CN105502353B - A kind of coated single-layer graphene oxide/carbon mano-tube composite and preparation method thereof - Google Patents
A kind of coated single-layer graphene oxide/carbon mano-tube composite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of coated single-layer graphene oxide/carbon mano-tube composites and preparation method thereof, the compound is rendered as particulate form, it be " shell " and with core-shell type package structure that the carbon nanotube for being acidified, cutting is " core " or the compound particles with being " dumpling wrapper " with single single-layer graphene oxide nanometer sheet and with closed " dumpling " shape package structure that the carbon nanotube for being acidified, cutting is " filling for dumplings " that the compound particles, which have with single-layer graphene oxide nanometer sheet,.The solution of the present invention has the characteristics that simple and convenient, easily operated.Bending because of graphene oxide layer and surface institute negative electrical charge, the composite material energy high degree of dispersion obtained are not easy to reunite and lump, easily stored, while it is also easy to restore obtained Graphene/carbon nanotube composite material.For the novel special construction of this coated, having theoretical research to be proved it has extremely strong electric conductivity and mechanical performance.
Description
Technical field
The invention belongs to materials science and engineering technical fields, and in particular to a kind of coated mono-layer graphite oxide
Alkene/carbon mano-tube composite and preparation method thereof.
Background technology
Graphite (being piled up to get up in layer by graphene) is most soft in minerals, but is separated into a carbon atom thickness
After the graphene of degree, performance then mutates, and grit diamond is also high, but possesses good toughness, and can be bent.It is auspicious
The academy of sciences of allusion quotation imperial family once likens its intensity in this way when promulgating Nobel Prize in physics in 2010:Utilize single-layer graphene system
The hammock of work can carry the rabbit of a 4kg.It can be evaluated whether in this way, if multi-layer graphene is stacked together, make its thickness
If degree is identical as food fresh-keeping film, 2 tons of heavy automobiles can be carried.
Graphene and carbon nanotube are all an excellent peacekeeping Two-dimensional Carbon materials, be respectively provided with it is one-dimensional and it is two-dimensional respectively to
The opposite sex has similar property in electricity and mechanics etc.;But due to structure difference, they also have many differences.Knot
Although the complete graphene of structure has many advantages, such as excellent electric conductivity, thermal conductivity and mechanical property, due to depositing between graphene layer
In very strong intermolecular force, easily reunite, it is difficult to disperse, the deficiencies of poor compatibility.Yin Fande between carbon nanotube
Magnificent force effect can also reunite.The advantages of in order to combine the two, graphene and carbon nanotube are provided commonly for by researcher
Composite material forms tridimensional network and is shown than any one homogenous material more by the synergistic effect between them
Excellent performance makes it have in ultracapacitor, solar cell, display, biological detection, fuel cell etc. good
Application prospect.The graphene oxide of deep oxidation is a kind of important presoma of graphene, and easily reduction forms graphene, can lead to
It crosses organic covalent, non-covalent strategy and functional modification is carried out to it, to realize dispersion, dissolving, molding and the processing of graphene.
The Graphene/carbon nanotube composite material studied mostly exists with tridimensional network, due to carbon nanomaterial
It is relatively weak in Van der Waals force laterally between layers with extremely strong covalent bond between carbon plane, lead to electric conductivity outside face
It is restricted, to influence the conductive capability of carbon material entirety, this makes some scientific research personnel go to pursue other special constructions
To further increase its performance.Theoretical research, which is proved three-dimensional column structure, has extremely strong electric conductivity and mechanical performance, in addition,
Also several special graphene/carbon nano-tube composite constructions, such as graphene film package winding carbon nanotube, graphene sheet layer
It is connect with carbon nanotube tube wall and (is similar to leaf and branch).Wherein, graphene film package winding carbon nanotube obtained is multiple
The preparation of condensation material needs hot conditions and metal composite catalyst.In the prior art, prepare coated single-layer graphene oxide/
The method condition of carbon mano-tube composite is difficult, graphene oxide and carbon nanometer in compound troublesome in poeration and prepared
The problem of pipe is unevenly distributed, these objective realities hinders coated single-layer graphene oxide/carbon nano tube compound material
Using.
