CN105869897A - Preparation method and application of hollow material CeO2@TiO2 - Google Patents

Preparation method and application of hollow material CeO2@TiO2 Download PDF

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CN105869897A
CN105869897A CN201610492803.2A CN201610492803A CN105869897A CN 105869897 A CN105869897 A CN 105869897A CN 201610492803 A CN201610492803 A CN 201610492803A CN 105869897 A CN105869897 A CN 105869897A
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ceo
tio
hollow
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CN105869897B (en
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韩贵
王敏
白静怡
李丹阳
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Yangzhou University
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Yangzhou University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2027Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2036Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/542Dye sensitized solar cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention discloses a preparation method and application of a hollow material CeO2@TiO2 and relates to the technical field of preparation of dye sensitized solar cell photo-anode materials. The preparation method includes: using a hydrothermal method to prepare carbon balls; utilizing the hydrothermal method to prepare the hollow material CeO2@TiO2; coating P25 size and the hollow material CeO2@TiO2 on FTO glass through screen printing; calcining at high temperature to obtain a photo-anode material; preparing a photo-anode. A hollow material CeO2@TiO2 nano film prepared can effectively absorb visible light, utilization rate of sunlight is increased, electron transmission is accelerated, and charge recombination is reduced; due to hollow structure, specific surface area of the nano film is increased, dye adsorption is facilitated, and performance of cells is improved greatly.

Description

A kind of hollow material CeO2@TiO2Preparation method and applications
Technical field
The present invention relates to the preparation of dye-sensitized solar cell anode material, applied technical field.
Background technology
Entering new century, along with the sustained and rapid development of global economy, the demand of the energy is grown with each passing day by the mankind, and the energy is the important substance guarantee that human society is depended on for existence and development.With resource-constrained, with serious pollution fossil energy is main energy resource structure, it is unlimited to be progressively changed into resource, cleaning clean regenerative resource is main variation, compound energy resource structure, development solaode will be the important component part in new energy development, also be to ensure national energy and Environmental security, promote the strategic choice that national economy is inevitable with social sustainable development.Compared with other solaodes, the advantage of DSSC is fairly obvious, and its technique is simple, and practical application foreground is good, low cost etc..DSSC becomes quite varied because of its application of above feature, and presents huge social benefit.
DSSC is by conductive substrates, light anode, constitute several parts such as electrode, dye sensitizing agent, electrolyte, and wherein light anode as the carrier of photosensitizer and collects the most crucial part that the medium of electronics and transmission electronics is DSSC.For nano material, the micro/nano structure of hollow is because the structure of its uniqueness gives them the character of uniqueness: specific surface area is big, superior light scattering effect etc..Report hollow material on all preceding, titanium dioxide hollow ball is because its high-specific surface area, and to the absorption of dyestuff well, superior light scattering effect becomes the light anode material that DSSC one is critically important.Until at present, improving the titanium dioxide hollow ball performance as dye-sensitized solar cell anode material by a lot of modes.Nano Ce O2@TiO2Material owing to there are other ingredients of band structure and DSSC matching, electrical conductivity is high, pattern is special so that it is become a kind of important dye-sensitized solar cell anode material.Hollow structure CeO2@TiO2Being combined of material, it has higher specific surface area, and the ability of absorbing dye is strong, it is thus possible to absorb more visible ray.And the recombination energy of this material reduces its degree of crystallinity, maintain titanium dioxide relative stability in high-temperature calcination.
But at present, the most not by hollow structure CeO in prior art2@TiO2Light anode material is for the report of DSSC.
Summary of the invention
The invention aims to provide a kind of production technology simple, equipment cost is low, and energy consumption is little, can be effectively improved a kind of hollow-core construction CeO of solar cell photoelectric conversion efficiency2@TiO2The preparation method of dye-sensitized solar cell anode material.
