IP Library › Granted Patent US 12,252,402
Granted Patent B2
US 12,252,402 · App. 18/473,674 · Granted Mar 18, 2025

Apparatus and method for plasma synthesis of graphitic products including graphene

Inventors: Dale Andrew Pennington (Cambridge, GB); Aaron Robert Clayton (Cambridge, GB); Katarzyna Luiza Juda (Cambridge, GB); Catharina Paukner (Cambridge, GB); Lukasz Kurzepa (Cambridge, GB); Robert Henry St. John Cooper (Cambridge, GB); Krzysztof Kazimierz Koziol (Cambridge, GB); Jerome Yi-Zhe Joaug (Cambridge, GB)
Assignee: Levidian Nanosystems Limited
C01B32/184B01D46/023B01J19/088B01J19/126B01J19/129H05H1/46B01J2219/0869B01J2219/0875B01J2219/0892C01B2204/04H05H1/4622
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,252,402
App. No.
18/473,674
Granted
Mar 18, 2025
Kind
B2
Abstract

Apparatus for plasma synthesis of graphitic products including graphene, comprising: a plasma nozzle coupled to a reaction chamber; means for supplying a process gas to the plasma nozzle, the process gas comprising a carbon-containing species; and means for supplying radio frequency radiation to the process gas within the plasma nozzle, so as to produce a plasma within the nozzle in use, and thereby cause cracking of the carbon-containing species; wherein the plasma nozzle is arranged such that an afterglow of the plasma extends into the reaction chamber, the cracked carbon-containing species also passes into the reaction chamber, and the cracked carbon-containing species recombines within the afterglow, so as to form graphitic products including graphene. A method of plasma-synthesising graphitic products including graphene is also provided.

Claims (38)

1. An apparatus for plasma synthesis of graphitic products including graphene, the apparatus comprising:

a reaction chamber having an exit at a bottom of the reaction chamber;

a plasma nozzle coupled to the reaction chamber;

a gas supply for supplying a process gas comprising a carbon-containing species to the plasma nozzle; and

a source of radio frequency radiation for supplying radio frequency radiation to the process gas within the plasma nozzle in use, so as to produce a plasma within the plasma nozzle in use, and thereby cause cracking of the carbon-containing species;

wherein the plasma nozzle is arranged such that, in use, an afterglow of the plasma extends into the reaction chamber, the cracked carbon-containing species also passes into the reaction chamber, and the cracked carbon-containing species recombines within the afterglow, so as to form graphitic products including graphene; and

wherein the apparatus further comprises a gas filtration system attached above the reaction chamber, for collecting solid graphitic products including graphene from the gas phase, the gas filtration system including a filter arranged such that, in use, solid graphitic products including graphene collected by the filter fall down, through the reaction chamber, for extraction through the exit at the bottom of the reaction chamber.

2. The apparatus according to claim 1 , wherein the plasma nozzle is shaped and configured so as to cause, in use, at least one vortex to be formed in the process gas within the plasma nozzle, said at least one vortex being subjected to said radio frequency radiation.

3. The apparatus according to claim 2 , wherein the plasma nozzle is shaped and configured so as to cause, in use, multiple vortices to be formed in the process gas within the plasma nozzle, said multiple vortices being subjected to said radio frequency radiation.

4. The apparatus according to claim 3 , wherein the plasma nozzle is shaped and configured so as to cause, in use, three vortices to be formed in the process gas within the plasma nozzle, said three vortices being subjected to said radio frequency radiation.

5. The apparatus according to claim 4 , wherein the plasma nozzle comprises:

at least one inlet for receiving a stream of the process gas, that forms a first vortex in use;

an open end in communication with the reaction chamber; and

a vortex-reflecting end opposite the open end;

wherein the plasma nozzle is internally tapered towards the open end;

such that, in use, a second vortex is created by the vortex-reflecting end, and a third vortex is produced by reflection of the second vortex from the vortex-reflecting end.

6. The apparatus according to claim 1 , wherein the source of radio frequency radiation comprises a microwave generator, the microwave generator being coupled to a waveguide arranged to direct the radiation to the plasma nozzle in use.

