Structural micro-porous carbon anode for rechargeable lithium-ion batteries

• US 5,426,006 A
• Filed: 04/16/1993
• Issued: 06/20/1995
• Est. Priority Date: 04/16/1993
• Status: Expired due to Fees

• Current Assignee: Sandia Corporation (Martin Marietta Corporation)
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Delnick, Frank M., Sylwester, Alan P., Even, William R. Jr., Zifer, Thomas, Wang, James C. F.
• Primary Examiner(s): KALAFUT, STEPHEN J
• Application Number:
  US08/049,696
• Time in Patent Office: 795 Days
• Field of Search: 429/218, 423/445, 252/182.1
• US Class Current: 429/221
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/96 Carbon-based electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A secondary battery having a rechargeable lithium-containing anode, a cathode and a separator positioned between the cathode and anode with an organic electrolyte solution absorbed therein is provided. The anode comprises three-dimensional microporous carbon structures synthesized from polymeric high internal phase emulsions or materials derived from this emulsion source, i.e., granules, powders, etc.

Claims

1. A secondary battery comprising:

a positive electrode capable of reversibly incorporating a lithium atom;

a rechargeable lithium atom-containing negative electrode comprising of three-dimensional porous, carbon structures having a network of cells separated from each other by walls and interconnected by holes through said walls, wherein the cells have diameters in the range of approximately 1 to 100 μ

m, wherein the carbon structures have a macroscopic density of less than 1.0 g/cc; and

a non-aqueous electrolyte solution connecting said positive electrode and negative electrode.

2. The secondary battery as defined in claim 1 wherein the carbon structures have randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in lateral extent.

3. The rechargeable electrode as defined in claim 2 wherein the carbon structures have a spacing of (002) planes (d₀₀₂) as determined by X-ray diffraction of 3.7 Å

or more, and wherein the carbon structures have the ratio of the peak strength at 1,360 cm^-1 to the peak strength at 1,580 cm of a deconvoluted Raman spectrum of approximately 1.

4. The secondary battery as defined in claim 3 wherein the positive electrode comprises of second three-dimensional porous carbon structures having a network of cells separated from each other by walls and interconnected by holes through said walls, wherein the cells have diameters in the range of approximately 1 to 100 μ

m, wherein the carbon structures have a macroscopic density of less than 1.0 g/cc.

5. The secondary battery as defined in claim 4 wherein the carbon structures of said positive electrode has randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in lateral extent.

6. The rechargeable electrode as defined in claim 5 wherein the carbon structures have a spacing of (002) planes (d₀₀₂) as determined by X-ray diffraction of 3.7 Å

or more, and wherein the carbon structures have the ratio of the peak strength at 1,360 cm^-1 to the peak strength at 1,580 cm^-1 of a deconvoluted Raman spectrum of approximately 1.

7. The secondary battery as defined in claim 3 wherein the positive electrode comprises a sulfide compound.

8. The secondary battery as defined in claim 7 wherein the sulfide compound is selected from the group consisting of iron sulfide, cobalt sulfide, molybdenum sulfide, and titanium sulfide.

9. The secondary battery as defined in claim 8 wherein the positive electrode comprises a lithiated metal oxide.

10. The secondary battery as defined in claim 9 wherein the metal oxide is selected from the group consisting of lithiated vanadium oxides lithiated manganese oxide, and lithiated nickel oxide.

11. A method of preparing three dimensional microporous carbon structures suitable for energy storage applications wherein the carbon structures have a network of cells separated from each other by walls and interconnected by holes through said walls, wherein the cells have diameters in the range of approximately 1 to 100 μ

m. wherein the carbon structures have a macroscopic density of less than approximately 1.0 g/cc, that conaprises the steps of;

mixing a first liquid that comprises a solvent, dissolved therein, polymerizable precursor materials and a surfactant and a second liquid that comprises a temporary pore former to form an emulsion, wherein the first liquid forms a continuous phase and the second liquid forms an internal phase in the emulsion;

causing polymerization of the polymerizable precursor materials in the continuous phase such that a cellular polymeric material is formed;

removing the solvent, surfactant and internal phase from said cellular polymeric material; and

carbonizing said cellular polymeric material to form said three dimensional microporous carbon structures.

12. The method of preparing three dimensional microporous carbon structures as defined in claim 11 wherein the carbon structures have randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in lateral extent.

13. The method of preparing three dimensional microporous carbon structures as defined in claim 12 wherein the carbon structures have a spacing of (002) planes (d₀₀₂) as determined by X-ray diffraction of 3.7 Å

or more, and wherein the carbon structures have the ratio of the peak strength at 1,360 cm^-1 to the peak strength at 1,580 cm^-1 of a deconvoluted Raman spectrum of approximately 1.

14. The method of preparing three dimensional microporous carbon structures as defined in claim 12 wherein the polymerizable precursor materials comprise one or more chain extending species and one or more cross-linking species.

15. The method of preparing three dimensional microporous carbon structures as defined in claim 14 wherein the polymerizable precursor materials comprise divinylbenzene and methacrylonitrile.

16. The method of preparing three dimensional microporous carbon structures as defined in either claim 14 or 15 wherein the temporary pore former comprises water.

17. The method of preparing three dimensional microporous carbon structures as defined in claim 16 further comprising the step of cooling the emulsion to stabilize it.

18. The method of preparing three-dimensional microporous carbon structures as defined in claim 11 further comprising the step of adding a surface active agent to stabilize the continuous phase.

19. The method of preparing three-dimensional microporous carbon structures as defined in claim 16 further comprising the step of adding co-solvents, solutes, or modifying salts into said emulsion.

20. A rechargeable electrode suitable for use in secondary batteries prepared by a process comprising the steps of:

mixing a first liquid that comprises a solvent, dissolved therein, polymerizable precursor materials and a surfactant and a second liquid that comprises a temporary pore former to form an emulsion, wherein the first liquid forms a continuous phase and the second liquid forms an internal phase in the emulsion;

causing polymerization of the polymerizable precursor materials in the continuous phase such that a cellular polymeric material is formed;

removing the solvent, surfactant and internal phase from said cellular polymeric material; and

carbonizing said cellular polymeric material to form said three dimensional structures.

21. The rechargeable electrode as defined in claim 20 wherein the carbon structures have randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in lateral extent.

22. The rechargeable electrode as defined in claim 21 wherein the carbon structures have a spacing of (002) planes (d₀₀₂) as determined by X-ray diffraction of 3.7 Å

or more, and wherein the carbon structures have the ratio of the peak strength at 1,360 cm^-1 to the peak strength at 1,580 cm^-1 of a deconvoluted Raman spectrum of approximately 1.

23. The rechargeable electrode as defined in claim 21 wherein the polymerizable precursor materials comprise one or more chain extending species and one or more cross-linking species.

24. The rechargeable electrode as defined in claim 23 wherein the polymerizable precursor materials comprise divinylbenzene and methacrylonitrile.

25. The rechargeable electrode as defined in either claim 23 or 24 wherein the temporary pore former comprises water.

26. The rechargeable electrode as defined in claim 25 wherein the process of preparing the rechargeable electrode further comprises the step of cooling the emulsion to stabilize it.

27. The rechargeable electrode as defined in claim 20 wherein the process of preparing the rechargeable electrode further comprises adding co-solvents, solutes, or modifying salts into said emulsion.

28. The rechargeable electrode as defined in claim 25 wherein the process of preparing the rechargeable electrode further comprises adding co-solvents, solutes, or modifying salts into said emulsion.

29. An energy storage device having an electrode comprising three dimensional microporous carbon structures wherein the carbon structures have a network of cells separated from each other by walls and interconnected by holes through said walls, wherein the cells have diameters in the range of approximately 1 to 100 μ

m, wherein the carbon structures have a macroscopic density of less than approximately 1.0 g/cc, and wherein the rechargeable electrode is prepared by a process comprising the steps of;

mixing a first liquid that comprises a solvent, dissolved therein, polymerizable precursor materials and a surfactant and a second liquid that comprises a temporary pore former to form an emulsion, wherein the first liquid forms a continuous phase and the second liquid forms an internal phase in the emulsion;

causing polymerization of the polymerizable precursor materials in the continuous phase such that a cellular polymeric material is formed;

removing the solvent, surfactant and internal phase from said cellular polymeric material; and

carbonizing said cellular polymeric material to form said three dimensional microporous carbon structures.

30. The energy storage device as defined in claim 29 wherein the carbon structures have randomly oriented domains shown by transmission electron microscopy to contain approximately 4 to 10 lattice planes extending approximately 20 to 50 Å

in lateral extent.

31. The energy storage device as in claim 30 wherein the carbon structures have a spacing of (002) planes (d₀₀₂) as determined by X-ray diffraction of 3.7 Å

or more, and wherein the carbon structures have the ratio of the peak strength at 1,360 cm^-1 to the peak strength at 1,580 cm^-1 of a deconvoluted Raman spectrum of approximately 1.

32. The energy storage device as in claim 31 wherein the polymerizable precursor materials comprise one or more chain extending species and one or more cross-linking species.

33. The energy storage device as in claim 32 wherein the polymerizable precursor materials comprise divinylbenzene and methacrylonitrile.

34. The energy storage device as in claim 32 or 33 wherein the temporary pore former comprises water.

35. The energy storage device as in claim 34 wherein the process of preparing the three dimensional microporous carbon structures further comprises the step of cooling the emulsion to stabilize it.