CN105502353A - Wrapped monolayer graphene oxide/ carbon nano tube compound and preparation method thereof - Google Patents
Wrapped monolayer graphene oxide/ carbon nano tube compound and preparation method thereof Download PDFInfo
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- CN105502353A CN105502353A CN201510926115.8A CN201510926115A CN105502353A CN 105502353 A CN105502353 A CN 105502353A CN 201510926115 A CN201510926115 A CN 201510926115A CN 105502353 A CN105502353 A CN 105502353A
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Abstract
The invention discloses a wrapped monolayer graphene oxide/ carbon nano tube compound and a preparation method thereof. The compound is in a particle type; the compound particle has a core-shell type wrapping structure by adopting a monolayer graphene oxide nanosheet as a shell and an acidized and cut carbon nano tube as a core, or a closed dumpling-shaped wrapping structure by adopting a single monolayer graphene oxide nanosheet as a dumpling-wrapper and the acidized and cut carbon nano tube as a dumpling-stuffing. The technical scheme provided by the invention has the characteristics of simplicity, convenience, and easiness in operation. Due to the bending of a graphene oxide sheet layer and the electric charge loaded on the surface of the graphene oxide sheet layer, the obtained compound material can be highly dispersed, not easy liable to agglomeratereunite and cake, and easy to store, and meanwhile, the compound material can be easily reduced to obtain the graphene/ carbon nano tube compound material. The theoretical research proves that the wrapped novel special structure has strong electrical conductivity and mechanical performance.
Description
Technical field
The invention belongs to materials science and engineering technical field, be specifically related to a kind of coated single-layer graphene oxide/carbon mano-tube composite and preparation method thereof.
Background technology
Graphite (in layer being piled up by Graphene) is the softest in mineral substance, but after being separated into the Graphene of a carbon atom thickness, performance is then undergone mutation, and its grit diamond is also high, but has good toughness, and can bend.Royal Swedish Academy of Sciences once likened its intensity when Nobel Prize in physics in 2010 like this in promulgation: the hammock utilizing single-layer graphene to make can carry the rabbit of a 4kg.Can estimate like this, if be stacked together by multi-layer graphene, make its thickness identical with food fresh-keeping film, just can carry the automobile of 2 tons of weights.
Graphene and carbon nanotube are all excellent peacekeeping Two-dimensional Carbon materials, that have one dimension respectively with anisotropy that is two dimension, in electricity with mechanics etc., have similar character; But because structure is different, they also have a lot of difference.Although the Graphene of structural integrity has the advantages such as excellent electroconductibility, thermal conductivity and mechanical characteristics, owing to there is very strong Intermolecular Forces between graphene layer, very easily reunite, be difficult to dispersion, the deficiencies such as poor compatibility.Carbon nanotube is each other because van der Waals interaction also can be reunited.In order in conjunction with both advantage, Graphene and carbon nanotube are used for matrix material by researcher jointly, form tridimensional network, by the synergistic effect between them, show the performance more excellent than any one single-material, make it in ultracapacitor, solar cell, indicating meter, biological detection, fuel cell etc., have good application prospect.The graphene oxide of deep oxidation is a kind of important presoma of Graphene, and easily reduction forms Graphene, carries out functional modification by organic covalency, non-covalent strategy to it, to realize the dispersion of Graphene, dissolving, shaping and processing.
The Graphene/carbon nanotube composite material now studied exists mainly with tridimensional network, because carbon nanomaterial carbon interplanar has extremely strong covalent linkage laterally Van der Waals force is between layers relatively weak, electroconductibility outside face is caused to be restricted, thus affecting the conductive capability of carbon material entirety, this special construction making some scientific research personnel go to pursue other improves its performance further.Theoretical investigation has proved that three-dimensional columnar structure has extremely strong electroconductibility and mechanical property, in addition, also have several special graphene/carbon nano-tube composite structure, such as graphene film parcel winding carbon nanotube, graphene sheet layer are connected with carbon nanotube tube wall (being similar to leaf and branch).Wherein, the preparation that obtained graphene film parcel is wound around carbon nano tube compound material needs hot conditions and metal composite catalyst.In prior art, prepare the method condition difficulty of coated single-layer graphene oxide/carbon mano-tube composite, troublesome poeration, and graphene oxide and carbon nanotube skewness in prepared mixture, the problem of these outwardnesies hinders the application of coated single-layer graphene oxide/carbon nano tube compound material.
