Surface -controlled lithium ion-exchanging energy storage device

• US 20120164539A1
• Filed: 12/23/2010
• Published: 06/28/2012
• Est. Priority Date: 12/23/2010
• Status: Active Grant

• Current Assignee: Global Graphene Group, Inc.
• Original Assignee: Nanotek Instruments, Inc.
• Inventors: Zhamu, Aruna, Liu, ChenGuang, Neff, David, Jang, Bor Z.
• Granted Patent: US 9,166,252 B2
• Time in Patent Office: Days
• US Class Current: 429/300
• CPC Class Codes: H01G 11/36 Nanostructures, e.g. nanofibres, nanotubes or fullerenes
• CPC Class Codes: H01G 11/50 specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• 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 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/0566 Liquid materials
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/0445 Forming after manufacture of the electrode, e.g. first charge, cycling
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/137 Electrodes based on electro-active polymers
• CPC Class Codes: H01M 4/1399 of electrodes based on electro-active polymers
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H01M 4/602 : Polymers
• CPC Class Codes: H01M 4/604 : containing aliphatic main chain polymers
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors

Abstract

A surface-controlled, lithium ion-exchanging battery device comprising: (a) A positive electrode (cathode) comprising a first functional material having a first lithium-capturing or lithium-storing surface; (b) A negative electrode (anode) comprising a second functional material having a second lithium-capturing or lithium-storing surface; (c) A porous separator disposed between the two electrodes, and (d) A lithium-containing electrolyte (preferably liquid or gel electrolyte) in physical contact with the two electrodes; wherein at least one of the two electrodes contains therein a lithium source (e.g., lithium foil, lithium powder, stabilized lithium particles, etc) prior to the first charge or the first discharge cycle of the battery 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-controlled, lithium ion-exchanging battery device comprising:

(a) A positive electrode (cathode) comprising a first functional material having a first lithium-capturing or lithium-storing surface,

(b) A negative electrode (anode) comprising a second functional material having a second lithium-capturing or lithium-storing surface,

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

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

wherein at least one of the two electrodes contains therein a lithium source prior to the first charge or the first discharge cycle of the battery device.

2. The battery device of claim 1, wherein the electrolyte comprises liquid electrolyte or gel electrolyte.

3. The battery device of claim 1, wherein at least one of the two electrodes has a functional material having a functional group that reversibly reacts with a lithium atom or ion.

4. The battery device of claim 1, wherein both of the two electrodes have a functional material having a functional group that reversibly reacts with a lithium atom or ion.

5. The battery device of claim 1, wherein at least one of the two electrodes has a nano-structured functional material having a specific surface area no less than 100 m²/gram to store or support lithium ions or atoms thereon.

6. The battery device of claim 1, wherein both of the two electrodes have a nano-structured functional material having a specific surface area no less than 100 m²/gram to store or support lithium ions or atoms thereon.

7. The battery device of claim 5, wherein the specific surface area is no less than 500 m²/gram.

8. The battery device of claim 6, wherein the specific surface area is no less than 500 m²/gram.

9. The battery device of claim 1, wherein the lithium source comprises a lithium chip, lithium foil, lithium powder, surface stabilized lithium particles, or a combination thereof.

10. The battery device of claim 1 wherein a functional material is selected from the group consisting of:

(a) A 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 nano graphene platelet selected from a single-layer graphene sheet or multi-layer graphene platelet;

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

(d) A carbon nano-fiber, nano-wire, metal oxide nano-wire or fiber, conductive polymer nano-fiber, or a combination thereof.

(e) A carbonyl-containing organic or polymeric molecule;

(f) A functional material containing a carbonyl, carboxylic, or amine group; and

(g) Combinations thereof.

11. The battery device of claim 1 wherein both first functional material and second functional material are selected from the group consisting of:

(A) A 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 nano graphene platelet selected from a single-layer graphene sheet or multi-layer graphene platelet;

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

(D) A carbon nano-fiber, nano-wire, metal oxide nano-wire or fiber, conductive polymer nano-fiber, or a combination thereof

(E) A carbonyl-containing organic or polymeric molecule;

(F) A functional material containing a carbonyl, carboxylic, or amine group; and

(G) Combinations thereof.

