Perovskite crystallization method, lead-based organic-inorganic hybrid perovskite solar cell and preparation method thereof

Abstract

The invention belongs to the technical field of new materials and new energy, and discloses a perovskite crystallization method, a lead-based organic-inorganic hybrid perovskite solar cell and a preparation method thereof.The perovskite crystallization method comprises the steps that a lead iodide solution containing volatile DAP and rubidium and a formamidine hydriodate and methylamine hydrochloride mixed solution containing a GABA hydrogen bond network are spin-coated, and then [6, 7]-dicyclopentadiene is spin-coated in sequence; the preparation method comprises the following steps: adding a 2, 6-phenyl C61 methyl butyrate solution and a 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrene solution into a reaction kettle, evaporating a silver electrode, and assembling the lead-based organic-inorganic hybrid perovskite solar cell based on DAP and GABA double-intermediate synergy, thereby obtaining the lead-based organic-inorganic hybrid perovskite solar cell based on DAP and GABA double-intermediate synergy. A staged regulation and control strategy is provided, the quality of the perovskite thin film is remarkably improved, the photoelectric conversion efficiency (PCE) of the perovskite solar cell prepared through the synergistic effect of the double intermediates breaks through 25.5%, and 95% or above of the initial efficiency is still kept after the perovskite solar cell runs for 1200 hours at the maximum power.

Description

Technical Field

[0001] The present invention belongs to the fields of new material technology and new energy technology, and in particular relates to a method for collaboratively regulating perovskite crystallization by volatile polyamines and zwitterionic compounds, a method for preparing lead-based organic-inorganic hybrid perovskite solar cells, and solar cells. Background Art

[0002] Perovskite solar cells have become a research hotspot in the photovoltaic field due to their advantages such as high photoelectric conversion efficiency and low preparation cost. However, the crystallization quality of perovskite films directly determines the performance and stability of the device. Its growth process involves complex precursor dissolution-coordination-crystallization dynamics. Especially in the multi-step solution method preparation, how to coordinate the precursor dissociation and the reaction rate of the organic salt still poses a significant challenge. In the existing technology, researchers often control crystallization by introducing intermediates (such as methylamine chloride, dimethyl sulfoxide) or passivators (such as phenylethylamine bromide, thiourea), but there are still problems such as the mismatch between precursor dissociation and solvent penetration and the uncontrollable reaction kinetics of the organic salt.

[0003] First, although traditional volatile ligands (such as methylamine gas) can induce the formation of an intermediate phase, it is difficult to precisely control the dissociation energy of the PbI2 octahedron, resulting in uneven solvent penetration and a wide distribution of grain sizes. Moreover, a single ligand cannot take into account both the porous structure and the reaction kinetics, resulting in a low precursor conversion rate. In addition, during the perovskite conversion process, the deprotonation rate of organic salts (such as FAI) is too fast to easily induce disordered crystallization, forming pinholes and halogen vacancy defects. Although additives can be used to delay the reaction, their static passivation mechanism is difficult to dynamically adapt to changes in the crystallization path, and macromolecular additives are prone to blocking carrier transport channels, resulting in a limited filling factor.

[0004] Through the above analysis, the problems and defects of the existing technology are as follows:

[0005] (1) In the prior art, the method of regulating crystallization by introducing intermediates or passivating agents has problems such as mismatch between precursor dissociation and solvent penetration and uncontrollable organic salt reaction kinetics.

[0006] (2) Traditional volatile ligands make it difficult to precisely control the PbI2 octahedral dissociation energy, resulting in uneven solvent penetration and a wide distribution of grain sizes. Furthermore, a single ligand cannot take into account both the porous structure and the reaction kinetics, resulting in a low precursor conversion rate.

[0007] (3) During the perovskite conversion process, the deprotonation rate of organic salts is too fast, which can easily lead to disordered crystallization and form pinholes and halogen vacancy defects. Its static passivation mechanism is difficult to dynamically adapt to changes in the crystallization path, and macromolecular additives can easily block the carrier transport channel, resulting in a limited filling factor. Summary of the Invention

[0008] To overcome the problems existing in the related art, the present invention discloses a method for synergistically regulating perovskite crystallization using volatile polyamines and zwitterionic compounds, particularly a method for synergistically regulating perovskite crystallization based on a dual intermediate of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA), and its application in high-efficiency solar cells. The technical solution is as follows:

[0009] The present invention is achieved by a method for synergistically regulating perovskite crystallization using a volatile polyamine and a zwitterionic compound, comprising the following steps:

[0010] S1, spin coating of a lead iodide solution containing volatile 1,3-propylenediamine and rubidium;

[0011] S2, spin coating of a mixed solution of formamidine hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network;

[0012] S3, spin-coating [6,6]-phenyl C61 butyric acid methyl ester solution and 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution in sequence to achieve staged dynamic coordinated regulation of perovskite crystallization.

