CN106379896A - Graphene and preparation method thereof - Google Patents
Graphene and preparation method thereof Download PDFInfo
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- CN106379896A CN106379896A CN201610854015.3A CN201610854015A CN106379896A CN 106379896 A CN106379896 A CN 106379896A CN 201610854015 A CN201610854015 A CN 201610854015A CN 106379896 A CN106379896 A CN 106379896A
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention provides a preparation method of graphene. The preparation method comprises the steps that (1) tubular or flaky carbonaceous raw materials are added into concentrated sulfuric acid; after the uniform stirring in ice bath, potassium permanganate powder is added; the system temperature is controlled to be 20 to 30 DEG C; string is performed for 0.5 to 5h to obtain reaction liquid; (2) the reaction liquid is subjected to shearing dispersion treatment or ultrasonic treatment to obtain prestripped reaction liquid; (3) under the condition without stirring, de-ionized water is added into the prestripped reaction liquid for dilution; filtering is performed; solid obtained after the filtering is washed with hydrochloric acid; filtering and drying are performed to obtain black solid matters; (4) the black solid matters are subjected to high-temperature blasting treatment at 300 to 1200 DEG C to obtain a graphene crude product; (5) the graphene crude product is subjected to high-temperature graphitizing treatment to obtain purified graphene. The preparation method has the advantages that the process is simple; the productivity is high; the complete crystal face structure graphene with few layer number and good electrical conductivity can be obtained; the low-cost industrial production can be easily realized by the method.
Description
Technical field
The present invention relates to field of preparation of graphene, more particularly to a kind of Graphene and preparation method thereof.
Background technology
The two-dimension periodic honeycomb lattice structure that Graphene is made up of carbon hexatomic ring, it is to build other dimension carbon substrate
The elementary cell of material, the unique crystal structure of Graphene makes it have excellent light, electricity, mechanical property, therefore in Flied emission material
The fields such as material, gas sensor, energy storage obtain extensively applies.
The method preparing Graphene at present mainly has oxidation-reduction method, vapour deposition process, mechanical stripping method etc..Wherein, oxygen
Change reducing process wayward, prepared graphenic surface functional group and defect are more, thus leading to its electric conductivity poor；Gas phase is sunk
Area method Preparation equipment is expensive, and technological requirement is strict；The yield of the Graphene of mechanical stripping method preparation is relatively low, is not suitable for giving birth in a large number
Produce.Want to obtain that thickness is uniform, the number of plies is controlled, electric conductivity is good high-quality graphene remains in grapheme material preparation
Significant challenge.
Content of the invention
In view of this, the invention provides a kind of preparation method of Graphene, the method is using high temeperature chemistry oxidation explosion
Method prepares Graphene, and preparation process is simple is easy to operate, and the graphene product pattern obtaining is relatively regular, the number of plies is less, electric conductivity is good
Good, can be widely applied to lithium ion battery industry and electronic product industry.
In a first aspect, the invention provides a kind of preparation method of Graphene, comprising the following steps：
(1) carbon raw material is added in concentrated sulphuric acid, after ice bath stirs, adds potassium permanganate powder so that described height
Potassium manganate powder, by concentrated sulphuric acid submergence, controls system temperature at 20～30 DEG C after described potassium permanganate is added completely into, stirring
0.5～5h, obtains reactant liquor, and wherein, described carbon raw material is in a tubular form or lamellar；
(2) above-mentioned reactant liquor is carried out shear decentralized processing or supersound process, obtain the reactant liquor after prestripping；
(3) in the case of not stirring, it is slowly added to deionized water dilution in the reactant liquor after described prestripping, and mistake
Filter, is washed using hydrochloric acid to gained solid after filtering, and after filtering, being dried, obtains black solid content；
(4) described black solid content is carried out high temperature explosion treatment 20～60s at 300～1200 DEG C, obtain Graphene
Crude product；
(5) described Graphene crude product is carried out high temperature graphitization process, obtain Graphene after purification.
