Hydrogen storage hydride electrode materials

US 4,849,205 A
Filed: 11/17/1987
Issued: 07/18/1989
Est. Priority Date: 11/17/1987
Status: Expired

First Claim

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1. A material for hydride hydrogen storage and a hydride electrode, said material comprising the composition formula selected from the group consisting of:

space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c Cr.sub.d M.sub.x H.sub.y,where M equals any of Al, Si, V, Mn, Fe, Co, Cu, Nb, Ag, Pd, and rare earth metals, and where a, b, c, d, and x are defined by;

0.1≦

a≦

1.4, 0.1≦

b≦

1.3, 0.25≦

c≦

1.95, 0.1≦

d≦

1.4, a+b+c+d=3, 0≦

x≦

0.2, and y>

0;
space="preserve" listing-type="equation">Ti.sub.a Cr.sub.b Zr.sub.c Ni.sub.d V.sub.3-a-b-c-d M.sub.x,where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, b, c, d, and x are defined by;

0.1≦

a≦

1.3, 0.1≦

b≦

1.2, 0.1≦

c≦

1.3, 0.2≦

d≦

1.95, 0.4≦

a+b+c+d≦

2.9, 0≦

x≦

0.2, and for x=0 and b=0.5, then a+c≠

0.5 and b≧

0.25;
space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c V.sub.3-a-b-c M.sub.x,where M equals any of Al, Si, Cr, Mn, Fe, Co, Cu, Nb, Ag, Pd, and rare earth metals, and where a, b, c, and x are defined as;

0.1≦

a≦

1.3, 0.1≦

b≦

1.3, 0.25≦

c≦

1.95, 0≦

x≦

0.2, and 0.6≦

a+b+c≦

2.9, and for x=0 then a+b≠

1 and 0.24≦

b≦

1.3; and
space="preserve" listing-type="equation">Ti.sub.a Mn.sub.b V.sub.c Ni.sub.d M.sub.x,where M equals any of Al, Si, Cr, Fe, Co, Cu, Nb, Zr, Ag, Pd, and rare earth metals, and were a, b, c, d, and x are defined by;

0.1≦

a≦

1.6, 0.1≦

b≦

1.6, 0.1≦

c≦

1.7, 0.2≦

d≦

2.0, a+b+c+d=3, and 0≦

x≦

0.2, and for x=0 then b+d≠

0.75.

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Abstract

Four groups of advanced hydrogen hydride storage and hydride electrode materials, consisting of two common elements, titanium and nickel. In the first group of materials, zirconium and chromium are added with the common elements. The second group of materials contain three additional elements in addition to the common elements, namely, chromium, zirconium and vanadium. The third group of materials contain also, in addition to the common elements, zirconium and vanadium. The fourth group of materials adds manganese and vanadium with the common elements. The preparation methods of the materials, as well as their hydride electrode are disclosed. Electrochemical studies indicate that these materials have high capacity, long cycle life and high rate capability.

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41 Claims

1. A material for hydride hydrogen storage and a hydride electrode, said material comprising the composition formula selected from the group consisting of:
- space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c Cr.sub.d M.sub.x H.sub.y,
  where M equals any of Al, Si, V, Mn, Fe, Co, Cu, Nb, Ag, Pd, and rare earth metals, and where a, b, c, d, and x are defined by;
  
  0.1≦
  
  a≦
  
  1.4, 0.1≦
  
  b≦
  
  1.3, 0.25≦
  
  c≦
  
  1.95, 0.1≦
  
  d≦
  
  1.4, a+b+c+d=3, 0≦
  
  x≦
  
  0.2, and y>
  
  0;
  space="preserve" listing-type="equation">Ti.sub.a Cr.sub.b Zr.sub.c Ni.sub.d V.sub.3-a-b-c-d M.sub.x,
  where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, b, c, d, and x are defined by;
  
  0.1≦
  
  a≦
  
  1.3, 0.1≦
  
  b≦
  
  1.2, 0.1≦
  
  c≦
  
  1.3, 0.2≦
  
  d≦
  
  1.95, 0.4≦
  
  a+b+c+d≦
  
  2.9, 0≦
  
  x≦
  
  0.2, and for x=0 and b=0.5, then a+c≠
  
  0.5 and b≧
  
  0.25;
  space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c V.sub.3-a-b-c M.sub.x,
  where M equals any of Al, Si, Cr, Mn, Fe, Co, Cu, Nb, Ag, Pd, and rare earth metals, and where a, b, c, and x are defined as;
  
