CN106698409A - Three-dimensional graphene foam as well as preparation method and application thereof - Google Patents
Three-dimensional graphene foam as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN106698409A CN106698409A CN201710051316.7A CN201710051316A CN106698409A CN 106698409 A CN106698409 A CN 106698409A CN 201710051316 A CN201710051316 A CN 201710051316A CN 106698409 A CN106698409 A CN 106698409A
- Authority
- CN
- China
- Prior art keywords
- graphene
- foam
- preparation
- dimensional
- dimensional graphene
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses three-dimensional graphene foam as well as a preparation method and application thereof. The preparation method comprises the following concrete steps: taking low-temperature heat-peelable graphene powder as a raw material, and carrying out a one-step sintering process, so that further reduction and defect repairing on graphene can be realized, and two-dimensional graphene powder also can be assembled into three-dimensional graphene foam. The prepared ultra-light graphene foam has ultrahigh electromagnetic shielding efficiency and ultrahigh adsorbing capability on an organic solvent, and has important application in the fields of electromagnetic shielding and organic pollutant adsorption. By utilizing the preparation method, simple and macroscopic quantity preparation of high-performance and multifunctional graphene foam can be realized, so that the preparation method has great market prospects.
Description
Technical field
The invention belongs to grapheme foam Material Field, and in particular to a kind of three-dimensional graphene foam and preparation method thereof and
Using.
Background technology
Just by the extensive concern of various circles of society since Graphene (graphene) self-discovery.Graphene is by individual layer sp2
What hydbridized carbon atoms were constituted, the preferable two-dimensional nano crystal with regular honeycomb.This nano material not only has tradition
The incomparable mechanical strength of nano material, also has the physical and chemical performances such as excellent electric, hot, light concurrently.Using Graphene as base
It is to utilize and transmit this molecular level thickness material in macro-scale that this construction unit prepares graphene-based three-dimensional macro aggregation
Multi-functional effective way.
Grapheme foam is a kind of typical graphene-based three-dimensional macro aggregation, the porous network structure of its interior three-dimensional
Impart the specific surface area (~100-900m of foam conduction good/hot, higher in itself2/ g) and ultralow density (~1-
40mg/cm3), it is had in fields such as ultracapacitor, lithium battery, electromagnetic shielding, pollutant absorption, suction ripple, catalyst carriers
There are great application prospect, such as document：Nano Letters,2012,12,2446-2451；Angewandte Chemie
International Edition,2012,51,11371-11375；Advanced Materials,2015,27,2049-
2053；Advanced Functional Materials,2012,22,4421-4425.
At present, the preparation method of grapheme foam includes the hot method of hydrothermal/solvent, sol-gel chemistry method, colloidal sol freezing
Method, template, such as document：ACS Nano,2010,4,4324-4330；Journal of the American Chemical
Society,132,14067-14069；Advanced Materials,2013,25,2554-2560；Nature
Materials,2011,10,424-428.First three methods are more similar, are all the preparation process with graphite oxide as starting point
It is main to include four big steps：(1) stripping of graphene oxide；(2) self assembling process or gelation process or colloidal sol of Graphene are cold
Jelly process；(3) freezing of wet gel or foam or supercritical CO2Drying process；(4) heat/electronation of xerogel or foam
Process.The above method is usually used in mesoporous and macropore grapheme foam preparation.Wherein, the self assembly and gelation of Graphene
The treatment of journey, freezing or supercritical drying and follow-up heat/electronation treatment are complex, time-consuming, increased the difficulty of experiment
The uncertainty of degree and result.Template grows Graphene frequently with chemical vapour deposition technique (CVD) on metal nickel foam, or
Person by loading Graphene prepared by chemical method to open-celled polyurethane foam, then or filling silica or polystyrene it is micro-
Ball waits until first to prepare the presoma of grapheme foam in graphene-structured.Then, external mould is removed by acid etch or thermal decomposition
The method of plate obtains the grapheme foam with macroporous structure, such as document：Advanced Materials,2013,25,1296-
1300；Advanced Materials,2013,25,5658-5662；Advanced Materials,2013,25,6692-
6698；Advanced Materials,2012,24,4419-4423；ACS Nano,2012,6,4020-4028.However, due to
The weaker Physical interaction of graphene film interlayer, removing template procedure, the skeleton structure of grapheme foam easily collapse and
Etching or pyrolytic process also more take, and cause the method to have larger limitation.In addition, by taking CVD as an example, it will to equipment
Ask higher and there are problems that template is difficult.
