CN111099581A - Method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by method - Google Patents
Method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by method Download PDFInfo
- Publication number
- CN111099581A CN111099581A CN201911390890.0A CN201911390890A CN111099581A CN 111099581 A CN111099581 A CN 111099581A CN 201911390890 A CN201911390890 A CN 201911390890A CN 111099581 A CN111099581 A CN 111099581A
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphite
- artificial graphite
- leftover
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 63
- 239000010439 graphite Substances 0.000 claims abstract description 63
- 239000004094 surface-active agent Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000007770 graphite material Substances 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005087 graphitization Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000000053 physical method Methods 0.000 abstract description 3
- 238000010008 shearing Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 47
- 239000000725 suspension Substances 0.000 description 12
- 238000004108 freeze drying Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- C01B2204/22—Electronic properties
-
- 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
Abstract
The invention provides a method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by the method, wherein the method comprises the following steps: mixing and dispersing the artificial graphite leftover materials and an organic solvent containing a surfactant to obtain a graphite turbid liquid, carrying out liquid phase stripping on the graphite turbid liquid to obtain a graphene dispersion liquid, and drying to obtain the graphene. The method adopts physical methods such as ultrasonic or shearing force to carry out in-situ liquid phase stripping on the leftover bits and pieces of the artificial graphite flakes in an organic solvent containing a surfactant to obtain the graphene, and can ensure that the structure and the performance of the graphene are not damaged. The invention adopts cheap and easily obtained leftover materials of the artificial graphite flakes as raw materials, changes waste into valuable, can effectively reduce the production cost, has controllable process and is suitable for industrialized popularization.
Description
Technical Field
The invention belongs to the technical field of graphite waste utilization, and relates to a method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by the method.
Background
Graphene is a two-dimensional planar sheet structure composed of sp2 hybridized carbon atoms. Graphene has excellent electrical, thermal, optical, and mechanical properties, and is therefore referred to as "magic material", "black gold", and the like. Due to these special properties, graphene can be applied in a wide variety of fields such as new energy, medical industry, aerospace, anticorrosive coatings, semiconductors, and the like. The development prospect of the graphene industry is bright, the market is huge, but a series of problems and restriction factors exist in the whole graphene industry development situation at present. The preparation of graphene is one of the bottlenecks that restrict the development of graphene applications. The mainstream preparation methods at present include a redox method, a chemical vapor deposition method, a liquid phase stripping method and the like. The oxidation-reduction method can be used for preparing graphene on a large scale, but in the preparation process, a large amount of strong oxidants such as concentrated sulfuric acid and potassium permanganate are used, so that a large amount of defects are introduced into the graphene structure while the environment is polluted. The chemical vapor deposition method can obtain high-quality graphene, but because the cost is high and the yield is low, the requirement of large-scale production cannot be met temporarily. The liquid phase stripping method is simple in operation and low in cost, and can be used for producing graphene on a large scale, but the quality of graphene products is greatly related to the quality of used graphite raw materials, so that the graphene produced by the liquid phase stripping method on the market at present has uneven quality, and most of the graphene is nano graphite sheets with more layers (>20 layers).
Therefore, the commercial application of graphene is not realized better, and how to prepare high-quality graphene with high efficiency and low cost is an urgent problem to be solved at present.
