Stretchable organic metals, composition, and use

• US 10,003,126 B2
• Filed: 04/22/2016
• Issued: 06/19/2018
• Est. Priority Date: 04/23/2015
• Status: Active Grant

• Current Assignee: University of Connecticut (State of Connecticut)
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Sotzing, Gregory Allen
• Primary Examiner(s): Kopec, Mark
• Assistant Examiner(s): Thomas, Jaison P
• Application Number:
  US15/135,898
• Publication Number:
  US 20160315380A1
• Time in Patent Office: 788 Days
• CPC Class Codes: D06M 11/45 Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
• CPC Class Codes: D06M 11/46 Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
• CPC Class Codes: D06M 11/73 with carbon or compounds thereof D06M11/67 takes precedence
• CPC Class Codes: D06M 11/79 with silicon dioxide, silicic acids or their salts
• CPC Class Codes: D06M 15/19 with synthetic macromolecular compounds with synthetic rubber D06M15/693
• CPC Class Codes: D06M 23/08 Processes in which the treating agent is applied in powder or granular form adhesives for multi-layer textile fabrics D06M17/00
• CPC Class Codes: D06N 2209/041 Conductive
• CPC Class Codes: D06N 7/00 Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material paper-based or board-based structures for surface covering D21H27/20
• CPC Class Codes: H01B 1/127 comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• CPC Class Codes: H01Q 1/273 Adaptation for carrying or wearing by persons or animals
• CPC Class Codes: H01Q 1/368 using carbon or carbon composite
• CPC Class Codes: H01Q 1/38 formed by a conductive layer on an insulating support patch antennas H01Q9/0407; microstrip dipole antennas H01Q9/065; microstrip slot antennas H01Q13/106; transmission line microstrip antennas H01Q13/206; manufacturing reflecting surfaces using insulating material for supporting the reflecting surface H01Q15/142

Abstract

Disclosed are stretchable electrically conductive structure comprising a stretchable insulating substrate comprising nucleophile derivatized nanoparticles located at the surface of the stretchable insulating substrate, wherein the stretchable insulating substrate is a fiber or fabric; and a conducting polymer: template polymer coating disposed on at least a portion of a surface of the stretchable insulating substrate through which a chemical bond forms between at least one anion of the template polymer and nucleophile derivatized nanoparticles located at the surface of the stretchable insulating substrate.

Claims

1. A stretchable electrically conductive structure, comprising

a stretchable insulating substrate comprising nucleophile derivatized nanoparticles located at the surface of the stretchable insulating substrate, wherein the stretchable insulating substrate is a fiber or fabric;

and

a conducting polymer;

template polymer coating disposed on at least a portion of a surface of the stretchable insulating substrate through which a chemical bond forms between at least one anion of the template polymer and nucleophile derivatized nanoparticles located at the surface of the stretchable insulating substrate;

optionally wherein the stretchable electrically conductive structure comprises a conductive organic particle disposed between the stretchable insulating substrate and the conducting polymer;

template polymer coating.

2. The stretchable electrically conductive structure of claim 1, wherein the stretchable insulating substrate is a woven fabric.

3. The stretchable electrically conductive structure of claim 1, wherein the stretchable insulating substrate is a polyester-polyurethane copolymer and optionally further comprises polyacrylic, polyamide, polycarbonate, polyether, polyester, polyethylene, polyimide, polyurethane, polyurea, polythiourea, polysiloxane, polyisoprene, polybutadiene, polyethylene oxide, polylactic acid, blends thereof or copolymers thereof.

4. The stretchable electrically conductive structure of claim 1, wherein the nucleophile derivatized nanoparticles is silicon dioxide (SiO₂), titanium dioxide (TiO₂), aluminum oxide, calcium oxide, amine functionalized nanoparticles, or a combination thereof.

5. The stretchable electrically conductive structure of claim 1, wherein the nanoparticles have a particle size of about 1 nanometer (nm) to about 1000 nm.

6. The stretchable electrically conductive structure of claim 1, wherein the nanoparticles are present on the surface of the stretchable insulating substrate in an amount of 0.05 to about 5% area relative to the total surface area of the stretchable insulating substrate.

7. The stretchable electrically conductive structure of claim 1, wherein the nanoparticles are present in the stretchable insulating substrate in an amount of about 0.05 to about 5 wt % based on the total weight of the stretchable insulating substrate.

8. The stretchable electrically conductive structure of claim 1, wherein the stretchable insulating substrate has a thickness of about 100 nm to about 5 mm.

9. The stretchable electrically conductive structure of claim 1, wherein the conducting polymer of the conducting polymer:

template polymer comprises units of a conducting monomer wherein the conducting monomer is thiophene, substituted thiophene, 3,4-ethylenedioxythiophene, thieno[3,4-b]thiophene, substituted thieno[3,4-b]thiophene, dithieno[3,4-b;

3′

,4′

-d]thiophene, thieno[3,4-b]furan, substituted thieno[3,4-b]furan, bithiophene, substituted bithiophene, pyrrole, substituted pyrrole, phenylene, substituted phenylene, naphthalene, substituted naphthalene, biphenyl and terphenyl and their substituted versions, phenylene vinylene, substituted phenylene vinylene, aniline, substituted aniline, a monomer of any one of structures (I)-(XXIX);

10. The stretchable electrically conductive structure of claim 1, wherein the template polymer comprises sulfonic acid groups, phosphoric acid groups, or a combination thereof.

11. The stretchable electrically conductive structure of claim 1, wherein the conducting polymer:

template polymer coating is a film or a pattern on the surface of the stretchable insulating substrate.

12. The stretchable electrically conductive structure of claim 1, wherein the conducting polymer:

template polymer coating has a thickness of about 40 nm to about 1 micrometer.

13. The stretchable electrically conductive structure of claim 1, wherein the conductive organic particle is graphene, graphite, a combination of graphene and graphite, carbon nanotubes, buckyballs, “

n-type”

small molecules, or a combination thereof.

14. The stretchable electrically conductive structure of claim 1, wherein the conductive organic particle is present in an amount of about 0.2 to about 20 wt % based on the total weight of the stretchable electrically conductive structure.

15. The stretchable electrically conductive structure of claim 1, having one or more of the following:

sheet resistance of about 1 to about 50 ohm/□

; and

conductivity greater than 5000 S/cm; and

exhibit an increase in resistance as a function of temperature at a temperature above 270K; and

substantially retains its original electrical conductive properties after undergoing a washing treatment, which may include laundry detergent; and

a hydrophobic treatment.

16. The stretchable electrically conductive structure of claim 1, wherein the conducting polymer:

template polymer is PEDOT;

PSS.

17. An article comprising the stretchable electrically conductive structure of claim 1.

18. The article of claim 17, is a flexible, all organic antennae.

19. A method of making a stretchable electrically conductive structure, comprising

providing a stretchable insulating substrate comprising nucleophile derivatized nanoparticles located at the surface of the stretchable insulating substrate, wherein the stretchable insulating substrate is a fiber or fabric;

forming a conducting polymer;

template polymer coating on at least a portion of a surface of the stretchable insulating substrate to form a stretchable electrically conductive structure,

optionally further wherein the stretchable insulating substrate is plasma treated before the forming the conducting polymer;

template polymer coating.

20. The method of claim 19, wherein the conducting polymer:

template polymer coating is formed using a casting process, tape casting, flow coating, spray coating, spin coating, ink jetting, dip coating, or a combination thereof.

21. The method of claim 19, further comprising, disposing a conductive organic particle on at least a portion of a surface of the stretchable insulating substrate.