CN106241782A - The preparation method of Graphene/carbon nanotube composite material - Google Patents
The preparation method of Graphene/carbon nanotube composite material Download PDFInfo
- Publication number
- CN106241782A CN106241782A CN201610601135.2A CN201610601135A CN106241782A CN 106241782 A CN106241782 A CN 106241782A CN 201610601135 A CN201610601135 A CN 201610601135A CN 106241782 A CN106241782 A CN 106241782A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- carbon nanotube
- nanotube composite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the preparation method of a kind of Graphene/carbon nanotube composite material.With graphite powder as raw material, the Hummers method after improving is used to obtain graphene oxide.Take graphene oxide and deionized water joins ultrasonic disperse in beaker, be subsequently adding Nickelous nitrate hexahydrate and hexamethylenetetramine stirs.Solution is transferred in reactor, reacts a period of time under constant temperature, and reaction terminates, and adding enough concentration is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black solid after sucking filtration, and vacuum drying obtains Graphene/carbon nanotube composite material.Lens result display CNT Diameter distribution is at 15 40nm, a length of micron order, and CNT is dispersed in system, thus realizes the most compound of Graphene and CNT.
Description
Technical field
The present invention relates to a kind of composite, be specifically related to the preparation method of a kind of Graphene/carbon nanotube composite material.
Belong to technical field of function materials.
Background technology
CNT has special construction as typical One-dimensional Quantum material with carbon element, and it is mainly by the carbon of hexagonal arrangement
The coaxial pipe of hollow of atomic building, because CNT regional area occurs that convex-concave causes its structure the most straight,
And present certain bending.Diameter distribution is generally kept in ten a few to tens of nanometers, and distribution of lengths is at micron order.And Graphene is made
For monolayer two dimensional crystal, wherein carbon atom be also be arranged to make up with sp2 hybridized orbital thus can regard CNT as graphite
Alkene curling forms.Both of which tool high connductivity, big specific surface area and good mechanical properties, have a wide range of applications.
Preparation method of carbon nano-tube is varied, and wherein the method with graphite as raw material is mainly: laser ablation method and electricity
Arc discharge method.CNT is at head from the carbon fiber that arc discharge method produces in 1991 by Japanese physicist Sumio Iijima
Secondary discovery.(s.lijima, nature 354,56 (1991)), wherein arc discharge method is that the ownership is for the most main in CNT
Want method.
And above-mentioned preparation method exists that experiment condition is harsh, complicated process of preparation and experimental cost cross high deficiency.
Summary of the invention
It is an object of the invention to as overcoming above-mentioned the deficiencies in the prior art, it is provided that the most controlled a kind of graphene/carbon is received
The preparation method of mitron composite, the present invention, first with graphite powder as raw material, uses the Hummers method after improving to obtain oxidation
Graphene, then with graphene oxide as raw material, nickel hydroxide, as reaction site synthesizing carbon nanotubes, finally prepares graphite
Alkene/carbon nano tube compound material.
For achieving the above object, the present invention uses following technical proposals:
The preparation method of Graphene/carbon nanotube composite material, operating procedure is as follows: (1) natural graphite powder is oxidized instead
Graphene oxide should be prepared；(2) graphene oxide reacts through supersonic, water-heating with Nickelous nitrate hexahydrate, hexamethylenetetramine, preparation
Graphene/carbon nanotube composite material.
Described step (1) operating procedure is as follows: adds 3g graphite powder and 2g sodium nitrate in beaker, slowly adds along wall of cup
Enter concentrated sulphuric acid 70mL and be stirred continuously；Under condition of ice bath, 30g potassium permanganate pressed powder is joined beaker the most in five times
In, continuously stirred 1h；In 35 DEG C of water-baths, continue stirring 2h, obtain mixed solution；140mL deionized water is slowly added into molten
In liquid and be stirred continuously 15min, system temperature rises to about 95 DEG C subsequently, continues stirring 3h；Dropping volume fraction is 30%
H2O2 until solution becomes glassy yellow；Reacting liquor while hot is filtered, and washs with dilute hydrochloric acid, remove unnecessary metal from
Son；By centrifuge washing lyophilization, prepare graphene oxide.
