Granted Patent B2

US 8,765,303 · App. 13/506,168 · Granted Jul 1, 2014

Abstract

Claims (46)

1. A lithium-ion cell comprising:

(a) A positive electrode (cathode) comprising a carbon or graphitic material selected from graphite worms, exfoliated graphite flakes, expanded graphite, chemically treated graphite with an inter-graphene planar separation no less than 0.4 nm, chemically etched or expanded soft carbon, chemically etched or expanded hard carbon, exfoliated activated carbon, chemically etched or expanded carbon black, chemically expanded multi-walled carbon nano-tube having a diameter from 1 to 100 nm, chemically expanded carbon nano-fiber having a diameter from 1 to 100 nm, or a combination thereof as the only cathode active material having a surface area to capture and store lithium thereon and wherein said cathode forms a meso-porous structure having a pore size in the range from 2 nm to 50 nm and a specific surface area greater than 50 m 2 /g;

(b) A negative electrode (anode) comprising an anode active material having a lithium-storing capacity no less than 400 mAh/g, wherein said anode active material consisting of an intercalation compound is mixed with a conductive additive and/or a resin binder to form a porous electrode structure, or coated onto a current collector in a coating or thin film form, and wherein said anode active material is not pre-lithiated and is lithium-free when the cell is made;

(c) A porous separator disposed between the anode and the cathode;

(d) A lithium-containing electrolyte in ionic contact with the anode and the cathode; and

(e) A lithium source disposed in at least one of the two electrodes when the cell is made.

2. The lithium-ion cell of claim 1 wherein said anode active material is silicon, germanium, tin, or tin oxide.

3. The lithium-ion cell of claim 1 wherein said cathode has a specific surface area greater than 100 m 2 /g.

4. The lithium-ion cell of claim 1 wherein said cathode has a specific surface area greater than 1,000 m 2 /g.

5. The lithium-ion of claim 1 wherein said cathode further contains a conductive filler selected from graphite or carbon particles, carbon black, expanded graphite particles, carbon nanotube having a diameter from 1 to 100 nm, carbon nano-fiber having a diameter from 1 to 100 nm, carbon fiber, conductive polymer, or a combination thereof.

6. The lithium-ion cell of claim 1 , wherein the lithium source comprises a lithium chip, lithium alloy chip, lithium foil, lithium alloy foil, lithium powder, lithium alloy powder, surface stabilized lithium particles, a mixture of lithium metal or lithium alloy with a lithium intercalation compound, lithium or lithium alloy film coated on a surface of an anode or cathode active material, or a combination thereof.

7. The lithium-ion cell of claim 1 wherein said anode active material contains a mixture of a high capacity anode material and a high rate capable anode material, wherein said high rate capable anode material is selected from nano-scaled particles or filaments of a transition metal oxide, Co 3 O 4 , Mn 3 O 4 , Fe 3 O 4 , or a combination thereof, wherein nano-scaled particles or filaments have a diameter or thickness from 0.1 nm to 100 nm, and said high capacity anode material is selected from Si, Ge, Sn, SnO, or a combination thereof.

8. The lithium-ion cell of claim 1 , wherein the anode active material is selected from the group consisting of:

(a) Non-lithiated silicon (Si), germanium (Ge), tin (Sn), and mixtures thereof;

(b) Non-lithiated alloys or intermetallic compounds of Si, Ge, Sn, and their mixtures;

(c) Non-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Sb, Bi, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof; and

(d) Non-lithiated salts or hydroxides of Sn.

9. The lithium-ion cell of claim 1 wherein said anode active material contains a nano material having a thickness or diameter less than 100 nm.

10. The lithium-ion cell of claim 1 , wherein the anode active material is a nano particle, nano disc, nano platelete, nano wire, nano-rod, nano belt, nano scroll, nano tube, nano filament, nano coating, or nano film, having a diameter or thickness from 0.1 nm to 100 nm, selected from the group consisting of:

(a) Non-lithiated silicon (Si), germanium (Ge), tin (Sn), and mixtures thereof;

(b) Non-lithiated alloys or intermetallic compounds of Si, Ge, Sn, and their mixtures;

(c) Non-lithiated oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or antimonides of Si, Ge, Sn, Sb, Bi, Al, Fe, Ti, Co, Ni, Mn, Cd, and mixtures or composites thereof; and

(d) Non-lithiated salts or hydroxides of Sn.

11. A lithium-ion cell comprising:

(A) A positive electrode (cathode) comprising a carbon or graphitic material selected from graphite worms, exfoliated graphite flakes, expanded graphite, chemically treated graphite with an inter-graphene planar separation no less than 0.4 nm, chemically etched or expanded soft carbon, chemically etched or expanded hard carbon, exfoliated activated carbon, chemically etched or expanded carbon black, chemically expanded multi-walled carbon nano-tube having a diameter from 1 to 100 nm, chemically expanded carbon nano-fiber having a diameter from 1 to 100 nm, or a combination thereof as the only cathode active material having a surface area to capture and store lithium thereon and wherein said cathode forms a meso-porous structure having a pore size in the range from 2 nm to 50 nm and having a specific surface area greater than 50 m 2 /g;

(B) A negative electrode (anode) comprising an anode active material for inserting and extracting lithium during a charge and discharge of said cell, wherein the anode active material is a nano particle, nano disc, nano platelet, nano wire, nano-rod, nano belt, nano scroll, nano tube, nano filament, nano coating, or nano film, having a diameter or thickness from 0.1 to 100 nm, selected from: (a) a pre-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), or a mixture thereof; (b) a pre-lithiated alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, or a mixture thereof; (c) a pre-lithiated oxide, carbide, nitride, sulfide, phosphide, selenide, telluride, or antimonide of Si, Ge, Sn, Pb, Sb, Bi; Zn, Al, Fe, Ti, Co, Ni, Mn, Cd, or a mixture or composite thereof, (d) a pre-lithiated salt or hydroxide of Sn; or (e) a pre-lithiated carbon or graphite material, and wherein said anode active material is electrically connected directly to an anode current collector or is connected to an anode current collector through a binder and/or a conductive additive;

(C) A porous separator disposed between the anode and the cathode; and

(D) A lithium-containing electrolyte in physical contact with the anode and the cathode.

12. The lithium-ion cell of claim 11 wherein said anode active material contains a mixture of a high capacity anode material and a high rate capable anode material, wherein said high rate capable anode material is selected from nano-scaled particles or filaments, having a diameter or thickness from 0.1 to 100 nm, of a lithium transition metal oxide, lithiated Co 3 O 4 , lithiated Mn 3 O 4 , lithiated Fe 3 O 4 , Li 4 Ti 5 O 12 , or a combination thereof, and said high capacity anode material is selected from pre-lithiated Si, Ge, Sn, SnO, or a combination thereof.

13. The lithium-ion cell of claim 11 , wherein said anode active material is prelithiated to a specific capacity of no less than 500 mAh/g based on the anode active material weight.

14. The lithium-ion cell of claim 11 , wherein said anode active material is prelithiated to a specific capacity of no less than 1000 mAh/g based on the anode active material weight.

15. The lithium-ion cell of claim 11 , wherein said anode active material is prelithiated to a specific capacity of no less than 2,000 mAh/g based on the anode active material weight.

16. The lithium-ion cell of claim 11 , wherein said anode active material is prelithiated to a specific capacity of no less than 3,000 mAh/g based on the anode active material weight.

17. A lithium-ion cell comprising:

(a) A positive electrode (cathode) comprising a carbon or graphitic material selected from graphite worms, exfoliated graphite flakes, expanded graphite, chemically treated graphite with an inter-graphene planar separation no less than 0.4 nm, chemically etched or expanded soft carbon, chemically etched or expanded hard carbon, exfoliated activated carbon, chemically etched or expanded carbon black, chemically expanded multi-walled carbon nano-tube having a diameter from 1 to 100 nm, chemically expanded carbon nano-fiber having a diameter from 1 to 100 nm, or a combination thereof, as the only cathode active material having a surface area to capture and store lithium thereon and wherein said cathode forms a meso-porous structure having a pore in the range of 2 nm to 50 nm and having a specific surface area greater than 50 m 2 /g;

(b) A negative electrode (anode) comprising an anode active material for inserting and extracting lithium during a charge and discharge of said cell, wherein said anode active material is selected from: (a) a pre-lithiated silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), manganese (Mn), cadmium (Cd), or a mixture thereof; (b) a pre-lithiated alloy or intermetallic compound of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd,or a mixture thereof; (c) a pre-lithiated oxide, carbide, nitride, sulfide, phosphide, selenide, telluride, or antimonide of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, Co, Ni, Mn, Cd, or a mixture or composite thereof, or (d) a pre-lithiated salt or hydroxide of Sn; and said anode active material is mixed with a conductive filler and a binder to form a porous electrode;

(c) A porous separator disposed between the anode and the cathode; and

(d) A lithium-containing electrolyte in physical contact with the two electrodes.

18. The lithium-ion cell of claim 17 , further containing a lithium source disposed in at least one of the two electrodes when the cell is made, wherein said lithium source comprises a lithium chip, lithium alloy chip, lithium foil, lithium alloy foil, lithium powder, lithium alloy powder, surface stabilized lithium particles, a mixture of lithium metal or lithium alloy with a lithium intercalation compound, lithium or lithium alloy film coated on a surface of an anode or cathode active material, or a combination thereof.

19. The lithium-ion cell of claim 1 , further comprising an anode current collector and/or cathode current collector that is a porous, electrically conductive material selected from metal foam, metal web or screen, perforated metal sheet, metal fiber mat, metal nanowire mat, porous conductive polymer film, conductive polymer nano-fiber mat or paper, conductive polymer foam, carbon foam, carbon aerogel, carbon xerox gel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber paper, graphene paper, graphene oxide paper, reduced graphene oxide paper, carbon nano-fiber paper, carbon nano-tube paper, or a combination thereof, wherein said nanowire, nano-fiber, or nano-tube has a diameter or thickness from 1 to 100 nm.

20. The lithium-ion cell of claim 11 , further comprising an anode current collector and/or cathode current collector that is a porous, electrically conductive material selected from metal foam, metal web or screen, perforated metal sheet, metal fiber mat, metal nanowire mat, porous conductive polymer film, conductive polymer nano-fiber mat or paper, conductive polymer foam, carbon foam, carbon aerogel, carbon xerox gel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber paper, graphene paper, graphene oxide paper, reduced graphene oxide paper, carbon nano-fiber paper, carbon nano-tube paper, or a combination thereof, wherein said nanowire, nano-fiber, or nano-tube has a diameter or thickness from 1 to 100 nm.

21. The lithium-ion cell of claim 17 , further comprising an anode current collector and/or cathode current collector that is a porous, electrically conductive material selected from metal foam, metal web or screen, perforated'metal sheet, metal fiber mat, metal nanowire mat, porous conductive polymer film, conductive polymer nano-fiber mat or paper, conductive polymer foam, carbon foam, carbon aerogel, carbon xerox gel, graphene foam, graphene oxide foam, reduced graphene oxide foam, carbon fiber paper, graphene paper, graphene oxide paper, reduced graphene oxide paper, carbon nano-fiber paper, carbon nano-tube paper, or a combination thereof, wherein said nanowire, nano-fiber, or nano-tube has a diameter or thickness from 1 to 100 nm.

22. The lithium-ion cell of claim 1 , wherein the electrolyte is organic liquid electrolyte, ionic liquid electrolyte, gel electrolyte, polymer electrolyte, or solid electrolyte containing a first amount of lithium ions when said cell is made.

23. The lithium-ion cell of claim 11 , wherein the electrolyte is organic liquid electrolyte, ionic liquid electrolyte, gel electrolyte, polymer electrolyte, or solid electrolyte containing a first amount of lithium ions when said cell is made.

24. The lithium-ion cell of claim 17 , wherein the electrolyte is organic liquid electrolyte, ionic liquid electrolyte, gel electrolyte, polymer electrolyte, or solid electrolyte containing a first amount of lithium ions when said cell is made.

25. The lithium-ion cell of claim 1 , wherein said anode, said cathode, or both contains less than 1% by weight oxygen.

Assignments (12)