CN105551828A - Nano titanium dioxide/graphene composite material and preparation method thereof - Google Patents
Nano titanium dioxide/graphene composite material and preparation method thereof Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- 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
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the nano composite preparation field and relates to a nano titanium dioxide/graphene composite material and a preparation method thereof. The method includes the following steps that: positively charged titanium dioxide sol and negatively charged graphene oxide sol are mixed together so as to form floc sediments; and sodium borohydride hydrothermal reduction is carried out, so that the nano titanium dioxide/graphene composite material can be obtained. The nano titanium dioxide/graphene composite material has large specific surface area and high electrochemical performance; the nano titanium dioxide/graphene composite material can be used as the electrode material of a super capacitor, so that the electrode material can have high specific capacity and high cyclic stability; the nano titanium dioxide/graphene composite material can be also used as the anode material of a lithium ion battery, so that the anode material can have high stability and little possibility of decay; selected preparation materials are safe, nontoxic, environmentally friendly and pollution-free; and the preparation process is simple, feasible and safe, does not introduce toxic substances, and is low in cost, and therefore, industrialization can be facilitated.
Description
Technical field
The invention belongs to Nano-composite materials field, particularly a kind of nanometer titanium dioxide/graphene composite material and preparation method thereof.
Background technology
Because petroleum resources are increasingly short, electric power and the energy are in the growth of each application demand, and researcher has to make great efforts the various energy storage equipment of exploitation.Ultracapacitor, because of the performance of its uniqueness, as fast charging and discharging, high power density and long circulation life etc. become supplementing of secondary cell, partly or entirely can substitute traditional chemical cell be used for the traction power source of vehicle and start the energy, and have than traditional chemical cell purposes more widely.
The material being applicable to ultracapacitor should have following characteristics: good conductivity, high surface area and suitable void size.Two kinds of the most frequently used electrode materials are material with carbon element and transition metal oxide.By finding the research of these two kinds of electrode materials, although material with carbon element is just widely used in ultracapacitor a long time ago, and there is larger specific area, the features such as higher electronic conductivity and good stability, but usually there is the problem that energy density is low and contacted with ions is limited in the ultracapacitor of carbon-based material; In contrast, the ultracapacitor of transition metal oxide base then has high ratio capacitance and high power density and energy density.But due to the electron conduction of metal oxide poor, along with the increase of sweep speed, the ratio capacitance of metal oxide based ultracapacitor can significantly reduce.Therefore, how metal oxide and material with carbon element compound are obtained a kind of high performance electrode material, and this compound can gather the advantage of two materials and the shortcoming weakening each material is the emphasis that those skilled in the art study always.
Graphene, i.e. mono-layer graphite crystal film are new materials that is stacking by periodic honey comb like carbon hexatomic ring ordered arrangement and the individual layer laminated structure formed.The thickness of single-layer graphene is only 0.35nm in theory, is the thinnest two-dimensional material found at present.It warpage can become the fullerene of zero dimension, can bend to the carbon nano-tube of one dimension, can also pile up and form three-dimensional graphite, and therefore, Graphene is the elementary cell forming other carbon-based materials.Graphene has high mechanical properties, the conductivity that large specific area is become reconciled.Its these special constructions and character make it be obtained in every field to apply widely.The Graphene utilizing certain methods to obtain also has much different premium properties from the composite nano materials of other materials.
Titanium dioxide, is commonly called as titanium dioxide, white solid or pulverous amphoteric oxide.General point Detitanium-ore-type and rutile-type.Rutile titanium dioxide is more stable and fine and close than anatase titanium dioxide, and have higher hardness, density, dielectric constant and refractive index, its covering power and tinting strength, tinting power are also higher.And anatase titanium dioxide is high at the luminance factor rutile titanium dioxide of visible ray shortwave part, band blue color, and lower than rutile-type to ultraviolet absorbability, photocatalytic activity is higher than rutile-type.Under certain condition, anatase titanium dioxide can be converted into rutile titanium dioxide.Because titanium dioxide has nontoxic, best opacity, best whiteness and brightness, be considered to a kind of Chinese white that performance is best in the world at present.Be applied to the industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, cosmetics.Because its fusing point is very high, be also used to manufacture fireproof glass, glaze, enamel, potter's clay, resistant to elevated temperatures experimental ware etc.
