CN105869897B - A kind of hollow material CeO2@TiO2Preparation method and applications - Google Patents

A kind of hollow material CeO2@TiO2Preparation method and applications Download PDF

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CN105869897B
CN105869897B CN201610492803.2A CN201610492803A CN105869897B CN 105869897 B CN105869897 B CN 105869897B CN 201610492803 A CN201610492803 A CN 201610492803A CN 105869897 B CN105869897 B CN 105869897B
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ceo
tio
hollow
temperature
dispersion liquid
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CN105869897A (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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    • 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
    • H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A kind of hollow material CeO2@TiO2Preparation and its application, be related to the preparing technical field of dye-sensitized solar cell anode material.Carbon bead is first prepared with hydro-thermal method, then hollow material CeO is prepared with hydro-thermal method2@TiO2, then by P25 slurries and hollow material CeO2@TiO2It is respectively coated on silk-screen printing on FTO glass, high-temperature calcination, obtains light anode material, finally prepare light anode again.Manufactured hollow material CeO2@TiO2Nanometer film can effectively absorb visible ray, strengthen the utilization rate to sunshine, accelerate the transmission of electronics, reduce the compound of electric charge, and hollow-core construction increases its specific surface area, be advantageous to adsorbance of the increase to dyestuff, significantly improve the performance of battery.

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
Into the new century, along with the sustained and rapid development of global economy, the mankind are growing day by day to the demand of the energy, energy Source is the important substance guarantee that human society is depended on for existence and development.With resource-constrained, based on serious pollution fossil energy Energy resource structure, it is unlimited with resource to be progressively changed into, and cleans the variation based on clean regenerative resource, the compound energy Structure, development solar cell will be important component in new energy development, and ensure national energy and Environmental security, Promote the national economy strategic choice inevitable with social sustainable development.Compared with other solar cells, the dye sensitization sun The advantage of energy battery is fairly obvious, and its technique is simple, and practical application foreground is good, and cost is low etc..DSSC because with Its application field of upper feature becomes quite varied, and shows huge social benefit.
DSSC by conductive substrates, light anode, to several parts such as electrode, dye sensitizing agent, electrolyte Form, wherein light anode is dye sensitization of solar electricity as the carrier and collection electronics of photosensitizer and the medium of transmission electronics The most crucial part in pond.For nano material, hollow micro/nano structure is because its unique structure assigns them unique property Matter：Specific surface area is big, superior light scattering effect etc..Report hollow material on all preceding, titanium dioxide hollow ball because Its high-specific surface area, well, it is critically important that superior light scattering effect turns into DSSC one to the absorption to dyestuff Light anode material.Until current, it is used as dye sensitization of solar by many modes to improve titanium dioxide hollow ball The performance of battery light anode material.Nano Ce O2@TiO2Material due to band structure and DSSC other Part matches, electrical conductivity is high, pattern is special, becomes a kind of important dye-sensitized solar cell anode material Material.Hollow structure CeO2@TiO2Material it is compound, it has higher specific surface area, and it is strong to adsorb the ability of dyestuff, so as to inhale Receive more visible rays.And the recombination energy of this material reduces its crystallinity, phase of the titanium dioxide in high-temperature calcination is maintained To stability.
But at present, in the prior art also not by hollow structure CeO2@TiO2Light anode material is used for dye sensitization The report of solar cell.
The content of the invention
The invention aims to provide a kind of simple production process, equipment cost is low, and energy consumption is small, can effectively improve the sun A kind of hollow-core construction CeO of energy cell photoelectric conversion efficiency2@TiO2The preparation side of dye-sensitized solar cell anode material Method.