Summary of the invention
For the problems of the prior art, the invention provides a kind of coated single-layer graphene oxide/carbon mano-tube composite and preparation method thereof, preparation method's condition of the present invention is simple, operate simple and easy, and preparation coated single-layer graphene oxide/carbon mano-tube composite good dispersity, be evenly distributed, have a wide range of applications space.
According to the first embodiment of the present invention, a kind of coated single-layer graphene oxide/carbon mano-tube composite is provided, it is characterized in that: this mixture is rendered as particulate form, it is " shell " and take the carbon nanotube of acidifying, cutting as the core-shell type package structure of " core " that this compound particles has with single-layer graphene oxide nanometer sheet, or this compound particles to have with single-layer graphene oxide nanometer sheet be " dumpling wrapper " and take the carbon nanotube of acidifying, cutting as closed " dumpling shape " or " closed clam " package structure of " filling for dumplings ".
In the present invention, in the ratio accounting for whole compound particles total quantity higher than 50% (preferably more than 60%, more preferably more than 70%, more preferably more than 80%, more preferably more than 90%.Generally 50-95%) described compound particles in, one or more carbon nanotube particulate surround by single single-layer graphene oxide sheet or wrap up, in " dumpling shape " or " closed clam ".Namely, the ratio that the coated single-layer graphene oxide/carbon mano-tube composite particulate of " dumpling shape " or " closed clam " accounts for whole compound particles total quantity is higher than 50% (more preferably more than 60%, more preferably more than 70%, more preferably more than 80%, more preferably more than 90%, be generally 50-95%.In this application, the median size of single-layer graphene oxide is 50-3000nm, preferred 100-2500nm, is preferably 150-2000nm, is more preferably 180-1000nm, is more preferably 200-600nm.
In this application, the mean length of the carbon nanotube of acidifying, cutting or mean particle size are 40-2500nm, and be preferably 70-2000nm, preferred 100-1500nm, is more preferably 130-800nm, is more preferably 150-400nm.
Preferably, the median size of single-layer graphene oxide is 1.1-2.5:1 with the ratio of the mean length of carbon nanotube or mean particle size, preferred 1.2-2.2:1, more preferably 1.4-2.0:1.
According to the second embodiment provided by the invention, provide the preparation method of a kind of coated single-layer graphene oxide/carbon mano-tube composite:
Prepare a method for coated single-layer graphene oxide/carbon mano-tube composite, the method comprises the following steps:
(1) single-layer graphene oxide is prepared: by the Hummers legal system improved for graphene oxide solution, peel off, be separated, obtain sediment A;
(2) prepare carbon nanotube: by carbon nanotube acidifying process, ultrasonic cut, be separated, obtain sediment B;
(3) coated mixture is prepared: be dissolved or dispersed in solvent by sediment A and obtain solution C, sediment B is dissolved or dispersed in solvent and obtains solution D, solution C and solution D are mixed to get mixture E, mixing, cultivate (or ageing), be separated, obtain coated mixture.
In the present invention, the described stripping of step (1) adopts ultrasonic stripping, and the time of ultrasonic stripping is 1-15h, is preferably 2-10h, is more preferably 4-8h.
In the present invention, separation in step (1) adopts centrifugation, and whizzer is at 3,000-10,000rmp (is preferably 4,000-8,000rmp, be more preferably 5,000-7, under condition 000rmp), centrifugation 10-100min (be preferably 20-60min, be more preferably 30-50min), takes out centrifugate, collect 6,000 ~ 20000rmp (is preferably 7,000-15,000rmp, be more preferably 8,000-12,000rmp) the sediment A of centrifugation 10-60min (be preferably 20-50min, more have and elect 30-40min as) under condition.
In the present invention, acidification described in step (2): adopt nitration mixture process, heating, (such as using deionized water) washing is to neutral.
In the present invention, nitration mixture in acidification is the mixture of nitric acid and sulfuric acid, wherein: the concentration of nitric acid used is that 10-80wt% (is preferably 30-75wt%, be more preferably 50-70wt%), the concentration of the vitriol oil is 70-98wt% (being preferably 80-95wt%), when forming nitration mixture, the volume ratio of nitric acid and sulfuric acid is 1:1-5, is preferably 1:2-4, such as 1:3.