The content of the invention
It is an object of the invention to provide a kind of three-dimensional graphene foam and its preparation method and application.Prepared ultralight three
Dimension grapheme foam has the electromagnet shield effect of superelevation and has the adsorption capacity of superelevation to organic solvent, can using the method
To realize prepared by high-performance, multi-functional the simple of grapheme foam, magnanimity, with huge market application foreground.
A kind of preparation method of three-dimensional graphene foam, comprises the following steps that：
(1) graphite oxide with chemical oxidization method preparation is peeled off at 80~500 DEG C and obtains graphene powder as raw material；
(2) graphene powder obtained in step (1) is pressed into mould, sintering obtains three at 600~3000 DEG C
Dimension grapheme foam.
The inventive method is that the graphene powder that Low Temperature Thermal is peeled off is raw material, and stone can be not only realized by a step sintering process
The further reduction and the reparation of defect of black alkene, the graphene powder of two dimension can also be assembled into the grapheme foam of three-dimensional.
In step (1), the graphite oxide is with natural flake graphite or graphite powder as raw material, with potassium permanganate, chloric acid
One or more in potassium and potassium ferrate etc. are oxidant, are prepared by chemical oxidization method.
In step (1), the time of the stripping is 1~10min.
In step (1), graphene powder is prepared using Low Temperature Thermal stripping, a certain amount of oxygen-containing functional group can be retained in stone
On black alkene lamella, allow it that Physical interaction is formed with the removing of oxygen-containing functional group even in follow-up sintering process
Generation interlayer is integrated, and is finally shaped to the grapheme foam with three-dimensional net structure.Do not contain using containing abundant directly herein
The reason for graphite oxide of oxygen functional group is：Graphite oxide being heated (>100 DEG C) when often occur " explosivity " expansion, can
Control property is poor.
Preferably, in step (2), pressure when graphene powder to be pressed into mould is 1~109Pa.To Graphene
The purpose that powder carries out pressurized treatments is to force the distance between graphene sheet layer close enough, and the process not only contributes to its piece
Layer forms effective physical action such as pi-pi accumulation in high-temperature sintering process, also contributes to induce its interlayer to integrate such as shape
Into graphite microcrystal etc., final molding is the grapheme foam of three-dimensional macro.
Preferably, in step (2), the sintering temperature of graphene powder is 1000~2200 DEG C.The temperature range is favourable
In obtaining the grapheme foam that specific surface area is higher, density is relatively low, skeleton structure is relatively stable.Within the specific limits, further
Reduce temperature to be although conducive to improving its specific surface area, reduce its density, but also can significantly weaken gained grapheme foam simultaneously
Mechanical strength, make that it is difficult to meet practical application and post-processing is processed；Though further rising high-temperature can improve gained Graphene
The intensity of foam, but its density can be greatly improved simultaneously, its specific surface area is reduced.Finally, until forming non-porous Graphene block
Body material.
In step (2), time of the sintering is 1min~100h, preferably, the time of the sintering be 30~
60min.Sintering time is too short to be unfavorable for the removing of oxygen-containing functional group on graphene film, and then influences its piece interlayer physical action
Form the carrying out integrated with interlayer, the mechanical property and electric conductivity of final influence gained three-dimensional graphene foam；During extension sintering
Though between to a certain extent improve gained three-dimensional graphene foam mechanics and electric property, can also increase the density of foam,
Simultaneously long heat treatment time can be significantly increased the energy consumption of the process, and its range of application is limited to a certain extent.
