

[0029] Wherein Et is ethyl, A represents fullerene, and n is an integer of 0-20.

[0030] Preferably, in step (1), the molar ratio of the compound represented by formula II to the acyl chloride compound represented by formula III is 1:(1-1.5), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5. In order to make the reaction more complete, the acyl chloride compound is in excess during the reaction.

[0031] Preferably, the reaction in step (1) is carried out in the presence of an alkaline substance.

[0032] Preferably, the alkaline substance is selected from triethylamine.

[0033] Preferably, the reaction in step (1) is carried out in an organic solvent selected from dichloromethane and / or chloroform.

[0034] Preferably, the reaction in step (1) is performed by adding the acyl chloride in an ice bath for 1-3 hours (e.g., 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours), and then continuing to stir the reaction at room temperature for 15-20 hours (e.g., 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours).

[0035] Preferably, in step (2), the molar ratio of the compound represented by formula IV to fullerene is 1:(1-1.5), such as 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5. In order to make the reaction more complete, fullerene is made excessive during the reaction.

[0036] Preferably, the reaction in step (2) is carried out at 2 The reaction is carried out in the presence of diazabicyclo (DBU). The presence of diazabicyclo is mainly to prevent fullerenes from aggregating to form polyfullerene adducts.

[0037] Preferably, the reaction in step (2) is carried out in an organic solvent, and the organic solvent is selected from toluene.

[0038] Preferably, the reaction temperature in step (2) is room temperature, and the reaction time is 22-26 h, for example 22 h, 23 h, 24 h, 25 h or 26 h.

[0039] Preferably, the molar ratio of the compound represented by formula V in step (3) to bromotrimethylsilane is 1:(1-1.5), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5.

[0040] Preferably, the reaction of the compound represented by formula V and bromotrimethylsilane in step (3) is carried out at room temperature, and the reaction time is 10-30 h, for example, 10 h, 13 h, 15 h, 18 h, 20 h, 23 h, 25 h, 28 h or 30 h.

[0041] Preferably, the reaction of the compound represented by formula V and bromotrimethylsilane in step (3) is carried out in an organic solvent selected from dichloromethane or chloroform.

[0042] Preferably, the hydrolysis reaction in step (3) is carried out in a mixed solvent of methanol and water.

[0043] Preferably, the hydrolysis reaction in step (3) is carried out at room temperature, and the hydrolysis reaction time is 10-30 h, for example, 10 h, 13 h, 15 h, 18 h, 20 h, 23 h, 25 h, 28 h or 30 h.

[0044] On the other hand, the present invention provides a perovskite solar cell, which comprises a first electrode layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a first carrier blocking layer, and a second electrode layer stacked in sequence, wherein the second carrier transport layer comprises a fullerene layer and a fullerene derivative layer, the fullerene derivative layer is located between the fullerene layer and the first carrier blocking layer, and the fullerene derivative layer is formed by the fullerene derivative as described above.

[0045] In the present invention, the fullerene derivative having the structure shown in Formula I as described above has an anchoring group phosphate group, which can capture the first carrier blocking layer SnOx to form a strong and stable covalent bond, thereby achieving stable adhesion between C60 and tin oxide.

[0046] Preferably, the first electrode layer is FTO glass or ITO glass.

[0047] Preferably, the first carrier transport layer is selected from NiOx layer, wherein 1≤x≤1.5, for example, x may be 1, 1.1, 1.2, 1.3, 1.4 or 1.5.

[0048] Preferably, the thickness of the first carrier transport layer is 15-20 nm, for example, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm or 20 nm.

[0049] Preferably, the general formula of the perovskite material of the perovskite light absorbing layer is ABY 3 , where A is CH 3 NH 3 + 、CH(NH 2 ) 2 + , Cs + or Rb + Any one or a combination of at least two of the following, B is Pb 2+ Sn 2+ Or Ge 2+ Any one or a combination of at least two of - Br - or I - Any one or a combination of at least two of the following.

