Electrode active composition, preparation method thereof, electrode, battery, and apparatus
This application relates to an electrode active composition, a preparation method thereof, an electrode, a battery, and an apparatus. The electrode active composition includes: a first component, the first component being lithium cobalt oxide particles; and a second component, the second component being ternary material particles. The first component includes lithium cobalt oxide particles with a particle size greater than 11 μm and lithium cobalt oxide particles with a particle size less than 6 μm, and a ratio in number of the lithium cobalt oxide particles with a particle size greater than 11 μm to the lithium cobalt oxide particles with a particle size less than 6 μm is 0.2-4.8, and in some embodiments, 0.2-2.8. A summed number of the lithium cobalt oxide particles with a particle size greater than 11 μm and the lithium cobalt oxide particles with a particle size less than 6 μm accounts for above 90% of a total number of particles in the first component.
1. An electrode active composition, comprising:
a plurality of first particles of lithium cobalt oxide having a formula of Li x Co y M 1 (1-y) O 2 , wherein x satisfies 0.95≤x≤1.05, y satisfies 0.8≤y≤1, and M 1 is selected from the group consisting of Zr, Mg, Ti, Sr, W, Nb, Al, P, F, S, and any combination thereof; and
a plurality of second particles, each one of the second particles having a core-coating layer structure, the core-coating layer structure comprising a core and a coating layer, wherein
the core of the second particles is a ternary material selected from the group consisting of lithium nickel cobalt aluminum oxide, lithium nickel manganese cobalt oxide, and a combination thereof; and
the coating layer is disposed on at least a partial surface of the core and comprises a reaction product of a sulfur-containing compound and a lithium-containing compound, the reaction product comprises Li, S, and O, S in the coating layer accounts for 400 ppm-5000 ppm in the second particles by weight, the reaction product further comprises an element selected from the group consisting of P, F, or a combination thereof, when the reaction product comprises P, P accounts for 500 ppm-3000 ppm in the second particles by weight, and when the reaction product comprises F, F accounts for 200 ppm-1500 ppm in the second particles by weight;
wherein the plurality of first particles comprise lithium cobalt oxide particles with a particle size greater than 11 μm and lithium cobalt oxide particles with a particle size less than 6 and a ratio in number of the lithium cobalt oxide particles with a particle size greater than 11 μm to the lithium cobalt oxide particles with a particle size less than 6 μm is 0.2-4.8; and
a summed number of the lithium cobalt oxide particles with a particle size greater than 11 and the lithium cobalt oxide particles with a particle size less than 6 μm accounts for above 90% of a total number of particles in the first particles.
2. The electrode active composition according to claim 1 , wherein a weight ratio of the first particles to the second particles is 1:1 to 9:1.
3. The electrode active composition according to claim 1 , wherein a particle size of the second particles is 2 μm-6 μm.
4. The electrode active composition according to claim 1 , wherein:
the second particles have at least a single crystal structure.
5. The electrode active composition according to claim 1 , wherein
a chemical formula of the lithium nickel manganese cobalt oxide is Li a Ni b Co c Mn d M 2 (1-b-c-d) O 2 , wherein 0.5≤a≤1.2, 0.65≤b≤1, 0<c≤0.35, 0<d≤0.35, and M 2 is selected from the group consisting of Zr, Zn, Ti, Sr, Sb, Y, W, Al, B, P, F, S, and any combination thereof; and
a chemical formula of the lithium nickel cobalt aluminum oxide is Li x Ni e Co f Al g M 3 (1-e-f-g) O 2 , 0.5≤x≤1.2, 0.5≤e≤1, 0<f≤0.5, 0<g≤0.5, and M 3 is selected from the group consisting of Zr, Mg, Ba, Ti, Sr, Sb, Y, W, B, or any combination thereof.
6. The electrode active composition according to claim 1 , wherein a compacted density of the electrode active composition is ≥4.05 g/cm 3 , and the compacted density is a density of a briquette formed by pressing the electrode active composition for 30 seconds under a pressure of 5 tons.
7. The electrode active composition according to claim 1 , wherein the coating layer further contains B and B accounts for 500 ppm-3000 ppm in the second particles by weight.
8. The electrode active composition according to claim 1 , wherein
the lithium-containing compound is selected from the group consisting of: Li 2 O, LiOH, Li 2 CO 3 , LiNO 3 , LiPF 6 , lithium oxalate, lithium acetate, and any combinations thereof.
9. The electrode active composition according to claim 1 , wherein the sulfur-containing compound is selected from the group consisting of: mercaptan, thiophenol, thioether, thioaldehyde, thioketone, thionocarboxylic acid, sulphoxide, sulfone, sulfur oxoacid, R1-S(═O) 2 —R2, R1-C(═S)—R2,
R1-C—S—C—R2, R1-S(═O) 2 —LiN—S(═O) 2 —R2, sulfamide, sulfamic acid, lithium bisfluorosulfonimide, thiopropionamide, thioisobutyramide, propylene sulfide, methyl ethyl sulfide, or and any combination thereof, wherein R1 and R2 are each independently selected from the group consisting of hydroxyl, amino, C 1-6 alkyl, aryl, a halogen atom selected from the group consisting of F, Cl, Br, and I, and a hydrogen atom.
10. A method of making an electrode active composition, the method comprising:
providing a plurality of first particles of lithium cobalt oxide having a formula of Li x Co y M 1 (1-y) O 2 , wherein x satisfies 0.95≤x≤1.05, y satisfies 0.8≤y≤1, and M 1 is selected from the group consisting of Zr, Mg, Ti, Sr, W, Nb, Al, P, F, S, and any combination thereof;
providing a plurality of second particles having a core-coating layer structure, wherein providing the plurality of second particles further comprises:
providing a core comprising a ternary material selected from the group consisting of lithium nickel cobalt aluminum oxide, lithium nickel manganese cobalt oxide, or a combination thereof;
providing a coating layer precursor comprising a sulfur-containing compound, wherein the sulfur-containing compound is selected from the group consisting of mercaptan, thiophenol, thioether, thioaldehyde, thioketone, thionocarboxylic acid, sulphoxide, sulfone, sulfur oxoacid, sulfamide, sulfamic acid, lithium bisfluorosulfonimide, thiopropionamide, thioisobutyramide, propylene sulfide, methyl ethyl sulfide, R1-S(═O) 2 —R2, R1-C(═S)—R2,
R1-C—S—C—R2, or R1-S(═O) 2 —LiN—S(═O) 2 —R2, and any combination thereof, wherein R1 and R2 are each independently selected from hydroxyl, amino, Ci- 6 alkyl, aryl, a halogen atom selected from the group consisting of F, Cl, Br, and I, and a hydrogen atom; and
treating the core with the coating layer precursor to form a reaction product as the coating layer on at least a part of a surface of the core, wherein the reaction product comprises Li, S, and O, and S in the coating layer accounts for 400 ppm-5000 ppm in the second particles by weight; and
mixing the plurality of first particles and the plurality of second particles;
wherein the plurality of first particles comprise first lithium cobalt oxide particles with a particle size greater than 11 μm and second lithium cobalt oxide particles with a particle size less than 6 μm, and a ratio in number of the lithium cobalt oxide particles with a particle size greater than 11 μm to the lithium cobalt oxide particles with a particle size less than 6 μm is 0.2-4.8; and
a summed number of the first lithium cobalt oxide particles with a particle size greater than 11 μm and the second lithium cobalt oxide particles with a particle size less than 6 μm accounts for above 90% of a total number of particles in the plurality of first particles.
11. The method according to claim 10 , further comprising: mixing the first lithium cobalt oxide particles and the second lithium cobalt oxide particles to obtain the plurality of first particles,
wherein a particle size D v 50 of the first lithium cobalt oxide particles is 17 μm-21 μm;
a particle size D v 50 of the second lithium cobalt oxide particles is 4 μm-8 μm; and
a weight ratio of the first lithium cobalt oxide particles to the second lithium cobalt oxide particles is 3:1 to 15:1.
12. The method according to claim 10 , wherein the core further comprises an alkaline lithium-containing compound on the surface of the core, and the reaction product is formed by a reaction of the alkaline lithium-containing compound and the sulfur-containing compound of the coating layer precursor.
13. The method according to claim 10 , wherein the coating layer precursor further comprises a neutral or acidic lithium-containing compound.
14. The method according to claim 10 , wherein treating the core with the coating layer precursor further comprises:
applying, on the surface of the core, a solution in which the coating layer precursor is dissolved; and
treating the core with the coating layer precursor at a temperature of 80° C.-300° C. for 3 h-20 h.
15. An electrode, wherein the electrode comprises the electrode active composition according to claim 1 .
16. A battery, wherein the battery comprises the electrode active composition according to claim 1 .
17. An apparatus, wherein the apparatus comprises the battery according to claim 16 , and the battery serves as a power supply unit or an energy storage unit of the apparatus; and
the apparatus is an electric apparatus, and the battery is configured to supply power to the electric apparatus.
18. The method according to claim 10 , wherein the coating layer precursor further comprises a fluorine-containing compound, the reaction product further comprises F, and F accounts for 200 ppm-1500 ppm in the second particles by weight.
19. The method according to claim 10 , wherein the coating layer precursor further comprises a phosphor-containing compound, the reaction product further comprises P, and P accounts for 500 ppm-3000 ppm in the second particles by weight.