WO2014026194A1 - Système et procédé de fonctionnalisation de graphène - Google Patents

Système et procédé de fonctionnalisation de graphène Download PDF

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Publication number
WO2014026194A1
WO2014026194A1 PCT/US2013/054566 US2013054566W WO2014026194A1 WO 2014026194 A1 WO2014026194 A1 WO 2014026194A1 US 2013054566 W US2013054566 W US 2013054566W WO 2014026194 A1 WO2014026194 A1 WO 2014026194A1
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Prior art keywords
graphenes
particles
graphene
chamber
boats
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PCT/US2013/054566
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English (en)
Inventor
Maurice Yvon BELISLE
Douglas Paul DUFAUX
Robert Wayne Dickinson
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High Temperature Physics, Llc
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Priority claimed from US13/864,080 external-priority patent/US9260308B2/en
Application filed by High Temperature Physics, Llc filed Critical High Temperature Physics, Llc
Publication of WO2014026194A1 publication Critical patent/WO2014026194A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
    • 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
    • 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
    • C01B32/194—After-treatment
    • 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
    • C01B32/194—After-treatment
    • C01B32/196—Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0809—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes employing two or more electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
    • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
    • B01J2219/0807—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges involving electrodes
    • B01J2219/0824—Details relating to the shape of the electrodes
    • B01J2219/0826—Details relating to the shape of the electrodes essentially linear
    • B01J2219/083—Details relating to the shape of the electrodes essentially linear cylindrical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0869—Feeding or evacuating the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0879—Solid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0894—Processes carried out in the presence of a plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • This invention pertains generally to the production of carbon nanomaterials and, more particularly, to a system and process for functionalizing graphene.
  • Carbon graphenes have a number of unique and desirable qualities, including extraordinary surface area, high electrical conductivity and capacitance, high thermal and mass transfer capability, magnetic properties, and extraordinary values of tensile strength and modulus of elasticity. With such attributes, carbon graphene structures are attractive to a number of important technologies and markets, including electrolytic storage media for lithium ion batteries and ultra capacitors, facilitated transport membranes for micro filtration, catalytic substrate materials, heat transfer materials for use in cooling light-emitting diodes (LEDs) and other applications, high frequency semiconductors capable of operating at frequencies as high as 100 gigahertz or more, hydrogen storage, conductive materials for flatscreen and liquid crystal displays (LCDs), and strengthening agents for advanced materials in wind turbines and automobiles.
  • electrolytic storage media for lithium ion batteries and ultra capacitors
  • facilitated transport membranes for micro filtration catalytic substrate materials
  • heat transfer materials for use in cooling light-emitting diodes (LEDs) and other applications
  • high frequency semiconductors capable of operating at frequencies as high as 100
  • Another object of the invention is to provide a system and process of the above character which overcome the limitations and disadvantages of systems and processes heretofore provided.
  • the graphene is highly purified, then functionalized in a vertical plasma reactor which can also deagglomerate and/or delaminate the graphene, as well as separating or classifying the functionalized graphene particles according to size.
  • the graphene is produced by combustion of magnesium (Mg) and carbon dioxide (CO 2 ) in a highly exothermic reaction.
  • Mg magnesium
  • CO 2 carbon dioxide
  • the graphene is separated from the other reaction products and purified in a series of washing, heating, and drying steps, following which it is functionalized and otherwise processed in the plasma reactor.
  • Figure 1 is a flow chart of one embodiment of a process for producing and processing graphene in accordance with the invention.
  • Figure 2 is a flow chart of an embodiment of a process for producing graphene that is purified and functionalized in accordance with the invention.
  • Figure 3 is a flow chart of one embodiment of a process for purifying graphene for functionalization in accordance with the invention.
  • Figure 4 is a flow chart of another embodiment of a process for purifying graphene for functionalization in accordance with the invention.
  • Figure 5 is a block diagram of one embodiment of a system for purifying graphene for functionalization in accordance with the invention.
  • Figure 6 is a block diagram illustrating the use of a pusher oven in the purification of graphene for functionalization in accordance with the invention.
  • Figure 7 is a vertical sectional view, somewhat schematic, of one embodiment of a reactor for functionalizing graphene in accordance with the invention. Detailed Description
  • the process for producing and processing graphene includes the steps of reacting magnesium (Mg) and carbon dioxide (CO2) together to produce the graphene, separating graphene particles from other reaction products and purifying the graphene particles, drying the graphene particles to remove water (H2O) and open reactive sites, and functionalizing the reactive sites in an ionized gas plasma.