In the present invention, the temperature of the heating after acidification is 60-100 DEG C (be preferably 70-98 DEG C, be more preferably 80-95 DEG C), and the time of heating is 1-15h, is preferably 2-10h, is more preferably 4-8h.
In the present invention, adopt deionized water wash to neutral after acidification and heat treated.
In the present invention, the time of ultrasonic cut described in step (2) is that 20-100min (is preferably 30-80min, be more preferably 40-60min), ultrasonic power is 200-500W (is preferably 250-450W, is more preferably 300-400W).
In the present invention, be separated in step (2) and adopt centrifugation, whizzer is 3,000-10,000rmp (is preferably 4,000-9,000rmp, be more preferably 5,000-8,000rmp) condition under centrifugation 10-100min (be preferably 20-80min, be more preferably 30-60min), take out centrifugate, collect 6,000 ~ 20,000rmp and (be preferably 7,000 ~ 15,000rmp, is more preferably 8, and 000 ~ 10,000rmp) the sediment B of centrifugation 10-60min under condition (be preferably 20-50min, be more preferably 30-40min).
In the present invention, step also comprises in (1): dry after being separated, and preferably adopts ambient temperature in vacuum dry.
In the present invention, step also comprises in (2): dry after being separated, vacuum-drying at preferred 30-90 DEG C, vacuum-drying at being more preferably 40-85 DEG C.
In the present invention, solvent described in step (3) is one or more in acid amides or nitrile, is preferably one or more in methane amide, acrylamide or acetonitrile, is more preferably N, one or more in dinethylformamide, N,N-DMAA or acetonitrile.
In the present invention, in step (3), in solution C, the concentration of sediment A is 0.2-2.0mg/mL, and be preferably as 0.3-1.5mg/mL, being more preferably as 0.4-1.2mg/mL, such as, is 1.0mg/mL.In solution D, the concentration of sediment B is 0.2-2.0mg/mL, and be preferably as 0.3-1.5mg/mL, being more preferably as 0.4-1.2mg/mL, such as, is 1.0mg/mL.
In the present invention, in step (3), the mixed volume of solution C and solution D is than being 1:0.5-3, is preferably 1:0.8-2, is more preferably 1:1-1.2, such as 1:1.
In the present invention, the mixing in step (3) adopts ultrasonic mixing, and the time of ultrasonic mixing is 1-30min, is preferably 3-20min, is more preferably 5-10min.
In the present invention, cultivate described in step (3) and adopt constant temperature incubator, temperature is 20-80 DEG C, is preferably 30-70 DEG C, is more preferably 40-60 DEG C.
In the present invention, in step (3), constant temperature cultivates the time is 0.5-10h, is preferably 1-8h, 2-6h.
In the present invention, separation described in step (3) adopts centrifugation, at 3,000-8,000rmp (is preferably 4,000-7,000rmp, be more preferably 5,000-6,000rmp) centrifugal 10-60min (be preferably 20-30min, be more preferably 30-40min) under condition, takes out centrifugate.Collect the sediment of 6,000 ~ 15,000rmp (be preferably 6,500-12,000rmp, be more preferably 6,000-10,000rmp) centrifugation 10-60min (be preferably 20-30min, be more preferably 30-40min).
In the present invention, step also comprises in (3): dry after being separated, and preferably adopts ambient temperature in vacuum dry.
According to the third embodiment provided by the invention, provide the purposes of a kind of coated single-layer graphene oxide/carbon mano-tube composite:
Coated single-layer graphene oxide/carbon mano-tube composite of the present invention and coated prepared according to the methods of the invention single-layer graphene oxide/carbon mano-tube composite are used for lithium ion battery negative material.
In the present invention, more than 60% the coated single-layer graphene oxide/carbon mano-tube composite of (preferably 70%, more preferably 80%) be by one or carbon nanotube particulate surround by single single-layer graphene oxide sheet or wrap up.Or in the mixture that the ownership system is standby, coated single-layer graphene oxide/the carbon mano-tube composite of the dumpling shape of (preferably 70%, more preferably 80%) " more than 60% " or " closed clam " be one or carbon nanotube (particulate) surround by single single-layer graphene oxide sheet or wrap up.
