Thin printable electrochemical cell utilizing a “picture frame” and methods of making the same

• US 8,029,927 B2
• Filed: 03/17/2006
• Issued: 10/04/2011
• Est. Priority Date: 03/22/2005
• Status: Active Grant

• Current Assignee: Blue Spark Innovations LLC
• Original Assignee: Blue Spark Technologies, Inc.
• Inventors: Tucholski, Gary R.
• Primary Examiner(s): Crepeau; Jonathan
• Assistant Examiner(s): DOUYETTE, KENNETH J
• Application Number:
  US11/378,520
• Publication Number:
  US 20060216586A1
• Time in Patent Office: 2,027 Days
• Field of Search: 429/162, 429/163, 429/185, 429/246, 429/234, 429/152, 429/224, 429/118, 429/127, 429/134, 429/93, 429/149, 429/111, 429/117, 429/213, 429/421, 429/218.1, 429/632, 429/229, 524/423, 320/107, 600/345, 607/1, 296/235
• US Class Current: 429/162
• CPC Class Codes: H01M 10/0436 Small-sized flat cells or batteries for portable equipment
• CPC Class Codes: H01M 10/365 Zinc-halogen accumulators
• CPC Class Codes: H01M 10/425 Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing printed circuits H05K1/00
• CPC Class Codes: H01M 12/085 Zinc-halogen cells or batteries
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/42 Alloys based on zinc
• CPC Class Codes: H01M 4/50 of manganese
• 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 50/105 Pouches or flexible bags
• CPC Class Codes: H01M 50/119 Metals
• CPC Class Codes: H01M 50/121 Organic material
• CPC Class Codes: H01M 50/124 having a layered structure
• CPC Class Codes: H01M 50/126 comprising three or more layers
• CPC Class Codes: H01M 50/133 Thickness
• CPC Class Codes: H01M 50/186 characterised by the disposition of the sealing members
• CPC Class Codes: H01M 50/193 Organic material
• CPC Class Codes: H01M 50/211 adapted for pouch cells
• CPC Class Codes: H01M 50/24 adapted for protecting batteries from their environment, e.g. from corrosion thermal insulation H01M10/658
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: H01M 6/42 : Grouping of primary cells into batteries H01M6/40 takes precedence
• CPC Class Codes: H01M 6/46 : of flat cells
• 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 29/49115 : including coating or impregnating

Abstract

A thin printed flexible electrochemical cell, and its method of manufacture, using a “picture frame” structure sealed, for example, with a high moisture and oxygen barrier polymer film and featuring, for example, a printed cathode deposited on an optional, highly conductive carbon printed cathode collector with a printed or a foil strip anode placed adjacent to the cathode. A viscous or gelled electrolyte is dispensed and/or printed in the cell, and a top laminate can then be sealed onto the picture frame. Such a construction could allow the entire cell to be made on a printing press, for example, as well as gives the opportunity to integrate the battery directly with an electronic application, for example.

Claims

1. A device comprising a flat, thin electrochemical cell for generating an electrical current, said cell including:

a first substrate layer comprising a polymeric film and an oxide barrier layer having a gas transmission rate that permits gas to escape;

a second substrate layer comprising a polymeric film and an oxide barrier layer having a gas transmission rate that permits gas to escape;

a cathode layer provided on at least one of said first substrate layer and said second substrate layer;

an anode layer provided on at least one of said first substrate layer and said second substrate layer;

an electrolyte layer in contact with said cathode layer and also in contact with said anode layer; and

a frame provided substantially around a perimeter of said cell and connecting said first substrate layer to said second substrate layer;

said frame together with said first and second substrate layers defining an inner space that encloses said electrolyte layer and at least portions of said cathode and anode layers.

2. The device of claim 1, wherein said frame is comprised of a polyester sheet having two adhesive layers, one on each side of said frame, said adhesive layer for adhesively connecting said first substrate layer to said second substrate layer.

3. The device of claim 2, wherein said adhesive layers utilize a release liner prior to the construction of said device.

4. The device of claim 1, further comprising a cathode collector layer provided between said substrate and said cathode layer.

5. The device of claim 4, wherein one or both of said anode layer and said cathode layer are comprised of a dried or cured ink.

6. The device of claim 5, wherein only one of said cathode layer and said anode layer is comprised of a dried or cured ink, and wherein the other of said cathode layer and said anode layer is comprised of a strip of material.

7. The device of claim 6, wherein said strip of material includes zinc.

8. The device of claim 6, where said strip of material is a laminate including an adhesive layer.

9. The device of claim 8, wherein said strip of material includes zinc.

10. The device of claim 1, wherein said frame provides means of accessing one or both of said cathode layer and said anode layer through said frame.

11. The device of claim 10, wherein said means of accessing is comprised of through-holes through said frame, and wherein said cell further comprises an adhesive layer for sealing said frame to one or both of said first substrate layer and said second substrate layer, said adhesive layer also for sealing said through-holes.

12. The device of claim 1, said cell further comprising an adhesive layer for sealing said frame to one or both of said first substrate layer and said second substrate layer.

