Methods of producing oxygen reduction catalyst

• US 6,689,711 B2
• Filed: 10/09/2001
• Issued: 02/10/2004
• Est. Priority Date: 10/09/2001
• Status: Expired due to Term

• Current Assignee: Zinc8 Energy Solutions, Inc.
• Original Assignee: Metallic Power, Inc.
• Inventors: Lefebvre, Mark C.
• Primary Examiner(s): Bell, Mark L.
• Assistant Examiner(s): Hailey, Patricia L.
• Application Number:
  US09/973,490
• Publication Number:
  US 20030069129A1
• Time in Patent Office: 854 Days
• Field of Search: 429/40, 429/44, 429/27, 502/101, 502/182-185, 502/200
• US Class Current: 502/185
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 27/24 Nitrogen compounds
• 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 2004/8689 Positive electrodes
• CPC Class Codes: H01M 4/886 Powder spraying, e.g. wet or dry powder spraying, plasma spraying
• CPC Class Codes: H01M 4/8882 Heat treatment, e.g. drying, baking
• CPC Class Codes: H01M 4/90 Selection of catalytic material
• CPC Class Codes: H01M 4/96 Carbon-based electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Methods of making an oxygen reduction catalyst are described in which carbon black, one or more metal-containing and/or nitrogen-containing precursor(s) are provided to a reaction zone, and the carbon black is rendered catalytically active. To form this catalytic activity, the carbon black and one or more metal-containing and/or nitrogen-containing precursor(s) are introduced to a reaction zone heated to a temperature of between about 600 and about 1000 degrees Celsius, and maintained together in the reaction zone for a cumulative time between 5 seconds and 240 minutes.

Claims

1. An oxygen reduction catalyst comprising (a) about 95 wt % to about 99.9 wt % carbon black, and (b) about 0.1 wt % to about 5.0 wt % metal, and (c) about 0.05 wt % to about 5.0 wt % nitrogen derived from non-polymerized molecules.

2. The catalyst of claim 1 in the form of a collection of catalyst particles.

3. The collection of claim 2 comprising not less than about 5 grams of such particles.

4. The collection of claim 2 wherein the particles are distributed in reasonably close proximity to each other.

5. The collection of claim 2, wherein the particles are distributed in the collection in an arrangement suitable for commercial distribution.

6. The collection of claim 2, wherein the particles are distributed in the collection as a supported matrix.

7. The collection of claim 6, wherein the distribution of the particles in the supported matrix is uniform.

8. The collection of claim 6, wherein the distribution of the particles in the supported matrix is random.

9. The collection of claim 6, wherein the supported matrix comprises an oxygen reduction cathode or a near-planar array.

10. The collection of claim 9, wherein the supported matrix comprises a near-planar array having a thickness in the range from about 0.0001 cm to about 10 cm and an area in the range from about 100 cm² to about 500 m².

11. The collection of claim 2, wherein the collection comprises in the range from about 5 grams of such particles to about 10000 kilograms of such particles.

12. The collection of claim 2, wherein the collection comprises in the range from about 10 grams of such particles to about 10 kilograms of such particles.

13. The collection of claim 2, wherein the collection comprises in the range from about 10 grams of such particles to about 50 grams of such particles.

14. The catalyst of claim 1, wherein the carbon black comprises exactly one property selected from the group consisting of a surface area of not less than 200 m²/gm, a resistivity of not greater than 0.01 Ω

-cm, and an internal volume (DBP absorption test) of not less than 150 cm^3/100 gm.

15. The catalyst of claim 1, wherein the carbon black comprises exactly two properties selected from the group consisting of a surface area of not less than 200 m²/gm, a resistivity of not greater than 0.01 Ω

-cm, and an internal volume (DBP absorption test) of not less than 150 cm^3/100 gm.

16. The catalyst of claim 1, wherein the carbon black comprises a surface area of not less than 200 m²/gm, a resistivity of not greater than 0.01 Ω

-cm, and an internal volume (DBP absorption test) of not less than 150 cm^3/100 gm.

17. The catalyst of claim 1, wherein the metal comprises a member of the group consisting of Fe, Co, Ru, Mn, Zn, Mo, Cr, Cu, V, Ni, Rh, and suitable combinations thereof.