In the present invention, multi-walled carbon nano-tubes: Nanjing Xian Feng Nono-material Science & Technology Ltd., caliber: 20-30 nanometer, pipe range: 0.5-2 micron, purity: >95%.By the Hummers legal system improved for graphene oxide solution, the Hummers method of improvement is with reference to DanielaCMarcano, DmitryVKosynkin, JacobMBerlin.Improvedsynthesisofgrapheneoxide, ACSnano, 2010,4 (8): 4806-4814.
In the present invention, atomic force microscope, model: DimensionIonPT, Bruker company limited of Switzerland dispatches from the factory.Laser Raman spectrometer and Raman Laser Scanning Confocal Microscope, model: JY-Laboram-010, French HORIBAJobinYvon company dispatches from the factory.
In the present invention, single single-layer graphene oxide nanometer sheet wraps up carbon nanotube completely, and namely carbon nanotube is by the closed parcel of single-layer graphene oxide.Be similar to " dumpling " shape, each single-layer graphene oxide is equivalent to " dumpling wrapper ", and carbon nanotube is equivalent to " filling for dumplings ".Single single-layer graphene oxide sheet wraps up the carbon nanotube of one or, and carbon nanotube is adopted closed parcel by single-layer graphene oxide completely.
In the present invention, described " dumpling shape " refers to that single-layer graphene oxide employing is closed and wraps up carbon nanotube completely, as " filling for dumplings " quilt " dumpling wrapper " wraps up completely.Coated single-layer graphene oxide/carbon mano-tube composite outer shape of the present invention can be irregular geometric shape, and just carbon nanotube is wrapped up by single-layer graphene oxide completely.
In the present invention, the median size of single-layer graphene oxide refers to the size of single-layer graphene oxide, average particle diameter, or perhaps the average path length of single-layer graphene oxide or the length of side.Because single-layer graphene oxide is irregular shape, slabbing, represents the size of the single-layer graphene oxide adopted in the present invention by median size.
In the present invention, whizzer, ultrasonic device, heating unit, Vacuumdrier, constant temperature incubator are the common equipment in state of the art, as long as can realize corresponding function, all can be applicable to the present invention.
Compared with prior art, the present invention has following Advantageous Effects:
1, coated single-layer graphene oxide/carbon mano-tube composite of the present invention, be similar to " dumpling " shape, single-layer graphene oxide is equivalent to " dumpling wrapper ", and carbon nanotube is equivalent to " filling for dumplings ".One piece of single-layer graphene oxide nanometer sheet wraps up a carbon nanotube, is uniformly distributed.
2, method of the present invention prepares coated single-layer graphene oxide/carbon mano-tube composite, does not need hot conditions and metal composite catalyst, and method is simple, operates simple and easy.
3, because coated single-layer graphene oxide/carbon mano-tube composite of the present invention is evenly distributed, the novel special construction of this coated, it has extremely strong electroconductibility and mechanical property to have theoretical investigation to prove.
4, the negative pole of lithium ion battery is prepared by coated single-layer graphene oxide/carbon mano-tube composite of the present invention, the performance of battery obtains and can significantly be promoted, its specific storage can reach more than 600mAh/g, and the specific storage of artificial plumbago negative pole common at present only has 370mAh/g, visible Graphene significantly can improve performance of lithium ion battery as negative material.
Accompanying drawing explanation
Fig. 1 is the atomic force microscope figure of stannic oxide/graphene nano tablet raw material of the present invention.
Fig. 2 is the thickness schematic diagram of stannic oxide/graphene nano tablet raw material of the present invention.
Fig. 3 is coated of the present invention single-layer graphene oxide/carbon mano-tube composite atomic force microscope figure.
Fig. 4 is the thickness schematic diagram of single-layer graphene oxide/carbon mano-tube composite of the present invention.
Fig. 5 is the atomic force microscope enlarged view of single-layer graphene oxide/carbon mano-tube composite of the present invention.
Fig. 6 is the thickness schematic diagram of single-layer graphene oxide/carbon mano-tube composite of the present invention.
