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Patent · US2022056599A1 · A1 · US

Vertical Branched Graphene

(11) Publication number
US2022056599A1
(21) Application number
17/434,896
(22) Filing date
2020-02-28
(30) Priority date
2019-03-01
(43) Publication date
2022-02-24
(51) IPC
C01B 32/186; C01B 32/194; C23C 16/26; C23C 16/44; C23C 16/50; C23C 16/56; C25B 1/02; C25B 11/065; C25B 3/07; C25B 3/26; H01B 1/04; H01M 4/62; C01B 32/184
(52) CPC
  • C25B Electrolytic or electrophoretic processes for the production of compounds or non-metals; apparatus therefor: 11/065, 1/02, 3/07, 3/26
  • B82Y Specific uses or applications of nanostructures; measurement or analysis of nanostructures; manufacture or treatment of nanostructures: 30/00, 40/00
  • C01B Non-metallic elements; compounds thereof; {metalloids or compounds thereof not covered by subclass C01C}: 2204/20, 2204/22, 2204/30, 2204/32, 32/18, 32/184, 32/186, 32/194
  • C01P Indexing scheme relating to structural and physical aspects of solid inorganic compounds: 2002/82, 2002/85, 2004/03, 2006/40
  • C23C Coating metallic material; coating material with metallic material; surface treatment of metallic material by diffusion into the surface, by chemical conversion or substitution; coating by vacuum evaporation, by sputtering, by ion implantation or by chemical vapour deposition, in general: 16/0245, 16/26, 16/4418, 16/50, 16/56
  • C30B Single-crystal growth; unidirectional solidification of eutectic material or unidirectional demixing of eutectoid material; refining by zone-melting of material; production of a homogeneous polycrystalline material with defined structure; single crystals or homogeneous polycrystalline material with defined structure; after-treatment of single crystals or a homogeneous polycrystalline material with defined structure; apparatus therefor: 25/00, 25/186, 29/02, 29/60, 33/12
  • H01B Cables; conductors; insulators; selection of materials for their conductive, insulating or dielectric properties: 1/04
  • H01G Capacitors; capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices of the electrolytic type: 11/34
  • H01M Processes or means, e.g. batteries, for the direct conversion of chemical energy into electrical energy: 4/587, 4/625, 4/9083
  • Y02E Reduction of greenhouse gas [ghg] emissions, related to energy generation, transmission or distribution: 60/10, 60/50
(73) Assignee
Commonwealth Scientific and Industrial Research Organization CSIRO; NewSouth Innovations Pty Ltd
(72) Inventors
Zhaojun Han; Constantine Tsounis; Rose Amal
(54) Title
Vertical Branched Graphene
(57) Abstract

Provided are a method for preparing a vertical branched graphene comprising treating a pristine vertical graphene with an inert plasma in the absence of an introduced carbon source to develop a vertical branched graphene. The method may also include pre-treating a substrate surface with an inert plasma; depositing a pristine vertical graphene onto the substrate surface by contacting the substrate surface with a deposition plasma comprising a carbon source gas for a deposition period. Also provided are a vertical branched graphene attached to a substrate surface, the vertical branched graphene having a trunk portion extending from the substrate surface, said trunk possessing an increased degree of branching as the distance from the substrate surface increases; and a freestanding branched graphene with a proximal end and a distal end, the proximal end comprising a trunk portion, the trunk portion possessing and increased degree of branching as the distance from the proximal end increases and the distance to the distal end decreases.

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Claims (1)