  • Mg magnesium
  • CO2 carbon dioxide
  • FIG. 2 illustrates an embodiment of the Mg CO2 process in which magnesium bars 1 1 are machined to produce chips 12 which are fed to a reactor 13 where they are combusted with CO2 from a liquid CO2 tank 14 in a highly exothermic reaction that produces temperatures which typically can range from about 1000°F (537°C) to about 7000°F (3872°C). MgO produced by the reaction is captured in a collector 16 and converted to magnesium which can be recycled and used in the reaction.
  • the reaction also produces a mixture of carbon and MgO products which are delivered to a grinder or blender 17 where they are reduced to finer particles and prepared for further processing.
  • the ground-up particles are washed first with deionized water 18 and then with hydrochloric acid (HCI) 19.
  • HCI hydrochloric acid
  • the carbon graphenes are inert to HCI, but the HCI reacts with unreacted magnesium in the mixture as well as the dissolved MgO and Mg(OH2) to form magnesium chloride (MgCI2) and water (H2O).
  • the solution of carbon graphenes and MgCI2 is filtered in a Buchner vacuum filter 21 to separate the graphenes from the MgCI2.
  • the graphenes are dried at a temperature on the order of 90°C in a low temperature oven 22, then further purified in a high temperature furnace 23 operating at a temperature on the order of 1600°C.
  • the graphene particles are then once again washed with HCI and water at 24, then further separated in a second Buchner vacuum filter 26.
  • the graphene particles from the second filter are dried in a low temperature oven 27 and collected at 28.
  • FIG. 3 Another embodiment of a process for separating and purifying the carbon and Mg reaction products is illustrated in Figure 3.
  • This process includes acid washing, filtering, and drying stages.
  • the acid washing is done in a loop that includes a mixing reservoir 32, a static inline mixer 33, and a pump 34, with a valve 36 between the pump and the mixer and a reaction period timer 37 which controls the length of the cycle.
  • reaction products 31 Prior to acid washing, reaction products 31 are screened and ground to provide particles of the desired size for further processing.
  • the products first go through a screening stage 38, and particles that are too big to pass through the screen are delivered to a grinding stage 39 where they are ground into finer particles which are fed back to the screen.
  • the particles which pass through the screen are delivered to mixing reservoir 32.
  • those steps can be omitted, and the reactor products can be fed directly to the mixing reservoir.
  • the acid washing is done with a diluted HCI solution that is prepared from concentrated HCI and deionized water from tanks 41 , 42 and stored in a holding reservoir 43, with a valve 44 between the holding and mixing reservoirs.
  • the acid washing process is initiated by opening valve 44 and introducing the diluted HCI solution into the mixing reservoir.
  • valve 44 is closed, valve 36 is opened, and pump 34 is turned on to circulate the aqueous solution from the mixing reservoir through inline static mixer 33 and back to the mixing reservoir.
  • the reactor product particles are introduced into the circulating solution and mixed with it as the solution continues to circulate around the loop that includes the reservoir, pump, and mixer.
  • the aqueous solution and graphene particles are pumped through another valve 46 to a filtration system 47 where the graphene particles are separated from the solution.
  • the filtration system includes a Buchner vacuum filter, and the pumping continues until the majority of the solution has been drained from the reservoir and mixer.
  • Deionized water from a tank 48 is then delivered to the pump through a valve 49 and flushed through the filtration system to neutralize the aqueous solution in it. Once the solution has been neutralized, water valve 49 is closed, the pump is turned off, and valve 46 is also closed.
  • Pressurized air from a tank 51 is then introduced into the filtration system through an air valve 52 to air dry the graphene particulate in the filter.
  • an air valve 52 to air dry the graphene particulate in the filter.
  • the air dried graphene is then placed in a low temperature drying oven 56 to complete the drying process and ensure the removal of all moisture from it.
  • the aqueous MgO/HCI solution produced by the process can be used in producing MgCI2 that can be used as feed stock for an electrolytic cell to make magnesium metal.
  • the embodiment of Figure 4 is generally similar to the embodiment of Figure 3, and like reference numerals designate corresponding elements and steps in the two.
