CN110136979A - Three-dimensional grapheme, preparation method and its be used for supercapacitor and absorbing material - Google Patents
Three-dimensional grapheme, preparation method and its be used for supercapacitor and absorbing material Download PDFInfo
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- CN110136979A CN110136979A CN201910505428.4A CN201910505428A CN110136979A CN 110136979 A CN110136979 A CN 110136979A CN 201910505428 A CN201910505428 A CN 201910505428A CN 110136979 A CN110136979 A CN 110136979A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
- H01Q17/008—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems with a particular shape
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Graphite alkenes supercapacitor theoretical capacity 550F g with higher‑1.It is most common method by removing, heat-treating graphene oxide to prepare related carbon negative pole material.In order to simplify the experiment condition of microwave removing graphene oxide, retain the oxygen-containing functional group of part graphene surface, enhance the wettability of carbon material surface, reduce electron-transport resistance, so the graphene oxide that the present invention is prepared using improved Hummers method is raw material, using household microwave oven as reactor, quickly, low cost prepares three-dimensional grapheme.The three-dimensional grapheme material of preparation shows fluffy powdered under macrostate, has up to 457m2g‑1Specific surface area, microscopic appearance shows the lamellar structure stacked mutually, the supercapacitor Carbon anode specific discharge capacity with higher (215F/g) of preparation and preferable circulation volume conservation rate (52% after 20000 circulations).And when this three-dimensional grapheme is used for the absorption field of electromagnetic wave, the reflection loss within the scope of 14.5-18GHz is up to -10dB.
Description
Technical field
The invention belongs to graphene new material technical field, it is related to a kind of three-dimensional grapheme, preparation method and its is used for
Supercapacitor and absorbing material, and in particular to a kind of method for quickly preparing three-dimensional grapheme in air atmosphere and be used for
Supercapacitor and electro-magnetic wave absorption field.
Background technique
Graphene is a kind of monoatomic layer two dimensional crystal, and carbon atom is with sp2Hydridization form is constituted.Graphene has very much
Excellent physical property, such as outstanding conductivity, excellent mechanical property etc..But extensive manufacture graphene still has very
Big challenge.Single layer or few layer are how prepared on a large scale and the grapheme material with processability is to solve graphene
The key with industrialized production is widely applied in material.The current widely used method for preparing graphene can substantially be divided into
Several classes below: mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, chemical synthesis, graphene oxide reduction method and
Longitudinally cutting carbon tube method etc. is several.But due to the above method there are preparation times long, at high cost, low output, synthesis condition is harsh
The disadvantages of constrain large-scale production.
Supercapacitor can be divided into double electric layers supercapacitor according to its energy storage mechnism and fake capacitance is super as energy storage device
Grade capacitor.Double electric layers supercapacitor is not related to relevant atomic in electrode material during the storage of energy and release
The transformation of chemical valence forms electron adsorption layer by the huge specific surface area of electrode material and reasonable pore-size distribution.Because of its tool
There is the advantages that instantaneous power is big, long service life to use frequently as power battery.But its energy density is relatively low, therefore improves
Its energy density is the key that research prepares related negative electrode material.And carbon material has benefited from that its is from a wealth of sources, and it is pollution-free, it is at low cost
Honest and clean advantage and attract attention.
Absorbing material be solve electromagenetic wave radiation pollution key factor, and influence radar invisible key factor it
One.Grapheme material has many advantages, such as good electric conductivity and special boundary effect for inhaling wave field.But it is still deposited
In the unmatched problem of the low electromagnetic parameter of magnetic loss.
Summary of the invention
For the lower electromagnetic parameter low with graphene absorbing material magnetic loss of super capacitor energy density in the prior art
Unmatched problem, the present invention provide a kind of three-dimensional grapheme and its preparation side for supercapacitor and electro-magnetic wave absorption
Method, its object is to: it provides under a kind of simple condition (air atmosphere, humble wave power), low cost, the three-dimensional stone of rapid synthesis
Black alkene material, and the three-dimensional grapheme material is superior to existing skill as the performance of Carbon anode capacitor and electromagnetic wave absorption material
Other grapheme materials in art.
The technical solution adopted by the invention is as follows:
A kind of preparation method of three-dimensional grapheme, includes the following steps:
[1] graphene oxide is prepared；
[2] graphene oxide is uniformly mixed with crystalline flake graphite, using crystalline flake graphite as auxiliary absorbing material, is utilized
Microwave heating obtains the fluffy three-dimensional grapheme powder of black lightweight.