7. The apparatus according to claim 1 , wherein the reaction chamber is configured to apply cooling to the afterglow on exiting the plasma nozzle.

8. The apparatus according to claim 7 , wherein the cooling comprises water cooling or gas cooling.

9. The apparatus according to claim 1 , wherein the plasma is generated at substantially atmospheric pressure.

10. The apparatus according to claim 1 , wherein the carbon-containing species comprises natural gas, or one or more of CH 4 , C 2 H 6 , C 2 H 4 , C 3 H 8 or C 4 H 10 .

11. The apparatus according to claim 1 , wherein the process gas further comprises a buffer gas.

12. The apparatus according to claim 11 , wherein the buffer gas comprises argon, nitrogen, helium, or carbon dioxide.

13. The apparatus according to claim 11 , wherein the ratio of carbon-containing species to buffer gas in the process gas is 50:50 or less;

optionally wherein the ratio of carbon-containing species to buffer gas in the process gas is around 20:80 or less.

14. The apparatus according to claim 1 , wherein, in use, the afterglow within the reaction chamber has an operating temperature lower than 3500° C.;

optionally wherein the operating temperature is lower than 1000° C.

15. The apparatus according to claim 1 , wherein, in use, the temperature just outside the plasma nozzle, at the carbon formation point within the afterglow, is in the range of 800° C. to 1200° C.;

optionally wherein, in use, the temperature just outside the plasma nozzle, at the carbon formation point within the afterglow, is in a range of 900° C. to 1000° C.

16. The apparatus according to claim 1 , wherein the apparatus comprises a plurality of plasma nozzles coupled to the reaction chamber.

17. The apparatus according to claim 1 , wherein the apparatus is configured to deliver gas around an interface between the plasma nozzle and the reaction chamber.

18. The apparatus according to claim 1 , wherein the apparatus is configured to remove graphitic product from walls of the reaction chamber.

19. The apparatus according to claim 1 , wherein the gas filtration system includes a gas blower for blowing gas to dislodge graphitic product from the filter.

20. A method of synthesizing graphitic products including graphene, the method comprising:

supplying a process gas to a plasma nozzle that is coupled to a reaction chamber, the process gas comprising a carbon-containing species; and

supplying radio frequency radiation to the process gas within the plasma nozzle, so as to produce a plasma within the plasma nozzle, and thereby cause cracking of the carbon-containing species;

wherein the plasma nozzle is arranged such that an afterglow of the plasma extends into the reaction chamber, the cracked carbon-containing species also passes into the reaction chamber, and the cracked carbon-containing species recombines within the afterglow, so as to form graphitic products including graphene; and

wherein the method further comprises subjecting the reaction chamber to gas filtration to collect solid graphitic products including graphene from the gas phase, wherein the gas filtration is performed using a gas filtration system that is attached above the reaction chamber and includes a filter arranged such that solid graphitic products including graphene collected by the filter fall down, through the reaction chamber, for extraction through an exit at a bottom of the reaction chamber.

