CN103332678B - The preparation method of Graphene and Graphene-complex oxide - Google Patents
The preparation method of Graphene and Graphene-complex oxide Download PDFInfo
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Abstract
The present invention relates to carbon material fabricating technology field, provide a kind of preparation method of Graphene, comprise the following steps (1) to be scattered in by graphene oxide in the solution of catechol and derivative thereof, hydro-thermal reaction obtains the Graphene that length and width dimensions reach 10-200 micron.The invention also discloses the even and preparation method of finely dispersed Graphene-complex oxide of oxide particle size, by Graphene and oxide precursor Solution Dispersion in aqueous, hydro-thermal reaction obtains Graphene-complex oxide.The present invention adopts hydrothermal method and aqueous systems, nontoxic, environmental protection, and the Graphene transparency of preparation is good, thinner; Obtained Graphene-oxide compound, granular size is homogeneous and be dispersed in Graphene, the problem such as solve Graphene and oxide particle is easily reunited, both disperse uneven and complicated process of preparation, equipment requirements is high, its goods can be applied in the fields such as ultracapacitor, lithium ion battery, electrochemical sensing widely.
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 the preparation method of the Graphene-complex oxide adopting this Graphene to prepare.
Background technology
Graphene (Graphene) is a kind of new carbon, as a kind of carbon material of New Two Dimensional structure, by people such as Novoselov in Late Cambrian (Novoselov, K.S. in 2004; 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 electroconductibility (7200S/m), larger theoretical specific surface area (2600m
2/ g), the superior performance such as high mechanical stability, therefore cause and pay close attention to widely.
Graphene (Graphene) refers to a kind of plates of the arrangement in hexagonal annular between carbon atom, be made up of one deck carbon atom, infinitely can extend at two-dimensional space, can be described as proper two-dirnentional structure material, simultaneously, it is considered to material the thinnest on universe, is also considered to material the most solid since the dawn of human civilization.
The method preparing Graphene at present mainly contains: (1) mechanically peel method, obtains self-existent single or multiple lift Graphene as successfully made graphite linings peel off by Nobel Prize in physics winner An Delie-lid nurses in 2010 and Constantine-Nuo Woxiaoluofu with the method first time of mechanically peel in 2004.Micromechanics stripping means is higher to equipment, process control requirements, is unsuitable for producing Graphene at low cost in enormous quantities.(2) thermal expansion graphite method, after ultrasonic disperse, solid-liquid separation and drying, prepares multi-layer graphene (CN101746755A).The method efficiency is low, output is little, can only be limited in laboratory and carry out small scale experiments.(3) chemical Vapor deposition process, the metallic film of current correlative study work many employings silicon chip or silicon chip load is as substrate, and carbon atom grows into Graphene (Li, X.S.etal.Science2009,324,1312 at deposited on substrates; Kim, K.S.etal.Nature2009,457,706), but the method is unsuitable for developing low cost in enormous quantities prepares graphene product, and cost compare is high.(4) electrolytic process.This method can synthesize a large amount of Graphenes, but the surface of the Graphene synthesized is all with a large amount of positive ions or negative ion or organism.(5) graphene oxide reduction method, the method comprises two steps: graphite forms graphite oxide through strong oxidizer oxidations such as potassium permanganate, and graphite oxide obtains Graphene through chemistry or thermal reduction.Because the method cost is lower, simple to operate, energy consumption is lower and be widely used.
The research that the oxidation reduction process chemical reduction method prepared in Graphene prepares Graphene has achieved positive progress, is considered to the effective ways preparing Graphene, and the normal reductive agent used has at present: hydrazine hydrate, Resorcinol, L halfcystine, xitix, sodium borohydride etc.But in these reductive agents, some is high toxicity, or inflammable, has great harm, be unfavorable for human users to environment and human body, simultaneously also to the healthy formation harm of operator.The Graphene of some reduction is not thorough, still the structure of graphene oxide is still remained, use because which limit it, and also can introduce other functional group in the process of reaction, thus affect the chemical property of Graphene and graphene/metal oxide mixture thereof.