It, (can in the presence of microwave radiation using minimal amount of crystalline flake graphite as wave absorbing agent after the technical solution
Utilize household microwave oven), Local Instantaneous high temperature is formed, is taken off to the oxygen-containing group avalanche type at initiated oxidation graphene surface and edge
It falls, to manufacture the three-dimensional grapheme powder of fluffy lightweight.This three-dimensional grapheme microscopic appearance is the sheet stone being stacked with
Ink sheet structure, and there is opening between lamella and lamella.And in the prior art, although there is also document reports to use scale
The case where graphite is as wave absorbing agent assisted microwave synthesis heated oxide graphene, but wave absorbing agent is separated with graphene oxide in document
Setting, wave absorbing agent effect is so that the disengaging of oxygen-containing group is more thorough, so that obtained graphene is single layer structure
And interlamellar spacing distance is smaller.This is different from the action principle in the application.
Preferably, step [1] method that graphene oxide is prepared includes the following steps:
[1-1] utilizes room-temperature water bath, and the concentrated sulfuric acid and concentrated phosphoric acid are mixed in proportion, are then successively slowly added to scale
Graphite and potassium permanganate persistently stir obtained mixing liquid at the reaction temperatures, and reaction terminates to obtain brown liquid；
[1-2] neutralizes remaining oxidant in the brown liquid using hydrogen peroxide and obtains golden solution, will be golden yellow
PH value of solution is adjusted to acidity, is centrifugally separating to obtain yellow mercury oxide；
Yellow mercury oxide freezing is dried under reduced pressure a couple of days and obtains graphene oxide by [1-3].
The preferred embodiment prepares graphene oxide by improved hummer method.
It is further preferred that the temperature being stirred to react in step [1-1] is 40-60 DEG C, the time of reaction is that 12-14 is small
When.
Preferably, the mixed proportion of graphene oxide and crystalline flake graphite is mass ratio 30:1 to 60:1.
Preferably, the power of microwave heating is 400 to 600W, and the time of microwave radiation is 10 to 30 seconds.
Provided in above-mentioned preferred embodiment be preferably after the parameter with better effects.
Preferably, microwave heating carries out in air atmosphere.Using the preferred embodiment, on the one hand make preparation condition more
Simplify, on the other hand also to remain part oxygen-containing group (predominantly carboxyl) in the three-dimensional grapheme being prepared, thus
The wellability for improving material is conducive to contact of the electrolyte with material, reduces ion transfer impedance.
The present invention also provides three-dimensional graphemes prepared by a kind of preparation method according to above-mentioned three-dimensional grapheme.This technology
The distance between three-dimensional grapheme lamella that scheme obtains is up to 200nm, much higher than the lamella distance of ordinary graphite alkene material, material
Expect that specific surface area reaches 457m2g-1.It is the flake graphite being stacked with from this three-dimensional grapheme microscopic appearance known to characterization result
Chip architecture, and there is opening between lamella and lamella.
The present invention also provides super capacitor anodes made of a kind of above-mentioned three-dimensional grapheme of application, utilize three-dimensional grapheme
As active material, nickel foam is as collector, and acetylene black is as conductive agent, and PVDF is as binder.It is made of this material
Carbon negative pole material shows higher specific discharge capacity and preferable circulation conservation rate for supercapacitor, for commercialization production
Carbon anode capacitor provides scheme.
The present invention also provides absorbing materials made of a kind of above-mentioned three-dimensional grapheme of application, and three-dimensional grapheme and paraffin are melted
Change mixing to suppress.The absorbing material has outstanding absorbing property.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. using crystalline flake graphite as raw material, while wave absorbing agent is also used as, in air atmosphere, and using domestic microwave
Furnace is quick, and synthetic surface contains the method for the three-dimensional grapheme of certain functional group at low cost.Stone is mass produced for commercialization
Black alkene provides scheme.
2. the distance between obtained three-dimensional grapheme lamella is up to 200nm, much higher than the lamella of ordinary graphite alkene material
Distance, material specific surface area reach 457m2g-1.It is the piece being stacked with from this three-dimensional grapheme microscopic appearance known to characterization result
Shape graphite chip architecture, and there is opening between lamella and lamella.
3. simplifying preparation condition more in air atmosphere, on the other hand making the three-dimensional being prepared
Also remain part oxygen-containing group (predominantly carboxyl) in graphene, to improve the wellability of material, be conducive to electrolyte with
The contact of material reduces ion transfer impedance.
4. the carbon negative pole material made of three-dimensional grapheme material of the invention shows higher for supercapacitor
Specific discharge capacity and preferably circulation conservation rate are to improve energy density of the carbon negative pole material for supercapacitor
Commercialization production Carbon anode capacitor provides scheme.
