CN104291332B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN104291332B CN104291332B CN201410545419.5A CN201410545419A CN104291332B CN 104291332 B CN104291332 B CN 104291332B CN 201410545419 A CN201410545419 A CN 201410545419A CN 104291332 B CN104291332 B CN 104291332B
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Abstract
The invention belongs to technical field of graphene preparation, relate to a kind of method that batch prepares Graphene. It is characterized in that, the step of preparation is as follows: prepare oxidizing aqueous Graphene; Oxidizing aqueous Graphene purifies; Preparation aqueous graphite feed alkene; Aqueous graphite feed alkene purifies; Prepared by graphene powder. The present invention proposes a kind of method that batch prepares Graphene, substantially increases the yield of Graphene, meets the requirement of batch production, reduces preparation cost; Meanwhile, poisonous raw material is not used, it is to avoid the harm to health; Prepare that a kind of defect is few, quality is high, fluffy do not reunite and with multi-solvents, there is the graphene powder of excellent compatibility.
Description
Technical field
The invention belongs to technical field of graphene preparation, relate to a kind of method that batch prepares Graphene.
Background technology
Graphene as a kind of emerging material with carbon element, is with a wide range of applications in new energy materials, catalysis material, biomaterial and all kinds of field of compound material due to the chemical constitution of its uniqueness, the performance such as specific surface area and impayable electricity, mechanics, calorifics of super large. The preparation method occurring in that numerous Graphene at present, for instance micromechanics stripping method, redox chemistry stripping method, solvent-thermal method, surface of SiC graphitization method, chemical vapour deposition technique etc. Disclosed documents and materials show, it is thus achieved that the Graphene that quality is good, productivity is high, yield is big, high purity, size uniform, the number of plies are few, defect is few is still that a difficult problem, there is many technical problems. Redox chemistry stripping method enjoys the high praise of researcher due to features such as its cost are low, technique is easily-controllable. The step of current redox chemistry stripping method is referring to (" graphene-structured, preparation method and performance characterization ", Zhu Hongwei, Xu Zhiping, the work such as Xie Dan, publishing house of Tsing-Hua University, 2011) its shortcoming is: the first, yield is little, and raw material injected volume is mg～g rank, being not suitable for mass production, preparation cost is high; The second, the big reducing agent of toxicity (such as hydrazine hydrate) is employed, health hazard is big, it is unfavorable for environmental conservation; 3rd, the defect of prepared Graphene is more, shows that the impurity ion content of Graphene is more, is easier to reunite, and degree of purity is not high enough, and size is uniform not, and the number of plies is more.
Summary of the invention
It is an object of the invention to: propose a kind of method that batch prepares Graphene, in order to improve yield, meet the requirement of batch production, reduce preparation cost; Avoid the harm to health, be conducive to environmental conservation; The graphene powder that defect is few, quality is good is provided.
The preparation method that the technical scheme is that a kind of Graphene, it is characterised in that the step of preparation is as follows:
1, oxidizing aqueous Graphene is prepared: concentrated sulphuric acid and phosphoric acid are respectively placed in 8h～12h in-20 DEG C～10 DEG C refrigerators;Take out and concentrated sulphuric acid mixed with phosphoric acid, pour into agitator and heater, volume be 100L～150L reactor in, the concentration of concentrated sulphuric acid is 98wt%, purity is analytical pure, the concentration of phosphoric acid is 97.0wt%, and purity is analytical pure, and the volume ratio of concentrated sulphuric acid and phosphoric acid is 8～10:1; Adding potassium permanganate in reactor, the quality adding potassium permanganate in every mL concentrated sulphuric acid is 0.1g～0.125g; Stirring 5min～10min, the rotating speed 100r/min～200r/min of agitator; The mass ratio adding native graphite, potassium permanganate and native graphite in reactor is 1:0.1～0.125, stirs 2h～3h, rotating speed 100r/min～200r/min; Then the temperature of solution in reactor is increased to 50 DEG C～70 DEG C, stirs 18h～24h, close heating, be cooled to room temperature, obtain graphene oxide thick liquid; The dilution of graphene oxide thick liquid deionization frozen water is obtained graphene oxide suspension, the volume ratio of graphene oxide thick liquid and frozen water volume is 1:5～10, add hydrogen peroxide, until the color of graphene oxide suspension becomes glassy yellow, stand 5h～24h, oxidizing aqueous Graphene in graphene oxide suspension is deposited to the lower floor of graphene oxide suspension, is taken out by the oxidizing aqueous Graphene in graphene oxide suspension;
2, oxidizing aqueous Graphene purifies: be placed on cellulose filter film by oxidizing aqueous Graphene, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7;
3, prepared by graphene oxide powder: by oxidizing aqueous Graphene lyophilization, obtain graphene oxide powder;
4, prepared by graphene powder: graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 400 DEG C～600 DEG C, and the recovery time is 2h～4h, obtains graphene powder.
