Spherical or spherical-like cathode material for a lithium battery, a battery and preparation method and application thereof
The present invention discloses a spherical or spherical-like lithium battery cathode material, a battery and preparation methods and applications thereof. The chemical formula of the cathode material is: Li a Ni x Co y Mn z M b O 2 , wherein 1.0≤a≤1.2; 0.0<b≤0.05; 0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50; x+y+z+b=1; M is one or two or more of Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Ba and a rare earth element. A single α-NaFeO 2 type layered structure of the cathode material is shown by a powder X-ray diffraction pattern and full width at half maximum FWHM (110) of the (110) diffraction peak near a diffraction angle 2θ of 64.9° is in the range of 0.073 to 0.145; the morphology of the cathode material is spherical or spherical-like primary particles and a small amount of secondary particles; the cumulative percentage of the number of particles having a particle diameter of 5 μm or less is usually larger than 60% in the number-basis particle sizes of primary particles and secondary particles agglomerated by primary particles of the cathode material. The cathode material in the present invention has excellent circulating performance, storage performance and safety performance under high temperature and high voltage, and is suitable for digital product, electric vehicle, electric bicycle, fast charging bus, passenger car, communication product, electric power and energy storage system etc.
1. A lithium ion battery cathode material of a spherical layered structure is characterized in that a chemical formula of said cathode material is Li a Ni x Co y Mn z M b O 2 , wherein 1.0≤a≤1.2; 0.002≤b≤0.05; 0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50; x+y+z+b=1; M is one or two or more of Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Ba and a rare earth element;
said lithium ion battery cathode material of a spherical layered structure is prepared by a method comprising at least the following steps:
dispersing a lithium source into a polyethylene glycol or an acrylamide aqueous colloid to prepare a colloid, and adding nickel-cobalt-manganese precursor according to a molar ratio of Li:(Ni+Co+Mn)=(1.0-1.2):(0.95-1.0) into the colloid to obtain a mixed material, and pre-sintering the mixed material at 400 to 800° C. and then sintering at 800 to 980° C., and cooling, and pre-pulverizing and classifying to obtain a lithium-nickel-cobalt-manganese-oxygen cathode material intermediate A, adding a solution of M source or a dispersion B into A to obtain a mixture C, and post-sintering the mixture C at 500 to 960° C., and cooling, and pulverizing and classifying to obtain a lithium ion battery cathode material of a spherical layered structure.
2. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that a doping amount b of the doping element M is 0.001 to 0.5.
3. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that said cathode material powder comprises primary particles of a morphology of spherical shape and a small amount of secondary particles agglomerated by primary particles under scanning electron microscope (SEM), wherein cumulative percentage of the number of particles having a particle diameter of 5 μm or less is generally greater than 60% in the number-basis sizes of primary particles and secondary particles agglomerated by primary particles of the cathode material.
4. The lithium ion battery cathode material of a spherical layered structure according to claim 2 is characterized in that a single α-NaFeO 2 type layered structure of said cathode material is shown by a powder X-ray diffraction pattern (XRD), and full width at half maximum FWHM (110) of the (110) diffraction peak near a diffraction angle 2θ of 64.9° is 0.073 to 0.145.
5. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that specific surface area of said cathode material measured by BET method is 0.3 to 0.9 m 2 /g.
6. The lithium ion battery cathode material of a spherical or layered structure according to claim 1 is characterized in that a median particle diameter of said cathode material is 3.0 to 8.0 μm.
7. A lithium ion battery is characterized by comprising the lithium ion battery cathode material of claim 1 as a positive electrode active material.
8. A lithium ion battery is characterized by comprising the lithium ion battery cathode material of claim 3 as a positive electrode active material.
9. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that said pre-sintering is carried out for 4 to 8 hours, and said sintering is carried out for 8 to 20 hours, and said post-sintering is carried out for 4 to 10 hours.
10. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that a pressure of said pre-pulverizing is 0.1 to 1.0 MPa.
11. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that a median particle diameter D50 of the nickel-cobalt-manganese precursor is 3 to 12 μm.
12. The lithium ion battery cathode material of a spherical layered structure according to claim 1 is characterized in that the M source is an oxide of one or two or more selected from the group consisting of Mg, Al, Ti, Zr, Y, Co, Ni, Mn, Ba and a rare earth element, or a salt thereof or an organic compound thereof, acetic acid salt, sulfate, hydroxyl compound, and ester compound etc.
13. A method for preparing a lithium ion battery cathode material of a spherical layered structure is characterized in that a chemical formula of said cathode material is Li a Ni x Co y Mn z M b O 2 , wherein 1.0≤a≤1.2; 0.0<b<0.05; 0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50; x+y+z+b=1; M is one or two or more of Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Ba and a rare earth element;
wherein said method comprises at least the following steps:
dispersing a lithium source into a polyethylene glycol or an acrylamide aqueous colloid to prepare a colloid, and adding nickel-cobalt-manganese precursor according to a molar ratio of Li:(Ni+Co+Mn)=(1.0-1.2):(0.95-1.0) into the colloid to obtain a mixed material, and pre-sintering the mixed material at 400 to 800° C. and then sintering at 800 to 980° C., and cooling, and pre-pulverizing and classifying to obtain a lithium-nickel-cobalt-manganese-oxygen cathode material intermediate A, adding a solution of M source or a dispersion B into A to obtain a mixture C, and post-sintering the mixture C at 500 to 960° C., and cooling, and pulverizing and classifying to obtain a lithium ion battery cathode material of a spherical layered structure.
14. The method according to claim 13 , which is characterized in that said cathode material powder comprises primary particles of a morphology of spherical shape and a small amount of secondary particles agglomerated by primary particles under scanning electron microscope (SEM), wherein cumulative percentage of the number of particles having a particle diameter of 5 μm or less is generally greater than 60% in the number-basis sizes of primary particles and secondary particles agglomerated by primary particles of the cathode material.
15. The method according to claim 13 , which is characterized in that a doping amount b of the doping element M is 0.001 to 0.5.
16. The method according to claim 13 , which is characterized in that said pre-sintering is carried out for 4 to 8 hours, and said sintering is carried out for 8 to 20 hours, and said post-sintering is carried out for 4 to 10 hours.
17. The method according to claim 13 , which is characterized in that a pressure of said pre-pulverizing is 0.1 to 1.0 MPa.
18. The method according to claim 13 , which is characterized in that the lithium source used is one or two or more mixture of lithium carbonate, lithium hydroxide monohydrate, lithium nitrate and lithium acetate.
19. The method according to claim 13 , which is characterized in that the nickel-cobalt-manganese precursor used is one or more selected from the group consisting of nickel-cobalt-manganese hydroxide, nickel-cobalt-manganese carboxyl oxide, and nickel-cobalt-manganese oxide.
20. The method according to claim 13 , which is characterized in that adding the M source comprises one or two or more selected from the group consisting mechanical mixing, co-precipitation, and emulsification.