CN103332678A - Preparation methods of graphene and graphene-oxide compound - Google Patents
Preparation methods of graphene and graphene-oxide compound Download PDFInfo
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Abstract
The invention relates to the technical field of carbon material preparation and provides a preparation method of graphene. The preparation method comprises the following step that graphene oxide is dispersed in a solution of catechol or its derivatives and the mixed solution undergoes a hydrothermal reaction to produce the graphene having particle length and width of 10-200 microns. The invention also discloses a preparation method of a graphene-oxide compound comprising uniform-size and uniformly-dispersed oxide particles. The preparation method comprises that the graphene and an oxide precursor solution are dispersed in an aqueous solution and the mixed solution undergoes a hydrothermal reaction to produce the graphene-oxide compound. The preparation methods adopt a hydrothermal method and a water system, do not produce toxins and are environmentally friendly. The graphene has good transparency and small thickness. The graphene-oxide compound comprises the uniform-size oxide particles uniformly dispersed in the graphene, solves the problems of easy aggregation of the graphene and the oxide particles, uneven dispersion of the graphene and the oxide particles, complex preparation processes and high equipment requirements, and can be widely used in fields of supercapacitors, lithium ion batteries and electrochemical sensing.
Description
Technical field
The present invention relates to new function carbon material technical field, be specifically related to a kind of preparation method of graphene, and adopt the preparation method of the Graphene-complex oxide of this Graphene preparation.
Background technology
Graphene (Graphene) is a kind of new carbon, as a kind of carbon material of novel two-dirnentional structure, finds (Novoselov, K.S. first in 2004 by people such as Novoselov; Geim, A.K.; Morozov, S.V.; Jiang, D.; Zhang, Y.; Dubonos, S.V.; Grigorieva, I.V.; Firsov, A.A.Science2004,306,666-9).Graphene is as a kind of carbon material of novel bi-dimensional cellular shape structure, and it has good electrical conductivity (7200S/m), bigger theoretical specific surface area (2600m
2/ g), superior performance such as high mechanical stability, so caused widely and paid close attention to.
Graphene (Graphene) refers to be between the carbon atom a kind of plates that hexagonal annular is arranged, constituted by one deck carbon atom, can infinitely extend at two-dimensional space, can be described as proper two-dirnentional structure material, simultaneously, it is considered to material the thinnest on the universe, also is considered to the most solid since the dawn of human civilization material.
The method that prepare at present Graphene mainly contains: (1) mechanically peel method, and as the first time successfully making graphite linings peel off acquisition self-existent single or multiple lift Graphene by Nobel Prize in physics winner An Delie-lid nurse in 2010 and Constantine-Nuo Woxiaoluofu with the method for mechanically peel in 2004.The micromechanics stripping means is had relatively high expectations to equipment, process control, is unsuitable for producing at low cost in enormous quantities Graphene.(2) thermal expansion graphite method after ultra-sonic dispersion, solid-liquid separation and drying, is prepared multi-layer graphene (CN101746755A).This method efficient is low, output is little, can only be limited to carry out small scale experiments in the laboratory.(3) chemical Vapor deposition process, the metallic film that silicon chip or silicon chip load are adopted in correlative study work at present more is as substrate, and carbon atom deposition growing on substrate becomes Graphene (Li, X.S.et al.Science2009,324,1312; Kim, K.S.et al.Nature2009,457,706), but this method is unsuitable for developing low-cost preparation Graphene product in enormous quantities, and cost is than higher.(4) electrolytic process.This method can be synthesized a large amount of Graphenes, but the surface of the Graphene that synthesizes all has a large amount of positive ions or negative ion or organism.(5) graphene oxide reduction method, this method comprise two steps: graphite forms graphite oxide through strong oxidizer oxidations such as potassium permanganate, and graphite oxide gets Graphene through chemistry or thermal reduction.Because this method cost is lower, simple to operate, energy consumption is lower and be widely used.
