Method to fabricate a reliable electrical storage device and the device thereof

• US 6,005,764 A
• Filed: 11/06/1995
• Issued: 12/21/1999
• Est. Priority Date: 09/18/1992
• Status: Expired due to Fees

• Current Assignee: Ultracap Technologies Corp.
• Original Assignee: Pinnacle Research Institute, Inc.
• Inventors: Poplett, James M., Tong, Robert R., Anderson, Ronald L., Nelson, James P., Goodwin, Mark L., Tsai, K. C., Mason, Gary E., McEwen, Alan B.
• Primary Examiner(s): Kincaid, Kristine
• Assistant Examiner(s): Dinkins, Anthony
• Application Number:
  US08/553,850
• Time in Patent Office: 1,506 Days
• Field of Search: 361/502-510, 361/516, 361/512, 361/523, 361/525-529, 361/532-533, 429/163-176, 427/247-249, 430/129
• US Class Current: 361/500
• CPC Class Codes: H01G 11/22 Electrodes
• 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 11/46 Metal oxides
• CPC Class Codes: H01G 11/52 Separators
• 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 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0409 by a doctor blade method, slip-casting or roller coating
• CPC Class Codes: H01M 4/0416 involving impregnation with a solution, dispersion, paste or dry powder H01M4/0438 takes precedence
• CPC Class Codes: H01M 4/0419 involving spraying
• CPC Class Codes: H01M 4/0428 Chemical vapour deposition
• CPC Class Codes: H01M 4/0438 by electrochemical processing electroless electrochemical plating C23C18/54
• CPC Class Codes: H01M 4/045 Electrochemical coating; Electrochemical impregnation
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• 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 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
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries

Abstract

The present invention relates to an improved method to produce an electrical storage device having useful characteristics such as higher charge density, small volume, long-term reliable charge/discharge cycles, low leakage current, and the like. The dry preunit has useful properties in that it can be stored for long periods prior to contact with a non-aqueous or aqueous electrolyte. When the electrode surfaces are contacted with a non-aqueous or aqueous electrolyte, the novel capacitors produced are useful as a portable power supply in applications such as in defibrillator, electrical vehicles, radiotelephones etc.

Claims

1. An improved dry preunit of an electrical storage device produced by a method to produce a dry preunit of an electrical storage device for storage of electrical charge in a condition to have the electrode surfaces contacted with a non-aqueous or aqueous electrolyte, which method comprises:

(a) preparing a thin in thickness substantially flat sheet of electrically conducting support material coated on each flat side with the same or different thin layer of a second electrically conducting material having a high surface area, optionally with the provision that both flat sides of the electrically conducting support metal is a thin sheet having the perimeter edge surfaces in a condition selected from the group consisting of;

(i) perimeter edge surfaces having a thin layer of second electrically perimeter conducting material present,

(ii) edge surfaces which are partly devoid of second electrically conducting material, and

(iii) perimeter edge surfaces which are devoid of second electrically conducting material;

(b) creating an ion permeable or semipermeable space separator stable to the aqueous or non-aqueous electrolyte which separator is obtained by steps selected from the group consisting of;

(i) depositing substantially uniform in height groups of electrically insulating microprotrusions, on the surface of at least one side of a thin layer of electrically conducting material,

(ii) placing a thin precut ion permeable or semipermeable separator on one surface of the second electrically conducting material,

(iii) casting an ion permeable or semipermeable thin layer on the surface of at least one side of the electrically conducting material, and

(iv) creating a thin air space as separator;

(c) contacting the perimeter edge surface of one or both sides of the thin sheet of step (b) with one or more thin layers of synthetic organic polymer as a gasket material selected from the group consisting of a thermoplastic and a thermoset polymer;

(d) placing on or within the gasket material and optionally across the thin sheet at least one thin cord of a different material which cord has a higher melting point (T_m) greater than the gasket polymer material and does not melt, flow, or permanently adhere to the gasket under the processing conditions;

(e) producing a repeating layered stack of the thin flat articles of sheet coated with metal oxide and separator produced in step (d) optionally having the end sheets consisting of a thicker support;

(f) heating the stack produced in step (e) at a temperature and applied pressure effective to cause the synthetic gasket material to flow, to adhere to, and to seal the edges of the stack creating a solid integral stack of layers of alternating electrically conductive sheet coated with second electrically conducting material and the ion permeable separator, optionally such that the gasket material creates a continuous integral polymer enclosure;

(g) cooling the solid integral stack of step (f) optionally in an inert gas under slight pressure; and

(h) removing the at least one thin cord of different material between each layer creating at least one small opening between the layers of electrically conducting sheet coated with second electrically conducting material.