5. the absorbing material of three-dimensional grapheme material production provided by the invention has outstanding absorbing property.
Detailed description of the invention
Examples of the present invention will be described by way of reference to the accompanying drawings, in which:
Fig. 1 is the electron-microscope scanning figure (SEM figure) of three-dimensional grapheme in embodiment 1；
Fig. 2 is the electron-microscope scanning figure (SEM figure) in another site of three-dimensional grapheme in embodiment 1；
Fig. 3 is the electron binding energy figure of three-dimensional grapheme in embodiment 1；
Fig. 4, which is that carbon negative pole material made of three-dimensional grapheme is different in three-electrode system in embodiment 1, sweeps following under speed
Ring volt figure；
Fig. 5 be in embodiment 1 carbon negative pole material made of three-dimensional grapheme in three-electrode system under different current densities
Charge and discharge electrograph；
Fig. 6 be in embodiment 1 carbon negative pole material made of three-dimensional grapheme in three-electrode system under 10A/g current density
Long circulating charge and discharge electrograph；
Fig. 7 is the geomery schematic diagram of absorbing material compacting cyclization in embodiment 1；
It is 2 to arrive that Fig. 8, which is that three-dimensional grapheme is used as absorbing material to be pressed into after the ring of different-thickness in frequency in embodiment 1,
Electromagnetic wave absorption performance figure under 18GHz；
Fig. 9 is the Raman map of three-dimensional grapheme and graphene oxide in embodiment 1；
Figure 10 is the XRD diagram with graphene oxide of three-dimensional grapheme in embodiment 1；
Figure 11 is the transmission electron microscope picture (TEM) and selective electron diffraction figure of three-dimensional grapheme in embodiment 1；
Figure 12 is the BET and pore-size distribution statistical chart of three-dimensional grapheme in embodiment 1；
Figure 13 is the EDS figure of graphene oxide in embodiment 1；
Figure 14 is the EDS figure of three-dimensional grapheme in embodiment 1.
Figure 15 is the infared spectrum of three-dimensional grapheme and graphene oxide in embodiment 1.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
It elaborates below with reference to Fig. 1 to Figure 15 to the present invention.
The present invention provides a kind of using crystalline flake graphite as wave absorbing agent, and under room temperature environment, in air atmosphere, utilization is micro-
Wave heating (using household microwave oven as reactor), the method that low-power quickly produces three-dimensional grapheme, and by the method
The three-dimensional grapheme material of preparation is used for the absorbing material of double electric layers supercapacitor and electromagnetic wave.This three-dimensional grapheme material
The distance between lamella reaches 457m up to 200nm, material specific surface area2g-1.Its step are as follows:
Step 1: graphene oxide is prepared using improved hummers method: measuring the concentrated sulfuric acid and concentrated phosphoric acid, volume ratio
Example be 9:1 (180ml:20ml), 2 to 4 grams of crystalline flake graphite, 7 to 10 grams of potassium permanganate, hydrogen peroxide concentration 20%-30%.
Step 2: the concentrated sulfuric acid measured and concentrated phosphoric acid are successively poured slowly into clean three-neck flask by room-temperature water bath,
And it is stirred continuously.Then crystalline flake graphite and potassium permanganate are successively slowly added to.The mixing liquid in three-neck flask is taken the photograph 50 again
Family name's degree continued mechanical stirs 12 to 14 hours.The generation of brown liquid can be observed at the end of reaction.
Step 3: above-mentioned brown liquid is poured slowly into 200 into 300ml deionized water by cleaning separation graphene oxide,
Guarantee that it does not send bumping, and is stirred continuously.Hydrogen peroxide is added dropwise until mixed liquor after being reduced to room temperature in liquid temperature to be mixed
Become golden yellow.Continuously use deionized water eccentric cleaning to neutrality this golden yellow solution again.It is centrifugated out yellow mercury oxide ,-
35 to -40 degrees Celsius of freezings are dried under reduced pressure a couple of days and obtain graphene oxide.
Step 4: microwave removes graphene oxide, weighs graphene oxide and crystalline flake graphite, mass ratio arrives for 30:1
60:1.It is uniformly mixed in suprasil crucible, then silica crucible (not salable) is transferred in household microwave oven 400 watts extremely
It is irradiated 10-30 seconds under 600 watts of power.Observe that the fluffy three-dimensional grapheme powder of a large amount of black lightweights is raw after reaction
At.
Step 5: the preparation of supercapacitor carbon negative pole material: according to reduced graphene, PVDF and acetylene black mass ratio 8:
1:1 is fabricated to mixed slurry, and nickel foam is collector, and electro-chemical test is carried out in the KOH of 6mol/L.
Step 6: the preparation of wave absorbing agent: weighing the three-dimensional grapheme material and paraffin of mass ratio 5:85 to 11:89,80 to
90 degrees Celsius of thawings, are uniformly mixed, and continue the cyclization of compacting in 20 to 30 seconds in the case where pressure is 2MPa.
Below by specific embodiment, the following further describes the technical solution of the present invention.
Embodiment 1:
Step 1: production graphene oxide measures 180 milliliters of concentrated sulfuric acids in advance and 20 milliliters of concentrated phosphoric acids weighs 3 grams of squamas again
Piece graphite.
Step 2: room-temperature water bath.The concentrated sulfuric acid, concentrated phosphoric acid and crystalline flake graphite are slowly successively poured into three necks for cleaning drying
In flask.Then weighed potassium permanganate (9 grams) are added 4 times several times, and keep bath temperature at 50 degrees Celsius, machinery stirs
It mixes 12 hours.The mixed solution containing graphene oxide is prepared.
Step 3: after reacting end and being cooled to room temperature, mixing liquid is slowly poured into ready 200ml in advance and is gone
It in ionized water, continues waiting for solution and is cooled to room temperature, hydrogen peroxide is added dropwise using rubber head dropper at this time, until mixed solution becomes
For golden yellow, there is no until bubble generation.
Step 4: the separation of graphene oxide: the golden yellow mixed liquor that step 3 obtains repeatedly is centrifuged (8000r/min,
It is neutral for 8min) and repeatedly being cleaned with deionized water to pH, obtains yellow mercury oxide.Yellow mercury oxide is rapidly frozen into ice cube again,
It is put into freeze drier, freezing is dried under reduced pressure a couple of days and obtains dry graphene oxide.
Step 5: microwave removes graphene oxide, weighs 20 milligrams of crystalline flake graphites as wave absorbing agent.60 milligrams are weighed again to arrive
1 gram of graphene oxide.The two is uniformly mixed and is placed in transparent silica crucible (not salable).Silica crucible is transferred to again
In household microwave oven, microwave power be adjusted in low fiery (500w) or moderate heat (600w).Time is kept for 15 seconds.It passes through scanning electricity
There is opening between lamella and lamella it can be found that its microscopic appearance is the flake graphite chip architecture being stacked in mirror figure,
Distance is about 200nm between its lamella.
Step 6: the preparation of carbon negative pole material, according to reduced graphene, PVDF is fabricated to acetylene black mass ratio 8:1:1
Mixed slurry, nickel foam are collector, and mixed slurry is equably applied in foam nickel base, and 80 degrees Celsius of dryings 13 are small
When, the load quality of active material is about 2.5 ± 0.5mg/cm on each working electrode-2.And electricity is carried out in the KOH of 6mol/L
Test chemical.Using to instrument include Shanghai occasion electrochemical workstation CHI660D and blue electrical measurement test system.In current density
When for 0.5A/g, specific discharge capacity is up to (215F/g), and in 10A/g, is also able to maintain the specific capacitance of 170F/g.Show
The three-dimensional graphene oxide as made from microwave removing has preferable multiplying power retentivity.Under the current density of 10A/g,
After 20000 circulations, capacity retention ratio 52% illustrates using the microstructure of graphene made from this method in charge and discharge
Have in electric process and keeps well.
Step 7: three-dimensional grapheme material and paraffin, mass ratio 8:92 are weighed respectively.It is filled under being 80 degrees Celsius in temperature
Divide mixing.Keep compacting in 30 seconds cyclic under pressure 2MPa.Its annulus outer diameter is 6.96 millimeters, and internal diameter is 3.04 millimeters, in frequency
It carries out inhaling wave test under being 2 to 18GHz.The result shows that as shown in figure 8, with a thickness of 1.5mm, when frequency is 14.5 to 18GHz
There is the up to reflection loss of -10dB.
Embodiment 2:
Step 1: production graphene oxide measures 180 milliliters of concentrated sulfuric acids in advance and 20 milliliters of concentrated phosphoric acids weighs 3 grams of squamas again
Piece graphite.
Step 2: room-temperature water bath.The concentrated sulfuric acid, concentrated phosphoric acid and crystalline flake graphite are slowly successively poured into three necks for cleaning drying
In flask.Then weighed potassium permanganate (9 grams) are added 6 times several times, and keep bath temperature at 50 degrees Celsius, machinery stirs
It mixes 14 hours.The mixed solution containing graphene oxide is prepared.
