Lithium-manganese composite oxides for lithium ion battery and process for preparing same
A lithium-manganese composite oxide for a lithium ion battery having a good cycle property at high-temperature and battery property of high capacity is provided. A spinel type lithium-manganese composite oxide for a lithium ion battery represented by a general formula: Li 1+x Mn 2-y M y O 4 (wherein M is one or more elements selected from Al, Mg, Si, Ca, Ti, Cu, Ba, W and Pb, and, −0.1≦x≦0.2, and 0.06≦y≦0.3), and when D10, D50 and D90 are defined as a particle size at which point the cumulative frequency of volume reaches 10%, 50% and 90% respectively, d10 is not less than 2 μm and not more than 5 μM, d50 is not less than 6 μm and not more than 9 μm, and d90 is not less than 12 μm and not more than 15 μM, and BET specific surface area thereof is greater than 1.0 m 2 /g and not more than 2.0 m 2 /g, and the tap density thereof is not less than 0.5 g/cm 3 and less than 1.0 g/cm 3 .
1. A spine type lithium-manganese composite oxide for a lithium ion battery represented by a general formula Li 1+x Mn 2-y M y O 4 , wherein
M is one or more elements selected from Al, Mg, Si, Ca, Ti, Cu, Ba, W and Pb, and, −0.1≦x≦0.2, and 0.06≦y≦0.3, and
when d10, d50 and d90 are defined as a particle size at which point the cumulative frequency of volume reaches 10%, 50% and 90% respectively, d10 is not less than 2 μm and not more than 5 μm, d50 is not less than 6 and not more than 9 μm, and d90 is not less than 12 μm and not more than 15 μm,
the BET specific surface area is greater than 1.0 m 2 /g and not more than 2.0 m 2 /g, and
the tap density is not less than 0.5 g/cm 3 and less than 0.9 g/cm 3 .
2. The lithium-manganese composite oxide according to claim 1 , wherein M is Al.
3. The lithium-manganese composite oxide according to claim 2 , wherein the lattice constants satisfy the following empirical formula: A=8.343−0.250B±0.005 wherein, A is the lattice constant ({acute over (Å)}), B is the molar ratio of the amount of Li to the total amount of Mn and M calculated from the analyzed values.
4. The lithium-manganese composite oxide according to claim 1 , wherein (1+x)/2 corresponding to the molar ratio of Li to the total amount of Mn and M is not less than 0.51 and not more than 0.58.
5. The lithium-manganese composite oxide according to claim wherein when 2 g of powder of the lithium-manganese composite oxide is introduced into a cylindrical metal mold having a diameter of 20 mm, and pressed with a pressing pressure of 0.5 ton/cm 2 using a uniaxial press to shape, the density of the obtained compact is 1.0 g/cm 3 or more and 2.0 g/cm 3 or less.
6. A method for preparing the lithium-manganese composite oxide according to claim 1 , comprising:
providing a mixture or coprecipitate containing one or more elements selected from Al, Mg, Si, Ca, Ti, Cu, Ba, W and Pb, in addition to Li and Mn;
oxidizing the mixture or coprecipitate in an atmosphere of air, using a continuous-type furnace wherein the oxidation is performed by the following successive steps:
1) heating the mixture or coprecipitate at a rate of 350° C./hour or more and 700° C./hour or less to a first given temperature of 350-700° C.;
2) oxidizing the mixture or coprecipitate at the first given temperature for 3-9 hours;
3) without cooling, further heating the mixture or coprecipitate at a rate of 250° C./hour or less to a second given temperature of 800-1000° C.;
4) oxidizing the mixture or coprecipitate at the second given temperature for 1-5 hours; and then 5) furnace-cooling the mixture or coprecipitate at a rate of 300° C./hour or less.
7. A positive electrode for a lithium ion battery, wherein the lithium-manganese composite oxide according to any one of claims 1 - 5 comprises a positive electrode active material.
8. A lithium ion battery comprising the positive electrode according to claim 7 .