3-carboxybenzenesulfonic acid sodium modified nickel oxide hole transport layer, trans-perovskite solar cell comprising same, and preparation method and application thereof

Abstract

The application relates to the technical field of solar cells, and discloses a 3-carboxybenzenesulfonic acid sodium modified nickel oxide hole transport layer, a trans-perovskite solar cell comprising the same, and a preparation method and application thereof. The trans-perovskite solar cell comprises an ITO conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, an interface modification layer and a metal electrode which are sequentially arranged, and the hole transport layer comprises 3-carboxybenzenesulfonic acid sodium modified nickel oxide. The average grain size of the perovskite film, the open-circuit voltage, the short-circuit current density, the fill factor and / or the photoelectric conversion efficiency of the trans-perovskite solar cell are improved by introducing 3-carboxybenzenesulfonic acid sodium into the nickel oxide hole transport layer.

Description

Technical Field

[0001] This invention relates to the field of solar cells, specifically to a sodium 3-carboxybenzenesulfonate modified nickel oxide hole transport layer, an inverted perovskite solar cell including the same, and its preparation method and application. Background Technology

[0002] Perovskite solar cells have become a research hotspot due to their high photoelectric conversion efficiency, low cost, and solution processability. In inverted (pin) perovskite solar cells, the hole transport layer is typically made of nickel oxide (NiO). x Nickel oxide (NiO) is characterized by its high light transmittance, good energy level matching, and high hole mobility. However, the presence of numerous defect states and dangling bonds on the nickel oxide surface leads to contact with non-ideal perovskite interfaces, inducing carrier recombination and reducing device performance.

[0003] Existing technologies often employ interface modification strategies to improve the contact between nickel oxide and the perovskite layer, such as using self-assembled monolayers, polymers, or small-molecule modifiers. However, existing methods are often complex, costly, or have limited modification effects. Furthermore, the average grain size of perovskite films prepared using existing methods is too small, and the open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency of inverted perovskite solar cells prepared using existing methods urgently need improvement. Therefore, developing a simple, efficient, and low-cost nickel oxide interface modification strategy is of great significance for improving the performance of inverted perovskite solar cells. Summary of the Invention

[0004] This invention provides a 3-carboxybenzenesulfonate-modified nickel oxide hole transport layer, an inverted perovskite solar cell including the same, a method for its preparation, and its application, in order to solve the problems of excessively small average grain size of perovskite thin films and / or the urgent need to improve the open-circuit voltage, short-circuit current density, fill factor, and / or photoelectric conversion efficiency of inverted perovskite solar cells.

[0005] In a first aspect, the present invention provides an inverted perovskite solar cell, the cell comprising, sequentially arranged, an ITO (Indium-Tin Oxide) conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, an interface modification layer, and a metal electrode, wherein the hole transport layer comprises nickel oxide modified with sodium 3-carboxybenzenesulfonate.

[0006] In one alternative implementation, at least one of the following is satisfied: The open-circuit voltage of the inverted perovskite solar cell is not less than 1.08 V; The short-circuit current density of the inverted perovskite solar cell is not less than 24.74 mA cm-². The fill factor of the inverted perovskite solar cell is not less than 73%; The photoelectric conversion efficiency of the inverted perovskite solar cell is not less than 18%.

[0007] In one alternative implementation, at least one of the following is satisfied: The open-circuit voltage of the inverted perovskite solar cell is 1.08-1.15 V; The short-circuit current density of the inverted perovskite solar cell is 25.17-25.31 mA cm⁻². The fill factor of the inverted perovskite solar cell is 73.09-82.78%. The photoelectric conversion efficiency of the inverted perovskite solar cell is 19.97-24.25%.

[0008] In one alternative implementation, at least one of the following is satisfied: The open-circuit voltage of the inverted perovskite solar cell is 1.11-1.15 V; The short-circuit current density of the inverted perovskite solar cell is 25.18-25.31 mA cm⁻². The fill factor of the inverted perovskite solar cell is 79.88-82.78%. The photoelectric conversion efficiency of the inverted perovskite solar cell is 22.45-24.25%.

