CN105692608A - Method for preparing graphene through one step of oxidation and reduction - Google Patents
Method for preparing graphene through one step of oxidation and reduction Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene through one step of oxidation and reduction. The preparation method comprises the following steps that graphite oxide obtained by conducting oxidation on graphite powder is dissolved in a mixed solution containing organic solvent and water at a preset temperature, a reducing agent is added at the same time, ultrasonic treatment is conducted on the mixture, and graphene dispersion liquid is obtained; vacuum filtration cleaning is conducted on the obtained graphene dispersion liquid, the obtained filtrate is dried, and the graphene is obtained. According to the method for preparing the graphene through one step of oxidation and reduction, three stages of oxidation, stripping and reduction in a traditional oxidation reduction method for preparing the graphene are simplified into two stages, namely, the oxidation stage and the stripping reduction stage, particularly, the stripping stage and the reduction stage are reduced into one step, the stripping stage and the reduction stage are carried out simultaneously, the reaction time is shortened, the production efficiency is improved, and a new method for industrial production of the graphene is provided.
Description
Technical field
The present invention relates to technical field prepared by Graphene, more particularly, relate to a kind of method utilizing oxidoreduction one step to prepare Graphene。
Background technology
Graphene be a kind of by monolayer carbon atom through SP2The material with carbon element of the honeycomb hexatomic ring two-dimensional structure that hydridization is formed。Graphene has the performance that high-specific surface area, the resistivity less than silver, high electron mobility, high heat-conduction coefficient, good mechanical flexibility and mechanical strength, high sensitivity low noise etc. are excellent, it has attracted large quantities of researcher to be applied to study widely, and its range of application has had been directed to the fields such as physics, chemistry, environment, biology, medical science, material。But controlled, production in enormous quantities Graphene is still the difficult problem perplexing vast researcher, also allows the development of Graphene industry stagnate。
Emerge in an endless stream about the report of graphene preparation method based on the tempting application prospect of Graphene。These methods can be divided into " from top to bottom " and " from bottom to top " two class method。It is the class method separating Graphene from graphite, expanded graphite from top to bottom, such as methods such as mechanical stripping method, oxidation-reduction method, liquid phase stripping method, electrochemical stripping method, arc discharge method, nanotube patterning methods；It is that carbon atom becomes a class method of Graphene at Grown from bottom to top, such as chemical vapour deposition technique, epitaxial growth method, organic synthesis method, solvent-thermal method etc.。Wherein oxidation-reduction method is simple with its technique, with low cost, produce device simple, advantage that yield is the highest, the method becoming most potentiality large-scale production Graphene。
Prepare in Graphene in traditional oxidation-reduction method, it is necessary to graphite oxidation is the oxidation stage of graphite oxide by experience, graphite oxide is peeled off the stripping bench for graphene oxide, graphene oxide is reduced to the reduction phase of Graphene。This technique there is problems in that (1) each stage of reaction exists the factor affecting product performance, and the superposition of influence factor causes the instability of end product；(2) the loaded down with trivial details length consuming time of technique。Cleaning at oxidation stage, oxidation reaction and graphite oxide need to consume the plenty of time；The consumption of indefinite time is had according to product requirements at stripping bench；Also the consumption of indefinite time is had according to different method of reducing at reduction phase。
Summary of the invention
In order to solve in prior art exist the oxidation-reduction method such as preparing Graphene length consuming time, efficiency low, it is difficult to for problems such as large-scale industrial productions, it is an object of the invention to provide a kind of method utilizing oxidoreduction one step to prepare Graphene。
