Composite cathode active material, cathode and lithium battery that include the composite cathode active material, and method of preparing the composite cathode active material
A composite cathode active material, a cathode and a lithium battery that include the composite cathode active material, and a method of preparing the composite cathode active material, the composite cathode active material including a compound having an olivine crystal structure; and an inorganic material, the inorganic material including at least one selected from the group of a metal carbonitride and a carbonitride.
1. A composite cathode active material, comprising:
a compound having an olivine crystal structure; and
an inorganic material, the inorganic material including at least one selected from the group of a metal carbonitride and a carbonitride,
when the inorganic material includes the metal carbonitride, the metal carbonitride is represented by Formula 1, below:
M″ b C 1-a N a [Formula 1]
wherein, in Formula 1, 0<a<1, 0<b<1, and M″
is at least one element selected from the group of titanium, calcium, magnesium, zinc, nickel, cobalt, aluminum, zirconium, iron, copper, tantalum, niobium, vanadium, tungsten, molybdenum, silicon, uranium, and thorium, and
when the inorganic material includes the carbonitride, the carbonitride is represented by Formula 2 below:
C 1-a N a Formula 2
wherein, in Formula 2 above, 0<a<1.
2. The composite cathode active material as claimed in claim 1 , wherein the inorganic material includes the metal carbonitride, the metal carbonitride including at least one selected from the group of titanium carbonitride, calcium carbonitride, magnesium carbonitride, molybdenum carbonitride, zinc carbonitride, nickel carbonitride, cobalt carbonitride, aluminum carbonitride, zirconium carbonitride, iron carbonitride, and copper carbonitride.
3. The composite cathode active material as claimed in claim 1 , wherein the inorganic material includes the carbonitride, the carbonitride including at least one selected from the group of C 3 N 4 , CN, and C 3 N.
4. The composite cathode active material as claimed in claim 1 , wherein the compound having the olivine crystal structure is represented by Formula 3, below:
Li x Me y M z PO 4-d X d [Formula 3]
wherein, in Formula 3, 0.6≦x≦1.4, 0<y≦1, 0≦z<1, and 0≦d≦0.2;
Me includes at least one selected from the group of iron, manganese, nickel, and cobalt;
M includes at least one selected from the group of magnesium, calcium, copper, neodymium, strontium, barium, titanium, zirconium, niobium, molybdenum, tungsten, zinc, aluminum, and silicon; and
X includes at least one selected from the group of sulfur and fluorine.
5. The composite cathode active material as claimed in claim 1 , wherein the compound having the olivine crystal structure is represented by Formula 4, below:
Li x Mn 1-z M′ z PO 4-d X d [Formula 4]
wherein, in Formula 4, 0.6≦x≦1.4, 0≦z<1, and 0≦d≦0.2;
M′ includes at least one selected from the group of Fe, Ni, Co, Mg, Ca, Cu, Nd, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, and Si; and
X includes at least one selected from the group of sulfur and fluorine.
6. The composite cathode active material as claimed in claim 1 , wherein the compound with the olivine crystal structure includes at least one selected from the group of LiFePO 4 , LiFe 1-a Mn a PO 4 (0<a<1), and LiMnPO 4 .
7. The composite cathode active material as claimed in claim 1 , wherein the inorganic material is in the form of one selected from the group of a nanoparticle, a nanofiber, a nanomesh, and a nanotube.
8. The composite cathode active material as claimed in claim 1 , wherein the inorganic material has a Mohs hardness that is greater than a Mohs hardness of the compound with the olivine crystal structure.
9. The composite cathode active material as claimed in claim 1 , wherein the inorganic material has a Mohs hardness of about 1 or greater.
10. The composite cathode active material as claimed in claim 1 , wherein the inorganic material has an electrical conductivity higher than that of amorphous carbon.
11. The composite cathode active material as claimed in claim 1 , wherein the inorganic material has an electrical conductivity of about 10 S/cm or greater.
12. The composite cathode active material of claim 1 , wherein the composite cathode active material is represented by Formula 5 or Formula 6, below:
(1- r )Li x Me y M z PO 4-d X d - r M″ b C 1-a N a [Formula 5]
(1- r )Li x Me y M z PO 4-d X d - r C 1-a N a [Formula 6]
wherein, in Formulae 5 and 6, 0.6≦x≦1.4, 0<y≦1, 0≦z<1, 0≦d≦0.2, 0<r<1, 0<a<1, and 0<b<1;
Me includes at least one selected from the group of iron, manganese, nickel, and cobalt;
M includes at least one selected from the group of magnesium, calcium, copper, neodymium, strontium, barium, titanium, zirconium, niobium, molybdenum, tungsten, zinc, aluminum, and silicon;
M″ includes at least one selected from the group of titanium, calcium, magnesium, zinc, nickel, cobalt, aluminum, zirconium, iron, copper, tantalum, niobium, vanadium, tungsten, molybdenum, silicon, uranium, and thorium; and
X includes at least one selected from the group of sulfur and fluorine.
13. The composite cathode active material as claimed in claim 12 , wherein 0.0001<r≦0.3.
14. The composite cathode active material as claimed in claim 1 , wherein the composite cathode active material is represented by Formula 7 or Formula 8, below:
(1- r )Li x Mn 1-z M′ z PO 4-d X d - r M″ b C 1-a N a [Formula 7]
(1- r )Li x Mn 1-z M′ z PO 4-d X d - r C 1-a N a [Formula 8]
wherein, in Formulae 7 and 8, 0.6≦x≦1.4, 0≦z≦0.2, 0≦d≦0.2, 0<r<1, 0<a<1, and 0<b<1;
M′ includes at least one selected from the group of Fe, Ni, Co, Mg, Ca, Cu, Nd, Sr, Ba, Ti, Zr, Nb, Mo, W, Zn, Al, and Si;
X includes at least one selected from the group of sulfur and fluorine; and
M″ includes at least one selected from the group of titanium, calcium, magnesium, zinc, nickel, cobalt, aluminum, zirconium, iron, copper, tantalum, niobium, vanadium, tungsten, molybdenum, silicon, uranium, and thorium.
15. The composite cathode active material as claimed in claim 14 , wherein 0.0001<r≦0.3.
16. The composite cathode active material as claimed in claim 1 , wherein the composite cathode active material further includes a carbonaceous material.
17. The composite cathode active material as claimed in claim 16 , wherein the carbonaceous material is included in an amount of about 0.1 wt % to about 30 wt %, based on a total weight of the composite cathode active material.
18. A cathode comprising the composite cathode active material as claimed in claim 1 .
19. A lithium battery comprising the cathode as claimed in claim 18 .
20. The composite cathode active material as claimed in claim 1 , wherein the inorganic material includes the carbonitride.
21. The composite cathode active material as claimed in claim 1 , wherein M″ is at least one element selected from the group of titanium, calcium, magnesium, zinc, aluminum, zirconium, iron, copper, tantalum, niobium, vanadium, tungsten, molybdenum, uranium, and thorium.
22. The composite cathode active material as claimed in claim 1 , wherein the inorganic material includes the metal carbontride and the metal carbonitride is TiCN.