CN115536014A - Method for electrochemically preparing graphene - Google Patents
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- CN115536014A CN115536014A CN202211151441.2A CN202211151441A CN115536014A CN 115536014 A CN115536014 A CN 115536014A CN 202211151441 A CN202211151441 A CN 202211151441A CN 115536014 A CN115536014 A CN 115536014A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
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- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 150000004770 chalcogenides Chemical class 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229910003321 CoFe Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910003153 β-FeOOH Inorganic materials 0.000 claims 1
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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
-
- 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
-
- 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
- C01B2204/32—Size or surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Nanotechnology (AREA)
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Abstract
The invention relates to the technical field of inorganic material preparation, and particularly discloses a method for electrochemically preparing graphene. The method comprises the following steps: placing a base material on a nickel net loaded with an oxygen evolution catalyst, and then wrapping and tabletting the nickel net and the base material by adopting a titanium net to form an electrode anode, wherein the base material comprises crystalline flake graphite, polytetrafluoroethylene and ethanol; inserting the electrode anode and the electrode cathode into an electrolyte to form an electrolytic system, applying voltage, and stripping the electrochemical anode to obtain a graphene anode; and soaking the graphene anode into an organic solvent to obtain a suspension containing graphene, and purifying the suspension containing graphene to obtain powder graphene. The method for electrochemically preparing graphene can generate gas and a concentrated acid environment automatically in the anode electrolysis process, and graphene with large transverse size, few layers and thin sheets can be obtained.
Description
Technical Field
The invention relates to the technical field of inorganic material preparation, in particular to a method for electrochemically preparing graphene.
Background
The graphene material has a special structure, excellent performance, rich energy storage of raw materials and low price, and has a very wide application prospect in a plurality of fields such as materials, chemistry, physics, biology, environment, energy sources and the like, and the key of the research and application of the graphene is the preparation technology of the graphene. China has abundant graphite deposits as a large graphite reserve country, and the exploitation cost is low. The natural graphite is used as a raw material to prepare the graphene in a stripping manner, so that the production cost can be greatly reduced, and the large-scale production of the powder graphene is facilitated. In the existing graphene preparation technology, methods such as mechanical stripping, liquid phase stripping and chemical stripping are available in terms of stripping methods.
At present, when graphene is industrially prepared, a graphite rod is generally used as a raw material, and the graphene is prepared by adopting a stripping method in an organic solvent, strong acid, strong base or strong oxidant, so that a large amount of waste liquid and pollutants are generated in the preparation process, the difficulty of environmental protection treatment is increased, the cost is greatly increased due to the fact that the graphite rod is used as the raw material, and the wide popularization and application of the graphene are limited. Although researchers try to prepare graphene by stripping by replacing reagents such as strong acid and strong base, it is still difficult to satisfy both the requirements of environmental friendliness and industrial mass production.
The electrochemical method gradually enters the visual field of researchers due to simple preparation process, low energy consumption and low cost. However, the electrochemical method is extremely dependent on an electrolyte in the preparation process, so that the stripped graphene has high oxidation degree and is thick, and the stripping speed is slow when the graphite electrode is subjected to electrochemical expansion, so that the industrial requirement is difficult to realize.
Disclosure of Invention
In view of this, the present application provides a method for electrochemically preparing graphene, wherein a specific metal mesh is used to prepare an electrochemical anode to be stripped, and a local concentrated acid environment generated near the anode promotes oxygen and other gases to be rapidly and efficiently inserted between graphite layers, so as to obtain a graphene with a size greater than 1 μm; graphene with the number of layers less than 5.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a method of electrochemically preparing graphene, the method comprising the steps of:
placing a base material on a nickel net loaded with an oxygen evolution catalyst, and then wrapping and tabletting the nickel net and the base material by adopting a titanium net to form an electrode anode, wherein the base material comprises crystalline flake graphite, polytetrafluoroethylene and ethanol;
inserting the electrode anode and the electrode cathode into electrolyte to form an electrolytic system, applying voltage, and stripping the electrochemical anode to obtain a graphene anode;
and step three, soaking the graphene anode into an organic solvent to obtain a turbid liquid containing graphene, and purifying the turbid liquid containing graphene to obtain powdered graphene.
