CN107055521A - The method and the graphene microballoon of prepare with scale height rule spherical graphite alkene microballoon - Google Patents
The method and the graphene microballoon of prepare with scale height rule spherical graphite alkene microballoon Download PDFInfo
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- CN107055521A CN107055521A CN201710169677.1A CN201710169677A CN107055521A CN 107055521 A CN107055521 A CN 107055521A CN 201710169677 A CN201710169677 A CN 201710169677A CN 107055521 A CN107055521 A CN 107055521A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention relates to the method for prepare with scale height rule spherical graphite alkene microballoon and the graphene microballoon, belong to technical field of graphene.The method of prepare with scale high dispersive graphene microballoon; by graphene oxide and/or graphene dispersion into water or other solvents; add into globule; graphene oxide and/or graphene dispersing solution are obtained after mixing; then the graphene oxide and/or graphene are spray-dried; it is refined into it powdered, after cyclonic separation and high-temperature process, obtains height rule spherical graphite alkene microballoon.The inventive method is simple and easy to apply；The graphene microballoon of preparation, high degree of dispersion is conducive to playing the functional characteristic of graphene high-ratio surface.
Description
Technical field
The present invention relates to the method for prepare with scale height rule spherical graphite alkene microballoon and the graphene microballoon is provided, belonged to
In technical field of graphene.
Background technology
Graphene (Graphene) is a kind of new material for the individual layer laminated structure being made up of carbon atom, and it has superelevation
Electron mobility (15000cm2/ Vs), low resistivity (10-6Ω cm), high ratio surface (2630m2/ g), high heat conduction
Coefficient (5300W/mK), high mechanical strength is widely used in the fields such as biology, chemistry, physics, material.
Due to the unique laminated structure of graphene, it is easy to reunite in actual use, so as to influence graphite
The performance of the performances such as alkene specific surface area.Accordingly, it would be desirable to be assembled to graphene, three-dimensional structure is formed, increases its anti-stacking energy
Power.
In existing assemble method, though Jiaxin Huang paper can obtain the graphene ball with regular spherical,
Its using ultrasonic atomizatio increase temperature pyrolysis by the way of be industrially difficult to, unit interval production capacity is low, and product collects difficult,
Be not suitable for large-scale industrial production.
By also having trial before being spray-dried assembling graphene, Chinese invention patent CN201510773548 discloses one
The preparation method of controllable three-dimensional grapheme microballoon is planted, using graphene oxide, Supporting Media as raw material, appropriate solvent modulation is added
Into slurry, graphene oxide/support nanocrystal composition is obtained by spray drying, then redox graphene, obtain graphene/
Nanocrystal composition is supported, by dissolving supporter, controllable three-dimensional grapheme microballoon is obtained.But such product lacks regular ball
Shape.
The graphene microballoon can with prepare with scale with regular spherical is technically still difficult at present.
The content of the invention
The purpose of the present invention is to prepare high-ratio surface, high dispersive, the graphene microballoon with regular spherical, and provides a kind of
Efficiently, the method for prepare with scale high dispersive graphene microballoon simple and easy to apply.
The technical scheme adopted by the invention to solve the technical problem is that：
A kind of method of prepare with scale high dispersive graphene microballoon, by graphene oxide and/or graphene dispersion to water
Or in other solvents, add into and graphene oxide and/or graphene dispersing solution are obtained after globule, mixing, then by the oxidation
Graphene and/or graphene spray drying, are refined into it powdered, after cyclonic separation and high-temperature process, obtain height
Regular spherical graphene microballoon.
The source of all raw materials is not particularly limited in the present invention, is commercially available.