The carbonaceous material adopting tubulose or lamellar in the application, as reaction raw material, is easy to potassium permanganate, concentrated sulphuric acid enters
Enter between the tube wall of carbonaceous material or interlayer, be substantially inserted in prestripping between the layer wall of carbonaceous material, subsequently in high temperature action
Under the conditions of, make full use of the strong oxidizing property of concentrated sulphuric acid and potassium permanganate, make concentrated sulphuric acid between interposed layer wall, potassium permanganate quickly anti-
Gas should being produced, thus playing blast action, so that the layer of carbonaceous material and interlayer is reached and peel off and broken effect, thus being obtained
Graphene.
In step (1), gained reactant liquor is the suspension in blackish green, and predominantly potassium permanganate is dissolved in concentrated sulphuric acid and and carbon
Color after the miscible rear, potassium permanganate of material and concentrated sulphuric acid partial reaction.In step (3), described black solid content is Gao Meng
The prestripping product that sour potassium, concentrated sulphuric acid obtain after being intercalation into layer wall, contains potassium permanganate, concentrated sulphuric acid and the two reaction between its layer of wall
Product.
Preferably, in step (1), it is conductive that described carbon raw material includes CNT, expanded graphite, crystalline flake graphite and KS-6
One or more of white carbon black.The carbonaceous material of described tubulose or lamellar each means the microstructure of carbonaceous material.Wherein, described
Tubulose carbonaceous material includes but is not limited to CNT；Described lamellar carbonaceous material including but not limited to as crystalline flake graphite,
Expanded graphite, KS-6.
In the application, when controlling addition potassium permanganate powder, described potassium permanganate powder should so may be used by concentrated sulphuric acid submergence
Intercalator (concentrated sulphuric acid, potassium permanganate) is made preferably to enter between layer of carbonaceous material wall.Control potassium permanganate former relative to carbonaceous simultaneously
Material is excessive, and in such step (1), potassium permanganate is less with strong sulfuric acid response, and the overwhelming majority is attached in carbonaceous material, with
Being easy to the later stage carries out high temeperature chemistry explosion.
Preferably, in step (1), the volume of described concentrated sulphuric acid is (5～350) with the mass ratio of described potassium permanganate powder
mL:1g.More preferably (8～200)：1.More preferably (25～150)：1, or (10～50)：1.
Preferably, in step (1), described potassium permanganate powder is (0.5～20) with the mass ratio of described carbon raw material:1.
More preferably (1.5～15)：1.More preferably (2～5)：1.
It is further preferred that when described carbon raw material is CNT, described potassium permanganate powder and described carbon nanometer
The mass ratio of pipe is (0.5～20):1.
It is further preferred that when described carbon raw material is lamellar material with carbon element (as crystalline flake graphite, expanded graphite, KS-6),
Described potassium permanganate powder is (1.5～10) with the mass ratio of described lamellar material with carbon element:1.
Preferably, in step (1), the mixing time after potassium permanganate powder is added to be 0.5-1.5h.
In the application, in step (1), the stirring after potassium permanganate powder is added to be to carry out at 20～30 DEG C, it is to avoid mistake
High temperature makes potassium permanganate, concentrated sulphuric acid react, and causes to lose efficacy during subsequent high temperature explosion.
In the application step (2), described reactant liquor is carried out with prestripping process (shearing dispersion or ultrasonic), carbonaceous can be made
Raw material is in pre- cleavage or precrushing state, increases interlamellar spacing or the wall spacing of carbonaceous material, is easy to subsequently preferably it be entered
Row high temperature explosion, obtains the less graphene product of the number of plies.
Preferably, in step (2), ultrasonic power during described supersound process is 250-1000W, and ultrasonic time is 0.5-
6h.
Preferably, in step (2), shear rate during described shearing decentralized processing is 500-3000r/min, when scattered
Between be 1～7h.
In the application step (3), slowly diluted in the case of not stirring using deionized water, one can wash away
So as to pH value reaches 7, two slowly to dilute the free sulfuric acid being detained in reactant liquor after prestripping, can avoid being attached to carbon
Potassium permanganate in material, concentrated sulphuric acid etc. are flushed away, in order to avoid having influence on follow-up high temeperature chemistry explosion.
Preferably, in step (3), the molar concentration of the hydrochloric acid of described washing is 4～12mol/L.Using salt acid elution
Part concentrated sulphuric acid can be removed and react the oxide generating (as MnO with potassium permanganate2).
