CN116075166A - Perovskite solar cell with electron transport layer modified by alkali metal acetate and preparation method thereof - Google Patents
Perovskite solar cell with electron transport layer modified by alkali metal acetate and preparation method thereof Download PDFInfo
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- CN116075166A CN116075166A CN202310255003.9A CN202310255003A CN116075166A CN 116075166 A CN116075166 A CN 116075166A CN 202310255003 A CN202310255003 A CN 202310255003A CN 116075166 A CN116075166 A CN 116075166A
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Abstract
The invention belongs to the technical field of perovskite solar cells, and provides a perovskite solar cell with an alkali metal acetate modified electron transport layer, which comprises: a substrate; an electron transport layer disposed on the surface of the substrate; an alkali metal acetate modification layer arranged on the surface of the electron transport layer; the perovskite light absorption layer is arranged on the surface of the alkali metal acetate modification layer; the hole transmission layer is arranged on the surface of the perovskite light absorption layer; and an electrode arranged on the surface of the hole transport layer. According to the invention, the electron transport layer is modified by alkali metal acetate, so that on one hand, the alkali metal acetate can passivate the surface defects of the electron transport layer, and the charge transport capacity is improved; on the other hand, alkali metal acetate can diffuse into perovskite, so that the crystallinity of perovskite and interface contact between perovskite and an electron transport layer are improved, and the performance and stability of the device are improved.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a perovskite solar cell with an alkali metal acetate modified electron transport layer and a preparation method thereof.
Background
Perovskite solar cells become the most industrially potential novel photovoltaic technology with the advantages of low cost and high efficiency. In perovskite solar cells, the interfacial contact between the perovskite absorber layer and the charge transport layer plays a critical role in the performance and stability of the overall solar cell device. The common electron transport layers such as titanium dioxide, tin dioxide and the like are weak in combination with the perovskite layer, and the interface carrier transmission loss is large, so that the performance and stability of the device are finally affected. Therefore, how to improve device performance is an important point of research in the art.
Disclosure of Invention
In view of the above, the invention aims to provide a perovskite solar cell with an alkali metal acetate modified electron transport layer and a preparation method thereof.
The invention provides a perovskite solar cell of an alkali metal acetate modified electron transport layer, which comprises the following components:
a substrate;
an electron transport layer disposed on the surface of the substrate;
an alkali metal acetate layer disposed on the surface of the electron transport layer;
the perovskite light absorption layer is arranged on the surface of the alkali metal acetate layer;
the hole transmission layer is arranged on the surface of the perovskite light absorption layer;
and an electrode arranged on the surface of the hole transport layer.
Preferably, the material of the electron transport layer is at least one selected from titanium dioxide and tin dioxide.
Preferably, the alkali metal acetate in the alkali metal acetate layer is one or more selected from sodium acetate, potassium acetate, rubidium acetate and cesium acetate.
Preferably, the thickness of the alkali metal acetate layer is 3-10 nm.
Preferably, the hole transport layer is made of one or more materials selected from the group consisting of Spiro-OMeTAD and PTAA.
Preferably, the perovskite light absorbing layer is made of a material selected from halide perovskite; the crystal structure of the halide perovskite is 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; b is selected from divalent metal ions; x is selected from halogen ions.
Preferably, the electrode is selected from at least one of gold, silver, copper, carbon electrode, transparent conductive oxide electrode.
Preferably, the thickness of the electron transport layer is 10-40 nm;
the thickness of the perovskite light absorption layer is 200-500 nm;
the thickness of the hole transport layer is 100-300 nm;
the thickness of the electrode is 50-150 nm.
The invention provides a preparation method of a perovskite solar cell with an alkali metal acetate modified electron transport layer, which comprises the following steps:
preparing an electron transport layer on the surface of a substrate;
preparing an alkali metal acetate layer on the surface of the electron transport layer;
preparing a perovskite absorption layer on the surface of the alkali metal acetate layer;
preparing a hole transport layer on the surface of the perovskite absorption layer;
and preparing an electrode on the surface of the hole transport layer.
Preferably, the method of preparing an alkali metal acetate layer includes:
coating an alkali metal acetate solution on the surface of the electron transport layer, and then performing heat treatment to obtain an alkali metal acetate modification layer;
the concentration of the alkali metal acetate solution is 0.5-10 mg/mL.
Preferably, the heat treatment temperature is 80-150 ℃; the heat treatment time is 5-30 minutes.
The invention modifies the common electron transport layer, provides a perovskite solar cell with the electron transport layer modified by alkali metal acetate, adopts the alkali metal acetate to modify the electron transport layer, and can passivate the surface defect of the electron transport layer on one hand and improve the charge transport capacity; on the other hand, alkali metal acetate can diffuse into perovskite, so that the crystallinity of perovskite and interface contact between perovskite and an electron transport layer are improved, and the performance and stability of the device are improved.
