CN114032560A - Graphene and preparation method thereof - Google Patents
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- CN114032560A CN114032560A CN202111304733.0A CN202111304733A CN114032560A CN 114032560 A CN114032560 A CN 114032560A CN 202111304733 A CN202111304733 A CN 202111304733A CN 114032560 A CN114032560 A CN 114032560A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 26
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229950011008 tetrachloroethylene Drugs 0.000 claims abstract description 18
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 13
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 claims abstract description 13
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 22
- 239000002608 ionic liquid Substances 0.000 claims description 12
- -1 1-butyl-3-methylimidazolium hexafluorophosphate Chemical compound 0.000 claims description 10
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000003011 anion exchange membrane Substances 0.000 claims description 7
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 238000004140 cleaning Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 238000000861 blow drying Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/135—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
Abstract
The invention discloses a preparation method of graphene, which comprises the following steps: electrolyzing tetrachloroethylene in an electrolytic cell, wherein the electrolytic cell comprises: a cathode, an anode, a catholyte and an anolyte, the catholyte and the anolyte being separated by a membrane; adding tetrachloroethylene into the catholyte, and electrolyzing to obtain graphene; the cathode is a copper nickel zinc alloy electrode, and the anode is a titanium ruthenium-coated inert electrode. The invention also discloses graphene prepared according to the preparation method of the graphene. Compared with the traditional method, the method has many incomparable advantages, such as high reaction speed, mild condition, high reaction efficiency, simple and controllable operation and environmental protection; the existing production process can be effectively simplified, the economic benefit of graphene production is further improved, and the problem of environmental pollution is solved.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to graphene and a preparation method thereof.
Background
Graphene has been a research hotspot in multiple scientific fields due to a special two-dimensional structure and excellent physicochemical properties, and is concerned by the scientific and industrial fields. However, in order to further study and apply the graphene, the most critical problem is to solve the large-scale preparation of high-quality graphene.
In the existing preparation method, the yield of graphene is very low and the time consumption is long by a mechanical stripping method, and only basic research can be met; the Chemical Vapor Deposition (CVD) method has harsh experimental conditions and low yield, and the obtained graphene sheet layer has uneven thickness, and the epitaxial growth method is also suitable for large-scale application; the carbon nanotube melting method and the thermal reduction method have complicated steps and harsh reaction conditions. Compared with the method, the reduction oxidation graphite method has the advantages of easily available raw materials, low cost, simple operation, large-scale production and the like, and attracts high attention of researchers, but the method also has some problems such as insufficient product reduction, long time consumption, more defects, easy agglomeration and the like. Therefore, the research on the preparation method of graphene with low cost and high efficiency has great significance for basic research and wide application, and becomes a key and difficult subject in the related fields.
Aiming at various defects of the existing graphene preparation technology, the method aims to solve the problems that the number of layers and the size of graphene cannot be accurately controlled by a solid phase method and the efficiency is low; toxic and explosive hazardous chemicals in the liquid phase method have negative effects on the subsequent application of the graphene; and the technical problems of high cost and difficult process of the gas phase method. The invention provides a novel graphene preparation method.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides the graphene and the preparation method thereof, compared with the traditional method, the graphene and the preparation method thereof have many incomparable advantages, such as high reaction speed, mild condition, high reaction efficiency, simple and controllable operation and environmental friendliness; the existing production process can be effectively simplified, the economic benefit of graphene production is further improved, and the problem of environmental pollution is solved.
The invention provides a preparation method of graphene, which comprises the following steps: electrolyzing tetrachloroethylene in an electrolytic cell, wherein the electrolytic cell comprises: a cathode, an anode, a catholyte and an anolyte, the catholyte and the anolyte being separated by a membrane;
adding tetrachloroethylene into the catholyte, and electrolyzing to obtain graphene; the cathode is a copper nickel zinc alloy electrode, and the anode is a titanium ruthenium-coated inert electrode.
Preferably, the catholyte is a mixture of an ionic liquid and polyvinylpyrrolidone.
Preferably, in the catholyte, the ionic liquid is a mixture of 1-butyl-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium hexafluorophosphate.
Preferably, the volume ratio of the 1-butyl-3-methylimidazole chloride salt to the 1-butyl-3-methylimidazole hexafluorophosphate salt is 50: 1-3.
Preferably, the volume-to-weight ratio (mL/g) of the ionic liquid to the polyvinylpyrrolidone in the catholyte is 102-106: 0.5-1.
