Cathode materials for lithium-ion secondary cells
First Claim
1. A crystalline material comprising atoms of lithium, oxygen, and at least one transition metal, the material further comprising divalent cations on sites within atom layers of the crystalline material including said atoms of said at least one transition metal.
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Abstract
Crystalline lithiated transition metal oxide materials having a rhombohedral R-3m crystal structure includes divalent cations selected and added in amounts so that all or a portion of the divalent cations occupy sites in transition metal atom layers within the materials'"'"' crystal lattice. The lithiated transition metal oxides are useful as cathode materials in lithium-ion secondary cells. The materials include, but are not limited to, Li1+x Ni1-y My Nx O2(1+x) and Li1 Ni1-y My Nx Op, wherein M is a transition metal selected from titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum, and N is a group II element selected from magnesium, calcium, strontium, barium, and zinc. The materials provide improved cyclability and high voltage capacity as cathodes in lithium-ion secondary cells. Processes for producing the divalent cation-containing lithium transition metal oxide materials of the invention are also disclosed.
164 Citations
36 Claims
-
1. A crystalline material comprising atoms of lithium, oxygen, and at least one transition metal, the material further comprising divalent cations on sites within atom layers of the crystalline material including said atoms of said at least one transition metal.
- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 16, 17, 30, 31, 32, 33, 34, 35, 36)
- 12. The material recited in claim 1 having the composition
- space="preserve" listing-type="equation">Li.sub.1+x Ni.sub.1-y M.sub.y N.sub.x O.sub.2(1+x)
wherein; M is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum; N is selected from the group consisting of magnesium, calcium, strontium, barium, and zinc; 0≦
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum; and0≦
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc.
- 13. The material recited in claim 1 having the composition
- space="preserve" listing-type="equation">Li.sub.1 Ni.sub.1-y M.sub.y N.sub.x O.sub.p
wherein; M is selected from the group consisted of titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum; N is selected from the group consisting of magnesium, calcium, strontium, barium, and zinc; 0≦
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum;0≦
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc; and2(1+x/2)≦
p≦
2(1+x).
- space="preserve" listing-type="equation">Li.sub.1+x Ni.sub.1-y M.sub.y N.sub.x O.sub.2(1+x)
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum; and
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc.
- space="preserve" listing-type="equation">Li.sub.1 Ni.sub.1-y M.sub.y N.sub.x O.sub.p
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is itanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum;
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc; and
p≦
2 (1+x).
- space="preserve" listing-type="equation">Li.sub.1+x NiN.sub.x O.sub.2(1+x)
x≦
0.25.
- x≦
0.15.
- space="preserve" listing-type="equation">Li.sub.1+x Ni.sub.1-y Co.sub.y N.sub.x O.sub.2(1+x )
y≦
0.4; and
x≦
0.25.
- x≦
0.15.
- space="preserve" listing-type="equation">Li.sub.1+x CoN.sub.x O.sub.2(1+x)
x≦
0.25.
- x≦
0.15.
- p≦
2.06.
- 14. A cathode for an electrochemical cell, the cathode comprising a crystalline material comprising atoms of lithium, oxygen, and at least one transition metal, said material further comprising divalent cations on sites within atom layers of said material including atoms of said at least one transition metal.
-
18. A lithium-ion secondary cell comprising:
-
a cathode comprising a crystalline material comprising atoms of lithium, oxygen, and at least one transition metal, said material further comprising divalent cations on sites within atom layers of said material including atoms of said at least one transition metal; an anode that is compatible with said cathode; and an electrolyte that is compatible with said cathode and said anode. - View Dependent Claims (19, 20, 21)
- 20. The lithium-ion secondary cell recited in claim 18, wherein said material has the composition
- space="preserve" listing-type="equation">Li.sub.1+x Ni.sub.1-y M.sub.y N.sub.x O.sub.2(1+x)
wherein; M is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum; N is selected from the group consisting of magnesium, calcium, strontium, barium, and zinc; 0≦
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum; and0≦
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc.
-
- 21. The lithium-ion secondary cell recited in claim 18, wherein said material has the composition
- space="preserve" listing-type="equation">Li.sub.1 Ni.sub.1-y M.sub.y N.sub.x O.sub.p
wherein; M is selected from the group consisted of titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum; N is selected from the group consisting of magnesium, calcium, strontium, barium, and zinc; 0≦
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum;0≦
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc; and2 (1+x/2)≦
p≦
2 (1+x).
-
22. A process for producing a lithium transition metal oxide crystalline material, the process comprising:
-
combining at least an amount of a lithium-containing material, an amount of a transition metal-containing material, and an amount of a material containing atoms of at least one element selected from the group consisting of group II elements and zinc to yield a homogenous solid therefrom; and heat treating said homogenous solid to produce an active crystalline lithium transition metal oxide material that contains atoms of said at least one element selected from the group consisting of group II elements and zinc, said amounts selected so that in said active material said atoms of said at least one element selected from the group consisting of group II elements and zinc occupy sites within crystal layers of said active material including transition metal atoms. - View Dependent Claims (23, 24, 25, 26, 27, 28)
- 27. The process recited in claim 22 wherein said active crystalline lithium transition metal oxide material containing atoms of at least one element selected from the group consisting of group II elements and zinc has the composition
- space="preserve" listing-type="equation">Li.sub.1+x Ni.sub.1-y M.sub.y N.sub.x O.sub.2(1+x)
wherein; M is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum; N is selected from the group consisting of magnesium, calcium, strontium, barium, and zinc; 0≦
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y=0.4 when M4 is aluminum; and0≦
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc.
-
- 28. The process recited in claim 22 wherein said active crystalline lithium transition metal oxide material containing atoms of at least one element selected from the group consisting group II elements and zinc has the composition
- space="preserve" listing-type="equation">Li.sub.1 Ni.sub.1-y M.sub.y N.sub.x O.sub.p
wherein; M is selected from the group consisted of titanium, vanadium, chromium, manganese, iron, cobalt, and aluminum; N is selected from the group consisting of magnesium, calcium, strontium, barium, and zinc; 0≦
y≦
1 when M is cobalt or manganese;
0≦
y≦
0.5 when M is titanium, vanadium, chromium, or iron; and
y≦
0.4 when M is aluminum;0≦
x≦
0.25 when N is magnesium or calcium; and
0≦
x≦
0.1 when N is strontium, barium, or zinc; and2 (1+x/2)≦
p≦
2 (1+x).
-
29. A process for producing a lithium-ion secondary cell, the process comprising fabricating the cell from:
-
a cathode comprising a crystalline material comprising atoms of lithium, oxygen, and at least one transition metal, said material further comprising divalent cations on sites within atom layers of said material including atoms of said at least one transition metal; an anode that is compatible with said cathode; and an electrolyte that is compatible with said cathode.
-
Specification