Novel perovskite solar cell

Abstract

The invention discloses a novel perovskite solar cell, which sequentially comprises a transparent substrate, a first electrode, a carrier transport layer and a second electrode, and is characterized in that the carrier transport layer comprises a perovskite current-carrying transmission layer enabling charge carriers to directionally move; the perovskite current-carrying transmission layer is composed of a perovskite precursor doped with a metal ion Mn < + >, so that the perovskite current-carrying transmission layer has polarity, and the metal ion Mn < + > is a 3 + or 1 + metal ion. According to the perovskite solar cell, the perovskite current-carrying transmission layer with polarity is formed by doping metal ions, and the current carrier transmission layer and the optical active layer are combined, so that the use of a charge transmission material in the perovskite solar cell is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of perovskite cells, and in particular to a novel perovskite solar cell. Background Art

[0002] With the continuous growth of global energy demand and the improvement of environmental awareness, the market demand for solar cells continues to expand. Perovskite solar cells are gradually becoming an important choice in the solar cell market with their unique advantages and broad development prospects. Perovskite is a type of chemical structure with the formula ABX3 (A + For MA + , F.A. + , Cs + etc.; B is Pb 2+ , Sn 2+ etc.; X is a halogen or pseudohalogen ion, such as I - Br - , Cl - , CN - Perovskite solar cells use perovskite structure halides as light absorption layer materials, and have the characteristics of adjustable band gap, high absorption coefficient, low temperature coefficient, lightness, thinness and flexibility. Its basic principle is to convert light energy into electrical energy through the photovoltaic effect, that is, under light, perovskite materials absorb photons and generate electron-hole pairs. These carriers are separated inside the battery and transported to the external circuit to generate current. As the third generation of solar cell technology, perovskite solar cells are gradually becoming the focus of the solar cell field with their high energy conversion efficiency, low cost and environmental protection characteristics.

[0003] Charge transport materials play a vital role in perovskite solar cells and are divided into two types: electron transport materials and hole transport materials, which are responsible for extracting photogenerated charges and preventing charge recombination, respectively, and are crucial to the photoelectric conversion efficiency and stability of the battery. At present, the common electron transport materials are mainly TiO2 and SnO2. However, these inorganic semiconductors generally require high-temperature heat treatment processes, which is not conducive to the preparation of flexible batteries. At the same time, they are sensitive to ultraviolet light, which affects the photovoltaic performance and stability of the battery. The common hole transport material is mainly Sprio-OMeTAD, but its synthesis process is complicated, the yield is low, and the price is expensive, which is not suitable for large-scale industrial applications. Summary of the invention

[0004] In view of the above-mentioned shortcomings, the present invention proposes a novel perovskite solar cell, which utilizes doped metal ions to form a polar perovskite carrier transport layer, combines the carrier transport layer and the photoactive layer, thereby reducing the use of charge transport materials in the perovskite solar cell.

[0005] To achieve the above object, the present invention provides the following technical solution: a novel perovskite solar cell, the cell sequentially comprises a transparent substrate, a first electrode, a carrier transport layer, and a second electrode, the carrier transport layer comprises a perovskite current transport layer for directing charge carriers, the perovskite current transport layer is doped with metal ions M n+ The perovskite precursor is composed of a metal ion M n+ It is a 3+ or 1+ metal ion.

[0006] As an improvement, the perovskite precursor is composed of an organic halide perovskite material with an ABX3 structure, and metal ions are doped in the perovskite precursor in the form of halides or pseudo-halides, including but not limited to MI n ,MBr n 、MCl n MF n or MCN n .

[0007] As an improvement, the carrier transport layer includes a doped metal ion M n+ The perovskite precursor constitutes a polar perovskite current transport layer, the perovskite precursor is doped with metal ions of 3+, 1+ or a combination of the two, and the battery structure is a transparent substrate, a first electrode, a perovskite current transport layer doped with 3+ metal ions, a second electrode or a transparent substrate, a first electrode, a perovskite current transport layer doped with 1+ metal ions, a second electrode or a transparent substrate, a first electrode, a perovskite current transport layer doped with 3+ metal ions, a perovskite current transport layer doped with 1+ metal ions, and a second electrode.

