EP4291527A1 - Graphene production method - Google Patents
Graphene production methodInfo
- Publication number
- EP4291527A1 EP4291527A1 EP22705562.1A EP22705562A EP4291527A1 EP 4291527 A1 EP4291527 A1 EP 4291527A1 EP 22705562 A EP22705562 A EP 22705562A EP 4291527 A1 EP4291527 A1 EP 4291527A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- expanded graphite
- graphene
- graphite
- high shear
- shear mixing
- 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 227
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 129
- 239000010439 graphite Substances 0.000 claims abstract description 129
- 238000002156 mixing Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 239000002064 nanoplatelet Substances 0.000 claims description 16
- 238000009830 intercalation Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 230000002687 intercalation Effects 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003701 mechanical milling Methods 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims 1
- 206010040844 Skin exfoliation Diseases 0.000 description 15
- 238000004299 exfoliation Methods 0.000 description 15
- 230000007547 defect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960003964 deoxycholic acid Drugs 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- FHHPUSMSKHSNKW-SMOYURAASA-M sodium deoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 FHHPUSMSKHSNKW-SMOYURAASA-M 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- WHIRALQRTSITMI-UJURSFKZSA-N (1s,5r)-6,8-dioxabicyclo[3.2.1]octan-4-one Chemical compound O1[C@@]2([H])OC[C@]1([H])CCC2=O WHIRALQRTSITMI-UJURSFKZSA-N 0.000 description 1
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- 102100030310 5,6-dihydroxyindole-2-carboxylic acid oxidase Human genes 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- 101000773083 Homo sapiens 5,6-dihydroxyindole-2-carboxylic acid oxidase Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 235000019416 cholic acid Nutrition 0.000 description 1
- 229960002471 cholic acid Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
-
- 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for the production of graphene, the method comprising the steps of: a. mixing expanded graphite in a liquid to provide a mixture, and b. exfoliating the expanded graphite by exposing the mixture to a high shear mixing assembly to produce graphene
Description
Graphene Production Method
Technical Field of the Invention
The present invention relates to a method for producing graphene, to the graphene produced by the method and to a coating or composite comprising graphene. Background to the Invention
Few-layer graphene may be produced by following a “top-down” method which involves the physical exfoliation of graphite. In the past this has been achieved by mechanically exfoliating 2D materials in solid-state, e.g., by micromechanical cleavage and ball milling. However, these methods fail to provide a sufficient yield and satisfactory flake sizes while remaining defect free. It is also known to exfoliate graphite in the liquid phase by dispersing graphite in a solvent (aqueous or organic), exfoliating the graphite into smaller fragments, partially exfoliated graphite (graphene nanoplatelets) and few-layer graphene, e.g., by high shear mixing and then separating few-layer graphene from the other fragments. Although liquid phase exfoliation of graphite enables greater yields of few-layer graphene to be obtained relative to the solid-state exfoliation of 2D materials, the yields of few-layer graphene are still limited because it is typically produced using a batch production method. Therefore, there is a need for a low-cost method for producing defect-free few-layer graphene in greater yields. It is an object of embodiments of the invention to provide a method for increasing the yield of graphene, particularly few-layer graphene.
It is an object of embodiments of the invention to provide a method for producing defect-free graphene in high yields.
It is an object of embodiments of the invention to a provide a cost-effective method for producing graphene in high yields, particularly few-layer graphene.
Summary of the Invention
According to a first aspect of the invention there is provided a method for the production of graphene, the method comprising the steps of: a. mixing expanded graphite in a liquid to provide a mixture, and b. exfoliating the expanded graphite by exposing the mixture to a high shear mixing assembly to produce graphene.
It has been found that significant increases in the yield of few-layer graphene are obtainable by subjecting expanded graphite to a high shear mixing treatment. Moreover, the few-layer graphene obtained is defect-free or substantially defect-free and can be produced at low cost. Accordingly, the above method is a low-cost and scalable method for producing few-layer graphene with no or few defects.
In some embodiments the high shear mixing assembly may be located in a container for dispersing the expanded graphite in the liquid. The temperature of the container may be adjusted in order to avoid or at least minimise the number of defects in the exfoliated graphene. Suitably, the container may be kept at an ambient temperature. The container may be provided with a water jacket which is operable to achieve the desired temperature. In some embodiments the water jacket may be provided within the container.
