CN116113295A - Perovskite solar cell and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of solar cells, and provides a perovskite solar cell, which comprises: a substrate; a first charge transport layer disposed on the surface of the substrate; the perovskite layer is arranged on the surface of the first charge transmission layer, and the perovskite layer contains 4-methyl nicotine hydrochloride; a second charge transport layer disposed on a surface of the perovskite layer; and an electrode arranged on the surface of the second charge transmission layer. According to the invention, the 4-methyl nicotine hydrochloride additive is introduced into the perovskite precursor, N, O of the additive can act with low-coordination lead, and Cl ions can passivate halogen defects, so that the perovskite crystallization quality is obviously improved, and the trap state density is reduced.

Description

Perovskite solar cell and preparation method thereof

Technical Field

The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell and a preparation method thereof.

Background

Perovskite solar cells have been developed rapidly in recent decades by virtue of their advantages of high efficiency, low cost, simple preparation, etc., and have become the most commercially viable novel photovoltaic technology. In perovskite solar cells, the perovskite absorber layer is critical, and its quality directly affects the photoelectric conversion efficiency and stability of the overall cell. Therefore, the quality of the perovskite film is improved, the defect state density of the film is reduced, and the reduction of non-radiative recombination is beneficial to improving the photoelectric conversion efficiency of the device.

Disclosure of Invention

In view of the above, an object of the embodiments of the present invention is to provide a perovskite solar cell and a method for manufacturing the same, where the perovskite solar cell provided by the present invention has a better photoelectric conversion efficiency.

The invention provides a perovskite solar cell, comprising:

a substrate;

a first charge transport layer disposed on the surface of the substrate;

the perovskite layer is arranged on the surface of the first charge transmission layer, and the perovskite layer contains 4-methyl nicotine hydrochloride;

a second charge transport layer disposed on a surface of the perovskite layer;

and an electrode arranged on the surface of the second charge transmission layer.

Preferably, the perovskite layer further comprises a halide perovskite; the crystal structure of the halide perovskite is ABX ₃ A is at least one selected from organic cations and inorganic cations, more preferably at least one selected from formamidine ions (FA), methylamine ions (MA) and cesium ions (Cs); b is at least one selected from divalent metal ions, more preferably from lead ions (Pb) and stannous ions (Sn); x is selected from at least one of halogen ion, more preferably iodine ion (I), bromine ion (Br) and chlorine ion (Cl).

Preferably, the molar ratio of the 4-methyl nicotinic hydrochloride to the halide perovskite is (0.1% -10%): 1.

preferably, the thickness of the perovskite layer is 200-500 nm.

Preferably, the electrode is selected from one or more of a metal electrode, a carbon electrode and a transparent conductive oxide electrode; the thickness is 50-150 nm.

Preferably, the material of the first charge transport layer is selected from TiO ₂ 、SnO ₂ 、NiO _x One or more of PTAA; the thickness is 10-40 nm.

Preferably, the material of the second charge transport layer is selected from one or more of Spiro-OMeTAD, PCBM, C60; the thickness is 50-300 nm.

The invention provides a preparation method of the perovskite solar cell, which comprises the following steps:

a substrate;

preparing a first charge transport layer on the surface of the substrate;

preparing a perovskite layer on the surface of the first charge transport layer;

preparing a second charge transport layer on the surface of the perovskite layer;

and preparing an electrode on the surface of the second charge transport layer.

Preferably, the preparation method of the perovskite layer comprises the following steps:

coating the perovskite precursor solution on the surface of the first charge transport layer, and then annealing to obtain a perovskite layer;

4-methyl nicotine hydrochloride is added into the perovskite precursor solution.

Preferably, the annealing temperature is 100-200 ℃; the annealing time is 5-20 minutes.

The invention provides a method for improving the performance of a perovskite solar cell, which applies 4-methyl nicotine hydrochloride to the perovskite solar cell to improve the performance of the perovskite solar cell. According to the invention, the 4-methyl nicotine hydrochloride additive is introduced into the perovskite precursor, N, O of the additive can act with low-coordination lead, and Cl ions can passivate halogen defects, so that the perovskite crystallization quality is obviously improved, and the trap state density is reduced. According to the invention, the additive is introduced into the perovskite precursor, so that the crystallization process of perovskite is adjusted, the crystal growth of perovskite is optimized, and the quality of a film can be effectively improved.

