CN102569761A - Titanium dioxide/graphene nanocomposite material and preparation method and application thereof - Google Patents
Titanium dioxide/graphene nanocomposite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a titanium dioxide/graphene nanocomposite material, a preparation method of the nanocomposite material and application of the nanocomposite material in the field of energy source and cleaning environment. The graphene accounts for 1-25wt% and the balance is titanium dioxide. Morphology of the titanium dioxide is a mesoporous structure or a structure with a dominant high energy surface, and titanium dioxide is scattered uniformly on the surface of graphene. According to the invention, by adopting a titanium source and graphene as initial materials, and water or organic solvents as reaction solvents, the nanocomposite material with titanium dioxide with the mesoporous structure or a titanium dioxide nano sheet with the dominant high energy surface compounded with graphene can be obtained through hydrothermal synthesis or a hydrolysis reaction. The invention can be carried out in an aqueous solution system and the crystallinity of the product is high. The composite material can be applied to a cathode material of a power ion battery, has a higher charge-discharge capacity, is excellent in high current charge and discharge, stable in circulating performance, has very good photocatalytic performance and can be used to light degradation of organic pollutants and water photolysis for preparing hydrogen.
Description
Technical field
The present invention relates to a kind of titanium dioxide/graphene composite material and preparation method thereof and use at the energy and cleaning ambient field, particularly this composite material is in the application of power lithium-ion battery and photocatalysis field.
Background technology
Environmental pollution and energy crisis have caused the extensive concern of countries in the world.At present, automobile approximately consumes 45% of crude output, and discharges a large amount of greenhouse gases carbon dioxide; Also contain other dusty gas such as sulfur dioxide and nitrogen oxide in the vehicle exhaust.Exploitation does not have the oligosaprobic electric automobile of discharging; Become the eager task of the common approval in countries in the world; The government department of a lot of automobile manufacturing companies, battery manufacturer, chemical reagents corporation and various countries has dropped into substantial contribution and manpower, quickens the research and development of electric automobile.In existing battery, the capacity density and the energy density of lithium ion battery are higher, are acknowledged as electrokinetic cell the most likely; But also there are some technical bottlenecks in lithium ion battery itself, makes its widely-used being restricted in automobile.At present; The negative material that commercial lithium ion battery adopted nearly all is carbon/graphite material, but because the current potential of the electrode potential of carbon and lithium is very approaching, when battery overcharge; The part lithium ion possibly deposit in carbon electrodes, forms Li dendrite and causes safety issue.On the other hand; Because when carbon/graphite electrode material discharges and recharges for the first time; Can form the middle phase (SEI film) of solid electrolyte at carbon surface; Cause bigger irreversible capacity loss, and the generation of phase has increased the electrode/electrolyte interface impedance in the middle of the solid electrolyte, be unfavorable for the reversible embedding of Li+ and deviate from.Simultaneously, existing commercial negative material has reached the limit of performance, and carbon negative pole material can't overcome and exist shortcoming and defect, and the breakthrough of new material technology becomes the urgent task of lithium ion battery development of new generation.Seek the novel negative material that security performance is better, specific capacity is higher, cycle life is longer, become the focus of Study on Li-ion batteries using.Titanium dioxide is a kind of high performance lithium ionic cell cathode material with characteristics such as long-life, safety and environmental protections.Compare with carbon negative pole material, titanic oxide material has lot of advantages, as:
(1) high (the 1.7V Vs Li/Li of titanic oxide material embedding lithium current potential
+), no SEI film forms in the first charge-discharge process, and energy conversion efficiency is higher;
(2) lithium metal or alloy do not appear in titanic oxide material in charge and discharge process, and be safe;
(3) titanic oxide material crystal structure in cyclic process does not change good stability.
Therefore, titanic oxide material can be used as the good negative material of lithium-ion-power cell.But because titanic oxide material is a kind of semi-conducting material, thereby electron conduction is relatively poor, the rate charge-discharge poor performance.