The present invention mixes two or more various sizes of crystalline flake graphite, wherein, the crystalline flake graphite is ability
Crystalline flake graphite known to the personnel of domain, is not particularly limited, preferably expanded graphite；The size of the crystalline flake graphite is excellent
Elect 2~300 μm as, can be using not from raw material the most after two of which or two or more various sizes of crystalline flake graphite mixing
The bulk density of mixture, more preferably 2~5 kinds various sizes of crystalline flake graphites, then excellent are improved with the cooperative effect between size
Difference is 2~300 μm between electing the size of various sizes of crystalline flake graphite as；More preferably 2~80 μm, it is further preferred that
2~50 μm.The mass ratio of large scale crystalline flake graphite and small size crystalline flake graphite between any two between various sizes of crystalline flake graphite
It is (20~1)：(1~1), such as when crystalline flake graphite is two kinds of different sizes, large scale crystalline flake graphite and small size scale stone
The ratio of ink between the two is preferably (20~1)：(1~1), more preferably (5~1)：1, it is further preferably 2:1.
Described graphene oxide, graphene particle diameter are in 300nm~300 μm；The graphene oxide and/or graphene with
Mass ratio into globule is (50:1)~(1:5) it is preferably, (50:1)~(1:2) (25, are more preferably:1)~(1:1) it is, more excellent
Elect (10 as:1)~(5:1).
The temperature of spray drying is 100 DEG C~400 DEG C, preferably 100 DEG C~300 DEG C, more preferably 150 DEG C~250 DEG C.
The condition of mixing is：15 DEG C~100 DEG C stir 30s~24h, preferably 1min~12h, more preferably 5min~
12h。
The condition of high-temperature process is：1~48h is heated at 100 DEG C~1200 DEG C；Preferably：100 DEG C~300 DEG C processing 1
After~12h, then after 300 DEG C~450 DEG C handle 1~12h, 450 DEG C~600 DEG C 1~12h of processing, then at 600 DEG C~900 DEG C
Handle 1~12h；More preferably：2~48h is handled in 300 DEG C~600 DEG C, inert atmosphere, 600 DEG C~1200 are then heated to
DEG C, 5~48h is handled in the inert atmosphere containing vapor or carbon dioxide or nitrogen or argon gas.
The solvent is polar solvent and/or non-polar solven.
It is described into globule be carbon nanomaterial, i.e. size in the range of 1-100nm, component using carbon as essential element,
Including but not limited to nano-sized carbon, single armed CNT, multi-walled carbon nanotube, acetylene black, graphene, graphene quantum dot, oxidation
Graphene；.
The present invention also provides the graphene microballoon prepared using the above method, and graphene is constituted three-dimensional regular in the mode of reuniting
Chondritic, graphene microsphere radius is at 100nm-50 μm, preferably 100nm-30 μm, more preferably 300nm-20 μm；Graphene
Microballoon tap density is 0.05g/cm3-0.7g/cm3, preferably 0.1~0.5g/cm3, more preferably 0.2~0.5g/cm3；Graphite
The specific surface area of alkene microballoon is 300~3000m2/ g, preferably 800~3000m2/ g, more preferably 1200~3000m2/g。
The invention provides a kind of regular graphene microballoon, the graphene microballoon is with extremely regular chondritic
While, also with superhigh specific surface area and higher tap density.
The graphene has many excellent properties of graphene, is inhaled available for capacitor electrode material, battery material, selenium
Enclosure material, catalyst material carrier.
Present invention has the advantages that：A kind of method of prepare with scale high dispersive graphene microballoon of the present invention is simple easy
OK；The graphene microballoon of preparation, high degree of dispersion is conducive to playing the functional characteristic of graphene high-ratio surface；The present invention by
Carbon nanomaterial is introduced in graphene oxide dispersion, because carbon nanomaterial and graphene are all carbon material, compatible degree is higher,
During spray drying, homogeneous effective contraction can be achieved so that the degree of isotropy of product is improved, with height rule
It is spherical.Solid composite material can be directly obtained using spray drying process, further evaporation, the processing step of crushing operation is saved；
And the prepare with scale of high dispersive graphene composite material can be realized.
Brief description of the drawings
Fig. 1 is the SEM figures of graphene microballoon prepared by embodiment 2.