In step (2), graphene powder is sintered in a vacuum or under the protection of inert gas and obtains three-dimensional grapheme
Foam.
In step (2), the mould only influences the global shape of gained three-dimensional graphene foam, and mould is unrestricted in itself
It is fixed, it is resistant to 600~3000 DEG C.
Present invention also offers a kind of three-dimensional graphene foam prepared according to the above method, the three-dimensional grapheme
The aperture of foam is 2nm~200 μm, and density is 10~50mg/cm3, specific surface area is 10~600m2/g。
Present invention also offers application of the above-mentioned three-dimensional graphene foam in electromagnetic shielding field.By the three-dimensional graphite
Alkene foam improves the capability of electromagnetic shielding of material by building good conductive network as the skeleton of electromagnetic shielding material.
Present invention also offers above-mentioned three-dimensional graphene foam Adsorption of Organic field application.The three-dimensional stone
Black alkene foam has the rate of adsorption (about 12g/s) and adsorbance (47~110g/g) higher of superelevation to organic pollution, leads to
Cross that the three-dimensional graphene foam of saturation absorption is burnt or distilled and can remove its organic pollution for being adsorbed, realize three
Tie up the recycling of grapheme foam.
Compared with prior art, the present invention has the advantages that：
(1) graphene film of two dimension is not only assembled into high-temperature sintering process the three-dimensional graphene foam of macroscopic view, while also
It is to realize the further reduction of Graphene and significantly repaired defect thereon, substantially increases the work(of gained grapheme foam
Can property such as conduction, heat conduction, electromagnetic shielding and chemical property；
(2) by adjusting mould and control sintering temperature shape that can within the specific limits to three-dimensional graphene foam and close
Degree carries out free regulation and control；
(3) graphene powder from two dimension realizes one-step method preparation to three-dimensional grapheme foam, substantially reduces it
Manufacturing cycle；
(4) experimental facilities needed for whole preparation process is simple, is easy to the extensive preparation of three-dimensional graphene foam.
Brief description of the drawings
Fig. 1 is the outside drawing of three-dimensional graphene foam prepared by embodiment 1；
Fig. 2 is the ESEM shape appearance figure of three-dimensional graphene foam prepared by embodiment 1；
Fig. 3 is that grapheme foam composite prepared by embodiment 1 is imitated in the electromagnetic shielding of X-band (8.2~12.4GHz)
Can result figure；
Fig. 4 is the ESEM shape appearance figure of graphene powder prepared by comparative example 1；
Fig. 5 is the grapheme foam composite of the preparation of embodiment 1 and the graphene composite material of the preparation of comparative example 1 in X
The electromagnet shield effect comparison diagram of wave band；
Fig. 6 is the grapheme foam composite of the preparation of embodiment 2 and the graphene composite material of the preparation of comparative example 2 in X
The electromagnet shield effect comparison diagram of wave band；
Fig. 7 is the grapheme foam composite of the preparation of embodiment 3 and the graphene composite material of the preparation of comparative example 3 in X
The electromagnet shield effect comparison diagram of wave band；
Fig. 8 is the saturated extent of adsorption of the three-dimensional graphene foam to different types of organic pollution of the preparation of embodiment 1；
Fig. 9 is the ESEM shape appearance figure of graphene powder prepared by comparative example 5.
Specific embodiment
The present invention is specifically described with reference to the accompanying drawings and examples.
Embodiment 1
(1) graphite oxide prepared by chemical oxidization method is placed in a conventional oven carry out hot soarfing from and reduction, hot soarfing from
Temperature is 200 DEG C, and splitting time is 5min.Finally, the fluffy graphene powder of black is obtained.