18. The catalyst of claim 17, wherein the metal comprises Fe.

19. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and a reducing agent to a reaction zone; and

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes.

20. The method of claim 19 wherein the carbon black comprises exactly one property selected from the group consisting of a surface area of not less than 200 m²/gm, a resistivity of not greater than 0.01 Ω

-cm, and an internal volume (DBP absorption test) of not less than 150 cm^3/100 gm.

21. The method of claim 19 wherein the carbon black comprises exactly two properties selected from the group consisting of a surface area of not less than 200 m²/gm, a resistivity of not greater than 0.01 Ω

-cm, and an internal volume (DBP absorption test) of not less than 150 cm^3/100 gm.

22. The method of claim 19 wherein the carbon black comprises a surface area of not less than 200 m ¹ gm, a resistivity of not greater than 0.01 Ω

-cm, and an internal volume (DBP absorption test) of not less than 150 cm^3/100 gm.

23. The method of claim 19 wherein the one or more metal-containing and/or nitrogen-containing precursor(s) comprises at least one precursor comprising a metal and at least one precursor comprising a nitrogen.

24. The method of claim 23 wherein the metal is selected from the group consisting of alkali elements, alkali salts, alkali-containing compounds, alkaline earth elements, alkaline earth salts, alkaline earth-containing compounds, transition block elements, transition block salts, transition block-containing compounds, lanthanoid block elements, lanthanoid block salts, lanthanoid block-containing compounds, actinoid block elements, actinoid block salts, actinoid block-containing compounds, and suitable combinations thereof.

25. The method of claim 24, wherein the metal is selected from the group consisting of Fe, Fe salts, Fe-containing compounds, Co, Co salts, Co-containing compounds, Ru, Ru salts, Ru-containing compounds, Mn, Mn salts, Mn-containing compounds, Zn, Zn salts, Zn-containing compounds, Mo, Mo salts, Mo-containing compounds, Cr, Cr salts, Cr-containing compounds, Cu, Cu salts, Cu-containing compounds, V, V salts, V-containing compounds, Ni, Ni salts, Ni-containing compounds, Rh, Rh salts, Rh-containing compounds, and suitable combinations of any two or more thereof.

26. The method of claim 24, wherein the metal is selected from the group consisting of Fe, Fe salts, Fe-containing compounds, and suitable combinations of any two or more thereof.

27. The method of claim 23 wherein the nitrogen comprises ammonia, acetonitrile, hydrazine, pyrrole, urea, any nitrogen-salt or nitrogen-containing compound that can serve as a nitrogen donor to a metal at a temperature in the range from about 600 to about 1000 degrees Celsius, and suitable combinations thereof.

28. The method of claim 19 wherein the one or more metal-containing and/or nitrogen-containing precursor(s) comprises at least one precursor comprising both a metal and a nitrogen.

29. The method of claim 28 wherein the precursor comprising both a metal and a nitrogen comprises a metal macrocycle comprising a metal and a nitrogen.

30. The method of claim 29 wherein the metal is Fe.

31. The method of claim 19 wherein the reducing agent is selected from the group comprising hydrogen, carbon monoxide, any gas that can serve to provide a reducing atmosphere at a temperature in the range(s) from about 600 to about 1000 degrees Celsius, and suitable combinations of any two or more thereof.

32. The method of claim 19, further comprising providing a gas mixture comprising a carrier gas, a nitrogen-containing precursor comprising a nitrogen-containing gas, and a reducing agent comprising a reducing gas to the reaction zone.

33. The method of claim 32, further comprising providing a metal precursor comprising a metal salt fluid to the reaction zone.

34. The method of claim 33, further comprising combining carbon black particles and the metal salt fluid to form an atomized carbon black/metal fluid suspension that is introduced to the reaction zone.

35. The method of claim 34, further comprising entraining the suspension in the gas mixture.

36. The method of claim 34, further comprising causing the gas mixture to flow along a flow path through the reaction zone, and introducing the suspension to the reaction zone through the flow of the gas mixture.

37. The method of claim 34, further comprising forming the atomized carbon black/metal fluid suspension using an atomizer.

