CN104843678A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN104843678A CN104843678A CN201510153347.4A CN201510153347A CN104843678A CN 104843678 A CN104843678 A CN 104843678A CN 201510153347 A CN201510153347 A CN 201510153347A CN 104843678 A CN104843678 A CN 104843678A
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Abstract
The present invention belongs to the technical field of graphene preparation, and particularly relates to a preparation method of graphene. The preparation method comprises the steps: in the process of preparation of graphite oxide, firstly a diluent with a proper temperature is selected and injected into a reactor; and secondly, a low-medium temperature reaction product is added into the diluent, so that the temperature of a diluted reactant is accurately controlled, and phenomenon that the partial temperature is overhigh in the dilution process is prevented. Compared to the prior art, when the graphene is prepared by using the method provided by the invention, the prepared graphene is relatively high in specific surface area, and the batch stability is remarkably higher.
Description
Technical field
The invention belongs to technical field of graphene, particularly a kind of preparation method of Graphene.
Background technology
2004, strong K sea nurse (AndreK.Geim) of peace moral etc. of Univ Manchester UK adopted mechanically peel method to prepare Graphene (Graphene) first, has pulled open the prelude of the preparation of this material, operational research thus.So-called Graphene, refers to a kind of plates of the arrangement in hexagonal annular between carbon atom, is usually made up of single or multiple lift graphite flake layer, infinitely can extends at two-dimensional space, can be described as proper two-dirnentional structure material.It has the outstanding advantages such as specific surface area is large, electrical and thermal conductivity performance is excellent, thermal expansivity is low: specifically, high specific surface area (calculated value: 2630m
2/ g); High conductivity, carrier transport rate (200000cm
2/ Vs); High heat conductance (5000W/mK); High strength, high Young's modulus (1100GPa), breaking tenacity (125GPa).Therefore its in energy storage field, thermal conduction field and Materials with High Strength field have great utilization prospect.
The existing method preparing Graphene mainly contains micromechanics stripping method, ultrahigh vacuum(HHV) Graphene epitaxial growth method, oxidation-reduction method, chemical Vapor deposition process (CVD), solvent stripping method, electrolytic process and solvent-thermal method.In this serial of methods, oxidation-reduction method realizes one of optimal selection that Graphene prepared in enormous quantities.
But when adopting oxidation style to prepare graphite oxide, the oxygenant used is the oxygenant such as the vitriol oil, potassium permanganate often; And in order to more fully by graphite oxidation, often need to carry out pyroreaction; But the strong oxidizer of high density at high temperature exists great potential safety hazard, and oxygenant Problem of Failure can be there is, cause the failure of whole oxidizing reaction.Therefore in actual production process, often to low middle temperature reaction should after product in add a certain amount of thinner after carry out pyroreaction again, thus to overcome the above problems.But when adding thinner in strong oxidizer, will amount of heat be discharged, cause reactant local temperature too high, affect the quality of the Graphene finally prepared.
In view of this, a kind of new graphene preparation method of necessary exploitation, adds the reactant local temperature too high problem caused in thinner process when preparing graphite oxide for solving.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and a kind of graphene preparation method provided: namely in graphite oxide preparation process, first the thinner of suitable temp is selected to inject reflecting device, afterwards low middle temperature reaction product is added in this thinner, thus realize the accurate control of the temperature of charge after to dilution, and prevent the generation of the too high phenomenon of local temperature in dilution.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for Graphene, mainly comprises the steps:
Step 1, pre-reaction slurry configures: mixed under the environment of-20 DEG C ~ 80 DEG C by the reactant containing carbon material and oxidizing substance, obtain pre-reaction slurry;
Step 2, low-temp reaction: under pre-reaction slurry step 1 obtained is placed in the environment of-20 DEG C ~ 80 DEG C, reaction is no more than 24h, namely obtains low-temp reaction product;
Step 3, dilution: be that the thinner splendid attire of-20 DEG C ~ 100 DEG C is in reactor by temperature, low-temp reaction product step 2 obtained afterwards injects above-mentioned reactor, adopt heat exchange means to make to dilute the rapid diffusion loss of heat produced simultaneously, guarantee that reactant does not occur that local temperature crosses high state, finally obtains diluent;
Step 4, pyroreaction: diluent step 3 obtained carries out pyroreaction under being placed in the environment of 45 DEG C ~ 200 DEG C and is no more than 24h, obtains high-temperature reaction product, i.e. the graphite slurry of grafting oxygenated functional group;
Step 5, purifying: the raw material that in removing step 4, unreacted is complete and/or the impurity produced in reacting, then dry, pulverizing, obtains the powdered graphite of grafting oxygenated functional group;
Step 6, cleavage: powdered graphite step 5 obtained is placed in protective atmosphere, heating cleavage, obtains finished product Graphene.