[0050] Preferably, the thickness of the perovskite light absorbing layer is 200-900nm, for example, 200nm, 250nm, 280nm, 300nm, 330nm, 350nm, 380nm, 400nm, 450nm, 480nm, 500nm, 550nm, 580nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm or 900nm.

[0051] Preferably, the thickness of the fullerene layer is 15-25 nm, for example, 15 nm, 18 nm, 20 nm, 23 nm or 25 nm.

[0052] Preferably, the thickness of the fullerene derivative layer is 5-10 nm, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm or 10 nm.

[0053] Preferably, the first carrier blocking layer is selected from SnOx layer, 1≤x≤2; for example, x can be 1, 1.3, 1.5, 1.8 or 2, etc.

[0054] Preferably, the thickness of the first carrier blocking layer is 5-15 nm, for example, 5 nm, 7 nm, 9 nm, 10 nm, 12 nm, 14 nm or 15 nm.

[0055] Preferably, the second electrode layer is selected from any one of Au, Ag or a low temperature carbon electrode.

[0056] In another aspect, the present invention provides a method for preparing the perovskite solar cell as described above, the method comprising the following steps:

[0057] a. preparing a first carrier transport layer on the first electrode layer;

[0058] b. coating a perovskite precursor solution on the first carrier transport layer and annealing to form a perovskite layer;

[0059] c. evaporating a fullerene layer on the perovskite layer;

[0060] d. coating a fullerene derivative precursor solution on the fullerene layer to prepare a fullerene derivative layer;

[0061] e. preparing a first carrier blocking layer on the fullerene derivative layer;

[0062] f. Preparing a second electrode layer on the first carrier blocking layer.

[0063] Preferably, the annealing in step b is annealing at 150° C. for 15-25 min, such as 15 min, 18 min, 20 min, 23 min or 25 min.

[0064] Preferably, the perovskite precursor solution in step b comprises a perovskite material and a solvent.

[0065] Preferably, the general formula of the perovskite material is ABY 3 , where A is CH 3 NH 3 + 、CH(NH 2 ) 2 + , Cs + or Rb + Any one or a combination of at least two of the following, B is Pb 2+ Sn 2+ Or Ge 2+ Any one or a combination of at least two of - Br - or I- Any one or a combination of at least two of the following.

[0066] Preferably, the solvent includes one or a combination of at least two of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylacetamide (DMAC), N,N-dimethylpropylene urea (DMPU), acetonitrile (ACN) or 2-mercaptoethanol (2-ME).

[0067] Preferably, the concentration of the perovskite material in the perovskite precursor solution is 0.8-1.5M, for example 0.8M, 1.0M, 1.2M, 1.4M or 1.5M.

[0068] Preferably, the solvent of the fullerene derivative precursor solution in step d is isopropyl alcohol (IPA).

[0069] Preferably, the molar concentration of the fullerene derivative precursor solution is 1-5 mM, for example, 1 mM, 1.5 mM, 2 mM, 2.5 mM, 3 mM, 3.5 mM, 4 mM, 4.5 mM or 5 mM.

[0070] In another aspect, the present invention provides a perovskite solar cell module, wherein the perovskite solar cell module comprises the perovskite solar cell as described above.

[0071] On the other hand, the present invention provides a perovskite tandem solar cell, which includes a top cell located on the light-receiving surface and a bottom cell located on the back of the top cell, wherein the top cell includes the perovskite solar cell as described above, and the bottom cell includes a crystalline silicon solar cell or a thin-film solar cell.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] The present invention modifies fullerenes to enhance their adhesion to tin oxide, and the modified fullerene surface will produce stronger adhesion, especially under the working conditions of solar cells, such as high temperature, high humidity, ultraviolet radiation and mechanical stress. The performance and stability of the solar cell using the fullerene derivatives of the present invention are significantly improved, and the improved adhesion of the improved functional layer will reduce the manufacturing cost of the solar cell because it reduces problems in production, such as remanufacturing and maintenance costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1It is a schematic structural diagram of the fullerene layer, the fullerene derivative layer, and the first carrier blocking layer in the perovskite solar cell of the present invention, wherein 1 is the fullerene layer, 2 is the fullerene derivative layer, and 3 is the first carrier blocking layer. DETAILED DESCRIPTION

