Self-organized and electrically conducting PEDOT polymer matrix for applications in sensors and energy generation and storage

Patent metadata

Field	Value
Publication number	US-11111586-B2
Application number	US-201715439585-A
Country	US
Kind code	B2
Filing date	Feb 22, 2017
Priority date	Feb 23, 2016
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

The present invention relates to a one-step process for preparation of “in-situ” or “ex-situ” self-organized and electrically conducting polymer nanocomposites using thermally initiated polymerization of a halogenated 3,4-ethylenedioxythiophene monomer or its derivatives. This approach does not require additional polymerization initiators or catalysts, produce gaseous products that are naturally removed without affecting the polymer matrix, and do not leave by-product contaminants. It is demonstrated that self-polymerization of halogenated 3,4-ethylenedioxythiophene monomer is not affected by the presence of a solid-state phase in the form of nanoparticles and results in formation of 3,4-polyethylenedioxythiophene (PEDOT) nanocomposites.

First claim

What is claimed is:

1. An electrochemical polymerization method, consisting of:
forming, in one step, an electrically conducting nanocomposite from a halogenated 3,4-ethylenedioxythiophene (EDOT) and electrically conductive nanoparticles by processing the nanocomposite by “in-situ” self-polymerization; and wherein PEDOT polymer nanocomposites are produced by the “in-situ” self-polymerization of the halogenated EDOT comprising no catalysts or initiators.

2. An electrochemical polymerization method, comprising:
forming a polymer nanocomposite film by suspending silicon solid-state nanoparticles in a brominated halogenated 3,4-ethylenedioxythiophene (EDOT) or EDOT derivatives monomer organic mixture which is homogeneously dispersed around the surface of the nanoparticles forming an electrically conducting polymer matrix, wherein the 3,4-ethylenedioxythiophene comprises 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) resulting in a conjugated poly(3,4-ethlenedioxythiophene) PEDOT;
forming polymer PEDOT chains in the self-polymerization process around the nanoparticles;
heating the brominated halogenated 3,4-ethylenedioxythiophene in the presence the silicon solid-state nanoparticles to a temperature between 70-80 degrees Celsius for a period of time ranging from 12-48 hours; and
linking each particle in a continuous conducting and binding polymer network to an adjacent particle resulting in high percolation;
wherein the PEDOT polymer is doped with an LiPF 6 electrolyte and comprises a weight ratio of 50 wt. %-50 wt. % for the brominated halogenated 3,4-ethylenedioxythiophene (EDOT) and the silicon solid-state nanoparticles.

3. The method of claim 2 , wherein the PEDOT polymer nanocomposites operate up to at least 4.5 V.

4. The method of claim 3 , wherein the PEDOT polymer nanocomposites can be used in high-voltage cathodes.

5. An electrochemical polymerization method, comprising:
preparing a monomer solution by dissolving 0.1 grams of halogenated 3,4-ethylenedioxythiophene in acetonitrile, stirring the monomer solution for about two hours and sonicating the initial monomer solution for about 15 minutes;
adding 0.1 grams of SiNPs to the monomer solution, stirring the monomer solution for about two hours and sonicating the initial monomer solution for about 15 minutes for preparing an SiNPs-DBEDOT slurry;
depositing the SiNPs-DBEDOT slurry onto an anode substrate, drying the an SiNPs-DBEDOT slurry on the anode substrate overnight, and heating the an SiNPs-DBEDOT slurry at 80 degrees Celsius for 48 hours in vacuum;
wherein the electrochemical polymerization method is an “in-situ” one-step polymerization consisting of no catalysts or initiators.

6. The method of claim 5 , further comprising:
forming a conducting polymer PEDOT or PEDOT derivatives from the halogenated monomer precursor to produce a conducting and self-polymerized 3D nanocomposite matrix.

7. The method of claim 6 , wherein the conducting polymer or PEDOT derivatives are formed from 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) or DBEDOT derivative to produce the conducting and self-polymerized 3D nanocomposite matrix.

8. The method of claim 6 , further comprising:
producing PEDOT nanocomposites matrix from the halogenated monomer precursor by “in-situ” self-polymerization of DBEDOT or DBEDOT derivatives in a one-step polymerization process.

9. The method of claim 6 , wherein the conducting polymer PEDOT or PEDOT derivatives formed from the DBEDOT or DBEDOT derivatives is mixed with an organic solvent of acetonitrile and a solid-state phase in the form of nanoparticles.

10. The method of claim 5 , wherein the halogenated monomer EDOT forms a homogeneous solution with an organic solvent of acetonitrile in presence of a solid-state phase introduced to the solution in the form of solid-state nanoparticles.

11. The method of claim 5 , wherein an organic solvent of acetonitrile in the presence of the halogenated monomer EDOT mixed with solid-state nanoparticles evaporates during the self-organized polymerization process resulting in formation of a solid-state nanocomposite.

12. The method of claim 7 , further comprising:
removing gaseous products from the forming conducting polymer thereby naturally forming the solid-state nanocomposite.

13. The method of claim 6 , further comprising:
processing the PEDOT polymer nanocomposites without cleaning or separation processes.

14. The method of claim 5 , wherein a time period for self-polymerization of the nanocomposite ranges based on a weight percent of the solid-state phase and film thickness.

15. The method of claim 5 , further comprising:
encapsulating one or more nanostructures with a monomer precursor during self-polymerization.

16. The method of claim 15 , wherein the nanostructures comprise nanoparticles, nanotubes, or nanorods.

17. The method of claim 5 ; wherein electrical stability of the self-polymerizing nanocomposites has a voltage range from 0.05 to 4.5 V.

Assignees

• South Dakota Board Of Regents

Inventors

• Smirnova Alevtina
• Mcgraw Michael
• Kolla Praveen

Classifications

• C25B11/055 Primary

  characterised by the substrate or carrier material · CPC title

• Y02E10/549

  Organic PV cells · CPC title

• C08G61/126

  with a five-membered ring containing one sulfur atom in the ring · CPC title

• C08G2261/512

  Hole transport · CPC title

• H01G11/86

  specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34) · CPC title