One as the preparation method of Graphene of the present invention is improved, and step 1 comprises KMnO at described oxidizing substance
4, ammoniacal liquor, HNO
3, H
3pO
4, H
3asO
4, H
2sO
4, H
2seO
4, H
6teO
6, HF, HCl, HClO, HClO
3, HClO
4, HBrO
3, HBrO
4, H
5iO
6and HIO
3in at least one or/and containing NO
3 -, PO
4 3-, AsO
4 3-, SO
4 2-, SeO
4 2-, TeO
6 6-, F
-, Cl
-, ClO
-, ClO
3 -, ClO
4 -, BrO
3 -, BrO
4 -, IO
6 5-and IO
3 –at least one in an alkali metal salt of ion.
One as the preparation method of Graphene of the present invention is improved, and the basic comprising unit of carbon material described in step 1 is graphene sheet layer, comprises crystalline flake graphite and/or micro crystal graphite.
One as the preparation method of Graphene of the present invention is improved, and it is characterized in that, the mass ratio of described oxidizing substance and described carbon material is 1:0.001 ~ 1.
One as the preparation method of Graphene of the present invention is improved, and the slurry of pre-reaction described in step 1 configuration temperature is-10 DEG C ~ 40 DEG C.
One as the preparation method of Graphene of the present invention is improved, and during the employing of low-temp reaction described in step 2 single step reaction, temperature of reaction is-20 DEG C ~ 80 DEG C; When adopting polystep reaction, the temperature of reaction often walked is respectively T
1, T
2t
n, wherein-20 DEG C≤T
1<T
2<T
3... <T
n≤ 80 DEG C, and have at least the temperature of reaction of a step to be more than or equal to 30 DEG C, n is the number of steps of reaction, n>=2.
One as the preparation method of Graphene of the present invention is improved, thinner described in step 3 is water, the acid solution of water or the salts solution of water, the acid solution of water is hydrochloric acid, aqueous nitric acid, aqueous sulfuric acid etc., and the salts solution of water is Alkitrate, potassium sulfate solution, sodium nitrate aqueous solution etc.; The temperature of described thinner is 0 DEG C ~ 95 DEG C; Described heat exchange means is that stirring, convection current, radiation are or/and supersound process.
One as the preparation method of Graphene of the present invention is improved, and the temperature of the dilution described in step 3 controls at 0 DEG C ~ 200 DEG C.
One as the preparation method of Graphene of the present invention is improved, and the mass ratio of thinner described in step 3 and described low-temp reaction product is 0.05 ~ 5:1.
One as the preparation method of Graphene of the present invention is improved, and the protective atmosphere described in step 6 is nitrogen atmosphere, inert gas atmosphere or vacuum atmosphere; The temperature of described cleavage is 80 DEG C ~ 3000 DEG C.
Beneficial effect of the present invention is: different from traditional graphene preparation method, when adopting present method to prepare Graphene, the Graphene batch consistence prepared is obviously better: in dilution stage, first will have the thinner injecting reactor of certain temperature, the temperature of the rear mixture of dilution can be regulated by the temperature of thinner; Simultaneously, low-temp reaction product is injected thinner, applies thermodiffusion measure, simultaneously under the effect of Macrodilution agent, effectively the spread heat that dilution produces can be come, guarantee the controllability of whole dilution temperature and effectively avoid the too high problem of local temperature.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in detail, but embodiments of the present invention are not limited thereto.