2. An improved dry preunit of an electrical storage device produced by an improved method which results in a dry preunit of an electrical storage device for storage of electrical charge in a condition to have the electrode surfaces contacted with a non-aqueous or aqueous electrolyte, which method comprises:

(a) obtaining a thin thickness flat metal sheet support wherein the metal is selected from the group consisting of titanium, zirconium, iron, copper, lead, tin, nickel, zinc and combinations thereof, having a thickness of between about 0.1 and 10 mil coated on each flat surface with a thin layer of at least one metal oxide having a high surface area independently selected from metal oxides of the group consisting of tin, lead, vanadium, titanium, ruthenium, tantalum, rhodium, osmium, iridium, iron, cobalt, nickel, copper, molybdenum, niobium, chromium, manganese, lanthanum, lanthanum series metals and combinations thereof, possibly containing small percentage of additives to enhance electrical conductivity,

wherein said thin metal oxide layer has a thickness of between about 0.1 and 100 microns,

with the proviso that both flat surfaces of the electrically conducting sheet may have the perimeter edge surfaces devoid of metal oxide;

(b) creating an ion permeable space separator which is stable to the aqueous or non-aqueous electrolyte by methods selected from the group consisting of;

(i) depositing a substantially uniform in height array of electrically insulating microprotrusions which are stable to an aqueous or non-aqueous electrolyte having a height of between about 0.1 and 10 mil on the surface of one or both sides of the thin layer of metal oxide,

(ii) placing a thin precut ion permeable electrically insulating separator having a thickness of between about 0.1 and 10 mil on one flat surface of the metal oxide layer;

(iii) casting an ion permeable or semipermeable separator having a thickness of between about 0.1 and 10 mil on at least one surface of the second electrically conducting material; and

(iv) creating a thin air space as a separator;

(c) contacting the perimeter edge surface of one or both sides of the thin electrically conducting sheet of step (b) with one or more thin layers of synthetic organic polymer as a gasket material wherein the polymer is selected from the group consisting of polyimides, polyethylenes, polypropylenes, polysulfone, fluorinated polymer, partly fluorinated polymer and combinations thereof;

(d) placing on or within the gasket material and optionally across the thin flat sheet at least one thin cord of a different material which has a higher melting temperature (T_m) than the polymeric gasket material, which cord does not melt, flow or adhere to the gasket material under the processing conditions described herein;

(e) assembling a repeating layered stack of the thin flat articles of sheet coated with metal oxide and separator produced in step (d) optionally having end sheets having only one side coated and/or being made of thicker support material;

(f) heating the layered stack of step (e) at 0 to 100°

C. greater than T_m causing the gasket material to flow, to adhere to, and to seal the edges of the layered stack creating a solid integral layered stack of sheet and separator optionally enclosing the stack in an integral polymer enclosure;

(g) cooling to ambient temperature the solid integral stack of step (f) in an inert environment; and

(h) removing the at least one thin cord between each layer creating at least one small opening between the electrode layers.

3. An electrical energy storage device, comprising:

first and second substrates, each having a planar face;

first and second electrodes consisting of a thin film of metal or metal oxide deposited on said respective substrate planar faces, the thin film being less than 10,000 Angstroms thick;

spacers, comprising particles of electrically non-conductive material disposed between the first and second electrodes;

the first and second electrodes arranged so that the spacers form a uniform gap of less than 20 microns between the electrodes, and the spacers cover less than 10% of the area of either electrode;

an electrolyte disposed in the gap between the electrodes; and

sealing means disposed between the first and second electrodes to seal the gap.

4. The electrical energy storage device of claim 3, wherein the electrolyte is an ion conducting species solvated in an aqueous or organic medium.

5. The electrical energy storage device of claim 3, wherein the first and second electrodes are different materials.

6. The electrical energy storage device of claim 3 wherein the substrates are selected from the group consisting of ceramic, plastic, glass and metal.

7. The electrical energy storage device of claim 3, wherein the substrates serve as a current collector.

8. The electrical energy storage device of claim 3, wherein the spacers are selected from the group consisting of glass spheres, chopped glass fibers, plastic spheres, chopped plastic fibers, ceramic, and polystyrene/divinylbenzene spheres.

9. An electrical energy storage device, comprising:

a first substrate having a planar face;

a first electrode consisting of a thin film of metal or metal oxide less than 10,000 Angstroms thick deposited on the face of the first substrates;

spherical plastic spacers uniformly dispersed on the first electrode at a density of less than about 1000 spacers per square millimeter of the electrode area;

a second substrate having a planar face;

a second electrode consisting of a thin film of metal or metal oxide deposited on the face of the second substrate;

the first and second substrates arranged so that the first and second electrodes face each other and are separated by the spherical plastic spacers, the spacers providing a gap of less than about 20 microns between the electrodes;

an aqueous electrolyte disposed in the gap; and

means for sealing the electrolyte in the electrical energy storage device.

