Aluminum batteries comprising metal-oxide, metal-fluoride, metal-sulfide, or sulfur cathodes

• US 8,715,853 B1
• Filed: 08/25/2010
• Issued: 05/06/2014
• Est. Priority Date: 08/25/2010
• Status: Active Grant

• Current Assignee: HRL Laboratories LLC (The Boeing Co.)
• Original Assignee: HRL Laboratories LLC (The Boeing Co.)
• Inventors: Vajo, John J., Gross, Adam F., Liu, Ping, Hicks-Garner, Jocelyn, Sherman, Elena, Van Atta, Sky
• Primary Examiner(s): RHEE, JANE J
• Application Number:
  US12/868,479
• Time in Patent Office: 1,350 Days
• Field of Search: 429/200, 429/209, 429/221, 429/220, 429/223, 429/219
• US Class Current: 429/209
• CPC Class Codes: H01M 10/054 Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 10/399 Cells with molten salts
• CPC Class Codes: H01M 2300/0031 Chlorinated solvents
• CPC Class Codes: H01M 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/044 Activating, forming or electrochemical attack of the supporting material
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/36 Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 4/463 Aluminium based
• CPC Class Codes: H01M 4/48 of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/483 for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/5815 Sulfides
• CPC Class Codes: H01M 4/582 Halogenides
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/80 Porous plates, e.g. sintered carriers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Variations of the invention provide an improved aluminum battery consisting of an aluminum anode, a non-aqueous electrolyte, and a cathode comprising a metal oxide, a metal fluoride, a metal sulfide, or sulfur. The cathode can be fully reduced upon battery discharge via a multiple-electron reduction reaction. In some embodiments, the cathode materials are contained within the pore volume of a porous conductive carbon scaffold. Batteries provided by the invention have high active material specific energy densities and good cycling stabilities at a variety of operating temperatures.

Claims

1. An aluminum battery comprising an aluminum-containing anode, a non-aqueous electrolyte, and a cathode,

wherein said cathode comprises one or more cathode active materials selected from the group consisting of metal (M) oxides and metal (M) fluorides;

and

wherein said battery has a multiple-electron-reduction discharge state wherein the ratio of the number of Al atoms to the number of M atoms in the cathode is about 0.4 or greater.

2. The aluminum battery of claim 1, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 0.6 or greater.

3. The aluminum battery of claim 2, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 0.8 or greater.

4. The aluminum battery of claim 3, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 1.0 or greater.

5. The aluminum battery of claim 4, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 1.2 or greater.

6. The aluminum battery of claim 1, wherein said cathode active material is one or more metal oxides selected from the group consisting of CuO, P₂O₅, SnO₂, PbO₂, FeO, Fe₂O₃, CoO, Co₂O₃, NiO, and AgO.

7. The aluminum battery of claim 1, wherein said cathode active material is one or more metal fluorides selected from the group consisting of CoF₂, CoF₃, FeF₂, FeF₃, CuF₂, MoF₅, and SnF₄.

8. The aluminum battery of claim 1, wherein said non-aqueous electrolyte is a mixture of aluminum chloride and an organic salt selected from the group consisting of n-butyl pyridinium chloride, 1-methyl-3-ethylimidazolium chloride, 1,2-dimethyl-3-propylimidazolium chloride, 1,4-dimethyl-1,2,4-triazolium chloride, and any combinations thereof.

42. The aluminum battery of claim 1, wherein said cathode has a particle size below 1 micrometer.

9. An aluminum battery comprising an aluminum-containing anode, a non-aqueous electrolyte, and a cathode, said cathode comprising:

(a) one or more cathode active materials selected from the group consisting of a metal (M) oxide, a metal (M) fluoride, a metal (M) sulfide, and sulfur (M); and

(b) a conductive material with pores having at least one dimension below about one micrometer, wherein said cathode active material is contained within said pores,

wherein said battery has a multiple-electron-reduction discharge state wherein the ratio of the number of Al atoms to the number of M atoms in the cathode is about 0.4 or greater.

10. The aluminum battery of claim 9, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 0.6 or greater.

11. The aluminum battery of claim 10, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 0.8 or greater.

12. The aluminum battery of claim 11, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 1.0 or greater.

13. The aluminum battery of claim 12, wherein said ratio of the number of Al atoms to the number of M atoms in the cathode is about 1.2 or greater.