In recent years, with the rapid development of the consumer electronics industry, artificial graphite sheets are widely used for heat dissipation of electronic products. At present, the artificial graphite has a mature market and sufficient capacity, the total annual capacity is about ten million, and the competition among manufacturers is intense and the artificial graphite enters a price fight stage. The artificial graphite heat radiating fin takes Polyimide (PI) as a raw material, and the preparation process comprises high-temperature treatment, calendaring treatment, die cutting and the like. After the high-temperature treatment, the polyimide film is graphitized into a graphite film. In the subsequent die cutting process of the graphite film, partial unusable leftover materials are inevitably generated, and a large amount of waste is caused. The artificial graphite leftover materials are turned into wealth and are precisely processed into products with high added values, so that the cost of the artificial graphite radiating fin can be further reduced, resources can be saved, and waste can be avoided. Compared with the natural graphite powder raw material commonly used in the liquid phase stripping method, the artificial graphite leftover bits and pieces are subjected to high-temperature graphitization treatment, so that the purity is higher, the graphite crystal structure is more complete, and the artificial graphite leftover bits and pieces are theoretically more suitable to be used as the raw material for preparing graphene.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing graphene by utilizing artificial graphite leftover materials and the graphene obtained by the method. The invention adopts cheap and easily obtained leftover materials of the artificial graphite flakes as raw materials, changes waste into valuable, can effectively reduce the production cost, has controllable process and is suitable for industrialized popularization.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing graphene from artificial graphite leftover materials, wherein the method comprises:
mixing and dispersing the artificial graphite leftover materials and an organic solvent containing a surfactant to obtain a graphite turbid liquid, carrying out liquid phase stripping on the graphite turbid liquid to obtain a graphene dispersion liquid, and drying to obtain the graphene.
The method adopts physical methods such as ultrasonic or shearing force to carry out in-situ liquid phase stripping on the leftover bits and pieces of the artificial graphite flakes in an organic solvent containing a surfactant to obtain the graphene, and can ensure that the structure and the performance of the graphene are not damaged. The invention adopts cheap and easily obtained leftover materials of the artificial graphite flakes as raw materials, changes waste into valuable, can effectively reduce the production cost, has controllable process and is suitable for industrialized popularization.
As a preferred technical scheme of the invention, the artificial graphite leftover material is generated by the following steps:
in the process of producing the artificial graphite flake by using the polyimide raw material, the artificial graphite leftover bits and pieces are produced by die cutting after high-temperature graphitization.
As a preferable technical scheme, the method also comprises the step of crushing the artificial graphite leftover materials before mixing and dispersing.
In a preferred embodiment of the present invention, the pulverization is carried out in a pulverization device.
Preferably, the crushing device is a jet mill.
Preferably, the jet mill has a power of > 30kW, which may be, for example, 35kW, 40kW, 45kW, 50kW, 55kW, 60kW, 65kW, 70kW, 75kW, 80kW, 85kW, 90kW, 95kW or 100kW, but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the air pressure of the jet mill is > 0.7MPa, and may be, for example, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2.0MPa, but not limited to the values listed, and other values not listed in the range of values are also applicable.
In a preferred embodiment of the present invention, the particle size D50 of the graphite fine powder obtained by pulverizing the above-mentioned artificial graphite scraps is less than 100. mu.m, and may be, for example, 10 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm or 95 μm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
In a preferred embodiment of the present invention, the surfactant is one or a combination of at least two of polyvinylpyrrolidone, polyvinyl alcohol, and carboxymethylcellulose, and may be, for example, a combination of polyvinylpyrrolidone and polyvinyl alcohol, a combination of polyvinyl alcohol and carboxymethylcellulose, or a combination of polyvinylpyrrolidone and carboxymethylcellulose.
Preferably, the organic solvent comprises one or a combination of at least two of methanol, ethanol, isopropanol, acetone, cyclohexanone, N-methyl formamide, N-methyl acetamide, N-methyl pyrrolidone, toluene, styrene, dimethyl sulfoxide, chloroform, tetrahydrofuran, pyridine and polyphosphoric acid.
The amount ratio of the surfactant to the organic solvent is preferably 1g (100 to 1000) mL, and may be, for example, 1g:100mL, 1g:200mL, 1g:300mL, 1g:400mL, 1g:500mL, 1g:600mL, 1g:700mL, 1g:800mL, 1g:900mL or 1g:1000mL, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned values are also applicable.
