CN102530931A - 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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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 the nano material preparation technical field.
Background technology
As everyone knows; One-dimensional nano line and two-dimentional Graphene have performances such as the electricity, light, magnetic, heat of high-specific surface area and many and its structure and morphologic correlation; Utilize the 26S Proteasome Structure and Function characteristic of Graphene and nano wire; Carry out the design of structure composite design, function composite design and compound method, can prepare and have 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 the stratiform sandwich structure; The silicon nano of 2-50nm uniformly is scattered here and there on the every lamella of Graphene; Separate by silicon nano in the middle of the adjacent Graphene lamella, and the lamella overlapping edges together, constitutes uniform stratiform conductive network structure.CN201110067559.2 discloses a kind of field-causing electron emtting cathode 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.Employing the present invention technology; Can select multiple catalytic metal such as iron, cobalt, gold on Graphene, to grow 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, have multifunctional nano composite materials such as electricity, light, magnetic, heat, can be applicable to fields such as lithium ion battery, ultracapacitor, solar cell, transmitter, catalysis.
The present invention provides a kind of nano composite material graphitiferous alkene and nano wire based on Graphene; Situ catalytic grow nanowire on the Graphene; The preparation method is heated oxide graphite and metal catalytic agent composition; Graphite oxide is reduced into Graphene, and metallic particles catalytic growth nano wire, one-step synthesis go out nano wire and graphene nano matrix material.
Described nano wire comprises solid nano wire and hollow Nano pipe; Solid nano wire comprises silicon, silit, silicon oxide, silica carbon, silicon nitride, SP 1, 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; With metal load on graphite oxide; Become in the Graphene process to add reaction raw materials at heating reduction-oxidation graphite; The metal nanoparticle that utilizes the Graphene surface to form, situ catalytic grows nano wire, prepares the nano composite material of nano wire and Graphene.
Described graphite oxide adopts the chemical oxidization method preparation, and the graphite oxide surface and the interlayer of this method preparation 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, preferred iron, cobalt, nickel, copper, gold.
Described metal load is that metal-salt is directly mixed or IX in liquid phase with graphite oxide in the mode on the graphite oxide.Directly mixing is to utilize graphite oxide surface hydroxyl, carboxyl, epoxy isoreactivity group to combine with metals ion; IX is in graphite oxide solution, to add basic soln such as ammoniacal liquor, utilizes the graphite oxide surface active groups that ammonia radical ion is adsorbed on the graphite oxide, and presoma metals ion displacement ammonia radical ion loads on the graphite oxide.Adopt aforesaid method, can be on graphite oxide, like iron, cobalt, nickel, manganese, zinc, copper, gold and silver, platinum, titanium, tin etc. with metal load commonly used.
Described heating reduction-oxidation graphite is heated oxide graphite, and deoxidation expand into graphene film.
Described reaction raw materials is siliceous at least, the precursor of a kind of element in the carbon, nitrogen, boron, zinc, titanium, manganese, and reaction raw materials is grow nanowire under the heating of metal katalysis.
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 methods that prepare nano wire commonly used, and general nano wire can both be used this prepared in one of two ways.
Described thermal evaporation is an example with the grow silicon nanowires, 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; With the carbon nano-tube is 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, and the 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 preferred temperature is 800-1200 ℃.
Adopt the technology of to invent, can prepare by Graphene, constitute nano composite material, can also prepare the matrix material that nano particle and Graphene are formed, also can prepare the matrix material that constitutes 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 multiple metal nanoparticle on the 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, silit, silicon oxide, silica carbon, silicon nitride, SP 1, 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 red stone, nickel oxide, powder blue, manganese oxide, cupric oxide, White tin oxide, titanium oxide and mixing thereof; Or iron, cobalt, nickel, manganese, zinc, copper, gold and silver, platinum and mixing thereof, preferred red stone, powder blue, gold nano grain.
In the process of the present invention's technology heated oxide mineral carbon load catalyzer grow nanowire; Graphite oxide surface and the deoxidation of interlayer oxy radical; Expansion obtains Graphene; Heating reduction-oxidation graphite and one step of catalytic growth nano wire accomplish, and prepare the nano composite material of graphitiferous alkene, nano wire and nano particle.This method technological process is simple, can a large amount of continuously preparation nano composite material, be fit to large-scale production.
Adopt this method; The preferred reaction raw materials of element such as the presoma of metals such as iron, cobalt, gold and siliceous, nitrogen, carbon; In-situ preparing goes out the nano composite material that is made up of nano wires such as silicon nanowires, beta-silicon nitride nanowire, carbon nanotube and Graphene, can be applicable to fields such as lithium ion battery, ultracapacitor, solar cell, transmitter, catalyzer.
Description of drawings
Fig. 1: the graphite oxide of the present invention's technology preparation adds the Graphene SEM figure of thermal reduction preparation.
Fig. 2: the matrix material SEM figure that contains silicon nanowires and Graphene of the present invention's technology preparation.
Fig. 3: the matrix material SEM figure that contains silicon nanowires and Graphene of the present invention's technology preparation.
Fig. 4: the carbon nanotube of the present invention's technology preparation and the matrix material SEM figure of Graphene.
Fig. 5: the carbon nanotube of the present invention's technology preparation and the matrix material TEM figure of Graphene.
Fig. 6: the carbon nanotube of the present invention's technology preparation and the matrix material TEM figure of Graphene.
