CN104291332A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN104291332A CN104291332A CN201410545419.5A CN201410545419A CN104291332A CN 104291332 A CN104291332 A CN 104291332A CN 201410545419 A CN201410545419 A CN 201410545419A CN 104291332 A CN104291332 A CN 104291332A
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Abstract
The invention belongs to the technical field of graphene preparation and relates to a method of preparing graphene in batch. The preparation method is characterized by comprising the following steps: preparing water-containing graphene oxide; purifying the water-containing graphene oxide; preparing water-containing graphene; purifying the water-containing graphene; and preparing graphene powder. The invention discloses the method of preparing graphene in batch. By adopting the method, the yield of the graphene is greatly increased, the batch-type production needs are met, and the preparation cost is lowered. Meanwhile, poisonous raw materials are not used, so that harm on a human body is avoided; the graphene powder which is few in defects, high in quality, fluffy and good in compatibility with various solvents and is not agglomerated is prepared.
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 carbon material, is with a wide range of applications in new energy materials, photocatalyst material, biomaterial and all kinds of field of compound material due to performances such as the chemical structure of its uniqueness, the specific surface area of super large and impayable electricity, mechanics, calorifics.The current preparation method occurring numerous Graphene, such as micromechanics stripping method, redox chemistry stripping method, solvent-thermal method, surface of SiC greying method, chemical Vapor deposition process etc.Disclosed documents and materials show, obtaining good, that productive rate is high, output is large, high purity, size uniform, the number of plies are few, defect the is few Graphene of quality is still 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 controlled.The step of current redox chemistry stripping method is see (" Graphene---structure, preparation method and performance characterization ", Zhu Hongwei, Xu Zhiping, the work such as Xie Dan, press of Tsing-Hua University, 2011) its shortcoming is: the first, output is little, and raw material injected volume is mg ~ g rank, be not suitable for mass production, preparation cost is high; The second, the large reductive agent of toxicity (as hydrazine hydrate) is employed, large to Health hazard, be unfavorable for environment protection; Three, the defect of prepared Graphene is more, and show that the impurity ion content of Graphene is more, more easily reunite, purity is not high enough, and size is even not, and the number of plies is more.
Summary of the invention
The object of the invention is: propose a kind of method that batch prepares Graphene, to improve output, meet the requirement of batch production, reduce preparation cost; Avoid, to the harm of HUMAN HEALTH, being conducive to environment protection; The graphene powder that defect is few, quality is good is provided.
Technical scheme of the present invention is: a kind of preparation method of Graphene, is characterized in that, the step of preparation is as follows:
1, oxidizing aqueous Graphene is prepared: the vitriol oil and phosphoric acid are placed in respectively-20 DEG C ~ 10 DEG C refrigerator 8h ~ 12h; Take out and the vitriol oil mixed with phosphoric acid, pour into agitator and well heater, volume is in the reactor of 100L ~ 150L, the concentration of the vitriol oil is 98wt%, purity is analytical pure, the concentration of phosphoric acid is 97.0wt%, and purity is analytical pure, and the volume ratio of the vitriol oil and phosphoric acid is 8 ~ 10:1; In reactor, add potassium permanganate, the quality adding potassium permanganate in every mL vitriol oil is 0.1g ~ 0.125g; Stir 5min ~ 10min, the rotating speed 100r/min ~ 200r/min of agitator; In reactor, add natural graphite, the mass ratio of potassium permanganate and natural graphite 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, leave standstill 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 is purified: be placed in by oxidizing aqueous Graphene 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;
3, graphene oxide powder preparation: by oxidizing aqueous Graphene lyophilize, obtain graphene oxide powder;
4, graphene powder preparation: graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 400 DEG C ~ 600 DEG C, and the recovery time is 2h ~ 4h, obtains graphene powder.
Advantage of the present invention is: propose a kind of method that batch prepares Graphene, substantially increases the output of Graphene, meets the requirement of batch production, reduces preparation cost; Meanwhile, do not use poisonous starting material, avoid the harm to HUMAN HEALTH, be conducive to environment protection; 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.As seen from Figure 1, wave number 1628cm
-1it is the C=C stretching vibration peak of phenyl ring on Graphene.Wave number 1403cm
-1, 1049cm
-1be the vibration of hydroxyl-OH in-plane deformation and stretching vibration peak respectively, but peak is strong very faint, other oxy radicals are (as 1728cm
-1the C=O vibration of neighbouring carboxylic acid, carbonyl, 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 clean, residual 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
-1d peak and the G peak of Graphene respectively, the faint by force and broadening in peak, and other 2D peak (2700cm
-1near) also do not occur, illustrate that Graphene is stripped comparatively abundant, quality is good.