Oxidation reduction process prepares the research that chemical reduction method in the Graphene prepares Graphene and has obtained positive progress, is considered to prepare the effective ways of Graphene, and the normal reductive agent that uses has at present: hydrazine hydrate, Resorcinol, the L halfcystine, xitix, sodium borohydride etc.But some is high toxicity in these reductive agents, and is perhaps inflammable, and environment and human body are had great harm, is unfavorable for personnel operation, also health of operators is constituted harm simultaneously.The Graphene of some reduction is not thorough, still the structure that has still kept graphene oxide, therefore limit it and used, and in the process of reaction, also can introduce other functional group, thereby influenced the chemical property of Graphene and Graphene/metal oxide compounds thereof.
The method of the matrix material of preparation Graphene-metal oxide mainly contains at present: (1) spraying thermal decomposed deposition method, people such as Zhang adopt spraying thermal decomposed deposition method to synthesize the mixture of Graphene/zinc oxide, this method requires relatively stricter to instrument, production cost is than higher; (2) microwave irradiation/method of radiating, people such as Yan adopt the method for microwave radiation to prepare the mixture of Graphene/tricobalt tetroxide, this method prepares fairly simple, but operation is relatively more dangerous, and nano particle can not be dispersed in the surface of Graphene uniformly in the mixture of preparation.(3) ink jet printing art method, people such as manga adopt ink jet printing art method to prepare the photoconduction conductive film mixture of Graphene/titanium dioxide, and this method is operated more loaded down with trivial details to the equipment requirements strictness.(4) molecule engrafting method, people such as tang have prepared the photoconduction conductive film of Graphene/titanium dioxide by the molecule engrafting method, and this method is to the control strictness of experiment condition, experiment poor reproducibility, operational difficulty.(5) hydrothermal method, this method is simple, and security is good, is to develop the reasonable method for preparing Graphene and metal oxide compounds at present.
In the present hydrothermal method, also have the following disadvantages, metal oxide particle occurred in the synthetic mixture and seriously reunited, Graphene is reunited, thereby distributing uniformly appears in metal oxide particle Graphene surface again, and the uneven first-class problem of the granular size of preparation has influenced its performance.Therefore, be necessary to provide a kind of Graphene and metal oxide even compound effective ways.
Summary of the invention
The objective of the invention is to overcome the drawback that the prior art for preparing Graphene need use the big organic solvent of toxicity, a kind of employing aqueous systems be provided first, and reaction temperature and, technology preparation method of graphene simple, with low cost.
Another object of the present invention be to provide a kind of adopt aqueous systems, reaction temperature and, the preparation method of finely dispersed Graphene-complex oxide, solved in prior art gained Graphene-complex oxide that Graphene is easily reunited, metal oxide particle is easily reunited, both disperse inhomogeneous, the inhomogenous problem of granular size.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of graphene may further comprise the steps:
(1) preparation Graphene:
Take by weighing a certain amount of catechol or catechol derivatives, be dissolved in and obtain the catechol or derivatives thereof solution that mass concentration is 0.05g/ml in the solvent, graphene oxide is ground to form powder, taking by weighing a certain amount of graphene oxide powder joins in the solution of catechol or derivatives thereof, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 0.5～4h, dispersion liquid is changed in the autoclave, autoclave is placed hydro-thermal reaction 12～48h under 80～200 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.
Catechol derivatives described in the step (2) is one of Dopamine HCL, alpha-methyldopa amine, dopa; Described solvent is one or more in water, methyl alcohol, ethanol, Virahol, formic acid, the acetic acid.
The mass ratio of the graphene oxide described in the step (2) and catechol or derivatives thereof is 1: 0.1～1: 10.
Adopt above-mentioned Graphene to prepare the method for Graphene-complex oxide, may further comprise the steps:
(a) take by weighing a certain amount of oxide precursor, being dissolved in and obtaining mass concentration in the solvent is 0.15～0.4g/ml oxide precursor liquid solution, and the Graphene of above-mentioned steps (2) gained is ground to form powder, takes by weighing a certain amount of Graphene powder;
(b) load weighted Graphene powder is added in the oxide precursor liquid solution, mix, ultra-sonic dispersion 0.5～4h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 12～72h under 120～200 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains Graphene-complex oxide.