[0013] Another object of the present invention is to provide a method for preparing a lead-based organic-inorganic hybrid perovskite solar cell implementing the method, wherein the method for preparing a lead-based organic-inorganic hybrid perovskite solar cell comprises:

[0014] (1) preparing an aqueous solution of nickel oxide with a concentration of 0.1-1.5 mg / mL, spin-coating the aqueous solution of nickel oxide on a cleaned indium tin oxide conductive glass substrate, and annealing to obtain a hole transport layer;

[0015] (2) preparing an ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid with a concentration of 0.2-5 mg / mL, spin-coating the ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid on the surface of the hole transport layer prepared in step (1), and annealing to obtain a self-assembled molecular layer;

[0016] (3) PbI2 and RbI are weighed and dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide to obtain a lead iodide solution containing rubidium; 0.1-0.3 mg of 1,3-propylenediamine is then dissolved in the lead iodide solution containing rubidium, and the mixture is heated to dissolve to obtain a lead iodide solution containing volatile 1,3-propylenediamine and rubidium;

[0017] (4) spin coating a lead iodide solution containing volatile 1,3-propylenediamine and rubidium on the surface of the self-assembled molecular layer prepared in step (2), and annealing to obtain a rubidium-containing lead iodide film with vertically distributed cavities;

[0018] (5) spin coating an isopropyl alcohol solution of a mixture of formamidine hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network on the surface of the rubidium lead iodide film prepared in step (4), and annealing at high temperature in air to obtain a lead-based organic-inorganic hybrid perovskite film;

[0019] (6) spin-coating the lead-based organic-inorganic hybrid perovskite film prepared in step (5) with a [6,6]-phenyl C61 butyric acid methyl ester solution and a 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution in sequence, and annealing to obtain an electron transport layer;

[0020] (7) A silver electrode is evaporated on the surface of the electron transport layer in step (6) to assemble a lead-based organic-inorganic hybrid perovskite solar cell based on the synergistic effect of 1,3-propylenediamine and γ-aminobutyric acid as a double intermediate.

[0021] In step (3), the molar concentration of the solute PbI2 is 1-1.8 mol / L, and the molar concentration of RbI is 0.01-0.018 mol / L; the volume ratio of the mixed solution of N,N-dimethylformamide and dimethyl sulfoxide is 9:1;

[0022] The concentration of 1,3-propylenediamine in the rubidium-containing lead iodide solution is 0.1-0.3 mg / mL, the heating and dissolving temperature of the rubidium-containing lead iodide solution is 60-80° C., and the heating and dissolving time is 24-48 hours.

[0023] In step (4), the spin coating speed of the rubidium-containing lead iodide film is 2300-2500 r / min, the annealing temperature is 60-80° C., and the annealing time is 60-90 s.

[0024] In step (5), the concentration of γ-aminobutyric acid in the mixed isopropanol solution containing the γ-aminobutyric acid hydrogen bond network is 0.05-0.2 mg / mL, the concentration of formamidine hydroiodide is 70-110 mg / mL, and the concentration of methylamine hydrochloride is 7-11 mg / mL.

[0025] In step (5), the isopropanol solution of formamidine hydroiodide and methylamine hydrochloride containing the γ-aminobutyric acid hydrogen bond network is spin-coated at a speed of 2700-2900 r / min, the annealing temperature is 150-170° C., and the annealing time is 10-15 min.

[0026] In step (6), the concentration of the [6,6]-phenyl C61 butyric acid methyl ester solution is 20 mg / mL, and the concentration of the 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline solution is 2 mg / mL.