(2) by 0.66g, the graphene powder is encased in size for φ under the pressure of 54kPaOutward5cm×φIt is interior4cm×5cm
Graphite crucible in, be placed in processing 1h in High Purity Nitrogen atmosphere at 1500 DEG C in high temperature furnace, obtain density for 19mg/cm3、
BET specific surface area is 338m2The three-dimensional graphene foam of/g.The outward appearance of gained three-dimensional graphene foam is as shown in figure 1, scanning electricity
Mirror shape appearance figure as shown in Fig. 2 resulting three-dimensional graphene foam not only has good compressive property and mechanical strength, together
When, also with continuous vermiform skeleton (Graphene aggregate) and macroporous structure (aperture size is in tens micron orders).The knot
Structure not only imparts its specific surface area higher, also imparts its excellent electromagnet shield effect.
For the ease of the test of capability of electromagnetic shielding, the three-dimensional graphene foam epoxy encapsulation is obtained into Graphene
Foamed composite, the quality of three-dimensional graphene foam is the 1.2% of grapheme foam composite.Afterwards, the sample is cut
To different thickness (0.5mm, 1.0mm, 2.0mm) and test their electromagnetism in X-band (8.2~12.4GHz) with waveguide method
Shield effectiveness, influence of the study sample thickness to its capability of electromagnetic shielding.As a result result as shown in figure 3, show：The shielding of sample
Performance can increase with the increase of its thickness.The increase that reason is mainly thickness of sample is conducive to improving material on incident electromagnetic wave
Reflection and absorption loss, and then greatly improve its shield effectiveness.
Comparative example 1
Compared with Example 1, in differing only in step (2), graphene powder is encased in nothing during graphite crucible
Apply pressure, other conditions are identical.Result shows：Graphene powder is not shaped to such as the three-dimensional grapheme bubble in embodiment 1
Foam, its pattern are as shown in figure 4, be still the loose graphene powder of black.Main cause be heat treatment process in, unpressed stone
In black alkene powder, graphene film interlamellar spacing is excessive, it is difficult to effective interaction is formed in heat treatment process and is integrated with interlayer,
It is set to be difficult to be shaped to grapheme foam.
Gained graphene powder is dispersed in graphene composite material is obtained in epoxy resin, the matter of graphene powder
It is the 1.2% of the graphene composite material to measure, and afterwards, the sample is switched into thickness for 2.0mm.
It is the grapheme foam composite and the gained graphene composite material of comparative example 1 of 2.0mm by thickness in embodiment 1
Their electromagnet shield effects in X-band are tested with waveguide method, as a result its result as shown in figure 5, show：Contain three-dimensional grapheme
The average electromagnet shield effect of the sample (embodiment 1) of foam framework is about 34dB, and it is dispersed that the value is about graphene powder
4.9 times of sample (comparative example 1).Reason is mainly the skeleton of three-dimensional graphene foam structure in the epoxy resin-base of insulation
Good conductive network is built up, it is assigned compared with comparative example 1 (2.8 × 10-2S/m) conductance higher (58.4S/m).When entering radio
When magnetic wave runs into material, what the material with high conductivity can be inside the more electromagnetic wave energies of its reflected at interfaces and its
Multiple reflections loss of the conductive network to incident electromagnetic wave is also higher, assigns material capability of electromagnetic shielding higher.
Embodiment 2
Compared with Example 1, differ only in step (2), graphene powder is placed in high temperature furnace in high at 1000 DEG C
1h is processed in purity nitrogen atmosphere, the structure of gained three-dimensional graphene foam is similar to Example 1, but density is reduced to 11mg/cm3, BET
Specific surface area increases to 508m2/g。
The three-dimensional graphene foam epoxy encapsulation is obtained into grapheme foam composite, three-dimensional graphene foam
Quality be the 0.8% of grapheme foam composite, afterwards, the sample is switched to thickness for 2.0mm.