[0008] As an improvement, the carrier transport layer also includes a hole transport layer, the perovskite precursor is doped with 3+ metal ions, and the battery structure is a transparent substrate, a first electrode, a perovskite carrier transport layer doped with 3+ metal ions, a hole transport layer, and a second electrode.

[0009] As an improvement, the carrier transport layer also includes an electron transport layer, the perovskite precursor is doped with 1+ metal ions, and the battery structure is a transparent substrate, a first electrode, an electron transport layer, a perovskite carrier transport layer doped with 1+ metal ions, and a second electrode.

[0010] As an improvement, the preparation method of the battery includes the following steps:

[0011] S1: cleaning the transparent substrate containing the first electrode;

[0012] S2: Preparation of doped M n+ Perovskite current transport layer precursor solution for metal ions;

[0013] S3: depositing carrier transport layer;

[0014] S4: depositing the second electrode.

[0015] As an improvement, in step S1, the transparent substrate containing the first electrode is cleaned by ultrasonic wave with alcohol, pure water, detergent solution and alcohol in sequence, and the cleaning time is 10-30 minutes.

[0016] As an improvement, the perovskite current carrier transport layer precursor solution is prepared in step S2 by dissolving the compounds of MAI, PbI2, and metal ions in a mixed solvent containing DMF and DMSO, the total amount of added PbI2 and metal ion compound substances is equal to the amount of added MAI substance, and the volume ratio of DMF to DMSO is 9:1.

[0017] As an improvement, the deposition of the carrier transport layer in step S3 adopts a spin coating method. After the cleaned transparent substrate containing the first electrode is treated with ultraviolet ozone for 10-20 minutes, the perovskite carrier transport layer precursor solution is dripped on the surface of the transparent substrate containing the first electrode, and the solution is spin coated at a rotation speed of 4000 rpm for 10-30 seconds, and the anti-solvent is added during rotation.

[0018] As an improvement, in step S4, the second electrode is deposited by scraping carbon slurry or evaporating Ag or Au.

[0019] Compared with the prior art, the advantages of the present invention are:

[0020] (1) In the traditional solar cell preparation process, it is usually necessary to prepare the electron transport layer and the hole transport layer separately, which not only increases the complexity of the process flow, but also may introduce additional interface problems and costs. The novel perovskite solar cell uses a perovskite current transport layer doped with metal ions. In addition to the intrinsic photoelectric conversion function, the perovskite doped with metal ions has an enhanced built-in electric field due to the non-equipotential ions doped in the lattice, so that the charge carriers move in a directional manner, achieving the function of separation and extraction, thereby reducing the use of charge transport materials in perovskite solar cells, replacing the traditional electron transport layer or hole transport layer, thereby simplifying the preparation process and reducing the process steps;

[0021] (2) Since the perovskite current transport layer can simultaneously undertake the task of transporting electrons and holes by doping metal ions of different valence types, there is no need for additional electron transport layer or hole transport layer materials, which not only reduces the use of raw materials, but also reduces the dependence on rare or expensive materials, thereby helping to reduce the overall cost of the battery;

[0022] (3) Simplifying the process and reducing material usage directly lead to cost reduction. In addition, perovskite materials themselves have abundant sources and low costs, so the use of perovskite current transport layers can further reduce the manufacturing cost of batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments:

[0024] Figure 1 Schematic diagram of the JV curves of the novel structure perovskite solar cells of Examples 1 to 3 and the control group ITO / SnO2 / MAPbI3 / Ag. DETAILED DESCRIPTION

[0025] like Figure 1 As shown, a novel perovskite solar cell comprises a transparent substrate, a first electrode, a carrier transport layer, and a second electrode in sequence. The carrier transport layer comprises a perovskite carrier transport layer for directing charge carriers. The perovskite carrier transport layer is doped with metal ions M n+ The perovskite precursor is composed of a metal ion M n+ is a 3+ or 1+ metal ion, preferably, the metal ion M n+ Including but not limited to Bi 3+ , Fe 3+ , Cu + 、Eu 3 + 、In 3+ , Tl + 、Ag + Preferably, the transparent substrate containing the first electrode has a size of 1.2 cm × 1.2 cm × 0.12 cm. Preferably, the material of the first electrode includes but is not limited to indium tin oxide ITO, fluorine-doped tin oxide FTO. Preferably, the material of the second electrode includes but is not limited to C, Ag, Au, Ni, Cu.

