Thin printable flexible electrochemical cell and method of making the same

• US 8,722,235 B2
• Filed: 04/20/2005
• Issued: 05/13/2014
• Est. Priority Date: 04/21/2004
• Status: Active Grant

• Current Assignee: Blue Spark Innovations LLC
• Original Assignee: Blue Spark Technologies, Inc.
• Inventors: Tucholski, Gary R., Russell, Ed T., McComsey, Dennis W.
• Primary Examiner(s): Conley, Helen O
• Application Number:
  US11/110,202
• Publication Number:
  US 20050260492A1
• Time in Patent Office: 3,310 Days
• Field of Search: 429/122, 429/176, 429/163, 429/185
• US Class Current: 429/176
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• CPC Class Codes: H01M 2300/0014 Alkaline electrolytes
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/06 Electrodes for primary cells
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/66 Selection of materials
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 4/76 Containers for holding the active material, e.g. tubes, capsules
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: H01M 6/5011 for several cells simultaneously or successively
• 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 29/49115 including coating or impregnating

Abstract

A thin printed flexible electrochemical cell with a high moisture and oxygen barrier polymer film sealed and folded package featuring a printed cathode deposited on a highly conductive carbon printed cathode collector with a zinc foil anode or printed anode placed adjacent to the cathode. After the cell components are added to the special laminated polymer substrate, the web is processed automatically on a modified high-speed commercial horizontal pouch filling machine to complete the cell assembly process. In this process a starch coated paper separator layer may be inserted over the anode and the cathode, and then the aqueous electrolyte solution is added to the cell. To complete the process, all four edges of the cell are heat sealed to confine the cell components within the cell cavity and each cell is trimmed off the continuous web.

Claims

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

a substrate having an inner surface;

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

a second electrochemical layer covering another portion of said inner surface and adjacent to said first electrochemical layer;

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

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,

and

wherein said covering layer comprises a plurality of laminated layers that includes an oxide coated moisture barrier layer having a moisture vapor transmission rate that permits moisture vapor to escape through said plurality of laminated layers of the covering layer to an external environment, and does not include a metal foil layer.

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 includes a structural layer comprising said oxide coated moisture barrier layer and/or a heat sealing layer.

4. The battery of claim 1, wherein said plurality of laminated layers include:

an inner layer including a polymer film and/or a heat sealing coating;

said oxide coated moisture barrier layer;

a first adhesive layer for connecting said inner layer to said oxide coated moisture barrier layer;

an outer structural layer including an orientated polyester; and

a second adhesive layer for connecting said oxide coated moisture barrier layer to said outer structural layer.

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

6. The battery of claim 5, wherein said ink includes one or more of manganese dioxide, carbon, NiOOH, silver oxides Ag₂O and/or AgO, HgO, oxygen O₂ in the form of an air cell, and Vanadium oxide VO₂.

7. The battery of claim 5, wherein said second electrochemical layer is comprised of a strip of material laminated to said substrate.

8. The battery of claim 7, wherein said strip of material includes zinc.

9. The battery of claim 5, wherein said second electrochemical layer is comprised of a cured and/or dried ink.

10. The battery of claim 9, wherein said ink includes one or more of zinc, nickel, cadmium, metal hydrides of the AB₂ and the AB₃ types, iron, and FeS₂.

11. The battery of claim 5, further comprising a first collector layer between said first electrochemical layer and said substrate, said first collector layer having a higher conductivity than said first electrochemical layer and said substrate.

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

13. The battery of claim 12, further comprising a second collector layer between said second electrochemical layer and said substrate, said second collector layer having a higher conductivity than said second electrochemical layer and said substrate.

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

15. The battery of claim 1, further comprising a first collector layer between said first electrochemical layer and said substrate, said first collector layer having a higher conductivity than said first electrochemical layer and said substrate.

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

17. The battery of claim 16, further comprising a second collector layer between said second electrochemical layer and said substrate, said second collector layer having a higher conductivity than said second electrochemical layer and said substrate.

18. 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.

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

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

zinc chloride, ammonium chloride, zinc acetate, zinc bromide, zinc Iodide, zinc tartrate, zinc per-chlorate, potassium hydroxide, and sodium hydroxide.

21. The battery of claim 19, wherein said electrolyte includes a polymeric thickener and/or gel having one or more of:

carboxymethylcellulose;

polyvinyl alcohol;

a starch and/or modified starch;

ethyl and/or hydroxyl-ethyl cellulose;

methyl cellulose;

polyethylene oxide; and

polyacryamide.

22. The battery of claim 1, wherein one or both of said first electrochemical layer and said second electrochemical layer have been modified via treatment with corona and/or plasma.

23. The battery of claim 1, wherein:

the substrate includes a multi-layer laminate having;

an outer surface, and

the inner surface, wherein

said substrate forms a fold over itself, such that said inner surface forms a first inner side and a second inner side on opposite sides of an interior of said cell, and said outer surface defines a first outer side and a second outer side on opposite sides of the exterior of said battery cell;

the cell further comprising a collector layer, including a first cured and/or dried conductive ink, at least partially covering said first inner side;

wherein the first electrochemical layer includes a second cured and/or dried ink, at least partially covering said collector layer;

wherein the second electrochemical layer is disposed on one of said first inner side and said second inner side, wherein, if said second electrochemical layer is on said first inner side, said second electrochemical layer is adjacent to said first electrochemical layer;

wherein the electrolyte layer is disposed between said first inner side and said second inner side; and

the cell further comprising a connecting layer for connecting a portion of an outer perimeter of said first inner side to a portion of an outer perimeter of said second inner side to bind said first inner side to said second inner side for holding said substrate in the folded position, thereby forming said pouch for containing said electrolyte in the interior of said cell.

24. The battery of claim 1, wherein said first electrochemical layer includes an ink having a polymer binder of a class of high molecular weight that exceeds 950,000-grams/mole.

25. The battery of claim 1, wherein said first electrochemical layer includes an ink having a polymer binder including one or more of polyvinylpyrrolidone, polyvinyl alcohol, a starch, a modified starch, ethyl cellulose, hydroxy-ethyl cellulose;

methyl cellulose, polyethylene oxide, polyacryamide, and Teflon.

26. The battery of claim 1, wherein said first electrochemical layer includes an ink containing manganese dioxide (MnO2), carbon, and a polymer binder.

27. The battery of claim 26, wherein said polymer binder contains hydroxy-ethyl cellulose.

28. The battery of claim 5, wherein said ink of said first electrochemical layer includes a polymer binder of a class of high molecular weight that exceeds 950,000-grams/mole.

29. The battery of claim 5, wherein said ink contains manganese dioxide (MnO2), carbon, and a polymer binder.

30. The battery of claim 29, wherein said polymer binder contains hydroxy-ethyl cellulose.

31. The battery of claim 5, wherein said ink of said first electrochemical layer includes a polymer binder including one or more of polyvinylpyrrolidone, polyvinyl alcohol, a starch, a modified starch, ethyl cellulose, hydroxy-ethyl cellulose;

methyl cellulose, polyethylene oxide, polyacryamide, and Teflon.

32. The battery of claim 9, wherein said ink of said first electrochemical layer includes a polymer binder of a class of high molecular weight that exceeds 950,000-grams/mole.

33. The battery of claim 9, wherein said ink contains manganese dioxide (MnO2), carbon, and a polymer binder.

34. The battery of claim 33, wherein said polymer binder contains hydroxy-ethyl cellulose.

35. The battery of claim 9, wherein said ink of said first electrochemical layer includes a polymer binder including one or more of polyvinylpyrrolidone, polyvinyl alcohol, a starch, a modified starch, ethyl cellulose, hydroxy-ethyl cellulose;

methyl cellulose, polyethylene oxide, polyacryamide, and Teflon.

36. The battery of claim 23, wherein said ink of said first electrochemical layer includes a polymer binder of a class of high molecular weight that exceeds 950,000-grams/mole.

37. The battery of claim 23, wherein said ink contains manganese dioxide (MnO2), carbon, and a polymer binder.

38. The battery of claim 37, wherein said polymer binder contains hydroxy-ethyl cellulose.

39. The battery of claim 23, wherein said ink of said first electrochemical layer includes a polymer binder including one or more of polyvinylpyrrolidone, polyvinyl alcohol, a starch, a modified starch, ethyl cellulose, hydroxy-ethyl cellulose;

methyl cellulose, polyethylene oxide, polyacryamide, and Teflon.

40. The battery of claim 1, wherein:

the substrate includes a multi-layer laminate having the inner surface, wherein said substrate forms a fold over itself, such that said inner surface forms a first inner side and a second inner side on opposite sides of the interior of said cell;

the first electrochemical layer is on at least one of said first inner side and said second inner side, including a cured or dried ink having manganese dioxide (MnO2), carbon, and a polymer binder containing hydroxy-ethyl cellulose; and

the second electrochemical layer is on the same inner side as said first electrochemical layer.

41. The battery of claim 1, wherein:

the substrate includes a multi-layer laminate having the inner surface, wherein said substrate forms a fold over itself, such that said inner surface forms a first inner side and a second inner side on opposite sides of the interior of said cell;

the first electrochemical layer is on at least one of said first inner side and said second inner side of said substrate;

the second electrochemical layer is on at least one of said first inner side and said second inner side of said substrate and coplanar with said first electrochemical layer; and

the cell further comprising at least one sealing layer, wherein

said substrate and said at least one sealing layer form said pouch for substantially enclosing all of said layers within said pouch.

42. The battery of claim 1, further comprising:

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

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

wherein the second electrochemical layer is a second electrode 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;

wherein the electrolyte layer substantially covers said first electrode and substantially covers 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 electrolyte layer, and said substrate, said covering layer having a first contact hole for providing access to said contact and also having a second contact hole for providing access to said extension portion of said second electrode, 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 sealed pouch, and

wherein said first contact hole provides electrical access to said first electrode and said second contact hole provides electrical access to said second electrode.

43. The battery of claim 42, wherein said plurality of laminated layers includes a structural layer comprising said oxide coated moisture barrier layer and/or a heat sealing layer.

44. The battery of claim 42, wherein said plurality of laminated layers includes:

an inner layer including a polymer film and/or a heat sealing coating;

said oxide coated moisture barrier layer;

a first adhesive layer for connecting said inner layer to said oxide coated moisture barrier layer;

an outer structural layer including an orientated polyester; and

a second adhesive layer for connecting said oxide coated moisture barrier layer to said outer structural layer.

45. The battery of claim 44, wherein said covering layer sealed over said collector extension portion and said second electrode extension portion is sealed by means of heat on a perimeter of said cell as well as around the contact holes by means of the heat seal layer of the laminated substrate.

46. The battery of claim 42, wherein said plurality of laminated layers includes the oxide coated moisture barrier layer.

47. The battery of claim 42, wherein said collector is a highly conductive ink including carbon, and having a resisitivity of less than 50 ohms per square per mil.

48. The battery of claim 47, wherein said ink used for said first electrode has a weight composition of about 20-60% EMD K60MnO2, 5-25% KS6 Graphite, 0.1-0.70% hydroxyl-ethyl cellulose in 0.05-3% aqueous solution, and with a total of 30-50% water.

49. The battery of claim 42, wherein said second electrode includes an at least 95% pure zinc foil that is laminated to the substrate.

50. The battery of claim 42, wherein the separator/electrolyte includes a starch coated Kraft paper and about 23-32% (weight) aqueous solution of zinc chloride with about 0-0.8% (weight) of carboxymethylcellulose (CMC).

51. The battery of claim 42, wherein the separator/electrolyte includes a starch coated Kraft paper and an about 23-32% (weight) aqueous solution of zinc acetate with about 0-0.8% (weight) of carboxymethylcellulose (CMC).

52. The battery of claim 42, wherein the separator/electrolyte includes an about 23-32% (weight) aqueous solution of zinc chloride with about 0.0-0.8% (weight) of carboxymethylcellulose (CMC).

53. The battery of claim 42, wherein said covering layer sealed over said collector extension portion and said second electrode extension portion is sealed by means of a printable heat sensitive adhesive and/or a pressure sensitive adhesive.

54. The battery of claim 42, wherein said covering layer sealed over said collector extension portion and said second electrode extension portion is sealed by means of a printable heat sensitive adhesive and/or a pressure sensitive adhesive in a full or partial picture frame pattern.

55. The battery of claim 1, wherein:

the substrate is flexible and includes a non-conductive surface;

the first electrochemical layer is a cathode layer covering said non-conductive surface;

the second electrochemical layer is an anode layer covering said non-conductive surface, said anode layer being substantially coplanar with, and adjacent to, said cathode;

the electrolyte layer covers at least a portion of said anode and also covers at least a portion of said cathode, and

the cell further comprising at least one sealing layer, wherein said flexible substrate is comprised of a sheet of material folded over itself to form said sealing layer, and wherein said substrate and said at least one sealing layer form said pouch for substantially enclosing all of said layers within said pouch.

56. The battery of claim 55, wherein one or both of said cathode layer and said anode layer includes an ink.

57. The battery of claim 55, further comprising a collector layer between said non-conductive surface and one of said cathode and said anode.

58. The battery of claim 57, wherein one or more of said cathode layer, said anode layer, and said collector layer includes an ink.

59. The battery of claim 58, wherein said substrate includes a contact opening for providing electrical access to at least one of said cathode and said anode.

60. The battery of claim 58, wherein said ink includes a polymer binder having one or more of polyvinylpyrrolidone, polyvinyl alcohol, a starch, a modified starch, ethyl cellulose, hydroxy-ethyl cellulose;

methyl cellulose, polyethylene oxide, polyacryamide, and Teflon.

61. The battery of claim 57, wherein at least one of said cathode layer and said anode layer includes a first ink, and wherein said collector layer includes a second ink having a conductivity higher than said first ink.

62. The battery of claim 61, wherein said substrate includes a first contact hole therethrough and a second contact hole therethrough for providing electrical access to said cathode and said anode, respectively.

63. The battery of claim 61, wherein said first ink includes a polymer binder containing hydroxy-ethyl cellulose.

64. The battery of claim 1, wherein said substrate includes a first contact hole therethrough and a second contact hole therethrough for providing electrical access to said first and second electrochemical layers, respectively, and both of the first and second contact holes are located on a major surface of the substrate.

65. The battery of claim 64, wherein said first and second contact holes include at least one open side.

66. The battery of claim 1, wherein said substrate is comprised of a sheet of material folded over itself to form said covering layer, and wherein said inner surface is bound to itself to form said pouch.