Aqueous redox flow batteries comprising matched ionomer membranes

• US 9,692,077 B2
• Filed: 07/24/2013
• Issued: 06/27/2017
• Est. Priority Date: 07/27/2012
• Status: Active Grant

• Current Assignee: Lockheed Martin Energy LLC (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Advanced Energy Storage, LLC (Martin Marietta Corporation)
• Inventors: Jarvi, Thomas D., Esswein, Arthur J., Goeltz, John, King, Evan R., Amadeo, Desiree, Tyagi, Nitin, Reece, Steven Y.
• Primary Examiner(s): Alejandro, Raymond
• Application Number:
  US13/949,324
• Publication Number:
  US 20140051002A1
• Time in Patent Office: 1,434 Days
• CPC Class Codes: H01M 8/1032 having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• CPC Class Codes: H01M 8/1039 halogenated, e.g. sulfonated polyvinylidene fluorides
• CPC Class Codes: H01M 8/1067 characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
• 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 60/50 Fuel cells

Abstract

This invention is directed to aqueous redox flow batteries comprising ionically charged redox active materials and ionomer membranes, wherein the charge of the redox active materials is of the same sign as that of the ionomer, so as to confer specific improvements.

Claims

1. A flow battery comprising:

a first aqueous electrolyte comprising a first redox active material, the first redox active material being a first metal ligand coordination compound bearing a first ionic charge;

a second aqueous electrolyte comprising a second redox active material, the second redox active material being a second metal ligand coordination compound bearing a second ionic charge;

a first electrode in contact with said first aqueous electrolyte;

a second electrode in contact with said second aqueous electrolyte; and

a separator comprising an ionomer membrane disposed between said first and second aqueous electrolytes, the ionomer membrane comprising a polymer with ionized repeating units and electrically neutral repeating units;

wherein the first redox active material and the second redox active material differ from one another, the first ionic charge has a sign that is the same in an oxidized form and a reduced form of the first redox active material, the second ionic charge has a sign that is the same in an oxidized form and a reduced form of the second redox active material, and the signs of the first ionic charge and the second ionic charge are individually the same as a charge sign of the ionized repeating units in the ionomer membrane; and

wherein the flow battery operates or is capable of operating;

(a) where the first or second redox active materials comprise 3% or less of the molar flux of ions passing through the ionomer membrane;

or

(b) with a round trip current efficiency that is at least about 95%;

or

(c) at a current density of at least 100 mA/cm² with a round trip voltage efficiency of at least about 90%;

or

(d) with the electrolytes having an energy density of at least about 30 Wh/L;

or

(e) with a combination of any two or more of (a), (b), (c), and (d).

2. The flow battery of claim 1, wherein the ionomer membrane has a thickness of less than 100 μ

m.

3. The flow battery of claim 1, wherein the ionomer membrane comprises a fluoropolymer.

4. The flow battery of claim 1, wherein the ionized repeating units comprise covalently attached or embedded sulfonate, carboxylate, quaternary ammonium, sulfonium, phosphazenium, or guanidinium residues, or salts thereof.

5. The flow battery of claim 1, wherein at least one of the first and second redox active materials exhibits substantially reversible electrochemical kinetics.

6. The flow battery of claim 1, wherein at least one of the first electrode and the second electrode presents a surface of an allotrope of carbon to the first aqueous electrolyte or the second aqueous electrolyte.

7. The flow battery of claim 1, wherein first electrode presents a surface of an allotrope of carbon to the first aqueous electrolyte and the second electrode presents a surface of an allotrope of carbon to the second aqueous electrolyte.

8. The flow battery of claim 1, wherein the first and second aqueous electrolytes each exhibit a pH in a range of about 7 to about 13, about 8 to about 13, about 9 to about 13, about 10 to about 13, about 10 to about 12, or about 11.

9. The flow battery of claim 1, wherein both the first and second ionic charges are negative in the oxidized and reduced forms of the first redox active material and the second redox active material.

10. The flow battery of claim 9, wherein the first and second ionic charges range from −

2 to −

5 in the first redox active material and the second redox active material.

11. The flow battery of claim 1, where both the first and second ionic charges are positive in the oxidized and reduced forms of the first redox active material and the second redox active material.

12. The flow battery of claim 11, wherein the first and second ionic charges range from +2 to +5 in the first redox active material and the second redox active material.

13. The flow battery of claim 1, wherein the flow battery exhibits a round trip current efficiency of at least 98% over a state-of-charge in a range from about 35% to about 65%.

14. The flow battery of claim 1, further comprising:

an external electrical circuit in electrical communication with the first and second electrodes, said external electrical circuit being capable of charging or discharging the flow battery.

15. The flow battery of claim 1, wherein the first and second aqueous electrolytes have an energy density of at least 10 Wh/L, at least 20 Wh/L, or at least 30 Wh/L.

16. A method of operating the flow battery of claim 1, said method comprising:

charging said flow battery by an input of electrical energy or discharging said flow battery by a removal of electrical energy.

17. A method of operating the flow battery of claim 1, said method comprising:

applying a potential difference across the first and second electrodes, with an associated flow of electrons, so as to;

(a) reduce the first redox active material while oxidizing the second redox active material;

or

(b) oxidize the first redox active material while reducing the second redox active material.

18. A system comprising:

the flow battery of claim 1 and the system further comprising;

(a) a first chamber containing the first aqueous electrolyte and a second chamber containing the second aqueous electrolyte;

(b) at least one electrolyte circulation loop in fluidic communication with each chamber, said at least one electrolyte circulation loop comprising a storage tank and piping for containing and transporting the first and second aqueous electrolytes;

(c) control hardware and software; and

(d) an optional power conditioning unit.

19. The system of claim 18, the system being adapted for connection to an electrical grid configured so as to provide renewables integration, peak load shifting, grid firming, baseload power generation/consumption, energy arbitrage, transmission and distribution asset deferral, weak grid support, frequency regulation, or a combination thereof.

20. The system of claim 18, the system being configured to provide stable power for remote camps, forward operating bases, off-grid telecommunications, or remote sensors.