Fig. 3 is the X-ray diffraction spectrogram of Graphene prepared by the embodiment of the present invention 1.As can be seen from the XRD diffraction peak of Fig. 3 also, do not have obvious peak crystallization to occur, basic expressions is metamict, visible, and 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 finds out more intuitively, and the size of Graphene is comparatively large and evenly, surperficial zero defect, quality is good.
Fig. 5 is the scanning electron microscope ultimate analysis energy spectrogram of Graphene prepared by the embodiment of the present invention 1.Can also can see by spectrogram from Fig. 5, the impurity ion content of Graphene is very little.More than characterize visible, the preparation method described in specification sheets can obtain inclusion-free ion, does not fluffyly reunite, and high purity, size uniform, the number of plies is few, and defect is few, the graphene powder that quality is good, and productive rate is higher.
Embodiment
Below the present invention is described in further details.A preparation method for Graphene, is characterized in that, the step of preparation is as follows:
1, oxidizing aqueous Graphene is prepared: the vitriol oil and phosphoric acid are placed in respectively-20 DEG C ~ 10 DEG C refrigerator 8h ~ 12h; Take out and the vitriol oil mixed with phosphoric acid, pour into agitator and well heater, volume is in the reactor of 100L ~ 150L, the concentration of the vitriol oil is 98wt%, purity is analytical pure, the concentration of phosphoric acid is 97.0wt%, and purity is analytical pure, and the volume ratio of the vitriol oil and phosphoric acid is 8 ~ 10:1; In reactor, add potassium permanganate, the quality adding potassium permanganate in every ml vitriol oil is 0.1g ~ 0.125g; Stir 5min ~ 10min, the rotating speed 100r/min ~ 200r/min of agitator; In reactor, add natural graphite, the mass ratio of potassium permanganate and natural graphite 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, leave standstill 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 is purified: be placed in by oxidizing aqueous Graphene 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;
3, graphene oxide powder preparation: by oxidizing aqueous Graphene lyophilize, obtain graphene oxide powder;
4, graphene powder preparation: graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 400 DEG C ~ 600 DEG C, and the recovery time is 2h ~ 4h, obtains graphene powder.
Embodiment 1:
The 40.0L vitriol oil and 5.0L phosphoric acid are placed in refrigerator and cooled and freeze 8h.The mixed solution of the vitriol oil and phosphoric acid is poured in 100L reactor, then add 5kg potassium permanganate in solution, stir 8min, rotating speed 100r/min.In reactor, add 625g natural graphite again, stir 2h, rotating speed 100r/min.Temperature of reaction kettle is risen to 70 DEG C, close heating after stirring 18h and stir, being cooled to room temperature, obtaining 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, leave standstill 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 lyophilize 3 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 400 DEG C, and the time is 2 hours, obtains graphene powder, productive rate 88.6%, its infrared spectra is as Fig. 1, and Raman spectrum is as Fig. 2, X-ray diffraction spectrum is as Fig. 3, and microscopic appearance is as Fig. 4, and ultimate analysis is as Fig. 5.。
Embodiment 2:
The 40.0L vitriol oil and 5.0L phosphoric acid are placed in refrigerator and cooled and freeze 10h.The mixed solution of the vitriol oil and phosphoric acid is poured in 100L reactor, then add 5kg potassium permanganate in solution, stir 5min, rotating speed 200r/min.In reactor, add 500g natural graphite again, stir 2h, rotating speed 200r/min.Temperature of reaction kettle is risen to 50 DEG C, close heating after stirring 24h and stir, being cooled to room temperature, obtaining 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, leave standstill 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 lyophilize 4 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 450 DEG C, and the time is 2 hours, obtains graphene powder, productive rate 89.7%.
