CN108648918B - TiO 22(B)NWs/TiO2NP dye sensitization solar battery photo-anode and preparation method thereof - Google Patents

TiO 22(B)NWs/TiO2NP dye sensitization solar battery photo-anode and preparation method thereof Download PDF

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CN108648918B
CN108648918B CN201810440305.2A CN201810440305A CN108648918B CN 108648918 B CN108648918 B CN 108648918B CN 201810440305 A CN201810440305 A CN 201810440305A CN 108648918 B CN108648918 B CN 108648918B
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nws
anode
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CN108648918A (en
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郭敏
苏海军
杨露
张军
刘林
杨文超
黄太文
陈佳
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Northwestern Polytechnical 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
    • 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 relates to a TiO compound2(B)NWs/TiO2NP dye sensitization solar battery photo-anode and preparation method thereof, stirring hydrothermal method and preparation methodThermal treatment process for preparing bendable TiO with length of about 40 μm2(B) NWs, and preparing TiO by adopting a mechanical stirring method2(B)NWs/TiO2An NP composite structure. The dye-sensitized solar cell composed of the composite structure has TiO2(B) Excellent electron transport properties of NWs and TiO2The NP has a large specific surface area, so that the transmission rate of photo-generated electrons is improved, and meanwhile, the sufficient dye adsorption capacity can be met. Furthermore, TiO2(B) The light scattering effect of the NWs can effectively increase the light absorption, and finally the purpose of improving the photoelectric conversion efficiency of the dye-sensitized solar cell is achieved.

Description

TiO 22(B)NWs/TiO2NP dye sensitization solar battery photo-anode and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cell manufacturing, and relates to TiO2(B)NWs/TiO2An NP dye sensitization solar battery photo-anode and a preparation method.
Background
Since 1991, O' Regan andsince the development of dye-sensitized solar cells (DSSCs), they have received extensive attention due to their potential for low cost, simple fabrication methods, and high photoelectric conversion efficiency. Titanium dioxide nanoparticles (TiO)2NP) is an excellent photo-anode material for dye-sensitized solar cells due to the advantages of large specific surface area, simple preparation and the like. However, the labyrinth-like mesoporous structure prolongs the transmission path of electrons, and increases the probability of electron interface recombination and defect capture; meanwhile, the lower electron diffusion coefficient limits the photoelectric conversion efficiency of the cellThe steps are increased. Research finds that one-dimensional TiO2The nano-structure (nano-wires, NWs), nano-tubes (NTs), nano-rods (NR)) can improve the transmission rate and collection efficiency of photo-generated electrons, but the relatively small specific surface area thereof reduces the dye adsorption of the photo-anode, resulting in a reduction in the yield of photo-generated electrons, limiting the improvement of the photoelectric conversion efficiency of DSSC. Thus from one-dimensional TiO2Nanostructures and TiO2The composite structure composed of NP becomes a new direction for research. Wherein one-dimensional B phase TiO2(TiO2(B) Nanostructured materials due to their relatively open pore structure, rim [010 ]]The direction has special parallel pore channels, and the photocatalyst shows higher charge-discharge rate, high capacitance, excellent photocatalytic activity and electrochemical performance, so that the photocatalyst can be applied to the aspects of electrode materials of lithium and sodium batteries, catalysts, humidity sensing materials, sensitized solar batteries and the like.
To date, researchers in various countries have conducted a great deal of research work on one-dimensional nanocomposite structures, including TiO2NWs/TiO2NP，TiO2NT/TiO2NP，TiO2NR/TiO2NP, and the like. Through the search of the prior art, the research shows that2(B) In a composite nano-structured titanium dioxide photocatalyst and a method for preparing the same (patent application No. 201611157665.9), the inventors prepared a photocatalyst consisting of anatase phase titanium dioxide quantum dots and TiO2(B) A composite nanostructured photocatalyst formed by nano-sheets. The structure utilizes anatase phase and TiO2(B) The superior energy band alignment achieves high catalytic activity. However, the above synthesized TiO2(B) The length of the nano sheet is about 50nm, and the advantage of electron transmission performance is influenced to a certain extent when the nano sheet is applied to a photo-anode of a dye-sensitized solar cell. Therefore, the one-dimensional TiO with controllable length and radius and high length-diameter ratio is synthesized by a simple method2Nano structure and building TiO2(B)NWs/TiO2The NP composite light anode provides possibility for improving the electron transmission performance of the DSSC and improving the photoelectric conversion efficiency.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides TiO2(B)NWs/TiO2The NP dye sensitization solar battery photo-anode and the preparation method overcome the defect of short length of the nanowire prepared by the prior art and can prepare TiO with high length-diameter ratio2(B) NWs; the composite photo-anode structure with excellent electron transmission performance and large specific surface area is obtained.
