CN109384220A - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN109384220A CN109384220A CN201811377304.4A CN201811377304A CN109384220A CN 109384220 A CN109384220 A CN 109384220A CN 201811377304 A CN201811377304 A CN 201811377304A CN 109384220 A CN109384220 A CN 109384220A
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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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Abstract
The invention discloses a kind of methods for preparing graphene, the following steps are included: using novel expanded graphite as raw material, expanded graphite is aoxidized in a low temperature of 45 DEG C using Strong oxdiative liquid, then the redox graphene in 200 DEG C, cooling collect obtains high-quality graphene.Since present invention uses expanded graphites as raw material, this Expandable graphite sheet has the graphite linings expanded, this is advantageous for the infiltration and oxidation reaction later of acid solution.The synthesis technology eliminates the stripping process of ultrasonic wave using redox reaction is carried out under strong acid and low temperature, this allows for the graphene oxide prepared with very big size, and then is conducive to make conductive graphene.
Description
Technical field
The present invention relates to new material technology field, in particular to a kind of preparation method of graphene.
Background technique
Graphene is by the British scientist peace strong sea the K nurse of moral (Andre K.Geim) et al. the one of discovery in 2004
The two-dimentional carbon atom nanocrystal of kind.Due to its excellent electrical properties, unique structure and photoelectric property, graphene have many
Using, including transparent electrode, lithium battery, effect transistor etc..With going deep into for graphene research, the graphene of high quality is just
Entering the industry volume production stage from the laboratory research stage.However, main liquid phase stripping means generally requires ultrasound at present
Wave removes graphene, and during removing, ultrasonic wave inevitably can will cause a large amount of defects on the surface of graphene.
In addition, traditional oxidizing process uses strong acid in synthesis, high temperature, the reaction conditions such as high pressure, these violent reaction conditions can be right
Industrial production causes huge security risk.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods for preparing graphene, solve current graphene oxide
Brought huge security risk and the damage to its surface in the process of removing graphene in production process.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows:
A method of preparing graphene, comprising the following steps:
(1) expansion process is carried out under the conditions of to expansible graphite 700-900 DEG C in 1000W micro-wave oven, after natural cooling
Obtain quasiflake graphite powder；
(2) above-mentioned expanded graphite and the appropriate concentrated sulfuric acid are put into and carries out oxidation reaction in the reaction unit of ice-water bath；
When the reaction temperature is down to 10 DEG C, it is carefully added into 3g potassium permanganate, continues oxidation reaction；
(3) after the oxidation reaction carries out 1h, heating device switch is opened, the reaction unit is heated and aoxidize instead
It answers, keeps the oxidizing reaction temperature and stirring rate reaction 7h of setting；
(4) it is to be oxidized after the reaction was completed, cooling is slowly passed through by peristaltic pump into the reaction unit in 90min
Then it is cooling to be maintained at 30min in ice-water bath by water for the reaction unit；
(5) hydrogen peroxide solution is added into three-necked flask until the color of reaction solution no longer changes, 300ml alkene is then added
Hydrochloric acid solution, the graphene sediment being collected by filtration；Addition deionized water and the revolving speed in 13000r/min repeatedly again
Lower centrifuge washing sediment forms the graphene oxide water solution of 200ml until the pH value of solution rises to 4；
(6) obtained graphene oxide water solution is carried out purification to filter into film-form graphene oxide, and in 80 DEG C
Dry 2h；
(7) above-mentioned film-form graphene oxide is heated to 1h in 200 DEG C and carries out reduction reaction, collects and obtains after cooling
Graphene.
As a preferred embodiment, the expanded graphite that the oxidation reaction uses, sulfuric acid, the mass ratio of potassium permanganate
Example is 1:90:3.
As a preferred embodiment, the oxidizing reaction temperature set is 45 DEG C, stirring rate 120r/min.
As a preferred embodiment, when potassium permanganate is added in sulfuric acid, the reaction unit is placed in ice water
So as to reaction temperature control 0 DEG C or less 1 hour.
As a preferred embodiment, the mass fraction of the concentrated sulfuric acid is 98%, the mass fraction of hydrogen peroxide solution
It is 30%, the mass fraction of alkene hydrochloric acid solution is 3%.
The beneficial effects of the present invention are:
The graphene synthetic method is by low-temperature oxidation expanded graphite, since the speed of oxidation reaction is slower, controls in this way
The time of oxidation can control the oxidizability of graphite；This method is by using expanded graphite so as to avoid ultrasonic wave to graphite
The stripping damage of alkene influences.
Detailed description of the invention
Fig. 1 is XRD characteristic spectrum line chart of this method according to graphene film product made under different voltages strength condition.