Preferably, the anolyte is an ionic liquid.
Preferably, the anolyte is 1-butyl-3-methylimidazolium chloride.
Preferably, the membrane is an anion exchange membrane, preferably a homogeneous ion exchange membrane.
Preferably, the voltage of electrolysis is 5-10V.
Preferably, the electrolysis time is 2-4 h.
Preferably, the temperature of electrolysis is 200-.
Preferably, the volume ratio of the tetrachloroethylene to the ionic liquid in the catholyte is 10: 51-53.
Preferably, the distance between the cathode and the anode is 0.5-1.5 cm.
Preferably, the total volume of tetrachloroethylene and catholyte is the same as the volume of anolyte.
Preferably, the electrolysis is carried out in an inert gas atmosphere; the inert gas is preferably argon or the like.
Preferably, sonication is continued during electrolysis; the ultrasonic power is preferably 300-400W; the catholyte can be continuously stirred in the electrolysis process; the stirring speed is preferably 400-700 rmp.
Purifying after electrolysis to obtain graphene; the specific purification steps may be: and washing the electrolyzed cathode, uniformly mixing the washing solution and the electrolyzed cathode solution, performing solid-liquid separation, washing, and drying to obtain the graphene.
The invention also provides graphene prepared by the preparation method of the graphene.
Has the advantages that:
1. in the double-chamber electrolytic cell, copper-nickel-zinc alloy is selected as a cathode and appropriate catholyte is screened, so that the copper-nickel-zinc alloy and appropriate ionic liquid are catalyzed together, the reaction activation energy is reduced, and tetrachloroethylene is catalytically electrolyzed to generate graphene; tetrachloroethylene generates activated carbon atoms (or carbon-containing active groups) and chloride ions through electrocatalytic reaction at a cathode; the activated carbon atoms form graphene in the cathode chamber, and chloride ions generated by the cathode enter the surface of the anode through an anion exchange membrane to generate an electrode reaction to generate chlorine; the generated chlorine can be absorbed by alkali liquor (such as sodium hydroxide aqueous solution), so as to avoid the pollution to the environment. The reaction formula of tetrachloroethylene electrolysis is as follows: c2Cl4→graphene+Cl2↑。
2.1-butyl-3-methylimidazole chlorine salt and 1-butyl-3-methylimidazole hexafluorophosphate are matched with each other in a proper proportion, so that the catalyst has strong catalytic capability on tetrachloroethylene electrolysis, and the ionic liquid can be recycled, so that the cost is reduced; the cathode liquid and the anode liquid are separated by the diaphragm, so that side reaction during electrolysis can be avoided, and the later purification operation can be reduced; in the electrolytic process, continuous ultrasonic and continuous stirring are carried out, so that the generated graphene can be uniformly dispersed and suspended in the catholyte in the form of tiny particles, and the graphene can be prevented from being deposited on the surface of a cathode, so that the graphene is promoted to be separated from the surface of the cathode.
3. Compared with the traditional method, the method has many incomparable advantages, such as simple equipment, high reaction speed, mild conditions, high reaction efficiency, wide application range, simple operation and environmental protection. The method can effectively simplify the existing production process, further improve the economic benefit of graphene production and solve the problem of environmental pollution.