[0075] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0076] Preparation Example 1

[0077] This embodiment provides a preparation of a fullerene derivative (wherein n is 17), which comprises the following steps:

[0078]

[0079]

[0080] In dry CH 2 Cl 2 18-(dioxophosphoyl)-1-octadecanol (0.456 g, 1.122 mmol) and triethylamine (0.227 g, 0.32 mL, 2.244 mmol) were added to 1-octadecanol (25.0 mL), and methylmalonyl chloride (0.230 g, 0.18 mL, 1.683 mmol) was added dropwise at 0°C using a dropping funnel. The addition was completed within 30 min, and the reaction solution was stirred at 0°C for 2 h, and then at room temperature for 18 h. The crude material was purified by flash silica gel chromatography using pure ethyl acetate to obtain 0.481 g.

[0081]

[0082] 1 H-NMR (400 MHz, 19.7°C, CDCl 3 ):d[ppm]=1.21(m,28H,H-7–H-20),1.28(t, 3 J H23 / H24 =7.1Hz,4H,H-24),1.50–1.72(m,2H,H-5),1.83(m,2H,H-2),3.35(s,2H,H-7),3.38(t,3J H1 / H2 =6.8Hz,2H,H-1),3.72(s,3H,H-8),4.12(t, 3 J H5 / H6 =6.6Hz,2H,H-6);

[0083] 13CNMR (100.5MHz, 20.5°C, CDCl 3 ):d[ppm]=16.35(d, 3 J P / C24 =6.5Hz,C-24),22.26(d, 2 J P / C21 =5.5Hz,C-21),25.55(d, 1 J P / C22 =140.6Hz,C-22),25.64(C-7),28.30,28.96,29.05,29.25,29.37,29.43,29.46,29.50,29.54(C-6,C-8–C-19),30.48(d, 3 J P / C20 =16.6Hz,C-20),41.26(C-3),52.31(C-1),61.22(d, 2 JP / C23=6.5Hz,C-23),65.59(C-5),166.44,166.92(C-2,C-4); 31 P-NMR (161.8MHz, 21.6°C, CDCl3): d[ppm]=33.14(s,P).

[0084]

[0085]

[0086] Under nitrogen and light-proof conditions, C60 (2.688 g, 3.730 mmol) was dissolved in deoxygenated toluene (3500 mL) and nitrogen was bubbled for 30 min (all C60 must be completely dissolved; otherwise, a temporary excess of malonate will lead to polymer formation). When all C60 was dissolved, 1-methyl-3-(18-dioxophosphooctadecyl)malonate (0.378 g, 0.746 mmol) and I 2 (0.240 g, 0.952 mmol). After 10 minutes, a solution of DBU (0.273 g, 1.791 mmol) in deoxygenated toluene (200 mL) was added from a dropping funnel over 1 hour. The solution was stirred overnight at room temperature, and the red solution was applied to a dry-packed pre-treated silica gel column (l = 23 cm, d = 7 cm) for flash chromatography (first with pure toluene until all unreacted C60 was eluted, then with a mixture of toluene / ethanol = 20:1, on SiO 2The pure C60 was eluted by pure toluene, while its phosphonate was not eluted by toluene. The material (0.830 g) still contained the bis-adduct (s) and was purified by a second column (SiO 2 ; l=15cm, d=7cm, pure ethyl acetate) to obtain 0.709g.