Step 3: after reacting end and being cooled to room temperature, mixing liquid is slowly poured into ready 200ml in advance and is gone
It in ionized water, continues waiting for solution and is cooled to room temperature, hydrogen peroxide is added dropwise using rubber head dropper at this time, until mixed solution becomes
For golden yellow, there is no until bubble generation.
Step 4: the separation of graphene oxide, the golden yellow mixed liquor that step 3 obtains repeatedly is centrifuged (8000r/min,
8min) and being cleaned repeatedly with deionized water to pH is that neutrality will obtain yellow mercury oxide.It is rapidly frozen into ice cube again, is put into cold
In lyophilizer, freezing is dried under reduced pressure a couple of days and obtains dry graphene oxide.
Step 5: microwave removes graphene oxide, weighs 20 milligrams of crystalline flake graphites as wave absorbing agent.1 gram of oxygen is weighed again
Graphite alkene.The two is uniformly mixed and is placed in transparent silica crucible (not salable).It is micro- that silica crucible is transferred to household again
In wave furnace, microwave power is adjusted to moderate heat (600w).Time is kept for 10 seconds.
Step 6: three-dimensional grapheme material and paraffin, mass ratio 9:91 are weighed respectively.It is filled under being 80 degrees Celsius in temperature
Divide mixing.Keep compacting in 30 seconds cyclic under pressure 2MPa.Its annulus outer diameter is 6.96 millimeters, and internal diameter is 3.04 millimeters, in frequency
It carries out inhaling wave test under being 2 to 18GHz.The result shows that with a thickness of 4.5mm, frequency have when being 15 to 18GHz up to -10 arrive -
The reflection loss of 11dB.
The specific embodiment of the application above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
The limitation to the application protection scope therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, under the premise of not departing from technical scheme design, various modifications and improvements can be made, these belong to this
The protection scope of application.
Claims (9)
1. a kind of preparation method of three-dimensional grapheme, which comprises the steps of:
[1] graphene oxide is prepared；
[2] graphene oxide is uniformly mixed with crystalline flake graphite, using crystalline flake graphite as auxiliary absorbing material, utilizes microwave
Heating obtains the fluffy three-dimensional grapheme powder of black lightweight.
2. a kind of preparation method of three-dimensional grapheme described in accordance with the claim 1, which is characterized in that step [1] described preparation
The method for obtaining graphene oxide includes the following steps:
[1-1] utilizes room-temperature water bath, and the concentrated sulfuric acid and concentrated phosphoric acid are mixed in proportion, are then successively slowly added to crystalline flake graphite
With potassium permanganate, obtained mixing liquid is persistently stirred at the reaction temperatures, reaction terminates to obtain brown liquid；
[1-2] neutralizes remaining oxidant in the brown liquid using hydrogen peroxide and obtains golden solution, by golden solution
PH is adjusted to acidity, is centrifugally separating to obtain yellow mercury oxide；
Yellow mercury oxide freezing is dried under reduced pressure a couple of days and obtains graphene oxide by [1-3].
3. a kind of preparation method of three-dimensional grapheme according to claim 2, it is characterised in that: in the step [1-1]
The temperature being stirred to react is 40-60 DEG C, and the time of reaction is 12-14 hours.
4. a kind of preparation method of three-dimensional grapheme described in accordance with the claim 1, it is characterised in that: the graphene oxide with
The mixed proportion of crystalline flake graphite is mass ratio 30:1 to 60:1.
5. a kind of preparation method of three-dimensional grapheme described in accordance with the claim 1, it is characterised in that: the function of the microwave heating
Rate is 400 to 600W, and the time of microwave radiation is 10 to 30 seconds.
6. a kind of preparation method of three-dimensional grapheme described in accordance with the claim 1, it is characterised in that: the microwave heating is in sky
It is carried out in gas atmosphere.
7. three-dimensional grapheme prepared by a kind of preparation method of three-dimensional grapheme described in accordance with the claim 1.
8. a kind of apply super capacitor anode made of three-dimensional grapheme according to claim 7, it is characterised in that: benefit
Use three-dimensional grapheme as active material, nickel foam is as collector, and acetylene black is as conductive agent, and PVDF is as binder.
9. a kind of apply absorbing material made of three-dimensional grapheme according to claim 7, it is characterised in that: by three-dimensional stone
Black alkene is suppressed with paraffin melting mix.
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| CN111453730A (en) * | 2020-04-10 | 2020-07-28 | 电子科技大学 | Preparation method of biomass derived carbon nanosheet and supercapacitor thereof |
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