Technical scheme
TiO 22(B)NWs/TiO2The NP dye sensitization solar battery photo-anode is characterized in that: from TiO2(B) NWs and TiO2NP complex formation of, wherein TiO2(B) The mass percent of NWs is less than 70 percent; the TiO is2NWs is TiO phase B in crystal form structure2The shape is regular and the linear structure can be bent, and the length is about 40 mu m; the TiO is2NP is anatase phase TiO2And is in a spherical nano particle structure.
Preparing the TiO2(B)NWs/TiO2The method for sensitizing the photo-anode of the NP dye solar cell is characterized by comprising the following steps:
step 1, TiO2(B) Preparation of NWs: mixing 0.4g of P25 powder, 24g of NaOH and 60ml of water to form an alkaline mixed solution, transferring the alkaline mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a constant-temperature heating magnetic stirrer with a silicon oil bath, setting the hydrothermal reaction temperature to be 120-150 ℃, and the stirring rate to be 200r min-1～800r min-1Keeping the temperature for 18-24 h; after the hydrothermal reaction is finished, taking the reaction kettle out of the silicon oil bath and cooling to room temperature;
then carrying out subsequent treatment:
collecting a reaction product, washing with deionized water, and performing suction filtration for several times until the pH value is 9-10 to obtain a sodium titanate product;
mixing the obtained sodium titanate product with HNO with the concentration of 0.1M3The solution is mixed and stirred for 2 to 4 hours for H+Substituted Na+The ion exchange process of (a); then repeatedly washing and filtering with deionized water until the pH value is reachedObtaining titanic acid nano wire, and finally drying the reaction product in a forced air drying oven at 55-65 ℃ for 12-24 h;
and high-temperature calcination treatment: calcining the mixture for 2 to 4 hours at the temperature of 400 ℃ in a muffle furnace to obtain TiO2(B) NWs, the heating rate and the cooling rate are both 1-3 ℃ min-1；
Step 2, TiO2(B)NWs/TiO2Preparation of NP composite Structure: adding TiO into the mixture2(B)NWs、TiO2Mixing NP slurry and alcohol to obtain composite slurry, wherein the TiO is2(B) The mass range of NWs is 0.02 g-0.07 g, TiO2The mass range of NP sizing agent is 0.08-0.03 g, and the mass range of alcohol is 0.1-0.3 g;
and then the prepared composite slurry is coated on clean FTO by a doctor blade method.
When the alkaline mixed solution is mixed, ultrasonic dispersion is firstly carried out for 15min to 30min, and then closed stirring is carried out for 1h to 2h so as to lead the mixture to be uniform.
The TiO is2(B)NWs、TiO2After the NP slurry and alcohol are mixed, firstly carrying out ultrasonic dispersion for 10-20 min, then stirring for 2-3 h, and then continuing ultrasonic treatment for 15-30 min to obtain the uniformly mixed composite slurry.
