Direct growth of polyaniline nanotubes on carbon cloth for flexible and high-performance supercapacitors

• US 10,622,163 B2
• Filed: 03/29/2017
• Issued: 04/14/2020
• Est. Priority Date: 04/01/2016
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Kaner, Richard B., El-Kady, Maher F., Mousavi, Mir Fazlollah, Hashemi, Masumeh, Rahmanifar, Mohammad S.
• Primary Examiner(s): Ha, Nguyen T
• Application Number:
  US15/472,409
• Publication Number:
  US 20170287650A1
• Time in Patent Office: 1,112 Days
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• 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 11/36 Nanostructures, e.g. nanofibres, nanotubes or fullerenes
• CPC Class Codes: H01G 11/40 Fibres
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 11/70 characterised by their structure
• 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
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

The present disclosure further provides an exemplary energy storage device fabricated from rectangular-tube polyaniline (PANI) that is chemically synthesized by a simple and convenient method. The rectangular-tube PANI, as an active material, is synthesized on a functionalized carbon cloth (FCC) as a substrate, and the obtained composite is immobilized on a stainless steel mesh as a current collector. The present disclosure additionally presents a facile technique for the direct synthesis of PANI nanotubes, with rectangular pores, on chemically activated CC.

Claims

1. A supercapacitor comprising:

two or more electrodes, wherein at least one of the two or more electrodes comprises a functionalized carbon electrode comprising a carbon substrate and one or more conducting polymer nanotubes disposed on the carbon substrate, wherein the one or more conducting polymer nanotubes comprise polyaniline, poly(p-phenylene oxide), poly(p-phenylene sulfide), poly(3,4-ethylenedioxythiophene), polypyrrole, polythiophene, poly(3- alkythiophene), poly(3-methylthiophene), poly(3-hexylthiophene), or any combination thereof;

a current collector; and

a redox electrolyte in direct contact with an interior surface and an exterior surface of the one or more conducting polymer nanotubes.

2. The supercapacitor of claim 1, wherein the carbon substrate comprises carbon cloth, carbon fiber, amorphous carbon, glassy carbon, carbon nanofoam, carbon aerogel, graphene foam, or any combination thereof.

3. The supercapacitor of claim 1, wherein the one or more conducting polymer nanotubes have a length of 100 nanometers to 10,000 nanometers.

4. The supercapacitor of claim 1, wherein the one or more conducting polymer nanotubes have an outer width of 10 nanometers to 1,000 nanometers.

5. The supercapacitor of claim 1, wherein the one or more conducting polymer nanotubes have an inner width of 50 nanometers to 800 nanometers.

6. The supercapacitor of claim 1, wherein a surface of the one or more conducting polymer nanotubes contains a nanostructure.

7. The supercapacitor of claim 6, wherein the nanostructure comprises a nanorod, nanochain, nanofiber, nanoflake, nanoflower, nanoparticle, nanoplatelet, nanoribbon, nanoring, nanosheet, or any combination thereof.

8. The supercapacitor of claim 6, wherein the nanostructure has a length of 4 nanometers to 50 nanometers.

9. The supercapacitor of claim 6, wherein the nanostructure has a width of 4 nanometers to 50 nanometers.

10. The supercapacitor of claim 1, wherein the functionalized carbon electrode has an areal capacitance of 150 mF/cm² to 750 mF/cm².

11. The supercapacitor of claim 1, wherein the functionalized carbon electrode has a resistance which decreases after 1,000 cycles of bending by at most 8%.

12. The supercapacitor of claim 1, wherein the redox electrolyte comprises a quinone.

13. The supercapacitor of claim 1, wherein the supercapacitor has a working potential of 0.1 V to 1.7 V.

14. The supercapacitor of claim 1, wherein the supercapacitor has a gravimetric capacitance which, after 1,000 cycles of charging, decreases by at most 26%.

15. The supercapacitor of claim 1, wherein the supercapacitor has a gravimetric capacitance which is 125 F/g to 20,000 F/g.