  1. A method of preparing a vertical branched graphene comprising the step of: treating a pristine vertical graphene with an inert plasma in the absence of an introduced carbon source to develop a vertical branched graphene. 2. The method according to claim 1 wherein the inert plasma used to develop a vertical branched graphene is an Argon plasma. 3. The method according to claim 1 wherein the plasma is applied at a pressure of <5 Pa. 4. (canceled) 5. The method according to claim 1 wherein the plasma is applied at a radio frequency of 10-15 MHz. 6. The method according to claim 1 wherein the plasma is applied at a power of 500-2000 W. 7 - 13. (canceled) 14. The method according to claim 1 wherein the only heating applied is heating by the plasma. 15. (canceled) 16. A method of preparing a vertical branched graphene comprising the steps of: a) pre-treating a substrate surface with an inert plasma b) depositing a pristine vertical graphene onto the substrate surface by contacting the substrate surface with a deposition plasma comprising a carbon source gas for a deposition period; c) treating the vertical graphene with an inert plasma in the absence of an introduced carbon source to develop a vertical branched graphene with vertical branched graphene structure; and wherein the pristine vertical branched graphene comprises an interconnected network of vertical graphene sheets; and wherein the deposition plasma is at a pressure less than 2 Pa. 17 - 21. (canceled) 22. The method according to claim 16 wherein the deposition plasma comprising a carbon source is prepared by introducing a carbon source gas and hydrogen to the substrate surface without interruption of the inert plasma. 23. The method according to claim 16 wherein the carbon source is a single source directly introduced as a gaseous stream to the reaction chamber. 24. The method according to claim 16 wherein the carbon source gas is methane. 25 - 26. (canceled) 27. The method according to claim 16 wherein depositing vertical graphene takes place without external heating of the substrate and wherein the only heating applied is heating by the inert plasma; and wherein depositing vertical graphene takes place at <600° C. 28 - 30. (canceled) 31. The method according to claim 16 wherein after step b) but prior to step c) pressure is reduced to <2×10 −2 Pa to evacuate the carbon source gas and hydrogen. 32. (canceled) 33. The method according to claim 16 wherein the inert plasma used to develop vertical branched graphene is an Argon plasma. 34. The method according to claim 33 wherein the Argon plasma is applied at a pressure of 0.5 to 2 Pa. 35. The method according to claim 33 wherein the Argon plasma is applied at a radio frequency of 10-15 MHz. 36. The method according to claim 33 wherein the Argon plasma is applied at a power of 500-2000 W. 37 - 43. (canceled) 44. A vertical branched graphene attached to a substrate surface, the vertical branched graphene having a trunk portion extending from the substrate surface, said trunk possessing an increased degree of branching as the distance from the substrate surface increases, and wherein the relative ratio of the intensity of the Raman spectrum I D /I G peaks is 1.1 or above. 45 - 50. (canceled) 51. A freestanding branched graphene prepared by removing the vertical branched graphene of claim 44 from a substrate, and wherein the relative ratio of the intensity of the Raman spectrum I D /I G peaks is 1.1 or above. 52 - 55. (canceled) 56. A catalyst support comprising the vertical branched graphene of claim 44. 57. Use of the catalyst support of claim 56 in an electrocatalytic process. 58. The use of claim 57 in hydrogen or oxygen production; or in the production of a liquid carbon product; or in the production of one or more of n-propanol, ethanol or formate formed from the reduction of CO 2. 59 - 60. (canceled) 61. A catalyst support comprising the vertical branched graphene of claim 44 in an energy storage device, such as a battery or a supercapacitor. 62. A catalyst support comprising the freestanding branched graphene according to claim 51. 63. Use of the catalyst support of claim 62 in an electrocatalytic process. 64. The use of claim 63 in hydrogen or oxygen production; or in the production of a liquid carbon product; or in the production of one or more of n-propanol, ethanol or formate formed from the reduction of CO 2. 65. A catalyst support comprising the vertical branched graphene of claim 44 in an energy storage device, such as a battery or a supercapacitor.

Description

The invention relates to a new form of graphene having a hierarchical or branched structure and to processes for the preparation thereof. The hierarchical or branched graphene is useful in applications where high surface area graphene is required, such as energy storage devices and catalyst supports.

Graphene exhibits unique electronic, optical, chemical and mechanical properties. Because of its extremely high electron mobility (electrons move through graphene about 100 times faster than silicon), very low absorption in the visible spectrum and relative flexibility and elasticity (compared to inorganics such as indium tin oxide), supported horizontal graphene sheeting as an active functional material has been revolutionising the fields of flexible, transparent and ultra-light nano-devices, from optoelectronics to sensors. Graphene flakes, in which the graphene is exfoliated from any supporting surface, is also a highly useful material, having high thermal and electrical conductivity as well as being extremely lightweight.