12. The battery device of claim 1, wherein a functional material is selected from the group consisting of Poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene), Li_xC₆O₆ (x=1-3), Li₂(C₆H₂O₄), Li₂C₈H₄O₄ (Li terephthalate), Li₂C₆H₄O₄(Li trans-trans-muconate), 3,4,9,10-perylenetetracarboxylicacid-dianhydride (PTCDA) sulfide polymer, PTCDA, 1,4,5,8-naphthalene-tetracarboxylicacid-dianhydride (NTCDA), Benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8-tetrahydroxy anthraquinon, Tetrahydroxy-p-benzoquinone, and combinations thereof.

13. The battery device of claim 1, wherein a functional material is selected from the group consisting of Poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene), Li_xC₆O₆ (x=1-3), Li₂(C₆H₂O₄), Li₂C₈H₄O₄ (Li terephthalate), Li₂C₆H₄O₄(Li trans-trans-muconate), 3,4,9,10-perylenetetracarboxylicacid-dianhydride (PTCDA) sulfide polymer, PTCDA, 1,4,5,8-naphthalene-tetracarboxylicacid-dianhydride (NTCDA), Benzene-1,2,4,5-tetracarboxylic dianhydride, 1,4,5,8-tetrahydroxy anthraquinon, Tetrahydroxy-p-benzoquinone, and combinations thereof, and this functional material is combined with or supported by a nano-structured material selected from nano graphene, carbon nanotube, disordered carbon, nano graphite, metal nanowire, conductive nano-wire, carbon nano-fiber, polymeric nano-fiber.

14. The battery device of claim 10 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.

15. The battery device of claim 10 wherein said disordered carbon material contains less than 90% by volume of graphite crystals and at least 10% by volume of non-crystalline carbon.

16. The battery device of claim 1 wherein at least one of the functional materials is nano graphene selected from a single-layer graphene sheet or a multi-layer graphene platelet.

17. The battery device of claim 1 wherein both the first functional material and the second functional material comprise a nano graphene material selected from a single-layer graphene sheet or a multi-layer graphene platelet.

18. The battery device of claim 1 wherein at least one of the functional materials is single-walled or multi-walled carbon nanotube.

19. The battery device of claim 1 wherein both the first functional material and the second functional material comprise a single-walled or multi-walled carbon nanotube.

20. The battery device of claim 1 wherein at least one of the functional materials is a nano-structured material having a specific surface area of at least 1,000 m²/g.

21. The battery device of claim 1 wherein at least one of the functional materials is a nano-structured material having a specific surface area of at least 1,500 m²/g.

22. The battery device of claim 1 wherein at least one of the functional materials has a functional group selected from —

COOH, ═

O, —

NH₂, —

OR, or —

COOR, where R is a hydrocarbon radical.

23. The battery 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.

24. The battery device of claim 23, 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.

25. The battery device of claim 1 wherein said electrolyte comprises a lithium salt-doped ionic liquid.

26. The battery device of claim 1 wherein the electrolyte is a liquid electrolyte or a gel electrolyte.

27. The battery device of claim 1 wherein said device provides an energy density of no less than 100 Wh/kg and power density no lower than 15 Kw/kg, all based on the total electrode weight.

28. The battery device of claim 1 wherein said device provides an energy density of no less than 200 Wh/kg and power density no lower than 10 Kw/kg, all based on the total electrode weight.

29. The battery device of claim 1 wherein said device provides an energy density of no less than 300 Wh/kg and power density no less than 5 Kw/kg, all based on the total electrode weight.

30. The battery device of claim 1 wherein said device provides an energy density of no less than 300 Wh/kg or a power density no less than 100 Kw/kg, all based on the total electrode weight.

31. The battery device of claim 1 wherein said device provides a power density no less than 200 Kw/kg, based on the total electrode weight.

32. The battery device of claim 1 wherein said positive electrode has a thickness greater than 5 μ

m.

33. The battery device of claim 1 wherein said positive electrode has a thickness greater than 50 μ

m.

34. The battery device of claim 1 wherein said positive electrode has a thickness greater than 100 μ

M.