CN103708441A - Preparation method for graphene strip with millimeter length - Google Patents
Preparation method for graphene strip with millimeter length Download PDFInfo
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- CN103708441A CN103708441A CN201310412991.XA CN201310412991A CN103708441A CN 103708441 A CN103708441 A CN 103708441A CN 201310412991 A CN201310412991 A CN 201310412991A CN 103708441 A CN103708441 A CN 103708441A
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Abstract
The present invention discloses a preparation method for a graphene strip with a millimeter length. The preparation method comprises: 1) dispersing graphene oxide into water to prepare a graphene oxide suspension; 2) adding a chemical etching agent to the suspension, and carrying out stirring heating until the mixing solution is thickened into an ink color paste; 3) filtering, and washing to achieve the pH value of 6-8; 4) drying the washed solid product; 5) heating the dried powder in the protection of an inert gas to achieve a temperature of more than 200 DEG C so as to carry out a reaction; and 6) cooling to obtain the reduced graphene oxide strip with a length of more than 1 mm. According to the present invention, the method of the present invention adopts the preparation steps different from the preparation steps in the prior art to prepare the graphene oxide strip with the length of more than 1 mm, wherein the cost is low, and application requirements of the electronics industry can be met.
Description
Technical field
The invention belongs to Graphene technical field, relate to a kind of preparation method of Graphene band, especially a kind of preparation method of millimeters long Graphene band.
Background technology
Graphene is a kind of material with two dimension (2-D) lamellar structure of a monatomic thickness, because it is at machinery, and heat, chemistry, the excellent properties of electrochemistry aspect, makes it at solar cell, indicating meter, the aspects such as electrical energy storage and nesa coating obtain very large concern.The combination of a lot of extreme nature, as electricity is led, thermal conductance, physical strength, optical characteristics, characteristic of semiconductor etc., many research workers expect that the application of Graphene will bring breakthrough change in a lot of fields.Therefore, prepare Graphene and other Graphene class material and obtained great achievement.But the method for preparing big size graphene also only limits to chemical vapour deposition, micromechanics stripping means now.Above-mentioned two kinds of methods are expensive, can only prepare at present the sample purposes that makes a search.Sample prepared by chemical process is also only limited to micro-scale (generally at micro-meter scale) at present.Graphene to be applied in electronic industry, need to continue larger sized Graphene, as approached or over 1 millimeter; At present also there is not a kind of most suitable method, can prepare this Graphene.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of preparation method of Graphene band of millimeters long is provided, the method is by being different from the preparation process of prior art, can prepare the graphene oxide band that length is greater than 1 millimeter, not only cost is low, and can meet the application needs of electronic industry.
The object of the invention is to be achieved through the following technical solutions:
The preparation method of this millimeters long Graphene band, comprises the following steps:
1) graphene oxide is dispersed in water, prepares graphene oxide suspension, the concentration of graphene suspension is 0.01 – 100 grams per liters;
2) in suspension, add chemical etchant, stirring heating, until mixed solution is crowded into mass colour pasty state;
3) filter, and wash to pH=6～8;
4) solid product after washing is dry;
5) dry powder is heated under protection of inert gas and is greater than reaction at 200 ℃;
6) the graphene oxide band of cooling rear acquisition reduction, 1 millimeter of length >.
Further, above step 2) in, described chemical etchant is strongly alkaline compound or strongly-acid compound.
Further, the above strongly alkaline compound is a kind of or several mixture in NaOH, KOH, CaO, MgO.Described strongly alkaline compound is mixed with to solution, and its concentration is 0.01～10M.
Further, the above strongly-acid compound is HCl, H
2sO
4, H
3pO
4, HNO
3, a kind of or several mixture in HF.Described strongly-acid compound is mixed with to solution, and its concentration is 0.01～10M.
Further, above step 2) in, Heating temperature is 70～150 ℃, be 0.5～2 hour heat-up time.
Further, above step 4) drying operation is specially: under vacuum condition, dry, bake out temperature is 50～120 ℃, and be 5～48 hours time of drying.
Further, in above step 5), dry powder is placed in to tube furnace, in tube furnace, has protection of inert gas; Described rare gas element is nitrogen, argon gas, helium or neon.
In step 5), be divided into two stages:
(1) temperature of first stage is 180～400 ℃, and the soaking time in this stage is 0.2～3 hour;
(2) temperature of subordinate phase is 600～1200 ℃, and the soaking time in this stage is 0.5～3 hour.
