# US 2017/0287650 A1 · Direct growth of polyaniline nanotubes on carbon cloth for flexible and high-performance supercapacitors

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- Number: US 2017/0287650 A1
- Document ID: US20170287650A1
- Status: Published application
- Kind: A1
- Application number: 15/472,409
- Filed: 2017-03-29
- Published: 2017-10-05
- Earliest claimed: 2016-04-01
- Assignees: The Regents of the University of California
- Applicants: The Regents of the University of California
- Inventors: Richard B. Kaner; Maher F. El-Kady; Mir Fazlollah Mousavi; Masumeh Hashemi; Mohammad S. Rahmanifar
- Web page: https://patentgrep.com/patent/US20170287650A1

## CPC

- H01G 11/36: Nanostructures, e.g. nanofibres, nanotubes or fullerenes
- H01G 11/02: using combined reduction-oxidation reactions, e.g. redox arrangement or solion
- 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
- H01G 11/40: Fibres
- H01G 11/48: Conductive polymers
- H01G 11/70: characterised by their structure
- H01G 11/86: specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34)
- Y02E 60/13: Energy storage using capacitors
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## 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

### Claim 1

A supercapacitor comprising:
two or more electrodes, wherein at least one electrode comprises a functionalized carbon electrode;
a current collector; and
a redox electrolyte.

### Claim 2 (depends on 1)

The supercapacitor of claim 1, wherein the functionalized carbon electrode comprises:
a carbon substrate comprising carbon cloth, carbon fiber, amorphous carbon, glassy carbon, carbon nanofoam, carbon aerogel, graphene foam or any combination thereof; and
a conducting polymer disposed on the carbon substrate, 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.

### Claim 3 (depends on 2)

The supercapacitor of claim 2, wherein the conducting polymer has a morphology of one or more nanotubes.

### Claim 4 (depends on 3)

The supercapacitor of claim 3, wherein a nanotube has a length of 100 nanometers to 10,000 nanometers.

### Claim 5 (depends on 3)

The supercapacitor of claim 3, wherein a nanotube has an outer width of 10 nanometers to 1,000 nanometers.

### Claim 6 (depends on 3)

The supercapacitor of claim 3, wherein a nanotube has an inner width of 50 nanometers to 800 nanometers.

### Claim 7 (depends on 3)

The supercapacitor of claim 3, wherein a surface of a nanotube contains a nanostructure.

### Claim 8 (depends on 7)

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

### Claim 9 (depends on 7)

The supercapacitor of claim 7, wherein a nanostructure has a length of 4 nanometers to 50 nanometers.

### Claim 10 (depends on 7)

The supercapacitor of claim 7, wherein a nanostructure has a width of 4 nanometers to 50 nanometers.

### Claim 11 (depends on 2)

The supercapacitor of claim 2, wherein the functionalized carbon electrode has an areal capacitance of at least 150 mF/cm2 to 750 mF/cm2.

### Claim 12 (depends on 2)

The supercapacitor of claim 2, wherein the functionalized carbon electrode has a resistance, which decreases after 1,000 cycles of bending by at most 8%.

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 1)

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

### Claim 15 (depends on 1)

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

### Claim 16 (depends on 1)

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

### Claim 17 (depends on 1)

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

### Claim 18

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 nanotubes on the functionalized carbon substrate.

### Claim 19 (depends on 18)

The method of claim 18, wherein the functionalizing of a carbon substrate to form a functionalized carbon substrate comprises:
i) forming a functionalization solution;
ii) heating the functionalization solution;
iii) cooling the functionalization solution;
iv) displacing a piece of carbon substrate into the functionalization solution; and
v) rinsing a piece of functionalized carbon substrate.

### Claim 20 (depends on 19)

The method of claim 19, wherein the heating of the functionalization solution occurs at a temperature of 30° C. to 120° C.

### Claim 21 (depends on 19)

The method of claim 19, wherein the heating of the functionalization solution occurs for a period of time of 60 minutes to 240 minutes.

### Claim 22 (depends on 18)

The method of claim 18, further comprising a step of annealing the functionalized carbon substrate before the preparing of the functionalized carbon substrate.

### Claim 23 (depends on 22)

The method of claim 22, wherein the functionalized carbon substrate is annealed at a temperature of 100° C. to 400° C.

### Claim 24 (depends on 22)

The method of claim 22, wherein the functionalized carbon substrate is annealed for a period of time of 0.5 hours to 14 hours.

### Claim 25 (depends on 18)

The method of claim 18, 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.

### Claim 26 (depends on 25)

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

### Claim 27 (depends on 25)

The method of claim 25, wherein the drying occurs at a temperature of 30° C. to 120° C.

### Claim 28 (depends on 25)

The method of claim 25, wherein the drying occurs over a period of time of 3 hours to 12 hours.

### Claim 29 (depends on 18)

The method of claim 18, wherein the formulating of a polymerization fluid comprises:
i) forming a polymerization solution comprising:
a conducting polymer;
an acid;
a detergent;
water; and
an oxidizing agent;
ii) stirring the polymerization solution to form the polymerization fluid.

### Claim 30 (depends on 29)

The method of claim 29, 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.

### Claim 31 (depends on 29)

The method of claim 29, wherein the stirring of the polymerization solution occurs for a period of time of 10 minutes to 40 minutes.

### Claim 32 (depends on 18)

The method of claim 18, wherein the synthesizing of a nanotube 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 a functionalized carbon substrate from the polymerization fluid;
v) washing the functionalized carbon substrate; and
vi) drying the functionalized carbon substrate.

### Claim 33 (depends on 32)

The method of claim 32, wherein the storing of the functionalized carbon substrate in the polymerization fluid occurs at a temperature of 10° C. to 50° C.

### Claim 34 (depends on 32)

The method of claim 32, wherein the storing of the functionalized carbon substrate in the polymerization fluid occurs for a period of time of at least 8 hours.

### Claim 35 (depends on 32)

The method of claim 32, wherein the drying of the functionalized carbon substrate occurs at a temperature of 30° C. to 120° C.