Comparative example 1, pre-reaction slurry configures: according to graphite: potassium permanganate: the vitriol oil (mass concentration is 98%): the relationship between quality of SODIUMNITRATE=2:5:60:1, at the reactor of 6 DEG C, add the vitriol oil (concentration is 98%), SODIUMNITRATE, graphite and potassium permanganate, after stirring, obtain pre-reaction slurry;
Low-temp reaction: react 4h under pre-reaction slurry obtained above is placed in the environment of 6 DEG C, namely obtain low-temp reaction product;
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=0.5:1, select the deionized water of 25 DEG C as thinner, in above-mentioned low-temp reaction product, slowly add dilution, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Pyroreaction: diluent obtained above is warming up to 90 DEG C, keeps temperature to carry out the pyroreaction of 2h afterwards, namely obtains the graphite oxide slurry of grafting oxygenated functional group;
Purifying: with deionized water to the product after above-mentioned oxidizing reaction wash → filter → to wash → filter →... ... operation, removes hetero-ion wherein, obtains pure graphite oxide, afterwards dry, shatter and obtain graphite oxide powder.
Cleavage: by above-mentioned graphite oxide powder under nitrogen atmosphere, be warming up to 500 DEG C, cleavage obtains graphene powder.
Embodiment 1, with comparative example 1 unlike, the present embodiment comprises the steps:
Pre-reaction slurry configures: according to graphite: potassium permanganate: the vitriol oil (mass concentration is 98%): the relationship between quality of SODIUMNITRATE=2:5:60:1, at the reactor of 6 DEG C, add the vitriol oil (mass concentration is 98%), SODIUMNITRATE, graphite and potassium permanganate, after stirring, obtain pre-reaction slurry;
Low-temp reaction: react 4h under pre-reaction slurry obtained above is placed in the environment of 6 DEG C, namely obtain low-temp reaction product;
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=0.5:1, select the deionized water of 25 DEG C as thinner, first by deionized water injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Pyroreaction: diluent obtained above is warming up to 90 DEG C, keeps temperature to carry out the pyroreaction of 2h afterwards, namely obtains the graphite oxide slurry of grafting oxygenated functional group;
Purifying: with deionized water to the product after above-mentioned oxidizing reaction wash → filter → to wash → filter →... ... operation, removes hetero-ion wherein, obtains pure graphite oxide, afterwards dry, shatter and obtain graphite oxide powder.
Cleavage: by above-mentioned graphite oxide powder under nitrogen atmosphere, be warming up to 500 DEG C, cleavage obtains graphene powder.
Other is identical with comparative example 1, no longer repeats here.
Embodiment 2, as different from Example 1, the present embodiment comprises the steps:
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=0.05:1, select the deionized water of 25 DEG C as thinner, first by deionized water injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 3, as different from Example 1, the present embodiment comprises the steps:
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=5:1, select the deionized water of 25 DEG C as thinner, first by deionized water injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 4, as different from Example 1, the present embodiment comprises the steps:
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=0.5:1, select the deionized water of 0 DEG C as thinner, first by deionized water injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 5, as different from Example 1, the present embodiment comprises the steps:
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=0.5:1, select the deionized water of 95 DEG C as thinner, first by deionized water injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 6, as different from Example 1, the present embodiment comprises the steps:
Pre-reaction slurry configures: according to graphite: potassium permanganate: the vitriol oil (mass concentration is 98%): the relationship between quality of the relationship between quality (i.e. graphite: oxygenant=0.001:1) of SODIUMNITRATE=0.01:4:5:1, above-mentioned reactant is stirred in the reactor of-20 DEG C, obtains pre-reaction slurry.
Low-temp reaction: react 2h under pre-reaction slurry obtained above is placed in the environment of-20 DEG C, is warming up to-10 DEG C afterwards and continues reaction 2h, is finally warming up to 30 DEG C of reaction 30min and namely obtains low-temp reaction product;
Prepared by diluent: according to dilute sulphuric acid (concentration is 5wt%): the relationship between quality of low-temp reaction product=0.2:1, select the dilute sulphuric acid of-20 DEG C (concentration is 5wt%) as thinner, first by dilute sulphuric acid (concentration is 5wt%) injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Pyroreaction: diluent obtained above is warming up to 45 DEG C, keeps temperature to carry out the pyroreaction of 2h afterwards; Be warming up to 110 DEG C of reaction 30min again, namely obtain the graphite oxide slurry of grafting oxygenated functional group;
Purifying: with deionized water to the product after above-mentioned oxidizing reaction wash → filter → to wash → filter →... ... operation, removes hetero-ion wherein, obtains pure graphite oxide, afterwards dry, shatter and obtain graphite oxide powder.
