CN112830480B - Optimized preparation method of graphene - Google Patents
Optimized preparation method of graphene Download PDFInfo
- Publication number
- CN112830480B CN112830480B CN202110207384.4A CN202110207384A CN112830480B CN 112830480 B CN112830480 B CN 112830480B CN 202110207384 A CN202110207384 A CN 202110207384A CN 112830480 B CN112830480 B CN 112830480B
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite
- hydrogen peroxide
- ammonia water
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
-
- 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
- C01B2204/02—Single layer graphene
-
- 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
Abstract
An optimized graphene preparation method comprises the steps of carrying out preoxidation treatment on flake graphite, and carrying out oxidation intercalationAnd after obtaining the graphite intercalation compound, rapidly heating to realize expansion coupling stripping of the graphite intercalation compound, thereby preparing the graphene. The graphene prepared by the method has the average size distribution in micron level, the thickness of a lamella is 0.8nm, and the conductivity can reach 3.0 multiplied by 10 4 S/m。
Description
Technical Field
The invention relates to a technology in the field of nano materials, in particular to a nano material with the conductivity of 3.0 multiplied by 10 4 An optimized preparation method of S/m graphene.
Background
Chemical oxidation stripping can prepare graphene oxide from graphite on a large scale, and then graphene is obtained through chemical reduction. The Hummers method is a common method for preparing graphene oxide, and is mainly used for preparing graphite oxide by oxidizing and intercalating graphite with strong acids such as concentrated sulfuric acid and strong oxidants such as potassium permanganate. Therefore, harmful gas and waste water are generated in the reaction process and the post-treatment process, and the environmental pollution is serious. In addition, the Hummers method strong oxidation process typically introduces oxygen-containing functional groups on the graphite sheet and causes defects in its carbon skeleton. However, the reducing agents studied and used at present cannot reduce the structural defects of the carbon skeleton caused during the graphite oxidation intercalation process, and cannot completely remove all oxygen-containing functional groups in graphene oxide.
Disclosure of Invention
The invention provides an optimized preparation method of graphene, aiming at the problems that the existing chemical oxidation stripping-reduction method using graphite as a raw material is difficult to prepare high-conductivity graphene in batches and the preparation process is easy to cause environmental pollution, the high-conductivity graphene is prepared by carrying out pre-oxidation, oxidation intercalation and high-temperature rapid expansion coupling stripping on crystalline flake graphite, and strong acid and strong oxidant are avoided in the preparation process.
The invention is realized by the following technical scheme:
according to the preparation method, after the scale graphite is subjected to pre-oxidation treatment and is subjected to oxidation intercalation to obtain a graphite intercalation compound, the graphite intercalation compound is subjected to expansion coupling stripping through rapid heating, and thus the graphene is prepared.
The pre-oxidation treatment is preferably realized by adopting a mixed solution of hydrogen peroxide and ammonia water, and the active oxygen generated by decomposing the hydrogen peroxide is catalyzed by the ammonia water to pre-oxidize the graphite.
The pre-oxidation treatment specifically comprises the following steps: adding graphite into the mixed solution of ammonia water and hydrogen peroxide at room temperature, fully stirring for 30min, heating the mixed system to 40-80 ℃, and preserving heat for 2-6 h.
The pre-oxidation treatment is preferably carried out by filtering, washing and vacuum drying the reaction system.
The volume ratio of the ammonia water to the hydrogen peroxide to the deionized water in the mixed solution of the hydrogen peroxide and the ammonia water is 1:1:3-1:1:5, and the proportion of the graphite to the mixed solution of the hydrogen peroxide and the ammonia water is 2g (50-100) mL.
The oxidation intercalation is preferably realized by using a mixed solution of sodium perborate and glacial acetic acid.
The oxidation intercalation specifically comprises the following steps: at room temperature, adding sodium perborate into glacial acetic acid, fully stirring until the sodium perborate is dissolved, then adding pre-oxidized graphite into a mixed system, fully stirring for 10min, heating the mixed system to 40-80 ℃, and preserving heat for 2-12 h.
And (3) oxidizing intercalation, preferably finally washing the product by deionized water until the washing liquid is neutral, and drying in vacuum.
The ratio of the sodium perborate to the glacial acetic acid in the mixed solution of the sodium perborate and the glacial acetic acid is (20-40) g (100-200) mL.
