CN107161989A - A kind of preparation method of cellular three-dimensional grapheme - Google Patents
A kind of preparation method of cellular three-dimensional grapheme Download PDFInfo
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- CN107161989A CN107161989A CN201610127967.5A CN201610127967A CN107161989A CN 107161989 A CN107161989 A CN 107161989A CN 201610127967 A CN201610127967 A CN 201610127967A CN 107161989 A CN107161989 A CN 107161989A
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- dimensional grapheme
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- cellular
- polystyrene microsphere
- graphene
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- 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
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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
Abstract
The invention belongs to the preparing technical field of nano material, and in particular to a kind of preparation method of cellular three-dimensional grapheme.The technical scheme of the invention is：Using natural flake graphite as raw material, graphite oxide is prepared using Hummers methods；By graphite oxide and polystyrene microsphere preparation solution ultrasonic mixing, the polystyrene microsphere template that hydro-thermal reaction obtains graphene oxide parcel is carried out；Under weak basic condition, the graphene oxide of Surfaces of Polystyrene Microparticles is reduced to graphene using hydrazine hydrate；Under strongly alkaline conditions, using toluene removal polystyrene microsphere template, three-dimensional grapheme structure is obtained；Most handled afterwards through high-temperature activation, obtain cellular three-dimensional grapheme.The present invention prepares three-dimensional grapheme using one kettle way, and simple to operate, with low cost, the porous three-dimensional graphene of preparation has the advantages that high-specific surface area, high conductivity, strongly hydrophilic, can be widely applied to the fields such as conducing composite material, battery, electrochemical sensing.
Description
Technical field
The invention belongs to the preparing technical field of nano material, and in particular to a kind of preparation method of cellular three-dimensional grapheme.
Technical background
Graphene is a kind of new two-dimentional carbon nanomaterial, because it has unique optics, calorifics, electronics and mechanical performance, turn into nano material the most very powerful and exceedingly arrogant in materials science field in recent years, be widely used in the various fields such as ultracapacitor, battery, catalysis, biology sensor.But it is due to strong attraction between graphene sheet layer, causes the graphene of solid-state to lose the excellent properties such as the high-specific surface area that single dispersing graphene has due to aggregation.To solve this puzzlement, researchers will be joined together to form three-dimensional honeycomb shape skeleton structure per piece of graphite alkene, then solid graphite alkene can be made to show the excellent properties similar to monolithic graphite alkene.At present, the Major Difficulties that prepared by three-dimensional grapheme material are that graphene film is mutually assembled, and cause its density to be extremely difficult to minimum, are very restricted its performance and application.Chemical vapour deposition technique（CVD）It is the common method for preparing three-dimensional grapheme with hydro-thermal method, CVD growth conditions is harsh, it is difficult to realize the production in enormous quantities of three-dimensional grapheme；Although high temperature hydro-thermal method prepares three-dimensional grapheme with more pore structure, preparation process is complicated, is not suitable for industrialized production.
The content of the invention
It is an object of the invention to solve the deficiencies in the prior art and shortcoming, using one pot of preparation method, without the separation of intermediate, cellular three-dimensional grapheme is directly obtained, specific technical scheme is poly- including following step：
（1）Using natural flake graphite as raw material, it is slowly added in the concentrated sulfuric acid, adds the mixture of sodium nitrate and potassium permanganate, isothermal reaction 2
h；Deionized water and H are added into mixed liquor2O2, filter while hot.Native graphite is oxidized to graphite oxide in the process.
（2）By graphite oxide and polystyrene microsphere preparation solution ultrasonic mixing, 10 h are reacted at 70 DEG C, the polystyrene microsphere template of graphene oxide parcel is formed.Polystyrene microsphere preparation solution is absolute ethyl alcohol, polyvinylpyrrolidone, Triton
X-100（Emulsifying agent）, styrene, AMBN.
（3）Ammoniacal liquor and hydrazine hydrate are added into mixed liquor, graphene oxide is reduced to graphene, the polystyrene microsphere of graphene parcel is obtained.
（4）Potassium hydroxide and toluene are added into mixed liquor again, polystyrene microsphere is removed, obtains three-dimensional grapheme structure.
（5）Obtained three-dimensional grapheme is finally dried in vacuo 12 at 80 DEG C
H, 500 DEG C of high-temperature calcinations 2
H, obtains cellular three-dimensional grapheme.
The present invention compared with prior art, with advantages below and beneficial effect：
（1）The present invention prepares three-dimensional grapheme using one kettle way, and technological operation is simple, with low cost, is expected to realize the large-scale production of three-dimensional grapheme material.
（2）The inventive method is handled by high-temperature activation, solves the cellular three-dimensional grapheme structure more firm stable after the toxic chemical introduced in chemical reduction procedure and graphene agglomeration traits, and calcining.
（3）Porous three-dimensional graphene prepared by the inventive method has that conductance is high, specific surface area is big, porosity is high and the low advantage of density, can be widely applied to the fields such as heat-conductive composite material, energy storage material, sorbing material, chemical-biological sensing.