16. The supercapacitor of claim 1, wherein the supercapacitor has a gravimetric energy density which is 12 Wh/kg to 3,000 Wh/kg.

17. A method of fabricating a functionalized electrode comprising:

a) functionalizing a carbon substrate to form a functionalized carbon substrate;

b) preparing the functionalized carbon substrate;

c) formulating a polymerization fluid; and

d) synthesizing one or more conducting polymer nanotubes on the functionalized carbon substrate, wherein the one or more conducting polymer nanotubes comprise polyaniline, poly(p-phenylene oxide), poly(p-phenylene sulfide), poly(3,4-ethylenedioxythiophene), polypyrrole, polythiophene, poly(3-alkythiophene), poly(3-methylthiophene), poly(3-hexylthiophene), or any combination thereof.

18. The method of claim 17, wherein the functionalizing of the carbon substrate to form the functionalized carbon substrate comprises:

i) forming a functionalization solution;

ii) heating the functionalization solution;

iii) cooling the functionalization solution;

iv) displacing a piece of the carbon substrate into the functionalization solution to form a piece of the functionalized carbon substrate; and

v) rinsing the piece of the functionalized carbon substrate.

19. The method of claim 18, wherein the heating of the functionalization solution occurs at a temperature of 30°

C. to 120°

C.

20. The method of claim 18, wherein the heating of the functionalization solution occurs for a period of time of 60 minutes to 240 minutes.

21. The method of claim 17, further comprising a step of annealing the functionalized carbon substrate before the preparing of the functionalized carbon substrate.

22. The method of claim 21, wherein the functionalized carbon substrate is annealed at a temperature of 100°

C. to 400°

C.

23. The method of claim 21, wherein the functionalized carbon substrate is annealed for a period of time of 0.5 hours to 14 hours.

24. The method of claim 17, wherein the preparing of the functionalized carbon substrate comprises:

i) cutting a piece of the functionalized carbon substrate;

ii) submerging the piece of functionalized carbon substrate in a solvent solution;

iii) sonicating the piece of functionalized carbon substrate in the solvent solution; and

iv) drying the piece of functionalized carbon substrate.

25. The method of claim 24, wherein the sonicating occurs for a period of time of 15 minutes to 60 minutes.

26. The method of claim 24, wherein the drying occurs at a temperature of 30°

C. to 120°

C.

27. The method of claim 24, wherein the drying occurs over a period of time of 3 hours to 12 hours.

28. The method of claim 17, wherein the formulating of the polymerization fluid comprises:

i) forming a polymerization solution comprising;

a conducting polymer;

an acid;

a detergent;

water; and

an oxidizing agent; and

ii) stirring the polymerization solution to form the polymerization fluid.

29. The method of claim 28, wherein the conducting polymer comprises polyaniline, poly(p-phenylene oxide), poly(p-phenylene sulfide), poly(3,4-ethylenedioxythiophene), polypyrrole, polythiophene, poly(3-alkythiophene), poly(3-methylthiophene), poly(3-hexylthiophene), or any combination thereof.

30. The method of claim 28, wherein the stirring of the polymerization solution occurs for a period of time of 10 minutes to 40 minutes.

31. The method of claim 17, wherein the synthesizing of the one or more conducting polymer nanotubes on the functionalized carbon substrate comprises:

i) agitating the polymerization fluid;

ii) immersing the functionalized carbon substrate in the polymerization fluid;

iii) storing the functionalized carbon substrate in the polymerization fluid;

iv) removing the functionalized carbon substrate from the polymerization fluid;

v) washing the functionalized carbon substrate; and

vi) drying the functionalized carbon substrate.

32. The method of claim 31, wherein the storing of the functionalized carbon substrate in the polymerization fluid occurs at a temperature of 10°

C. to 50°

C.

33. The method of claim 31, wherein the storing of the functionalized carbon substrate in the polymerization fluid occurs for a period of time of at least 8 hours.

34. The method of claim 31, wherein the drying of the functionalized carbon substrate occurs at a temperature of 30°

C. to 120°

C.