Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material
A nickel-based active material for a lithium secondary battery, a method of preparing the nickel-based active material, and a lithium secondary battery including a positive electrode including the nickel-based active material, the nickel-based active material comprising a secondary particle having an outer portion with a radially arranged structure and an inner portion with an irregular porous structure, wherein the inner portion of the secondary particle has a larger pore size than the outer portion of the secondary particle.
1. A lithium nickel-based active material for a lithium secondary battery, the lithium nickel-based active material comprising;
a secondary particle having an outer portion with a structure of radially arranged plate particles,
a plurality of open pores at a surface of the secondary particle, and
an inner portion with a plurality of closed pores, each closed pore of the plurality of closed pores having an irregular porous structure and having walls that are closed so as to provide no connection to other pores,
the inner portion of the secondary particle having a larger pore size than the outer portion of the secondary particle, wherein a pore size of the inner portion of the secondary particle is 150 nm to 550 nm,
wherein the lithium nickel-based active material is prepared by a method in which a metal hydroxide is combined with a lithium hydroxide precursor, and which comprises a first heat treatment and a second heat treatment, the second heat treatment being performed with exhaust suppressed.
2. The lithium nickel-based active material of claim 1 , wherein a pore size of the outer portion of the secondary particle is less than 150 nm.
3. The lithium nickel-based active material of claim 1 , wherein the secondary particle further comprises an open pore having a size of less than 150 nm toward the center of the inner portion of the secondary particle.
4. The lithium nickel-based active material of claim 1 , wherein the lithium nickel-based active material comprises a plate particle having a long axis arranged in a radial direction.
5. The lithium nickel-based active material of claim 4 , wherein the plate particle has an average length of 150 nm to 500 nm and an average thickness of 100 nm to 200 nm, and a ratio of the average thickness to the average length is 1:2 to 1:5.
6. The lithium nickel-based active material of claim 1 , wherein the lithium nickel-based active material is an active material represented by Formula 1:
Li a (Ni 1-x-y-z Co x Mn y M z )O 2 . Formula 1
wherein, in Formula 1, M is an element selected from boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al), and
a, x, y, and z satisfy the following relations: 0.95≤a≤1.3, x≤(1−x−y−z), y≤(1−x−y−z), z≤(1−x−y−z), 0<x<1, 0≤y<1, and 0≤z<1.
7. The lithium nickel-based active material of claim 6 , wherein, in Formula 1, a, x, y, and z satisfy the following relations: 0.95≤a≤1.3, 0<x≤0.33, 0≤y≤0.05, 0≤z≤0.05, and 0.33≤(1-x-y-z)≤0.95.
8. The lithium nickel-based active material of claim 6 , wherein:
an amount of nickel in the lithium nickel-based active material is 33 mol % to 95 mol % based on a total amount of transition metals including nickel, cobalt, manganese, and M contained in the lithium nickel-based active material,
the amount of nickel in the lithium nickel-based active material is higher than that of manganese, and
the amount of nickel in the lithium nickel-based active material is higher than that of cobalt.
9. The lithium nickel-based active material of claim 1 , wherein the lithium nickel-based active material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , or LiNi 0.5 Co 0.1 Al 0.05 O 2 .
10. The lithium nickel-based active material of claim 1 , wherein an overall porosity of the lithium nickel-based active material is 1% to 8%.
11. A method of preparing the lithium nickel-based active material of claim 1 , the method comprising:
performing a first heat treatment on a mixture comprising a lithium hydroxide precursor and a metal hydroxide at a temperature of 600° C. to 800° C. in an oxidative gas atmosphere,
wherein the method further comprises performing a second heat treatment on the mixture at a temperature of 700° C. to 900° C. in an oxidative gas atmosphere, wherein the second heat treatment is performed at a higher temperature than the first heat treatment and with exhaust suppressed,
and the metal hydroxide is radial, porous, and includes plate particles.
