CN103833015A - Graphene and preparation method thereof - Google Patents
Graphene and preparation method thereof Download PDFInfo
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- CN103833015A CN103833015A CN201210483600.9A CN201210483600A CN103833015A CN 103833015 A CN103833015 A CN 103833015A CN 201210483600 A CN201210483600 A CN 201210483600A CN 103833015 A CN103833015 A CN 103833015A
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Abstract
The invention belongs to the field of electrochemistry, and discloses a graphene and a preparation method thereof, an electrode sheet, and a supercapacitor. The graphene preparation method comprises: preparing a graphene oxide suspension; preparing a zinc chloride and graphene oxide mixed solution; and preparing the graphene. With the graphene preparation method, the graphene with characteristics of high specific surface area and high conductivity 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 Graphene 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 chloride soln that is 30 ~ 50% by mass percent concentration joins in described graphene oxide suspension, stirs, and obtains the mixing solutions of muriate and graphene oxide;
The above-mentioned mixing solutions that obtains is filtered, and screening is carried out to drying treatment, more dried screening is put into retort furnace and under inert atmosphere, carry out high-temperature calcination, cooling after, washing, filter, dry, obtain described Graphene.
Preferably, the preparation method of described Graphene, wherein, the described ultrasonic dispersion treatment time is 0.5 ~ 3h.
Preferably, the preparation method of described Graphene, wherein, in the mixing solutions of described muriate and graphene oxide, the mass ratio of muriate and graphene oxide is 200 ~ 500:1.
Preferably, the preparation method of described Graphene, wherein, described muriate is zinc chloride, magnesium chloride or sodium-chlor
Preferably, the preparation method of described Graphene, wherein, in described drying treatment process, drying treatment temperature is 60 ~ 80 ℃, the drying treatment time is 24 ~ 48h.
Preferably, the preparation method of described Graphene, wherein, when described high-temperature calcination, temperature is 400 ~ 600 ℃, calcination time is 30 ~ 120min.
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, has following beneficial effect: 1, and the method can be prepared bigger serface Graphene, effectively prevents the reunion of graphene film interlayer; 2, because the diameter of zinc atom is greater than potassium atom, the Graphene micro pore volume that employing zinc chloride activation obtains is higher than KOH activation, and both apertures are similar simultaneously, are applied to electrode materials and are conducive to store electrolytic solution, improve power density; 3, the method technique is fairly simple, few to equipment corrosion, environmental pollution is little, and temperature of reaction is low, greatly reduces energy consumption.
Graphene prepared by the present invention, specific surface area can reach 1200 ~ 1900m
2/ g, prepare higher than the method for general thermal reduction ~ 900m
2/ g.
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 0.5 ~ 3h that is added to the water, obtaining concentration is the graphene oxide suspension of 1 ~ 20mg/ml;
S2, the chloride soln that is 30 ~ 50% by mass percent concentration join in described graphene oxide suspension, stir, and obtain the mixing solutions of muriate and graphene oxide; Wherein, in the mixing solutions of described muriate and graphene oxide, the mass ratio of muriate and graphene oxide is 200 ~ 500:1; Described muriate is zinc chloride, magnesium chloride or sodium-chlor;
S3, the mixing solutions that step S2 is obtained filter, screening is placed in 60 ~ 80 ℃ of drying treatment 24 ~ 48h, again dried screening is put into retort furnace, and under inert atmosphere (preferably argon atmosphere), in 400 ~ 600 ℃ high-temperature calcination 30 ~ 120min, cooling after, washing, filter, the dry Graphene that obtains.
The preparation method of Graphene provided by the invention, has following beneficial effect: 1, and the method can be prepared bigger serface Graphene, effectively prevents the reunion of graphene film interlayer; 2, because the diameter of zinc atom is greater than potassium atom, the Graphene micro pore volume that employing zinc chloride activation obtains is higher than KOH activation, and both apertures are similar simultaneously, are applied to electrode materials and are conducive to store electrolytic solution, improve power density; 3, the method technique is fairly simple, few to equipment corrosion, environmental pollution is little, and temperature of reaction is low, greatly reduces energy consumption.
Graphene prepared by the present invention, specific surface area can reach 1200 ~ 1900m
2/ g, prepare higher than the method for general thermal reduction ~ 900m
2/ g.
