CN102569761B - 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
- Publication number
- CN102569761B CN102569761B CN201010579607.1A CN201010579607A CN102569761B CN 102569761 B CN102569761 B CN 102569761B CN 201010579607 A CN201010579607 A CN 201010579607A CN 102569761 B CN102569761 B CN 102569761B
- Authority
- CN
- China
- Prior art keywords
- graphene
- titanium dioxide
- composite material
- titanium
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 apply 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; In vehicle exhaust, also contain other dusty gas as sulfur dioxide and nitrogen oxide.Exploitation is without the oligosaprobic electric automobile of discharge, become the eager task of the common accreditation in countries in the world, the government department of a lot of automobile manufacturing companies, battery manufacture manufacturer, chemical reagents corporation and various countries has dropped into substantial contribution and manpower, accelerates the research and development of electric automobile.In existing battery, capacity density and the energy density of lithium ion battery are higher, are acknowledged as most promising electrokinetic cell; But lithium ion battery itself also exists some technical bottlenecks, its being widely used in automobile is restricted.At present, the negative material that commercial lithium ion battery adopts is nearly all carbon/graphite material, but due to the electrode potential of carbon and the current potential of lithium very approaching, in the time of battery overcharge, part lithium ion may deposit in carbon electrodes, forms Li dendrite and cause safety issue.On the other hand, while discharging and recharging for the first time due to carbon/graphite electrode material, can form solid-electrolyte interphace (SEI film) at carbon surface, cause larger irreversible capacity loss, and the generation of solid-electrolyte interphace has increased electrode/electrolyte interface impedance, be unfavorable for the reversible embedding of Li+ and deviate from.Meanwhile, existing business negative material has reached the limit of performance, and carbon negative pole material cannot 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.Find the Novel anode 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 the characteristic such as long-life, safety and environmental protection.Compared 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
+), in first charge-discharge process, forming without SEI film, energy conversion efficiency is higher;
(2) there is not lithium metal or alloy in titanic oxide material in charge and discharge process, 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 poor, rate charge-discharge poor performance.
The titanium dioxide with plurality of advantages is also the highest catalysis material of the most extensive, the concerned degree of research in numerous catalysis materials, be considered to one of the most promising catalysis material, new development in particularly having applied taking new synthesis route, new method of modifying, sensitization solar battery since the nineties and nanosecond science and technology, as the scientific research of representative, have further been established the leading position of titanium dioxide in catalysis material massively.Although titanium dioxide based photocatalytic material has met the basic demand as a kind of good catalysis material, it is high and without visible light-responded two bottlenecks that extensive use is not still limited by the photocatalysis efficiency of material own.Many bibliographical informations employing new carbon such as carbon nano-tube, fullerene etc. be compounded to form composite material with titanium dioxide, due to both synergies, strengthened the photocatalysis performance of material to organic substance, pollutant.Material with carbon element-titanium dioxide possesses several reasons of more superior photo-catalysis capability: the larger specific area of (1) composite material has improved the adsorption capacity of material to organic pollution; (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 may be to the direction skew of corrigendum, and then has improved the utilance of long wavelength photons more; (4) carbon material surface absorbs after photon, and electronic injection, to titanium dioxide conduction band, is formed to reaction exciton (the superoxide radical O in order to degradable organic pollutant
2-and Hydroxyl 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 large specific area, high conductivity has broad application prospects it aspect lithium ion battery.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 due to it, low (< 60%) of efficiency 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 feature of utilizing its ultrathin flexible by Graphene and electrode material, can alleviate the volumetric expansion of electrode material granules in charge and discharge process, and its high conductivity can provide good conductive network for electronics.
Summary of the invention
The object of the invention is to provide a kind of titanium dioxide/graphene nano composite material and its preparation method and application, the technical problem solving is to improve the ion electronics ducting capacity of titanic oxide material, effectively improves 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 is 1～25wt% (preferable range is 10～20wt%), all the other are titanium dioxide; Wherein, the form of titanium dioxide is that meso-hole structure or high-energy surface are dominant, and titanium dioxide is all dispersed in Graphene surface.