Described step (2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse 1-in beaker
2h, is subsequently adding Ni (NO3) 2 6H2O and hexamethylenetetramine (HMTA) stirs；Solution transfers to 100mL reaction
Isothermal reaction in still；Reaction terminates, and the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black after sucking filtration
Solid, scrubbed vacuum drying, obtain Graphene/carbon nanotube composite material.
Described step (1) drying time 24～72h, vacuum 8-10pa, temperature :-10--50 DEG C.
The quality molal volume ratio of graphene oxide, Ni (NO3) 2 6H2O, HMTA and distilled water in described step (2):
65～100mg:3～8mmol:3～8mmol:65～190mL.
The reaction temperature of described step (2) isothermal reaction is 90～110 DEG C, the response time 3～4.5h.
Described washing be with distilled water by products therefrom washing to pH be neutrality,
Described step (2) vacuum drying vacuum: 0.06MPa-0.085Mpa；Temperature: 45-65 DEG C of time: 1.5-
3.5h。
In composite prepared by described step (2), CNT is multi-walled carbon nano-tubes, and caliber is 15-20nm, interlayer
Away from for 0.34nm.
Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
The mechanism of action of the present invention: weak base hexamethylenetetramine is dissolved in water and makes solution embody alkalescence, and nickel ion is weak
Under alkali environment, reaction generates nickel hydroxide.The growth of nickel hydroxide has anisotropy, generates diameter in all directions and is about
Several nanometers, and length is at micron-sized bar-shaped material, part graphene oxide sheet material cladding hydroxide in its growth course
Nickel, forms CNT with nickel hydroxide for reaction site curling, along with nickel hydroxide constantly grows, and free graphene film
Material is continuously replenished nickel hydroxide surface so that the length of CNT is increased.Reaction makes hydrogen by acid treatment after terminating
Nickel oxide all dissolves, and CNT and graphene-structured are unaffected, more just be can reach solid-liquid be kept completely separate by sucking filtration,
Finally obtain Graphene/carbon nanotube composite material.
Beneficial effects of the present invention:
1, the present invention proposes and a kind of prepares CNT with graphene oxide for raw material, final process obtain Graphene/
The preparation method of carbon nano tube compound material, preparing CNT for Graphene provides new way.
2, in composite prepared by the present invention, prepared CNT is uniformly dispersed, and improves graphene/carbon nanometer
The compound uniformity of pipe, and prepared CNT parameter is controlled.
3, in the present invention, nickel hydroxide is only used as reaction site, more reacts position along with the growth of nickel hydroxide provides
Point.Reaction passes through HCl treatment dissolved hydrogen nickel oxide after terminating, and obtains Graphene/carbon nanotube composite material after sucking filtration, compound
In material and there is not any metal composite.Experiment safety, easily operation simultaneously can be prepared on a large scale.
4, composite prepared by the present invention has high electron mobility speed, and electrical conductivity is up to 15000S/m, mechanical strength
Height, and to the absorption up to 90% of the wave band electromagnetic wave in 2-18GHz, in field of microwave absorption, there is important function.
5, the present invention is only by simple hydro-thermal one-step method, so that it may prepare finely dispersed graphene/carbon nano-tube composite wood
Material.
6, raw material of the present invention is cheap easily purchases, and experiment condition, technique are simple, and experimental facilities is conventional instrument.
Accompanying drawing explanation
Fig. 1 is graphite powder of the present invention, graphene oxide and the X-ray diffractogram of graphene/carbon nano composite material；
Fig. 2 is the scanning lens figure that the present invention prepares graphene oxide；
Fig. 3 is the lens drawings that the present invention prepares Graphene/carbon nanotube composite material；
Fig. 4 is the high power lens drawings of Graphene/carbon nanotube composite material of the present invention.
Detailed description of the invention
The present invention will be further elaborated with embodiment below in conjunction with the accompanying drawings, it should explanation, and the description below is only
It is to explain the present invention, its content is not defined.
The source that the present invention relates to raw material is as follows: natural graphite scale: 325 mesh, purity >=99%, and Qingdao Thailand of China is the closeest
Envelope company limited；Potassium permanganate: Chemical Reagent Co., Ltd., Sinopharm Group；Concentrated sulphuric acid: purity 95～98%, Dihua is won in Tianjin
Work company limited；Hydrogen peroxide: purity AR, Chemical Reagent Co., Ltd., Sinopharm Group；Dilute hydrochloric acid: by 10ml concentration 36～38%
Concentrated hydrochloric acid is diluted in the volumetric flask of 250mL, obtains dilute hydrochloric acid, Shanghai pilot scale Chemical Co., Ltd.；Nickelous nitrate hexahydrate: traditional Chinese medicines
Chemical reagent company limited of group；Hexamethylenetetramine: reagent company limited of traditional Chinese medicines group.
