CN102530931B - Graphene-based nano composite material and preparation method thereof - Google Patents
Graphene-based nano composite material and preparation method thereof Download PDFInfo
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- CN102530931B CN102530931B CN201110417951.5A CN201110417951A CN102530931B CN 102530931 B CN102530931 B CN 102530931B CN 201110417951 A CN201110417951 A CN 201110417951A CN 102530931 B CN102530931 B CN 102530931B
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Abstract
The invention relates to a graphene-based nano composite material and a preparation method of the composite material. The composite material contains graphene and nanowires, and has a preparation principle of in-site catalytic growth of nanowires on graphene. The preparation method comprises heating the mixture of graphite oxide and a metal catalyst; adding reaction materials including ethylene, silicane and so on; and growing nanowires and reducing graphite oxide to graphene by use of the metal particles as catalyst so as to prepare the nano composite material containing nanowires and graphene in one step. The method provided by the invention can be used for preparing composite materials containing graphene and nanowires, such as carbon nanotube, silicon and silicon carbide, and the composite materials can be applied in the fields of lithium ion battery, super capacitor, solar cell, sensor, catalyst, and so on.
Description
Technical field
The present invention relates to a kind of nano composite material based on Graphene and preparation method thereof, belong to nano material preparing technical field.
Background technology
As everyone knows, one-dimensional nano line has high-specific surface area and the performances such as many electricity relevant to its Structure and form, light, magnetic, heat with two-dimentional Graphene, utilize the structure and function characteristic of Graphene and nano wire, carry out structure composite design, function composite design and synthetic method design, can prepare and there is high-performance and multifunctional nanocomposites.For example, silicon nanowires has high lithium capacity, and Graphene has high conductivity, and silicon nanowires and Graphene is compound, can prepare the lithium electric material with heavy body and fast charging and discharging ability.CN201010561749.5 discloses a kind of silicon/graphene composite material of used as negative electrode of Li-ion battery, this matrix material is stratiform sandwich structure, the silicon nano of 2-50nm is scattered here and there uniformly on the every lamella of Graphene, in the middle of adjacent graphene sheet layer, by silicon nano, separated, and lamella overlapping edges together, form uniform stratiform conductive network structure.CN201110067559.2 discloses a kind of Field Electron Emission negative electrode based on Graphene/zinc oxide nanowire matrix material, this Graphene/zinc oxide nanometer composite material preparation method is first liquid deposition Graphene rete on electrode base board, in vapour deposition or hydrothermal method at Graphene surface growth zinc oxide nanowire.
Summary of the invention
The object of the present invention is to provide a kind of nano composite material based on Graphene and preparation method thereof, it is heated oxide mineral carbon load metal catalyst metallic particles situ catalytic grow nanowire on Graphene, and a step is prepared the nano composite material of nano wire and Graphene.Adopt the technology of the present invention, can select the multiple catalytic metal such as iron, cobalt, gold on Graphene, to grow the multiple nano wires such as carbon nanotube, silicon nanowires, silicon carbide nanometer line, utilize the multifunctionality of nano wire and the excellent properties of Graphene, and issuable Function Coupling effect, construct high-specific surface area, there is the multifunctional nano composite materials such as electricity, light, magnetic, heat, can be applicable to the fields such as lithium ion battery, ultracapacitor, solar cell, sensor, catalysis.
The invention provides a kind of nano composite material graphene-containing and nano wire based on Graphene, situ catalytic grow nanowire on Graphene, preparation method is heated oxide graphite and metal catalytic agent composition, graphite oxide is reduced into Graphene, metallic particles catalytic growth nano wire, one-step synthesis goes out nano wire and graphene nanocomposite material.
Described nano wire comprises solid nano wire and hollow Nano pipe, solid nano wire comprises silicon, silicon carbide, silicon oxide, silica carbon, silicon nitride, boron nitride, zinc oxide, titanium oxide, manganese oxide nano wire and mixing thereof, and nanotube comprises carbon nanotube, nano-tube, titanium oxide nanotubes, boron nitride nano-tube.
The step that the preparation method of a kind of nano composite material based on Graphene provided by the invention comprises is liquid-phase mixing graphite oxide and metal precursor, by metal load on graphite oxide, at heat reduction graphite oxide, become in Graphene process to add reaction raw materials, the metal nanoparticle that utilizes Graphene surface to form, situ catalytic grows nano wire, prepares the nano composite material of nano wire and Graphene.
Described graphite oxide adopts chemical oxidization method preparation, and graphite oxide surface and interlayer prepared by the method have hydroxyl, carboxyl, epoxy isoreactivity group.
