CN108373151A - A kind of preparation method of more fold hollow graphene microballoons - Google Patents
A kind of preparation method of more fold hollow graphene microballoons Download PDFInfo
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- 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
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- C01B2204/00—Structure or properties of graphene
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Abstract
The present invention provides a kind of preparation methods of more fold hollow graphene microballoons.The preparation method of the present invention includes the following steps：1) graphene oxide is prepared by Hummers improved methods using graphite as raw material, prepares graphene oxide water solution；2) graphene oxide water solution ultrasonic disperse is uniform；3) finely dispersed graphene oxide water solution is instilled dropwise in cryogenic liquid, obtains graphene oxide ice hockey；4) freeze-drying of graphene oxide ice hockey, centrifugation are purified, obtains more fold hollow graphene microballoons.The preparation method of the more fold hollow graphene microballoons of the present invention, operating procedure is simple, it is efficient, it is not necessarily to special or complex reaction equipment, it is at low cost, without additional additive, it is not required to pyroreaction, it is 0.5~10 μm that graphene oxide microballoon obtained, which has hollow structure, grain size, and surface is distributed a large amount of folds, is suitable for the large-scale industrial production of more fold hollow graphene microballoons.
Description
Technical field
The invention belongs to the preparing technical field of graphene oxide microballoon, it is related to a kind of more fold graphene oxide microballoons
Preparation method more particularly to a kind of preparation method of more fold hollow graphene microballoons.
Background technology
Since 2004 report graphene for the first time, because of its extremely excellent physical and chemical performance, constantly cause to come from physics
The continuous concern of each area research persons such as, chemistry, material science or even biomedicine.Graphene is a kind of with two-dimensional structure
Crystal, sp is passed through by single layer of carbon atom2Hydridization forms the two-dimensional structure with six side's honeycomb crystal lattices and constitutes, just because of
This unique structure make its with high intensity and hardness, huge specific surface area, excellent heat transfer, strong electric conductivity and
High carrier mobility and good optical characteristics, can be widely used in every field.Graphene oxide is chemical method
Prepare an important presoma of graphene.The surface of graphene oxide has a certain amount of carboxyl, carbonyl, epoxy group and hydroxyl
Base functional group causes graphene oxide layer structure to be changed and defect occur, to show the graphene with homogeneous structural
Different physical and chemical performances.Graphene oxide with functional group can be uniformly dispersed in many solvents, can be good at applying
In fields such as catalysis, dispersing aiies.
But involved graphene oxide thumping majority is all flat sheet (flat sheet) knot in the prior art
Structure, the structure are features possessed by exemplary two dimensional material.However the flat sheet structure of two-dimensional material makes its specific surface area
It is smaller compared with zero dimension material and one-dimensional material, limit its further applying in fields such as catalysis, energy storage, microelectronics.
Specific surface area relative to flat sheet structure, the graphene oxide with surface folding structure improves significantly, therefore, surface pleat
Wrinkleization also becomes current one of research hotspot.
CN105540573A discloses a kind of more fold dry state graphene oxide microballoons of highly dissoluble, the graphene oxide
Microballoon is formed by the single-layer graphene oxide piece gauffer that size is 1~200 μm, and microsphere diameter is 500nm~30 μm, and density is
0.08~0.2g/cm3, specific surface area is 10~2300m2/ g, carbon-to-oxygen ratio are 1.8~3, and it is more which also discloses highly dissoluble
The preparation method of fold dry state graphene oxide microballoon, includes the following steps：(1) organic solvent diluting Hummers methods are used to prepare
Obtained graphene oxide dispersion；The organic solvent and the mass ratio of graphene oxide dispersion are 1~50:1；(2) will
Dispersion liquid after step (1) dilution, graphene oxide microballoon is obtained by the method for atomization drying.The present invention by oxidation stone
Organic solvent is added in black alkene dispersion liquid and forms mixed dispersion liquid, then to have obtained the more folds of highly dissoluble dry for the method for atomization drying
State graphene oxide microballoon, but this method needs certain temperature that solvent is made to volatilize, and manufacturing cost is relatively high.
