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-9968900-B2
Application number	US-201514679400-A
Country	US
Kind code	B2
Filing date	Apr 6, 2015
Priority date	Jun 9, 2010
Publication date	May 15, 2018
Grant date	May 15, 2018

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 method for producing a precursor solution, comprising:
adding a cross-linking agent to a first mixture comprising water, a resorcinol compound, and a catalyst to produce a second mixture;
reacting the resorcinol compound and the cross-linking agent to produce a precursor solution; and
maintaining a reaction temperature of the resorcinol compound and the cross-linking agent at 40° C. to 99° C.

2. The method of claim 1 , wherein the reaction temperature is 40° C. to 80° C.

3. The method of claim 1 , wherein the reaction temperature is 45° C. to 55° C.

4. The method of claim 1 , wherein the resorcinol compound and the cross-linking agent are reacted at a molar ratio of 1:1.5 to 1:2.5.

5. The method of claim 1 , wherein the precursor solution has a refractive index of 1.4000 to 1.4300.

6. The method 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 method 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 any mixture thereof.

8. The method of claim 1 , wherein the catalyst comprises acetic acid having a chemical formula of CH 3 CO 2 H, hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, a sulfonic acid, or any mixture thereof.

9. The method of claim 1 , wherein the reaction temperature is 40° C. to 80° C.; the resorcinol compound comprises benzene-1,3-diol, phenol, or a mixture thereof; the cross-linking agent comprises formaldehyde; and the catalyst comprises acetic acid having a chemical formula of CH 3 CO 2 H.

10. The method of claim 1 , wherein the first mixture, the second mixture, or both the first mixture and the second mixture further comprise an alcohol that comprises methanol, diethylene glycol, 1,2-propane diol, 1,4-butane diol, 1,5-hexane diol, or any mixture thereof.

11. The method of claim 1 , 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.

12. The method of claim 1 , 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 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.

13. A method for producing a precursor solution, comprising:
heating a first mixture comprising water, a resorcinol compound, and an acidic catalyst to a temperature of about 30° C. to 99° C. to produce a heated mixture;
adding a cross-linking agent to the heated mixture to produce a second mixture;
reacting the resorcinol compound and the cross-linking agent in the second mixture to produce a precursor solution;
maintaining a reaction temperature of the resorcinol compound and the cross-linking agent at 40° C. to 99° C.;
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.

14. The method of claim 13 , wherein the reaction temperature is 40° C. to 80° C.

15. The method of claim 13 , wherein the cross-linking agent is added to the heated mixture as a continuous feed.

16. The method of claim 13 , wherein the cross-linking agent is added to the heated mixture as a plurality of batches.

17. The method of claim 13 , wherein the reaction temperature is 40° C. to 80° C.; the resorcinol compound comprises benzene-1,3-diol, phenol, or a mixture thereof; the cross-linking agent comprises formaldehyde; the acidic catalyst comprises acetic acid having a chemical formula of CH 3 CO 2 H; and the precursor solution has a refractive index of 1.4000 to 1.4300.

18. The method of claim 13 , wherein the reaction temperature does not exceed 80° C.

19. The method of claim 13 , wherein the sol-gel is a microporous sol-gel or a mesoporous sol-gel.

20. A method for producing a carbon aerogel or a carbon xerogel, comprising:
heating a first mixture comprising water, a resorcinol compound, and an acidic catalyst to a temperature of about 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;
maintaining the second mixture at a temperature of 40° C. to 99° C.;
reacting the resorcinol compound and the formaldehyde to produce a precursor solution;
maintaining a reaction temperature of the resorcinol compound and the formaldehyde at 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 one or more additional treatments to produce a carbon aerogel or a carbon xerogel, wherein the one or more additional treatments comprise grinding, freeze drying, cryogenic drying, supercritical drying, vacuum drying, evaporation drying, pyrolysis, or any combination thereof.

21. The method of claim 1 , wherein the catalyst comprises an acidic catalyst.

22. The method of claim 1 , the resorcinol compound and the cross-linking agent are reacted at a molar ratio of about 1:1 to about 1:2.

23. The method of claim 1 , wherein the cross-linking agent is added to the first mixture at a controlled rate to prevent a maximum temperature rate increase resulting from the reaction of the resorcinol compound and the cross-linking agent from exceeding 10° C. per minute.

Assignees

• Georgia Pacific Chemicals Llc

Inventors

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

Classifications

• 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

• C01B32/00

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