Drawings

Fig. 1 is a graph showing the results of battery performance test prepared in example 1;

fig. 2 is a graph showing the results of battery performance test prepared in example 2;

fig. 3 is a graph showing the results of the battery performance test prepared in comparative example 1;

fig. 4 is a graph showing the results of battery performance test prepared in comparative example 2.

Detailed Description

The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

The invention provides a perovskite solar cell, comprising:

a substrate;

a first charge transport layer disposed on the surface of the substrate;

the perovskite layer is arranged on the surface of the first charge transmission layer, and the perovskite layer contains 4-methyl nicotine hydrochloride;

a second charge transport layer disposed on a surface of the perovskite layer;

and an electrode arranged on the surface of the second charge transmission layer.

In the invention, the material of the substrate is preferably selected from FTO transparent conductive glass or ITO transparent conductive glass; the sheet resistance of the substrate is preferably 7-15 omega sq ^–1 More preferably 7Ω sq ^–1 。

In the present invention, the material of the first charge transport layer is preferably selected from TiO ₂ 、SnO ₂ 、NiO _x One or more of PTAA; the thickness of the first charge transport layer is preferably 10 to 40nm, more preferably 20 to 30nm, and most preferably 25nm.

In the present invention, the component of the perovskite layer preferably further comprises a halide perovskite, the crystal structure (component formula) of which is preferably ABX ₃ The method comprises the steps of carrying out a first treatment on the surface of the A is at least one selected from organic cations and inorganic cations, more preferably at least one selected from formamidine ions (FA), methylamine ions (MA) and cesium ions (Cs); b is at least one selected from divalent metal ions, more preferably from lead ions (Pb) and stannous ions (Sn); x is selected from at least one of halogen ion, more preferably iodine ion (I), bromine ion (Br) and chlorine ion (Cl).

In the present invention. The molar ratio of the 4-methyl-nicotine hydrochloride to the halide perovskite is preferably (0.01-0.10): 1, more preferably (0.02 to 0.08): 1, more preferably (0.03 to 0.06): 1, most preferably (0.04 to 0.05): 1.

in the present invention, the thickness of the perovskite layer is preferably 200 to 500nm, more preferably 300 to 400nm, and most preferably 350nm.

In the present invention, the material of the second charge-transporting layer is preferably selected from one or more of Spiro-OMeTAD, PCBM, C60; the thickness of the second charge transport layer is preferably 50 to 300nm, more preferably 100 to 200nm, and most preferably 150nm.

In the invention, the material of the electrode is preferably one or more selected from a metal electrode, a carbon electrode and a transparent conductive oxide electrode; the thickness of the electrode is preferably 50 to 150nm, more preferably 80 to 120nm, and most preferably 100nm.

The invention provides a preparation method of the perovskite solar cell, which comprises the following steps:

a substrate;

preparing a first charge transport layer on the surface of the substrate;

preparing a perovskite layer on the surface of the first charge transport layer;

preparing a second charge transport layer on the surface of the perovskite layer;

and preparing an electrode on the surface of the second charge transport layer.

In the embodiment of the invention, the substrate can be an FTO glass substrate, which can be cleaned by acetone, isopropanol and deionized water in sequence, and is treated by ultraviolet-ozone after being dried; the treatment time may be 10 to 30 minutes or 20 minutes.

In the present invention, the preparation method of the first charge transport layer is preferably one or more selected from the group consisting of chemical bath deposition, spray pyrolysis, magnetron sputtering, spin coating, and atomic layer deposition. The first charge transport layer can be prepared by a conventional method for preparing a first charge transport layer by one skilled in the art. In an embodiment of the present invention, the method for preparing the first charge transport layer may include:

and (3) placing the substrate into the first charge transport layer precursor solution, and then taking out, drying, washing and annealing to obtain the first charge transport layer.