In other embodiments the high shear mixing assembly may be located in a device connected to and located downstream of the container. The device may
comprise an in-line high shear mixer. Accordingly, the mixture may be exposed to an in-line high shear mixing assembly. In operation, actuation of the device causes the mixture to be drawn from the container through the in-line high shear mixing assembly. This in-line assembly ensures that a significant proportion, if not all, of the expanded graphite in the mixture is subjected to mechanical and hydraulic shear forces. As a result, further increases in the yield of few-layer graphene can be obtained.
In some embodiments the temperature of the mixture may be adjusted prior to exposing the mixture to the in-line high shear mixing assembly. Suitably, a device for reducing the temperature of the mixture may be provided between the container and the in-line high shear mixing assembly. The device may comprise a chiller unit.
Once the mixture has passed through the high shear mixing assembly it may be recirculated back to the container or directed elsewhere for further processing. Recirculating the mixture back to the container ensures that increased quantities of expanded graphite and/or exfoliated products thereof are exposed to the in-line high shear mixing assembly, which in turn enables high yields of few-layer graphene to be obtained.
In some embodiments the temperature of the mixture may be adjusted after it has passed through the in-line high shear mixing assembly, e.g., during recirculation of the mixture back to the container. Suitably, a device for reducing the temperature of the mixture may be provided between an in-line high shear mixing assembly outlet and a container inlet. The device may comprise a chiller unit.
In some embodiments a high shear mixing assembly may be located in the container and in the device located downstream of the container. In this way, the expanded graphite is subjected to shear forces in the container and when passing through the device which enables greater yields of graphene to be obtained. The high shear mixing assembly may comprise a rotor-stator assembly. The rotor may be rotated at least 6000 rpm. A rotational speed of less than 6000 rpm results in reduced yields of few-layer graphene which is undesirable. Suitably, the rotor may be rotated at 6000-9000 rpm. It was found that while a rotational speed of more than 9000 rpm does not further increase the yield, it may compromise the lateral size of few layer graphene particles.
The expanded graphite may be exfoliated for at least 8 hours. If the expanded graphite is exfoliated for less than 8 hours then the resulting mixture contains more graphene nanoplatelets (GNP) than few-layer graphene (FLP) which is undesirable. By increasing the exfoliation period to at least 8 hours increased quantities of few- layer graphene can be obtained. Suitably, the expanded graphite may be exfoliated for between 8 and 24 hours. Exfoliating the expanded graphite for more than 24 hours increases the yield of few-layer graphene, however, its lateral size may be reduced significantly.
In some embodiments the expanded graphite may be produced by intercalating graphite with an intercalation compound and thermally treating the intercalated graphite.
Expanded graphite may be obtained by heating the intercalated graphite at a temperature of 600 °C to 1200 °C. The intercalated graphite may be heated at a
temperature of at least 850°C, and in some embodiments the intercalated graphite may be heated at a temperature of 850°C to 1100°C. Suitably, the intercalated graphite may be heated at a temperature of 900°C to 1000°C. At temperatures below 600°C, only partial expansion of graphite occurs because the thermal energy provided is not substantial enough to weaken the van der Waal’s forces between adjacent graphene layers. At temperatures above 1200 °C, there is an increased risk that the graphite will thermally decompose unless the heat treatment is carried out under a carefully controlled environment. The temperature boundaries indicated above achieve a high expansion rate under a reduced oxygen environment. At temperatures above 1200°C, an inert gas environment may be required to avoid thermal decomposition of graphite.
In some embodiments, the thermal expansion of intercalated graphite is performed for a period of from at least 10 seconds to not more than 1 min. The thermal expansion of intercalated graphite may be performed for a period of from at least 20 to 30 seconds. The intercalated graphite may be heated in an inert atmosphere in order to prevent or at least reduce the formation of oxides. In some embodiments, the intercalated graphite may be heated using infrared radiation or by induction.
The expanded graphite may be produced by intercalating graphite with an intercalation compound and exposing the intercalated graphite to microwaves. The intercalated graphite may be exposed to microwaves for at least 60 seconds. Suitably, the intercalated graphite may be exposed to microwaves for 60 to 300 seconds. The power of the applied microwaves may be from 500 - 1000 W. Suitably the power may be from 700 - 800 W. The microwaves may have a frequency of 2.45 GHz.
The graphite from which the expanded graphite is produced may comprise natural graphite such as or highly oriented pyrolytic graphite ("HOPG")· Suitably the natural graphite may comprise vein graphite.
