Flexible and conductive waste tire-derived carbon/polymer composite paper as pseudocapacitive electrode

Patent metadata

Field	Value
Publication number	US-9941058-B2
Application number	US-201514852073-A
Country	US
Kind code	B2
Filing date	Sep 11, 2015
Priority date	May 26, 2015
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

A method of making a supercapacitor from waste tires, includes the steps of providing rubber pieces and contacting the rubber pieces with a sulfonation bath to produce sulfonated rubber; pyrolyzing the sulfonated rubber to produce a tire-derived carbon composite comprising carbon black embedded in rubber-derived carbon matrix comprising graphitized interface portions; activating the tire-derived carbon composite by contacting the tire-derived carbon composite with a specific surface area-increasing composition to increase the specific surface area of the carbon composite to provide an activated tire-derived carbon composite; and, mixing the activated tire-derived carbon composite with a monomer and polymerizing the monomer to produce a redox-active polymer coated, activated tire-derived carbon composite. The redox-active polymer coated, activated tire-derived carbon composite can be formed into a film. An electrode and a supercapacitor are also disclosed.

First claim

We claim:

1. A method of making a supercapacitor from waste tires, comprising the steps of:
providing rubber pieces;
contacting the rubber pieces with a sulfonation bath to produce sulfonated rubber;
pyrolyzing the sulfonated rubber to produce tire-derived carbon composite comprising carbon black embedded in sulfonated rubber-based carbon matrix with graphitized interface portions, wherein the pyrolizing comprises heating to at least 200° C.-2400° C., and comprises at least two stage heating at heating rates between 1 and 20° C./min;
activating the tire-derived carbon composite by contacting the tire-derived carbon composite with a specific surface area-increasing composition to increase the specific surface area of the carbon composite to provide activated tire-derived carbon composite;
mixing the activated tire-derived carbon composite with a monomer and polymerizing the monomer to produce a redox-active polymer coated, activated tire-derived carbon composite; and,
forming the redox-active polymer coated, activated tire-derived carbon composite into a film.

2. The method of claim 1 , further comprising the step of forming the redox-active polymer coated, activated tire-derived carbon film into an electrode.

3. The method of claim 2 , further comprising the step of forming a supercapacitor comprising the electrode.

4. The method of claim 3 , wherein the supercapacitor is a pseudocapacitor.

5. The method of claim 1 , wherein the graphitized interface portions comprise 10%-40% of the tire-derived carbon composite, by weight.

6. The method of claim 1 , wherein the temperature of the sulfonation bath is between −20° C. to 200° C.

7. The method of claim 1 , wherein the rubber pieces are contacted with the sulfonation bath for between 30 minutes and 5 days.

8. The method of claim 1 , wherein a first stage heating comprises heating to between room temperature and 400° C. at 1° C./min, and a second stage heating comprises heating to between 400 and 2400° C. at 2° C./min.

9. The method of claim 1 , wherein the pyrolizing time is between 1 min and 24 hours.

10. The method of claim 1 , wherein the activating step comprises contacting the tire-derived carbon with at least one selected from the group consisting of KOH, CO2 or ZnCl2.

11. The method of claim 10 , wherein KOH is mixed with the tire-derived carbon at a weight ratio of between 1:2 and 1:10.

12. The method of claim 1 , wherein the pore size after the activating step includes micropores of less than 2 nm, and mesopores of 2-10 nm.

13. The method of claim 12 , wherein the mesopores are 3-5 nm.

14. The method of claim 12 , wherein the pores are between 70%-90% micropores and between 10%-30% mesopores.

15. The method of claim 1 , wherein the specific surface area after the activating step is between 1000-2000 m 2 /g.

16. The method of claim 1 , wherein the rubber pieces are between 100 nm and 2 inches.

17. The method of claim 1 , wherein the rubber pieces comprise rubber particles of between 100 nm and 0.5 mm and rubber crumbs of between 0.5 mm to 2 inches.

18. The method of claim 1 , wherein the pyrolizing is conducted in an inert atmosphere.

19. The method of claim 1 , wherein graphitized portion comprises a layer spacing of between 3.5-4.7 angstroms.

20. The method of claim 1 , wherein the redox-active polymer comprises at least one selected from the group consisting of polyaniline, polypyrrole, and polythiophene.

21. The method of claim 1 , wherein the electrode has capacitance retention of over 95% after 10,000 cycles.

22. The method of claim 1 , wherein the polymer comprises 50%-90% of the redox-active polymer coated, activated tire-derived carbon composite, by weight.

23. The method of claim 1 , wherein the conductivity of the films is between 50-200 S/m.

24. The method of claim 1 , wherein the films can be bent to 180°.

25. The method of claim 1 , wherein the tire-derived carbon is mixed with monomer and oxidant at a ratio of (x) Monomer:(y) Oxidant:(z) tire-carbon where x=20-40%, y=20-40%, and z=30-50%.

26. A method of making a supercapacitor from waste tires, comprising the steps of:
providing rubber pieces;
contacting the rubber pieces with a sulfonation bath to produce sulfonated rubber;
pyrolyzing the sulfonated rubber to produce tire-derived carbon composite comprising carbon black embedded in sulfonated rubber-based carbon matrix with graphitized interface portions;
activating the tire-derived carbon composite by contacting the tire-derived carbon composite with a specific surface area-increasing composition to increase the specific surface area of the carbon composite to provide activated tire-derived carbon composite;
mixing the activated tire-derived carbon composite with a monomer and polymerizing the monomer to produce a redox-active polymer coated, activated tire-derived carbon composite; and,
forming the redox-active polymer coated, activated tire-derived carbon composite into a film;

wherein the tire-derived carbon is mixed with monomer and oxidant at a ratio of (x) Monomer:(y) Oxidant:(z) tire-carbon where x=20-40%, y=20-40%, and z=30-50%.

27. The method of claim 26 , wherein the oxidant is at least one selected from the group consisting of ammonium persulfate, iron chloride, and potassium dichromate.

28. The method of claim 26 , further comprising the step of forming the redox-active polymer coated, activated tire-derived carbon film into an electrode.

29. The method of claim 28 , wherein the electrode has capacitance retention of over 95% after 10,000 cycles.

30. The method of claim 28 , wherein the electrode has a capacitance of over 450 F/g at a scan rate of 1 mV/s, of over 200 F/g at a scan rate of 10 mV/s, and over 150 F/g at a scan rate of 100 mV/s.

31. The method of claim 26 , wherein the graphitized interface portions comprise 10%-40% of the tire-derived carbon composite, by weight.

32. The method of claim 26 , wherein the pyrolizing comprises at least two stage heating at heating rates between 1 and 20° C./min.

33. The method of claim 26 , wherein the pore size after the activating step includes micropores of less than 2 nm, and mesopores of 2-10 nm.

34. The method of claim 33 , wherein the pores are between 70%-90% micropores and between 10%-30% mesopores.

35. The method of claim 26 , wherein the redox-active polymer comprises at least one selected from the group consisting of polyaniline, polypyrrole, and polythiophene.

36. The method of claim 26 , wherein the conductivity of the films is between 50-200 S/m.

37. A method of making a supercapacitor from waste tires, comprising the steps of:
providing rubber pieces;
contacting the rubber pieces with a sulfonation bath to produce sulfonated rubber;
pyrolyzing the sulfonated rubber to produce tire-derived carbon composite comprising carbon black embedded in sulfonated rubber-based carbon matrix with graphitized interface portions;
activating the tire-derived carbon composite by contacting the tire-derived carbon composite with a specific surface area-increasing composition to increase the specific surface area of the carbon composite to provide activated tire-derived carbon composite;
mixing the activated tire-derived carbon c

Assignees

• Ut Battelle Llc
• Univ Drexel

Inventors

• Naskar Amit K
• Paranthaman Mariappan Parans
• Boota Muhammad
• Gogotsi Yury

Classifications

• Y02E60/13

  Energy storage using capacitors · CPC title

• H01G11/34 Primary

  characterised by carbonisation or activation of carbon · CPC title

• H01G11/38

  Carbon pastes or blends; Binders or additives therein · CPC title

• H01G11/86

  specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34) · CPC title

• H01G11/44

  Raw materials therefor, e.g. resins or coal · CPC title