[0027] Another object of the present invention is to provide a lead-based organic-inorganic hybrid perovskite solar cell, which is prepared by implementing the preparation method of the lead-based organic-inorganic hybrid perovskite solar cell. The cell is arranged in order from bottom to top: (1) a conductive substrate, (2) a nickel oxide hole transport layer, (3) a self-assembled molecular layer, (4) a lead-based organic-inorganic hybrid perovskite thin film layer, (5) a [6,6]-phenyl C61 butyric acid methyl ester electron transport layer, (6) a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline barrier layer and (7) a silver electrode layer;

[0028] Among them, the conductive substrate is an indium tin oxide transparent conductive substrate, the hole transport layer is a nickel oxide and small molecule self-assembly layer with a thickness of 20nm, the lead-based organic-inorganic hybrid perovskite layer is a lead-based organic-inorganic hybrid perovskite film with a thickness of 680nm after treatment with 1,3-propylenediamine and γ-aminobutyric acid diintermediates, the electron transport layer is a [6,6]-phenyl C61 butyric acid methyl ester film with a thickness of 20nm, the electron transport layer is a 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline film with a thickness of 6nm, and the counter electrode layer is a silver counter electrode layer with a thickness of 100nm.

[0029] Furthermore, the open circuit voltage of the battery is 1.00-1.16V and the short circuit current is 23-25mA·cm -2 , the filling factor is 0.80-0.86, and the photoelectric conversion efficiency is 18.5-24.5%.

[0030] Another object of the present invention is to provide an application of the lead-based organic-inorganic hybrid perovskite solar cell in a solar photovoltaic cell assembly and a photovoltaic curtain wall.

[0031] In combination with all the above technical solutions, the beneficial effects of the present invention are as follows:

[0032] First, in response to the problems of high precursor dissociation energy barrier, disordered crystallization and high defect density in the preparation process of traditional perovskite films, the present invention innovatively proposes a phased regulation strategy. First, volatile 1,3-propylenediamine (DAP) is used to coordinate with PbI2 to form a porous intermediate layer PbI2(DAP)2, which expands the PbI2 lattice spacing by more than 20%, thereby achieving the vertical distribution of PbI2 film cavities and the optimization of organic salt permeability. Subsequently, γ-aminobutyric acid (GABA) is introduced as an organic salt reaction kinetics regulator, and its organic amine group reacts with formamidinium ion (FA) to form a porous intermediate layer PbI2(DAP)2. +) forms a hydrogen bond network, slows down the deprotonation rate, induces ordered molecular exchange and inhibits the generation of halogen vacancies. This method significantly improves the quality of perovskite films, with grain sizes reaching 800-1500nm and defect density reduced by more than 33%. The photoelectric conversion efficiency (PCE) of perovskite solar cells prepared in this way exceeds 25.5%, and after running at maximum power for 1200 hours, it still maintains more than 95% of the initial efficiency. The present invention solves the industry problem of the difficulty in coordinated regulation of perovskite crystallization kinetics and thermodynamics through the synergistic effect of two intermediates, and provides an innovative solution for the large-scale preparation of high-performance, long-life perovskite photovoltaic devices.

[0033] Second, the present invention proposes for the first time a "gas-phase coordination-liquid-phase hydrogen bond" dual-intermediate synergistic mechanism, which realizes the precise optimization of the perovskite crystal growth path through a phased dynamic synergistic intervention mechanism, fundamentally improving the crystallization quality and carrier transport dynamics of lead-based organic-inorganic hybrid perovskite films, and obtaining high-performance lead-based organic-inorganic hybrid perovskite solar cells with low cost, high efficiency and long life. It has important theoretical significance and practical value, and has good market application prospects.

[0034] Compared to existing single-intermediate or static passivation technologies, this invention achieves precise optimization of the perovskite crystallization pathway through the phased synergistic action of volatile 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates. This technical solution has significantly increased the photoelectric conversion efficiency of lead-based organic-inorganic hybrid perovskite solar cells to over 25%.

[0035] The traditional static passivation strategy cannot adapt to the dynamic defect generation of perovskite under stress such as humidity, heat, and light. However, the present invention realizes the dynamic capture and repair of defects through the synergistic passivation mechanism of DAP and GABA. The pre-buried amino group (-NH2) of GABA and the ionized proton (H + ) forms a dual-site passivation network, providing technical support for extending the lifespan of organic-inorganic hybrid perovskite solar cells. Lead-based organic-inorganic hybrid perovskite solar cells fabricated using this technique maintained over 95% of their initial efficiency after 1200 hours of continuous testing in a nitrogen environment with a relative humidity of 40%, with no significant degradation in cell efficiency.

[0036] Third, the technical solution of this invention is expected to significantly enhance the commercial competitiveness of perovskite photovoltaic modules and photovoltaic curtain walls after transformation. High-quality thin films (grain size 800-1500nm, defect density 3.83×10 15 / cm 3), effectively reducing the manufacturing costs of optoelectronic devices. Its long-term stability meets international certification requirements and is expected to capture 20% of the mid-to-high-end perovskite photovoltaic market within five years, generating annual output value exceeding 10 billion yuan. Furthermore, this technology can be expanded to the field of perovskite-crystalline silicon tandem cells, helping to surpass the 33% efficiency threshold and seize the commanding heights of next-generation photovoltaic technology.