The rapid heating expansion coupling stripping is as follows: placing the graphite intercalation compound in the front end region (airflow downstream direction) of a quartz tube of a slide rail furnace, and filling argon into the furnace chamber, wherein the airflow is 50-100 mL/min; then the slide rail furnace is arranged at the rear end region and is heated to 900-1100 ℃ at the heating rate of 10 ℃/min, and then the furnace is rapidly moved to the sample position and is kept for 1-10 min.
Technical effects
The invention integrally solves the problems that the high-conductivity graphene is generally difficult to prepare in batch by using graphite as a raw material and a chemical oxidation stripping-reduction method in the prior art and the preparation process is easy to cause environmental pollution.
Compared with the prior art, the high-conductivity graphene is prepared from crystalline flake graphite, and the single-layer rate is more than 90%. Meanwhile, the use of strong acid and strong oxidant is avoided in the preparation process.
Drawings
Fig. 1 is an atomic force microscope image of graphene prepared in example 1 of the present invention; the inset is a height view.
Fig. 2 is an atomic force microscope image of graphene prepared in example 2 of the present invention; the inset is a height view.
Fig. 3 is an atomic force microscope image of graphene prepared in example 3 of the present invention; the inset is a height view.
Detailed Description
Example 1
In this embodiment, crystalline flake graphite is used as a raw material, and pre-oxidation, oxidation intercalation and high-temperature rapid expansion coupling stripping are used to prepare graphene, and the specific steps include:
step one, respectively measuring 10mL hydrogen peroxide, 10mL ammonia water and 30mL deionized water at room temperature, adding into a single-mouth bottle, and fully stirring for 10 min. And weighing 2g of graphite, adding the graphite into the system, fully stirring for 30min, heating the mixed system to 80 ℃, and fully reacting for 2 h. Finally, the reaction system was filtered, washed with water, and dried under vacuum.
Secondly, at room temperature, 30g of sodium perborate is weighed and added into 100mL of glacial acetic acid, and the mixture is fully stirred until the sodium perborate is dissolved. Adding the product obtained in the first step into the system, fully stirring for 10min, heating the mixed system to 80 ℃, and preserving heat for 2 h; and finally, filtering the mixed system, washing the mixed system by using deionized water until the washing liquid is neutral, collecting the precipitate, and drying the precipitate in vacuum.
And thirdly, placing the product obtained in the second step on the front end area (in the downstream direction of airflow) of a quartz tube of the slide rail furnace, and filling argon into the furnace chamber, wherein the airflow is 80 mL/min. The slide furnace was then placed in the back end zone and ramped up to 1000 ℃ at a ramp rate of 10 ℃/min, and the preheated furnace was then rapidly moved to the sample position and held for 2 min. And finally, quickly moving the furnace to a rear end region, taking out the sample from the tubular furnace after the system is naturally cooled, alternately washing the sample with deionized water and ethanol, and freeze-drying the washed sample to obtain the graphene.
And step four, weighing 100mg of graphene obtained in the step three, adding 200mL of DMF, and carrying out ultrasonic treatment for 10min by using an ultrasonic cleaner with the ultrasonic power of 200w to obtain 0.5mg/mL of graphene dispersion liquid. Then, the graphene dispersion was centrifuged at 8000rpm for 10min, and the supernatant and the precipitate were collected, respectively. And detecting the supernatant as a single-layer graphene dispersion liquid by an atomic force microscope, drying the precipitate, and weighing the precipitate to be 5mg, so that the yield of the single-layer graphene can be calculated to be 95%.
As shown in fig. 1, the results of an atomic force microscope and a height map show that the average size of the graphene prepared in this example is distributed in micron order, the thickness of the sheet layer is 0.8nm, which is a typical characteristic of single-layer graphene, and the single-layer rate is 95%. The obtained graphene has low structural damage degree and the conductivity of 3.0 multiplied by 10 4 S/m。
Example 2
The embodiment specifically comprises the following steps:
step 1, respectively measuring 10mL of hydrogen peroxide, 10mL of ammonia water and 40mL of deionized water at room temperature, adding into a single-mouth bottle, and fully stirring for 10 min. And weighing 2g of graphite, adding the graphite into the system, fully stirring for 30min, heating the mixed system to 60 ℃, and fully reacting for 4 h. Finally, the reaction was filtered, washed with water, and dried under vacuum.
