Lithium secondary battery comprising fine fibrous porous polymer membrane and fabrication method thereof

• US 20050053840A1
• Filed: 07/09/2004
• Published: 03/10/2005
• Est. Priority Date: 07/09/2003
• Status: Abandoned Application

• Current Assignee: Samshin Creation Co., Ltd.
• Original Assignee: Korea Advanced Institute of Science and Technology
• Inventors: Jo, Seong Mu, Lee, Wha Seop
• Application Number:
  US10/887,226
• Publication Number:
  US 20050053840A1
• Time in Patent Office: Days
• US Class Current: 429/247
• 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 2300/004 Three solvents
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/0473 Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
• 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 4/621 Binders
• CPC Class Codes: H01M 50/414 Synthetic resins, e.g. thermoplastics or thermosetting resins
• CPC Class Codes: H01M 50/417 Polyolefins
• CPC Class Codes: H01M 50/42 Acrylic resins
• CPC Class Codes: H01M 50/426 Fluorocarbon polymers
• CPC Class Codes: H01M 50/429 Natural polymers
• CPC Class Codes: H01M 50/44 Fibrous material
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Disclosed are a lithium secondary battery comprising a fibrous membrane/electrode composite in which an ultra-fine fibrous porous polymer membrane is combined with an electrode into one body and a hybrid type polymer electrolyte in which pores of the ultra-fine fibrous porous polymer membrane is impregnated with an organic electrolyte solution or a polymer electrolyte; and a fabrication method thereof.

Claims

1. A lithium secondary battery comprising:

(a) an electrospun fibrous membrane/electrode composite in which an ultra-fine fibrous porous polymer membrane is combined with an electrode into one body; and

(b) a hybrid type polymer electrolyte in which pores of the electrospun ultra-fine fibrous porous polymer membrane are impregnated with an organic electrolyte solution or a polymer electrolyte.

2. The lithium secondary battery according to claim 1, wherein fibers in the ultra-fine fibrous porous polymer membrane have a diameter of 1-3000 nm.

3. The lithium secondary battery according to claim 1, wherein the ultra-fine fibrous porous polymer membrane has a thickness of 1-100 μ

m.

4. The lithium secondary battery according to claim 1, wherein a polymer for the ultra-fine fibrous porous polymer membrane is selected from the group consisting of polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, poly(vinylpyrrolidone-vinylacetate), poly{bis[2-(2-methoxyethoxy)phosphagene]}, poly(ethyleneimide), polyethylene-glycol dialkylether, polyethyleneglycol dialkylester, polyethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxymethylene-oligo-oxyethylene), polypropyleneoxide, polyvinylacetate, polyurethane, polyetherurethane, polystyrene, polystyrene acrylonitrile copolymer, polyester, nylon, polyacrylonitrile, polyacrylonitrile methylmethacrylate copolymer, polymethylmethacrylate, polymethylmethacrylate copolymer, polyvinylchloride, poly(vinylidene fluoride), poly(vinylidenefluoride-co-hexafluoropropylene), perfluoropolymer and mixtures thereof.

5. The lithium secondary battery according to claim 1, wherein the organic electrolyte solution is an electrolyte in which a lithium salt is dissolved in an organic solvent, and the polymer electrolyte is a polymer/lithium salt complex or an electrolyte comprising a polymer and an organic electrolyte solution.

6. The lithium secondary battery according to claim 5, wherein the polymer electrolyte further comprises an inorganic additive selected from the group consisting of TiO₂, BaTiO₃, Li₂O, LiF, LiOH, Li₃N, BaO, Na₂O, Li₂CO₃, LiAlO₂, SiO₂Al₂O₃, PTFE and mixtures thereof.

7. The lithium secondary battery according to claim 5, wherein the lithium salt is selected from the group consisting of LiPF₆, LiClO₄, LiAsF₆, LiBF₄ and LiCF₃SO₃.

8. The lithium secondary battery according to claim 1, wherein a polymer for the polymer electrolyte is selected from the group consisting of cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, poly(vinylpyrrolidone-vinylacetate), poly{bis[2-(2-methoxyethoxy)phosphagene]}, poly(ethyleneimide), polyethyleneglycol dialkylether, polyethyleneglycol dialkylester, oligomers of polyethyleneglycol diacrylate and derivatives thereof, polyethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxymethylene-oligo-oxyethylene), polypropyleneoxide, polyether, polyvinylacetate, polyurethane, polyetherurethane, polystyrene, poly(styrene-acrylonitrile), polyacrylonitrile, poly(acrylonitrile-methylmethacrylate), polymethylmethacrylate and copolymers thereof, polyvinylchloride, poly(vinylidene fluoride), poly(vinylidenefluoride-co-hexafluoropropylene), perfluoro-polymers and mixtures thereof.

9. The lithium secondary battery according to claim 5, wherein the weight ratio of the polymer to the organic electrolyte solution in the electrolyte comprising a polymer and an organic electrolyte solution is in the range of 1:

1-50.

10. The lithium secondary battery according to claim 5, wherein the organic solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate and mixtures thereof.

11. The lithium secondary battery according to claim 1, wherein the fibrous membrane/electrode composite include a fibrous membrane/anode composite and a fibrous membrane/cathode composite.

12. The lithium secondary battery according to claim 11, wherein the anode comprises an anode active material selected from the group consisting of graphite, cokes, hard carbon, tin oxide, lithiated compounds thereof, lithium, lithium alloys and mixtures thereof.

13. The lithium secondary battery according to claim 11, wherein the cathode includes a cathode active material selected from the group consisting of LiClO₂, LiNiO₂, LiNiCoO₂, LiMn₂O₄, V₂O₅, V₆O₁₃ and mixtures thereof.

14. A method for fabricating a lithium secondary battery, comprising the steps of:

(a) electrospinning a polymer melt or a polymeric solution onto an earthed metal conveyor collector plate of an electrospinning apparatus while applying a voltage, to prepare an ultra-fine fibrous porous polymer membrane on the earthed metal conveyor collector plate;

(b) adhering an active surface of an electrode onto the ultra-fine fibrous porous polymer membrane prepared in step (a), hot pressing the resultant, and followed by separating the same from the collector plate, to obtain a fibrous membtane/electrode composite in which the ultra-fine fibrous porous polymer membrane is combined with the electrode into one body; and

(c) fabricating a lithium secondary battery with the fibrous membrane/electrode composite.

15. The method according to claim 14, wherein fibers in the ultra-fine fibrous porous polymer membrane have a diameter of 1-3000 nm.

16. The method according to claim 14, wherein the ultra-fine fibrous porous polymer membrane has a thickness of 1-100 μ

m.

17. The method according to claim 14, wherein the fibrous membrane/electrode composite includes a fibrous membrane/anode composite and a fibrous membrane/cathode composite.

18. The method according to claim 17, wherein the anode comprises an anode active material selected from the group consisting of graphite, cokes, hard carbon, tin oxide, lithiated compounds thereof, lithium, lithium alloys and mixtures thereof.

19. The method according to claim 17, wherein the cathode comprises a cathode active material selected from the group consisting of LiClO₂, LiNiO₂, LiNiCoO₂, LiMn₂O₄, V₂O₅, V₆O₁₃ and mixtures thereof.

20. The method according to claim 17, wherein the step (c) comprising the following sub-steps of:

(i) heat-laminating the fibrous membrane/cathode composite with the fibrous membrane/anode composite, to obtain an electrode body in which the cathode/fibrous membrane /anode are combined into one body; and

(ii) injecting an organic electrolyte solution or a polymer electrolyte into the electrode body.

21. The method according to claim 17, wherein the step (c) further comprises the following sub-steps of:

(i) respectively injecting an organic electrolyte solution or a polymer electrolyte into the fibrous membrane/cathode composite and the fibrous membrane/anode composite;

(ii) adhering the fibrous membrane/cathode composite and the fibrous membrane/anode composite anode to each other; and

(iii) laminating the resultant.

22. The method according to claim 14, wherein the polymer of the step (a) is selected from the group consisting of polyethylene, polypropylene, cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, poly(vinylpyrrolidone-vinylacetate), poly{bis[2-(2-methoxyethoxy)phosphagene]}, poly(ethyleneimide), polyethyleneglycol dialkylether, polyethyleneglycol dialkylester, polyethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxymethylene-oligo-oxyethylene), polypropyleneoxide, polyvinylacetate, polyurethane, polyetherurethane, polystyrene, polystyrene acrylonitrile copolymer, polyester, nylon, polyacrylonitrile, polyacrylonitrile methylmethacrylate copolymer, polymethylmethacrylate, polymethylmethacrylate copolymer, polyvinylchloride, poly(vinylidene fluoride), poly(vinylidenefluoride-co-hexafluoropropylene), perfluoro-polymer and mixtures thereof.

23. The method according to claim 20, wherein the organic electrolyte solution is an electrolyte in which a lithium salt is dissolved in an organic solvent, and the polymer electrolyte is a polymer/lithium salt complex or an electrolyte comprising a polymer and an organic electrolyte solution.

24. The method according to claim 23, wherein the lithium salt is selected from the group consisting of LiPF₆, LiClO₄, LiAsF₆, LiBF₄ and LiCF₃SO₃.

25. The method according to claim 23, wherein the polymer electrolyte further comprises an inorganic additive selected from the group consisting of TiO₂, BaTiO₃, Li₂O, LiF, LiOH, Li₃N, BaO, Na₂O, Li₂CO₃, LiAlO₂, SiO₂, Al₂O₃, PTFE and mixtures thereof.

26. The method according to claim 23, wherein the polymer for the polymer electrolyte is selected from the group consisting of cellulose, cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, poly(vinylpyrrolidone-vinylacetate), poly{bis[2-(2-methoxyethoxy)phosphagene]}, poly(ethyleneimide), polyethyleneglycol dialkylether, polyethyleneglycol dialkylester, triethyleneglycol dialkylether, oligomers of polyethyleneglycol diacrylate and derivatives thereof, polyethyleneoxide, polyethylenesuccinate, polyethylenesulfide, poly(oxymethylene-oligo-oxyethylene), polypropyleneoxide, polyether, polyvinylacetate, polyurethane, polyetherurethane, polystyrene, poly(styrene acrylonitrile), polyacrylonitrile, poly(acrylonitrile-methylmethacrylate), polymethylmethacrylate and copolymers thereof, polyvinylchloride, poly(vinylidene fluoride), poly(vinylidenefluoride-co-hexafluoropropylene), perfluoro-polymers and mixtures thereof.

27. The method according to claim 23, wherein the weight ratio of the polymer to the organic electrolyte solution in the electrolyte comprising a polymer and an organic electrolyte solution is in the range of 1:

1-50.

28. The method according to claim 23, wherein the organic solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate and mixtures thereof.