Secondary lithium ion battery containing a prelithiated anode

• US 8,241,793 B2
• Filed: 01/02/2009
• Issued: 08/14/2012
• Est. Priority Date: 01/02/2009
• 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): Vanoy, Timothy
• Application Number:
  US12/319,114
• Publication Number:
  US 20100173198A1
• Time in Patent Office: 1,320 Days
• Field of Search: 429/231.8, 429/231.9, 429/231.95
• US Class Current: 429/231.8
• 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 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/626 Metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A lithium ion battery that exhibits a significantly improved specific capacity and much longer charge-discharge cycle life. The battery comprises an anode active material that has been prelithiated and pre-pulverized. This anode may be prepared with a method that comprises (a) providing an anode active material; (b) intercalating or absorbing a desired amount of lithium into the anode active material to produce a prelithiated anode active material; (c) comminuting the prelithiated anode active material into fine particles with an average size less than 10 μm (preferably <1 μm and most preferably <200 nm); and (d) combining multiple fine particles of the prelithiated anode active material with a conductive additive and/or a binder material to form the anode. Preferably, the prelithiated particles are protected by a lithium ion-conducting matrix or coating material. Further preferably, the matrix material is reinforced with nano graphene platelets.

Claims

1. A lithium-ion battery comprising a cathode, an anode, a separator disposed between said cathode and said anode, and electrolyte in ionic contact with both the cathode and the anode, wherein said anode comprises fine particles of a first anode active material that has been prelithiated and pre-pulverized, having an average size less than 10 μ

m, and said first anode active material is not graphite-based or carbon-based.

2. The battery of claim 1, wherein said prelithiated and pre-pulverized particles have an average particle size less than 1 μ

m.

3. The battery of claim 1, wherein prelithiated and pre-pulverized particles have an average particle size less than 200 nm.

4. The battery of claim 1 wherein said first anode active material is selected from the group consisting of:

(a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), and cadmium (Cd);

(b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein said alloys or compounds are stoichiometric or non-stoichiometric;

(c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, or Cd, and their mixtures or composites; and

(d) combinations thereof.

5. The battery of claim 1 wherein said prelithiated anode active material is produced with a procedure comprising electrochemical lithiation of said active material.

6. The battery of claim 1 wherein said anode active material comprises silicon and said prelithiated particles comprise a prelithiated silicon represented by a chemical formula of Li₄Si,Li_4.4Si, or Li_xSi, wherein numerical x is between 1 and 4.4.

7. The battery of claim 1 wherein said prelithiated fine particles comprise a prelithiated silicon particle having a size less than 200 nm.

8. The battery of claim 1 wherein said anode active material comprises a doped semiconductor material.

9. The battery of claim 1 wherein said anode active material comprises a doped semiconductor material selected from Si or Ge doped with n-type and/or p-type dopants.

10. The battery of claim 1 wherein said anode further comprises an amorphous carbon or polymeric carbon that forms a coating on a surface of said prelithiated fine particles or form a matrix in which a prelithiated particle is dispersed.

11. The battery of claim 10 wherein said carbon coating has a thickness less than 1 μ

m.

12. The battery of claim 10 wherein said carbon is obtained from pyrolization of a polymer, pitch, or organic precursor, or obtained by chemical vapor deposition.

13. The battery of claim 1 wherein said anode further comprises a protective material that forms a coating on a surface of said prelithiated fine particles or form a matrix in which a prelithiated particle is dispersed.

14. The battery of claim 1 wherein said anode further comprises a desired amount of a second anode active material selected from particles of graphite, hard carbon, soft carbon, meso-carbon micro-bead, surface-modified graphite, carbon-coated graphite, or a combination thereof.

15. The battery of claim 1 wherein said anode comprises a conductive additive selected from the group consisting of carbon black, electro-spun nano fibers, carbonized 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, metal-coated nano wires, carbon-coated nano wires, metal-coated nano fibers, carbon-coated nano fibers, and combinations thereof.

16. The battery of claim 1 wherein said cathode does not contain a full capacity of lithium initially when the battery is assembled.

17. A lithium-ion battery comprising a cathode, an anode, a separator disposed between said cathode and said anode, and electrolyte in ionic contact with both the cathode and the anode, wherein said anode comprises fine particles of a first anode active material that contains lithium atoms prelithiated into a volume of at least one of said fine particles and said fine particles have a size less than 1 μ

m and wherein said first anode active material is selected from the group consisting of;

(a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), and cadmium (Cd);

(b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, or Cd with other elements, wherein said alloys or compounds are stoichiometric or non-stoichiometric;

(c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, or Cd, and their mixtures or composites; and

(d) combinations thereof.

18. The battery of claim 17 wherein said fine particles have a size less than 500 nm.

19. The battery of claim 17 wherein said fine particles have a size less than 200 nm.

20. The battery of claim 17 wherein said anode further comprises a desired amount of a second anode active material selected from particles of graphite, hard carbon, soft carbon, meso-carbon micro-bead, surface-modified graphite, carbon-coated graphite, or a combination thereof.

21. The battery of claim 17 wherein said anode comprises a conductive additive selected from the group consisting of carbon black, electro-spun nano fibers, carbonized 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, metal-coated nano wires, carbon-coated nano wires, metal-coated nano fibers, carbon-coated nano fibers, and combinations thereof.

22. The battery of claim 17 wherein said cathode does not contain a full capacity of lithium initially when the battery is assembled.

23. The battery of claim 17 wherein said cathode contains no lithium initially when the battery is assembled.

24. A lithium-ion battery comprising a cathode, an anode, a separator disposed between said cathode and said anode, and electrolyte in ionic contact with both the cathode and the anode, wherein said anode comprises:

(A) fine particles of a first anode active material that has been prelithiated, having an average size less than 10 μ

m;

(B) nano graphene platelets; and

(C) a protective matrix reinforced by said nano graphene platelets wherein said fine particles of a first anode active material and said graphene platelets are dispersed in said protective matrix to form a nanocomposite containing x weight fraction of fine particles, y weight fraction of graphene platelets, and z weight fraction of protective matrix, where 2%<

x<

90%;

2%<

y<

90%;

5%<

z<

80%; and

x+y+z=100%.

25. The lithium ion battery of claim 24 wherein said protective matrix comprises amorphous carbon, polymeric carbon, or meso-phase carbon.

26. The lithium ion battery of claim 24 wherein 10%<

x<

60%, 2%<

y<

30%, 5%<

z<

60%, and x+y+z=100%.

27. The battery of claim 24 wherein said fine particles have a size less than 500 nm.

28. The battery of claim 24 wherein said fine particles have a size less than 200 nm.

29. The battery of claim 24 wherein said cathode does not contain a full capacity of lithium initially when the battery is assembled.

30. The battery of claim 24 wherein said cathode contains no lithium initially when the battery is assembled.