The scraped photoanode is subjected to staged heating and drying treatment and subsequent heat treatment on a heating platform, and the heat treatment process comprises the following steps: keeping the temperature at 450 ℃ for 2-4 h, wherein the heating rate and the cooling rate are both 1-3 ℃ for min-1。
Advantageous effects
The invention provides TiO2(B)NWs/TiO2The light anode of the NP dye-sensitized solar cell and the preparation method thereof adopt a composite structure of titanium dioxide nanowires and nanoparticles. First, TiO with a length of forty microns was prepared2(B) NWs, using TiO2(B) NWs has excellent electron transport property, and promotes the rapid transport of photo-generated electrons; at the same time, the scattering effect of the nanowires enhances light absorption. Then adopting mechanical stirring method to stir TiO2(B) NWs and TiO2NP are mixed, TiO2The larger specific surface area of NP can ensure enough dye adsorption quantity, generate more photo-generated electrons and improve the photoelectric conversion efficiency of DSSCAnd (4) rate. Photo-anode prepared by the embodiment of the invention and conventional TiO2Compared with NP photo-anode, DSSC has short circuit current density of 10.46mAcm-2Increased to 14.03mAcm-2The photoelectric conversion efficiency is improved from 4.28% to 5.84%, and is improved by 36.4%.
Compared with the prior art, the invention has the following advantages:
(1)TiO2(B)NWs/TiO2the NP composite structure has two advantages of excellent electron transmission and larger specific surface area, not only improves the transmission rate of photo-generated electrons, but also ensures sufficient dye adsorption, thereby achieving the purpose of improving the DSSC photoelectric conversion efficiency.
(2)TiO2(B) The NWs has more excellent electron transport performance compared with anatase phase titanium dioxide nanowires.
Drawings
FIG. 1 is a view of TiO of the present invention2(B)NWs/TiO2The structure of the light anode of the NP composite structure-based dye-sensitized solar cell is schematically shown;
FIG. 2(a) shows TiO prepared according to the present invention2(B) The X-ray diffraction pattern of NWs, (b) is the TiO prepared according to the invention2(B) Scanning electron micrographs of NWs;
FIG. 3 shows a composite structure TiO prepared by the present invention2(B)NWs/TiO2NP photo-anode based DSSC and reference TiO2The short-circuit current and open-circuit voltage curve of the NP photo-anode-based DSSC under simulated 1.5G sunlight. Wherein 1 is TiO obtained as in example 12(B)NWs/TiO2DSSC prepared by NP photoanode, 2 is TiO obtained from example 52DSSC prepared by NP photo-anode.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
TiO2(B)NWs/TiO2the NP dye-sensitized solar cell photo-anode is made of TiO2(B) NWs and TiO2NP is complexed. TiO 22(B) The NWs can provide a direct transmission channel for photoproduction electrons, reduce the probability of electron recombination and promote the effective collection of the photoproduction electrons; TiO 22The large specific surface area of NP can be adsorbedEnough dye ensures higher light capture efficiency.
The photo-anode is made of TiO2(B) NWs and TiO2NP being homogeneously distributed, TiO2NWs is TiO phase B in crystal form structure2，TiO2NP is anatase phase TiO2，TiO2(B) The mass percentage of NWs is less than 70%. Wherein the TiO is2NWs is a linear structure with regular appearance and capable of being bent, and the length of the linear structure is about 40 mu m; TiO 22The NPs are spherical nanoparticle structures.
The TiO is2(B) The NWs is prepared by a stirring hydrothermal method and a heat treatment process, and the TiO is2(B)NWs/TiO2The NP composite structures are prepared by a mechanical stirring method.
The method comprises the following steps:
step 1, TiO2(B) Preparation of NWs: preparing an alkaline mixed solution, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a volume of 100ml and a polytetrafluoroethylene lining, placing the reaction kettle into a constant-temperature heating magnetic stirrer filled with a silicon oil bath, setting the hydrothermal reaction temperature to be 120-150 ℃, and the stirring speed to be 200r min-1～800rmin-1Keeping the temperature for 18-24 h; and after the hydrothermal reaction is finished, taking the reaction kettle out of the silicon oil bath, cooling to room temperature, collecting a reaction product, and performing subsequent treatment and high-temperature calcination treatment.
Step 2, TiO2(B)NWs/TiO2Preparation of NP composite Structure: weighing a certain mass of TiO2(B)NWs、 TiO2NP slurry and alcohol, wherein the three are mixed evenly, TiO2(B) The mass range of NWs is 0.02 g-0.07 g, TiO2The mass range of NP sizing agent is 0.08-0.03 g, and the mass range of alcohol is 0.1-0.3 g. And then the prepared composite slurry is coated on clean FTO by a doctor blade method.
