Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries

• US 8,236,452 B2
• Filed: 11/02/2009
• Issued: 08/07/2012
• Est. Priority Date: 11/02/2009
• Status: Active Grant

• Current Assignee: Honeycomb Battery Co. (Global Graphene Group, Inc.)
• Original Assignee: Nanotek Instruments, Inc.
• Inventors: Zhamu, Aruna, Jang, Bor Z.
• Primary Examiner(s): HENDRICKSON, STUART L
• Application Number:
  US12/589,999
• Publication Number:
  US 20110104571A1
• Time in Patent Office: 1,009 Days
• Field of Search: 429/231.95, 429/128
• US Class Current: 429/231.95
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/621 Binders
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

This invention provides a nano-structured anode composition for a lithium metal cell. The composition comprises: (a) an integrated structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein the nano-filaments have a transverse dimension less than 500 nm; and (b) micron- or nanometer-scaled particles of lithium, a lithium alloy, or a lithium-containing compound wherein at least one of the particles is surface-passivated or stabilized and the weight fraction of these particles is between 1% and 99% based on the total weight of these particles and the integrated structure together. Also provided is a lithium metal cell or battery, or lithium-air cell or battery, comprising such an anode. The battery exhibits an exceptionally high specific capacity, an excellent reversible capacity, and a long cycle life.

Claims

1. A nano-structured anode composition for a lithium metal cell, said composition comprising:

a) an integrated structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein said filaments have a transverse dimension less than 500 nm; and

b) micron- or nanometer-scaled particles of lithium, a lithium alloy, or a lithium-containing compound wherein at least one of said particles is stabilized or surface-passivated and the weight fraction of these particles is between 1% and 99% of the total weight of these particles and the integrated structure together.

2. The nano-structured anode composition of claim 1 wherein said filaments have a transverse dimension smaller than 100 nm.

3. The nano-structured anode composition of claim 1 wherein said filaments comprise an electrically conductive material selected from the group consisting of electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, nano-scaled graphene platelets, metal nano wires, and combinations thereof.

4. The nano-structured anode composition of claim 1 wherein said filaments comprise a fiber selected from the group consisting of an electrically conductive electro-spun polymer fiber, electro-spun polymer nanocomposite fiber comprising a conductive filler, nano carbon fiber obtained from carbonization of an electro-spun polymer fiber, electro-spun pitch fiber, and combinations thereof.

5. The nano-structured anode composition of claim 1 wherein said filaments comprise nano-scaled graphene platelets with a thickness less than 10 nm.

6. The nano-structured anode composition of claim 1 wherein said filaments comprise single-layer graphene.

7. The nano-structured anode composition of claim 1 wherein said integrated structure comprises a gradient structure.

8. The nano-structured anode composition of claim 1 wherein said integrated structure, when implemented in a lithium metal cell, comprises a gradient structure having a first surface facing an anode collector and a second surface facing a separator or cathode, wherein said first surface and said second surface have different nano-filament compositions, different physical densities, or different levels of porosity.

9. The nano-structured anode composition of claim 8 wherein said gradient structure is characterized by having levels of porosity increasing from a lower level at the first surface to a higher level at the second surface.

10. The nano-structured anode composition of claim 1 wherein the weight fraction of passivated or stabilized particles is between 10% and 90% of the total weight of these particles and the integrated structure together.

11. The nano-structured anode composition as defined in claim 1, wherein said nano-filaments are bonded by a binder material selected from a polymer, coal tar pitch, petroleum pitch, meso-phase pitch, coke, or a derivative thereof.

12. The nano-structured anode composition of claim 1 wherein said particles comprises lithium or lithium alloy particles that are surface-coated with carbon dioxide, fluorine, fluorine-containing compound, wax, lithium oxide, lithium nitride, lithium chloride, lithium bromide, sodium chloride, potassium chloride, petroleum pitch, coal tar pitch, polymer, organic substance, or inorganic material.

13. The nano-structured anode composition of claim 1 wherein said particles comprise a spherical particle, an ellipsoidal particle, a filament or fibrous particle, a wire, a cylindrical particle, or a needle-shape particle.

14. The nano-structured anode composition of claim 1 wherein the weight fraction of said particles is greater than 50%.

15. The nano-structured anode composition of claim 1 wherein the weight fraction of said particles is greater than 90%.

16. A lithium secondary battery comprising a positive electrode, a negative electrode comprising a nano-structured anode composition as defined in claim 1, and non-aqueous electrolyte, or electrolyte combined with a separator, disposed between said negative electrode and said positive electrode.

17. The lithium secondary battery as defined in claim 16, wherein said battery is discharged and recharged to a state that at least one of said nano-filaments is plated with a coating of lithium.

18. The lithium secondary battery according to claim 16, wherein said positive electrode comprises a cathode active material selected from the group consisting of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, a non-lithiated oxide of a transition metal, lithium iron phosphate, lithium vanadium phosphate, lithium manganese phosphate, a non-lithiated transition metal phosphate, a chalcogen compound, and combinations thereof.

19. The lithium secondary battery according to claim 16, wherein said positive electrode comprises a non-lithiated cathode active material.

20. The lithium secondary battery according to claim 18, wherein said positive electrode comprises sulfur, sulfur-containing molecule, sulfur-containing compound, sulfur-carbon polymer, or a combination thereof.

21. The lithium secondary battery according to claim 16, wherein said positive electrode comprises (a) an integrated structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein said filaments have a transverse dimension less than 500 nm;

and (b) a cathode active material bonded to or in physical contact with said integrated structure.

22. The lithium secondary battery according to claim 21, wherein said cathode active material comprises sulfur, a sulfur-containing molecule, a sulfur-containing compound, a sulfur-carbon polymer, or a combination thereof.

23. The lithium secondary battery according to claim 21, wherein said cathode active material contains a coating bonded to at least one of said filaments.

24. The lithium secondary battery according to claim 16, wherein said electrolyte is selected from the group consisting of polymer electrolyte, polymer gel electrolyte, solid-state electrolyte, composite electrolyte, soft matter phase electrolyte, and combinations thereof.

25. The lithium secondary battery according to claim 16, wherein said electrolyte is selected from non-aqueous liquid electrolyte, polymer electrolyte, polymer gel electrolyte, solid-state electrolyte, composite electrolyte, or soft matter phase electrolyte and at least portion of said electrolyte is hosted by a separator.

26. The lithium secondary battery according to claim 25, wherein said separator is porous having pores and at least portion of said electrolyte is hosted by pores of said separator.

27. The lithium secondary battery as defined in claim 16, wherein said battery provides a reversible specific capacity of no less than 500 mAh per gram of the total battery weight including anode, cathode, electrolyte, and separator components together.

28. The lithium secondary battery as defined in claim 16, wherein said battery provides a specific capacity of no less than 700 mAh per gram of the total battery weight including anode, cathode, electrolyte, and separator components together.

29. A lithium metal-air battery comprising an air cathode, an anode comprising a nano-structured composition as defined in claim 1, and electrolyte, or electrolyte combined with a separator, disposed between said anode and said air cathode.

30. The lithium metal-air battery of claim 29 wherein said filaments have a transverse dimension smaller than 100 nm.

31. The lithium metal-air battery of claim 29 wherein said filaments comprise an electrically conductive material selected from the group consisting of electro-spun nano fibers, vapor-grown carbon or graphite nano fibers, carbon or graphite whiskers, carbon nano-tubes, nano-scaled graphene platelets, metal nano wires, and combinations thereof.

32. The lithium metal-air battery of claim 29 wherein said filaments comprise a fiber selected from the group consisting of an electrically conductive electro-spun polymer fiber, electro-spun polymer nanocomposite fiber comprising a conductive filler, nano carbon fiber obtained from carbonization of an electro-spun polymer fiber, electro-spun pitch fiber, and combinations thereof.

33. The lithium metal-air battery of claim 29 wherein said filaments comprise nano-scaled graphene platelets with a thickness less than 10 nm.

34. The lithium metal-air battery of claim 29 wherein said filaments comprise single-layer graphene.

35. The lithium metal-air battery of claim 29 wherein said integrated structure comprises a gradient structure.

36. The lithium metal-air battery of claim 29 wherein the weight fraction of passivated or stabilized particles is between 10% and 90% of the total weight of these particles and the integrated structure together.

37. The lithium metal-air battery as defined in claim 29, wherein said nano-filaments are bonded by a binder material selected from a polymer, coal tar pitch, petroleum pitch, meso-phase pitch, coke, or a derivative thereof.

38. The lithium metal-air battery of claim 29 wherein said particles comprises lithium or lithium alloy particles that are surface-coated with carbon dioxide, fluorine, fluorine-containing compound, wax, lithium oxide, lithium nitride, lithium chloride, lithium bromide, sodium chloride, potassium chloride, petroleum pitch, coal tar pitch, polymer, organic substance, or inorganic material.

39. The lithium metal-air battery according to claim 29, wherein said air cathode comprises an integrated structure of electrically conductive nanometer-scaled filaments that are interconnected to form a porous network of electron-conducting paths comprising interconnected pores, wherein said filaments in said air cathode have a transverse dimension less than 500 nm.

40. The lithium metal-air battery according to claim 39, wherein said air cathode further comprises a catalyst coated on a surface of said filaments and said catalyst serves to catalyze a cathode reaction of reducing lithium oxide to lithium ions and oxygen during a battery re-charging operation.