At present, mainly contain two large classes about Graphene and titanium dioxide complex method, growth in situ and ex situ assembling.With regard to concrete preparation method, the incorporation way of conventional titanium dioxide has titanium source to introduce and pressed powder is introduced, Chinese patent literature as application publication number CN102600823A discloses a kind of preparation method of titanium dioxide/graphene composite material, the method adds butyl titanate in isopropyl acetone solution makes solution A, graphene dispersion is made solution B in deionized water and isopropyl acetone mixed solution, is further processed in solution A instillation solution B.And for example the Chinese patent literature of application publication number CN102569761A discloses a kind of preparation method of titanium dioxide/graphene nano composite material, and the party's rule titanium sulfate powder is joined in scattered graphene solution do further process.For another example the Chinese patent literature of application publication number CN102553559A discloses a kind of preparation method of graphene/nanometer compound, the method titania powder is carried out heat alkali liquid process obtain titanium dioxide nano-tube powder, this powder joined in graphene solution and processes.Above two kinds of methods introducing titanium dioxide have certain advantage and advance, but directly titanium source is added in graphene solution because hydrolysis and recombination reaction can not can cause both to combine not exclusively or can not the problem such as compound by Complete Synchronization, and introduce titania powder due to the contact of powder and liquid and may not cause each autoprecipitation comprehensively, only have mechanical mixture, there is no chemical bond.
Summary of the invention
The object of the invention is to the deficiency for existing preparation method, a kind of environmental protection, succinct, nanometer titanium dioxide/graphene composite material and preparation method thereof is efficiently provided.
The technical solution used in the present invention is as follows:
A kind of nanometer titanium dioxide/graphene composite material, in described composite material, the mass percentage of Graphene is 5-90%, and the mass percentage of titanium dioxide is 10-95%.
Further, in compound, titanium dioxide is elliposoidal, and size is 5-10nm.
The present invention still further provides a kind of preparation method of preferred nanometer titanium dioxide/graphene composite material, respectively the TiO 2 sol of positively charged and electronegative graphene oxide colloidal sol are mixed to form flocculent deposit, then obtain nanometer titanium dioxide/graphene composite material through sodium borohydride hydrothermal reduction.
Wherein, using the material of titaniferous as presoma, using water as solvent, acid, as catalyst and chelating agent, prepares stable water system TiO 2 sol.
Presoma, chelating agent, catalyst feed intake amount of substance than being 1:5-8:1.2-2.2:85-95 with water.
Presoma can be selected from the one in tetra-n-butyl titanate, tetrabutyl titanate, metatitanic acid n-propyl, isopropyl titanate.
As the one in the optional acetic acid of acid of chelating agent and catalyst, hydrochloric acid, nitric acid.
When preparing TiO 2 sol, under room temperature, chelating agent and presoma are fully mixed to get solution A, catalyst and water are fully mixed to get solution B, and solution B keeps the mixing speed of 10-20r/s, in solution A instillation solution B, after dripping off, continue to stir 2.5-3h and namely obtain TiO 2 sol.
The rate of addition of solution A preferably controls to drip/min at 30-60.
The concentration of TiO 2 sol is preferably 30-35mg/mL.
The titanium dioxide crystal form using sol-gel process to prepare is anatase, and the TiO 2 sol prepared is transparent and homogeneous shape, at room temperature can stable existence about 30 days.
Prepare graphite oxide with the hummer chemical method improved, in water, obtain the graphene oxide colloidal sol of bear electricity through ultrasonic disperse.
The concentration of graphene oxide colloidal sol is preferably 0.1-1mg/ml.
Preferably under stirring, TiO 2 sol is added in graphene oxide colloidal sol.Adding Way preferably drips.The mixing speed of graphene oxide colloidal sol is preferably 10-20r/s.
In hydrothermal reduction course of reaction, temperature preferably controls as 100-160 DEG C, and the reaction time is 12-30 hour.
The present invention's application colloidal sol electrostatic self-assembled principle, under stirring, TiO 2 sol is mixed with graphene oxide colloidal sol, colloidal tio 2 wherein mixes with graphene oxide colloid, the titanium dioxide micelle of positively charged forms flocculent deposit with electronegative graphene oxide micelle attracting polymerization, outwell supernatant, flocculence is precipitated turbid liquid to be transferred in hydrothermal reaction kettle, through the thermal reduction of sodium borohydride high-temperature water graphene oxide is reduced to Graphene and makes the amorphous titanium dioxide crystal of part obtain nanometer titanium dioxide/graphene composite material.In this process, due to the effect of electrostatic force and Van der Waals force, titanium dioxide can load be at graphenic surface easily, equably, and granular titanium dichloride load on graphene sheet layer, Graphene between layers stacking can be stoped, inhibit the heap sum of Graphene to reunite; On the other hand, Graphene, as an excellent electric conductor, effectively can improve the shortcoming of titanic oxide electronic poorly conductive, also prevents the gathering of titania nanoparticles simultaneously.