In an embodiment of the present invention, the first charge transport layer precursor solution may be a titanium tetrachloride solution, and the preparation method of the titanium tetrachloride solution may be to drop titanium tetrachloride dropwise into ice water; drying can be carried out in an oven, and the temperature of the drying can be 60-80 ℃ or 70 ℃; the drying time can be 50-70 minutes or 60 minutes; the washing can be carried out by adopting deionized water and absolute ethyl alcohol; the annealing temperature can be 160-200 ℃ or 180 ℃; the annealing time may be 20 to 40 minutes or 30 minutes.

In the present invention, the preparation method of the perovskite layer preferably comprises:

and coating the perovskite precursor solution on the surface of the first charge transport layer, and then annealing to obtain the perovskite (light absorption) layer.

In the invention, the perovskite precursor solution contains 4-methyl nicotine hydrochloride; the perovskite precursor solution preferably comprises: solute and solvent; the solute comprises: halide perovskite and 4-methyl-nicotine hydrochloride; the crystal structure of the halide perovskite is consistent with that of the technical scheme, and the halide perovskite can be one or more of methylimidine iodide, cesium iodide, lead iodide, methyl ammonium chloride, dimethylamine hydroiodide and the like; the molar ratio of the halide perovskite to the 4-methyl nicotine hydrochloride is consistent with that of the technical scheme; the solvent is preferably selected from one or more of DMF (N, N-dimethylformamide) and DMSO (dimethyl sulfoxide); the molar concentration of the perovskite precursor solution is preferably 0.5 to 1.5mol/L, more preferably 0.6 to 0.8mol/L.

In the present invention, the annealing temperature is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, and most preferably 140 to 160 ℃; the time for the annealing is preferably 5 to 20 minutes, more preferably 10 to 15 minutes.

In an embodiment of the present invention, a method for preparing a perovskite layer may include:

and spin-coating the perovskite precursor solution on the surface of the first charge transmission layer, then dripping an antisolvent, and then annealing to obtain the perovskite layer.

In an embodiment of the present invention, the solute in the perovskite precursor solution may include: FAI, pbI ₂ MACl and 4-methyl nicotine hydrochloride; pbI ₂ And the molar ratio of FAI may be (0.8 to 1.2): 1, may be 1:1, a step of; MACl and PbI ₂ The molar ratio of (2) may be (0.3 to 0.4): 1, may be 0.35:1, a step of; 4-methyl-nicotine hydrochloride and PbI ₂ The molar ratio of (3) may be (0.008 to 0.012): 1, may be 0.01:1, a step of; the concentration of the perovskite precursor solution can be 1-2 mol/L or 1.4mol/L; the solvent in the perovskite precursor solution may include DMF and DMSO; the volume ratio of DMF to DMSO may be (8-10): 1, may be 9:1.

in the embodiment of the invention, the speed of preparing the perovskite layer during spin coating can be 4000-6000 rpm or 5000rpm; the spin coating time can be 10-20 s or 15s; an antisolvent may be added dropwise at 10 s; the antisolvent may be anhydrous diethyl ether; the annealing temperature can be 100-200 ℃ or 150 ℃; the annealing time may be 15 to 25 minutes or 20 minutes.

In the present invention, the preparation method of the second charge transport layer is preferably one or more selected from the group consisting of spin coating, sputtering, and vacuum evaporation; the second charge transport layer can be prepared by one skilled in the art according to conventional methods for preparing a second charge transport layer. In an embodiment of the present invention, the method for preparing the second charge transport layer may include:

and spin-coating the second charge transport layer precursor solution on the surface of the perovskite layer to obtain the second charge transport layer.

In an embodiment of the present invention, the method for preparing the second charge transport layer precursor solution may include: 72mg of Spiro-OMeTAD and 39. Mu.l of 4-t-butylpyridine were dissolved in 1mL of chlorobenzene, and 23. Mu.l of 520mg mL were added ^-1 Is a solution of lithium bis (trifluoromethanesulfonyl) imide in acetonitrile. In the embodiment of the invention, the speed in spin coating during the preparation of the second charge transport layer may be 2000-4000 rpm or 3000rpm; the spin coating time may be 20 to 40 seconds or 30 seconds.