Embodiment 1:
In beaker, add 3g graphite powder and 2g sodium nitrate, keep away along cup and be slowly added to concentrated sulphuric acid 70mL and be stirred continuously；
Under condition of ice bath, 30g potassium permanganate pressed powder is joined in beaker the most in five times, continuously stirred 1h.35 DEG C of water-baths
Middle continuation stirs 2h, obtains mixed solution.140mL deionized water is slowly added in solution and is stirred continuously 15min, subsequently
System temperature rises to about 95 DEG C, continues stirring 3h；Dropping volume fraction is the H of 30%2O2Until solution becomes glassy yellow.
Reacting liquor while hot is filtered, and washs with dilute hydrochloric acid, remove unnecessary metal ion.It is 7 by centrifugal, washing to pH,
Lyophilization 48h, vacuum 8-pa, temperature :-10 DEG C of prepared graphene oxides, its crystal plane structure is confirmed by X-ray diffractometer,
Refering to accompanying drawing 1.XRD result shows: raw graphite goes out peak when 2 θ=26.6 °, and the characteristic diffraction peak of graphene oxide occurs
At its (001) crystal face of 2 θ=12 ° correspondences.By Debye-Scherrer formula to its crystal face away from calculating, graphite reaction is raw
After becoming graphene oxide, its interlamellar spacing has original 0.34nm to increase to 0.9nm, further illustrates and introduces at graphenic surface
Functional group.From scanning lens its pattern of figure observable of graphene oxide, refering to accompanying drawing 2: graphene oxide is that to have thickness thin
Sheet, surface has obvious fold.
Take 80mg graphene oxide and 80mL deionized water joins ultrasonic disperse 2h in beaker, be subsequently adding 4mmolNi
(NO3)2·6H2O and 4mmol hexamethylenetetramine stirs.Solution is transferred in 100mL reactor, isothermal reaction,
Reaction terminates, and adding enough concentration is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black solid, 60 DEG C of vacuum after sucking filtration
It is dried 12h, vacuum: 0.06MPa, obtains Graphene/carbon nanotube composite material.In XRD, diffraction maximum shifts from 2 θ=12 °
To 2 θ=26.2 °, interlamellar spacing has been returned to 0.34nm, and declaratives graphite oxide alkene reaction generates CNT, goes out peak also
More sharp-pointed than graphene oxide, illustrate that crystallinity gets a promotion.The lens drawings of Graphene/carbon nanotube composite material refers to accompanying drawing 3,
CNT Diameter distribution at 15-40nm, a length of micron order, CNT is dispersed in system, thus realize Graphene and
Uniformly being combined of CNT.
Graphene conversion ratio 99%.
Accompanying drawing 4 is high power lens drawings, clearly find out that CNT is multi-walled carbon nano-tubes, caliber length is about 18nm,
Interlamellar spacing is 0.34nm, and mesopore internal diameter is about 5nm.
Embodiment 2:
The preparation method of Graphene/carbon nanotube composite material, operating procedure is as follows: (1) natural graphite powder is oxidized instead
Graphene oxide should be prepared；(2) graphene oxide reacts through supersonic, water-heating with Nickelous nitrate hexahydrate, hexamethylenetetramine, preparation
Graphene/carbon nanotube composite material.
Step (1) operating procedure is with embodiment 1.
Step (2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse 1h in beaker, then
Add Ni (NO3) 2 6H2O and hexamethylenetetramine (HMTA) stirs；Solution is transferred in 100mL reactor permanent
Temperature reaction；Reaction terminates, and the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black solid after sucking filtration,
Scrubbed vacuum drying, obtains Graphene/carbon nanotube composite material.
Described sublimation drying 30～50h, temperature :-18 DEG C, vacuum: 9 handkerchiefs.
The quality molal volume ratio of graphene oxide, Ni (NO3) 2 6H2O, HMTA and distilled water in described step (2):
100mg:8mmol:8mmol:190mL.
