Partially surface-mediated lithium ion-exchanging cells and method for operating same

• US 20130059174A1
• Filed: 09/07/2011
• Published: 03/07/2013
• Est. Priority Date: 09/07/2011
• Status: Active Grant

• Current Assignee: Honeycomb Battery Co. (Global Graphene Group, Inc.)
• Original Assignee: Nanotek Instruments Group, LLC
• Inventors: Zhamu, Aruna
• Granted Patent: US 9,779,883 B2
• Time in Patent Office: Days
• US Class Current: 429/50
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/36 Nanostructures, e.g. nanofibres, nanotubes or fullerenes
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

A lithium super-battery cell comprising: (a) A cathode comprising a cathode active material having a surface area to capture or store lithium thereon, wherein the cathode active material is not a functionalized material and does not bear a functional group; (b) An anode comprising an anode current collector; (c) A porous separator disposed between the two electrodes; (d) A lithium-containing electrolyte in physical contact with the two electrodes, wherein the cathode active material has a specific surface area of no less than 100 m²/g being in direct physical contact with the electrolyte to receive lithium ions therefrom or to provide lithium ions thereto; and (e) A lithium source implemented at one or both of the two electrodes prior to a first charge or a first discharge cycle of the cell. This new generation of energy storage device exhibits the best properties of both the lithium ion battery and the supercapacitor.

Claims

1. A lithium super-battery cell comprising:

(a) A positive electrode (cathode) comprising a cathode active material having a surface area to capture or store lithium thereon, wherein the cathode contains no functionalized material that has a functional group to capture a lithium ion;

(b) A negative electrode (anode) being composed of an anode current collector and a lithium source implemented at the anode prior to a first discharge of the cell, wherein said lithium source is selected from a lithium chip, lithium alloy chip, lithium foil, lithium alloy foil, lithium powder, lithium alloy powder, surface stabilized lithium particles, or a combination thereof;

(c) A porous separator disposed between the two electrodes; and

(d) A lithium-containing electrolyte in physical contact with the two electrodes, wherein said cathode active material has a specific surface area of no less than 100 m²/g being in direct physical contact with said electrolyte to receive lithium ions therefrom or to provide lithium ions thereto.

2. The cell of claim 1, wherein said cell has an open-circuit voltage of at least 1.2 volts.

3. The cell of claim 1, wherein said device has an open-circuit voltage of at least 1.5 volts.

4. The cell of claim 1, wherein at least 90% of the lithium is stored on surfaces of said cathode active material, with said lithium being in direct physical contact with said cathode surfaces, when the device is in a discharged state.

5. The cell of claim 1, wherein the electrolyte is liquid electrolyte or gel electrolyte containing a first amount of lithium ions.

6. The cell of claim 1, wherein a charge or discharge operation of the cell does not involve lithium intercalation or solid state diffusion.

7. The cell of claim 5, wherein an operation of said device 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.

8. The cell of claim 1, wherein said cell operates in a voltage range of from 1.5 volts to 4.5 volts.

9. The cell of claim 1, wherein said device operates in a voltage range of from 1.5 volts to 4.0 volts.

10. The cell of claim 1, wherein said cell containing a liquid organic electrolyte operates in a voltage range above 3.8 volts.

11. The cell of claim 1, wherein said cathode has a specific surface area of no less than 500 m²/g that is in direct contact with said electrolyte.

12. The cell of claim 1, wherein said cathode has a specific surface area of no less than 1,000 m²/g that is in direct contact with said electrolyte.

13. The cell of claim 1, wherein said cathode has a specific surface area of no less than 1,500 m²/g that is in direct contact with said electrolyte.

14. The cell of claim 1, wherein said cathode has a specific surface area of no less than 2,000 m²/g that is in direct contact with said electrolyte.

15. The cell of claim 1, wherein no more than 10% of the lithium is stored in the bulk of said cathode active material when the device is in a discharged state.

18. The cell of claim 1 wherein said cathode active material, containing no functional group, is selected from:

(a) A porous disordered carbon material selected from a soft carbon, hard carbon, polymeric carbon or carbonized resin, meso-phase carbon, coke, carbonized pitch, carbon black, activated carbon, or partially graphitized carbon;

(b) A 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, or reduced graphene oxide;

(c) Exfoliated graphite;

(d) Meso-porous carbon;

(e) A carbon nanotube selected from a single-walled carbon nanotube or multi-walled carbon nanotube;

(f) A carbon nano-fiber, metal nano-wire, metal oxide nano-wire or fiber, or conductive polymer nano-fiber, or

(g) A combination thereof.

19. The cell of claim 1 wherein said cathode active material is a graphene material containing no functional group.

20. The cell of claim 18 wherein said disordered carbon material is formed of two phases with a first phase being graphite crystals or stacks of graphene planes and a second phase being non-crystalline carbon, and wherein the first phase is dispersed in the second phase or bonded by the second phase.

21. The cell of claim 1 wherein said cathode active material is a non-functionalized single-walled or multi-walled carbon nanotube (CNT), fluorinated CNT, hydrogenated CNT, nitrogenated CNT, boron-doped CNT, nitrogen-doped CNT, or doped CNT.