In the present invention, the method for producing the electrode is preferably selected from sputtering, vacuum evaporation, spin coating; the electrode can be prepared by a person skilled in the art according to a conventional method for preparing an electrode. In the embodiment of the invention, the vacuum degree can be lower than 10 < -4 > Pa when the electrode is prepared by adopting the vacuum evaporation method, and the deposition rate can be

Can also be +.>

According to the invention, the 4-methyl nicotine hydrochloride additive is introduced into the perovskite precursor, N, O of the additive can act with low-coordination lead, and Cl ions can passivate halogen defects, so that the perovskite crystallization quality is obviously improved, and the trap state density is reduced. According to the invention, the additive is introduced into the perovskite precursor, so that the crystallization process of perovskite is adjusted, the crystal growth of perovskite is optimized, and the quality of a film can be effectively improved.

Example 1

The FTO glass substrate is cleaned by acetone, isopropanol and deionized water in sequence, and is treated by ultraviolet-ozone for 20 minutes after being dried. 4.5mL of titanium tetrachloride is dropwise added into 200mL of ice water, the titanium tetrachloride solution is prepared by uniformly mixing, FTO glass is placed into the titanium tetrachloride solution, placed into a 70 ℃ oven for 60 minutes, taken out, washed clean by deionized water and absolute ethyl alcohol, and annealed for 30 minutes at 180 ℃. Preparation of FAPbI in a Nitrogen glove box ₃ Perovskite precursor solution (solute in perovskite precursor solution is FAI, pbI ₂ MACl and 4-methyl nicotinic hydrochloride, pbI ₂ Molar ratio to FAI is 1:1, MACl and PbI ₂ The molar ratio of (2) is 0.35:1, 4-methyl-nicotinic hydrochloride and PbI ₂ The molar ratio of (2) is 0.01: 1) The concentration is 1.4mol/L, and the volume ratio of the solvent is 9:1 in DMF and DMSO. 50 microliters of the perovskite precursor solution was dropped on the titanium dioxide layer, spin-coated at 5000rpm for 15s, and 150 microliters of anhydrous diethyl ether was added dropwise at 10s, and annealed at 150℃for 20 minutes. 72mg of Spiro-OMeTAD and 39. Mu.l of 4-t-butylpyridine were dissolved in 1mL of chlorobenzene, and 23. Mu.l of 520mg mL were added ^-1 Uniformly mixing the acetonitrile solution of the lithium bis (trifluoromethanesulfonyl) imide, and spin-coating at 3000rpm for 30s to prepare the solution on a perovskite layer; finally, preparing the silver electrode by a vacuum evaporation method, wherein the vacuum degree is lower than 10 ^-4 Pa, deposition rate

And obtaining the perovskite solar cell.

In the perovskite solar cell prepared in the embodiment 1 of the invention, the first charge transport layer is 20nm, the perovskite layer is 400nm, the second charge transport layer is 200nm, and the silver electrode is 70nm.

Example 2

The FTO glass substrate is cleaned by acetone, isopropanol and deionized water in sequence, and is treated by ultraviolet-ozone for 20 minutes after being dried. 4.5mL of titanium tetrachloride is dropwise added into 200mL of ice water, the titanium tetrachloride solution is prepared by uniformly mixing, FTO glass is placed into the titanium tetrachloride solution, placed into a 70 ℃ oven for 60 minutes, taken out, washed clean by deionized water and absolute ethyl alcohol, and annealed for 30 minutes at 180 ℃. Preparation of CsPbI in a Nitrogen glove box ₃ Perovskite precursor solution (solute in perovskite precursor solution is CsI, pbI ₂ DMAI and 4-methyl-nicotinic hydrochloride, the molar ratio is 1:1:1:0.01, concentration is 0.8mol/L, and solvent is DMF); 50 microliters of the perovskite precursor solution was dropped onto the titanium dioxide layer, spin-coated at 4000rpm for 30s, and annealed at 200 ℃ for 5 minutes. 72mg of Spiro-OMeTAD and 39. Mu.l of 4-t-butylpyridine were dissolved in 1mL of chlorobenzene, and 23. Mu.l of 520mg mL were added ^-1 Uniformly mixing the acetonitrile solution of the lithium bis (trifluoromethanesulfonyl) imide, and spin-coating at 3000rpm for 30s to prepare the solution on a perovskite layer; finally, preparing the silver electrode by a vacuum evaporation method, wherein the vacuum degree is lower than 10 ^-4 Pa, deposition rate

And obtaining the perovskite solar cell.