Drawings
FIG. 1 is a graph of current versus voltage for a perovskite solar cell prepared according to example 1 of the invention;
FIG. 2 is a graph of current versus voltage for a perovskite solar cell prepared according to example 2 of the invention;
fig. 3 is a current-voltage curve of the perovskite solar cell prepared according to comparative example 1 of the present invention.
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 of an alkali metal acetate modified electron transport layer, which comprises the following components:
a substrate;
an electron transport layer disposed on the surface of the substrate;
an alkali metal acetate layer disposed on the surface of the electron transport layer;
the perovskite light absorption layer is arranged on the surface of the alkali metal acetate layer;
a hole transport layer disposed on the surface of the perovskite absorption layer;
and an electrode arranged on the surface of the hole transport layer.
In the present invention, the substrate is preferably a conductive substrate; the substrate is preferably made of 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 electron transport layer is preferably selected from titanium dioxide and/or tin dioxide; the thickness of the electron transport layer is preferably 10 to 40nm, more preferably 20 to 30nm, and most preferably 25nm.
In the present invention, the alkali metal acetate of the alkali metal acetate layer is preferably at least one selected from sodium acetate, potassium acetate, rubidium acetate and cesium acetate.
In the present invention, the thickness of the alkali metal acetate (modified layer) is preferably 3 to 10nm, more preferably 4 to 8nm, and most preferably 5 to 6nm.
In the present invention, the material of the perovskite light absorbing layer is preferably selected from halide perovskite; the crystal structure (formula) of the halide perovskite 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 thickness of the perovskite light absorbing layer is preferably 200 to 500nm, more preferably 300 to 400nm, and most preferably 350nm.
In the present invention, the hole transport layer is preferably selected from the group consisting of Spiro-OMeTAD (2, 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene) and/or PTAA (poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ]).
In the present invention, the thickness of the hole transport layer is preferably 100 to 300nm, more preferably 150 to 250nm, and most preferably 200nm.
In the present invention, the material of the electrode is preferably at least one selected from gold, silver, copper, carbon electrode, and transparent conductive oxide electrode.
In the present invention, 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 a perovskite solar cell with an alkali metal acetate modified electron transport layer, which comprises the following steps:
preparing an electron transport layer on the surface of a substrate;
preparing an alkali metal acetate layer on the surface of the electron transport layer;
preparing a perovskite light absorption layer on the surface of the alkali metal acetate layer;
preparing a hole transport layer on the surface of the perovskite light absorption layer;
and preparing an electrode on the surface of the hole transport layer.
In the present invention, the preparation method of the perovskite solar cell of the alkali metal acetate modified electron transport layer preferably comprises the following steps:
forming an electron transport layer on the surface of the conductive substrate;
forming an alkali metal acetate modification layer on the surface of the electron transport layer;
preparing a perovskite light absorption layer on the surface of the alkali metal acetate modification layer;
forming a hole transport layer on the surface of the perovskite light absorption layer;
and preparing an electrode on the surface of the hole transport layer.
In the present invention, the substrate is preferably an FTO glass substrate, and the substrate is preferably cleaned and treated; the cleaning is preferably one-time cleaning by adopting acetone, isopropanol and water; the water is preferably deionized water; preferably drying after cleaning; the treatment is preferably an ultraviolet-ozone treatment; the time of the treatment is preferably 15 to 25 minutes, more preferably 20 minutes.
In the present invention, the electron transport layer is preferably prepared by a method selected from the group consisting of chemical bath deposition, atomic layer deposition and spin coating, more preferably chemical bath deposition.
In the present invention, the method for preparing the electron transport layer preferably includes:
and immersing the substrate in the electron transport layer precursor solution for heating, and then taking out, washing and annealing to obtain the first charge transport layer.
In the present invention, the electron transport layer precursor is preferably titanium tetrachloride; the solvent in the electron transport layer precursor solution is preferably water. In the present invention, the first charge transport layer precursor solution is preferably a titanium tetrachloride solution; the preparation method of the titanium tetrachloride solution preferably comprises the following steps:
dropwise adding titanium tetrachloride into ice water, and uniformly mixing to obtain titanium tetrachloride solution.
In the present invention, the volume ratio of titanium tetrachloride to water is preferably (2 to 5): 200, more preferably (3 to 4): 200.
in the present invention, the heating is preferably performed in an oven; the heating temperature is preferably 65-75 ℃, more preferably 70 ℃; the heating time is preferably 60 to 120 minutes, more preferably 80 to 100 minutes, and most preferably 90 minutes.
In the present invention, the washing is preferably performed with water, preferably deionized water, and ethanol, preferably absolute ethanol.
In the present invention, the annealing temperature is preferably 170 to 190 ℃, more preferably 180 ℃; the time for the annealing is preferably 30 to 60 minutes, more preferably 40 to 50 minutes.
In the present invention, the preparation method of the alkali metal acetate (modified) layer preferably includes:
and (3) coating the alkali metal acetate solution on the surface of the electron transport layer, and then performing heat treatment to obtain the alkali metal acetate modified layer.
In the invention, the solvent in the alkali metal acetate solution is preferably selected from one or more of water, ethanol and methanol; the concentration of the alkali metal acetate solution is preferably 0.5 to 10mg/mL, more preferably 1 to 8mg/mL, still more preferably 2 to 6mg/mL, and most preferably 4 to 5mg/mL. In the present invention, the preparation method of the alkali metal acetate solution preferably includes: dissolving alkali metal acetate into a solvent to obtain an alkali metal acetate solution; the alkali metal acetate is identical to the alkali metal acetate in the above technical scheme, and is not described herein.
In the present invention, the heat treatment temperature is preferably 80 to 150 ℃, more preferably 90 to 140 ℃, more preferably 100 to 130 ℃, and most preferably 120 ℃; the time of the heat treatment is preferably 5 to 30 minutes, more preferably 10 to 25 minutes, and most preferably 15 to 20 minutes.
In the present invention, the method for preparing the perovskite light absorbing layer preferably includes:
and (3) coating the perovskite solution on the surface of the alkali metal acetate layer, and then annealing to obtain the perovskite absorption layer.
In the present invention, the solute in the perovskite solution is preferably selected from cesium iodide, lead iodide, dimethylamine hydroiodide, and the like; the solvent in the perovskite solution is preferably selected from one or more of DMF (N, N-dimethylformamide) and DMSO (dimethyl sulfoxide); the molar concentration of the perovskite solution is preferably 0.5 to 1mol/L, more preferably 0.6 to 0.8mol/L.
In the present invention, it is preferable to spin-coat perovskite solution droplets on a substrate (alkali metal acetate layer); the rotation speed in the spin coating process is preferably 2500-3500 rpm, more preferably 2800-3200 rpm, most preferably 3000rpm; the spin-coating time is preferably 30 to 50s, more preferably 35 to 45s, and most preferably 50s.
In the present invention, the annealing temperature is preferably 150 to 210 ℃, more preferably 180 to 200 ℃; the time for the annealing is preferably 4 to 40 minutes, more preferably 10 to 30 minutes, and most preferably 20 minutes.
In the present invention, the method for preparing a hole transport layer preferably includes:
and spin-coating a precursor solution on the surface of the perovskite light absorption layer to obtain the hole transport layer.
In the present invention, the solute in the precursor solution is preferably selected from the group consisting of Spiro-OMeTAD, 4-t-butylpyridine, lithium bistrifluoromethane sulfonimide solution (520 mg mL) -1 Dissolved in acetonitrile); the solvent in the precursor solution is preferably selected from chlorobenzene; the mass concentration of the precursor solution is preferably Spiro-OMeTAD: 50-100 mg mL -1 Preferably 60 to 90mg mL -1 More preferably 70 to 80mg mL -1 The method comprises the steps of carrying out a first treatment on the surface of the 4-tert-butylpyridine: 30-50 mu L mL -1 Preferably 35 to 45. Mu.L mL -1 More preferably 40 mu LmL -1 The method comprises the steps of carrying out a first treatment on the surface of the Lithium bis (trifluoromethanesulfonyl) imide solution: 20-30 mu L mL -1 Preferably 22 to 26. Mu.L mL -1 More preferably 23. Mu.L mL -1 。
In the present invention, the spin-coating speed is preferably 2500 to 3500rpm, more preferably 2800 to 3200rpm, and most preferably 3000rpm; the spin-coating time is preferably 20 to 40 seconds, more preferably 25 to 35 seconds, and most preferably 30 seconds.
In the present invention, the method for preparing an electrode preferably includes:
and preparing the electrode on the hole transport layer through vacuum evaporation.
In the present invention, the vacuum degree in the vacuum evaporation process is preferably less than 10 -4 Pa, deposition rate is preferably
More preferably +.>
Most preferably +.>
According to the invention, the electron transport layer is modified by alkali metal acetate, so that on one hand, the alkali metal acetate can passivate the surface defects of the electron transport layer, and the charge transport capacity is improved; on the other hand, alkali metal acetate can diffuse into perovskite, so that the crystallinity of perovskite and interface contact between perovskite and an electron transport layer are improved, and the performance and stability of the device are 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 ℃. 2mg of potassium acetate was dissolved in 1mL of deionized water, spun at 3000rpm for 30s on the titania-coated substrate, and annealed at 100℃for 15 minutes. Preparation of CsPbI in a Nitrogen glove box 3 Perovskite precursor solution (solute in perovskite precursor solution is CsI, pbI 2 And DMAI in a molar ratio of 1:1:1, the concentration is 0.8mol/L, and the solvent is DMF); 50 microliters of the perovskite precursor solution was dropped on the potassium acetate modification layer, spin-coated at 4000rpm for 30s, and annealed at 210℃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.
In the perovskite solar cell prepared in the embodiment 1 of the invention, the electron transport layer is 20nm, the thickness of the potassium acetate layer is 3nm, the perovskite layer is 400nm, the hole transport layer is 200nm, and the silver electrode is 70nm.
Example 2
A perovskite solar cell was produced in accordance with the method of example 1, differing from example 1 in that the amount of potassium acetate used was 15mg and the thickness of the potassium acetate layer was 20nm.
Comparative example 1
A perovskite solar cell was produced according to the method of example 1, differing from example 1 in that no potassium acetate layer was produced.
Performance detection
At room temperature, using a 3A solar simulator at 100mW/cm 2 The photoelectric conversion efficiency of the cells prepared in examples and comparative examples was measured under light intensity, and the effective area of the cell was 0.09cm 2 . The test data are shown in FIGS. 1 to 3, and the short-circuit current density of the battery prepared in example 1 is 20.22mA/cm 2 Open circuit voltage 1.207V, fill factor 81.25%, photoelectric conversion efficiency 19.83%; the short-circuit current density of the battery prepared in example 2 was 18.93mA/cm 2 Open circuit voltage 1.117V, fill factor 72.11%, photoelectric conversion efficiency 15.25%; comparative example 1 the short-circuit current density of the battery prepared in comparative example 1 was 19.63mA/cm 2 Open circuit voltage 1.144V, fill factor 81.41% and photoelectric conversion efficiency 18.28%.
According to the invention, the electron transport layer is modified by alkali metal acetate, so that on one hand, the alkali metal acetate can passivate the surface defects of the electron transport layer, and the charge transport capacity is improved; on the other hand, alkali metal acetate can diffuse into perovskite, so that the crystallinity of perovskite and interface contact between perovskite and an electron transport layer are improved, and the performance and stability of the device are 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 having an alkali acetate modified electron transport layer, comprising:
a substrate;
an electron transport layer disposed on the surface of the substrate;
an alkali metal acetate layer disposed on the surface of the electron transport layer;
the perovskite light absorption layer is arranged on the surface of the alkali metal acetate layer;
the hole transmission layer is arranged on the surface of the perovskite light absorption layer;
and an electrode arranged on the surface of the hole transport layer.
2. The perovskite solar cell of the alkali metal acetate modified electron transport layer according to claim 1, wherein the electron transport layer is made of at least one material selected from titanium dioxide and tin dioxide.
3. The perovskite solar cell of the alkali acetate modified electron transport layer according to claim 1, wherein the alkali acetate in the alkali acetate layer is one or more selected from sodium acetate, potassium acetate, rubidium acetate and cesium acetate.
4. The perovskite solar cell of the alkali acetate modified electron transport layer according to claim 1, wherein the thickness of the alkali acetate layer is 3-10 nm.
5. The perovskite solar cell of the alkali metal acetate modified electron transport layer according to claim 1, wherein the hole transport layer is made of one or more materials selected from the group consisting of Spiro-ome tad and PTAA.
6. The perovskite solar cell of the alkali acetate modified electron transport layer according to claim 1, wherein the perovskite light absorbing layer is made of a material selected from the group consisting of halide perovskites.
7. The perovskite solar cell of the alkali acetate modified electron transport layer according to claim 1, wherein the electron transport layer has a thickness of 10-40 nm;
the thickness of the perovskite light absorption layer is 200-500 nm;
the thickness of the hole transport layer is 100-300 nm;
the thickness of the electrode is 50-150 nm.
8. A method of making a perovskite solar cell having an alkali acetate modified electron transport layer as defined in claim 1, comprising:
preparing an electron transport layer on the surface of a substrate;
preparing an alkali metal acetate layer on the surface of the electron transport layer;
preparing a perovskite absorption layer on the surface of the alkali metal acetate layer;
preparing a hole transport layer on the surface of the perovskite absorption layer;
and preparing an electrode on the surface of the hole transport layer.
9. The method of preparing an alkali acetate layer according to claim 8, wherein the method of preparing an alkali acetate layer comprises:
coating an alkali metal acetate solution on the surface of the electron transport layer, and then performing heat treatment to obtain an alkali metal acetate modification layer;
the concentration of the alkali metal acetate solution is 0.5-10 mg/mL.
10. The method according to claim 9, wherein the heat treatment temperature is 80 to 150 ℃; the heat treatment time is 5-30 minutes.
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| CN117412615A (en) * | 2023-12-15 | 2024-01-16 | 中节能万润股份有限公司 | Perovskite solar cell and preparation method thereof |
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