The invention provides a kind of method utilizing oxidoreduction one step to prepare Graphene, described preparation method comprises the following steps: after aoxidizing with graphite powder, the graphite oxide that obtains is dissolved in the mixed solution including organic solvent and water under predetermined temperature, is simultaneously introduced reducing agent and it is carried out supersound process obtains graphene dispersing solution；Gained graphene dispersing solution is carried out vacuum filtration cleaning, and dry gained filtrate obtains Graphene。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, the preparation method of described graphite oxide is more, such as Brodie method, Staudenmaier method and Hummers method etc., the method for graphite oxide powder is not carried out too much restriction by the present invention。But, present invention preferably uses the Hummers method of a kind of improvement and carry out the oxidation of graphite powder such that it is able to provide more excellent material condition for follow-up preparation。
The Hummers method improved comprises the following steps:
Graphite powder added in concentrated sulphuric acid and stir under condition of ice bath, add potassium permanganate after room temperature to be restored and continue stirring reaction, then with distilled water diluting under condition of ice bath, obtaining diluent；Being slowly added to by hydrogen peroxide in described diluent and continuously stirred, after placing a night, eccentric cleaning is to neutral, obtains graphite oxide。
Wherein, the particle diameter of described graphite powder is 0.42～150um；The mass concentration of described concentrated sulphuric acid is 96～98%, the mass concentration of described hydrogen peroxide is 0.1～30%, the mass volume ratio of described graphite powder and concentrated sulphuric acid is 0.1:100～1:10, the mass ratio of described graphite powder and potassium permanganate is 0.1:6～1:0.6, and the volume ratio of described concentrated sulphuric acid and hydrogen peroxide is 1:1～1:50。
The oxidation-reduction method that utilizes according to the present invention prepares the embodiment of simplification preparation method of Graphene, and the concentration of described graphite oxide is 0.02～10g/L, and in described mixed solution, the volume ratio of organic solvent and water is 1:0.01～1:100。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, described organic solvent is chitin, N, N-dimethyl acetylamide (DMAc), N, the combination of a kind of or at least two in dinethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP), wherein the deacetylation of chitin is 50%～90%。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, and described predetermined temperature is 5～90 DEG C, it is preferred to 40～60 DEG C。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, and the condition of described supersound process is be 42～80kHz and ultrasonic Treatment that ultrasonic power is 300～1200W 10～180 minutes by operating frequency。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, and the concentration of described reducing agent is 0.01～10g/L。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, and described reducing agent is the combination of a kind of or at least two in tea polyphenols, rhodioloside, anthocyanidin, ellagic acid, aminoacid。
Oxidoreduction one step that utilizes according to the present invention prepares the embodiment of method of Graphene, and the filter sizes used by described vacuum filtration is 0.1～10 μm。
Compared with prior art, the present invention has a characteristic that
(1) in the present invention, prepared by tradition in the oxidation-reduction method of Graphene aoxidize, peel off, reduction three phases be reduced to two stages, i.e. oxidation stage and stripping reduction phase, especially, stripping bench and reduction phase are reduced to a step so that peel off reduction phase and carry out simultaneously, have both shortened the response time, also improving production efficiency, the industrialized production for Graphene provides new method。
(2) the grapheme material size that the present invention prepares makes its lateral dimension within the scope of 0.02～3um because of the difference of raw material graphite powder order number, and thickness is within the scope of 0.8～2.4nm；Owing to whole preparation process relating to Oxidation, with part oxygen-containing functional group on prepared graphene layer, by XPS test the C/O ratio of Graphene is 8.1～20.7；The deoxidation of reduction process inevitably causes the defect of graphene layer, obtains I by Graphene is carried out Raman spectrum analysisD/IGValue is 0.02～1.18；The defect that graphenic surface exists makes its specific surface area in 78.9～240.1。