Compared with prior art, the present invention has following beneficial effect:
Employing of the present invention is different from chemical vapour deposition and the micromechanics stripping means of prior art, it is by preparing graphene suspension, then add chemical etchant, pass through again drying treatment, can be under the prerequisite reducing costs, prepare the graphene oxide band that length is greater than 1 millimeter, Graphene band prepared by the present invention can be applied in electronic industry, meet completely the larger sized Graphene of its needs (as approach or over 1 millimeter) requirement, effectively filled up current technological gap.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope of the present invention (SEM) photo; Wherein, (a) graphene oxide;
(b) reaction product of NaOH and graphene oxide mass ratio (mNaOH/mGO)=10 o'clock; (c) reaction product of (mNaOH/mGO)=26 o'clock; (d) reaction product of (mNaOH/mGO)=33 o'clock; (e) low resolution stereoscan photograph, a plurality of overlength Graphene strip lengths are over 1 millimeter; (f) high resolution scanning electromicroscopic photograph, Graphene belt surface cleans, smooth, there is no obvious impurity.
Fig. 2 is x x ray diffration pattern x; Wherein, (a) the x x ray diffration pattern x of graphite oxide, (b) the x x ray diffration pattern x of rmGO-10, (c) the x x ray diffration pattern x of rmGO-26, (d) the x x ray diffration pattern x of rmGO-33.
Fig. 3 is XPS spectrum figure; Wherein: (a) the O1sXPS spectrogram of O1sXPS spectrogram (f) rmGO-33 of XPS spectrum figure (e) graphite oxide of XPS spectrum figure (d) rmGO-33C1s of C1s XPS spectrum figure (c) rmGO-26C1s of C1s XPS spectrum figure (b) rmGO-10 of graphite oxide.
Fig. 4 is Raman spectrum; Wherein: (a) Raman spectrum of Raman spectrum (d) GO of Raman spectrum (c) rmGO-33 of the Raman spectrum of rmGO-10 (b) rmGO-26.
Fig. 5 is that NaOH etching oxidation Graphene is prepared overlength Graphene band schematic diagram, wherein: (a) first graphene film is become multi-cellular structure; (b) etching, mainly along micropore expansion, progressively around all etches away micropore; (c), when micropore band etches into border, remaining structure is exactly overlength Graphene band.
Embodiment
The preparation method of millimeters long Graphene band of the present invention, comprises the following steps:
1) graphene oxide is dispersed in water, prepares graphene oxide suspension, the concentration of graphene suspension is 0.01 – 100 grams per liters; 1 grams per liter preferably.
2) in suspension, add chemical etchant, stirring heating, until mixed solution is crowded into mass colour pasty state; Heating temperature is 70～150 ℃, and be 0.5～2 hour heat-up time.
Wherein, described chemical etchant is strongly alkaline compound or strongly-acid compound:
Described strongly alkaline compound is a kind of or several mixture in NaOH, KOH, CaO, MgO, and strongly alkaline compound is mixed with to solution, and its concentration is 0.01～10M.
Described strongly-acid compound is HCl, H
2sO
4, H
3pO
4, HNO
3, a kind of or several mixture in HF, and described strongly-acid compound is mixed with to solution, its concentration is 0.01～10M.
3) filter, and wash to pH=6～8;
4) solid product after washing is dry, be specially: under vacuum condition, dry, bake out temperature is 50～120 ℃, and be 5～48 hours time of drying.
5) dry powder is heated under protection of inert gas and is greater than reaction at 200 ℃;
This step is that dry powder is placed in to tube furnace, has protection of inert gas in tube furnace; Described rare gas element is nitrogen, argon gas, helium or neon.It is divided into following two stages:
(1) temperature of first stage is 180～400 ℃, and the soaking time in this stage is 0.2～3 hour;
(2) temperature of subordinate phase is 600～1200 ℃, and the soaking time in this stage is 0.5～3 hour.
6) the graphene oxide band of cooling rear acquisition reduction, 1 millimeter of length >.
The present invention is described in more detail by the following examples:
Embodiment 1
(1) graphene oxide taking a morsel is dispersed in water, and at ambient temperature, by ultrasonic apparatus, prepares graphene oxide suspension liquid, the about 1mg/mL of concentration ultrasonic half an hour
(2) by potassium hydroxide solution, if 1M(can be also pure KOH solid) slowly add the mixture of preparing KOH and GO in suspension, wherein KOH/GO mass ratio, between 10-100, is preferably between 30-60.
(3) mixture is placed in the oil bath of approximately 100 ℃, and continuous stirring and refluxing, until it is crowded into " mass colour pasty state ".
(4) with this understanding, continue insulation approximately 1 hour, to react completely as far as possible.
(5) then, mixture is carried out to vacuum filtration, be washed with distilled water to neutral pH and be about 7.