[0026] The perovskite precursor is composed of an organic halide perovskite material with an ABX3 structure, and metal ions are doped in the perovskite precursor in the form of halides or pseudo-halides, including but not limited to MI n ,MBr n 、MCl n MF n or MCN n , preferably, A + Including but not limited to MA + , F.A. + , Cs + , B includes but is not limited to Pb 2+ , Sn2+ , X is a halogen or pseudohalogen ion, including but not limited to I - ,Br - , Cl - , CN - Anions.

[0027] The perovskite precursor is doped with metal ions of 3+, 1+ or a combination of the two, and the battery structure is a transparent substrate, a first electrode, a perovskite current transport layer doped with 3+ metal ions, a second electrode or a transparent substrate, a first electrode, a perovskite current transport layer doped with 1+ metal ions, a second electrode or a transparent substrate, a first electrode, a perovskite current transport layer doped with 3+ metal ions, a perovskite current transport layer doped with 1+ metal ions, and a second electrode. Preferably, the battery structure includes but is not limited to ITO / MAPbI3:Bi 3+ / MAPbI3:Cu + / Au、ITO / CsPbI3:Bi 3+ / MAPbI3:Cu + / C.

[0028] The carrier transport layer also includes a hole transport layer. The perovskite precursor is doped with 3+ metal ions. The battery structure is a transparent substrate, a first electrode, a perovskite carrier transport layer doped with 3+ metal ions, a hole transport layer, and a second electrode. Preferably, the battery structure includes but is not limited to ITO / MAPbI3:Bi 3+ / MoO3 / C, ITO / MAPbI3:Bi 3+ / Ag.

[0029] The carrier transport layer also includes an electron transport layer. The perovskite precursor is doped with 1+ metal ions. The battery structure is a transparent substrate, a first electrode, an electron transport layer, a perovskite carrier transport layer doped with 1+ metal ions, and a second electrode. Preferably, the battery structure includes but is not limited to ITO / SnO2 / MAPbI3:Cu + / C or ITO / SnO2 / MAPbI3:Cu + / Au.

[0030] Embodiment 1

[0031] The method for preparing the battery comprises the following steps:

[0032] S1: ultrasonically clean the transparent substrate containing the first electrode using alcohol, pure water, detergent solution, and alcohol in sequence for 20 minutes;

[0033] S2: Weigh MAI and PbI2+BiI3 in equal molar ratios, wherein the amount of PbI2+BiI3 is 1, and the molar ratio of PbI2 to BiI3 is 0.99999:0.00001, dissolve MAI, PbI2 and BiI3 in a mixed solvent of DMF and DMSO to form a perovskite carrier transport layer precursor solution with a concentration of 1.5M, wherein the volume ratio of DMF to DMSO is 9:1, and stir the perovskite carrier transport layer precursor solution at a rotation speed of 800 rpm for 120 minutes, filter it, and set the filtrate aside;

[0034] S3.1: After the cleaned transparent substrate containing the first electrode is treated with UV ozone for 15 minutes, 40 μl of the perovskite carrier transport layer precursor solution is dripped on the surface of the transparent substrate containing the first electrode, and the solution is spin-coated at a rotation speed of 4000 rpm for 20 seconds. At the 10th second of the rotation, the anti-solvent chlorobenzene is dripped to form a doped Bi 3+ Perovskites of metal ions: Bi 3+ The wet film is placed on a hot plate at 130° C. for thermal annealing for 10 minutes, wherein the ambient air humidity is less than 40%;

[0035] S3.2: After cooling to room temperature, the perovskite formed: Bi 3+ Bi-doped thin film 3+ On the metal ion perovskite current transport layer, a hole transport layer Spiro-OMeTAD is spin-coated and dried by thermal annealing;

[0036] S4: A 200 nm thick Ag electrode is evaporated on the hole transport layer Spiro-OMeTAD.

