Surface-mediated lithium ion-exchanging energy storage device

• US 20130052489A1
• Filed: 08/30/2011
• Published: 02/28/2013
• Est. Priority Date: 08/30/2011
• Status: Active Grant

• Current Assignee: Honeycomb Battery Co. (Global Graphene Group, Inc.)
• Original Assignee: Chenguang Liu
• Inventors: Zhamu, Aruna, Liu, ChenGuang, Jang, Bor Z., Wang, Xiqing
• Granted Patent: US 8,889,298 B2
• Time in Patent Office: Days
• US Class Current: 429/50
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• 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 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/022 Electrodes made of one single microscopic fiber
• 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: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A surface-mediated, lithium ion-exchanging energy storage device comprising: (a) A positive electrode (cathode) comprising a cathode active material that is not a functional material (bearing no functional group reactive with lithium), but having a surface area to capture or store lithium thereon; (b) A negative electrode (anode) comprising an anode active material having a surface area to capture or store lithium thereon; (c) A porous separator disposed between the two electrodes; and (d) A lithium-containing electrolyte in physical contact with the two electrodes, wherein the anode active material and/or the cathode active material has a specific surface area of no less than 100 m²/g in direct physical contact with the electrolyte to receive lithium ions therefrom or to provide lithium ions thereto; wherein at least one of the two electrodes contains therein a lithium source prior to a first charge or a first discharge cycle of the energy storage device. This new generation of energy storage device exhibits the best properties of both the lithium ion battery and the supercapacitor.

Claims

1. A surface-mediated, lithium ion-exchanging energy storage device comprising:

(a) A positive electrode (cathode) comprising a cathode active material having a surface area to capture or store lithium thereon;

(b) A negative electrode (anode) comprising an anode active material having a surface area to capture or store lithium thereon;

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

(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 m²/g being in direct physical contact with said electrolyte to receive lithium ions therefrom or to provide lithium ions thereto;

wherein at least one of the two electrodes contains therein a lithium source prior to a first charge or a first discharge cycle of the energy storage device and wherein at least the cathode active material is not a functionalized material and does not bear a functional group.

2. The energy storage device of claim 1, wherein said device has an open-circuit voltage of at least 0.6 volts.

3. The energy storage device of claim 1, wherein said device has an open-circuit voltage of at least 0.8 volts.

4. The energy storage device of claim 1, wherein said device has an open-circuit voltage of at least 1.0 volts.

5. The energy storage device of claim 1, wherein said device has an open-circuit voltage of at least 1.2 volts.

6. The energy storage device of claim 1, wherein at least 90% of the lithium is stored on surfaces of said anode active material, with said lithium being in direct physical contact with said anode surfaces, when the device is in a charged state, or 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.

7. The energy storage device of claim 1, wherein the electrolyte is liquid electrolyte or gel electrolyte containing a first amount of lithium ions.

8. The energy storage device of claim 1, wherein a charge or discharge operation of said device does not involve lithium intercalation or solid state diffusion.

9. The energy storage device of claim 7, 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.

10. The energy storage device of claim 1, wherein said anode active material is not intercalated or de-intercalated with lithium when said device is in operation.

11. The energy storage device of claim 1, wherein said device operates in a voltage range of from 1.0 volts to 4.5 volts.

12. The energy storage device of claim 1, wherein said device operates in a voltage range of from 1.5 volts to 4.0 volts.

13. The energy storage device of claim 1, wherein said device operates in a voltage range above 1.5 volts.

14. The energy storage device of claim 1, wherein at least one of the two electrodes has a specific surface area of no less than 500 m²/g that is in direct contact with said electrolyte.

15. The energy storage device of claim 1, wherein at least one of the two electrodes has a specific surface area of no less than 1,000 m²/g that is in direct contact with said electrolyte.

16. The energy storage device of claim 1, wherein at least one of the two electrodes has a specific surface area of no less than 1,500 m²/g that is in direct contact with said electrolyte.

17. The energy storage device of claim 1, wherein at least one of the two electrodes has a specific surface area of no less than 2,000 m²/g that is in direct contact with said electrolyte.

18. The energy storage device of claim 1, wherein at least 80% of the lithium is stored on surfaces of said anode active material when the device is in a charged state, or at least 80% of the lithium is stored on surfaces of said cathode active material when the device is in a discharged state.

19. The energy storage device of claim 1, wherein an electric double layer mechanism contributes to less than 10% of the charge storage capacity of said device.

20. The energy storage device of claim 1, wherein no more than 20% of the lithium is stored in the bulk of said anode active material when the device is in a charged state, or no more than 20% of the lithium is stored in the bulk of said cathode active material when the device is in a discharged state.