In a preferred embodiment of the present invention, the amount ratio of the fine graphite powder obtained by pulverizing the artificial graphite scraps to the organic solvent containing the surfactant is 1g (50 to 100) mL, and may be, for example, 1g:50mL, 1g:55mL, 1g:60mL, 1g:65mL, 1g:70mL, 1g:75mL, 1g:80mL, 1g:85mL, 1g:90mL, 1g:95mL, or 1g:100mL, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned values are also applicable.
In a preferred embodiment of the present invention, in step (ii), the liquid phase stripping operation is performed in an ultrasonic generator, a high shear disperser, or a high speed ball mill.
Preferably, the liquid phase stripping operation is performed for 1 to 24 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
In a second aspect, the present invention provides a graphene prepared by the method of the first aspect.
In a preferred embodiment of the present invention, the lateral size distribution of the graphene is 2 to 10 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
Preferably, the number of graphene layers is 3 to 10, for example, 3, 4, 5, 6, 7, 8, 9 or 10 layers, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the specific surface area of the graphene is 300-600 m2G, may be, for example, 300m2/g、 320m2/g、340m2/g、360m2/g、380m2/g、400m2/g、420m2/g、440m2/g、 460m2/g、480m2/g、500m2/g、520m2/g、540m2/g、560m2G or 600m2In the following description,/g is not limited to the values listed, but other values not listed in the numerical range are equally applicable.
Preferably, the graphene has a conductivity of 1 × 105～5×105S/m may be, for example, 1.0X 105S/m、1.5×105S/m、2.0×105S/m、2.5×105S/m、3.0×105S/m、 3.5×105S/m、4.0×105S/m、4.5×105S/m or 5.0X 105S/m is, but not limited to, the recited values, and other unrecited values within the range of values are equally applicable.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between any of the above-recited numerical ranges not otherwise recited, and for the sake of brevity and clarity, the present disclosure is not intended to be exhaustive of the specific numerical values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
the method adopts physical methods such as ultrasonic or shearing force to carry out in-situ liquid phase stripping on the leftover bits and pieces of the artificial graphite flakes in an organic solvent containing a surfactant to obtain the graphene, and can ensure that the structure and the performance of the graphene are not damaged. The invention adopts cheap and easily obtained leftover materials of the artificial graphite flakes as raw materials, changes waste into valuable, can effectively reduce the production cost, has controllable process and is suitable for industrialized popularization.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for preparing graphene by utilizing artificial graphite leftover materials, which specifically comprises the following steps:
(1) the leftover material of artificial graphite is first treated into small graphite material of size over 1cm x 1 cm.
(2) And (2) putting the graphite raw material obtained in the step (1) into a jet mill, controlling the operation parameters of the jet mill to be 5kg/h, the pressure to be 0.8Mpa and the power to be 40kW, and crushing the graphite raw material to obtain graphite micro powder, wherein the particle size of the graphite micro powder is D50<100 mu m.
(3) Adding polyvinylpyrrolidone (PVP) serving as a surfactant into an organic solvent N-methylpyrrolidone (NMP), wherein the dosage ratio of the PVP to the NMP is 1g:500ml, and uniformly mixing to obtain a surfactant solution.
(4) Adding the graphite micro powder obtained in the step (2) into the surfactant solution obtained in the step (3), wherein the using amount ratio of the graphite micro powder to the surfactant solution is 1g to 100ml, and initially mixing to obtain a graphite suspension.
(5) And (5) carrying out ultrasonic treatment on the graphite suspension obtained in the step (4) in an ultrasonic generator for 1h to obtain a graphene dispersion liquid.
(6) And (5) carrying out freeze drying on the graphene dispersion liquid obtained in the step (5) to obtain graphene powder.
In the graphene powder product obtained in this example, 80% or more of graphene is within 5 layers, and 95% or more is within 10 layers. The transverse dimension is 80% concentrated in 4-10 μm. The specific surface area of the obtained graphene powder is 589m2The electric conductivity of the graphene powder is 3.3 multiplied by 105S/m。
Example 2
The embodiment provides a method for preparing graphene by utilizing artificial graphite leftover materials, which specifically comprises the following steps:
(1) the leftover material of artificial graphite is first treated into small graphite material of size over 1cm x 1 cm.