Although graphene is normally a flat, sheet like substance, it also has the ability to be deposited onto substrates such that graphene structures can be created in a way that allows for a degree of vertical orientation, that is, the primary direction of the graphene planes is orthogonal to the deposition surface. This vertical growth allows for the creation of controlled graphene microstructures, which are potentially useful in electron emission, bio-recognition and drug/gene/protein delivery applications among others.

Record as JSON 
{
  "publication_number": "US2022056599A1",
  "country": "US",
  "kind": "A1",
  "title": "Vertical Branched Graphene",
  "abstract": "Provided are a method for preparing a vertical branched graphene comprising treating a pristine vertical graphene with an inert plasma in the absence of an introduced carbon source to develop a vertical branched graphene. The method may also include pre-treating a substrate surface with an inert plasma; depositing a pristine vertical graphene onto the substrate surface by contacting the substrate surface with a deposition plasma comprising a carbon source gas for a deposition period. Also provided are a vertical branched graphene attached to a substrate surface, the vertical branched graphene having a trunk portion extending from the substrate surface, said trunk possessing an increased degree of branching as the distance from the substrate surface increases; and a freestanding branched graphene with a proximal end and a distal end, the proximal end comprising a trunk portion, the trunk portion possessing and increased degree of branching as the distance from the proximal end increases and the distance to the distal end decreases.",
  "claims": [
    "1. A method of preparing a vertical branched graphene comprising the step of: treating a pristine vertical graphene with an inert plasma in the absence of an introduced carbon source to develop a vertical branched graphene. 2. The method according to claim 1 wherein the inert plasma used to develop a vertical branched graphene is an Argon plasma. 3. The method according to claim 1 wherein the plasma is applied at a pressure of <5 Pa. 4. (canceled) 5. The method according to claim 1 wherein the plasma is applied at a radio frequency of 10-15 MHz. 6. The method according to claim 1 wherein the plasma is applied at a power of 500-2000 W. 7 - 13. (canceled) 14. The method according to claim 1 wherein the only heating applied is heating by the plasma. 15. (canceled) 16. A method of preparing a vertical branched graphene comprising the steps of: a) pre-treating a substrate surface with an inert plasma b) depositing a pristine vertical graphene onto the substrate surface by contacting the substrate surface with a deposition plasma comprising a carbon source gas for a deposition period; c) treating the vertical graphene with an inert plasma in the absence of an introduced carbon source to develop a vertical branched graphene with vertical branched graphene structure; and wherein the pristine vertical branched graphene comprises an interconnected network of vertical graphene sheets; and wherein the deposition plasma is at a pressure less than 2 Pa. 17 - 21. (canceled) 22. The method according to claim 16 wherein the deposition plasma comprising a carbon source is prepared by introducing a carbon source gas and hydrogen to the substrate surface without interruption of the inert plasma. 23. The method according to claim 16 wherein the carbon source is a single source directly introduced as a gaseous stream to the reaction chamber. 24. The method according to claim 16 wherein the carbon source gas is methane. 25 - 26. (canceled) 27. The method according to claim 16 wherein depositing vertical graphene takes place without external heating of the substrate and wherein the only heating applied is heating by the inert plasma; and wherein depositing vertical graphene takes place at <600° C. 28 - 30. (canceled) 31. The method according to claim 16 wherein after step b) but prior to step c) pressure is reduced to <2×10 −2 Pa to evacuate the carbon source gas and hydrogen. 32. (canceled) 33. The method according to claim 16 wherein the inert plasma used to develop vertical branched graphene is an Argon plasma. 34. The method according to claim 33 wherein the Argon plasma is applied at a pressure of 0.5 to 2 Pa. 35. The method according to claim 33 wherein the Argon plasma is applied at a radio frequency of 10-15 MHz. 36. The method according to claim 33 wherein the Argon plasma is applied at a power of 500-2000 W. 37 - 43. (canceled) 44. A vertical branched graphene attached to a substrate surface, the vertical branched graphene having a trunk portion extending from the substrate surface, said trunk possessing an increased degree of branching as the distance from the substrate surface increases, and wherein the relative ratio of the intensity of the Raman spectrum I D /I G peaks is 1.1 or above. 