21. The energy storage device of claim 1, wherein no more than 10% of the lithium is stored in the bulk of said anode active material when the device is in a charged state, or 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.

22. The energy storage device of claim 1, wherein an operation of said device does not involve lithium intercalation or de-intercalation.

23. The energy storage device of claim 1, wherein the lithium source comprises a lithium chip, lithium foil, lithium powder, surface stabilized lithium particles, lithium film coated on a surface of an anode or cathode active material, or a combination thereof.

24. The energy storage device of claim 1, wherein said anode active material is pre-loaded with lithium before or when the device is made.

25. The energy storage device 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 device is made.

26. The energy storage device 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.

27. The energy storage device of claim 1 wherein said anode active material 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 chemically or thermally 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.

28. The energy storage device of claim 1 wherein said cathode active material 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, functionalized 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.

29. The energy storage device of claim 1 wherein said anode active material or cathode active material is a graphene material containing no functional group.

30. The energy storage device of claim 1 wherein said anode active material or cathode active material does not include a functional group-bearing material, which active material 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 pristine graphene, graphene fluoride, hydrogenated graphene, nitrogenated graphene, boron-doped graphene, nitrogen-doped graphene, or chemically reduced graphene;

(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.

31. The energy storage device of claim 1 wherein said anode active material or cathode active material is a non-functionalized graphene material 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, or chemically or thermal reduced graphene.

32. The energy storage device of claim 27 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.

33. The energy storage device of claim 28 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.

34. The energy storage device of claim 1 wherein said anode active material or said cathode active material is a non-functionalized 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, doped graphene, or chemically or thermally reduced graphene oxide.

35. The energy storage device of claim 1 wherein said anode active material or said cathode active material is a non-functionalized single-walled or multi-walled carbon nanotube (CNT), oxidized CNT, fluorinated CNT, hydrogenated CNT, nitrogenated CNT, boron-doped CNT, nitrogen-doped CNT, or doped CNT.

36. The energy storage device of claim 1 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, Li₄Ti₅O₁₂, or a combination thereof.

37. The energy storage device of claim 36, 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.

38. The energy storage device of claim 1 wherein said electrolyte comprises a lithium salt-doped ionic liquid.

39. The energy storage device of claim 1 wherein said device provides an energy density of no less than 200 Wh/kg and power density no lower than 30 Kw/kg, all based on a single electrode weight.

40. The energy storage device of claim 1 wherein said device provides an energy density of no less than 300 Wh/kg and power density no lower than 40 Kw/kg, all based on a single electrode weight.

41. The energy storage device of claim 1 wherein said device provides an energy density of no less than 400 Wh/kg or power density no less than 50 Kw/kg, all based on a single electrode weight.

42. The energy storage device of claim 1 wherein said device provides an energy density of no less than 600 Wh/kg or a power density no less than 100 Kw/kg, all based on a single electrode weight.

43. The energy storage device of claim 1 wherein said positive electrode has a thickness greater than 5 μ

m.

44. The energy storage device of claim 1 wherein said positive electrode has a thickness greater than 50 μ

m.

45. The energy storage device of claim 1 wherein said positive electrode has a thickness greater than 100 μ

m.

46. A method of operating the energy storage device 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 device.

47. A method of operating the energy storage device 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 device.

48. A method of operating the energy storage device 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 device, and electrochemically driving said released lithium ions to said cathode where said released lithium ions are captured by said cathode active material surfaces.

49. The method of claim 48, 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 said anode active material surfaces using an external battery charging device.

51. The method of claim 49, wherein both the charge and discharge of said device do not involve lithium intercalation or solid state diffusion.

50. A method of operating a surface-mediated energy storage device, said method including:

(A) Providing a surface-mediated cell comprising an anode, a lithium source, a porous separator, liquid or gel electrolyte, and a cathode, wherein both the anode and the cathode have a non-functionalized material having lithium-capturing surfaces;

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

(C) Exchanging lithium ions between the lithium-capturing surfaces of said anode and the lithium-capturing surfaces of said cathode during a subsequent charge or discharge.

52. A method of operating a surface-mediated energy storage device, said method including:

(A) Providing a surface-mediated cell comprising an anode, a lithium source, a porous separator, electrolyte having an initial amount of lithium ions, and a cathode, wherein both the anode and the cathode have 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 device;

(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 the lithium-capturing surfaces of said anode and the lithium-capturing surfaces of said cathode during a subsequent charge or discharge operation, wherein said charge operation involves no lithium intercalation.

53. The method of claim 52, wherein said cathode surfaces have a specific surface area greater than 100 m²/g.

54. The method of claim 52, wherein said cathode surfaces have a specific surface area greater than 1,000 m²/g.

55. The method of claim 52, wherein said cathode surfaces have a specific surface area greater than 2,000 m²/g.