CN104925791A - Graphene, graphene colloidal sol, graphene powder and preparation method and preparation device - Google Patents
Graphene, graphene colloidal sol, graphene powder and preparation method and preparation device Download PDFInfo
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Abstract
The invention provides graphene, graphene hydrosol, and graphene powder obtained by drying the graphene hydrosol, wherein the edge of the graphene comprises active groups, and the active groups comprise amino groups. The preparation method of the graphene hydrosol comprises the following steps: (1), performing electrochemical intercalation and exfoliation on graphene to obtain graphene dispersed in electrolyte; the electrolyte after electrochemical intercalation and exfoliation contains both inorganic salt and amino acid; after intercalation, removing free inorganic salt and amino acid compounds from the solution to obtain the graphene hydrosol. According to the graphene, graphene colloidal sol, graphene powder and the preparation method and the preparation device, provided by the invention, the graphene hydrosol is provided, the use of a great deal of an organic solvent in the graphene hydrosol based on the organic solvent is reduced, the stability is good, the preparation method is simple, the operation is easy, the equipment and material requirements are low, the environmental friendliness is achieved, and the industrialization is facilitated.
Description
Technical field
The invention belongs to field of graphene, be specifically related to a kind of graphene sol and preparation method thereof.
Background technology
Graphene is just regarded as the novel material being enough to change the world once coming out, monoatomic layer nanostructure gives its superpower special performance, has the excellent performance such as electricity, optics, chemistry.Along with deepening continuously of studying Graphene, research direction is studied again to constantly bringing forth new ideas to Graphene Application Areas to graphene preparation method from initial the researchdevelopment of Graphene intrinsic performance.The two large challenges that the industrial applications of Graphene faces are can the technique of preparation in macroscopic quantity and the guarantee of Graphene high-quality.At present the oxidation reduction process severe reaction conditions of most possible macroscopic preparation of graphene need High Temperature High Pressure to material corrosion and equipment requirements high, strong acid is applied and strong oxidizer can cause Heavy environmental pollution in preparation process, graphene dispersion system is a large amount of with an organic solvent, be difficult to remove, these problems seriously constrain the application development of Graphene.
To sum up, the Graphene exploring non-organic solvent sol system is the demand of this area.
Summary of the invention
In order to overcome the deficiencies in the prior art, one of the object of the invention proposes a kind of Graphene, and described graphene edge contains active group, and described active group comprises amino group.
Preferably, described active group also comprises the combination of any a kind or at least 2 kinds in hydroxyl, carboxyl, carbonyl, epoxy group(ing);
Preferably, the C/O ratio >=5 of described Graphene, such as, 6,7,8,15,30,50 etc.;
Preferably, in described Graphene, the massfraction of carbon is 80% ~ 99%.
Two of object of the present invention is to provide a kind of solation of Graphene---the Graphene water-sol, and containing the Graphene of 0.001 ~ 100mg/mL as described in one of object in the described Graphene water-sol.
In the described Graphene water-sol, the concentration of Graphene is typical but non-limiting is 0.01mg/mL, 0.07mg/mL, 0.1mg/mL, 0.6mg/mL, 0.9mg/mL, 1.6mg/mL, 6mg/mL, 20mg/mL, 30mg/mL, 70mg/mL, 90mg/mL etc.
Three of the object of the invention there is provided a kind of graphene powder, and described graphene powder is obtained by graphene sol drying described in two of object; And described graphene powder directly can be dispersed in water the formation Graphene water-sol, and containing 0.001 ~ 100mg/mL Graphene in the Graphene water-sol formed.
In the described Graphene water-sol, the concentration of Graphene is typical but non-limiting is 0.01mg/mL, 0.07mg/mL, 0.1mg/mL, 0.6mg/mL, 0.9mg/mL, 1.6mg/mL, 6mg/mL, 20mg/mL, 30mg/mL, 70mg/mL, 90mg/mL etc.
The good stability of graphene sol provided by the invention, can reach 6 months not stratified.
Mode by graphene sol drying of the present invention does not limit, preferred self-spray drying or lyophilize.