There is a kind of method for the graphene oxide microballoon preparing surface folding in the prior art, is to utilize graphene oxide
Self assembly is stacked into complicated polyhedral structure, and to form fold, still, the component for the reaction that this preparation method is related to is multiple
It is miscellaneous, it is easy to introduce impurity in the fabulous graphene oxide microballoon of adsorptivity.
In conclusion provide it is a kind of it is simple for process, can be prepared in surface folding without etching agent and pyroreaction
The method of empty graphene oxide microballoon is necessary.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of more fold hollow graphene microballoons
Preparation method is not necessarily to special or complex reaction equipment without additional additive, at low cost, is not required to pyroreaction, oxidation obtained
Graphene microballoon has hollow structure, and grain size is 0.5~10 μm, and a large amount of fold is distributed in surface.
For this purpose, the present invention uses following technical scheme：
A kind of preparation method of more fold hollow graphene microballoons, the preparation method include the following steps：
1) using graphite as raw material, graphene oxide is prepared by Hummers improved methods, graphene oxide obtained is prepared
Graphene oxide water solution；
2) by graphene oxide water solution ultrasonic disperse made from step 1), it is water-soluble to obtain finely dispersed graphene oxide
Liquid；
3) finely dispersed graphene oxide water solution made from step 2) is instilled dropwise in cryogenic liquid, is aoxidized
Graphene ice hockey；
4) the graphene oxide ice hockey that step 3) obtains is freeze-dried, centrifuges purification, obtained in more folds
Empty graphene oxide microballoon.
The present invention prepares graphene oxide by Hummers improved methods, prepares graphene oxide water solution through ultrasonic disperse
After obtain finely dispersed graphene oxide water solution, finely dispersed graphene oxide water solution is instilled into cryogenic liquid dropwise
In obtain graphene oxide ice hockey, graphene oxide ice hockey is freeze-dried, purification is centrifuged and obtains more fold hollows
Graphene microballoon.It is not introduced into other additives in this method, etching agent is not added and avoids introducing impurity, solvent is not added i.e.
It avoids pyroreaction solvent volatilizees, by cryogenic liquid and is freeze-dried to obtain to surface a large amount of fold and tool is distributed with
There are more fold hollow graphene microballoons of hollow structure, simpler, production efficiency higher in technique, without special or multiple
Miscellaneous consersion unit, cost is lower, is suitable for the large-scale industrial production of more fold hollow graphene microballoons.
In step 3), the cryogenic liquid is liquid nitrogen or dry ice.
In step 3), the volume for often dripping the finely dispersed graphene oxide water solution is 0.01~0.1mL, such as often
Drip the finely dispersed graphene oxide water solution volume be 0.01mL, 0.02mL, 0.03mL, 0.04mL, 0.05mL,
0.06mL、0.07mL、0.08mL、0.09mL、0.1mL.If graphene oxide water solution is not to instill in cryogenic liquid dropwise,
It then cannot get spherical graphene oxide ice hockey, graphene oxide can be made broken the reason of stress cracking after freeze-dried
It splits, complete graphene oxide microballoon cannot be formed.
In step 4), the freeze-drying is vacuum freeze drying；Preferably, the temperature of the freeze-drying be -40~-
60 DEG C, such as the temperature of freeze-drying is -40 DEG C, -45 DEG C, -50 DEG C, -55 DEG C, -60 DEG C；The time of the freeze-drying is 12
~48h, for example, freeze-drying time be 12h, 15h, 16h, 18h, 20h, for 24 hours, 25h, 30h, 35h, 36h, 40h, 48h.
In step 4), the technique of the centrifugation purification is：Ice hockey after freeze-drying is scattered in solvent, vortex oscillation
After centrifuge, take supernatant dry after, obtain more fold hollow graphene microballoons；
Preferably, the solvent is one kind in ethyl alcohol, acetone；
Preferably, the rotating speed of the centrifugation is 800~1500r/min, such as the rotating speed of the centrifugation is
800r/min、900r/min、1000r/min、1100r/min、1200r/min、1300r/min、1400r/min、1500r/
min；The time of the centrifugation be 3~8min, such as centrifugation time be 3min, 4min, 5min, 6min, 7min,
8min。
Graphene oxide (abbreviation GO) is generally aoxidized through strong acid by graphite and is obtained.There are mainly three types of the sides for preparing graphite oxide
Method：Brodie methods, Staudenmaier methods and Hummers methods.Wherein, the timeliness of the preparation process of Hummers methods is relatively
It is also relatively safer in good and preparation process, it is current most common one kind.Hummers methods use the potassium permanganate in the concentrated sulfuric acid
With powdered graphite is oxidized react after, obtain brown edge have derivative carboxylic acid group and in the plane be mainly phenolic hydroxyl group and
The graphite flake of epoxy group, it is graphene oxide that this graphene layers can be vigorously stirred stripping through ultrasound or high shear, and
Stable, sundown single-layer graphene oxide suspension is formed in water.
The application prepares graphene oxide using Hummers improved methods, of the invention relative to conventional Hummers methods
Hummers improved methods are than the former less impurity and reduce the NO generated in reaction2、N2O4Equal toxic gases.
In step 1), the Hummers improved methods include the following steps：It is prepared and is mixed as raw material using the concentrated sulfuric acid and concentrated phosphoric acid
Acid solution prepares graphene oxide using graphite, mixed acid solution, potassium permanganate as raw material.
Preferably, the volume ratio of the concentrated sulfuric acid and concentrated phosphoric acid is (8~10) in the mixed acid solution:1, for example, the concentrated sulfuric acid and
The volume ratio of concentrated phosphoric acid is 8:1、9:1、10:1, preferably 9:1；The graphite, mixed acid solution, potassium permanganate mass ratio be
1:(180~185):(5~8), preferably 1:182.5:6.
The preparation process of graphene oxide described in step 1) is：
A) by H2SO4And H3PO4It is by volume (8~10):1 configuration mixed acid solution；
B) flaky graphite is taken to be mixed in single-necked flask with mixed acid solution, magnetic agitation keeps its mixing equal at room temperature
It is even；By the single-necked flask with mixed liquor as under ice-water bath, and it is slowly added to potassium permanganate thereto, magnetic agitation reaction 1
~2h, wherein the mass ratio of the graphite, mixed acid solution, potassium permanganate is 1:(180~185):(5~8)；
C) single-necked flask is placed in medium temperature thermostat water bath after the completion of reacting and is stirred, room temperature is cooled to, it then will reaction
Liquid is poured in the ice water containing 100mL, and hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly；Reaction
After complete, reaction product is used into dilute hydrochloric acid, ethyl alcohol, water centrifuge washing respectively, until pH is neutrality, sediment is freeze-dried, is obtained
To the graphene oxide.
Preferably, the preparation process of graphene oxide described in step 1) is：
A) by H2SO4And H3PO4It is by volume (8~10):1 configuration mixed acid solution；
B) flaky graphite is taken to be mixed in single-necked flask with mixed acid solution, magnetic agitation keeps its mixing equal at room temperature
It is even；By the single-necked flask with mixed liquor as under ice-water bath, and it is slowly added to potassium permanganate thereto, magnetic agitation reaction 1
~2h, wherein the mass ratio of the graphite, mixed acid solution, potassium permanganate is 1:(180~185):(5~8)；
C) single-necked flask is placed in medium temperature thermostat water bath after the completion of reacting and is stirred, room temperature is cooled to, it then will reaction
Liquid is poured in the ice water containing 100mL, and hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly；Reaction
After complete, reaction product is used into dilute hydrochloric acid, ethyl alcohol, water centrifuge washing respectively, until pH is neutrality, sediment is freeze-dried, is obtained
To the graphene oxide.
In step 1), the molar concentration of the graphene oxide water solution is 0.001~20mg/mL；The graphite oxide
The molar concentration of aqueous solution determines the size in hole, if the molar concentration of graphene oxide water solution is less than 0.001mg/mL,
Then cause aperture too big or hole rupture and do not become incomplete hole, if the molar concentration of graphene oxide water solution is more than
20mg/mL then causes graphene oxide to occur to reunite or do not become hole；Therefore rubbing for graphene oxide water solution need to rationally be controlled
Your concentration, for example, the molar concentration of the graphene oxide water solution is 0.001mg/mL, 0.005mg/mL, 0.01mg/mL,
0.02mg/mL、0.05mg/mL、0.08mg/mL、0.1mg/mL、0.2mg/mL、0.3mg/mL、0.4mg/mL、0.5mg/mL、
0.6mg/mL、0.7mg/mL、0.8mg/mL、0.9mg/mL、1mg/mL、2mg/mL、3mg/mL、4mg/mL、5mg/mL、6mg/
mL、7mg/mL、8mg/mL、9mg/mL、10mg/mL、11mg/mL、12mg/mL、13mg/mL、14mg/mL、15mg/mL、16mg/
mL、17mg/mL、18mg/mL、19mg/mL、20mg/mL。
Preferably, the molar concentration of the graphene oxide water solution is 1~10mg/mL.
In step 2), the purpose of ultrasonic disperse is to avoid the reunion of graphene oxide, convenient for step 3) and step 4) at
Hole, the frequency of the ultrasonic disperse are 15~25KHz, for example, the frequency of ultrasonic disperse is 15KHz, 16KHz, 17KHz, 18KHz,
19KHz、20KHz、21KHz、22KHz、23KHz、24KHz、25KHz；The time of the ultrasonic disperse is 150~200min, example
If the time of ultrasonic disperse is 150min, 160min, 170min, 180min, 190min, 200min.
The grain size of more fold hollow graphene microballoons is 0.5~10 μm, such as more fold hollow graphite
The grain size of alkene microballoon be 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9
μm、10μm。
As the preferred embodiment of the present invention, a kind of preparation method of more fold hollow graphene microballoons includes following step
Suddenly：
1) mixed acid solution is prepared as raw material using the concentrated sulfuric acid and concentrated phosphoric acid, is original with graphite, mixed acid solution, potassium permanganate
Material prepares graphene oxide, wherein the graphite, mixed acid solution, potassium permanganate mass ratio be 1:182.5:6, it will be made
Graphene oxide be configured to molar concentration be 0.001~20mg/mL graphene oxide water solution；
2) by graphene oxide water solution made from step 1) under the frequency of 15~25KHz ultrasonic disperse 150~
200min obtains finely dispersed graphene oxide water solution；
3) finely dispersed graphene oxide water solution made from step 2) is instilled dropwise in cryogenic liquid, is aoxidized
Graphene ice hockey, wherein the volume for often dripping the finely dispersed graphene oxide water solution is 0.01~0.1mL；
4) 12~48h of freeze-drying will be carried out at a temperature of -40~-60 DEG C of graphene oxide ice hockey that step 3) obtains,
Ice hockey after freeze-drying is scattered in solvent, the rotating speed of 800~1500r/min centrifuges 3~8min after vortex oscillation,
After taking supernatant to dry, more fold hollow graphene microballoons are obtained.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of more fold hollow graphene microballoons of the invention, without additional additive, without any
Etching agent is to avoid introducing impurity；Be not required to pyroreaction, solvent is not added avoids pyroreaction and solvent volatilizees, pass through by
Finely dispersed graphene oxide water solution instills cryogenic liquid dropwise, and freeze-drying can make graphene oxide microballoon obtained
With hollow structure, and a large amount of fold, and the grain size of more fold hollow graphene microballoons obtained is distributed in surface
It is 0.5~10 μm.
(2) preparation method of more fold hollow graphene microballoons of the invention, operating procedure is simple, preparation efficiency
Height is not necessarily to special or complex reaction equipment, at low cost, and the large-scale industry for being suitable for more fold hollow graphene microballoons is given birth to
Production.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the graphene oxide that the embodiment of the present invention 1 is selected；
Fig. 2 is the scanning electron microscope (SEM) photograph of more fold hollow graphene microballoons prepared by the embodiment of the present invention 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of the sample prepared after the embodiment of the present invention 2 is freeze-dried；
Fig. 4 is the scanning electron microscope (SEM) photograph of the sample prepared after the embodiment of the present invention 3 is freeze-dried；
Fig. 5 is more fold hollow graphene microballoons scanning electricity that the embodiment of the present invention 4 is prepared after centrifugation
Mirror figure.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.
Unless specific instructions, various raw materials of the invention are commercially available buys, or is prepared according to the conventional method of this field
It obtains.
Embodiment 1
Graphene oxide (as shown in Figure 1) prepared by Hummers improved methods is selected to configure graphene oxide water solution.It takes
10mg graphene oxides are added with 10mL deionized waters in conical flask, and magnetic agitation 1h is to be configured to the oxygen of 1mg/mL at room temperature
Graphite aqueous solution.Then tentatively mixed graphene oxide water solution cell pulverization instrument will be selected as under ice-water bath
Carry out ultrasonic disperse 3h.Then the graphene oxide water solution of mixing is instilled with dropper in the small test tube equipped with liquid nitrogen dropwise,
Often the volume of drop graphene oxide water solution is 0.02mL, and graphene oxide water solution can be rapidly cooled solidification, and to form brown small
Ice hockey after freeze-drying is scattered in solvent, to carrying out freeze-drying 48h at a temperature of its -40 DEG C after vortex oscillation by ball
The rotating speed of 800r/min centrifuges 8min, to get to the hollow graphene microballoon of more folds after taking supernatant to dry, this
The scanning electron microscope (SEM) photograph of graphene oxide microballoon prepared by embodiment is as shown in Figure 2.As seen from Figure 2, made from the present embodiment
Graphene oxide microsphere surface carries many folds.
Embodiment 2
30mg graphene oxides are taken to be added in conical flask with 10mL deionized waters, magnetic agitation 1h is to be configured at room temperature
The graphene oxide water solution of 3mg/mL.Then it will tentatively mixed graphene oxide water solution be selected as under ice-water bath
Cell pulverization instrument carries out ultrasonic disperse 3h.Then the graphene oxide water solution of mixing is instilled dropwise with dropper equipped with liquid nitrogen
In small test tube, the volume for often dripping graphene oxide water solution is 0.05mL, and graphene oxide water solution can be rapidly cooled solidification
Brown bead is formed, to being freeze-dried for 24 hours at a temperature of its -50 DEG C, the sample of preparation after the present embodiment is freeze-dried
Scanning electron microscope (SEM) photograph it is as shown in Figure 3.As seen from Figure 3, after freeze-dried, the graphene oxide hollow microsphere of formation adsorbs
In the surface with porose porous oxidation graphene, i.e., at this point, containing porous graphene oxide sheet in the sample prepared simultaneously
Material and graphene oxide microballoon with fold.Ice hockey after freeze-drying is scattered in solvent, 1000r/ after vortex oscillation
The rotating speed of min centrifuges 5min, and after taking supernatant to dry, the hollow graphene microballoon of more folds can be obtained.
Embodiment 3
50mg graphene oxides are taken to be added in conical flask with 10mL deionized waters, magnetic agitation 1h is to be configured at room temperature
The graphene oxide water solution of 5mg/mL.Then it will tentatively mixed graphene oxide water solution be selected as under ice-water bath
Cell pulverization instrument carries out ultrasonic disperse 3h.Then the graphene oxide water solution of mixing is instilled dropwise with dropper equipped with liquid nitrogen
In small test tube, the volume for often dripping graphene oxide water solution is 0.03mL, and graphene oxide water solution can be rapidly cooled solidification
Brown bead is formed, to carrying out freeze-drying 12h at a temperature of its -60 DEG C, by the scanning electricity of the ice hockey sample after freeze-drying
Mirror figure is as shown in Figure 4, it can be seen that the surface of graphene oxide microballoon carries many folds in sample.
Embodiment 4
Sample after embodiment 3 is freeze-dried is with 1:10 ratio is scattered in absolute ethyl alcohol；To dispersion liquid with
1000rpm/min speed is centrifuged, and can purify the graphene oxide microballoon in lyophilized products；Take the supernatant after centrifugation
Graphene oxide shown in fig. 5 can be observed on silicon chip and being positioned in 45 DEG C of baking oven dry in drop under surface sweeping Electronic Speculum
The surface of microballoon carries fold, and has hollow structure.