Preferably, the volume of deionized water described in step (3) is more than the volume of described concentrated sulphuric acid.It is further preferred that
The volume of described deionized water is 3～5 times of the volume of described concentrated sulphuric acid.
In step (3), described drying is to carry out below 40 DEG C.Preferably, in step (3), the temperature of described drying is
20～40 DEG C.For example, it may be drying at room temperature it is also possible to (be for example vacuum dried) is dried at less than 40 DEG C.Control dry
Dry temperature is less than 40 DEG C, prevents too high temperature from so that the potassium permanganate between entrance layer of carbonaceous material wall, concentrated sulphuric acid is reacted, makes
Become and lost efficacy during subsequent high temperature explosion.
Preferably, in step (4), the temperature of described high temperature explosion treatment is 500～1000 DEG C.Can be for example 600,
700、800、850、900℃.Further preferably become 800～1000 DEG C.The gas that high temperature explosion in step (4) produces is dense sulfur
Between acid and potassium permanganate, reaction produces oxygen or potassium permanganate decomposes itself and produces oxygen.
In step (5), described high temperature graphitization processes and not only can ensure that the structure of material is preferable, and can further serve as
To thermal reduction and purification effect, and then the purity of raising material, prepare high-quality Graphene.
Preferably, described high temperature graphitization processes and specifically includes following steps：
Described Graphene crude product is placed in pyrographite stove, enters at 1100～3000 DEG C and under protective gas protection
Row high temperature purification treatment.
The graphene preparation method that first aspect present invention provides, its preparation technology is simpler, and degree of controllability is higher, is suitable for big
Batch production, the quality of obtained Graphene is higher,Its pattern rule, the number of plies is less
(most of number of plies is 3-10 layer), and electric conductivity is good, and electrical conductivity is up to 104s/m.
Second aspect, the embodiment of the present invention additionally provides the graphite being prepared by the preparation method of first aspect present invention
Alkene.
Preferably, the average number of plies of described Graphene is 3-10 layer, and electrical conductivity is up to 104More than s/m.
Graphene obtained by the present invention can be applicable to quasiconductor, lithium ion battery industry, electronic product industry microelectronics
The fields such as device.
The advantage of the embodiment of the present invention will partly illustrate in the following description, a part according to description be aobvious and
It is clear to, or can be known by the enforcement of the embodiment of the present invention.
Brief description
Fig. 1 is the electron scanning micrograph of the Graphene of the embodiment of the present invention 1.
Specific embodiment
Described below is the preferred implementation of the embodiment of the present invention it is noted that common skill for the art
For art personnel, on the premise of without departing from embodiment of the present invention principle, some improvements and modifications can also be made, these improvement
It is also considered as the protection domain of the embodiment of the present invention with retouching.
Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to
Under specific embodiment.In the range of constant principal right, carrying out change that can be suitable is implemented.
If no special instructions, reagent use herein is commercial reagent.
Embodiment 1
A kind of preparation method of Graphene, comprises the steps：
1st, the CNT (nanosecond science and technology limited company of German side of Shenzhen, caliber 40～60nm) of 10g is added to
In the concentrated sulphuric acid of 200mL, after stirring under ice bath, add the potassium permanganate of 25g, (25 DEG C) magnetic agitation at normal temperatures
60min, obtains the CNT turbid solution of blackish green；
2nd, above-mentioned CNT turbid solution is placed in ultrasonic device (water bath sonicator or sonde-type Strong dispersion Ultrasound Instrument)
In, 60min is processed with the power ultrasonic of 500W, obtains the reactant liquor after prestripping；
3rd, subsequently the reactant liquor after above-mentioned prestripping is slowly diluted with the deionized water of 800mL, obtains brown turbid solution,
Use Vacuum filtration device sucking filtration clean again, obtain filter cake, then add 100mL concentrated hydrochloric acid (12mol/L) again to remove in filter cake
The MnO that concentrated sulphuric acid is generated with potassium permanganate2Deng oxide, finally filtered, and dried at room temperature, obtained black solid
Thing；
4th, black solid content is put in resistance furnace, constant temperature 1min at 800 DEG C, obtain black puffy sample；
5th, the sample in step 4 is placed in 1800 DEG C of pyrographite stoves (zhuzhou,hunan Jin Rui company) and carries out remove impurity process
6h, thus obtain high purity graphite alkene powder body.