Compared with the prior art, the method for electrochemically preparing graphene has the following advantages:
this application adopts the great titanium net of size to wrap nickel net, substrate, and the sandwich structure's of preparation sandwich as the substrate positive pole, after applying voltage, the interlamination of scale graphite is opened, and a large amount of hydrones, electrolyte ion enter into the interlamination, recycle titanium net, nickel net arouse oxygen evolution catalyst's catalytic action, take place at the positive pole and evolve oxygen reaction and produce oxygen, the H who generates simultaneously in this process at the positive pole + Ions and transferred anions form a local strong acid environment, under the action of a concentrated acid environment, the edge of graphite is oxidized, and oxygen and other gases, acid radical ions and oxidation functional groups are promoted to be rapidly and efficiently inserted between graphite layers, so that the crystalline flake graphite is gradually expanded, the graphite sheet layer is stripped by overcoming the action of van der Waals force, and the graphene with the transverse dimension larger than 1 mu m, the number of layers smaller than 5 and the thickness of the sheet layer is obtained.
The method for electrochemically preparing graphene automatically generates gas and a concentrated acid environment in the anode electrolysis process to obtain graphene with large transverse size, few layers and thin sheets.
Optionally, the oxygen evolution catalyst is hydrotalcite, a non-noble metal chalcogenide, cobalt phosphate or β -FeOOH.
Further optionally, the hydrotalcite is NiFe LDH or CoFe LDH.
Further optionally, the non-noble metal chalcogenide is CoS or CoSe.
The production of oxygen can be accelerated by the optimized oxygen evolution catalyst, the anode can rapidly reach a concentrated acid environment, the reaction process is accelerated, the graphene yield is greatly improved, the graphene prepared by the method is thinner, the quality is higher, and the method can be used for preparing ultrathin graphene powder on a large scale.
Optionally, the mesh sizes of the titanium mesh and the nickel mesh are both 150 meshes to 400 meshes.
Optionally, the thickness of the oxygen evolution catalyst on the titanium mesh is 1 nm-10 nm.
Optionally, the mass ratio of the crystalline flake graphite to the polytetrafluoroethylene is 4-9.
Optionally, the mass ratio of the polytetrafluoroethylene to the ethanol is 1.
The scale graphite and the polytetrafluoroethylene are mixed and bonded together according to the optimal proportion of the scale graphite to the polytetrafluoroethylene and the ethanol, so that the scale graphite in the anode is not easy to leak, and the natural scale graphite with low cost is ensured to be possible to be used as a raw material to be stripped.
Optionally, the organic solvent is N-methylpyrrolidone or N, N-dimethylformamide.
Optionally, the concentration of the electrolyte in the electrolyte is 0.3 mol/L-1 mol/L.
Optionally, the electrolyte in the electrolyte is ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, ammonium nitrate, sodium nitrate, ammonium phosphate, sodium phosphate or potassium perchlorate.
Further optionally, the electrolyte in the electrolyte is ammonium sulfate, sodium sulfate, potassium sulfate, or magnesium sulfate.
By means of the preferred electrolyte, H is formed at the anode during the electrolytic stripping process + Ions and transferred anions can form a local strong acid environment, SO 4 2 The anions are very lowHas a reduction potential of 0.20V and is easy to generate SO 2 Gas, under locally acidic conditions, oxygen, SO 2 And the gases are quickly and efficiently inserted between the graphite layers, so that the aim of stripping the graphite is fulfilled.
2H 2 O-4e→4H + +O 2 ↑
Optionally, the material of the electrode cathode is platinum, nickel, copper or graphite.
Further optionally, the cathode electrode is made of graphite, such as graphite-corresponding plate, wire or bar.
Optionally, the electrode cathode and the electrode anode are placed in the electrolyte in parallel, and the distance between the electrode cathode and the electrode anode is 2 cm-10 cm.
Through the optimal distance between the cathode and the anode, the generated gas is ensured to rapidly enter the layers of the crystalline flake graphite, the van der Waals force between the layers is damaged, and the graphene is rapidly stripped.
Optionally, the voltage is a continuous dc voltage, a pulsed dc voltage, or an ac voltage.
Further optionally, the voltage is a continuous dc voltage.
Optionally, the electrochemical anode stripping conditions are as follows: the voltage is 10V-30V, and the electrolysis time is 10 min-20 min.
By the preferable anode peeling conditions, the efficient insertion of gas such as oxygen between the graphite layers is promoted, so that the scale graphite is gradually expanded and the graphite sheets are peeled off against the van der waals force.
Optionally, the purification specifically comprises:
carrying out ultrasonic treatment and centrifugal treatment on the suspension containing graphene to obtain a dispersion liquid containing graphene;
and (3) adding ethanol into the dispersion liquid containing the graphene, performing suction filtration and drying to obtain graphene powder.
Optionally, the ultrasonic treatment conditions are as follows: the power is 100W-200W, and the time is 10 min-60 min.
Optionally, the centrifugation conditions are as follows: the speed is 4000rpm to 10000rpm, and the times are 2 to 3.
Optionally, the drying temperature is 50-70 ℃.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a reaction mechanism of electrochemical exfoliation of graphene provided in example 1 of the present invention;
fig. 2 is an X-ray diffraction pattern of graphene provided in example 1 of the present invention;
fig. 3 is a raman spectrum of graphene provided in example 1 of the present invention;
FIG. 4 is a TEM image of the graphene provided in example 1 of the present invention;
fig. 5 is an atomic force microscope image of graphene provided in example 1 of the present invention;
FIG. 6 is a transmission electron microscope image of graphene provided by comparative example 1 of the present invention;
fig. 7 is a transmission electron microscope image of graphene provided in comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment of the invention provides a method for electrochemically preparing graphene, which comprises the following steps:
step one, weighing 0.09g of natural crystalline flake graphite and 0.01g of polytetrafluoroethylene, uniformly mixing, and then dropwise adding 0.1mL of alcohol to form a base material;
growing NiFe LDH with the thickness of 5nm on a nickel net with the mesh number of 150 by adopting a solution in-situ growth method, then placing a base material on the nickel net, wrapping the nickel net and the base material by adopting a 150-mesh titanium net with larger size, and tabletting to obtain an electrode anode;
step two, under the condition of 14 ℃, preparing an ammonium sulfate solution with the concentration of 0.5mol/L as an electrolyte, taking a graphite rod as an electrode cathode, inserting the prepared electrode anode and the prepared electrode cathode into the electrolyte in parallel, wherein the distance between the electrode cathode and the electrode anode is 8cm, forming an electrolysis system, turning on a power supply to apply continuous direct current voltage with the voltage of 20V, and carrying out electrochemical anode stripping for 15min to obtain a graphene anode, wherein the reaction process is shown in figure 1;
soaking the graphene anode into N-methyl pyrrolidone to obtain a suspension containing graphene, performing ultrasonic treatment on the suspension containing graphene for 40min under the condition of 100W, performing centrifugal treatment under the condition of 4000rpm, taking supernatant, and centrifuging at the rotating speeds of 6000rpm and 8000rpm respectively to obtain a dispersion liquid containing graphene;
and (3) adding ethanol into the dispersion liquid containing the graphene, performing suction filtration, and drying at 60 ℃ to obtain graphene powder.
Example 2
The embodiment of the invention provides a method for electrochemically preparing graphene, which comprises the following steps:
step one, weighing 0.04g of natural crystalline flake graphite, uniformly mixing with 0.01g of polytetrafluoroethylene, and then dropwise adding 0.15mL of alcohol to form a base material;
adopting a solution in-situ growth method to grow CoFe LDH with the thickness of 1nm on a nickel net with the mesh number of 300 meshes, then placing a base material on the nickel net, then adopting a 300-mesh titanium net with larger size to wrap the nickel net and the base material, and tabletting to obtain an electrode anode;
step two, preparing a sodium sulfate solution with the concentration of 0.35mol/L as an electrolyte at the temperature of 20 ℃, taking a graphite rod as a cathode, inserting the prepared electrode anode and the prepared electrode cathode into the electrolyte in parallel, wherein the distance between the electrode cathode and the electrode anode is 2cm, forming an electrolytic system, turning on a power supply to apply continuous direct current voltage, and taking the voltage as 10V to perform electrochemical anode stripping for 20min to obtain a graphene anode;
soaking the graphene anode into N-methylpyrrolidone to obtain a suspension containing graphene, performing ultrasonic treatment on the suspension containing graphene under the condition of 200W for 20min, performing centrifugal treatment under the condition of 4000rpm, taking supernate, and then performing centrifugation at 6000rpm and 10000rpm respectively to obtain a dispersion liquid containing graphene;
and (3) adding ethanol into the dispersion liquid containing the graphene, performing suction filtration, and drying at 50 ℃ to obtain graphene powder.
Example 3
The embodiment of the invention provides a method for electrochemically preparing graphene, which comprises the following steps:
step one, weighing 0.05g of natural crystalline flake graphite and 0.01g of polytetrafluoroethylene, uniformly mixing, and then dropwise adding 0.06mL of alcohol to form a base material;
adopting a solution in-situ growth method to grow CoSe with the thickness of 10nm on a nickel net with the mesh number of 400 meshes, then placing a base material on the nickel net, then adopting a titanium net with the larger size of 400 meshes to wrap the nickel net and the base material, and tabletting to obtain an electrode anode;
step two, under the condition of 20 ℃, preparing an ammonium nitrate solution with the concentration of 1mol/L as an electrolyte, taking a graphite rod as a cathode, inserting the prepared electrode anode and the prepared electrode cathode into the electrolyte in parallel, wherein the distance between the electrode cathode and the electrode anode is 10cm, forming an electrolytic system, turning on a power supply to apply continuous direct current voltage, and performing electrochemical anode stripping for 10min to obtain a graphene anode, wherein the voltage is 30V;
soaking the graphene anode into N-methylpyrrolidone to obtain a suspension containing graphene, carrying out ultrasonic treatment on the suspension containing graphene under the condition of 150W for 60min, carrying out centrifugal treatment under the condition of 4000rpm, taking supernate, and then respectively centrifuging at the rotating speeds of 7000rpm and 9000rpm to obtain a dispersion liquid containing graphene;
and (3) adding ethanol into the dispersion liquid containing the graphene, performing suction filtration, and drying at 70 ℃ to obtain graphene powder.
Test example 1
The results of XRD, raman spectroscopy, transmission electron microscopy and atomic force microscopy of the graphene powder prepared in example 1 are shown in fig. 2 to 5.
As can be seen from fig. 2, the (002) crystal plane of graphene corresponds to the diffraction peak at 26.3 °, and the corresponding interlayer distance is
Interlayer spacing with respect to graphite
This indicates that the graphene prepared in example 1 of the present invention contains a small amount of functional groups, such as — OH, etc., on the surface.
As can be seen from FIG. 3, in the Raman spectrum, the G peak, which is the main characteristic peak of graphene, appears at 1580cm -1 Nearby, this is represented by sp 2 In-plane vibration of carbon atoms; the D peak is at 1350cm -1 Nearby, the edge is more or defect-caused, and in addition, the G peak is significantly higher than the D peak, thereby illustrating that the graphene prepared in example 1 of the present invention has high quality.
As can be seen from the transmission electron micrograph of fig. 4, the graphene prepared in example 1 of the present invention exhibits wrinkles, thereby illustrating that the prepared graphene is extremely thin.
As can be seen from the atomic force microscope image of fig. 5, the thickness of the graphene is about 0.7nm, and thus it can be seen that the graphene prepared in example 1 of the present invention has a nearly single-layer structure.
The graphene prepared in the embodiments 2 to 3 achieves substantially the same technical effect as the graphene prepared in the embodiment 1.
The same effects as those of example 1 can be achieved as long as the kind and thickness of the oxygen evolution catalyst, the specification of the titanium mesh, the specification of the nickel mesh, the mass ratio of the crystalline flake graphite/polytetrafluoroethylene/ethanol, the kind and concentration of the electrolyte, the anode stripping conditions, and the purification conditions are within the scope of the present application.
In order to better illustrate the technical solution of the present invention, further comparison is made below by comparing examples of the present invention with comparative examples.