The graphite from which expanded graphite is produced may have a lateral size of more than 50 pm. In some embodiments the graphite may have a lateral size of from at least 100 pm and up to 500 pm. Suitably, the lateral size of the graphite may be from at least 180 pm up to 300 pm. The use of graphite having a larger lateral size increases the rate of expansion in the presence of intercalating agents and heat. This in turn enables increased yields of FLG to be obtained after high shear mixing. Moreover, due to the increased rate of expansion less energy may be required to produce FLG so that the exfoliation time and shear force can be reduced.
The intercalation compound may comprise a strongly oxidising acid such a sulfuric acid, nitric acid, phosphoric acid, perchloric acid, chromic acid or a combination thereof. Other oxidising agents that could be used as intercalation compounds include potassium chlorate, potassium permanganate, potassium dichromate, hydrogen peroxide, metal halides, acetic acid, zinc sulphate heptahydrate, sodium pyrophosphate or combinations thereof. However, the oxidative nature of these materials can cause defects in graphene. In order to obtain defect free products, inert intercalants such as quaternary ammonium sulphate or ammonium sulphate may be used.
The expanded graphite may be defect-free or substantially defect-free.
The expanded graphite may be subjected to a mechanical milling treatment prior to the step of high shear mixing. In particular, the expanded graphite may be
provided in a ball milling vessel and subjected to a ball milling treatment, or it may be subjected to a fluidised bed air milling treatment to reduce the lateral size of the expanded graphite layers.
In some embodiments the ball milling treatment may be performed for a period of from at least 4 hours to not more than 10 hours. The ball milling of expanded graphite may be performed for a period of from at least 5 hours to not more than 8 hours. Suitably, ball milling may be performed for a period of from at least 6 hours to not more than 7 hours.
In some embodiments the ball milling vessel may be rotated at a speed of from at least 200 rpm to not more than 600 rpm. In other embodiments the ball milling vessel may be rotated at a speed of at a speed of from at least 300 rpm to not more than 500 rpm. Suitably, the ball milling vessel may be rotated at a speed of at a speed of from at least 350 rpm to not more than 450 rpm.
The expanded graphite may be screened after the mechanical milling treatment in order to obtain expanded graphite having a pre-determined lateral size. By mechanically milling expanded graphite and then screening it to obtain expanded graphite having a pre-determined size, improved yields of FLG can be obtained after high shear mixing relative to expanded graphite which has not been mechanically milled or screened but is of substantially the same size. The expanded graphite may have a mean lateral particle size of 5-30 microns.
In some embodiments, the expanded graphite may have a mean lateral particle size of 10-20 microns. The use of expanded graphite that has been mechanically milled and screened to obtain expanded graphite having a mean particle size of 10-20 microns
enables greater yields of quality FLG to be obtained after high shear mixing. Suitably, the expanded graphite may have a mean lateral particle size of 15-20 microns.
The liquid may comprise water and/or a solvent. Suitably, the liquid may comprise de-ionised water. The solvent may comprise cyrene (dihydrolevoglucosenone), N-methyl-2-pyrrolidone (NMP), N - dimethylformamide (DMF), N,N-dimethylacetamide (DM AC), dimethyl sulfoxide (DMSO), g- butyrolactone (GBL), ortho dichloro benzene (ODAC), butyl acetate, toluene or a combination thereof.
The ratio of expanded graphite to liquid may be from 0.01:1 to 0.1 to 1. Suitably, the ratio may be from 0.03:1 to 0.08:1. In some embodiments the ratio may be 0.05:1.
The mixture may comprise a surfactant. The mixture may comprise surfactants and dispersing agents. The mixture may comprise anionic surfactants, non-ionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, fluoro- surfactants, polymeric surfactants and combinations thereof. In particular, the mixture for water based dispersions may comprise one or more of Disperbyk 2010, Disperbyk 2080, Disperbyk 2012, Antiterra 250, Disperbyk 190 (manufactured by BYK), a salt of cholic acid such as sodium deoxycholate (SDC), sodium dodecylbenzenesulfonate (SDBS), cetyltrimethylammonium bromide (CATB) and for solvent based dispersions Disperbyk 2050 , Anti-Terra-U 100, BYK-9076, Disperbyk- 110 and Disperbyk- 2025.