Described metal precursor is the metal-salt of iron, cobalt, nickel, manganese, zinc, copper, gold and silver, platinum, tin, titanium or their mixing, preferably iron, cobalt, nickel, copper, gold.
The mode of described metal load on graphite oxide is that metal-salt is directly mixed or ion-exchange in liquid phase with graphite oxide.Directly mixing is to utilize graphite oxide surface hydroxyl, carboxyl, epoxy isoreactivity group to be combined with metal ion; Ion-exchange is in graphite oxide solution, to add the basic solutions such as ammoniacal liquor, utilizes graphite oxide surface active groups that ammonia radical ion is adsorbed on graphite oxide, and presoma metal ion displacement ammonia radical ion loads on graphite oxide.Adopt aforesaid method, can be by conventional metal load on graphite oxide, as iron, cobalt, nickel, manganese, zinc, copper, gold and silver, platinum, titanium, tin etc.
Described heat reduction graphite oxide, is heated oxide graphite, and deoxidation, expand into graphene film.
Described reaction raw materials is at least siliceous, the precursor of a kind of element in carbon, nitrogen, boron, zinc, titanium, manganese, and reaction raw materials is grow nanowire under heating of metal katalysis.
The preferred carbon source of described reaction raw materials and silicon source, carbon source preferred alcohol, acetone, methane, ethene, the preferred elemental silicon in silicon source, silicon oxide, silane.
It is that reaction raw materials grows nano wire on metallic particles under hot conditions that described situ catalytic grows nano wire.Growth pattern comprises thermal evaporation or chemical Vapor deposition process, and this is two kinds of conventional methods of preparing nano wire, and general nano wire can be prepared by these two kinds of modes.
Described thermal evaporation, take grow silicon nanowires as example, and heat solid silicon source produces silicon vapor, and silicon vapor is grow silicon nanowires on graphite oxide or graphene-supported metal catalyst.
Described chemical vapour deposition, take carbon nano-tube as example, graphite oxide or graphene-supported metal catalyst and carbon source are sent into high-temperature reactor simultaneously, cracking catalyst is condensed into nano-metal particle, carbon source Pintsch process goes out active substance, catalytic growth carbon nanotube on nano-metal particle.
The temperature of described metallic particles catalytic growth nano wire is 300-1400 ℃, and preferably temperature is 800-1200 ℃.
Adopt this invention technology, can prepare by Graphene, form nano composite material, can also prepare the matrix material that nano particle and Graphene form, also can prepare the matrix material being formed by Graphene, nano wire and nano particle.
The present invention prepares nano composite material, and liquid-phase mixing and ion exchange method can load on various metals nano particle on graphite oxide, and thermal evaporation and chemical Vapor deposition process can be at the multiple nano wires of metallic particles catalytic growth.Nano wire can be but be not limited to silicon, silicon carbide, silicon oxide, silica carbon, silicon nitride, boron nitride, titanium oxide, zinc oxide, manganese oxide nano wire and mixing thereof, preferred silicon nanowires, silicon carbide nanometer line; Nanotube can be but be not limited to carbon nanotube, nano-tube, titanium oxide nanotubes, boron nitride nano-tube, preferred carbon nanotube; Nano particle can be but be not limited to ferric oxide, nickel oxide, cobalt oxide, manganese oxide, cupric oxide, stannic oxide, titanium oxide and mixing thereof, or iron, cobalt, nickel, manganese, zinc, copper, gold and silver, platinum and mixing thereof, preferential oxidation iron, cobalt oxide, gold nano grain.
In the process of the technology of the present invention heated oxide mineral carbon load catalyzer grow nanowire, graphite oxide surface and the deoxidation of interlayer oxy radical, expansion obtains Graphene, heat reduction graphite oxide and catalytic growth nano wire one step complete, and prepare the nano composite material of graphene-containing, nano wire and nano particle.The method technological process is simple, and preparation nano composite material that can be a large amount of is continuously applicable to large-scale production.
Adopt the method, the preferred reaction raw materials of the element such as the presoma of the metal such as iron, cobalt, gold and siliceous, nitrogen, carbon, original position is prepared the nano composite material consisting of the nano wires such as silicon nanowires, beta-silicon nitride nanowire, carbon nanotube and Graphene, can be applicable to the fields such as lithium ion battery, ultracapacitor, solar cell, sensor, catalyzer.
Accompanying drawing explanation
Fig. 1: Graphene SEM figure prepared by graphite oxide heat reduction prepared by the technology of the present invention.
Fig. 2: the matrix material SEM figure of silicon-containing nano line prepared by the technology of the present invention and Graphene.
