High energy density redox flow device

• US 8,722,226 B2
• Filed: 12/16/2010
• Issued: 05/13/2014
• Est. Priority Date: 06/12/2008
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: 24M Technologies, Inc.
• Inventors: Chiang, Yet-Ming, Carter, William Craig, Duduta, Mihai, Limthongkul, Pimpa
• Primary Examiner(s): Conley, Helen O
• Application Number:
  US12/970,773
• Publication Number:
  US 20110189520A1
• Time in Patent Office: 1,244 Days
• Field of Search: 429/105, 429/101, 429/81
• US Class Current: 429/105
• 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 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.

2. The energy storage system of claim 1, wherein the finest particles present in at least 5 vol % of the total volume, is at least a factor of 7 smaller than the largest particles present in at least 5 vol % of the total volume.

3. The energy storage system of claim 1, wherein the finest particles present in at least 5 vol % of the total volume, is at least a factor of 10 smaller than the largest particles present in at least 5 vol % of the total volume.

4. The energy storage system of claim 1, wherein the ion storage compound particles have a bidisperse size distribution in which the two maxima differ in size by at least a factor of 5.

5. The energy storage system of claim 1, wherein the particle packing fraction is at least 50 vol %, preferably at least 55 vol %, more preferably at least 60 vol %, still more preferably at least 65 vol %, and still more preferably at least 70 vol %.

6. The energy storage system of claim 1, wherein the particles have morphology that is at least equiaxed.

7. The energy storage system of claim 2, the particle size of the maxima for the larger particles is at least 1 micrometer and preferably at least 10 micrometers.

8. The energy storage system of claim 1, further comprising a redox mediator.

9. The energy storage system of claim 8, wherein the redox mediator is soluble in the semi-solid composition and comprises multiple oxidation states.

10. The energy storage system of claim 8, wherein the redox mediator comprises a redox metal ion selected from iron, vanadium, chromium and zinc and mixtures thereof.

11. The energy storage system of claim 8, wherein the redox mediator comprises ferrocene.

12. The energy storage system of claim 1, wherein the semi-solid ion-storing redox composition further comprises an electronically conductive material.

13. The energy storage system of claim 12, wherein the electronically conductive material comprises a conductive inorganic compound.

14. The energy storage system of claim 12, wherein 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.

15. The energy storage system of claim 12, wherein the electronically conductive material comprises an electronically conductive polymer.

16. The energy storage system of claim 15, wherein the electronically conductive polymer 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.

17. The energy storage system of claim 12, wherein the electronically conductive material coats the ion storage compound particles.

18. The energy storage system of claim 1, wherein the one or both of the positive and negative current collector is coated with an electronically conductive material.

19. The energy storage system of claim 17, wherein the conductive-coating material is selected from the group consisting of carbon, a metal, metal carbide, metal nitride, metal oxide, conductive polymers, 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.

20. The energy storage system of claim 15, wherein the conductive polymer is a compound that reacts in-situ to form a conductive polymer on the surface of the current collector.

21. The energy storage system of claim 20, wherein the compound comprises 2-hexylthiophene and oxidizes at a high potential to form a conductive polymer coating on the current collector.

22. The energy storage system of claim 1, further comprising:

at least one storage tank external to the flow cell for holding, delivering and/or receiving the flowable semi-solid composition; and

a cut-off valve for reversibly isolating the storage tank from the flow cell.

23. The energy storage system of claim 1,

wherein 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 one of said positive and negative electroactive zone comprises an aqueous redox solution capable of taking up or releasing said ions during operation of the cell and an electronically conductive material.

24. The energy storage system of claim 23, wherein 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.

25. The energy storage system of claim 23, wherein the electronically conductive material is selected from the group consisting of solid inorganic conductive materials, 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.

26. The energy storage system of claim 1, wherein the particle packing fraction is at least 55 vol %.

27. The energy storage system of claim 1, wherein the particle packing fraction is at least 60 vol %.

28. The energy storage system of claim 1, wherein the particle packing fraction is at least, at least 70 vol %.

29. The energy storage system of claim 12, wherein the electronically conductive material forms a percolative conductive pathway.

30. The energy storage system of claim 23, wherein the electronically conductive material forms a percolative conductive pathway.