Electrochemical Energy Storage Systems and Methods

• US 20120077095A1
• Filed: 09/09/2011
• Published: 03/29/2012
• Est. Priority Date: 09/09/2010
• Status: Active Grant

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: ROUMI, Farshid, Roumi, Jamshid
• Granted Patent: US 9,831,043 B2
• Time in Patent Office: Days
• US Class Current: 429/405
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/10 Multiple hybrid or EDL capacitors, e.g. arrays or modules housings, cases, encapsulations or mountings thereof H01G11/78
• CPC Class Codes: H01G 11/18 against thermal overloads, e.g. heating, cooling or ventilating
• CPC Class Codes: H01G 11/26 characterised by their structure, e.g. multi-layered, porosity or surface features
• 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 11/70 characterised by their structure
• CPC Class Codes: H01G 2/08 Cooling arrangements; Heating arrangements; Ventilating arrangements
• CPC Class Codes: H01G 9/0003 Protection against electric or thermal overload; cooling arrangements; means for avoiding the formation of cathode films H01G9/12 takes precedence
• CPC Class Codes: H01G 9/0029 Processes of manufacture
• CPC Class Codes: H01G 9/048 characterised by their structure H01G11/22 takes precedence
• CPC Class Codes: H01G 9/07 Dielectric layers
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 10/6554 Rods or plates
• CPC Class Codes: H01M 12/02 Details of electrodes H01M4/00; of non-active parts H01M50/00
• CPC Class Codes: H01M 12/065 with plate-like electrodes or stacks of plate-like electrodes
• CPC Class Codes: H01M 4/02 Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: H01M 4/664 : Ceramic materials
• CPC Class Codes: H01M 4/70 : characterised by shape or form
• CPC Class Codes: H01M 4/86 : Inert electrodes with catalytic activity, e.g. for fuel cells
• CPC Class Codes: H01M 4/8605 : Porous electrodes
• CPC Class Codes: H01M 4/88 : Processes of manufacture
• CPC Class Codes: H01M 6/02 : Details of electrodes H01M4/00; of non-active parts H01M50/00
• CPC Class Codes: H01M 6/5038 : Heating or cooling of cells or batteries
• CPC Class Codes: H01M 8/002 : Shape, form of a fuel cell
• CPC Class Codes: H01M 8/0206 : Metals or alloys
• CPC Class Codes: H01M 8/0213 : Gas-impermeable carbon-containing materials
• CPC Class Codes: H01M 8/0215 : Glass; Ceramic materials
• CPC Class Codes: H01M 8/0247 : characterised by the form characterised by a channel configuration H01M8/0258
• CPC Class Codes: H01M 8/04067 : Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
• CPC Class Codes: H01M 8/20 : Indirect fuel cells, e.g. fuel cells with redox couple being irreversible H01M8/18 takes precedence
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49204 : Contact or terminal manufacturing

Abstract

A three-dimensional electrode array for use in electrochemical cells, fuel cells, capacitors, supercapacitors, flow batteries, metal-air batteries and semi-solid batteries.

Claims

1. A three-dimensional electrode array comprising:

a plurality of plate electrodes, wherein each plate electrode includes an array of apertures, wherein the plate electrodes are arranged in a substantially parallel orientation such that the each aperture of an individual plate electrode is aligned along an alignment axis passing through an aperture of each of all other plate electrodes; and

a plurality of rod electrodes, wherein the plurality of rod electrode are not in physical contact with the plurality of plate electrodes and arranged such that each rod electrode extends a length along an alignment axis passing through an aperture of each plate electrode; and

wherein a first surface area includes a cumulative surface area the plurality of plate electrodes, wherein a second surface area includes a cumulative surface area of each aperture array and wherein a third surface area includes a cumulative surface area of each of the plurality of rod electrodes.

2. The three-dimensional electrode array of claim 1, wherein the plurality of rod electrodes are not in electrical contact with the plurality of plate electrodes.

3. The three-dimensional electrode array of claim 1, wherein the three-dimensional electrode array is a component of a device selected from the group consisting of:

a primary electrochemical cell, a secondary electrochemical cell, a fuel cell, a capacitor, a supercapacitor, a flow battery, a metal-air battery and a semi-solid battery.

