CN103833013A - Graphene and preparation method thereof - Google Patents
Graphene and preparation method thereof Download PDFInfo
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- CN103833013A CN103833013A CN201210483589.6A CN201210483589A CN103833013A CN 103833013 A CN103833013 A CN 103833013A CN 201210483589 A CN201210483589 A CN 201210483589A CN 103833013 A CN103833013 A CN 103833013A
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Abstract
The invention belongs to the field of electrochemistry, and discloses a graphene and a preparation method thereof. The graphene preparation method comprises: preparing a graphene oxide suspension; preparing a zinc salt and graphene oxide mixed solution; and preparing the graphene. With the graphene preparation method, the high specific surface area graphene can be obtained, the operation steps are simplified, and the production cost is substantially reduced.
Description
Technical field
The present invention relates to Graphene field, relate in particular to a kind of Graphene and preparation method thereof.
Background technology
The strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, pay attention to widely because its unique structure and photoelectric property have been subject to people.Mono-layer graphite is due to its large specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.As: 1, high strength, Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm2/V*s); 4, high specific surface area, (calculated value: 2,630m2/g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.
Up to the present, known to the method for preparing Graphene have multiple, as (1) micromechanics stripping method.This method can only produce the very limited graphene film of quantity, can be used as fundamental research; (2) ultrahigh vacuum(HHV) Graphene epitaxial growth method.The structural limitations of the expensive and sequin of this method its application; (3) chemical Vapor deposition process (CVD).This method can meet the requirement that high-quality graphene is prepared in mass-producing, but cost is higher, complex process.(4) solvent stripping method.This method shortcoming is that productive rate is very low, limits its commercial applications; (5) oxidation-reduction method.This method is a kind of common method that the most simply can obtain in a large number Graphene, more conventional method of reducing is chemical reduction (hydrazine hydrate, quadrol, sodium borohydride etc. make reductive agent) and Rapid Thermal reduction, but after the whole bag of tricks reduction, all can there is the process of a reunion in Graphene, cause the specific surface area of Graphene less than normal, be generally less than 900m
2/ g.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide the preparation method of the Graphene that a kind of specific surface area is higher.
Technical scheme of the present invention is as follows:
A preparation method for Graphene, comprises the steps:
By the graphite oxide ultrasonic dispersion treatment that is added to the water, obtaining concentration is the graphene oxide suspension of 1 ~ 20mg/ml;
The zinc solution that is 30 ~ 50% by massfraction joins in described graphene oxide suspension, stirs, and obtains the mixing solutions of zinc salt and graphene oxide;
The above-mentioned mixing solutions that obtains is filtered, and screening do to microwave heating activation processing, cooling after, through pickling, washing, filtration, be dried, obtain described Graphene.
Preferably, the preparation method of described Graphene, wherein, the described ultrasonic dispersion treatment time is 1 ~ 2h.
Preferably, the preparation method of described Graphene, wherein, in the mixing solutions of described zinc salt and graphene oxide, the mass ratio of zinc salt and graphene oxide is 50 ~ 300:1.
Preferably, the preparation method of described Graphene, wherein, when described zinc salt and graphene oxide suspension agitation, churning time is 1 ~ 5h.
Preferably, the preparation method of described Graphene, wherein, described zinc salt is zinc chloride, zinc sulfate or zinc nitrate.
Preferably, the preparation method of described Graphene, wherein, when described microwave heating activation is processed, microwave power is 200 ~ 900W, be 1 ~ 15 minute heat-up time.
Preferably, the preparation method of described Graphene, wherein, when the product that processing obtains to microwave heating activation carries out pickling, adopts the dilute hydrochloric acid solution that volume fraction is 5 ~ 10%.
The present invention also provides a kind of Graphene, and this Graphene adopts above-mentioned preparation method to make.
The preparation method of Graphene provided by the invention, the method adopts microwave heating activation, can prepare graphene with high specific surface, and specific surface area reaches 1000 ~ 1900m
2/ g; In addition, without at high temperature carrying out, can reduce energy consumption, and shorter several minutes of reaction times just can complete whole priming reaction, shorten the reaction times, improve production efficiency, reduce production cost.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of Graphene of the present invention.