[0037] This invention innovatively addresses the international technical bottleneck of kinetic and thermodynamic mismatch during perovskite thin film crystallization through a phased dual-intermediate synergistic control strategy, filling the gap in the field of step-by-step controllable crystallization of lead-based organic-inorganic hybrid systems. Its pioneering synergistic mechanism of DAP-induced porous intermediate layer (lattice spacing expansion rate >20%) and GABA hydrogen bond network sustained release effect overcomes the limitations of traditional single-phase control technology, which cannot balance precursor dissociation, molecular ordering, and defect suppression. It achieves the core industrialization indicators of photoelectric conversion efficiency greater than 25.5% and long-term stability (T80 >3000h), promoting perovskite photovoltaic technology from laboratory to large-scale application, and providing China with an original, efficient and stable technology path for the global new energy industry.

[0038] This invention successfully overcomes the long-standing mismatch between crystallization dynamics and thermodynamics in the field of perovskite photovoltaics: the traditional process has a film defect density higher than 10 for a long time due to the dense arrangement of precursors and disordered molecular exchange. 16 / cm 3 The grain size is limited to 200-500nm. Through the synergistic mechanism of DAP-induced porous intermediate layer (lattice expansion rate 20%) and GABA hydrogen bond network regulation, orderly molecular exchange, efficient crystal phase transformation, good crystal orientation and synchronous suppression of defects at grain boundaries (defect density 3.83×10 15 / cm 3 ), breaking the efficiency-stability inversion relationship (PCE>25.5% and T80>3000h).

[0039] This invention successfully overcomes the long-standing technical prejudice in the field of perovskite photovoltaics that "kinetic and thermodynamic regulation cannot be achieved at the same time" through a phased dual intermediate synergistic strategy. Traditional processes generally use single additives or annealing optimization, which makes it difficult to balance the expansion of the precursor lattice and the orderly exchange of molecules, resulting in limited defect density and grain size. This technology uses DAP to construct a porous intermediate layer (lattice expansion rate 20.8%), which cooperates with the GABA hydrogen bond network to achieve high-quality films (grain size 800-1500nm, defect density 3.83×10 15 / cm 3 ), breaking the efficiency-stability inversion relationship (PCE>25.5% and T80>3000h). BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and, together with the description, serve to explain the principles of the present disclosure;

[0041] Figure 1 This is a flow chart of a method for collaboratively regulating perovskite crystallization using volatile polyamines and zwitterionic compounds, provided in an embodiment of the present invention;

[0042] Figure 2 1 is a structural diagram of a lead-based organic-inorganic hybrid perovskite solar cell device prepared in Example 1 of the present invention;

[0043] Figure 3 1 are scanning electron microscope images provided by the embodiments of the present invention; wherein (a) is a scanning electron microscope image of the lead-based organic-inorganic hybrid perovskite film prepared in Example 1, and (b) is a scanning electron microscope image of the film prepared in Comparative Example 1;

[0044] Figure 4 is a JV curve diagram of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of the present invention and the solar cell prepared in Comparative Example 1;

[0045] Figure 5 This is a light stability test chart of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of the present invention;

[0046] Figure 6 1 is a JV curve diagram of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 2, Example 3, and Example 4 of the present invention;

[0047] In the figure: 1. Conductive substrate; 2. Hole transport layer; 3. Self-assembled molecular layer; 4. Lead-based organic-inorganic hybrid perovskite thin film layer; 5. [6,6]-phenyl C61 butyric acid methyl ester (PCBM) electron transport layer; 6. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) blocking layer; 7. Silver electrode layer. DETAILED DESCRIPTION

[0048] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. The following description sets forth numerous specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0049] The innovation of this invention lies in: the invention innovatively constructs a synergistic control system of volatile polyamine (DAP) and zwitterionic compound (GABA), breaking through the thermodynamic-kinetic synergistic optimization problem of perovskite crystallization. DAP forms a porous intermediate PbI2(DAP)2 with PbI2, constructs vertical channels to enhance the penetration of organic salts, realizes orderly molecular exchange, and completely volatilizes without residue after annealing; GABA reacts with FA through amino groups. + Forming a hydrogen bond network to delay deprotonation, its carboxyl group chelates Pb 2+ The halogen vacancy formation energy is further suppressed. After the perovskite crystallization is optimized, the grain size reaches 800-1500nm and the bulk defect density is 3.83×10 15 / cm 3 The device efficiency reached 25.52% and maintained over 95% after 1200 hours of operation at the maximum power point, providing an innovative solution for the large-scale preparation of high-performance, long-life perovskite photovoltaic devices.