The preparation method of described titanium dioxide/graphene nano composite material, adopting titanium source and Graphene is initial feed, taking water or organic solvent (one or more in ethanol, ethylene glycol, isopropyl alcohol, N methyl pyrrolidone) as reaction dissolvent, by Hydrothermal Synthesis or hydrolysis, obtain having the compound nano composite material of the titanium dioxide of meso-hole structure or titanium dioxide nanoplate that high-energy surface is dominant and Graphene.Concrete preparation method:
Hydrothermal Synthesis process: acid is joined in graphene aqueous solution, stir, taking titanium salt powder joins and in above-mentioned solution, stirs 10～120 minutes (optimization range 30～60 minutes), this solution is put into airtight container, react after 1～8 hour at 50～200 DEG C, by the black precipitate cleaning, drying obtaining, can obtain mesoporous TiO 2 nanosphere and the graphene composite material of Anatase.Wherein, preparation condition is Graphene, titanium salt and sour weight ratio=1: (5～20): (80～200), graphene aqueous solution concentration is 0.2～0.8g/L, 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, nitric acid.This composite material is to be evenly distributed on Graphene and to form at the mesoporous TiO 2 ball of 10～300nm by size, 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 to Graphene stirs 10～60 minutes, puts into 100～180 DEG C of reactions of air-tight bottle 10～24 hours gained solution; Then gained is precipitated to eccentric cleaning and dry, obtain titanium dioxide nanoplate and graphene composite material that high-energy surface is dominant.Wherein, Graphene and titanium salt weight ratio=1: 5～30, the concentration of organic solution 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, N methyl pyrrolidone.This composite material is that feature is that thickness is being anchored at tightly on graphene sheet layer of titanium dioxide nanoplate of 2～20nm, and specific area is 50～350m
2/ g.
In the preparation method of titanium dioxide/graphene composite material of the present invention, described graphene powder is the standby graphene oxide of conventional chemical legal system (GO), then obtains through thermal reduction, and it is of a size of 0.1 micron～10 microns.
In the present invention, titanium dioxide/graphene nano composite material is in power lithium-ion battery material or field of photocatalytic material application.
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 Graphene bi-material, obtain Novel Titanium dioxide/graphene composite material, can control titanium dioxide pattern or surface texture, to carry out original position compound with Graphene, pass through hydro-thermal reaction, do not add template, obtain titanium dioxide and be dispersed in the titanium dioxide/graphene nano composite material on Graphene.
2, by controlling reaction condition, can obtain different structure titanium dioxide/graphene composite material.The wherein compound nano composite material of mesoporous TiO 2 nanosphere and Graphene, [TiO] being generated by the hydrolysis of titanium source
2+group diffuses between graphene layer by electrostatic attraction, heterogeneous nucleation growth under certain condition, and Graphene plays the effect of structure inducer, and without any need for template preparation, size is evenly distributed on Graphene at the mesoporous TiO 2 ball of 10-300nm.Because having narrower nano aperture, mesoporous material distributes, large specific area, good permeability, and Graphene forms good three-dimensional conductive network, pore structure and Graphene provide favourable passage for lithium ion and electronics, thereby make material there is more excellent high rate performance and cycle performance, under the multiplying power of 50C, there is the stable discharging specific capacity of 96mAh/g.Meanwhile, this material also has higher photocatalytic activity.In titanium dioxide and graphene composite material that high-energy surface is dominant, being anchored at tightly on graphene sheet layer of the titanium dioxide nanoplate that thickness is 2～20nm, this material has larger specific area.High-energy surface has lower lithium ion and embeds potential barrier, is more conducive to the embedding of lithium ion.The titanium dioxide that this high-energy surface is dominant and graphene composite material have better high rate performance.Under the multiplying power of 120C (20.1A/g), there is the discharge capacity of 100mAh/g, demonstrate good high rate charge-discharge performance.
3, technique 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 compared with high charge-discharge capacity, excellent high current charge-discharge, stable circulation performance.Also there is extraordinary photocatalysis performance, can be for organic pollution light degradation and photolysis water hydrogen.
Brief description of the drawings
Fig. 1 is the scintigram of mesoporous TiO 2 ball/graphene composite material of preparing of embodiment 1;
Fig. 2 is the adsorption curve figure of mesoporous TiO 2 ball/graphene composite material of preparing of embodiment 1; In figure, curve a represents adsorption curve; Curve b represents desorption curve.