(2) And (2) putting the graphite raw material obtained in the step (1) into a jet mill, controlling the operation parameters of the jet mill to be 5kg/h, the pressure to be 0.8Mpa and the power to be 35kW, and crushing the graphite raw material to obtain graphite micro powder, wherein the particle size of the graphite micro powder is D50<100 mu m.
(3) Adding surfactant carboxymethyl cellulose into organic solvent ethanol, wherein the dosage ratio of the carboxymethyl cellulose to the ethanol is 1g to 100ml, and uniformly mixing to obtain the surfactant solution.
(4) Adding the graphite micro powder obtained in the step (2) into the surfactant solution obtained in the step (3), wherein the using amount ratio of the graphite micro powder to the surfactant solution is 1g:50ml, and initially mixing to obtain a graphite suspension.
(5) And (5) carrying out ultrasonic treatment on the graphite suspension obtained in the step (4) in an ultrasonic generator for 1h to obtain a graphene dispersion liquid.
(6) And (5) carrying out freeze drying on the graphene dispersion liquid obtained in the step (5) to obtain graphene powder.
In the graphene powder product obtained in this example, 60% or more of graphene is within 5 layers, and 80% or more is within 10 layers. The transverse dimension is 80% concentrated in 3-7 μm. The specific surface area of the obtained graphene powder is 364m2The electric conductivity of the graphene powder is 1.6 multiplied by 105S/m。
Example 3
The embodiment provides a method for preparing graphene by utilizing artificial graphite leftover materials, which specifically comprises the following steps:
(1) the leftover material of artificial graphite is first treated into small graphite material of size over 1cm x 1 cm.
(2) And (2) putting the graphite raw material obtained in the step (1) into a jet mill, controlling the operation parameters of the jet mill to be 5kg/h, the pressure to be 0.8Mpa and the power to be 40kW, and crushing the graphite raw material to obtain graphite micro powder, wherein the particle size of the graphite micro powder is D50<100 mu m.
(3) Adding polyvinylpyrrolidone (PVP) as a surfactant into isopropanol as an organic solvent, wherein the dosage ratio of the PVP to the isopropanol is 1g:300ml, and uniformly mixing to obtain a surfactant solution.
(4) Adding the graphite micro powder obtained in the step (2) into the surfactant solution obtained in the step (3), wherein the using amount ratio of the graphite micro powder to the surfactant solution is 1g:65ml, and initially mixing to obtain a graphite suspension.
(5) And (4) carrying out ultrasonic treatment on the graphite suspension liquid obtained in the step (4) in an ultrasonic generator for 10 hours to obtain a graphene dispersion liquid.
(6) And (5) carrying out freeze drying on the graphene dispersion liquid obtained in the step (5) to obtain graphene powder.
In the graphene powder product obtained in this example, 70% or more of graphene is within 5 layers, and 90% or more is within 10 layers. The transverse dimension is 80% concentrated in 2-8 μm. The specific surface area of the graphene powder is 435m2The electric conductivity of the graphene powder is 2.6 multiplied by 105S/m。
Example 4
The embodiment provides a method for preparing graphene by utilizing artificial graphite leftover materials, which specifically comprises the following steps:
(1) the leftover material of artificial graphite is first treated into small graphite material of size over 1cm x 1 cm.
(2) And (2) putting the graphite raw material obtained in the step (1) into a jet mill, controlling the operation parameters of the jet mill to be 5kg/h, the pressure to be 0.85Mpa and the power to be 45kW, and crushing the graphite raw material to obtain graphite micro powder, wherein the particle size of the graphite micro powder is D50<100 mu m.
(3) Adding a surfactant polyvinylpyrrolidone (PVP) into an organic solvent acetone, wherein the dosage ratio of the PVP to the acetone is 1g:500ml, and uniformly mixing to obtain a surfactant solution.