Nanometer titanium dioxide/graphene composite material of the present invention can be applicable to the fields such as ultracapacitor, lithium ion battery, solar cell, photocatalysis.
Compared with prior art, tool has the following advantages in the present invention:
Titanium dioxide/graphene composite material specific area of the present invention is large, and have good chemical property, can be used as the electrode material of ultracapacitor, specific capacity is high, good cycling stability.Can also lithium ion battery anode material be used for, good stability, not easily decay.Selected prepares material safety non-toxic, environment friendly and pollution-free; Preparation technology is simple and easy to do, safety, does not introduce noxious substance, with low cost, is convenient to carry out industrialization.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of graphene oxide in embodiment 1, redox graphene, titanium dioxide, titanium dioxide/graphene oxide, titanium dioxide/graphene compound;
Fig. 2 is the infared spectrum of graphene oxide in embodiment 1, redox graphene, titanium dioxide/graphene oxide, titanium dioxide/graphene;
Fig. 3 is the transmission electron microscope picture of the titanium dioxide/graphene that embodiment 1 obtains;
Fig. 4 is the cyclic voltammogram that the titanium dioxide/graphene compound difference of embodiment 2 sweeps under speed;
Fig. 5 is the stable circulation linearity curve of titanium dioxide/graphene as electrode material for super capacitor of embodiment 2;
Fig. 6 is that the titanium dioxide/graphene of embodiment 3 is as stable circulation linearity curve during lithium electricity anode material.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
A preparation method for nanometer titanium dioxide/graphene composite material, comprises the following steps:
(1) graphene oxide colloid is prepared: use the hummer legal system improved for graphite oxide, add in the concentrated sulfuric acid (98wt%, 69ml) of ice bath by crystalline flake graphite (2g), stir 30min, potassium permanganate (8g) is added in above-mentioned solution, stir 2h.Move into 35 DEG C of stirred in water bath 12h.Divide and add 276ml deionized water three times, after adding, add H
2o
2(30%, 25ml) is centrifugal, washing, dry, grinds and obtains graphite oxide.The graphite oxide powder ultrasonic getting 0.2g is scattered in 400ml deionized water, obtains the graphene oxide colloid that concentration is 0.5mg/ml.
(2) colloidal tio 2 is prepared: glacial acetic acid (20.00ml) and butyl titanate (20.00ml) mix and blend 30min are obtained solution A, glacial acetic acid (5.00ml) and deionized water (95ml) are mixed to get solution B, solution A is instilled in the solution B under stirring (10-20r/s), rate of addition controls to drip/min at 30-60, drips off the colloidal tio 2 that namely rear stirring 3h obtains transparent and homogeneous.
(3) nanometer titanium dioxide/graphene composite material is prepared: get 14.4ml colloidal tio 2 instillation stirring (10-20r/s, graphene oxide colloid (400ml down together), 0.5mg/ml), drip ultrasonic 30min completely, incline supernatant, turbid for floccule liquid is transferred in pyroreaction still, add 0.5g sodium borohydride, 140 DEG C of reaction 14h, after reacting completely, cooling, centrifugal, dry, grind and obtain titanium dioxide/graphene composite material, wherein titanium dioxide mass content is 70%, and Graphene mass content is 30%.
The specific area preparing composite material is comparatively large, is 289.4m
2g
-1, desorption average pore size is 2.97nm, and the titanium dioxide/graphene composite material prepared is mesoporous material.
Fig. 1 is the XRD collection of illustrative plates of graphene oxide, redox graphene, titanium dioxide, titanium dioxide/graphene oxide, titanium dioxide/graphene compound; Visible, in composite material GO 10.7 ° characteristic peak due to remove background can not manifest on figure, and rGO 25.3 ° characteristic peak due to TiO
225.3 ° of characteristic peaks of (101) crystal face overlapping and can not manifest on collection of illustrative plates, so composite material collection of illustrative plates only demonstrates TiO
2characteristic peak, from TiO
2/ GO and TiO
2the XRD collection of illustrative plates of/rGO sample is found out, the intensity at the sample characteristic peak after sodium borohydride hydrothermal reduction obviously strengthens, and the amorphous titanium dioxide of these declaratives obtains crystallization.