4. The three-dimensional electrode array of claim 1, wherein a ratio of the second surface area to the first surface area is selected over the range of 1 to 5.

5. The three-dimensional electrode array of claim 1, wherein a ratio of the second surface area to the third surface area is selected over the range of 0.2 to 5, 0.2 to 1 or 1 to 5.

6. The three-dimensional electrode array of claim 1, wherein each of the plurality of plate electrodes has one or more lateral dimensions selected over the range of 20 nm to 20 m and a thickness dimension selected over the range of 20 nm to 5 cm;

wherein a distance between each of the plurality of plate electrodes is selected over the range of 10 nm to 5 cm;

wherein each of the plurality of rod electrodes has a length selected over the range of 50 nm to 20 m or selected over the range of 5 mm to 1 m and a diameter or a lateral dimension selected over the range of 9 nm to 20 cm or selected over the range of 1 mm to 2 cm; and

wherein each aperture has a diameter or a lateral dimension selected over the range of 10 nm to 20 cm or selected over the range of 1 mm to 2 cm.

7. The three-dimensional electrode array of claim 1, comprising 5 or more plate electrodes and 50 or more rod electrodes.

8. The three-dimensional electrode array of claim 1, further comprising an electrolyte positioned between each of the plurality of plate electrodes and each of the plurality of rod electrodes.

9. The three-dimensional electrode array of claim 8, wherein the electrolyte comprises a first electrolyte surrounding each of the plurality of plate electrodes and a second electrolyte surrounding each of the plurality of rod electrodes.

10. The three-dimensional electrode array of claim 8, wherein the three-dimensional electrode array is a component of an electrochemical cell and wherein the electrochemical cell is selected from the group consisting of:

a primary cell, a secondary cell, a lead-acid cell, a lithium cell, a lithium ion cell, a zinc-carbon cell, an alkaline cell, a nickel-cadmium cell, a nickel metal hydride cell, a silver oxide cell, a sodium sulfur cell, a solid electrochemical cell a fluid electrochemical cell, a flow battery, a fuel cell, a semi-solid battery and a metal-air battery.

11. The three-dimensional electrode array of claim 1, wherein the three-dimensional electrode array is a component of a capacitor or a supercapacitor, and wherein the three-dimensional electrode array further comprises a dielectric material positioned between each of the plurality of plate electrodes and each of the plurality of rod electrodes.

12. The three-dimensional electrode array of claim 1, wherein each of the plurality of plate electrodes comprises a current collector;

wherein each of the plurality of rod electrodes comprises a current collector;

or wherein each of the plurality of plate electrodes and each of the plurality of rod electrodes comprises a current collector.

13. The three-dimensional electrode array of claim 12, wherein one or more current collectors are positioned in thermal communication with a heat sink or a heat source.

14. The three-dimensional electrode array of claim 12, wherein each current collector comprises a heat pipe.

15. The three-dimensional electrode array of claim 12, wherein each current collector is a structural element of the three-dimensional electrode array or provides structural support to the three-dimensional electrode array.

16. The three-dimensional electrode array of claim 1, further comprising one or more heat transfer rods arranged such that each heat transfer rod extends a length along an alignment axis passing through an aperture of each plate electrode and wherein at least one of the one or more heat transfer rods are positioned in thermal communication with a heat sink or a heat source.

17. The three-dimensional electrode array of claim 1, further comprising an inert coating on a surface of each aperture, thereby preventing an oxidation reaction or a reduction reaction from occurring at plate electrode apertures at positions covered by the inert coating.

18. The three-dimensional electrode array of claim 1, wherein at least one rod electrode comprises a composite rod electrode comprising a rod electrode inner core and a rod electrode outer shell surrounding the rod electrode inner core and wherein the rod electrode inner core comprises a first electrode material, and wherein the rod electrode outer shell comprises a second electrode material different from the first electrode material, and wherein at least one plate electrode comprises the first electrode material.

19. The three-dimensional electrode array of claim 1, wherein at least one plate electrode comprises a composite plate electrode comprising a plate electrode inner layer and a plate electrode outer shell surrounding the rod electrode inner layer and wherein the plate electrode inner layer comprises a first electrode material, and wherein the plate electrode outer shell comprises a second electrode material different from the first electrode material, and wherein at least one rod electrode comprises the first electrode material.

20. The three-dimensional electrode array of claim 1, wherein at least one rod electrode comprises a group of rod electrodes, wherein the group of rod electrodes is arranged such that the group of rod electrodes extends a length along an alignment axis passing through an aperture of each plate electrode.

21. The three-dimensional electrode array of claim 1, wherein the three-dimensional electrode array comprises a component of a fuel cell and wherein the three-dimensional electrode array further comprises a fuel fluid positioned in contact with one or more plate electrodes, one or more rod electrodes or both one or more plate electrodes and one or more rod electrodes and wherein the three-dimensional electrode array further comprises an oxygen containing fluid positioned in contact with one or more plate electrodes, one or more rod electrodes or both one or more plate electrodes and one or more rod electrodes.

22. The three-dimensional electrode array of claim 1, wherein the three-dimensional electrode array comprises a component of a metal-air battery and wherein at least one rod electrode comprises a metal or at least one plate electrodes comprises a metal or both at least one rod electrode and at least one plate electrode comprise a metal, and wherein the three-dimensional electrode array further comprises an oxygen containing fluid positioned in contact with one or more plate electrodes, one or more rod electrodes or both one or more plate electrodes and one or more rod electrodes.

23. The three-dimensional electrode array of claim 1, wherein at least one rod electrode comprises a porous rod or wherein at least one rod electrode comprises a hollow rod electrode with porous walls.

24. The three-dimensional electrode array of claim 1, wherein the three-dimensional electrode array comprises a component of a flow battery and wherein the three-dimensional electrode array further comprise a plurality of tubes, wherein the plurality of tubes are arranged such that each tube extends a length along an alignment axis passing through an aperture of each plate electrode and wherein at least one rod electrode is positioned within each tube.

25. The three-dimensional electrode array of claim 24, wherein a space within each tube between an inner wall of the tube and a surface of a rod electrode is filled with a fluid, an electrolyte, an aqueous solution or a gas.

26. The three-dimensional electrode array of claim 25, wherein the fluid, electrolyte, aqueous solution or gas flows along an alignment axis passing through an aperture of each plate electrode.

27. The three-dimensional electrode array of claim 24, wherein a space between an outer wall of each and wall of one or more apertures is filled with a fluid, an electrolyte, an aqueous solution or a gas.

28. The three-dimensional electrode array of claim 27, wherein the fluid, electrolyte, aqueous solution or gas flows along an alignment axis passing through an aperture of each plate electrode.

29. A method of controlling a temperature of an electrochemical cell, the method comprising the steps of:

providing an electrochemical cell comprising;

a plurality of plate electrodes, wherein each plate electrode includes an array of apertures, wherein the plate electrodes are arranged in a substantially parallel orientation such that the each aperture of an individual plate electrode is aligned along an alignment axis passing through an aperture of each of all other plate electrodes; and

a plurality of rod electrodes, wherein the plurality of rod electrode are not in physical contact with the plurality of plate electrodes and arranged such that each rod electrode extends a length along an alignment axis passing through an aperture of each plate electrode;

wherein a first surface area includes a cumulative surface area the plurality of plate electrodes, wherein a second surface area includes a cumulative surface area of each aperture array and wherein a third surface area includes a cumulative surface area of each of the plurality of rod electrodes;

wherein each of the plurality of plate electrodes comprises a current collector, wherein each of the plurality of rod electrodes comprises a current collector or wherein each of the plurality of plate electrodes comprises a current collector and each of the plurality of rod electrodes comprises a current collector; and

positioning one or more of the current collectors in thermal communication with a heat sink or a heat source.

30. A method of controlling a temperature of an electrochemical cell, the method comprising the steps of:

providing an electrochemical cell comprising;

a plurality of plate electrodes, wherein each plate electrode includes an array of apertures, wherein the plate electrodes are arranged in a substantially parallel orientation such that the each aperture of an individual plate electrode is aligned along an alignment axis passing through an aperture of each of all other plate electrodes; and

a plurality of rod electrodes, wherein the plurality of rod electrode are not in physical contact with the plurality of plate electrodes and arranged such that each rod electrode extends a length along an alignment axis passing through an aperture of each plate electrode;

one or more heat transfer rods arranged such that each heat transfer rod extends a length along an alignment axis passing through an aperture of each plate electrode;

wherein a first surface area includes a cumulative surface area the plurality of plate electrodes, wherein a second surface area includes a cumulative surface area of each aperture array and wherein a third surface area includes a cumulative surface area of each of the plurality of rod electrodes;

wherein each of the plurality of plate electrodes comprises a current collector, wherein each of the plurality of rod electrodes comprises a current collector or wherein each of the plurality of plate electrodes comprises a current collector and each of the plurality of rod electrodes comprises a current collector; and

positioning one or more of the heat transfer rods in thermal communication with a heat sink or a heat source.

31. A method of making an electrode array, the method comprising the steps of:

providing a plurality of plate electrodes, wherein each plate electrode includes an array of apertures;

arranging the plurality of plate electrodes in a substantially parallel orientation such that the each aperture of an individual plate electrode is aligned along an alignment axis passing through an aperture of each of all other plate electrodes;

providing a plurality of rod electrodes;

and arranging the plurality of rod electrodes such that the plurality of rod electrode are not in physical contact with the plurality of plate electrodes and such that each rod electrode extends a length along an alignment axis passing through an aperture of each plate electrode.

32. A redox flow energy storage device comprising:

a first electrode current collector in the form of a rods, a second electrode current collector in the form of a grid or a grating of crossed bars, and an ion-permeable membrane separating said positive and negative current collectors;

a first electrode disposed between the first electrode current collector and the ion-permeable membrane;

the first electrode current collector and the ion-permeable membrane defining a first electroactive zone accommodating the first electrode;

a second electrode disposed between the second electrode current collector and the ion-permeable membrane;

the second electrode current collector and the ion-permeable membrane defining a second electroactive zone accommodating the negative electrode;

wherein at least one of the first and second electrode comprises a flowable semi-solid or condensed liquid ion-storing redox composition capable of taking up or releasing ions during operation of the cell; and

wherein the first electrode is a positive electrode, the first current collector is a positive electrode current collector, the first electroactive zone is a positive electroactive zone, the second electrode is a negative electrode, the second current collector is a negative electrode current collector, and the second electroactive zone is a negative electroactive zone;

or wherein the first electrode is a negative electrode, the first current collector is a negative electrode current collector, the first electroactive zone is a negative electroactive zone, the second electrode is a positive electrode, the second current collector is a positive electrode current collector, and the second electroactive zone is a positive electroactive zone.

33. A method of operating a redox flow energy storage device, comprising the steps of:

providing a redox flow energy storage device of claim 32; and

transporting the flowable semi-solid or condensed liquid ion-storing redox composition into the electroactive zone during operation of the device.

34. A redox flow battery comprising a stack of perforated plate electrodes and a group of rod electrodes, wherein each rod electrode passes through an aperture of each plate electrode, and anolyte and catholyte compartments divided from each other by an ionically selective and conductive separator and having respective electrodes;

and anolyte and catholyte tanks, with respective pumps and pipeworks to provide fluid communication between the respective anolyte and catholyte tanks and compartements; and

wherein the pumps circulate the electrolytes to and from the tanks, to the compartments and back to the tanks, and wherein electricity flows to a load; and

wherein the electrolyte lines are provided with tappings via which fresh electrolyte can be added and further tappings via which spent electrolyte can be withdrawn, the respective tappings being for anolyte and catholyte; and

wherein, on recharging, via a coupling for lines to all the tappings, a remote pump pumps fresh anolyte and fresh catholyte from remote storages and draws spent electrolyte to other remote storages.