Four of object of the present invention is to provide a kind of preparation method of Graphene as described in one of object, comprises the steps:
(1) graphite electrochemistry intercalation is peeled off the Graphene obtaining and disperse in the electrolyte; Simultaneously containing amino acid and inorganic salt in the electrolytic solution that described electrochemical intercalation is peeled off.
Five of object of the present invention is to provide a kind of preparation method of graphene sol as described in two of object, and described method for carry out step (2) after step (1):
Inorganic salt after the stripping of removing step (1) electrochemical intercalation in ionogen and amino acids, obtain the Graphene water-sol.
Six of object of the present invention is to provide a kind of preparation method of graphene powder as described in two of object, and described method for carry out step (3) after step (2):
The Graphene water-sol that step (2) prepares is carried out drying, obtains graphene powder.
Mode by graphene sol drying of the present invention does not limit, preferred self-spray drying or lyophilize.
The preparation method of graphene sol of the present invention is the electrochemical intercalation method under amino acid effect, inorganic salts and amino acids reagent is only used in technological process, non-environmental-pollution, reaction can be completed at normal temperatures and pressures, equipment and materials requires lower, the graphene sol of preparation can keep stable for a long time, is with a wide range of applications in fields such as alloy, matrix material, anticorrosion, catalysis.
The present invention is under electrochemical reaction and amino acid effect, graphite carbon source sublayer is peeled off, generates active group in graphene edge simultaneously---amino, due to the effect of graphene edge absorption amino group, there is wetting ability, after ultrasonic disperse, form more stable water-sol system.Graphene prepared by the present invention is easy to application, and preparation method does not damage environment, non-pollutant discharge, and processing condition are gentle, is more suitable for technique and amplifies and promote.
Amino acids of the present invention is the combination of any a kind or at least 2 kinds be selected from Pidolidone, phenylalanine, tyrosine or tryptophane;
Preferably, in described electrolytic solution, amino acid whose concentration is 0.01 ~ 0.05mol/L, such as 0.02mol/L, 0.03mol/L, 0.04mol/L etc.;
Preferably, described inorganic salt are soluble sulphate or soluble nitrate, be selected from sodium sulfate, potassium sulfate, ammonium sulfate, SODIUMNITRATE, the combination of any a kind or at least 2 kinds in ammonium nitrate, the typical but non-limiting combination comprising sodium sulfate and potassium sulfate of described combination, the combination of sodium sulfate and SODIUMNITRATE, SODIUMNITRATE, the combination etc. of ammonium nitrate and potassium sulfate;
Preferably, in described electrolytic solution, the concentration of inorganic salt is 0.01 ~ 1mol/L, such as 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.09mol/L etc.
The described electrochemical intercalation of step of the present invention (1) is peeled off and is carried out under magnetic field, and the intensity in described magnetic field is preferably 10 ~ 100mT, such as 15mT, 19mT, 25mT, 36mT, 58mT, 75mT, 83mT, 95mT etc.
The applying in magnetic field can improve the intercalation speed at graphite edge further.
In the described electrochemical intercalation stripping process of step of the present invention (1), reaction electrode is connected with positive source, and material is graphite type material, preferred graphite rod or graphite paper, further preferred graphite paper; Be connected with power cathode electrode, material is any a kind in graphite type material, platinum, copper or palladium electrode material, preferred graphite type material.
In the present invention, the material of reaction electrode is graphite material is the raw material that intercalation prepares Graphene; The material of electrode is not limited, but preferred graphite material, other impurity can not be introduced in electrolytic solution like this and cost is lower.
Preferably, reaction electrode number >=2 that the described electrochemical intercalation of step (1) is peeled off, preferably 3 ~ 6.
Increase the number of reaction electrode-positive electrode, can corresponding increase speed of response, enhance productivity.The number of the present invention to reaction electrode is not specifically limited, and in large-scale production, those skilled in the art can according to practical situation, and as the size of electrolyzer, voltage, electrode size etc. are selected reaction electrode number.