Fig. 3 is mesoporous TiO 2 ball/graphene composite material charge and discharge cycles figure under different multiplying prepared by embodiment 1;
Fig. 4 is that (curve a), (b) (curve is rhodamine B degradation curve chart c) with simple Graphene for curve for pure titanic oxide material for mesoporous TiO 2 ball/graphene composite material of preparing of embodiment 1;
Fig. 5 is mesoporous TiO 2 ball/graphene composite material (curve a represents) of preparing of embodiment 1 and the photodissociation aquatic products hydrogen performance map of pure titanic oxide material (curve b represents);
Fig. 6 is the scintigram of the pure titinium dioxide ball material prepared of comparative example 1;
Fig. 7 is pure titinium dioxide ball material charge and discharge cycles figure under different multiplying prepared by comparative example 1;
Fig. 8 is the scintigram of titanium dioxide nanoplate/graphene composite material of being dominant of high-energy surface prepared by embodiment 5;
Fig. 9 is titanium dioxide nanoplate/graphene composite material charge and discharge cycles figure under different multiplying that high-energy surface prepared by embodiment 5 is dominant;
Figure 10 is titanium dioxide nanoplate material charge and discharge cycles figure under different multiplying that high-energy surface prepared by comparative example 2 is dominant.
Embodiment
Described in following examples, the preparation method of electrode slice comprises step:
Titanium dioxide/graphene nano composite powder is mixed in mass ratio with binding agent (Kynoar PVDF) and graphite powder at 8: 1: 1, drip METHYLPYRROLIDONE, said mixture is worn into pulpous state to be coated on copper current collector, then it is dried at 120 DEG C under vacuum, obtain battery lead plate.Lithium ion battery has been assembled in vacuum glove box, electrochemical property test condition is: voltage range 1.0V～3.0V, electrolyte is 1mol/LLiPF6/EC: DMC (1: 1), be metal lithium sheet to electrode, charge-discharge magnification is 1C (168mA/g), and probe temperature is 20 DEG C.
In embodiment, photolytic activity test selects rhodamine B (Rhodamine B) as target analyte, and concrete reaction is as follows:
Using titanium dioxide/graphene nano composite material as catalysis material, fully mix after 30min through magnetic agitation, be distributed in rhodamine B solution, after adsorption equilibrium, start to open light source light photograph, interval different target time sampling 5mL.The solution of obtaining, with the centrifugal 5min of 5000r/min, is got to the settled solution after centrifugal, carry out measurement of concetration with spectrophotometer.The reaction of photodissociation water is carried out in the glass system of vacuum, and catalysis material is distributed to (containing the methyl alcohol of 10% volume ratio) in 300mL reacting solution through magnetic agitation.Before illumination, whole glass system is vacuumized, vacuum degree reaches below 50Pa, and the temperature of whole reaction is controlled at 3-9 DEG C of left and right.Light source used is the xenon lamp of 300W, adopts top irradiation mode.The gas producing fully mixes through the glass circulatory system, sends the gas of generation to gas-chromatography carry out quantitative analysis with argon gas as carrier gas.Chromatogram used is the Agilent-6890N that Agilent company of the U.S. produces, thermal conductivity cell detector (TCD), and post case temperature is 100 DEG C.
The 5ml concentrated sulfuric acid (98wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.5g/L, stir, take 5g titanium sulfate powder and join in above-mentioned solution and stir 30 minutes, this solution is put into air-tight bottle, 100 DEG C of reactions 6 hours.The black precipitate obtaining is washed three times with clear water, at 80 DEG C, dry, can obtain titanium dioxide and graphene composite material.[TiO] being generated by the hydrolysis of titanium source in this process
2+group diffuses between graphene layer by electrostatic attraction, heterogeneous nucleation growth under certain condition, the effect that Graphene plays structure inducer is prepared the mesoporous TiO 2 nanosphere of Anatase and the compound nano composite material of Graphene without any need for template, size is evenly distributed on Graphene at the mesoporous TiO 2 ball of 100nm, hole average diameter is at 4.6nm, and specific area is 170m
2/ g.