[0050] Example 1, as Figure 1 As shown, the method for collaboratively regulating perovskite crystallization by volatile polyamines and zwitterionic compounds provided in an embodiment of the present invention includes the following steps:

[0051] S1, spin coating of a lead iodide solution containing volatile 1,3-propylenediamine and rubidium;

[0052] S2, spin coating of a mixed solution of formamidine hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network;

[0053] S3, spin-coating [6,6]-phenyl C61 butyric acid methyl ester solution and 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution in sequence to achieve staged dynamic coordinated regulation of perovskite crystallization.

[0054] In the embodiment of the present invention, taking 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) as dopants, the preparation method of a lead-based organic-inorganic hybrid perovskite solar cell based on a double intermediate of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) specifically includes the following steps:

[0055] (1) preparing an aqueous solution of nickel oxide with a concentration of 1 mg / mL, wherein the nickel oxide is the solute and water is the solvent;

[0056] (2) 100 μL of nickel oxide aqueous solution was spin-coated on a cleaned ITO conductive glass substrate at a speed of 2000 r / min for 30 seconds, and then annealed at 120°C for 5 minutes to obtain a hole transport layer;

[0057] (3) preparing a 1 mg / mL ethanol solution of [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid, wherein [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid is the solute and ethanol is the solvent;

[0058] (4) Spin-coat 100 μL of an ethanol solution of [2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid onto the hole transport layer at a speed of 3000 r / min for 30 seconds, and then anneal at 100°C for 10 minutes to obtain a self-assembled molecular layer;

[0059] (5) A certain amount of PbI2 and RbI were dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (the volume ratio of N,N-dimethylformamide and dimethyl sulfoxide was 9:1) to obtain a rubidium-containing lead iodide solution; wherein the molar concentration of the solute PbI2 in the mixed solution was 1.8 mol / L, and the molar concentration of the solute CsI in the mixed solution was 0.018 mol / L; 1,3-propylenediamine (DAP) was then added to make the concentration of 1,3-propylenediamine in the rubidium-containing lead iodide solution 0.2 mg / mL; after magnetic stirring at 70°C for 24 h, the solution was filtered using a polytetrafluoroethylene filter to obtain a DAP-coordinated rubidium-containing lead iodide solution;

[0060] (6) Spin coating 75 μL of rubidium-containing lead iodide solution on the self-assembled molecular layer at a spin coating speed of 2500 r / min for 30 s; then annealing at 70°C for 60 s using a constant temperature heating stage to obtain a rubidium-containing lead iodide film;

[0061] (7) 110 μL of a mixed isopropanol solution of formamidine hydroiodide and methylamine hydrochloride containing 0.1 mg / mL of a γ-aminobutyric acid (GABA) hydrogen bond network was spin-coated onto a rubidium-containing lead iodide film, wherein the GABA concentration in the mixed isopropanol solution was 0.1 mg / mL, the formamidine hydroiodide concentration was 90 mg / mL, and the methylamine hydrochloride concentration was 10 mg / mL; the solution was magnetically stirred at room temperature for 30 min until completely dissolved; the spin coating speed was 2900 r / min, and the spin coating time was 30 s; the solution was annealed on a constant temperature heating table at 150°C in air for 10 min to obtain a lead-based organic-inorganic hybrid perovskite film of a dual intermediate of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA);

[0062] (8) The lead-based organic-inorganic hybrid perovskite film of the dual intermediate of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) prepared in step (7) was spin-coated with 20 mg / mL [6,6]-phenyl C61 butyric acid methyl ester solution and 2 mg / mL 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution in sequence, with a spin coating speed of 2000 r / min and a spin coating time of 180 s.

[0063] (9) Silver electrodes were evaporated to prepare lead-based organic-inorganic hybrid perovskite solar cells with dual intermediates of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA).