Embodiment
The preparation method of Graphene provided by the invention, as shown in Figure 1, its process flow steps is as follows:
S1, by the graphite oxide ultrasonic dispersion 1 ~ 2h that is added to the water, obtaining concentration is the graphene oxide suspension of 1 ~ 20mg/ml;
S2, the zinc solution that is 30 ~ 50% by massfraction join in described graphene oxide suspension, stir 1 ~ 5h, obtain the mixing solutions of zinc salt and graphene oxide; Wherein, in the mixing solutions of described zinc salt and graphene oxide, the mass ratio of zinc salt and graphene oxide is 50 ~ 300:1; Described zinc salt is zinc chloride, zinc sulfate or zinc nitrate.
S3, the mixing solutions that step S2 is obtained filter, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 200 ~ 900W, to screening carry out microwave heating activation process 1 ~ 15 minute, cooling after, the dilute hydrochloric acid solution that is 5 ~ 10% through volume fraction carries out pickling, then through washing, filtration, dry, obtain Graphene.
The preparation method of Graphene provided by the invention, the method adopts microwave heating activation, can prepare graphene with high specific surface, and specific surface area reaches 1000 ~ 1900m
2/ g; In addition, without at high temperature carrying out, can reduce energy consumption, and shorter several minutes of reaction times just can complete whole priming reaction, shorten the reaction times, improve production efficiency, reduce production cost.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1h, forming concentration is 1mg/ml graphene oxide suspension,
(2) liquor zinci chloridi that preparation massfraction is 30%, joins liquor zinci chloridi in above-mentioned graphene oxide suspension, stirs 1h, obtains the mixing solutions of zinc salt and graphene oxide, wherein; The mass ratio of zinc chloride and graphene oxide is 50:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 200W, to screening carry out microwave heating activation process 15 minutes, cooling after, the dilute hydrochloric acid solution that is 5% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 2
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 2h, forming concentration is 20mg/ml graphene oxide suspension,
(2) solution of zinc sulfate that preparation massfraction is 50%, joins solution of zinc sulfate in above-mentioned graphene oxide suspension, stirs 5h, obtains the mixing solutions of zinc salt and graphene oxide, wherein; The mass ratio of zinc sulfate and graphene oxide is 300:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 900W, to screening carry out microwave heating activation process 1 minute, cooling after, the dilute hydrochloric acid solution that is 10% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 3
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.5h, forming concentration is 10mg/ml graphene oxide suspension,
(2) zinc nitrate solution that preparation massfraction is 33%, joins zinc nitrate solution in above-mentioned graphene oxide suspension, stirs 2h, obtains the mixing solutions of zinc salt and graphene oxide, wherein; The mass ratio of zinc nitrate and graphene oxide is 100:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 300W, to screening carry out microwave heating activation process 13 minutes, cooling after, the dilute hydrochloric acid solution that is 6% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 4
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.7h, forming concentration is 15mg/ml graphene oxide suspension,
(2) zinc nitrate solution that preparation massfraction is 35%, joins zinc nitrate solution in above-mentioned graphene oxide suspension, stirs 2.5h, obtains the mixing solutions of zinc nitrate and graphene oxide, wherein; The mass ratio of zinc nitrate and graphene oxide is 150:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 400W, to screening carry out microwave heating activation process 10 minutes, cooling after, the dilute hydrochloric acid solution that is 7% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 5
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.2h, forming concentration is 5mg/ml graphene oxide suspension,
(2) liquor zinci chloridi that preparation massfraction is 40%, joins liquor zinci chloridi in above-mentioned graphene oxide suspension, stirs 3h, obtains the mixing solutions of zinc chloride and graphene oxide, wherein; The mass ratio of zinc chloride and graphene oxide is 200:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 500W, to screening carry out microwave heating activation process 8 minutes, cooling after, the dilute hydrochloric acid solution that is 8% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 6
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.4h, forming concentration is 8mg/ml graphene oxide suspension,
(2) liquor zinci chloridi that preparation massfraction is 43%, joins liquor zinci chloridi in above-mentioned graphene oxide suspension, stirs 3.5, obtains the mixing solutions of zinc chloride and graphene oxide, wherein; The mass ratio of zinc chloride and graphene oxide is 250:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 600W, to screening carry out microwave heating activation process 6 minutes, cooling after, the dilute hydrochloric acid solution that is 9% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 7
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.6h, forming concentration is 13mg/ml graphene oxide suspension,
(2) liquor zinci chloridi that preparation massfraction is 45%, joins liquor zinci chloridi in above-mentioned graphene oxide suspension, stirs 4h, obtains the mixing solutions of zinc chloride and graphene oxide, wherein; The mass ratio of zinc chloride and graphene oxide is 270:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 700W, to screening carry out microwave heating activation process 5 minutes, cooling after, the dilute hydrochloric acid solution that is 10% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
Embodiment 8
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.8h, forming concentration is 17mg/ml graphene oxide suspension,
(2) solution of zinc sulfate that preparation massfraction is 38%, joins solution of zinc sulfate in above-mentioned graphene oxide suspension, stirs 3h, obtains the mixing solutions of zinc sulfate and graphene oxide, wherein; The mass ratio of zinc sulfate and graphene oxide is 220:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is placed in porcelain crucible with cover, then porcelain crucible is placed in microwave oven, under the microwave power of 800W, to screening carry out microwave heating activation process 3 minutes, cooling after, the dilute hydrochloric acid solution that is 8% through volume fraction carries out pickling, then through washing, filtration, dry, obtain the Graphene of high-specific surface area.
