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

• US 10,711,140 B2
• Filed: 01/16/2020
• Issued: 07/14/2020
• Est. Priority Date: 03/14/2014
• Status: Active Grant

• Current Assignee: Group14 Technologies Inc.
• Original Assignee: Group14 Technologies Inc.
• Inventors: Costantino, Henry R., Chang, Alan Tzu-Yang, Kron, Benjamin E., Sakshaug, Avery J., Thompkins, Leah A., Feaver, Aaron M.
• Primary Examiner(s): Dunn, Colleen P
• Application Number:
  US16/745,197
• Publication Number:
  US 20200148886A1
• Time in Patent Office: 180 Days
• Field of Search: None
• CPC Class Codes: C01B 32/05 Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
• CPC Class Codes: C01P 2002/82 by IR- or Raman-data
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/14 Pore volume
• CPC Class Codes: C01P 2006/17 Pore diameter distribution
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C08F 2/02 Polymerisation in bulk
• CPC Class Codes: C08G 14/08 Ureas; Thioureas
• CPC Class Codes: C08G 69/44 Polyester-amides
• CPC Class Codes: C08G 73/0638 with at least three nitrogen atoms in the ring
• CPC Class Codes: C08G 73/065 Preparatory processes
• CPC Class Codes: C08G 8/22 Resorcinol
• CPC Class Codes: C08L 2201/54 Aqueous solutions or dispersions
• CPC Class Codes: C08L 61/34 Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
• CPC Class Codes: C08L 77/12 Polyester-amides
• CPC Class Codes: C08L 79/04 Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C09C 1/48 Carbon black
• CPC Class Codes: 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
• CPC Class Codes: H01G 11/34 characterised by carbonisation or activation of carbon
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/06 : Lead-acid accumulators semi-lead accumulators H01M10/20
• CPC Class Codes: H01M 12/08 : composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors

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.

Claims

1. A method for preparing a carbon material, comprising:

a. preparing a mixture by physically blending polymer precursors, wherein the mixture comprises less than 10% solvent by weight, and the polymer precursors comprise monomers;

b. aging the mixture at a temperature for a time sufficient for the polymer precursors to react with each other and form a polymer; and

c. pyrolyzing the polymer in an inert atmosphere.

2. The method of claim 1, wherein the inert atmosphere comprises nitrogen gas.

3. The method of claim 1, wherein the temperature ranges from 500 to 2400°

C.

4. The method of claim 1, wherein the polymer precursors comprise hexamethylenetetramine and bisphenol A.

5. The method of claim 4, wherein the hexamethylenetetramine and bisphenol A are present at a mole ratio between 0.05:

1 and 5;

1, respectively.

6. The method of claim 1, wherein the pyrolyzing is performed in a rotary kiln, a microwave kiln, a pusher-type kiln, an elevator kiln, or a fluid bed reactor.

7. The method of claim 1, further comprising activating the pyrolyzed polymer in an atmosphere comprising carbon dioxide, carbon monoxide, steam, oxygen or combinations thereof.

8. The method of claim 7, wherein the activating is performed at a temperature ranging from 800 to 1300°

C.

9. The method of claim 7, wherein the polymer precursors comprise hexamethylenetetramine and bisphenol A.

10. The method of claim 9, wherein the hexamethylenetetramine and bisphenol A are present at a mole ratio between 0.05:

1 and 5;

1, respectively.

11. The method of claim 7, wherein the activating is performed in a rotary kiln, a microwave kiln, a pusher-type kiln, an elevator kiln, or a fluid bed reactor.

12. A method for preparing a carbon material, comprising:

a. preparing a mixture by physically blending polymer precursors, wherein the mixture comprises less than 10% solvent by weight, and the polymer precursors comprise monomers; and

b. heating the mixture at temperatures ranging from 500 to 2400°

C. in an inert atmosphere comprising nitrogen gas.

13. The method of claim 12, wherein the polymer precursors comprise hexamethylenetetramine and bisphenol A.

14. The method of claim 13, wherein the hexamethylenetetramine and bisphenol A are present at a mole ratio between 0.05:

1 and 5;

1, respectively.

15. The method of claim 12, wherein the heating is performed in a rotary kiln, a microwave kiln, a pusher-type kiln, an elevator kiln, or a fluid bed reactor.

16. A method for preparing a carbon material, comprising:

a. preparing a mixture by physically blending polymer precursors, wherein the mixture comprises less than 10% solvent by weight, and the polymer precursors comprise monomers; and

b. heating the mixture at temperatures ranging from 800 to 1300°

C. in an atmosphere comprising carbon dioxide, carbon monoxide, steam, oxygen or combinations thereof.

17. The method of claim 16, wherein the polymer precursors comprise hexamethylenetetramine and bisphenol A.

18. The method of claim 17, wherein the hexamethylenetetramine and bisphenol A are present at a mole ratio between 0.05:

1 and 5;

1, respectively.

19. The method of claim 16, wherein the heating is performed in a rotary kiln, a microwave kiln, a pusher-type kiln, an elevator kiln, or a fluid bed reactor.