Spinning, processing, and applications of carbon nanotube filaments, ribbons, and yarns

• US 20020113335A1
• Filed: 09/04/2001
• Published: 08/22/2002
• Est. Priority Date: 11/03/2000
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Zakhidov, Anvar A., Baughman, Ray H., Kozlov, Mikhail, Matrunich, Jim, Lobovsky, Alex, Morris, Robert C.
• Granted Patent: US 6,682,677 B2
• Time in Patent Office: Days
• US Class Current: 264/184
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: D01D 5/06 Wet spinning methods D01D5/0046 takes precedence
• CPC Class Codes: D01F 9/1278 Carbon monoxide
• CPC Class Codes: D10B 2101/122 Nanocarbons
• CPC Class Codes: Y10S 977/742 Carbon nanotubes, CNTs
• CPC Class Codes: Y10S 977/75 Single-walled
• CPC Class Codes: Y10S 977/762 Nanowire or quantum wire, i.e. axially elongated structure having two dimensions of 100 nm or less
• CPC Class Codes: Y10S 977/842 for carbon nanotubes or fullerenes
• CPC Class Codes: Y10S 977/888 Shaping or removal of materials, e.g. etching

Abstract

Coagulation spinning produces structures such as fibers, ribbons, and yarns of carbon nanotubes. Stabilization, orientation, and shaping of spun materials are achieved by post-spinning processes. Advantages include the elimination of core-sheath effects due to carbonaceous contaminants, increasing mechanical properties, and eliminating dimensional instabilities in liquid electrolytes that previously prohibited the application of these spun materials in electrochemical devices. These advances enable the application of coagulation-spun carbon nanotube fibers, ribbons, and yarns in actuators, supercapacitors, and in devices for electrical energy harvesting.

Claims

1. A process of making a structure containing carbon nanotubes which comprises:

forming a uniform suspension of carbon nanotubes in a liquid;

coagulation spinning the suspension to form the structure; and

annealing the structure at an annealing temperature or temperatures sufficient to stabilize the structure against swelling and loss of mechanical strength upon immersion in water or other liquid.

2. The process of claim 1, wherein the structure is a fiber, ribbon or yarn.

3. The process of claim 1, wherein the water or other liquid is used as a component of an electrolyte.

4. The process of claim 1, wherein the maximum annealing temperature is between about 200°

C. and about 2100°

C.

5. The process of claim 1, wherein the maximum annealing temperature is between about 400°

C. and about 1200°

C.

6. The process of claim 1, wherein the carbon nanotubes comprise single-wall carbon nanotubes.

7. The process of claim 6, wherein the average diameter of the single-wall carbon nanotubes is in the range of about 0.6 nm to about 0.9 nm.

8. The process of claim 6, wherein the carbon nanotubes in the suspension are made at high pressure from carbon monoxide, the nanotubes being free of carbonaceous contaminants.

9. The process according to claim 6, wherein a diameter distribution of the carbon nanotubes is bimodal with a first peak centered in the range of about 0.6 nm to about 0.9 nm and a second peak at a larger diameter in the range of about 1.0 nm to about 2.0 nm.

10. The process of claim 1, wherein the annealing is performed after a step of weaving or winding the structure.

11. The process of claim 1, wherein the annealing is performed while the structure is under a state of tension.

12. The process of claim 11, wherein either the tension is between about 10 MPa to about 300 MPa or the structure is maintained at substantially constant length.

13. The process of claim 1, wherein the annealing is performed in inert or reducing atmosphere and a maximum annealing temperature is above about 600°

C.

14. The process of claim 1, wherein the annealing is performed in an atmosphere of steam.

15. The process of claim 1, wherein the step of coagulation spinning is performed using a shear-flow-inducing nozzle.

16. The process of claim 1, wherein the suspension of carbon nanotubes comprises a surfactant, water, and nanotubes synthesized by metal-particle-catalyzed disproportionation of carbon monoxide.

17. The process of claim 16, wherein the surfactant is sodium dodecyl sulfate.

18. The process of claim 1, wherein the coagulation spinning occurs in a polymer containing solution.

19. The process of claim 18, wherein the polymer in the polymer containing solution is poly(vinyl alcohol).

20. A coagulation spun structure comprising single-wall carbon nanotubes, the structure swelling by less than about 10% in diameter when immersed in water.

21. The structure of claim 20, wherein the structure comprises fiber, ribbon or yarn.

22. The structure of claim 20, wherein the single-wall carbon nanotubes have an average diameter in the range of about 0.6 nm to about 0.9 nm

23. The structure of claim 20, wherein the structure further comprises an electromechanical actuator, a supercapacitor or a woven article.

24. The structure of claim 21, wherein the fiber, ribbon, or yarn forms a winding on a mandrel.

25. The structure of claim 20, wherein the structure forms a main hydrogen storing element for a hydrogen storage device.

29. The process of claim 28, wherein the jet is formed in an orifice which has a cross section that is neither round, elliptical, square, or rectangular.

30. The process of claim 28, wherein the jet is injected from a tubular channel of decreasing diameter into an annular stream of the second coagulation liquid that flows coaxial with and surrounding the jet.

31. The process of claim 30, wherein a major proportion of the coaxially flowing coagulation solution is removed through a section of porous wall flow tube located downstream of the converging flow field.

32. The process of claim 31, wherein two or more liquid streams, which each contain a nanotube structure in the coagulation liquid, are combined into a single flow stream containing two or more nanotube structures.

33. The process of claim 28, wherein the carbon nanotubes are free of carbonaceous impurities and the average diameter of the single-wall carbon nanotubes is in the range of about 0.6 nm to about 0.9 nm.

34. The process of claim 28, wherein the second coagulation liquid contains a polymer.

35. The process of claim 34, wherein said polymer is poly(vinyl alcohol).

36. The process of claim 28 that further includes annealing the fiber, ribbon, or yarn at a maximum annealing temperature of between about 200°

C. to about 2100°

C.

26. A fiber, ribbon or yarn comprising greater than about 90 weight percent carbon single-wall nanotubes, wherein average diameter of the single-wall carbon nanotubes is about in the range of about 0.6 nm to about 0.9 nm.

27. A fiber comprising single-wall carbon nanotubes, the fiber containing no binding agent or carbonaceous impurities.

28. A process of coagulation spinning of a fiber, ribbon, or yarn, which comprises:

providing a first liquid comprising a uniform dispersion of single-wall-carbon nanotubes; and

injecting the first liquid as a jet into a second coagulation liquid, the jet being formed in an orifice of decreasing diameter, which creates a converging flow field at close to the point of injection into the second coagulation liquid.