38. The method of claim 37, wherein the atomizer forms the atomized carbon black/metal fluid suspension by atomizing a carbon black containing fluid and a metal containing fluid.

39. The method of claim 38, wherein the atomizer forms the atomized carbon black/metal fluid suspension by ultrasound or aerosol.

40. The method of claim 34, wherein the carbon black comprises a fluid selected from the group consisting of organic fluids and aqueous fluids.

41. The method of claim 40, wherein the metal salt comprises a metal salt containing fluid independently selected from the group consisting of organic fluids and aqueous fluids.

42. The method of claim 32 further comprising forming the gas mixture prior to heating -the gas mixture.

43. The method of claim 19, further comprising employing the catalyst in an oxygen-reduction cathode.

44. The method of claim 43, further comprising employing the catalyst in an oxygen-reduction cathode in a battery.

45. The method of claim 43, further comprising employing the catalyst in an oxygen-reduction cathode in a fuel cell.

46. The method of claim 45, further comprising employing the catalyst in a fuel cell which comprises a member of the group selected from metal-based fuel cells and hydrogen-based fuel cells.

47. The method of claim 45, further comprising employing the catalyst in a fuel cell comprising a member selected from the group consisting of acid-based fuel cells and alkaline-based fuel cells.

48. The method of claim 45, further comprising employing the catalyst in a fuel cell comprising a member of the group selected from metal-based fuel cells.

49. The method of claim 45, further comprising employing the catalyst in a fuel cell comprising a zinc-air fuel cell.

50. The method of claim 43, further comprising employing the catalyst in an oxygen-reduction cathode in a chlor alkali process for generating chlorine and base from a solution of alkali chloride using a membrane.

51. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

maintaining the temperature in the reaction zone via heating with a heat source.

52. The method of claim 51 wherein the heat source comprises a furnace.

53. The method of claim 52, wherein the furnace is selected from the group consisting of resistively heated furnaces, microwave-based furnaces, induction-based furnaces, infrared-based furnaces, flame-based furnaces, and suitable combinations thereof.

54. The method of claim 53, wherein the temperature is achieved by adjusting the furnace temperature and/or adjustment of the reactant flow rate through the reaction zone.

55. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

introducing a carrier gas to the reaction zone, wherein the carrier gas comprises nitrogen, argon, helium, or suitable combinations thereof.

56. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone, wherein the one or more metal-containing and/or nitrogen-containing precursor(s) comprises at least one precursor comprising a metal and at least one precursor comprising a nitrogen, and the nitrogen-containing precursor comprises ammonia; and

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes.

57. A method of making particles of a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

producing the particles at a production rate of not less than about 10 grams per day.

58. The method of claim 57, wherein the particles are produced at a production rate of not less than about 100 grams per day.

59. The method of claim 57, wherein the particles are produced at a production rate of not less than about 1000 grams per day.

60. A method of making particles of a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

producing the particles at a production rate in the range from about 10 grams per day to about 100 kilograms per hour.

61. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

maintaining the reaction zone vertical tube surrounded in part by a heating element.

62. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

maintaining the reaction zone rotating kiln tilted at an angle from the horizontal.

63. A method of making a catalyst, the method comprising:

providing carbon black, one or more metal-containing and/or nitrogen-containing precursor(s), and an optional reducing agent to a reaction zone;

heating the reaction zone to a temperature of between about 600 and about 1000 degrees Celsius and maintaining the carbon black, the one or more metal-containing and/or nitrogen-containing precursor(s), and the reducing agent in the reaction zone while so heated for a cumulative time in the range from between about 5 seconds and about 240 minutes; and

providing carbon black particles widely dispersed over a supporting surface to the reaction zone.

64. A method of making a catalyst, comprising:

entraining an atomized carbon black/metal salt fluid suspension in a gas mixture comprising a nitrogen-containing gas, a reducing gas, and a carrier gas;

directing the gas mixture and entrained suspension along a flow path past a heat source;

heating the gas mixture and entrained suspension so that the temperature at the surface of the atomized carbon black/metal salt fluid suspension is in the range from about 600 to about 1000 degrees Celsius; and

heating the gas mixture and entrained suspension for a cumulative time in the range from about 5 seconds to about 240 minutes.