Amorphous metal alloy compositions for reversible hydrogen storage and electrodes made therefrom

• US 4,923,770 A
• Filed: 09/02/1988
• Issued: 05/08/1990
• Est. Priority Date: 03/29/1985
• Status: Expired due to Fees

• Current Assignee: Standard Oil Company (BP PLC)
• Original Assignee: Standard Oil Company (BP PLC)
• Inventors: Harris, Jonathan H., Grasselli, Robert K., Henderson, Richard S., Tenhover, Michael A.
• Primary Examiner(s): Walton, Donald L.
• Application Number:
  US07/243,109
• Time in Patent Office: 613 Days
• Field of Search: 429/101, 429/209, 429/218, 420/900
• US Class Current: 429/101
• CPC Class Codes: C01B 3/0031 Intermetallic compounds; Metal alloys; Treatment thereof
• CPC Class Codes: C01B 3/0047 containing a rare earth metal; Treatment thereof
• CPC Class Codes: C01B 3/0052 also containing titanium
• CPC Class Codes: C01B 3/0057 also containing nickel
• CPC Class Codes: C22C 45/10 with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
• CPC Class Codes: H01M 10/345 Gastight metal hydride accumulators
• CPC Class Codes: H01M 4/383 Hydrogen absorbing alloys
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y10S 420/90 Hydrogen storage

Abstract

The present invention provides a novel amorphous metal alloy composition which reversibly stores hydrogen and is useful as the hydrogen storage electrode in an energy storage device. The amorphous metal alloy is made up of at least three elements with at least one element of Ag, Hg, or Pt; at least one element of Pb, Cu, Cr, Mo, W, Ni, Al, Co, Fe, Zn, Cd, Ru or Mn: and at least one element of Ca, Mg, Ti, Zr, Hf, Nb, V or Ta.

Claims

1. A reversible hydrogen storage material consisting essentially of an amorphous metal alloy of the formula:

space="preserve" listing-type="equation">A.sub.a M.sub.b M'"'"'.sub.c

wherein

A is at least one element selected from the group consisting of Ag, Hg, and Pt;

M is at least one metal selected from the group consisting of Pb, Cu, Cr, Mo, W, Ni, Al, Co, Fe, Zn, Ru, Cd, and Mn;

M'"'"' is at least one element selected from the group consisting of Ca, Mg, Ti, Zr, Hf, Nb, V and Ta; and

wherein

a ranges from about 0.005 to about 0.80;

b ranges from about 0.05 to about 0.70; and

c ranges from about 0.08 to about 0.95.

2. The reversible hydrogen storage material in accordance with claim 1 wherein A is Pt.

3. The reversible hydrogen storage material in accordance with claim 1 wherein M is at least one metal selected from the group consisting of Mn, Ru, Fe, Cu, Ni, Cr, Mo, Al, Co and W.

4. The reversible hydrogen storage material in accordance with claim 1 wherein M is at least one metal selected from the group consisting of Ni, Co, and Mo.

5. The reversible hydrogen storage material in accordance with claim 1 wherein M, is Zr, Ti, Ca, Mg or a combination thereof.

6. The reversible hydrogen storage material in accordance with claim 1 wherein a ranges from about 0.05 to about 0.75;

b ranges from about 0.1 to about 0.7; and

c ranges from about 0.2 to about 0.85.

7. The reversible hydrogen storage material in accordance with claim 1 wherein a ranges from 0.05 to about 0.1;

b ranges from about 0.5 to about 0.7; and

c ranges from about 0.3 to about 0.8.

8. The reversible hydrogen storage material in accordance with claim 1 wherein said amorphous metal alloy comprises Pt, Ni, and Zr.

9. The reversible hydrogen storage material in accordance with claim 8 wherein said amorphous metal alloy comprises is Pt₅, Ni₄₂ Zr₃₇.

10. An electrode for reversibly storing hydrogen comprising essentially of an amorphous metal alloy of the formula:

space="preserve" listing-type="equation">A.sub.a M.sub.b M'"'"'.sub.c

wherein

A is at least one metal selected from the group consisting of Ag, Hg and Pt;

M is at least one metal selected from the group consisting of Pb, Cu, Cr, Mo, W, Ni, Al, Co, Fe, Zn, Ru, Cd, and Mn;

M'"'"' is at least one of the elements selected from the group consisting of Ca, Mg, Ti, Zr, Hf, V, Nb and Ta; and

wherein a ranges from about 0.005 to about 0.80;

b ranges from 0.05 to about 0.70; and

c ranges from about 0.08 to abuot 0.95.

11. The electrode in accordance with claim 10 wherein A is Pt;

M is at least one of Mo, Co, Fe, Ni and Mn; and

M, is at least one of Zr, Cd and Mg; and

wherein said electrode is operable in an alkaline environment.

12. The electrode in accordance with claim 11 wherein M is at least 50% of said alloy.

13. The electrode in accordance with claim 10 wherein said electrode consisting essentially of said amorphous metal alloy disposed on a substrate.

14. The electrode in accordance with claim 13 wherein said substrate is titanium.

15. The electrode in accordance with claim 13 wherein said substrate is tantalum.

16. The electrode in accordance with claim 10 wherein said electrode consisting essentially of a thin film of said amorphous metal alloy.

17. The electrode in accordance with claim 10 wherein said electrode consisting essentially of said amorphous metal alloy disposed in powder form.

18. The electrode in accordance with claim 10 wherein A is Pt;

M is at least one of Ru, Pb, Cu, Cr, W and Mo; and

M'"'"' is at least one of Zr and Nb; and

wherein said electrode is operable in an acid or neutral environment.

19. An energy storage device comprising:

a working electrode, a counter electrode, electrically isolated from said working electrode;

an electrolyte in contact with the working electrode and the counter electrode, and means for collecting electrical current therefrom;

the working electrode consisting essentially of an amorphous metal alloy of the formula;

space="preserve" listing-type="equation">A.sub.a M.sub.b M'"'"'.sub.c

wherein

A is at least one metal selected from the group consisting of Ag, Hg and Pt;

M is at least one metal selected from the group consisting of Pb, Cu, Cr, Mo, W, Ni, Al, Co, Fe, Zn, Ru, Cd and Mn;

M'"'"' is at least one of the elements selected from the group consisting of Ca, Mg, Ti, Zr, Hf, V, Nb and Ta; and

wherein

a ranges from about 0.005 to about 0.80;

b ranges from 0.05 to about 0.70; and

c ranges from about 0.08 to about 0.95.

20. The energy storage device in accordance with claim 19 wherein said working electrode is at least fifty percent amorphous.

21. The energy storage device in accordance with claim 19 wherein A is Pt;

M is at least one of Mo, Co, Fe, Ni and Mn; and

M'"'"' is at least one of Zr, Ca and Mg; and

wherein said electrolyte is alkaline in nature.

22. The energy storage device in accordance with claim 21 wherein M is at least 50% of said working electrode.

23. The energy storage device in accordance with claim 21 wherein said counter electrode is nickel hydroxide.

24. The energy storage device in accordance with claim 21 wherein said alkaline electrolyte is potassium hydroxide.

25. The energy storage device in accordance with claim 21 wherein said alkaline electrolyte is sodium hydroxide.

26. The energy storage device in accordance with claim 19 wherein said working electrode is fully discharged in operation.

27. The energy storage device in accordance with claim 19 wherein A is Pt;

M is at least one of Ru, Pb, Cu, Cr, Mo and W; and

M'"'"' is at least one of Zr, Nb and Ti; and

wherein said electrolyte is acidic in nature.

28. The energy storage device in accordance with claim 27 wherein said counter electrode is graphite.

29. The energy storage device in accordance with claim 27 wherein said counter electrode is Pb-oxide.

30. The energy storage device in accordance with claim 27 wherein said acid electrolyte is selected from the group consisting of H₂ SO₄, HCI, HNO₃, H₃ P₀₄, acetic acid and mixtures thereof.

31. The energy storage device in accordance with claim 27 wherein said acid electrolyte is H2S04.

32. The energy storage device in accordance with claim 27 wherein said acid electrolyte is H3PO₄.