In the 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 obtaining is made to electrode slice, and respectively with multiplying power 0.5C, 1C, 5C, 10C, 20C, 30C, 50C, charging/discharging voltage scope 1.0～3.0V, records the chemical property of resulting materials in embodiment as shown in Figure 3.Get this composite material of 50mg and put into 100ml, 4 × 10
-5in M rhodamine B solution, after a sample adsorption equilibrium is got in absorption illumination for first 2 minutes, start to open light source light photograph, a sample is got at interval for 5 minutes.Fig. 4 is that this composite material is prepared pure titanic oxide material (rhodamine B degradation curve chart) with simple Graphene and comparative example 1.The reaction of photodissociation water is carried out in the glass system of vacuum, and catalysis material is distributed to (containing the methyl alcohol of 10% volume ratio) in 300mL reacting solution through magnetic agitation.Before illumination, whole glass system is vacuumized, vacuum degree reaches below 50Pa, and the temperature of whole reaction is controlled at 3～9 DEG C of left and right.Light source used is the xenon lamp of 300W, adopts top irradiation mode.Fig. 5 is the performance map of preparing pure titanic oxide material in this composite material and comparative example 1.
Can be found out by Fig. 1-Fig. 5: Graphene plays the effect of derivant, can, in the situation that not adding any template, can prepare mesoporous anatase titanium dioxide and graphene nanocomposite 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 provide favourable passage for lithium ion and electronics, thereby make material have more excellent high rate performance and cycle performance.In embodiment 1, mesoporous TiO 2 and the graphene composite material of preparation, also have higher light degradation photodissociation water efficiency with respect to the material in comparative example 1.
Comparative example 1
As different from Example 1, do not add graphene powder in preparation process, the pure titinium dioxide particle size obtaining is 700nm, and Fig. 6 is the scanned photograph of this pure titinium dioxide material.The powder obtaining is made to electrode slice, and respectively with multiplying power 0.5C, 1C, 5C, 10C, 20C, 30C, 50C, charging/discharging voltage scope 1.0～3.0V, records the chemical property of resulting materials in embodiment as shown in Figure 7.
Embodiment 2
Difference from Example 1 is, the 5ml concentrated sulfuric acid (98wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.3g/L, stir, taking 3.5g titanium sulfate powder joins in above-mentioned solution and stirs 30 minutes, this solution is put into air-tight bottle, 80 DEG C of reactions 2 hours.Then by centrifugal gained black precipitate, by washed with de-ionized water 3 times, 80 DEG C of vacuumizes, obtain the compound nano composite material of the nano titania of Anatase and Graphene, the titanium dioxide granule that particle size is 50nm in this composite material is dispersed in Graphene surface, pore-size distribution is 2～50nm, and specific area is 110m
2/ g.
In the present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 14wt%, and all the other are titanium dioxide.
Embodiment 3
Difference from Example 1 is, 4.6ml hydrochloric acid (37wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.3g/L, stir 10 minutes by ultrasonic gained solution dispersion 2 hours, add butyl titanate solution to be added drop-wise in configured solution and stir half an hour, then gained solution is placed in to air-tight bottle 80 DEG C of reactions 12 hours.Then by centrifugal gained black precipitate, by washed with de-ionized water 3 times, 80 DEG C of vacuumizes, can obtain the compound nano composite material of the mesoporous TiO 2 nanosphere of Anatase and Graphene, the titanium dioxide granule that particle size is 200～300nm in this composite material is dispersed in Graphene surface, pore-size distribution is 5～100nm, and specific area is 69m
2/ g.
In the present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 9wt%, and all the other are titanium dioxide.
Difference from Example 1 is, the 5ml concentrated sulfuric acid (98wt%) is joined in the graphene aqueous solution that 100ml concentration is 0.3g/L, stir, taking 3.5g titanium sulfate powder joins in above-mentioned solution and stirs 30 minutes, be positioned in air-tight bottle and stir half an hour, then gained solution is reacted 4 hours at 100 DEG C.Then by centrifugal gained black precipitate, by washed with de-ionized water 3 times, 80 DEG C of vacuumizes, obtain the compound nano composite material of the mesoporous TiO 2 nanosphere of Anatase and Graphene, size is dispersed in Graphene surface at 30nm titanium dioxide granule, hole average diameter is at 2～10nm, and specific area is 142m
2/ g.
In the present embodiment titanium dioxide/graphene nano composite material, the shared ratio of Graphene is 18wt%, and all the other are titanium dioxide.
Embodiment 5
Difference from Example 1 is, by 3ml tetraisopropyl titanate, the ethanolic solution that joins 40ml concentration and be 0.7g/L Graphene stirs 40 minutes, and gained solution is put into 180 DEG C of reactions of air-tight bottle 24 hours.Then gained is precipitated to eccentric cleaning, 80 DEG C of oven dry, obtain titanium dioxide and graphene nanocomposite material.In the titanium dioxide/graphene composite material that the method is prepared, titanium dioxide is 001 laminated structure that (high-energy surface) is dominant, and lamellar spacing is closely anchored on Graphene at 5nm, and specific area is 270m
2/ g.
