Electrode active material and preparation method thereof, electrode, battery, and apparatus
The present invention relates to an electrode active material, a preparation method thereof, an electrode, a battery, and an apparatus. The electrode active material includes: a core and a coating layer, where the core includes a ternary material, the coating layer coats the core, the coating layer includes a reaction product of a sulfur-containing compound and a lithium-containing compound, and the reaction product includes element Li, element S, and element O.
1. An electrode active material comprising:
a core comprising a ternary material selected from the group consisting of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and a combination thereof; and
a coating layer disposed on at least part of a surface of the core, wherein the coating layer is formed by curing a solution disposed on the surface of the core, the solution comprises an organic sulfur-containing compound, and the coating layer is a reaction product of the organic sulfur-containing compound and comprises Li, S, and O,
wherein the organic sulfur-containing compound comprises one selected from the group consisting of mercaptan, thiophenol, thioether, thioaldehyde, thioketone, thiocarboxylic acid, sulfoxide, sulfone, sulfur oxoacid, a derivative of sulfur oxoacid, and any combination thereof.
2. The electrode active material according to claim 1 , wherein the sulfur oxoacid is selected from the group consisting of sulfonic acid, sulfinic acid, sulfenic acid, and any combination thereof.
3. The electrode active material according to claim 1 , wherein the derivative of sulfur oxoacid is selected from the group consisting of an ester of the sulfur oxoacid, an acyl halide of the sulfur oxoacid, an amide of the sulfur oxoacid, and a lithium amide salt of the sulfur oxoacid, and any combination thereof.
4. The electrode active material according to claim 1 , wherein the organic sulfur-containing compound is selected from the group consisting of R1-S(═O) 2 —R2, R1-C(═S)—R2,
R1-C—S—C—R2, or R1-S(═O) 2 —LiN—S(═O) 2 —R2, wherein R1 and R2 are each independently selected from the group consisting of hydroxyl, amino, C 1-6 alkyl, aryl, halogen, and hydrogen.
5. The electrode active material according to claim 4 , wherein the organic sulfur-containing compound comprises R1-S(═O) 2 —R2, wherein R1 is hydroxyl, and R2 is selected from the group consisting of amino, C 1-6 alkyl, and halogen.
6. The electrode active material according to claim 4 , wherein the organic sulfur-containing compound comprises R1-C(═S)—R2, wherein R1 is hydroxyl, and R2 is selected from the group consisting of amino, C 1-6 alkyl, and halogen.
7. The electrode active material according to claim 4 , wherein the organic sulfur-containing compound comprises
wherein R1 and R2 each are hydrogen or C 1-6 alkyl.
8. The electrode active material according to claim 4 , wherein the organic sulfur-containing compound comprises R1-C—S—C—R2, wherein R1 and R2 each are hydrogen or C 1-6 alkyl.
9. The electrode active material according to claim 4 , wherein the organic sulfur-containing compound comprises R1-S(═O) 2 —LiN—S(═O) 2 —R2, where R1 and R2 each are halogen.
10. The electrode active material according to claim 1 , wherein the organic sulfur-containing compound further comprises one selected from the group consisting of sulfamide, aminomethanesulfonic acid, lithium bisfluorosulfonimide, thio-propionamide, thio-isobutyramide, propylene sulfide, methyl ethyl sulfide, and any combination thereof.
11. The electrode active material according to claim 1 , wherein the solution further comprises a lithium containing compound selected from the group consisting of Li 2 O, LiOH and Li 2 CO 3 , LiNO 3 , LiPF 6 , lithium oxalate, lithium acetate, LiCIO 4 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiAlCl 4 , LIN(CF 3 SO 2 ) 2 , LiC(SO 2 CF 3 ) 3 , and any combination thereof.
12. The electrode active material according to claim 1 , wherein a weight content of S in the electrode active material is 500-5000 ppm.
13. The electrode active material according to claim 1 , wherein the solution further comprises a boron-containing compound, the reaction product further comprises B, and a weight content of B in the electrode active material is 500-3000 ppm.
14. The electrode active material according to claim 1 , wherein the solution further comprises a phosphorus-containing compound, the reaction product further comprises P, and a weight content of element P in the electrode active material is 200-1500 ppm.
15. The electrode active material according to claim 1 , wherein the solution further comprises a fluorine-containing compound, the reaction product further comprises F, and a weight content of element F in the electrode active material is 500-3000 ppm.
16. The electrode active material according to claim 1 , wherein a chemical formula of the lithium nickel cobalt manganese oxides is Li x Ni a Co b Mn c M 1 (1-a-b-c) O 2 , wherein 0.5≤x≤1.2, 0.3<a≤1, 0<b≤0.5, 0<c≤0.6, and M 1 is selected from one or more of Zr, Zn, Ti, Sr, Sb, Y, W, Al, B, P, and F; and
a chemical formula of the lithium nickel cobalt aluminum oxides is Li x Ni d Co e Al f M 2 (1-d-e-f) O 2 , wherein 0.5≤x≤1.2, 0.5<d≤1, 0<e≤0.5, 0<f≤0.5, and M 2 is selected from one or more of Zr, Mg, Ba, Ti, Sr, Sb, Y, W, and B.
17. The electrode active material according to claim 1 , wherein a particle size D v 50 of the electrode active material is 1-25 μm.
18. A method of making an electrode active material comprising a core and a coating layer, the method comprising:
providing a core comprising a ternary material selected from the group consisting of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or a combination thereof;
providing a solution comprising an organic sulfur-containing compound, the organic sulfur-containing compound;
applying the solution on at least a surface of the core; and
curing the solution to form the coating layer disposed on the surface of the core,
wherein the coating layer comprises a reaction product of the organic sulfur-containing compound, and the reaction product comprises Li, S, and O,
wherein the organic sulfur-containing compound is selected from the group consisting of mercaptan, thiophenol, thioether, thioaldehyde, thioketone, thiocarboxylic acid, sulfoxide, sulfone, sulfur oxoacid, a derivative of sulfur oxoacid, and any combination thereof.
19. The method according to claim 18 , wherein the organic sulfur-containing compound further comprises one selected from the group consisting of sulfamide, aminomethanesulfonic acid, lithium bisfluorosulfonimide, thio-propionamide, thio-isobutyramide, propylene sulfide, methyl ethyl sulfide, and any combination thereof.
20. The method according to claim 18 , wherein the solution further comprises a lithium containing compound selected from the group consisting of Li 2 O, LiOH and Li 2 CO 3 , LiNO 3 , LiPF 6 , lithium oxalate, lithium acetate, LiClO 4 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiAlCl 4 , LiN(CF 3 SO 2 ) 2 , LiC(SO 2 CF 3 ) 3 , and any combination thereof.