Brief description of the drawings
Fig. 1 prepares the flow chart of cellular three-dimensional grapheme for the present invention；
Fig. 2 is the SEM figures of the graphene oxide parcel polystyrene microsphere template obtained in embodiment 2；
Fig. 3 is the SEM figures of obtained cellular three-dimensional grapheme in the case where amplifying 5000 multiples in embodiment 3；
Fig. 4 is the SEM figures of obtained cellular three-dimensional grapheme in the case where amplifying 100,000 multiples in embodiment 3；
Fig. 5 is the XRD of the cellular three-dimensional grapheme obtained in embodiment 3.
Embodiment
Technical scheme is described in detail with specific embodiment below in conjunction with the accompanying drawings, but the explanation of the embodiment, it is only a part of embodiment of the present invention, wherein most is not limited to that.
Embodiment 1
1.
Graphite oxide is prepared by raw material of natural flake graphite
The present invention use one kettle way to prepare the process chart of cellular three-dimensional grapheme as shown in figure 1, the specific step for wherein preparing graphite oxide gather for：
Weigh 5
G natural flake graphites add 115
In the mL concentrated sulfuric acids, 2.5 g sodium nitrate and 15 are slowly added to after stirring
The mixture of g potassium permanganate, 0 DEG C of reaction 2
h.It is warming up to 35 DEG C of constant temperature 30
Min, is slowly added dropwise 230
ML ultra-pure water；It is continuously heating to 98 DEG C of reactions 15
After min, 700 are added
ML warm water and 200 mL
5% H2O2, filter while hot.Filter cake with 5% HCl（v/v）Fully washing, until without SO in filtrate4 2（Use BaCl2Solution is detected).Product is dried in vacuo 24 at 50 DEG C
H, obtains graphite oxide.
Embodiment 2
2.
Graphene oxide wraps up the preparation of polystyrene microsphere template
Take 25
ML absolute ethyl alcohols, 1 g polyvinylpyrrolidones, 0.4
g Triton X-100（Emulsifying agent）、7
ML styrene, 0.25 g AMBNs and 0.2
G graphite oxides, ultrasonic disperse.Lead to nitrogen gas stirring 1 at 70 DEG C
H, make oxidized graphite flake be completely exfoliated and polystyrene microsphere growth-promoting media be uniformly covered on graphite oxide surface formed polystyrene microsphere " bulb ".Then 70 DEG C of thermally grown liquid of logical nitrogen are added（25
ML ethanol, 7 mL styrene, 0.125
G GDMAs）, 70 DEG C of constant temperature stirring reactions 10
H, obtains the mixed liquor that graphene oxide wraps up polystyrene microsphere template.
The SEM for the graphene oxide parcel polystyrene microsphere template that embodiment 2 is obtained is as shown in Fig. 2 as seen from the figure, polystyrene microsphere is evenly dispersed in surface of graphene oxide.
Embodiment 3
3.
The preparation of cellular three-dimensional grapheme
The graphene oxide that embodiment 2 is obtained wraps up polystyrene microsphere template mixed liquor ultrasonic disperse, is separately added into 2.8
mL（V/v, 28%）Ammoniacal liquor and 0.4
mL（V/v, 35%）Hydrazine hydrate.By the mixed solution in 95 DEG C of stirred in water bath backflows 1
H, product is washed through filtering, washing, alcohol.Then 6
Ultrasound etching 12 in M KOH
H, is washed to neutrality, toluene removal polystyrene microsphere is added, through the isolated three-dimensional grapheme of separatory funnel.Obtained three-dimensional grapheme is dried in vacuo 12 at 80 DEG C
H, then it is placed in 500 DEG C of calcinings 2 in logical nitrogen tube furnace
H, obtains drastic reduction and the cellular three-dimensional grapheme peeled off.
As shown in Figure 3 and Figure 4, as seen from the figure, three-dimensional grapheme prepared by the present invention has obvious complex three-dimensional loose structure to SEM of the cellular three-dimensional grapheme that embodiment 3 is obtained under different amplification, and pore size is uniform.Fig. 5 characterizes for the XRD of the cellular three-dimensional grapheme of the preparation of the present invention, as seen from the figure, and obtained three-dimensional grapheme is height reduction graphitized products.
Above example is Core Implementation of the invention; but embodiments of the present invention are simultaneously not restricted to the described embodiments; other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine or simplification; equivalent substitute mode is should be, is included in protection scope of the present invention.
Claims (7)
1. a kind of preparation method of cellular three-dimensional grapheme, base is characterised by, is comprised the following steps：
（1）Using natural flake graphite as raw material, graphite oxide is prepared using Hummers methods；
（2）By graphite oxide and polystyrene microsphere preparation solution ultrasonic mixing, hydro-thermal reaction is carried out, the polystyrene microsphere template of graphene oxide parcel is formed；
（3）To step（2）Weak base and hydrazine hydrate are added in obtained mixed liquor, graphene oxide is reduced to graphene, the polystyrene microsphere of graphene parcel is obtained；
（4）To step（3）Highly basic and toluene are added in obtained mixed liquor, polystyrene microsphere is removed, obtains three-dimensional grapheme structure；
（5）By step（4）Obtained three-dimensional grapheme high-temperature activation processing, obtains cellular three-dimensional grapheme.