Priority Claims (1)
GB 1410639 · Jun 13, 2014 · national
Continuity (2)
Continuation 15318377
Related Publication 20240010499A1 · Jan 11, 2024
References Cited (72)
US 5349154A · Harker et al. · 1994 [cited by applicant]
US 6099696A · Schwob et al. · 2000 [cited by applicant]
US 7771666B2 · De La Veaux et al. · 2010 [cited by applicant]
US 8071906B2 · Smiljanic et al. · 2011 [cited by applicant]
US 9221688B2 · Hung et al. · 2015 [cited by applicant]
US 11802052B2 · Pennington · 2023 [cited by examiner]
US 20020151604A1 · Detering et al. · 2002 [cited by applicant]
US 20040262145A1 · Duzhev et al. · 2004 [cited by applicant]
US 20060006153A1 · Lee et al. · 2006 [cited by applicant]
US 20070280863A1 · Wira · 2007 [cited by applicant]
US 20080056928A1 · Bunce et al. · 2008 [cited by applicant]
US 20090214799A1 · Simard et al. · 2009 [cited by applicant]
US 20100072430A1 · Gergely et al. · 2010 [cited by applicant]
US 20100301212A1 · Dato et al. · 2010 [cited by applicant]
US 20100314788A1 · Hung et al. · 2010 [cited by applicant]
US 20120034137A1 · Rispy · 2012 [cited by applicant]
US 20120090982A1 · Fullerton et al. · 2012 [cited by applicant]
US 20130022530A1 · Mercuri · 2013 [cited by applicant]
US 20140030447A1 · Lee et al. · 2014 [cited by applicant]
US 20140045342A1 · Mallick et al. · 2014 [cited by applicant]
US 20140219906A1 · Kim et al. · 2014 [cited by applicant]
US 20140159572A1 · Risby et al. · 2014 [cited by applicant]
US 20150098877A1 · Hendricksen · 2015 [cited by applicant]
US 20150129544A1 · Davis · 2015 [cited by applicant]
US 20160217979A1 · Kim et al. · 2016 [cited by applicant]
US 20190006151A1 · Paukner et al. · 2019 [cited by applicant]
GB 2490355A · 2012 [cited by applicant]
JP H0483874B2 · 1992 [cited by applicant]
JP 2006247446A · 2006 [cited by applicant]
JP 2013040151A · 2013 [cited by applicant]
KR 1020070099536A · 2007 [cited by applicant]
KR 20100110216A · 2010 [cited by applicant]
KR 1020110055946 · 2012 [cited by applicant]
WO 03062146A1 · 2003 [cited by applicant]
WO 2005058755A1 · 2005 [cited by applicant]
WO 2010094969A1 · 2010 [cited by applicant]
WO 2010094972A1 · 2010 [cited by applicant]
WO 2012147054A1 · 2012 [cited by applicant]
WO 2013049498A1 · 2013 [cited by applicant]
Yang et al., “Differentiation of alkane isomers through binding energy spectra and total momentum cross sections”, New J. Chem., vol. 38, pp. 1031-1039 (2014). [cited by applicant]
Sun et al., “Methane activation on Fe4 cluster: A density functional theory study”, Chemical Physics Letters 550, pp. 41-46 (2012). [cited by applicant]
Merlo-Sosa et al., “Dodecane decomposition in a radio-frequency (RF) plasma reactor”, International Journal of Chemical Reactor Engineering, vol. 3, p. 1542 (2005). [cited by applicant]
Ogunbesan et al., “Experimental validation of local thermal equilibrium in a MW plasma torch for hydrogen production”, Int. J. Hyd. Energy 38, pp. 15210-15218 (2013). [cited by applicant]
Juda et al., “Large scale synthesis of carbon nanoforms in a novel atmospheric pressure microwave plasma reactor”, Proceedings of ISPC 21 (Aug. 2013). [cited by applicant]
Taratova et al., “Microwave plasmas applied for the synthesis of free standing graphene sheets”, Journal of Physics. D: Applied Physics 47, 385501, pp. 1-11 (Aug. 22, 2014). [cited by applicant]
Wu et al., “Efficient and Large-Scale Synthesis of Few-Layered Graphene Using an Arc-Discharge Method and Conductivity Studies of the Resulting Films”, Nano Research, vol. 3(9), pp. 661-669 (Sep. 2010). [cited by applicant]
Leins et al., “An Atmospheric Pressure Microwave Plasma Torch” (2011). [cited by applicant]
Fauchais et al., “Thermal Spray Fundamentals: From Powder to Part”, Chapter 2, Overview of Thermal Spray, Springer: New York, pp. 17-72 (2014). [cited by applicant]
Heidenreich et al., “Fuel, Hot gas filtration—A review”, vol. 104, pp. 83-94 (2013). [cited by applicant]