Oxide compound described in the step (a) is ZrO
2, TiO
2, SiO
2, SnO
2, MnO
2, Co
3O
4One of or NiO.
Oxide precursor described in the step (a) is five nitric hydrate zirconiums, eight hydration zirconium oxychlorides, zirconium iso-propoxide and tetrabutyl zirconate, tetraethoxy, vinyltriethoxysilane, γ-glycidyl ether propyl trimethoxy silicane, tetrabutyl titanate, titanium tetrachloride, Titanium Nitrate, tin tetrachloride, stannous oxalate, manganese acetate, manganous sulfate, cobalt dichloride, Xiao Suangu, one of nickel hydroxide.
Solvent described in the step (a) is any one or a few in water, ethanol, the Virahol.
The mass ratio of described Graphene and oxide precursor is 1: 0.1～1: 90.
Graphene/metal oxide compounds can be widely used in fields such as lithium ion battery, ultracapacitor and electrochemical sensing.
Beneficial effect of the present invention is as follows:
(1) the present invention adopt hydrothermal method with catechol and derivative thereof as reductive agent, the graphene oxide reduction is made Graphene, utilize in catechol and the derivative thereof hydroxyl easily and hydroxyl, carboxyl effect on the graphene oxide, make and form π-pi-conjugated between the phenyl ring of catechol and derivative thereof and the graphene oxide, thereby can make graphene oxide under the environment of hydro-thermal, occur peeling off layer by layer, prepare abundant, the thinner and transparent good Graphene of reduction reaction.
(2) catechol and the derivative thereof of the present invention's employing, it is a kind of organic phenols that is present in a large number in fruit and the vegetables, the source is abundant, and cost is low, and it is to carry out in the solution of the water of catechol and derivative thereof or alcohol, acid that the present invention simultaneously prepares Graphene, adopt aqueous systems to prepare Graphene first, reaction temperature and, it is lower to consume energy, output is higher, and sufficient reacting, avoided using the big organic solvent of toxicity.
(3) Graphene-complex oxide of the present invention's preparation, be that Graphene is joined in the water, alcoholic solution of oxide precursor, adopt reaction temperature and hydro-thermal reaction, environmental friendliness, technology is simple, green safety avoids using toxicity or inflammable organic liquid, thereby avoids bringing very big threat to experimenter's safety.
(4) Graphene-complex oxide of the present invention's preparation, the oxide nano particles size evenly and uniformly is dispersed on the Graphene.
(5) Graphene of gained of the present invention-complex oxide excellent property can be widely used in fields such as lithium ion battery, ultracapacitor and electrochemical sensing.
Below in conjunction with accompanying drawing and embodiment, the present invention is further described.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the Graphene of embodiment 1 gained;
Fig. 2 is the transmission electron microscope picture of the mixture of embodiment 9 gained Graphene-zirconium dioxides.
Embodiment
Embodiment 1:
See also Fig. 1, the invention provides a kind of preparation method of graphene, may further comprise the steps: (1) preparation Graphene:
Take by weighing a certain amount of catechol or catechol derivatives, be dissolved in and obtain the catechol or derivatives thereof solution that mass concentration is 0.05g/ml in the solvent, graphene oxide is ground to form powder, taking by weighing a certain amount of graphene oxide powder joins in the solution of catechol or derivatives thereof, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 0.5～4h, dispersion liquid is changed in the autoclave, autoclave is placed hydro-thermal reaction 12～48h under 80～200 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.
Catechol derivatives described in the step (2) is one of Dopamine HCL, alpha-methyldopa amine, dopa; Described solvent is one or more in water, methyl alcohol, ethanol, Virahol, formic acid, the acetic acid.
The mass ratio of the graphene oxide described in the step (2) and catechol or derivatives thereof is 1: 0.1～1: 10.
