CN104150470A - Metal-solution reduction method for preparing graphene - Google Patents
Metal-solution reduction method for preparing graphene Download PDFInfo
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- CN104150470A CN104150470A CN201410370439.3A CN201410370439A CN104150470A CN 104150470 A CN104150470 A CN 104150470A CN 201410370439 A CN201410370439 A CN 201410370439A CN 104150470 A CN104150470 A CN 104150470A
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Abstract
The invention particularly relates to a metal-solution reduction method for preparing graphene. A graphene oxide water solution with low concentration is subjected to reduction treatment by a compound reduction system of iron powder and hydrochloric acid, so as to prepare graphene powder. The graphene oxide water solution with low concentration is subjected to reduction treatment by the compound reduction system of metal iron powder and hydrochloric acid, so that the metal-solution reduction method is low in raw material cost, nontoxic, easy to operate, and beneficial to mass production, and has a wide large-scale industrial application prospect. According to the metal-solution reduction method, a dilute solution is adopted, so that the whole reaction process is small in influence on the environment; liquid waste only contains a few of ions, so that the treatment cost is low.
Description
(1) technical field
The invention belongs to new energy materials technology of preparing, particularly a kind of metal-solution reduction of preparing Graphene.
(2) background technology
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital forms hexangle type and is the individual layer flat film that honeycomb lattice (honeycomb crystal lattice) is arranged formation, only has the two-dimensional material of a carbon atom thickness.Graphene be at present the thinnest be in the world the hardest nano material also, it is almost completely transparent, only absorbs 2.3% light; Thermal conductivity is up to 5300W/mK, and higher than carbon nanotube and diamond, under normal temperature, its electronic mobility surpasses 15000cm
2/ (Vs), ratio nano carbon pipe or silicon wafer height again, and resistivity only approximately 10
-6Ω cm, lower than copper or silver, be the material of world resistivity minimum.Graphene has the physical and chemical performance of excellence like this, gradually for transparent conductive film, nano electron device (transistor, the interconnected internal memory semi-conductor of transistor circuit), conductive ink, the fields such as solar cell, lithium cell, ultracapacitor, sensor and biological medicine.
At present, the preparation method of Graphene mainly contains mechanical process and chemical method, mechanical process comprises micromechanics partition method, metallic surface chemical Vapor deposition process (CVD), silicon carbide epitaxial growth method etc., and chemical method mainly comprises chemical dispersion method, oxidation reduction process and graphite layers chemical combination method etc.Wherein oxidation reduction process application is comparatively extensive, because desired raw material is cheap and easy to get, but the chemical reduction fado that reduction-oxidation graphite adopts contains poisonous strong reductant as hydrazine hydrate, sodium borohydride etc., easy contaminate environment, high temperature (1000 ℃ of >) reduction is high to equipment requirements, and yied of redution is on the low side, be unfavorable for mass production.In a word, at present there is the problems such as the high and environmental pollution of cost is serious in the preparation method of Graphene, thereby need to seek a kind of low cost, nonpolluting method to realize the mass production of Graphene.
(3) summary of the invention
The present invention is in order to make up the deficiencies in the prior art, a kind of simple to operate, pollution-free, metal-solution reduction of preparing Graphene that can mass production is provided, solve prior art high for the preparation of the cost of Graphene, seriously polluted, and prepare the problems such as the quality of Graphene is low.
The present invention is achieved through the following technical solutions:
Metal-solution reduction of preparing Graphene, its special character is: by iron powder and the compound reduction system reducing of hydrochloric acid, process the graphite oxide aqueous solution of dilute concentration, prepare graphene powder.
Metal-solution reduction of preparing Graphene of the present invention, comprises the following steps:
(1) graphene oxide: first, 50-200g natural graphite and the 1.25-5L nitration mixture that is comprised of the 1.12-4.5L vitriol oil and 0.13-0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 125-500g potassium permanganate; Afterwards, sealed reactor is also warming up to 75-85 ℃ of reaction 1-4 hour, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution;
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0-36g iron powder and 0.3-2.4L under magnetic agitation, 60-100 ℃ of reaction 1-6 hour; Then standing, by hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain.
Metal-solution reduction of preparing Graphene of the present invention in step (2), adds the concentrated hydrochloric acid of 6.0g iron powder and 1.2L under magnetic agitation, and 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain.
Metal-solution reduction of preparing Graphene of the present invention, iron powder purity >99.0%, concentrated hydrochloric acid massfraction concentration be 36%.
Metal-solution reduction of preparing Graphene of the present invention, the number of plies of the graphene powder of preparation is 4-10 layer, the about 110.8m of specific surface area
2/ g, the about 1000-3000S/m of specific conductivity.
The invention has the beneficial effects as follows: the present invention adopts metal iron powder and the compound reduction system of hydrochloric acid to reduce to process the graphite oxide aqueous solution of dilute concentration, raw materials cost is cheap, nontoxic, simple to operate, be beneficial to batch production, there are the bright prospects of heavy industrialization application; In the present invention, all adopted the solution of dilute concentration, whole reaction process is very little on the impact of environment, and only contains a small amount of ion in waste liquid, and processing cost is low.