Accompanying drawing explanation
Fig. 1 illustrates that the Graphene to preparing in example 1 of the present invention is scanned ultramicroscope (SEM) observable surface topography map。
Fig. 2 illustrates that the Graphene to preparing in example 1 of the present invention carries out atomic force microscope (AFM) observable surface topography map。
Fig. 3 illustrates the infrared spectrogram of Graphene and the graphite powder and graphite oxide prepared in example 3 of the present invention。
Fig. 4 illustrates the x-ray photoelectron spectroscopy analysis chart of Graphene and the graphite oxide prepared in example 3 of the present invention。
Fig. 5 illustrates the Raman spectrogram of the Graphene prepared in example 5 of the present invention。
Detailed description of the invention
All features disclosed in this specification, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way。
This specification (include any accessory claim, summary and accompanying drawing) disclosed in any feature, unless specifically stated otherwise, all can by other equivalences or there is the alternative features of similar purpose replaced。That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics。
Below the method that the present invention utilizes oxidoreduction one step prepare Graphene is described in detail。
Exemplary embodiment according to the present invention, the described method utilizing oxidoreduction one step to prepare Graphene includes following multiple step。
Step 1:
Graphite powder is oxidized to graphite oxide。
Wherein, the method for graphite oxide powder is not carried out too much restriction by the present invention, for instance, it would however also be possible to employ Brodie method, Staudenmaier method and Hummers method etc.。
But, present invention preferably uses the Hummers method of a kind of improvement and carried out the oxidation of graphite powder such that it is able to provide more excellent material condition for follow-up ultrasonic stripping reduction。
Specifically, the Hummers method of described improvement comprises the following steps:
First, graphite powder added in concentrated sulphuric acid and stir under condition of ice bath, add potassium permanganate after room temperature to be restored and continue stirring reaction, then with distilled water diluting under condition of ice bath, obtaining diluent；
Then, being slowly added to by hydrogen peroxide in described diluent and continuously stirred, after placing a night, eccentric cleaning is to neutral, obtains graphite oxide。
In above-mentioned steps, concrete experiment parameter condition includes: the mass concentration of concentrated sulphuric acid is 96～98%, the mass concentration of hydrogen peroxide is 0.1～30%, the mass volume ratio of graphite powder and concentrated sulphuric acid is 0.1:100～1:10, the mass ratio of graphite powder and potassium permanganate is 0.1:6～1:0.6, and the volume ratio of concentrated sulphuric acid and hydrogen peroxide is 1:1～1:50。Wherein, the particle diameter of the graphite powder that the present invention uses is preferably 0.42～150um。
Step 2:
The graphite oxide that step 1 prepares is dissolved in the mixed solution including organic solvent and water of predetermined temperature, is simultaneously introduced reducing agent and it is carried out supersound process obtains graphene dispersing solution。Wherein, supersound process is not only by the speed of the motion raising reduction reaction of Accelerating reduction agent molecule, also as a kind of mode peeling off Graphene；The mixed liquor of organic solvent and water is then as dispersant, control suitable graphite layers from assist ultrasonic overcome Van der Waals force to peel off while, also prevent the Graphene obtained from reuniting, it is peel off the key factor simultaneously carried out with reduction process, owing to partial reduction agent is likely to immiscible with part organic solvent, so water is also necessary exist。
According to a preferred embodiment of the invention, the concentration controlling graphite oxide is 0.02～10g/L, and to control the volume ratio of organic solvent and water in mixed solution be 1:0.01～1:100。Wherein, organic solvent can be that (deacetylation of chitin is preferably 50%～90% to chitin, such as 50%, 60%, 70%, 80%, 90%), N, the combination of a kind of or at least two in N-dimethyl acetylamide (DMAc), DMF (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP)；Described combination such as DMAc/DMF, DMAc/DMSO, chitin/NMP, chitin/DMSO etc., described combined volume ratio is for 1:10～10:1, it is preferable that organic solvent that dispersion effect is best or its combination。