[0064] Figure 2 This is a device structure diagram of a lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of the present invention. The cell comprises, arranged from bottom to top, a conductive substrate 1, a nickel oxide hole transport layer 2, a self-assembled molecular layer 3, a lead-based organic-inorganic hybrid perovskite thin film layer 4, a [6,6]-phenyl C61 butyric acid methyl ester (PCBM) electron transport layer 5, a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) barrier layer 6, and a silver electrode layer 7. The conductive substrate 1 is an indium tin oxide (ITO) transparent conductive substrate, the hole transport layers 2 and 3 are nickel oxide and small molecule self-assembly layers with a thickness of 20 nm, the lead-based organic-inorganic hybrid perovskite layer 4 is a lead-based organic-inorganic hybrid perovskite film with a thickness of 680 nm treated with 1,3-propylenediamine and γ-aminobutyric acid diintermediates, the PCBM electron transport layer 5 is a [6,6]-phenyl C61 butyric acid methyl ester film with a thickness of 20 nm, the BCP blocking layer 6 is a 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline film with a thickness of 6 nm, and the counter electrode layer 7 is a silver counter electrode layer with a thickness of 100 nm.

[0065] In control example 1, a solar cell with a lead-based organic-inorganic hybrid perovskite thin film without the addition of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates was constructed. The steps of control example 1 of the present invention are substantially the same as those of Example 1, except that in step (5), the molar concentration of the solute PbI2 in the mixed solution is 1.2 mol / L, and the molar concentration of the solute CsI in the mixed solution is 0.012 mol / L; in step (7), the concentration of formamidine hydroiodide is 90 mg / mL, and the concentration of methylamine hydrochloride is 10 mg / mL.

[0066] The scanning electron microscope images of the lead-based organic-inorganic hybrid perovskite film prepared in Example 1 of the present invention and the film prepared in Comparative Example 1 are as follows: Figure 3 The solar cells prepared in Example 1 and Comparative Example 1 were tested, and the test results are shown below:

[0067] The test was carried out under standard test conditions (AM1.5 lighting). Figure 4 The JV curves of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of the present invention and the solar cell prepared in Comparative Example 1 are shown in FIG. Figure 4 As shown in FIG. 1 , the photoelectric conversion efficiency of the solar cell device of the experimental group prepared in Example 1 of the present invention in the reverse scanning is 25.52%, the open circuit voltage is 1.166 V, and the short circuit current is 25.51 mA / cm 2 The fill factor is 85.80%. The photoelectric conversion efficiency of the solar cell device of comparative example 1 in the forward scan is 21.87%, the open circuit voltage is 1.066V, and the short circuit current is 24.85mA / cm 2 , the fill factor is 82.60%. From this, it can be seen that the addition of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates can significantly improve the quality of perovskite films, increase the fill factor and open circuit voltage, and improve the photoelectric conversion efficiency.

[0068] Figure 5 This is a light stability test diagram of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of the present invention. Figure 5 As shown, the solar cell prepared in Example 1 of the present invention can maintain 95.2% of its initial efficiency after 1200 hours in a nitrogen atmosphere at 50°C. This shows that the lead-based organic-inorganic hybrid perovskite solar cell with crystallization regulated by the dual intermediates of 1,3-propylenediamine (DAP) and γ-aminobutyric acid (GABA) in the embodiment of the present invention has good photoelectric conversion efficiency and stability.

[0069] Example 2. The preparation process of this example is generally the same as that of Example 1, and the similarities are not repeated here. The difference is that γ-aminobutyric acid (GABA) is not added in step (7), and a lead-based organic-inorganic hybrid perovskite solar cell is constructed.

[0070] Example 3. The preparation process of this example is generally the same as that of Example 1, and the similarities are not repeated here. The difference is that 1,3-propylenediamine (DAP) is not added in step (5), and a lead-based organic-inorganic hybrid perovskite solar cell is constructed.

[0071] Example 4. The preparation process of this example is generally the same as that of Example 1, and the similarities are not repeated here. The difference is that in step (5), 0.2 mg / mL of 1,3-propylenediamine (DAP) is replaced by 0.3 mg / mL of 1,3-propylenediamine (DAP), and in step (7), 0.1 mg / mL of γ-aminobutyric acid (GABA) is replaced by 0.2 mg / mL of γ-aminobutyric acid (GABA), and a lead-based organic-inorganic hybrid perovskite solar cell is constructed.