In the 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, by the powder obtaining by method smear packed battery in embodiment 1, respectively with multiplying power 1C, 5C, 10C, 20C, 30C, 50C, 120C, charging/discharging voltage scope 1.0～3.0V, records the chemical property of resulting materials in embodiment as shown in Figure 9.
Comparative example 2
As different from Example 5, preparation process in do not add graphene powder, prepare the titanium dioxide powder that 001 pure face is dominant, by the powder obtaining by method smear packed battery in embodiment 1.With multiplying power 1C, 5C, 10C, 20C, 30C, 50C, 120C, charging/discharging voltage scope 1.0～3.0V, records the chemical property of resulting materials in embodiment as shown in Figure 10 respectively.
Embodiment 5 shows to have the titanium dioxide of high-energy surface with the composite material of Graphene has higher high rate performance with the result of comparative example 2, still has the specific capacity of 94mAh/g at 120C (charging complete in 30 seconds).
Claims (4)
1. a preparation method for titanium dioxide/graphene nano composite material, is characterized in that: in this composite material, the shared ratio of Graphene is 1～25wt%, and all the other are titanium dioxide; Wherein, the form of titanium dioxide is meso-hole structure, and titanium dioxide is dispersed in Graphene surface; The preparation method of this composite material is: adopting titanium source and Graphene is initial feed, taking water or organic solvent as reaction dissolvent, by Hydrothermal Synthesis process, obtains having the compound nano composite material of the titanium dioxide of meso-hole structure and Graphene; Described Hydrothermal Synthesis process is as follows:
Acid is joined in graphene aqueous solution, stir, taking titanium salt powder joins in above-mentioned solution and stirs 10～120 minutes, this solution is put into airtight container, react after 1～8 hour at 50～200 DEG C, by the black precipitate cleaning, drying obtaining, can obtain mesoporous TiO 2 nanosphere and the graphene composite material of Anatase; Wherein, preparation condition is Graphene, titanium salt and sour weight ratio=1:(5～20): (80～200), graphene aqueous solution concentration is 0.2～0.8g/L, 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, nitric acid.
2. according to the preparation method of titanium dioxide/graphene nano composite material claimed in claim 1, it is characterized in that, this composite material is to be evenly distributed on Graphene and to form at the mesoporous TiO 2 ball of 10～300nm by size, and its aperture is at 2～150nm, and specific area is 40～180m
2/ g.
3. according to the preparation method of titanium dioxide/graphene nano composite material claimed in claim 1, it is characterized in that: in this composite material, the shared ratio of Graphene is 10～20wt%.
4. according to the preparation method's of titanium dioxide/graphene nano composite material claimed in claim 1 application, it is characterized in that: the preparation method of described titanium dioxide/graphene nano composite material applies at power lithium-ion battery Material Field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010579607.1A CN102569761B (en) | 2010-12-08 | 2010-12-08 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010579607.1A CN102569761B (en) | 2010-12-08 | 2010-12-08 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102569761A CN102569761A (en) | 2012-07-11 |
| CN102569761B true CN102569761B (en) | 2014-06-25 |
Family
ID=46414639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010579607.1A Expired - Fee Related CN102569761B (en) | 2010-12-08 | 2010-12-08 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102569761B (en) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084062B (en) * | 2013-01-28 | 2015-05-27 | 福建省辉锐材料科技有限公司 | Device for purifying air and keeping freshness |
| CN103203252B (en) * | 2013-04-23 | 2015-05-13 | 武汉大学 | Preparation method of three-dimensional net structure composite material |
| CN103382362B (en) * | 2013-08-06 | 2016-01-13 | 大连海事大学 | A kind of polyurethane Composite Coating with antifouling property and preparation method thereof |
| KR101785268B1 (en) | 2013-12-10 | 2017-10-16 | 삼성에스디아이 주식회사 | Negative active material and lithium battery including the material, and method for manufacturing the material |