Invention content
For the problems of the prior art, it is compound that the present invention provides a kind of coated single-layer graphene oxide/carbon nanotube
Object and preparation method thereof, preparation method condition of the invention is simple, and operation is simple, and the coated mono-layer graphite oxide prepared
Alkene/carbon mano-tube composite good dispersion is evenly distributed, and has a wide range of applications space.
According to the first embodiment of the invention, a kind of coated single-layer graphene oxide/carbon mano-tube composite is provided,
It is characterized in that:The compound is rendered as particulate form, which, which has with single-layer graphene oxide nanometer sheet, is
" shell " and have with single layer oxygen for the core-shell type package structure of " core " or the compound particles with the carbon nanotube for being acidified, cutting
Graphite alkene nanometer sheet be " dumpling wrapper " and with closed " dumpling shape " that the carbon nanotube for being acidified, cutting is " filling for dumplings " or
" clam of closure " package structure.
In the present invention, in the ratio for accounting for whole compound particles total quantitys higher than 50% (preferably 60% or more, more preferably
70% or more, more preferable 80% or more, more preferable 90% or more.Usually 50-95%) the compound particles in, one
Or multiple carbon nanotube particles are surrounded or are wrapped up by single single-layer graphene oxide piece, are in " dumpling shape " or " clam shell of closure
Shape ".That is, the coated single-layer graphene oxide/carbon mano-tube composite particle of " dumpling shape " or " clam of closure " accounts for entirely
The ratio of portion's compound particles total quantity be above 50% (more preferable 60% or more, more preferable 70% or more, more preferable 80% with
On, more preferable 90% or more, usually 50-95%.In this application, the average grain diameter of single-layer graphene oxide is 50-
3000nm, preferably 100-2500nm, preferably 150-2000nm, more preferably 180-1000nm, more preferably 200-600nm.
In this application, the average length or average particle size for the carbon nanotube be acidified, cut are 40-2500nm, preferably
70-2000nm, preferably 100-1500nm, more preferably 130-800nm, more preferably 150-400nm.
Preferably, the ratio of the average grain diameter of single-layer graphene oxide and the average length of carbon nanotube or average particle size is
1.1-2.5:1, preferably 1.2-2.2:1, more preferable 1.4-2.0:1.
According to second of embodiment provided by the invention, a kind of coated single-layer graphene oxide/carbon nanotube is provided
The preparation method of compound:
A method of coated single-layer graphene oxide/carbon mano-tube composite being prepared, this approach includes the following steps:
(1) single-layer graphene oxide is prepared:Graphene oxide solution is prepared with improved Hummers methods, is removed, separation,
Obtain sediment A;
(2) carbon nanotube is prepared:Carbon nanotube acidification is handled, ultrasonic cut, detaches, obtain sediment B;
(3) coated compound is prepared:Sediment A is dissolved or dispersed in solvent and obtains solution C, sediment B is molten
It solving or is scattered in solvent and obtain solution D, solution C and solution D are mixed to get mixture E, mixing cultivates (or ageing), point
From obtaining coated compound.
In the present invention, step (1) stripping is removed using ultrasound, and the time of ultrasound stripping is 1-15h, preferably 2-
10h, more preferably 4-8h.
In the present invention, the separation in step (1), which uses, centrifuges, and centrifuge (is preferably in 3,000-10,000rmp
4,000-8,000rmp, more preferably 5,000-7,000rmp) under conditions of centrifuge 10-100min (preferably 20-
60min, more preferably 30-50min), taking-up centrifugate, collection 6,000~20000rmp (preferably 7,000-15,000rmp,
More preferably 8,000-12,000rmp) under the conditions of centrifuge 10-60min (preferably 20-50min, be more selected as 30-
Sediment A 40min).
In the present invention, acidification described in step (2):It is handled, is heated using nitration mixture, (such as with deionized water) washes
It washs to neutrality.
In the present invention, the nitration mixture in acidification is the mixture of nitric acid and sulfuric acid, wherein:Nitric acid used it is a concentration of
10-80wt% (preferably 30-75wt%, more preferably 50-70wt%), a concentration of 70-98wt% of the concentrated sulfuric acid is (preferably
80-95wt%), when forming nitration mixture, the volume ratio of nitric acid and sulfuric acid is 1:1-5, preferably 1:2-4, such as 1:3.