The present invention is prepared by following step：
1）Prepare carbon（Carbon is abbreviated as C）Bead：Glucose is dissolved in deionized water, forms D/W, D/W is placed in autoclave again hydro-thermal reaction is carried out under 180 DEG C of temperature environment, it is cold after reaction terminates But to room temperature, isolate after solid phase after centrifuge washing, dried 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 nitric acid The mixed solution of cerium and carbon bead；
4）The mixed solution of cerous nitrate and carbon bead is placed in autoclave and enters water-filling under 160 DEG C of temperature environment Thermal response；
5）After hydro-thermal reaction terminates, room temperature is cooled to, takes solid formation after centrifuge washing, is dried 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）It is scattered in absolute ethyl alcohol, Obtain solid material C@CeO2And hydroxypropyl cellulose（HPC）Dispersion liquid；
7）By solid material C@CeO2And hydroxypropyl cellulose（HPC）Dispersion liquid stirred under ultrasound condition, obtain To solid material C@CeO2Dispersion liquid；
8）By butyl titanate（TBOT）Mixed with ethanol, form the mixed solution of butyl titanate and ethanol；
9）The mixed solution of butyl titanate and ethanol is added drop-wise to solid material C@CeO2It is agitated in dispersion liquid, shape Into mixed solution；
10）Mixed solution is warming up to 80 DEG C, flow back 100 min；
11）After backflow terminates, room temperature is cooled to, separation obtains solid formation, then by solid formation centrifuge washing, in 70 DEG C of temperature Lower drying, obtain solid material C@CeO2@TiO2；
12）By solid material C@CeO2@TiO2It is placed in calcining furnace, is warming up to temperature with 10 DEG C/min heating rate 1h is kept after 500 DEG C, obtains hollow structure material CeO2@TiO2。
Simple production process of the present invention, equipment cost is low, and energy consumption is small, and raw material are nontoxic, and low, work is required to labor technical Industry production cost is only the 1/4~1/3 of silicon solar cell, the CeO being prepared into2@TiO2Composite structure is novel, in sky Bulbus cordis shape, size is between 250~350nm.Using titanium dioxide and ceria composite and the compound preparation of titanium dioxide Photo-anode film there is superior light scattering effect.
Further, step 2 of the present invention）In：The mixing ratio of the carbon bead and deionized water be 15mg: 1mL~ 3mL.Enable to carbon ball to be fully dispersed in solvent under the ratio, good dispersion, be not easy to reunite, facilitate ensuing cerous nitrate It is sufficiently adhering to surface.
The step 3）In：The cerous nitrate aqueous solution is with carbon bead dispersion liquid mixed volume than 1: 1.In order to making under the ratio Cerous nitrate adheres completely to carbon ball surface, and reaction is abundant, and pattern is homogeneous.
The step 1）With step 5）In：Each centrifugal rotational speed is 7000~9000 r/min, and the time is 5~10 min.This Centrifugal rotational speed and the particle that our required particle diameters can be obtained under the time, avoid the inhomogenous situation of grain diameter；Remove Some unnecessary impurity.
The step 6）In：Solid material C@CeO2, hydroxypropyl cellulose（HPC）And deionized water（DIW）Mixing matter Amount is than being 2: 1: 6；Solid material C@CeO2, hydroxypropyl cellulose（HPC）And deionized water（DIW）Total amount and absolute ethyl alcohol Mixing ratio is 90mg: 4 mL~7mL.In order to by solid material C@CeO under the proportioning2It is fully dispersed in solvent, disperses Property it is good, solution is uniform, addition surfactant the interface state of its solution system is changed, be advantageous to permeate, surface is attached .
The step 8）In：The butyl titanate（TBOT）Mixed volume ratio with ethanol is 1: 5.Under matching herein, The medicine ball material C@CeO of butyl titanate cladding2Effect is preferable, and titanium dioxide is uniformly adhered on solid material surface, pattern, Uniform particle diameter, stability is good, and dispersing uniformity is also preferable.
The step 9）In：The mixed solution of the butyl titanate and ethanol and solid material C@CeO2Dispersion liquid mixes It is 1: 9~11 to close volume ratio；The speed of the dropwise addition is 0.4~0.6 mL/min.The mixing ratio is the ratio in the case of theory Value, in order to which titanium dioxide to be coated on to C@CeO completely2Outside, be attached to surface, reaction is complete, is advantageous to performance Improve；Under this rate of addition, the mixed solution of butyl titanate and ethanol is slowly added to, reaction speed can be allowed to slow down, made It must react complete and avoid particle and agglomeration occur.