Preferably, the electric current that the described electrochemical intercalation of step (1) is peeled off is constant current, the preferably constant current of 0.1 ~ 1A.The size of described constant current is typical but non-limiting is 0.2A, 0.4A, 0.6A, 0.8A etc.
Preferably, the temperature of reaction that the described electrochemical intercalation of step (1) is peeled off is 0 ~ 30 DEG C, such as 3 DEG C, 7 DEG C, 13 DEG C, 17 DEG C etc.; Reaction times is 0.5 ~ 10h, such as 0.6h, 0.9h, 3h, 6h, 8h etc.
As optimal technical scheme, the preparation method of graphene sol of the present invention comprises the steps:
(1) electrochemical intercalation peels off graphite: reaction electrode and be graphite paper to electrode, electrolytic solution is soluble sulphate or soluble nitrate and the amino acid whose aqueous solution, in electrolytic solution, the concentration of soluble sulphate or soluble nitrate is 0.1mol/L, and amino acid whose concentration is 0.02mol/L; The external direct current power supply of access 5V, electric current is 0.5A, positive source ligation electrode, and controlling temperature of reaction is 15 DEG C, carries out electrochemical stripping 3h, obtains the Graphene disperseed in the electrolyte;
(2) inorganic salt in solution and amino acid is removed: the dispersion Graphene in the electrolyte step (1) obtained filters successively, washing, centrifugal, remove non-intercalation or insufficient graphite microchip, free inorganic salt and the amino acid of intercalation, then ultrasonic 2h obtains the Graphene water-sol;
Alternatively, the Graphene water-sol lyophilize 30h that step (2) prepares by (3) obtains graphene powder; The graphene powder obtained again through ultrasonic disperse in water, obtain the Graphene water-sol.
Seven of the object of the invention be to provide a kind of for object four described in prepare the electrochemical intercalation stripping off device of Graphene, described device comprises: power supply; For the electrolyzer of splendid attire electrolytic solution; Be placed at least 1 reaction electrode of electrolyzer; Be placed at least 1 of electrolyzer to electrode; First wire, for being connected reaction electrode with the positive pole of power supply; Second wire, for being connected to electrode with the negative pole of power supply; Described first wire and/or the second wire have at least 2 outlet lines, and the end of outlet line described in every root connects an electrode.
As a kind of embodiment of the object of the invention seven, described reaction electrode and to electrode arrangement be in a cell linear interval arrangement or the circle spacing arrangement;
To the arrangement distance of electrode and reaction electrode, the area of electrode, electrolytical concentration in electrolyzer of the present invention, the present invention is not specifically limited, and the current density of the reaction electrode that those skilled in the art can limit according to the present invention and actual demand are determined voluntarily.
In described embodiment, in described electrolyzer, the current density of reaction electrode is 0.01 ~ 1A/cm
2;
As the another kind of embodiment of the object of the invention seven, described reaction electrode and be to electrode arrangement in a cell: reaction electrode with to electrode for the center of circle, be evenly distributed on circumferentially same.
Preferably, described reaction electrode and/or to the shape of electrode independently selected from any a kind in line, post, sheet, block, powder;
Preferably, the material of described reaction electrode is graphite type material, preferred graphite rod or graphite paper, further preferred graphite paper;
Preferably, the described material to electrode is the combination of any a kind or at least 2 kinds in graphite type material, platinum, copper or palladium electrode material, preferred graphite type material, further preferably graphite rod or graphite paper, particularly preferably graphite paper.
Preferably, the material of described electrolyzer is corrosion resistant insulating material, any a kind in preferred glass, quartz, macromolecular material.
Preferably, the shape of described electrolyzer is circular or square;
Preferably, the volume of described electrolyzer is 0.001 ~ 1000L.
Preferably, the voltage of described power supply is 0.1 ~ 100V.
Preferably, described electrolyzer is provided with fixing slide calliper rule, and described slide calliper rule have the scale for marking distance, and for the fixture of fixed electorde.
Preferably, described fixture is any a kind in intermediate plate, screwing type or spring pinchcock.