(6) solid product is placed on rapidly under approximately 80 ℃ of conditions to vacuum-drying approximately 20 hours.
(7) last, dry powder moving is passed into argon gas stream in once-through pipe still (approximately 50 mm dia) and with the flow velocity of 150sccm.First be heated to approximately 280 ℃ and be incubated approximately 30 minutes, then slowly with the speed of approximately 5 ℃/min, heat to approximately 800 ℃, and keep approximately 1 hour, be then cooled to the graphite oxide ene product that obtains partial reduction after room temperature.The graphene oxide length of drastic reduction can reach >1 millimeter, from then on can gather in the crops overlength Graphene band.
Embodiment 2
(1) graphene oxide taking a morsel is dispersed in water, and at ambient temperature, by ultrasonic apparatus, prepares graphene oxide suspension liquid, the about 1mg/mL of concentration ultrasonic half an hour;
(2) by sodium hydroxide solution, if 1M(can be also pure NaOH solid) slowly add the mixture of preparing NaOH and GO in suspension, NaOH/GO mass ratio, between 10-100, is preferably between 20-40.
(3) mixture is placed in the oil bath of approximately 100 ℃, and continuous stirring and refluxing, until it is crowded into " mass colour pasty state ".
(4) with this understanding, continue insulation and reflux approximately 1 hour, to react completely as far as possible.
(5) then, mixture is carried out to vacuum filtration, be washed with distilled water to neutral pH and be about 7.
(6) solid product is placed on rapidly under approximately 80 ℃ of conditions to vacuum-drying approximately 20 hours.
(7) last, dry powder moving is passed into argon gas stream in once-through pipe still (approximately 50 mm dia) and with the flow velocity of 150sccm.First be heated to approximately 280 ℃ and be incubated approximately 30 minutes, then slowly with the speed of approximately 5 ℃/min, heat to approximately 800 ℃, and keep approximately 1 hour, be then cooled to the graphite oxide ene product that obtains partial reduction after room temperature.The graphene oxide length of drastic reduction can reach >1 millimeter, from then on can gather in the crops overlength Graphene band.
Embodiment 3
(1) graphene oxide taking a morsel is dispersed in water, and at ambient temperature, by ultrasonic apparatus, prepares graphene oxide suspension liquid, the about 1mg/mL of concentration ultrasonic half an hour;
(2), by sodium hydroxide solution, as slowly adding, 1M in suspension, prepares Na
2the mixture of O and GO, Na
2o/GO mass ratio, between 10-100, is preferably between 15-30.
(3) mixture is placed in the oil bath of approximately 100 ℃, and continuous stirring and refluxing, until it is crowded into " pasty state of ink shape ".
(4) with this understanding, continue insulation and reflux approximately 1 hour, to react completely as far as possible.
(5) then, mixture is carried out to vacuum filtration, be washed with distilled water to neutral pH and be about 7.
(6) solid product is placed on rapidly under approximately 80 ℃ of conditions to vacuum-drying approximately 20 hours.
(7) last, dry powder moving is passed into argon gas stream in once-through pipe still (approximately 50 mm dia) and with the flow velocity of 150sccm.First be heated to approximately 280 ℃ and be incubated approximately 30 minutes, then slowly with the speed of approximately 5 ℃/min, heat to approximately 800 ℃, and keep approximately 1 hour, be then cooled to the graphite oxide ene product that obtains partial reduction after room temperature.The graphene oxide length of drastic reduction can reach >1 millimeter, from then on can gather in the crops overlength Graphene band.
Embodiment 4
(1) graphene oxide taking a morsel is dispersed in water, and at ambient temperature, by ultrasonic apparatus, prepares graphene oxide suspension liquid, the about 1mg/mL of concentration ultrasonic half an hour;
(2) by calcium oxide solution, if 1M(can be also pure CaO solid) slowly add the mixture of preparing CaO and GO in suspension, CaO/GO mass ratio, between 10-100, is preferably between 15-30.
(3) mixture is placed in the oil bath of approximately 100 ℃, and continuous stirring and refluxing, until it is crowded into " mass colour pasty state ".
(4) with this understanding, continue insulation and reflux approximately 1 hour, to react completely as far as possible.
(5) then, mixture is carried out to vacuum filtration, be washed with distilled water to neutral pH and be about 7.
(6) solid product is placed on rapidly under approximately 80 ℃ of conditions to vacuum-drying approximately 20 hours.