The method preparing the matrix material of Graphene-metal oxide at present mainly contains: (1) spray-wall interaction sedimentation, the people such as the Zhang mixture of Graphene/zinc oxide that adopted spray-wall interaction sedimentation to synthesize, this method is relatively stricter to instrument requirements, and production cost is higher; (2) microwave irradiation/method of radiating, the people such as the Yan mixture of Graphene/tricobalt tetroxide that adopted the method for microwave radiation to prepare, this legal system is for fairly simple, but operation is more dangerous, and in the mixture of preparation, nano particle can not be dispersed in the surface of Graphene uniformly.(3) Ink Jet Printing method, the people such as manga have adopted Ink Jet Printing legal system for the photoconductive films mixture of Graphene/titanium dioxide, and this method is strict to equipment requirements, operates more loaded down with trivial details.(4) molecule engrafting method, the people such as tang have prepared the photoconductive films of Graphene/titanium dioxide by molecule engrafting method, and this method is strict to the control of experiment condition, experiment poor reproducibility, operational difficulty.(5) hydrothermal method, the method is simple, and security is good, is to develop the reasonable method preparing Graphene and metal oxide compounds at present.
In current hydrothermal method, also have the following disadvantages, in the mixture of synthesis, occurred metal oxide particle serious agglomeration, Graphene is reunited, thus metal oxide particle can not occur uniform distribution by graphenic surface again, the uneven first-class problem of granular size of preparation, have impact on its performance.Therefore, the effective ways that a kind of Graphene and the even compound of metal oxide are provided are necessary.
Summary of the invention
The object of the invention is to overcome prior art and prepare the drawback that Graphene needs to use the organic solvent that toxicity is large, provide first and a kind ofly adopt aqueous systems, and reaction temperature and, the preparation method of technique 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, solve that Graphene in prior art gained Graphene-complex oxide is easily reunited, metal oxide particle is easily reunited, both dispersions are uneven, the inhomogenous problem of granular size.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for Graphene, comprises the following steps:
(1) Graphene is prepared:
Take a certain amount of catechol or catechol derivatives, be dissolved in solvent and obtain the catechol or derivatives thereof solution that mass concentration is 0.05g/ml, graphene oxide is ground to form powder, taking a certain amount of graphene oxide powder joins in the solution of catechol or derivatives thereof, after magnetic agitation is uniformly dispersed, ultrasonic disperse 0.5 ~ 4h, dispersion liquid is proceeded in autoclave, autoclave is placed in hydro-thermal reaction 12 ~ 48h under 80 ~ 200 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtains Graphene.
Catechol derivatives described in 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, acetic acid.
The mass ratio of the graphene oxide described in 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, comprise the following steps:
A () takes a certain amount of oxide precursor, being dissolved in solvent and obtaining mass concentration is 0.15 ~ 0.4g/ml oxide precursor liquid solution, the Graphene of above-mentioned steps (2) gained is ground to form powder, takes a certain amount of graphene powder;
B load weighted Graphene powder adds in oxide precursor liquid solution by (), be uniformly mixed, ultrasonic disperse 0.5 ~ 4h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 12 ~ 72h under 120 ~ 200 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains Graphene-complex oxide.
Oxide compound described in step (a) is ZrO
2, TiO
2, SiO
2, SnO
2, MnO
2, Co
3o
4one of or NiO.
Oxide precursor described in 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, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, one of nickel hydroxide.
Solvent described in step (a) is any one or a few in water, ethanol, Virahol.
Described Graphene and the mass ratio of oxide precursor are 1: 0.1 ~ 1: 90.
Graphene/metal oxide mixture can be widely used in lithium ion battery, the field such as ultracapacitor and electrochemical sensing.