Embodiment
Under the guidance of technical scheme of the present invention; The Hummer method is synthesized graphite oxide; Pickling process or ion exchange method prepare catalyzer such as graphite oxide load iron, cobalt, nickel, copper, gold; Thermal evaporation and chemical Vapor deposition process are prepared the nano composite material that contains silicon nanowires and Graphene, and chemical Vapor deposition process is prepared the matrix material of carbon nanotube and Graphene.
Embodiment 1
With 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 adds 9ml zero(ppm) water; 90 ℃ of insulation 15min add 1ml ydrogen peroxide 50 (concentration 30wt.%) and 5ml zero(ppm) water, with Hydrogen chloride (concentration 3wt%) with zero(ppm) water is centrifugal, wash; Preparing graphite oxide, is in solution to mix drying at 10: 1 with graphite oxide and iron nitrate by carbon and iron atom mol ratio; Prepare the graphite oxide supported ferric catalyst, press carbon and silicon mass ratio 1: 1 and mix with silica flour, 10 ℃/min is heated to 1200 ℃ in hydrogen and argon gas gas mixture; Be incubated 60min in the argon gas, lower the temperature, prepare the matrix material of silicon nanowires and Graphene.
Prepare graphite oxide by embodiment 1, in graphite oxide solution dropping ammonia to pH=9.5, ultrasonic 15min.0.3g 2,2 '-bipy dipyridyl is added 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 soln are mixed magnetic agitation 9h, oven dry; Obtain the graphite oxide load gold catalyst, 10 ℃/min is heated to 700 ℃ in hydrogen and argon gas gas mixture, and 100ml/min feeds silane 30min; Lower the temperature, prepare the nano composite material of silicon nanowires and Graphene.
Embodiment 3
Prepare the graphite oxide load cobalt catalyst with embodiment 1 essentially identical process; Pressing carbon and silicon mol ratio 1: 1 mixes with silica flour; 10 ℃/min is heated to 1250 ℃ in the argon shield gas in vacuum tightness 0.01 normal atmosphere; Insulation 60min lowers the temperature, and prepares the nano composite material of silicon nanowires and Graphene.
Embodiment 4
Press embodiment 1 preparation graphite oxide supported ferric catalyst, 10 ℃/min is heated to 1050 ℃ in Ar gas, insulation 120min; Insulation 30min under argon gas and hydrogen mixed gas; Be cooled to 850 ℃, 100ml/min feeds ethylene gas, reaction 15min; Lower the temperature in the argon gas, prepare the nano composite material of carbon nanotube and Graphene.
Embodiment 5
Prepare graphite oxide by embodiment 1, the 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, carbon nanotube and graphene composite material are prepared in cooling.
Claims (10)
1. the nano composite material based on Graphene is characterized in that, with metal catalyst and graphite oxide Hybrid Heating situ catalytic grow nanowire, graphite oxide is reduced into Graphene, forms the nano composite material of nano wire and Graphene.
2. by the said nano composite material of claim 1, it is characterized in that described nano wire comprises solid nano wire and hollow Nano pipe.
3. by the described nano composite material of claim 2; It is characterized in that described solid nano wire comprises silicon, silit, silicon oxide, silicon oxide carbide, silicon nitride, SP 1, zinc oxide, titanium oxide, manganese oxide nano wire and mixing thereof, described hollow Nano pipe comprises carbon nanotube, nano-tube, titanium oxide nanotubes, boron nitride nano-tube.
4. by the described preparation method of claim 1, it is characterized in that described metal catalyst is iron, cobalt, nickel, copper, gold and silver, platinum.
5. one kind based on nano composite material of Graphene and preparation method thereof; It is characterized in that; Liquid-phase mixing graphite oxide and metal precursor on graphite oxide, become metal load in the Graphene process to add reaction raw materials at heating reduction-oxidation graphite; Metal catalytic grows nano wire, prepares the nano composite material of nano wire and Graphene.
6. by the described preparation method of claim 5, it is characterized in that described reaction raw materials is the presoma of one or more elements in siliceous, carbon, nitrogen, boron, zinc, titanium, the manganese, reaction raw materials is through thermal evaporation or chemical vapor deposition growth nano wire.
7. by the described preparation method of claim 5, it is characterized in that described metal precursor is directly mixed or IX loads on metals ion on the graphite oxide in liquid phase.
8. the preparation method of the described nano composite material based on Graphene of a claim 1; It is characterized in that with graphite metal-salt and graphite oxide being mixed in liquid phase, prepare the metal catalyst of graphite oxide load for the raw material chemical oxidization method prepares graphite oxide; Heating reduction-oxidation graphite becomes Graphene; Add carbon source or silicon source in the process, the metal catalytic grow nanowire forms the nano composite material that Graphene and nano wire constitute.
9. by the described method of claim 8, it is characterized in that described chemical oxidization method prepares graphite oxide, described Heating temperature is 300-1400 ℃, preferred 800-1200 ℃.
10. by the described method of claim 8, it is characterized in that described carbon source preferred alcohol, acetone, methane, ethene, the preferred elemental silicon in silicon source, silicon oxide, silane; Described metal catalyst is iron, cobalt, nickel, copper, gold; Described nano wire is carbon nanotube, silicon nanowires, silica white nano-wire, silicon carbide nanometer line.
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