CN112093796A - Preparation method of sulfur-nitrogen doped graphene material - Google Patents
Preparation method of sulfur-nitrogen doped graphene material Download PDFInfo
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- CN112093796A CN112093796A CN202011015162.4A CN202011015162A CN112093796A CN 112093796 A CN112093796 A CN 112093796A CN 202011015162 A CN202011015162 A CN 202011015162A CN 112093796 A CN112093796 A CN 112093796A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
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- 239000000843 powder Substances 0.000 claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 45
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- 239000011593 sulfur Substances 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
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- 238000000034 method Methods 0.000 claims abstract description 22
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- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
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- 239000002904 solvent Substances 0.000 claims description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- KYWWFMUUMKLHES-UHFFFAOYSA-N 4-(phenyldisulfanyl)aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=CC=C1 KYWWFMUUMKLHES-UHFFFAOYSA-N 0.000 claims description 3
- TZQVSGOOKNNDFU-UHFFFAOYSA-N 4-phenylsulfanylaniline Chemical compound C1=CC(N)=CC=C1SC1=CC=CC=C1 TZQVSGOOKNNDFU-UHFFFAOYSA-N 0.000 claims description 3
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 3
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 claims description 3
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- AEHWKBXBXYNPCX-UHFFFAOYSA-N ethylsulfanylbenzene Chemical compound CCSC1=CC=CC=C1 AEHWKBXBXYNPCX-UHFFFAOYSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000380131 Ammophila arenaria Species 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 241001394244 Planea Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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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
- C01B2204/04—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
Abstract
The invention relates to the technical field of doped graphene preparation, in particular to a preparation method of a sulfur-nitrogen doped graphene material, which comprises the following steps: (1) providing a graphite oxide dispersion liquid; (2) providing a material dispersion containing sulfur and nitrogen elements; (3) mixing the graphite oxide dispersion liquid and the substance dispersion liquid containing the sulfur and nitrogen elements to obtain a mixed solution, and carrying out stirring or ultrasonic treatment on the mixed solution, and carrying out freeze drying or heating drying and pulverizing to obtain a compound of the graphite oxide and the substance containing the sulfur and nitrogen elements; (4) and performing thermal expansion treatment on the composite powder to obtain the sulfur-nitrogen doped graphene material. The method can realize large-scale preparation of sulfur-doped graphene powder, nitrogen-doped graphene powder or sulfur-nitrogen co-doped graphene powder; the thermal expansion temperature is low, and the doped graphene powder can be prepared with low energy consumption; the preparation process is simple and easy to realize industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation of doped graphene, in particular to a preparation method of a sulfur-nitrogen doped graphene material.
Background
Graphene is a two-dimensional planar structure composed of a single layer of carbon atoms, three of whose four valence electrons are sp2The hybridized orbital and three adjacent carbon atoms form a honeycomb structure with plane regular hexagon connection, and valence electrons perpendicular to the plane of the carbon atoms form large electrons on two sides of a lattice plane
A key. In 2004, the physicist Andeli Helm and Constantin Norway Showcov, Manchester university, UK, succeeded in achieving mechanical exfoliationIn the experiment, graphene is separated from graphite and unique physical properties of the graphene are revealed, and two people also obtain a 2010 Nobel prize together due to research on 'pioneering experiments on two-dimensional graphene materials'.
The special two-dimensional structure of graphene determines that the graphene has unique and abundant properties: the graphene has extremely high strength and thermal conductivity, the Young modulus of the graphene can reach 1TPa, and the thermal conductivity can reach 5300W/mK; in addition, graphene exhibits good electrical conductivity and very high electron mobility, nonlinear optical properties, and quantum hall effect at room temperature. Due to the unique and excellent properties, the graphene has wide application, for example, the graphene has potential application prospects in various fields such as solar cells, field effect transistors, field emission materials, touch screens, sensitive sensors, super capacitors, composite materials and the like.
The preparation of graphene with high quality, low cost and large scale cannot be avoided in order to realize the potential application of the extraordinary physical properties of graphene in materials. At present, the preparation method of graphene powder mainly comprises the following steps: the method for ultrasonically stripping the graphite powder in the solvent can be used for large-scale powder preparation, but the obtained graphene has a thicker sheet layer and cannot well reflect the performance of the graphene; the graphene is obtained by reducing the oxidized graphene powder, the method can also realize large-scale preparation of the graphene powder, but the prepared graphene powder contains more oxygen-containing functional groups, and meanwhile, the complete lattice structure of the graphene is also damaged, so that the electrical conductivity and the thermal conductivity are reduced, and the exertion of the excellent performance of the graphene is influenced. Recent research proves that the graphene doping can effectively improve the conductivity of the graphene. In order to improve the performance of graphene powder prepared by oxidation reduction, a preparation method for preparing a sulfur-nitrogen doped graphene material in a large scale is provided.