Cleavage: by graphite oxide powder under an argon, is warming up to 80 DEG C, and part cleavage obtains Graphene presoma, obtains Graphene finished product after being warming up to 3000 DEG C afterwards.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 7, as different from Example 1, the present embodiment comprises the steps:
Pre-reaction slurry configures: according to graphite: potassium permanganate: nitric acid: the relationship between quality of the relationship between quality (i.e. graphite: oxygenant=1:1) of sodium sulfate=4:1:2:1, say that the reactor that above-mentioned reactant is placed in 40 DEG C stirs, be warming up to 80 DEG C afterwards, obtain pre-reaction slurry.
Low-temp reaction: react 2h under pre-reaction slurry obtained above is placed in the environment of 80 DEG C, namely obtain low-temp reaction product;
Prepared by diluent: according to potassium chloride solution (concentration is 1wt%): the relationship between quality of low-temp reaction product=0.1:1, select the potassium chloride solution (concentration is 1wt%) of 100 DEG C as thinner, first by potassium chloride solution (concentration is 1wt%) injecting reactor, afterwards low-temp reaction product is slowly injected above-mentioned thinner, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Pyroreaction: diluent obtained above is warming up to 200 DEG C, keeps temperature to carry out the pyroreaction of 2h afterwards; Namely the graphite oxide slurry of grafting oxygenated functional group is obtained;
Purifying: with deionized water to the product after above-mentioned oxidizing reaction wash → filter → to wash → filter →... ... operation, removes hetero-ion wherein, obtains pure graphite oxide, afterwards dry, shatter and obtain graphite oxide powder.
Cleavage: by graphite oxide powder under an argon, is warming up to 100 DEG C, and part cleavage obtains Graphene presoma, obtains Graphene finished product after being warming up to 350 DEG C afterwards.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 8, as different from Example 7, the present embodiment comprises the steps:
Pre-reaction slurry configures: according to graphite: potassium permanganate: phosphoric acid: the relationship between quality of the relationship between quality (i.e. graphite: oxygenant=0.02:1) of potassium sulfate=1:1:19:30, above-mentioned reactant is stirred in the reactor of-10 DEG C, obtains pre-reaction slurry.
Other is identical with embodiment 7, no longer repeats here.
Respectively 10 repetitive operations are carried out to comparative example 1 and embodiment 1-embodiment 8, the specific surface area of each batch of Graphene in test and comparison example and embodiment.
Table 1, the temperature fluctuation of comparative example and embodiment and the Graphene specific surface area table of preparation
The comparative example that contrast table is a kind and each embodiment can obtain, and when adopting method of the present invention to prepare Graphene, dilution stage, can control the generation of a large amount of dense smoke in journey effectively; When low-temp reaction product is mainly injected diluent by this, a large amount of diluents can effectively disperse to dilute the heat produced, thus prevents the too high situation of local temperature from occurring; Accordingly, the specific surface area of the Graphene prepared is higher, and lot stability significantly promotes (namely the specific surface area waving interval of Graphene prepared of different batches is less).In addition, by controlling consumption and the temperature of thinner, the temperature of diluting rear reaction solution can effectively be controlled, and dilution rate; Thus reach the object improving formation efficiency and improve product qualities.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a preparation method for Graphene, is characterized in that, mainly comprises the steps:
Step 1, pre-reaction slurry configures: mixed under the environment of-20 DEG C ~ 80 DEG C by the reactant containing carbon material and oxidizing substance, obtain pre-reaction slurry;
Step 2, low-temp reaction: under pre-reaction slurry step 1 obtained is placed in the environment of-20 DEG C ~ 80 DEG C, reaction is no more than 24h, namely obtains low-temp reaction product;
Step 3, dilution: be that the thinner splendid attire of-20 DEG C ~ 100 DEG C is in reactor by temperature, low-temp reaction product step 2 obtained afterwards injects above-mentioned reactor, adopt heat exchange means to make to dilute the rapid diffusion loss of heat produced simultaneously, guarantee that reactant does not occur that local temperature crosses high state, finally obtains diluent;
Step 4, pyroreaction: diluent step 3 obtained carries out pyroreaction under being placed in the environment of 45 DEG C ~ 200 DEG C and is no more than 24h, obtains high-temperature reaction product, i.e. the graphite slurry of grafting oxygenated functional group;
Step 5, purifying: the raw material that in removing step 4, unreacted is complete and/or the impurity produced in reacting, then dry, pulverizing, obtains the powdered graphite of grafting oxygenated functional group;
Step 6, cleavage: powdered graphite step 5 obtained is placed in protective atmosphere, heating cleavage, obtains finished product Graphene.