The ratio of expanded graphite to surfactant may be from 2:1 to 10:1. Suitably, the ratio may be from 4:1 to 8:1. In some embodiments the ratio may be 5:1. When the ratio of expanded graphite: surfactant is below 2:1, expanded graphite is not
adequately dispersed and stabilised in the liquid which can lead to agglomeration of expanded graphite, smaller fragments such as graphene nanoplatelets and few-layer graphene. If the expanded graphite: surfactant ratio is greater than 10:1 then the concentration of the expanded graphite particles is too low and the impact of the shear force felt by individual particles is insignificant which leads to an inefficient exfoliation process.
The method may comprise the steps of separating graphene nanoplatelets from few-layer graphene and exposing a dispersion of the separated graphene nanoplatelets to the high shear mixing assembly to produce few-layer graphene. Alternatively, the separated graphene nanoplatelets may be freeze dried and stored.
The method may be a continuous method for producing graphene. The cost of producing graphene may be reduced when it is produced using a continuous or a semi-continuous production method rather than a batch-wise production method.
According to a second aspect of the invention there is provided graphene produced according to the method of the first aspect of the invention. The graphene according to the second aspect of the invention may, as appropriate, include any or all features described in relation to the method according to the first aspect of the invention.
In some embodiments the graphene obtained from the method may be oxide free or substantially free from oxide defects.
According to a third aspect of the invention there is provided a coating or composite comprising the graphene according to the second aspect of the invention. The coating or composite according to the third aspect of the invention may, as
appropriate, include any or all features described in relation to the method according to the first aspect of the invention or the graphene according to the second aspect of the invention.
Detailed Description of the Invention In order that the invention may be more clearly understood one or more embodiments thereof will now be described, by way of example only, with reference to the accompanying drawings, of which:
Figure 1 shows Raman spectra of graphene produced by passing expanded graphite through an in-line high shear mixing assembly. Figure 2 shows Raman Spectra of graphene produced by passing non-expanded graphite through an in-line high shear mixing assembly.
Figure 3 shows a schematic of apparatus including an in-line high shear mixier for exfoliating expanded graphite.
To obtain expanded graphite, 3 g of vein graphite (99 % purity) having a particle size range of 100 - 500 um is soaked in an intercalant solution for at least 4 hours. The intercalant solution is prepared by mixing 1 g of an oxidiser such as KMnC with 16 mL of a strong acid such as H2SO4. Accordingly, the ratio of expanded graphite: oxidiser: acid is 3:1:16. The intercalated graphite is filtered, dried, and then heated at 1000 °C under a reduced oxygen environment for 30 seconds. Accordingly, the expansion of graphite is facilitated by intercalation and the subsequent heat shock.
The expanded graphite particles have a large lateral size and in order to improve the exfoliation process efficiencies (reduced energy consumption and
increased exfoliation rate), the particle size was reduced. This was achieved by ball milling the expanded graphite particles in a ball milling vessel for 6 hours using a 1-2 L Vertical Benchtop Square Planetary Ball Mill, (0.75 to 1.5 KW ) containing 1 to 2 mm diameter ceramic balls. The ball milling vessel was rotated at 400 rpm and the process was stopped for 30 min at every 30 min to avoid overheating. The material is then sieved in a vibratory sifting screen to obtain expanded graphite with an average lateral particle size of 15 to 20 microns.
In embodiments where larger volumes (> 2L) of expanded graphite are to be mechanically milled the expanded graphite is fed into a Hosokawa Opposed Jet Mill AFG, (2 kW, 17000 - 22000 rpm) to reduce the lateral particle size. The particles were subjected to milling and screening at 20000 rpm for 6 hrs. The resulting product has a particle size distribution, d50, of about 5-20 microns.
In one embodiment, expanded graphite, a liquid and surfactants are added to a mixing vessel 1 to form a mixture. The expanded graphite has an average particle size of 15-20 microns and a layer spacing of >0.4nm. The liquid may be water or an organic solvent and the choice of liquid and surfactants will depend on the application in which the obtained few-layer graphene is to be used. In this embodiment 1000 g of expanded graphite is mixed with 20 L de-ionised water and 200 g of Disperbyk 2010, a surfactant manufactured by BYK. The mixing vessel 1 comprises a mixing element 2 which is operable to mechanically mix the expanded graphite, liquid and surfactants so that the expanded graphite remains dispersed in the liquid. The mixing element 2 rotates at 2000 rpm.