The alkaline mixed solution in the step 1 is prepared by mixing 0.4g of P25 powder, 24g of NaOH and 60ml of water, ultrasonically dispersing for 15-30 min, and then stirring for 1-2 h in a closed manner to uniformly mix.
The subsequent treatment comprises the steps of washing with a large amount of deionized water, and carrying out suction filtration for a plurality of times until the pH value is 9-10; then will obtainWith 0.1M HNO3The solution is mixed and stirred for 2 to 4 hours for the ion exchange process (H)+Substituted Na+) (ii) a And washing the obtained suspension with deionized water for multiple times, performing suction filtration until the pH value is 7, obtaining the titanic acid nanowire, and finally drying the reaction product in a forced air drying oven at 55-65 ℃ for 12-24 h.
The high-temperature calcination treatment is to place the dried sample in a muffle furnace to calcine at 400 ℃ for 2-4 h to obtain TiO2(B) NWs, the heating rate and the cooling rate are both 1-3 ℃ min-1。
TiO in the step 22(B)NWs/TiO2The specific preparation process of NP is as follows: firstly carrying out ultrasonic dispersion for 10-20 min, then stirring for 2-3 h, and then continuing ultrasonic treatment for 15-30 min to obtain uniformly mixed slurry.
And after the step 2, carrying out staged heating and drying treatment and subsequent heat treatment on the coated photo-anode on a heating platform. The heat treatment process comprises the following steps: keeping the temperature at 450 ℃ for 2-4 h (the heating rate and the cooling rate are both 1-3 ℃ for min)-1)。
The technical solution of the present invention is described in detail by 7 examples.
Example 1
The TiO is2(B)NWs/TiO2The photo-anode of the NP composite structure-based dye-sensitized solar cell is made of TiO2(B) NWs and TiO2NP is complexed. TiO 22(B) The NWs can provide a direct transmission channel for photoproduction electrons, so that the probability that the electrons are captured by defects and are compounded is reduced, and the effective collection of the photoproduction electrons is promoted; TiO 22The larger specific surface area of the NP can absorb enough dye, so that higher light capture efficiency is ensured.
The TiO is2NWs is a regular and bendable linear structure with the length of about 40 mu m and a crystal structure of B-phase TiO2；TiO2NP spherical nanostructure, average diameter of 20nm, anatase phase TiO2. From TiO2(B) NWs and TiO2Composite structure with uniformly distributed NP, wherein TiO2(B) The mass percentage of NWs is as follows: 0 to 70 percent. The TiO is2(B) The NWs is prepared by a stirring hydrothermal method and a heat treatment process, and the TiO is2(B)NWs/TiO2The NP composite structures are prepared by a mechanical stirring method.
The TiO is2(B) The mass percentage of NWs is 20%.
In 6 embodiments of the invention, the TiO is2(B)NWs/TiO2TiO of NP composite structure dye sensitization solar battery photo-anode2(B) NWs content and TiO2(B) The NWs have different morphologies and structures, which are shown in Table 1
Examples 1 2 3 4 5 6 7
TiO2(B) NWs hydrothermal agitation Rate (r min)-1) 800 0 200 400 800 800 800
TiO2(B) NWs content (wt%) 50 50 50 50 0 20 70
The preparation of the TiO provided by the invention2(B)NWs/TiO2The specific process of the dye-sensitized solar cell photo-anode with the NP composite structure is as follows:
the TiO is2(B) The NWs is prepared by a stirring hydrothermal method and a heat treatment process, and the TiO is2(B)NWs/TiO2The NP composite structures are prepared by a mechanical stirring method.
The TiO is2(B) The morphological structure of the NWs is controlled by the stirring rate of the hydrothermal reaction, wherein the stirring rate is 0-800 r min-1；TiO2(B) The NWs content is 0 g-0.07 g.
Preparation of the TiO as set forth in this example2(B)NWs/TiO2The specific process of the dye-sensitized solar cell photo-anode with the NP composite structure is as follows:
step 1, TiO2(B) Preparation of NWs: preparing an alkaline mixed solution, transferring the mixed solution into a stainless steel high-pressure reaction kettle with a volume of 100ml and a polytetrafluoroethylene lining, placing the reaction kettle into a constant-temperature heating magnetic stirrer filled with a silicon oil bath, setting the hydrothermal reaction temperature at 150 ℃ and the stirring speed at 0-800 r min-1And keeping the temperature for 24 hours.
The alkaline mixed solution is prepared by mixing 0.4g of P25 powder, 24g of NaOH and 60ml of water, ultrasonically dispersing for 15min, and then stirring for 1h in a sealed manner to uniformly mix.
Step 2, taking out the reaction kettle from the silicon oil bath after the hydrothermal reaction is finished, cooling to room temperature, collecting the reaction productWashing the product with a large amount of deionized water, and performing suction filtration for several times until the pH value is 9; then the obtained sodium titanate product and HNO with the concentration of 0.1M are mixed3The solution was mixed and stirred for 4H for the ion exchange process (H)+Substituted Na+) (ii) a And washing the obtained suspension with deionized water for multiple times, performing suction filtration until the pH value is 7, obtaining the titanic acid nanowire, and finally drying the reaction product in a blast drying oven at 60 ℃ for 24 hours.
And 3, high-temperature calcination treatment: placing the prepared sample in a muffle furnace at 400 ℃ for heat preservation for 2h to obtain TiO2(B) NWs. Wherein the heating rate and the cooling rate are both 1 ℃ for min-1。
Step 4, TiO2(B)NWs/TiO2Preparation of NP composite Structure: weighing a certain mass of TiO2(B)NWs、 TiO2NP slurry and alcohol, wherein the three are mixed evenly, TiO2(B) The NWs comprises the following components in percentage by mass: 0g to 0.07g of TiO2The weight of NP is 1 g-0.03 g, and the weight of alcohol is 0 g-0.3 g. The prepared composite slurry was knife coated on clean FTO using a doctor blade method.
The TiO is2(B)NWs/TiO2The specific preparation process of the NP composite structure comprises the following steps: firstly carrying out ultrasonic dispersion for 10min, then stirring for 2h, and then continuing ultrasonic treatment for 15min to obtain uniformly mixed slurry.
And step 5, adopting a staged heating method for drying treatment and heat treatment. The specific process comprises the following steps: drying the coated photo-anode on a heating platform at 30 ℃ for 2h, at 70 ℃ for 2h and at 100 ℃ for 2 h; after drying, carrying out heat treatment, wherein the process comprises the following steps: keeping the temperature at 450 ℃ for 2h (the heating rate and the cooling rate are both 1 ℃ for min)-1)。
Step 6, preparing a Pt counter electrode: sucking appropriate amount of 5mM chloroplatinic acid isopropanol solution with a dropper, dripping onto conductive glass, naturally drying, tearing off 3M adhesive tape, placing in a muffle furnace at 380 deg.C for 30min, and cooling to room temperature to obtain Pt counter electrode (wherein the heating rate is 1 deg.C for min)-1The cooling rate is 3 ℃ min-1)。
Step 7, assembling and testing the DSSC: mixing all the materials50% TiO prepared in example 12(B)NWs/50％TiO2Placing the NP composite photoanode in an N719 dye, soaking for 24h at 60 ℃ in a dark place, taking out, washing for 2 times by using alcohol, removing unadsorbed dye, and then drying. And then the heat-sealing film is taken as a diaphragm, the sensitized photo-anode and the Pt counter electrode are oppositely assembled together, electrolyte is dripped between the two electrodes by utilizing the capillary action and then is clamped by a clamp to assemble the DSSC with the typical sandwich structure, and then the photoelectric conversion efficiency of the cell can be tested.
Figure BDA0001655727380000091
Table 1 shows the results of the tests of examples 1 and 5
TABLE 1 attached hereto TiO prepared according to the invention2(B)NWs/TiO2Dye-sensitized solar cell assembled by NP composite structure and conventional TiO2Comparison of NP solar cells
Figure BDA0001655727380000092
FIG. 3 is based on TiO2(B)NWs/TiO2NP composite photo anode base DSSC and reference TiO2The short-circuit current and open-circuit voltage curve of the NP photo-anode-based DSSC under simulated 1.5G sunlight. Wherein 1 is TiO obtained as in example 12(B)NWs/TiO2DSSC prepared by NP photoanode, 2 is TiO obtained from example 52DSSC prepared by NP photo-anode. FIG. 3 demonstrates TiO-based2(B)NWs/TiO2The NP composite light anode base DSSC can increase the short-circuit current of the battery, so that the photoelectric conversion efficiency of the battery is improved.

Claims (4)

1. Preparation of TiO2(B)NWs/TiO2The method for sensitizing the photo-anode of the NP dye solar cell is characterized by comprising the following steps: TiO 22(B)NWs/TiO2The photo-anode of the NP dye-sensitized solar cell is made of TiO2(B) NWs and TiO2NP complex formation of, wherein TiO2(B) The mass percent of NWs is less than 70 percent; the TiO is2NWs has a crystal structure ofB phase TiO2The shape is regular and the linear structure can be bent, and the length is about 40 mu m; the TiO is2NP is anatase phase TiO2Spherical nanoparticle structure;
the method comprises the following specific steps:
step 1, TiO2(B) Preparation of NWs: mixing 0.4g of P25 powder, 24g of NaOH and 60ml of water to form an alkaline mixed solution, transferring the alkaline mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a constant-temperature heating magnetic stirrer with a silicon oil bath, setting the hydrothermal reaction temperature to be 120-150 ℃, and the stirring rate to be 200r min-1～800r min-1Keeping the temperature for 18-24 h; after the hydrothermal reaction is finished, taking the reaction kettle out of the silicon oil bath and cooling to room temperature;
then carrying out subsequent treatment:
collecting a reaction product, washing with deionized water, and performing suction filtration for several times until the pH value is 9-10 to obtain a sodium titanate product;
mixing the obtained sodium titanate product with HNO with the concentration of 0.1M3The solution is mixed and stirred for 2 to 4 hours for H+Substituted Na+The ion exchange process of (a); washing with deionized water for many times, performing suction filtration until the pH value is 7 to obtain the titanic acid nanowire, and finally drying the reaction product in a forced air drying oven at 55-65 ℃ for 12-24 h;
and high-temperature calcination treatment: calcining the mixture for 2 to 4 hours at the temperature of 400 ℃ in a muffle furnace to obtain TiO2(B) NWs, the heating rate and the cooling rate are both 1-3 ℃ min-1；
Step 2, TiO2(B)NWs/TiO2Preparation of NP composite Structure: adding TiO into the mixture2(B)NWs、TiO2Mixing NP slurry and alcohol to obtain composite slurry, wherein the TiO is2(B) The mass range of NWs is 0.02 g-0.07 g, TiO2The mass range of NP sizing agent is 0.08-0.03 g, and the mass range of alcohol is 0.1-0.3 g;
and then the prepared composite slurry is coated on clean FTO by a doctor blade method.
2. The method of claim 1, wherein: when the alkaline mixed solution is mixed, ultrasonic dispersion is firstly carried out for 15min to 30min, and then closed stirring is carried out for 1h to 2h so as to lead the mixture to be uniform.
3. The method of claim 1, wherein: the TiO is2(B)NWs、TiO2After the NP slurry and alcohol are mixed, firstly carrying out ultrasonic dispersion for 10-20 min, then stirring for 2-3 h, and then continuing ultrasonic treatment for 15-30 min to obtain the uniformly mixed composite slurry.
4. The method of claim 1, wherein: the scraped photoanode is subjected to staged heating and drying treatment and subsequent heat treatment on a heating platform, and the heat treatment process comprises the following steps: keeping the temperature at 450 ℃ for 2-4 h, wherein the heating rate and the cooling rate are both 1-3 ℃ for min-1。
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