14. The aluminum battery of claim 9, wherein said conductive material includes a porous conductive scaffold.

15. The aluminum battery of claim 14, wherein said porous conductive scaffold is a porous conductive carbon scaffold.

16. The aluminum battery of claim 9, wherein said cathode active material is one or more metal oxides selected from the group consisting of CuO, P₂O₅, SnO₂, PbO₂, FeO, Fe₂O₃, CoO, Co₂O₃, NiO, and AgO.

17. The aluminum battery of claim 9, wherein said cathode active material is one or more metal fluorides selected from the group consisting of CoF₂, CoF₃, FeF₂, FeF₃, CuF₂, MoF₅, and SnF₄.

18. The aluminum battery of claim 9, wherein said cathode active material is one or more metal sulfides selected from the group consisting of FeS₂ and NiS₂.

19. The aluminum battery of claim 9, wherein said cathode active material includes sulfur.

20. The aluminum battery of claim 9, wherein said non-aqueous electrolyte is a mixture of aluminum chloride and an organic salt selected from the group consisting of n-butyl pyridinium chloride, 1-methyl-3-ethylimidazolium chloride, 1,2-dimethyl-3-propylimidazolium chloride, 1,4-dimethyl-1,2,4-triazolium chloride, and any combinations thereof.

21. The aluminum battery of claim 9, wherein said aluminum battery has an active material specific energy density in excess of 400 Wh/kg.

22. The aluminum battery of claim 21, wherein said active material specific energy density is at least 800 Wh/kg.

43. The aluminum battery of claim 9, wherein said cathode has a particle size below 1 micrometer.

23. A cathode for an aluminum battery, said cathode comprising one or more cathode active materials selected from the group consisting of metal oxides and metal fluorides, wherein said cathode has a multiple-electron-reduction cathode discharge state wherein the ratio of the total number of discharged electrons to the number of cathode metal atoms is greater than 1.0.

24. The cathode of claim 23, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 1.5 or more.

25. The cathode of claim 24, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 2.0 or more.

26. The cathode of claim 25, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 2.5 or more.

27. The cathode of claim 26, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 3.0 or more.

28. The cathode of claim 23, wherein said cathode active material is one or more metal oxides selected from the group consisting of CuO, P₂O₅, SnO₂, PbO₂, FeO, Fe₂O₃, CoO, Co₂O₃, NiO, and AgO.

29. The cathode of claim 23, wherein said cathode active material is one or more metal fluorides selected from the group consisting of CoF₂, CoF₃, FeF₂, FeF₃, CuF₂, MoF₅, and SnF₄.

44. The cathode of claim 23, wherein said cathode has a particle size below 1 micrometer.

30. A cathode for an aluminum battery, said cathode comprising:

(a) a cathode active material selected from the group consisting of a metal oxide, a metal fluoride, a metal sulfide, and sulfur; and

(b) a conductive material with pores having at least one dimension below about one micrometer, wherein said cathode active material is contained within said pores,

wherein said cathode has a multiple-electron-reduction cathode discharge state wherein the ratio of the total number of discharged electrons to the number of cathode metal atoms is greater than 1.0.

31. The cathode of claim 30, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 1.5 or more.

32. The cathode of claim 31, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 2.0 or more.

33. The cathode of claim 32, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 2.5 or more.

34. The cathode of claim 33, wherein said ratio of the total number of discharged electrons to the number of cathode metal atoms is about 3.0 or more.

35. The cathode of claim 30, wherein said conductive material includes a porous conductive scaffold.

36. The cathode of claim 35, wherein said porous conductive scaffold is a porous conductive carbon scaffold.

37. The cathode of claim 30, wherein said cathode active material is one or more metal oxides selected from the group consisting of CuO, P₂O₅, SnO₂, PbO₂, FeO, Fe₂O₃, CoO, Co₂O₃, NiO, and AgO.

38. The cathode of claim 30, wherein said cathode active material is one or more metal fluorides selected from the group consisting of CoF₂, CoF₃, FeF₂, FeF₃, CuF₂, MoF₅, and SnF₄.

39. The cathode of claim 30, wherein said cathode active material is one or more metal sulfides selected from the group consisting of FeS₂ and NiS₂.

40. The cathode of claim 30, wherein said cathode active material includes sulfur.

41. An aluminum battery cathode comprising, in a multiple-electron-reduction discharge state, a reduced metal having an oxidation number of 0 and an aluminum compound selected from the group consisting of an aluminum oxide, an aluminum fluoride, and an aluminum sulfide.

45. The cathode of claim 41, wherein said cathode has a particle size below 1 micrometer.