Hydrogen storage hydride electrode materials

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.

What is claimed is: 
     
       1. A material for hydride hydrogen storage and a hydride electrode, said material comprising the composition formula selected from the group consisting of:   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 .Iadd.wherein Ti+Zr≦1.2.Iaddend.;   Ti.sub.a Cr.sub.b Zr.sub.c Ni.sub.d V.sub.3-a-b-c-d M.sub.x,       .Iadd.and hydrides thereof.Iaddend.,   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.]. .Iadd.0.5.Iaddend.≦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.]. .Iadd.wherein Ti+Zr≦0.80 and V≦1.4.[.;   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     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.].     
     
     
       2. A hydride of the material .[.o.]. .Iadd.of .Iaddend.claim 1 comprising the composition formula selected from the group consisting of:   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.]. .Iadd.0.1.Iaddend.≦c≦1.3, 0.2≦d≦1.95, .[.0.4.]. .Iadd.0.5 .Iaddend.≦a+b+c+d≦.[.2.4.]. .Iadd.2.9, .Iaddend.0≦x≦0.2 .[., and for x=0, and b=0.5, then a+c≠0.5 and b≧0.25;     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     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 where 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   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:   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.]. .Iadd.0.15≦b≦1.0, .Iaddend.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.]. .Iadd.7 .Iaddend.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   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   Ti.sub.a Mn.sub.b V.sub.c Ni.sub.d,      were a, b, c, and d, are defined by: 1.6, 0.1≦a≦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,.]. .Iadd.for hydrogen storage and a hydride electrode, .Iaddend.wherein said composition formula is   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.]. .Iadd.where .Iaddend.a, b, c, d, and x are defined by: 0.1≦a≦1.6, .[.0.1≦b≦1.6.]. .Iadd.0.3<b<1.0, .Iaddend.0.1≦c≦1.7, 0.2≦d≦2.0, a+b+c+d=3 and .[.0≦x≦0.2.].   
     
     
        .Iadd.0<x≦0.2 and Ti+Zr≧1.2.Iaddend.. 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   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.]. .Iadd.0.1.Iaddend.≦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.]. .Iadd.19 .Iaddend.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   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.]. .Iadd.22 .Iaddend.in the form of at least one hydride electrode for an 
     
     
        electrochemical energy storage system. 24. A material as defined in claim .[.22.]. .Iadd.21.Iaddend., wherein the composition formula is:   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.]. .Iadd.25 .Iaddend.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   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 hybride of the material of claim 27. 29. The material of claim .[.27.]. .Iadd.28 .Iaddend.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   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   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:     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;     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     Ti.sub.a Zr.sub.b Ni.sub.i-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     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 3 in the form of at least one hydride   
     
     
        electrode for an electrochemical energy storage system..]. .Iadd.42.  A material for hydrogen storage and a hydride electrode selected from the group consisting of: Ti 0 .3 Zr 1 .0 Ni 1 .4 Cr 0 .3 ;   Ti 0 .5 Zr 0 .8 Ni 1 .2 Cr 0 .5 ;   Ti 0 .5 Zr 0 .8 Ni 1 .2 Cr 0 .5 Mn 0 .1 ; and hydrides thereof. .Iaddend. .Iadd.43. A material for hydrogen storage and a hydride electrode selected from the group consisting of:   Ti 0 .4 Cr 0 .4 Zr 0 .2 Ni 0 .6 V 1 .4 ;   Ti 0 .3 Cr 0 .3 Zr 0 .5 Ni 1 .15 V 0 .45 ;   Ti 0 .3 Cr 0 .3 Zr 0 .4 Ni 0 .6 V 1 .4 ;   Ti 0 .3 Cr 0 .3 Zr 0 .5 Ni 0 .7 V 1 .2 Cu 0 .1 ; and   
     
     
        hydrides thereof. .Iaddend. .Iadd.44.  A material for hydrogen storage and a hydride electrode, wherein said material having composition formula consisting of: Ti a  Zr b  Ni c  Cr d  M x  ; and hydrides thereof, where M is selected from the group consisting 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: 0.25≦a≦1.0, 0.2≦b≦1.0, 0.8≦c≦1.6, 0.3≦d≦1.0, a+b+c+d=3, 0≦x≦0.2, wherein Ti+Zr is≦1.2. .Iaddend. .Iadd.45. The material of claim 44 in the form of at least one hydride electrode for an electrochemical energy storage system. .Iaddend. .Iadd.46. A material for hydrogen storage and a hydride electrode, wherein said material having composition formula consisting of:   Ti a  Cr b  Zr c  Ni d  V 3-a-b-c-d  M x  ; and hydrides thereof, where M is selected from the group consisting 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: 0.15≦a≦1.0, 0.15≦b≦1.0, 0.2≦c≦1.0, 0.4≦d≦1.7, 1.5 ≦a+b+c+d≦2.3 and 0≦x≦0.2, Ti +Zr≦0.8,   
     
     
        V≦1.4 and for x=0, b=0.5 then a+c≠0.5. .Iaddend. .Iadd.47. The material of claim 46 in the form of at least one hydride electrode for an electrochemical energy storage system. .Iaddend.