12. The method of claim 11 , wherein the metal hydroxide is a compound represented by Formula 2:
(Ni 1-x-y-z Co x Mn y M z )(OH) 2 . Formula 2
wherein, in Formula 2, M is an element selected from boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al), and
x, y, and z satisfy the following relations: x≤(1-x-y-z), y≤(1-x-y-z), z≤(1-x-y-z), 0<x<1, 0≤y<1, and 0≤z<1.
13. A lithium secondary battery comprising:
a positive electrode comprising the lithium nickel-based active material of claim 1 ;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode.
14. The lithium secondary battery of claim 13 , wherein a pore size of the outer portion of the lithium nickel-based active material is less than 150 nm.
15. The lithium secondary battery of claim 13 , further comprising an open pore having a size of less than 150 nm in an inner portion of a secondary particle of the lithium nickel-based active material.
16. The lithium secondary battery of claim 13 , wherein the lithium nickel-based active material comprises a plate particle having a long axis arranged in a radial direction.
17. The lithium secondary battery of claim 16 , wherein the plate particle has an average length of 150 nm to 500 nm and an average thickness of 100 nm to 200 nm, and a ratio of the average thickness to the average length is 1:2 to 1:5.
18. The lithium secondary battery of claim 13 , wherein the lithium nickel-based active material is an active material represented by Formula 1:
Li a (Ni 1-x-y-z Co x Mn y M z )O 2 . Formula 1
wherein, in Formula 1, M is an element selected from boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al), 0.95≤a≤1.3, x≤(1-x-y-z), y≤(1-x-y-z),0<x<1, 0≤y<1, and 0≤z<1.
19. The lithium secondary battery of claim 13 , wherein the lithium nickel-based active material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , or LiNi 0.5 Co 0.1 Al 0.05 O 2 .
20. A lithium nickel-based active material for a lithium secondary battery, the lithium nickel-based active material comprising a secondary particle having an outer portion comprising:
radially arranged particles comprising a plurality of radially arranged plate particles, each having a long axis arranged in a radial direction;
non-radially arranged particles mixed with the radially arranged particles in an amount of 0.01 wt % to 20 wt %;
a plurality of open pores at a surface of the secondary particle; and
an inner portion with a plurality of closed pores, each having an irregular porous structure,
wherein the inner portion of the secondary particle has-a larger pore size than the outer portion of the secondary particle,
wherein each plate particle of the plurality of plate particles has-an average length of 150 nm to 380 nm and an average thickness of 100 nm to 200 nm, and a ratio of the average thickness to the average length is 1:2 to 1:5, and
wherein the lithium nickel-based active material is prepared by a method in which a metal hydroxide is combined with a lithium hydroxide precursor, and which comprises a first heat treatment and a second heat treatment, the second heat treatment being performed with exhaust suppressed.
21. The lithium nickel-based active material of claim 20 , wherein a pore size of the inner portion of the secondary particle is 150 nm to 1 μm, and a pore size of the outer portion of the secondary particle is less than 150 nm.
22. The lithium nickel-based active material of claim 20 , wherein the lithium nickel-based active material is an active material represented by Formula 1:
Li a (Ni 1-x-y-z Co x Mn y M z )O 2 . Formula 1
wherein, in Formula 1, M is an element selected from boron (B), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zirconium (Zr), and aluminum (Al), and
a, x, y, and z satisfy the following relations: 0.95≤a≤1.3, x≤(1−x−y−z), y≤(1−x−y−z), z≤(1−x−y−z), 0<x<1, 0≤y<1, and 0≤z<1.
23. The_lithium nickel-based active material of claim 20 , wherein the lithium nickel-based active material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , or LiNi 0.5 Co 0.1 Al 0.05 O 2 .
24. The lithium nickel-based active material of claim 20 , wherein an overall porosity of the lithium nickel-based active material is 1% to 8%.
25. A lithium secondary battery comprising:
a positive electrode comprising the lithium nickel-based active material of claim 20 ;
a negative electrode; and
an electrolyte between the positive electrode and the negative electrode.