CN113053673B - Working electrode of dye-sensitized solar cell and preparation method thereof - Google Patents

Working electrode of dye-sensitized solar cell and preparation method thereof Download PDF

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CN113053673B
CN113053673B CN202110258978.8A CN202110258978A CN113053673B CN 113053673 B CN113053673 B CN 113053673B CN 202110258978 A CN202110258978 A CN 202110258978A CN 113053673 B CN113053673 B CN 113053673B
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CN113053673A (en
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张国良
唐波
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Changzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention discloses a working electrode of a dye-sensitized solar cell and a preparation method thereof; the working electrode of the dye-sensitized solar cell sequentially comprises a transparent conductive substrate, a Cu-MOF composite graphene material nano array and a titanium dioxide nano array, wherein an overlapped part is arranged between the Cu-MOF composite graphene material nano array and the titanium dioxide nano array. The Cu-MOF is stable due to the graphene composite Cu-MOF material; meanwhile, the overlapped part is convenient for the electric connection of the transparent conductive substrate and the conduction band of the titanium dioxide, and the longer transmission time of electrons in the film is avoided. The photoelectric conversion efficiency reaches 6.13%.

Description

Working electrode of dye-sensitized solar cell and preparation method thereof
Technical Field
The invention relates to the technical field of dye-sensitized solar cells, in particular to a dye-sensitized solar cell, a working electrode thereof and a preparation method of the working electrode.
Background
The structure of the dye-sensitized solar cell can be divided into four parts: working electrode, sensitizing dye, electrolyte and counter electrode. Preparing a layer of nano-porous semiconductor film on a transparent conductive substrate to form a working electrode, generally called a photo-anode, wherein the photo-anode outputs electrons, and is actually the negative electrode of a power supply and the counter electrode is the positive electrode of the power supply from the perspective of the power supply; a sensitizing dye is adsorbed on the nano-porous semiconductor film; the counter electrode is generally a conductive metal plated with a layer of platinum, or carbon or other metals can be used to replace the platinum, and the electrolyte is filled between the working electrode and the counter electrode. The titanium dioxide nanocrystalline film has been used as the nanoporous semiconductor film of the working electrode to achieve the primary success. However, the conductivity of the pure titanium dioxide nanocrystalline film is poor, the transmission time of electrons in the film is long, and the electrons and electrolyte are accelerated
Figure BDA0002969152420000011
Complexing of ions; the titanium dioxide nanocrystalline film has poor light scattering property and poor light absorption; resulting in poor photoelectric conversion efficiency of the cell.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide a working electrode of a dye-sensitized solar cell and a preparation method of the working electrode, wherein the working electrode has good light absorption performance and good photoelectric conversion rate.
The invention provides a working electrode of a dye-sensitized solar cell, which comprises a transparent conductive substrate and a semiconductor material, and further comprises a Cu-MOF composite graphene material.
Further, the working electrode of the dye-sensitized solar cell sequentially comprises a transparent conductive substrate, a Cu-MOF composite graphene material nano array and a titanium dioxide nano array, wherein an overlapping part is arranged between the Cu-MOF composite graphene material nano array and the titanium dioxide nano array.
The invention provides a preparation method of a working electrode of a dye-sensitized solar cell, which comprises the following steps:
the method comprises the following steps: preparing a Cu-MOF composite graphene oxide material;
step two: dispersing the Cu-MOF composite graphene oxide material into a suspension in deionized water, wherein the concentration range of the Cu-MOF composite graphene oxide material in the suspension is 0.3-0.5 mg/ml; and scanning the suspension using cyclic voltammetry with a transparent conductive substrate: soaking a transparent conductive substrate in the suspension liquid, taking the transparent conductive substrate as a working electrode, reducing the Cu-MOF composite graphene oxide material into a Cu-MOF composite graphene material, and modifying the Cu-MOF composite graphene material on the surface of the transparent conductive substrate in a nano-array manner;
step three, when the step two is carried out to 1/2-3/4 (the step when the step is carried out to 1/2-3/4 is controlled by time, particularly 1/2-3/4 of the time required for completely depositing the Cu-MOF composite graphene oxide material in the suspension on the transparent conductive substrate); adding titanium tetrachloride into the suspension obtained in the second step, and simultaneously dropwise adding hydrochloric acid, wherein the dropwise adding amount of the hydrochloric acid is 1/5-1/10% of that of the titanium tetrachloride, and the mass concentration of the hydrochloric acid is 30%; continuously scanning by cyclic voltammetry for 15-30 min; the titanium dioxide is generated on the conductive substrate modified with the Cu-MOF composite graphene material in a nano array manner, and the titanium dioxide nano array and the Cu-MOF composite graphene material nano array have an overlapping part, so that the conductive substrate modified with the Cu-MOF composite graphene material nano array and the titanium dioxide nano array is formed.
