Positive electrode active substance for lithium secondary battery and process for producing the same
A positive electrode active material is produced by firing, as a cobalt source, a mixture of a) substantially spherical large particle size cobalt hydroxide or tricobalt tetraoxide having a sharp particle size distribution, and b) small particle size cobalt hydroxide or tricobalt tetraoxide, in a proportion of from 9:1 to 1:2 as the cobalt atomic ratio, at a temperature of from 700° C. to 1050° C. in an oxygen-comprising atmosphere.
1. A process for producing a positive electrode active material, comprising:
firing, as a cobalt source, a mixture of substantially spherical large particle size cobalt hydroxide or tricobalt tetraoxide having such a sharp particle size distribution that the average particle size D 50 is from 7 to 20 μm, the average particle size D 10 is at least 50% of the average particle size D 50 and the average particle size D 90 is at most 150% of the average particle size D 50 , and small particle size cobalt hydroxide or tricobalt tetraoxide having an average particle size D 50 of from 10 to 30% of the average particle size D 50 of the large particles, in a proportion of from 9:1 to 1:2 as the cobalt atomic ratio, at a temperature of from 700° C. to 1050° C. in an oxygen-comprising atmosphere, to obtain said positive electrode active material which comprises
a lithium-cobalt composite oxide represented by the formula Li p Co x M y O z F a (wherein M is a transition metal element other than Co or an alkaline earth metal element, 0.9≦p≦1.1, 0.980≦x≦1.000, 0≦y≦0.02, 1.9≦z≦2.1, x+y=1 and 0≦a≦0.02) and comprising a mixture comprising substantially spherical first particles of lithium-cobalt composite oxide having such a sharp particle size distribution that the volume basis cumulative size D 10 is at least 50% of the average particle size D 50 , and the volume basis cumulative size D 90 is at most 150% of the average particle size D 50 , and second particles of lithium-cobalt composite oxide filling the space among the above lithium-cobalt composite oxide particles, in a mass ratio of first particles/second particles of from 1/2 to 9/1.
2. The production process according to claim 1 , wherein the large particle size cobalt hydroxide or tricobalt tetraoxide has a press density of from 1.7 to 3.0 g/cm 3 , and the small particle size cobalt hydroxide or tricobalt tetraoxide has a press density of from 1.7 to 3.0 g/cm 3 .
3. The production process according to claim 1 , wherein each of the large particle size cobalt hydroxide or tricobalt tetraoxide and the small particle size cobalt hydroxide or tricobalt tetraoxide has a specific surface area of from 2 to 20 m 2 /g.
4. The production process according to claim 1 , wherein the large particle size or small particle size cobalt hydroxide has a half value width of the diffraction peak on (001) plane at 2θ=19+1° of from 0.18 to 0.35° and a half value width of the diffraction peak on (101) plane at 2θ=38±1° of from 0.15 to 0.35°, in an X-ray diffraction spectrum using CuKα-ray.