[0072] The solar cells prepared in Examples 2-4 were tested respectively, and the test results are shown below:

[0073] The test was carried out under standard test conditions (AM1.5 lighting). Figure 6 The JV curves of the lead-based organic-inorganic hybrid perovskite solar cells prepared in Examples 2-4 of the present invention are shown in FIG. Figure 6 As shown in Example 2 of the present invention, when 0.2 mg / mL of 1,3-propylenediamine (DAP) was used, the photoelectric conversion efficiency of the prepared solar device in the reverse scan was 24.44%, the open circuit voltage was 1.149 V, and the short circuit current was 25.36 mA / cm 2 , the fill factor is 83.87%. In Example 3 of the present invention, when 0.1 mg / mL of γ-aminobutyric acid (GABA) is used, the photoelectric conversion efficiency of the prepared solar device in the reverse scan is 24.51%, the open circuit voltage is 1.138 V, and the short circuit current is 25.42 mA / cm 2 , the fill factor is 84.72%. When 0.3 mg / mL of 1,3-propylenediamine (DAP) and 0.2 mg / mL of γ-aminobutyric acid (GABA) are used in Example 4 of the present invention, the photoelectric conversion efficiency of the prepared solar device in the reverse scan is 24.87%, the open circuit voltage is 1.163 V, and the short circuit current is 25.12 mA / cm 2 , the filling factor is 85.10%.

[0074] Table 1 shows the relevant parameters of the lead-based organic-inorganic hybrid perovskite solar cells prepared in Examples 1-4 of the present invention and Comparative Example 1. As shown in Table 1, compared with Comparative Example 1, Examples 1-4 of the present invention all have an improvement effect. Further comparison of Examples 1-4 shows that the improvement effect is most obvious when the addition amount of 1,3-propylenediamine (DAP) is 0.2 mg / mL and the addition amount of γ-aminobutyric acid (GABA) is 0.1 mg / mL in Example 1 of the present invention, which is the preferred additive dosage.

[0075] Table 1 Process parameters of lead-based organic-inorganic hybrid perovskite solar cells of Comparative Example 1 and Examples 1-4

[0076]

[0077]

[0078] Experimental design, experimental group and control group:

[0079] Experimental group: adopting the staged regulation strategy of the present invention;

[0080] Step 1: Add 1,3-propylenediamine (DAP) to the PbI2 precursor solution to form a porous intermediate layer PbI2(DAP)2, which is then spin-coated and annealed (100°C, 10 minutes).

[0081] Step 2: Add γ-aminobutyric acid (GABA) to the formamidinium lead iodide (FAI) solution, spin-coat, and then perform secondary annealing (150°C, 15 minutes).

[0082] Control group: Traditional one-step perovskite film preparation:

[0083] The mixed solution of PbI2 and FAI was directly spin-coated, and the annealing conditions were the same as those of the experimental group (150°C, 15 minutes).

[0084] Evaluation indicators:

[0085] Precursor lattice spacing: X-ray diffractometer analysis of lattice spacing changes;

[0086] Perovskite crystal quality: grain size.

[0087] Perovskite defect density: measuring trap state density using the space charge limited current method.

[0088] The comparison results of key performance data between the experimental group and the control group are shown in Table 2.

[0089] Table 2 Comparison of key performance data between the experimental group and the control group

[0090]

[0091] This experiment proved through quantitative data that the phased control strategy can significantly improve the quality of perovskite films and device performance, break through the efficiency-stability balance bottleneck, and provide a reliable technical path for industrial applications.

[0092] The above description is only a preferred specific implementation method of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with this technical field within the technical scope disclosed by the present invention and within the spirit and principles of the present invention should be covered by the scope of protection of the present invention.

Claims

1. A method for synergistically regulating perovskite crystallization by volatile polyamines and zwitterionic compounds, characterized in that: The method comprises the following steps: S1, spin coating of a lead iodide solution containing volatile 1,3-propylenediamine and rubidium; S2, spin coating of a mixed solution of formamidine hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network; S3, spin-coating [6,6]-phenyl C61 butyric acid methyl ester solution and 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution in sequence to achieve staged dynamic coordinated regulation of perovskite crystallization.

