Flexible thin printed battery and device and method of manufacturing same

• US 7,625,664 B2
• Filed: 01/12/2006
• Issued: 12/01/2009
• Est. Priority Date: 02/12/2002
• Status: Expired due to Term

• Current Assignee: Energizer Brands, LLC (Energizer Holdings, Inc.)
• Original Assignee: Eveready Battery Company Incorporated (Energizer Holdings, Inc.)
• Inventors: Langan, Richard A., Zhang, Jing, Schubert, Mark A., Tucholski, Gary R., Bailey, John C., Zheng, Guanghong, Webber, Andrew, Hilmi, Abdelkader, Feddrix, Frank H., Tudron, Frank B.
• Primary Examiner(s): HODGE, ROBERT W
• Application Number:
  US11/332,635
• Publication Number:
  US 20060115717A1
• Time in Patent Office: 1,419 Days
• Field of Search: None
• US Class Current: 429/124
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/0002 Aqueous electrolytes
• CPC Class Codes: H01M 2300/0014 Alkaline electrolytes
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0414 by screen printing
• CPC Class Codes: H01M 4/06 Electrodes for primary cells
• CPC Class Codes: H01M 4/08 Processes of manufacture
• CPC Class Codes: H01M 4/244 Zinc electrodes
• CPC Class Codes: H01M 4/26 Processes of manufacture
• CPC Class Codes: H01M 4/50 of manganese
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/623 fluorinated polymers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 50/121 Organic material
• CPC Class Codes: H01M 50/42 Acrylic resins
• CPC Class Codes: H01M 50/463 : Separators, membranes or diaphragms characterised by their shape
• CPC Class Codes: H01M 50/497 : Ionic conductivity
• CPC Class Codes: H01M 6/045 : characterised by aqueous electrolyte
• CPC Class Codes: H01M 6/12 : with flat electrodes
• CPC Class Codes: H01M 6/22 : Immobilising of electrolyte
• CPC Class Codes: H01M 6/40 : Printed batteries , e.g. thin film batteries
• 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
• CPC Class Codes: Y10T 29/49108 : Electric battery cell making
• CPC Class Codes: Y10T 29/4911 : including sealing
• CPC Class Codes: Y10T 29/49114 : including adhesively bonding
• CPC Class Codes: Y10T 29/49115 : including coating or impregnating

Abstract

A flat, flexible electrochemical cell is provided. The within invention describes various aspects of the flat, flexible electrochemical cell. A printed anode is provided that obviates the need for a discrete anode current collector, thereby reducing the size of the battery. An advantageous electrolyte is provided that enables the use of a metallic cathode current collector, thereby improving the performance of the battery. Printable gelled electrolytes and separators are provided, enabling the construction of both co-facial and co-planar batteries. Cell contacts are provided that reduce the potential for electrolyte creepage in the flat, flexible electrochemical cells of the within invention.

Claims

1. A battery including an electrochemical cell, said electrochemical cell comprising:

a substrate having an inner surface and a plurality of laminated layers, wherein said plurality of laminated layers includes a high-moisture barrier layer;

a first printed ink electrochemical layer covering some portion of said inner surface;

a second printed ink electrochemical layer covering another portion of said inner surface;

an electrolyte layer substantially covering and in contact with both said first electrochemical layer and said second electrochemical layer;

a covering layer covering said electrolyte layer and bound to said substrate to form a pouch for sealing said electrolyte layer in an interior of said cell, wherein the covering layer is sealed to the substrate at at least one seal junction to form a seal area bounded by inner and outer boundaries;

at least one electrode inner current collector having first and second opposing ends, wherein the first end of the current collector contacts one of the first and second electrochemical layers and the second end of the current collector is positioned within the seal junction; and

at least one electrode external terminal having first and second ends, wherein the first end of the external terminal is positioned within the seal junction and the second end of the external terminal is positioned external the seal junction, wherein the internal current collector and the external terminal are discrete structures, and wherein the second end of the current collector and the first end of the external terminal terminate within the seal junction at a location distanced from the inner and outer boundaries of the seal junction.

2. The battery of claim 1 further comprising a plurality of said electrochemical cells electrically connected together all sharing said substrate in common.

3. The battery of claim 1, wherein said plurality of laminated layers further includes a structural layer having an integrated barrier and/or a heat sealing layer.

4. The battery of claim 1, wherein said plurality of laminated layers further includes an inner layer including a polymer film and/or a heat sealing coating;

and wherein said high-moisture barrier layer comprises a polymer.

5. The battery of claim 1, wherein said plurality of laminated layers include a metalized layer.

6. The battery of claim 1, wherein said first printed ink of said first electrochemical layer is comprised of a cured and/or dried ink.

7. The battery of claim 6, wherein said first printed ink includes one or more of manganese dioxide and carbon.

8. The battery of claim 6, wherein said second electrochemical layer is comprised of a cured and/or dried second printed ink.

9. The battery of claim 8, wherein said second printed ink includes zinc.

10. The battery of claim 6, wherein the at least one electrode internal current collector comprises a first electrically conducting collector layer between said first electrochemical layer and said substrate.

11. The battery of claim 10, wherein said first electrically conducting collector layer is comprised of a cured and/or dried conductive ink.

12. The battery of claim 11, wherein the at least one electrode internal current collector comprises a second electrically conducting collector layer between said second electrochemical layer and said substrate.

13. The battery of claim 12, wherein said second conducting collector layer is comprised of a cured and/or dried conductive ink.

14. The battery of claim 1, wherein the at least one electrode internal current collector comprises a first electrically conducting collector layer between said first electrochemical layer and said substrate.

15. The battery of claim 14, wherein said first electrically conducting collector layer is comprised of a cured and/or dried conductive ink.

16. The battery of claim 15 further comprising a second electrically conducting collector layer between said second electrochemical layer and said substrate.

17. The battery of claim 1, wherein said battery includes series and/or parallel connections for connecting to an electronic application circuit thereby allowing the use of unit cells.

18. The battery of claim 1, wherein said electrolyte layer includes an absorbent separator layer soaked in electrolyte.

19. The battery of claim 18, wherein said electrolyte includes one or more of:

zinc chloride, ammonium chloride, zinc acetate, potassium hydroxide and sodium hydroxide.

20. The battery of claim 18, wherein said electrolyte includes a polymeric thickener and/or gel comprising polyethylene oxide.

21. The battery of claim 1, wherein said first printed ink of said first electrochemical layer is comprised of a polymer binder.

22. The battery of claim 1, wherein said first printed ink of said first electrochemical layer is comprised of a polymer binder including one or more of polyvinylpyrrolidone and polyethylene oxide.

23. The battery of claim 1, wherein said first printed ink of said first electrochemical layer is comprised of manganese dioxide (MnO₂), carbon and a polymer binder.

24. The battery of claim 6, wherein said ink of said first electrochemical layer includes a polymer binder.

25. The battery of claim 6, wherein said ink contains manganese dioxide (MnO₂), carbon and a polymer binder.

26. The battery of claim 6, wherein said ink of said first electrochemical layer includes a polymer binder including one or more of polyvinylpyrrolidone and polyethylene oxide.

27. The battery of claim 8, wherein said ink of said first electrochemical layer includes a polymer binder.

28. The battery of claim 8, wherein said ink contains manganese dioxide (MnO₂), carbon and a polymer binder.

29. The battery of claim 8, wherein said ink of said first electrochemical layer includes a polymer binder including one or more of polyvinylpyrrolidone and polyethylene oxide.

30. The battery of claim 1, wherein said substrate comprises a substrate material defining upper and lower substrate layers, including a multi-layer laminate and having an outer surface and the inner surface, wherein said at least one electrode internal current collector comprises a collector layer including a conductive cured and/or dried conductive ink at least partially covering said inner surface, wherein the first printed ink comprises a cured and/or dried ink, at least partially covering said collector layer, and wherein the covering layer comprises a connecting layer for connecting a portion of an outer perimeter of said inner surface to an outer perimeter of a second surface to bind said first inner surface to the second surface, thereby forming the pouch for containing the electrolyte layer in the interior of said cell.

31. The battery of claim 30, wherein the upper and lower substrate layers are formed of two separate sheets.

32. The battery of claim 30, wherein said ink of said first electrochemical layer includes a polymer binder.

33. The battery of claim 30, wherein said ink contains manganese dioxide (MnO₂), carbon and a polymer binder.

34. The battery of claim 30, wherein said ink of said first electrochemical layer includes a polymer binder including one or more of polyvinylpyrrolidone and polyethylene oxide.

35. The battery of claim 1, wherein the second electrochemical layer is coplanar with the first electrochemical layer.

36. The battery of claim 1, wherein the electrochemical cell further comprises:

a printed collector covering a first portion of said inner surface, said collector having a primary portion, and an extension portion extending toward an edge of said inner surface;

a printed metallic contact partially covering said extension portion of said collector;

a heat-sensitive adhesive partially covering said inner surface and partially covering said collector;

a printed first electrode comprising the first electrochemical layer and covering at least a portion of said primary portion of said collector;

a second electrode comprising the second electrochemical layer and covering a second portion of said inner surface and adjacent to said collector, and having a primary portion and an extension portion extending toward said edge of said inner surface; and

a separator/electrolyte layer comprising the electrolyte layer and substantially covering said first electrode and substantially covering said second electrode primary portion, wherein the covering layer has an inner surface covering all of said collector, said first electrode, said second electrode primary portion, said separator/electrolyte layer, and said substrate, and wherein a part of said covering layer is sealed to a part of said inner surface using said adhesive, said covering layer also being sealed over said collector extension portion and said second electrode extension portion thereby forming the pouch, and wherein electrical access to said first electrode and said second electrode is provided through said pouch.

37. The battery of claim 36, wherein said plurality of laminated layers includes a structural layer having an integrated barrier and/or a heat sealing layer.

38. The battery of claim 36, wherein said plurality of laminated layers includes an inner layer including a polymer film and/or a heat sealing coating.

39. The battery of claim 38, wherein said covering layer sealed over said collector extension portion and said second electrode extension portion is heat sealed on a perimeter of said cell by means of the heat seal layer of the laminated substrate.

40. The battery of claim 36, wherein said plurality of laminated layers includes a metalized coated moisture barrier layer.

41. The battery of claim 36, wherein said collector is a highly conductive ink including carbon.

42. The battery of claim 36, wherein said ink of said first electrode comprises electrolytic manganese dioxide and graphite.

43. The battery of claim 36, wherein the separator/electrolyte includes a starch coated Kraft paper and an aqueous solution comprising zinc chloride.

44. The battery of claim 36, wherein the separator/electrolyte includes a starch coated Kraft paper and an aqueous solution comprising zinc acetate.

45. The battery of claim 36, wherein the separator/electrolyte includes an aqueous solution of zinc chloride.

46. The battery of claim 36, wherein said covering layer sealed over said collector extension portion and said second electrode extension portion is sealed by means of a heat-sensitive adhesive and/or a pressure sensitive adhesive.

47. The battery of claim 1, wherein the thickness of said printed layers are between 10 and 250 microns.

48. The battery of claim 1, wherein the at least one electrode inner current collector is a cathode current collector and said first printed electrochemical layer comprises a printed anode and wherein said inner surface comprises a nonconductive substrate, wherein said printed anode is printed directly onto said substrate and said electrochemical cell is devoid of a distinct anode current collector.

49. The battery of claim 48, wherein the printed anode comprises a printed zinc ink.

50. The battery of claim 1, wherein said internal current collector and said external terminal are not in physical contact within the seal junction.

51. A flat flexible battery comprising a substrate, first and second electrodes separately layered on the substrate, at least one electrode internal current collector having first and second opposing ends and at least one electrode external terminal having first and second ends, an electrolyte layer covering the first and second electrodes and a flexible nonconductive packaging material, said packaging material sealed together at at least one seal junction to form a seal area bounded by inner and outer boundaries and a sealed housing surrounding said electrodes, wherein said internal current collector and said external terminal are discrete structures, and wherein said internal current collector first end contacts one of said electrodes, said internal current collector second end is positioned within said seal junction, said external terminal first end is positioned within said seal junction and said external terminal second end is positioned external said seal junction and external said housing, wherein the second end of the at least one electrode internal current collector is positioned within said seal junction at a location distanced from the inner and outer boundaries of the seal junction, and wherein the external terminal first end is positioned within the seal junction at a location distanced from the inner and outer boundaries of the seal junction.