The Graphene that the present embodiment is obtained is black powder, and its loft can reach 800mL/g, and its powder body electrical conductivity
For 2 × 104s/m.The present embodiment products therefrom is scanned electron microscope observation, result is as shown in figure 1, mark in Fig. 1
Chi is 500nm, and each little lattice represent 50nm.
It will be seen from figure 1 that the structure of gained graphene product is more complete, thinner thickness, average thickness is that 2～3nm is left
Right it can be determined that the number of plies less (about 3-10 layer) that goes out gained Graphene.
Embodiment 2
A kind of preparation method of Graphene, comprises the steps：
1st, 5g expanded graphite is added in the concentrated sulphuric acid of 200mL, after stirring under ice bath, adds the permanganic acid of 25g
Potassium, (20 DEG C) magnetic agitation 100min, obtains the turbid solution of blackish green at normal temperatures；
2nd, above-mentioned turbid solution is placed in high speed dispersing shear equipment, with the shear rate dispersing shear 2h of 1500r/min,
Obtain the reactant liquor after prestripping；
3rd, subsequently the reactant liquor after above-mentioned prestripping is slowly diluted with the deionized water of 1000mL, obtain brown muddy
Liquid, cleaner with Vacuum filtration device sucking filtration, obtain filter cake, then add 200mL hydrochloric acid (8mol/L) again to remove in filter cake
MnO2Deng, finally filtered, and dry at 40 DEG C, obtain black solid content；
4th, black solid content is put in tube furnace, constant temperature 1min at 1000 DEG C, obtain black puffy sample；
5th, the sample in step 4 is placed in 2200 DEG C of pyrographite stoves and carries out remove impurity process 10h, thus obtaining high-purity stone
Black alkene powder body.
The Graphene that the present embodiment is obtained is black powder, and its loft can reach 650mL/g, and its powder body electrical conductivity
For 1 × 104s/m.
Embodiment 3
A kind of preparation method of Graphene, comprises the steps：
1st, the crystalline flake graphite of 2g is added in the concentrated sulphuric acid of 100mL, after stirring under ice bath, adds the permanganic acid of 4g
Potassium, (25 DEG C) magnetic agitation 1.5h, obtains the turbid solution of blackish green at normal temperatures；
2nd, above-mentioned turbid solution is placed in ultrasonic device, 180min is processed with the power ultrasonic of 250W, after obtaining prestripping
Reactant liquor；
3rd, subsequently the reactant liquor after above-mentioned prestripping is slowly diluted with the deionized water of 500mL, obtains brown turbid solution,
Use Vacuum filtration device sucking filtration clean again, obtain filter cake, then add 150mL hydrochloric acid (6mol/L) again to remove in filter cake
MnO2Deng, finally filtered, and vacuum drying at 35 DEG C, obtain black solid content；
4th, black solid content is put in resistance furnace, constant temperature 30s at 900 DEG C, obtain black puffy sample；
5th, the sample in step 4 is placed in 1600 DEG C of pyrographite stoves and carries out remove impurity process 8h, thus obtaining high-purity stone
Black alkene powder body.
The Graphene that the present embodiment is obtained is black powder, and its loft can reach 900mL/g, and its powder body electrical conductivity
For 3 × 104s/m.
Comparative example 1
A kind of preparation method of Graphene, comprises the steps：
1st, the CNT of 10g is added in the concentrated sulphuric acid of 200mL, after stirring under ice bath, adds the Gao Meng of 3g
Sour potassium, (25 DEG C) magnetic agitation 1h, obtains the turbid solution of blackish green at normal temperatures；
2nd, above-mentioned turbid solution is placed in ultrasonic device, 60min is processed with the power ultrasonic of 500W, after obtaining prestripping
Reactant liquor；
3rd, subsequently the reactant liquor after above-mentioned prestripping is slowly diluted with the deionized water of 800mL, obtains brown turbid solution,
Use Vacuum filtration device sucking filtration clean again, obtain filter cake, then add 100mL concentrated hydrochloric acid again to remove the MnO in filter cake2,
Afterwards through filtering and drying at room temperature, obtain black solid content；
4th, black solid content is put in resistance furnace, at 800 DEG C, constant temperature 1min, obtains black sample.