The reaction temperature of described step (2) isothermal reaction is 100 DEG C, response time 4.0h.
Described washing be with distilled water by products therefrom washing to pH be neutrality,
Described vacuum drying vacuum: 0.085Mpa；Temperature: 65 DEG C of time: 3.5h.
In described composite, CNT is multi-walled carbon nano-tubes, and caliber is 40nm, and interlamellar spacing is 0.34nm.
Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
Embodiment 3:
The preparation method of Graphene/carbon nanotube composite material, it is characterised in that operating procedure is as follows: (1) native graphite
Graphene oxide is prepared in the oxidized reaction of powder；(2) graphene oxide and Nickelous nitrate hexahydrate, hexamethylenetetramine are through supersonic, water-heating
Reaction, prepares Graphene/carbon nanotube composite material.
Step (1) operating procedure is with embodiment 1.Different technical parameters is: described sublimation drying 50h, temperature :-
40 DEG C, vacuum: 10 handkerchiefs.
Described step (2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse in beaker
1.5h, is subsequently adding Ni (NO3) 2 6H2O and hexamethylenetetramine (HMTA) stirs；It is anti-that solution transfers to 100mL
Answer isothermal reaction in still；Reaction terminates, and the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black after sucking filtration
Color solid, scrubbed vacuum drying, obtain Graphene/carbon nanotube composite material.
The quality molal volume ratio of graphene oxide, Ni (NO3) 2 6H2O, HMTA and distilled water in described step (2):
65mg:3mmol:3mmol:65mL.
The reaction temperature of described step (2) isothermal reaction is 110 DEG C, response time 5h.
Described washing be with distilled water by products therefrom washing to pH be neutrality；
Described step (2) vacuum drying vacuum: 0.065MPa；Temperature: 50 DEG C of time: 2.0h.
In composite prepared by described step (2), CNT is multi-walled carbon nano-tubes, and caliber is 28nm, and interlamellar spacing is
0.34nm。
Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
Embodiment 4:
The preparation method of Graphene/carbon nanotube composite material, operating procedure is as follows: (1) natural graphite powder is oxidized instead
Graphene oxide should be prepared；(2) graphene oxide reacts through supersonic, water-heating with Nickelous nitrate hexahydrate, hexamethylenetetramine, preparation
Graphene/carbon nanotube composite material.
Step (1) operating procedure is with embodiment 1.Different technical parameters is: described sublimation drying 72h, temperature :-
35 DEG C, vacuum: 8.5 handkerchiefs.
Described step (2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse in beaker
1.8h, is subsequently adding Ni (NO3) 2 6H2O and hexamethylenetetramine (HMTA) stirs；It is anti-that solution transfers to 100mL
Answer isothermal reaction in still；Reaction terminates, and the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black after sucking filtration
Color solid, scrubbed vacuum drying, obtain Graphene/carbon nanotube composite material.
The quality molal volume ratio of graphene oxide, Ni (NO3) 2 6H2O, HMTA and distilled water in described step (2):
72mg:4mmol:2.5mmol:100mL.
The reaction temperature of described step (2) isothermal reaction is 100 DEG C, response time 4.0h.
Described washing be with distilled water by products therefrom washing to pH be neutrality,
Described vacuum drying vacuum: 0.07MPaa；Temperature: 55 DEG C of time: 2.5h.
In composite prepared by described step (2), CNT is multi-walled carbon nano-tubes, and caliber is 30nm, and interlamellar spacing is
0.34nm。
Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
Embodiment 5:
The preparation method of Graphene/carbon nanotube composite material, graphite oxide is prepared in the oxidized reaction of (1) natural graphite powder
Alkene；(2) graphene oxide reacts through supersonic, water-heating with Nickelous nitrate hexahydrate, hexamethylenetetramine, prepares graphene/carbon nano-tube
Composite.
Step (1) operating procedure is with embodiment 1.Different technical parameters is: described sublimation drying 24h, temperature :-
50 DEG C, vacuum: 9.5 handkerchiefs.
Described step (2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse in beaker
1.2h, is subsequently adding Ni (NO3) 2 6H2O and hexamethylenetetramine (HMTA) stirs；It is anti-that solution transfers to 100mL
Answer isothermal reaction in still；Reaction terminates, and the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black after sucking filtration
Color solid, scrubbed vacuum drying, obtain Graphene/carbon nanotube composite material.