Adopt above-mentioned Graphene to prepare the method for Graphene-complex oxide, may further comprise the steps:
(a) take by weighing a certain amount of oxide precursor, being dissolved in and obtaining mass concentration in the solvent is 0.15～0.4g/ml oxide precursor liquid solution, and the Graphene of above-mentioned steps (2) gained is ground to form powder, takes by weighing a certain amount of Graphene powder;
(b) load weighted Graphene powder is added in the oxide precursor liquid solution, mix, ultra-sonic dispersion 0.5～4h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 12～72h under 120～200 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains Graphene-complex oxide.
Oxide compound described in the step (a) is ZrO
2, TiO
2,SiO
2,SnO
2,MnO
2, Co
3O
4One of or NiO.
Oxide precursor described in the step (a) is five nitric hydrate zirconiums, eight hydration zirconium oxychlorides, zirconium iso-propoxide and tetrabutyl zirconate, tetraethoxy, vinyltriethoxysilane, γ-glycidyl ether propyl trimethoxy silicane, tetrabutyl titanate, titanium tetrachloride, Titanium Nitrate, tin tetrachloride, stannous oxalate, manganese acetate, manganous sulfate, cobalt dichloride, Xiao Suangu, one of nickel hydroxide.
Solvent described in the step (a) is any one or a few in water, ethanol, the Virahol.
The mass ratio of described Graphene and oxide precursor is 1: 0.1～1: 90.
Graphene/metal oxide compounds can be widely used in fields such as lithium ion battery, ultracapacitor and electrochemical sensing.
Embodiment 2:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, substantially the same manner as Example 1, its difference is:
Described preparation method of graphene realizes as follows:
(1) graphite oxidation:
Under ice-water bath-4 ℃, 3g graphite and 1.5g SODIUMNITRATE are joined in the 500ml there-necked flask, under agitation slowly add 120mL massfraction 98% vitriol oil and 18g potassium permanganate successively, be warming up to then under 35 ℃ of waters bath with thermostatic control and stir 0.5h, slowly add the dilution of 140mL deionized water again, stirred 10 minutes, add 120ml60 ℃ hot water, continue again to stir 10 minutes, add the H of 30mL massfraction 30%
2O
2, leave standstill after-filtration, fully washing leaching cake washs to neutral, then filter cake is dispersed in the water, ultrasonic 6h, 45 ℃ of following vacuum-dryings obtain graphene oxide.
(2) preparation Graphene:
Take by weighing a certain amount of catechol and be dissolved in formic acid, obtaining mass concentration is the catechol solution of 0.05g/ml, the graphene oxide of step (1) gained is ground to form powder, take by weighing a certain amount of graphene oxide powder, make that the mass ratio of graphene oxide and catechol is 1: 0.1, join in the catechol solution, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 0.5h changes dispersion liquid in the autoclave over to, and autoclave is placed hydro-thermal reaction 24h under 80 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.Characterize through transmission electron microscope(TEM), obtained large stretch of large-area Graphene, Graphene is thinner, and is very transparent, and reduction very abundant obtains the Graphene that large stretch of and length and width dimensions reach the 10-200 micron.
Embodiment 3:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, with embodiment 1,2 basic identical, its difference is:
A kind of preparation method of graphene, realize as follows:
(1) graphite oxidation:
Under ice-water bath-4～0 ℃, 4g graphite and 2g SODIUMNITRATE are joined in the 500ml there-necked flask, under agitation slowly add 150mL massfraction 98% vitriol oil and 12g potassium permanganate successively, be warming up to then under 35 ℃ of waters bath with thermostatic control and stir 1h, slowly add the dilution of 160mL deionized water again, stirred 10 minutes, add 160ml60 ℃ hot water, continue again to stir 10 minutes, add the H of 22.75mL massfraction 30%
2O
2, leave standstill after-filtration, fully washing leaching cake washs to neutral, then filter cake is dispersed in the water, ultrasonic 6h, 45 ℃ of following vacuum-dryings obtain graphene oxide.