[0087]

[0088] 1 H-NMR (400 MHz, 26.9°C, CDCl 3 ):d[ppm]=1.22–1.84(m,34H,H-6–H-22),1.29(t,3JH23 / H24=7.1Hz,6H,H-24),4.07(m,7H,H-1,H-23),4.48(t,3JH5 / H6=6.5Hz,2H,H-5);

[0089] 13 C-NMR (100.5 MHz, 22.0 °C, CDCl 3 ):d[ppm]=16.42(d,3JP / C24=6.5Hz,C-24),22.31(d,2JP / C21=5.5Hz,C-21),25.60(d,1JP / C22=140.6Hz,C-22),25.90(C-7),28.49,29.04 ,29.15,29.33,29.54,29.59,29.63(C-6,C-8,C-9,C-10,C-11,C-12,C -13,C-14,C-15,C-16,C-17,C-18,C-19),30.55(d,3JP / C20=16.6Hz,C -20),52.07(C-3),53.91(C-1),61.29(d,2JP / C23=6.5Hz,C-23),65.25(C-5),71.45(C60,sp2-C),138.83,139.03,140.85,141.80,141.84 ,142.10,142.88,142.91,142.98,143.79,144.52,144.59,144.80,14 5.03,145.09,145.16,145.23(C60sp3-C),163.51,164.02(C-2,C-4);

[0090] 31 P-NMR (161.8 MHz, 26.9 ° C, CDCl 3 ):d[ppm]=33.14(s,P).

[0091]

[0092] Under nitrogen protection, (1-methoxy-3-(18-diethylphosphonic acid octadecyloxy)-methane)-1,2-dihydrofullerene (100 mg) was dissolved in toluene (40.0 ml). The solution was cooled with a mixture of sodium chloride and ice. BrSiMe was slowly added. 3 (Trimethylsilyl bromide, 2.0 mL). The solution was stirred in a cooling bath for 1.5 hours and then at room temperature for 24 hours. Toluene, hexamethyldisiloxane, and excess bromotrimethylsiloxane were removed under vacuum. To remove any remaining traces of reagents, dry toluene (5.0 mL) was added and then removed under vacuum. This process was repeated four times. The residue was dissolved in CHCl 3 (50.0 mL). CH 3 OH (20.0 mL) and H 2 O (2.0 mL), stirred at room temperature for 24 h, and the remaining solvents except water were removed under vacuum. 50 mL of acetone was added to the brown suspension. Phosphoric acid was separated with a funnel, washed thoroughly with acetone, and dried under vacuum. The acid (which still contained a considerable amount of hemiethyl ester) was dissolved in CHCl under nitrogen. 3 (35 mL), the solution was cooled with a mixture of sodium chloride and ice. BrSiMe 3 (5.0 mL). The solution was stirred in the cooling bath for 1.5 h and then at room temperature for 24 h. This process was repeated. After the fourth deprotection procedure, the product was treated with CHCl 3 The compound was purified by dissolving it in acetone and precipitating it. This process was repeated twice. In order to precipitate all the phosphonic acid, CHCl was removed on a rotary evaporator. 3 , 71 mg of the target compound was obtained.

[0093]

[0094] 1 H-NMR (400 MHz, 21.5 ° C, CDCl 3 ):d[ppm]=1.18–1.80(m,34H,H-6–H-22),4.43(t, 3 J H5 / H6 =6.5Hz,2H,H-5); 13 C-NMR (100.5 MHz, 26.9 ° C, CDCl 3 ):d[ppm]=22.43(d, 2 J P / C21 =4.9Hz,C-21),26.49(d,1 J P / C22 =140.9Hz,C-22),25.87(C-7),28.44,29.11,29.38,29.53,29.55,29.62(C-6, C-8,C-9,C-10,C-11,C-12,C-13,C-14,C-15,C-16,C-17,C-18,C-19),30.59(d, 3 J P / C20 =17.6Hz,C-20),52.03(C-3),53.91(C-1),67.47(C-5),71.39(C60,sp2-C),138.77,138.98,140.82,141.75,141.79,142.07,14 2.84,142.88,142.95,143.75,144.49,144.55,144.76,144.97,145.04,145.13,145.18(C60sp3-C),163.56,164.06(C-2,C-4);

[0095] 31 P-NMR (161.8 MHz, 22.7 ° C, CDCl 3 ):d[ppm]=33.93(s,P);

[0096] IR(ATR):n[cm -1 ]=2917,2846,2359,2330,1745,1460,1430,1267,1234,1207,1185,1097,1060,1004,943,738,703,670,580,525.