In addition, the invention also discloses the hollow structure material CeO of preparation2@TiO2Preparing DSSC Application in light anode material.
On FTO glass, using silk screen print method, by hollow material CeO2@TiO2Coated in P25 film surfaces, through high temperature Calcining, obtains dye-sensitized solar cell anode material.
Above P25 films be grain diameter be about 25nm titania slurry formed film.
The present invention uses screen-printing deposition, reduces surface defect, and larger ratio can be obtained in less size Surface area, 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, and is compared with existing P25 light anodes battery efficiency and adds 25.3%.
Further, the temperature environment of the high-temperature calcination is 450 DEG C, and the time is 30 min, with 10 DEG C/min during calcining Heating rate temperature is warming up to 450 DEG C.Calcining can make to form good electrical contact between particle under the conditions of this.
P25 slurries are first coated on FTO glass, after sintered, then hollow material CeO are coated on P25 pulp layers2@ TiO2, then carry out high-temperature calcination；The P25 pulp layers coat 7~9 layers altogether, often coat one layer of sintering once；The hollow CeO2@ TiO22~3 layers are coated altogether, often coat one layer of sintering once.The film of operating method coating is than more uniform, and every layer of thickness Degree can control；Circulation is so multiple, mainly allows its P25 film to reach certain thickness so that efficiency reaches highest re-coating The hollow material done；Applied in two coats material reaches certain thickness also for its material so that light anode material efficiency reaches To highest, so as to which electricity conversion is optimal.
Brief description of the drawings
Fig. 1 is hollow-core construction composite CeO made of the present invention2@TiO2Flied emission transmission electron microscope picture TEM.
Fig. 2 is hollow-core construction composite CeO made of the present invention2@TiO2Field emission scanning electron microscope figure SEM.
Fig. 3 is hollow-core construction composite CeO made of the present invention2@TiO2With hollow-core construction composite TiO2X penetrate Line diffraction XRD.
Fig. 4 is hollow-core construction composite CeO made of the present invention2@TiO2, hollow-core construction composite TiO2With P25's UV-vis DRS abosrption spectrogram.
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 for the DSSC being respectively prepared using comparative example and two embodiments Figure.
Embodiment
First, hollow material CeO is prepared2@TiO2：
1. substrate is cleaned：
FTO glass is cut into long 5 cm, wide 2 cm size, is placed in large beaker, respectively with acetone, ethanol, deionization Sequentially it is cleaned by ultrasonic 20 min in water, is taken out after having cleaned, oven for drying is standby.
2. prepare C beads：
The glucose that concentration is 0.55 mM is dissolved in deionized water, is made into glucose solution, then glucose solution is turned The h of hydro-thermal reaction 4 under 180 DEG C of temperature environment is placed in into 50 mL autoclave.After reaction terminates, room temperature is cooled to, Centrifuge out solid phase, then by solid phase centrifuge washing, dried at a temperature of 80 DEG C, obtain C beads；
Wherein, centrifugal rotational speed is 7000~8000 r/min, the min of centrifugation time 5~10.
3. prepare hollow-core construction composite CeO2@TiO2：
（1）With 15mg: 1mL~3mL mixing ratio, C beads are taken into appropriate ultrasonic disperse in deionized water, then herein The cerous nitrate aqueous solution that isometric concentration is 0.5 M is added in dispersion liquid.The min of magnetic stirrer 30~60, ultrasound 30~60 min, it is well mixed.
（2）The above-mentioned mixed solution to stir is transferred to 160 DEG C of temperature ring is placed in 50ml autoclave The h of hydro-thermal reaction 6 under border.After reaction terminates, room temperature is cooled to, centrifuges out solid formation, then by its solid formation centrifuge washing, Dried at a temperature of 80 DEG C, obtain a kind of solid material C@CeO2。
Wherein centrifugal rotational speed is 7000~8000 r/min, the min of centrifugation time 5~10.