13. The device of claim 12, wherein said adhesive layer is comprised of a sealing caulk.

14. The device of claim 1,

wherein said frame is about as thick as the sum of a thickness of said electrolyte layer and at least one of said anode layer and said cathode layer, and wherein

said device is substantially flat and of a thickness of about that of the thickness of said frame added to the thickness of each of said substrate layers.

15. The device of claim 1, said first substrate layer and said second substrate each further comprising a heat sealing layer.

16. The device of claim 1, further comprising an electronic component formed concurrently with said cell.

17. The device of claim 1, further comprising a plurality of said cells electrically connected together to form a substantially flat battery.

18. The device of claim 17, wherein said plurality of cells share at least a portion of the same frame.

19. The device of claim 1, wherein said anode layer and said cathode layer are both provided on the same one of said first substrate layer and said second substrate layer, such that said anode layer and said cathode layer are substantially co-planar.

20. The device of claim 1, wherein said anode layer and said cathode layer are arranged in a co-facial manner.

21. The device of claim 1, wherein said anode layer and said cathode layer are arranged in a co-planar manner.

22. The device of claim 1, said electrolyte layer comprising a gel or liquid.

23. The device of claim 1, wherein said inner space contains at least a majority of each of said cathode layer and said anode layer.

24. The device of claim 1, wherein said frame is comprised of an ink.

25. The device of claim 1, wherein said frame is comprised of a UV cured dielectric material.

26. The device of claim 1, said frame being a unitary frame that is substantially thicker than each one of said cathode layer, said anode layer, and said electrolyte layer.

27. The device of claim 1, further comprising a separator layer disposed within said inner space, in between said cathode and anode layers.

28. The device of claim 1, further comprising a starch ink printed over and in contact with at least one of said anode and cathode layers.

29. The device of claim 28, said starch ink comprising an electrolyte.

30. The device of claim 1, said electrolyte being in the form of a solution having a freezing point below −

20°

C.

31. The device of claim 1, said electrolyte comprising an aqueous solution of 23-43% ZnCl₂ and 0.1-2% carboxymethylcellulose.

32. The device of claim 1, said cathode layer being printed from an aqueous composition comprising about 20-60% manganese dioxide, about 2-25% graphite and about 0.5%-15% of an aqueous solution of comprising about 20-60% polyvinylpyrrolidone and about 0.1-20% of distilled water to provide a dry lay down weight of about 0.03-0.25 grams per square inch.

33. The device of claim 1, said frame comprising a cured or dried adhesive ink.

34. The device of claim 1, said frame comprising a UV cured dielectric adhesive material.

35. The device of claim 1, said electrolyte layer comprising a separator soaked with an electrolyte solution, said separator being in contact with said cathode and anode layers.

36. The device of claim 35,

wherein said frame is about as thick as the sum of the thickness of said electrolyte layer and at least one of said anode layer and said cathode layer, and wherein

said electrochemical cell has a thickness of about that of the thickness of said frame added to the thickness of each of said substrate layers.

37. The device of claim 1, said frame comprising pressure sensitive adhesive.

38. The device of claim 1, said electrochemical cell having a substantially uniform thickness.

39. The device of claim 1, said first substrate barrier layer being effective to prevent excessive moisture transmission therethrough.

40. A method of manufacturing a device including an electrochemical cell, said method comprising the step of forming said cell, said forming including the steps of:

providing a first substrate layer and a second substrate layer, at least one of which including a laminated web having a plurality of layers;

printing one of a cathode layer and an anode layer on one of said first substrate layer and said second substrate layer;

providing, by printing or some other process, the other of said cathode layer and said anode layer on one of said first substrate layer and said second substrate layer;

providing a frame on one of said first substrate layer and said second substrate layer;

providing an electrolyte layer, said electrolyte layer comprising a viscous liquid; and

connecting the other of said first substrate layer and said second substrate layer to said frame to form an inner substantially sealed space containing said cathode layer, said anode layer, and said electrolyte layer;

to thereby produce the device of claim 1.

41. The method of claim 40, further comprising the step of forming an electrically powered component, concurrent with the forming of said cell, wherein said component is included in said device.

42. The method of claim 40, wherein said frame is printed on said one of said first substrate layer and said second substrate layer.

43. The device of claim 26, said frame being connected to said lower and upper substrate layers via respective intermediate adhesive layers.

44. A device comprising a flat electrochemical cell for generating an electrical current, said cell including:

a first substrate layer comprised of a plurality of laminated layers including an oxide barrier layer having a gas transmission rate that permits gas to escape;

a second substrate layer;

a cathode layer provided on at least one of said first substrate layer and said second substrate layer;

an anode layer provided on at least one of said first substrate layer and said second substrate layer;

an electrolyte layer in contact with said cathode layer and also in contact with said anode layer; and

a frame connecting and sealing said first substrate layer to said second substrate layer to form an inner space containing said electrolyte layer, and also containing at least a major portion of said cathode layer and at least a major portion of said anode layer within said inner space, wherein

at least one of said anode layer and said cathode layers is comprised of a cured or dried ink.

45. The device of claim 44, wherein only one of said cathode layer and said anode layer is comprised of a dried or cured ink, and wherein the other of said cathode layer and said anode layer is comprised of a strip of material.

46. The device of claim 44, wherein said frame provides means of accessing one or both of said cathode layer and said anode layer through said frame.

47. The device of claim 44, further comprising an electronic component manufactured concurrently with said cell.

48. The device of claim 44, further comprising a plurality of said cells electrically connected together to form a battery.

49. The device of claim 44, wherein said anode layer and said cathode layer are both provided on the same one of said first substrate layer and said second substrate layer and wherein said anode layer and said cathode layer are substantially co-planar.

50. The device of claim 49, wherein only one of said cathode layer and said anode layer is comprised of a dried or cured ink, and wherein the other of said cathode layer and said anode layer is comprised of a strip of material.

51. The device of claim 44, wherein said device is formed into a substantially flat shape of a thickness about that of the thickness of said frame added to the thickness of each of said substrate layers.

52. The device of claim 44, wherein one or both of said substrate layers include all of a structural layer, an oxide barrier layer, and a heat sealing layer.

53. The device of claim 44 wherein one or both of (1) a cathode collector layer is provided between said cathode layer and said at least one of said first substrate layer and said second substrate layer upon which said cathode layer is provided;

and (2) an anode collector layer is provided between said anode layer and said at least one of said first substrate layer and said second substrate layer upon which said anode layer is provided.

54. The device of claim 44, said electrolyte layer comprising a separator layer soaked with electrolyte for keeping both said anode layer and said cathode layer wet with said electrolyte.

55. The device of claim 44, wherein said anode layer and said cathode layer are arranged in a co-facial manner.

56. The device of claim 44, said second substrate comprising a plurality of laminated layers.

57. The device of claim 44, said electrolyte layer further comprising a separator in contact with said cathode and anode layers, said separator being soaked with a liquid comprising an electrolyte.

58. The device of claim 44, said electrochemical cell having a substantially uniform thickness.

59. The device of claim 44, said first substrate barrier layer being effective to prevent excessive moisture transmission therethrough.

60. A device comprising a flat electrochemical cell for generating an electrical current, said cell including:

a first substrate layer;

a second substrate layer;

a cathode layer provided on said first substrate layer or said second substrate layer;

an anode layer provided the same of said first substrate layer and said second substrate layer as said cathode layer, wherein said anode layer and said cathode layer are thereby arranged in a co-planar manner;

an electrolyte layer in contact with said cathode layer and also in contact with said anode layer; and

a frame connecting and sealing said first substrate layer to said second substrate layer to form an inner space containing said electrolyte layer, and also containing at least a major portion of said cathode layer and at least a major portion of said anode layer within said inner space, wherein

at least one of said anode layer and said cathode layer is comprised of a cured or dried ink.

61. A battery comprising at least one cell, said at least one cell including:

a first substrate layer comprised of a plurality of laminated layers including at least a structural layer, an oxide barrier layer having a gas transmission rate that permits gas to escape, and a sealing layer;

a second substrate layer comprised of a plurality of laminated layers including at least a structural layer, an oxide barrier layer having a gas transmission rate that permits gas to escape, and a sealing layer;

a cathode collector layer provided on at least one of said first substrate layer and said second substrate layer;

a cathode layer provided on said cathode collector layer;

an anode layer provided on at least one of said first substrate layer and said second substrate layer or provided on an anode collector layer provided on at least one of said first substrate layer and said second substrate layer;

an electrolyte layer including an electrolyte in contact with said anode layer and said cathode layer; and

a frame around a perimeter of said cell for connecting said first substrate layer to said second substrate layer to form an inner space for containing said electrolyte within said inner space along with at least a portion of said anode layer and at least a portion of said cathode layer, wherein

said inner space is substantially sealed off from an exterior of said cell.

62. The battery of claim 61, wherein said electrolyte layer includes a separator layer for keeping both said anode layer and said cathode layer wet with said electrolyte.

63. The battery of claim 61, wherein said electrolyte layer includes a means for forming said electrolyte layer into a viscous liquid in contact with said anode layer and said cathode layer.

64. The battery of claim 61, wherein said cathode layer is comprised of an ink.

65. The battery of claim 64, wherein said cathode collector layer is comprised of a different ink than said cathode layer.

66. The battery of claim 65, wherein said anode layer is comprised of a strip including zinc.

67. The battery of claim 61, where at least a portion of said cathode collector layer faces at least a portion of said anode layer.

68. The battery of claim 61, wherein said anode layer is substantially coplanar with, and adjacent to, said cathode layer.

69. The battery of claim 61, wherein said frame includes:

an inner frame; and

an outer frame, wherein

a frame space is formed between said inner frame and said outer frame.

70. The battery of claim 69, wherein said frame space is sealed for containing said electrolyte within said cell should said inner frame develop a leak.

71. The battery of claim 61, wherein said cathode 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.

72. A label comprising the battery of claim 61 and further comprising an adhesive layer.

73. A medical device comprising the battery of claim 61.

74. The battery of claim 61, said frame being a unitary frame.