Step 2, weighing 20g of sodium perborate at room temperature, adding into 200mL of glacial acetic acid, and fully stirring until the sodium perborate is dissolved. Adding the product obtained in the step (1) into the system, fully stirring for 10min, heating the mixed system to 60 ℃, and preserving heat for 8 h; and finally, filtering the mixed system, washing the mixed system by using deionized water until the washing liquid is neutral, collecting the precipitate, and drying the precipitate in vacuum.
And 3, placing the product obtained in the step 2 in the front end area (in the downstream direction of airflow) of a quartz tube of the slide rail furnace, and filling argon into the furnace chamber, wherein the flow rate of the argon is 50 mL/min. The slide furnace was then placed in the back end region and ramped up to 900 ℃ at a ramp rate of 10 ℃/min, and the preheated furnace was then rapidly moved to the sample position and held for 10 min. And finally, quickly moving the furnace to a rear end region, taking out the sample from the tubular furnace after the system is naturally cooled, alternately washing the sample with deionized water and ethanol, and freeze-drying the washed sample to obtain the graphene.
And step 4, weighing 100mg of graphene obtained in the step 3, adding 200mL of DMF, and carrying out ultrasonic treatment for 10min by using an ultrasonic cleaner with the ultrasonic power of 200w to obtain 0.5mg/mL of graphene dispersion liquid. Then, the graphene dispersion was centrifuged at 8000rpm for 10min, and the supernatant and the precipitate were collected, respectively. And detecting the supernatant as a single-layer graphene dispersion liquid by an atomic force microscope, drying the precipitate, and weighing 10mg, thereby obtaining that the yield of the single-layer graphene is 90%.
As shown in fig. 2, the results of the atomic force microscopy and the height mapping show that the graphene prepared in this example has an average size in micron level, a lamella thickness of 0.8nm, and a monolayer rate of 90%. The graphene has a conductivity of 1.9 × 10 4 S/m。
This example differs from example 1 in that: step 1, increasing the volume ratio of hydrogen peroxide, ammonia water and deionized water, reducing the reaction temperature and increasing the reaction time; step 2, the using amount of sodium perborate is reduced, the using amount of glacial acetic acid is increased, the reaction temperature is reduced, and the reaction time is increased; in step 3, the gas flow is reduced, the reaction temperature is reduced, and the reaction time is increased.
Example 3
The embodiment specifically comprises the following steps:
step one, respectively measuring 10mL hydrogen peroxide, 10mL ammonia water and 50mL deionized water at room temperature, adding into a single-mouth bottle, and fully stirring for 10 min. And weighing 2g of graphite, adding the graphite into the system, fully stirring for 30min, heating the mixed system to 40 ℃, and fully reacting for 6 h. Finally, the reaction system was filtered, washed with water, and dried under vacuum.
Secondly, at room temperature, weighing 40g of sodium perborate, adding into 150mL of glacial acetic acid, and fully stirring until the sodium perborate is dissolved. Adding the product of the first step into the system, fully stirring for 10min, heating the mixed system to 40 ℃, and preserving heat for 12 h; and finally, filtering the mixed system, washing the mixed system by using deionized water until the washing liquid is neutral, collecting the precipitate, and drying the precipitate in vacuum.
And thirdly, placing the product obtained in the second step at the front end area (in the downstream direction of airflow) of a quartz tube of the slide rail furnace, and filling argon into the furnace chamber, wherein the airflow is 100 mL/min. The slide furnace was then placed in the rear end region and the temperature was raised to 1100 ℃ at a rate of 10 ℃/min, and the preheated furnace was then rapidly moved to the sample position and held for 5 min. And finally, quickly moving the furnace to a rear end region, taking out the sample from the tubular furnace after the system is naturally cooled, alternately washing the sample with deionized water and ethanol, and freeze-drying the washed sample to obtain the graphene.