The present invention is prepared by following step:
1) carbon (Carbon is abbreviated as C) bead is prepared: be dissolved in deionized water by glucose, form D/W, again D/W is placed in autoclave under the temperature environment of 180 DEG C, carries out hydro-thermal reaction, after reaction terminates, it is cooled to room temperature, isolate after solid phase after centrifuge washing, dry at a temperature of 80 DEG C, obtain carbon bead;
2) by carbon bead ultrasonic disperse in deionized water, carbon bead dispersion liquid is obtained;
3) under ultrasound condition, the cerous nitrate aqueous solution that concentration is 0.5 M is added in carbon bead dispersion liquid, obtains cerous nitrate and the mixed solution of carbon bead;
4) mixed solution of cerous nitrate and carbon bead is placed in autoclave under the temperature environment of 160 DEG C, carries out hydro-thermal reaction;
5) after hydro-thermal reaction terminates, it is cooled to room temperature, takes after solid formation washs by centrifugation, dry at a temperature of 80 DEG C, obtain solid material C@CeO2
6) by solid material C@CeO2, hydroxypropyl cellulose (HPC) and deionized water (DIW) be scattered in dehydrated alcohol, obtain solid material C@CeO2Dispersion liquid with hydroxypropyl cellulose (HPC);
7) by solid material C@CeO2Stir under ultrasound condition with the dispersion liquid of hydroxypropyl cellulose (HPC), obtain solid material C@CeO2Dispersion liquid;
8) butyl titanate (TBOT) is mixed with ethanol, form the mixed solution of butyl titanate and ethanol;
9) mixed solution of butyl titanate Yu ethanol is added drop-wise to solid material C@CeO2In dispersion liquid, agitated, form mixed solution;
10) mixed solution being warming up to 80 DEG C, reflux 100 min;
11) after backflow terminates, being cooled to room temperature, separation obtains solid formation, then by solid formation centrifuge washing, dries, obtain solid material C@CeO at a temperature of 70 DEG C2@TiO2
12) by solid material C@CeO2@TiO2It is placed in calcining furnace, keeps 1h after temperature being warming up to 500 DEG C with the heating rate of 10 DEG C/min, obtain hollow structure material CeO2@TiO2
Production technology of the present invention is simple, and equipment cost is low, and energy consumption is little, and raw material is nontoxic, requires low to labor technical, and industrial production cost is only the 1/4~1/3 of silicon solar cell, the CeO being prepared as2@TiO2Composite structure is novel, and in hollow ball-shape, size is between 250~350nm.The photo-anode film using titanium dioxide and ceria composite and titanium dioxide to be combined preparation has superior light scattering effect.
Further, step 2 of the present invention) in: described carbon bead is 15mg: 1mL~3mL with the mixing ratio of deionized water.Enable to carbon ball under this ratio be fully dispersed in solvent, good dispersion, be difficult to reunite, facilitate ensuing cerous nitrate to be sufficiently adhering to surface.
In described step 3): cerous nitrate aqueous solution and carbon bead dispersion liquid mixed volume ratio 1: 1.In order to be able to make cerous nitrate adhere completely to carbon ball surface under this ratio, fully, pattern is homogeneous in reaction.
In described step 1) and step 5): each centrifugal rotational speed is 7000~9000 r/min, the time is 5~10 min.This centrifugal rotational speed and the granule of particle diameter required for us can be obtained under the time, it is to avoid the inhomogenous situation of grain diameter;Remove some unnecessary impurity.
In described step 6): solid material C@CeO2, the mixing quality ratio of hydroxypropyl cellulose (HPC) and deionized water (DIW) be 2: 1: 6;Solid material C@CeO2, hydroxypropyl cellulose (HPC) and the total amount of deionized water (DIW) be 90mg: 4 mL~7mL with the mixing ratio of dehydrated alcohol.In order to by solid material C@CeO under this proportioning2Being fully dispersed in solvent, good dispersion, solution is uniform, adds surfactant and makes the interface state of its solution system change, is conducive to infiltration, surface attachment.
In described step 8): described butyl titanate (TBOT) is 1: 5 with the mixed volume ratio of ethanol.Under this proportioning, the medicine ball material C@CeO of butyl titanate cladding2Effect is preferable, and solid material surface adheres to titanium dioxide, pattern, uniform particle diameter, good stability uniformly, and dispersing uniformity is preferable.
In described step 9): the mixed solution of described butyl titanate and ethanol and solid material C@CeO2The mixed volume ratio of dispersion liquid is 1: 9~11;The speed of described dropping is 0.4~0.6 mL/min.This mixing ratio is the ratio in the case of theory, in order to titanium dioxide is coated on C CeO completely2Outside, be attached to surface, reaction completely, the beneficially raising of performance;Under this rate of addition, the mixed solution of butyl titanate with ethanol is slowly added to, it is possible to allow response speed slow down so that reaction completely and avoids granule and agglomeration occurs.