(4) Adding the graphite micropowder obtained in the step (2) into the surfactant solution obtained in the step (3), wherein the using amount ratio of the graphite micropowder to the surfactant solution is 1g:75ml, and preliminarily mixing to obtain a graphite suspension.
(5) And (4) carrying out ultrasonic treatment on the graphite suspension liquid obtained in the step (4) in an ultrasonic generator for 15h to obtain a graphene dispersion liquid.
(6) And (5) carrying out freeze drying on the graphene dispersion liquid obtained in the step (5) to obtain graphene powder.
In the graphene powder product obtained in this example, 70% or more of graphene is within 5 layers, and 90% or more is within 10 layers. The transverse dimension is 80% concentrated in 3-10 μm. The specific surface area of the graphene powder was measured to be 302m2The electric conductivity of the graphene powder is 1.9 multiplied by 105S/m。
Example 5
The embodiment provides a method for preparing graphene by utilizing artificial graphite leftover materials, which specifically comprises the following steps:
(1) the leftover material of artificial graphite is first treated into small graphite material of size over 1cm x 1 cm.
(2) And (2) putting the graphite raw material obtained in the step (1) into a jet mill, controlling the operation parameters of the jet mill to be 5kg/h, the pressure to be 0.9Mpa and the power to be 50kW, and crushing the graphite raw material to obtain graphite micro powder, wherein the particle size of the graphite micro powder is D50<100 mu m.
(3) Adding a surfactant polyvinylpyrrolidone (PVP) into an organic solvent N-methylformamide with the dosage ratio of 1g to 700ml, and uniformly mixing to obtain a surfactant solution.
(4) Adding the graphite micro powder obtained in the step (2) into the surfactant solution obtained in the step (3), wherein the using amount ratio of the graphite micro powder to the surfactant solution is 1g:85ml, and initially mixing to obtain a graphite suspension.
(5) And (4) carrying out ultrasonic treatment on the graphite suspension liquid obtained in the step (4) in an ultrasonic generator for 20 hours to obtain a graphene dispersion liquid.
(6) And (5) carrying out freeze drying on the graphene dispersion liquid obtained in the step (5) to obtain graphene powder.
In the graphene powder product obtained in this embodiment, 90% or more of graphene is within 5 layers, and 98% or more is within 10 layers. The transverse dimension is 90% concentrated in 4-10 μm. The specific surface area of the obtained graphene powder is 635m2The electric conductivity of the graphene powder is 4.5 multiplied by 105S/m。
Example 6
The embodiment provides a method for preparing graphene by utilizing artificial graphite leftover materials, which specifically comprises the following steps:
(1) the leftover material of artificial graphite is first treated into small graphite material of size over 1cm x 1 cm.
(2) And (2) putting the graphite raw material obtained in the step (1) into a jet mill, controlling the parameters of the jet mill to be 5kg/h, the pressure to be 1.0Mpa and the power to be 50kW, and crushing the graphite raw material to obtain graphite micro powder, wherein the particle size of the graphite micro powder is D50<100 mu m.
(3) Adding a surfactant polyvinyl alcohol into an organic solvent N-methylacetamide, wherein the dosage ratio of the polyvinyl alcohol to the N-methylacetamide is 1g to 1000ml, and uniformly mixing to obtain a surfactant solution.
(4) Adding the graphite micro powder obtained in the step (2) into the surfactant solution obtained in the step (3), wherein the using amount ratio of the graphite micro powder to the surfactant solution is 1g to 100ml, and initially mixing to obtain a graphite suspension.
(5) And (4) carrying out ultrasonic treatment on the graphite suspension liquid obtained in the step (4) in an ultrasonic generator for 24 hours to obtain a graphene dispersion liquid.
(6) And (5) carrying out freeze drying on the graphene dispersion liquid obtained in the step (5) to obtain graphene powder.