Fig. 2 is that the SEM of graphene microballoon prepared by embodiment 2 clearly schemes.
Embodiment
Technical scheme is described in detail below.
Embodiment 1
Particle diameter is 300nm graphene oxide aqueous dispersions, mixes, is stirred at room temperature into globule with organic molecule
5min, GO are 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, obtains powder
End.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating schedule
300 DEG C are warming up to for 100 DEG C, 10 DEG C/min, 300 DEG C of 1h, 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, and 450 DEG C rise
Warm to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.The scattered graphene that secures satisfactory grades is micro-
Ball, the radius of a ball is 100nm-30um.
Embodiment 2
Particle diameter is 1 μm of graphene oxide aqueous dispersions, is mixed with organic molecule into globule, 5min is stirred at room temperature,
GO is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, obtains powder.Enter
One step cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating schedule is 100
DEG C it is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, and 450 DEG C are warming up to
600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphene microballoon,
The radius of a ball is 100nm-40um.
Embodiment 3
Particle diameter is 300 μm of graphene oxide aqueous dispersions, mixes, is stirred at room temperature into globule with organic molecule
5min, GO are 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, obtains powder
End.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating schedule
300 DEG C are warming up to for 100 DEG C, 10 DEG C/min, 300 DEG C of 1h, 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, and 450 DEG C rise
Warm to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.The scattered graphene that secures satisfactory grades is micro-
Ball, the radius of a ball is 100nm-50um.
Embodiment 4
Particle diameter is 300nm graphene aqueous dispersions, is mixed with organic molecule into globule, 5min, stone are stirred at room temperature
Black alkene is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, obtains powder.
Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating schedule is
100 DEG C are warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450 DEG C of heatings
To 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.The scattered graphene that secures satisfactory grades is micro-
Ball, the radius of a ball is 100nm-30um.
Embodiment 5
Particle diameter is 300nm graphene polar solvent dispersion liquid, mixes, is stirred at room temperature into globule with organic molecule
5min, graphene is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 100nm-30um.
Embodiment 6
Particle diameter is 300nm graphene non-polar solven dispersion liquid, mixes, is stirred at room temperature into globule with organic molecule
5min, graphene is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 100nm-30um.
Embodiment 7
Particle diameter is 300nm graphene oxide aqueous dispersions, mixes, is stirred at room temperature into globule with organic nano material
5min, GO are 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, obtains powder
End.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating schedule
300 DEG C are warming up to for 100 DEG C, 10 DEG C/min, 300 DEG C of 1h, 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, and 450 DEG C rise
Warm to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.The scattered graphene that secures satisfactory grades is micro-
Ball, the radius of a ball is 100nm-30um.
Embodiment 8
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
5min is stirred, GO is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 100nm-30um.
Embodiment 9
Particle diameter is 300nm graphene oxide aqueous dispersions, mixes, is stirred at room temperature into globule with metal nano material
5min, GO are 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, obtains powder
End.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating schedule
300 DEG C are warming up to for 100 DEG C, 10 DEG C/min, 300 DEG C of 1h, 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, and 450 DEG C rise
Warm to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.The scattered graphene that secures satisfactory grades is micro-
Ball, the radius of a ball is 100nm-30um.
Embodiment 10
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with metal oxide nano-material into globule, at room temperature
5min is stirred, GO is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 100nm-30um.
Embodiment 11
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at 40 DEG C
5min is stirred, GO is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 100nm-30um.
Embodiment 12
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, 100 DEG C
Lower stirring 5min, GO are 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100
DEG C, obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming,
Heating schedule is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C
1h, 450 DEG C are warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, and 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades
Graphene microballoon is dissipated, the radius of a ball is 100nm-30um.
Embodiment 13
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
5h is stirred, GO is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, is obtained
Powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heat up journey
Sequence is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450 DEG C
It is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphene
Microballoon, the radius of a ball is 100nm-30um.
Embodiment 14
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 50 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 100nm-30um.