[0097] MS (MALDI-TOF, dctb): m / z=1169 (M + ),M=1169.17g / mol.

[0098] Example 1

[0099] This embodiment provides a perovskite solar cell, and the preparation method thereof comprises the following steps:

[0100] First, a 150 μm thick N-type single crystal silicon wafer is sequentially pre-cleaned with ozone deionized water, post-cleaned with an ozone hydrofluoric acid mixed solution, and finally cleaned and etched with a hydrofluoric acid / nitric acid mixed solution to form an N-type crystalline silicon wafer with a double-sided velvet surface;

[0101] A 2nm intrinsic hydrogenated amorphous silicon passivation layer is deposited on both sides of the front and back of the N-type silicon by PECVD to form the first passivation layer located on the front of the N-type crystalline silicon wafer. Then, a 9nm P-type hydrogenated amorphous silicon doping layer and a 6nm N-type hydrogenated amorphous silicon doping layer are deposited on both sides to form the second passivation layer located on the back of the N-type crystalline silicon wafer, thereby having a symmetrical double-sided cell structure.

[0102] About 30nm of ITO is deposited on the N-type surface amorphous silicon by sputtering to obtain the bottom battery.

[0103] 15nm NiOx and 400nm perovskite (CH(NH 2 ) 2 PbI 3 ) 0.83 Cs 0.17 Pb(I 0.82 Br 0.18 ) 3 (The band gap of the perovskite absorption layer is 1.66eV), 1nmLiF, the substrate enters the evaporation chamber to deposit 12nmC60, and a 5nmC60 derivative layer is prepared by slit coating to increase the adhesion of the film layer. The n in the derivative is 17, and 9nmSnO is deposited by ALD (atomic layer deposition). 2 ; 110nm IZO and 90nm MgF are deposited on the front and back of the battery in sequence 2 ; Screen-print Ag grid lines with a thickness of about 180nm on the front and back of the battery, and sinter and solidify them.

[0104] Example 2

[0105] This embodiment provides a perovskite solar cell, and the preparation method thereof comprises the following steps:

[0106] 20nmNiO was prepared on FTO glass x , 500nm Cs 0.17 FA 0.83 PbI 3 Perovskite absorption layer; 15nmC60 is prepared by evaporation deposition; a 5nmC60 derivative layer is prepared by slit coating to increase the adhesion of the film layer, where n in the derivative is 17; 15nmSnO is formed by ALD 2 ; Then deposit 50nmITO and 70nmCu.

[0107] Example 3

[0108] This embodiment provides a perovskite solar cell, and the preparation method thereof comprises the following steps:

[0109] The PEN (polyethylene naphthalate) / ITO substrate was cleaned by ultrasonic cleaning with detergent, deionized water, acetone and anhydrous ethanol, and then dried with a nitrogen gun; the power of ultrasonic cleaning was 100 Hz, the time of ultrasonic cleaning was 15 minutes, and then laser P1 was scratched.

[0110] Prepare 18nm NiOx hole transport layer and 500nm Cs 0.17 FA 0.83 PbI 3 Perovskite absorption layer, 15nmC60 is prepared by evaporation deposition, and an 8nmC60 derivative layer is prepared by slit coating to increase the adhesion of the film layer, where n in the derivative is 17, and 15nmSnO is formed by ALD 2 ; Laser Scribing P2

[0111] Then 50nm ITO and 70nm Cu are deposited, and P3 is laser scribed to complete the component preparation.

[0112] Example 4

[0113] This embodiment provides a method for preparing a solar cell module, which is different from Example 2 in that the derivative n is 16, and the synthesis method refers to Preparation Example 1, except that the dioxyphosphoryl long-chain alcohol used in the preparation process is replaced with a raw material of the corresponding chain length.

[0114] The remaining steps refer to Example 2.

[0115] Example 5

[0116] This embodiment provides a method for preparing a solar cell, which is different from Example 2 in that the derivative n is 15, and the synthesis method refers to Preparation Example 1, except that the dioxyphosphoryl long-chain alcohol used in the preparation process is replaced with a raw material of the corresponding chain length.