Specific embodiment
The purpose of the present invention is to propose to a kind of methods for preparing graphene, prepare graphene using low-temperature oxidation reduction method.
To reach this purpose, it is raw material that following synthesis methods, which have used expanded graphite meterial, and is used in the synthesis process special
The three-necked flask ice bath reactor of door design.The method of the graphite ene oxidation reaction the following steps are included:
(1) expanded graphite is weighed according to the ratio to be placed in right cylinder-shaped beaker, which is put into the microwave of 1000w, 800 DEG C
Stove heating 10 seconds.The graphite expansion can be obtained quasiflake graphite powder by microwave heating.
(2) concentrated sulfuric acid and 1g that the mass fraction that 50ml is injected in the three-necked flask of volume 500ml is 98% expand stone
Ink.Then the three-necked flask is put into ice bath and starts mechanical stirring to 120 rpms.When acid liquor temperature be down to 10 DEG C with
After lower, it is slowly added to 3g potassium permanganate.
(3) it after potassium permanganate being added, keeps mechanical stirring rotor in 120 rpms of stirring and 0 DEG C of ice-water bath 1h, beats
The temperature switch of warm table is opened, reaction system is heated to 45 DEG C, keeps the temperature and mechanical stirring 7h.
(4) it is to be oxidized after the reaction was completed, within 90 minutes time, 150ml cooling water is slowly pumped into three by peristaltic pump
In mouth flask, ice cube is added in a water bath, and keeps ice bath 30 minutes cooling.
(5) hydrogen peroxide solution that mass fraction is 30% is added into three-necked flask until the color of reaction solution no longer changes
Become, the alkene hydrochloric acid solution that 300ml mass fraction is 3%, the graphene sediment being collected by filtration then is added；Add repeatedly again
Enter with deionized water and the centrifuge washing sediment under the revolving speed of 13000r/min, until the pH value of solution rises to 4, is formed
The graphene oxide water solution of 200ml.
Sample cleanup the following steps are included:
(1) it is filtered using vacuum filtration method, filter membrane is the PVDF semi-permeable membrane that aperture is 0.1 μm, semi-transparent before filtering
Film is needed by ethyl alcohol complete wetting；During the filtration process, graphene oxide is in vacuum filter cup by carefully repeatedly clear with pure water
It washes repeatedly, subsequent Graphite Cake is transferred in conical hopper bottle, is cleaned repeatedly with ethyl alcohol, washing lotion ultrasonication in 1L cold water
4 minutes.
(2) graphene oxide solution is centrifuged 60min with 4400rpm revolving speed in 50ml centrifuge tube, after centrifugation to solution,
It is cleaned repeatedly with ethyl alcohol and ultrapure water, centrifuge tube is also by ultrasonication repeatedly to remove unwanted particle.The step is used for
Remaining various salt and acid in dissolution and diluting reaction repeat the above steps until wash clean.
(3) graphene oxide after cleaning sufficiently, which is easily re-dispersed the pH for detecting solution in aqueous solution and is confirmed as, is in
In the identical neutrality of ultrapure water.
(4) it is refrigerated to drying to obtained graphene oxide water solution, the graphene oxide water solution of 5mL is put into ice
- 40 DEG C are refrigerated in case, which, which is transferred in freeze drier, is dried.By -40 DEG C of frozen dried, formed
Spongiform graphene porous material.
(5) in order to obtain conductive film, 4.8ml product solution has been filtered using 0.1 μm of MCE semi-permeable membrane, and will filter
Biscuit is dry, weighs film quality.
Examine final product the following steps are included:
To make the actual concentrations data for obtaining product solution, 4.8ml product solution has been filtered using 0.1 μm of MCE semi-permeable membrane,
And gained film drying will be filtered, weigh film quality.The graphene film of black, which is covered on, to be filtered on film, 4 points of Jandel spies
Needle test result shows that the average resistance of the film surface of 10 μ m-thicks is 56.47 Ω.In test process, four linearly aligned
Syringe needle passes through repeatedly contact film more than four times uniformly in contact with film surface, the average value of recording surface resistance.
It makes XRD test sample: shearing the graphene oxide film disk of lower diameter 7.5mm with puncher fixed point, it will be thin
Film is suspended in 100ml deionized water, and the thick liquid obtained with 90 minutes centrifuging and takings of centrifuge 10000rpm revolving speed is for being stained with
It encloses to state and cuts thin slice on the XRD sample stage of unformed silicon substrate.It is model aBruker used in XRD test
The X-ray diffractometer of D8Advancediffractometer, and it is mounted with graphite monochromator.It the use of ray length is 1mm.
