Carbon nanotube composite structure and method of manufacturing the same
View Patent ↗Provided are a carbon nanotube structure more excellent in electric conductivity, thermal conductivity, and mechanical strength, and a method of manufacturing the carbon nanotube structure. A carbon nanotube composite structure is characterized by including: a first carbon nanotube structure in which functional groups bonded to plural carbon nanotubes are chemically bonded and mutually cross-linked to construct a network structure; and a second carbon nanotube structure in which functional groups bonded to plural carbon nanotubes are chemically bonded and mutually cross-linked to construct a network structure, the second carbon nanotube structure being combined with the network structure of the first carbon nanotube structure.
1. A method of manufacturing a carbon nanotube composite structure comprising:
supplying a first solution containing plural first carbon nanotubes having functional groups to a surface of a substrate;
cross-linking the plural first carbon nanotubes with the functional groups to form a cured cross-linked first carbon nanotube structure;
supplying a second solution containing plural second carbon nanotubes having functional groups to the cured cross-linked first carbon nanotube structure and penetrating the second solution into the cured cross-linked first carbon nanotube structure; and
cross-linking the plural second carbon nanotubes with the functional groups in the second solution to form a cross-linked carbon nanotube composite structure.
2. The method of claim 1 , wherein an average diameter of the carbon nanotubes in the first solution is different from an average diameter of the carbon nanotubes in the second solution.
3. A method of manufacturing a carbon nanotube composite structure according to claim 1 , wherein main carbon nanotubes in the first solution are multi-wall carbon nanotubes, and main carbon nanotubes in the second solution are single-wall carbon nanotubes.
4. The method of claim 1 , wherein:
at least one of the first solution and the second solution contains a cross-linking agent that cross-links the plural functional groups together; and
the cross-linking agent is not self-polymerizable.
5. The method of claim 4 , wherein:
each of the functional groups in at least one of the first solution and the second solution is at least one functional group selected from the group consisting of —OH, —COOH, —COOR (where R represents a substituted or unsubstituted hydrocarbon group), —COX (where X represents a halogen atom), —NH 2 , and —NCO; and
the cross-linking agent is capable of prompting a cross-linking reaction with the selected functional groups.
6. The method of claim 4 , wherein:
the cross-linking agent is at least one cross-linking agent selected from the group consisting of a polyol, a polyamine, a polycarboxylic acid, a polycarboxylate, a polycarboxylic acid halide, a polycarbodiimide, and a polyisocyanate; and
each of the functional groups in at least one of the first solution and the second solution is capable of prompting a cross-linking reaction with the selected cross-linking agent.
7. The method of claim 4 , wherein:
each of the functional groups in at least one of the first solution and the second solution is at least one functional group selected from the group consisting of —OH, —COOH, —COOR (where R represents a substituted or unsubstituted hydrocarbon group), —COX (where X represents a halogen atom), —NH 2 , and —NCO;
the cross-linking agent is at least one cross-linking agent selected from the group consisting of a polyol, a polyamine, a polycarboxylic acid, a polycarboxylate, a polycarboxylic acid halide, a polycarbodiimide, and a polyisocyanate; and
the functional groups and the cross-linking agents are respectively selected for a combination capable of prompting a mutual cross-linking reaction.
8. The method of claim 5 , wherein each of the functional groups is —COOR (where R represents a substituted or unsubstituted hydrocarbon group).
9. The method of claim 8 , wherein the cross-linking agent is a polyol.
10. The method of claim 8 , wherein the cross-linking agent is at least one cross-linking agent selected from the group consisting of glycerin, ethylene glycol, butenediol, hexynediol, hydroquinone, and naphthalenediol.
11. The method of claim 1 , wherein at least one of the first solution and the second solution further contains a solvent.
12. The method of claim 4 , wherein the cross-linking agent also functions as a solvent.
13. The method of claim 1 , wherein a reaction forming the chemical bonding in at least one of the first cross-linking step and the second cross-linking step is a reaction for chemically bonding the plural functional groups of a same type.
14. The method of claim 13 , wherein at least one of the first solution and the second solution further contains an additive that forms the chemical bonding among the plural functional groups of a same type.
15. The method of claim 14 , wherein the reaction is dehydration condensation and the additive is a condensation agent.
16. The method of claim 15 , wherein each of the functional groups is at least one functional group selected from the group consisting of —COOR (where R represents a substituted or unsubstituted hydrocarbon group), —COOH, —COX (where X represents a halogen atom), —OH, —CHO—, and —NH 2 .
17. The method of claim 16 , wherein each of the functional groups is —COOH.
18. The method of claim 15 , wherein the condensation agent is at least one condensation agent selected from the group consisting of sulfuric acid, N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide, and dicyclohexyl carbodiimide.
19. The method of claim 14 , wherein the reaction is a substitution reaction and the additive is a base.
20. The method of claim 19 , wherein each of the functional groups is at least one functional group selected from the group consisting of —NH 2 , —X (where X represents a halogen atom), —SH, —OH, —OSO 2 CH 3 , and —OSO 2 (C 6 H 4 )CH 3 .
21. The method of claim 19 , wherein the base is at least one base selected from the group consisting of sodium hydroxide, potassium hydroxide, pyridine, and sodium ethoxide.
22. The method of claim 13 , wherein the reaction is an addition reaction.
23. The method of claim 22 , wherein each of the functional groups is at least one functional group selected from the group consisting of —OH and —NCO.
24. The method of claim 13 , wherein the reaction is an oxidative reaction.
25. The method of claim 24 , wherein each of the functional groups is —SH.
26. The method of claim 24 , wherein the solution further contains an oxidative reaction accelerator.
27. The method of claim 26 , wherein the oxidative reaction accelerator is iodine.