Aluminum-ferricyanide battery

• US 5,472,807 A
• Filed: 11/30/1993
• Issued: 12/05/1995
• Est. Priority Date: 11/30/1993
• Status: Expired due to Term

• Current Assignee: the united states of america as represented by the secretary of the navy
• Original Assignee: the united states of america as represented by the secretary of the navy
• Inventors: Licht, Stuart L., Marsh, Catherine L.
• Primary Examiner(s): Willis, Jr., Prince
• Assistant Examiner(s): NUZZOLILLO, MARIA
• Application Number:
  US08/168,787
• Time in Patent Office: 735 Days
• Field of Search: 429/188, 429/206, 429/207, 429/223
• US Class Current: 429/188
• CPC Class Codes: H01M 12/04 composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
• CPC Class Codes: H01M 4/463 Aluminium based
• CPC Class Codes: H01M 4/58 of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 6/04 Cells with aqueous electrolyte
• CPC Class Codes: H01M 6/34 Immersion cells, e.g. sea-water cells

Abstract

A battery capable of producing high current densities with a high charge acity is described which includes an aluminum anode, a ferricyanide electrolyte and a second electrode capable of reducing ferricyanide electrolyte which is either dissolved in an alkaline solution or alkaline seawater solution. The performance of the battery is enhanced by high temperature and high electrolyte flow rates.

Claims

1. An electrical storage cell comprising two electrochemical half cells positioned in electrochemical contact with one another, at least one of said two half cells comprising:

seawater used as an aqueous salt solution comprising ferricyanide anions, the solution comprising at least about 0.001 molar ferricyanide;

a current transferring electrocatalytic electrode positioned in electron-transferring contact with said aqueous solution; and

the remaining half cell of said two half cells including an anode of material comprised of aluminum at least about 99.99% purity.

2. The electrical storage cell of claim 1 wherein said anode is comprised of an aluminum alloy.

3. An electrical storage cell of claim 1 wherein said seawater used as an aqueous salt solution comprises a multi-phase redox couple having a ferricyanide salt solution and solid phase ferricyanide salts.

4. The electrical storage cell of claim 1 wherein said electrocatalytic electrode comprises a porous material.

5. The electrical storage cell of claim 4 wherein said porous material is nickel.

6. The electrical storage cell of claim 1 in which said electrocatalytic electrode is comprising a metal and an insoluble metal ferricyanide salt.

7. The electrical storage cell of claim 6 wherein said metal having insoluble ferricyanide salt is selected from the group of metals consisting of copper, cobalt, manganese, molybdenum, iridium, zinc, lead, platinum, palladium, nickel and alloys thereof.

8. The electrical storage cell of claim 1 in which said electrocatalytic electrode is comprising a carbon electrode.

9. The electrical storage cell of claim 1 wherein said electrocatalytic electrode is made of graphite.

10. The electrical storage cell of claim 1 further characterized in that said seawater used as the aqueous solution comprises a ferricyanide salt containing at least one cation selected from the group consisting of Li⁺ ions, Na⁺ ions, K⁺ ions, Cs⁺ ions, NH₄⁺ ions, Mg²⁺ ions, Ca²⁺ ions, Ba²⁺ ions and Al³⁺ ions.

11. The electrical storage cell of claim 1 further characterized in that said ferricyanide anion includes a CN^- ligand selected from a group consisting of NH₃, H₂ O, NO₂, and Fe(CN)₅ ^2---.

12. The electrical cell of claim 1 which is further characterized in that said ferricyanide is replaced by ferrocene/ferrocenium.

13. An electrical storage cell of claim 1 in which said seawater used as the aqueous solution includes a hydroxide compound with at least one cation selected from the group consisting of Li⁺ ions, Na⁺ ions, K⁺ ions, Cs⁺ ions, NH⁴⁺ ions, Mg²⁺ ions, Ca²⁺ ions, Ba²⁺ ions, and Al³⁺ ions.

14. An electrical storage cell of claim 1 wherein said seawater used as the aqueous solution includes at least one of a plurality of halides, nitrates and sulfates with at least one cation selected from the group consisting of Li⁺ ions, Na⁺ ions, K⁺ ions, Cs⁺ ions, NH₄ ⁺ ions, Mg²⁺ ions, Ca²⁺ ions, Ba²⁺ ions, and Al³⁺ ions.

15. The electrical storage cell of claim 1 in which said seawater used as the aqueous solution having conductivity ranging from about 0.001 millimho/cm to about 2 mho/cm.

16. An electrical storage cell of claim 1 wherein sodium stannate and gallium oxide are added to said salt solution.

17. The electrical storage cell of claim 1 further comprising means for impeding transfer of chemically reactive species between said seawater used as the aqueous solution and said redox species of said other half cell.

18. The electrical storage cell of claim 17 wherein said means for impeding chemically reactive ion transfer comprises a membrane positioned to separate said first solution from said redox species.

19. The electrical storage cell of claim 18 in which said membrane passes ions to effect ion current transfer.

20. The electrical storage cell of claim 1 which further includes a heat exchanger for controlling temperature of said ferricyanide electrolyte solution.

21. The electrical storage cell of claim 1 which further includes a gas separator for controlling gas buildup in the cell.

22. The electrical storage cell of claim 1 which further includes a solid separator for controlling solid buildup in the cell.

23. The electrical storage cell of claim 1 which further includes an electrolyte reservoir to introduce and store said seawater used as the aqueous solution.

24. The electrical storage cell of claim 1 which additionally includes an electrolyte regulator to regulate the concentration of salts in said seawater used as the aqueous solution.

25. The electrical storage cell of claim 1 which further includes a manifold to distribute flow within said storage cell.

26. The electrical storage cell of claim 1 which further includes a pump to circulate flow of said solution within said seawater used as are cell.

27. The electrical storage cell of claim 1 wherein said aluminum anode is replaced by a material selected from the group consisting of a lithium anode of at least 99.99% purity, and a lithium alloy.

28. The electrical storage cell of claim 1 wherein said anode material is replaced by a calcium anode of at least 99.99% purity.

29. The electrical storage cell of claim 1 wherein the aluminum anode is replaced by a magnesium anode material.

30. A method of generating a direct current between a first contact point and a second contact point in an electrical storage cell including two half cells having seawater used as an aqueous salt solution including ferricyanide anions, a current transferring electrocatalytic electrode positioned in said aqueous solution and an anode which includes the steps of:

providing said aqueous salt solution comprising ferricyanide anions, said solution comprising 0.001 m by weight;

positioning a solid electrode in electron-transferring contact with said aqueous solution and in electron-transferring contact with said second contact point;

providing an aluminum redox couple complementary to said ferricyanide anions, positioned in ion-current transferring contact with said aqueous solution and in electron-transferring contact with said second contact point;

establishing electrical contact with said first contact point and said second contact point; and

whereby said ferricyanide anions are reduced and said aluminum is oxidized, generating an electrical current and potential between said first contact point and said second contact point.

31. The method of claim 30 wherein the aluminum anode is replaced with a lithium anode material.

32. The method of claim 30 wherein the aluminum anode is replaced with calcium.

33. The method of claim 30 wherein the ferricyanide is replaced with ferrocenium.

34. The method of claim 31 wherein the ferricyanide is replaced with ferrocenium.

35. The method of claim 32 wherein the ferricyanide is replaced with ferrocenium.

36. The method of claim 30 wherein the aluminum anode is replaced with a magnesium anode.

37. The method of claim 36 wherein the ferricyanide is replaced with ferrocenium.