In the present invention, the temperature of the heating after acidification be 60-100 DEG C (preferably 70-98 DEG C, more preferably 80-
95 DEG C), the time of heating is 1-15h, preferably 2-10h, more preferably 4-8h.
In the present invention, it adopts and is washed with deionized to neutrality after acidification and heat treatment.
In the present invention, the time of ultrasonic cut described in step (2) be 20-100min (preferably 30-80min, it is more excellent
It is selected as 40-60min), ultrasonic power is 200-500W (preferably 250-450W, more preferably 300-400W).
In the present invention, in step (2) separation using centrifuging, centrifuge 3,000-10,000rmp (preferably 4,
000-9,000rmp, more preferably 5,000-8,000rmp) under conditions of centrifuge 10-100min (preferably 20-80min,
More preferably 30-60min), centrifugate is taken out, collects 6, (preferably 7,000~15,000rmp are more excellent by 000~20,000rmp
Be selected as 8,000~10,000rmp) under the conditions of centrifuge 10-60min (preferably 20-50min, more preferably 30-40min)
Sediment B.
In the present invention, further include in step (1):It is dry after separation, it is preferred to use to be dried in vacuo at room temperature.
In the present invention, further include in step (2):It is dry after separation, it is dried in vacuo at preferably 30-90 DEG C, more preferably
It is dried in vacuo at 40-85 DEG C.
In the present invention, solvent described in step (3) is one or more in amide or nitrile, preferably formamide,
It is one or more in acrylamide or acetonitrile, more preferably n,N-Dimethylformamide, N,N-DMAA or second
It is one or more in nitrile.
In the present invention, in step (3) in solution C sediment A a concentration of 0.2-2.0mg/mL, be preferably 0.3-
1.5mg/mL is more preferably 0.4-1.2mg/mL, for example, 1.0mg/mL.A concentration of 0.2- of sediment B in solution D
2.0mg/mL is preferably 0.3-1.5mg/mL, is more preferably 0.4-1.2mg/mL, for example, 1.0mg/mL.
In the present invention, the mixed volume ratio of solution C and solution D is 1 in step (3):0.5-3, preferably 1:0.8-2,
More preferably 1:1-1.2 such as 1:1.
In the present invention, the mixing in step (3) is using ultrasonic mixing, and the time of ultrasonic mixing is 1-30min, preferably
3-20min, more preferably 5-10min.
In the present invention, it is cultivated described in step (3) and uses constant temperature incubator, temperature is 20-80 DEG C, preferably 30-70
DEG C, more preferably 40-60 DEG C.
In the present invention, constant temperature cultivates the time as 0.5-10h, preferably 1-8h, 2-6h in step (3).
In the present invention, separation described in step (3) is using centrifuging, 3,000-8,000rmp (preferably 4,
000-7,000rmp, more preferably 5,000-6,000rmp) under the conditions of centrifugation 10-60min (preferably 20-30min, more preferably
For 30-40min), take out centrifugate.Collection 6,000~15,000rmp (preferably 6,500-12,000rmp, more preferably 6,
000-10,000rmp) centrifuge the sediment of 10-60min (preferably 20-30min, more preferably 30-40min).
In the present invention, further include in step (3):It is dry after separation, it is preferred to use to be dried in vacuo at room temperature.
According to the third embodiment provided by the invention, a kind of coated single-layer graphene oxide/carbon nanotube is provided
The purposes of compound:
By coated single-layer graphene oxide/carbon mano-tube composite of the present invention and packet prepared according to the methods of the invention
Type single-layer graphene oxide/carbon mano-tube composite is wrapped up in for lithium ion battery negative material.
In the present invention, more than 60% (preferably 70%, more preferable coated single-layer graphene oxide/carbon nanometer 80%)
Pipe compound is surrounded or is wrapped up by single single-layer graphene oxide piece by one or a carbon nanotube particle.Or all
In the compound of preparation, the package of " more than 60% (preferably 70%, more preferable dumpling shape 80%) " or " clam of closure "
Type single-layer graphene oxide/carbon mano-tube composite is one or a carbon nanotube (particle) by single single-layer graphene oxide
Piece is surrounded or is wrapped up.
