CATHODE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERY, PREPARATION METHOD THEREFOR, AND LITHIUM SECONDARY BATTERY COMPRISING SAME
The present disclosure relates to a cathode active material for a lithium secondary battery, a preparation method therefor, and a lithium secondary battery comprising same, and the cathode active material includes a lithium nickel cobalt manganese-based oxide represented by Chemical Formula 1 including secondary particles obtained by agglomerating at least one primary particle, and a metal oxide particles having a nano-sized average diameter (D50) and disposed inside the secondary particles. Li a [Ni x Co y Mn z ] t M 1-t O 2-p X p . [Chemical Formula 1]
1 . A cathode active material for a lithium secondary battery, comprising
a lithium nickel cobalt manganese-based oxide represented by Chemical Formula 1 including secondary particles obtained by agglomerating at least one primary particle; and
metal oxide particles having a nano-sized average diameter (D50) and disposed inside the secondary particles,
Li a [Ni x Co y Mn z ] t M 1-t O 2-p X p [Chemical Formula 1]
wherein, in Chemical Formula 1,
M is any one element selected from Al, Mg, Sn, Ca, Ge, Ga, B, Ti, Mo, Nb, and W
X is any one element selected from F, N, and P,
0.8≤a≤1.3,
0.60≤x≤0.95, 0<y≤0.2, 0<z≤0.2, x+y+z=1, 0≤t≤1, and 0≤p≤0.1.
2 . The cathode active material of claim 1 , wherein in Chemical Formula 1, 0.8≤x≤0.95, 0<y≤0.1, and 0<z≤0.1.
3 . The cathode active material of claim 1 , wherein the metal oxide comprises at least one selected from ZrO 2 , WO 3 , CeO 2 , TiO 2 , HfO 2 , Co 3 O 4 , La 2 O 3 , BaO, SrO, and a combination thereof.
4 . The cathode active material of claim 1 , wherein the metal oxide has an average particle diameter (D50) of 50 nm to 800 nm.
5 . The cathode active material of claim 1 , wherein a metal content of the metal oxide is 0.1 wt % to 0.7 wt % based on 100 wt % of the cathode active material.
6 . The cathode active material of claim 1 , wherein the secondary particles comprise a core portion in which a nickel molar content is constant and a shell portion which surrounds the outer surface of the core portion and has a concentration gradient in which a nickel molar content gradually decreases in a direction from the interface with the core portion to the outermost surface.
7 . The cathode active material of claim 1 , which further comprises a coating layer disposed on the surface of the secondary particles.
8 . A method of preparing a cathode active material for a lithium secondary battery, comprising
preparing a hydroxide precursor particle including nickel, cobalt, and manganese;
subjecting the hydroxide precursor particles to first firing to prepare porous oxide precursor particles;
mixing the oxide precursor particles and a metal oxide to prepare a first mixture;
mixing the first mixture and a lithium raw material to prepare a second mixture; and
subjecting the second mixture to second firing.
9 . The method of claim 8 , wherein the first firing is performed by increasing a temperature up to 400° C. to 800° C. at 1.0° C./min to 5.0° C./min, and maintaining for 3 hours to 20 hours.
10 . The method of claim 8 , wherein the first firing is performed while blowing air or oxygen at a rate of 10 mL/min to 50 L/min.
11 . The method of claim 8 , wherein in the mixing the oxide precursor particles and a metal oxide to prepare a first mixture, a doping raw material is further included.
12 . The method of claim 8 , wherein
the preparing of the hydroxide precursor particle including nickel, cobalt, and manganese comprises
preparing a first metal salt solution and a second metal salt solution each including a nickel raw material, a cobalt raw material, a manganese raw material, and a solvent, and having different molar concentrations of the nickel raw material;
a first co-precipitating in which a core portion is formed by supplying the first metal salt solution at a constant concentration to a reactor in which the pH is maintained constant and a chelating agent;
second co-precipitating in which a product forming a shell portion surrounding the outer surface of the core portion is formed by gradually decreasing a feed rate of the first metal salt aqueous solution and at the same time gradually increasing a feed rate of the second metal salt aqueous solution after the first co-precipitating; and
drying the product.
13 . A lithium secondary battery comprising
the cathode including a cathode active material of claim 1 ;
an anode; and
a non-aqueous electrolyte.