  0.1≦
  
  a≦
  
  1.3, 0.1≦
  
  b≦
  
  1.3, 0.25≦
  
  c≦
  
  1.95, 0≦
  
  x≦
  
  0.2, and 0.6≦
  
  a+b+c≦
  
  2.9, and for x=0 then a+b≠
  
  1 and 0.24≦
  
  b≦
  
  1.3; and
  space="preserve" listing-type="equation">Ti.sub.a Mn.sub.b V.sub.c Ni.sub.d M.sub.x,
  where M equals any of Al, Si, Cr, Fe, Co, Cu, Nb, Zr, Ag, Pd, and rare earth metals, and were a, b, c, d, and x are defined by;
  
  0.1≦
  
  a≦
  
  1.6, 0.1≦
  
  b≦
  
  1.6, 0.1≦
  
  c≦
  
  1.7, 0.2≦
  
  d≦
  
  2.0, a+b+c+d=3, and 0≦
  
  x≦
  
  0.2, and for x=0 then b+d≠
  
  0.75.
- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41)
- - 2. A hydride of the material o claim 1 comprising the composition formula selected from the group consisting of:
    - space="preserve" listing-type="equation">Ti.sub.a Cr.sub.b Zr.sub.c Ni.sub.d V.sub.3-a-b-c-d M.sub.x,
      where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, b, c, d, and x are defined by;
      
      0.1≦
      
      a≦
      
      1.3, 0.1≦
      
      b≦
      
      1.2, 0.≦
      
      c≦
      
      1.3, 0.2≦
      
      d≦
      
      1.95 0.4≦
      
      a+b+c+d≦
      
      2.4, 0≦
      
      x≦
      
      0.2, and for x=0 and b=0.5, then a+c≠
      
      0.5 and b≧
      
      0.25;
      space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c V.sub.3-a-b-c M.sub.x,
      where M equals any of Al, Si, Cr, Fe, Co, Cu, Nb, Ag, Pd, and rare earth metals, and were a, b, c, d, and x are defined as;
      
      0.1≦
      
      a≦
      
      1.3, 0.1≦
      
      b≦
      
      1.3, 0.25≦
      
      c≦
      
      1.95, 0≦
      
      x≦
      
      0.2, and 0.6≦
      
      a+b+c≦
      
      2.9, and for x=0 then a+b≠
      
      1 and 0.24≦
      
      b≦
      
      1.3; and
      space="preserve" listing-type="equation">Ti.sub.a Mn.sub.b V.sub.c Ni.sub.d M.sub.x,
      where M equals any of Al, Si, Cr, Fe, Co, Cu, Nb, Zr, Ag, Pd, and rare earth metals, and were a, b, c, d, and x are defined by;
      
      0.1≦
      
      a≦
      
      1.6, 0.1≦
      
      b≦
      
      1.6, 0.1≦
      
      c≦
      
      1.7, 0.2≦
      
      d≦
      
      2.0, a+b+c+d=3, and 0≦
      
      x≦
      
      0.2, and for x=0 then b+d≠
      
      0.75.
  - 3. The material of claim 1 in the form of at least one hydride electrode for an electrochemical energy storage system.
  - 4. A material as defined in claim 1, wherein said composition formula is
    
    space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c Cr.sub.d H.sub.y,
    where a, b, c, and d are defined by;
    
    0.1≦
    
    a≦
    
    1.4, 0.1≦
    
    b≦
    
    1.3, 0.25≦
    
    c≦
    
    1.95, 0.1≦
    
    d≦
    
    1.4, y>
    
    0 and a+b+c+d=3.
- 5. The material of claim 4 in the form of at least one hydride electrode for an electrochemical energy storage system.
- 6. A material as defined in claim 1, wherein said composition formula is:
  - space="preserve" listing-type="equation">Ti.sub.a Cr.sub.b Zr.sub.c Ni.sub.d V.sub.3-a-b-c-d,
    where a, b, c, and d, are defined by;
    