| CN103915611A (en) * | 2014-04-08 | 2014-07-09 | 童东革 | Water-based aluminum ion battery positive electrode material and preparation method thereof |
| CN104009238A (en) * | 2014-06-20 | 2014-08-27 | 福州大学 | Method for in-situ synthesis of compound of rutile TiO2 mesocrystal and graphene |
| CN104157833B (en) * | 2014-08-25 | 2016-02-17 | 厦门大学 | A kind of Graphene/titanium dioxide composite porous material and its production and use |
| CN104226253B (en) * | 2014-10-13 | 2017-02-15 | 武汉大学 | Graphene oxide-TiO2 composite material and preparation method and application thereof |
| CN104495918B (en) * | 2014-12-23 | 2016-05-25 | 陕西科技大学 | The preparation method of particulate titanium dioxide/two-dimensional nano titanium carbide composite |
| CN104998630A (en) * | 2015-06-25 | 2015-10-28 | 上海第二工业大学 | Titanium dioxide/graphene nanocomposite, and normal-temperature preparation method and application thereof |
| CN105609776B (en) * | 2016-02-21 | 2018-10-30 | 钟玲珑 | A kind of preparation method of graphene/titanium dioxide hollow ball/sulphur composite material |
| CN105742642B (en) * | 2016-03-28 | 2018-03-30 | 上海应用技术学院 | A kind of preparation method of lithium ion battery negative material |
| CN107302081A (en) * | 2016-04-15 | 2017-10-27 | 华为技术有限公司 | Negative material and preparation method thereof, battery and preparation method thereof |
| CN105826515A (en) * | 2016-05-16 | 2016-08-03 | 北京师范大学 | Lithium ion battery cathode material and application thereof |
| CN105977460B (en) * | 2016-05-20 | 2018-10-09 | 北京师范大学 | A kind of graphene composite material, preparation method and application |
| CN105870446A (en) * | 2016-05-26 | 2016-08-17 | 江苏深苏电子科技有限公司 | Preparation method of modified graphene lithium ion battery anode material |
| CN106082201B (en) * | 2016-06-25 | 2019-04-16 | 上海大学 | The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load |
| CN107673307A (en) * | 2016-08-01 | 2018-02-09 | 福建新峰二维材料科技有限公司 | Germanium/graphene/titanium dioxide nanofiber composite material and preparation method thereof and battery |
| CN106328959A (en) * | 2016-08-15 | 2017-01-11 | 江苏师范大学 | Preparation method of TiO2-Graphene composite material |
| CN106784714B (en) * | 2016-12-29 | 2019-04-02 | 陕西煤业化工技术研究院有限责任公司 | A kind of silicon-based composite anode material for Li-ion battery and preparation method thereof |
| CN107039639A (en) * | 2017-02-22 | 2017-08-11 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of high power capacity sodium-ion battery |
| CN107528062A (en) * | 2017-03-31 | 2017-12-29 | 上海大学 | A kind of preparation method of lithium battery tin base cathode material |
| CN107115855A (en) * | 2017-04-24 | 2017-09-01 | 华东理工大学 | Controllable graphene composite titanium dioxide mesoporous single crystals mixture of a kind of charge migration and preparation method thereof |
| CN108499582A (en) * | 2018-04-04 | 2018-09-07 | 昆明理工大学 | A kind of preparation method of composite photo-catalyst |
| CN108751168B (en) * | 2018-06-08 | 2020-10-30 | 常州大学盱眙凹土研发中心 | Preparation method of anatase type flower-like rhombic titanium dioxide/graphene composite material for photo-generated cathode corrosion prevention |
| CN111097398B (en) * | 2018-10-29 | 2023-01-13 | 中国石油化工股份有限公司 | Catalytic composite material, preparation method thereof and catalytic oxidation method of cycloolefin |
| CN109585760A (en) * | 2018-12-11 | 2019-04-05 | 广东永邦新能源股份有限公司 | A kind of flexibility lithium ceramic cell and preparation method thereof |
| CN109786705A (en) * | 2019-01-17 | 2019-05-21 | 禹城贝尔新材料有限公司 | A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure |
| CN109718752B (en) * | 2019-01-27 | 2021-11-12 | 安徽大学 | graphene/TiO2Nanocomposite and method for preparing same |
| CN109950595A (en) * | 2019-03-27 | 2019-06-28 | 天津工业大学 | Titania modified low-dimensional carbon material/chitosan proton exchange membrane and its preparation method and application |
| CN111013655B (en) * | 2019-12-26 | 2023-12-01 | 常州纳欧新材料科技有限公司 | Preparation method of polyaniline/titanium dioxide/graphene composite material for photocatalytic desulfurization |
| CN111454691B (en) * | 2020-04-14 | 2021-06-08 | 大连理工大学 | Graphene/amorphous titanium dioxide nanorod composite material, preparation method and application thereof |