Drawings
Fig. 1 is a transmission electron micrograph of graphene prepared in example 1.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of graphene comprises the following steps:
respectively putting a titanium ruthenium-coated inert electrode and a copper nickel zinc alloy electrode into water at 40-100 ℃ for cleaning, then ultrasonically cleaning by using an organic solvent, activating, and blow-drying for later use;
to 100mL of 1-butyl-3-methylimidazolium chloride salt (abbreviated as [ Bmim ]]Cl) was added 4mL of 1-butyl-3-methylimidazolium hexafluorophosphate ([ Bmim for short)]PF6) 0.75g of polyvinylpyrrolidone, stirring and uniformly mixing by ultrasonic to obtain catholyte; then adding 20mL of tetrachloroethylene into the catholyte and uniformly mixing to obtain a solution A;
taking a double-chamber electrolytic cell, wherein a cathode chamber and an anode chamber are separated by an anion exchange membrane; placing the double-chamber electrolytic cell in a heater, then placing a copper-nickel-zinc alloy electrode in a cathode chamber, placing a titanium ruthenium-coated inert electrode in an anode chamber, keeping the distance between the two electrodes at 1cm, then introducing argon into the heater and the electrolytic cell at the flow rate of 150mL/min to remove air in the heater and the electrolytic cell, then heating to 275 ℃ at the speed of 7.5 ℃/min and preserving heat; switching on a stabilized voltage power supply, pouring 20mL of the solution A into the cathode chamber, and pouring 20mL of 1-butyl-3-methylimidazole chloride into the anode chamber to serve as an anolyte;
and arranging a stirrer in the cathode chamber, continuously stirring at the speed of 550rmp, continuously performing ultrasonic treatment on the cathode chamber at the power of 350W, adjusting the voltage of an electrolytic tank to 7.5V, continuously performing ultrasonic treatment, stirring, maintaining constant temperature and constant pressure, electrolyzing for 3 hours, absorbing chlorine generated by an anode by alkali liquor, stopping electrolysis and heating, cooling to room temperature, closing an argon valve, taking out the electrolytic tank, cleaning the electrolyzed cathode, uniformly mixing a cleaning solution and the electrolyzed cathode solution, performing solid-liquid separation, washing and drying to obtain the graphene.
The graphene obtained in example 1 was used for detection, and the result is shown in fig. 1. Fig. 1 is a transmission electron micrograph of graphene prepared in example 1.
As can be seen from fig. 1, graphene was successfully prepared by the method of the present invention.
Example 2
A preparation method of graphene comprises the following steps:
respectively putting a titanium ruthenium-coated inert electrode and a copper nickel zinc alloy electrode into water at 40-100 ℃ for cleaning, then ultrasonically cleaning by using an organic solvent, activating, and blow-drying for later use;
adding 2mL of 1-butyl-3-methylimidazole hexafluorophosphate and 0.5g of polyvinylpyrrolidone into 100mL of 1-butyl-3-methylimidazole chloride salt, stirring and uniformly mixing by ultrasonic waves to obtain catholyte; then adding 20mL of tetrachloroethylene into the catholyte and uniformly mixing to obtain a solution A;
taking a double-chamber electrolytic cell, wherein a cathode chamber and an anode chamber are separated by an anion exchange membrane; placing the double-chamber electrolytic cell in a heater, then placing a copper-nickel-zinc alloy electrode in a cathode chamber, placing a titanium ruthenium-coated inert electrode in an anode chamber, keeping the distance between the two electrodes at 0.5cm, then introducing argon into the heater and the electrolytic cell at a flow rate of 200mL/min to remove air in the heater and the electrolytic cell, then heating to 350 ℃ at a speed of 5 ℃/min and preserving heat; switching on a stabilized voltage power supply, pouring 20mL of the solution A into the cathode chamber, and pouring 20mL of 1-butyl-3-methylimidazole chloride into the anode chamber to serve as an anolyte;
and arranging a stirrer in the cathode chamber, continuously stirring at the speed of 400rmp, continuously performing ultrasonic treatment on the cathode chamber at the power of 400W, adjusting the voltage of an electrolytic tank to 5V, continuously performing ultrasonic treatment, stirring and maintaining constant temperature and constant pressure for electrolysis for 4h, absorbing chlorine generated by an anode by alkali liquor, stopping electrolysis and heating, cooling to room temperature, closing an argon valve, taking out the electrolytic tank, cleaning the electrolyzed cathode, uniformly mixing a cleaning solution and the electrolyzed cathode solution, performing solid-liquid separation, washing and drying to obtain the graphene.