Fig. 7 is the Raman spectrum comparison diagram of single-layer graphene oxide/carbon mano-tube composite of the present invention.
Wherein in Fig. 2,4 and 6, nanometer represents the height of compound particles, and micron represents the length of compound particles.
Embodiment
Here is specific embodiment prepared by coated of the present invention single-layer graphene oxide/carbon mano-tube composite, and following examples are intended to further describe the present invention, and unrestricted the present invention.
Embodiment 1
(1) preparation of single-layer graphene oxide nanometer sheet: prepare graphite oxide by the Hummers method (Marcano, etc., ACSnano, 2010,4 (8): 4806) improved.Take 3g Graphite Powder 99 to put in 500mL three-necked flask, add the dense H of 360mL
2sO
4and 40mLH (98%)
3pO
4(85%), under condition of ice bath, slowly 18gKMnO is added
4, stir 12h at mixed solution being held in 50 DEG C, after the mixed solution be obtained by reacting is cooled to room temperature, is poured on the ice cube be made up of 400mL deionized water, under agitation slowly adds about 3mLH
2o
2(30%), after mixture is filtered, with HCl (10%) centrifuge washing 5 times under 10,000rmp rotating speed.Then, products therefrom is loaded dialysis tubing, dialyse 3 weeks, then be placed in the dry 48h of vacuum freeze drier to constant weight, obtain brown graphite oxide.The graphite oxide solution of preparation 1mg/mL, ultrasonic stripping 4h, adopts supercentrifuge centrifugation under 8,000rmp condition, extracting centrifugal liquid, collects the single-layer graphene oxide nanometer sheet of centrifugation 30min under 12,000 rev/min of condition, ambient temperature in vacuum drying.
(2) process of carbon nanotube: at HNO
3with H
2sO
4(V
nitric acid: V
sulfuric acidfor 1:3) nitration mixture in, the concentration of nitric acid is 65%, and the concentration of sulfuric acid is 98%, reflux carbon nanotube 6h at 80 DEG C, after multiple times of filtration and deionized water wash to filtrate are neutrality, to the carbon nanotube ultrasonic cut 30min of acidifying, ultrasonic power is 300W; Adopt supercentrifuge centrifugation 40min under 6,000rmp condition, extracting centrifugal liquid, collect the acidifying of centrifugation 30min under 10,000rmp condition, the carbon nanotube of cutting, vacuum-drying at 60 DEG C, wait until that to prepare matrix material for subsequent use.
In step (1), the median size of gained single-layer graphene oxide is 220nm, and mean length or the mean particle size of the acidifying of gained in step (2), the carbon nanotube of cutting are 160nm.
(3) graphene oxide/carbon mano-tube composite preparation: select N, dinethylformamide makes solvent, compound concentration is the carbon nano-tube solution D after the single-layer graphene oxide solution C of 1mg/mL and acidifying cutting, solution C and solution D are mixed to get mixture E, after ultrasonic mixing 5min according to volume ratio 1:1 ratio; In constant temperature incubator, 2h is cultivated under 50 DEG C of conditions; Centrifugal 30min under 6,000rmp condition, takes out centrifugate, and the sediment of centrifugation 30min under collection 10,000rmp condition, ambient temperature in vacuum is dry.Obtain coated single-layer graphene oxide/carbon mano-tube composite.Productive rate is 82%.
By electron microscope observation with to Photomicrograph analysis, the ratio that the coated single-layer graphene oxide/carbon mano-tube composite particulate of " dumpling shape " or " closed clam " accounts for whole compound particles total quantity is about 89%.
Embodiment 2
Repeat embodiment 1, just step (1) the described time of peeling off the ultrasonic stripping of employing is 6h, is separated and adopts centrifugation, whizzer is centrifugation 50min under the condition of 6,000rmp, takes out centrifugate, the sediment A of centrifugation 20min under collection 12,000rmp condition.Productive rate is 84%.
Embodiment 3
Repeat embodiment 1, just in step (2), the massfraction of nitric acid is 40%, and the massfraction of the vitriol oil is 80%, and the volume ratio of nitric acid and sulfuric acid is 1:2; The temperature of acidification heating is 90 DEG C, and the time of heating is 3h; The time of ultrasonic cut is 60min, and ultrasonic power is 200W; Described separation adopts centrifugation, and whizzer is centrifugation 20min under the condition of 8,000rmp, takes out centrifugate, the sediment B of centrifugation 20min under collection 12,000rmp condition.Dry after being separated, vacuum-drying at 80 DEG C.Productive rate is 56%.