Compared with prior art, the present invention has following beneficial effect:
(1) the invention provide a kind of graphene sol-Graphene water-sol that can disperse in non-organic solvent, avoid the use of a large amount of organic solvent in the graphene sol based on organic solvent, the development for Graphene provides a new direction;
(2) good stability of the Graphene water-sol provided by the invention, its can reach 6 months not stratified;
(3) preparation method of the Graphene water-sol provided by the invention is simple, easy to operate, and equipment and materials requires low, is easy to industrialization;
(4) present invention also offers the electrochemical stripping device prepared for the Graphene water-sol, greatly can improve the preparation speed of the Graphene water-sol of the present invention, enhance productivity.
Accompanying drawing explanation
Fig. 1 is that the Graphene water-sol that embodiment prepares leaves standstill the steady state after 6 months; Wherein from left to right be followed successively by: colloidal sol 1., colloidal sol 2., colloidal sol 3., colloidal sol 4., colloidal sol 5., colloidal sol 6.;
Fig. 2 is the photo of the graphene powder that embodiment 1 step (3) prepares;
Fig. 3 is the Tyndall phenomenon that 1. colloidal sol be diluted to 0.1mg/mL and 0.001mg/mL, and middle bottle is contrast deionized water;
Fig. 4 is the SEM figure of the Graphene that embodiment 1 prepares;
Fig. 5 be the Graphene for preparing of embodiment 1 AFM figure;
Fig. 6 is the Raman spectrogram of the Graphene prepared under differing temps (0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C);
Fig. 7 for described in embodiment 4 for the preparation of the structural representation of the electrochemical stripping device of graphene sol;
Fig. 8 for described in embodiment 4 for the preparation of the structural representation vertical view of the fixing slide calliper rule of the electrochemical stripping device of graphene sol;
The schematic diagram that Fig. 9 is reaction electrode and arranges to the circle spacing of electrode;
Figure 10 be with to electrode for center of circle reaction electrode is evenly distributed on same schematic diagram circumferentially;
Wherein, 1 is power supply; 2 is the first wire; 3 is fixing slide calliper rule; 4 is intermediate plate; 5 is liquid level of electrolyte; 6 is the second wire; 8 is electrolyzer; 9 is scale; 10 is draw-in groove; 11 is reaction electrode; 12 is to electrode; 13 is thermostatic bath; 14 is water inlet pipe; 15 is water level sensor; 16 is constant temperature water tank.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A preparation method for the Graphene water-sol, comprises the steps:
(1) electrochemical intercalation peels off graphite:
Reaction electrode and be flexible graphite paper to electrode, is of a size of 4cm × 6cm × 0.05cm; The external direct current power supply of access 5V, electric current is 0.5A; Electrolytic solution is the metabisulfite solution 900mL of 0.1mol/L, and adds the Pidolidone of 3.9725g wherein, makes its concentration be 0.03mol/L; Controlling temperature of reaction is 15 DEG C, carries out electrochemical stripping 3h, obtains the Graphene disperseed in the electrolyte;
(2) remove inorganic salt and amino acid: the dispersion Graphene suction filtration in the electrolyte step (1) obtained, deionized water washes away unnecessary ionogen; Under 2000rpm, centrifugal 10min removes non-intercalation or the insufficient graphite microchip of intercalation afterwards; Finally add deionized water supersound process 2h and prepare Graphene water-sol system; Be designated as colloidal sol 1., wherein the concentration of Graphene is 8.5mg/mL;
(3) Graphene water-sol system lyophilize 30h step (2) obtained obtains graphene powder; Be designated as powder 1.;
(4) graphene powder that step (5) obtains is dispersed in water, ultrasonic 2h, obtains graphene sol system; Be designated as colloidal sol 2., wherein the concentration of Graphene is 10mg/mL.