Embodiment 3:
The 45.0L vitriol oil and 5.0L phosphoric acid are placed in refrigerator and cooled and freeze 12h.The mixed solution of the vitriol oil and phosphoric acid is poured in 150L reactor, then add 5kg potassium permanganate in solution, stir 10min, rotating speed 150r/min.In reactor, add 556g natural graphite again, stir 3h, rotating speed 150r/min.Temperature of reaction kettle is risen to 50 DEG C, close heating after stirring 18h and stir, being cooled to room temperature, obtaining 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, leave standstill 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 lyophilize 3 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 500 DEG C, and the time is 3 hours, obtains graphene powder, productive rate 91.2%.
Embodiment 4:
The 45.0L vitriol oil and 5.0L phosphoric acid are placed in refrigerator and cooled and freeze 8h.The mixed solution of the vitriol oil and phosphoric acid is poured in 100L reactor, then add 5kg potassium permanganate in solution, stir 8min, rotating speed 200r/min.In reactor, add 556g natural graphite again, stir 3h, rotating speed 200r/min.Temperature of reaction kettle is risen to 60 DEG C, close heating after stirring 24h and stir, being cooled to room temperature, obtaining 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, leave standstill 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 lyophilize 4 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 550 DEG C, and the time is 3 hours, obtains graphene powder, productive rate 88.9%.
Embodiment 5:
The 50.0L vitriol oil and 5.0L phosphoric acid are placed in refrigerator and cooled and freeze 10h.The mixed solution of the vitriol oil and phosphoric acid is poured in 150L reactor, then add 5kg potassium permanganate in solution, stir 5min, rotating speed 100r/min.In reactor, add 500g natural graphite again, stir 2h, rotating speed 100r/min.Temperature of reaction kettle is risen to 70 DEG C, close heating after stirring 20h and stir, being cooled to room temperature, obtaining 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, leave standstill 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 lyophilize 3 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 600 DEG C, and the time is 3 hours, obtains graphene powder, productive rate 92.0%.
Embodiment 6:
The 50.0L vitriol oil and 5.0L phosphoric acid are placed in refrigerator and cooled and freeze 12h.The mixed solution of the vitriol oil and phosphoric acid is poured in 150L reactor, then add 5kg potassium permanganate in solution, stir 10min, rotating speed 150r/min.In reactor, add 625g natural graphite again, stir 2h, rotating speed 150r/min.Temperature of reaction kettle is risen to 60 DEG C, close heating after stirring 20h and stir, being cooled to room temperature, obtaining 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, leave standstill 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 lyophilize 4 days, obtain graphene oxide powder; Graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 600 DEG C, and the time is 4 hours, obtains graphene powder, productive rate 87.8%.
Claims (1)
1. a preparation method for Graphene, is characterized in that, the step of preparation is as follows:
1.1, oxidizing aqueous Graphene is prepared: the vitriol oil and phosphoric acid are placed in respectively-20 DEG C ~ 10 DEG C refrigerator 8h ~ 12h; Take out and the vitriol oil mixed with phosphoric acid, pour into agitator and well heater, volume is in the reactor of 100L ~ 150L, the concentration of the vitriol oil is 98wt%, purity is analytical pure, the concentration of phosphoric acid is 97.0wt%, and purity is analytical pure, and the volume ratio of the vitriol oil and phosphoric acid is 8 ~ 10:1; In reactor, add potassium permanganate, the quality adding potassium permanganate in every mL vitriol oil is 0.01g ~ 0.125g; Stir 5min ~ 10min, the rotating speed 100r/min ~ 200r/min of agitator; In reactor, add natural graphite, the mass ratio of potassium permanganate and natural graphite 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, leave standstill 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 is purified: be placed in by oxidizing aqueous Graphene 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;
1.3, graphene oxide powder preparation: by oxidizing aqueous Graphene lyophilize, obtain graphene oxide powder;
1.4, graphene powder preparation: graphene oxide powder is placed in the reduction of argon gas atmosphere stove interior heat, reduction temperature is 400 DEG C ~ 600 DEG C, and the recovery time is 2h ~ 4h, obtains graphene powder.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242520A (en) * | 2019-07-17 | 2021-01-19 | 珠海冠宇电池股份有限公司 | PTC material of graphene microsphere based on multi-branch structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242520A (en) * | 2019-07-17 | 2021-01-19 | 珠海冠宇电池股份有限公司 | PTC material of graphene microsphere based on multi-branch structure and preparation method and application thereof |
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