CN102464314A - Graphene solution and preparation method thereof - Google Patents
Graphene solution and preparation method thereof Download PDFInfo
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- CN102464314A CN102464314A CN2010105424721A CN201010542472A CN102464314A CN 102464314 A CN102464314 A CN 102464314A CN 2010105424721 A CN2010105424721 A CN 2010105424721A CN 201010542472 A CN201010542472 A CN 201010542472A CN 102464314 A CN102464314 A CN 102464314A
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Abstract
The invention discloses a graphene solution, comprising an organic solvent and graphene, wherein, the organic solvent is an amide solvent and/or an alkanone solvent, and the concentration of the graphene is 0.06-0.6 mg/mL. The preparation method comprises the following steps: under enclosed conditions, heating a graphene organic phase solution having a concentration of 0.1-1 mg/mL for 2-12 h at a temperature of 90-200 DEG C, and carrying out heat treatment. The concentration of graphene in the graphene solution is larger than 0.06 mg/mL. Compared with graphene solutions obtained without adding a stabilizing agent in the prior art, the concentration of graphene in the graphene solution disclosed herein is greatly increased. According to the invention, by using the amide and/or alkanone solvent as the organic solvent and the introduction of reducing agent or stabilizing agent molecules is not needed additionally in the process of reducing the organic phase solution of graphene oxides. The invention has a wide application prospect in the field of graphene materials and devices.
Description
Technical field
The present invention relates to a kind of graphite single-layer sheet solution and preparation method thereof.
Background technology
Graphite single-layer sheet (graphene) is commonly called as Graphene, since the advantage of aspects such as its electricity, calorifics and mechanical property, the extremely concern of researcher in recent years.Material and device based on the graphite single-layer sheet are with a wide range of applications at numerous areas such as energy storage material, bio-sensing, gas adsorption and catalytic materials.And as the primitive of constructing of these materials and device, can the graphite single-layer sheet realize the preparation of high quality high yield, also just becomes these materials and device and really move towards the bottleneck and foundation stone (Dreyer, the D. that produce and use; Park, S.; Bielawski, C.Chem.Soc.Rev.2010,39,228-240).
At present, the preparation method of graphite single-layer sheet mainly can be divided into five kinds: chemical Vapor deposition process, mechanically peel method, epitaxial growth method, chemical synthesis process and chemical reduction method.In these methods, first three belongs to physical method, and back two kinds is chemical process.Though physical method can obtain comparatively perfectly graphite single-layer sheet, productive rate is low, cost is higher, unsuitable mass production; Chemical synthesis process, the synthesis step of polycyclic aromatic hydrocarbons is many, productive rate is low, can not synthesize the bigger graphite single-layer sheet of area; And chemical reduction method; Promptly reduce graphite single-layer sheet oxide process; Be present unique method that can realize preparing in a large number the graphite single-layer sheet, but also there is certain deficiency in this method: there is certain defective in the graphite single-layer sheet of preparation, and the oxygen-containing functional group on surface also is difficult to remove fully.
Document (Nethravathi, C.; Rajamathi, M.Carbon 2008,46,1994-1998) propose to adopt solvent-thermal method reduction graphite single-layer sheet oxide compound.Solvent-thermal method is meant through in the pressurized vessel of sealing, and raw material is dispersed in the organic solvent, under the condition of HTHP, carries out chemical reaction then, is a kind of method of liquid-phase reduction graphite single-layer sheet oxide compound of green.
Solvent-thermal method has obtained investigator's concern as the method for the liquid-phase reduction graphite single-layer sheet oxide compound of green; Yet; Owing to there is stronger model ylid bloom action power between the graphite single-layer sheet; Pile up easily between the graphite single-layer sheet, thereby assemble, this has just limited the further modification and the application of graphite single-layer sheet.Be easy to take place to assemble this problem to the graphite single-layer sheet, a kind of solution is through covalent linkage or non covalent bond effect the graphite single-layer sheet to be modified, and makes the graphite single-layer sheet can be good at being dispersed in the solvent.
The existing graphite single-layer sheet solution for preparing because in the preparation process, introduced a large amount of reductive agents and/or stablizer, makes that solution is not to be simple graphite single-layer sheet solution.Simultaneously, do not modify if do not add stablizer, the concentration of graphite single-layer sheet is also lower in the graphite single-layer sheet solution, thereby has limited its further application, and therefore exploring a kind of preparation method that can obtain the graphite single-layer sheet solution of high density becomes inexorable trend.
Summary of the invention
The objective of the invention is to overcome graphite single-layer sheet solution that prior art for preparing obtains piles up easily and assembles; Thereby limited the further modification of graphite single-layer sheet and the defective of application, a kind of high density is provided and need not to add graphite single-layer sheet solution that tensio-active agent modifies and preparation method thereof.
The invention provides a kind of graphite single-layer sheet solution, wherein, said graphite single-layer sheet solution contains organic solvent and graphite single-layer sheet, and said organic solvent is amide solvent and/or alkane ketone solvent, and the concentration of said graphite single-layer sheet is 0.06-0.6mg/mL.
The invention provides a kind of method for preparing graphite single-layer sheet solution, this method comprises, in confined conditions, the graphite single-layer sheet oxide compound organic solution that with concentration is 0.1-1mg/mL is heat-treated 90-200 ℃ of heating 2-12 hour down; Wherein, the organic solvent in the said graphite single-layer sheet oxide compound organic solution is acid amides and/or alkane ketone.
The concentration of the graphite single-layer sheet in the graphite single-layer sheet solution of the present invention is greater than 0.06mg mL
-1, and the concentration without the graphite single-layer sheet solution of modifying of prior art for preparing is generally 0.01-0.03mg mL
-1(Hernandez, Y.; Nicolos, V.; Lotya, M.; Blighe, F.; Sun, Z.; De, S.; Mcgovern, I.; Holland, B.; Byrne, M.; Gun ' ko, Y.; Boland, J.; Niraj.P.; Duesberg.G.; Krishnamurthy, S.; Goodhue, R.; Hutchison, J.; Scardaci, V.; Ferrari, A.; Coleman, J.High-yield Production of Graphene by Liquid-phase Exfoliation of Graphite.Nat.Nanotechnol.2008,3,563-568; Hamilton, C.; Lomeda, J.; Sun, Z.; Tour, J.; Barron A.High-yield Organic Dispersions of Unfunctionalized Graphene.Nano Lett.2009; 9; 3460-3462.), the concentration that does not add the graphite single-layer sheet solution of stablizer acquisition more of the prior art improves greatly.And graphite single-layer sheet solution of the present invention almost only contains graphite single-layer sheet and organic solvent; The graphite single-layer sheet solution that obtains than a large amount of reductive agent of the introducing of prior art and/or stablizer is purer, helps the further modification and the functionalization of graphite single-layer sheet.
Contriver of the present invention is in research process; The unexpected discovery; Adopt method of the present invention; Through adopting amide solvent and/or alkane ketone solvent as organic solvent, in the process of the organic phase solution of reduction graphite single-layer sheet oxide compound, do not need extra introducing reductive agent or stablizer molecule can obtain graphite single-layer sheet solution, and can be under the condition of the graphite single-layer sheet oxide soln of higher concentration preparation graphite single-layer sheet solution; Reduced the severity of reaction conditions; Simultaneously can be in the preparation process through temperature of reaction and reaction times being controlled the reducing degree of graphite single-layer sheet oxide compound, further modification and functionalization that this helps the graphite single-layer sheet more have wide application prospect at graphite single-layer sheet material and devices field.
Description of drawings
Fig. 1 is the photo of DMF solution of graphite single-layer sheet of photo and one embodiment of the present invention of the DMF solution of graphite single-layer sheet oxide compound, (a) is the photo of the DMF solution of graphite single-layer sheet oxide compound, and its concentration is 0.5mg/mL; (b) be the photo of the DMF solution of graphite single-layer sheet of the present invention, its concentration is 0.3mg/mL.
Fig. 2 is AFM (AFM) photo (a) and the height map (b) of graphite single-layer sheet oxide compound.
Fig. 3 is the AFM photo (a) and the height map (b) of graphite single-layer sheet of the present invention.
Fig. 4 is the x-ray photoelectron spectroscopy figure of the graphite single-layer sheet of graphite single-layer sheet oxide compound and one embodiment of the present invention.
The Raman spectrogram of the graphite single-layer sheet that Fig. 5 prepares under condition of different temperatures for graphite single-layer sheet oxide compound and the present invention.
Embodiment
The invention provides a kind of graphite single-layer sheet solution, wherein, said graphite single-layer sheet solution contains organic solvent and graphite single-layer sheet, and said organic solvent is amide solvent and/or alkane ketone solvent, and the concentration of said graphite single-layer sheet is 0.06-0.6mg/mL.
Under the preferable case, the concentration of said graphite single-layer sheet is 0.28-0.6mg/mL.
Although carbonatoms all can be realized the object of the invention with the graphite single-layer sheet of the ratio of oxygen atomicity arbitrarily, under the preferable case, the carbonatoms of said graphite single-layer sheet is 4-8 with the ratio of oxygen atomicity, is preferably 4-6.
According to the present invention, although adopt said amide solvent and/or alkane ketone solvent can realize the object of the invention as organic solvent, contriver of the present invention finds that the amide solvent when employing is N; Dinethylformamide, DMAC N,N, N, N-DEF, N; When one or more in the N-diethyl acetamide, alkane ketone solvent are N-Methyl pyrrolidone and/or N-vinyl pyrrolidone, the graphite single-layer sheet solution better effects if of acquisition; Graphite single-layer sheet solution is more stable; And N, dinethylformamide, N-Methyl pyrrolidone are cheap, therefore from cost consideration; The especially preferred said organic solvent of the present invention is N, dinethylformamide and/or N-Methyl pyrrolidone.
The method for preparing graphite single-layer sheet solution of the present invention comprises with concentration being the graphite single-layer sheet oxide compound organic phase solution of 0.1-1mg/mL, in confined conditions, heats 2-12 hour down at 90-200 ℃, heat-treats; Preferably heated 2-10 hour down, heat-treat at 100-180 ℃.
Under the preferable case; In order to make the graphite single-layer sheet oxide compound organic phase solution dispersive before the thermal treatment more even; Thereby make the graphite single-layer sheet solution that obtains after the thermal treatment more stable; Can in advance graphite single-layer sheet oxide compound organic phase solution be carried out supersound process, the method for said supersound process can adopt conventional ultrasonic processing method, does not detail at this.
Under the preferable case, it is centrifugal that method of the present invention comprises that also the product that thermal treatment is obtained carries out, and the upper solution that obtains after centrifugal is a graphite single-layer sheet solution, and the graphite single-layer sheet solution that obtains after centrifugal is more stable.
Although being the graphite single-layer sheet oxide compound organic phase solution of 0.1-1mg/mL, employing concentration all can realize the object of the invention; But in this concentration range; Although more the graphite single-layer sheet oxide compound organic phase solution of lower concentration prepares graphite single-layer sheet solution and is more prone to; But in order to obtain the graphite single-layer sheet solution of higher concentration, the present invention preferably adopts the graphite single-layer sheet oxide compound organic phase solution of 0.45-1mg/mL.
The kind of said organic solvent details in preamble, repeats no more at this.
The method for preparing graphite single-layer sheet oxide compound organic phase solution of the present invention can adopt the conventional method for preparing graphite single-layer sheet oxide compound organic phase solution to prepare, and for example can prepare according to following steps:
(1) preparation graphite single-layer sheet oxide compound deionized water solution
Under 20-30 ℃ of temperature, natural flake graphite and SODIUMNITRATE are joined in the vitriol oil, the mixture that obtains was cooled off 10-100 minute with 0-2 ℃ of ice-water bath; After the cooling, add potassium permanganate, ice-water bath is withdrawn at 2-10 ℃; Kept 50-200 hour, and obtained the mixture of brown.The weight ratio of wherein said each component of mixture is a natural flake graphite: SODIUMNITRATE: the vitriol oil: potassium permanganate=1: 0.5-1: 45-80: 3-5.
Add the deionized water dilution, keep 20-120min, add the hydrogen peroxide solution of 3wt% then, the Manganse Dioxide that in remaining potassium permanganate and reaction, generates all is transformed into manganous sulfate, obtains jonquilleous suspension-s.At last with not having sulfate ion in deionized water repetitive scrubbing to the suspension-s.Suspension-s is separated through centrifugal (2560 * g 5000rpm), removes the deposition of centrifuge tube bottom, and the solution that obtains is graphite single-layer sheet oxide compound deionized water solution.
(2) preparation graphite single-layer sheet oxide compound organic phase solution
Use amide solvent and/or alkane ketone solvent that the resulting graphite single-layer sheet of step (1) oxide compound deionized water solution is handled, can obtain corresponding graphite single-layer sheet oxide compound organic phase solution.
Concrete, for example can carry out (the DMF solution with preparation graphite single-layer sheet oxide compound is example) according to following steps: get the deionized water solution of the graphite single-layer sheet oxide compound that step (1) obtains, centrifugal 10-100 minute (12400 * g; 11000rpm), remove supernatant liquid, add the volume of DMF then to original deionized water solution; Again disperse, after waiting to be uniformly dispersed, recentrifuge 10-100 minute (12400 * g; 11000rpm); Remove supernatant liquid, can repeat above operation 1-10 time, can obtain the organic phase solution of graphite single-layer sheet oxide compound required for the present invention.
Above-mentioned various raw materials all can adopt the conventional raw material that uses in this area, all can be through being purchased acquisition.
In order to make the object of the invention, technical scheme and advantage clearer, the present invention is at length explained below in conjunction with accompanying drawing and embodiment.
Among the present invention, the photo of the photo of the DMF solution of graphite single-layer sheet oxide compound and the DMF solution of graphite single-layer sheet is taken through pick up camera and is obtained.
AFM (AFM) photo is in AFM (model: VEECO Dimension3100, manufacturer: U.S. Wei Yike (Veeco) precision instrument company) record.
X-ray photoelectron spectroscopy figure is in x-ray photoelectron spectroscopy appearance (model: VG Scientific ESCALab220i-XL, manufacturer: record Britain VG scientific instrument company).Carbon atom and oxygen atomicity can directly obtain in test result, can obtain the ratio of carbonatoms and Sauerstoffatom through contrast carbonatoms and oxygen atomicity.
Raman spectrogram records at Reinshaw micro confocal Raman spectrometer (Britain Reinshaw company).
The measuring method of the concentration of graphite single-layer sheet solution: the graphite single-layer sheet solution of measuring certain volume (V); The deionized water of adding and solution equal volume filters and collects the black solid of separating out, and uses alcohol flushing; 100 ℃ of dryings are after 6 hours; The quality of weighing black solid (m) is calculated through following formula, can obtain the concentration (M) of graphite single-layer sheet solution.
M＝m/V
The deionized water solution of preparation graphite single-layer sheet oxide compound.
Under 20 ℃, getting the 2.0g fineness is that 325 purpose flaky graphites and 1.5g SODIUMNITRATE are added in the 80mL vitriol oil (98 weight %), the mixture that obtains is placed in the beaker of 500mL and to cool off 30min with ice-water bath, to temperature be 8 ℃, obtain suspension-s.
Under 5 ℃, (the size of stirrer: 6cm), 9.0g potassium permanganate is added in the above-mentioned suspension-s (whenever added once under the stirring velocity of 700r/min at a distance from 15 minutes; Each 1.5g that adds), then ice-water bath is withdrawn, kept 120 hours; The 150mL deionized water is added (whenever added once at a distance from 5 minutes, add 50mL at every turn), after half a hour; Add the ydrogen peroxide 50 of 250mL 3wt%, obtain jonquilleous solution.With the existence that does not have sulfate ion in deionized water centrifuge washing to the jonquilleous solution; Then solution centrifugal is separated (2560 * g; 3000rpm); Obtain the graphite single-layer sheet oxide compound deionized water solution of 6mg/mL, add the graphite single-layer sheet oxide compound deionized water solution that the deionized water dilution obtains 4mg/mL then, the carbonatoms of graphite single-layer sheet oxide compound and the ratio of oxygen atomicity are C/O=2.
Preparation embodiment 2
The DMF solution of preparation graphite single-layer sheet oxide compound.
Get the deionized water solution of the graphite single-layer sheet oxide compound among the preparation embodiment 1, (12400 * g 11000rpm), removed supernatant liquid in centrifugal 30 minutes; Add N then, dinethylformamide (DMF, Beijing Chemical Plant, northization reagent) is to the volume of the deionized water solution of initial graphite single-layer sheet oxide compound; Again disperse, and recentrifuge 30 minutes (12400 * g, 11000rpm); Remove supernatant liquid, disperse again with DMF again, repeat above operation 5 times; Obtain the DMF solution of graphite single-layer sheet oxide compound, the concentration of graphite single-layer sheet oxide compound is 4mg/mL, and the carbonatoms of graphite single-layer sheet oxide compound and the ratio of oxygen atomicity are C/O=2.
Preparation embodiment 3
The nmp solution of preparation graphite single-layer sheet oxide compound.
Consistent with the method for preparation embodiment 2; Different is that the organic solvent that adds is N-Methyl pyrrolidone (NMP; Beijing Chemical Plant, northization reagent), obtain the nmp solution of graphite single-layer sheet oxide compound; The concentration of graphite single-layer sheet oxide compound is 4mg/mL, and the carbonatoms of graphite single-layer sheet oxide compound and the ratio of oxygen atomicity are C/O=2.
Preparation embodiment 4
The DMAC N,N solution of preparation graphite single-layer sheet oxide compound.
Consistent with the method for preparation embodiment 2; Different is that the organic solvent that adds is DMAC N,N (DMAC, Beijing Chemical Plant; Northization reagent); Obtain the DMAC solution of graphite single-layer sheet oxide compound, the concentration of graphite single-layer sheet oxide compound is 4mg/mL, and the carbonatoms of graphite single-layer sheet oxide compound and the ratio of oxygen atomicity are C/O=2.
Preparation Comparative Examples 1-5
Methyl alcohol, ethanol, terepthaloyl moietie, DMSO, the THF solution of preparation graphite single-layer sheet.
Consistent with the method for preparation embodiment 2, different is that the organic solvent that adds is respectively methyl alcohol (Beijing Chemical Plant, northization reagent), ethanol (Beijing Chemical Plant; Northization reagent), terepthaloyl moietie (Beijing Chemical Plant, northization reagent), DMSO 99.8MIN. (DMSO, Beijing Chemical Plant; Northization reagent), THF (THF; The Beijing Chemical Plant, northization reagent), obtain corresponding graphite single-layer sheet oxide compound organic phase solution respectively; The concentration of the graphite single-layer sheet oxide compound that obtains is 4mg/mL, and the carbonatoms of graphite single-layer sheet oxide compound and the ratio of oxygen atomicity are C/O=2.
The DMF solution of the graphite single-layer sheet oxide compound that obtains of preparation embodiment 2 is added DMF be diluted to 0.5mg/mL; Get 30mL, ultrasonic 30 minutes (power 80W), the volume of packing into are autoclave (Beijing auspicious one-tenth great achievement plant and instrument ltd of 50mL; Model: KH-50), 120 ℃ were heated 2 hours.Afterwards that products therefrom is centrifugal, (922 * g 3000rpm), obtains the DMF solution of graphite single-layer sheet, and the concentration of graphite single-layer sheet is 0.3mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=4.5 to collect upper solution.
Fig. 1 is the photo of the DMF solution of the graphite single-layer sheet of photo and the embodiment 1 of the DMF solution of the graphite single-layer sheet oxide compound of preparation embodiment 2, and a is the photo of the DMF solution of the graphite single-layer sheet oxide compound for preparing embodiment 2, and its concentration is 0.5mg/mL; B is the photo of DMF solution of the graphite single-layer sheet of present embodiment preparation, and its concentration is 0.3mg/mL.
Fig. 2 is AFM (AFM) photo (a) and the height map (b) of graphite single-layer sheet oxide compound
To the 5 μ m, it highly is about 1nm to the size of lamella that can find out graphite oxide from the AFM photo about 500nm.
Fig. 3 is the AFM photo (a) and the height map (b) of the graphite single-layer sheet of present embodiment preparation.
Can find out that from the AFM photo size of the lamella of graphite single-layer sheet compares the lamella of graphite oxide and reduce to some extent, it highly is about 0.7nm;
Fig. 4 is the x-ray photoelectron spectroscopy figure of the graphite single-layer sheet of graphite single-layer sheet oxide compound and present embodiment preparation.
X-ray photoelectron spectroscopy through contrast graphite single-layer sheet oxide compound and graphite single-layer sheet can be found the O of graphite single-layer sheet
1sThe peak is compared graphite oxide and is obviously weakened, and this has just explained that a large amount of oxygen-containing functional group in graphite oxide surface is removed in the solvent thermal process.
The Raman spectrogram of the graphite single-layer sheet that Fig. 5 prepares for graphite single-layer sheet oxide compound and embodiments of the invention 1-4.
In the Raman spectrogram, 1350 and 1590cm
-1Correspond respectively to graphite oxide and graphite single-layer sheet D and G peak, the Raman spectrogram of comparative example 1-4 can find out that along with the raising of temperature of reaction, the ratio of the graphite single-layer sheet D peak of acquisition and the intensity at G peak raises gradually.
Raman spectrogram through contrast graphite single-layer sheet oxide compound and graphite single-layer sheet can be found out; No matter under which temperature of reaction, the ratio of the D peak of graphite single-layer sheet of the present invention and the intensity at G peak all increases than the ratio of the intensity at the D peak of graphite single-layer sheet oxide compound and G peak to some extent.This mainly is that size reduces (this point also can embody) in the AFM photo because in the solvent heat treatment process, graphite single-layer sheet lamella can divide; This just causes the edge carbon atomicity to increase; Because the increase of fringing effect, the D peak intensity increases, thereby the D peak increases with G peak intensity ratio gradually.(Pan，D.；Zhang，J.；Li，Z.；Wu，M.Hydrothermal?Route?for?Cutting?Graphene?Sheets?into?Blue-Luminescent?Graphene?Quantum?Dots.Adv.Mater.2010，22，734-738)
Embodiment 2
Method according to embodiment 1 prepares graphite single-layer sheet solution; Different is that Heating temperature is 160 ℃; Obtain the DMF solution of graphite single-layer sheet, the concentration of graphite single-layer sheet is 0.29mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=5.0.
Embodiment 3
Method according to embodiment 1 prepares graphite single-layer sheet solution, and different is that Heating temperature is 180 ℃.Obtain the DMF solution of graphite single-layer sheet, the concentration of graphite single-layer sheet is 0.28mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=5.2.
Embodiment 4
Method according to embodiment 1 prepares graphite single-layer sheet solution, and different is that Heating temperature is 200 ℃.Obtain the DMF solution of graphite single-layer sheet, the concentration of graphite single-layer sheet is 0.28mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=6.
Embodiment 5
Method according to embodiment 1 prepares graphite single-layer sheet solution; Different is to heat 3h down in 100 ℃; Obtain the DMF solution of graphite single-layer sheet, the concentration of graphite single-layer sheet is 0.35mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=4.2.
Embodiment 6
Method according to embodiment 1 prepares graphite single-layer sheet solution; Different is to heat 10h down in 160 ℃; Obtain the DMF solution of graphite single-layer sheet, the concentration of graphite single-layer sheet is 0.28mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=5.2.
Embodiment 7
The nmp solution of the graphite single-layer sheet oxide compound that obtains of preparation embodiment 3 is added NMP be diluted to 0.5mg/mL; Get 30mL, ultrasonic 30 minutes (power 80W), the volume of packing into are autoclave (Beijing auspicious one-tenth great achievement plant and instrument ltd of 50mL; Model: KH-50), 120 ℃ were heated 2 hours.(922 * g 3000rpm), obtains the nmp solution of graphite single-layer sheet to centrifugal collection upper solution, and the concentration of graphite single-layer sheet is 0.3mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=4.5.
Embodiment 8
N with the graphite single-layer sheet oxide compound that obtains of preparation embodiment 4; The N-dimethylacetamide solution adds DMAC N,N and is diluted to 0.5mg/mL, gets 30mL; Ultrasonic 30 minutes (power 80W); The volume of packing into be 50mL autoclave (Beijing auspicious one-tenth great achievement plant and instrument ltd, model: KH-50), 120 ℃ the heating 2 hours.(922 * g 3000rpm), obtains the DMAC N,N solution of graphite single-layer sheet to centrifugal collection upper solution, and the concentration of graphite single-layer sheet is 0.3mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=4.6.
Embodiment 9
Consistent with the method for embodiment 1; The DMF solution that different is will prepare the graphite single-layer sheet oxide compound that embodiment 2 obtains adds DMF and is diluted to 1mg/mL; 120 ℃ were heated 2 hours; Obtain the DMF solution of graphite single-layer sheet, the concentration of graphite single-layer sheet is 0.6mg/mL, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=4.5.
Comparative Examples 1-5
Methyl alcohol (ethanol, terepthaloyl moietie, DMSO, the THF) solution of the corresponding graphite single-layer sheet oxide compound that preparation Comparative Examples 1-5 is obtained adds coordinative solvent and is diluted to 0.1mg/mL; Get 30mL; Ultrasonic 30 minutes (power 80W); The volume of packing into be 50mL autoclave (Beijing auspicious one-tenth great achievement plant and instrument ltd, model: KH-50), 120 ℃ the heating 2 hours; All graphite single-layer sheet oxygenate conversion is a graphite single-layer sheet solid, and the carbonatoms of graphite single-layer sheet and the ratio of oxygen atomicity are C/O=4.5.
Claims (10)
1. graphite single-layer sheet solution; It is characterized in that; Said graphite single-layer sheet solution contains organic solvent and graphite single-layer sheet, and said organic solvent is amide solvent and/or alkane ketone solvent, and the concentration of graphite single-layer sheet is 0.06-0.6mg/mL in the said graphite single-layer sheet solution.
2. solution according to claim 1, wherein, the concentration of graphite single-layer sheet is 0.28-0.6mg/mL in the said graphite single-layer sheet solution.
3. solution according to claim 1 and 2, wherein, said organic solvent is N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N, N-DEF, N, one or more in N-diethyl acetamide, N-Methyl pyrrolidone and the N-vinyl pyrrolidone.
4. solution according to claim 3, wherein, said organic solvent is N, dinethylformamide and/or N-Methyl pyrrolidone.
5. solution according to claim 1 and 2, wherein, the carbonatoms of said graphite single-layer sheet and the ratio of oxygen atomicity are 4-8.
6. method for preparing graphite single-layer sheet solution, this method comprise, in confined conditions, the graphite single-layer sheet oxide compound organic solution that with concentration is 0.1-1mg/mL is heat-treated 90-200 ℃ of heating 2-12 hour down; It is characterized in that the organic solvent in the said graphite single-layer sheet oxide compound organic solution is acid amides and/or alkane ketone.
7. method according to claim 6, wherein, the concentration of said graphite single-layer sheet oxide compound organic solution is 0.45-1mg/mL.
8. according to claim 6 or 7 described methods, wherein, said amide solvent is N; Dinethylformamide, N; N-N,N-DIMETHYLACETAMIDE, N, N-DEF, N, one or more in N-diethyl acetamide, N-Methyl pyrrolidone and the N-vinyl pyrrolidone.
9. method according to claim 8, wherein, said organic solvent is N, dinethylformamide and/or N-Methyl pyrrolidone solution.
10. method according to claim 6, wherein, said heat treated temperature 100-180 ℃, the time is 2-10 hour.
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