Energy storage device and methods of manufacture

• US 5,800,857 A
• Filed: 09/30/1996
• Issued: 09/01/1998
• Est. Priority Date: 09/18/1992
• Status: Expired due to Term

• Current Assignee: Ultracap Technologies Corp.
• Original Assignee: Pinnacle Research Institute, Inc.
• Inventors: Ahmad, Nazir, Tsai, Keh-Chi
• Primary Examiner(s): LUSIGNAN, MICHAEL R
• Application Number:
  US08/718,569
• Time in Patent Office: 701 Days
• Field of Search: 29/25.03, 29/25.41, 29/25.42, 29/623.5, 427/58, 427/79, 427/80, 427/81, 427/126.3, 427/282, 427/284, 361/301.4, 361/503, 361/522-527, 361/541, 429/42, 429/212, 429/217, 429/223
• US Class Current: 427/80
• CPC Class Codes: H01G 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• CPC Class Codes: H01G 11/30 characterised by their material
• CPC Class Codes: H01G 11/70 characterised by their structure
• CPC Class Codes: H01G 11/80 Gaskets; Sealings
• CPC Class Codes: H01G 11/84 Processes for the manufacture of hybrid or EDL capacitors, or components thereof
• CPC Class Codes: H01M 10/0418 with bipolar electrodes
• CPC Class Codes: H01M 4/00 Electrodes
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0438 by electrochemical processing electroless electrochemical plating C23C18/54
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/557 Plate-shaped terminals
• CPC Class Codes: H01M 6/48 with bipolar electrodes
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A dry preunit (10), includes a plurality of cells (110, 112, 114) in a true bipolar configuration, which are stacked and bonded together, to impart to the device an integral and unitary construction. Each cell (114) includes two electrically conductive electrodes (111A, 111B) that are spaced apart by a predetermined distance. The cell (114) also includes two identical dielectric gaskets (121, 123) that are interposed, in registration with each other, between the electrodes (111A, 111B), for separating and electrically insulating these electrodes. When the electrodes (111A, 111B), and the gaskets (121, 123) are bonded together, at least one fill gap (130) is formed for each cell. Each cell (114) also includes a porous and conductive coating layer (119, 120) that is formed on one surface of each electrode. The coating layer (119) includes a set of closely spaced-apart peripheral microprotrusions (125), and a set of distally spaced-apart central microprotrusions (127). These microprotrusions (125, 127) impart structural support to the cells, and provide additional insulation between the electrodes. An energy storage device (10A) such as a capacitor, is created with the addition of an electrolyte to the gap (130) of the dry preunit (10) and subsequent sealing of the fill ports. Organic polymers in organic solvents are used to seal the edges of electrodes of porous metal oxides, metal nitrides, or metal carbides to reduce or eliminate leakage current. The preparation of metal nitrides and metal carbides are claimed for electrode use.

Claims

1. An improved method to produce a sealable and electrically insulating band of organic polymer on the perimeter edges of an individual electrode for use in an energy storage device, which method comprises:

A. obtaining a thin flat electrode comprising a thin porous metal oxide, nitride or carbide coated on a thin electrode substrate with or without insulating separators applied to one or both of the flat porous metal oxide, nitride or carbide surfaces;

B. dissolving at least one organic polymer in at least one organic solvent to obtain a solution having a viscosity sufficiently low to permit the solution to penetrate the porous metal oxide, metal nitride, or metal carbide;

C. coating the edge perimeter of each of the flat electrode with the polymer solvent solution of step B wherein the total surface area of organic polymer on one side covers between about 5 and 25% of the total area of the flat surface of one side of the electrode from each perimeter edge to create a continuous substantially uniform edge coating of organic polymer and having a thickness effective to stop shunt or leakage current; and

D. removing the at least one organic solvent from the organic polymer edge coating by maintaining the coated electrode at ambient temperature and pressure for between about 0.1 and 1000 min followed by heating at between about 20° and

150°

C. for between about 0.1 and 10 hr, optionally under vacuum conditions, producing an edge seal effective to stop or to reduce up to about 99% of any leakage current, wherein the thin flat electrode is not a component of a nickel metal hydride electrochemical cell.

2. The improved method of claim 1 wherein the organic polymer and solvent of step (B) comprises a solvent, thermoplastic elastomer and optionally one or more organic polymer additives to achieve the viscosity properties of between about 300 and 3000 centipoise.

3. The improved method of claim 2 wherein the thermoplastic elastomer comprises a styrene-butylene/ethylene polymer.

4. The improved method of claim 2 wherein the at least one organic solvent has a boiling point of about 200°

C. or less at ambient pressure.

5. The improved method of claim 4 wherein at least one organic solvent is selected from an aliphatic hydrocarbon, alcohol, ester, ether, ketone, aromatic hydrocarbon or mixtures thereof.

6. The improved method of claim 4 wherein at least one organic solvent is a mixture of an aromatic hydrocarbon selected from benzene, toluene, xylene or mixtures thereof and an alcohol selected from methanol, ethanol, n-propanol, isopropanol, butanol or mixtures thereof.

