High efficiency iron electrode and additives for use in rechargeable iron-based batteries

• US 9,577,298 B2
• Filed: 06/15/2012
• Issued: 02/21/2017
• 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
• Primary Examiner(s): Laios, Maria J
• Application Number:
  US13/524,761
• Publication Number:
  US 20130149615A1
• Time in Patent Office: 1,712 Days
• Field of Search: 429402-405
• US Class Current: 1/1
• 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 iron electrode comprising carbonyl iron, a polymeric binder, and an additive for suppressing hydrogen evolution at the iron electrode during charging of the iron-based rechargeable battery, wherein the additive includes bismuth sulfide in an amount from 5 to 10 w/w % bismuth sulfide of the weight of the iron electrode.

2. The iron electrode of claim 1, wherein the iron electrode comprises approximately 76 w/w % carbonyl iron, approximately 10 w/w % soluble additive, approximately 9 w/w % polymeric binder, and approximately 5 w/w % bismuth sulfide.

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

4. The electrode of claim 3, wherein the organosulfur additive is an alkanethiol.

5. The electrode of claim 4, wherein the alkanethiol has a chain length in the range of n=6 to n=8.

6. The iron electrode of claim 3, wherein the organosulfur additive is selected from the group consisting of linear and cyclic thiols, dithiols, and thioethers.

7. The iron electrode of claim 6, 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.

8. The iron electrode of claim 1 having approximately 50-99 w/w % carbonyl iron and approximately 5-30 w/w % polymeric binder.

9. The iron electrode of claim 1 made by 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 the iron electrode, the iron electrode being a pressed-plate iron electrode.

10. An iron-air rechargeable battery, comprising:

an iron electrode comprising carbonyl iron, a polymeric binder, and bismuth sulfide, wherein the bismuth sulfide is present in an amount from 5 to 10 w/w % bismuth sulfide of the weight of the iron electrode;

an air electrode spaced from the iron electrode; and

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

11. The iron-air rechargeable battery of claim 10, wherein at least one of the iron electrode and the electrolyte includes an organosulfur additive.

12. The battery of claim 11, wherein the organosulfur additive is an alkanethiol.

13. The battery of claim 12, wherein the alkanethiol has a chain length in the range of n=6 to n=8.

14. The iron-air rechargeable battery of claim 11, wherein the organosulfur additive is selected from the group consisting of linear and cyclic thiols, dithiols, and thioethers.

15. The iron-air rechargeable battery of claim 14, 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.

16. An iron-air rechargeable battery, comprising:

an iron electrode that includes bismuth sulfide in an amount from 5 to 10 w/w % bismuth sulfide of the weight of the iron electrode;

an air electrode spaced from the iron electrode; and

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

17. The battery of claim 16, wherein the organosulfur additive is an alkanethiol.

18. The battery of claim 17, wherein the alkanethiol has a chain length in the range of n=6 to n=8.

19. The iron-air rechargeable battery of claim 16, wherein the organosulfur additive is selected from the group consisting of linear and cyclic thiols, dithiols, and thioethers.

20. The iron-air rechargeable battery of claim 19, 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.