Comparative example 2
Compared with Example 2, in differing only in step (2), graphene powder is encased in nothing during graphite crucible
Apply pressure, other conditions are identical.Result shows, should under the conditions of graphene powder and unformed, be still graphite that black is loose
Alkene powder.
Gained graphene powder is dispersed in graphene composite material is obtained in epoxy resin, the matter of graphene powder
It is the 0.8% of the graphene composite material to measure, and afterwards, the sample is switched into thickness for 2.0mm.
The gained grapheme foam composite of embodiment 2 is surveyed with the gained graphene composite material of comparative example 2 with waveguide method
Their electromagnet shield effects in X-band are tried, as a result its result as shown in fig. 6, show：Sample with grapheme foam skeleton
The average electromagnet shield effect of (embodiment 2) is about 16dB, and the value is about the dispersed sample of graphene powder (comparative example 2)
2.7 times.Reason is similar to embodiment 1, and mainly embodiment 2 is compared with comparative example 2 (3.9 × 10-6S/m) conductance higher
(7.2S/m).Additionally, compared to embodiment 1, the electrical conductivity of the gained grapheme foam composite of embodiment 2 decreases, it is main
Want reason be Graphene in the gained grapheme foam composite of embodiment 2 reduction degree it is relatively low, in general, sintering higher
Temperature is conducive to improving the reducing degree that Low Temperature Thermal peels off Graphene.
Embodiment 3
Compared with Example 1, differ only in step (2), graphene powder is placed in high temperature furnace in high at 2200 DEG C
1h is processed in purity nitrogen atmosphere, the structure of gained three-dimensional graphene foam is similar to Example 1, but density increases to 34mg/cm3,
BET specific surface area reduces to 108m2/g。
The three-dimensional graphene foam epoxy encapsulation is obtained into grapheme foam composite, three-dimensional graphene foam
Quality be the 3.3% of grapheme foam composite, afterwards, the sample is switched to thickness for 2.0mm.
Comparative example 3
Compared with Example 3, in differing only in step (2), graphene powder is encased in nothing during graphite crucible
Apply pressure, other conditions are identical.Result shows, should under the conditions of graphene powder and unformed, be still graphite that black is loose
Alkene powder.
Gained graphene powder is dispersed in graphene composite material is obtained in epoxy resin, the matter of graphene powder
It is the 3.3% of the graphene composite material to measure, and afterwards, the sample is switched into thickness for 2.0mm.
The gained grapheme foam composite of embodiment 3 is surveyed with the gained graphene composite material of comparative example 3 with waveguide method
Their electromagnet shield effects in X-band are tried, as a result its result as shown in fig. 7, show：Sample with grapheme foam skeleton
The average electromagnet shield effect of (embodiment 3) is about 40dB, and the value is about the dispersed sample of graphene powder (comparative example 3)
4.4 times.Reason is similar to embodiment 1, and mainly embodiment 4 has conductance higher compared with comparative example 4 (0.2S/m)
(130.5S/m).Additionally, for compared with embodiment 1, the electrical conductivity and shielding properties of embodiment 4 are higher, are primarily due to the Graphene
Graphene has reduction degree higher in foamed composite.
Comparative example 4
Compared with Example 1, differ only in step (2), graphene powder is placed in high temperature furnace in high-purity at 500 DEG C
1h is processed in nitrogen atmosphere, is as a result shown：Graphene powder and unformed under the sintering temperature, is still graphene powder, it is impossible to
The structure of three-dimensional graphene foam in such as embodiment 1.Reason is relatively low heat treatment temperature is unfavorable for it being its piece interlayer physical
The enhancing of interaction is more difficult to promote the integration of graphene sheet layer, causes the graphene film of two dimension to be difficult to be assembled into three-dimensional
The grapheme foam of network structure.
In sum, the sintering temperature in step (2) prepares three-dimensional graphene foam to the inventive method influences larger, institute
The conductive and electromagnet shield effect of the three-dimensional graphene foam for obtaining can typically increase with the rising of temperature in sintering process.