7. The improved method of claim 1 wherein the perimeter edge of each thin electrode has the porous metal oxide, metal nitride, or metal carbide coating removed such that at least one organic polymer coating directly contacts and adheres to the electrode substrate.

8. The improved method of claim 1 wherein in step B the organic polymer is a styrene-butadiene elastomer, the organic solvent is a mixture of toluene and isopropanol in a ratio of between about 1/4 to 4/1, and

the styrene-butadiene elastomer is present in between about 5 and 20% by weight of elastomer and solvents.

9. The improved method of claim 1 wherein in step C, at least one organic polymer dissolved in at least one organic solvent, the electrode substrate is edge coated by:

multiple dipping of the electrode in the solution;

at least one coating using screen printing of the solution;

at least one coating using stencil printing of the solution;

mechanically placing the solution on the substrate using a syringe;

or

mechanically placing the solution on the substrate using an applicator.

10. The improved method of claim 8 wherein in step C:

at least one organic polymer dissolved in at least one organic solvent, the electrode substrate is edge coated by;

multiple dipping of the electrode in the solution;

at least one coating using screen printing of the solution;

at least one coating using stencil printing of the solution;

mechanically placing the solution on the substrate using a syringe;

or mechanically placing the solution on the substrate using an applicator.

11. An improved method of produce an organic polymer sealed electrical storage device having improved electrical short resistant properties, which the method comprises:

A. obtaining the organic polymer edge coated electrode produced by the method of claim 1;

B. dissolving at least one organic polymer in at least one or more organic solvent producing a solution having a viscosity of between about 3,000 and 40,000 centipoise;

C. coating each electrode edge one or more times using the solution of step B to obtain a coating thickness of between about 1 and 10 mil creating a thin pregasket;

D. stacking multiple edge coated electrodes substantially matching the thin pregaskets produced in step C while the organic polymer coating is still solvent wet and tacky to the touch, to create a solvent wet capacitor preunit device having multiple electrical cells;

E. removing the organic solvent from the matched pregaskets formed in step D and from the capacitor preunit device of the stacked electrodes by maintaining the device for between about 1 and 20 hr at ambient pressure and temperature, followed by heating at between about 80°

-250°

C. until at least one organic solvent is essentially removed; and

F. creating a dry preunit of an electrical storage device having an organic polymer sealed edge, wherein the thin flat electrode is not a component of a nickel metal hydride electrochemical cell.

12. The improved method of claim 11 wherein the organic polymer comprises a thermoplastic elastomer and optionally one or more organic polymer additives to achieve the viscosity properties.

13. The improved method of claim 12 wherein the thermoplastic elastomer comprises a styrene-butylene/ethylene polymer.

14. The method of claim 12 wherein the at least one organic solvent has a boiling point of about 200°

C. or less at ambient pressure.

15. The improved method of claim 14 wherein at least one organic solvent is selected from the group consisting of aliphatic hydrocarbon, alcohol, ester, ether, ketone, aromatic hydrocarbon and mixtures thereof.

16. The improved method of claim 14 wherein at least one organic solvent is a mixture of an aromatic hydrocarbon and an alcohol.

17. The improved method of claim 11 wherein the perimeter edge of each thin electrode has the porous oxide coating removed such that at least one organic polymer coating directly contacts and adheres to the electrode substrate.

18. The improved method of claim 11 wherein instep B the organic polymer is a styrene-butadiene elastomer, the organic solvent is a mixture of toluene and isopropanol in a ratio of between about 1/4 to 4/1, and the styrene-butadiene elastomer is present in between about 5 and 40% by weight of elastomer and solvents present.

19. The improved method of claim 11 wherein in step C, at least one organic polymer dissolved in at least one organic solvent, the electrode substrate is edge coated by:

multiple dipping of the electrode in the solution;

at least one coating using screen printing of the solution;

at least one coating using stencil printing of the solution;

mechanically placing the solution on the substrate using a syringe;

or

mechanically placing the solution on the substrate using an applicator.

20. The improved method of claim 11 wherein

in step C, at least one organic polymer dissolved in at least one organic solvent, the electrode substrate is edge coated by:

multiple dipping of the electrode in the solution;

at least one coating using screen printing of the solution;

at least one coating using stencil printing of the solution;

mechanically placing the solution on the substrate using a syringe;

or mechanically placing the solution on the substrate using an applicator.

21. The improved method of claim 1 for use in electrode construction scheduled from wet cell construction, dry cell construction, fill port construction, or compression seal construction, adhesive construction.

22. The improved method of claim 1 wherein in step (C) the uniform edge coating of organic polymer has a thickness of between about 0.01 and 1 mil.

23. The improved method of claim 22 wherein the thickness is between about 0.1 and 0.5 mil.

24. An improved method to produce an electrode for an energy storage device, which method comprises coating a thin metal electrically conducting substrate with a porous high surface area metal nitride or metal carbide.

25. The improved method of claim 24 wherein the thin metal substrate is independently selected from tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, indium, chromium, manganese, lanthanum, lanthanum series metal, alloys or combination thereof, and

the porous metal nitride or metal carbide is independently selected from tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, indium, chromium, manganese, lanthanum, lanthanum series metal, or combinations thereof, and the energy storage device is a battery or a capacitor.