It addition, the invention also discloses the hollow structure material CeO of preparation2@TiO2Application in preparing dye-sensitized solar cell anode material.
On FTO glass, use silk screen print method, by hollow material CeO2@TiO2It is coated in P25 film surface, through high-temperature calcination, obtains dye-sensitized solar cell anode material.
Above P25 thin film is the thin film that grain diameter is about that the titania slurry of 25nm is formed.
The present invention uses screen-printing deposition, reduce surface defect, and bigger specific surface area can be obtained in less size, and accelerate electric transmission, reduce charge recombination, photoanode surface adsorpting dye molecule can be effectively improved so that the photoelectric transformation efficiency of battery significantly improves, compare with existing P25 light anode cell efficiency and add 25.3%.
Further, the temperature environment of described high-temperature calcination is 450 DEG C, and the time is 30 min, and during calcining, temperature is warming up to 450 DEG C by the heating rate with 10 DEG C/min.Under the conditions of Gai, calcining can make to be formed between particle good electrical contact.
FTO glass first coats P25 slurry, sintered after, then on P25 pulp layer, coat hollow material CeO2@TiO2, then carry out high-temperature calcination;Described P25 pulp layer coats 7~9 layers altogether, and often coating one layer sintering is once;Described hollow CeO2@TiO2Coating 2~3 layers altogether, often coating one layer sintering is once.The thin film ratio of this operational approach coating is more uniform, and the thickness of every layer can control;Circulation the most repeatedly, mainly allows its P25 thin film reach certain thickness so that efficiency reaches the highest and is coated with done hollow material;Applied in two coats material reaches certain thickness also for its material so that light anode material efficiency reaches the highest, thus electricity conversion is optimum.
Accompanying drawing explanation
Fig. 1 is the hollow-core construction composite CeO that the present invention makes2@TiO2Flied emission transmission electron microscope picture TEM.
Fig. 2 is the hollow-core construction composite CeO that the present invention makes2@TiO2Field emission scanning electron microscope figure SEM.
Fig. 3 is the hollow-core construction composite CeO that the present invention makes2@TiO2With hollow-core construction composite TiO2X-ray diffraction XRD figure.
Fig. 4 is the hollow-core construction composite CeO that the present invention makes2@TiO2, hollow-core construction composite TiO2UV-vis DRS abosrption spectrogram with P25.
Fig. 5 is dye-sensitized solar cell anode composite surface material field emission scanning electron microscope figure SEM of the present invention.
Fig. 6 is the I-V characteristic curve chart of the DSSC using comparative example and two embodiments to be respectively prepared.
Detailed description of the invention
One, hollow material CeO is prepared2@TiO2:
1. substrate is cleaned:
FTO glass being cut into long 5 cm, the size of wide 2 cm, is placed in large beaker, respectively with sequentially ultrasonic cleaning 20 min in acetone, ethanol, deionized water, taking-up after having cleaned, oven for drying is standby.
2. preparation C bead:
The glucose that concentration is 0.55 mM is dissolved in deionized water, is made into glucose solution, then glucose solution goes to be placed in the autoclave of 50 mL hydro-thermal reaction 4 h under the temperature environment of 180 DEG C.After reaction terminates, being cooled to room temperature, centrifugation goes out solid phase, then by solid phase centrifuge washing, dries, obtain C bead at a temperature of 80 DEG C;
Wherein, centrifugal rotational speed is 7000~8000 R/min, centrifugation time 5~10 min。
3. preparation hollow-core construction composite CeO2@TiO2:
(1) with 15mg: 1mL~3mL mixing ratio, C bead is taken appropriate ultrasonic disperse in deionized water, in this dispersion liquid, then adds the cerous nitrate aqueous solution that isopyknic concentration is 0.5 M.Magnetic stirrer 30~60 min, ultrasonic 30~60 min, mix homogeneously.