2. A method for preparing a lead-based organic-inorganic hybrid perovskite solar cell by implementing the method of claim 1, characterized in that: The preparation method of the lead-based organic-inorganic hybrid perovskite solar cell comprises: (1) preparing an aqueous solution of nickel oxide with a concentration of 0.1-1.5 mg / mL, spin-coating the aqueous solution of nickel oxide on a cleaned indium tin oxide conductive glass substrate, and annealing to obtain a hole transport layer; (2) preparing an ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid with a concentration of 0.2-5 mg / mL, spin-coating the ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid on the surface of the hole transport layer prepared in step (1), and annealing to obtain a self-assembled molecular layer; (3) PbI2 and RbI are weighed and dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide to obtain a lead iodide solution containing rubidium; 0.1-0.3 mg of 1,3-propylenediamine is then dissolved in the lead iodide solution containing rubidium, and the mixture is heated to dissolve to obtain a lead iodide solution containing volatile 1,3-propylenediamine and rubidium; (4) spin coating a lead iodide solution containing volatile 1,3-propylenediamine and rubidium on the surface of the self-assembled molecular layer prepared in step (2), and annealing to obtain a rubidium-containing lead iodide film with vertically distributed cavities; (5) spin coating an isopropyl alcohol solution of a mixture of formamidine hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network on the surface of the rubidium lead iodide film prepared in step (4), and annealing at high temperature in air to obtain a lead-based organic-inorganic hybrid perovskite film; (6) spin-coating the lead-based organic-inorganic hybrid perovskite film prepared in step (5) with a [6,6]-phenyl C61 butyric acid methyl ester solution and a 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution in sequence, and annealing to obtain an electron transport layer; (7) A silver electrode is evaporated on the surface of the electron transport layer in step (6) to assemble a lead-based organic-inorganic hybrid perovskite solar cell based on the synergistic effect of 1,3-propylenediamine and γ-aminobutyric acid as a double intermediate.

3. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, wherein: In step (3), the molar concentration of the solute PbI2 is 1-1.8 mol / L, and the molar concentration of RbI is 0.01-0.018 mol / L; the volume ratio of the mixed solution of N,N-dimethylformamide and dimethyl sulfoxide is 9:1; The concentration of 1,3-propylenediamine in the rubidium-containing lead iodide solution is 0.1-0.3 mg / mL, the heating and dissolving temperature of the rubidium-containing lead iodide solution is 60-80° C., and the heating and dissolving time is 24-48 hours.

4. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, wherein: In step (4), the spin coating speed of the rubidium-containing lead iodide film is 2300-2500 r / min, the annealing temperature is 60-80° C., and the annealing time is 60-90 s.

5. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, wherein: In step (5), the concentration of γ-aminobutyric acid in the mixed isopropanol solution containing the γ-aminobutyric acid hydrogen bond network is 0.05-0.2 mg / mL, the concentration of formamidine hydroiodide is 70-110 mg / mL, and the concentration of methylamine hydrochloride is 7-11 mg / mL.

6. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, wherein: In step (5), the isopropanol solution of formamidine hydroiodide and methylamine hydrochloride containing the γ-aminobutyric acid hydrogen bond network is spin-coated at a speed of 2700-2900 r / min, the annealing temperature is 150-170° C., and the annealing time is 10-15 min.

7. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, characterized in that: In step (6), the concentration of the [6,6]-phenyl C61 butyric acid methyl ester solution is 20 mg / mL, and the concentration of the 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline solution is 2 mg / mL.

8. A lead-based organic-inorganic hybrid perovskite solar cell, characterized in that: The cell is prepared by implementing the preparation method of the lead-based organic-inorganic hybrid perovskite solar cell according to any one of claims 2 to 7, and the cell comprises, arranged from bottom to top, (1) a conductive substrate, (2) a nickel oxide hole transport layer, (3) a self-assembled molecular layer, (4) a lead-based organic-inorganic hybrid perovskite thin film layer, (5) a [6,6]-phenyl C61 butyric acid methyl ester electron transport layer, (6) a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline barrier layer, and (7) a silver electrode layer; Among them, the conductive substrate is an indium tin oxide transparent conductive substrate, the hole transport layer is a nickel oxide and small molecule self-assembly layer with a thickness of 20nm, the lead-based organic-inorganic hybrid perovskite layer is a lead-based organic-inorganic hybrid perovskite film with a thickness of 680nm after treatment with 1,3-propylenediamine and γ-aminobutyric acid diintermediates, the electron transport layer is a [6,6]-phenyl C61 butyric acid methyl ester film with a thickness of 20nm, the electron transport layer is a 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline film with a thickness of 6nm, and the counter electrode layer is a silver counter electrode layer with a thickness of 100nm.

9. The lead-based organic-inorganic hybrid perovskite solar cell according to claim 8, characterized in that: The open circuit voltage of the battery is 1.00-1.16V and the short circuit current is 23-25mA·cm -2 , the filling factor is 0.80-0.86, and the photoelectric conversion efficiency is 18.5-24.5%.

10. Use of the lead-based organic-inorganic hybrid perovskite solar cell according to claim 9 in solar photovoltaic cell components and photovoltaic curtain walls.

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