Granted Patent B2

US 8,895,189 · App. 13/385,105 · Granted Nov 25, 2014

Abstract

Claims (57)

1. A surface-mediated, lithium ion-exchanging cell (SMC) comprising:

(a) A positive electrode (cathode) comprising a carbon-based cathode active material having a surface area to capture and store lithium thereon, wherein the cathode active material has an electrode thickness greater than 5 μm; and wherein said cathode active material or anode active material is selected from: (A) porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, activated carbon, or partially graphitized carbon; (B) graphene material selected from a single-layer sheet or multi-layer platelet of graphene, graphene oxide having less than 5% by weight oxygen, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, functionalized graphene, or reduced graphene oxide; (C) exfoliated graphite; (D) meso-porous carbon; (E) carbon aerogel or carbon foam, or a combination thereof;

(b) A negative electrode (anode) comprising an anode current collector alone, or combined anode current collector and anode active material having a surface area to capture or store lithium thereon;

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

(d) A lithium-containing electrolyte in physical contact with the two electrodes, wherein said anode active material and/or said cathode active material has a specific surface area no less than 100 m 2 /g which is in direct physical contact with said electrolyte to receive lithium ions therefrom or to provide lithium ions thereto and at least said cathode has a specific surface area no less than 100 m 2 /g which is in direct physical contact with said electrolyte; and

(e) A lithium source disposed in at least one of the two electrodes or pre-lithiated into or onto said anode when the cell is made, and the cell has an open-circuit voltage (OCV) of at least 0.8 volts prior to a first charge or discharge cycle of the cell;

wherein said cell operates between a lower voltage limit and an upper voltage limit wherein the lower voltage limit is lower than said OCV and the upper voltage limit is between 3.8 volts and 4.5 volts.

2. The SMC cell of claim 1 wherein said anode active material is selected from: (a) porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, activated carbon, or partially graphitized carbon; (b) graphene material selected from a single-layer sheet or multi-layer platelet of graphene, graphene oxide having less than 5% by weight oxygen, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, functionalized graphene, or reduced graphene oxide; (c) exfoliated graphite; (d) meso-porous carbon; (f) non-functionalized carbon nano-fiber, (g) carbon aerogel or carbon foam, or a combination thereof.

3. The SMC cell of claim 1 wherein said cathode active material or anode active material is selected from carbon aerogel or foam, graphene-enhanced carbon aerogel, carbon nanotube-enhanced carbon aerogel, or a combination thereof.

4. The SMC 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.

5. The SMC cell of claim 1 , wherein said lower voltage limit is selected from 0.6 volts to 1.2 volts.

6. The SMC cell of claim 1 , wherein said cathode has a thickness greater than 50 μm.

7. The SMC cell of claim 2 , wherein said cathode is not formed by a layer-by-layer method.

8. The SMC cell of claim 1 , wherein said anode and/or cathode active material contains less than 5% by weight oxygen.

9. The SMC cell of claim 1 , wherein said cell has an open-circuit voltage of at least 2.5 volts.

10. The SMC cell of claim 1 , wherein at least one of the anode current collector or cathode current collector 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.

11. The SMC cell of claim 1 , wherein said carbon-based cathode active material forms a meso-porous electrode structure having a pore size in the range of 2 nm and 10 nm and is selected from soft carbon, hard carbon, meso-phase carbon, carbon black, activated carbon, multi-layer platelet of graphene, graphene oxide, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, functionalized graphene, or reduced graphene oxide, exfoliated graphite, meso-porous carbon, non-functionalized and no-oxidized multi-walled carbon nanotube, non-functionalized carbon nano-fiber, carbon aerogel or foam, graphene-enhanced carbon aerogel, nanotube-enhanced carbon aerogel, or a combination thereof; wherein at least 30% of the lithium is stored on surfaces of said cathode active material when the cell is in a discharged state.

12. The SMC cell of claim 1 , wherein a discharge operation of said cell involves both lithium intercalation into the interior of said cathode active material and lithium adsorption on surfaces of said cathode active material.

13. The SMC cell of claim 1 , wherein the electrolyte is liquid electrolyte or gel electrolyte containing a first amount of lithium ions when said cell is made.

14. The SMC cell of claim 13 , wherein an operation of said cell involves an exchange of a second amount of lithium ions between said cathode and said anode and said second amount of lithium is greater than said first amount.

15. The SMC cell of claim 1 , wherein said anode active material is not intercalated or de-intercalated with lithium when said cell is in operation.

16. The SMC cell of claim 1 , wherein at least one of the two electrodes has a specific surface area of no less than 500 m 2 /g that is in direct contact with said electrolyte.

17. The SMC cell of claim 1 , wherein at least one of the two electrodes has a specific surface area of no less than 1,000 m 2 /g that is in direct contact with said electrolyte.

18. The SMC cell of claim 1 , wherein at least one of the two electrodes has a specific surface area of no less than 1,500 m 2 /g that is in direct contact with said electrolyte.

19. The SMC cell of claim 1 , wherein at least one of the two electrodes has a specific surface area of no less than 2,000 m 2 /g that is in direct contact with said electrolyte.

20. The SMC cell of claim 1 , wherein said anode active material is pre-loaded with lithium before or when the cell is made.

21. The SMC cell of claim 1 , wherein said anode active material is prelithiated with a surface area being pre-coated or pre-plated with lithium before or when said cell is made.