| CN111755686B (en) * | 2020-07-07 | 2021-06-15 | 佛山科学技术学院 | Mesoporous titanium dioxide composite carbon nanotube film electrode material and preparation method and application thereof |
| CN114373938B (en) * | 2021-01-15 | 2024-02-02 | 西安石油大学 | Preparation method of nickel-based three-dimensional ordered titanium dioxide/graphene composite material and application of nickel-based three-dimensional ordered titanium dioxide/graphene composite material in lithium ion battery |
| CN113948691B (en) * | 2021-10-15 | 2023-03-10 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
| CN114142080B (en) * | 2021-11-25 | 2024-04-05 | 东莞市茂盛新能源科技有限公司 | Super-capacity graphene battery and preparation method thereof |
| CN114948762A (en) * | 2021-12-31 | 2022-08-30 | 北京福纳康生物技术有限公司 | Fullerene powder material and preparation method and application thereof |
| CN114853061B (en) * | 2022-04-29 | 2023-08-04 | 芜湖天弋能源科技有限公司 | Preparation method of porous flaky sodium ion battery anode material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
-
2010
- 2010-12-08 CN CN201010579607.1A patent/CN102569761B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890344A (en) * | 2010-07-27 | 2010-11-24 | 华东理工大学 | Preparation method of graphene/titanium dioxide composite photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| P25-Graphene Composite as a High Performance Photocatalyst;Hao Zhang，et al.;《ACS NANO》;20091230;第4卷(第1期);380-386 * |
| TiO2-Graphene Nanocomposites. UV-Assisted Photocatalytic Reduction of Graphene Oxide;Graeme Williams，et al.;《ACS NANO》;20080703;第2卷(第7期);1487-1491 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102569761A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102569761B (en) | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof | |
| Feng et al. | Boosting high-rate zinc-storage performance by the rational design of Mn 2 O 3 nanoporous architecture cathode | |
| CN106935860B (en) | A kind of carbon intercalation V2O3Nano material, preparation method and application | |
| Wu et al. | Proton inserted manganese dioxides as a reversible cathode for aqueous Zn-ion batteries | |
| CN104993125B (en) | A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C | |
| CN104016405B (en) | A kind of flower-shaped mesoporous titanium dioxide material and preparation method thereof and application | |
| CN103682302B (en) | The method of the nano-electrode material of atomization drying synchronized compound porous graphene parcel | |
| CN103682296B (en) | A kind of preparation method of nanoscale lithium titanate material with high specific capacity | |
| CN102569769B (en) | Preparation method for lithium titanate and graphene composite electrode materials | |
| CN102569771B (en) | SnO2-Li4Ti5O12 composite electrode material and preparation method thereof | |
| CN103682368A (en) | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery | |
| Bai et al. | Hierarchical 3D micro-/nano-V2O5 (vanadium pentoxide) spheres as cathode materials for high-energy and high-power lithium ion-batteries | |
| CN104900861B (en) | A kind of lithium hydrogentitanate Li H Ti O material and preparation method thereof | |
| CN103560019B (en) | A kind of zinc ion hybrid super capacitor | |
| CN105514378A (en) | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof | |
| CN103682340B (en) | A kind of iron-based fluoride nano material with hierarchy and its preparation method and application | |
| CN105575675A (en) | Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor | |
| Sun et al. | A facile synthesis of mesoporous TiO2 sub-microsphere host for long life lithium-sulfur battery cathodes | |
| Yue et al. | Nanostructured transition metal nitride composites as energy storage material | |
| CN105883940A (en) | Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery | |
| CN105390677A (en) | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof | |
| CN104409712A (en) | Preparation method of carbon and nitrogen coated lithium titanate material | |
| CN104860348A (en) | Nanosheet-constructed titanium dioxide, and preparation method and application thereof | |
| Alharthi et al. | Hydrothermal synthesis of α-SnWO4: Application to lithium-ion battery and photocatalytic activity | |
| Hou et al. | Hexagonal-layered Na0. 7MnO2. 05 via solvothermal synthesis as an electrode material for aqueous Na-ion supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140625 Termination date: 20201208 |