  • the acid washing process is done in a mixing reservoir 58, rather than circulating the aqueous solution and graphene particles through a separate mixer.
  • the mixing is done by mixing blades 59 which are driven by a motor 61 .
  • Communication between mixing reservoir 58 and the pump and filtration system is controlled by a valve 62 which is connected between the reservoir and the pump.
  • the reactor product 31 is shown as being fed directly to the mixing reservoir, rather than going through the screening and grinding stages. However, if the feedstock particles need to be reduced in size, the chips can be screened and ground as in the embodiment of Figure 3.
  • the acid washing cycle in this embodiment is initiated by opening valve 44 to admit the dilute HCI solution to the mixing reservoir, then closing the valve and turning on the mixer. The reactor product particles are then introduced into the mixer, and the mixing continues until the acid wash process is completed.
  • valve 62 When the acid wash is completed, valve 62 is opened, and the pump is turned on to transfer the aqueous solution and graphene particles from the mixer reservoir to the filtration system. As in the previous embodiment, the pumping continues until the majority of the solution has been drained from the reservoir.
  • the filter is then flushed with deionized water from tank 48, after which valve 62 is closed, the pump is turned off, and the graphene particles in the filter are dried with pressurized air from air tank 51 . The air dried graphene particles are removed from the filter and placed in low temperature drying oven 56 to complete the moisture removal process.
  • CO2 and magnesium are introduced into a reactor furnace 66 where they are combusted together in a highly exothermic oxidation-reduction reaction, as discussed above, producing a mixture of carbon and magnesium oxide (MgO) products which are delivered to a preparation stage 67 where they are ground into finer particles and prepared forfurther processing. These particles are processed ultrasonically in deionized water in a sonifier 68, then washed in hydrochloric acid (HCI). The carbon graphenes are inert to HCI, but the HCI reacts with unreacted magnesium in the mixture as well as the dissolved MgO and Mg(OH2) to form magnesium chloride (MgCI2) and water (H2O).
  • HCI hydrochloric acid
  • the aqueous MgCI2 solution and carbon graphenes are filtered in a vacuum filter 69 to separate the graphenes from the MgCI2.
  • the graphenes are dried in a dryer 71 and recycled back through the sonification, filter, dryer, and heating stages to further purify them.
  • the number of times the graphenes are recycled is determined by the level of purity desired, and is typically on the order of three or four times per cycle batch.
  • the graphenes are discharged through a product line 72.
  • Magnesium oxide (MgO) produced by the Mg-CO2 reaction is collected and converted to magnesium which is recycled for use in the reaction.
  • gaseous MgO from the reactor is collected and solidified in a collector 73, then washed with HCI and converted to MgCI2 in a dissolver 74.
  • This MgCI2 is dried in a dryer 75 along with the MgCI2 that was separated from the carbon graphenes in filter 69.
  • the dried MgCI2 is then separated into magnesium and chlorine by electrolysis in a cell 76.
  • the magnesium is cooled in a cooler 77, then collected and ground into finer particles, e.g. 400 Mesh, in a collector and grinder 78.
  • the magnesium particles from the grinder are fed back to reactor 66 and used in the combustion process.
  • the magnesium can also be reduced to finer particles by other means such as cutting or cooling small droplets from a melt.
  • Chlorine, hydrogen, and HCI utilized in the process are provided by a cell 79 to which hydrogen (H2) and methane (CH4) are supplied along with the chlorine from electrolysis cell 76.
  • the purified graphene from the embodiments of Figures 2 - 5 is further purified in a high temperature pusher oven 84.
  • the oven has a heating cavity 86 and a graphite tube 87 which passes through the cavity.
  • the graphite particles to be treated are placed in graphite boats 88 which are pushed through the tube between a loader/pusher station 89 and an unloading station 91 at opposite ends of the tube.
  • the interior of the tube and the boats within the tube are flooded with an inert gas such as argon (Ar) or nitrogen (N) from a pressurized source 92 to maintain an inert gas atmosphere within the boats and tube to prevent combustion of the carbon in the boats.
  • an inert gas such as argon (Ar) or nitrogen (N)
  • the pusher oven is electrically operated and is typically operated at temperatures ranging from about 800°C to about 1600°C.