Performance test:
Graphene C/O ratio is 10.15; The massfraction of graphene carbon is 90.3%;
Stability: the graphene sol system that step (1) and step (4) obtain is placed in sample bottle and leaves standstill, observe whether layering; Result is still in stable collosol state after showing 6 months; (Fig. 1 is that the Graphene water-sol that embodiment prepares leaves standstill the steady state after 6 months to result such as Fig. 1; Wherein from left to right be followed successively by: colloidal sol 1., colloidal sol 2., colloidal sol 3., colloidal sol 4., colloidal sol 5., colloidal sol 6.) shown in;
Fig. 2 shows the photo of the graphene powder that step (3) obtains;
Fig. 3 is that 1. colloidal sol add deionized water and be diluted to Tyndall phenomenon when concentration is 0.1mg/mL and 0.001mg/mL to Graphene content;
Fig. 4 is the SEM figure of the Graphene that embodiment 1 prepares;
Fig. 5 be the Graphene for preparing of embodiment 1 AFM figure.
Embodiment 1 step (1) temperature of reaction is adjusted to 0 DEG C, 5 DEG C, 10 DEG C, 20 DEG C; Fig. 6 is the Raman spectrogram of the Graphene prepared under differing temps (0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C).As can be seen from Figure 6, along with the reduction of temperature, D peak diminishes, and edge active group tails off.
Embodiment 2
A preparation method for the Graphene water-sol, comprises the steps:
(1) electrochemical intercalation peels off graphite:
Reaction electrode and be flexible graphite paper to electrode, is of a size of 4cm × 6cm × 0.05cm; The external direct current power supply of access 5V, electric current is 0.5A; Electrolytic solution is the amine nitrate solution 900mL of 0.2mol/L, and adds the phenylalanine of 7.4334g wherein, makes its concentration be 0.05mol/L; Controlling temperature of reaction is 10 DEG C, carries out electrochemistry 3h, obtains the Graphene disperseed in the electrolyte;
(2) remove inorganic salt and amino acid: the dispersion Graphene suction filtration in the electrolyte step (1) obtained, deionized water washes away unnecessary ionogen; Under 2000rpm, centrifugal 10min removes non-intercalation or the insufficient graphite microchip of intercalation afterwards; 3. last supersound process 2h prepares Graphene water-sol system; Wherein the concentration of Graphene is 5.5mg/mL;
(3) Graphene water-sol system lyophilize 30h step (2) obtained obtains graphene powder;
Performance test:
Graphene C/O ratio is 6.15; The massfraction of graphene carbon is 85.1%.
Embodiment 3
A preparation method for the Graphene water-sol, is with the difference of embodiment 1:
In the additional 50mT magnetic field of the electrolyzer of electrochemical intercalation; 4. the graphene sol system that wherein step (2) prepares is designated as colloidal sol, and wherein the concentration of Graphene is 1.5mg/mL;
The product yield of the present embodiment comparatively embodiment 1 improves 15%;
Performance test:
Graphene C/O ratio is 11.59; The massfraction of graphene carbon is 91.6%.
Embodiment 4
A preparation method for the Graphene water-sol, is with the difference of embodiment 3, and described electrochemical stripping carries out in for the preparation of the electrochemical stripping device of graphene sol;
The described electrochemical stripping device for the preparation of graphene sol comprises: power supply;
Rectangle glass electrolyzer 8, is of a size of 100cm × 130cm × 200cm, for splendid attire electrolytic solution;
Fixing slide calliper rule 3, are set up in above electrolyzer 8, and do not contact with liquid level of electrolyte 5; Described fixing slide calliper rule 3 comprise: the scale 9 being carved with mark distance, and for the intermediate plate 4 of fixed electrode film; Scale 9 is provided with draw-in groove 10 along its length, and intermediate plate 4 is arranged on draw-in groove 10, and can slide along scale 9 length direction; Intermediate plate 4 can be fixed on the optional position of draw-in groove 10 by nut;
Power supply 1 positive pole draws the first wire 2, and described first wire 2 has 5 outlet lines, and the end winding support of every root outlet line is on the intermediate plate 4 of described fixing slide calliper rule 3; Intermediate plate 4 is fixed with the graphite paper as reaction electrode 11 towards a side of electrolytic solution;
Power supply 1 negative pole draws the second wire 6, and described second wire 6 has 5 outlet lines, and the end winding support of every root outlet line is on the intermediate plate 4 of described fixing slide calliper rule 3; Intermediate plate 4 is fixed with towards a side of electrolytic solution the graphite paper be used as electrode 12;
Power supply 1 voltage is 5V, and electric current is 1.5A;
Reaction electrode 11 and electrode 12 interval is arranged; And adjacent reaction electrode 11 be 4cm to the distance of electrode 12;
Outside described electrolyzer 8, thermostatic bath 13 is set, for controlling the temperature of electrolyzer 8;
Described electrolyzer 8 is provided with water level induction hutch water device, for controlling the water level of electrolyzer 8; Described water level induction hutch water device comprises constant temperature water tank 16, the water inlet pipe 14 be communicated with constant temperature water tank 16, and be arranged at the water level sensor 15 in electrolyzer 8, described water level sensor 15 is connected with water inlet pipe 14 switch by controller.
Fig. 7 for described in embodiment 4 for the preparation of the structural representation of the electrochemical stripping device of graphene sol;
Fig. 8 for described in embodiment 4 for the preparation of the structural representation vertical view of the fixing slide calliper rule of the electrochemical stripping device of graphene sol;
In identical electrochemical stripping time 3h, the product yield of graphene sol is 3 times of embodiment 1; Can find out, the number increasing reaction electrode under the same conditions effectively can improve reaction efficiency;
Performance test:
Graphene C/O ratio is 9.04; The massfraction of graphene carbon is 89.5%; In the graphene sol obtained, the concentration of Graphene is 4mg/mL.
Embodiment 4 provide for the preparation of in the electrochemical stripping device of graphene sol, reaction electrode and can also arranging (as shown in Figure 9 for the circle spacing to electrode arrangement in a cell, the schematic diagram that Fig. 9 is reaction electrode and arranges to the circle spacing of electrode), or with to electrode for center of circle reaction electrode is evenly distributed on same circumferentially (as shown in Figure 10, Figure 10 be with to electrode for center of circle reaction electrode is evenly distributed on same schematic diagram circumferentially).
Embodiment 5
A kind of preparation method of the Graphene water-sol, be to be added with magnetic field in electrochemical stripping process with the difference of embodiment 1, field direction is perpendicular to the sense of current, carries out 2 groups of experiments, magnetic field size is respectively as 10mT and 100mT, product yield respectively comparatively embodiment 1 improve 2% and 17%;
Performance test:
Graphene C/O is respectively than being 10.23 and 11.05; The massfraction of graphene carbon is respectively 90.7% and 91.2%; In the graphene sol obtained, the concentration of Graphene is 5mg/mL.
Embodiment 6
A preparation method for the Graphene water-sol, is with the difference of embodiment 1, and the concentration of Pidolidone is 0.04mol/L, and the concentration of sodium sulfate is 0.01mol/L; 5. the graphene sol that step (2) obtains is designated as colloidal sol, and wherein the concentration of Graphene is 1mg/mL;
Performance test:
Graphene C/O ratio is 32.16; The massfraction of graphene carbon is 96.5%.
Embodiment 7
A preparation method for the Graphene water-sol, is with the difference of embodiment 1, and the concentration of Pidolidone is 0.01mol/L, and the concentration of sodium sulfate is 1mol/L; 6. the graphene sol that step (2) obtains is designated as colloidal sol, and wherein the concentration of Graphene is 2.5mg/mL;
Performance test:
Graphene C/O ratio is 6.35; The massfraction of graphene carbon is 86.2%.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a Graphene, is characterized in that, described graphene edge contains active group, and described active group comprises amino group.
2. Graphene as claimed in claim 1, is characterized in that, described active group also comprises the combination of any a kind or at least 2 kinds in hydroxyl, carboxyl, carbonyl, epoxy group(ing);
Preferably, the C/O of described Graphene is than >=5;
Preferably, in described Graphene, the massfraction of carbon is 80% ~ 99%.
3. a graphene sol, is characterized in that, described graphene sol is for by the Graphene water-sol obtained soluble in water for Graphene described in claim 1 or 2
Preferably, 0.001 ~ 100mg/mL Graphene as claimed in claim 1 or 2 is contained in the described Graphene water-sol.
4. a graphene powder, is characterized in that, described graphene powder is obtained by graphene sol drying described in claim 3;
Described graphene powder is again dispersed in water and forms the Graphene water-sol.
5. a preparation method for Graphene as claimed in claim 1 or 2, is characterized in that, described method comprises the steps:
(1) graphite electrochemistry intercalation is peeled off the Graphene obtaining and disperse in the electrolyte; Simultaneously containing amino acid and inorganic salt in the electrolytic solution that described electrochemical intercalation is peeled off.
6. a preparation method for graphene sol as claimed in claim 3, is characterized in that, described method for carry out step (2) after step (1):
Free inorganic salt and amino acids in ionogen after the stripping of removing step (1) electrochemical intercalation, obtain the Graphene water-sol.
7. a preparation method for graphene powder as claimed in claim 4, is characterized in that, described method for carry out step (3) after step (2):
Graphene water-sol drying step (2) prepared obtains graphene powder.
8. the method as described in one of claim 5 ~ 7, is characterized in that, described amino acids is the combination of any a kind or at least 2 kinds be selected from Pidolidone, phenylalanine, tyrosine or tryptophane;
Preferably, in described electrolytic solution, amino acid whose concentration is 0.01 ~ 0.05mol/L;
Preferably, described inorganic salt are soluble sulphate or soluble nitrate, the combination of any a kind or at least 2 kinds preferably in sodium sulfate, potassium sulfate, ammonium sulfate, SODIUMNITRATE, ammonium nitrate;
Preferably, in described electrolytic solution, the concentration of inorganic salt is 0.01 ~ 1mol/L;
Preferably, the described electrochemical intercalation of step (1) is peeled off and is carried out under magnetic field, and the intensity in described magnetic field is preferably 10 ~ 100mT.
Preferably, in the described electrochemical intercalation stripping process of step (1), reaction electrode connects positive source, and material is graphite type material, preferred graphite rod or graphite paper, further preferred graphite paper; To Electrode connection power cathode, material is any a kind in graphite type material, platinum, copper or palladium electrode material, preferred graphite type material;
Preferably, reaction electrode number >=2 that the described electrochemical intercalation of step (1) is peeled off, preferably 3 ~ 6;
Preferably, the electric current that the described electrochemical intercalation of step (1) is peeled off is constant current, the preferably constant current of 0.1 ~ 1A;
Preferably, the temperature of reaction that the described electrochemical intercalation of step (1) is peeled off is 0 ~ 30 DEG C; Reaction times is 0.5 ~ 10h.
9. the method as described in one of claim 5 ~ 8, is characterized in that, described method comprises the steps:
(1) electrochemical intercalation peels off graphite: reaction electrode and be graphite paper to electrode, electrolytic solution is soluble sulphate or soluble nitrate and the amino acid whose aqueous solution, in electrolytic solution, the concentration of soluble sulphate or soluble nitrate is 0.1mol/L, and amino acid whose concentration is 0.02mol/L; The external direct current power supply of access 5V, electric current is 0.5A, positive source ligation electrode, and controlling temperature of reaction is 15 DEG C, carries out electrochemical stripping 3h, obtains the Graphene disperseed in the electrolyte;
(2) inorganic salt and amino acid is removed: the dispersion Graphene in the electrolyte step (1) obtained filters successively, washing, centrifugal, remove non-intercalation or insufficient graphite microchip, free inorganic salt and the amino acid of intercalation, then ultrasonic 2h obtains the Graphene water-sol;
Alternatively, the Graphene water-sol lyophilize 30h that step (2) prepares by (3) obtains graphene powder; The graphene powder obtained again through ultrasonic disperse in water, obtain the Graphene water-sol.
10., for preparing an electrochemical intercalation stripping off device for Graphene as claimed in claim 5, described device comprises: power supply; For the electrolyzer of splendid attire electrolytic solution; Be placed at least 1 reaction electrode of electrolyzer; Be placed at least 1 of electrolyzer to electrode; First wire, for being connected reaction electrode with the positive pole of power supply; Second wire, for being connected to electrode with the negative pole of power supply; Described first wire and/or the second wire have at least 2 outlet lines, and the end of outlet line described in every root connects an electrode;
Preferably, described reaction electrode and to electrode arrangement be in a cell linear interval arrangement, the circle spacing arrange, or with to electrode for center of circle reaction electrode is evenly distributed on same circumferentially in any a kind;
Preferably, described electrolyzer is provided with fixing slide calliper rule, and described slide calliper rule have the scale for marking distance, and for the fixture of fixed electorde;
Preferably, outside described electrolyzer, thermostatic bath is set, for controlling the temperature of electrolyzer;
Preferably, described electrolyzer is provided with water level induction hutch water device, for controlling the water level of electrolyzer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510303286.5A CN104925791B (en) | 2015-06-05 | 2015-06-05 | A kind of graphene, its colloidal sol, powder and preparation method and preparation facilities |
| CN201611104763.6A CN106744874B (en) | 2015-06-05 | 2015-06-05 | A kind of graphene, its colloidal sol, powder and preparation method and preparation facilities |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510303286.5A CN104925791B (en) | 2015-06-05 | 2015-06-05 | A kind of graphene, its colloidal sol, powder and preparation method and preparation facilities |
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| CN201611104763.6A Division CN106744874B (en) | 2015-06-05 | 2015-06-05 | A kind of graphene, its colloidal sol, powder and preparation method and preparation facilities |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104925791A true CN104925791A (en) | 2015-09-23 |
| CN104925791B CN104925791B (en) | 2018-02-06 |
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| CN105417536A (en) * | 2015-12-31 | 2016-03-23 | 北京科技大学 | Method for preparing graphene quantum dots with adjustable oxygen content |
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| CN108232180A (en) * | 2017-12-19 | 2018-06-29 | 刘博文 | A kind of graphene/titanium dioxide/LiFePO4 aeroge cell positive material and preparation method thereof |
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| CN103130218A (en) * | 2013-03-25 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Preparation method of graphene |
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| CN2700345Y (en) * | 2004-04-21 | 2005-05-18 | 深圳市危险废物处理站 | Radiating type electrode electrolytic cell |
| CN103204494A (en) * | 2012-01-16 | 2013-07-17 | 中央研究院 | Device and method used for scale production of graphene and graphene oxide |
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| CN103991862B (en) * | 2013-12-27 | 2016-02-03 | 杭州金马能源科技有限公司 | Electrochemistry efficiently peels off the method preparing high-quality graphene |
| CN204873850U (en) * | 2015-06-05 | 2015-12-16 | 中国科学院过程工程研究所 | Device of electrochemistry intercalation preparation graphite alkene |
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2015
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130218A (en) * | 2013-03-25 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Preparation method of graphene |
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| CN108912606A (en) * | 2018-06-26 | 2018-11-30 | 常州兴烯石墨烯科技有限公司 | A kind of graphene conductive heat generating pastes and preparation method thereof |
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| CN113170699A (en) * | 2020-08-18 | 2021-07-27 | 山西大同大学 | Graphene synergistic morchella culture medium and preparation method and application thereof |
| CN111924832A (en) * | 2020-09-23 | 2020-11-13 | 广西师范大学 | Device and method for producing graphene by electrochemically stripping graphite from electrode array |
| CN111943181A (en) * | 2020-09-23 | 2020-11-17 | 广西师范大学 | Annular stripping device and stripping method for producing graphene by graphite powder electrochemical method |
| CN114342936A (en) * | 2022-02-21 | 2022-04-15 | 合肥高尔生命健康科学研究院有限公司 | Bactericide for preventing anthracnose of dendrobium nobile and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106744874A (en) | 2017-05-31 |
| CN104925791B (en) | 2018-02-06 |
| CN106744874B (en) | 2019-06-25 |
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