[0117] The remaining steps refer to Example 2.

[0118] Example 6

[0119] This embodiment provides a method for preparing a solar cell, which is different from Example 2 in that the derivative n is 13, and the synthesis method refers to Preparation Example 1, except that the dioxyphosphoryl long-chain alcohol used in the preparation process is replaced with a raw material of the corresponding chain length.

[0120] The remaining steps refer to Example 2.

[0121] Example 7

[0122] This embodiment provides a method for preparing a solar cell, which is different from Example 2 in that the derivative n is 12, and the synthesis method refers to Preparation Example 1, except that the dioxyphosphoryl long-chain alcohol used in the preparation process is replaced with a raw material of the corresponding chain length.

[0123] The remaining steps refer to Example 2.

[0124] Example 8

[0125] This embodiment provides a method for preparing a solar cell.

[0126] The difference from Example 2 is that the derivative n is 18, and the synthesis method refers to Preparation Example 1, except that the dioxyphosphoryl long-chain alcohol used in the preparation process is replaced with a raw material of the corresponding chain length.

[0127] The remaining steps refer to Example 2.

[0128] Comparative Example 1

[0129] The only difference from Example 2 is that there is no C60 fullerene derivative layer.

[0130] Comparative Example 2

[0131] The fullerene derivative used in Example 2 was replaced with a C60 fullerene derivative with the following structure:

[0132] .

[0133] Comparative Example 3

[0134] The only difference from Example 2 is that there is no C60 layer, and a 5 nm C60 derivative layer is directly prepared on the perovskite absorption layer.

[0135] The performance of the perovskite solar cells of the embodiments and comparative examples were tested in the following manner: a single-junction perovskite cell with an area of ​​300×300 cm was tested at 25° C. and standard AM1.5 lighting conditions.

[0136] Stability test: In a nitrogen atmosphere, without packaging, the light is continuously irradiated for 1000 hours. The stability is expressed as the percentage of the efficiency after illumination to the initial efficiency.

[0137] The test results are shown in Table 1:

[0138] Table 1

[0139]

[0140] Moreover, there is no film peeling phenomenon when the C60 derivative layer is passed through, while some battery modules without the C60 derivative layer have film peeling phenomenon.

[0141] In terms of stability, after adding the C60 derivative layer, the efficiency can still be maintained at more than 84.3% of the initial efficiency under 10,000 hours of continuous illumination.

[0142] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the fullerene derivatives, the perovskite solar cells containing the fullerene derivatives, and the preparation methods and applications thereof, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A fullerene derivative, characterized in that: The fullerene derivative has a structure as shown in the following formula I: ； Formula I Wherein A represents fullerene, and n is an integer of 0-20.

2. The fullerene derivative according to claim 1, characterized in that A is C60 or C70; n is 12-18.

3. The method for preparing a fullerene derivative according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: (1) The compound represented by formula II reacts with the acyl chloride compound represented by formula III to obtain the compound represented by formula IV. The reaction formula is as follows: ； (2) The compound represented by formula IV reacts with fullerene to obtain the compound represented by formula V. The reaction formula is as follows: ； (3) The compound represented by formula V is reacted with bromotrimethylsilane, and then subjected to a hydrolysis reaction to obtain the compound represented by formula I. The reaction formula is as follows: ； Wherein Et is ethyl, A represents fullerene, and n is an integer of 0-20.

