High Energy Density Redox Flow Device

• US 20140154546A1
• Filed: 12/16/2011
• Published: 06/05/2014
• Est. Priority Date: 06/12/2008
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: 24M Technologies, Inc.
• Inventors: Carter, W. Craig, Chiang, Yet-Ming, Duduta, Mihai, Limthongkul, Pimpa
• Granted Patent: US 9,614,231 B2
• Time in Patent Office: Days
• US Class Current: 429/101
• CPC Class Codes: B60L 50/64 Constructional details of batteries specially adapted for electric vehicles
• CPC Class Codes: H01M 8/0206 Metals or alloys
• CPC Class Codes: H01M 8/0215 Glass; Ceramic materials
• CPC Class Codes: H01M 8/0221 Organic resins; Organic polymers
• CPC Class Codes: H01M 8/0228 in the form of layered or coated products
• CPC Class Codes: H01M 8/0234 Carbonaceous material
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• 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 60/50 Fuel cells
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

Redox flow devices are described including a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone; wherein at least one of said positive and negative electroactive zone comprises a flowable semi-solid composition comprising ion storage compound particles capable of taking up or releasing said ions during operation of the cell, and wherein the ion storage compound particles have a polydisperse size distribution in which the finest particles present in at least 5 vol % of the total volume, is at least a factor of 5 smaller than the largest particles present in at least 5 vol % of the total volume.

Claims

1. A flow cell energy storage system comprising:

a positive electrode current collector, a negative electrode current collector, and an ion-permeable membrane separating said positive and negative current collectors, positioned and arranged to define a positive electroactive zone and a negative electroactive zone;

wherein at least one of said positive and negative electroactive zone comprises a flowable electrode composition comprising an ion storage compound capable of taking up or releasing said ions during operation of the cell and a conductive network of electronically conductive particles.

2. The energy storage system of claim 1, wherein electronically conductive particles form a percolating network throughout the entirety of the electroactive zone.

3. The energy storage system of claim 1, wherein electronically conductive particles form a percolating network for a portion of the electroactive zone.

4. The energy storage system of claim 1, wherein electronically conductive particles do not form agglomerates in the flowable electrode composition.

5. The energy storage system of claim 1, wherein the electronically conductive particles comprises 0.5 to 10% by volume of the flowable electrode composition, and preferably, the electronically conductive particles comprises 0.5 to 5% by volume of the flowable electrode composition.

6. The energy storage system of claim 1, wherein the flowable electrode composition comprises a condensed liquid composition.

7. The energy storage system of claim 1, wherein the flowable electrode composition comprises a semi-solid composition.

8. The energy storage system of claim 1, wherein the ion storage compound comprises an electronically insulating organic or organometallic redox compound.

9. The energy storage system of claim 1, wherein the ion storage compound comprises an aqueous redox reagent.

10. The energy storage system of claim 1, wherein the electronically conductive particles comprise a conductive inorganic compound, and optionally,

the electronically conductive material is selected from the group consisting of metals, metal carbides, metal nitrides, metal oxides, and allotropes of carbon including carbon black, graphitic carbon, carbon fibers, carbon microfibers, vapor-grown carbon fibers (VGCF), fullerenic carbons including “

buckyballs”

, carbon nanotubes (CNTs), multiwall carbon nanotubes (MWNTs), single wall carbon nanotubes (SWNTs), graphene sheets or aggregates of graphene sheets, and materials comprising fullerenic fragments and mixtures thereof.

11. The energy storage system of claim 1, wherein the electronically conductive particles comprise an electronically conductive polymer, and optionally,

the electronically conductive material is selected from the group consisting of polyaniline or polyacetylene based conductive polymers or poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyazulene, polyfluorene, polynaphtalene, polyanthracene, polyfuran, polycarbazole, tetrathiafulvalene-substituted polystyrene, ferrocence-substituted polyethylene, carbazole-substituted polyethylene, polyoxyphenazine, polyacenes, or poly(heteroacenes) and mixtures thereof.

12. The energy storage system of claim 8, wherein the organic redox-active storage materials is selected from the group consisting of electronically insulating compounds such as polynitroxide or organic radical electrodes, carbonyl based organics, and oxocarbons and carboxylate, including compounds such as Li₂C₆O₆, Li₂C₈H₄O₄, and Li₂C₆H₄O₄, organosulfur compounds, ionic liquid molecules functionalized with a redox-active transition metal, transition metal acetylacetonate complexes (for example, ruthenium, vanadium, chromium or manganese acetylacetonate), metal bipyridine complexes (for example, Fe(bipy)₃, Ru(bipy)₃, VO(bipy)₃, Ni(bipy)₃, and similar compounds such as Ni(phen)₃ and Fe(phen)₃.

13. The energy storage system of claim 1, wherein the flowable electrode composition does not flow during operation.

14. The energy storage system of claim 13, wherein the flowable electrode composition is flowable during assembly.

15. The energy storage system of claim 6, wherein the condensed liquid composition is a solid at the temperature of operation and the system provides a stationary nonflowing electrode.

16-28. -28. (canceled)