Comparative example 1
This comparative example provides a process for electrochemically preparing graphene, similar to example 1, with the exception that: the nickel mesh was replaced with a copper mesh.
Comparative example 2
This comparative example provides a process for electrochemically preparing graphene, similar to example 1, with the exception that: the titanium mesh was replaced with tungsten mesh.
The results of transmission electron microscope analysis of the graphenes prepared in the comparative examples 1 and 2 are shown in fig. 6 to 7, and it can be seen from the drawings that the graphenes are thick and the preparation of single-layer graphenes is difficult to realize, therefore, the preparation of the anode with a sandwich-like structure by coating the graphenes with a specific metal mesh is beneficial to promoting the scale graphite to gradually expand and open, and the grapheme with a transverse dimension larger than 1 μm, a layer number smaller than 5 and a thin layer thickness is formed.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A method for electrochemically preparing graphene is characterized in that: the method comprises the following steps:
placing a base material on a nickel net loaded with an oxygen evolution catalyst, and then wrapping and tabletting the nickel net and the base material by adopting a titanium net to form an electrode anode, wherein the base material comprises crystalline flake graphite, polytetrafluoroethylene and ethanol;
inserting the electrode anode and the electrode cathode into electrolyte to form an electrolytic system, applying voltage, and stripping the electrochemical anode to obtain a graphene anode;
and step three, soaking the graphene anode into an organic solvent to obtain a turbid liquid containing graphene, and purifying the turbid liquid containing graphene to obtain powdered graphene.
2. The method of electrochemically preparing graphene according to claim 1, wherein: the oxygen evolution catalyst is hydrotalcite, non-noble metal chalcogenide, cobalt phosphate or beta-FeOOH.
3. The method of electrochemically preparing graphene according to claim 2, wherein: the hydrotalcite is NiFe LDH or CoFe LDH; and/or
The non-noble metal chalcogenide is CoS or CoSe.
4. The method of electrochemically preparing graphene according to claim 1, characterized in that: the mesh sizes of the titanium mesh and the nickel mesh are both 150 meshes to 400 meshes; and/or
The thickness of the oxygen evolution catalyst on the titanium mesh is 1 nm-10 nm.
5. The method of electrochemically preparing graphene according to claim 1, wherein: the mass ratio of the crystalline flake graphite to the polytetrafluoroethylene is 4-9; and/or
The mass ratio of the polytetrafluoroethylene to the ethanol is 1-12; and/or
The organic solvent is N-methyl pyrrolidone.
6. The method of electrochemically preparing graphene according to claim 1, wherein: the concentration of the electrolyte in the electrolyte is 0.3-1 mol/L; and/or
The electrolyte in the electrolyte is ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, ammonium nitrate, sodium nitrate, ammonium phosphate, sodium phosphate or potassium perchlorate.
7. The method of electrochemically preparing graphene according to claim 1, wherein: the cathode of the electrode is made of platinum, nickel, copper or graphite; and/or
The electrode cathode and the electrode anode are arranged in the electrolyte in parallel, and the distance between the electrode cathode and the electrode anode is 2 cm-10 cm.
8. The method of electrochemically preparing graphene according to claim 1, wherein: the voltage is continuous direct current voltage, pulse direct current voltage or alternating current voltage; and/or
The conditions for electrochemical anode stripping are as follows: the voltage is 10V-30V, and the electrolysis time is 10 min-20 min.
9. The method of electrochemically preparing graphene according to claim 1, wherein: the purification specifically comprises the following steps:
carrying out ultrasonic treatment and centrifugal treatment on the suspension containing the graphene to obtain a dispersion liquid containing the graphene;
and (3) adding ethanol into the dispersion liquid containing the graphene, performing suction filtration and drying to obtain graphene powder.
10. The method of electrochemically preparing graphene according to claim 9, wherein: the ultrasonic treatment conditions are as follows: the power is 100W-200W, and the time is 10 min-60 min; and/or
The conditions of the centrifugal treatment are as follows: the speed is 4000rpm to 10000rpm, and the times are 2 to 3; and/or
The drying temperature is 50-70 ℃.
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