(7) last, dry powder moving is passed into argon gas stream in once-through pipe still (approximately 50 mm dia) and with the flow velocity of 150sccm.First be heated to approximately 280 ℃ and be incubated approximately 30 minutes, then slowly with the speed of approximately 5 ℃/min, heat to approximately 800 ℃, and keep approximately 1 hour, be then cooled to the graphite oxide ene product that obtains partial reduction after room temperature.The graphene oxide length of drastic reduction can reach >1 millimeter, from then on can gather in the crops overlength Graphene band.
The microscopic appearance feature of observing sample by the scanning electron microscope (SEM200) that operates and a transmission electron microscope (Tecnai G2F20S-TWIN) under 20KV high pressure.
Referring to Fig. 2: the crystalline structure of determining product by powder x-ray diffraction (X-ray diffraction (XRD), the Cu-K α radiation of DX2000).Wherein, (a) being the x x ray diffration pattern x of graphite oxide, is (b) the x x ray diffration pattern x of rmGO-10, is (c) the x x ray diffration pattern x of rmGO-26, is (d) the x x ray diffration pattern x of rmGO-33.
As shown in Figure 3: x-ray photoelectron spectroscopy (XPS) is to test by a PHI1600 spectrograph of being furnished with monochromatic AlK α-x-ray source.Wherein: (a) the O1sXPS spectrogram of O1sXPS spectrogram (f) rmGO-33 of XPS spectrum figure (e) graphite oxide of XPS spectrum figure (d) rmGO-33C1s of C1s XPS spectrum figure (c) rmGO-26C1s of C1s XPS spectrum figure (b) rmGO-10 of graphite oxide.
Fig. 1 is scanning electron microscope (SEM) photo: wherein, (a) graphene oxide, is even leaf sheet; (b) reaction product of NaOH and graphene oxide mass ratio (mNaOH/mGO)=10 o'clock, is fold film like; (c) reaction product of (mNaOH/mGO)=26 o'clock, has long Graphene band, also has sheet fold film; (d) reaction product of (mNaOH/mGO)=33 o'clock, only separative long Graphene band; (e) low resolution stereoscan photograph, a plurality of overlength Graphene strip lengths are over 1 millimeter; (f) high resolution scanning electromicroscopic photograph, Graphene belt surface cleans, smooth, there is no obvious impurity.
Table one: the preparation condition of four kinds of samples and morphology characterization
Table 1 represents that the different mass of NaOH and rmGO is than corresponding pattern, and wherein GO represents not add NaOH in sample, and the sample of preparing gained is sheet; RmGO-10 represents that the mass ratio of NaOH and rmGO is 10:1, and the sample of preparing gained is curling shape; RmGO-26 represents that the mass ratio of NaOH and rmGO is 26:1, and the sample of preparing gained is slight spiral, and reach～300 μ m of the length of sample segment, and width is 5～10 μ m; RmGO-33 represents that the mass ratio of NaOH and rmGO is 33:1, and the sample of preparing gained is height-oriented spiral, and the length > 500 μ m of sample, and width is 5 μ m.
Table two: four kinds of sample strength ratios that D is with and G is with in Raman spectrum
Table two is corresponding with Fig. 4 Raman spectrogram, and wherein rmGO-10 represents that the mass ratio of NaOH and rmGO is 10:1, and rmGO-26 represents that the mass ratio of NaOH and rmGO is 26:1, and rmGO-33 represents that the mass ratio of NaOH and rmGO is 33:1.G band (～1587cm in Raman spectrum
-1place) be owing to there being sp in Graphene
2the figure spectrum signal that the existence of the C-C of hydridization forms.The increase of defect concentration can cause at～1350cm
-1the increase of the D band intensity at place.The strength ratio increase that G band strength declines and D band and G are with all with graphitizing process in SP
2the two key regeneration of C=C has relation.Table 2 has been listed the I(D of three rmGO samples)/I(G) ratio of (strength ratio that represents D peak and G peak).As the faint reductive action of mNaOH:mrmGO=10, I(D)/I(G) be only 1.05; When NaOH concentration is increased to mNaOH:mrmGO=26, I(D)/I(G) value just rises to 1.64.When mNaOH:mrmGO is further increased to 33, I(D)/I(G) ratio will continue to rise to 1.72.I(D obviously) ratio/I(G) and the reduction degree of sample have very large relation.
Fig. 2 has provided X-ray diffraction (XRD) figure.In 2 θ=10.24 °, locate, GO has an obvious peak value, corresponding GO thin slice crystal face (001).GO by chemical reduction after, oxygen-containing functional group is removed from the interlayer of interlamellar spacing, a lot of Graphene band configurations starts to form.This can pass through sample rmGO-10, and the broad peak (002) that rmGO-26 and rmGO-33 locate approximately 2 θ=25.8 ° to form confirms, as Fig. 2 (b), 3(c) and 3(d)) shown in.In addition, sample rmGO-26 compares rmGO-10 with rmGO-33 have stronger and narrower X-ray diffraction peak, and this proves that the above two have the existence of more Graphene band reduction structure.