In the graphene powder product obtained in this example, 70% or more of graphene is within 5 layers, and 90% or more is within 10 layers. The transverse dimension is 80% concentrated in 2-8 μm. The specific surface area of the graphene powder is 321m2The electric conductivity of the graphene powder is 1.8 multiplied by 105S/m。
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing graphene by utilizing artificial graphite leftover materials is characterized by comprising the following steps:
mixing and dispersing the artificial graphite leftover materials and an organic solvent containing a surfactant to obtain a graphite turbid liquid, carrying out liquid phase stripping on the graphite turbid liquid to obtain a graphene dispersion liquid, and drying to obtain the graphene.
2. The method of claim 1, wherein the artificial graphite scrap is produced by:
in the process of producing the artificial graphite flake by using the polyimide raw material, the artificial graphite leftover bits and pieces are produced by die cutting after high-temperature graphitization.
3. The method of claim 1 or 2, further comprising comminuting the scrap graphite material prior to the mixing and dispersing.
4. A method according to claim 3, wherein said comminuting is performed in a comminuting device;
preferably, the crushing device is a jet mill;
preferably, the power of the jet mill is more than 30 kW;
preferably, the air pressure of the jet mill is more than 0.7 MPa.
5. The method as claimed in claim 3 or 4, wherein the particle size D50 of the graphite micropowder obtained by pulverizing the artificial graphite leftover is less than 100 μm.
6. The method according to any one of claims 1 to 5, wherein the surfactant is one or a combination of at least two of polyvinylpyrrolidone, polyvinyl alcohol, or carboxymethylcellulose;
preferably, the organic solvent comprises one or a combination of at least two of methanol, ethanol, isopropanol, acetone, cyclohexanone, N-methylformamide, N-methylacetamide, N-methylpyrrolidone, toluene, styrene, dimethyl sulfoxide, chloroform, tetrahydrofuran, pyridine and polyphosphoric acid;
preferably, the dosage ratio of the surfactant to the organic solvent is 1g (100-1000) mL.
7. The method according to any one of claims 1 to 6, wherein the using amount ratio of the graphite micropowder obtained by crushing the artificial graphite leftover material to the organic solvent containing the surfactant is 1g (50-100) mL.
8. The method of any one of claims 1-7, wherein the liquid phase stripping operation is performed in an ultrasonic generator, a high shear disperser, or a high speed ball mill;
preferably, the time of the liquid phase stripping operation is 1-24 h.
9. Graphene prepared by the method of any one of claims 1 to 8.
10. The graphene according to claim 9, wherein the lateral size distribution of the graphene is 2-10 μm;
preferably, the number of layers of the graphene is 3-10;
preferably, the specific surface area of the graphene is 300-600 m2/g；
Preferably, the graphene has a conductivity of 1 × 105～5×105S/m。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911390890.0A CN111099581A (en) | 2019-12-30 | 2019-12-30 | Method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911390890.0A CN111099581A (en) | 2019-12-30 | 2019-12-30 | Method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111099581A true CN111099581A (en) | 2020-05-05 |
Family
ID=70425628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911390890.0A Pending CN111099581A (en) | 2019-12-30 | 2019-12-30 | Method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111099581A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2601513A (en) * | 2020-12-02 | 2022-06-08 | Lig Nanowise Ltd | Graphene Production Method |
| CN115417404A (en) * | 2022-09-26 | 2022-12-02 | 科泽新材料股份有限公司 | Method for preparing graphene oxide by using waste graphene film leftover materials |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN104495828A (en) * | 2014-12-31 | 2015-04-08 | 深圳市铭晶科技有限公司 | Method for preparing graphene through liquid-phase stripping method |
| CN107673338A (en) * | 2017-11-13 | 2018-02-09 | 中南大学 | A kind of method for preparing graphene using discarded graphite electrode |