And fourthly, washing and drying the conductive substrate modified with the Cu-MOF composite graphene material nano array and the titanium dioxide nano array by using deionized water, and taking the conductive substrate after drying as the working electrode of the dye-sensitized solar cell.
Dye sensitized solar cellIn operation of a battery, the electrons typically go through the following 7 processes: 1, a dye is excited by light to change from a ground state to an excited state, and electrons jump from the highest occupied molecular orbit to the lowest unoccupied molecular orbit; 2, the dye molecules in the excited state inject electrons into the conduction band of the semiconductor; and 3, the electrons in the conduction band are transmitted to the rear contact surface of the semiconductor in the nanocrystal network and then flow into an external circuit: 4, electrons and
Figure BDA0002969152420000021
ion binding to form I-Ions, equivalent to electrons, enter the electrolyte; 5, I-The dye is regenerated by ion reduction of the oxidation state dye; 6 electrons transported in the nanocrystalline film on the surface and into the pores of the titanium dioxide film
Figure BDA0002969152420000031
Ion recombination (dark current channel one); and 7, recombination between electrons in a semiconductor conduction band and the dye in the titanium oxide (dark current channel II).
At present, in a common graphene battery technology, a graphene material is modified to a counter electrode, the counter electrode releases electrons to an electrolyte, a reduction reaction occurs, and the graphene material cannot be oxidized. The application of the graphene material is completely different from the technical principle of the conventional graphene battery at present, although the graphene material is used for the working electrode of the dye-sensitized solar cell, the graphene material is not in direct contact with the electrolyte, and the graphene material can continuously receive electrons output from a semiconductor conduction band, so that the graphene material cannot be oxidized.
The main functions of the graphene material in the invention are as follows: firstly, the composite material is compounded with a Cu-MOF material, so that the structure of the Cu-MOF material becomes stable; secondly, the conductivity of the contact position between the titanium dioxide layer and the transparent conductive substrate is enhanced, because the conductivity of the titanium dioxide nanocrystalline film is poor, the electrons transmitted in the nanocrystalline film are on the surface and enter the holes of the titanium dioxide film
Figure BDA0002969152420000032
The ion recombination is more, the graphene material can enhance the conductivity between the transparent conductive substrate and the titanium dioxide nanocrystalline film and reduce the electrons transmitted in the nanocrystalline film on the surface and entering the holes of the titanium dioxide film
Figure BDA0002969152420000033
The ions are compounded, and the photoelectric conversion efficiency is improved. The effect of the graphene material is completely different from the effect of applying the graphene material to the field of batteries in the prior art.
Further, the scanning potential interval of the cyclic voltammetry scanning is-1.0-1.0V, and the scanning rate is 100 mV/s.
Further, the mass ratio of the Cu-MOF composite graphene oxide material to titanium tetrachloride is 1:4-20, and the thickness of the whole deposited layer needs to be controlled to be 2-5 microns.
Further, the specific method for preparing the Cu-MOF composite graphene oxide material comprises the following steps:
s1, adding 1 part of graphene oxide into a solvent, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, and adding 6 parts of H3BTC and 13 parts of Cu (NO)3)2﹒3H2Dissolving O in the dispersion liquid of the graphene oxide and fully mixing the O and the dispersion liquid to obtain a mixed liquid;
s2, heating the mixed solution at 85 ℃ for more than 18h, then cooling at room temperature, performing suction filtration after cooling, washing the product obtained by suction filtration with DMF to remove unreacted impurities, and obtaining crystals;
and S3, drying the obtained crystal in a vacuum drying oven at 65 ℃ for more than 20h to obtain the Cu-MOF composite graphene oxide material.
Further, the solvent contains 1 part of water, 1 part of ethanol, and 1 part of DMF.
The invention provides a dye-sensitized solar cell, and a working electrode of the dye-sensitized solar cell is the working electrode of the dye-sensitized solar cell.
The invention provides working electrode slurry of a dye-sensitized solar cell, which contains a Cu-MOF composite graphene material.
The invention has the beneficial effects that: the microscopic structure of the Cu-MOF composite graphene material is that metal frame materials with very high conductivity and specific surface area are sparsely distributed between an upper layer of graphene and a lower layer of graphene; light can increase the scattering property of light when passing through the metal framework material, but the individual Cu-MOF is easy to collapse, and the Cu-MOF is more stable due to the graphene composite Cu-MOF material; meanwhile, the overlapped part is convenient for the electric connection of the transparent conductive substrate and the conduction band of the titanium dioxide, and the longer transmission time of electrons in the film is avoided. The photoelectric conversion efficiency reaches 6.13%.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following embodiments.
As shown in fig. 1: the embodiment provides a working electrode of a dye-sensitized solar cell, which sequentially comprises a transparent conductive substrate 1, a Cu-MOF composite graphene material nano array 2 and a titanium dioxide nano array 3, wherein an overlapping part 4 is arranged between the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3.
The first embodiment is as follows:
the preparation method comprises the following steps:
step one, S1, adding 1 part of graphene oxide into a solvent, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, and adding 6 parts of trimesic acid (H)3BTC) and 13 parts of Cu (NO)3)2﹒3H2Dissolving O in the dispersion liquid of the graphene oxide and fully mixing the O and the dispersion liquid to obtain a mixed liquid;
s2, heating the mixed solution at 85 ℃ for more than 18h, then cooling at room temperature, performing suction filtration after cooling, washing the product obtained by suction filtration with DMF to remove unreacted impurities, and obtaining crystals;
and S3, drying the obtained crystal in a vacuum drying oven at 65 ℃ for more than 20h to obtain the Cu-MOF composite graphene oxide material.
Dispersing 1 part of Cu-MOF composite graphene oxide material into a suspension in deionized water; scanning the suspension by using a transparent conductive substrate 1 through a cyclic voltammetry method, reducing the Cu-MOF composite graphene oxide material into a Cu-MOF composite graphene material, and modifying the Cu-MOF composite graphene material on the surface of the transparent conductive substrate 1 in a nano-array manner, wherein the specific material of the transparent conductive substrate is indium tin oxide transparent conductive film glass;
when the second step is carried out to 1/2 (which means 1/2 of complete deposition time, for example, when 10min is needed for complete deposition to a solution without containing the Cu-MOF composite graphene oxide material, titanium tetrachloride is added to the solution at 5 min), 10 parts of titanium tetrachloride is added to the solution, meanwhile, one part of hydrochloric acid with the mass concentration of 30% is dropwise added, and scanning is continuously carried out by adopting a cyclic voltammetry method, wherein the scanning time is 30min, so that titanium dioxide is generated on the conductive substrate modified with the Cu-MOF composite graphene material in a nano array manner, the thickness of the whole modified deposition layer is 3 micrometers, the titanium dioxide nano array 3 and the Cu-MOF composite graphene material nano array 2 are provided with an overlapping part 4, and the conductive substrate modified with the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 is formed;
wherein the scanning potential interval of the cyclic voltammetry scanning is-1.0-1.0V, and the scanning rate is 100 mV/s.
And fourthly, washing and drying the conductive substrate modified with the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 by using deionized water to serve as the working electrode of the dye-sensitized solar cell.
Comparative example one: compared with the working electrode of the first embodiment, the working electrode of the dye-sensitized solar cell is mainly different in that the nano-array 2 of the unmodified Cu-MOF composite graphene material is obtained, and other operations are the same as those of the first embodiment. The obtained working electrode of the dye-sensitized solar cell sequentially comprises a transparent conductive substrate 1 and a titanium dioxide nano array 3.
