Redox flow battery system and cell stack

• US 6,475,661 B1
• Filed: 04/24/2000
• Issued: 11/05/2002
• Est. Priority Date: 01/28/1998
• Status: Expired due to Fees

• Current Assignee: SandBox Enterprises LLC (U.S. Silica Holdings, Inc.)
• Original Assignee: Squirrel Holdings Ltd.
• Inventors: Pellegri, Alberto, Broman, Barry Michael
• Primary Examiner(s): Kalafut, Stephen
• Assistant Examiner(s): ANTHONY, JULIAN
• Application Number:
  US09/463,624
• Time in Patent Office: 925 Days
• Field of Search: 429/105, 429/72
• US Class Current: 429/105
• CPC Class Codes: H01M 50/77 with external circulating path
• CPC Class Codes: H01M 8/04186 of liquid-charged or electrolyte-charged reactants
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A redox flow battery composed of a plurality of cells in electrical series defined by a stacked and repetitive arrangement of a conductive intercell separator having a generally bipolar function, a positive electrode, an ion exchange membrane, a negative electrode and another conductive intercell separator, is operated by flowing a positive half-cell electrolyte containing reducible and oxidizable ions of a first redox couple through the compartments containing the positive electrodes and a negative half-cell electrolyte containing reducible and oxidizable ions of a second redox couple through the compartments containing the negative electrodes in cascade in a counter or equi-current mode. The difference of cell voltage between the first and the last cell of the stack is sensibly reduced and by-pass currents are substantially eliminated thus resulting in an increased overall faradic efficiency. A cell stack architecture provided with ducting for implementing the two counter current cascaded flows of the positive and negative electrolytes is described. The alternated used of cationic and anionic membranes compensate for unbalanced water transport through the membranes.

Claims

1. A method of operating a redox flow battery comprising a plurality of cells in electrical series defined by a stacked and repetitive arrangement of a conductive intercell separator having a generally bipolar function, a positive electrode, an ion exchange membrane, a negative electrode and another conductive intercell separator, each electrode being confined in a flow compartment, comprising:

flowing a positive half-cell electrolyte containing reducible and oxidizable ions of a first redox couple through the compartments containing said positive electrodes and flowing a negative half-cell electrolyte containing reducible and oxidizable ions of a second redox couple through the compartments containing said negative electrodes,

wherein each of said negative half-cell electrolyte and said positive half-cell electrolyte separately flow through respective compartments of said stack in cascade through the plurality of cells by

introducing each electrolyte with a given state of charge into the respective compartment of a first cell, at one end of the stack, and

recovering each electrolyte from the respective compartment of a last cell of the stack, at the other end thereof, in a modified state of charge depending on the level and direction of electric current passed through the battery during a transit time through a given volume of electrolyte.

2. The method of claim 1, wherein said electrolytes circulate though respective recirculation tanks.

3. The method of claim 1, wherein each of said electrolytes is flown from a respective charged electrolyte storing tank to a respective discharged electrolyte recovery tank during a discharge phase and in the opposite direction during a charge phase of operation.

4. The method of claim 3, wherein said respective charged electrolyte tanks are disposed at an elevated level above said plurality of cells, and said discharged electrolyte tanks are disposed at a lower level that the elevated level of said plurality of cells.

5. The method according to claim 1, wherein the respective streams of negative half-cell electrolyte and positive half-cell electrolyte in cascade through the plurality of cells of the stack are conducted in an equicurrent mode.

6. The method of claim 1, further comprising interrupting a liquid vein of each of two respective streams of electrolyte along their respective paths.

7. The method of claim 1, wherein the redox flow battery employs a V(III)/V(II) redox couple in the negative half-cell electrolyte and a V(V)/V(IV) redox couple in the positive half-cell electrolyte.

8. A method of operating a redox flow battery comprising a plurality of cells in electrical series defined by a stacked and repetitive arrangement of a conductive intercell separator having a generally bipolar function, a positive electrode, an ion exchange membrane, a negative electrode and another conductive intercell separator, each electrode being confined in a flow compartment, comprising:

flowing a positive half-cell electrolyte containing reducible and oxidizable ions of a first redox couple through the compartments containing said positive electrodes and flowing a negative half-cell electrolyte containing reducible and oxidizable ions of a second redox couple through the compartments containing said negative electrodes;

flowing said negative half-cell electrolyte and said positive half-cell electrolyte through respective compartments of said stack in cascade through the plurality of cells by

introducing each electrolyte with a given state of charge into the respective compartment of a first cell, at one end of the stack, and

recovering each electrolyte from the respective compartment of a last cell of the stack, at the other end thereof, in a modified state of charge depending on the level and direction of electric current passed through the battery during a transit time through a given volume of electrolyte,

wherein respective streams of negative half-cell electrolyte and positive half-cell electrolyte flow in cascade through the plurality of cells of the stack are conducted in a countercurrent mode.

9. The method according to claim 8, wherein, in a discharge phase, the two streams of negative half-cell electrolyte and of positive half-cell electrolyte, respectively, outlet from the respective flow compartment of the respective last cell of the stack or of a plurality of stacks hydraulically fed in cascade, are recovered in a unified electrolyte tank and, in a charge phase, the spent electrolyte is flown from said unified tank in two separate streams, respectively of negative half-cell electrolyte and positive half-cell electrolyte, through the respective flow compartments of the cells of the stack or of the plurality of stacks and each stream, outlet from the respective flow compartment of the respective last cell, is collected separately in a respective charged electrolyte tank.

10. The method of claim 9, wherein said respective charged electrolyte tank is disposed at an elevated level above said plurality of cells, and said unified electrolyte tank is disposed at a level lower than the elevated level of said plurality of cells.

11. A redox flow battery plant, comprising:

a plurality of stacked cells in electrical series defined by a stacked and repetitive arrangement of a conductive intercell separator having a generally bipolar function;

a positive electrode;

an ion exchange membrane;

a negative electrode;

another conductive intercell separator,

wherein each electrode is confined in a flow compartment;

at least a storage tank for a positive half-cell electrolyte;

at least a storage tank for a negative half-cell electrolyte;

negative half-cell electrolyte ducting and pumping means for flowing said negative half-cell electrolyte solution through respective flow compartments of said cells; and

positive half-cell electrolyte ducting and pumping means for flowing said positive half-cell electrolyte solution through respective flow compartments of said cells,

wherein said negative half-cell electrolyte and said positive half-cell electrolyte ducting include means for flowing said positive half-cell electrolyte solution and said negative half-cell electrolyte solution in cascade from a respective flow compartment of a first cell of said plurality of stacked cells, to the respective flow compartment of a last cell of said plurality of stacked cells.

12. The redox flow battery system of claim 11, further comprising:

a first charged negative half-cell electrolyte storing tank;

a second spent negative half-cell electrolyte recovery tank;

a third charged positive half-cell electrolyte storing tank; and

a fourth spent positive half-cell electrolyte recovery tank;

said negative half-cell electrolyte and said positive half-cell electrolyte being flown from their respective charged electrolyte storage tanks to their respective spent electrolyte recovery tanks during a discharge phase of the battery, and from said respective spent electrolyte recovery tanks to said respective charged electrolyte storing tanks during a charging phase of the battery.

13. The redox flow battery system of claim 12, wherein said respective charged electrolyte storage tanks are disposed at an elevated level above said cells, and said spent electrolyte recovery tanks are disposed at a level lower than the level of said cells.

14. The redox flow battery system of claim 11, wherein said ducting means comprise at least a liquid vein interrupter along a flow path of each of said positive and negative half-cell electrolytes.

15. The redox flow battery system of claim 14, wherein each of said at least a liquid interrupter is in a form of a flood-and-drip column installed at an inlet of an electrolyte tank.

16. The redox flow battery system of claim 11, wherein the ion exchange membranes of said plurality of stacked cells are alternately cationic and anionic.

17. The redox flow battery system according to claim 16, wherein a type of ion exchange membrane alternates from a cell to a next cell.

18. (Amended) The redox flow battery system according to claim 16, wherein a type of ion exchange membrane alternates from a stack of cells to a next stack of cells.

19. A redox flow battery plant, comprising:

a plurality of stacked cells in electrical series defined by a stacked and repetitive arrangement of a conductive intercell separator having a generally bipolar function;

a positive electrode;

an ion exchange membrane;

a negative electrode;

another conductive intercell separator,

wherein each electrode is confined in a flow compartment;

at least a storage tank for a positive half-cell electrolyte;

at least a storage tank for a negative half-cell electrolyte;

negative half-cell electrolyte ducting and pumping means for flowing said negative half-cell electrolyte solution through respective flow compartments of said cells;

positive half-cell electrolyte ducting and pumping means for flowing said positive half-cell electrolyte solution through respective flow compartments of said cells,

a first charged negative half-cell electrolyte storing tank;

a second spent negative half-cell electrolyte recovery tank;

a third charged positive half-cell electrolyte storing tank; and

a fourth spent positive half-cell electrolyte recovery tank;

wherein said negative half-cell electrolyte and said positive half-cell electrolyte ducting include means for flowing said positive half-cell electrolyte solution and said negative half-cell electrolyte solution in cascade from a respective flow compartment of a first cell of said plurality of stacked cells, to the respective flow compartment of a last cell of said plurality of stacked cells,

said negative half-cell electrolyte and said positive half-cell electrolyte being flown from their respective charged electrolyte storage tanks to their respective spent electrolyte recovery tanks during a discharge phase of the battery, and from said respective spent electrolyte recovery tanks to said respective charged electrolyte storing tanks during a charging phase of the battery,

wherein said spent electrolyte recovery tanks are unified in a single recovery tank where said spent negative half-cell and positive half-cell electrolytes, circulated through the respective compartments of said plurality of stacked cells in a counter current mode, are mixed together.