Simultaneously, the concentration controlling reducing agent is 0.01～10g/L, and reducing agent can be the combination of a kind of or at least two in tea polyphenols, rhodioloside, anthocyanidin, ellagic acid, aminoacid, described combination is tea polyphenols/anthocyanidin, rhodioloside/aminoacid, ellagic acid/tea polyphenols etc. such as, described combination quality is than for 1:10～10:1, it is preferable that reducing agent that reduction effect is best and combination thereof。
For reaction condition, it is possible to use heating in water bath control mixed solution temperature be 5～90 DEG C and preferably control be 40～60 DEG C with reach the best reaction effects。The condition controlling supersound process is: in order to suitable in commercial production, control supersonic frequency in conventional industrial frequency 25～130kHz, again because supersonic frequency is more high, cavitation effect is more weak, the bubble density produced is more dense, promote the probability that reducing agent contacts with oxygenated functional group more high, reduce more complete；And supersonic frequency is more high, ultrasonic impact power is more little, just can play the effect of stripping when impulsive force is more than the Van der Waals force of graphite layers。Therefore, ultrasonic operating frequency should not too high also should not be too low, it is preferable that in the scope of 42～80kHz。It addition, ultrasonic power and sonication treatment time are respectively set to 300～1200W and 10～180 minute, thus realizing the stripping reduction effect of the best。Wherein it is possible to adopt the instruments such as ultrasonic washing unit to carry out supersound process。
And, this step is actually the stripping in the oxidation-reduction method that tradition is prepared Graphene and two stages of reduction are reduced to the step simultaneously carried out and peel off reduction phase, shortening the response time and improve production efficiency, the industrialized production for Graphene provides new method。
Step 3:
Step 2 gained graphene dispersing solution is carried out vacuum filtration cleaning, and dry gained filtrate obtains Graphene。Wherein, the filter sizes used by vacuum filtration is preferably 0.1～10 μm。
On the whole, the present invention is with graphite powder for raw material, the Hummers legal system improved is adopted to obtain graphite oxide, graphite oxide is dissolved in the organic solvent of uniform temperature and the mixed solution of water, it is simultaneously introduced reducing agent and under certain frequency, power, carries out ultrasonic stripping reduction treatment, then product vacuum sucking filtration cleaning-drying being obtained grapheme material。Wherein it is possible to adopt the modes such as vacuum lyophilization。
A specific embodiment according to the present invention, concrete preparation method is as follows:
(1) according to the Hummers method improved, adding 1.5g graphite powder in 100mL concentrated sulphuric acid, ice bath, after 1 hour, adds KMnO45.0g, then reacts 6 hours at normal temperatures, then is diluted when ice bath with 200mL distilled water；After liquid to be diluted cooling, it is added dropwise over the hydrogenperoxide steam generator that 120mL mass concentration is 5%, by distilled water eccentric cleaning to neutral after placing a night。Wherein, the particle diameter of graphite powder is 6.5 μm～0.15mm。
(2) organic solvent is become mixed solution with distilled water according to the proportional arrangement of 1:0.01～1:100, wherein organic solvent is that (deacetylation of chitin is 50%～90% to chitin, such as 50%, 60%, 70%, 80%, 90%), N, the combination of a kind of or at least two in N-dimethyl acetylamide (DMAc), DMF (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP)。
(3) toward the mixed solution water-bath (or ice bath) prepared to 5～90 DEG C, it is subsequently adding the graphite oxide of 0.02～10g/L and the reducing agent of 0.01～10g/L, wherein, reducing agent is the one in tea polyphenols, rhodioloside, anthocyanidin, ellagic acid, aminoacid or at least two combination。
(4) mixed solution in (3) is placed in ultrasonic washing unit and processes 10～180 minutes with the operating frequency of 42～80kHz and the power ultrasonic of 300～1200W。Then the graphene dispersing solution obtained carries out vacuum filtration, and the filter membrane filtered is 0.1～10um。