Comparative example two: compared with the working electrode of the first embodiment, the working electrode of the dye-sensitized solar cell has the main difference that the Cu-MOF composite graphene material is replaced by graphene, and other operations are the same as those of the first embodiment. The obtained working electrode of the dye-sensitized solar cell sequentially comprises a transparent conductive substrate 1, graphene and a titanium dioxide nano-array 3.
Comparative example three: compared with the working electrode of the first embodiment, the working electrode of the dye-sensitized solar cell is mainly different in that the Cu-MOF composite graphene material is replaced by the Cu-MOF material, and other operations are the same as those of the first embodiment. The working electrode of the dye-sensitized solar cell sequentially comprises a transparent conductive substrate 1, a Cu-MOF material and a titanium dioxide nano array 3.
The working electrodes of the dye-sensitized solar cells obtained in the first, second and third examples are respectively used as working electrodes, and sensitizing dye (the raw material of the sensitizing dye is a polypyridine complex sensitizer) is adsorbed in the titanium dioxide nano array 3 of the working electrode; the counter electrode is made of conductive metal plated with a layer of platinum, and electrolyte (the electrolyte is liquid with imidazole iodide salt) is filled between the counter electrode and the working electrode to form the dye-sensitized solar cell. The following data were obtained in an environment with a 50000Lux illumination intensity:
table 1:
Figure BDA0002969152420000061
Figure BDA0002969152420000071
the above experiment shows that: in the second comparative example, the addition of the graphene layer between the transparent conductive substrate 1 and the titanium dioxide nanoarray 3 can reduce the photoelectric conversion efficiency by a small amount; it is inferred that the graphene layer blocks the incidence of light to cause a decrease in photoelectric conversion efficiency; in the third comparative example, the addition of the Cu-MOF material between the transparent conductive substrate 1 and the titanium dioxide nanoarray 3 enhances the photoelectric conversion efficiency, but the photoelectric conversion efficiency is greatly reduced in a period of time, which is inferred to be possibly because the Cu-MOF material can increase the scattering of light and strengthen the electrical connection between the transparent conductive substrate 1 and the titanium dioxide nanoarray 3, but is unstable; in the first embodiment, the Cu-MOF composite graphene material nano array 2 is added between the transparent conductive substrate 1 and the titanium dioxide nano array 3, so that the photoelectric conversion efficiency is enhanced, the structure is stable, the photoelectric conversion efficiency is improved after one week of use compared with that in the beginning of detection, and the Cu-MOF composite graphene material exerts an unexpected technical effect.
The differences between the second example, the third example, the fourth comparative example and the fifth comparative example compared with the first example are as follows: step two was performed to add titanium tetrachloride thereto to varying degrees and the comparison results are shown in table 2.
Table 2:
Figure BDA0002969152420000072
Figure BDA0002969152420000081
the above experiment shows that: step two, when carried out to 1/2-3/4, was more effective in adding titanium tetrachloride thereto. However, the photoelectric conversion efficiency of titanium tetrachloride added at the beginning of the second step is greatly reduced. The conclusion is that the overlapping part 4 between the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 is beneficial to improving the electric conduction performance between the two; however, if the Cu-MOF composite graphene material nano array 2 is too close to the electrolyte, a part of electrons can be directly conducted into the electrolyte
Figure BDA0002969152420000082
Reaction to form I1。
Example four:
step one, S1, adding 1 part of graphene oxide into a solvent, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, and adding 6 parts of H3BTC and 13 parts of Cu (NO)3)2﹒3H2Dissolving O in the dispersion liquid of the graphene oxide and fully mixing the O and the dispersion liquid to obtain a mixed liquid;
s2, heating the mixed solution at 85 ℃ for more than 18h, then cooling at room temperature, performing suction filtration after cooling, washing the product obtained by suction filtration with DMF to remove unreacted impurities, and obtaining crystals;
and S3, drying the obtained crystal in a vacuum drying oven at 65 ℃ for more than 20h to obtain the Cu-MOF composite graphene oxide material.
Dispersing 1 part of Cu-MOF composite graphene oxide material into a suspension in deionized water; scanning the suspension by using a transparent conductive substrate 1 through a cyclic voltammetry method, reducing the Cu-MOF composite graphene oxide material into a Cu-MOF composite graphene material, and modifying the Cu-MOF composite graphene material on the surface of the transparent conductive substrate 1 in a nano-array manner, wherein the specific material of the transparent conductive substrate is indium tin oxide transparent conductive film glass;
when the second step is carried out to 1/2 (which means 1/2 of complete deposition time, for example, if complete deposition needs 10min until the solution does not contain the Cu-MOF composite graphene oxide material, titanium tetrachloride is added into the solution at 5 min), 4 parts of titanium tetrachloride is added into the solution, and simultaneously, one part of hydrochloric acid with the mass concentration of 30% is dropwise added and scanning is continuously carried out by adopting cyclic voltammetry for 30 min; titanium dioxide is generated on the conductive substrate modified with the Cu-MOF composite graphene material in a nano array manner, the titanium dioxide nano array 3 and the Cu-MOF composite graphene material nano array 2 are provided with an overlapping part 4, so that the conductive substrate modified with the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 is formed, and the thickness of the whole modified deposition layer is 3 micrometers; wherein the scanning potential interval of the cyclic voltammetry scanning is-1.0-1.0V, and the scanning rate is 100 mV/s.
And fourthly, washing and drying the conductive substrate modified with the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 by using deionized water to serve as the working electrode of the dye-sensitized solar cell.
Example five:
step one, S1, adding 1 part of graphene oxide into a solvent, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, and adding 6 parts of H3BTC and 13 parts of Cu (NO)3)2﹒3H2Dissolving O in the dispersion liquid of the graphene oxide and fully mixing the O and the dispersion liquid to obtain a mixed liquid;
s2, heating the mixed solution at 85 ℃ for more than 18h, then cooling at room temperature, performing suction filtration after cooling, washing the product obtained by suction filtration with DMF to remove unreacted impurities, and obtaining crystals;
and S3, drying the obtained crystal in a vacuum drying oven at 65 ℃ for more than 20h to obtain the Cu-MOF composite graphene oxide material.
Dispersing 1 part of Cu-MOF composite graphene oxide material into a suspension in deionized water; scanning the suspension by using a transparent conductive substrate 1 through a cyclic voltammetry method, reducing the Cu-MOF composite graphene oxide material into a Cu-MOF composite graphene material, and modifying the Cu-MOF composite graphene material on the surface of the transparent conductive substrate 1 in a nano-array manner, wherein the specific material of the transparent conductive substrate is indium tin oxide transparent conductive film glass;
step three: when the second step proceeded to 1/2 (which refers to 1/2 of the complete deposition time, e.g., 10min was required for complete deposition into a solution without the Cu-MOF composite graphene oxide material, titanium tetrachloride was added thereto at 5 min), 20 parts titanium tetrachloride was added thereto, simultaneously, dropwise adding a part of hydrochloric acid with the mass concentration of 30% and continuously scanning by adopting a cyclic voltammetry for 30min to enable the titanium dioxide to be generated on the conductive substrate modified with the Cu-MOF composite graphene material in a nano-array manner, the titanium dioxide nano array 3 and the Cu-MOF composite graphene material nano array 2 are provided with an overlapping part 4, so that a conductive substrate modified with the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 is formed, and the thickness of the whole modified deposition layer is 3 micrometers; wherein the scanning potential interval of the cyclic voltammetry scanning is-1.0-1.0V, and the scanning rate is 100 mV/s.
And fourthly, washing and drying the conductive substrate modified with the Cu-MOF composite graphene material nano array 2 and the titanium dioxide nano array 3 by using deionized water to serve as the working electrode of the dye-sensitized solar cell.
Figure BDA0002969152420000101
The above experiment shows that: the mass ratio of the Cu-MOF composite graphene oxide material to titanium tetrachloride is 1:4-20, so that the photoelectric conversion efficiency can be improved, and preferably is 1: 10.
Comparative example six: the working electrode of the dye-sensitized solar cell sequentially comprises a transparent conductive substrate, a titanium dioxide nano-array and a Cu-MOF material.
If titanium dioxide is formed by first modification and then the Cu-MOF composite graphene oxide material is obtained by modification, titanium dioxide is arranged on one side, close to the transparent conductive substrate, of the finally formed working electrode of the dye-sensitized solar cell, a Cu-MOF composite graphene oxide material is arranged on one side, close to the electrolyte, of the finally formed working electrode of the dye-sensitized solar cell, when the graphene material is in direct contact with the electrolyte, oxidation reaction occurs on the electrolyte in contact with the working electrode, electrons are output from the working electrode, the working electrode is easy to oxidize, the Cu-MOF composite graphene oxide material can be oxidized into the Cu-MOF composite graphene oxide material, the conductivity of the graphene oxide material is poor, electrons in the electrolyte close to one side of the working electrode are not favorably transferred to the working electrode, and the photoelectric conversion efficiency is poor.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent replacements, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The working electrode of the dye-sensitized solar cell is characterized by sequentially comprising a transparent conductive substrate, a Cu-MOF composite graphene material nano array and a titanium dioxide nano array, wherein an overlapping part is arranged between the Cu-MOF composite graphene material nano array and the titanium dioxide nano array.
2. A method for preparing a working electrode of a dye-sensitized solar cell according to claim 1, comprising preparing a titanium dioxide semiconductor material on a transparent conductive substrate (1), characterized in that the method further comprises: and modifying the working electrode of the dye-sensitized solar cell by using a Cu-MOF composite graphene material.
3. The method for preparing the working electrode of the dye-sensitized solar cell according to claim 2, characterized in that the preparation method specifically comprises:
preparing a Cu-MOF composite graphene oxide material;
dispersing the Cu-MOF composite graphene oxide material into a suspension in deionized water; scanning the suspension by using a transparent conductive substrate through cyclic voltammetry, reducing the Cu-MOF composite graphene oxide material into a Cu-MOF composite graphene material, and modifying the Cu-MOF composite graphene oxide material on the surface of the transparent conductive substrate in a nano-array manner;
when the second step is carried out to 1/2-3/4, adding titanium tetrachloride, simultaneously dropwise adding hydrochloric acid and continuously scanning by adopting a cyclic voltammetry method to enable titanium dioxide to be generated on the conductive substrate modified with the Cu-MOF composite graphene material in a nano array manner, wherein the titanium dioxide nano array and the Cu-MOF composite graphene material nano array have overlapped parts, so that the conductive substrate modified with the Cu-MOF composite graphene material nano array and the titanium dioxide nano array is formed;
and fourthly, washing and drying the conductive substrate modified with the Cu-MOF composite graphene material nano array and the titanium dioxide nano array by using deionized water to serve as the working electrode of the dye-sensitized solar cell.
4. The method for preparing the working electrode of the dye-sensitized solar cell according to claim 3, characterized in that the sweep potential interval of the cyclic voltammetry sweep is-1.0-1.0V, and the sweep rate is 100 mV/s.
5. The preparation method of the working electrode of the dye-sensitized solar cell according to claim 3, characterized in that the mass ratio of the Cu-MOF composite graphene oxide material to titanium tetrachloride is 1: 4-20.
6. The preparation method of the working electrode of the dye-sensitized solar cell according to claim 3, wherein the specific method for preparing the Cu-MOF composite graphene oxide material is as follows:
s1, adding 1 part of graphene oxide into a solvent, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, and adding 6 parts of H3BTC and 13 parts of Cu (NO)3)2﹒3H2Dissolving O in the dispersion liquid of the graphene oxide and fully mixing the O and the dispersion liquid to obtain a mixed liquid;
s2, heating the mixed solution at 85 ℃ for more than 18h, then cooling at room temperature, performing suction filtration after cooling, washing the product obtained by suction filtration with DMF to remove unreacted impurities, and obtaining crystals;
and S3, drying the obtained crystal in a vacuum drying oven at 65 ℃ for more than 20h to obtain the Cu-MOF composite graphene oxide material.
7. The method for preparing the working electrode of the dye-sensitized solar cell according to claim 6, characterized in that the solvent is mixed by water, ethanol and DMF in a mass ratio of 1:1: 1.
8. The dye-sensitized solar cell according to claim 1, wherein the working electrode of the dye-sensitized solar cell is the working electrode of the dye-sensitized solar cell.
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