（3）By solid material C@CeO obtained above2, hydroxypropyl cellulose（HPC）, deionized water（DIW）Mix in proportion Merging is scattered in alcohol solvent, is stirred, each 30~120 min of ultrasound.
Wherein solid material C@CeO2, hydroxypropyl cellulose（HPC）, deionized water（DIW）Mixing quality ratio be 2: 1: 6；Solid material C@CeO2, hydroxypropyl cellulose（HPC）, deionized water（DIW）Mixing gross mass and ethanol volume it is scattered Than for 90 mg: 4mL~7mL.
（4）In dispersion liquid obtained above, butyl titanate is added dropwise with 0.4~0.6 mL/min rate of addition （TBOT）With the mixed liquor of ethanol, after stirring 12h, mixed solution is formed.
Wherein butyl titanate（TBOT）Mixed volume ratio with ethanol is 1: 5；Butyl titanate（TBOT）With ethanol Total amount and the volume ratio of dispersion liquid are 1: 9~11.
（5）Mixed solution obtained above is warming up to 80 DEG C, flow back 100 min.After backflow terminates, room temperature is cooled to, Centrifuge out solid formation, then by its solid formation centrifuge washing, dried at a temperature of 70 DEG C, obtain 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@CeO obtained above2@TiO2Through high-temperature calcination, the hollow-core construction dye sensitization sun is obtained Can battery light 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.
2nd, Characterization of The Products
Fig. 1 illustrates hollow-core construction composite CeO prepared by the present invention2@TiO2Flied emission transmission electron microscope picture TEM, from This material of it can be seen from the figure that 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, from This material of it can be seen from the figure that is hollow ball, multiplication factor：× 65420, pattern is homogeneous.
Fig. 3 illustrates hollow-core construction composite CeO made of the present invention2@TiO2With hollow-core construction composite TiO2's X-ray diffraction XRD.By contrasting XRD standard card PDF#33-0831, composite CeO2@TiO2With composite TiO2 XRD spectrum it is consistent with standard spectrum, it is prepared material to illustrate this material.In composite CeO2@TiO2With composite TiO2 XRD diffraction maximums in, 25.3°With 48.1°Diffraction maximum be to belong to TiO2's.28.6°,33.1°,47.5°,56.3°,59.1°, 69.4°,76.7°Diffraction maximum respectively with（111）、（200）、（220）、（311）、（222）、（400）、（331）Crystallographic plane diffraction peak phase It coincide.It is also seen that composite CeO from figure2@TiO2Crystallinity also decrease.This explanation CeO2It may be scattered in TiO2Lattice in.
Fig. 4 illustrates hollow-core construction composite CeO made of the present invention2@TiO2, hollow-core construction composite TiO2With P25 UV-vis DRS abosrption spectrogram.CeO is may know that by consulting literatures2@TiO2The band-gap energy of composite is low In TiO2's.And as can be seen from the figure：With composite TiO2Compared with pure P25, composite CeO2@TiO2Absorption Edge is gradually moved toward visible region.For composite TiO2Absorption edge about in 430 nm, and composite CeO2@TiO2Absorption edge about to 510 nm.It is possible thereby to illustrate composite CeO2@TiO2Can more effectively it inhale Receive visible ray.
3rd, application example：
It is prepared by P25 slurries：Take 0.5g P25,1 mL（5% ethyl cellulose terpinol）It is added to 10 mL absolute ethyl alcohols In round bottom beaker, stir one day, ultrasound one day, then rotary evaporation, ethanol therein is evaporated completely.Obtain uniform and stable P25 slurries.
Comparative example：
The preparation of dye-sensitized solar cell anode：P25 slurries are coated on FTO glass using silk-screen printing, Drying at room temperature, it is put into tube furnace and calcines, is raised to 450 DEG C with 10 DEG C/min heating rate, calcines 30 min, Temperature fall. Apply one layer and burn one layer, apply 7~9 layers, place into N719 dyestuffs and soak 12~24 h, rinsed well with absolute ethyl alcohol, obtain dyestuff Sensitization solar battery light anode.