Beneficial effect of the present invention is as follows:
(1) the present invention adopts hydrothermal method using catechol and derivative thereof as reductive agent, by obtained for graphene oxide reduction Graphene, utilize the hydroxyl of hydroxyl easily and on graphene oxide in catechol and derivative thereof, carboxyl effect, make to be formed between the phenyl ring of catechol and derivative thereof and graphene oxide π-pi-conjugated, thus graphene oxide can be made to occur peeling off layer by layer under the environment of hydro-thermal, prepare reduction reaction fully, the thinner and Graphene that the transparency is good.
(2) the present invention adopt catechol and derivative, it is a kind of organic phenols be present in a large number in fruit and vegetables, abundance, cost is low, and it is carry out in the solution of the water of catechol and derivative thereof or alcohol, acid that simultaneously the present invention prepares Graphene, aqueous systems is adopted to prepare Graphene first, reaction temperature and, consume energy lower, output is higher, and sufficient reacting, avoid the organic solvent using toxicity large.
(3) Graphene-complex oxide of preparing of the present invention, Graphene is joined in the water of oxide precursor, alcoholic solution, adopt reaction temperature and hydro-thermal reaction, environmental friendliness, technique is simple, green safety, avoids using toxicity or inflammable organic liquid, thus avoids bringing very large threat to the safety of experimenter.
(4) Graphene-complex oxide of preparing of the present invention, oxide nano particles size evenly and be dispersed in uniformly on Graphene.
(5) Graphene-complex oxide excellent property of gained of the present invention, can be widely used in lithium ion battery, the field such as ultracapacitor and electrochemical sensing.
Below in conjunction with accompanying drawing and embodiment, the present invention is further described.
Accompanying drawing explanation
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 dioxide.
Embodiment
Embodiment 1:
Refer to Fig. 1, the invention provides a kind of preparation method of Graphene, comprise the following steps: (1) prepares Graphene:
Take a certain amount of catechol or catechol derivatives, be dissolved in solvent and obtain the catechol or derivatives thereof solution that mass concentration is 0.05g/ml, graphene oxide is ground to form powder, taking a certain amount of graphene oxide powder joins in the solution of catechol or derivatives thereof, after magnetic agitation is uniformly dispersed, ultrasonic disperse 0.5 ~ 4h, dispersion liquid is proceeded in autoclave, autoclave is placed in hydro-thermal reaction 12 ~ 48h under 80 ~ 200 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtains Graphene.
Catechol derivatives described in 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, acetic acid.
The mass ratio of the graphene oxide described in 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, comprise the following steps:
A () takes a certain amount of oxide precursor, being dissolved in solvent and obtaining mass concentration is 0.15 ~ 0.4g/ml oxide precursor liquid solution, the Graphene of above-mentioned steps (2) gained is ground to form powder, takes a certain amount of graphene powder;
B load weighted Graphene powder adds in oxide precursor liquid solution by (), be uniformly mixed, ultrasonic disperse 0.5 ~ 4h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 12 ~ 72h under 120 ~ 200 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains Graphene-complex oxide.
Oxide compound described in step (a) is ZrO
2, TiO
2,siO
2,snO
2,mnO
2, Co
3o
4one of or NiO.
Oxide precursor described in 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, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, one of nickel hydroxide.
Solvent described in step (a) is any one or a few in water, ethanol, Virahol.
Described Graphene and the mass ratio of oxide precursor are 1: 0.1 ~ 1: 90.
Graphene/metal oxide mixture can be widely used in lithium ion battery, the field such as ultracapacitor and electrochemical sensing.
Embodiment 2:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, substantially the same manner as Example 1, its difference is:
The preparation method of described Graphene realizes as follows:
(1) graphite oxidation:
At ice-water bath-4 DEG C, 3g graphite and 1.5g SODIUMNITRATE are joined in 500ml there-necked flask, under agitation slowly add 120mL massfraction 98% vitriol oil and 18g potassium permanganate successively, then 0.5h is stirred under being warming up to 35 DEG C of waters bath with thermostatic control, slowly add the dilution of 140mL deionized water again, stir 10 minutes, add the hot water of 120ml60 DEG C, continue stirring again 10 minutes, add the H of 30mL massfraction 30%
2o
2, filter after leaving standstill, abundant washing leaching cake, washing is to neutral, and be then dispersed in water by filter cake, ultrasonic 6h, at 45 DEG C, vacuum-drying obtains graphene oxide.
