LOW-GASSING CARBON MATERIALS FOR IMPROVING PERFORMANCE OF LEAD ACID BATTERIES

• US 20180294484A1
• Filed: 10/14/2016
• Published: 10/11/2018
• Est. Priority Date: 10/15/2015
• Status: Abandoned Application

• Current Assignee: BASF SE
• Original Assignee: EnerG2 Technologies, Incorporated
• Inventors: Fredrick, Sarah, Sakshaug, Avery J., Kron, Benjamin E., Hubble, Dion, Costantino, Henry R., Feaver, Aaron M., Thompkins, Leah A., Alspaugh, Virginia Katherine, Hamilton, Phil, Geramita, Katharine, Mekelburg, Cory, Reuter, Frank, Grose, Jacob Ebenstein, Von Benten, Rebekka
• Application Number:
  US15/766,321
• Publication Number:
  US 20180294484A1
• Time in Patent Office: Days
• 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: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/14 Pore volume
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/80 Compositional purity
• CPC Class Codes: G01N 27/308 at least partially made of carbon
• CPC Class Codes: H01M 10/06 Lead-acid accumulators semi-lead accumulators H01M10/20
• CPC Class Codes: H01M 2004/029 Bipolar electrodes
• CPC Class Codes: H01M 2220/10 Batteries in stationary systems, e.g. emergency power source in plant
• CPC Class Codes: H01M 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 4/14 Electrodes for lead-acid accumulators
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/627 Expanders for lead-acid accumulators
• CPC Class Codes: H01M 4/628 Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

Carbon materials having low gassing properties and electrodes and electrical energy storage devices, especially lead-acid batteries, comprising the same are provided.

Claims

1. A carbon material comprising less than an absolute value of 10 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

2. The carbon material of claim 1, comprising less than an absolute value of 5 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

3. The carbon material of claim 1, comprising less than an absolute value of 3 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

4. The carbon material of claim 1, comprising less than an absolute value of 2.5 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

5. The carbon material of claim 1, comprising less than an absolute value of 2 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

6. The carbon material of claim 1, comprising less than an absolute value of 1.5 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

7. The carbon material of claim 1, comprising less than an absolute value of 1.0 mA/mg current at −

1.6 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

29. The carbon material of any one of claims 1-28, comprising at least 15% nitrogen by weight.

30. The carbon material of any one of claims 1-29, comprising a BET specific surface area of at least 300 m²/g.

32. The carbon material of any one of claim 29-31, comprising between 15% and 30% nitrogen by weight.

33. The carbon material of any one of claims 29-31, comprising up to 20% nitrogen by weight.

34. The carbon material of any one of claims 29-31, comprising up to from 20% to 25% nitrogen by weight.

35. The carbon materials of any one of claims 1-34, comprising less than 500 PPM of total impurities.

36. The carbon material of claim 35, wherein the impurities are elements having an atomic number greater than 10.

37. The carbon material of any one of claim 35 or 36, wherein the level of iron is less than 30 ppm iron, the level of copper is less than 30 ppm, less than 20 ppm nickel, less than 20 ppm manganese, and less then 10 ppm chlorine.

38. The carbon material of any of claims 1-37, wherein the total surface area of the carbon material residing in pores less than 20 angstroms ranges from 20% to 60%.

39. The carbon material of any one of claims 1-37, wherein the total surface area of the carbon material residing in pores less than 20 angstroms ranges from 40% to 60%.

40. The carbon material of any one of claims 1-37, wherein the total surface area of the carbon material residing in pores greater than 20 angstroms ranges from 60% to 99%.

41. The carbon material of any of claims 1-37, wherein the total surface area of the carbon material residing in pores less than 20 angstroms ranges from 80% to 95%.

42. The carbon material of any one of claims 1-41, wherein the ash content of the carbon is less than 0.03%.

43. The carbon material of any one of claims 1-41, wherein the ash content of the carbon is less than 0.01%.

44. The carbon material of any one of claims 1-43, wherein the carbon material comprises a pyrolyzed polymer cryogel.

45. The carbon material of any one claims 1-43, wherein the carbon material comprises a pyrolzyed and activated polymer cryogel.