45 - 50. (canceled) 51. A freestanding branched graphene prepared by removing the vertical branched graphene of claim 44 from a substrate, and wherein the relative ratio of the intensity of the Raman spectrum I D /I G peaks is 1.1 or above. 52 - 55. (canceled) 56. A catalyst support comprising the vertical branched graphene of claim 44. 57. Use of the catalyst support of claim 56 in an electrocatalytic process. 58. The use of claim 57 in hydrogen or oxygen production; or in the production of a liquid carbon product; or in the production of one or more of n-propanol, ethanol or formate formed from the reduction of CO 2. 59 - 60. (canceled) 61. A catalyst support comprising the vertical branched graphene of claim 44 in an energy storage device, such as a battery or a supercapacitor. 62. A catalyst support comprising the freestanding branched graphene according to claim 51. 63. Use of the catalyst support of claim 62 in an electrocatalytic process. 64. The use of claim 63 in hydrogen or oxygen production; or in the production of a liquid carbon product; or in the production of one or more of n-propanol, ethanol or formate formed from the reduction of CO 2. 65. A catalyst support comprising the vertical branched graphene of claim 44 in an energy storage device, such as a battery or a supercapacitor."
  ],
  "description_excerpt": "The invention relates to a new form of graphene having a hierarchical or branched structure and to processes for the preparation thereof. The hierarchical or branched graphene is useful in applications where high surface area graphene is required, such as energy storage devices and catalyst supports.\n\nGraphene exhibits unique electronic, optical, chemical and mechanical properties. Because of its extremely high electron mobility (electrons move through graphene about 100 times faster than silicon), very low absorption in the visible spectrum and relative flexibility and elasticity (compared to inorganics such as indium tin oxide), supported horizontal graphene sheeting as an active functional material has been revolutionising the fields of flexible, transparent and ultra-light nano-devices, from optoelectronics to sensors. Graphene flakes, in which the graphene is exfoliated from any supporting surface, is also a highly useful material, having high thermal and electrical conductivity as well as being extremely lightweight.\n\nAlthough graphene is normally a flat, sheet like substance, it also has the ability to be deposited onto substrates such that graphene structures can be created in a way that allows for a degree of vertical orientation, that is, the primary direction of the graphene planes is orthogonal to the deposition surface. This vertical growth allows for the creation of controlled graphene microstructures, which are potentially useful in electron emission, bio-recognition and drug/gene/protein delivery applications among others.",
  "cpc": [
    "C25B 11/065",
    "B82Y 30/00",
    "B82Y 40/00",
    "C01B 2204/20",
    "C01B 2204/22",
    "C01B 2204/30",
    "C01B 2204/32",
    "C01B 32/18",
    "C01B 32/184",
    "C01B 32/186",
    "C01B 32/194",
    "C01P 2002/82",
    "C01P 2002/85",
    "C01P 2004/03",
    "C01P 2006/40",
    "C23C 16/0245",
    "C23C 16/26",
    "C23C 16/4418",
    "C23C 16/50",
    "C23C 16/56",
    "C25B 1/02",
    "C25B 3/07",
    "C25B 3/26",
    "C30B 25/00",
    "C30B 25/186",
    "C30B 29/02",
    "C30B 29/60",
    "C30B 33/12",
    "H01B 1/04",
    "H01G 11/34",
    "H01M 4/587",
    "H01M 4/625",
    "H01M 4/9083",
    "Y02E 60/10",
    "Y02E 60/50"
  ],
  "ipc": [
    "C01B 32/186",
    "C01B 32/194",
    "C23C 16/26",
    "C23C 16/44",
    "C23C 16/50",
    "C23C 16/56",
    "C25B 1/02",
    "C25B 11/065",
    "C25B 3/07",
    "C25B 3/26",
    "H01B 1/04",
    "H01M 4/62",
    "C01B 32/184"
  ],
  "assignees": [
    "Commonwealth Scientific and Industrial Research Organization CSIRO",
    "NewSouth Innovations Pty Ltd"
  ],
  "inventors": [
    "Zhaojun Han",
    "Constantine Tsounis",
    "Rose Amal"
  ],
  "filing_date": "2020-02-28",
  "publication_date": "2022-02-24",
  "priority_date": "2019-03-01",
  "application_number": "US-202017434896-A",
  "family_id": "72336901",
  "cited_by_count": 7
}

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