The signal of Fig. 5 image use the mechanism of sodium hydroxide to graphene oxide etching process.First, oxidized graphite flake layer structure can be etched into one very microporous film, as shown in figure (a).Along with sodium hydroxide constantly increases, etching is still continuing, and micropore is also on the increase, and hole area is corresponding expansion also, causes adjacent holes to couple together, and develops into one " hole canal ".Then, along with the continuation of etching process, hole canal will be constantly elongated, when two adjacent " hole canals " link together, will form a long band structure, this process can be seen in figure (c), finally, the graphene sheet layer etching that can be decomposed becomes rectangular or long band.Because formed " hole canal " can be crooked in the process of etching, so graphene sheet layer finally can form the graphene nanobelt that a length substantially exceeds the mm length of original film dimensions.
Claims (10)
1. a preparation method for millimeters long Graphene band, is characterized in that, comprises the following steps:
1) graphene oxide is dispersed in water, prepares graphene oxide suspension, the concentration of graphene suspension is 0.01 – 100 grams per liters;
2) in suspension, add chemical etchant, stirring heating, until mixed solution is crowded into mass colour pasty state;
3) filter, and wash to pH=6～8;
4) solid product after washing is dry;
5) dry powder is heated under protection of inert gas and is greater than reaction at 200 ℃;
6) the graphene oxide band of cooling rear acquisition reduction, 1 millimeter of length >.
2. the preparation method of millimeters long Graphene band according to claim 1, is characterized in that step 2) in, described chemical etchant is strongly alkaline compound or strongly-acid compound.
3. the preparation method of millimeters long Graphene band according to claim 2, is characterized in that, described strongly alkaline compound is a kind of or several mixture in NaOH, KOH, CaO, MgO.
4. according to the preparation method of the millimeters long Graphene band described in claim 2 or 3, it is characterized in that, described strongly alkaline compound is mixed with to solution, and its concentration is 0.01～10M.
5. the preparation method of millimeters long Graphene band according to claim 2, is characterized in that, described strongly-acid compound is HCl, H
2sO
4, H
3pO
4, HNO
3, a kind of or several mixture in HF.
6. according to the preparation method of the millimeters long Graphene band described in claim 2 or 5, it is characterized in that, described strongly-acid compound is mixed with to solution, and its concentration is 0.01～10M.
7. the preparation method of millimeters long Graphene band according to claim 1, is characterized in that step 2) in, Heating temperature is 70～150 ℃, be 0.5～2 hour heat-up time.
8. the preparation method of millimeters long Graphene band according to claim 1, is characterized in that, step 4) drying operation is specially: under vacuum condition, dry, bake out temperature is 50～120 ℃, and be 5～48 hours time of drying.
9. the preparation method of millimeters long Graphene band according to claim 1, is characterized in that, in step 5), dry powder is placed in to tube furnace, has protection of inert gas in tube furnace; Described rare gas element is nitrogen, argon gas, helium or neon.
10. the preparation method of millimeters long Graphene band according to claim 1, is characterized in that, in step 5), is divided into two stages:
(1) temperature of first stage is 180～400 ℃, and the soaking time in this stage is 0.2～3 hour;
(2) temperature of subordinate phase is 600～1200 ℃, and the soaking time in this stage is 0.5～3 hour.
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| CN105967175A (en) * | 2016-05-16 | 2016-09-28 | 河南工业大学 | Preparation method of water-soluble fluorinated graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913599A (en) * | 2010-08-13 | 2010-12-15 | 东华大学 | Method for preparing graphene nanobelt |
| US20130164209A1 (en) * | 2009-10-23 | 2013-06-27 | Jae-Kap Lee | Method for preparing graphene ribbons where structure is controlled |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130164209A1 (en) * | 2009-10-23 | 2013-06-27 | Jae-Kap Lee | Method for preparing graphene ribbons where structure is controlled |
| CN101913599A (en) * | 2010-08-13 | 2010-12-15 | 东华大学 | Method for preparing graphene nanobelt |
Non-Patent Citations (1)
| Title |
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| LI LI ZHANG ET AL.: "Highly Conductive and Porous Activated Reduced Graphene Oxide Films for High-Power Supercapacitors", 《NANO LETTERS》 * |
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| CN105967175A (en) * | 2016-05-16 | 2016-09-28 | 河南工业大学 | Preparation method of water-soluble fluorinated graphene |
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