Embodiment 4
Compared with Example 1, differ only in step (1), hot exfoliation temperature is 120 DEG C, and splitting time is 5min, its
His condition is identical.The structure of gained three-dimensional graphene foam is similar to Example 1, but density is reduced to 15mg/cm3, BET specific surfaces
Product increases to 370m2/g。
Embodiment 5
Compared with Example 1, differ only in step (1), hot exfoliation temperature is 400 DEG C, and splitting time is 5min, its
His condition is identical.The structure of gained three-dimensional graphene foam is similar to Example 1, but density increases to 25mg/cm3, BET specific surfaces
Product is down to 270m2/g。
Embodiment 6
In order to test absorption property of the three-dimensional graphene foam to organic pollution, three-dimensional prepared by 0.2g embodiments 1
Grapheme foam is placed in 5s or so in excessive organic solvent, it is ensured that it reaches saturation adsorbed state.Then bubble is sucked with filter paper
The excessive solvent of foam remained on surface, the weight change tested before and after the absorption of its saturation, calculates it and various organic pollutions is satisfied
And adsorbance.As a result result as shown in figure 8, show：The three-dimensional graphene foam is to the organic solvent not only absorption with superelevation
Speed (about 12g/s) also has adsorbance (47~110g/g) higher.Think, the absorption speed high of three-dimensional graphene foam
Super wetability and high porosity (about 99.1%) of the rate mainly with it to organic solvent are relevant, and three-dimensional graphene foam is porous
Structure imparts itself superhigh specific surface area again, it is adsorbed about 47~110 times of own wt by capillarity
Organic pollution.Additionally, can remove it and adsorbed by being burnt to the three-dimensional graphene foam that saturation is adsorbed or being distilled
Organic solvent, realize the recycling of three-dimensional graphene foam.
Comparative example 5
Compared with Example 1, in differing only in step (1), using high temperature hot soarfing from preparing graphene powder, hot soarfing from
Temperature is 600 DEG C, and splitting time is 5min, and other conditions are identical.Result shows, should under the conditions of graphene powder and unformed,
Still for the graphene powder ESEM shape appearance figure of black compression is as shown in Figure 9, it is impossible to obtain such as three-dimensional grapheme in embodiment 1
The structure of foam, main cause is higher for the hot exfoliation temperature of starting graphite alkene powder, and oxygen-containing functional group removing is excessive, preloads
Pressure process is too low, it is difficult to graphene film interlayer is carried out effective contact and effective physics phase is then formed in subsequent process
Interaction and interlayer are integrated, and cause it to be difficult to be shaped to three-dimensional graphene foam.
Claims (8)
1. a kind of preparation method of three-dimensional graphene foam, it is characterised in that comprise the following steps that：
(1) graphite oxide with chemical oxidization method preparation is peeled off at 80~500 DEG C and obtains graphene powder as raw material；
(2) graphene powder obtained in step (1) is pressed into mould, sintering obtains three-dimensional stone at 600~3000 DEG C
Black alkene foam.
2. the preparation method of three-dimensional graphene foam according to claim 1, it is characterised in that in step (2), by graphite
Pressure when alkene powder is pressed into mould is 1~109Pa。
3. the preparation method of three-dimensional graphene foam according to claim 1, it is characterised in that in step (2), Graphene
The sintering temperature of powder is 1000~2200 DEG C.
4. the preparation method of three-dimensional graphene foam according to claim 1, it is characterised in that in step (2), the burning
The time of knot is 1min~100h.
5. a kind of three-dimensional graphene foam, it is characterised in that the three-dimensional graphene foam is according to any one of Claims 1 to 4
Described method is prepared.
6. three-dimensional graphene foam according to claim 5, it is characterised in that the aperture of the three-dimensional graphene foam is
2nm~200 μm, density is 10~50mg/cm3, specific surface area is 10~600m2/g。
7. application of a kind of three-dimensional graphene foam according to claim 5 in electromagnetic shielding field.