Example 3
A preparation method of graphene comprises the following steps:
respectively putting a titanium ruthenium-coated inert electrode and a copper nickel zinc alloy electrode into water at 40-100 ℃ for cleaning, then ultrasonically cleaning by using an organic solvent, activating, and blow-drying for later use;
adding 6mL of 1-butyl-3-methylimidazole hexafluorophosphate and 1g of polyvinylpyrrolidone into 100mL of 1-butyl-3-methylimidazole chloride salt, stirring and uniformly mixing by ultrasonic waves to obtain catholyte; then adding 20mL of tetrachloroethylene into the catholyte and uniformly mixing to obtain a solution A;
taking a double-chamber electrolytic cell, wherein a cathode chamber and an anode chamber are separated by an anion exchange membrane; placing the double-chamber electrolytic cell in a heater, then placing a copper-nickel-zinc alloy electrode in a cathode chamber, placing a titanium ruthenium-coated inert electrode in an anode chamber, keeping the distance between the two electrodes at 1.5cm, then introducing argon into the heater and the electrolytic cell at the flow rate of 100mL/min to remove air in the heater and the electrolytic cell, then heating to 200 ℃ at the speed of 10 ℃/min and preserving heat; switching on a stabilized voltage power supply, pouring 20mL of the solution A into the cathode chamber, and pouring 20mL of 1-butyl-3-methylimidazole chloride into the anode chamber to serve as an anolyte;
and arranging a stirrer in the cathode chamber, continuously stirring at the speed of 700rmp, continuously performing ultrasonic treatment on the cathode chamber at the power of 300W, adjusting the voltage of an electrolytic tank to 10V, continuously performing ultrasonic treatment, stirring and maintaining constant temperature and constant pressure for electrolysis for 2h, absorbing chlorine generated by an anode by alkali liquor, stopping electrolysis and heating, cooling to room temperature, closing an argon valve, taking out the electrolytic tank, cleaning the electrolyzed cathode, uniformly mixing a cleaning solution and the electrolyzed cathode solution, performing solid-liquid separation, washing and drying to obtain the graphene.
Example 4
A preparation method of graphene comprises the following steps:
respectively putting a titanium ruthenium-coated inert electrode and a copper nickel zinc alloy electrode into water at 40-100 ℃ for cleaning, then ultrasonically cleaning by using an organic solvent, activating, and blow-drying for later use;
adding 3mL of 1-butyl-3-methylimidazole hexafluorophosphate and 0.8g of polyvinylpyrrolidone into 100mL of 1-butyl-3-methylimidazole chloride salt, stirring and uniformly mixing by ultrasonic waves to obtain catholyte; then adding 20mL of tetrachloroethylene into the catholyte and uniformly mixing to obtain a solution A;
taking a double-chamber electrolytic cell, wherein a cathode chamber and an anode chamber are separated by an anion exchange membrane; placing the double-chamber electrolytic cell in a heater, then placing a copper-nickel-zinc alloy electrode in a cathode chamber, placing a titanium ruthenium-coated inert electrode in an anode chamber, keeping the distance between the two electrodes at 0.8cm, then introducing argon into the heater and the electrolytic cell at the flow rate of 170mL/min to remove air in the heater and the electrolytic cell, then heating to 300 ℃ at the speed of 8 ℃/min and preserving heat; switching on a stabilized voltage power supply, pouring 20mL of the solution A into the cathode chamber, and pouring 20mL of 1-butyl-3-methylimidazole chloride into the anode chamber to serve as an anolyte;
and arranging a stirrer in the cathode chamber, continuously stirring at the speed of 500rmp, continuously performing ultrasonic treatment on the cathode chamber at the power of 320W, adjusting the voltage of an electrolytic tank to 7V, continuously performing ultrasonic treatment, stirring, maintaining the constant temperature and the constant pressure, performing electrolysis for 3.5h, absorbing chlorine generated at the anode by alkali liquor, stopping electrolysis and heating, cooling to room temperature, closing an argon valve, taking out the electrolytic tank, cleaning the electrolyzed cathode, uniformly mixing a cleaning solution and the electrolyzed cathode solution, performing solid-liquid separation, washing and drying to obtain the graphene.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of graphene is characterized by comprising the following steps: electrolyzing tetrachloroethylene in an electrolytic cell, wherein the electrolytic cell comprises: a cathode, an anode, a catholyte and an anolyte, the catholyte and the anolyte being separated by a membrane;
adding tetrachloroethylene into the catholyte, and electrolyzing to obtain graphene; the cathode is a copper nickel zinc alloy electrode, and the anode is a titanium ruthenium-coated inert electrode.
2. The method for preparing graphene according to claim 1, wherein the catholyte is a mixture of an ionic liquid and polyvinylpyrrolidone.
3. The method for preparing graphene according to claim 2, wherein in the catholyte, the ionic liquid is a mixture of 1-butyl-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium hexafluorophosphate; preferably, the volume ratio of the 1-butyl-3-methylimidazole chloride salt to the 1-butyl-3-methylimidazole hexafluorophosphate salt is 50: 1-3; preferably, the volume-to-weight ratio (mL/g) of the ionic liquid to the polyvinylpyrrolidone in the catholyte is 102-106: 0.5-1.
4. The method for preparing graphene according to any one of claims 1 to 3, wherein the anolyte is an ionic liquid; preferably, the anolyte is 1-butyl-3-methylimidazolium chloride.
5. The method for preparing graphene according to any one of claims 1 to 4, wherein the membrane is an anion exchange membrane.
6. The method for producing graphene according to any one of claims 1 to 5, wherein the voltage for electrolysis is 5 to 10V; preferably, the electrolysis time is 2-4 h; preferably, the temperature of electrolysis is 200-.
7. The method for preparing graphene according to any one of claims 1 to 6, wherein the volume ratio of tetrachloroethylene to the ionic liquid in the catholyte is 10:51 to 53.
8. The method for producing graphene according to any one of claims 1 to 7, wherein the distance between the cathode and the anode is 0.5 to 1.5 cm; preferably, the total volume of tetrachloroethylene and catholyte is the same as the volume of anolyte.
9. The method for producing graphene according to any one of claims 1 to 8, wherein electrolysis is performed in an inert gas atmosphere; preferably, sonication is continued during electrolysis.
10. Graphene obtained by the method for producing graphene according to any one of claims 1 to 9.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
| CN101634032A (en) * | 2009-08-14 | 2010-01-27 | 南京大学 | Green and fast electrochemical preparation method for graphene |
| CN102465309A (en) * | 2010-11-10 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| KR20120103987A (en) * | 2011-03-11 | 2012-09-20 | 인하대학교 산학협력단 | Method of manufacturing graphene using electronic decomposition |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| CN103407998A (en) * | 2013-07-19 | 2013-11-27 | 华侨大学 | Preparation method of high concentration and small flake diameter graphene dispersion |
| CN105624722A (en) * | 2016-01-05 | 2016-06-01 | 北京金吕能源科技有限公司 | Method for preparing graphene or carbon nanotubes by electrolyzing carbon dioxide |
| US20160168726A1 (en) * | 2013-08-06 | 2016-06-16 | The University Of Manchester | Production of graphene and graphane |
| CN109072457A (en) * | 2016-02-17 | 2018-12-21 | 金属电解有限公司 | The method for preparing grapheme material |
| CN109321932A (en) * | 2018-10-30 | 2019-02-12 | 深圳大学 | Graphene and the preparation method and application thereof |
| JP2020050577A (en) * | 2018-09-28 | 2020-04-02 | 国立大学法人宇都宮大学 | Manufacturing method of graphene dispersion |
| CN111575725A (en) * | 2020-05-18 | 2020-08-25 | 中国华能集团清洁能源技术研究院有限公司 | CO (carbon monoxide)2Method for preparing graphene through electrochemical conversion |
-
2021
- 2021-11-05 CN CN202111304733.0A patent/CN114032560A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462719A (en) * | 2009-01-16 | 2009-06-24 | 北京大学 | Preparation of graphene |
| CN101634032A (en) * | 2009-08-14 | 2010-01-27 | 南京大学 | Green and fast electrochemical preparation method for graphene |
| CN102465309A (en) * | 2010-11-10 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| KR20120103987A (en) * | 2011-03-11 | 2012-09-20 | 인하대학교 산학협력단 | Method of manufacturing graphene using electronic decomposition |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| CN103407998A (en) * | 2013-07-19 | 2013-11-27 | 华侨大学 | Preparation method of high concentration and small flake diameter graphene dispersion |
| US20160168726A1 (en) * | 2013-08-06 | 2016-06-16 | The University Of Manchester | Production of graphene and graphane |
| CN105624722A (en) * | 2016-01-05 | 2016-06-01 | 北京金吕能源科技有限公司 | Method for preparing graphene or carbon nanotubes by electrolyzing carbon dioxide |
| CN109072457A (en) * | 2016-02-17 | 2018-12-21 | 金属电解有限公司 | The method for preparing grapheme material |
| JP2020050577A (en) * | 2018-09-28 | 2020-04-02 | 国立大学法人宇都宮大学 | Manufacturing method of graphene dispersion |
| CN109321932A (en) * | 2018-10-30 | 2019-02-12 | 深圳大学 | Graphene and the preparation method and application thereof |
| CN111575725A (en) * | 2020-05-18 | 2020-08-25 | 中国华能集团清洁能源技术研究院有限公司 | CO (carbon monoxide)2Method for preparing graphene through electrochemical conversion |
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