The Graphene of embodiment 1 ~ 8 preparation is tested to the specific surface area obtaining by BET as shown in table 1:
Table 1
Graphene specific surface area prepared by conventional thermal reduction method is ~ 900m
2/ g, as shown in Table 1, the present invention obtains Graphene specific surface area and has substantially exceeded ordinary method.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. a preparation method for Graphene, is characterized in that, comprises the steps:
By the graphite oxide ultrasonic dispersion treatment that is added to the water, obtaining concentration is the graphene oxide suspension of 1 ~ 20mg/ml;
The zinc solution that is 30 ~ 50% by massfraction joins in described graphene oxide suspension, stirs, and obtains the mixing solutions of zinc salt and graphene oxide;
The above-mentioned mixing solutions that obtains is filtered, and screening is carried out to microwave heating activation processing, cooling after, through pickling, washing, filtration, dry, obtain described Graphene.
2. the preparation method of Graphene according to claim 1, is characterized in that, the described ultrasonic dispersion treatment time is 1 ~ 2h.
3. the preparation method of Graphene according to claim 1, is characterized in that, in the mixing solutions of described zinc salt and graphene oxide, the mass ratio of zinc salt and graphene oxide is 50 ~ 300:1.
4. the preparation method of Graphene according to claim 1, is characterized in that, when described zinc salt and graphene oxide suspension agitation, churning time is 1 ~ 5h.
5. according to the preparation method of the Graphene described in claim 1,3 or 4, it is characterized in that, described zinc salt is zinc chloride, zinc sulfate or zinc nitrate.
6. the preparation method of Graphene according to claim 1, is characterized in that, when described microwave heating activation is processed, microwave power is 200 ~ 900W, and be 1 ~ 15 minute heat-up time.
7. the preparation method of Graphene according to claim 1, is characterized in that, when the product that processing obtains to microwave heating activation carries out pickling, adopts the dilute hydrochloric acid solution that volume fraction is 5 ~ 10%.
8. a Graphene, is characterized in that, this Graphene adopts the arbitrary described preparation method of claim 1 ~ 6 to make.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250821A (en) * | 2018-01-11 | 2018-07-06 | 绍兴文理学院 | Graphene dispersion method for graphene-based anticorrosive paint |
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| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102107870A (en) * | 2011-03-23 | 2011-06-29 | 中国科学院山西煤炭化学研究所 | Method for quickly preparing reduced graphene by using microwaves |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
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| CN101391767A (en) * | 2008-11-03 | 2009-03-25 | 浙江大学城市学院 | Method for preparing active carbon by using waste walnut outer peel |
| CN101767784A (en) * | 2010-01-12 | 2010-07-07 | 山东理工大学 | Preparation method of mesoporous carbon electrode material for ionic liquid super capacitor |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
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| CN108250821B (en) * | 2018-01-11 | 2020-04-21 | 绍兴文理学院 | Graphene dispersion method for graphene-based anticorrosive paint |
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Application publication date: 20140604 |