(2) preparation Graphene:
It is water-soluble to take by weighing a certain amount of Dopamine HCL, obtain the aqueous solution that mass concentration is the Dopamine HCL of 0.05g/ml, the graphene oxide of step (1) gained is ground to form powder, take by weighing a certain amount of graphene oxide powder, make that the mass ratio of graphene oxide and catechol is 1: 5, join in the aqueous solution of Dopamine HCL, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 4h changes dispersion liquid in the autoclave over to, and autoclave is placed hydro-thermal reaction 12h under 200 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.
Embodiment 4:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, all basic identical with embodiment 1,2,3, its difference is:
A kind of preparation method of graphene, realize as follows:
(1) graphite oxidation:
Under 0 ℃ of ice-water bath, 3.5g graphite and 1.5g SODIUMNITRATE are joined in the 500ml there-necked flask, under agitation slowly add 135mL massfraction 98% vitriol oil and 9g potassium permanganate successively, be warming up to then under 35 ℃ of waters bath with thermostatic control and stir 0.75h, slowly add the dilution of 140mL deionized water again, stirred 10 minutes, the hot water that adds 140ml60 ℃ continues to stir 10 minutes again, adds the H2O2 of 22.5mL massfraction 30%, leave standstill after-filtration, fully washing leaching cake washs to neutral, then filter cake is dispersed in the water, ultrasonic 6h, 45 ℃ of following vacuum-dryings obtain graphene oxide.
(2) preparation Graphene:
Take by weighing a certain amount of alpha-methyldopa amine and be dissolved in ethanol, obtain the alcoholic solution of mass concentration 0.05g/ml alpha-methyldopa amine, the graphene oxide of step (1) gained is ground to form powder, take by weighing a certain amount of graphene oxide powder, make that the mass ratio of graphene oxide and catechol is 1: 10, join in the alcoholic solution of alpha-methyldopa amine, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 2.3h changes dispersion liquid in the autoclave over to, and autoclave is placed hydro-thermal reaction 48h under 140 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.
Embodiment 5:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, all basic identical with embodiment 1,2,3,4, its difference is:
A kind of preparation method of graphene, realize as follows:
(1) graphite oxidation:
Under ice-water bath-4～0 ℃, 3g graphite and 1.75g SODIUMNITRATE are joined in the 500ml there-necked flask, under agitation slowly add 150mL massfraction 98% vitriol oil and 14g potassium permanganate successively, be warming up to then under 35 ℃ of waters bath with thermostatic control and stir 1h, slowly add the dilution of 120mL deionized water again, stirred 10 minutes, add 160ml60 ℃ hot water, continue again to stir 10 minutes, add the H of 22.5mL massfraction 30%
2O
2, leave standstill after-filtration, fully washing leaching cake washs to neutral, then filter cake is dispersed in the water, ultrasonic 6h, 45 ℃ of following vacuum-dryings obtain graphene oxide.
(2) preparation Graphene:
Take by weighing a certain amount of catechol and be dissolved in formic acid, obtaining mass concentration is the catechol solution of 0.05g/ml, the graphene oxide of step (1) gained is ground to form powder, take by weighing a certain amount of graphene oxide powder, make that the mass ratio of graphene oxide and catechol is 1: 10, join in the catechol solution, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 2h changes dispersion liquid in the autoclave over to, and autoclave is placed hydro-thermal reaction 48h under 180 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.
Embodiment 6:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, with embodiment 1,2,3,4,5 basic identical, its difference is:
A kind of preparation method of Graphene-oxide compound, realize as follows:
(a) it is water-soluble to take by weighing a certain amount of five nitric hydrate zirconiums, obtaining mass concentration is the 0.2g/ml zirconium nitrate aqueous solution, to grind to form powder according to the Graphene of embodiment 5 gained, and take by weighing a certain amount of Graphene powder, the mass ratio that makes Graphene and five nitric hydrate zirconiums is 1: 0.1.
(b) load weighted Graphene is joined in the zirconium nitrate aqueous solution, mix, ultra-sonic dispersion 2h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 18h under 140 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains Graphene-complex oxide.Characterize through transmission electron microscope(TEM), obtained the mixture of large stretch of large-area Graphene/zirconium dioxide.