  • the boats are pushed through the tube in stepwise fashion, and the residence time of the boats in the oven cavity can be varied from about one half hour to as many hours as desired. With a residence time of about 4 hours, for example, the purity level of the graphene product is greater than 99 percent.
  • the highly purified graphene particles from the pusher oven are functional ized in a plasma reactor 96 where they can also be deagglomerated and/or delaminated, and separated or classified according to size.
  • the reactor has a vertically extending cylindrical housing or tower 97 which is fabricated of a suitable material such as stainless steel and might typically have a height or length on the order of 100 feet and a diameter on the order of about 2 - 6 inches.
  • the tower can, however, be of any suitable dimensions and can, for example, range in height from about 10 feet, or less, to about 500 feet, or more.
  • a hopper 98 for receiving the purified graphene material 99 and a grinder 101 for reducing that material to a desired particle size, such as 200 microns, for example.
  • An inlet section 102 extends between the bottom of the grinder and the top of the tower, with a filter 103 at the bottom of the inlet section for passing particles of the desired size to a reactor chamber 104 within the tower.
  • the inlet section includes a discharge chute 106 for particles that are too large to pass through the filter.
  • the inlet section and discharge chute are provided with vacuum interlocks 107, 108 which allow the particles to pass while maintaining a vacuum within the reactor.
  • a second filter screen 1 1 1 is provided at the lower end of the tower with a first outlet 1 12 below the screen for particles passing through the screen and a second outlet 1 13 above the screen for particles that do not pass through it.
  • Vacuum interlocks 1 14, 1 16 allow the particles to pass through the outlets while maintaining the vacuum within the reactor.
  • Output filter 1 1 1 is chosen in accordance with the size of the particles to be produced and corresponds generally to the size of input filter 103. Thus, for example, with a 200 micron input filter, the output filter might have a size of 300 microns.
  • Vibrators 1 17 are mounted on the outer side of tower wall 97 to prevent the graphene material from adhering to the chamber walls.
  • Plasma generating electrodes 1 18 extend vertically within the reactor chamber and are supported by a lower electrode support 1 19, an upper electrode support 121 , and a middle electrode support 122.
  • a DC voltage VE on the order of 15KV to 35KV is applied between the electrodes and the reactor wall 97.
  • Inlet ports 123, 124, and 126 are provided for the introduction of gases for ionization in the chamber to form a plasma for functionalizing the graphene particles.
  • the gases are chosen in accordance with the desired functions, and different gases can be used in different regions of the chamber.
  • Suitable gases for functionalizing the graphene include oxygen, nitrogen, water vapor, hydrogen peroxide, carbon dioxide, ammonia, ozone, carbon monoxide, silane, dimethysilane, trimethylsilane, tetraetoxysilane, hexamethyldisioxane, chloro-silanes, fluoro-silanes, ethylene diamine, maleic anhydride, arylamine, acetylene, methane, ethane , propane, butane, ethylene oxide, hydrogen, air, sulfur dioxide, hydrogen, sulfonyl precursors, argon, helium, alcohols, methanol, ethanol, propanol, carbon tetrafluoride, carbon tetrachloride, carbon tetrabromide, chlorine, fluorine, bromine, and combinations thereof.
  • inlet ports 123, 124, and 126 being spaced apart along the length of the reactor, different gases can be introduced through different ones of the ports and ionized to form different plasmas in different regions of the reactor.
  • a vacuum pump (not shown) is connected to a vacuum port 127 for maintaining a partial vacuum in the reactor chamber, and cryogenic gases can be introduced into the chamber through a cryogenic port 128 to cool the reactor and deagglomerate graphene clusters, if necessary.
  • cryogenic gases can be introduced into the chamber through a cryogenic port 128 to cool the reactor and deagglomerate graphene clusters, if necessary.
  • deagglomeration can increase the surface area of the graphene that is exposed to the plasma and functionalized.
  • the cryogenic port can be omitted, if desired.
  • liquid injection port 129 which is positioned toward the lower end of the reaction chamber and can be utilized for introducing liquid into the lower portion of the chamber to direct the functionalized graphene particles toward the output filter and thereby aid in the collection of the particles.
  • Functionalizing gas is introduced into the reactor chamber through one or more of the inlet ports 123, 124, 126. As discussed above, different gases can be employed to impart different functions to the graphene particles in different sections of the chamber. Electrodes 1 18 are then energized to ionize the gas(es) and form one or more functionalizing plasmas in the chamber.