Fig. 2 is the infared spectrum of graphene oxide, redox graphene, titanium dioxide/graphene oxide, titanium dioxide/graphene, TiO
2/ GO collection of illustrative plates can be seen 3400,1730,1620,1218 and 1056cm
-1the FT-IR peak at place is caused by the skeleton structure of O-H stretching vibration, C=O stretching vibration, phenyl ring, C-C stretching vibration and C-O stretching vibration respectively.FT-IR spectra has a large amount of oxygen-containing functional groups on GO surface.By TiO
2the FT-IR spectrogram of/rGO can be found out, sodium borohydride hydrothermal treatment consists result in the remarkable decline of oxygen-containing functional group content, this demonstrates GO and is reduced in order to rGO.
Fig. 3 is the transmission electron microscope picture of obtained titanium dioxide/graphene composite material, as can be seen from Figure 3, titania nanoparticles equably load is not reunited on graphene sheet layer, and the particle of titanium dioxide is in oval spherical, short radius is about 5nm, and major radius is about 10nm.
Embodiment 2
A preparation method for nanometer titanium dioxide/graphene composite material, comprises the following steps:
Graphene oxide colloid and colloidal tio 2 is prepared according to the method that embodiment 1 is same, measure the graphene oxide colloid (400ml under 6.2ml colloidal tio 2 instillation stirring, 0.5mg/ml), drip ultrasonic 30min completely, incline supernatant, turbid for floccule liquid is transferred in pyroreaction still, add 0.5g sodium borohydride, 140 DEG C of reaction 14h, after reacting completely, cooling, centrifugal, drying, grinds and obtains titanium dioxide and Graphene mass ratio is the titanium dioxide/graphene composite material of 5:5.
Titanium dioxide/graphene compound, acetylene black, PTFE are mixed with the mass ratio of mass ratio 80:10:10, add ethanol in proper amount, ultrasonic disperse, be coated in nickel foam, dry, compressing tablet, does cyclic voltammetry curve and measures (see figure 4), can be calculated the ratio capacitance when sweeping speed and being 5mv/s and is up to 145F/g.Can find out that material has good cyclical stability from the charging and discharging curve of accompanying drawing 5.
Embodiment 3
A preparation method for nanometer titanium dioxide/graphene composite material, comprises the following steps:
Graphene oxide colloid and colloidal tio 2 is prepared according to the method for embodiment 1, measure the graphene oxide colloid (400ml under 2.6ml colloidal tio 2 instillation stirring, 0.5mg/ml), drip ultrasonic 30min completely, incline supernatant, turbid for floccule liquid is transferred in pyroreaction still, add 0.5g sodium borohydride, 140 DEG C of reaction 14h, after reacting completely, cooling, centrifugal, drying, to grind and obtain mass ratio be titanium dioxide and Graphene mass ratio is the titanium dioxide/graphene composite material of 3:7.Titanium dioxide/graphene compound, acetylene black, PVDF, mix with the ratio of mass ratio 80:10:10, add a certain amount of NMF(1-methyl pyrrolidone), grinding pulping, is coated on Copper Foil, dries, cut-parts, be assembled into button cell, discharge and recharge instrument is measured, obtain stable circulation linearity curve as shown in Figure 6.
Embodiment 4
A preparation method for nanometer titanium dioxide/graphene composite material, comprises the following steps:
Graphene oxide colloid and colloidal tio 2 is prepared according to the method for embodiment 1, measure the graphene oxide colloid (400ml under 6.2ml colloidal tio 2 instillation stirring, 0.5mg/ml), drip ultrasonic 30min completely, incline supernatant, turbid for floccule liquid is transferred in pyroreaction still, add 0.5g sodium borohydride, 120 DEG C of reaction 12h, after reacting completely, cooling, centrifugal, drying, grinds and obtains titanium dioxide and Graphene mass ratio is the titanium dioxide/graphene composite material of 5:5.