    0.1≦
    
    a≦
    
    1.3, 0.25≦
    
    b≦
    
    1.2, 0.1≦
    
    c≦
    
    1.3, 0.2≦
    
    d≦
    
    1.95, 0.4≦
    
    a+b+c+d≦
    
    2.9, and if b=0.5, then a+c≠
    
    0.5.
- 7. A hydride of the material of claim 6.
- 8. The material of claim 6 in the form of at least one hydride electrode for an electrochemical energy storage system.
- 9. A material as defined in claim 1, wherein said composition formula is
  
  space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.c V.sub.3-a-b-c,
  where a, b, and c are defined as;
  
  0.1≦
  
  a≦
  
  1.3, 0.24≦
  
  b≦
  
  1.3, a+b.1, 0.25≦
  
  c≦
  
  1.95, and 0.6≦
  
  a+b+c≦
  
  2.9.
10. A hydride of the material of claim 9.
11. The material of claim 10 in the form of at least one hydride electrode for an electrochemical energy storage system.
12. A material as defined in claim 1, wherein said composition formula is

space="preserve" listing-type="equation">Ti.sub.a Mn.sub.b V.sub.c Ni.sub.d,
were a, b, c, and d, are defined by;

0.1≦

a≦

1.6, 0.1≦

b≦

1.6, 0.1≦

c≦

1.7, 0.2≦

d≦

2.0, b+d≠

0.75 and a+b+c+d=3.

13. A hydride of the material of claim 12.

14. The material of claim 13 in the form of at least one hydride electrode for an electrochemical energy storage system.

15. A material as defined in claim 1, wherein said composition formula is

space="preserve" listing-type="equation">Ti.sub.a Mn.sub.b V.sub.c Ni.sub.d M.sub.x,
where M equals any of Al, Si, Cr, Fe, Co, Cu, Nb, Zr, Ag, Pd, and rare earth metals, and were a, b, c, d, and x are defined by;

0.1≦

a≦

1.6, 0.1≦

b≦

1.6, 0.1≦

c≦

1.7, 0.2≦

d≦

2.0, a+b+c+d=3 and 0≦

x≦

0.2.

16. A hydride of the material of claim 15.

17. The material of claim 15 in the form of at least one hydride electrode for an electrochemical energy storage system.

18. A material as defined in claim 1, wherein said composition formula

space="preserve" listing-type="equation">Ti.sub.a Cr.sub.a Zr.sub.c Ni.sub.d V.sub.3-2a-c-d M.sub.x,
where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, c, d, and x are defined by;

0.25≦

a≦

1.2, 0.1≦

c≦

1.2, 0.2≦

d≦

1.95, 0.9≦

2a+c+d≦

2.8, and 0≦

x≦

0.2.

19. A hydride of the material of claim 18.

20. The material of claim 18 in the form of at least one hydride electrode for an electrochemical energy storage system.

21. A material as defined in claim 1, wherein the composition formula is

space="preserve" listing-type="equation">Ti.sub.a Cr.sub.b Zr.sub.1-a-b Ni.sub.d V.sub.2-d M.sub.x,
where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, b, d, and x are defined by;

0.1≦

a≦

0.8, 0.1≦

b≦

0.8, 0.25≦

d≦

1.95, 0≦

x≦

0.2, and for x=0, then b≠

0.5 and b≧

0.25.

22. A hydride of the material of claim 21.

23. The material of claim 21 in the form of at least one hydride electrode for an electrochemical energy storage system.

24. A material as defined in claim 22, wherein the composition formula is

space="preserve" listing-type="equation">Ti.sub.a Cr.sub.a Zr.sub.1-2a Ni.sub.d V.sub.2-d M.sub.x,
where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, d, and x are defined by;

0.1≦

a≦

0.45, 0.25≦

d≦

1.95, 0≦

x≦

0.2 and when x=0 then a≧

0.25.

25. A hydride of the material of claim 24.

26. The material of claim 19 in the form of at least one hydride electrode for an electrochemical energy storage system.

27. A material as defined in claim 1, wherein the composition formula is

space="preserve" listing-type="equation">Ti.sub.a Cr.sub.a Zr.sub.c Ni.sub.2-c V.sub.1-2a M.sub.x,
where M equals any of Al, Si, Mn, Co, Cu, Fe, Nb, Ag, Pd, and rare earth metals, and where a, c, and x are defined by;

0.1≦

a≦

0.45, 0.2≦

c≦

1.2, 0≦

x≦

0.2 and if x=0 then a≧

0.25.

28. A hydride of the material of claim 27.

29. The material of claim 27 in the form of at least one hydride electrode for an electrochemical energy storage system.

30. A material as defined in claim 10, wherein the composition formula is

space="preserve" listing-type="equation">Ti.sub.a Zr.sub.1.2+t-a-d Ni.sub.1.8-t V.sub.d,
where a, d, and t are defined as;

0.1≦

a≦

0.3 and 0.62≦

a≦

1.3, 0.2≦

d≦

1.8, 0≦

t≦

1.55, 0≦

t-a-d≦

1.2 and -0.1≦

a+d-t≦

0.96.

31. A hydride of the material of claim 30.

32. The material of claim 30 in the form of at leat one hydride electrode for an electrochemical energy storage system.

33. A material as defined in claim 1, wherein the composition formula is

space="preserve" listing-type="equation">Ti.sub.a Zr.sub.y-a Ni.sub.c V.sub.3-y-c M.sub.x,
where M equals any of Al, Si, Cr, Mn, Fe, Co, Cu, Nb, Ag, Pd, and rare earth metals, and where a, c, x, and y are defined as;

0.1≦

a≦

1.3, 0.2≦

c≦

1.95, 0≦

x≦

0.2, and 0.7≦

y≦

1.6.

34. A hydride of the material of claim 33.

35. The material of claim 33 in the form of at least one hydride electrode for an electrochemical energy storage system.

36. A material as defined in claim 1, wherein the composition formula is selected from the group consisting of:

space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.2-b V.sub.1-a,
where a, and b are defined as;

0.1≦

a≦

0.8, 0.24≦

b≦

1.2, a+b≠

1;
space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.1-a V.sub.2-b,
where a, and b are defined as;

0.2≦

a≦

0.75, 0.24≦

b≦

1.2, a+b≠

1; and
space="preserve" listing-type="equation">Ti.sub.a Zr.sub.b Ni.sub.1-b V.sub.2-a,
where a, and b are defined as;

0.1≦

a≦

1.3, 0.24≦

b≦

0.75, a+b≠

1.

37. A hydride of the material of claim 36.

38. The material of claim 36 in the form of at least one hydride electrode for an electrochemical energy storage system.

39. A material as defined in claim 1, wherein the composition formula is

space="preserve" listing-type="equation">Ti.sub.a Cr.sub.b Zr.sub.c Ni.sub.1.95-t V.sub.1.05+t-a-b-c,
where a, b, c, and t are defined by;

0.1≦

a≦

1.2, 0.1≦

b≦

1.2, 0.1≦

c≦

1.2, 0≦

t≦

1.75, and for b=0.5, then a+c=0.5.

40. A hydride of the material of claim 39.

41. The material of claim 37 in the form of at least one hydride electrode for an electrochemical energy storage system.

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Current Assignee
Energy Conversion Devices
Original Assignee
Kuochih Hong
Inventors
Hong, Kuochih
Primary Examiner(s)
BOS, STEVEN J

Application Number

US07/122,042
Time in Patent Office

609 Days
Field of Search

420/906, 420/588, 420/580, 420/424, 420/417, 420/421, 923/604
US Class Current

423/644
CPC Class Codes

C01B 3/0005   Reversible uptake of hydrog...

C01B 3/0031   Intermetallic compounds; Me...

C22C 19/03   based on nickel

C22C 19/05   with chromium

H01M 4/242   Hydrogen storage electrodes

H01M 4/383   Hydrogen absorbing alloys

Y02E 60/10   Energy storage using batteries

Y02E 60/32   Hydrogen storage

Y02E 60/36   Hydrogen production from no...

Y10S 420/90   Hydrogen storage

Hydrogen storage hydride electrode materials

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Hydrogen storage hydride electrode materials

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