The electron transport layer in the perovskite solar cell prepared in example 2 of the invention is 20nm, the perovskite layer is 400nm, the hole transport layer is 200nm, and the silver electrode is 70nm.

Comparative example 1

A perovskite solar cell was prepared according to the method of example 1, differing from example 1 in that 4-methylnicotinic hydrochloride was not added to the perovskite precursor solution.

Comparative example 2

A perovskite solar cell was prepared according to the method of example 2, differing from example 2 in that 4-methylnicotinic hydrochloride was not added to the perovskite precursor solution.

Performance detection

At room temperature, using a 3A solar simulator at 100mW/cm ² Test examples and comparative examples were prepared at light intensityThe photoelectric conversion efficiency of the cell of (2) was 0.09cm ² . The test data are shown in FIGS. 1 to 4, and the short-circuit current density of the battery prepared in example 1 is 25.55mA/cm ² Open circuit voltage 1.089V, fill factor 78.72%, photoelectric conversion efficiency 21.91%; the short-circuit current density of the battery prepared in example 2 was 19.47mA/cm ² Open circuit voltage 1.133V, fill factor 80.46%, photoelectric conversion efficiency 17.75%; comparative example 1 the short-circuit current density of the battery prepared in comparative example 1 was 25.71mA/cm ² Open circuit voltage 1.068V, fill factor 74.59%, photoelectric conversion efficiency 20.48%; comparative example 2 the short-circuit current density of the battery prepared in comparative example 2 was 19.12mA/cm ² Open circuit voltage 1.091V, fill factor 80.45%, photoelectric conversion efficiency 16.79%.

According to the invention, the 4-methyl nicotine hydrochloride additive is introduced into the perovskite precursor, N, O of the additive can act with low-coordination lead, and Cl ions can passivate halogen defects, so that the perovskite crystallization quality is obviously improved, and the trap state density is reduced. According to the invention, the additive is introduced into the perovskite precursor, so that the crystallization process of perovskite is adjusted, the crystal growth of perovskite is optimized, and the quality of a film can be effectively improved.

While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.

Claims (10)

1. A perovskite solar cell, comprising:

a substrate;

a first charge transport layer disposed on the surface of the substrate;

the perovskite layer is arranged on the surface of the first charge transmission layer, and the perovskite layer contains 4-methyl nicotine hydrochloride;

a second charge transport layer disposed on a surface of the perovskite layer;

and an electrode arranged on the surface of the second charge transmission layer.

2. The perovskite solar cell of claim 1, wherein the perovskite layer further comprises: halide perovskite.

3. The perovskite solar cell according to claim 2, wherein the molar ratio of 4-methyl nicotinic hydrochloride to halide perovskite is (0.1% -10%): 1.

4. the perovskite solar cell of claim 1, wherein the perovskite layer has a thickness of 200-500 nm.

5. The perovskite solar cell according to claim 1, wherein the material of the first charge transport layer is one or more selected from titanium dioxide, tin dioxide, niOx, PTAA; the thickness is 10-40 nm.

6. The perovskite solar cell according to claim 1, wherein the material of the second charge transport layer is selected from one or more of Spiro-OMeTAD, PCBM, C60; the thickness is 50-300 nm.

7. The perovskite solar cell according to claim 1, wherein the electrode is selected from one or more of a metal electrode, a carbon electrode, a transparent conductive oxide electrode; the thickness is 50-150 nm.

8. A method of fabricating a perovskite solar cell as claimed in claim 1, comprising:

a substrate;

preparing a first charge transport layer on the surface of the substrate;

preparing a perovskite layer on the surface of the first charge transport layer;

preparing a second charge transport layer on the surface of the perovskite layer;

and preparing an electrode on the surface of the second charge transport layer.

9. The method of claim 8, wherein the method of producing the perovskite layer comprises:

coating the perovskite precursor solution on the surface of the first charge transport layer, and then annealing to obtain a perovskite layer;

4-methyl nicotine hydrochloride is added into the perovskite precursor solution.

10. The method of claim 9, wherein the annealing temperature is 100-200 ℃; the annealing time is 5-20 minutes.

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