[0037] A perovskite solar cell doped with 3+ metal ions, including a perovskite current transport layer and a hole transport layer, was prepared. The cell structure is: ITO / MAPbI3:Bi 3+ / Spiro-OMeTAD / Ag.

[0038] like Figure 1 As shown in Table 1, after the solar simulator test, the short-circuit current density J of the battery sc 19.15mA / cm 2 , open circuit voltage V oc It is 1.026V, the photoelectric conversion efficiency is 12.467%, the fill factor is 63.42%, the series resistance Rs is 70.37ohm, and the parallel resistance Rsh is 15350ohm.

[0039] Embodiment 2

[0040] The method for preparing the battery comprises the following steps:

[0041] S1: ultrasonically clean the transparent substrate containing the first electrode using alcohol, pure water, detergent solution, and alcohol in sequence for 20 minutes;

[0042] S2: Weigh MAI and PbI2+CuI in equal molar ratios, wherein the sum of PbI2+CuI is 1, and the molar ratio of PbI2 to CuI is 0.99999:0.00001, dissolve MAI, PbI2 and BiI3 in a mixed solvent of DMF and DMSO to form a 1.5M perovskite carrier transport layer precursor solution, wherein the volume ratio of DMF to DMSO is 9:1, and stir the perovskite carrier transport layer precursor solution at a rotation speed of 800 rpm for 120 minutes, filter it, and set the filtrate aside;

[0043] S3.1: After the cleaned transparent substrate containing the first electrode is treated with UV ozone for 15 minutes, 40 μl of SnO2 sol is dripped on the surface of the transparent substrate containing the first electrode, and the surface is spin-coated at a rotation speed of 4000 rpm for 20 seconds, and annealed on a hot stage at 150°C for 30 minutes;

[0044] S3.2: After cooling to room temperature, the transparent substrate containing the first electrode is cleaned again with UV ozone for 15 minutes, 40 μl of the perovskite carrier transport layer precursor solution is dripped on the surface of the transparent substrate containing the first electrode, and the solution is spin-coated at a rotation speed of 4000 rpm for 30 seconds. At the 10th second of the rotation, the anti-solvent ethyl acetate is dripped to form a Cu doped substrate. + Perovskite of metal ions: Cu + The wet film is placed on a hot plate at 130° C. for thermal annealing for 10 minutes, wherein the ambient air humidity is less than 40%;

[0045] S4: Perovskite formed in: Cu + Thin film Cu + A 200nm thick Ag electrode is evaporated on the perovskite current transport layer of metal ions.

[0046] A perovskite solar cell doped with 1+ metal ions, including a perovskite current transport layer and an electron transport layer, was prepared. The cell structure is: ITO / SnO2 / MAPbI3:Cu + / Ag.

[0047] like Figure 1 As shown in Table 1, after the solar simulator test, the short-circuit current density J of the battery sc 20.80mA / cm 2 , open circuit voltage V ocIt is 1.026V, the photoelectric conversion efficiency is 14.556%, the fill factor is 68.20%, the series resistance Rs is 55.45ohm, and the parallel resistance Rsh is 46494ohm.

[0048] Embodiment 3

[0049] The method for preparing the battery comprises the following steps:

[0050] S1: ultrasonically clean the transparent substrate of the first electrode using alcohol, pure water, detergent solution, and alcohol in sequence for 20 minutes;

[0051] S2: Weigh MAI and PbI2+BiI3 in equal molar ratios, wherein the amount of PbI2+BiI3 is 1, and the molar ratio of PbI2 to BiI3 is 0.99999:0.00001, dissolve MAI, PbI2 and BiI3 in a mixed solvent of DMF and DMSO to form a perovskite carrier transport layer precursor solution with a concentration of 1.5M, wherein the volume ratio of DMF to DMSO is 9:1, and stir the perovskite carrier transport layer precursor solution at a rotation speed of 800 rpm for 120 minutes, filter it, and set the filtrate aside;

[0052] S3.1: After the transparent substrate of the cleaned first electrode is treated with UV ozone for 15 minutes, 40 μl of the perovskite carrier transport layer precursor solution is dripped on the surface of the transparent substrate containing the first electrode, and the solution is spin-coated at a rotation speed of 4000 rpm for 20 seconds. At the 10th second of the rotation, the anti-solvent chlorobenzene is dripped to form a doped Bi 3+ Perovskites of metal ions: Bi 3+ The wet film is placed on a hot plate at 130° C. for thermal annealing for 10 minutes, wherein the ambient air humidity is less than 40%;

[0053] S3.2: After cooling to room temperature, the perovskite formed: Bi 3+ Bi-doped thin film 3+ The first perovskite current transport layer of metal ions was evaporated with a perovskite precursor powder mixed with MAI and PbI2+AgI in equal molar ratio to form a layer of MAPbI3:AgI with a thickness of 300nm. + Thin film is doped with Ag + The second perovskite current transport layer of metal ions is cooled to room temperature, wherein PbI2+AgI is equal to 1, and the molar ratio of PbI2 to AgI is 0.99999:0.00001;

[0054] S4: In MAPbI3:Ag + Thin film is doped with Ag + A 200nm thick Ag electrode is evaporated on the second perovskite current transport layer of metal ions.

[0055] A perovskite solar cell doped with 3+ and 1+ metal ions including a perovskite current transport layer was prepared, and its cell structure is: ITO / MAPbI3:Bi 3+ / MAPbI3:Ag 1+ / Ag.

[0056] like Figure 1 As shown in Table 1, after the solar simulator test, the short-circuit current density J of the battery sc 21.18 mA / cm 2 , open circuit voltage V oc It is 1.024V, the photoelectric conversion efficiency is 15.504%, the fill factor is 71.45%, the series resistance Rs is 53.77ohm, and the parallel resistance Rsh is 27436ohm.

[0057] Table 1 Photoelectric performance of the novel perovskite solar cells of Examples 1 to 3 and the control group ITO / SnO2 / MAPbI3 / Ag

[0058]

[0059] In the prior art, the carrier transport layer is a vital part in perovskite solar cells, and is mainly divided into two types: an electron transport layer and a hole transport layer, which collect the carriers generated by the light excitation of the perovskite thin film layer. The former is responsible for collecting electrons, and the latter collects holes. In perovskite solar cells, the collection of electrons is relatively important, so the material of the electron transport layer is more important; the hole transport layer is not necessary, and sometimes the battery can still operate without this functional layer, but the photoelectric conversion efficiency is low. In Table 1, the control group ITO / SnO2 / MAPbI3 / Ag battery uses the SnO2 electron transport layer, which is currently widely used and has better performance, so compared with the MAPbI3:Bi used in the present invention 3+ The perovskite current transport layer is used as the electron transport layer of the battery (ITO / MAPbI3:Bi 3+ / Sprio-OMeTAD / Ag) is less efficient. 1+ The photovoltaic performance of the cell with the perovskite current transport layer as the hole transport layer is higher than that of the cell without the hole transport layer structure (the efficiency of the control group is 14.465%), so ITO / SnO2 / MAPbI3:Cu 1+ / Ag battery (efficiency of 14.556%) performed better than the control group. 3+ The perovskite current transport layer as the electron transport layer and MAPbI3:Ag 1+The perovskite solar cell with the perovskite current transport layer as the hole transport layer showed improved photovoltaic performance due to the double-layer perovskite light absorption layer, and was the most efficient cell group in this group of experiments (15.504%).

[0060] like Figure 1 As shown in the figure, it can be clearly seen that MAPbI3:Bi 3+ The photovoltaic performance of the cell is greatly reduced due to the perovskite current transport layer as the electron transport layer and the photoactive layer. 3+ The perovskite current transport layer as the electron transport layer and MAPbI3:Ag + The short-circuit current density of the perovskite current transport layer as a double photoactive layer of the hole transport layer should theoretically be greatly improved, but its current did not show a significant increase, which indicates that the electron extraction performance of the electron transport layer formed by doping metal ions in the present invention has the potential to be further improved in the future.

[0061] The above description is only for the best embodiment of the present invention, but it should not be understood as limiting the claims. The present invention is not limited to the above embodiments, and its specific structure is allowed to be changed. All changes made within the scope of protection of the independent claims of the present invention are within the scope of protection of the present invention.

Claims

1. A novel perovskite solar cell, characterized in that: The battery comprises a transparent substrate, a first electrode, a carrier transport layer, and a second electrode in sequence. The carrier transport layer comprises a perovskite carrier transport layer for directional movement of charge carriers. The perovskite carrier transport layer is doped with metal ions M n+ The perovskite precursor is composed of, so that the perovskite current transport layer has polarity, the metal ion M n+ It is a 3+ or 1+ metal ion.

2. A novel perovskite solar cell according to claim 1, characterized in that: The perovskite precursor is composed of an organic halide perovskite material with an ABX3 structure, and the metal ions are doped in the perovskite precursor in the form of halides or pseudo-halides, including but not limited to MI n ,MBr n 、MCl n MF n or MCN n .

3. A novel perovskite solar cell according to claim 2, characterized in that: The perovskite precursor is doped with metal ions of 3+, 1+ or a combination of the two, and the battery structure is a transparent substrate, a first electrode, a perovskite current transport layer doped with 3+ metal ions, a second electrode or a transparent substrate, a first electrode, a perovskite current transport layer doped with 1+ metal ions, a second electrode or a transparent substrate, a first electrode, a perovskite current transport layer doped with 3+ metal ions, a perovskite current transport layer doped with 1+ metal ions, and a second electrode.

4. A novel perovskite solar cell according to claim 2, characterized in that: The carrier transport layer also includes a hole transport layer, the perovskite precursor is doped with 3+ metal ions, and the battery structure includes a transparent substrate, a first electrode, a perovskite carrier transport layer doped with 3+ metal ions, a hole transport layer, and a second electrode.

5. A novel perovskite solar cell according to claim 2, characterized in that: The carrier transport layer also includes an electron transport layer, the perovskite precursor is doped with 1+ metal ions, and the battery structure includes a transparent substrate, a first electrode, an electron transport layer, a perovskite carrier transport layer doped with 1+ metal ions, and a second electrode.

6. A novel perovskite solar cell according to claim 1, characterized in that: The method for preparing the battery comprises the following steps: S1: cleaning the transparent substrate containing the first electrode; S2: Preparation of the doped M n+ Perovskite current transport layer precursor solution for metal ions; S3: depositing the carrier transport layer; S4: depositing the second electrode.

7. A novel perovskite solar cell according to claim 6, characterized in that: In the step S1, the transparent substrate containing the first electrode is cleaned by ultrasonic wave with alcohol, pure water, detergent solution and alcohol in sequence, and the cleaning time is 10-30 minutes.

8. A novel perovskite solar cell according to claim 7, characterized in that: In step S2, the perovskite current carrier transport layer precursor solution is prepared by dissolving the compounds of MAI, PbI2 and metal ions in a mixed solvent containing DMF and DMSO, the total amount of the added compounds of PbI2 and metal ions is equal to the amount of MAI substance added, and the volume ratio of DMF to DMSO is 9:

1.

9. A novel perovskite solar cell according to claim 8, characterized in that: In the step S3, the deposition of the carrier transport layer is carried out by spin coating. After the cleaned transparent substrate containing the first electrode is treated with ultraviolet ozone for 10-20 minutes, a perovskite carrier transport layer precursor solution is dripped on the surface of the transparent substrate containing the first electrode, and the solution is spin coated at a rotation speed of 4000 rpm for 10-30 seconds, and an anti-solvent is dripped during rotation.

10. A novel perovskite solar cell according to claim 9, characterized in that: In the step S4, the second electrode is deposited by scraping carbon slurry or evaporating Ag or Au.

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