Embodiment 15
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 1 with the mass ratio into globule:5.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C, is obtained
Powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heat up journey
Sequence is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450 DEG C
It is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphene
Microballoon, the radius of a ball is 300nm-20um.
Embodiment 16
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-50um.
Embodiment 17
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 200 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-50um.
Embodiment 18
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 400 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, N at last2Gas shielded, temperature programming, heating
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-50um.
Embodiment 19
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting at last, and aqueous vapor shielded, temperature programming rises
Warm program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h,
450 DEG C are warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, and 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered
Graphene microballoon, the radius of a ball is 300nm-50um.
Embodiment 20
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, CO 2 gas-shielded, program at last
Heating, heating schedule is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min,
450 DEG C of 1h, 450 DEG C are warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, and 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.
Secure satisfactory grades scattered graphene microballoon, and the radius of a ball is 300nm-50um.
Embodiment 21
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, argon gas protection, temperature programming, heating at last
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-50um.
Embodiment 22
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, argon gas protection, temperature programming, heating at last
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 4h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-50um.
Embodiment 23
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, argon gas protection, temperature programming, heating at last
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 4h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 2h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-30um.
Embodiment 24
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, argon gas protection, temperature programming, heating at last
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 4h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 2h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 2h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-40um.
Embodiment 25
Particle diameter is 300nm graphene oxide aqueous dispersions, is mixed with inorganic nonmetallic nanometer material into globule, at room temperature
12h is stirred, GO is 10 with the mass ratio into globule:1.Uniform mixed liquor is spray-dried, spray drying temperature is 100 DEG C,
Obtain powder.Further cyclonic separation obtains microballoon.Most microballoon is placed in Muffle kiln roasting, argon gas protection, temperature programming, heating at last
Program is 100 DEG C and is warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 4h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 2h, 450
DEG C it is warming up to 600 DEG C, 10 DEG C/min, 600 DEG C of 2h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 8h.Secure satisfactory grades scattered graphite
Alkene microballoon, the radius of a ball is 300nm-30um.
Comparative example 1
Particle diameter is spray-dried for 300nm graphene oxide aqueous dispersions, spray drying temperature is 100 DEG C, obtains powder.
Further cyclonic separation obtains powder, non-microballoon.Muffle kiln roasting is placed on, argon gas is protected, temperature programming, heating schedule is
100 DEG C are warming up to 300 DEG C, 10 DEG C/min, 300 DEG C of 1h, and 300 DEG C are warming up to 450 DEG C, 10 DEG C/min, 450 DEG C of 1h, 450 DEG C of heatings
To 600 DEG C, 10 DEG C/min, 600 DEG C of 1h, 600 DEG C are warming up to 900 DEG C, 10 DEG C/min, 900 DEG C of 1h.Graphene powder is obtained, it is non-micro-
Ball.
Subordinate list：
The embodiment 1 of table 1 is contrasted with the graphene microballoon in comparative example 1
| Embodiment 1 | Comparative example 1 | |
| Shape | Regular spherical | It is random |
| Tap density | 0.2-0.5g/cm3 | 0.01-0.03g/cm3 |
| Specific surface area | 1200-3000m2/g | 300-1500m2/g |
Claims (10)
1. a kind of method of prepare with scale height rule spherical graphite alkene microballoon, it is characterised in that：By graphene oxide and/or
Graphene dispersion adds into and graphene oxide and/or graphene dispersing solution is obtained after globule, mixing into water or other solvents,
Then the graphene oxide and/or graphene are spray-dried, are refined into it powdered, at cyclonic separation and high temperature
After reason, height rule spherical graphite alkene microballoon is obtained.
2. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 1, it is characterised in that
Described graphene oxide, graphene particle diameter are at 300 nanometers~300 microns；The graphene oxide and/or graphene and balling-up
The mass ratio of agent is (50:1)~(1:5) it is preferably, (50:1)~(1:2) (25, are more preferably:1)~(1:1), more preferably
(10:1)~(5:1).
3. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 1, it is characterised in that
The temperature of spray drying is 100 DEG C~400 DEG C, preferably 100 DEG C~300 DEG C, more preferably 150 DEG C~250 DEG C.
4. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 1, it is characterised in that
The condition of mixing is：30s~24h, more preferably preferably 1min~12h, 5min~12h are stirred at 15 DEG C~100 DEG C.
5. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 1, it is characterised in that
The condition of high-temperature process is：1~48h is heated at 100 DEG C~1200 DEG C；Preferably：After 100 DEG C~300 DEG C 1~12h of processing,
Again 300 DEG C~450 DEG C handle 1~12h after, 450 DEG C~600 DEG C processing 1~12h, then 600 DEG C~900 DEG C handle 1~
12h；More preferably：In 300 DEG C~600 DEG C, inert atmosphere handle 2~48h, then heat to 600 DEG C~1200 DEG C, containing
There is 5~48h of processing in the inert atmosphere of vapor or carbon dioxide or nitrogen or argon gas.
6. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 1, it is characterised in that
The solvent is polar solvent and/or non-polar solven.
7. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 1, it is characterised in that
It is described to be at least one kind, including organic molecule, organic nano material, inorganic nonmetallic nanometer material, metal nano into globule
Material, metal oxide nano-material it is independent into globule, or graphene with foregoing individually into being combined into that globule is composited
Globule.
8. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 7, it is characterised in that
Organic nano material includes high molecule nano material, conducting polymer nano material, molecule tree nano material；Macromolecule is formed to receive
The macromolecule of rice material includes but is not limited to polyethylene, polypropylene, polyvinyl chloride, polyelectrolyte；Form conducting polymer nanometer
The macromolecule of material includes but is not limited to polyacetylene, polypyrrole, polyaniline, polythiophene, poly- enedioxy thiophene phenol；Molecule tree nanometer
Material surface has positive charge group, negative electrical charge group or neutral group, with 1-6 for chondritic, particle diameter 1-10nm.
9. a kind of method of prepare with scale height rule spherical graphite alkene microballoon according to claim 7, it is characterised in that
Inorganic nonmetallic nanometer material includes carbon nanomaterial, and carbon nanomaterial includes but is not limited to nano-sized carbon, single armed CNT, many
Wall carbon nano tube, acetylene black, graphene, graphene quantum dot, graphene oxide；Metal nano material include but is not limited to gold,
Silver, copper, iron, cobalt, nickel, ruthenium, platinum, palladium；Formed metal oxide nano-material metal include but is not limited to gold, silver, copper, iron,
Cobalt, nickel, ruthenium, platinum, palladium；Non-metal simple-substance nano material includes but is not limited to：Sulphur, carbon, silicon, phosphorus.
10. the graphene microballoon prepared using such as any methods describeds of claim 1-9, it is characterised in that：Graphene is to reunite
Mode constitutes three-dimensional regular chondritic, and graphene microsphere radius is at 100nm-50 μm, preferably 100nm-30 μm, more preferably
300nm-20μm；Graphene microballoon tap density is 0.05g/cm3-0.7g/cm3, preferably 0.1~0.5g/cm3, more preferably
0.2~0.5g/cm3；The specific surface area of graphene microballoon is 300~3000m2/ g, preferably 800~3000m2/ g, more preferably
1200~3000m2/g。
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| CN107655226A (en) * | 2017-10-13 | 2018-02-02 | 杭州高烯科技有限公司 | A kind of graphene microballoon for solar absorption agent and preparation method thereof |
| CN108117064A (en) * | 2018-03-01 | 2018-06-05 | 上海理工大学 | A kind of preparation method of fold graphene |
| CN108419426A (en) * | 2018-03-05 | 2018-08-17 | 沈阳航空航天大学 | Coated with silica magnetic graphene tiny balloon and its magnanimity preparation method |
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| CN108565435A (en) * | 2018-05-09 | 2018-09-21 | 东南大学 | A kind of preparation method of graphene porous particle |
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