In the present invention, multi-walled carbon nanotube:Nanjing Xian Feng Nono-material Science & Technology Ltd., caliber:20-30 nanometers,
Pipe range:0.5-2 microns, purity:>95%.Graphene oxide solution, improved Hummers methods are prepared with improved Hummers methods
With reference to Daniela C Marcano, Dmitry V Kosynkin, Jacob M Berlin.Improved synthesis of
Graphene oxide, ACS nano, 2010,4 (8):4806-4814.
In the present invention, atomic force microscope, model:Dimension Ion PT, the manufacture of Bruker Co., Ltds of Switzerland.
Laser Raman spectrometer and Raman Laser Scanning Confocal Microscope, model:JY-Laboram-010, French HORIBA Jobin Yvon are public
Department's manufacture.
In the present invention, the single fully wrapped around carbon nanotube of single-layer graphene oxide nanometer sheet, i.e., carbon nanotube is by single layer
The closed package of graphene oxide.Similar to " dumpling " shape, each single-layer graphene oxide is equivalent to " dumpling wrapper ", carbon nanotube
It is equivalent to " filling for dumplings ".Single single-layer graphene oxide piece wraps up one or one carbon nanotube, the complete coverlet of carbon nanotube
Layer graphene oxide uses closed package.
In the present invention, described " dumpling shape " refers to that single-layer graphene oxide uses closed fully wrapped around carbon nanotube,
As " filling for dumplings " quilt " dumpling wrapper " is fully wrapped around.Coated single-layer graphene oxide/carbon mano-tube composite of the present invention
Outer shape can be irregular geometric shape, and only carbon nanotube is wrapped up by single-layer graphene oxide completely.
In the present invention, the average grain diameter of single-layer graphene oxide refers to the size of single-layer graphene oxide, average
Grain size, or perhaps the average path length or the length of side of single-layer graphene oxide.Since single-layer graphene oxide is irregular shape
Shape, slabbing indicate the size of the single-layer graphene oxide used in the present invention with average grain diameter.
In the present invention, centrifuge, ultrasonic device, heating device, vacuum drier, constant temperature incubator are that this field is existing
There is the commonly used equipment in technology, as long as corresponding function can be realized, can be suitably used for 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 invention, is analogous to " dumpling " shape, single layer oxygen
Graphite alkene is equivalent to " dumpling wrapper ", and carbon nanotube is equivalent to " filling for dumplings ".One piece of single-layer graphene oxide nanometer sheet package one
Root carbon nanotube, is uniformly distributed.
2, method of the invention prepares coated single-layer graphene oxide/carbon mano-tube composite, does not need hot conditions
And metal composite catalyst, method is simple, and operation is simple.
3, since coated single-layer graphene oxide/carbon mano-tube composite of the present invention is evenly distributed, this coated
Novel special construction, have theoretical research be proved it have extremely strong electric conductivity and mechanical performance.
4, coated single-layer graphene oxide/carbon mano-tube composite of the present invention is prepared to the cathode of lithium ion battery,
The performance of battery has obtained significantly being promoted, and specific capacity can reach 600mAh/g or more, and common at present
The specific capacity of artificial plumbago negative pole only has 370mAh/g, it is seen that graphene can greatly improve lithium ion battery as negative material
Performance.
Description of the drawings
Fig. 1 is the atomic force microscopy diagram 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 single-layer graphene oxide/carbon mano-tube composite atomic force microscopy diagram of the present invention.
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 drawing 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 that the Raman spectrum of single-layer graphene oxide/carbon mano-tube composite of the present invention compares figure.
Wherein in Fig. 2,4 and 6, nanometer indicates that the height of compound particles, micron indicate the length of compound particles.
Specific implementation mode
Here is specific embodiment prepared by coated single-layer graphene oxide of the present invention/carbon mano-tube composite, below
Embodiment is further intended to that the present invention will be described in detail, is not intended to limit the present invention.
Embodiment 1
(1) preparation of single-layer graphene oxide nanometer sheet:With improved Hummers methods (Marcano, etc., ACS
nano,2010,4(8):4806) graphite oxide is prepared.It weighs 3g graphite powders to put into 500mL three-neck flasks, it is dense that 360mL is added
H2SO4(98%) and 40mL H3PO4(85%), under condition of ice bath, 18g KMnO are slowly added to4, mixed liquor is held in 50 DEG C
Lower stirring 12h after being cooled to room temperature mixed liquor obtained by the reaction, is poured on the ice cube made of 400mL deionized waters, is stirring
It mixes down and is slowly added to about 3mL H2O2(30%), it after mixture being filtered, is centrifuged and is washed under 10,000rmp rotating speeds with HCl (10%)
It washs 5 times.Then, products therefrom is packed into bag filter, dialysed 3 weeks, then be placed in vacuum freeze drier and dry 48h to constant weight, obtained
To the graphite oxide of brown.Prepare the graphite oxide solution of 1mg/mL, ultrasound stripping 4h, using supercentrifuge 8,000rmp
Under the conditions of centrifuge, extracting centrifugal liquid, collect 12,000 rev/min under the conditions of centrifuge 30min single-layer graphene oxide receive
Rice piece, is dried in vacuo at room temperature.
(2) processing of carbon nanotube:In HNO3With H2SO4(VNitric acid:VSulfuric acidIt is 1:3) in nitration mixture, nitric acid it is a concentration of
65%, a concentration of the 98% of sulfuric acid, carbon nanotube 6h is heated to reflux at 80 DEG C, through being filtered for multiple times and deionized water is washed to filtrate
After being in neutrality, to carbon nanotube the ultrasonic cut 30min, ultrasonic power 300W of acidification;Using supercentrifuge 6,
Centrifuge 40min under the conditions of 000rmp, extracting centrifugal liquid is collected and centrifuges the acidification of 30min under the conditions of 10,000rmp, cuts
The carbon nanotube cut is dried in vacuo at 60 DEG C, remains to prepare composite material spare.
The average grain diameter of gained single-layer graphene oxide is 220nm, acidification, the cutting of the middle gained of step (2) in step (1)
Carbon nanotube average length or average particle size be 160nm.
(3) prepared by graphene oxide/carbon mano-tube composite:Selection n,N-Dimethylformamide makees solvent, compound concentration
Be the single-layer graphene oxide solution C and the carbon nano-tube solution D after acidification cutting of 1mg/mL, by solution C and solution D according to
Volume ratio 1:1 ratio is mixed to get mixture E, after ultrasonic mixing 5min;Under the conditions of 50 DEG C 2h is cultivated in constant temperature incubator;
30min is centrifuged under the conditions of 6,000rmp, takes out centrifugate, collects the sedimentation of centrifugation 30min under the conditions of 10,000rmp
Object is dried in vacuo at room temperature.Up to coated single-layer graphene oxide/carbon mano-tube composite.Yield is 82%.
It is analyzed by electron microscope observation and to microphoto, the coated list of " dumpling shape " or " clam of closure "
It is about 89% that layer graphene oxide/carbon mano-tube composite particle, which accounts for the ratio of whole compound particles total quantitys,.
Embodiment 2
Embodiment 1 is repeated, only step (1) stripping uses the time that ultrasound is removed to be detached using centrifugation point for 6h
From centrifuge centrifuges 50min under conditions of 6,000rmp, takes out centrifugate, collects centrifugation point under the conditions of 12,000rmp
Sediment A from 20min.Yield is 84%.
Embodiment 3
Embodiment 1 is repeated, only the mass fraction of nitric acid is 40% in step (2), and the mass fraction of the concentrated sulfuric acid is 80%,
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;Ultrasonic cut when
Between be 60min, ultrasonic power 200W;Using centrifuging, centrifuge centrifuges under conditions of 8,000rmp to be divided for the separation
From 20min, centrifugate is taken out, collects the sediment B of centrifugation 20min under the conditions of 12,000rmp.It is dry after separation, 80
It is dried in vacuo at DEG C.Yield is 56%.
Embodiment 4
Embodiment 1 is repeated, only solvent N,N-DMAA described in step (3).Yield is 75%.