Embodiment 1：
The preparation of dye-sensitized solar cell anode：P25 slurries are coated on FTO glass using silk-screen printing, Drying at room temperature, it is put into tube furnace and calcines, is raised to 450 DEG C with 10 DEG C/min heating rate, calcines 30 min, Temperature fall. Apply one layer and burn one layer, be painted with 7~9 layers.Finally it is coated with two layers of hollow material TiO2, still it is raised to 10 DEG C/min heating rate 450 DEG C, 30 min are calcined, one layer is applied and burns one layer, Temperature fall.It is put into N719 dyestuffs and soaks 12~24 h, is rushed with absolute ethyl alcohol Wash clean, obtain dye-sensitized solar cell anode.
Embodiment 2：
The preparation of dye-sensitized solar cell anode:P25 slurries are coated on FTO glass using silk-screen printing, Drying at room temperature, it is put into tube furnace and calcines, is raised to 450 DEG C with 10 DEG C/min heating rate, calcines 30 min, Temperature fall. Apply one layer and burn one layer, be painted with 7~9 layers.Finally it is coated with three layers of hollow material CeO2@TiO2, still with 10 DEG C/min heating rate 450 DEG C are raised to, calcines 30 min, one layer is applied and burns one layer, Temperature fall.It is put into N719 dyestuffs and soaks 12~24 h, with anhydrous second Alcohol is rinsed well, obtains dye-sensitized solar cell anode.
4th, performance test
By dye-sensitized solar cell anode made from above comparative example and two embodiments, as dye sensitization too Positive energy battery step is as follows：Assembled battery first, platinum electrode is used as to electrode, it is by the conduction of working electrode up, and right Electrode conducting surface directed downwardly is picked up with clip to press from both sides into sandwich structure, then inject electrolyte between electrodes, carry out dyestuff The I-V curve test of sensitization solar battery.
Fig. 5 illustrates dye-sensitized solar cell anode composite surface material field emission scanning electron microscope figure of the present invention SEM.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, pattern are homogeneous.
Fig. 6 illustrates the I-V characteristic for the DSSC being respectively prepared using comparative example and two embodiments Curve map.In figure, curve a is the I-V characteristic curve of DSSC made of comparative example, and curve b is embodiment 1 The I-V characteristic curve of manufactured DSSC, curve c are DSSC made of embodiment 2 I-V characteristic curve.
The photoelectric properties contrast table of DSSC packaged by light anode of the following table for more than prepared by each example：
It can be seen that from the data in table 1 and Fig. 6, using DSSC produced by the present invention（DSSC）Light sun Pole is assembled into DSSC as working electrode, compared with comparison example, the short-circuit current density of embodiment 1~2（Jsc）And photoelectricity Conversion efficiency（η）All strengthen.Short-circuit current density（Jsc）Up to 17.316 mA/cm2, fill factor, curve factor（FF）Reach 61.5%, photoelectric transformation efficiency（η）Up to 7.949%.These are test result indicates that CeO2@TiO2Hollow material can effectively be inhaled Visible ray is received, utilization rate of the nano thin-film to sunshine is enhanced, effectively increases photoelectric transformation efficiency.