(4) accompanying drawing explanation
The x-ray diffraction pattern (XRD) of the Graphene that accompanying drawing 1 is prepared for metal-solution reduction;
The scanning electron microscope (SEM) photograph of Graphene prepared by accompanying drawing 2 metals-solution reduction (SEM);
The transmission electron microscope picture (TEM) of the Graphene that accompanying drawing 3 is prepared for metal-solution reduction;
Atomic power (AFM) figure (a) of the Graphene that accompanying drawing 4 is prepared for metal-solution reduction;
The height survey sheet (b) of the Graphene that accompanying drawing 5 is prepared for metal-solution reduction;
The thickness of Graphene approximately 4.0 nm.
(5) embodiment
Embodiment 1
The present embodiment Graphene preparation process is:
(1) graphene oxide: adopt the airtight legal system of phosphoric acid that I take charge of independent research for graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 110.8m of specific surface area
2/ g, the about 2795.6S/m of specific conductivity.
Embodiment 2
The present embodiment Graphene preparation process is:
(1) graphene oxide: adopt the airtight legal system of phosphoric acid that I take charge of independent research for graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 75 ℃ of reactions 4 hours, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (sulfuric acid) and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 6 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 1492S/m of specific conductivity.
Embodiment 3
The present embodiment Graphene preparation process is:
(1) graphene oxide: adopt the airtight legal system of phosphoric acid that I take charge of independent research for graphene oxide: first, 200g natural graphite and the 5L nitration mixture that is comprised of the 4.5L vitriol oil and 0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 500g potassium permanganate; Afterwards, sealed reactor is also warming up to 85 ℃ of reactions 1 hour, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 1 hour; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 1754S/m of specific conductivity.
Embodiment 4
The present embodiment Graphene preparation process is:
Step (1) is identical with embodiment 1.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0g iron powder and 1.2L under magnetic agitation, 60 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 822.7S/m of specific conductivity.
Embodiment 5
The present embodiment Graphene preparation process is:
Step (1) is identical with embodiment 1.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0g iron powder and 1.2L under magnetic agitation, 100 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 2360.2S/m of specific conductivity.
Embodiment 6
The present embodiment Graphene preparation process is:
Step (1) is identical with embodiment 1.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0g iron powder and 0.3L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 525.0S/m of specific conductivity.
Embodiment 7
The present embodiment Graphene preparation process is:
Step (1) is identical with embodiment 1.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0g iron powder and 2.4L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 1989.0S/m of specific conductivity.
Embodiment 8
The present embodiment Graphene preparation process is:
Step (1) is identical with embodiment 1.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 18g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 2486.0S/m of specific conductivity.
Embodiment 9
The present embodiment Graphene preparation process is:
Step (1) is identical with embodiment 1.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 36g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 3228.6S/m of specific conductivity.
Embodiment 10
The present embodiment Graphene preparation process is:
(1) graphene oxide: adopt the airtight legal system of phosphoric acid that I take charge of independent research for graphene oxide: first, 50g natural graphite and the 1.25L nitration mixture that is comprised of the 1.12L vitriol oil and 0.13L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 125g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 110m of specific surface area
2/ g, the about 2695.7S/m of specific conductivity.
Embodiment 11
The present embodiment Graphene preparation process is:
(1) graphene oxide: adopt the airtight legal system of phosphoric acid that I take charge of independent research for graphene oxide: first, 125g natural graphite and the 2L nitration mixture that is comprised of the 1.7L vitriol oil and 0.3L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 200g potassium permanganate; Afterwards, sealed reactor is also warming up to 80 ℃ of reactions 2 hours, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid (hydrochloric acid) and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution.
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6g iron powder and 1.5L under magnetic agitation, 80 ℃ are reacted 5 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain, the about 110m of specific surface area
2/ g, the about 2845.4S/m of specific conductivity.
Embodiment 12
Because gained Graphene performance is similar, now take the present embodiment 1 as example, be analyzed as follows:
The x-ray diffraction pattern of sample prepared by Fig. 1 metal-solution reduction (XRD), the broad peak between 20-27 degree shows that this sample is grapheme material;
The scanning electron microscope (SEM) photograph of Graphene prepared by Fig. 2 metal-solution reduction (SEM), known graphene powder is comprised of the micro-nano sheet structure of puffy;
Fig. 3 is the transmission electron microscope picture (TEM) of the Graphene prepared of metal-solution reduction, and the microtexture of known graphene powder comprises micro-nano of a large amount of thin layer;
Fig. 4 is atomic power (AFM) figure (a) of the Graphene prepared of metal-solution reduction, and known graphene powder has the micro-nano chip architecture of thin layer;
Fig. 5 is the height survey sheet (b) of the Graphene prepared of metal-solution reduction, the about 4nm of thickness that the thin layer of known graphene powder is micro-nano.