8. application of a kind of three-dimensional graphene foam according to claim 5 in Adsorption of Organic field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710051316.7A CN106698409B (en) | 2017-01-23 | 2017-01-23 | A kind of three-dimensional graphene foam and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710051316.7A CN106698409B (en) | 2017-01-23 | 2017-01-23 | A kind of three-dimensional graphene foam and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106698409A true CN106698409A (en) | 2017-05-24 |
| CN106698409B CN106698409B (en) | 2019-04-16 |
Family
ID=58908888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710051316.7A Active CN106698409B (en) | 2017-01-23 | 2017-01-23 | A kind of three-dimensional graphene foam and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106698409B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110387215A (en) * | 2019-05-30 | 2019-10-29 | 中国人民解放军国防科技大学 | Graphene foam phase-change composite material with sparse thermal protection structure and preparation method thereof |
| CN111138206A (en) * | 2020-01-11 | 2020-05-12 | 西安交通大学 | Amorphous carbon modified SiC nanowire continuous three-dimensional network structure wave-absorbing foam and preparation method thereof |
| CN111362256A (en) * | 2020-03-12 | 2020-07-03 | 杭州高烯科技有限公司 | Preparation method of graphene electromagnetic shielding material |
| CN111943182A (en) * | 2019-05-15 | 2020-11-17 | 英属维京群岛商艾格生科技股份有限公司 | Graphene powder and method for improving graphene defects |
| CN114633528A (en) * | 2022-03-22 | 2022-06-17 | 江苏万华拓谷新材料科技有限公司 | Composite material with wave-absorbing and electromagnetic shielding properties and preparation method thereof |
| CN115353099A (en) * | 2022-08-18 | 2022-11-18 | 西北工业大学 | Porosity and pore diameter controllable multi-boundary graphene foam and preparation method thereof |
| CN115893385A (en) * | 2022-12-13 | 2023-04-04 | 之江实验室 | Self-supporting three-dimensional graphene framework, composite material, and preparation method and application of composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530937A (en) * | 2012-03-15 | 2012-07-04 | 武汉大学 | Method for preparing high-quality graphene on large scale |
| CN103880004A (en) * | 2014-04-11 | 2014-06-25 | 吉林建筑大学 | Method for preparing graphene material at high temperature and high pressure |
| CN105858642A (en) * | 2015-01-22 | 2016-08-17 | 中国科学院上海应用物理研究所 | Porous graphene material, and preparation method and application thereof |
-
2017
- 2017-01-23 CN CN201710051316.7A patent/CN106698409B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530937A (en) * | 2012-03-15 | 2012-07-04 | 武汉大学 | Method for preparing high-quality graphene on large scale |
| CN103880004A (en) * | 2014-04-11 | 2014-06-25 | 吉林建筑大学 | Method for preparing graphene material at high temperature and high pressure |
| CN105858642A (en) * | 2015-01-22 | 2016-08-17 | 中国科学院上海应用物理研究所 | Porous graphene material, and preparation method and application thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943182A (en) * | 2019-05-15 | 2020-11-17 | 英属维京群岛商艾格生科技股份有限公司 | Graphene powder and method for improving graphene defects |
| CN110387215A (en) * | 2019-05-30 | 2019-10-29 | 中国人民解放军国防科技大学 | Graphene foam phase-change composite material with sparse thermal protection structure and preparation method thereof |
| CN111138206A (en) * | 2020-01-11 | 2020-05-12 | 西安交通大学 | Amorphous carbon modified SiC nanowire continuous three-dimensional network structure wave-absorbing foam and preparation method thereof |
| CN111138206B (en) * | 2020-01-11 | 2021-04-20 | 西安交通大学 | Amorphous carbon modified SiC nanowire continuous three-dimensional network structure wave-absorbing foam and preparation method thereof |
| CN111362256A (en) * | 2020-03-12 | 2020-07-03 | 杭州高烯科技有限公司 | Preparation method of graphene electromagnetic shielding material |