Disclosure of Invention
In order to overcome the defects of the existing preparation technology of the sulfur-nitrogen doped graphene material, the invention provides a preparation method of the sulfur-nitrogen doped graphene material.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a sulfur-nitrogen doped graphene material comprises the following steps:
(1) providing a graphite oxide dispersion liquid;
(2) providing a material dispersion containing sulfur and nitrogen elements;
(3) mixing the graphite oxide dispersion liquid and the substance dispersion liquid containing the sulfur and nitrogen elements to obtain a mixed solution, and carrying out stirring or ultrasonic treatment on the mixed solution, and carrying out freeze drying or heating drying and pulverizing to obtain a compound of the graphite oxide and the substance containing the sulfur and nitrogen elements;
(4) and performing thermal expansion treatment on the composite powder to obtain the sulfur-nitrogen doped graphene material.
According to another embodiment of the present invention, the graphite oxide dispersion liquid in the step (1) further includes a solvent and graphite oxide dispersed in the solvent, the solvent includes one or a mixture of two or more of water, ethanol, methanol, NMP, DMF, tetrahydrofuran and isopropanol, and the concentration of the graphite oxide dispersion liquid is 0.1-15 mg/ml.
According to another embodiment of the present invention, the substance containing sulfur and nitrogen in step (2) further comprises one or more of elemental sulfur, thiourea, ammonia, urea, hydrazine hydrate, melamine, dimethyl sulfoxide, sulfur trioxide, sulfamide, ammonium thiocyanate, phenylene sulfide, ethylphenyl sulfide, ethionine, ethylene thiourea, ammonium thiosulfate, thiophenol, diphenyl disulfide, aminodiphenyl sulfide, aminodiphenyl disulfide.
According to another embodiment of the present invention, the solvent further comprising the dispersion liquid of the elemental sulfur and nitrogen-containing substance in the step (2) comprises water, ethanol, methanol, benzene, toluene, xylene, anisole, toluene,N,NOne or more than two mixed solutions of dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, carbon disulfide and N-methylpyrrolidone, wherein the concentration of the substance dispersion liquid of the sulfur and nitrogen elements is 0.1-10 mol/L.
According to another embodiment of the invention, the method further comprises the step of subjecting the mixed solution in the step (3) to stirring or ultrasonic treatment to obtain a composite of graphite oxide and sulfur-nitrogen-containing substance, wherein the stirring time is 10 minutes to 24 hours, and the ultrasonic time is 1 minute to 8 hours.
According to another embodiment of the invention, the method further comprises the step (3) of heating and drying the compound of graphite oxide and sulfur-nitrogen-containing substance, and pulverizing to obtain compound powder, or freeze-drying to obtain compound powder.
According to another embodiment of the invention, the method further comprises the step (3) of heating and drying the compound of the graphite oxide and the sulfur and nitrogen-containing substance to obtain a compound block, wherein the heating temperature is 50-90 ℃, and a pulverizer is adopted in the compound block pulverizing process.
According to another embodiment of the invention, the mass ratio of the graphite oxide to the sulfur-nitrogen-containing substance in the composite of the graphite oxide and the sulfur-nitrogen-containing substance in the step (3) is 1: 1-100: 1.
According to another embodiment of the invention, the compound powder in the step (4) is subjected to thermal expansion treatment to obtain the sulfur-nitrogen doped graphene material, the thermal expansion temperature range is 250-1050 ℃, the content of sulfur and nitrogen elements in the sulfur-nitrogen doped graphene material is 0.01-55%, and the number of layers of the sulfur-nitrogen doped graphene material graphene sheets is 1-5.
The invention has the beneficial effects that: the method can realize large-scale preparation of sulfur-doped graphene powder, nitrogen-doped graphene powder or sulfur-nitrogen co-doped graphene powder; the thermal expansion temperature is low, and the doped graphene powder can be prepared with low energy consumption; the preparation process is simple, and industrial large-scale production is easy to realize; the prepared doped graphene powder has excellent performance, and can be widely used in the fields of preparing graphene devices, supercapacitors, lithium ion batteries and the like.
Detailed Description
A preparation method of a sulfur-nitrogen doped graphene material is characterized by comprising the following steps:
(1) providing a graphite oxide dispersion liquid;
(2) providing a material dispersion containing sulfur and nitrogen elements;
(3) mixing the graphite oxide dispersion liquid and the substance dispersion liquid containing the sulfur and nitrogen elements to obtain a mixed solution, and carrying out stirring or ultrasonic treatment on the mixed solution, and carrying out freeze drying or heating drying and pulverizing to obtain a compound of the graphite oxide and the substance containing the sulfur and nitrogen elements;
(4) and performing thermal expansion treatment on the composite powder to obtain the sulfur-nitrogen doped graphene material.
