# US 11,111,586 B2 · Self-organized and electrically conducting PEDOT polymer matrix for applications in sensors and energy generation and storage

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- Number: US 11,111,586 B2
- Document ID: US11111586B2
- Status: Granted
- Kind: B2
- Application number: 15/439,585
- Filed: 2017-02-22
- Published: 2017-08-24
- Granted: 2021-09-07
- Earliest claimed: 2016-02-23
- Assignees: South Dakota Board of Regents
- Applicants: South Dakota Board of Regents
- Inventors: Alevtina Smirnova; Michael McGraw; Praveen Kolla
- Web page: https://patentgrep.com/patent/US11111586B2

## CPC

- C25B 3/00: Electrolytic production of organic compounds
- C08G 61/121: {derived from organic halides}
- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- C25B 11/055: characterised by the substrate or carrier material
- H01G 9/028: Organic semiconducting electrolytes, e.g. TCNQ
- H01G 11/48: Conductive polymers
- H01G 11/86: specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34)
- H01M 4/608: {containing heterocyclic rings}
- H01M 4/9008: {Organic or organo-metallic compounds}
- H10K 85/1135: {Polyethylene dioxythiophene [PEDOT]; Derivatives thereof}
- C08G 2261/1424: containing ether groups, including alkoxy
- C08G 2261/228: Polymers, i.e. more than 10 repeat units
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/40: Polymerisation processes
- C08G 2261/512: Hole transport
- C08G 2261/91: Photovoltaic applications
- C08L 65/00: Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers
- H10K 71/60: Forming conductive regions or layers, e.g. electrodes
- H10K 2102/00: Constructional details relating to the organic devices covered by this subclass
- Y02E 10/549: Organic PV cells
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## 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.

## Claims

### Claim 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.

### Claim 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 LiPF6 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.

### Claim 3 (depends on 2)

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

### Claim 4 (depends on 3)

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

### Claim 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.

### Claim 6 (depends on 5)

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.

### Claim 7 (depends on 6)

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.

### Claim 8 (depends on 6)

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.

### Claim 9 (depends on 6)

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.

### Claim 10 (depends on 5)

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.

### Claim 11 (depends on 5)

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.

### Claim 12 (depends on 7)

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

### Claim 13 (depends on 6)

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

### Claim 14 (depends on 5)

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.

### Claim 15 (depends on 5)

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

### Claim 16 (depends on 15)

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

### Claim 17 (depends on 5)

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