An in-line high shear mixing apparatus 3 by Silverson (RTM) is provided downstream of the mixing vessel 1. A pipe 4 extends between a mixing vessel outlet 5 and a high shear mixing apparatus inlet 6 so that in use the mixture is continuously drawn from the mixing vessel 1 into the high shear mixing apparatus 3. The high shear mixing apparatus 3 comprises a rotor-stator assembly (not shown) for high shear mixing the expanded graphite in the liquid. The stator in this embodiment comprises a plurality of square perforations for the mixture to flow through and the rotor comprises one or more blades that is/are arranged to be rotated relative to the stator. In this embodiment the rotor is rotated at 8000 rpm for 8 hours. The in-line high shear mixing apparatus 3 comprises an in-line high shear mixing apparatus outlet 7. The in-line high shear mixing apparatus outlet 7 is connected to a mixing vessel inlet 8 via a recirculation pipe 9. Once the mixture has passed through the rotor-stator assembly of the in-line high shear mixing apparatus 3 it is recirculated back into the mixing vessel 1 via the recirculation pipe 9. In this way, expanded graphite and graphite fragments are continuously subjected to high mechanical and hydraulic shear forces which enables greater yields of few-layer graphene to be obtained. The recirculation pipe 9 may comprise a valve 10 connected to a conduit 11 which leads to another container 12 or apparatus for respectively storing or further processing the exfoliated graphene once high shear mixing of the mixture is complete.
The exfoliated graphene is allowed to settle for 24 hours. Graphene nanoplatelets in the mixture containing exfoliated graphene settle to the bottom of the container while the few-layer graphene remains dispersed in the aqueous supernatant which lies above the graphene nanoplatelets. Separation of few-layer graphene from
the graphene nanoplatelets is achieved by decanting the supernatant from the container.
To enable 100 % conversion of expanded graphite into few-layer graphene, the obtained graphene nanoplatelets may be re-introduced into the mixing vessel 1 for further exfoliation by the in-line high shear mixing apparatus 3. Alternatively, the graphene nanoplatelets themselves may be used in the manufacture of composite materials for example.
The supernatant was diluted 1:5 ratio with deionised water and applied on a silicon grid. The film formed on the grid was exposed to a temperature of 300°C in a vacuum oven to remove the surfactants. Raman Spectroscopy was used to characterise few- layer graphene and the results are shown in Table 1 below. The results confirmed that exposing expanded graphite to an in-line high shear exfoliation treatment enables few-layer graphene to be obtained and that it is characterised by D, G and 2D peaks at 1348 cm 1, 1575 cm 1 and 2692 cm 1 respectively. Table 1 also shows the results of a comparative experiment in which expanded graphite was replaced by non-expanded graphite (TIMREX® SFG 75 Graphite by Imerys).
Both graphene samples have a 2D peak at closer wavelength positions. The shape, position and the intensity of 2D peak indicates that the materials is graphene rather than graphite. Higher values for the intensity ratio of I2D/IG and sharpness of the 2D peak indicates that the exfoliation rate of expanded graphite is higher and that the number of layers in few-layer graphene is lower compared to graphene obtained from the exfoliation of non-expanded graphite.
The ID/IG ratio is a measure of the extent of defects in graphene layers, and the values for the graphene materials produced from the exfoliation of expanded and non-expanded graphite are 0.64 and 0.54 respectively. These values are similar, but higher than the ID/IG value obtained for graphite which indicates that a similar level of defects or structural disorders have been introduced into both graphene materials. The extent of the defects introduced during the high shear exfoliation can be reduced by optimising the operating parameters such as cycle length, rotor speed and the temperature of the high shear mixing vessel.
Table 1: Raman spectra parameters of few layer graphene obtained from the in-line high shear mixing of non-expanded graphite and expanded graphite.
The yield of few-layer graphene was also determined. This was achieved by separating few-layer graphene from the graphene nanoplatelets in the manner described above, drying the separated graphene nanoplatelets by freeze drying or vacuum drying and then weighing the dried graphene nanoplatelets. The results are summarised in Table 2 which shows that a 5% yield of few-layer graphene was obtained from the in-line high shear exfoliation of non-expanded graphite, whereas a
70% yield of few-layer graphene was obtained when expanded graphite was subjected to an in-line high shear mixing treatment.
Table 2: Yield of few layer graphene obtained from the in-line high shear mixing of non-expanded graphite and expanded graphite.
From the above results it can be seen that the in-line high shear mixing of expanded graphite enables few-layer graphene with no or few defects to be obtained in very high yields. Accordingly, the method provides a low-cost and scalable production method for graphene.
The one or more embodiments are described above by way of example only. Many variations are possible without departing from the scope of protection afforded by the appended claims.