Claims (5)
1. metal-solution reduction of preparing Graphene, is characterized in that: by iron powder and the compound reduction system reducing of hydrochloric acid, process the graphite oxide aqueous solution of dilute concentration, prepare graphene powder.
2. metal-solution reduction of preparing Graphene according to claim 1, is characterized in that: comprise the following steps:
(1) graphene oxide: first, 50-200g natural graphite and the 1.25-5L nitration mixture that is comprised of the 1.12-4.5L vitriol oil and 0.13-0.5L strong phosphoric acid are mixed in reactor and even by automatically controlled magnetic stirrer, lower than 20 ℃ in the situation that, slowly add 125-500g potassium permanganate; Afterwards, sealed reactor is also warming up to 75-85 ℃ of reaction 1-4 hour, and product is taken out from reactor lower end, is diluted to 40L solution, adds 0.6L hydrogen peroxide to obtain glassy yellow graphite oxide solution; Then, with acid and water, replace centrifuge washing, to pH value of solution=5-6, remove foreign ion; Finally, ultrasonic dispersion graphite oxide, configures certain density graphene oxide solution;
(2) metal-solution reduction: 1.5L 0.5mg/mL graphene oxide solution is transferred in reactor, adds the concentrated hydrochloric acid of 6.0-36g iron powder and 0.3-2.4L under magnetic agitation, 60-100 ℃ of reaction 1-6 hour; Then standing, by hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain.
3. metal-solution reduction of preparing Graphene according to claim 2, is characterized in that: in step (2), add the concentrated hydrochloric acid of 6.0g iron powder and 1.2L under magnetic agitation, 90 ℃ are reacted 3 hours; Then standing 0.5 hour, by 5wt% hydrochloric acid filtering and washing, remove residual iron powder, then wash suction filtration deacidification; Last lyophilize, grinds the graphene powder that sieves to obtain.
4. according to the metal-solution reduction of preparing Graphene described in claim 2 or 3, it is characterized in that: iron powder purity >99.0%, concentrated hydrochloric acid massfraction concentration be 36%.
5. according to the metal-solution reduction of preparing Graphene described in claim 2 or 3, it is characterized in that: the number of plies of the graphene powder of preparation is 4-10 layer the about 110.8m of specific surface area
2/ g, the about 1000-3000S/m of specific conductivity.
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Cited By (8)
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| CN106276879A (en) * | 2016-08-19 | 2017-01-04 | 苏州思创源博电子科技有限公司 | A kind of preparation method of Graphene fin |
| CN106332327A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Preparation method for composite graphene electrothermal film |
| CN106957053A (en) * | 2017-04-13 | 2017-07-18 | 山东玉皇新能源科技有限公司 | A kind of iron powder is the method for the quick macroscopic preparation of graphene of reducing agent |
| CN106987736A (en) * | 2017-04-15 | 2017-07-28 | 苏州南尔材料科技有限公司 | A kind of preparation method of aluminium silicon-carbon alloy electronic package material |
| CN106995889A (en) * | 2017-04-15 | 2017-08-01 | 苏州南尔材料科技有限公司 | A kind of preparation method of aluminium alloy electronic package material |
| CN107190171A (en) * | 2017-06-11 | 2017-09-22 | 苏州南尔材料科技有限公司 | A kind of preparation method for strengthening albronze |
| CN107190172A (en) * | 2017-06-14 | 2017-09-22 | 苏州南尔材料科技有限公司 | A kind of carbon particle Al alloy composite preparation method |
| CN107267791A (en) * | 2017-06-11 | 2017-10-20 | 苏州南尔材料科技有限公司 | One kind enhancing aluminium alloy preparation method |
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| CN106276879A (en) * | 2016-08-19 | 2017-01-04 | 苏州思创源博电子科技有限公司 | A kind of preparation method of Graphene fin |
| CN106332327A (en) * | 2016-08-19 | 2017-01-11 | 苏州思创源博电子科技有限公司 | Preparation method for composite graphene electrothermal film |
| CN106957053A (en) * | 2017-04-13 | 2017-07-18 | 山东玉皇新能源科技有限公司 | A kind of iron powder is the method for the quick macroscopic preparation of graphene of reducing agent |
| CN106987736A (en) * | 2017-04-15 | 2017-07-28 | 苏州南尔材料科技有限公司 | A kind of preparation method of aluminium silicon-carbon alloy electronic package material |
| CN106995889A (en) * | 2017-04-15 | 2017-08-01 | 苏州南尔材料科技有限公司 | A kind of preparation method of aluminium alloy electronic package material |
| CN107190171A (en) * | 2017-06-11 | 2017-09-22 | 苏州南尔材料科技有限公司 | A kind of preparation method for strengthening albronze |
| CN107267791A (en) * | 2017-06-11 | 2017-10-20 | 苏州南尔材料科技有限公司 | One kind enhancing aluminium alloy preparation method |
| CN107190172A (en) * | 2017-06-14 | 2017-09-22 | 苏州南尔材料科技有限公司 | A kind of carbon particle Al alloy composite preparation method |
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Application publication date: 20141119 |