The quality molal volume ratio of graphene oxide, Ni (NO3) 2 6H2O, HMTA and distilled water in described step (2):
94mg:6.5mmol:3.8mmol:125mL.
The reaction temperature of described step (2) isothermal reaction is 105 DEG C, response time 3.5h.
Described washing be with distilled water by products therefrom washing to pH be neutrality,
Described step (2) vacuum drying vacuum: 0.075MPa；Temperature: 60 DEG C of time: 3.0h.
In described step (2) composite, CNT is multi-walled carbon nano-tubes, and caliber is 35nm, and interlamellar spacing is
0.34nm。
Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
Embodiment 6:
The preparation method of Graphene/carbon nanotube composite material, operating procedure is as follows: (1) natural graphite powder is oxidized instead
Graphene oxide should be prepared；(2) graphene oxide reacts through supersonic, water-heating with Nickelous nitrate hexahydrate, hexamethylenetetramine, preparation
Graphene/carbon nanotube composite material.
Step (1) operating procedure is with embodiment 1.Different technical parameters is: described sublimation drying 36h, temperature :-
45 DEG C, vacuum: 8.6 handkerchiefs.
Described step (2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse in beaker
1.6h, is subsequently adding Ni (NO3) 2 6H2O and hexamethylenetetramine (HMTA) stirs；It is anti-that solution transfers to 100mL
Answer isothermal reaction in still；Reaction terminates, and the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black after sucking filtration
Color solid, scrubbed vacuum drying, obtain Graphene/carbon nanotube composite material.
The quality molal volume ratio of graphene oxide, Ni (NO3) 2 6H2O, HMTA and distilled water in described step (2):
85mg:6.5mmol:6.5mmol:185mL.
The reaction temperature of described step (2) isothermal reaction is 105 DEG C, response time 4.5h.
Described washing be with distilled water by products therefrom washing to pH be neutrality.
Described vacuum drying vacuum: 0.08MPaa；Temperature: 65 DEG C of time: 3.0h.
In composite prepared by described step (2), CNT is multi-walled carbon nano-tubes, and caliber is 15-40nm, interlayer
Away from for 0.34nm.
Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
Although the detailed description of the invention of the present invention is described by the above-mentioned accompanying drawing that combines, but not the present invention is protected model
The restriction enclosed, on the basis of technical scheme, those skilled in the art need not pay creative work and can do
The various amendments gone out or deformation are still within protection scope of the present invention.
Claims (10)
1. the preparation method of Graphene/carbon nanotube composite material, it is characterised in that operating procedure is as follows: (1) natural graphite powder
Graphene oxide is prepared in oxidized reaction；(2) graphene oxide is anti-through supersonic, water-heating with Nickelous nitrate hexahydrate, hexamethylenetetramine
Should, prepare Graphene/carbon nanotube composite material.
Graphene/carbon nanotube composite material preparation method the most according to claim 1, it is characterised in that described step
(1) operating procedure is as follows: adds 3g graphite powder and 2g sodium nitrate in beaker, is slowly added to concentrated sulphuric acid 70mL not along wall of cup
Disconnected stirring；Under condition of ice bath, 30g potassium permanganate pressed powder is joined in beaker the most in five times, continuously stirred 1h；35
DEG C water-bath continues stirring 2h, obtains mixed solution；140mL deionized water is slowly added in solution and is stirred continuously
15min, system temperature rises to about 95 DEG C subsequently, continues stirring 3h；Dropping volume fraction is the H of 30%2O2Until solution becomes
For glassy yellow；Reacting liquor while hot is filtered, and washs with dilute hydrochloric acid, remove unnecessary metal ion；Wash cold by centrifugation
Lyophilizing is dry, prepares graphene oxide.
Graphene/carbon nanotube composite material preparation method the most according to claim 1, it is characterised in that described step
(2) operating procedure is as follows: take graphene oxide and deionized water joins ultrasonic disperse 1-2h in beaker, be subsequently adding Ni
(NO3)2·6H2O and hexamethylenetetramine stir；Solution transfers to isothermal reaction in 100mL reactor；Reaction knot
Bundle, the concentration adding excess is 1mol/L HCl treatment dissolved hydrogen nickel oxide, takes black solid after sucking filtration, and scrubbed vacuum is done
Dry, obtain Graphene/carbon nanotube composite material.