Titanium dioxide with plurality of advantages also is to study the most extensively, receive the highest catalysis material of degree of concern in numerous catalysis materials; Be considered to one of the most promising catalysis material; New development and nanosecond science and technology in particularly having used with new synthesis route, new method of modifying, sensitization solar battery since the nineties are the scientific research of representative, have further established the leading position of titanium dioxide in catalysis material massively.Though the titanium dioxide based photocatalytic material has satisfied the basic demand as a kind of good catalysis material, extensive use still is limited by not high and no visible light-responded two bottlenecks of the photocatalysis efficiency of material own.Many bibliographical informations the employing new carbon be compounded to form composite material such as CNT, fullerene etc. with titanium dioxide because both synergy has strengthened the photocatalysis performance of material to organic substance, pollutant.Material with carbon element-titanium dioxide possesses the several reasons of more superior photo-catalysis capability: the bigger specific area of (1) composite material has improved material to the organic pollutant adsorption ability; (2) formation of material with carbon element-titanium dioxide interface heterojunction has improved compound between light induced electron and hole; (3) than pure titinium dioxide, the Fermi level of composite material maybe be to the direction skew of corrigendum, and then has improved the utilance of long wavelength photons more; (4) after carbon material surface absorbs photon, electronics is injected into the titanium dioxide conduction band, forms reaction exciton (superoxide radical O in order to degradable organic pollutant
2-and hydroxyl radical free radical HO.
Graphene has desirable two dimensional crystal structure, is made up of hexagonal lattice.Since successfully being prepared, Graphene has caused the research boom that one is new in worldwide.Because Graphene has big specific area, high conductivity makes it aspect lithium ion battery, have broad application prospects.Graphene is directly as lithium ion battery negative material, and its first charge-discharge capacity can reach 400-800mAh/g, and the capacity after stablizing can reach 380-450mAh/g, apparently higher than the lithium ion battery of conventional graphite material.But since its efficient low (＜60%) and lower volume energy density are to limit this material directly as the principal element of lithium ion battery negative material first.At present, great majority research concentrates on carries out the compound characteristic of utilizing its ultrathin flexible with Graphene and electrode material, can alleviate the volumetric expansion of electrode material granules in charge and discharge process, and its high conductivity can provide the favorable conductive network for electronics.
Summary of the invention
The object of the invention provides a kind of titanium dioxide/graphene nano composite material; The technical problem that solves is to improve the ion electronics ducting capacity of titanic oxide material, effectively improves the rate charge-discharge performance and the photocatalytic activity of material.
Technical scheme of the present invention is:
A kind of titanium dioxide/graphene nano composite material, the shared ratio of Graphene are that (preferable range is 10～20wt%) to 1～25wt%, and all the other are titanium dioxide; Wherein, the form of titanium dioxide is that meso-hole structure or high energy face are dominant, and titanium dioxide all is dispersed in the Graphene surface.
The preparation method of said titanium dioxide/graphene nano composite material; Adopting titanium source and Graphene is initial feed; With water or organic solvent (one or more in ethanol, ethylene glycol, isopropyl alcohol, the N methyl pyrrolidone) is reaction dissolvent; Synthetic or the hydrolysis through hydro-thermal obtains having the titanium dioxide of meso-hole structure or titanium dioxide nanoplate and the compound nano composite material of Graphene that the high energy face is dominant.Concrete preparation method:
Hydro-thermal building-up process: acid is joined in the graphene aqueous solution; Stir; Take by weighing the titanium salt powder and join and stir 10～120 minutes (optimization range 30～60 minutes) in the above-mentioned solution, this solution is put into airtight container, 50～200 ℃ of reactions after 1～8 hour; With the black precipitate cleaning, drying that obtains, can obtain the mesoporous TiO 2 nanosphere and the graphene composite material of anatase phase.Wherein, preparation condition is Graphene, titanium salt and sour weight ratio=1: (5～20): (80～200), graphene aqueous solution concentration are 0.2～0.8g/L, and addition is calculated ratio according to pure Graphene.Titanium salt is titanium sulfate, titanium tetrachloride or tetraisopropyl titanate, and acid is one or more in hydrochloric acid, sulfuric acid, the nitric acid.This composite material is to be evenly distributed on the Graphene at the mesoporous TiO 2 ball of 10～300nm by size to constitute, and its aperture is at 2～150nm, and specific area is 40～180m
2/ g.
Hydrolytic process: the organic solution that titanium salt is joined Graphene stirred 10～60 minutes, put into 100～180 ℃ of reactions of air-tight bottle 10～24 hours to gained solution; Then gained is precipitated the eccentric cleaning oven dry, promptly get titanium dioxide nanoplate and graphene composite material that the high energy face is dominant.Wherein, Graphene and titanium salt weight ratio=1: 5～30, the organic solution concentration 0.4～1g/L of Graphene, addition is calculated ratio according to pure Graphene.Titanium salt is titanium sulfate, titanium tetrachloride, tetraisopropyl titanate or butyl titanate, and the organic solvent that Graphene organic solution is used is selected from one or more in ethanol, ethylene glycol, isopropyl alcohol, the N methyl pyrrolidone.This composite material is that characteristic is that thickness is being anchored at tightly on the Graphene lamella of titanium dioxide nanoplate of 2～20nm, and specific area is 50～350m
2/ g.