Embodiment 4
Repeat embodiment 1, just solvent N,N-DMAA described in step (3).Productive rate is 75%.
Embodiment 5
Repeat embodiment 1, just solvent acetonitrile described in step (3).Productive rate is 72%.
Embodiment 6
Repeat embodiment 1, just the mixture of solvent DMF and N,N-DMAA described in step (3), the volume ratio of two kinds of solvents is 1:1.Productive rate is 77%.
Embodiment 7
Repeat embodiment 1, just in solution C, the concentration of sediment A is 0.5mg/mL, and in solution D, the concentration of sediment B is 0.5mg/mL.In step (3), the mixed volume of solution C and solution D is than being 1:2.Productive rate is 67%.
Embodiment 8
Repeat embodiment 1, just in step (3), the time of ultrasonic mixing is 20min.Cultivate and adopt constant temperature incubator, temperature is 35 DEG C, and it is 8h that constant temperature cultivates the time.Be separated and adopt centrifugation, centrifugal 50min under 6,000rmp condition, take out centrifugate, collect the sediment of 8,000rmp centrifugation 10min.Productive rate is 72%.
Testing method
Coated single-layer graphene oxide/carbon mano-tube composite atomic force microscope embodiment 1 prepared and laser Raman spectrometer and Raman Laser Scanning Confocal Microscope characterize.
From Fig. 1 and Fig. 2, the stannic oxide/graphene nano sheet of preparation has single layer structure, and thickness is about 1.5nm.
From Fig. 3, Fig. 4, Fig. 5 and Fig. 6, the matrix material obtained have with single-layer graphene oxide sheet be " dumpling wrapper ", " being with the carbon nanotube after cutting " filling for dumplings " " class dumpling " coated special construction; its altitude range is 10 ~ 40nm, and the wrap altitude range of about 72% concentrates on 20 ~ 30nm.This mixture high dispersing, does not reunite, does not lump.
As seen from Figure 7, also occurred that is positioned at a 1326cm in the Raman spectrogram of matrix material
-1the D peak at place, but its G peak position and stannic oxide/graphene nano sheet (1589cm
-1) and cutting after acidifying carbon nanotube (1577cm
-1) compare, appear at lower frequency place (1573cm
-1), this shows to there occurs pi-pi accumulation reaction between single-layer graphene oxide nanometer sheet and carbon nanotube, also illustrates that the matrix material of coated special construction is successfully prepared.
Claims (11)
1. coated single-layer graphene oxide/carbon mano-tube composite, it is characterized in that: this mixture is rendered as particulate form, it is " shell " and take the carbon nanotube of acidifying, cutting as the core-shell type package structure of " core " that this compound particles has with single-layer graphene oxide nanometer sheet, or this compound particles to have with single-layer graphene oxide nanometer sheet be " dumpling wrapper " and take the carbon nanotube of acidifying, cutting as closed " dumpling shape " or " closed clam " package structure of " filling for dumplings ".
2. mixture according to claim 1, is characterized in that: accounting for the ratio of whole compound particles total quantity higher than in the described compound particles of 50%, one or more carbon nanotube particulate surround by single single-layer graphene oxide sheet or wrap up; Or the ratio that the coated single-layer graphene oxide/carbon mano-tube composite particulate of " dumpling shape " or " closed clam " accounts for whole compound particles total quantity is 50-95%.
3. mixture according to claim 1 and 2, is characterized in that: the median size of described single-layer graphene oxide is 50-3000nm, preferred 100-2500nm, is preferably 150-2000nm, is more preferably 180-1000nm, is more preferably 200-600nm,
And/or
The mean length of the carbon nanotube of described acidifying, cutting or mean particle size are 40-2500nm, and be preferably 70-2000nm, preferred 100-1500nm, is more preferably 130-800nm, is more preferably 150-400nm;
Preferably, the median size of single-layer graphene oxide is 1.1-2.5:1 with the ratio of the mean length of carbon nanotube or mean particle size, preferred 1.2-2.2:1, more preferably 1.4-2.0:1.
