Electrochemical capacitor

• US 6,426,863 B1
• Filed: 11/25/1999
• Issued: 07/30/2002
• Est. Priority Date: 11/25/1999
• Status: Expired due to Fees

• Current Assignee: Alfred J. Longhi Jr, Government of the United States of America
• Original Assignee: Lithium Werks Technology BV
• Inventors: Munshi, M. Zafar A.
• Primary Examiner(s): Dinkins, Anthony
• Application Number:
  US09/449,443
• Time in Patent Office: 978 Days
• Field of Search: 361/503, 361/504, 361/505, 361/508, 361/511, 361/525, 361/527
• US Class Current: 361/503
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• 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 11/32 Carbon-based
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01G 11/58 Liquid electrolytes
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 10/4264 with capacitors
• CPC Class Codes: H01M 2004/029 Bipolar electrodes
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 4/668 Composites of electroconductive material and synthetic resins
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• 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: Y02E 60/13 Energy storage using capacitors

Abstract

An electrochemical capacitor includes an ionically conductive polymer thin film, a liquid electrolyte absorbed in the polymer thin film, and thin flexible active electrode layers constituting anode and cathode composed of energy dense material of high intrinsic surface area positioned at either side of the electrolyte-retaining polymer thin film to tightly sandwich it between the electrode layers. In one embodiment, the capacitor includes a polymer electrolyte in which a polymer thin film is cast from the base polymer and impregnated with the electrolyte solution, which contains a salt for ionic conduction. In another embodiment, the base polymer material includes an ionically conducting polymer, a perfluorocarbon polymer backbone to which sulfonic acid sites are permanently anchored. The energy dense material of the electrode layers may be physically mixed with battery active material to enhance the capacity and discharge time of the capacitor. In fabrication, the electrode material is reduced to particle size suitable for application to a thin film metallized polymer substrate, and applied directly and adherently on opposite sides of the substrate by injection, spraying, or evaporation, and a final thin flexible film of each electrode is formed with a desired thickness by use of rods if a slurry, or by controlling the extent of spray or evaporation, followed by curing. In another embodiment, the electrode elements are laminated directly onto opposite sides of a single- or double-metallized polymer substrate.

Claims

1. An electrochemical capacitor, comprising an ionically conductive polymer thin film, liquid electrolyte retained in said thin film, and thin flexible active electrode layers constituting an anode and a cathode composed of energy dense material of high intrinsic surface area positioned at either side of said thin film to tightly sandwich said electrolyte-retaining thin film therebetween.

2. The electrochemical capacitor of claim 1, wherein said electrode layers have a thickness in a range from about 1 micron to about 100 microns.

3. The electrochemical capacitor of claim 1, wherein said electrode layers comprise an electrode active material blended with a polymer electrolyte.

4. An electrochemical capacitor, comprising an ionically conductive polymer thin film, a liquid electrolyte retained in said thin film, and thin flexible active electrolyte layers constituting an anode and a cathode composed or energy dense material of high intrinsic surface area positioned at either side of said thin film to tightly sandwich said electrolyte-retaining thin film therebetween, wherein said energy dense material consists of at least one first group material possessing properties of high exchange current density, intrinsically high surface area, and high charge capacity in combination with at least one second group material essentially having exceptionally high redox capacity.

5. The electrochemical capacitor of claim 4, wherein said energy dense material has a composition comprising about 1% to 99% by weight of said energy dense material of said first group material and the remainder of said energy dense material comprising said second group material.

6. The electrochemical capacitor of claim 4, wherein said first group material is based on activated carbon.

7. The electrochemical capacitor of claim 4, wherein said first group material comprises valve metal oxide selected from the group consisting of oxides of titanium, zirconium, hafnium, niobium, tantalum, molybdenum, tungsten, ruthenium, iridium, platinum, palladium, osmium, gold, and rhenium.

8. The electrochemical capacitor of claim 7, wherein said second group material comprises battery active material selected from the group consisting of oxides, sulfides and selenides, including any of MnO₂, LiMn₂O₄, Li_xMnO₂, MoS₂, MoS₃, MoV₂O₈, CoO₂, Li_xCoO₂, V₆O₁₃, V₂O₅, V₃O₈, VO₂, V₂S₅, TiS₂, NbSe₃, Cr₂O₅, Cr₃O₈, WO₃, Li_xNiO₂, Li_xN_yCo_zO₂, Li_xNi_yMn_zO₂, Li_xCo_yMn_zO₂, and lithium doped electronically conducting polymers including polypyrrole, polyaniline, and polyacetylene.

9. The electrochemical capacitor of claim 4, wherein said first group material is physically mixed with said second group material as said energy dense material in said electrode layers to enhance the discharge time of said capacitor.

10. A thin film electrochemical capacitor, comprising a resilient flexible ionically conductive polymeric thin film including a base polymer with inorganic filler dispersed therein to increase surface area and porosity of said polymeric thin film;

a liquid electrolyte composed of liquid polymer, organic solvent electrolyte and a salt in solution impregnated in said polymeric thin film to form a gelled thin film polymer electrolyte; and

a pair of spaced-apart flexible thin film electrodes, each of said electrodes adhered to a current collector thereon, wherein said polymeric thin film is tightly sandwiched between said pair of thin film electrodes.

11. The thin film electrochemical capacitor of claim 10, wherein said polymer electrolyte is a cation conductor.

12. The thin film electrochemical capacitor of claim 10, wherein said polymer electrolyte is dimensionally stable and of high mechanical strength.

13. The thin film electrochemical capacitor of claim 10, wherein said polymer electrolyte is temperature stable up to 120°

C.

14. The thin film electrochemical capacitor of claim 10, wherein said polymer electrolyte is in the form of a very thin film.

15. The thin film electrochemical capacitor of claim 10, wherein said polymer electrolyte has low resistance and high flexibility.

16. The thin film electrochemical capacitor of claim 10, wherein each said current collector is a very thin structure chosen from the group consisting of metallic elements 1 to 10 μ

m thick and metallized plastics 0.5 to 50 μ

m thick.

17. The thin film electrochemical capacitor of claim 10, wherein each said current collector is a metallic current collector selected from the group consisting of aluminum, nickel, copper, titanium, stainless steel, and an alloy including inconel.

18. The thin film electrochemical capacitor of claim 10, wherein said base polymer has a predominantly amorphous structure.

19. A thin film electrochemical capacitor, comprising a resilient flexible ionically conductive polymeric electrolyte thin film including a base polymer with inorganic filler dispersed therein to increase surface area and porosity of said polymeric thin film;

a liquid electrolyte composed of liquid polymer, organic solvent electrolyte and a salt in solution impregnated in said polymeric thin film; and

a pair of spaced-apart flexible thin film electrodes, each of said electrodes adhered to a current collector thereon, wherein said polymeric electrolyte thin film is tightly sandwiched between said pair of thin film electrodes, wherein each said current collector is a metallized polymer current collector comprising a polymer substrate about 0.5-50 μ

m thick and a metallization layer up to 1 μ

m thick overlying at least a portion of said polymer substrate.

20. The thin film electrochemical capacitor of claim 19, wherein said polymer substrate of each of said thin film electrodes is selected from a group of polymers including PET, PP, PPS, PEN, PVDF and PE, said metallization layer on each said polymer substrate forming an electrically conductive layer thereon.

21. The thin film electrochemical capacitor of claim 20, wherein each metallized polymer substrate has a thickness in a range from about 0.5 micron to about 50 microns.

22. The thin film electrochemical capacitor of claim 20, wherein each said metallization layer is selected from a group consisting of aluminum, copper, nickel, titanium, inconel, stainless steel, zinc, gold, and carbon.

23. The thin film electrochemical capacitor of claim 20, wherein each said electrode is a valve metal oxide.

24. The thin film electrochemical capacitor of claim 23, wherein each said metallization layer is titanium.

25. The thin film electrochemical capacitor of claim 24, wherein each said valve metal oxide is RuO₂.

26. A thin film electrochemical capacitor, comprising a resilient flexible ionically conductive polymeric electrolyte thin film including a base polymer with inorganic filler dispersed therein to increase surface area and porosity of said polymeric thin film;

a liquid electrolyte composed of liquid polymer, organic solvent electrolyte and a salt in solution impregnated in said polymeric thin film; and

a pair of spaced-apart flexible thin film electrodes, each of said electrodes adhered to a current collector thereon, wherein said polymeric electrolyte thin film is tightly sandwiched between said pair of thin film electrodes, wherein each of said thin film electrodes comprises a layer of polymer material, and a low resistance metallization layer having a conductivity in a range from about 0.01 ohm per square to about 1 ohm per square overlying and adhered to a side of said layer of polymer material.

27. The thin film electrochemical capacitor of claim 26, wherein each of said thin film electrodes has a thickness in a range from about 0.5 micron to about 50 microns.

28. The thin film electrochemical capacitor of claim 26, wherein each said layer of polymer material has a non-metallized margin with a width in a range from about one mm to about three mm.

29. The thin film electrochemical capacitor of claim 28, wherein each said layer of polymer material has a low resistance metallization layer of said conductivity adhered to each side thereof, and both sides of said layer of polymer material have a non-metallized margin with said width at the same edge of said layer of polymer material.

30. The thin film electrochemical capacitor of claim 29, wherein active electrode material is applied over said low resistance metallization layer on each said layer of polymer material and not on said non-metallized margin of said layer of polymer material.

31. The thin film electrochemical capacitor of claim 30, wherein said active electrode material comprises RuO₂.