It should be understood that; above-mentioned embodiment and the example below that the present invention describes in detail are merely to illustrate the present invention rather than restriction the scope of the present invention, and some nonessential improvement and adjustment that those skilled in the art makes according to the foregoing of the present invention belong to protection scope of the present invention。The parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in hereafter example。
Below in conjunction with example, the method that oxidoreduction one step prepares Graphene that utilizes of the present invention is described further。
Example 1:
The graphite powder that mean diameter is 13um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, and according to the volume ratio of 1:5, DMSO (dimethyl sulfoxide) and distilled water are configured to mixed solution, heats the solution obtained to 40 DEG C under water-bath；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 0.55g/L, is simultaneously introduced the tea polyphenols of certain mass, and the concentration making tea polyphenols is 2.0g/L；Then solution is placed in ultrasonic washing unit and adds up 30 minutes with the operating frequency of 50kHz and the supersound process (if temperature is more than 40 DEG C in ultrasonic procedure, continue supersound process after being down to 40 DEG C) of 700W, again the filter membrane of the graphene dispersing solution 0.22um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。Observe with the surface topography of the scanning electron microscope Graphene to preparing, concrete as it is shown in figure 1, as shown in Figure 1, gained Graphene be irregular flexible accordion, and its transparency difference illustrates the Graphene number of plies difference of preparation。Size characteristic analysis is carried out again with the atomic force microscope Graphene to preparing, as in figure 2 it is shown, the lateral dimension of gained Graphene is about 2um, thickness is about 1.2nm, Graphene theoretic throat according to monolayer is that 0.34nm infers, the Graphene obtained is about 3～4 layers。
Example 2:
The graphite powder that mean diameter is 6.5um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, and according to the volume ratio of 1:1, DMAc and distilled water are configured to mixed solution, heats the solution obtained to 80 DEG C under water-bath；Then adding in this mixed solution for graphite oxide and controlling the concentration of graphite oxide is 1.0g/L, is simultaneously introduced the rhodioloside of certain mass, and the concentration making rhodioloside is 4.0g/L；Then solution is placed in ultrasonic washing unit and processes (if temperature is more than 80 DEG C in ultrasonic procedure, continue supersound process after being down to 80 DEG C) accumulative 20 minutes with the operating frequency of 50kHz and the power ultrasonic of 1000W, again the filter membrane of the graphene dispersing solution 0.22um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。Carrying out size characteristic analysis with the atomic force microscope Graphene to preparing, the lateral dimension of gained Graphene is about 1.5um, and thickness is about 1.2nm, and the Graphene obtained is about 3～4 layers。
Example 3:
The graphite powder that mean diameter is 2.6um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, and according to the volume ratio of 1:1:1, DMAc, NMP and distilled water are configured to mixed solution, heats the solution obtained to 60 DEG C under water-bath；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 3.0g/L, is simultaneously introduced the anthocyanidin of certain mass, and the concentration making anthocyanidin is 2.5g/L；Then solution is placed in ultrasonic washing unit and processes (if temperature is more than 60 DEG C in ultrasonic procedure, continue supersound process after being down to 60 DEG C) accumulative 60 minutes with the operating frequency of 60kHz and the power ultrasonic of 800W, again the filter membrane of the graphene dispersing solution 0.22um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。Carrying out size characteristic analysis with the atomic force microscope Graphene to preparing, the lateral dimension of gained Graphene is about 1.5um, and thickness is about 1.8nm, is that 0.34nm infers according to the Graphene theoretic throat of monolayer, and the Graphene obtained is about 4～5 layers。
The Graphene structure of functional groups simultaneously prepared by Fourier infrared spectrograph comparative analysis graphite powder, graphite oxide and this example, increases from graphite to graphite oxide oxygen-containing functional group as shown in Figure 3, and the Graphene oxygen-containing functional group after reduction reduces。