10. The electrical energy storage device of claim 9, wherein the first and second electrodes are different materials.

11. The electrical energy storage device of claim 9, wherein the first and second substrates are selected from the group consisting of ceramic, plastic, glass and metal.

12. The electrical energy storage device of claim 9, wherein the substrate serves as a current collector.

13. An electrical energy storage device, comprising:

a first substrate having an electrode comprising a thin film of titanium between about 500 Angstroms and about 2000 Angstroms thick deposited on a planar face of the substrate;

a second substrate having an electrode comprising a thin film of titanium between about 500 Angstroms and about 200 Angstroms thick deposited on a planar face of the substrate;

the first and second substrates arranged in parallel fashion so that the first electrode is in the proximity of and facing the second electrode;

polystyrene-divinyl benzene spheres disposed between the first and second electrodes forming uniform gap of less than 20 microns between the electrodes, and the spheres covering less than 10% of the area of either electrode;

an electrolyte disposed in the gap between the electrodes; and

sealing means disposed between the first and second substrates to seal the gap.

14. An electrical energy storage device, which device comprises:

(A) at least two thin in thickness substantially flat sheets of electrically conducting support material which are coated on each flat side with the same or a different thin layer of a second electrically conducting material having a high surface area, with the provision that both flat sides of the electrically conducting support is a sheet having the perimeter edge surfaces in a condition selected from the group consisting of;

(i) perimeter edges having a thin layer of second electrically conducting material,

(ii) perimeter edges which are partially devoid of second electrically conducting material, and

(iii) perimeter edges which are devoid of second electrically conducting material;

(B) an ion permeable or semipermeable space separator chemically and electrically stable to the aqueous or non-aqueous electrolyte, which separator is selected from the group consisting of;

(i) multiple substantially uniform in height groups of electrically insulating microprotrusions, on the surface of at least one side of a thin layer of electrically conducting material,

(ii) a thin precut ion permeable or semipermeable separator on one surface of the second electrically conducting material,

(iii) a cast ion permeable or semipermeable thin layer on the surface of at least one side of the electrically conducting material, and

(iv) a thin air space as separator;

(C) perimeter edge surfaces of one or both sides of the thin sheet of part (B) in contact with one or more thin layers of synthetic organic polymer as a gasket material selected from the group consisting of a thermoplastic polymer and a thermoset polymer;

(D) an aqueous or non-aqueous ion conducting electrolyte disposed in the space between the electrodes which optionally includes an ion-conducting species; and

(E) sealing means disposed between each electrode to seal the gap or space and to retain the electrolyte.

15. The electrical energy storage device of claim 14, wherein the electrolyte is an ion conducting species solvated in a liquid selected from the group consisting of an aqueous medium, an organic medium or combinations thereof.

16. The electrical energy storage device of claim 14 wherein the electrically conducting support material of part (A) is selected from the group consisting of ceramic, plastic, glass and metal.

17. The electrical energy storage device of claim 14, wherein the support material serves as a current collector.

18. The electrical energy storage device of claim 14, wherein the space separators of part (B) are selected from the group consisting of glass spheres, glass fibers, plastic spheres, glass microprotrusions, plastic microprotrusions, plastic fibers, ceramic spheres, and polystyrene-divinylbenzene spheres.

19. An electrical energy storage device, comprising:

a first substrate having a planar face;

a first electrode consisting of a thin film of metal or metal oxide less than 10,000 Angstroms (1 mm) thick deposited on the face of the first substrate;

spherical plastic electrically insulating spacers uniformly dispersed on the first electrode at a density of less than about 1000 spacers per square millimeter of the electrode area;

a second substrate having a planar face;

a second electrode consisting of a thin film of metal or metal oxide deposited on the face of the second substrate;

the first and second substrates arranged so that the first and second electrodes face each other and are separated by the spherical plastic spacers, the spacers providing a gap of less than about 20 microns between the electrodes;

an aqueous electrolyte disposed in the gap; and

means for sealing the electrolyte in the electrical energy storage device.

20. An electrical energy storage device, comprising:

a first electrically conducting support material having an electrode comprising a thin film of ruthenium or titanium between about 500 Angstroms and about 2000 Angstroms thick deposited on a planar face of the support material;

a second electrically conducting support material having an electrode comprising a thin film of ruthenium or titanium between about 500 Angstroms and about 200 Angstroms thick deposited on a planar face of the support material;

the first and second substrates arranged in parallel fashion so that the first electrode is in the proximity of and facing the second electrode;

polystyrene-divinyl benzene spheres as electrically insulating spacers disposed between the first and second electrodes forming uniform gap of less than 20 microns between the electrodes, and the spheres covering less than 10% of the area of either electrode;

an electrolyte disposed in the gap between the electrodes; and

sealing means disposed between the first and second substrates to seal the gap.