Among the preparation method of titanium dioxide/graphene composite material of the present invention, said graphene powder obtains through thermal reduction for the graphene oxide (GO) of conventional chemical method preparation then, and it is of a size of 0.1 micron～10 microns.
Among the present invention, titanium dioxide/graphene nano composite material is used at power lithium-ion battery material or field of photocatalytic material.
The invention has the beneficial effects as follows:
1, Graphene is as a kind of novel material with carbon element, and itself and composite titania material also should have more superior photo-catalysis capability.The present invention combines titanium dioxide and two kinds of materials of Graphene; Obtain Novel Titanium dioxide/graphene composite material; May command titanium dioxide pattern or surface texture, to carry out original position compound with Graphene, through hydro-thermal reaction; Do not add template, obtain titanium dioxide and be dispersed in the titanium dioxide/graphene nano composite material on the Graphene.
2, through the control reaction condition, can obtain different structure titanium dioxide/graphene composite material.The compound nano composite material of mesoporous TiO 2 nanosphere and Graphene wherein, [TiO] that generates by the hydrolysis of titanium source
2+Group diffuses between graphene layer through electrostatic attraction, heterogeneous nucleation growth under certain condition, and Graphene plays the effect of structure inducer, and without any need for the template preparation, size is evenly distributed on the Graphene at the mesoporous TiO 2 ball of 10-300nm.Because having narrower nano aperture, mesoporous material distributes; Big specific area; Good penetration property, and Graphene forms good three-dimensional conductive network, and pore structure and Graphene are that lithium ion and electronics provide favourable passage; Thereby make material have more excellent high rate performance and cycle performance, under the multiplying power of 50C, have the stable discharging specific capacity of 96mAh/g.Simultaneously, this material also has higher photocatalytic activity.In the titanium dioxide and graphene composite material that the high energy face is dominant, thickness is being anchored at tightly on the Graphene lamella of titanium dioxide nanoplate of 2～20nm, and this material has bigger specific area.The high energy mask has lower lithium ion to embed potential barrier, more helps the embedding of lithium ion.Titanium dioxide and graphene composite material that this high energy face is dominant have better high rate performance.The discharge capacity that under the multiplying power of 120C (20.1A/g), has 100mAh/g demonstrates good high rate charge-discharge performance.
3, technology of the present invention is simple, and cost is low, can in solution system, carry out.Composite material can be applicable to power ion battery negative material, has higher charge/discharge capacity, excellent high current charge-discharge, stable circulation performance.Also have extraordinary photocatalysis performance, can be used for organic pollution light degradation and photolysis water hydrogen.
Description of drawings
Fig. 1 is the scintigram of the mesoporous TiO 2 ball/graphene composite material of embodiment 1 preparation;
Fig. 2 is the adsorption curve figure of the mesoporous TiO 2 ball/graphene composite material of embodiment 1 preparation; Among the figure, curve a representes adsorption curve; Curve b representes the desorption curve.
Fig. 3 is mesoporous TiO 2 ball/graphene composite material charge and discharge cycles figure under different multiplying of embodiment 1 preparation;
Fig. 4 be embodiment 1 preparation mesoporous TiO 2 ball/graphene composite material (curve a), pure titanic oxide material (curve b) and simple Graphene (curve c) degraded rhodamine B curve chart;
Fig. 5 is the photodissociation aquatic products hydrogen performance map of mesoporous TiO 2 ball/graphene composite material (curve a representes) with the pure titanic oxide material (curve b representes) of embodiment 1 preparation;
Fig. 6 is the scintigram of the pure titinium dioxide ball material of Comparative Examples 1 preparation;
Fig. 7 is pure titinium dioxide ball material charge and discharge cycles figure under different multiplying of Comparative Examples 1 preparation;
Fig. 8 is the scintigram of titanium dioxide nanoplate/graphene composite material of being dominant of the high energy face of embodiment 5 preparation;
Fig. 9 is titanium dioxide nanoplate/graphene composite material charge and discharge cycles figure under different multiplying that the high energy face of embodiment 5 preparations is dominant;
Figure 10 is titanium dioxide nanoplate material charge and discharge cycles figure under different multiplying that the high energy face of comparative example 2 preparations is dominant.