22. The SMC cell of claim 1 , wherein the anode active material or the cathode active material has a surface area that does not contain a functional group thereon, and said functional group-free surface is exposed to said electrolyte.

23. The SMC cell of claim 1 wherein said electrolyte comprises an organic liquid electrolyte, gel electrolyte, a lithium salt-containing ionic liquid, or a combination thereof.

24. The SMC cell of claim 1 wherein said positive electrode has a thickness greater than 100 μm.

25. A surface-mediated, lithium ion-exchanging cell (SMC) comprising:

(A) A positive electrode (cathode) comprising a carbon-based cathode active material having a surface area to capture or store lithium thereon, wherein the cathode active material is selected from: (a) porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, activated carbon, or partially graphitized carbon; (b) graphene material selected from a single-layer sheet or multi-layer platelet of graphene, graphene oxide having less than 5% by weight oxygen, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, functionalized graphene, or reduced graphene oxide; (c) exfoliated graphite; (d) meso-porous carbon; (e) carbon aerogel or carbon foam, or a combination thereof;

(B) A negative electrode (anode) comprising an anode current collector alone or a combination of an anode current collector and an anode active material having a surface area to capture or store lithium thereon;

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

(D) A lithium-containing electrolyte in physical contact with the two electrodes, wherein said anode active material and/or said cathode active material has a specific surface area of no less than 100 m 2 /g which is in direct physical contact with said electrolyte to receive lithium ions therefrom or to provide lithium ions thereto; and

(E) A lithium source disposed in at least one of the two electrodes or pre-lithiated into said anode when the cell is made, and the cell has an open-circuit voltage (OCV) of at least 0.8 volts prior to a first charge or discharge cycle of the cell;

wherein said cell operates between a lower voltage limit and an upper voltage limit wherein said lithium source provides an amount of lithium sufficient for said anode to retain a non-zero lithium content when said cell is discharged to the lower voltage limit.

26. The SMC cell of claim 25 wherein said lithium source contains an amount of lithium sufficient for said anode to retain a non-zero lithium content equivalent to at least 10% of the total anode weight, including said anode current collector and anode active material weights combined, when said device is discharged to the lower voltage limit.

27. The SMC cell of claim 25 wherein said lithium source is selected from lithium metal, a lithium metal alloy, a mixture of lithium metal or lithium alloy with a lithium intercalation compound, a lithiated compound, lithiated titanium dioxide, lithium titanate, lithium manganate, a lithium transition metal oxide, Li 4 Ti 5 O 12 , or a combination thereof.

28. The SMC cell of claim 27 , wherein the lithium intercalation compound or lithiated compound is selected from the following groups of materials:

(a) 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), and mixtures thereof;

(b) Lithiated alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Co, Ni, Mn, Cd, and their mixtures;

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

(d) Lithiated salts or hydroxides of Sn.

29. The SMC cell of claim 25 wherein said anode active material is selected from: (a) porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, activated carbon, or partially graphitized carbon; (b) graphene material selected from a single-layer sheet or multi-layer platelet of graphene, graphene oxide, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, functionalized graphene, or reduced graphene oxide; (c) exfoliated graphite; (d) meso-porous carbon; (e) carbon aerogel or carbon foam, graphene-enhanced carbon aerogel, carbon nanotube-enhanced carbon aerogel, or a combination thereof.

30. The SMC cell of claim 25 wherein said electrolyte comprises an organic liquid electrolyte, a gel electrolyte, a lithium salt-doped ionic liquid, or a combination thereof.

31. The SMC cell of claim 25 wherein said positive electrode has a thickness greater than 100 μm.

32. A surface-mediated, lithium ion-exchanging cell (SMC) comprising:

(A) A positive electrode (cathode) comprising a carbon-based cathode active material having a non-functionalized surface area to capture or store lithium thereon, wherein said cathode active material or anode active material is selected from: (a) porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, activated carbon, or partially graphitized carbon; (b) graphene material selected from a single-layer sheet or multi-layer platelet of graphene, graphene oxide having less than 5% by weight oxygen, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, functionalized graphene, or reduced graphene oxide; (c) exfoliated graphite; (d) meso-porous carbon; (e) carbon aerogel or carbon foam, or a combination thereof;

(B) A negative electrode (anode) comprising an anode current collector alone or a combination of an anode current collector and an anode active material having a surface area to capture or store lithium thereon;

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

(D) A lithium-containing ionic liquid electrolyte in physical contact with the two electrodes, wherein said anode active material and/or said cathode active material has a specific surface area no less than 100 m 2 /g which is in direct physical contact with said electrolyte to receive lithium ions therefrom or to provide lithium ions thereto; and

(E) A lithium source disposed in at least one of the two electrodes or pre-lithiated into or onto said anode when the cell is made, and the cell has an open-circuit voltage (OCV) of at least 0.8 volts prior to a first charge or discharge cycle of the cell;

wherein said cell operates between a lower voltage limit and an upper voltage limit wherein said lithium source provides an amount of lithium sufficient for said anode to retain a non-zero lithium content when said cell is discharged to the lower voltage limit.

33. A stack of SMC device comprising at least two SMC cells of claim 1 connected in series or in parallel.

34. A stack of SMC device comprising at least two SMC cells of claim 25 connected in series or in parallel.

35. A stack of SMC device comprising at least two SMC cells of claim 32 connected in series or in parallel.

Assignments (12)