Embodiment 7:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, all basic identical with embodiment 1,2,3,4,5,6, its difference is:
A kind of preparation method of Graphene-oxide compound, realize as follows:
(a) take by weighing a certain amount of tin tetrachloride and be dissolved in ethanol, obtaining mass concentration is 0.15g/ml tin tetrachloride alcoholic solution, to grind to form powder according to the Graphene of embodiment 5 gained, and take by weighing a certain amount of Graphene powder, the mass ratio that makes Graphene and tin tetrachloride is 1: 45.
(b) load weighted Graphene is joined in the zirconium nitrate aqueous solution, mix, ultra-sonic dispersion 1h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 27h under 160 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains Graphene-complex oxide.
Embodiment 8:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, with embodiment 1,2,3,4,5,6,7 basic identical, its difference is:
A kind of preparation method of Graphene-oxide compound, realize as follows:
(a) it is water-soluble to take by weighing a certain amount of tetraethoxy, obtaining mass concentration is the 0.2g/ml tetraethoxy aqueous solution, to grind to form powder according to the Graphene of embodiment 5 gained, and take by weighing a certain amount of Graphene powder, the mass ratio that makes Graphene and tetraethoxy is 1: 80.
(b) load weighted Graphene is joined in the zirconium nitrate aqueous solution, mix, ultra-sonic dispersion 3h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 48h under 200 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains the mixture of Graphene/silicon-dioxide.
Embodiment 9:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, all basic identical with embodiment 1,2,3,4,5,6,7,8, its difference is:
A kind of preparation method of Graphene-oxide compound realizes as follows:
(a) it is water-soluble to take by weighing a certain amount of eight hydration zirconium oxychlorides, obtaining mass concentration is the 0.4g/ml zirconium oxychloride aqueous solution, to grind to form powder according to the Graphene of embodiment 5 gained, and take by weighing a certain amount of Graphene powder, the mass ratio that makes Graphene and eight hydration zirconium oxychlorides is 1: 0.1.
(b) load weighted Graphene is joined in the zirconium nitrate aqueous solution, mix, ultra-sonic dispersion 0.5h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 24h under 120 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains the mixture of Graphene/zirconium dioxide.Characterize through transmission electron microscope(TEM), obtained large stretch of large-area mixture.
Embodiment 10:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, basic identical with one of embodiment 1-9, its difference is:
A kind of preparation method of Graphene-oxide compound realizes as follows:
(a) it is water-soluble to take by weighing a certain amount of manganese acetate, and obtaining mass concentration is the 0.25g/ml manganese acetate aqueous solution, will grind to form powder according to the Graphene of embodiment 5 gained, takes by weighing a certain amount of Graphene powder, and the mass ratio that makes Graphene and manganese acetate is 1: 25.
(b) load weighted Graphene is joined in the manganese acetate aqueous solution, mix, ultra-sonic dispersion 2h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 12h under 200 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains the mixture of Graphene/Manganse Dioxide.
Embodiment 11:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, all basic identical with embodiment 1-10, its difference is:
A kind of preparation method of Graphene-oxide compound realizes as follows:
(a) take by weighing a certain amount of cobalt chloride and be dissolved in Virahol, obtaining mass concentration is 0.2g/ml cobalt chloride alcoholic solution, will grind to form powder according to the Graphene of embodiment 5 gained, takes by weighing a certain amount of Graphene powder, and the mass ratio that makes Graphene and cobalt chloride is 1: 60.
(b) load weighted Graphene is joined in the cobalt chloride alcoholic solution, mix, ultra-sonic dispersion 3h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 42h under 180 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains the mixture of Graphene/cobalt dioxide.
Embodiment 12:
The preparation Graphene that present embodiment provides and the preparation method of Graphene-complex oxide, all basic identical with embodiment 1-11, its difference is:
A kind of preparation method of Graphene-oxide compound, realize as follows:
(a) take by weighing a certain amount of tetrabutyl titanate and be dissolved in ethanol, obtaining mass concentration is the tetrabutyl titanate alcoholic solution of 0.3g/ml, to grind to form powder according to the Graphene of embodiment 5 gained, and take by weighing a certain amount of Graphene powder, the mass ratio that makes Graphene and tetrabutyl titanate is 1: 90.
