High Efficiency Iron Electrode and Additives for Use in Rechargeable Iron-Based Batteries

• US 20130149615A1
• Filed: 06/15/2012
• Published: 06/13/2013
• Est. Priority Date: 06/15/2011
• Status: Active Grant

• Current Assignee: University of Southern California
• Original Assignee: University of Southern California
• Inventors: Narayan, Sri R., Prakash, G.K. Surya, Aniszfeld, Robert, Manohar, Aswin, Malkhandi, Souradip, Yang, Bo
• Granted Patent: US 9,577,298 B2
• Time in Patent Office: Days
• US Class Current: 429/405
• CPC Class Codes: H01M 10/26 Selection of materials as electrolytes
• CPC Class Codes: H01M 10/30 Nickel accumulators H01M10/34 takes precedence
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 12/065 with plate-like electrodes or stacks of plate-like electrodes
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2220/10 Batteries in stationary systems, e.g. emergency power source in plant
• CPC Class Codes: H01M 4/12 of consumable metal or alloy electrodes use of alloy compositions as active materials H01M4/38
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An iron electrode and a method of manufacturing an iron electrode for use in an iron-based rechargeable battery are disclosed. In one embodiment, the iron electrode includes carbonyl iron powder and one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin for suppressing hydrogen evolution at the iron electrode during charging of the iron-based rechargeable battery. An iron-air rechargeable battery including an iron electrode comprising carbonyl iron is also disclosed, as is an iron-air battery wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

Claims

1. An iron electrode for use in an iron-based rechargeable battery, the electrode comprising carbonyl iron and one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin for suppressing hydrogen evolution at the iron electrode during charging of the iron-based rechargeable battery.

2. The electrode of claim 1, wherein the additive includes bismuth sulfide.

3. The electrode of claim 2, wherein the iron electrode comprises approximately 50-99 w/w % carbonyl iron, approximately 5-30 w/w % polymeric binder, and approximately 1-10 w/w % bismuth sulfide.

4. The electrode of claim 1, further comprising an organosulfur additive.

5. The electrode of claim 4, wherein the organosulfur additive is an alkanethiol.

6. The electrode of claim 5, wherein the alkanethiol has a chain length in the range of n=6 to n=8.

7. The electrode of claim 4, wherein the organosulfur additive is selected from the group consisting of linear and cyclic thiols, dithiols, and thioethers.

8. The electrode of claim 7, wherein the organosulfur additive is selected from the group consisting of 3,6-dioxa-1,8-octanedithiol, p-dithiane, 1,2-ethanedithiol, bismethylthiomethane, 1-octanethiol, sodium propanethiolate, and hexanethiol.

9. An iron-air rechargeable battery, comprising:

an iron electrode comprising carbonyl iron;

an air electrode spaced from the iron electrode; and

an electrolyte in contact with the iron electrode and the air electrode.

10. The battery of claim 9, wherein the iron electrode includes one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin.

11. The battery of claim 10, wherein the additive includes bismuth sulfide.

12. The battery of claim 11, wherein the iron electrode comprises approximately 50-99 w/w % carbonyl iron, approximately 5-30 w/w % polymeric binder, and approximately 1-10 w/w % bismuth sulfide.

13. The battery of claim 9, wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

14. The battery of claim 13, wherein the organosulfur additive is an alkanethiol.

15. The battery of claim 14, wherein the alkanethiol has a chain length in the range of n=6 to n=8.

16. The battery of claim 13, wherein the organosulfur additive is selected from the group consisting of linear and cyclic thiols, dithiols, and thioethers.

17. The battery of claim 16, wherein the organosulfur additive is selected from the group consisting of 3,6-dioxa-1,8-octanedithiol, p-dithiane, 1,2-ethanedithiol, bismethylthiomethane, 1-octanethiol, sodium propanethiolate, and hexanethiol.

18. An iron-air rechargeable battery, comprising:

an iron electrode;

an air electrode spaced from the iron electrode; and

an electrolyte in contact with the iron electrode and the air electrode, wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

19. The battery of claim 18, wherein the organosulfur additive is an alkanethiol.

20. The battery of claim 19, wherein the alkanethiol has a chain length in the range of n=6 to n=8.

21. The battery of claim 18, wherein the organosulfur additive is selected from the group consisting of linear and cyclic thiols, dithiols, and thioethers.

22. The battery of claim 21, wherein the organosulfur additive is selected from the group consisting of 3,6-dioxa-1,8-octanedithiol, p-dithiane, 1,2-ethanedithiol, bismethylthiomethane, 1-octanethiol, sodium propanethiolate, and hexanethiol.

23. The battery of claim 18, wherein the iron electrode comprises carbonyl iron.

24. The battery of claim 18, wherein the iron electrode includes one of a metal sulfide additive or metal oxide additive selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin.

25. The battery of claim 24, wherein the additive includes bismuth sulfide.

26. A method for manufacturing an iron electrode for use in an iron-based rechargeable battery, the method comprising:

combining carbonyl iron powder with a polymeric binder to create a mixture;

coating a metallic grid with the mixture; and

heating and applying pressure to the grid to form a pressed-plate iron electrode.

27. The method of claim 26, further comprising combining one of a metal sulfide additive or metal oxide additive in the mixture selected from the group of metals consisting of bismuth, lead, mercury, indium, gallium, and tin.

28. The method of claim 27, wherein the additive includes bismuth sulfide.

29. The method of claim 26, further comprising charging and discharging the formed electrode a plurality of times to allow the discharge capacity to increase to a stable value and the electrode to reach a lower hydrogen evolution rate.