The invention have the advantage that and propose a kind of method that batch prepares Graphene, substantially increase the yield of Graphene, meet the requirement of batch production, reduce preparation cost; Meanwhile, do not use poisonous raw material, it is to avoid harm to health, be conducive to environmental conservation; Provide the graphene powder that defect is few, quality is good.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of Graphene prepared by the embodiment of the present invention 1. It can be seen from figure 1 that wave number 1628cm-1It it is the C=C stretching vibration peak of phenyl ring on Graphene. Wave number 1403cm-1, 1049cm-1Being the vibration of hydroxyl-OH in-plane deformation and stretching vibration peak respectively, but peak is strong very faint, other oxy radicals are (such as 1728cm-1Near carboxylic acid, carbonyl C=O vibration, 640cm-1Neighbouring cyclic ketones in-plane bending vibration, 1257cm-1Near C-O-C skeletal vibration peak) characteristic peak do not occur yet, illustrates that Graphene is reduced very fully, very totally, remain without other groups.
Fig. 2 is the Raman spectrogram of Graphene prepared by the embodiment of the present invention 1. From the Raman spectrogram of Fig. 2,1364cm-1And 1605cm-1Being D peak and the G peak of Graphene respectively, peak is faint by force and broadening, and other 2D peak (2700cm-1Near) also do not occur, illustrating that Graphene is stripped relatively abundant, quality is good.
Fig. 3 is the X-ray diffraction spectra figure of Graphene prepared by the embodiment of the present invention 1. From the XRD diffraction maximum of Fig. 3 it is also seen that, it does not have significantly peak crystallization occurs, basic expressions is amorphous state, it is seen then that the number of plies of Graphene is few, and the diffraction between interlamellar spacing is not reflected.
Fig. 4 is the scanning electron microscope microscopic appearance figure of Graphene prepared by the embodiment of the present invention 1.The Flied emission SEM of Fig. 4 more finds out intuitively, Graphene larger in size and uniform, and surface zero defect, quality is good.
Fig. 5 is the scanning electron microscope elementary analysis energy spectrogram of Graphene prepared by the embodiment of the present invention 1. From the energy spectrogram of Fig. 5 it can also be seen that the impurity ion content of Graphene is very little. More than characterizing visible, preparation method described in description can obtain free from admixture ion, fluffy does not reunite, and high purity, size uniform, the number of plies is few, and defect is few, the graphene powder that quality is good, and productivity is higher.
Detailed description of the invention
Below the present invention is described in further details. The preparation method of a kind of Graphene, it is characterised in that the step of preparation is as follows:
1, oxidizing aqueous Graphene is prepared: concentrated sulphuric acid and phosphoric acid are respectively placed in 8h～12h in-20 DEG C～10 DEG C refrigerators; Take out and concentrated sulphuric acid mixed with phosphoric acid, pour into agitator and heater, volume be 100L～150L reactor in, the concentration of concentrated sulphuric acid is 98wt%, purity is analytical pure, the concentration of phosphoric acid is 97.0wt%, and purity is analytical pure, and the volume ratio of concentrated sulphuric acid and phosphoric acid is 8～10:1; Adding potassium permanganate in reactor, the quality adding potassium permanganate in every ml concentrated sulphuric acid is 0.1g～0.125g; Stirring 5min～10min, the rotating speed 100r/min～200r/min of agitator; The mass ratio adding native graphite, potassium permanganate and native graphite in reactor is 1:0.1～0.125, stirs 2h～3h, rotating speed 100r/min～200r/min; Then the temperature of solution in reactor is increased to 50 DEG C～70 DEG C, stirs 18h～24h, close heating, be cooled to room temperature, obtain graphene oxide thick liquid; The dilution of graphene oxide thick liquid deionization frozen water is obtained graphene oxide suspension, the volume ratio of graphene oxide thick liquid and frozen water volume is 1:5～10, add hydrogen peroxide, until the color of graphene oxide suspension becomes glassy yellow, stand 5h～24h, oxidizing aqueous Graphene in graphene oxide suspension is deposited to the lower floor of graphene oxide suspension, is taken out by the oxidizing aqueous Graphene in graphene oxide suspension;
2, oxidizing aqueous Graphene purifies: be placed on cellulose filter film by oxidizing aqueous Graphene, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7;
3, prepared by graphene oxide powder: by oxidizing aqueous Graphene lyophilization, obtain graphene oxide powder;
4, prepared by graphene powder: graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 400 DEG C～600 DEG C, and the recovery time is 2h～4h, obtains graphene powder.
Embodiment 1:
40.0L concentrated sulphuric acid and 5.0L phosphoric acid is placed in refrigerator freezing 8h. The mixed liquor of concentrated sulphuric acid Yu phosphoric acid is poured in 100L reactor, then in solution, adds 5kg potassium permanganate, stir 8min, rotating speed 100r/min. In reactor, add 625g native graphite again, stir 2h, rotating speed 100r/min. Temperature of reaction kettle is risen to 70 DEG C, closes heating and stirring after stirring 18h, be cooled to room temperature, obtain graphene oxide thick liquid. The dilution of graphene oxide thick liquid 250L deionization frozen water is obtained graphene oxide suspension, adds 500mL hydrogen peroxide, till the color of graphene oxide suspension becomes glassy yellow, stand 5h, take out the oxidizing aqueous Graphene of lower floor. Oxidizing aqueous Graphene is placed on cellulose filter film, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7;By oxidizing aqueous Graphene lyophilization 3 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 400 DEG C, and the time is 2 hours, obtains graphene powder, productivity 88.6%, its infrared spectrum such as Fig. 1, Raman spectrum is Fig. 2 such as, X-ray diffraction spectra is Fig. 3 such as, and microscopic appearance is Fig. 4 such as, and elementary analysis is Fig. 5 such as. .
Embodiment 2:
40.0L concentrated sulphuric acid and 5.0L phosphoric acid is placed in refrigerator freezing 10h. The mixed liquor of concentrated sulphuric acid Yu phosphoric acid is poured in 100L reactor, then in solution, adds 5kg potassium permanganate, stir 5min, rotating speed 200r/min. In reactor, add 500g native graphite again, stir 2h, rotating speed 200r/min. Temperature of reaction kettle is risen to 50 DEG C, closes heating and stirring after stirring 24h, be cooled to room temperature, obtain graphene oxide thick liquid. The dilution of graphene oxide thick liquid 300L deionization frozen water is obtained graphene oxide suspension, adds 600mL hydrogen peroxide, till the color of graphene oxide suspension becomes glassy yellow, stand 8h, take out the oxidizing aqueous Graphene of lower floor. Oxidizing aqueous Graphene is placed on cellulose filter film, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7; By oxidizing aqueous Graphene lyophilization 4 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 450 DEG C, and the time is 2 hours, obtains graphene powder, productivity 89.7%.
Embodiment 3:
45.0L concentrated sulphuric acid and 5.0L phosphoric acid is placed in refrigerator freezing 12h. The mixed liquor of concentrated sulphuric acid Yu phosphoric acid is poured in 150L reactor, then in solution, adds 5kg potassium permanganate, stir 10min, rotating speed 150r/min. In reactor, add 556g native graphite again, stir 3h, rotating speed 150r/min. Temperature of reaction kettle is risen to 50 DEG C, closes heating and stirring after stirring 18h, be cooled to room temperature, obtain graphene oxide thick liquid. The dilution of graphene oxide thick liquid 350L deionization frozen water is obtained graphene oxide suspension, adds 700mL hydrogen peroxide, till the color of graphene oxide suspension becomes glassy yellow, stand 12h, take out the oxidizing aqueous Graphene of lower floor. Oxidizing aqueous Graphene is placed on cellulose filter film, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7; By oxidizing aqueous Graphene lyophilization 3 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 500 DEG C, and the time is 3 hours, obtains graphene powder, productivity 91.2%.
Embodiment 4:
45.0L concentrated sulphuric acid and 5.0L phosphoric acid is placed in refrigerator freezing 8h. The mixed liquor of concentrated sulphuric acid Yu phosphoric acid is poured in 100L reactor, then in solution, adds 5kg potassium permanganate, stir 8min, rotating speed 200r/min. In reactor, add 556g native graphite again, stir 3h, rotating speed 200r/min. Temperature of reaction kettle is risen to 60 DEG C, closes heating and stirring after stirring 24h, be cooled to room temperature, obtain graphene oxide thick liquid. The dilution of graphene oxide thick liquid 400L deionization frozen water is obtained graphene oxide suspension, adds 800mL hydrogen peroxide, till the color of graphene oxide suspension becomes glassy yellow, stand 24h, take out the oxidizing aqueous Graphene of lower floor. Oxidizing aqueous Graphene is placed on cellulose filter film, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7;By oxidizing aqueous Graphene lyophilization 4 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 550 DEG C, and the time is 3 hours, obtains graphene powder, productivity 88.9%.
Embodiment 5:
50.0L concentrated sulphuric acid and 5.0L phosphoric acid is placed in refrigerator freezing 10h. The mixed liquor of concentrated sulphuric acid Yu phosphoric acid is poured in 150L reactor, then in solution, adds 5kg potassium permanganate, stir 5min, rotating speed 100r/min. In reactor, add 500g native graphite again, stir 2h, rotating speed 100r/min. Temperature of reaction kettle is risen to 70 DEG C, closes heating and stirring after stirring 20h, be cooled to room temperature, obtain graphene oxide thick liquid. The dilution of graphene oxide thick liquid 450L deionization frozen water is obtained graphene oxide suspension, adds 900mL hydrogen peroxide, till the color of graphene oxide suspension becomes glassy yellow, stand 24h, take out the oxidizing aqueous Graphene of lower floor. Oxidizing aqueous Graphene is placed on cellulose filter film, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7; By oxidizing aqueous Graphene lyophilization 3 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 600 DEG C, and the time is 3 hours, obtains graphene powder, productivity 92.0%.
Embodiment 6:
50.0L concentrated sulphuric acid and 5.0L phosphoric acid is placed in refrigerator freezing 12h. The mixed liquor of concentrated sulphuric acid Yu phosphoric acid is poured in 150L reactor, then in solution, adds 5kg potassium permanganate, stir 10min, rotating speed 150r/min. In reactor, add 625g native graphite again, stir 2h, rotating speed 150r/min. Temperature of reaction kettle is risen to 60 DEG C, closes heating and stirring after stirring 20h, be cooled to room temperature, obtain graphene oxide thick liquid. The dilution of graphene oxide thick liquid 550L deionization frozen water is obtained graphene oxide suspension, adds 1000mL hydrogen peroxide, till the color of graphene oxide suspension becomes glassy yellow, stand 24h, take out the oxidizing aqueous Graphene of lower floor. Oxidizing aqueous Graphene is placed on cellulose filter film, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7; By oxidizing aqueous Graphene lyophilization 4 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 600 DEG C, and the time is 4 hours, obtains graphene powder, productivity 87.8%.
Claims (1)
1. the preparation method of a Graphene, it is characterised in that the step of preparation is as follows:
1.1, oxidizing aqueous Graphene is prepared: concentrated sulphuric acid and phosphoric acid are respectively placed in 8h～12h in-20 DEG C～10 DEG C refrigerators; Take out and concentrated sulphuric acid mixed with phosphoric acid, pour into agitator and heater, volume be 100L～150L reactor in, the concentration of concentrated sulphuric acid is 98wt%, purity is analytical pure, the concentration of phosphoric acid is 97.0wt%, and purity is analytical pure, and the volume ratio of concentrated sulphuric acid and phosphoric acid is 8～10:1; Adding potassium permanganate in reactor, the quality adding potassium permanganate in every mL concentrated sulphuric acid is 0.125g; Stirring 5min～10min, the rotating speed 100r/min～200r/min of agitator; The mass ratio adding native graphite, potassium permanganate and native graphite in reactor is 1:0.1～0.125, stirs 2h～3h, rotating speed 100r/min～200r/min;Then the temperature of solution in reactor is increased to 50 DEG C～70 DEG C, stirs 18h～24h, close heating, be cooled to room temperature, obtain graphene oxide thick liquid; The dilution of graphene oxide thick liquid deionization frozen water is obtained graphene oxide suspension, the volume ratio of graphene oxide thick liquid and frozen water volume is 1:5～10, add hydrogen peroxide, until the color of graphene oxide suspension becomes glassy yellow, stand 5h～24h, oxidizing aqueous Graphene in graphene oxide suspension is deposited to the lower floor of graphene oxide suspension, is taken out by the oxidizing aqueous Graphene in graphene oxide suspension;
1.2, oxidizing aqueous Graphene purifies: be placed on cellulose filter film by oxidizing aqueous Graphene, with the oxidizing aqueous Graphene of deionized water wash of flowing, until the pH value of oxidizing aqueous Graphene is 6～7;
1.3, prepared by graphene oxide powder: by oxidizing aqueous Graphene lyophilization, obtain graphene oxide powder;
1.4, prepared by graphene powder: graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior-heat, and reduction temperature is 400 DEG C～600 DEG C, and the recovery time is 2h～4h, obtains graphene powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167311A (en) * | 2011-03-09 | 2011-08-31 | 华侨大学 | Method for preparing graphene on large scale |
| CN103274396A (en) * | 2013-06-20 | 2013-09-04 | 电子科技大学 | Preparation method of grapheme and ferriferrous oxide composite nanometer material |
| WO2014058235A1 (en) * | 2012-10-09 | 2014-04-17 | 주식회사 그래핀올 | Method for forming graphene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102167311A (en) * | 2011-03-09 | 2011-08-31 | 华侨大学 | Method for preparing graphene on large scale |
| WO2014058235A1 (en) * | 2012-10-09 | 2014-04-17 | 주식회사 그래핀올 | Method for forming graphene oxide |
| CN103274396A (en) * | 2013-06-20 | 2013-09-04 | 电子科技大学 | Preparation method of grapheme and ferriferrous oxide composite nanometer material |
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