Graphene/carbon nanotube composite material preparation method the most according to claim 2, it is characterised in that described step
(1) lyophilization 30～50h, vacuum 8-10pa.
Graphene/carbon nanotube composite material preparation method the most according to claim 3, it is characterised in that described step
(2) graphene oxide, Ni (NO in3)2·6H2O, HMTA and distilled water quality molal volume ratio: 65～100mg:3～
8mmol:3～8mmol:65～190mL.
Graphene/carbon nanotube composite material preparation method the most according to claim 3, it is characterised in that described step
(2) reaction temperature of isothermal reaction is 90～110 DEG C, the response time 3～4.5h.
7., according to the Graphene/carbon nanotube composite material preparation method preparation method described in Claims 2 or 3, its feature exists
It is to be neutrality by products therefrom washing to pH with distilled water in, described washing,
Graphene/carbon nanotube composite material preparation method the most according to claim 3, it is characterised in that described step
(2) vacuum drying vacuum: 0.06MPa-0.085Mpa；Temperature: 45-65 DEG C of time: 1.5-3.5h.
Ink alkene/multi-wall carbon nano-tube composite material preparation method preparation method the most according to claim 3, its feature exists
In, in composite prepared by described step (2), CNT is multi-walled carbon nano-tubes, and caliber is 15-40nm, and interlamellar spacing is
0.34nm。
10. Graphene/multi-wall carbon nano-tube composite material, is to prepare according to preparation method according to any one of claim 1-8
Obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610601135.2A CN106241782B (en) | 2016-07-27 | 2016-07-27 | The preparation method of Graphene/carbon nanotube composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610601135.2A CN106241782B (en) | 2016-07-27 | 2016-07-27 | The preparation method of Graphene/carbon nanotube composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106241782A true CN106241782A (en) | 2016-12-21 |
| CN106241782B CN106241782B (en) | 2018-02-16 |
Family
ID=57603290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610601135.2A Active CN106241782B (en) | 2016-07-27 | 2016-07-27 | The preparation method of Graphene/carbon nanotube composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106241782B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147399A (en) * | 2017-12-29 | 2018-06-12 | 苏州南尔材料科技有限公司 | A kind of preparation method of three-dimensional grapheme nickel oxide sensor material |
| CN108301013A (en) * | 2018-02-14 | 2018-07-20 | 中氧科技（广州）有限公司 | A kind of preparation method for the modified anode of lead dioxide generating ozone |
| CN108899476A (en) * | 2018-07-17 | 2018-11-27 | 大同新成新材料股份有限公司 | A kind of preparation process of the graphene-based composite negative pole material of lithium battery |
| CN109456031A (en) * | 2017-09-06 | 2019-03-12 | 南开大学 | Microwave absorbing material and preparation method thereof comprising carbon nanotube and graphene oxide |
| CN112811503A (en) * | 2021-01-26 | 2021-05-18 | 中南大学 | Method for recycling organic phenol pollutants |
| CN112811414A (en) * | 2021-01-12 | 2021-05-18 | 无锡东恒新能源科技有限公司 | Preparation method of super-hydrophobic material |
| CN115055672A (en) * | 2022-06-15 | 2022-09-16 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583654A (en) * | 2012-02-22 | 2012-07-18 | 上海大学 | Preparation method of nanometer compounding capacitor type desalting electrode of carbon nanometer pipe/graphene sandwich structure |
| CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
-
2016
- 2016-07-27 CN CN201610601135.2A patent/CN106241782B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583654A (en) * | 2012-02-22 | 2012-07-18 | 上海大学 | Preparation method of nanometer compounding capacitor type desalting electrode of carbon nanometer pipe/graphene sandwich structure |
| CN102765713A (en) * | 2012-08-16 | 2012-11-07 | 西南石油大学 | Fast preparation method for carbon nano tube/ graphene sandwich structure mateirals |
Non-Patent Citations (2)
| Title |
|---|
| XI’AN CHEN ET AL.: "One-pot hydrothermal synthesis of reduced graphene oxide/carbon nanotube/a-Ni(OH)2 composites for high performance electrochemical supercapacitor", 《JOURNAL OF POWER SOURCES》 * |
| YUXI XU ET AL.: "One-step strategy to graphene/Ni(OH)2 composite hydrogels electrode materials", 《NANO RESEARCH》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456031A (en) * | 2017-09-06 | 2019-03-12 | 南开大学 | Microwave absorbing material and preparation method thereof comprising carbon nanotube and graphene oxide |
| CN108147399A (en) * | 2017-12-29 | 2018-06-12 | 苏州南尔材料科技有限公司 | A kind of preparation method of three-dimensional grapheme nickel oxide sensor material |
| CN108301013A (en) * | 2018-02-14 | 2018-07-20 | 中氧科技（广州）有限公司 | A kind of preparation method for the modified anode of lead dioxide generating ozone |
| CN108899476A (en) * | 2018-07-17 | 2018-11-27 | 大同新成新材料股份有限公司 | A kind of preparation process of the graphene-based composite negative pole material of lithium battery |
| CN108899476B (en) * | 2018-07-17 | 2020-07-28 | 大同新成新材料股份有限公司 | Preparation process of lithium battery graphene-based composite negative electrode material |
| CN112811414A (en) * | 2021-01-12 | 2021-05-18 | 无锡东恒新能源科技有限公司 | Preparation method of super-hydrophobic material |
| CN112811503A (en) * | 2021-01-26 | 2021-05-18 | 中南大学 | Method for recycling organic phenol pollutants |
| CN115055672A (en) * | 2022-06-15 | 2022-09-16 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
| CN115055672B (en) * | 2022-06-15 | 2023-10-24 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106241782B (en) | 2018-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106241782A (en) | The preparation method of Graphene/carbon nanotube composite material | |
| Tahir et al. | Enhanced photocatalytic performance of visible-light active graphene-WO3 nanostructures for hydrogen production | |
| CN105251484B (en) | Three-dimensional structure redox graphene/nanometer metallic silver aeroge and preparation method | |
| Song et al. | A hydrothermal method for preparation of α-Fe2O3 nanotubes and their catalytic performance for thermal decomposition of ammonium perchlorate | |
| Zhou et al. | Metal-free carbon nanotube–SiC nanowire heterostructures with enhanced photocatalytic H 2 evolution under visible light irradiation | |
| CN102641736B (en) | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof | |
| Pavasupree et al. | Synthesis and characterization of vanadium oxides nanorods | |
| CN102530931B (en) | Graphene-based nano composite material and preparation method thereof | |
| Shi et al. | NaNbO 3 nanostructures: facile synthesis, characterization, and their photocatalytic properties | |
| CN102225754B (en) | Preparation method of graphene oxide and preparation method of graphene | |
| Ma et al. | Microwave synthesis of cellulose/CuO nanocomposites in ionic liquid and its thermal transformation to CuO | |
| CN103771485B (en) | A kind of controllable method for preparing of cupric oxide three-dimensional manometer self-assembly | |
| CN108502926B (en) | BiOCl nano-rings and its synthetic method | |
| WO2012083511A1 (en) | Preparation method and use of manganese dioxide nano-rod | |
| CN105561965B (en) | A kind of preparation method of flower-shaped ZnO/ graphenes complex microsphere | |
| CN100595140C (en) | Method for preparing composite material of nano-indium stannum oxide/multi-wall carbon nano-tube | |
| Liu et al. | Hydrothermal synthesis of CdTe quantum dots–TiO2–graphene hybrid | |
| Tahir et al. | Functionalized role of highly porous activated carbon in bismuth vanadate nanomaterials for boosted photocatalytic hydrogen evolution and synchronous activity in water | |
| CN113998734B (en) | Bi 5 O 7 Preparation method of Br nanosheets | |
| CN106215968A (en) | A kind of carbon cladding CuO composite of the nitrogen that adulterates and preparation method thereof | |
| CN104445340B (en) | By the preparation method of the octahedra cerium oxide of nanometer blocks self-assembly | |
| CN110180523A (en) | A kind of non-metal porous carbon nanocatalyst and preparation method thereof | |
| He et al. | H2SO4-assisted hydrothermal preparation of γ-AlOOH nanorods | |
| CN103203234B (en) | Preparation method of high-dispersion supported nano metal Fe-based catalyst | |
| CN106082201B (en) | The graphene composite nano material and preparation method thereof of ultra-thin TiOx nano piece load |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |