ULTRAPURE SYNTHETIC CARBON MATERIALS

• US 20110002086A1
• Filed: 07/01/2010
• Published: 01/06/2011
• Est. Priority Date: 07/01/2009
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: EnerG2 Technologies, Incorporated (BASF SE)
• Inventors: Scott, William D., Feaver, Aaron M., Costantino, Henry R.
• Granted Patent: US 8,404,384 B2
• Time in Patent Office: Days
• US Class Current: 361/502
• CPC Class Codes: C01B 32/00 Carbon; Compounds thereof C01B21/00, C01B23/00 take precedence; percarbonates C01B15/10; carbon black C09C1/48
• 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: C01B 32/318 characterised by the starting materials
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/80 Compositional purity
• 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 11/32 Carbon-based
• CPC Class Codes: H01G 11/34 characterised by carbonisation or activation of carbon
• CPC Class Codes: H01G 11/48 Conductive polymers
• CPC Class Codes: H01G 9/042 characterised by the material H01G11/22 takes precedence
• 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 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/96 Carbon-based electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

The present application is generally directed to ultrapure synthetic carbon materials having both high surface area and high porosity, ultrapure polymer gels and devices containing the same. The disclosed ultrapure synthetic carbon materials find utility in any number of devices, for example, in electric double layer capacitance devices and batteries. Methods for making ultrapure synthetic carbon materials and ultrapure polymer gels are also disclosed.

Claims

1. An ultrapure synthetic carbon material comprising a total impurity content of less than 500 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

2. The carbon material of claim 1, wherein the carbon material is an ultrapure synthetic amorphous carbon material.

3. The carbon material of claim 1, wherein the carbon material comprises a total impurity content of less than 200 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

4. The carbon material of claim 1, wherein the ash content of the carbon material is less than 0.03% as calculated from proton induced x-ray emission data.

5. The carbon material of claim 1, wherein the ash content of the carbon material is less than 0.01% as calculated from proton induced x-ray emission data.

6. The carbon material of claim 1, wherein the carbon material comprises at least 95% carbon by weight as measured by combustion analysis and proton induced x-ray emission.

7. The carbon material of claim 1, wherein the carbon material comprises less than 3 ppm iron as measured by proton induced x-ray emission.

8. The carbon material of claim 1, wherein the carbon material comprises less than 1 ppm nickel as measured by proton induced x-ray emission.

9. The carbon material of claim 1, wherein the carbon material comprises less than 5 ppm sulfur as measured by proton induced x-ray emission.

10. The carbon material of claim 1, wherein the carbon material comprises less than 1 ppm chromium as measured by proton induced x-ray emission.

11. The carbon material of claim 1, wherein the carbon material comprises less than 1 ppm copper as measured by proton induced x-ray emission.

12. The carbon material of claim 1, wherein the carbon material comprises less than 100 ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, less than 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel, less than 140 ppm copper, less than 5 ppm chromium and less than 5 ppm zinc as measured by proton induced x-ray emission.

13. The carbon material of claim 1, wherein the carbon material comprises less than 50 ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, less than 10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, less than 1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc as measured by proton induced x-ray emission.

14. The carbon material of claim 1, wherein the carbon material comprises less than 3.0% oxygen, less than 0.1% nitrogen and less than 0.5% hydrogen as determined by combustion analysis.

15. The carbon material of claim 1, wherein the carbon material comprises less than 1.0% oxygen as determined by combustion analysis.

16. The carbon material of claim 1, wherein the carbon material comprises a pyrolyzed ultrapure polymer cryogel.

17. The carbon material of claim 1, wherein the carbon material comprises an activated ultrapure polymer cryogel.

18. The carbon material of claim 1, wherein the carbon material comprises a BET specific surface area of at least 1500 m²/g.

19. The carbon material of claim 1, wherein the carbon material comprises a BET specific surface area of at least 2000 m²/g.

20. The carbon material of claim 1, wherein the carbon material comprises a BET specific surface area of at least 2400 m²/g.

21. The carbon material of claim 1, wherein the carbon material comprises a pore volume of at least 0.7 cc/g.

22. An ultrapure polymer gel comprising carbon, hydrogen, oxygen and a total impurity content of less than 500 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

23. The ultrapure polymer gel of claim 22, wherein the ultrapure polymer gel comprises a total impurity content of less than 200 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

24. The ultrapure polymer gel of claim 22, wherein the ultrapure polymer gel is a dried ultrapure polymer gel.

25. The dried ultrapure polymer gel of claim 24 comprising a BET specific surface area of at least 400 m²/g.

26. The ultrapure polymer gel of claim 22, wherein the ultrapure polymer gel is prepared by admixing one or more miscible solvents, one or more phenolic compounds, one or more aldehydes and one or more catalysts.

27. The ultrapure polymer gel of claim 26, wherein the ultrapure polymer gel is prepared by admixing water, acetic acid, resorcinol, formaldehyde and ammonium acetate.

28. A device comprising an ultrapure synthetic carbon material, wherein the ultrapure synthetic carbon material comprises a total impurity content of less than 500 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

29. The device of claim 28, wherein the carbon material is an ultrapure synthetic amorphous carbon material.

30. The device of claim 28, wherein the device is an electric double layer capacitor (EDLC) device comprising:

a) a positive electrode and a negative electrode wherein each of the positive and the negative electrodes comprise the ultrapure synthetic carbon material;

b) an inert porous separator; and

c) an electrolyte;

wherein the positive electrode and the negative electrode are separated by the inert porous separator.

31. The EDLC device of claim 30, wherein the EDLC device comprises a gravimetric power of at least 15 W/g.

32. The EDLC device of claim 30, wherein the EDLC device comprises a volumetric power of at least 10 W/cc.

33. The EDLC device of claim 30, wherein the EDLC device comprises a gravimetric energy of at least 20.0 Wh/kg.

34. The EDLC device of claim 30, wherein the EDLC device comprises a volumetric energy of at least 10.0 Wh/liter.

35. The EDLC device of claim 30, wherein the EDLC device comprises a gravimetric capacitance of at least 25 F/g as measured by constant current discharge from 2.7 V to 0.1 V with a 5 second time constant employing a 1.8 M solution of tetraethylammonium-tetrafluoroborate in acetonitrile electrolyte and a current density of 0.5 A/g.

36. The EDLC device of claim 30, wherein the EDLC device comprises a volumetric capacitance of at least 20 F/cc as measured by constant current discharge from 2.7 V to 0.1 V with a 5 second time constant employing a 1.8 M solution of tetraethylammonium-tetrafluoroborate in acetonitrile electrolyte and a current density of 0.5 A/g.

37. The EDLC device of claim 30, wherein the carbon material comprises a total impurity content of less than 200 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

38. The EDLC device of claim 30, wherein the ash content of the carbon material is less than 0.03% as calculated from proton induced x-ray emission data.

39. The EDLC device of claim 30, wherein the ash content of the carbon material is less than 0.01% as calculated from proton induced x-ray emission data.

40. The EDLC device of claim 30, wherein the carbon material comprises at least 95% carbon as measured by combustion analysis and proton induced x-ray emission.

41. The EDLC device of claim 30, wherein the carbon material comprises less than 3 ppm iron as measured by proton induced x-ray emission.

42. The EDLC device of claim 30, wherein the carbon material comprises less than 1 ppm nickel as measured by proton induced x-ray emission.

43. The EDLC device of claim 30, wherein the carbon material comprises less than 5 ppm sulfur as measured by proton induced x-ray emission.

44. The EDLC device of claim 30, wherein the carbon material comprises less than 1 ppm chromium as measured by proton induced x-ray emission.

45. The EDLC device of claim 30, wherein the carbon material comprises less than 1 ppm copper as measured by proton induced x-ray emission.

46. The EDLC device of claim 30, wherein the carbon material comprises less than 100 ppm sodium, less than 300 ppm silicon, less than 100 ppm calcium, less than 50 ppm sulfur, less than 20 ppm iron, less than 10 ppm nickel, less than 140 ppm copper, less than 5 ppm chromium and less than 5 ppm zinc as measured by proton induced x-ray emission.

47. The EDLC device of claim 30, wherein the carbon material comprises an activated ultrapure polymer cryogel.

48. The EDLC device of claim 30, wherein the carbon material comprises a BET specific surface area of at least 1500 m²/g.

49. The EDLC device of claim 30, wherein the carbon material comprises a BET specific surface area of at least 2000 m²/g.

50. The EDLC device of claim 30, wherein the carbon material comprises a BET specific surface area of at least 2400 m²/g.

51. The device of claim 28, wherein the device is a battery.

52. The device of claim 51, wherein the device is a lithium/carbon battery, zinc/carbon, lithium air battery or lead acid battery.

53. An electrode comprising an ultrapure synthetic carbon material and a binder, wherein the ultrapure synthetic carbon material comprises a total impurity content of less than 500 ppm of elements having atomic numbers ranging from 11 to 92 as measured by proton induced x-ray emission.

54. The electrode of claim 53, wherein the carbon material is an ultrapure synthetic amorphous carbon material.

55. A method for making an ultrapure synthetic carbon material, the method comprising reacting one or more polymer precursors under acidic conditions in the presence of a volatile basic catalyst to obtain an ultrapure polymer gel.

56. The method of claim 55, wherein the carbon material is an ultrapure synthetic amorphous carbon material.

57. The method of claim 55, further comprising admixing the one or more polymer precursors in a solvent comprising acetic acid and water.

58. The method of claim 55, wherein the volatile basic catalyst comprises ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium hydroxide, or combinations thereof.

59. The method of claim 55, wherein the one or more polymer precursors comprise resorcinol and formaldehyde.

60. The method of claim 55 further comprising:

(a) freeze drying the ultrapure polymer gel to obtain an ultrapure polymer cryogel;

(b) pyrolyzing the ultrapure polymer cryogel to obtain a pyrolyzed ultrapure cryogel; and

(c) activating the pyrolyzed ultrapure cryogel to obtain ultrapure synthetic activated carbon material.