Claims
1. A method for the production of graphene, the method comprising the steps of: a. mixing expanded graphite in a liquid to provide a mixture, and b. exfoliating the expanded graphite by exposing the mixture to a high shear mixing assembly to produce graphene.
2. A method according to claim 1, wherein the method comprises exposing the mixture to an in-line high shear mixing assembly.
3. A method according to claim 2, wherein the mixture is drawn from a container through the in-line high shear mixing assembly.
4. A method according to claim 3, wherein the mixture is drawn from the container through the in-line high shear mixing assembly and recirculated to the container.
5. A method according to any of claims 1 to 4, wherein the high shear mixing assembly comprises a rotor-stator assembly.
6. A method according to claim 5, wherein the rotor is rotated at 6000-9000 rpm.
7. A method according to any preceding claim, wherein the expanded graphite is exfoliated for between 8 and 24 hours.
8. A method according to any preceding claim, wherein the graphite from which expanded graphite is produced has a lateral size of 100-500 pm.
9. A method according to any preceding claim, wherein the expanded graphite is produced by intercalating graphite with an intercalation compound and thermally treating the intercalated graphite.
10. A method according to claim 9, wherein the thermal treatment of intercalated graphite is performed for a period 10 seconds to not more than 1 min.
11. A method according to claim 9 or claim 10, wherein the intercalated graphite is heated from 600-1200 °C.
12. A method according to any of claims 8 to 11, wherein the expanded graphite is produced by intercalating graphite with an intercalation compound and exposing the intercalated graphite to microwaves.
13. A method according to any of claims 8 to 12, wherein the expanded graphite is subjected to a mechanical milling treatment.
14. A method according to claim 13, wherein the expanded graphite is provided in a ball milling vessel and subjected to a ball milling treatment.
15. A method according to claim 14, wherein the ball milling treatment is performed for a period of from at least 4 hours to not more than 10 hours.
16. A method according to claim 15, wherein the ball milling vessel is rotated at a speed of from at least 200 rprn to not more than 600 rpm.
17. A method according to claim 13, wherein the expanded graphite is subjected to a fluidised bed air milling treatment.
18. A method according to any of claims 13 to 17, wherein the expanded graphite obtained after ball milling or fluidised bed air milling is screened to obtain expanded graphite having a mean particle size of 10-20 microns.
19. A method according to claim 18, wherein the expanded graphite has a mean particle size of 15-20 microns.
20. A method according to any preceding claim, wherein the expanded graphite is defect-free or substantially defect-free.
21. A method according to any preceding claim, wherein the liquid comprises water and/or a solvent.
22. A method according to claim 21, wherein the solvent comprises Cyrene, N- methyl-2-pyrrolidone, Dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, g-butyrolactone, ortho dichloro benzene, dimethyl sulfoxide, butyl acetate and toluene.
23. A method according to any preceding claim, wherein the ratio of expanded graphite to liquid is from 0.01:1 to 0.1 to 1.
24. A method according to any preceding claim, wherein the mixture comprises a surfactant.
25. A method according to claim 24, wherein the surfactant comprises anionic surfactants, non-ionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, fluoro-surfactants, polymeric surfactants and combinations thereof.
26. A method according to claim 24 or claim 25, wherein the ratio of expanded graphite to surfactant is from 2:1 to 10:1.
27. A method according to any preceding claim, comprising the steps of separating graphene nanoplatelets from few-layer graphene and exposing a dispersion of the separated graphene nanoplatelets to the high shear mixing assembly to produce graphene.
28. A method according to any preceding claim, wherein the graphene is produced using a continuous or semi-continuous process.
29. Graphene produced according to the method of any preceding claim.
30. Graphene according to claim 29, wherein the graphene comprises oxide-free graphene.
31. A coating comprising the graphene according to claim 29 or claim 30.
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| GBGB2101925.2A GB202101925D0 (en) | 2021-02-11 | 2021-02-11 | Graphene production method |
| PCT/GB2022/050373 WO2022172021A1 (en) | 2021-02-11 | 2022-02-11 | Graphene production method |
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| CN105084353B (en) * | 2015-08-19 | 2018-11-13 | 杭州万杵材料科技有限公司 | A kind of production method of grapheme material |
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| GB201612960D0 (en) * | 2016-07-27 | 2016-09-07 | Talga Advanced Mat Gmbh | Pre-treament coating composition and a method for producing the same |
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| US10822239B2 (en) * | 2017-04-19 | 2020-11-03 | Global Graphene Group, Inc. | Microwave system and method for graphene production |
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