  • Graphene particles 99 are introduced into the reactor through hopper 98 and grinder 101 , with the smaller particles dropping through inlet filter 103 and the larger particles being diverted through discharge chute 106 where they are collected and returned to the hopper.
  • the particles passing through the filter continue to fall vertically between the electrodes and through the plasma in the chamber.
  • the residence time of the particles in the plasma is determined primarily by the height of the tower or length of the chamber, and vibrators 1 17 prevent the particles from adhering to the chamber walls.
  • a cryogenic gas can be introduced into the chamber through cryogenic port 128 to cool the chamber and, together with the high voltage applied to the electrodes, break up the clusters without further disintegration of the particles. If deagglomeration is not needed, the cryogenic port remains closed, and the gas is not used.
  • the high DC voltage in the chamber can also produce a delamination of the particles by generating heat between the layers or by applying an instantaneous different charge to the layers that causes them to separate.
  • the Van De Whals forces are not strong enough to keep the particles together.
  • a liquid can be introduced through injection port 129 to flush the functionalized, deagglomerated, and/or delaminated graphene particles through the outlet filter for separation or classification by size.
  • the reactor could have a torroidal shape, and the material to be functionalized could be spun continuously through the torroidal chamber and the plasma formed therein.
  • This embodiment can have all of the features of the vertical reactor, but the residence time of the particles in the plasma is not limited by the length of the reactor and can be whatever is needed or desired.
  • the invention has a number of important features and advantages. It provides graphenes that are highly purified and functionalized. The process is highly scalable and capable of producing graphene on a commercial scale. The combination of washing, heating, and drying the graphene particles results in a product having a purity greater than 99 percent, and with the long, vertical reactor, the graphene particles can be functionalized in different ways by different plasmas as they drop through the reactor.
  • the reactor also has the ability to deagglomerate and/or delaminate the graphene particles and expose more surface area to the plasma. It also serves as a particle separator in which the functionalized particles are separated or classified according to size.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un système et un procédé dans lesquels du graphène, qui peut être fabriqué à une échelle industrielle, est hautement purifié, puis fonctionnalisé dans un réacteur plasma vertical qui peut également désagglomérer et/ou cliver le graphène, ainsi que séparer ou classer les particules de graphène fonctionnalisé selon leur dimension. Dans un mode de réalisation décrit, le graphène est fabriqué par combustion de magnésium (Mg) et de dioxyde de carbone (CO2) dans une réaction extrêmement exothermique. Le graphène est séparé des autres produits de réaction et purifié dans une série d'étapes de lavage, de chauffage et de séchage, après quoi il est fonctionnalisé et autrement traité dans le réacteur plasma.
PCT/US2013/054566 2012-08-10 2013-08-12 Système et procédé de fonctionnalisation de graphène WO2014026194A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201261682182P 2012-08-10 2012-08-10
US61/682,182 2012-08-10
US13/864,080 US9260308B2 (en) 2011-04-19 2013-04-16 Nanomaterials and process for making the same
US13/864,080 2013-04-16

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CN103935989A (zh) * 2014-04-09 2014-07-23 中国科学院山西煤炭化学研究所 一种可燃溶剂还原制备石墨烯的方法
WO2019083986A1 (fr) * 2017-10-24 2019-05-02 Graphene Technologies, Inc. Carbones modifiés en réseau et leur fonctionnalisation chimique
CN114132921A (zh) * 2021-04-28 2022-03-04 宁波中乌新材料产业技术研究院有限公司 一种制备石墨烯纳米粒子的电化学方法
CN115386214A (zh) * 2022-10-09 2022-11-25 万华化学（宁波）有限公司 一种耐候无卤阻燃聚碳酸酯合金材料及其制备方法
US11618809B2 (en) 2017-01-19 2023-04-04 Dickinson Corporation Multifunctional nanocomposites reinforced with impregnated cellular carbon nanostructures

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CN114132921A (zh) * 2021-04-28 2022-03-04 宁波中乌新材料产业技术研究院有限公司 一种制备石墨烯纳米粒子的电化学方法
CN115386214A (zh) * 2022-10-09 2022-11-25 万华化学（宁波）有限公司 一种耐候无卤阻燃聚碳酸酯合金材料及其制备方法
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