Fig. 3: the matrix material SEM figure of silicon-containing nano line prepared by the technology of the present invention and Graphene.
Fig. 4: the matrix material SEM figure of carbon nanotube prepared by the technology of the present invention and Graphene.
Fig. 5: the matrix material TEM figure of carbon nanotube prepared by the technology of the present invention and Graphene.
Fig. 6: the matrix material TEM figure of carbon nanotube prepared by the technology of the present invention and Graphene.
Embodiment
Under the guidance of technical solution of the present invention, Hummer method is synthesized graphite oxide, pickling process or ion exchange method are prepared the catalyzer such as graphite oxide load iron, cobalt, nickel, copper, gold, thermal evaporation and chemical Vapor deposition process are prepared the nano composite material of silicon-containing nano line and Graphene, and chemical Vapor deposition process is prepared the matrix material of carbon nanotube and Graphene.
Embodiment 1
By the 4g vitriol oil and 0.2g graphite mixing ice bath, add 0.6g potassium permanganate, stir, heating in water bath to 35 ℃, insulation 30min, add 9ml distilled water, 90 ℃ of insulation 15min, add 1ml hydrogen peroxide (concentration 30wt.%) and 5ml distilled water, centrifugal with dilute hydrochloric acid (concentration 3wt%) and distilled water, washing, prepare graphite oxide, by graphite oxide and iron nitrate, by carbon and iron atom mol ratio, be in solution to mix at 10: 1, dry, prepare graphite oxide supported ferric catalyst, press carbon and silicon mass ratio with silica flour mixes at 1: 1, in hydrogen and argon gas gas mixture, 10 ℃/min is heated to 1200 ℃, in argon gas, be incubated 60min, cooling, prepare the matrix material of silicon nanowires and Graphene.
By embodiment 1, prepare graphite oxide, in graphite oxide solution, drip ammoniacal liquor to pH=9.5, ultrasonic 15min.0.3g 2,2 '-bipy dipyridyl is added to 110ml 4 * 10
-6the aqueous solution of chloraurate of mol/ml, ultrasonic 30min.Add ammoniacal liquor to pH=10.5, ultrasonic 5min.Hydrochloro-auric acid and graphite oxide basic solution are mixed, and magnetic agitation 9h, dries, obtain graphite oxide load gold catalyst, in hydrogen and argon gas gas mixture, 10 ℃/min is heated to 700 ℃, and 100ml/min passes into silane 30min, lower the temperature, prepare the nano composite material of silicon nanowires and Graphene.
Embodiment 3
Process substantially the same manner as Example 1 is prepared graphite oxide load cobalt catalyst; press carbon and silicon mol ratio with silica flour mixes at 1: 1; in vacuum tightness 0.01 normal atmosphere, in argon shield gas, 10 ℃/min is heated to 1250 ℃; insulation 60min; lower the temperature, prepare the nano composite material of silicon nanowires and Graphene.
Embodiment 4
By embodiment 1, prepare graphite oxide supported ferric catalyst, in Ar gas, 10 ℃/min is heated to 1050 ℃, insulation 120min, under argon gas and hydrogen mixed gas, be incubated 30min, be cooled to 850 ℃, 100ml/min passes into ethylene gas, reaction 15min, in argon gas, lower the temperature, prepare the nano composite material of carbon nanotube and Graphene.
Embodiment 5
By embodiment 1, prepare graphite oxide, 10ml graphite oxide is mixed with 10ml ethanol, 0.5g ferrocene, 0.1 thiophene, ultrasonic 10min, 12ml/h injection mixed solution 45min in 1170 ℃ of argon gas, cooling, prepares carbon nanotube and graphene composite material.
Claims (1)
1. the preparation method of the nano composite material based on Graphene, it is characterized in that through step be: by the 4g vitriol oil and 0.2g graphite mixing ice bath, add 0.6g potassium permanganate, stir, heating in water bath to 35 ℃, insulation 30min, add 9mL distilled water, 90 ℃ of insulation 15min, the 1 mL hydrogen peroxide and the 5mL distilled water that add concentration 30 wt%, centrifugal with dilute hydrochloric acid and the distilled water of concentration 3wt%, washing, prepare graphite oxide, by graphite oxide and iron nitrate, by carbon and iron atom mol ratio, be in solution to mix at 10: 1, dry, prepare graphite oxide supported ferric catalyst, press carbon and silicon mass ratio with silica flour mixes at 1: 1, in hydrogen and argon gas gas mixture, 10 ℃/min is heated to 1200 ℃, in argon gas, be incubated 60min, cooling, prepare the matrix material of silicon nanowires and Graphene.
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