Comparative example
50mg graphene oxides are taken to be added in conical flask with 10mL deionized waters, magnetic agitation 1h is to be configured at room temperature
The graphene oxide water solution of 5mg/mL.Then it will tentatively mixed graphene oxide water solution be selected as under ice-water bath
Cell pulverization instrument carries out ultrasonic disperse 3h.Then the graphene oxide water solution dropper of 0.5mL mixings is once instilled and is equipped with
In the small test tube of liquid nitrogen, graphene oxide water solution cooling is dry by freezing to carrying out freeze-drying 12h at a temperature of its -60 DEG C
The scanning of sample after dry is unable to get complete graphene oxide microballoon.
It is anti-to be not required to high temperature without additional additive for the preparation method of more fold hollow graphene microballoons of the present invention
It answers, so that graphene oxide microballoon obtained is reached hollow structure, and surface is distributed a large amount of fold, and more pleats obtained
The grain size of wrinkle hollow graphene microballoon is 0.5~10 μm.The preparation of more fold hollow graphene microballoons of the present invention
Method, operating procedure is simple, and preparation efficiency is high, is not necessarily to special or complex reaction equipment, at low cost, is suitable for more fold hollows
The large-scale industrial production of graphene microballoon.
Above example only is used for illustrating the method detailed of the present invention, and the invention is not limited in above-mentioned method detaileds, i.e.,
Do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the present invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection of concrete mode
Deng all falling within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of preparation method of more fold hollow graphene microballoons, which is characterized in that the preparation method includes as follows
Step：
1) using graphite as raw material, graphene oxide is prepared by Hummers improved methods, graphene oxide obtained is matched into oxygenerating
Graphene aqueous solution；
2) by graphene oxide water solution ultrasonic disperse made from step 1), finely dispersed graphene oxide water solution is obtained；
3) finely dispersed graphene oxide water solution made from step 2) is instilled dropwise in cryogenic liquid, obtains graphite oxide
Alkene ice hockey；
4) the graphene oxide ice hockey that step 3) obtains is freeze-dried, centrifuges purification, obtain the hollow oxygen of more folds
Graphite alkene microballoon.
2. preparation method according to claim 1, which is characterized in that in step 3), the cryogenic liquid is liquid nitrogen or does
Ice；
Preferably, the volume for often dripping the finely dispersed graphene oxide water solution is 0.01~0.1mL.
3. preparation method according to claim 1 or 2, which is characterized in that in step 4), the freeze-drying is that vacuum is cold
It is lyophilized dry；
Preferably, the temperature of the freeze-drying is -40~-60 DEG C, and the time of the freeze-drying is 12~48h.
4. according to the preparation method described in one of claim 1-3, which is characterized in that in step 1), the Hummers improved methods
Include the following steps：Mixed acid solution is prepared as raw material using the concentrated sulfuric acid and concentrated phosphoric acid, with graphite, mixed acid solution, potassium permanganate
Graphene oxide is prepared for raw material.
5. preparation method according to claim 4, which is characterized in that the concentrated sulfuric acid and concentrated phosphoric acid in the mixed acid solution
Volume ratio is (8~10):1, preferably 9:1；
Preferably, the graphite, mixed acid solution, potassium permanganate mass ratio be 1:(180~185):(5~8), preferably 1:
182.5:6。
6. preparation method according to claim 4 or 5, which is characterized in that the preparation of graphene oxide described in step 1)
Process is：
A) by H2SO4And H3PO4It is by volume (8~10):1 configuration mixed acid solution；
B) flaky graphite is taken to be mixed in single-necked flask with mixed acid solution, magnetic agitation makes it be uniformly mixed at room temperature；It will
Single-necked flask with mixed liquor is slowly added to potassium permanganate as under ice-water bath thereto, and magnetic agitation reacts 1~2h,
The wherein described graphite, mixed acid solution, potassium permanganate mass ratio be 1:(180~185):(5~8)；
C) single-necked flask is placed in medium temperature thermostat water bath after the completion of reacting and is stirred, room temperature is cooled to, then falls reaction solution
In the ice water containing 100mL, hydrogen peroxide is added dropwise dropwise thereto until solution becomes glassy yellow after stirring evenly；It has reacted
Afterwards, reaction product is used into dilute hydrochloric acid, ethyl alcohol, water centrifuge washing respectively, until pH is neutrality, sediment is freeze-dried, is obtained
The graphene oxide.