With x-ray photoelectron spectroscopy, it being carried out elementary analysis again, the C/O ratio of the Graphene that this example prepares is become 10.51 from the 1.9 of graphite oxide；And can be seen that the C=C peak of graphite oxide becomes by force after reduction by spectrogram Fig. 4 from it, otherwise C-O and C=O is then。The Graphene specific surface area analyzing this example prepared with N2 adsorption surface analysis instrument is 150.87m2/g。
Example 4:
The graphite powder that mean diameter is 18um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, chitin (deacetylation is 70%) and distilled water are configured to mixed solution according to the volume ratio of 3:2, the solution obtained is heated to 25 DEG C under water-bath；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 5.0g/L, is simultaneously introduced the ellagic acid of certain mass, and the concentration making ellagic acid is 0.5g/L；Then solution is placed in ultrasonic washing unit under the ice-water bath being interrupted and processes accumulative 80 minutes with the operating frequency of 60kHz and the power ultrasonic of 400W, again the filter membrane of the graphene dispersing solution 0.45um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。With x-ray photoelectron spectroscopy, it being carried out elementary analysis, its C/O ratio is 9.47；The Graphene specific surface area analyzing this example prepared with N2 adsorption surface analysis instrument is 160.79m2/g。
Example 5:
The graphite powder that mean diameter is 0.64um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, and according to the volume ratio of 1:2:2, DMF, DMAc and distilled water are configured to mixed solution, heats the solution obtained to 50 DEG C under water-bath；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 4.0g/L, is simultaneously introduced the aminoacid of certain mass, and making amino acid whose concentration is 4.0g/L；Then solution is placed in ultrasonic washing unit and processes (if temperature is more than 50 DEG C in ultrasonic procedure, continue supersound process after being down to 50 DEG C) accumulative 40 minutes with the operating frequency of 42kHz and the power ultrasonic of 900W, again the filter membrane of the graphene dispersing solution 0.1um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。The Graphene prepared carries out the observation of apparent form, and its lateral dimension is about 0.3um, and thickness is about 1.2nm；And it is carried out Raman spectrum analysis, as it is shown in figure 5, record its defective value ID/IGIt is 0.25。
Example 6:
The graphite powder that mean diameter is 0.42um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, and according to the volume ratio of 2:3, NMP and distilled water are configured to mixed solution, heats the solution obtained to 55 DEG C under water-bath；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 0.8g/L, adds tea polyphenols and anthocyanidin according to the mass ratio of 1:1 simultaneously, and the concentration making reducing agent is 1.5g/L；Then solution is placed in ultrasonic washing unit and processes (if temperature is more than 55 DEG C in ultrasonic procedure, continue supersound process after being down to 55 DEG C) accumulative 90 minutes with the operating frequency of 70kHz and the power ultrasonic of 750W, again the filter membrane of the graphene dispersing solution 0.1um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。The Graphene prepared carries out the observation of apparent form, and its lateral dimension is about 0.2um, and thickness is about 1.2nm；With x-ray photoelectron spectroscopy, it being carried out elementary analysis, its C/O ratio is 17.01。
Example 7:
The graphite powder that mean diameter is 25um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, chitin (deacetylation is 80%) and distilled water are configured to mixed solution according to the volume ratio of 4:1, the solution obtained is heated to 80 DEG C under water-bath；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 1.6g/L, adds aminoacid and ellagic acid according to the mass ratio of 2:1 simultaneously, and the concentration making reducing agent is 0.8g/L；Then solution is placed in ultrasonic washing unit and processes (if temperature is more than 80 DEG C in ultrasonic procedure, continue supersound process after being down to 80 DEG C) accumulative 120 minutes with the operating frequency of 42kHz and the power ultrasonic of 1200W, again the filter membrane of the graphene dispersing solution 0.45um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。With x-ray photoelectron spectroscopy, it being carried out elementary analysis, its C/O ratio is 16.71。