Embodiment
The preparation method of the said electrode slice of following examples comprises step:
Titanium dioxide/graphene nano composite powder is mixed by mass ratio with binding agent (Kynoar PVDF) and graphite powder at 8: 1: 1; Drip the N-N-methyl-2-2-pyrrolidone N-; Said mixture is worn into pulpous state to be coated on the copper collector; With its 120 ℃ of oven dry down under vacuum, obtain battery lead plate then.Lithium ion battery is assembled completion in vacuum glove box; The electrochemical property test condition is: voltage range 1.0V～3.0V, electrolyte are 1mol/LLiPF6/EC: DMC (1: 1), are metal lithium sheet to electrode; Charge-discharge magnification is 1C (168mA/g), and probe temperature is 20 ℃.
Among the embodiment, the photolytic activity test selects for use rhodamine B (Rhodamine B) as the target analyte, the concrete reaction as follows:
Titanium dioxide/graphene nano composite material as catalysis material, after magnetic agitation is fully mixed 30min, is distributed in the rhodamine B solution, begins to open the light source light photograph after the adsorption equilibrium, at interval different target time sampling 5mL.The solution of obtaining with the centrifugal 5min of 5000r/min, is got the settled solution after centrifugal, carry out measurement of concetration with spectrophotometer.Photodissociation water is reflected at and carries out in the glass system of vacuum, and catalysis material is distributed to (methyl alcohol that contains 10% volume ratio) in the 300mL reacting solution through magnetic agitation.Before the illumination, whole glass system is vacuumized, vacuum degree reaches below the 50Pa, and the temperature of entire reaction is controlled at about 3-9 ℃.Used light source is the xenon lamp of 300W, adopts the top irradiation mode.The gas that produces fully mixes through the glass circulatory system, sends the gas that produces to gas-chromatography with argon gas as carrier gas and carries out quantitative analysis.Used chromatogram is the Agilent-6890N that U.S. Agilent company produces, thermal conductivity cell detector (TCD), and post oven temperature, degree is 100 ℃.
Embodiment 1
The 5ml concentrated sulfuric acid (98wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.5g/L, stir, take by weighing 5g titanium sulfate powder and join in the above-mentioned solution and to stir 30 minutes, this solution is put into air-tight bottle, 100 ℃ of reactions 6 hours.The black precipitate that obtains is given a baby a bath on the third day after its birth time with clear water,, can obtain titanium dioxide and graphene composite material 80 ℃ of oven dry down.[TiO] that in this process, generates by the hydrolysis of titanium source
2+Group diffuses between graphene layer through electrostatic attraction; Heterogeneous nucleation growth under certain condition; The mesoporous TiO 2 nanosphere and the compound nano composite material of Graphene of anatase phase prepared in the effect that Graphene plays structure inducer without any need for template; Size is evenly distributed on the Graphene at the mesoporous TiO 2 ball of 100nm, and the hole average diameter is at 4.6nm, and specific area is 170m
2/ g.
In present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 12wt%, and all the other are titanium dioxide.
Fig. 1 is the compound scanned photograph of mesoporous TiO 2 ball/Graphene, and Fig. 2 is the N of this composite material
2Adsorption curve.The powder that obtains is processed electrode slice, respectively with multiplying power 0.5C, 1C, 5C, 10C, 20C, 30C, 50C, charging/discharging voltage scope 1.0～3.0V, the chemical property that records gained material among the embodiment is seen shown in Figure 3.Get this composite material of 50mg and put into 100ml, 4 * 10
-5In the M rhodamine B solution, begin to open the light source light photograph after a sample adsorption equilibrium was got in absorption illumination in preceding 2 minutes, got a sample at interval in 5 minutes.Fig. 4 is this composite material and simple Graphene and the pure titanic oxide material (degraded rhodamine B curve chart) of comparative example 1 preparation.Photodissociation water is reflected at and carries out in the glass system of vacuum, and catalysis material is distributed to (methyl alcohol that contains 10% volume ratio) in the 300mL reacting solution through magnetic agitation.Before the illumination, whole glass system is vacuumized, vacuum degree reaches below the 50Pa, and the temperature of entire reaction is controlled at about 3～9 ℃.Used light source is the xenon lamp of 300W, adopts the top irradiation mode.Fig. 5 is the performance map for preparing pure titanic oxide material in this composite material and the comparative example 1.
