Methods for producing precursor solutions and sol-gels for nano-engineered carbon materials and nano-engineered carbon materials created therefrom

Patent metadata

Field	Value
Publication number	US-10399055-B2
Application number	US-201815959433-A
Country	US
Kind code	B2
Filing date	Apr 23, 2018
Priority date	Jun 9, 2010
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

Methods of manufacturing nano-engineered carbon materials, such as carbon aerogels and carbon xerogels, and methods of manufacturing precursor solutions and sol-gels for making the same are provided. A method for manufacturing a precursor solution comprises programmed-addition of a cross-linking agent to a component mixture comprising a resorcinol compound. A method for manufacturing a sol-gel comprises subjecting a precursor solutions to at least one heat treatment. Methods for producing nano-engineered carbon materials from precursor solutions and sol-gels are also provided. Methods for using the nano-engineered carbon materials are also disclosed. The resulting nano-engineered carbon materials can be useful in a range of products including, supercapacitor applications, high-surface-area electrodes, fuel cells, and desalination systems.

First claim

What is claimed is:

1. A process for making a precursor solution, comprising:
adding a cross-linking agent to a first mixture comprising water and a resorcinol compound to produce a second mixture comprising the cross-linking agent, water, and resorcinol compound;
reacting the resorcinol compound and the cross-linking agent in the presence of the water to produce the precursor solution, wherein the resorcinol compound and the cross-linking agent are reacted at a reaction temperature of 30° C. to 99° C.

2. The process of claim 1 , wherein the reaction temperature of the resorcinol compound and the cross-linking agent is 40° C. to 99° C.

3. The process of claim 2 , further comprising:
cooling the precursor solution to a temperature of less than 40° C. to produce a cooled precursor solution; and
heating the cooled precursor solution to a temperature of 60° C. to 99° C. for 12 hours to 96 hours to produce a sol-gel.

4. The process of claim 1 , wherein the reaction temperature of the resorcinol compound and the cross-linking agent is 45° C. to 55° C.

5. The process of claim 1 , wherein the second mixture has a molar ratio of the resorcinol compound to the cross-linking agent of 1:1 to 1:2.

6. The process of claim 1 , wherein the resorcinol compound is represented by formula (I):

wherein each R a , R b , R c , and R d is independently selected from the group consisting of: hydrogen; hydroxy; a halide; nitro; benzo; carboxy; acyl; alkyl; alkenyl; unsubstituted or substituted methacrylate; unsubstituted or substituted acrylate; silyl ether; siloxanyl; aryl; aralkyl; and alkaryl; and
wherein at least two of R a , R c , and R d are hydrogen.

7. The process of claim 1 , wherein the cross-linking agent comprises formaldehyde, paraformaldehyde, a trioxane, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, cinnamaldehyde, benzaldehyde, furfural, acetone, methyl ethyl ketone, or a mixture thereof.

8. The process of claim 1 , wherein the first mixture further comprises a catalyst.

9. The process of claim 8 , wherein the catalyst comprises, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, a sulfonic acid, acetic acid having a chemical formula of CH 3 CO 2 H, or a mixture thereof.

10. The process of claim 1 , wherein the first mixture, the second mixture, or both the first mixture and the second mixture further comprise methanol, diethylene glycol, 1,2-propane diol, 1,4-butane diol, 1,5-hexane diol, or a mixture thereof.

11. The process of claim 1 , wherein the reaction temperature of the resorcinol compound and the cross-linking agent is 40° C. to 99° C., the method further comprising:
cooling the precursor solution to a temperature of less than 40° C. to produce a cooled precursor solution;
sealing the cooled precursor solution in a container; and
heating the cooled precursor solution in the sealed container to a temperature of 60° C. to 99° C. for 12 hours to 96 hours to produce a sol-gel.

12. A process for making a precursor solution, comprising:
heating a first mixture comprising water and a resorcinol compound to a temperature of 30° C. to 99° C. to produce a heated mixture comprising the water and the resorcinol compound;
adding a cross-linking agent to the heated mixture to produce a second mixture comprising the water, the resorcinol compound, and the cross-linking agent;
reacting the resorcinol compound and the cross-linking agent in the presence of the water to produce a precursor solution, wherein the resorcinol compound and the cross-linking agent are reacted at a reaction temperature of 30° C. to 99° C.

13. The process of claim 12 , wherein the reaction temperature of the resorcinol compound and the cross-linking agent is 40° C. to 80° C.

14. The process of claim 12 , wherein the cross-linking agent is added to the heated mixture as a continuous feed.

15. The process of claim 12 , wherein the cross-linking agent is added to the heated mixture as a plurality of batches.

16. The process of claim 12 , wherein:
the reaction temperature of the resorcinol compound and the cross-linking agent is 40° C. to 99° C.,
the resorcinol compound comprises benzene-1,3-diol, phenol, or a mixture thereof, and
the cross-linking agent comprises formaldehyde.

17. The process of claim 16 , wherein the second mixture has a molar ratio of the resorcinol compound to the cross-linking agent of 1:1 to 1:2.

18. The process of claim 17 , further comprising
cooling the precursor solution to a temperature of less than 40° C. to produce a cooled precursor solution; and
heating the precursor solution to a temperature of 60° C. to 99° C. for 12 hours to 96 hours to produce a sol-gel.

19. The process of claim 18 , wherein the sol-gel is a microporous sol-gel or a mesoporous sol-gel.

20. A process for making a carbon aerogel or a carbon xerogel, comprising:
heating a first mixture comprising water and a resorcinol compound to a temperature of 30° C. to 99° C. to produce a heated mixture, wherein the resorcinol compound comprises benzene-1,3-diol, phenol, or a mixture thereof;
adding formaldehyde to the heated mixture to produce a second mixture comprising the water, the resorcinol compound, and the formaldehyde, wherein the second mixture is maintained at a temperature of 30° C. to 99° C.;
reacting the resorcinol compound and the formaldehyde in the presence of the water to produce a precursor solution, wherein the resorcinol compound and the formaldehyde are reacted at a temperature of 40° C. to 99° C.;
cooling the precursor solution to a temperature of less than 40° C. to produce a cooled precursor solution;
heating the cooled precursor solution to a temperature of 60° C. to 99° C. for 12 hours to 96 hours to produce a sol-gel; and
subjecting the sol-gel to an additional treatment to produce a carbon aerogel or a carbon xerogel, wherein the additional treatment comprises grinding, freeze drying, cryogenic drying, supercritical drying, vacuum drying, evaporation drying, pyrolysis, or any combination thereof.

Assignees

• Georgia Pacific Chemicals Llc

Inventors

• Mulik Sudhir M
• Ludvik Joseph F
• Fleming Robert W
• Lee Christopher M

Classifications

• C01B32/00

  Carbon; Compounds thereof (C01B21/00, C01B23/00 take precedence; percarbonates C01B15/10; carbon black C09C1/48) · CPC title

• B01J13/0091 Primary

  Preparation of aerogels, e.g. xerogels · CPC title

• C01B32/05

  Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30 · CPC title