| CN107934948A (en) * | 2017-12-22 | 2018-04-20 | 大连理工大学 | The preparation method and graphene of a kind of graphene |
| US20180229193A1 (en) * | 2015-08-11 | 2018-08-16 | Graphenest, S.A. | Method and device for production of graphene or graphene-like materials |
-
2019
- 2019-12-30 CN CN201911390890.0A patent/CN111099581A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN104495828A (en) * | 2014-12-31 | 2015-04-08 | 深圳市铭晶科技有限公司 | Method for preparing graphene through liquid-phase stripping method |
| US20180229193A1 (en) * | 2015-08-11 | 2018-08-16 | Graphenest, S.A. | Method and device for production of graphene or graphene-like materials |
| CN107673338A (en) * | 2017-11-13 | 2018-02-09 | 中南大学 | A kind of method for preparing graphene using discarded graphite electrode |
| CN107934948A (en) * | 2017-12-22 | 2018-04-20 | 大连理工大学 | The preparation method and graphene of a kind of graphene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2601513A (en) * | 2020-12-02 | 2022-06-08 | Lig Nanowise Ltd | Graphene Production Method |
| WO2022118029A1 (en) * | 2020-12-02 | 2022-06-09 | LIG Nanowise Limited | Graphene production method |
| CN115417404A (en) * | 2022-09-26 | 2022-12-02 | 科泽新材料股份有限公司 | Method for preparing graphene oxide by using waste graphene film leftover materials |
| CN115417404B (en) * | 2022-09-26 | 2024-01-12 | 科泽新材料股份有限公司 | Method for preparing graphene oxide from waste graphene film scraps |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111799464B (en) | MXene/graphene composite nanosheet, preparation method and application thereof, electrode plate and application thereof | |
| CN105110318B (en) | A kind of graphene water paste and preparation method thereof | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| EP3056469B1 (en) | Production method for graphene | |
| CN102807213B (en) | Electrochemistry prepares the method for Graphene | |
| CN104973591B (en) | High-quality graphene and preparation method thereof | |
| CN105948033A (en) | Method of preparing graphene by means of wet microwave stripping | |
| CN101429336B (en) | Process for producing carbon nano-tube/polyaniline conductive composite material | |
| CN111099581A (en) | Method for preparing graphene by utilizing artificial graphite leftover materials and graphene obtained by method | |
| CN104058395A (en) | Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite | |
| CN111559743B (en) | Preparation method and application of graphene powder | |
| CN107686108B (en) | Method for preparing reduced graphene oxide by dielectric barrier discharge plasma | |
| CN104891485A (en) | Method for preparing nano graphite sheet | |
| CN109110750B (en) | Method for preparing graphene by using expanded graphite | |
| CN111017916A (en) | Preparation method of graphene with controllable layer number | |
| CN110112384A (en) | A kind of preparation method of porous graphene silicium cathode material | |
| CN105420794B (en) | A kind of preparation method of graphene/ferriferrous oxide composite material | |
| CN113173579B (en) | Macroscopic quantity preparation method of graphene | |
| CN113149016B (en) | Preparation method of high-purity spherical nanometer silicon powder with adjustable particle size | |
| CN112694083B (en) | Method for continuously producing graphene quantum dot slurry on large scale | |
| CN110322986B (en) | Preparation method of high-fluidity graphene conductive paste | |
| CN112408369A (en) | Method for preparing graphene by efficiently stripping graphite in green mode | |
| CN106560942B (en) | A kind of processing method of Silicon Based Anode Materials for Lithium-Ion Batteries | |
| CN111573659B (en) | Preparation method of nitrogen-doped graphene | |
| CN110577210A (en) | preparation method of powder of graphene and graphene derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211230 Address after: No.21, Shuidong Park, Gongchuan Town, Yong'an City, Sanming City, Fujian Province Applicant after: Shenruimene Technology (Fujian) Co.,Ltd. Address before: 518100 east side of 4th floor, building 1, Huike Industrial Park, Shiyan street, Bao'an District, Shenzhen, Guangdong Applicant before: Shenzhen Shen Rui Graphene Technology Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200505 |