Can be found out by Fig. 1-Fig. 5: Graphene plays the effect of derivant, can under the situation of not adding any template, can prepare mesoporous anatase titanium dioxide and graphene nano composite material.Mesoporous TiO 2 is of a size of 50-200nm, the mesoporous 2～20nm that is of a size of.Specific area is 170m
2/ g.Pore structure and Graphene are that lithium ion and electronics provide favourable passage, thereby make material have more excellent high rate performance and cycle performance.The mesoporous TiO 2 and the graphene composite material of preparation also have higher light degradation photodissociation water efficient with respect to the material in the comparative example 1 among the embodiment 1.
Comparative example 1
Different with embodiment 1 is, in the preparation process, does not add graphene powder, and the pure titinium dioxide particle size that obtains is 700nm, and Fig. 6 is the scanned photograph of this pure titinium dioxide material.The powder that obtains is processed electrode slice, respectively with multiplying power 0.5C, 1C, 5C, 10C, 20C, 30C, 50C, charging/discharging voltage scope 1.0～3.0V, the chemical property that records gained material among the embodiment is seen shown in Figure 7.
Embodiment 1 shows that with the structure of comparative example 1 Graphene plays the effect of derivant, can under the situation of not adding any template, form mesoporous titanium dioxide.Pore structure and Graphene are that lithium ion and electronics provide favourable passage, thereby make material have more excellent high rate performance and cycle performance.The mesoporous TiO 2 and the graphene composite material of preparation also have higher light degradation photodissociation water efficient with respect to the material in the comparative example 1 among the embodiment 1.
Be with embodiment 1 difference; The 5ml concentrated sulfuric acid (98wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.3g/L, stir, take by weighing 3.5g titanium sulfate powder and join in the above-mentioned solution and to stir 30 minutes; This solution is put into air-tight bottle, 80 ℃ of reactions 2 hours.Then that the gained black precipitate is centrifugal; With washed with de-ionized water 3 times; 80 ℃ of vacuumizes, obtain the nano titania and the compound nano composite material of Graphene of anatase phase, particle size is that the titanium dioxide granule of 50nm is dispersed in the Graphene surface in this composite material; Pore-size distribution is 2～50nm, and specific area is 110m
2/ g.
In present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 14wt%, and all the other are titanium dioxide.
Be with embodiment 1 difference; 4.6ml hydrochloric acid (37wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.3g/L; Stir 10 minutes with the ultrasonic dispersion of gained solution 2 hours; Adding butyl titanate drips of solution is added in the solution that is disposed and stirs half an hour, places air-tight bottle 80 ℃ of reactions 12 hours gained solution then.Then that the gained black precipitate is centrifugal; With washed with de-ionized water 3 times; 80 ℃ of vacuumizes, can obtain the mesoporous TiO 2 nanosphere and the compound nano composite material of Graphene of anatase phase, particle size is that the titanium dioxide granule of 200～300nm is dispersed in the Graphene surface in this composite material; Pore-size distribution is 5～100nm, and specific area is 69m
2/ g.
In present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 9wt%, and all the other are titanium dioxide.
Embodiment 4
Be with embodiment 1 difference; The 5ml concentrated sulfuric acid (98wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.3g/L; Stir; Take by weighing 3.5g titanium sulfate powder and join in the above-mentioned solution and to stir 30 minutes, be positioned in the air-tight bottle and stir half an hour, then with gained solution 100 ℃ of reactions 4 hours.Then that the gained black precipitate is centrifugal; With washed with de-ionized water 3 times; 80 ℃ of vacuumizes, obtain the mesoporous TiO 2 nanosphere and the compound nano composite material of Graphene of anatase phase, size is dispersed in the Graphene surface at the 30nm titanium dioxide granule; The hole average diameter is at 2～10nm, and specific area is 142m
2/ g.
In present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 18wt%, and all the other are titanium dioxide.
Be that with embodiment 1 difference with the 3ml tetraisopropyl titanate, the ethanolic solution that joins 40ml concentration and be the 0.7g/L Graphene stirred 40 minutes, put into 180 ℃ of reactions of air-tight bottle 24 hours to gained solution.Then gained is precipitated eccentric cleaning,, promptly get titanium dioxide and graphene nano composite material 80 ℃ of oven dry.In titanium dioxide/graphene composite material that this method is prepared, titanium dioxide is 001 laminated structure that (high energy face) is dominant, and lamellar spacing closely is anchored on the Graphene at 5nm, and specific area is 270m
2/ g.
In present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 15wt%, and all the other are titanium dioxide.