Embodiment 5
Embodiment 1 is repeated, only solvent acetonitrile described in step (3).Yield is 72%.
Embodiment 6
Embodiment 1 is repeated, only solvent n,N-Dimethylformamide and N,N-DMAA described in step (3)
Mixture, the volume ratios of two kinds of solvents is 1:1.Yield is 77%.
Embodiment 7
Repeat embodiment 1, only in solution C sediment A a concentration of 0.5mg/mL, sediment B's is a concentration of in solution D
0.5mg/mL.The mixed volume ratio of solution C and solution D is 1 in step (3):2.Yield is 67%.
Embodiment 8
Embodiment 1 is repeated, only the time of ultrasonic mixing is 20min in step (3).It cultivates and uses constant temperature incubator, temperature
Degree is 35 DEG C, and constant temperature cultivates the time as 8h.Separation centrifuges 50min using centrifuging under the conditions of 6,000rmp, takes out centrifugation
Liquid collects the sediment that 8,000rmp centrifuges 10min.Yield is 72%.
Test method
Coated single-layer graphene oxide/carbon mano-tube composite atomic force microscope prepared by embodiment 1 and swash
Light Raman spectrometer and Raman Laser Scanning Confocal Microscope are characterized.
From Fig. 1 and Fig. 2 as it can be seen that the stannic oxide/graphene nano piece prepared has single layer structure, thickness is about 1.5nm.
By Fig. 3, Fig. 4, Fig. 5 and Fig. 6 as it can be seen that the composite material obtained has with single-layer graphene oxide piece for " dumpling
Skin ", " being with the carbon nanotube after cutting " filling for dumplings " " class dumpling " coated special construction, altitude range be 10~
40nm, about 72% wrappage altitude range concentrate on 20~30nm.The compound high degree of dispersion, does not reunite, does not lump.
As seen from Figure 7, also occur one in the raman spectrum of composite material and be located at 1326cm-1The peaks D at place, but its peak G
Position and stannic oxide/graphene nano piece (1589cm-1) and cutting after acidification carbon nanotube (1577cm-1) compare, it appears in more
(1573cm at low frequency-1), this shows pi-pi accumulation has occurred between single-layer graphene oxide nanometer sheet and carbon nanotube anti-
It answers, also illustrates that the composite material of coated special construction is successfully prepared.
Claims (32)
1. a kind of coated single-layer graphene oxide/carbon mano-tube composite, it is characterised in that:The compound is rendered as particle shape
Formula, it is " shell " and with the carbon nanotube that is acidified, cuts for " core " which, which has with single-layer graphene oxide nanometer sheet,
Core-shell type package structure or the compound particles have with single-layer graphene oxide nanometer sheet be " dumpling wrapper " and with acidification,
The carbon nanotube of cutting is closed " the dumpling shape " or " clam of closure " package structure of " filling for dumplings ";
Wherein:The average grain diameter of the single-layer graphene oxide is 50-3000nm, and the carbon nanotube for being acidified, cutting is put down
Equal length or average particle size are 40-2500nm.
2. compound according to claim 1, it is characterised in that:It is higher than in the ratio for accounting for whole compound particles total quantitys
In 50% compound particles, one or more carbon nanotube particles are surrounded or are wrapped by single single-layer graphene oxide piece
It wraps up in;Or the coated single-layer graphene oxide/carbon mano-tube composite particle of " dumpling shape " or " clam of closure " accounts for whole
The ratio of compound particles total quantity is 50-95%.
3. compound according to claim 1 or 2, it is characterised in that:The average grain diameter of single-layer graphene oxide is received with carbon
The average length of mitron or the ratio of average particle size are 1.1-2.5:1.
4. compound according to claim 3, it is characterised in that:The average grain diameter of the single-layer graphene oxide is 100-
2500nm,
And/or
The average length or average particle size of the carbon nanotube of the acidification, cutting are 70-2000nm;
The ratio of the average grain diameter of single-layer graphene oxide and the average length of carbon nanotube or average particle size is 1.2-2.2:1.