Example 8:
The graphite powder that mean diameter is 1.6um is oxidized to graphite oxide by the Hummers method adopting above-mentioned improvement, and according to the volume ratio of 1:1:1:1, DMAc, DMF, NMP and distilled water are configured to mixed solution, by the solution that obtains at ice bath to 10 DEG C；Then being added in this mixed solution by graphite oxide and controlling the concentration of graphite oxide is 6.0g/L, adds tea polyphenols, aminoacid and rhodioloside according to the mass ratio of 2:1:1 simultaneously, and the concentration making reducing agent is 5.5g/L；Then solution is placed in ultrasonic washing unit under ice bath state to process 180 minutes with the operating frequency of 80kHz and the power ultrasonic of 300W, again the filter membrane of the graphene dispersing solution 0.1um obtained is carried out vacuum filtration cleaning, finally adopt vacuum lyophilization product to obtain Graphene。With x-ray photoelectron spectroscopy, it being carried out elementary analysis, its C/O ratio is 19.23。
The invention is not limited in aforesaid detailed description of the invention。The present invention expands to any new feature disclosed in this manual or any new combination, and the step of the arbitrary new method disclosed or process or any new combination。
Claims (9)
1. one kind utilizes the method that oxidoreduction one step prepares Graphene, it is characterized in that, described preparation method comprises the following steps: after aoxidizing with graphite powder, the graphite oxide that obtains is dissolved in the mixed solution including organic solvent and water under predetermined temperature, is simultaneously introduced reducing agent and it is carried out supersound process obtains graphene dispersing solution；Gained graphene dispersing solution is carried out vacuum filtration cleaning, and dry gained filtrate obtains Graphene。
2. the method utilizing oxidoreduction one step to prepare Graphene according to claim 1, it is characterised in that the particle diameter of described graphite powder is 0.42～150um。
3. the method utilizing oxidoreduction one step to prepare Graphene according to claim 1, it is characterised in that the concentration of described graphite oxide is 0.02～10g/L, and in described mixed solution, the volume ratio of organic solvent and water is 1:0.01～1:100。
4. the method utilizing oxidoreduction one step to prepare Graphene according to any one of claim 1 to 3, it is characterized in that, described organic solvent is chitin, N, N-dimethyl acetylamide (DMAc), N, the combination of a kind of or at least two in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone (NMP), wherein the deacetylation of chitin is 50%～90%。
5. the method utilizing oxidoreduction one step to prepare Graphene according to claim 1, it is characterised in that described predetermined temperature is 5～90 DEG C, it is preferred to 40-60 DEG C。
6. the method utilizing oxidoreduction one step to prepare Graphene according to claim 1, it is characterised in that the condition of described supersound process is be 42～80kHz and ultrasonic Treatment that ultrasonic power is 300～1200W 10～180 minutes by operating frequency。
7. the method utilizing oxidoreduction one step to prepare Graphene according to claim 1, it is characterised in that the concentration of described reducing agent is 0.01～10g/L。
8. utilize, according to claim 1 or 7, the method that oxidoreduction one step prepares Graphene, it is characterised in that described reducing agent is the combination of a kind of or at least two in tea polyphenols, rhodioloside, anthocyanidin, ellagic acid, aminoacid。
9. the method utilizing oxidoreduction one step to prepare Graphene according to claim 1, it is characterised in that the filter sizes used by described vacuum filtration is 0.1～10 μm。
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| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
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| CN109295699A (en) * | 2018-09-30 | 2019-02-01 | 河南工程学院 | A method of improving graphene finish fabric electric conductivity, conductivity uniformity and durability |
| CN114105127A (en) * | 2022-01-14 | 2022-03-01 | 曲靖华金雨林科技有限责任公司 | Method for preparing graphene |
| CN114572969A (en) * | 2022-02-11 | 2022-06-03 | 中国科学技术大学先进技术研究院 | Microfluidic reaction system and method for preparing reduced graphene oxide |
| CN114572969B (en) * | 2022-02-11 | 2023-08-18 | 中国科学技术大学先进技术研究院 | Microfluidic reaction system and method for preparing reduced graphene oxide |
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