(b) load weighted Graphene is joined in the tetrabutyl titanate alcoholic solution, mix, ultra-sonic dispersion 4h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 72h under 180 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains the mixture of Graphene/titanium dioxide.
Although described embodiment and accompanying drawing have been described the present invention in detail, itself should not be considered to limitation of the present invention.The present invention is not limited to above-mentioned embodiment, adopt same as the previously described embodiments or similar raw material and preparation method or to the institute within its described context change, equivalents and improved preparation method, all within protection scope of the present invention.
Claims (9)
1. a preparation method of graphene is characterized in that, may further comprise the steps:
(1) preparation Graphene:
Take by weighing a certain amount of catechol or catechol derivatives, be dissolved in and obtain the catechol or derivatives thereof solution that mass concentration is 0.05g/ml in the solvent, graphene oxide is ground to form powder, taking by weighing a certain amount of graphene oxide powder joins in the solution of catechol or derivatives thereof, after magnetic agitation is uniformly dispersed, ultra-sonic dispersion 0.5～4h, dispersion liquid is changed in the autoclave, autoclave is placed hydro-thermal reaction 12～48h under 80～200 ℃ of water-baths, with sample filtering, washing, vacuum-drying obtains Graphene.
2. preparation method of graphene according to claim 1 is characterized in that, the catechol derivatives described in the step (2) is one of Dopamine HCL, alpha-methyldopa amine, dopa; Described solvent is one or more in water, methyl alcohol, ethanol, Virahol, formic acid, the acetic acid.
3. preparation method of graphene according to claim 1 is characterized in that, the mass ratio of the graphene oxide described in the step (2) and catechol or derivatives thereof is 1: 0.1～1: 10.
4. adopt one of claim 1～3 described Graphene to prepare the method for Graphene-complex oxide, it is characterized in that, may further comprise the steps:
(a) take by weighing a certain amount of oxide precursor, being dissolved in and obtaining mass concentration in the solvent is 0.15～0.4g/ml oxide precursor liquid solution, and the Graphene of above-mentioned steps (2) gained is ground to form powder, takes by weighing a certain amount of Graphene powder;
(b) load weighted Graphene powder is added in the oxide precursor liquid solution, mix, ultra-sonic dispersion 0.5～4h, then dispersion liquid is transferred in the autoclave, autoclave is placed hydro-thermal reaction 12～72h under 120～200 ℃ of water-baths, with sample suction filtration, absolute ethanol washing, vacuum-drying obtains Graphene-complex oxide.
5. the preparation method of Graphene-complex oxide according to claim 4 is characterized in that, the oxide compound described in the step (a) is ZrO
2, TiO
2,SiO
2,SnO
2,MnO
2, Co
3O
4One of or NiO.
6. the preparation method of Graphene-complex oxide according to claim 4, it is characterized in that, oxide precursor described in the step (a) is five nitric hydrate zirconiums, eight hydration zirconium oxychlorides, zirconium iso-propoxide and tetrabutyl zirconate, tetraethoxy, vinyltriethoxysilane, γ-glycidyl ether propyl trimethoxy silicane, tetrabutyl titanate, titanium tetrachloride, Titanium Nitrate, tin tetrachloride, stannous oxalate, manganese acetate, manganous sulfate, cobalt dichloride, Xiao Suangu, one of nickel hydroxide.
7. the preparation method of Graphene-complex oxide according to claim 4 is characterized in that, the solvent described in the step (a) is any one or a few in water, ethanol, the Virahol.
8. the preparation method of Graphene-complex oxide according to claim 4 is characterized in that, the mass ratio of described Graphene and oxide precursor is 1: 0.1～1: 90.
9. the preparation method of Graphene/metal oxide compounds according to claim 4 is characterized in that, Graphene/metal oxide compounds can be widely used in fields such as lithium ion battery, ultracapacitor and electrochemical sensing.
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