The graphite oxide dispersion liquid in the step (1) comprises a solvent and graphite oxide dispersed in the solvent, wherein the solvent comprises one or a mixed solution of more than two of water, ethanol, methanol, NMP, DMF, tetrahydrofuran and isopropanol, and the concentration of the graphite oxide dispersion liquid is 0.1-15 mg/ml.
The sulfur and nitrogen element-containing substance in the step (2) comprises one or more of elemental sulfur, thiourea, ammonia water, urea, hydrazine hydrate, melamine, dimethyl sulfoxide, sulfur trioxide, sulfamide, ammonium thiocyanate, phenylene sulfide, ethyl phenyl sulfide, ethionine, ethylene thiourea, ammonium thiosulfate, thiophenol, diphenyl disulfide, aminodiphenyl sulfide, aminodiphenyl disulfide.
The solvent of the substance dispersion liquid containing the sulfur and nitrogen element in the step (2) comprises water, ethanol, methanol, benzene, toluene, xylene, anisole,N,NOne or more than two mixed solutions of dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, carbon disulfide and N-methylpyrrolidone, wherein the concentration of the substance dispersion liquid of the sulfur and nitrogen elements is 0.1-10 mol/L.
And (3) stirring or ultrasonically treating the mixed solution in the step (3) to obtain a compound of graphite oxide and a sulfur-nitrogen-containing substance, wherein the stirring time is 10 minutes to 24 hours, and the ultrasonic time is 1 minute to 8 hours.
And (4) heating and drying the compound of the graphite oxide and the sulfur and nitrogen-containing substance in the step (3) and pulverizing to obtain compound powder or freeze-drying to obtain the compound powder.
And (3) heating and drying the compound of the graphite oxide and the sulfur and nitrogen-containing substance to obtain a compound block, wherein the heating temperature is 50-90 ℃, and a crusher is adopted in the compound block powder making process.
The mass ratio of the graphite oxide to the sulfur-nitrogen-containing substance in the compound of the graphite oxide and the sulfur-nitrogen-containing substance in the step (3) is 1: 1-100: 1.
And (3) performing thermal expansion treatment on the composite powder in the step (4) to obtain a sulfur and nitrogen doped graphene material, wherein the thermal expansion temperature range is 250-1050 ℃, the content of sulfur and nitrogen elements in the sulfur and nitrogen doped graphene material is 0.01-55%, and the number of layers of graphene sheets of the sulfur and nitrogen doped graphene material is 1-5.
According to the invention, graphite oxide and sulfur and nitrogen containing substances are mixed, large-scale preparation of sulfur-doped graphene powder, nitrogen-doped graphene powder or sulfur and nitrogen co-doped graphene powder can be realized after thermal expansion treatment, and large-scale preparation of graphene materials with different sulfur and nitrogen contents can be realized by controlling the mass ratio of the graphite oxide to the sulfur and nitrogen containing substances.
Compared with other technologies for preparing the sulfur-nitrogen doped graphene material, the method has the innovative points that the method can be used for realizing large-scale preparation of sulfur-doped graphene powder, nitrogen-doped graphene powder or sulfur-nitrogen element co-doped graphene powder; the thermal expansion temperature is low, and the doped graphene powder can be prepared with low energy consumption; the preparation process is simple, and industrial large-scale production is easy to realize; the prepared doped graphene powder has excellent performance, and can be widely used in the fields of preparing graphene devices, supercapacitors, lithium ion batteries and the like.
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The first embodiment is as follows: the preparation method of the sulfur-doped graphene comprises the following steps:
(1) adding 100ml of 0.1mg/ml ethanol dispersion of graphite oxide into a 500ml beaker; adding 300ml of 0.1mol/L carbon disulfide solution of elemental sulfur into the dispersion liquid and stirring for 10 minutes;
(2) stirring the mixed solution obtained in the step (1) for 10 minutes by using a magnetic stirrer to obtain a mixed solution of graphite oxide and elemental sulfur;
(3) heating the mixed solution to obtain a solid of a flaky mixture, wherein the heating temperature is 50 ℃, and performing vacuum drying;
(4) crushing the flaky solid by a crusher to obtain powder of a mixture;
(5) and heating the mixture powder in an air atmosphere, and expanding the powder to obtain the sulfur-doped graphene powder.
Example two: the preparation method of the nitrogen-doped graphene comprises the following steps:
(1) adding 100ml of 2mg/ml graphite oxide aqueous dispersion into a 500ml beaker; 200ml of a 3mol/L methanolic solution of melamine are added to the dispersion and stirred for 12 hours;
(2) performing ultrasonic treatment on the mixed solution obtained in the step (1) for 30 minutes to obtain a mixed solution of graphite oxide and melamine;
(3) freeze-drying the mixed solution to obtain powder of the mixture, heating to 60 ℃, and vacuum-drying;
(4) and heating the mixture powder in an air atmosphere, and expanding the powder to obtain the nitrogen-doped graphene powder.