24. The cell of claim 1 wherein said electrolyte comprises a lithium salt-doped ionic liquid.

25. The cell of claim 1 wherein said positive electrode has a thickness greater than 100 μ

m.

26. A method of operating the cell of claim 1, said method including implementing a lithium source at the anode and ionizing said lithium source to release lithium ions into said electrolyte during the first discharge cycle of said cell.

27. A method of operating the cell of claim 1, said method including implementing a lithium source at the cathode and operating said lithium source to release lithium ions into said electrolyte during the first charge cycle of said cell.

28. A method of operating the cell of claim 1, said method including implementing a lithium source at the anode, ionizing said lithium source to release lithium ions into said electrolyte during the first discharge cycle of said cell, and electrochemically driving said released lithium ions to said cathode where said released lithium ions are captured by said cathode active material surfaces.

29. The method of claim 28, further comprising a step of releasing lithium ions from said cathode surfaces during a re-charge cycle of said device, electrically driving said released lithium ions to an anode current collector surface or said lithium source using an external battery charging device.

16. A lithium super-battery cell comprising:

(a) A positive electrode (cathode) of a non-functionalized graphene material having no functional group to capture a lithium ion, wherein said graphene material is selected from a single-layer sheet or multi-layer platelet of pristine graphene, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, metal-doped graphene, reduced graphene oxide with less than 5% by weight of oxygen, or a combination thereof;

(b) A negative electrode (anode) comprising an anode current collector;

(c) A porous separator disposed between the two electrodes;

(d) A lithium-containing electrolyte in physical contact with the two electrodes, wherein said cathode active material has a specific surface area of no less than 100 m²/g being in direct physical contact with said electrolyte to receive lithium ions therefrom or to provide lithium ions thereto; and

(e) A lithium source implemented in the anode or the cathode prior to a first discharge or a first charge cycle of the cell, wherein said lithium source is selected from a lithium intercalation compound, a lithiated compound, lithiated titanium dioxide, lithium titanate, lithium manganate, a lithium transition metal oxide, Li₄Ti₅O₁₂, or a combination thereof.

17. The cell of claim 16, 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), or a mixture thereof;

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

(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, or a mixture or composite thereof;

(d) Lithiated salts or hydroxides of Sn;

(e) Prelithiated graphite or prelithiated carbon material;

or

(f) A combination thereof.

22. The cell of claim 16, wherein the lithium source is in a thin film or fine particle form having a dimension less than 100 nm.

23. The cell of claim 16, wherein the lithium source is in a thin film or fine particle form having a dimension less than 20 nm

30. A method of operating a lithium super-battery cell, said method including:

(A) Providing a lithium super-battery cell comprising an anode, a lithium source, a porous separator, liquid or gel electrolyte, and a cathode, wherein the cathode has a non-functionalized material having lithium-capturing surfaces and said cell has an open-circuit voltage from 0.5 volts to 2.0 volts;

(B) Releasing lithium ions from said lithium source into said electrolyte during the first discharge of said cell; and

(C) Exchanging lithium ions between the anode and the lithium-capturing surfaces of said cathode during a subsequent charge or discharge in a cell operating in a voltage range of 1.5 volts and 4.5 volts.

31. The method of claim 30, wherein both the charge and discharge of said cell do not involve lithium intercalation or solid state diffusion.

32. The method of claim 30, wherein said lithium source is a prelithiated compound or lithium intercalation compound and said step (B) of releasing lithium ions from said lithium source occurs in a first voltage range, and wherein an operation of said cell occurs in a second voltage range different from the first voltage range.

33. The method of claim 30, wherein said lithium source is a prelithiated graphite or prelithiated carbon material.

34. The method of claim 32, wherein said lithium source is a prelithiated graphite, prelithiated carbon material, lithiated titanium dioxide, lithium titanate, lithium manganate, a lithium transition metal oxide, Li₄Ti₅O₁₂, or a combination thereof.

35. A method of operating a lithium super-battery cell, said method including:

(A) Providing a lithium super-battery cell comprising an anode, a lithium source, a porous separator, electrolyte having an initial amount of lithium ions, and a cathode, wherein the cathode has a material having lithium-capturing surfaces in contact with said electrolyte;

(B) Releasing lithium ions from said lithium source into said electrolyte during the first discharge of said cell;

(C) Operating said cathode to capture lithium ions from said electrolyte and store said captured lithium on cathode surfaces; and

(D) Exchanging an amount of lithium ions, greater than said initial amount, between said anode and the lithium-capturing surfaces of said cathode during a subsequent charge or discharge operation.

36. The method of claim 35 wherein said cell has an open-circuit voltage of said cell is from 0.5 volts to 2.0 volts.

37. The method of claim 35 wherein said exchanging of lithium ions operates up to a voltage limit of no less than 4.0 volts.

38. The method of claim 35 wherein said charge or discharge operation involves no lithium intercalation.

39. The method of claim 35, wherein said cathode surfaces have a specific surface area greater than 100 m²/g.

40. The method of claim 35, wherein said cathode surfaces have a specific surface area greater than 1,000 m²/g.

41. The method of claim 35, wherein said cathode surfaces have a specific surface area greater than 2,000 m²/g.