4. The preparation method according to claim 3, characterized in that: In step (1), the molar ratio of the compound represented by formula II to the acyl chloride compound represented by formula III is 1:(1-1.5); The reaction in step (1) is carried out in the presence of an alkaline substance; the alkaline substance is selected from triethylamine; The reaction in step (1) is carried out in an organic solvent selected from dichloromethane and / or chloroform; The reaction in step (1) is to add the acyl chloride compound in an ice bath and react for 1-3 hours, and then continue to stir and react for 15-20 hours at room temperature; In step (2), the molar ratio of the compound represented by formula IV to fullerene is 1:(1-1.5); The reaction in step (2) is carried out in the presence of I2 and a diazabicyclo; The reaction in step (2) is carried out in an organic solvent, and the organic solvent is selected from toluene; The reaction temperature in step (2) is room temperature and the reaction time is 22-26 hours; In step (3), the molar ratio of the compound represented by formula V to bromotrimethylsilane is 1:(1-1.5); Step (3) The reaction of the compound represented by formula V with bromotrimethylsilane is carried out at room temperature, and the reaction time is 10-30 hours; Step (3) The reaction of the compound represented by formula V with bromotrimethylsilane is carried out in an organic solvent selected from dichloromethane or chloroform; The hydrolysis reaction in step (3) is carried out in a mixed solvent of methanol and water; The hydrolysis reaction in step (3) is carried out at room temperature, and the hydrolysis reaction time is 10-30 hours.

5. A perovskite solar cell, characterized in that: The perovskite solar cell comprises a first electrode layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a first carrier blocking layer, and a second electrode layer stacked in sequence, wherein the second carrier transport layer comprises a fullerene layer and a fullerene derivative layer, wherein the fullerene derivative layer is located between the fullerene layer and the first carrier blocking layer, and wherein the fullerene derivative layer is formed by the fullerene derivative according to claim 1 or 2.

6. The perovskite solar cell according to claim 5, characterized in that: The first electrode layer is FTO glass or ITO glass; The first carrier transport layer is selected from a NiOx layer, where 1≤x≤1.5; The thickness of the first carrier transport layer is 15-20 nm; The general formula of the perovskite material of the perovskite light absorbing layer is ABY3, wherein A is CH3NH3 + 、CH(NH2)2 + , Cs + or Rb + Any one or a combination of at least two of the following, B is Pb 2+ Sn 2+ Any one or a combination of at least two of - Br - or I - Any one or a combination of at least two of the following: The thickness of the perovskite light absorbing layer is 200-900nm; The thickness of the fullerene layer is 15-25 nm; The thickness of the fullerene derivative layer is 5-10 nm; The first carrier blocking layer is selected from SnOx layer, 1≤x≤2; The thickness of the first carrier blocking layer is 5-15 nm; The second electrode layer is selected from any one of Au, Ag or a low temperature carbon electrode.

7. A method for preparing a perovskite solar cell according to claim 5 or 6, characterized in that: The preparation method comprises the following steps: a. preparing a first carrier transport layer on the first electrode layer; b. coating a perovskite precursor solution on the first carrier transport layer and annealing to form a perovskite layer; c. evaporating a fullerene layer on the perovskite layer; d. coating a fullerene derivative precursor solution on the fullerene layer to prepare a fullerene derivative layer; e. preparing a first carrier blocking layer on the fullerene derivative layer; f. Preparing a second electrode layer on the first carrier blocking layer.

8. The preparation method according to claim 7, characterized in that: The annealing in step b is annealing at 150° C. for 15-25 min; The perovskite precursor solution in step b comprises a perovskite material and a solvent; The general formula of the perovskite material is ABY3, where A is CH3NH3 + 、CH(NH2)2 + , Cs + or Rb + Any one or a combination of at least two of the following, B is Pb 2+ Sn 2+ Any one or a combination of at least two of - Br - or I - Any one or a combination of at least two of the following: The solvent includes one or a combination of at least two of N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, dimethylacetamide, N,N-dimethylpropyleneurea, acetonitrile or 2-mercaptoethanol; The concentration of the perovskite material in the perovskite precursor solution is 0.8-1.5M; The solvent of the fullerene derivative precursor solution in step d is isopropanol; The molar concentration of the fullerene derivative precursor solution is 1-5 mM.

9. A perovskite solar cell module, characterized in that: The perovskite solar cell module comprises the perovskite solar cell according to claim 5 or 6.

10. A perovskite tandem solar cell, characterized in that: The perovskite tandem solar cell comprises a top cell located on the light-receiving surface and a bottom cell located on the back of the top cell, wherein the top cell comprises the perovskite solar cell as claimed in claim 5 or 6, and the bottom cell comprises a crystalline silicon solar cell or a thin-film solar cell.

Images