And step four, weighing 100mg of graphene obtained in the step three, adding 200mL of DMF, and carrying out ultrasonic treatment for 10min by using an ultrasonic cleaner with the ultrasonic power of 200w to obtain 0.5mg/mL of graphene dispersion liquid. Then, the graphene dispersion was centrifuged at 8000rpm for 10min, and the supernatant and the precipitate were collected, respectively. And detecting the supernatant as a single-layer graphene dispersion liquid by an atomic force microscope, drying the precipitate, and weighing 8mg, thereby calculating that the yield of the single-layer graphene is 92%.
As shown in fig. 3, the results of the atomic force microscopy and the height mapping show that the graphene prepared in this example has an average size in micron level, a lamella thickness of 0.8nm, and a monolayer rate of 92%. The graphene has a conductivity of 2.3 × 10 4 S/m。
This example differs from example 1 in that: in the first step, the volume ratio of hydrogen peroxide, ammonia water and deionized water is increased, the reaction temperature is reduced, and the reaction time is increased; secondly, the using amount of sodium perborate and glacial acetic acid is increased, the reaction temperature is reduced, and the reaction time is increased; in the third step, the gas flow is increased, the reaction temperature is increased, and the reaction time is increased.
Compared with the prior art, the method takes the crystalline flake graphite as the raw material, and prepares the graphene with high conductivity by utilizing pre-oxidation, oxidation intercalation and high-temperature expansion coupling stripping under the condition of not using strong acid and strong oxidant, and the single-layer rate is more than 90 percent.
The foregoing embodiments may be modified in many different ways by one skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and not by the preceding embodiments, and all embodiments within their scope are intended to be limited by the scope of the invention.
Claims (4)
1. An optimized preparation method of graphene is characterized in that after scale graphite is subjected to pre-oxidation treatment and is subjected to oxidation intercalation to obtain a graphite intercalation compound, expansion coupling stripping of the graphite intercalation compound is realized through rapid heating, so that graphene is prepared;
the pre-oxidation treatment is realized by adopting a mixed solution of hydrogen peroxide and ammonia water, and the active oxygen generated by decomposing the hydrogen peroxide under the catalysis of the ammonia water is used for pre-oxidizing the graphite;
the oxidation intercalation is realized by adopting a mixed solution of sodium perborate and glacial acetic acid;
the pre-oxidation treatment specifically comprises the following steps: adding graphite into an ammonia water and hydrogen peroxide mixed solution at room temperature, fully stirring for 30min, heating the mixed system to 40-80 ℃, and preserving heat for 2-6 h;
the oxidation intercalation specifically comprises the following steps: at room temperature, adding sodium perborate into glacial acetic acid, fully stirring until the sodium perborate is dissolved, then adding pre-oxidized graphite into a mixed system, fully stirring for 10min, heating the mixed system to 40-80 ℃, and preserving heat for 2-12 h;
the rapid heating is as follows: raising the temperature to 900-1100 ℃ at a temperature rise rate of 10 ℃/min.
2. The optimized preparation method of graphene as claimed in claim 1, wherein the volume ratio of ammonia water to hydrogen peroxide to deionized water in the mixed solution of hydrogen peroxide and ammonia water is 1:1:3-1:1:5, and the ratio of graphite to the mixed solution of hydrogen peroxide and ammonia water is 2g (50-100) mL.
3. The optimized preparation method of graphene as claimed in claim 1, wherein the ratio of sodium perborate to glacial acetic acid in the mixed solution of sodium perborate and glacial acetic acid is (20-40) g (100-200) mL.