Chen et al., “The Thermal Decomposition of Methane. I. Kinetics of the Primary Decomposition to C2H6 + H2; Rate Constant for the Homogeneous Unimolecular Dissociation of Methane and its Pressure Dependence”, Canadian Jo… [cited by applicant]
United Kingdom Search Report for counterpart patent application No. GB1510364.1 dated Jun. 25, 2015. [cited by applicant]
International Search Report for PCT/GB2015/051745 dated Aug. 19, 2015. [cited by applicant]
Novoselov et al., “A roadmap for graphene”, Nature, vol. 490, pp. 192-200 (Oct. 2012). [cited by applicant]
Segal, M., “Selling graphene by the ton”, Nature Nanotechnology, vol. 4, pp. 612-614 (Oct. 2009). [cited by applicant]
Subrahmanyam et al., “Simple method of preparing graphene nakes by an arc-discharge method”, The Journal of Physical Chemistry C Letters, vol. 113, pp. 4257-4259 (Feb. 2009). [cited by applicant]
Chen et al., “Mass-production of highly-crystalline few-layer graphene sheets by arc discharge in various H2-inert gas mixtures”, Chemical Physics Letters, vol. 538, pp. 72-76 (Apr. 2012). [cited by applicant]
Meunier et al., “Homogeneous nucleation of graphene hanoflakes (GNFs) in thermal plasma: Tuning the 2D nanoscale geometry”, 21st International Symposium on Plasma Chemistry, pp. 1-4 (Aug. 2013). [cited by applicant]
Anekaway et al., “Synthesis of graphene-based conductive thin films by plasma-enhanced chemical vapor deposition in a CO/H2 microwave discharge system”, 21st International Symposium on Plasma Chemistry (2013). [cited by applicant]
Tatarova et al., “Microwave plasma based single step method for free standing graphene synthesis at atmospheric conditions”, Applied Physics Letters, vol. 103, pp. 134101-134105 (Sep. 2013). [cited by applicant]
Dato et al., “Clean and highly ordered graphene synthesized in the gas phase”, Chemical Communications, pp. 6095-6097 (Aug. 2009). [cited by applicant]
Novoselov et al., “Electric field effect in atomically thin carbon films”, Science, vol. 306, pp. 666-669 (Oct. 2004). [cited by applicant]
Castelain et al., “Supramolecular assembly of graphene with functionalized poly fluorene-alt-phenylene): the role of the anthraquinone pendant groups”, Chemical Communications, vol. 47, pp. 7677-7679 (May 2011). [cited by applicant]
Yan et al., “Solution-chemistry approach to graphene nanostructures”, Journal of Materials Chemistry, vol. 21, pp. 3295-3300 (2011). [cited by applicant]
Emstev et al., “Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide”, Nature Materials, vol. 8, pp. 203-207 (Mar. 2009). [cited by applicant]
Wursbauer et al., “Molecular beam growth of graphene nanocrystals on dielectric substrates”, Carbon, vol. 50, pp. 4822-4829 (2012). [cited by applicant]
Dhar et al., “A new route to graphene layers by selective laser ablation”, AIP Advances, vol. 1, p. 022109 (2011). [cited by applicant]
McAllister et al., “Single sheet functionalized graphene by oxidation and thermal expansion of graphite”, Chemistry of Materials, vol. 19, pp. 4396-4404 (2007). [cited by applicant]
Vlassiouk et al., “Large scale atmospheric pressure chemical vapor deposition of graphene”, Carbon, vol. 54, pp. 58-67 (2013). [cited by applicant]
Reina et al., “Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition”, Nano Letters, vol. 9, No. 1, pp. 30-35 (2009). [cited by applicant]
Angstron Materials; Vorbeck Materials in Jessup, Maryland; XG Sciences in East Lansing, Michigan. [cited by applicant]
Hernandez et al., “High-yield production of graphene by liquid-phase exfoliation of graphite”, Nanotechnology, vol. B, pp. 563-568 (Sep. 2008). [cited by applicant]
Dato et al., “Substrate-free microwave synthesis of graphene: experimental conditions ⋅0 nd hydrocarbon precursors”, New Journal of Physics, vol. 12, p. 125013 (2010). [cited by applicant]