[0009] Secondly, the present invention also provides a method for preparing the above-mentioned inverted perovskite solar cell, comprising the following steps: Step 1: Prepare a nickel oxide hole transport layer on an ITO conductive substrate; Step 2: Coat the nickel oxide hole transport layer with sodium 3-carboxybenzenesulfonate solution and anneal it to obtain the modified hole transport layer; Step 3: Prepare a perovskite light-absorbing layer on the modified hole transport layer; Step 4: Sequentially deposit an electron transport layer, an interface modification layer, and a metal electrode on the perovskite light-absorbing layer.

[0010] In one alternative implementation, at least one of the following is satisfied: The thickness of the nickel oxide hole transport layer is 10–40 nm; The concentration of the sodium 3-carboxybenzenesulfonate solution is 0.5–3 mg / mL; The solvent for the sodium 3-carboxybenzenesulfonate solution is ethanol or isopropanol; The annealing temperature in step two is 80–150 ℃; The annealing time in step two is 5–20 min; In step two, the coating is applied by spin coating; In step three, the perovskite precursor solution is spin-coated onto the upper surface of the nickel oxide hole transport layer. The spin-coating conditions are: low speed 1000 rpm spin-coating for 10 s, followed by high speed 5000 rpm spin-coating for 30 s. In step four, a perovskite light-absorbing layer is deposited by spin coating.

[0011] In one alternative implementation, at least one of the following is satisfied: in step two, the nickel oxide hole transport layer is deposited by spin coating at a spin coating speed of 3000 rpm to 5000 rpm. The concentration of the sodium 3-carboxybenzenesulfonate solution is 1–2 mg / mL.

[0012] In one alternative implementation, at least one of the following is satisfied: in step two, the hole transport layer is deposited by spin coating at a rotation speed of 4000 rpm; The concentration of the sodium 3-carboxybenzenesulfonate solution is 1 mg / mL.

[0013] Thirdly, the present invention also provides the application of sodium 3-carboxybenzenesulfonate in the nickel oxide hole transport layer of a modified inverted perovskite solar cell.

[0014] Fourthly, the present invention also provides the application of sodium 3-carboxybenzenesulfonate modified nickel oxide hole transport layer in inverted perovskite solar cells.

[0015] Fifthly, the present invention also provides a nickel oxide hole transport layer modified with sodium 3-carboxybenzenesulfonate, characterized in that the nickel oxide hole transport layer is modified with sodium 3-carboxybenzenesulfonate.

[0016] In one alternative embodiment, the nickel oxide hole transport layer is used in an inverted perovskite solar cell.

[0017] In a sixth aspect, the present invention also provides a method for preparing a nickel oxide hole transport layer modified with sodium 3-carboxybenzenesulfonate, characterized in that a nickel oxide hole transport layer modified with sodium 3-carboxybenzenesulfonate is used.

[0018] In one alternative implementation, at least one of the following is satisfied: A sodium 3-carboxybenzenesulfonate solution was coated onto the nickel oxide layer of the nickel oxide hole transport layer. Annealing is performed to obtain a modified hole transport layer.

[0019] In one alternative implementation, at least one of the following is satisfied: The concentration of the sodium 3-carboxybenzenesulfonate solution is 0.5–3 mg / mL; The coating is applied by spin coating.

[0020] In one alternative embodiment, the concentration of the sodium 3-carboxybenzenesulfonate solution is 1–2 mg / mL.

[0021] In one optional embodiment, the concentration of the sodium 3-carboxybenzenesulfonate solution is 1 mg / mL.

[0022] In this invention, the perovskite precursor solution can be any conventional perovskite precursor solution in the art. Optionally, the perovskite precursor solution includes lead iodide, lead bromide, formamidinium hydroiodate, methylammonium bromide, methylammonium chloride, and cesium iodide. Optionally, the solvent of the perovskite precursor solution includes a mixed solvent of dimethylformamide and dimethyl sulfoxide, and more preferably, the volume ratio of dimethylformamide to dimethyl sulfoxide is 4:1. Further optionally, the perovskite precursor solution comprises, by mass, 676 parts lead iodide, 27.5 parts lead bromide, 232 parts formamidinium hydroiodate, 8 parts methylammonium bromide, 15.2 parts methylammonium chloride, and 19.5 parts cesium iodide; even more optionally, the perovskite precursor solution comprises 676 parts lead iodide, 27.5 parts lead bromide, 232 parts formamidinium hydroiodate, 8 parts methylammonium bromide, 15.2 parts methylammonium chloride, and 19.5 parts cesium iodide. The unit of mass is optionally mg.

[0023] The technical solution of this invention has the following advantages: 1. This invention provides a 3-carboxybenzenesulfonate-modified nickel oxide hole transport layer and an inverse perovskite solar cell. By introducing 3-carboxybenzenesulfonate, the sulfonic acid and carboxyl groups of 3-carboxybenzenesulfonate can form coordination bonds with the nickel oxide surface, filling oxygen vacancies, improving energy level alignment, and passivating interface defects, thereby improving hole extraction efficiency, suppressing nonradiative recombination, and enhancing cell performance. The sulfonic acid and carboxyl groups in the 3-carboxybenzenesulfonate can bind to defect sites on the nickel oxide surface, reducing the interface state density, improving energy level alignment, and enhancing hole transport capability. Interface nonradiative recombination is significantly suppressed, and the device's photoelectric conversion efficiency and fill factor are improved.

[0024] 2. In this invention, by adjusting the concentration of sodium 3-carboxybenzenesulfonate solution to 1–2 mg / mL, the open-circuit voltage (Voc), fill factor (FF), and photoelectric conversion efficiency (PCE) are simultaneously improved.

[0025] 3. In this invention, by adjusting the concentration of sodium 3-carboxybenzenesulfonate solution to 1 mg / mL, the open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and photoelectric conversion efficiency (PCE) are simultaneously improved.

[0026] 4. The method for preparing the nickel oxide hole transport layer and the method for preparing the inverted perovskite solar cell provided by the present invention have simple preparation processes, low cost, good repeatability, and are suitable for large-scale production. Attached Figure Description

[0027] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0028] Figure 1 The XRD patterns of the perovskite films of the comparative example and Example 1 are shown, where the diffraction intensity is in units of au. Detailed Implementation

[0029] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0030] Unless otherwise specified, all experimental steps or conditions in the examples were performed according to conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0031] Example 1 The method for fabricating inverted perovskite solar cells includes the following steps: (1) After cleaning and drying the ITO transparent conductive glass substrate, the treated ITO substrate was treated with ultraviolet light and ozone. Nickel oxide nanoparticle solution was spin-coated onto the treated ITO glass and annealed at 100 °C for 10 min to prepare a nickel oxide hole transport layer with a thickness of about 20 nm.

[0032] (2) Prepare an ethanol solution (1 mg / mL) of sodium 3-carboxybenzenesulfonate (CAS No.: 17625-03-5, a commercially available product), spin-coat it onto the nickel oxide hole transport layer at 4000 rpm, and anneal at 100 ℃ for 10 min to obtain the modified hole transport layer.

[0033] (3) Preparation of perovskite precursor solution: 676 mg of lead iodide, 27.5 mg of lead bromide, 232 mg of formamidinium hydroiodate, 8 mg of methylammonium bromide, 15.2 mg of methylammonium chloride, and 19.5 mg of cesium iodide were weighed and dissolved in a mixed solvent of dimethylformamide and dimethyl sulfoxide (volume ratio 4:1). The mixture was heated and stirred at 60 °C for 1 hour to prepare the perovskite precursor solution. The perovskite precursor solution was then spin-coated onto the surface of the modified nickel oxide hole transport layer. The spin-coating conditions were: low speed 1000 rpm spin-coating for 10 s, followed by high speed 5000 rpm spin-coating for 30 s. After completion, the substrate was transferred to a heating stage and annealed at 100 °C for 30 min to obtain the perovskite light-absorbing layer.

[0034] (4) Spin-coating the electron transport layer (PCBM) and the interface modification layer (BCP) in sequence, and evaporating the Ag electrode to complete the device fabrication.

[0035] Example 2 The nickel oxide hole transport layer was modified with a sodium 3-carboxybenzenesulfonate solution at a concentration of 2 mg / mL, and the rest was the same as in Example 1.

[0036] Example 3 The nickel oxide hole transport layer was modified with a sodium 3-carboxybenzenesulfonate solution at a concentration of 3 mg / mL, and the rest was the same as in Example 1.

[0037] Comparative Example 1 The nickel oxide hole transport layer was not modified with sodium 3-carboxybenzenesulfonate; otherwise, it was the same as in Example 1.

[0038] Experimental Example 1 The inverted perovskite solar cells prepared in the examples and comparative examples were tested.

[0039] By observing the perovskite films obtained in the comparative examples and Example 1, it can be seen that the surface of the perovskite films is free of obvious defects, and the particles are uniformly and densely arranged. The perovskite grain size in Example 1 is increased. Statistical analysis of the perovskite grain size reveals the following: the average grain size of the perovskite obtained from unmodified tin oxide (Comparative Example 1) is 628 nm; the average grain size of the perovskite obtained from nickel oxide modified with a 1 mg / mL sodium 3-carboxybenzenesulfonate solution (Example 1) is 744 nm; when the concentration of the sodium 3-carboxybenzenesulfonate solution is increased to 2 mg / mL (Example 2), the average grain size is 726 nm; and when the concentration of the sodium 3-carboxybenzenesulfonate solution is increased to 3 mg / mL (Example 3), the average grain size is 713 nm. Therefore, the introduced sodium 3-carboxybenzenesulfonate layer can increase the grain size of the perovskite film.

[0040] Figure 1 The figures show the XRD patterns of the perovskite films in the comparative example and Example 1. As can be seen from the figures, after modification with sodium 3-carboxybenzenesulfonate (Example 1), the diffraction peaks at approximately 14° and 28° are significantly enhanced, indicating that the crystallinity of the perovskite film is improved, the quality of the perovskite film is enhanced, and this is beneficial for reducing defect states in the perovskite film.

[0041] Performance tests, including current density, voltage, and photoelectric conversion efficiency, were conducted on the perovskite solar cells of Comparative Example 1 and Example 1. The results showed that the open-circuit voltage (Voc) of Comparative Example 1 was 1.08 V, and the short-circuit current density (Jsc) was 25.37 mAcm². -2 The fill factor (FF) was 68.89%, the power conversion efficiency (PCE) was 18.94%, and the open-circuit voltage of the perovskite solar cell in Example 1 was 1.15 V, with a short-circuit current density of 25.31 mA cm⁻¹. -2 The fill factor was 82.78%, and the photoelectric conversion efficiency was 24.25%. Example 1 achieved the highest photoelectric conversion efficiency. The improved device performance can be attributed to the sodium 3-carboxybenzenesulfonate-modified perovskite buried interface, which improved the quality of the perovskite film, reduced defects at the perovskite interface, and increased radiative recombination efficiency, thereby improving the device's photoelectric conversion efficiency. In Example 2, the device's open-circuit voltage was 1.11 V, and the short-circuit current density was 25.17 mA cm⁻¹. -2 The fill factor is 79.88%, and the photoelectric conversion efficiency is 22.45%. In Example 3, the open-circuit voltage of the device is 1.08 V, and the short-circuit current density is 25.18 mA cm⁻¹. -2 The fill factor is 73.09%, and the photoelectric conversion efficiency is 19.97%.

[0042] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A reverse perovskite solar cell, characterized in that, The battery comprises an ITO conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, an interface modification layer, and a metal electrode arranged sequentially. The hole transport layer comprises nickel oxide modified with sodium 3-carboxybenzenesulfonate. The preparation method of the hole transport layer includes coating a sodium 3-carboxybenzenesulfonate solution onto the nickel oxide hole transport layer and performing an annealing treatment to obtain a modified hole transport layer.

2. The inverted perovskite solar cell according to claim 1, characterized in that, Meet at least one of the following: The open-circuit voltage of the inverted perovskite solar cell is not less than 1.08 V; The short-circuit current density of the inverted perovskite solar cell is not less than 24.74 mA cm⁻¹. - ²; The fill factor of the inverted perovskite solar cell is not less than 73%; The photoelectric conversion efficiency of the inverted perovskite solar cell is not less than 18%.

3. The method for preparing the inverted perovskite solar cell according to claim 1 or 2, characterized in that, Includes the following steps: Step 1: Prepare a nickel oxide hole transport layer on an ITO conductive substrate; Step 2: Coat the nickel oxide hole transport layer with sodium 3-carboxybenzenesulfonate solution and anneal it to obtain the modified hole transport layer; Step 3: Prepare a perovskite light-absorbing layer on the modified hole transport layer; Step 4: Sequentially deposit an electron transport layer, an interface modification layer, and a metal electrode on the perovskite light-absorbing layer.

4. The preparation method according to claim 3, characterized in that, Meet at least one of the following: The thickness of the nickel oxide hole transport layer is 10–40 nm; The concentration of the sodium 3-carboxybenzenesulfonate solution is 0.5–3 mg / mL; The solvent for the sodium 3-carboxybenzenesulfonate solution is ethanol or isopropanol; The annealing temperature in step two is 80–150 ℃; The annealing time in step two is 5–20 min; In step two, the coating is applied by spin coating; In step three, the perovskite precursor solution is spin-coated onto the upper surface of the nickel oxide hole transport layer. The spin-coating conditions are: low speed 1000 rpm spin-coating for 10 s, followed by high speed 5000 rpm spin-coating for 30 s. In step four, a perovskite light-absorbing layer is deposited by spin coating.

5. The preparation method according to claim 4, characterized in that, Meet at least one of the following: In step two, the hole transport layer of nickel oxide is deposited by spin coating at a speed of 3000 rpm to 5000 rpm. The concentration of the sodium 3-carboxybenzenesulfonate solution is 1–2 mg / mL.

6. The application of sodium 3-carboxybenzenesulfonate in a nickel oxide hole transport layer in a modified inverted perovskite solar cell, wherein the method for preparing the hole transport layer includes: A modified hole transport layer is obtained by coating a nickel oxide hole transport layer with a sodium 3-carboxybenzenesulfonate solution and then annealing it.

7. The application of a sodium 3-carboxybenzenesulfonate modified nickel oxide hole transport layer in an inverted perovskite solar cell, wherein the method for preparing the hole transport layer includes: A modified hole transport layer is obtained by coating a nickel oxide hole transport layer with a sodium 3-carboxybenzenesulfonate solution and then annealing it.

8. A sodium 3-carboxybenzenesulfonate modified nickel oxide hole transport layer, characterized in that, The nickel oxide hole transport layer is modified with sodium 3-carboxybenzenesulfonate. The preparation method of the hole transport layer includes: coating the nickel oxide hole transport layer with sodium 3-carboxybenzenesulfonate solution and annealing it to obtain the modified hole transport layer.

9. A method for preparing a sodium 3-carboxybenzenesulfonate modified nickel oxide hole transport layer, characterized in that, A nickel oxide hole transport layer modified with sodium 3-carboxybenzenesulfonate is prepared by: coating a nickel oxide hole transport layer with a sodium 3-carboxybenzenesulfonate solution and annealing it to obtain the modified hole transport layer.

10. The preparation method according to claim 9, characterized in that, Meet at least one of the following: The concentration of the sodium 3-carboxybenzenesulfonate solution is 0.5–3 mg / mL; The solvent for the sodium 3-carboxybenzenesulfonate solution is ethanol or isopropanol; The annealing temperature in step two is 80–150 ℃; The annealing time in step two is 5–20 min; The coating is applied by spin coating.

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