All samples are tested under same temperature and humidity, and relative humidity is 41% in experiment, and temperature is 23.5 DEG C.Experiment gained spectrum
Line background passes through BrukerDiffrac.Eva4 software and corrects and drawn by OriginPro9.0.
As shown in Figure 1, the graphene oxide composite material has obvious characteristic peak at 10.5 °, 24 ° and 27.5 ° respectively.The peak XRD letter
Number the result shows that: 25 DEG C oxidation grapheme materials in contain graphite content.And with the raising of oxidizing reaction temperature, 10.5 °
XRD peak-to-peak signal intensity gradually reinforce, this shows in 45 DEG C of oxidation reaction, and all graphite is all oxidized to graphite oxide
Alkene.
In conjunction with attached drawing, the embodiments of the present invention are described in detail above, but the present invention is not limited to described implementations
Mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiments
A variety of change, modification, replacement and modification are carried out, are still fallen in protection scope of the present invention.
Claims (5)
1. a kind of method for preparing graphene, which comprises the following steps:
(1) expansion process is carried out under the conditions of to expansible graphite 700-900 DEG C in 1000W micro-wave oven, is obtained after natural cooling
Quasiflake graphite powder；
(2) above-mentioned expanded graphite and the appropriate concentrated sulfuric acid are put into and carries out oxidation reaction in the reaction unit of ice-water bath；Work as institute
It states reaction temperature and is down to 10 DEG C, be carefully added into appropriate potassium permanganate, continue oxidation reaction；
(3) after the oxidation reaction carries out 1h, heating device switch is opened, the reaction unit is heated and carries out oxidation reaction, protect
Hold the oxidizing reaction temperature and stirring rate reaction 7h of setting；
(4) it is to be oxidized after the reaction was completed, into the reaction unit, by peristaltic pump, to be slowly passed through 150ml cold in 90min
Then it is cooling to be maintained at 30min in ice-water bath by but water for the reaction unit；
(5) hydrogen peroxide solution is added into three-necked flask until the color of reaction solution no longer changes, 300ml alkene hydrochloric acid is then added
Solution, the graphene sediment being collected by filtration；Again repeatedly addition deionized water and under the revolving speed of 13000r/min from
Heart washing precipitate obtains graphene oxide water solution until the pH value of solution rises to 4；
(6) obtained graphene oxide water solution is carried out purification to filter into film-form graphene oxide, and dry in 80 DEG C
2h；
(7) above-mentioned film-form graphene oxide is heated to 1h in 200 DEG C and carries out reduction reaction, is collected after cooling and obtains graphite
Alkene.
2. the method according to claim 1 for preparing graphene, it is characterised in that: the expansion stone that the oxidation reaction uses
Ink, sulfuric acid, the mass ratio of potassium permanganate are 1:90:3.
3. the method according to claim 1 for preparing graphene, it is characterised in that: the oxidizing reaction temperature set as
45 DEG C, stirring rate 120r/min.
4. the method according to claim 1 for preparing graphene, it is characterised in that: when potassium permanganate is added in sulfuric acid,
The reaction unit be placed in ice water so as to reaction temperature control 0 DEG C or less 1 hour.
5. the method according to claim 1 for preparing graphene, it is characterised in that: the mass fraction of the concentrated sulfuric acid is
98%, hydrogen peroxide solution mass fraction is 30%, and alkene hydrochloric acid solution mass fraction is 3%.
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| CN201811377304.4A CN109384220A (en) | 2018-11-19 | 2018-11-19 | A kind of preparation method of graphene |
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| CN201811377304.4A CN109384220A (en) | 2018-11-19 | 2018-11-19 | A kind of preparation method of graphene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342501A (en) * | 2019-08-28 | 2019-10-18 | 徐州宇帆机电科技有限公司 | A kind of method that pulsed high energy microwave quickly restores preparation high quality reduced graphene |
| CN110435259A (en) * | 2019-08-12 | 2019-11-12 | 林绵绵 | A kind of sound insulation environment-friendly materials and preparation method thereof for decoration |
-
2018
- 2018-11-19 CN CN201811377304.4A patent/CN109384220A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110435259A (en) * | 2019-08-12 | 2019-11-12 | 林绵绵 | A kind of sound insulation environment-friendly materials and preparation method thereof for decoration |
| CN110435259B (en) * | 2019-08-12 | 2022-06-28 | 深圳市集洁号环保科技有限公司 | Sound-insulation environment-friendly material for decoration and preparation method thereof |
| CN110342501A (en) * | 2019-08-28 | 2019-10-18 | 徐州宇帆机电科技有限公司 | A kind of method that pulsed high energy microwave quickly restores preparation high quality reduced graphene |
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