(2) Graphene is prepared:
Take a certain amount of catechol and be dissolved in formic acid, obtain the catechol solution that mass concentration is 0.05g/ml, the graphene oxide of step (1) gained is ground to form powder, take a certain amount of graphene oxide powder, the mass ratio of graphene oxide and catechol is made to be 1: 0.1, join in catechol solution, after magnetic agitation is uniformly dispersed, ultrasonic disperse 0.5h, proceeds to dispersion liquid in autoclave, autoclave is placed in hydro-thermal reaction 24h under 80 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtains Graphene.Characterize through transmission electron microscope(TEM), obtain large stretch of large-area Graphene, Graphene is thinner, very transparent, reduction very abundant, obtains the Graphene that large stretch of and length and width dimensions reach 10-200 micron.
Embodiment 3:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, substantially identical with embodiment 1,2, its difference is:
A preparation method for Graphene, realizes as follows:
(1) graphite oxidation:
At ice-water bath-4 ~ 0 DEG C, 4g graphite and 2g SODIUMNITRATE are joined in 500ml there-necked flask, under agitation slowly add 150mL massfraction 98% vitriol oil and 12g potassium permanganate successively, then 1h is stirred under being warming up to 35 DEG C of waters bath with thermostatic control, slowly add the dilution of 160mL deionized water again, stir 10 minutes, add the hot water of 160ml60 DEG C, continue stirring again 10 minutes, add the H of 22.75mL massfraction 30%
2o
2, filter after leaving standstill, abundant washing leaching cake, washing is to neutral, and be then dispersed in water by filter cake, ultrasonic 6h, at 45 DEG C, vacuum-drying obtains graphene oxide.
(2) Graphene is prepared:
Take a certain amount of Dopamine HCL water-soluble, 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 a certain amount of graphene oxide powder, the mass ratio of graphene oxide and catechol is made to be 1: 5, join in the aqueous solution of Dopamine HCL, after magnetic agitation is uniformly dispersed, ultrasonic disperse 4h, proceeds to dispersion liquid in autoclave, autoclave is placed in hydro-thermal reaction 12h under 200 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtains Graphene.
Embodiment 4:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, all substantially identical with embodiment 1,2,3, its difference is:
A preparation method for Graphene, realizes as follows:
(1) graphite oxidation:
At ice-water bath 0 DEG C, 3.5g graphite and 1.5g SODIUMNITRATE are joined in 500ml there-necked flask, under agitation slowly add 135mL massfraction 98% vitriol oil and 9g potassium permanganate successively, then 0.75h is stirred under being warming up to 35 DEG C of waters bath with thermostatic control, slowly add the dilution of 140mL deionized water again, stir 10 minutes, add the hot water of 140ml60 DEG C, continue stirring again 10 minutes, add the H2O2 of 22.5mL massfraction 30%, filter after leaving standstill, abundant washing leaching cake, washing is to neutral, then filter cake is dispersed in water, ultrasonic 6h, at 45 DEG C, vacuum-drying obtains graphene oxide.
(2) Graphene is prepared:
Take 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 a certain amount of graphene oxide powder, the mass ratio of graphene oxide and catechol is made to be 1: 10, join in the alcoholic solution of alpha-methyldopa amine, after magnetic agitation is uniformly dispersed, ultrasonic disperse 2.3h, dispersion liquid is proceeded in autoclave, autoclave is placed in hydro-thermal reaction 48h under 140 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtain Graphene.