Claims (10)

  1. A kind of 1. hollow material CeO2@TiO2Preparation method, it is characterised in that comprise the following steps：
    1）Glucose is dissolved in deionized water, forms D/W, then D/W is placed in autoclave In carry out hydro-thermal reaction under 180 DEG C of temperature environment, after reaction terminates, be cooled to room temperature, washed after isolating solid phase through centrifugation After washing, dried 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, by concentration be 0.5M the cerous nitrate aqueous solution add carbon bead dispersion liquid in, obtain cerous nitrate and The mixed solution of carbon bead；
    4）It is anti-that the mixed solution of cerous nitrate and carbon bead is placed in autoclave the progress hydro-thermal under 160 DEG C of temperature environment Should；
    5）After hydro-thermal reaction terminates, room temperature is cooled to, takes solid formation after centrifuge washing, dries, obtains at a temperature of 80 DEG C Solid material C@CeO2；
    6）By solid material C@CeO2, hydroxypropyl cellulose and deionized water be scattered in absolute ethyl alcohol, obtain solid material C@ CeO2With the dispersion liquid of hydroxypropyl cellulose；
    7）By solid material C@CeO2Stirred with the dispersion liquid of hydroxypropyl cellulose under ultrasound condition, obtain solid material C@CeO2Dispersion liquid；
    8）Butyl titanate is mixed with ethanol, forms the mixed solution of butyl titanate and ethanol；
    9）The mixed solution of butyl titanate and ethanol is added drop-wise to solid material C@CeO2It is agitated in dispersion liquid, form mixing Solution；
    10）Mixed solution is warming up to 80 DEG C, flow back 100 min；
    11）After backflow terminates, room temperature is cooled to, separation obtains solid formation, then by solid formation centrifuge washing, at a temperature of 70 DEG C Drying, obtains solid material C@CeO2@TiO2；
    12）By solid material C@CeO2@TiO2It is placed in calcining furnace, temperature is warming up to 500 DEG C with 10 DEG C/min heating rate After keep 1h, obtain hollow structure material CeO2@TiO2。
  2. 2. hollow material CeO according to claim 12@TiO2Preparation method, it is characterised in that the step 2）In：It is described The mixing ratio of carbon bead and deionized water is 15mg: 1mL~3mL.
  3. 3. hollow material CeO according to claim 12@TiO2Preparation method, it is characterised in that the step 3）In：Nitric acid The cerium aqueous solution is with carbon bead dispersion liquid mixed volume than 1: 1.
  4. 4. hollow material CeO according to claim 12@TiO2Preparation method, it is characterised in that the step 1）And step 5）In：Each centrifugal rotational speed is 7000~9000 r/min, and the time is 5~10 min.
  5. 5. hollow material CeO according to claim 12@TiO2Preparation method, it is characterised in that the step 6）In：It is solid Material C@CeO2, hydroxypropyl cellulose and deionized water mixing quality ratio be 2: 1: 6；Solid material C@CeO2, hydroxy propyl cellulose Element and the total amount of deionized water and the mixing ratio of absolute ethyl alcohol are 90 mg: 4~7 mL.
  6. 6. hollow material CeO according to claim 12@TiO2Preparation method, it is characterised in that the step 8）In：It is described The mixed volume of butyl titanate and ethanol ratio is 1: 5.
  7. 7. hollow material CeO according to claim 12@TiO2Preparation method, it is characterised in that the step 9）In：It is described The mixed solution of butyl titanate and ethanol and solid material C@CeO2The mixed volume ratio of dispersion liquid is 1: 9~11；The drop The speed added is 0.4~0.6 mL/min.
  8. 8. hollow material CeO made from preparation method as claimed in claim 12@TiO2Preparing DSSC Application in light anode material, it is characterised in that：On FTO glass, using silk screen print method, by hollow material CeO2@TiO2Apply P25 film surfaces are overlayed on, through high-temperature calcination, obtain dye-sensitized solar cell anode material.
  9. 9. hollow material CeO according to claim 82@TiO2In dye-sensitized solar cell anode material is prepared Application, it is characterised in that：The temperature environment of the high-temperature calcination is 450 DEG C, and the time is 30 min, with 10 DEG C/min during calcining Heating rate temperature is warming up to 450 DEG C.
  10. 10. hollow material CeO according to claim 8 or claim 92@TiO2Preparing dye-sensitized solar cell anode material Application in material, it is characterised in that：P25 slurries are first coated on FTO glass, after sintered, then sky are coated on P25 pulp layers Core material CeO2@TiO2, then carry out high-temperature calcination；The P25 pulp layers coat 7~9 layers altogether, often coat one layer of sintering once；Institute State hollow CeO2@TiO22~3 layers are coated altogether, often coat one layer of sintering once.
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