THREE-DIMENSIONAL (3D) PRINTING OF GRAPHENE MATERIALS

• US 20190308880A1
• Filed: 07/12/2017
• Published: 10/10/2019
• Est. Priority Date: 07/12/2016
• Status: Active Application

• Current Assignee: Rice University
• Original Assignee: Rice University
• Inventors: Tour, James M., Sha, Junwei, Li, Yilun, Miller, Jordan, Kinstlinger, Ian, Cofer, Savannah, Chyan, Yieu
• Application Number:
  US16/317,404
• Publication Number:
  US 20190308880A1
• Time in Patent Office: Days
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: C01B 2204/22 Electronic properties
• CPC Class Codes: C01B 2204/26 Mechanical properties
• CPC Class Codes: C01B 2204/32 Size or surface area
• CPC Class Codes: C01B 32/184 Preparation
• CPC Class Codes: C01B 32/186 by chemical vapour deposition [CVD]
• CPC Class Codes: C01B 32/194 After-treatment
• CPC Class Codes: C01P 2002/01 depicted by a TEM-image
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/24 Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/17 Pore diameter distribution
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/90 Other properties not specified above
• CPC Class Codes: H01B 1/04 mainly consisting of carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01B 13/0016 for heat treatment
• CPC Class Codes: H01B 13/0036 Details
• CPC Class Codes: H01G 11/24 characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
• CPC Class Codes: H01G 11/26 : characterised by their structure, e.g. multi-layered, porosity or surface features
• CPC Class Codes: H01G 11/32 : Carbon-based
• CPC Class Codes: H01G 11/44 : Raw materials therefor, e.g. resins or coal
• CPC Class Codes: H01G 11/86 : specially adapted for electrodes carbonisation or activation of carbon for the manufacture of electrodes H01G11/34
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors

Abstract

Three-dimensional (3D) printing of graphene materials and methods and apparatuses for making same. In some embodiments, combined metal powder and carbon growth sources (such as powder Ni and sucrose) are utilized in the 3D printing process. In other embodiments, metal powders with binders (such as powder Ni and a polymer bases binder) are utilized in the 3D printing process. The metal in the resulting 3D printed composite material can then be etched or otherwise removed yielding the 3D printed graphene materials.

Claims

1. A method of making a 3D graphene material comprising:

(a) mixing a metal powder and a carbon source to form a metal and carbon source mixture, wherein

(i) the carbon source is not graphene, graphene oxide, or a graphene derivative, and

(ii) at least some of the metal powder is covered by the carbon source;

(b) utilizing a 3D printing process to fuse the metal powder in the metal and carbon source mixture into a specific structure;

(c) converting the carbon source in the metal and carbon source mixture into graphene sheets that cover the metal powder to form a graphene and metal scaffold; and

(d) removing the metal from the graphene and metal scaffold to form the 3D graphene material.

2. The method of claim 1, wherein the step of utilizing the printing process to fuse the metal powder into the specific structure is performed while performing the step of converting the carbon source into the graphene sheets that cover the metal powder.

3. The method of claim 1, wherein a laser is utilized to convert the carbon source into the graphene sheets that cover the metal powder.

6. The method of claim 3, wherein the laser is set at a scanning speed of at least about 1000 mm/min.

7. The method of claim 3, wherein the laser is set at a power of at least 4 W.

10. The method of claim 1, wherein the metal powder comprises a metal is selected from a group consisting of Ni, Cu, Ni—

Cu alloys, Ru, Ag, Fe, Co, Al, and combinations and alloys thereof.

11. The method of claim 1, wherein the metal powder comprise Ni.

12. The method of claim 1, wherein the metal powder has an average particle size in the range between about 100 nm and about 1 cm.

15. The method of claim 1, wherein the carbon source comprises a material selected from a group consisting of sucrose, polymethyl methacrylate, glucose, poly(phenylene sulfide), carbohydrates, poly(acrylonitrile), polysaccharides, polyimide, and combinations thereof.