Embodiment 5:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, all substantially identical with embodiment 1,2,3,4, its difference is:
A preparation method for Graphene, realizes as follows:
(1) graphite oxidation:
At ice-water bath-4 ~ 0 DEG C, 3g graphite and 1.75g SODIUMNITRATE are joined in 500ml there-necked flask, under agitation slowly add 150mL massfraction 98% vitriol oil and 14g potassium permanganate successively, then 1h is stirred under being warming up to 35 DEG C of waters bath with thermostatic control, slowly add the dilution of 120mL deionized water again, stir 10 minutes, add the hot water of 160ml60 DEG C, continue stirring again 10 minutes, add the H of 22.5mL massfraction 30%
2o
2, filter after leaving standstill, abundant washing leaching cake, washing is to neutral, and be then dispersed in water by filter cake, ultrasonic 6h, at 45 DEG C, vacuum-drying obtains graphene oxide.
(2) Graphene is prepared:
Take a certain amount of catechol and be dissolved in formic acid, obtain the catechol solution that mass concentration is 0.05g/ml, the graphene oxide of step (1) gained is ground to form powder, take a certain amount of graphene oxide powder, the mass ratio of graphene oxide and catechol is made to be 1: 10, join in catechol solution, after magnetic agitation is uniformly dispersed, ultrasonic disperse 2h, proceeds to dispersion liquid in autoclave, autoclave is placed in hydro-thermal reaction 48h under 180 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtains Graphene.
Embodiment 6:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, substantially identical with embodiment 1,2,3,4,5, its difference is:
A preparation method for Graphene-oxide compound, realizes as follows:
A () takes a certain amount of five nitric hydrate zirconiums water-soluble, obtaining mass concentration is the 0.2g/ml zirconium nitrate aqueous solution, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and five nitric hydrate zirconiums be 1: 0.1.
B load weighted Graphene joins in the zirconium nitrate aqueous solution by (), be uniformly mixed, ultrasonic disperse 2h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 18h under 140 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains Graphene-complex oxide.Characterize through transmission electron microscope(TEM), obtain the mixture of large stretch of large-area Graphene/zirconium dioxide.
Embodiment 7:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, all substantially identical with embodiment 1,2,3,4,5,6, its difference is:
A preparation method for Graphene-oxide compound, realizes as follows:
A () takes a certain amount of tin tetrachloride and is dissolved in ethanol, obtaining mass concentration is 0.15g/ml tin tetrachloride alcoholic solution, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and tin tetrachloride be 1: 45.
B load weighted Graphene joins in the zirconium nitrate aqueous solution by (), be uniformly mixed, ultrasonic disperse 1h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 27h under 160 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains Graphene-complex oxide.
Embodiment 8:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, substantially identical with embodiment 1,2,3,4,5,6,7, its difference is:
A preparation method for Graphene-oxide compound, realizes as follows:
A () takes a certain amount of tetraethoxy water-soluble, obtaining mass concentration is the 0.2g/ml tetraethoxy aqueous solution, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and tetraethoxy be 1: 80.
B load weighted Graphene joins in the zirconium nitrate aqueous solution by (), be uniformly mixed, ultrasonic disperse 3h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 48h under 200 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains the mixture of graphene/silicon dioxide.
Embodiment 9:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, all substantially 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 () takes a certain amount of eight hydration zirconium oxychlorides water-soluble, obtaining mass concentration is 0.4g/ml zirconium oxychloride aqueous solution, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and eight hydration zirconium oxychlorides be 1: 0.1.
B load weighted Graphene joins in the zirconium nitrate aqueous solution by (), be uniformly mixed, ultrasonic disperse 0.5h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 24h under 120 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains the mixture of Graphene/zirconium dioxide.Characterize through transmission electron microscope(TEM), obtain large stretch of large-area mixture.
Embodiment 10:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, substantially identical with one of embodiment 1-9, its difference is:
A kind of preparation method of Graphene-oxide compound realizes as follows:
A () takes a certain amount of manganese acetate water-soluble, obtaining mass concentration is the 0.25g/ml manganese acetate aqueous solution, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and manganese acetate be 1: 25.
B load weighted Graphene joins in the manganese acetate aqueous solution by (), be uniformly mixed, ultrasonic disperse 2h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 12h under 200 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains the mixture of Graphene/Manganse Dioxide.