Embodiment 5
A preparation method for titanium dioxide/graphene nano composite material, comprises the following steps:
Graphene oxide colloid and colloidal tio 2 is prepared according to the method for embodiment 1, measure the graphene oxide colloid (400ml under 6.2ml colloidal tio 2 instillation stirring, 0.5mg/ml), drip ultrasonic 30min completely, incline supernatant, turbid for floccule liquid is transferred in pyroreaction still, add 0.5g sodium borohydride, 120 DEG C of reaction 30h, after reacting completely, cooling, centrifugal, drying, grinds and obtains titanium dioxide and Graphene mass ratio is the titanium dioxide/graphene composite material of 5:5.
Claims (10)
1. the preparation method of a nanometer titanium dioxide/graphene composite material, it is characterized in that, respectively the TiO 2 sol of positively charged and electronegative graphene oxide colloidal sol are mixed to form flocculent deposit, then obtain nanometer titanium dioxide/graphene composite material through sodium borohydride hydrothermal reduction.
2. the preparation method of nanometer titanium dioxide/graphene composite material as claimed in claim 1, it is characterized in that, the concentration of graphene oxide colloidal sol is 0.1-1mg/ml, and the concentration of TiO 2 sol is 30-35mg/mL.
3. the preparation method of nanometer titanium dioxide/graphene composite material as claimed in claim 1, is characterized in that, under 10-20r/s mixing speed, TiO 2 sol is added in graphene oxide colloidal sol.
4. the preparation method of the nanometer titanium dioxide/graphene composite material as described in as arbitrary in claim 1-3, it is characterized in that, in hydrothermal reaction process, temperature is 100-160 DEG C, and the reaction time is 12-30 hour.
5. the preparation method of nanometer titanium dioxide/graphene composite material as claimed in claim 4, is characterized in that, using the material of titaniferous as presoma, using water as solvent, acid, as catalyst and chelating agent, prepares TiO 2 sol.
6. the preparation method of nanometer titanium dioxide/graphene composite material as claimed in claim 5, is characterized in that, presoma, chelating agent, catalyst feed intake amount of substance than being 1:5-8:1.2-2.2:85-95 with water.
7. the preparation method of nanometer titanium dioxide/graphene composite material as claimed in claim 6, it is characterized in that, when preparing TiO 2 sol, under room temperature, chelating agent and presoma are fully mixed to get solution A, catalyst and water are fully mixed to get solution B, solution B keeps the mixing speed of 10-20r/s, in solution A instillation solution B, after dripping off, continue to stir 2.5-3h and namely obtain TiO 2 sol.
8. the preparation method of nanometer titanium dioxide/graphene composite material as claimed in claim 7, it is characterized in that, the rate of addition of solution A is that 30-60 drips/min.
9. the nanometer titanium dioxide/graphene composite material that claim 1-8 either method is obtained, it is characterized in that, in described composite material, the mass percentage of Graphene is 5-90%.
10. nanometer titanium dioxide/graphene composite material as claimed in claim 9, it is characterized in that, in compound, titanium dioxide is elliposoidal, and size is 5-10nm.
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| CN106252607A (en) * | 2016-08-11 | 2016-12-21 | 郑州大学 | Hemicentrotus seu Strongylocentrotus shape nanometer Tixsn1 xo2the preparation method of/Graphene three-dimensional composite material and the application on lithium ion battery negative thereof |
| CN106450234A (en) * | 2016-12-05 | 2017-02-22 | 新疆维吾尔自治区产品质量监督检验研究院 | Spherical titania/graphene flexible composite material preparation method |
| CN106450243A (en) * | 2016-12-15 | 2017-02-22 | 新疆维吾尔自治区产品质量监督检验研究院 | Preparation method of flexible composite material of spherical titanium dioxide/graphene |
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| CN113948691A (en) * | 2021-10-15 | 2022-01-18 | 佛山科学技术学院 | Titanium dioxide composite material and application thereof as energy storage material |
| CN115072842A (en) * | 2022-06-17 | 2022-09-20 | 深圳大学 | Composite electrode, preparation method thereof and plasma disinfectant water generating device |
| CN115849861A (en) * | 2022-11-22 | 2023-03-28 | 安徽宇航派蒙健康科技股份有限公司 | Composite graphene heat-conducting film and preparation method thereof |
| CN116387484A (en) * | 2023-04-07 | 2023-07-04 | 湖南金阳烯碳新材料股份有限公司 | Preparation method of graphene composite material, graphene composite material and application of graphene composite material |
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