16. The method of claim 1, wherein the carbon source comprises sucrose.

17. The method of claim 1, wherein weight ratio of the metal powder to the carbon source is between about 1:

1 and 20;

1.

18. The method of claim 1, wherein the 3D graphene material is selected from a group consisting of in-situ N-doped graphene foams, carbon nanotube/graphene composites, carbon fibers, carbon nanotube fibers, carbon nanoonions/graphene composites, phosphorene foams, 3D MX and/or MX₂ foams, and combinations thereof, wherein

(a) M is selected from a group consisting of Mo, W, Bi, Hf, Ga, Ge, Ta, Sn, Zn, Cd, Pb, B, Nb, Zr, and combinations thereof, and

(b) X is selected from a group consisting of S, N, Se, P, and combinations thereof.

19. The method of claim 1, wherein the 3D graphene material has a porosity of at least 98%.

21. The method of claim 1, wherein the 3D graphene material is a graphene foam.

22. The method of claim 1, wherein the 3D graphene material has an average pore diameter in the range between 1 nm and about 1 cm.

25. The method of claim 1, wherein the 3D graphene material comprises a surface area ranging from about 50 m²/g to about 2,500 m²/g.

26. The method of claim 1, wherein the 3D graphene material has an electrical conductivity ranging from about 6.9 S/cm and about 10.5 D/cm.

27. The method of claim 1, wherein the 3D graphene material has a mechanical robustness that is at least about 11 kPa storage modulus.

28. The method of claim 1, wherein the 3D graphene material has a damping capacity of at least 0.05.

29. The method of claim 1, wherein the step of removing the metal to form the 3D graphene material comprises etching away the metal.

33. The method of claim 1, wherein the metal powder is at room temperature and the metal powder and the carbon source are converted into graphene sheets that cover the metal powder without preheating.

34. The method of claim 1, wherein the step of converting the carbon source into graphene sheets that cover the metal powder is performed in air.

35. The method of claim 1, wherein the step of converting the carbon source into graphene sheets that cover the metal powder is performed in an atmosphere of H₂, Ar, or both.

36. The method of claim 1 wherein the step of converting the carbon source into graphene sheets that cover the metal powder further comprises a step of heat treatment.

39. The method of claim 1, wherein the step of mixing the metal powder and the carbon source to form the metal and carbon source mixture comprises mixing the metal powder and the carbon source in water, and then removing the water to form the metal and carbon source mixture.

40. The method of claim 1, wherein

(a) the carbon source is an organic polymer, and

(b) the step of mixing the metal powder and the carbon source to form the metal and carbon source mixture comprises mixing the metal powder and the carbon source in a solvent, and then removing the solvent to form the metal and carbon source mixture.

41. The method of claim 1 further comprising incorporating the 3D graphene material into a device.

42. The method of claim 41, wherein the device is selected from is a group consisting of electrodes, battery electrodes, capacitors, supercapacitors, batteries, lithium batteries, lithium ion batteries, photovoltaic devices, photovoltaic cells, transistors, current collectors, fuel cell devices, water desalination devices, capacitive deionization devices, water-splitting devices, water-oil separation devices, water/gas purification devices, sensors, mechanical dampening devices, cell scaffolds for artificial wood, scaffolds for growth of bone or animal/human tissue in vivo or in vitro, scaffolds for neuronal growth in vitro or in vivo, and spinal cord regeneration scaffolds.

43. The method of claim 1 further comprising incorporating the 3D graphene material into an electrode.

44. The method of claim 43 further comprising incorporating the electrode into a device that is selected from a group consisting of capacitors, supercapacitors, batteries, lithium batteries, lithium ion batteries, photovoltaic devices, photovoltaic cells, transistors, current collectors, fuel cell devices, water desalination devices, capacitive deionization devices, water-splitting devices, water-oil separation devices, water/gas purification devices, sensors, and mechanical dampening devices.

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