Fig. 8 is the scanned photograph figure of this titanium dioxide/graphene composite material; With the powder that obtains by method smear packed battery among the embodiment 1; Respectively with multiplying power 1C, 5C, 10C, 20C, 30C, 50C, 120C; Charging/discharging voltage scope 1.0～3.0V, the chemical property that records gained material among the embodiment is seen shown in Figure 9.
Comparative example 2
Different with embodiment 5 is, in the process of preparation, does not add graphene powder, prepares the titanium dioxide powder that 001 pure face is dominant, with the powder that obtains by method smear packed battery among the embodiment 1.Respectively with multiplying power 1C, 5C, 10C, 20C, 30C, 50C, 120C, charging/discharging voltage scope 1.0～3.0V, the chemical property that records gained material among the embodiment is seen shown in Figure 10.
The embodiment 5 and the result of comparative example 2 show to have the titanium dioxide of high energy face and the composite material of Graphene and have higher high rate performance, still have the specific capacity of 94mAh/g at 120C (charging in 30 seconds finishes).
Claims (8)
1. titanium dioxide/graphene nano composite material, it is characterized in that: the shared ratio of Graphene is 1～25wt%, and all the other are titanium dioxide; Wherein, the form of titanium dioxide is that meso-hole structure or high energy face are dominant, and titanium dioxide all is dispersed in the Graphene surface.
2. according to the described titanium dioxide of claim 1/graphene nano composite material, it is characterized in that: the shared ratio of Graphene is preferably 10～20wt%.
3. the preparation method of the described titanium dioxide of claim 1/graphene nano composite material; It is characterized in that: adopting titanium source and Graphene is initial feed; With water or organic solvent is reaction dissolvent; Synthetic or the hydrolysis through hydro-thermal obtains having the titanium dioxide of meso-hole structure or titanium dioxide nanoplate and the compound nano composite material of Graphene that the high energy face is dominant.
4. according to the preparation method of the described titanium dioxide of claim 3/graphene nano composite material, it is characterized in that the hydro-thermal building-up process is following:
Acid is joined in the graphene aqueous solution; Stir; Take by weighing the titanium salt powder and join and stirred in the above-mentioned solution 10～120 minutes, this solution is put into airtight container, 50～200 ℃ of reactions after 1～8 hour; With the black precipitate cleaning, drying that obtains, can obtain the mesoporous TiO 2 nanosphere and the graphene composite material of anatase phase; Wherein, preparation condition is Graphene, titanium salt and sour weight ratio=1: (5～20): (80～200), graphene aqueous solution concentration are 0.2～0.8g/L, and addition is calculated ratio according to pure Graphene; Titanium salt is titanium sulfate, titanium tetrachloride or tetraisopropyl titanate, and acid is one or more in hydrochloric acid, sulfuric acid, the nitric acid.
5. according to the preparation method of the described titanium dioxide of claim 4/graphene nano composite material; It is characterized in that; This composite material is to be evenly distributed on the Graphene at the mesoporous TiO 2 ball of 10～300nm by size to constitute, and its aperture is at 2～150nm, and specific area is 40～180m
2/ g.
6. according to the preparation method of the described titanium dioxide of claim 3/graphene nano composite material, it is characterized in that hydrolytic process is following:
The organic solution that titanium salt is joined Graphene stirred 10～60 minutes, put into 100～180 ℃ of reactions of air-tight bottle 10～24 hours to gained solution; Then gained is precipitated the eccentric cleaning oven dry, promptly get titanium dioxide nanoplate and graphene composite material that the high energy face is dominant; Wherein, Graphene and titanium salt weight ratio=1: 5～30, the organic solution concentration 0.4～1g/L of Graphene, addition is calculated ratio according to pure Graphene; Titanium salt is titanium sulfate, titanium tetrachloride, tetraisopropyl titanate or butyl titanate, and the organic solvent that Graphene organic solution is used is selected from one or more in ethanol, ethylene glycol, isopropyl alcohol, the N methyl pyrrolidone.
7. according to the preparation method of the described titanium dioxide of claim 6/graphene nano composite material; It is characterized in that; This composite material is that characteristic is that thickness is being anchored at tightly on the Graphene lamella of titanium dioxide nanoplate of 2～20nm, and specific area is 50～350m
2/ g.
8. according to the application of the described titanium dioxide of claim 1/graphene nano composite material, it is characterized in that: titanium dioxide/graphene nano composite material is used at power lithium-ion battery material or field of photocatalytic material.
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