46. The carbon material of any one of claims 1-43, wherein the carbon material comprises a pyrolyzed polymer.

47. The carbon material of any one of claims 1-43, wherein the carbon material comprises a pyrolyzed and activated polymer.

48. The carbon material of claim 1-47, wherein the carbon material comprises a BET specific surface area of at least 1000 m²/g.

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

50. The carbon material of any one of claims 1-49, wherein the carbon material comprises a total pore volume between 0.1 to 0.3 cc/g.

51. The carbon material of any one of claims 1-49, wherein the carbon material comprises a total pore volume between 0.3 to 0.5 cc/g.

52. The carbon material of any one of claims 1-49, wherein the carbon material comprises a total pore volume between 0.5 to 0.7 cc/g.

53. The carbon material of any one of claims 1-49, wherein the carbon material comprises a total pore volume between 0.7 to 1.0 cc/g.

54. The carbon material of any one of claims 1-53, wherein the carbon material comprises a water absorption of greater than 0.6 g H₂O/cc of pore volume in the carbon material.

55. The carbon material of any one of claims 1-53, wherein the carbon material comprises a water absorption of greater than 1.0 g H₂O/cc of pore volume in the carbon material.

56. The carbon material of any one of claims 1-53, wherein the carbon material comprises a water absorption of greater than 2.0 g H₂O/cc of pore volume in the carbon material.

57. The carbon material of any one of claims 1-56, wherein the carbon material comprises a pore volume ranging from 0.4 cc/g to 1.4 cc/g and an R factor of 0.2 or less at relative humidities ranging from about 10% to 100%.

58. The carbon material of claim 57, wherein the carbon material comprises an R factor of 0.6 or less.

59. The carbon material of any one of claim 57 or 58, wherein the carbon material comprises a pore volume ranging from 0.6 cc/g to 1.2 cc/g.

60. The carbon material of any one of claims 1-59, wherein the carbon material has a pH less than 7.5.

61. The carbon material of any one of claims 1-59, wherein the carbon material has a pH between pH 3.0 and 7.5.

62. The carbon material of any one of claims 1-59, wherein the carbon material has a pH between pH 5.0 and 7.0.

63. The carbon material of any one of claims 1-62, comprising a Dv, 50 between 1.0 and 10.0 um.

64. The carbon material of any one of claims 1-62, comprising a Dv, 50 between 10.0 and 20.0 um.

65. The carbon material of any one of claims 1-62, comprising a Dv, 50 between 20.0 and 50.0 um.

66. The carbon material of any one of claims 1-62, comprising a Dv, 50 between 40.0 and 80.0 um.

67. The carbon material of any one of claims 1-66, wherein the carbon material comprises more than 85% micropores, less than 15% mesopores, and less than 1% macropores.

68. The carbon material of any one of claims 1-66, wherein the carbon material comprises less than 50% micropores, more than 50% mesopores, and less than 0.1% macropores.

69. The carbon material of any one of claims 1-66, wherein the carbon material comprises less than 30% micropores and greater than 70% mesopores.

70. An electrical energy storage device comprising a carbon material according to any one of claims 1-69.

71. The device of claim 70, wherein the device is a battery comprising:

a) at least one positive electrode comprising a first active material in electrical contact with a first current collector;

b) at least one negative electrode comprising a second active material in electrical contact with a second current collector; and

c) an electrolyte;

wherein the positive electrode and the negative electrode are separated by an inert porous separator, and wherein at least one of the first or second active materials comprises a carbon material according to any one of claims 1-69.

72. The device of claim 71, where the carbon material comprises 0.1 to 2% of the negative electrode.

73. The device of claim 71, where the carbon material comprises 0.2 to 1% of the negative electrode.

74. The device of claim 71, where the carbon material comprises 0.3 to 0.7% of the negative electrode.

75. The device of any one of claims 71-72, wherein the electrolyte comprises sulfuric acid and water.

76. The device of any one of claims 71-74, wherein the electrolyte comprises silica gel.

77. The device of any of claims 71-76, wherein at least one electrode further comprises an expander.

78. Use of the carbon material of any one of claims 1-69 in an electrical energy storage device.

79. The use of claim 78, wherein the electrical energy storage device is a battery.

80. The use of claim 78 or 79 or the device of any one of claims 70-78, wherein the electrical energy storage device is in a microhybrid, start-stop hybrid, mild-hybrid vehicle, vehicle with electric turbocharging, vehicle with regenerative braking, hybrid vehicle, an electric vehicle, industrial motive power such as forklifts, electric bikes, golf carts, aerospace applications, a power storage and distribution grid, a solar or wind power system, a power backup system such as emergency backup for portable military backup, hospitals or military infrastructure, and manufacturing backup or a cellular tower power system.

81. Use of a device comprising the carbon material of any one of claims 1-69 for storage and distribution of electrical energy.

82. The use of claim 81, wherein the device is a battery.

83. The use of any one of claim 81 or 82, wherein the device is in a microhybrid, start-stop hybrid, mild-hybrid vehicle, vehicle with electric turbocharging, vehicle with regenerative braking, hybrid vehicle, an electric vehicle, industrial motive power such as forklifts, electric bikes, golf carts, aerospace applications, a power storage and distribution grid, a solar or wind power system, a power backup system such as emergency backup for portable military backup, hospitals or military infrastructure, and manufacturing backup or a cellular tower power system.

8. A carbon material producing less than 100 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

9. The carbon material of claim 8, wherein the carbon material produces less than 50 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

10. The carbon material of claim 8, wherein the carbon material produces less than 30 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

11. The carbon material of claim 8, wherein the carbon material produces less than 25 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

12. The carbon material of claim 8, wherein the carbon material produces less than 20 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

13. The carbon material of claim 8, wherein the carbon material produces less than 10 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

14. The carbon material of claim 8, wherein the carbon material produces less than 5 (mA/mg)/(V) at −

1.55 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

15. A carbon material producing less than 200 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

16. The carbon material of claim 15, wherein the carbon material produces less than 100 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

17. The carbon material of claim 15, wherein the carbon material produces less than 50 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

18. The carbon material of claim 15, wherein the carbon material produces less than 40 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

19. The carbon material of claim 15, wherein the carbon material produces less than 20 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

20. The carbon material of claim 15, wherein the carbon material produces less than 10 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

21. The carbon material of claim 15, wherein the carbon material produces less than 5 (mA/mg)²/(V) at −

1.52 V vs Hg/Hg₂SO₄ when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

22. A carbon material producing less than 5:

1 (mA/mg current at −

1.6 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

23. The carbon material of claim 22, wherein the carbon material produces less than 4:

1 (mA/mg current at −

1.6 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

24. The carbon material of claim 22, wherein the carbon material produces less than 3:

1 (mA/mg current at −

1.6 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

25. The carbon material of claim 22, wherein the carbon material produces less than 2:

1 (mA/mg current at −

1.6 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

26. A carbon material producing between 0.75:

1 to 1.25;

1 (mA/mg current at −

1.4 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

27. The carbon material of claim 26, wherein the carbon material produces between 0.85:

1 to 1.15;

1 (mA/mg current at −

1.4 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

28. The carbon material of claim 26, wherein the carbon material produces between 0.9:

1 to 1.1;

1 (mA/mg current at −

1.4 V vs Hg/Hg2SO4);

(mA/mg current at 1.2 V vs Hg/Hg2SO4) when tested by cyclic voltammetry as a working electrode on a substrate comprising lead and employing a platinum counter electrode in the presence of electrolyte comprising sulfuric acid.

31. A carbon material comprising at least 15% nitrogen by weight and a BET specific surface area of at least 300 m²/g.