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 0.5h, forming concentration is 1mg/ml graphene oxide suspension,
(2) liquor zinci chloridi that preparation mass percent is 30%, joins liquor zinci chloridi in above-mentioned graphene oxide suspension, stirs 1h, 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 in 60 ℃ of dry 48h, again dried screening is put into retort furnace, 400 ℃ of reaction 120min, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 2
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 3h, forming concentration is 20mg/ml graphene oxide suspension,
(2) magnesium chloride solution that preparation mass percent is 50%, joins magnesium chloride solution in above-mentioned graphene oxide suspension, stirs 5h, obtains the mixing solutions of magnesium chloride and graphene oxide, wherein; The mass ratio of magnesium chloride and graphene oxide is 500:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 80 ℃ of dry 24h, again dried screening is put into retort furnace, 600 ℃ of reaction 30min, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 3
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1h, forming concentration is 5mg/ml graphene oxide suspension,
(2) sodium chloride solution that preparation mass percent is 35%, joins sodium chloride solution in above-mentioned graphene oxide suspension, stirs 2h, obtains the mixing solutions of sodium-chlor and graphene oxide, wherein; The mass ratio of sodium-chlor and graphene oxide is 300:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 65 ℃ of dry 42h, again dried screening is put into retort furnace, 450 ℃ of reaction 100min, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 4
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 2h, forming concentration is 10mg/ml graphene oxide suspension,
(2) liquor zinci chloridi that preparation mass percent 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 350:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 70 ℃ of dry 36h, again dried screening is put into retort furnace, 500 ℃ of reaction 75min, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 5
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.5h, forming concentration is 15mg/ml graphene oxide suspension,
(2) preparation mass percent be 45%, magnesium chloride solution, will, magnesium chloride solution joins in above-mentioned graphene oxide suspension, stirs 4h, obtain, the mixing solutions of magnesium chloride and graphene oxide, wherein; , magnesium chloride and graphene oxide mass ratio be 400:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 75 ℃ of dry 30h, again dried screening is put into retort furnace, 550 ℃ of reaction 50min, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
Embodiment 6
(1) graphite oxide is added to the water to formation suspension, ultrasonic dispersion 1.3h, forming concentration is 12mg/ml graphene oxide suspension,
(2) sodium chloride solution that preparation mass percent is 38%, joins sodium chloride solution in above-mentioned graphene oxide suspension, stirs 3h, obtains the mixing solutions of sodium-chlor and graphene oxide, wherein; The mass ratio of sodium-chlor and graphene oxide is 450:1;
(3) mixing solutions above-mentioned steps (2) being obtained filters, screening is in 77 ℃ of dry 28h, again dried screening is put into retort furnace, 520 ℃ of reaction 60min, cooling after, washing, filter, the dry Graphene that obtains high-specific surface area.
The Graphene of embodiment 1 ~ 6 preparation is tested to the specific surface area obtaining by BET as shown in table 1:
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Specific surface area m 2/g | 1308 | 1916 | 1236 | 1557 | 1681 | 1819 |
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 (7)
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 chloride soln that is 30 ~ 50% by mass percent concentration joins in described graphene oxide suspension, stirs, and obtains the mixing solutions of muriate and graphene oxide;
The above-mentioned mixing solutions that obtains is filtered, and screening is carried out to drying treatment, more dried screening is put into retort furnace and under inert atmosphere, carry out high-temperature calcination, cooling after, washing, filter, 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 0.5 ~ 3h.
3. the preparation method of Graphene according to claim 1, is characterized in that, in the mixing solutions of described zinc chloride and graphene oxide, the mass ratio of muriate and graphene oxide is 200 ~ 500:1.
4. according to the preparation method of the Graphene described in claim 1 or 3, it is characterized in that, described muriate is zinc chloride, magnesium chloride or sodium-chlor.
5. the preparation method of Graphene according to claim 1, is characterized in that, in described drying treatment process, drying treatment temperature is 60 ~ 80 ℃, and the drying treatment time is 24 ~ 48h.
6. the preparation method of Graphene according to claim 1, is characterized in that, when described high-temperature calcination, temperature is 400 ~ 600 ℃, and calcination time is 30 ~ 120min.
7. a Graphene, is characterized in that, this Graphene adopts the arbitrary described preparation method of claim 1 ~ 6 to make.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229786A (en) * | 2014-09-18 | 2014-12-24 | 苏州经贸职业技术学院 | Preparation method for graphene with high electric conductivity |
| CN106241784A (en) * | 2016-07-27 | 2016-12-21 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the grapheme material of multilevel hierarchy |
| CN106315563A (en) * | 2016-07-27 | 2017-01-11 | 中国科学院宁波材料技术与工程研究所 | Graphene material of ordered structure and preparing method thereof |
| CN106629674A (en) * | 2016-09-22 | 2017-05-10 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing graphene by oxidation reduction |
| CN111363944A (en) * | 2018-12-25 | 2020-07-03 | 上海核威实业有限公司 | Bearing alloy blank, bearing alloy, bearing material, and preparation method and application thereof |
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| CN101332992A (en) * | 2008-07-31 | 2008-12-31 | 福建师范大学 | Method for preparing tung cell-based active carbon by zinc chloride chemical activation method |
| 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 |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
| CN102543483A (en) * | 2012-01-17 | 2012-07-04 | 电子科技大学 | Preparation method of graphene material of supercapacitor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101332992A (en) * | 2008-07-31 | 2008-12-31 | 福建师范大学 | Method for preparing tung cell-based active carbon by zinc chloride chemical activation method |
| WO2012030415A1 (en) * | 2010-09-03 | 2012-03-08 | Board Of Regents, The University Of Texas System | Ultracapacitor with a novel carbon |
| 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 |
| CN102543483A (en) * | 2012-01-17 | 2012-07-04 | 电子科技大学 | Preparation method of graphene material of supercapacitor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229786A (en) * | 2014-09-18 | 2014-12-24 | 苏州经贸职业技术学院 | Preparation method for graphene with high electric conductivity |
| CN106241784A (en) * | 2016-07-27 | 2016-12-21 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the grapheme material of multilevel hierarchy |
| CN106315563A (en) * | 2016-07-27 | 2017-01-11 | 中国科学院宁波材料技术与工程研究所 | Graphene material of ordered structure and preparing method thereof |
| CN106315563B (en) * | 2016-07-27 | 2019-02-19 | 中国科学院宁波材料技术与工程研究所 | A kind of grapheme material of ordered structure and preparation method thereof |
| CN106629674A (en) * | 2016-09-22 | 2017-05-10 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing graphene by oxidation reduction |
| CN106629674B (en) * | 2016-09-22 | 2019-02-22 | 林飘飘 | A kind of method of preparing grapheme through oxidation reduction |
| CN111363944A (en) * | 2018-12-25 | 2020-07-03 | 上海核威实业有限公司 | Bearing alloy blank, bearing alloy, bearing material, and preparation method and application thereof |
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Application publication date: 20140604 |