Compared with Example 1, in this comparative example 1, potassium permanganate consumption reduces to 3g, gained black sample fluffy
Degree only reaches 50mL/g, and sample segment not explosion.
Comparative example 2
1st, 5g expanded graphite is added in the concentrated sulphuric acid of 200mL, after stirring under ice bath, adds the permanganic acid of 25g
Potassium, (20 DEG C) magnetic agitation 100min, obtains the turbid solution of blackish green at normal temperatures；
2nd, subsequently above-mentioned suspension is slowly diluted with the deionized water of 1000mL, obtain brown turbid solution, then use vacuum
Suction filtration device sucking filtration is clean, obtains filter cake, then adds 200mL concentrated hydrochloric acid again to remove the MnO in filter cake2, finally carried out
Filter, and dry at room temperature, obtain black solid content；
3rd, black solid content is put in tube furnace, constant temperature 1min at 1000 DEG C, obtain puffy sample.
The sample that this comparative example 2 is obtained is black powder, only reaches due to not carrying out its loft of pre- shear treatment
100mL/g.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of preparation method of Graphene is it is characterised in that comprise the following steps：
(1) carbon raw material is added in concentrated sulphuric acid, after ice bath stirs, adds potassium permanganate powder so that described permanganic acid
Potassium powder, by concentrated sulphuric acid submergence, controls system temperature at 20～30 DEG C after described potassium permanganate is added completely into, stirring 0.5～
5h, obtains reactant liquor, and wherein, described carbon raw material is in a tubular form or lamellar；
(2) above-mentioned reactant liquor is carried out shear decentralized processing or supersound process, obtain the reactant liquor after prestripping；
(3) in the case of not stirring, it is slowly added to deionized water dilution in the reactant liquor after described prestripping, and filters,
Gained solid after filtering is washed using hydrochloric acid, through filtering, being dried, obtains black solid content；
(4) described black solid content is carried out high temperature explosion treatment 20～60s at 300～1200 DEG C, obtain Graphene crude product；
(5) described Graphene crude product is carried out high temperature graphitization process, obtain Graphene after purification.
2. preparation method as claimed in claim 1 it is characterised in that described carbon raw material include CNT, expanded graphite,
One or more of crystalline flake graphite and KS-6 conductive black.
3. preparation method as claimed in claim 1 is it is characterised in that in step (1), the volume of described concentrated sulphuric acid and described height
The mass ratio of potassium manganate powder is (5～350):1mL/g.
4. preparation method as claimed in claim 3 is it is characterised in that the matter of described potassium permanganate powder and described carbon raw material
Amount ratio is (0.5～20):1.
5. preparation method as claimed in claim 4 it is characterised in that when described carbon raw material be lamellar material with carbon element when, described
Potassium permanganate powder is (1.5～10) with the mass ratio of described lamellar material with carbon element:1.
6. preparation method as claimed in claim 1 is it is characterised in that ultrasonic power in step (2), during described supersound process
For 250-1000W, ultrasonic time is 0.5-6h；Shear rate during described shearing decentralized processing is 500-3000r/min, dispersion
Time be 1～7h.
7. preparation method as claimed in claim 1 is it is characterised in that in step (3), described drying is to enter below 40 DEG C
OK.
8. preparation method as claimed in claim 1 is it is characterised in that in step (4), the temperature of described high temperature explosion treatment is
500～1000 DEG C.
9. preparation method as claimed in claim 1 is it is characterised in that in step (5), described high temperature graphitization processes concrete bag
Include following steps：
Described Graphene crude product is placed in pyrographite stove, at 1100～3000 DEG C and under protective gas protection, carries out height
Warm purification process 2-12h.
10. the Graphene that described preparation method as arbitrary in claim 1～9 prepares.
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| CN108774890A (en) * | 2018-06-29 | 2018-11-09 | 杭州白熊科技有限公司 | Temperature self controlled electrically-heated fiber of organic PTC based on graphene and its preparation method and application |
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| CN106379896B (en) | 2019-06-14 |
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