(2) the above-mentioned mixed solution stirred is transferred in the autoclave of 50ml to be placed in hydro-thermal reaction 6 h under the temperature environment of 160 DEG C.After reaction terminates, being cooled to room temperature, centrifugation goes out solid formation, then by its solid formation centrifuge washing, dries at a temperature of 80 DEG C, obtains a kind of solid material C@CeO2
Wherein centrifugal rotational speed is 7000~8000 R/min, centrifugation time 5~10 min。
(3) by solid material C@CeO obtained above2, hydroxypropyl cellulose (HPC), deionized water (DIW) is mixed in proportion and is scattered in alcohol solvent, stirring, and ultrasonic each 30~120 min。
Wherein solid material C@CeO2, hydroxypropyl cellulose (HPC), the mixing quality ratio of deionized water (DIW) is 2: 1: 6;Solid material C@CeO2, hydroxypropyl cellulose (HPC), the mixing gross mass of deionized water (DIW) is 90 mg: 4mL~7mL with the dispersion ratio of ethanol volume.
(4) in dispersion liquid obtained above, drip the mixed liquor of butyl titanate (TBOT) and ethanol with the rate of addition of 0.4~0.6 mL/min, after stirring 12h, form mixed solution.
Wherein butyl titanate (TBOT) is 1: 5 with the mixed volume ratio of ethanol;Butyl titanate (TBOT) and the total amount of ethanol are 1: 9~11 with the volume ratio of dispersion liquid.
(5) mixed solution obtained above being warming up to 80 DEG C, reflux 100 min.After backflow terminates, being cooled to room temperature, centrifugation goes out solid formation, then by its solid formation centrifuge washing, dries at a temperature of 70 DEG C, obtains a kind of solid material C@CeO2@TiO2
Wherein centrifugal rotational speed is 3000~4500 r/min, and centrifugation time is 5~10 min.
(6) by solid material C@obtained above CeO2@TiO2Through high-temperature calcination, obtain hollow-core construction dye-sensitized solar cell anode material C eO2@TiO2
Wherein calcining heat is 500 DEG C, and the time is 1 h, and calcining heating rate is 10 DEG C/min.
Two, Characterization of The Products
Fig. 1 illustrates hollow-core construction composite CeO prepared by the present invention2@TiO2Flied emission transmission electron microscope picture TEM, as can be seen from the figure this material is hollow ball, and size is between 250~350 nm.
Fig. 2 illustrates hollow-core construction composite CeO prepared by the present invention2@TiO2Field emission scanning electron microscope figure SEM, as can be seen from the figure this material is hollow ball, and amplification: × 65420, pattern is homogeneous.
Fig. 3 illustrates the hollow-core construction composite CeO that the present invention makes2@TiO2With hollow-core construction composite TiO2X-ray diffraction XRD figure.By contrast XRD standard card PDF#33-0831, composite CeO2@TiO2With composite TiO2XRD figure spectrum consistent with standard spectrum, illustrate that this material is prepared material.At composite CeO2@TiO2With composite TiO2XRD diffraction maximum in, 25.3°With 48.1°Diffraction maximum be belonging to TiO2's.28.6°,33.1°,47.5°,56.3°,59.1°,69.4°,76.7°Diffraction maximum match with (111), (200), (220), (311), (222), (400), (331) crystallographic plane diffraction peak respectively.It is also seen that composite CeO from figure2@TiO2Degree of crystallinity also decrease.This illustrates CeO2TiO may be scattered in2Lattice in.
Fig. 4 illustrates the hollow-core construction composite CeO that the present invention makes2@TiO2, hollow-core construction composite TiO2UV-vis DRS abosrption spectrogram with P25.CeO is may know that by consulting literatures2@TiO2The band-gap energy of composite is less than TiO2's.And as can be seen from the figure: with composite TiO2Compare with pure P25, composite CeO2@TiO2Absorption edge be gradually moved toward visible region.For composite TiO2Absorption edge about at 430 nm, and composite CeO2@TiO2Absorption edge about to 510 nm.It can be said that bright composite CeO2@TiO2Can more effectively absorb visible ray.
Three, application example:
Prepared by P25 slurry: take 0.5g P25,1 mL(5% ethyl cellulose terpineol) and 10 mL dehydrated alcohol join in round bottom beaker, stir one day, ultrasonic one day, then rotary evaporation, ethanol therein is evaporated completely.Obtain uniform and stable P25 slurry.
Comparative example:
The preparation of dye-sensitized solar cell anode: use silk screen printing to be coated on FTO glass by P25 slurry, drying at room temperature, put in tube furnace and calcine, be raised to 450 DEG C with the heating rate of 10 DEG C/min, calcine 30 min, Temperature fall.It is coated with one layer and burns one layer, be coated with 7~9 layers, place into N719 dyestuff and soak 12~24 h, rinse well with dehydrated alcohol, obtain dye-sensitized solar cell anode.
Embodiment 1 :
The preparation of dye-sensitized solar cell anode: use silk screen printing to be coated on FTO glass by P25 slurry, drying at room temperature, put in tube furnace and calcine, be raised to 450 DEG C with the heating rate of 10 DEG C/min, calcine 30 min, Temperature fall.It is coated with one layer and burns one layer, be painted with 7~9 layers.Finally it is coated with two-layer hollow material TiO2, still it is raised to 450 DEG C with the heating rate of 10 DEG C/min, calcines 30 min, be coated with one layer and burn one layer, Temperature fall.Put into N719 dyestuff and soak 12~24 h, rinse well with dehydrated alcohol, obtain dye-sensitized solar cell anode.
Embodiment 2 :
The preparation of dye-sensitized solar cell anode: use silk screen printing to be coated on FTO glass by P25 slurry, drying at room temperature, put in tube furnace and calcine, be raised to 450 DEG C with the heating rate of 10 DEG C/min, calcine 30 min, Temperature fall.It is coated with one layer and burns one layer, be painted with 7~9 layers.Finally it is coated with three layers of hollow material CeO2@TiO2, still it is raised to 450 DEG C with the heating rate of 10 DEG C/min, calcines 30 min, be coated with one layer and burn one layer, Temperature fall.Put into N719 dyestuff and soak 12~24 h, rinse well with dehydrated alcohol, obtain dye-sensitized solar cell anode.
Four, performance test
The dye-sensitized solar cell anode that above comparative example and two embodiments are prepared, as follows as DSSC step: first assembled battery, using platinum electrode is to electrode, by the conducting surface of working electrode upward, pick up with to electrode conducting surface clip down, press from both sides into sandwich structure, then inject electrolyte between electrodes, carry out the I-V curve test of DSSC.
Fig. 5 illustrates dye-sensitized solar cell anode composite surface material field emission scanning electron microscope figure SEM of the present invention.As can be seen from the figure the even particle distribution of mesoporous TiO 2, CeO2@TiO2Hollow ball is evenly distributed on titanium dioxide surface, and pattern is homogeneous.
Fig. 6 illustrates the I-V characteristic curve chart of the DSSC using comparative example and two embodiments to be respectively prepared.In figure, curve a is the I-V characteristic curve of the DSSC that comparative example is made, and curve b is the I-V characteristic curve of the DSSC that embodiment 1 is made, and curve c is the I-V characteristic curve of the DSSC that embodiment 2 is made.
Following table is the photoelectric properties contrast table of the DSSC packaged by light anode prepared by above each example:
Data from table 1 and Fig. 6 can be seen that, using the DSSC(DSSC for preparing of the present invention) light anode is as working electrode, being assembled into DSSC, compared with comparison example, short-circuit current density (Jsc) and the photoelectric transformation efficiency (η) of embodiment 1~2 have strengthened.Short-circuit current density (Jsc) is up to 17.316 mA/cm2, fill factor, curve factor (FF) reaches 61.5%, photoelectric transformation efficiency (η) up to 7.949%.These test result indicate that CeO2@TiO2Hollow material can effectively absorb visible ray, enhances the nano thin-film utilization rate to sunlight, is effectively increased photoelectric transformation efficiency.

Claims (10)

1. a hollow material CeO2@TiO2Preparation method, it is characterised in that comprise the following steps:
1) glucose is dissolved in deionized water, form D/W, again D/W is placed in autoclave under the temperature environment of 180 DEG C, carries out hydro-thermal reaction, after reaction terminates, it is cooled to room temperature, isolate after solid phase after centrifuge washing, dry at a temperature of 80 DEG C, obtain carbon bead;
2) by carbon bead ultrasonic disperse in deionized water, carbon bead dispersion liquid is obtained;
3) under ultrasound condition, the cerous nitrate aqueous solution that concentration is 0.5M is added in carbon bead dispersion liquid, obtains cerous nitrate and the mixed solution of carbon bead;
4) mixed solution of cerous nitrate and carbon bead is placed in autoclave under the temperature environment of 160 DEG C, carries out hydro-thermal reaction;
5) after hydro-thermal reaction terminates, it is cooled to room temperature, takes after solid formation washs by centrifugation, dry at a temperature of 80 DEG C, obtain solid material C@CeO2
6) by solid material C@CeO2, hydroxypropyl cellulose and deionized water be scattered in dehydrated alcohol, obtain solid material C@CeO2Dispersion liquid with hydroxypropyl cellulose;
7) by solid material C@CeO2Stir under ultrasound condition with the dispersion liquid of hydroxypropyl cellulose, obtain solid material C@CeO2Dispersion liquid;
8) butyl titanate is mixed with ethanol, form the mixed solution of butyl titanate and ethanol;
9) mixed solution of butyl titanate Yu ethanol is added drop-wise to solid material C@CeO2In dispersion liquid, agitated, form mixed solution;
10) mixed solution being warming up to 80 DEG C, reflux 100 min;
11) after backflow terminates, being cooled to room temperature, separation obtains solid formation, then by solid formation centrifuge washing, dries, obtain solid material C@CeO at a temperature of 70 DEG C2@TiO2
12) by solid material C@CeO2@TiO2It is placed in calcining furnace, keeps 1h after temperature being warming up to 500 DEG C with the heating rate of 10 DEG C/min, obtain hollow structure material CeO2@TiO2
Hollow material CeO the most according to claim 12@TiO2Preparation method, it is characterised in that described step 2) in: the mixing ratio of described carbon bead and deionized water is 15mg: 1mL~3mL.
Hollow material CeO the most according to claim 12@TiO2Preparation method, it is characterised in that in described step 3): cerous nitrate aqueous solution and carbon bead dispersion liquid mixed volume ratio 1: 1.
Hollow material CeO the most according to claim 12@TiO2Preparation method, it is characterised in that in described step 1) and step 5): each centrifugal rotational speed is 7000~9000 r/min, the time is 5~10 min.
Hollow material CeO the most according to claim 12@TiO2Preparation method, it is characterised in that in described step 6): solid material C@CeO2, the mixing quality ratio of hydroxypropyl cellulose and deionized water be 2: 1: 6;Solid material C@CeO2, hydroxypropyl cellulose and the total amount of deionized water be 90 mg: 4~7 mL with the mixing ratio of dehydrated alcohol.
Hollow material CeO the most according to claim 12@TiO2Preparation method, it is characterised in that in described step 8): described butyl titanate is 1: 5 with the mixed volume ratio of ethanol.
Hollow material CeO the most according to claim 12@TiO2Preparation method, it is characterised in that in described step 9): the mixed solution of described butyl titanate and ethanol and solid material C@CeO2The mixed volume ratio of dispersion liquid is 1: 9~11;The speed of described dropping is 0.4~0.6 mL/min.
8. hollow material CeO as claimed in claim 12@TiO2Application in preparing dye-sensitized solar cell anode material, it is characterised in that: on FTO glass, use silk screen print method, by hollow material CeO2@TiO2It is coated in P25 film surface, through high-temperature calcination, obtains dye-sensitized solar cell anode material.
Hollow material CeO the most according to claim 82@TiO2Application in preparing dye-sensitized solar cell anode material, it is characterised in that: the temperature environment of described high-temperature calcination is 450 DEG C, and the time is 30 min, and during calcining, temperature is warming up to 450 DEG C by the heating rate with 10 DEG C/min.
Hollow material CeO the most according to claim 8 or claim 92@TiO2Application in preparing dye-sensitized solar cell anode material, it is characterised in that: on FTO glass, first coat P25 slurry, sintered after, then on P25 pulp layer, coat hollow material CeO2@TiO2, then carry out high-temperature calcination;Described P25 pulp layer coats 7~9 layers altogether, and often coating one layer sintering is once;Described hollow CeO2@TiO2Coating 2~3 layers altogether, often coating one layer sintering is once.
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