4. The optimized graphene preparation method according to claim 1, wherein the expansion-coupled exfoliation is: placing the graphite intercalation compound on the front end region of a quartz tube of a slide rail furnace, and filling argon into the furnace chamber, wherein the flow rate of the argon is 50-100 mL/min; then the slide rail furnace is arranged at the rear end area and is heated to 900 ℃ and 1100 ℃ at the heating rate of 10 ℃/min, and then the furnace is rapidly moved to the sample position and is kept for 1min-10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110207384.4A CN112830480B (en) | 2021-02-25 | 2021-02-25 | Optimized preparation method of graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110207384.4A CN112830480B (en) | 2021-02-25 | 2021-02-25 | Optimized preparation method of graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112830480A CN112830480A (en) | 2021-05-25 |
| CN112830480B true CN112830480B (en) | 2022-09-23 |
Family
ID=75933209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110207384.4A Active CN112830480B (en) | 2021-02-25 | 2021-02-25 | Optimized preparation method of graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112830480B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN102001642A (en) * | 2009-09-02 | 2011-04-06 | 中国科学院金属研究所 | Method for producing graphene belts in controllable macroscopic quantity by chemically cutting grapheme |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090028777A1 (en) * | 2007-07-27 | 2009-01-29 | Aruna Zhamu | Environmentally benign chemical oxidation method of producing graphite intercalation compound, exfoliated graphite, and nano-scaled graphene platelets |
| CN105293476B (en) * | 2015-11-16 | 2018-07-10 | 复旦大学 | A kind of preparation method of large scale graphene oxide or graphene |
| CN105752977B (en) * | 2016-04-29 | 2017-12-12 | 江苏超电新能源科技发展有限公司 | A kind of technology of preparation method of high conductivity graphene powder |
| CN106185902B (en) * | 2016-07-18 | 2017-12-22 | 中国科学院兰州化学物理研究所 | A kind of method that clean oxidation technology prepares the controllable graphene oxide of size |
| CN108083260B (en) * | 2016-11-23 | 2020-03-31 | 比亚迪股份有限公司 | High-expansion-volume graphene aggregate and preparation method and application thereof |
| CN106882803B (en) * | 2017-03-10 | 2019-04-05 | 江南石墨烯研究院 | A kind of method and device thereof preparing graphene oxide |
| CN108423667A (en) * | 2018-05-29 | 2018-08-21 | 李训祺 | A kind of graphene production technology |
-
2021
- 2021-02-25 CN CN202110207384.4A patent/CN112830480B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN102001642A (en) * | 2009-09-02 | 2011-04-06 | 中国科学院金属研究所 | Method for producing graphene belts in controllable macroscopic quantity by chemically cutting grapheme |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112830480A (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3056468B1 (en) | Graphene production method | |
| JP6300930B2 (en) | Method for producing graphene | |
| Wang et al. | An efficient, soluble, and recyclable multiwalled carbon nanotubes-supported TEMPO for oxidation of alcohols | |
| CN102671661B (en) | Multi-walled carbon nanotube-loaded nano ferroferric oxide catalyst and preparation method and application thereof | |
| CN101559918B (en) | Preparation method of graphene/cadmium sulfide quantum dot composite material applied to photoelectric conversion | |
| CN110860289A (en) | Preparation method and application of metal monoatomic material | |
| CN104528707A (en) | Preparation method of high-conductivity graphene membrane | |
| CN102586946A (en) | High-strength graphene ordered porous fibers and preparation method thereof | |
| CN102730678A (en) | Device and method for preparing graphene powder | |
| CN109650379B (en) | Single-walled carbon nanotube gradient oxidation purification method | |
| CN102765714B (en) | Preparation method of graphite oxide with high degree of oxidation and high dispersibility | |
| CN106744894A (en) | A kind of preparation method of graphene powder | |
| CN112830480B (en) | Optimized preparation method of graphene | |
| CN102157358B (en) | Method for synthesizing carbon nano tube and zinc oxide heterostructure by hydrothermal method | |
| Mombeshora et al. | Understanding oxidative reaction of carbon nanoplatelets towards tailored physicochemical properties | |
| CN105060272B (en) | A kind of using artemia chorion as carbon source low temperature under prepare the method for CNT | |
| CN102267725A (en) | Method for preparing ultrafine tungsten oxide with template method | |
| CN108394886B (en) | Method for preparing carbon quantum dots by cutting graphite oxide based on strong base, product and application thereof | |
| Bian et al. | A novel poly (p-styrenesulfonic acid) grafted carbon nanotube/graphene oxide architecture with enhanced catalytic performance for the synthesis of benzoate esters and fatty acid alkyl esters | |
| CN106238080A (en) | The method that p-doped porous graphene and preparation method thereof aoxidizes with catalysis benzylamine | |
| CN109158098A (en) | Expanded graphite solid catalyst carrier, preparation method and complex solid catalyst and preparation method | |
| CN112811416A (en) | Preparation method of single-layer graphene oxide based on semi-coke | |
| CN110550623B (en) | Method for preparing high-quality large-size graphene on large scale | |
| KR101141716B1 (en) | Large-scale manufacturing method of high-surface area iron oxide nanoparticles | |
| CN103771395A (en) | Graphene material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |