Alkyne derivative-containing carbon electrode full-inorganic perovskite battery and preparation method thereof

Abstract

The invention discloses a carbon electrode full-inorganic perovskite cell comprising an alkyne derivative and a preparation method thereof, and belongs to the technical field of perovskite solar cells. According to the method, tetra (4-ethynylphenyl) methane (TEPM) is introduced into a perovskite precursor solution, and the method is obviously different from a traditional process. Ethynyl (-C is equivalent to CH) in TEPM molecules has sp hybrid carbon atoms, lone pair electrons of the acetenyl (-C is equivalent to CH) can serve as ligands to form coordinate bonds with under-coordinated Pb < 2 + > in perovskite, and defects are effectively passivated; meanwhile, TEPM regulates and controls the crystallization process of the perovskite thin film through a steric hindrance effect and pi-pi interaction, and the morphology and the crystallization quality of the thin film are improved; and the conjugated structure can also enhance the charge transfer efficiency and reduce the non-radiative recombination loss.

Description

Technical Field

[0001] This invention belongs to the field of perovskite solar cell preparation technology, specifically relating to an all-inorganic perovskite solar cell with a carbon electrode including alkyne derivatives and its preparation method. Background Technology

[0002] Energy is the core driving force behind human socio-economic development, but traditional fossil fuels are gradually being depleted, and global warming is intensifying, making the development of renewable and clean energy an urgent priority. Solar energy, as a green and renewable energy source, has attracted much attention, and converting it into electricity through solar cells is an effective way to utilize it. The cost-effectiveness, photoelectric conversion efficiency, and stability of solar cells are key factors determining whether solar energy can become a primary energy source.

[0003] Perovskite solar cells (PSCs) are photovoltaic devices that use lead halide perovskite as the photoactive material. Perovskite materials possess excellent light absorption coefficients, long charge diffusion lengths, and tunable band gaps, making them ideal photovoltaic semiconductor materials. In 2024, Professor Rao Huashang's team at South China Agricultural University achieved a photoelectric conversion efficiency (PCE) of 19.08% using CsPbI3 PSCs with carbon electrodes. However, due to numerous bulk defects in perovskite, limitations in fabrication processes, and large interfacial energy level mismatches, the PCE of C-PSCs is still lower than that of all-inorganic perovskite solar cells with metal electrodes. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a carbon electrode all-inorganic perovskite solar cell including alkyne derivatives and its preparation method, so as to solve the problem of low efficiency of all-inorganic carbon electrode perovskite solar cells caused by many defects in the light-absorbing layer of the all-inorganic perovskite.

[0005] To achieve the above objectives, the present invention employs the following technical solution: A method for preparing an all-inorganic carbon electrode perovskite solar cell comprising alkyne derivatives includes the following steps: S1, Pre-treated conductive glass substrate; S2, deposit an electron transport layer on the FTO layer, wherein the electron transport layer is TiO2 or SnO2; S3, spin-coating a CsPbI3 all-inorganic perovskite precursor solution onto the electron transport layer, followed by annealing to obtain an all-inorganic perovskite light-absorbing layer; the all-inorganic perovskite precursor solution contains tetrakis(4-ethynylphenyl)methane. S4, a carbon electrode is prepared on an all-inorganic perovskite light-absorbing layer.

[0006] A further improvement of the present invention is that: Preferably, in S3, the concentration of tetra(4-ethynylphenyl)methane in the all-inorganic perovskite precursor solution is 0.5-4 mg / mL.

[0007] Preferably, in S3, the preparation process of the CsPbI3 all-inorganic perovskite precursor solution is as follows: HPbI3 and CsI are dissolved in a solvent, tetra(4-ethynylphenyl)methane is added, and the mixture is stirred to obtain the all-inorganic perovskite precursor solution, wherein the solvent is a mixed solution of DMF and DMSO.

[0008] Preferably, in S3, the concentration of perovskite in the CsPbI3 all-inorganic perovskite precursor solution is 0.7-1.1 mol / L.

[0009] Preferably, in S3, the spin coating speed is 1000-3000 rpm and the spin coating time is 40 s.

[0010] Preferably, in S3, the annealing temperature is 190℃ and the annealing time is 13-17 min.

[0011] Preferably, in S4, the preparation process of the carbon electrode is as follows: the perovskite film is placed in a carbon scraping mold, the carbon paste is scraped onto the perovskite film, and annealed at 100°C for 15-25 min.

[0012] An all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative, obtained by any of the above preparation methods, comprises a conductive glass substrate, an electron transport layer, an all-inorganic perovskite light-absorbing layer, and a carbon electrode stacked from one side to the other; wherein the all-inorganic perovskite light-absorbing layer contains tetrakis(4-ethynylphenyl)methane.

[0013] Preferably, the thickness of the all-inorganic perovskite light-absorbing layer is 600 nm.

[0014] Preferably, the thickness of the carbon electrode is 30 μm.

[0015] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a method for preparing an all-inorganic perovskite solar cell with a carbon electrode comprising an alkyne derivative. This method differs significantly from traditional processes by introducing tetra(4-ethynylphenyl)methane (TEPM) into a perovskite precursor solution. In the TEPM molecule, the ethynyl group (-C≡CH) has sp-hybridized carbon atoms, and the alkyne group (C≡C) targets and coordinates undercoordinated Pb. 2+ Able to work with both CH and I - Hydrogen bonds are formed, and the two sites work together to selectively target core defects, reducing defect density and achieving "Pb 2 + +I -"Dual precision passivation of defects" – on the one hand, alkyne coordination delays crystallization, passivates defects at two sites, and optimizes the interface by shifting energy levels upward, while simultaneously improving the stability of the hydrophobic framework. TEPM regulates the crystallization process of perovskite films through steric hindrance effects and π-π interactions, improving film morphology and crystallization quality; its conjugated structure also enhances charge transport efficiency and reduces non-radiative recombination losses; after adding TEPM to the perovskite precursor solution, its interaction with the perovskite components can adjust the film bandgap, improve crystallization quality, and increase the battery open-circuit voltage. V OC This method significantly improves photoelectric conversion efficiency (PCE). It is simple to operate and highly reproducible. Optimization of the TEPM concentration revealed that performance improvement is limited below 1 mg / mL; at 2 mg / mL, the film quality is optimal, with significant improvements in both cell efficiency and stability (Example 1 achieved an efficiency of 19.79%). In summary, the introduction of TEPM can effectively passivate film defects and suppress charge recombination, ultimately resulting in a highly efficient and stable all-inorganic perovskite solar cell. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the structure of the all-inorganic carbon electrode perovskite solar cell prepared by the present invention; In the diagram: 1 is conductive glass; 2 is electron transport layer; 3 is all-inorganic perovskite light-absorbing layer; 4 is carbon electrode; Figure 2 This is a performance comparison chart of the undoped and doped alkyne derivative inorganic perovskite solar cells described in Example 1 of the present invention; Figure 3 This is a comparison of X-ray diffraction (XRD) images of undoped and doped alkyne derivative inorganic perovskite films described in Example 1 of the present invention; Figure 4 This is a comparison of the steady-state fluorescence (PL) spectra of undoped and doped alkyne derivative inorganic perovskite films described in Example 1 of this invention.

[0017] Figure 5 This is a comparison of the ultraviolet photoelectron spectroscopy (UPS) of undoped and doped alkyne derivative inorganic perovskite films described in Example 1 of this invention.

[0018] Figure 6 This refers to the capacitance-voltage test of undoped and doped alkyne derivative inorganic perovskite solar cells described in Example 1 of this invention. CV )curve. Detailed Implementation

[0019] The present invention will now be described in further detail with reference to the accompanying drawings: To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0020] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0021] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0022] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0023] The first aspect of this invention discloses a method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative, the method comprising the following steps: Step 1: Clean the conductive glass substrate; The conductive glass substrate 1 is fluorine-doped tin oxide (FTO) conductive glass, which is ultrasonically cleaned in ethanol, isopropanol and acetone for 10-30 min each, and then dried with a nitrogen gun.

[0024] Step 2: Prepare the electron transport layer; An electron transport layer was prepared on a conductive glass substrate by water bath deposition, and the material of the electron transport layer was TiO2 or SnO2.

[0025] Step 3: Prepare an all-inorganic perovskite light-absorbing layer; Preparation of an all-inorganic perovskite precursor solution; HPbI3 and CsI were dissolved in a solvent, and TEPM (0.5-4 mg / mL) was added. Finally, the solution was dissolved in a mixed solution of DMF and DMSO with a volume ratio of 4:1. The concentration of the prepared all-inorganic perovskite precursor solution was 0.7-1.1 mol / L.

[0026] (2) The all-inorganic perovskite precursor solution was spin-coated onto the surface of the electron transport layer at a spin-coating speed of 1000-3000 rpm for 40 s; the annealing temperature was 190°C. o C, annealing time is 13-17 min.

[0027] Step 4: Prepare the carbon electrode; The perovskite film was placed in a carbon scraping mold, and commercial carbon paste was uniformly scraped onto the film using a polytetrafluoroethylene rod. The device was then placed on a hot plate at 100°C for annealing for 15-25 minutes.

[0028] The second aspect of the present invention discloses an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative, wherein the cell structure comprises, from bottom to top, a conductive glass 1, an electron transport layer 2, an all-inorganic perovskite light-absorbing layer 3 and a carbon electrode 4 stacked sequentially.

[0029] The inorganic perovskite light-absorbing layer 3 has a thickness of 600 nm, the electrode is made of carbon material with a thickness of 30~70 µm, and the electron transport layer is made of TiO2 or SnO2. Due to the low reflectivity of the carbon electrode, a relatively thick perovskite film is required to ensure sufficient reflectivity inside the perovskite solar cell.

[0030] The following description, in conjunction with specific embodiments, provides further details.

[0031] Comparative Example Step 1: Clean the conductive glass substrate; The conductive glass substrate 1 is fluorine-doped tin oxide (FTO) conductive glass, which is ultrasonically cleaned in ethanol, isopropanol and acetone for 30 min each, and then dried with a nitrogen gun.

[0032] Step 2: Prepare the electron transport layer; An electron transport layer TiO2 was prepared on a conductive glass substrate by water bath deposition. The FTO substrate was subjected to ultraviolet ozone treatment for 15 min. The electron transport layer was made of TiO2, the hydrothermal holding temperature was 70℃, and the precursor was TiCl4.

[0033] Step 3: Prepare an all-inorganic perovskite light-absorbing layer; (1) Preparation of an all-inorganic perovskite precursor solution; The process for preparing the CsPbI3 perovskite precursor solution is as follows: Hydrogen lead iodine (HPbI3) and cesium iodide (CsI) (molar ratio = 1:1.1) are dissolved in a mixed solvent of DMF and DMSO (V / V = 4:1) to prepare a 1 M CsPbI3 perovskite precursor solution.

[0034] (2) The prepared inorganic CsPbI3 perovskite precursor solution was spin-coated onto the electron transport layer to prepare an all-inorganic perovskite light-absorbing layer. The spin-coating process consisted of two stages: the first stage had a spin speed of 1000 rpm and a spin-coating time of 10 s; the second stage had a spin speed of 3000 rpm and a spin-coating time of 40 s; the annealing temperature was 190°C. o C, an inorganic perovskite light-absorbing layer was prepared by annealing for 15 min; Step 4: Prepare the carbon electrode; The perovskite film was placed in a carbon scraping mold, and commercial carbon paste was uniformly scraped onto the film using a polytetrafluoroethylene rod. The device was then annealed on a hot plate at 100°C for 20 min.

[0035] Example 1 Step 1: Clean the conductive glass substrate; The conductive glass substrate 1 is fluorine-doped tin oxide (FTO) conductive glass, which is ultrasonically cleaned in ethanol, isopropanol and acetone for 30 min each, and then dried with a nitrogen gun.

[0036] Step 2: Prepare the electron transport layer; An electron transport layer of TiO2 was prepared on a conductive glass substrate by water bath deposition. The FTO substrate was then subjected to ultraviolet ozone treatment for 15 min. The electron transport layer was made of TiO2. 2， The hydrothermal insulation temperature is 70℃, and the precursor is TiCl4.

[0037] Step 3: Prepare an all-inorganic perovskite light-absorbing layer; (1) Preparation of an all-inorganic perovskite precursor solution; The process for preparing the CsPbI3 perovskite precursor solution is as follows: lead hydrogen iodine (HPbI3) and cesium iodide (CsI) (molar ratio = 1:1.1) are dissolved in a mixed solvent of DMF and DMSO (V / V = 4:1) to prepare a 1 M CsPbI3 perovskite precursor solution. The concentration of TEPM in the precursor solution is 2 mg / mL.

[0038] (2) The prepared inorganic CsPbI3 perovskite precursor solution was spin-coated onto the electron transport layer to prepare an all-inorganic perovskite light-absorbing layer. The spin-coating process consisted of two stages: the first stage had a spin speed of 1000 rpm and a spin-coating time of 10 s; the second stage had a spin speed of 3000 rpm and a spin-coating time of 40 s; the annealing temperature was 190°C. o C, an inorganic perovskite light-absorbing layer was prepared by annealing for 15 min; Step 4: Prepare the carbon electrode; The perovskite film was placed in a carbon scraping mold, and commercial carbon paste was uniformly scraped onto the film using a polytetrafluoroethylene rod. The device was then annealed on a hot plate at 100°C for 20 min.

[0039] In this example, a perovskite solar cell structure comprising an all-inorganic carbon electrode and an alkyne derivative is obtained, as shown below. Figure 1 As shown, it includes, in sequence, a conductive glass layer (1), an electron transport layer (2), an inorganic perovskite light-absorbing layer (3), and a carbon electrode (4). The inorganic perovskite light-absorbing layer (3) has a thickness of 600 nm, and the carbon electrode has a thickness of 50 μm.

[0040] like Figure 2 As shown, TEPM doping can improve the open-circuit voltage and fill factor of all-inorganic perovskite solar cells, and the cell efficiency is also greatly improved to 19.79%.

[0041] like Figure 3 As shown in the XRD comparison diagram of the TEPM-doped all-inorganic perovskite film and the traditional inorganic perovskite film, the peak intensity is significantly enhanced, indicating that the crystallinity of the perovskite film is improved.

[0042] from Figure 4 The image shows a comparison of the photoperiod (PL) peaks of the TEPM-doped all-inorganic perovskite film and the traditional all-inorganic perovskite film. The enhanced PL peak further proves that the crystallinity of the film has improved.

[0043] like Figure 5 As shown, the perovskite film treated with TEPM has a higher conduction band and Fermi level, which makes the optimized perovskite film and carbon electrode have a more matched energy arrangement, which is conducive to reducing the electron transfer barrier and increasing the open circuit voltage of the device.

[0044] like Figure 6 As shown, the built-in electric field of perovskite solar cells treated with TEPM is larger. The increased built-in electric field between the hole transport layer and the perovskite light-absorbing layer is beneficial for charge separation and collection, which helps to improve the open-circuit voltage of the device.

[0045] Example 2 In this example, the concentration of TEPM added to the prepared perovskite precursor solution was 1 mg / ml. Other steps were the same as in Example 1. In this example, the efficiency of the perovskite solar cell containing TEPM additive was 19.23%. Parameters not mentioned in this embodiment were the same as in Example 1.

[0046] Example 3 In this example, the concentration of TEPM added to the prepared perovskite precursor solution was 3 mg / ml. Other steps were the same as in Example 1. In this example, the efficiency of the perovskite solar cell containing TEPM additive was 19.08%. Parameters not mentioned in this embodiment were the same as in Example 1.

[0047] Example 4 In this example, the concentration of TEPM added to the prepared perovskite precursor solution was 4 mg / ml. In this example, the efficiency of the perovskite solar cell containing TEPM additive was 18.08%. Parameters not mentioned in this embodiment are the same as in Example 1.

[0048] Example 5 In this example, the concentration of TEPM added to the perovskite precursor solution containing TEPM was 0.5 mg / ml. All parameters not mentioned in this embodiment are the same as in Example 1.

[0049] Example 6 In this example, the concentration of TEPM added to the perovskite precursor solution containing TEPM was 1.5 mg / ml. All parameters not mentioned in this embodiment are the same as in Example 1.

[0050] Example 7 In this example, the concentration of TEPM added to the perovskite precursor solution containing TEPM was 2.5 mg / ml. All parameters not mentioned in this embodiment are the same as in Example 1.

[0051] Example 8 In this example, the concentration of TEPM added to the perovskite precursor solution containing TEPM was 3.5 mg / ml. All parameters not mentioned in this embodiment are the same as in Example 1.

[0052] Example 9 In this embodiment, the electron transport layer is SnO2. To prepare the electron transport layer, a 0.1 M SnO2 solution is spin-coated onto an FTO substrate and annealed at 200°C for 30 min. Parameters not mentioned in this embodiment are the same as in Example 1.

[0053] Example 10 In this embodiment, the concentration of CsPbI3 in the all-inorganic perovskite precursor solution is 0.7 mol / L. All parameters not mentioned in this embodiment are the same as in Example 1.

[0054] Example 11 In this embodiment, the concentration of CsPbI3 in the all-inorganic perovskite precursor solution is 0.8 mol / L. All parameters not mentioned in this embodiment are the same as in Example 1.

[0055] Example 12 In this embodiment, the concentration of CsPbI3 in the all-inorganic perovskite precursor solution is 0.9 mol / L. All parameters not mentioned in this embodiment are the same as in Example 1.

[0056] Example 13 In this embodiment, the concentration of CsPbI3 in the all-inorganic perovskite precursor solution is 1.1 mol / L. All parameters not mentioned in this embodiment are the same as in Example 1.

[0057] Example 14 In this embodiment, the annealing time of CsPbI3 in the all-inorganic perovskite precursor solution is 13 min. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0058] Example 15 In this embodiment, the annealing time of CsPbI3 in the all-inorganic perovskite precursor solution is 14 min. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0059] Example 16 In this embodiment, the annealing time of CsPbI3 in the all-inorganic perovskite precursor solution is 16 min. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0060] Example 17 In this embodiment, the annealing time of CsPbI3 in the all-inorganic perovskite precursor solution is 17 min. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0061] Example 18 In this embodiment, the electrode is a carbon electrode with a thickness of 30 µm. All parameters not mentioned in this embodiment are the same as in Example 1.

[0062] Example 19 In this embodiment, the electrode is a carbon electrode with a thickness of 40 µm. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0063] Example 20 In this embodiment, the electrode is a carbon electrode with a thickness of 60 µm. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0064] Example 21 In this embodiment, the electrode is a carbon electrode with a thickness of 70 µm. All parameters not mentioned in this embodiment are the same as those in Example 1.

[0065] Example 22 In this embodiment, the carbon electrode annealing temperature is 100°C and the annealing time is 15 min. All parameters not mentioned in this embodiment are the same as in Example 1.

[0066] Example 23 In this embodiment, the carbon electrode annealing temperature is 100°C and the annealing time is 25 min. All parameters not mentioned in this embodiment are the same as in Example 1.

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an all-inorganic carbon electrode perovskite solar cell comprising alkyne derivatives, characterized in that, Includes the following steps: S1, Pre-treated conductive glass substrate; S2, deposit an electron transport layer on the FTO layer, wherein the electron transport layer is TiO2 or SnO2; S3, spin-coating a CsPbI3 all-inorganic perovskite precursor solution onto the electron transport layer, followed by annealing to obtain an all-inorganic perovskite light-absorbing layer; the all-inorganic perovskite precursor solution contains tetrakis(4-ethynylphenyl)methane. S4, a carbon electrode is prepared on an all-inorganic perovskite light-absorbing layer.

2. The method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative according to claim 1, characterized in that, In S3, the concentration of tetra(4-ethynylphenyl)methane in the all-inorganic perovskite precursor solution is 0.5-4 mg / mL.

3. The method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative according to claim 1, characterized in that, In S3, the preparation process of the CsPbI3 all-inorganic perovskite precursor solution is as follows: HPbI3 and CsI are dissolved in a solvent, tetrakis(4-ethynylphenyl)methane is added, and the mixture is stirred to obtain the all-inorganic perovskite precursor solution. The solvent is a mixed solution of DMF and DMSO.

4. The method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative according to claim 1, characterized in that, In S3, the concentration of perovskite in the CsPbI3 all-inorganic perovskite precursor solution is 0.7-1.1 mol / L.

5. The method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative according to claim 1, characterized in that, In S3, the spin coating speed is 1000-3000 rpm and the spin coating time is 40 s.

6. The method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative according to claim 1, characterized in that, In S3, the annealing temperature is 190℃ and the annealing time is 13-17 min.

7. The method for preparing an all-inorganic carbon electrode perovskite solar cell comprising an alkyne derivative according to claim 1, characterized in that, In S4, the preparation process of the carbon electrode is as follows: the perovskite film is placed in a carbon scraping mold, the carbon paste is scraped onto the perovskite film, and annealed at 100°C for 15-25 min.

8. A perovskite solar cell comprising an alkyne derivative and prepared by any one of claims 1-7, characterized in that, It includes a conductive glass substrate, an electron transport layer, an inorganic perovskite light-absorbing layer, and a carbon electrode stacked from one side to the other; the inorganic perovskite light-absorbing layer contains tetra(4-ethynylphenyl)methane.

9. The all-inorganic carbon electrode perovskite solar cell comprising alkyne derivatives according to claim 8, characterized in that, The thickness of the all-inorganic perovskite light-absorbing layer is 600 nm.

10. The all-inorganic carbon electrode perovskite solar cell comprising alkyne derivatives according to claim 9, characterized in that, The thickness of the carbon electrode is 30 μm.

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