5. compound according to claim 4, it is characterised in that:The average grain diameter of the single-layer graphene oxide is 150-
2000nm,
And/or
The average length or average particle size of the carbon nanotube of the acidification, cutting are 100-1500nm;
The ratio of the average grain diameter of single-layer graphene oxide and the average length of carbon nanotube or average particle size is 1.4-2.0:1.
Appoint 6. preparing a kind of method of coated single-layer graphene oxide/carbon mano-tube composite or preparing in claim 1-5
The method of one coated single-layer graphene oxide/carbon mano-tube composite, this approach includes the following steps:
(1) single-layer graphene oxide is prepared:Graphene oxide solution is prepared with improved Hummers methods, is removed, separation obtains
Sediment A;
(2) carbon nanotube is prepared:Carbon nanotube acidification is handled, ultrasonic cut, detaches, obtain sediment B;
(3) coated compound is prepared:Sediment A is dissolved or dispersed in solvent and obtains solution C, sediment B is dissolved or
It is scattered in solvent and obtains solution D, solution C and solution D are mixed to get mixture E, mixing is cultivated, and separation obtains coated
Compound.
7. according to the method described in claim 6, it is characterized in that:Step (1) stripping is removed using ultrasound, ultrasound stripping
Time be 1-15h
And/or
Separation described in step (1) uses centrifugal separation, centrifuge to be centrifuged under conditions of 3,000-10,000rmp
10-100min takes out centrifugate, collects 6, the sediment A of 10-60min is centrifuged under the conditions of 000~20,000rmp.
8. according to the method described in claim 7, it is characterized in that:The time of ultrasound stripping is 2-10h in step (1).
9. according to the method described in any one of claim 6-8, it is characterised in that:Acidification described in step (2):Using
Nitration mixture processing, heating, washing to neutrality;And/or
Using 60~100 DEG C of temperature, the time of heating is 1-15h for wherein nitration mixture treated heating.
10. according to the method described in claim 9, it is characterized in that:It is washed with deionized to neutrality;The nitration mixture is nitric acid
With the mixture of sulfuric acid, wherein:A concentration of 10-80% (wt) of nitric acid used, a concentration of 70-98% of the concentrated sulfuric acid used
(wt), when forming nitration mixture, the volume ratio of nitric acid and sulfuric acid is 1:1-5;And/or
The time wherein heated after nitration mixture processing is 2-10h.
11. according to the method described in claim 10, it is characterized in that:When forming nitration mixture, the volume ratio of nitric acid and sulfuric acid is 1:
2-4;And/or
The time wherein heated after nitration mixture processing is 4-8h.
12. according to the method described in any one of claim 6-8,10 or 11, it is characterised in that:It is ultrasonic described in step (2)
The time of cutting be 20-100min, ultrasonic power 200-500W,
And/or
Separation described in step (2) uses centrifugal separation, centrifuge to be centrifuged under conditions of 3,000-10,000rmp
10-100min takes out centrifugate, collects 6, the sediment B of 10-60min is centrifuged under the conditions of 000~20,000rmp.
13. according to the method described in claim 9, it is characterized in that:The time of ultrasonic cut described in step (2) is 20-
100min, ultrasonic power 200-500W,
And/or
Separation described in step (2) uses centrifugal separation, centrifuge to be centrifuged under conditions of 3,000-10,000rmp
10-100min takes out centrifugate, collects 6, the sediment B of 10-60min is centrifuged under the conditions of 000~20,000rmp.
14. according to the method described in any one of claim 6-8,10,11 or 13, it is characterised in that:Step is also wrapped in (1)
It includes:It uses after separation and is dried in vacuo at room temperature,
And/or
Step further includes in (2):It is dried in vacuo at 30-90 DEG C after separation.
15. according to the method described in claim 9, it is characterized in that:Step further includes in (1):Using true at room temperature after separation
Sky is dry,
And/or
Step further includes in (2):It is dried in vacuo at 30-90 DEG C after separation.
16. according to the method for claim 12, it is characterised in that:Step further includes in (1):Using true at room temperature after separation
Sky is dry,
And/or
Step further includes in (2):It is dried in vacuo at 30-90 DEG C after separation.
17. according to the method described in any one of claim 6-8,10,11,13,15 or 16, it is characterised in that:In step (3)
The solvent be it is one or more in amides or nitrile,
And/or
In step (3) in solution C sediment A a concentration of 0.2-2.0mg/mL, a concentration of 0.2- of sediment B in solution D
2.0mg/mL。
18. according to the method described in claim 9, it is characterized in that:Solvent described in step (3) is in amides or nitrile
It is one or more,
And/or
In step (3) in solution C sediment A a concentration of 0.2-2.0mg/mL, a concentration of 0.2- of sediment B in solution D
2.0mg/mL。
19. according to the method for claim 12, it is characterised in that:Solvent described in step (3) is in amides or nitrile
It is one or more,
And/or
In step (3) in solution C sediment A a concentration of 0.2-2.0mg/mL, a concentration of 0.2- of sediment B in solution D
2.0mg/mL。
20. according to the method for claim 17, it is characterised in that:Solvent described in step (3) is formamide, acrylamide
Or it is one or more in acetonitrile.
21. the method according to claim 18 or 19, it is characterised in that:Solvent described in step (3) is formamide, propylene
It is one or more in amide or acetonitrile.
22. according to the method for claim 20, it is characterised in that:Solvent described in step (3) is N, N- dimethyl formyls
It is one or more in amine, N,N-DMAA or acetonitrile.
23. according to the method described in any one of claim 6-8,10,11,13,15,16,18-20 or 22, it is characterised in that:
The mixed volume ratio of solution C and solution D is 1 in step (3):0.5-3,
And/or
For mixing described in step (3) using ultrasonic mixing, the time of ultrasonic mixing is 1-30min.
24. according to the method described in claim 9, it is characterized in that:The mixed volume ratio of solution C and solution D is in step (3)
1:0.5-3,
And/or
For mixing described in step (3) using ultrasonic mixing, the time of ultrasonic mixing is 1-30min.
25. according to the method for claim 12, it is characterised in that:The mixed volume ratio of solution C and solution D in step (3)
It is 1:0.5-3,
And/or
For mixing described in step (3) using ultrasonic mixing, the time of ultrasonic mixing is 1-30min.
26. according to the method for claim 23, it is characterised in that:The mixed volume ratio of solution C and solution D in step (3)
It is 1:0.8-2,
And/or
The time of ultrasonic mixing is 3-20min in step (3).
27. the method according to claim 24 or 25, it is characterised in that:The mixture of solution C and solution D in step (3)
Product is than being 1:0.8-2,
And/or
The time of ultrasonic mixing is 3-20min in step (3).
28. according to the method described in any one of claim 6-8,10,11,13,15,16,18-20,22 or 24-26,
It is characterized in that:It is cultivated described in step (3) and uses constant temperature incubator, temperature is 20-80 DEG C,
And/or
Constant temperature cultivates the time as 0.5-10h.
29. according to the method described in claim 9, it is characterized in that:It is cultivated described in step (3) and uses constant temperature incubator, temperature
Degree is 20-80 DEG C,
And/or
Constant temperature cultivates the time as 0.5-10h.
30. according to the method for claim 12, it is characterised in that:It is cultivated described in step (3) and uses constant temperature incubator, temperature
Degree is 20-80 DEG C,
And/or
Constant temperature cultivates the time as 0.5-10h.
31. according to the method for claim 28, it is characterised in that:The temperature cultivated described in step (3) is 30-70 DEG C,
And/or
Constant temperature cultivates the time as 1-8h;
Separation described in step (3) uses centrifugal separation, and 10-60min is centrifuged under the conditions of 3,000-8,000rmp, takes out
Centrifugate collects 6, and 000~15,000rmp centrifuges the sediment of 10-60min,
And/or
Step further includes in (3):It uses after separation and is dried in vacuo at room temperature.
32. the method according to claim 29 or 30, it is characterised in that:The temperature cultivated described in step (3) is 30-70
DEG C, and/or
Constant temperature cultivates the time as 1-8h;
Separation described in step (3) uses centrifugal separation, and 10-60min is centrifuged under the conditions of 3,000-8,000rmp, takes out
Centrifugate collects 6, and 000~15,000rmp centrifuges the sediment of 10-60min,
And/or
Step further includes in (3):It uses after separation and is dried in vacuo at room temperature.
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