2. a kind of preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that：Step is poly-（1）Specially：In the concentrated sulfuric acid that natural flake graphite is slowly added to stirring, the mixture of sodium nitrate and potassium permanganate, the h of isothermal reaction 2 are slow added into；Deionized water dilution is added into mixed liquor, H is added2O2, filter while hot；Native graphite is oxidized to graphite oxide in the process.
3. a kind of preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that：Step is poly-（2）Described polystyrene microsphere preparation solution is absolute ethyl alcohol, polyvinylpyrrolidone, Triton
X-100（Emulsifying agent）, styrene, AMBN.
4. a kind of preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that：Step is poly-（2）The preparation method of described graphene oxide parcel polystyrene microsphere template is seed mediated growth method（One pot reaction）, i.e., grow up in surface of graphene oxide generation " bulb " and " bulb " and to form polystyrene microsphere.
5. a kind of preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that：Step is poly-（3）Described weak base is ammoniacal liquor, and reducing agent is hydrazine hydrate.
6. a kind of preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that：Step is poly-（4）Described highly basic is potassium hydroxide, and polystyrene microsphere template remover is toluene.
7. a kind of preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that：Step is poly-（5）The high-temperature activation treatment conditions：Vacuum drying：Temperature is 80 DEG C, and the time is 12 h；Calcining and activating condition：Nitrogen flow rate is 200 mL/min, and heating rate is 20 DEG C/min, and calcining heat is 500 DEG C, and the time is 2 h, and rate of temperature fall is 20 DEG C/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977768A (en) * | 2017-05-03 | 2017-07-25 | 杭州高烯科技有限公司 | A kind of method that spitball shape graphene improves the impact strength of nylon 6 |
| CN107651676A (en) * | 2017-09-26 | 2018-02-02 | 昆明理工大学 | A kind of optimization method for the water dispersible for improving graphene |
| CN109173989A (en) * | 2018-09-04 | 2019-01-11 | 电子科技大学 | Three-dimensional grapheme macroscopic body loads nano zero-valence iron composite material and preparation method |
| CN109233941A (en) * | 2018-10-26 | 2019-01-18 | 四川碳世界科技有限公司 | A kind of ball shaped nano graphene lubricating oil and preparation method thereof |
| CN109455708A (en) * | 2018-12-12 | 2019-03-12 | 中国科学院新疆理化技术研究所 | A kind of preparation method of super-hydrophobic three-dimensional grapheme film |
| CN109796682A (en) * | 2018-12-18 | 2019-05-24 | 武汉金牛经济发展有限公司 | Heat-resisting PPR pipe of toughening and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333280A (en) * | 2013-06-17 | 2013-10-02 | 厦门大学 | Method for regulating monodispersity of polystyrene microsphere based on hydrothermal treatment |
-
2016
- 2016-03-08 CN CN201610127967.5A patent/CN107161989A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333280A (en) * | 2013-06-17 | 2013-10-02 | 厦门大学 | Method for regulating monodispersity of polystyrene microsphere based on hydrothermal treatment |
Non-Patent Citations (2)
| Title |
|---|
| GUANNAN YIN ET AL.: "Preparation of graphene oxide coated polystyrene microspheres by Pickering emulsion polymerization", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 严琳: "3D石墨烯复合材料构建及在传感器中的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977768A (en) * | 2017-05-03 | 2017-07-25 | 杭州高烯科技有限公司 | A kind of method that spitball shape graphene improves the impact strength of nylon 6 |
| CN106977768B (en) * | 2017-05-03 | 2019-01-01 | 杭州高烯科技有限公司 | A kind of method that spitball shape graphene improves 6 impact strength of nylon |
| CN107651676A (en) * | 2017-09-26 | 2018-02-02 | 昆明理工大学 | A kind of optimization method for the water dispersible for improving graphene |
| CN109173989A (en) * | 2018-09-04 | 2019-01-11 | 电子科技大学 | Three-dimensional grapheme macroscopic body loads nano zero-valence iron composite material and preparation method |
| CN109233941A (en) * | 2018-10-26 | 2019-01-18 | 四川碳世界科技有限公司 | A kind of ball shaped nano graphene lubricating oil and preparation method thereof |
| CN109455708A (en) * | 2018-12-12 | 2019-03-12 | 中国科学院新疆理化技术研究所 | A kind of preparation method of super-hydrophobic three-dimensional grapheme film |
| CN109796682A (en) * | 2018-12-18 | 2019-05-24 | 武汉金牛经济发展有限公司 | Heat-resisting PPR pipe of toughening and preparation method thereof |
| CN109796682B (en) * | 2018-12-18 | 2021-08-17 | 武汉金牛经济发展有限公司 | Toughened heat-resistant PPR pipe and preparation method thereof |
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Application publication date: 20170915 |