Positive pole active material for lithium secondary battery and manufacturing method thereof, lithium secondary battery

Abstract

The present disclosure relates to a positive active material for a lithium rechargeable battery and a lithium rechargeable battery including the same, which include a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2, and a content of the first compound is 65 wt % or more based of the positive active material of 100 wt %.Lia1Nib1Coc1Mnd1M1e1M2f1O2-f1   [Chemical Formula 1]Lia2Nib2Coc2Mnd2M3e2M4f2O2-f2   [Chemical Formula 2]Chemical Composition 1 and 2 of each composition and molar ratio is as defined in the specification. Each composition and molar ratio of Chemical Formula 1 and 2 is as defined in the specification.

1 . A positive active material for a lithium rechargeable battery, comprising:
 a nickel-based lithium metal oxide particle doped with Zr and Al; and   a coating layer disposed on the surface of the nickel-based lithium metal oxide particle,   wherein the nickel-based lithium metal oxide particle includes   a core portion, and   a shell portion surrounding the core portion and forming a concentration gradient in which a concentration of nickel gradually decreases from an interface with the core portion toward an outer direction, and   the coating layer includes an oxyhydroxide of a rare earth element.   
     
     
         2 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 the rare earth element is at least one among cerium (Ce), cobalt (Co), tungsten (W), lanthanum (La), hafnium (Hf), and selenium (Se).   
     
     
         3 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 a primary particle of the nickel-based lithium metal oxide particle has a rod shape with an aspect ratio of 1 or more.   
     
     
         4 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 the nickel-based metal oxide particle including the core portion and the shell portion has an average composition represented by Chemical Formula 4 below:
   Li m4 [Ni 1-w4-x4-y4-z4 Co w4 M1 x4 M2 y4 M3 z4 ] n4 O 2-p4 X p4    [Chemical Formula 4]
 
   (in Chemical Formula 4,   M1 is one element selected from a group including Mn, Mg, Sn, Ca, Ge, and Ga,   M2is Zr,   M3 is Al,   X is one element selected from a group including F, N, and P,   w4, x4, y4, z4, and p4 are respectively 0<w4≤0.2, 0<x4≤0.2, 0<y4≤0.006, 0<z4≤0.006, 0<w4+x4+y4+z4≤0.4 and 0≤p4≤0.1,   0.95≤m4≤1.1, and 0.95≤n4≤1.1).   
     
     
         5 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 a doping amount of Zr in the nickel-based lithium metal oxide particle is 2000 ppm to 5000 ppm.   
     
     
         6 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 a doping amount of A in the nickel-based lithium metal oxide particle is 100 ppm to 1500 ppm.   
     
     
         7 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 a molar ratio of Zr:Al in the nickel-based lithium metal oxide particles is 15:1 to 0.4:1.   
     
     
         8 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 the composition of the core portion of the nickel-based lithium metal oxide particle is represented by Chemical Formula 5 in the entire region:
   Li m5 [Ni 1-w5-x5-y5-z5 Co w5 M1 x5 M2 y5 M3 z5 ] n5 O 2-p5 X p5    [Chemical Formula 5]
 
   (in Chemical Formula 5,   M1 is one element selected from a group including Mn, Mg, Sn, Ca, Ge, and Ga,   M2 is Zr, M3 is Al,   X is one element selected from a group including F, N, and P,   w5, x5, y5, z5, and p5 are respectively 0≤w5≤0.1, 0≤x5≤0.1, 0<y5≤0.005, 0<z5≤0.006, 0≤w5+x5+y5+z5≤0.2, and 0≤p5≤0.1,   0.95≤m5≤1.1, and 0.95≤n5≤1.1).   
     
     
         9 . The positive active material for the lithium rechargeable battery of  claim 8 , wherein
 the composition of the shell portion of the nickel-based lithium metal oxide particle is represented by Chemical Formula 5 in the interface with the core portion, is represented by Chemical Formula 6 at the outermost part of the shell portion, and each molar content of the nickel (Ni), M1, M2, and M3 is gradually changed from the interface to the outermost part:
   Li m6 [Ni 1-w6-x6-y6-z6 Co w6 M1 x6 M2 y6 M3 z6 ] n6 O 2-p6 X p6    [Chemical Formula 6]
 
   (in Chemical Formula 6,   M1 is one element selected from a group including Mn, Mg, Sn, Ca, Ge, and Ga,   M2 is Zr, M3 is Al,   X is one element selected from a group including F, N, and P,   w6, x6, y6, z6, and p6 are respectively 0<w6≤0.3, 0<x6≤0.3, 0<y6≤0.007, 0<z6≤0.006, 0<w6+x6+y6+z6≤0.5, and 0≤p6≤0.1, 0.95≤m6≤1.1, and 0.95≤n6≤1.1).   
     
     
         10 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 the nickel-based lithium metal oxide particle includes   a first compound having an average particle diameter of 10 μm to 30 μm, and   a second compound having an average particle diameter of 1 μm to 6 μm.   
     
     
         11 . The positive active material for the lithium rechargeable battery of  claim 10 , wherein
 the mixture weight ratio of the first compound and second compound is 60:40 to 90:10.   
     
     
         12 . The positive active material for the lithium rechargeable battery of  claim 1 , wherein
 the nickel-based lithium metal oxide particle has 50% or more of a value of Equation 3 below:
     R 2/( R 2+ D 2)*100%   [Equation 3]
 
   in Equation 3, R2 is a radius of the core portion in the nickel-based metal oxide particle, and D2 is a thickness of the shell portion in the nickel-based metal oxide particle.   
     
     
         13 . The positive active material for the lithium rechargeable battery of  claim 12 , wherein
 the nickel-based lithium metal oxide particle has 75% or more of a value of Equation 3 above.   
     
     
         14 . A lithium rechargeable battery comprising:
 a negative electrode;   a positive electrode including the positive active material for the lithium rechargeable battery of  claim 1 ; and   an electrolyte.