Example three: the preparation method of the sulfur-nitrogen co-doped graphene comprises the following steps:
(1) adding 100ml of 15mg/ml graphite oxide aqueous dispersion into a 500ml beaker; adding 200ml of 10mol/L tetrahydrofuran solution of thiourea into the dispersion and stirring for 24 hours;
(2) carrying out ultrasonic treatment on the mixed solution obtained in the step (1) for 8 hours to obtain a mixed dispersion liquid of graphite oxide and thiourea;
(3) freeze-drying the mixed solution to obtain powder of the mixture, heating to 90 ℃, and vacuum-drying;
(4) and heating the mixture powder in an air atmosphere, and expanding the powder to obtain the nitrogen-doped graphene powder.
The foregoing description is intended to be illustrative rather than limiting, and it will be appreciated by those skilled in the art that many modifications, variations or equivalents may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A preparation method of a sulfur-nitrogen doped graphene material is characterized by comprising the following steps:
(1) providing a graphite oxide dispersion liquid;
(2) providing a material dispersion containing sulfur and nitrogen elements;
(3) mixing the graphite oxide dispersion liquid and the substance dispersion liquid containing the sulfur and nitrogen elements to obtain a mixed solution, and carrying out stirring or ultrasonic treatment on the mixed solution, and carrying out freeze drying or heating drying and pulverizing to obtain a compound of the graphite oxide and the substance containing the sulfur and nitrogen elements;
(4) and performing thermal expansion treatment on the composite powder to obtain the sulfur-nitrogen doped graphene material.
2. The method according to claim 1, wherein the graphite oxide dispersion liquid in the step (1) comprises a solvent and graphite oxide dispersed in the solvent, the solvent comprises one or a mixture of two or more of water, ethanol, methanol, NMP, DMF, tetrahydrofuran and isopropanol, and the concentration of the graphite oxide dispersion liquid is 0.1-15 mg/ml.
3. The method according to claim 1, wherein the sulfur and nitrogen-containing substance in step (2) comprises one or more of elemental sulfur, thiourea, ammonia, urea, hydrazine hydrate, melamine, dimethyl sulfoxide, sulfur trioxide, sulfamide, ammonium thiocyanate, phenylene sulfide, ethylphenyl sulfide, ethionine, ethylene thiourea, ammonium thiosulfate, thiophenol, diphenyl disulfide, aminodiphenyl sulfide, aminodiphenyl disulfide.
4. The method according to claim 1, wherein the solvent of the dispersion liquid of the sulfur-nitrogen-containing substance in step (2) comprises water, ethanol, methanol, benzene, toluene, xylene, anisole, toluene, and mixtures thereof,N,NOne or more than two mixed solutions of dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, carbon disulfide and N-methylpyrrolidone, wherein the concentration of the substance dispersion liquid of the sulfur and nitrogen elements is 0.1-10 mol/L.
5. The method for preparing the sulfur-nitrogen-doped graphene material according to claim 1, wherein the mixed solution in the step (3) is subjected to stirring or ultrasonic treatment to obtain a composite of graphite oxide and a sulfur-nitrogen-containing substance, wherein the stirring time is 10 minutes to 24 hours, and the ultrasonic time is 1 minute to 8 hours.
6. The method according to claim 1, wherein the compound of graphite oxide and sulfur-nitrogen-containing substance in step (3) is heated, dried and pulverized to obtain compound powder, or is freeze-dried to obtain compound powder.
7. The preparation method of the sulfur-nitrogen doped graphene material according to claim 1, wherein the compound of the graphite oxide and the sulfur-nitrogen containing substance in the step (3) is heated and dried to obtain a compound block, the heating temperature is 50-90 ℃, and a pulverizer is adopted in the compound block pulverizing process.
8. The method for preparing the sulfur-nitrogen-doped graphene material as claimed in claim 1, wherein the mass ratio of the graphite oxide to the sulfur-nitrogen-containing substance in the composite of the graphite oxide and the sulfur-nitrogen-containing substance in the step (3) is 1: 1-100: 1.
9. The preparation method of the sulfur-nitrogen-doped graphene material according to claim 1, wherein the compound powder in the step (4) is subjected to thermal expansion treatment to obtain the sulfur-nitrogen-doped graphene material, the thermal expansion temperature range is 250-1050 ℃, the content of sulfur and nitrogen elements in the sulfur-nitrogen-doped graphene material is 0.01-55%, and the number of layers of graphene sheets of the sulfur-nitrogen-doped graphene material is 1-5.
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