4. prepare a kind of method of coated single-layer graphene oxide/carbon mano-tube composite or prepare the method for coated single-layer graphene oxide/carbon mano-tube composite according to any one of claim 1-3, the method comprises the following steps:
(1) single-layer graphene oxide is prepared: by the Hummers legal system improved for graphene oxide solution, peel off, be separated, obtain sediment A;
(2) prepare carbon nanotube: by carbon nanotube acidifying process, ultrasonic cut, be separated, obtain sediment B;
(3) coated mixture is prepared: be dissolved or dispersed in solvent by sediment A and obtain solution C, sediment B is dissolved or dispersed in solvent and obtains solution D, solution C and solution D are mixed to get mixture E, mixing, cultivate (or ageing), be separated, obtain coated mixture.
5. method according to claim 4, is characterized in that: the described stripping of step (1) adopts ultrasonic stripping, and the time of ultrasonic stripping is 1-15h, is preferably 2-10h, is more preferably 4-8h,
And/or
Be separated described in step (1) and adopt centrifugal separation, whizzer is centrifugation 10-100min under the condition of 3,000-10,000rmp, takes out centrifugate, the sediment A of centrifugation 10-60min under collection 6,000 ~ 20,000rmp conditions.
6. the method according to claim 4 or 5, is characterized in that: acidification described in step (2): adopt nitration mixture process, heating, and (such as using deionized water) washing is to neutral; Preferably, described nitration mixture is the mixture of nitric acid and sulfuric acid, wherein: the concentration of nitric acid used is 10-80% (wt), the concentration of the vitriol oil used is 70-98% (wt), when forming nitration mixture, the volume ratio of nitric acid and sulfuric acid is 1:1-5, is preferably 1:2-4, such as 1:3; And/or
Heating wherein after nitration mixture process adopts the temperature of 60 ~ 100 DEG C, and the time of heating is 1-15h, is preferably 2-10h, is more preferably 4-8h.
7. the method according to any one of claim 4-6, is characterized in that: the time of ultrasonic cut described in step (2) is 20-100min, and ultrasonic power is 200-500W,
And/or
Be separated described in step (2) and adopt centrifugal separation, whizzer is centrifugation 10-100min under the condition of 3,000-10,000rmp, takes out centrifugate, the sediment B of centrifugation 10-60min under collection 6,000 ~ 20,000rmp conditions.
8. the method according to any one of claim 4-7, is characterized in that: step also comprises in (1): dry after being separated, and preferably adopts ambient temperature in vacuum dry,
And/or
Step also comprises in (2): dry after being separated, vacuum-drying at preferred 30-90 DEG C.
9. the method according to any one of claim 4-8, it is characterized in that: solvent described in step (3) is one or more in amides or nitrile, be preferably in methane amide, acrylamide or acetonitrile one or more, be more preferably N, dinethylformamide, N, one or more in N-DMAA or acetonitrile
And/or
In step (3), in solution C, the concentration of sediment A is 0.2-2.0mg/mL, and in solution D, the concentration of sediment B is 0.2-2.0mg/mL.
10. the method according to claim 4-9, is characterized in that: in step (3), the mixed volume of solution C and solution D is than being 1:0.5-3, is preferably 1:0.8-2, is more preferably 1:1-1.2,
And/or
Mixing described in step (3) adopts ultrasonic mixing, and the time of ultrasonic mixing is 1-30min, is preferably 3-20min, is more preferably 5-10min.
11., according to the method in claim 4-10 described in any one, is characterized in that: cultivate described in step (3) and adopt constant temperature incubator, temperature is 20-80 DEG C, is preferably 30-70 DEG C, is more preferably 40-60 DEG C,
And/or
It is 0.5-10h that constant temperature cultivates the time, is preferably 1-8h, 2-6h;
Preferably, the separation described in step (3) adopts centrifugal separation, centrifugal 10-60min under 3,000-8,000rmp condition, takes out centrifugate, collects the sediment of 6,000 ~ 15,000rmp centrifugation 10-60min,
And/or
Step also comprises in (3): dry after being separated, and preferably adopts ambient temperature in vacuum dry.
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