Embodiment 11:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, all substantially identical with embodiment 1-10, its difference is:
A kind of preparation method of Graphene-oxide compound realizes as follows:
A () takes a certain amount of cobalt chloride and is dissolved in Virahol, obtaining mass concentration is 0.2g/ml cobalt chloride alcoholic solution, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and cobalt chloride be 1: 60.
B load weighted Graphene joins in cobalt chloride alcoholic solution by (), be uniformly mixed, ultrasonic disperse 3h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 42h under 180 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains the mixture of Graphene/cobalt dioxide.
Embodiment 12:
The preparation method of what the present embodiment provided prepare Graphene and Graphene-complex oxide, all substantially identical with embodiment 1-11, its difference is:
A preparation method for Graphene-oxide compound, realizes as follows:
A () takes a certain amount of tetrabutyl titanate and is dissolved in ethanol, obtain the tetrabutyl titanate alcoholic solution that mass concentration is 0.3g/ml, Graphene according to embodiment 5 gained is ground to form powder, takes a certain amount of graphene powder, make the mass ratio of Graphene and tetrabutyl titanate be 1: 90.
B load weighted Graphene joins in tetrabutyl titanate alcoholic solution by (), be uniformly mixed, ultrasonic disperse 4h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 72h under 180 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains the mixture of Graphene/titanium dioxide.
Although described embodiment and accompanying drawing describe 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 within the context described in it change, the preparation method of equivalents and improvement, all within protection scope of the present invention.
Claims (6)
1. a preparation method for Graphene-complex oxide, is characterized in that, comprises the following steps:
A () takes a certain amount of oxide precursor, being dissolved in solvent and obtaining mass concentration is 0.15 ~ 0.4g/ml oxide precursor liquid solution, Graphene is ground to form powder, takes a certain amount of graphene powder;
B load weighted Graphene powder adds in oxide precursor liquid solution by (), be uniformly mixed, ultrasonic disperse 0.5 ~ 4h, then dispersion liquid is transferred in autoclave, autoclave is placed in hydro-thermal reaction 12 ~ 72h under 120 ~ 200 DEG C of water-baths, by sample suction filtration, absolute ethanol washing, vacuum-drying, obtains Graphene-complex oxide;
Wherein, described Graphene adopts following steps to be prepared from:
Take a certain amount of catechol or catechol derivatives, be dissolved in solvent and obtain the catechol or derivatives thereof solution that mass concentration is 0.05g/ml, graphene oxide is ground to form powder, taking a certain amount of graphene oxide powder joins in the solution of catechol or derivatives thereof, after magnetic agitation is uniformly dispersed, ultrasonic disperse 0.5 ~ 4h, dispersion liquid is proceeded in autoclave, autoclave is placed in hydro-thermal reaction 12 ~ 48h under 80 ~ 200 DEG C of water-baths, by sample filtering, washing, vacuum-drying, obtains Graphene;
Described catechol derivatives is one of Dopamine HCL, alpha-methyldopa amine, dopa; Described solvent is one or more in water, methyl alcohol, ethanol, Virahol, formic acid, acetic acid;
The mass ratio of described graphene oxide and catechol or derivatives thereof is 1:0.1 ~ 1:10.
2. the preparation method of Graphene-complex oxide according to claim 1, is characterized in that, the oxide compound described in step (a) is ZrO
2, TiO
2,siO
2,snO
2,mnO
2, Co
3o
4one of or NiO.
3. the preparation method of Graphene-complex oxide according to claim 1, it is characterized in that, oxide precursor described in 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, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, one of nickel hydroxide.
4. the preparation method of Graphene-complex oxide according to claim 1, is characterized in that, the solvent described in step (a) is any one or a few in water, ethanol, Virahol.
5. the preparation method of Graphene-complex oxide according to claim 1, is characterized in that, described Graphene and the mass ratio of oxide precursor are 1:0.1 ~ 1:90.
6. the preparation method of graphene/oxide mixture according to claim 1, is characterized in that, the graphene/oxide mixture obtained is applied to lithium ion battery, ultracapacitor or electrochemical sensing field.
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