2. a preparation method for Graphene according to claim 1, is characterized in that, step 1 comprises KMnO at described oxidizing substance
4, ammoniacal liquor, HNO
3, H
3pO
4, H
3asO
4, H
2sO
4, H
2seO
4, H
6teO
6, HF, HCl, HClO, HClO
3, HClO
4, HBrO
3, HBrO
4, H
5iO
6and HIO
3in at least one or/and containing NO
3 -, PO
4 3-, AsO
4 3-, SO
4 2-, SeO
4 2-, TeO
6 6-, F
-, Cl
-, ClO
-, ClO
3 -, ClO
4 -, BrO
3 -, BrO
4 -, IO
6 5-and IO
3 –at least one in an alkali metal salt of ion.
3. a preparation method for Graphene according to claim 1, is characterized in that, the basic comprising unit of carbon material described in step 1 is graphene sheet layer, comprises crystalline flake graphite and/or micro crystal graphite.
4. a preparation method for the Graphene described in any one of claims 1 to 3, is characterized in that, the mass ratio of described oxidizing substance and described carbon material is 1:0.001 ~ 1.
5. a preparation method for Graphene according to claim 1, is characterized in that, the slurry of pre-reaction described in step 1 configuration temperature is-10 DEG C ~ 40 DEG C.
6. a preparation method for Graphene according to claim 1, is characterized in that, during the employing of low-temp reaction described in step 2 single step reaction, temperature of reaction is-20 DEG C ~ 80 DEG C; When adopting polystep reaction, the temperature of reaction often walked is respectively T
1, T
2t
n, wherein-20 DEG C≤T
1<T
2<T
3... <T
n≤ 80 DEG C, and have at least the temperature of reaction of a step to be more than or equal to 30 DEG C, n is the number of steps of reaction, n>=2.
7. a preparation method for Graphene according to claim 1, is characterized in that, thinner described in step 3 is water, the acid solution of water or the salts solution of water; The temperature of described thinner is 0 DEG C ~ 95 DEG C; Described heat exchange means is that stirring, convection current, radiation are or/and supersound process.
8. a preparation method for Graphene according to claim 1, is characterized in that, the temperature of the dilution described in step 3 controls at 0 DEG C ~ 200 DEG C.
9. a preparation method for Graphene according to claim 1, is characterized in that, the mass ratio of thinner described in step 3 and described low-temp reaction product is 0.05 ~ 5:1.
10. a preparation method for Graphene according to claim 1, is characterized in that, the protective atmosphere described in step 6 is nitrogen atmosphere, inert gas atmosphere or vacuum atmosphere; The temperature of described cleavage is 80 DEG C ~ 3000 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948107A (en) * | 2010-09-15 | 2011-01-19 | 天津大学 | Method for preparing and purifying graphene by microwave radiation under vacuum |
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
-
2015
- 2015-04-01 CN CN201510153347.4A patent/CN104843678A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948107A (en) * | 2010-09-15 | 2011-01-19 | 天津大学 | Method for preparing and purifying graphene by microwave radiation under vacuum |
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
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Application publication date: 20150819 |