Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same

Patent metadata

Field	Value
Publication number	US-12173165-B2
Application number	US-202318297478-A
Country	US
Kind code	B2
Filing date	Apr 7, 2023
Priority date	Mar 14, 2014
Publication date	Dec 24, 2024
Grant date	Dec 24, 2024

Abstract

The present application is directed to methods for solvent-free preparation of polymers and their subsequent processing into activated carbon materials. These methods unexpectedly demonstrate ability to tune pore structure in the polymer gel and carbon produced there from, while also providing distinct advantages over the current art.

First claim

The invention claimed is:

1. A method for preparing a polymer, the method comprising physical blending of a solvent-free mixture of solid particles comprising solid polymer precursors by one of ball milling, jet milling, Fritsch milling or planetary milling, and aging the solvent-free mixture at a temperature and for a time sufficient for the one or more polymer precursors to react with each other and form a polymer gel, and wherein the solvent-free mixture comprises less than 1% solvent by weight.

2. The method of claim 1 , wherein the solvent-free mixture comprises less than 0.1% solvent by weight.

3. The method of claim 1 , wherein the temperature is at or above the glass transition temperature of one or more species of polymer precursor particles.

4. The method of claim 1 , wherein the temperature is at or above the melting temperature of one or more species of polymer precursor particles.

5. The method of claim 1 , wherein the temperature is at or above 30 C below the melting temperature of one or more species of polymer precursor particles.

6. The method of claim 1 , wherein the polymer precursors are selected from an amine-containing compound, an alcohol-containing compound and a carbonyl-containing compound.

7. The method of claim 1 , wherein the polymer precursors are selected from an alcohol, a phenol compound, a polyalcohol, a sugar, an alkyl amine, an aromatic amine, an aldehyde, a ketone, a carboxylic acid, an ester, melamine, a urea, an acid halide and an isocyanate.

8. The method of claim 7 , wherein the phenolic compound is phenol, resorcinol, naphthol, bisphenol A, or any combination thereof.

9. The method of claim 7 , wherein the sugar is fructose, sucrose, glucose, or any combination thereof.

10. The method of claim 7 , wherein the carboxylic acid is acetic acid, formic acid, oxalic acid, lactic acid, citric acid, cyanuric acid, or any combination thereof.

11. The method of claim 1 , wherein the polymer precursors further comprise hexamethylenetetramine.

12. The method of claim 11 , wherein the polymer precursors comprise hexamethylenetetramine and bisphenol A present at a mole ratio between 0.05:1 to 5:1.

13. The method of claim 1 , further comprising pyrolyzing the solvent free polymer gel particles in an inert atmosphere at temperatures ranging from 500° C. to 2400° C. to obtain pyrolyzed porous carbon.

14. The method of claim 13 , further comprising activating the porous carbon to obtain activated porous carbon by a method comprising contacting the pyrolyzed polymer gel particles with an atmosphere comprising carbon dioxide, carbon monoxide, steam, oxygen or combinations thereof at a temperature may ranging from 800° C. to 1300° C.

15. A carbon having a maximum theoretical capacitance of greater than 26 F/cm 3 ,
wherein:
the carbon is formed from a mixture comprising hexamethylenetetramine and bisphenol A, such that a mole ratio of the hexamethylenetetramine to the bisphenol A ranges from 1.63:1 to 5:1;
a pore structure of the carbon comprises at least 97.8% micropores;
nitrogen content of the carbon is 1-8%;
BET surface area of carbon ranges from about 1,500 m 2 /g to about 2,000 m 2 /g; and
the capacitance is measured at a current density of 0.5 Amp/g employing an electrolyte comprising tetraethylammonium tetrafluoroborate in acetonitrile.

16. The carbon of claim 15 , wherein the maximum theoretical capacitance of greater than 27 F/cm 3 .

17. The carbon of claim 15 , wherein the maximum theoretical capacitance of greater than 28 F/cm 3 .

18. The carbon of claim 15 , wherein the maximum theoretical capacitance of greater than 29 F/cm 3 .

19. An electrode comprising a carbon material according to claim 15 .

Assignees

• Group14 Technologies Inc

Inventors

• Costantino Henry R
• Chang Alan Tzu-Yang
• Kron Benjamin E
• Sakshaug Avery J
• Thompkins Leah A
• Feaver Aaron M

Classifications

• C08L2201/54

  Aqueous solutions or dispersions · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• C08L77/12

  Polyester-amides · CPC title

• C08G73/065

  Preparatory processes · CPC title

• C08G73/0638

  with at least three nitrogen atoms in the ring · CPC title