| CN111362256B (en) * | 2020-03-12 | 2021-11-02 | 杭州高烯科技有限公司 | Preparation method of graphene electromagnetic shielding material |
| CN114633528A (en) * | 2022-03-22 | 2022-06-17 | 江苏万华拓谷新材料科技有限公司 | Composite material with wave-absorbing and electromagnetic shielding properties and preparation method thereof |
| CN115353099A (en) * | 2022-08-18 | 2022-11-18 | 西北工业大学 | Porosity and pore diameter controllable multi-boundary graphene foam and preparation method thereof |
| CN115893385A (en) * | 2022-12-13 | 2023-04-04 | 之江实验室 | Self-supporting three-dimensional graphene framework, composite material, and preparation method and application of composite material |
| CN115893385B (en) * | 2022-12-13 | 2023-07-25 | 之江实验室 | Self-supporting three-dimensional graphene framework, composite material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106698409B (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106698409B (en) | A kind of three-dimensional graphene foam and its preparation method and application | |
| Li et al. | A generalizable strategy for constructing ultralight three-dimensional hierarchical network heterostructure as high-efficient microwave absorber | |
| Zhao et al. | Biomass-derived porous carbon-based nanostructures for microwave absorption | |
| CN107585758B (en) | Graphene aerogel and preparation method and application thereof | |
| Aslam et al. | Low cost 3D bio-carbon foams obtained from wheat straw with broadened bandwidth electromagnetic wave absorption performance | |
| CN105731447A (en) | Preparation method of three-dimensional hierarchical porous nitrogen-doped graphene and product | |
| CN108811478B (en) | A kind of three-layer laminated MXene electromagnetic shielding foam and preparation method | |
| CN106783197B (en) | A kind of ZIF-8 pyrolysis porous carbon-graphene composite material and its preparation method and application | |
| Zhao et al. | Pore structure control of mesoporous carbon as supercapacitor material | |
| CN101759178B (en) | Preparation method for hollow carbon hemisphere | |
| CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
| CN107857249A (en) | A kind of preparation method of N doping annular hollow carbon nano-material | |
| CN103787327A (en) | One-step preparation method of hollow spherical porous graphite for supercapacitor | |
| CN104694989B (en) | A kind of preparation method of graphene-based metallic composite | |
| Chen et al. | State-of-the-art synthesis strategy for nitrogen-doped carbon-based electromagnetic wave absorbers: from the perspective of nitrogen source | |
| CN108172793A (en) | Centrifuge the method for preparing three-dimensional carbon foam/graphene oxide based composites | |
| Li et al. | Ultralight Coral-like hierarchical Fe/CNTs/Porous carbon composite derived from biomass with tunable microwave absorption performance | |
| CN113718371B (en) | MXene aerogel fiber, preparation method and application thereof | |
| CN105417521A (en) | Method for preparing fluorene-based hierarchical porous carbon nanosheets for super capacitors | |
| Wang et al. | Nanoporous resorcinol-formaldehyde based carbon aerogel for lightweight and tunable microwave absorption | |
| CN111099587A (en) | Preparation method of bamboo leaf-based carbon material with high specific surface area | |
| Cai et al. | Facile and scalable preparation of ultralight cobalt@ graphene aerogel microspheres with strong and wide bandwidth microwave absorption | |
| Xiao et al. | A simple CaCO3-assisted template carbonization method for producing nitrogen-containing nanoporous carbon spheres and its electrochemical improvement by the nitridation of azodicarbonamide | |
| CN112265982A (en) | Preparation method of N-doped graphene/graphene nanoribbon composite aerogel | |
| CN114031065B (en) | Silicon carbide fiber/carbon mixed aerogel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |