Double layer capacitor and its manufacturing method

• US 6,341,057 B1
• Filed: 06/30/2000
• Issued: 01/22/2002
• Est. Priority Date: 11/05/1997
• Status: Expired due to Fees

• Current Assignee: Danionics International A/S
• Original Assignee: Danionics A/S
• Inventors: Beck, Hans Christian, Schou, Michael, Nissen, Ole Stig
• Primary Examiner(s): Reichard, Dean A.
• Assistant Examiner(s): Ha, Nguyen T
• Application Number:
  US09/530,870
• Time in Patent Office: 571 Days
• Field of Search: 361/502, 361/517, 361/418, 361/523, 361/525, 361/503-506, 361/524, 428/209
• US Class Current: 361/502
• CPC Class Codes: H01G 11/28 arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
• CPC Class Codes: H01G 11/72 specially adapted for integration in multiple or stacked hybrid or EDL capacitors
• CPC Class Codes: H01G 11/84 Processes for the manufacture of hybrid or EDL capacitors, or components thereof
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y10T 428/24917 including metal layer

Abstract

A double layer capacitor and a method for producing the same wherein the double layer capacitor comprises a conductive coating based on binders of the melamine resin type such that the conductive coating is present at the interfaces between the current collectors and the electrodes. The double layer capacitor thus produced has good mechanical and chemical integrity and flexibility and is suitable for use in combination with batteries.

Claims

1. A double layer capacitor which comprises a conductive coating comprising a melamine resin binder, at the interfaces between current collectors and electrodes, the conductive coating is provided from a mixture composed essentially of:

5-50% by weight of carbon blacks;

5-20% by weight of graphite;

5-40% by weight of a melamine resin binder and polymerisation reaction partner;

25-85% by weight of solvent; and

0-10% by weight of auxiliary materials selected from the group consisting of dispersing agents, defoaming agents and rheological control agents.

2. A double layer capacitor according to claim 1, in which the carbon black of the conductive coating is selected from the group consisting of furnace blacks, acetylene blacks and lampblacks.

3. A double layer capacitor according to claim 1, wherein the graphite of the conductive coating has a particle size in the range of 0.5-20 μ

m.

4. A double layer capacitor according to claim 1, in which the polymerisation reaction partner is an alkyd resin.

5. A double layer capacitor according to claim 1, in which the solvent of the conductive coating mixture is selected from the group of alcohols R¹—

OH, wherein R¹ represents C₁-C₄ alkyl, and glycols and glycol ethers R²—

(OCHR³CH₂)_n—

OH, n=1-3, wherein R² represents hydrogen or C₁-C₄ alkyl and wherein R³ represents hydrogen or methyl.

6. A double layer capacitor according to claim 1, in which the auxiliary materials of the conductive coating mixture are selected from the group of non-ionic, anionic, cationic or amphoteric dispersing agents, preferably anionic dispersing agents, mineral oil or silicone oil defoaming agents, preferably silicone oil defoaming agents, organo clay, silica or castor oil derivative rheological control agents, preferably organo clay rheological control agents, or any mixture thereof.

7. A double layer capacitor which comprises a conductive coating comprising a melamine resin binder, at the interfaces between current collectors and electrodes and wherein the conductive coating comprises the XZ302 screen printing dye.

8. A method for the fabrication of a double layer capacitor comprising the steps of:

mixing carbon blacks and graphites in an alcohol, a glycol or glycol either with a polymerization reaction partner, a dispersing agent and defoaming agent to produce a mill base;

adding melamine resin and a rheological control agent to obtain a uniform conductive coating paste;

applying conductive coating paste onto a current collector by coating or printing to produce a conductive coating;

curing said conductive coating by heating to 100-150°

C. for 10-30 minutes;

preparing an electrode paste as described above from active carbon, binder, solvent and optionally graphite and auxiliary materials;

applying said electrode paste onto the conductive coating by coating or printing to produce a conductive coating-electrode laminate;

sandwiching between two conductive coating-electrode laminates a porous separator to form a capacitor laminate;

confining said capacitor laminate in a polymer coated metal pouch;

preparing the electrolyte solution by dissolving the electrolyte salt in the electrolyte solvent;

impregnating the capacitor laminate with the electrolyte solution;

sealing the pouch.

9. A method for the fabrication of a double layer capacitor according to claim 8, in which the coating or printing technique is a screen printing, gravure printing or a slot die coating technique.

10. A double layer capacitor, which comprises an ion-conducting phase, at least one electrode and at least one current collector having an interface with said at least one electrode, and a conductive coating comprising a melamine resin binder provided at said interface between said current collector and said at least electrode.

11. A double layer capacitor according to claim 10, wherein said melamine resin is an alkylated melamine formaldehyde resin.

12. A double layer capacitor according to claim 11, in which said melamine resin is a methylated melamine formaldehyde resin.

13. A double layer capacitor according to claim 10, wherein said conductive coating is provided from a mixture composed essentially of

5-50% by weight of carbon black;

5-20% by weight of graphite;

5-40% by weight of melamine resin binder and polymerization reaction partner;

25-85% by weight of solvent; and

0-10% by weight of auxiliary materials.

14. A double layer capacitor according to claim 13 wherein said auxiliary materials are selected from the group consisting of dispersing agents, defoaming agents and rheological control agents.

15. A double layer capacitor according to claim 14, wherein said conductive coating is provided from a mixture composed essentially of

10-40% by weight of carbon black;

5-15% by weight of graphite;

10-30% by weight of melamine resin binder and polymerization reaction partner;

30-74% by weight of solvent; and

1-5% by weight of auxiliary materials.

16. A double layer capacitor according to claim 14, wherein said conductive coating is provided from a mixture composed essentially of

20-25% by weight of carbon black;

10-15% by weight of graphite;

15-25% by weight of melamine resin binder and polymerization reaction partner;

35-53% by weight of solvent; and

2-5% by weight of auxiliary materials.

17. A double layer capacitor according to claim 13, wherein said carbon black is selected from the group consisting of furnace blacks, acetylene blacks and lampblacks.

18. A double layer capacitor according to claim 13, wherein said graphite has a particle size in the range of 0.5-20 μ

m.

19. A double layer capacitor according to claim 13, wherein said graphite has a particle size in the range of 0.5-10 μ

m.

20. A double layer capacitor according to claim 13, in which said polymerization reaction partner is an alkyd resin.

21. A double layer capacitor according to claim 13, wherein said solvent is selected from the group consisting of alcohols for formula R¹—

OH, wherein R¹ represents C₁-C₄ alkyl, and glycols and glycol ethers of formula R²—

(OCHR³CH₂)_n—

OH, wherein n=1-3, R² represents hydrogen or C₁-C₄ alkyl and R³ represents hydrogen or methyl.

22. A double layer capacitor according to claim 13, wherein said auxiliary material is one or more materials selected from the group consisting of non-ionic, anionic, cationic and amphoteric dispersing agents, mineral oil and silicone oil defoaming agents, organo clay, silica and castor oil derivative rheological control agents.

23. A double layer capacitor according to claim 22, wherein said auxiliary material is one or more materials selected from the group consisting of anionic dispersing agents, silicone oil defoaming agents and organo clay rheological control agents.

24. A double layer capacitor according to claim 11, wherein said conductive coating is a screen printing dye which includes a melamine resin binder.

25. A double layer capacitor according to claim 11, wherein said ion conducting phase includes an electrolyte salt which is one or more tetraalkylammonium salts.

26. A double layer capacitor according to claim 25, wherein said one or more tetraalkylammonium salts is selected from the group consisting of tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammoniumtetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate and tetrabutylammonium hexafluorophosphate.

27. A double layer capacitor according to claim 26 wherein said tetraalkylammonium salt is tetraethylammonium tetrafluoroborate.

28. A double layer capacitor according to claim 11 wherein said ion conducting phase includes a solvent selected from the group consisting of carbonates, lactones and nitriles.

29. A double layer capacitor according to claim 28, wherein said solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ

-butyrolactone, γ

-valerolactone, acetonitrile and mixtures thereof.

30. A double layer capacitor according to claim 29, wherein said solvent is γ

-butyrolaconte.

31. A double layer capacitor according to claim 11, wherein said current collector is a metal current collector.

32. A double layer capacitor according to claim 31 wherein said metal is selected from the group consisting of nickel, copper and aluminum.

33. A double layer capacitor according to claim 32 wherein said metal is aluminum.

34. A method of making a double layer capacitor as claimed in claim 20, which comprises the steps of:

(i) mixing carbon black and graphite in an alcohol, a glycol or glycol ether with polymerization reaction partner, a dispersing agent and a defoaming agent to produce a mill base;

(ii) adding melamine resin and a rheological control agent to obtain a uniform conductive coating paste;

(iii) applying said conductive coating paste onto a current collector by coating or printing to produce a conductive coating;

(iv) curing said conductive coating by heating to 100-150°

C. for 10-30 minutes;

(v) preparing an electrode paste from active carbon, binder, solvent and optionally graphite and auxiliary materials in a manner analogous to steps (i) to (iv) above;

(vi) applying said electrode paste onto said conductive coating by coating or printing to produce a conductive coating-electrode laminate;

(vii) sandwiching a porous separator between two conductive coating-electrode laminates to form a capacitor laminate;

(viii) confining said capacitor laminate in a polymer coated metal pouch;

(ix) preparing an electrolyte solution by dissolving electrolyte salt in electrolyte solvent;

(x) impregnating said capacitor laminate with the electrolyte solution; and

(xi) sealing said pouch.

35. A method according to claim 34, in which said coating or printing technique is selected from the group consisting of screen printing, gravure printing and slot die coating techniques.

60. A hybrid combination comprising a double layer capacitor according to claim 11 operatively combined with a battery.

61. A hybrid combination according to claim 60 wherein said double layer capacitor and said battery are in parallel combination.

36. A double layer capacitor comprising at least one carbon electrode structure with a polymer binder, a non-aqueous electrolyte and at least one metal foil current collector having an interface with said at least one carbon electrode structure, and a conductive coating comprising a melamine resin binder provided at said interface between said at least one current collector and said at least one electrode structure.

37. A double layer capacitor according to claim 36, wherein said melamine resin is an alkylated melamine formaldehyde resin.

38. A double layer capacitor according to claim 37, wherein said melamine resin is a methylated melamine formaldehyde resin.

39. A double layer capacitor according to claim 36, wherein said conductive coating is provided from a mixture composed essentially of:

5-50% by weight of carbon black;

5-20% by weight of graphite;

5-40% by weight of melamine resin binder and polymerization reaction partner;

25-85% by weight of solvent; and

0-10% by weight of auxiliary materials.

40. A double layer capacitor according to claim 39 wherein said auxiliary materials are selected from the group consisting of dispersing agents, defoaming agents and rheological control agents.

41. A double layer capacitor according to claim 40 wherein said conductive coating is provided from a mixture composed essentially of:

10-40% by weight of carbon black;

5-15% by weight of graphite;

10-30% by weight of melamine resin binder and polmerization reaction partner;

30-74% by weight of solvent; and

1-5% by weight of auxiliary materials.

42. A double layer capacitor according to claim 40, wherein said conductive coating is provided from a mixture composed essentially of:

20-25% by weight of carbon black;

10-15% by weight of graphite;

15-25% by weight of melamine resin binder and polymerization reaction partner;

35-53% by weight of solvent; and

2-5% by weight of auxiliary materials.

43. A double layer capacitor according to claim 39, wherein said carbon black is selected from the group consisting of furnace blacks, acetylene blacks and lampblacks.

44. A double layer capacitor according to claim 39, wherein said graphite has a particle size in the range of 0.5-20 μ

m.

45. A double layer capacitor according to claim 39, wherein said graphite has a particle size in the range of 0.5-10 μ

m.

46. A double layer capacitor according to claim 39, wherein said polymerization reaction partner is an alkyd resin.

47. A double layer capacitor according to claim 39, wherein said solvent is selected from the group consisting of alcohols of formula R¹—

OH, wherein R¹ represents C₁-C₄ alkyl, and glycols and glycol ethers of formula R²—

(OCHR³CH₂)_n—

OH, wherein n=1-3, R² represents hydrogen or C₁-C₄ alkyl and R³ represents hydrogen or methyl.

48. A double layer capacitor according to claim 39, wherein said auxiliary material is one or more materials selected from the group consisting of non-ionic, anionic, cationic and amphoteric dispersing agents, mineral oil and silicone oil defoaming agents, organo clay, silica and castor oil derivative rheological control agents.

49. A double layer capacitor according to claim 48, wherein said auxiliary material is one or more materials selected from the group consisting of anionic dispersing agents, silicone oil defoaming agents and organo clay rheological control agents.

50. A double layer capacitor according to claim 36, wherein said conductive coating is a screen printing dye which includes a melamine resin binder.

51. A double layer capacitor according to claim 36, wherein said ion conducting phase includes an electrolyte salt which is one or more tetraalkylammonium salts.

52. A double layer capacitor according to claim 51, wherein said one or more tetraalkylammonium salts is selected from the group consisting of tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammoniumtetrafluoroborate, tetrabutylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate and tetrabutylammonium hexafluorophosphate.

53. A double layer capacitor according to claim 52 wherein said tetraalkylammonium salt is tetraethylammonium tetrafluoroborate.

54. A double layer capacitor according to claim 36 wherein said ion conducting phase includes a solvent selected from the group consisting of carbonates, lactones and nitriles.

55. A double layer capacitor according to claim 54, wherein said solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ

-butyrolactone, γ

-valerolactone, acetonitrile and mixtures thereof.

56. A double layer capacitor according to claim 55, wherein said solvent is γ

-butyrolactone.

57. A double layer capacitor according to claim 36, wherein said current collector is a metal current collector.

58. A double layer capacitor according to claim 57 wherein said metal is selected from the group consisting of nickel, copper and aluminum.

59. A double layer capacitor according to claim 58 wherein said metal is aluminum.

62. A hybrid combination comprising a double layer capacitor according to claim 36 operatively combined with a battery.

63. A hybrid combination according to claim 62 wherein said double layer capacitor and said battery are in parallel combination.