7. according to claim 1-6 any one of them preparation methods, which is characterized in that in step 1), the graphene oxide
The molar concentration of aqueous solution is 0.001~20mg/mL；
Preferably, the molar concentration of the graphene oxide water solution is 1~10mg/mL.
8. according to claim 1-7 any one of them preparation methods, which is characterized in that in step 2), the ultrasonic disperse
Frequency is 15~25KHz, and the time of the ultrasonic disperse is 150~200min.
9. according to claim 1-8 any one of them preparation methods, which is characterized in that in step 4), the centrifugation purification
Technique is：Ice hockey after freeze-drying is scattered in solvent, is centrifuged after vortex oscillation, after taking supernatant to dry, is obtained
More fold hollow graphene microballoons；
Preferably, the solvent is one kind in ethyl alcohol, acetone；
Preferably, the rotating speed of the centrifugation is 800~1500r/min, and the time of the centrifugation is 1~8min；
Preferably, the grain size of more fold hollow graphene microballoons is 0.5~10 μm.
10. according to claim 1-9 any one of them preparation methods, which is characterized in that the preparation method includes following step
Suddenly：
1) mixed acid solution is prepared as raw material using the concentrated sulfuric acid and concentrated phosphoric acid, using graphite, mixed acid solution, potassium permanganate as raw material system
Standby graphene oxide, wherein the graphite, mixed acid solution, potassium permanganate mass ratio be 1:(180~185):(5~8),
Graphene oxide obtained is configured to the graphene oxide water solution that molar concentration is 0.001~20mg/mL；
2) by graphene oxide water solution made from step 1) under the frequency of 15~25KHz 150~200min of ultrasonic disperse, obtain
To finely dispersed graphene oxide water solution；
3) finely dispersed graphene oxide water solution made from step 2) is instilled dropwise in cryogenic liquid, obtains graphite oxide
Alkene ice hockey, wherein the volume for often dripping the finely dispersed graphene oxide water solution is 0.01~0.1mL；
4) 12~48h of freeze-drying will be carried out at a temperature of -40~-60 DEG C of graphene oxide ice hockey that step 3) obtains, it will be cold
Be lyophilized it is dry after ice hockey be scattered in solvent, after vortex oscillation 800~1500r/min rotating speed centrifuge 1~8min, take
After clear liquid drying, more fold hollow graphene microballoons are obtained.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793143A (en) * | 2018-08-15 | 2018-11-13 | 南通百川新材料有限公司 | A kind of method of graphene industrialized production |
| CN110681549A (en) * | 2019-09-24 | 2020-01-14 | 西安交通大学 | High-heat-conductivity super-hydrophobic flue gas condensation heat exchange surface and preparation method and device thereof |
| CN111393867A (en) * | 2020-04-15 | 2020-07-10 | 安徽扬子地板股份有限公司 | Special composite floor for geothermal and preparation method thereof |
| CN114408911A (en) * | 2022-01-17 | 2022-04-29 | 哈尔滨工业大学 | Preparation method of graphene-based aerogel with ultra-fast light-thermal response |
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| CN110681549A (en) * | 2019-09-24 | 2020-01-14 | 西安交通大学 | High-heat-conductivity super-hydrophobic flue gas condensation heat exchange surface and preparation method and device thereof |
| CN111393867A (en) * | 2020-04-15 | 2020-07-10 | 安徽扬子地板股份有限公司 | Special composite floor for geothermal and preparation method thereof |
| CN114408911A (en) * | 2022-01-17 | 2022-04-29 | 哈尔滨工业大学 | Preparation method of graphene-based aerogel with ultra-fast light-thermal response |
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