Method for preparing positive electrode additives of lithium secondary battery
The present disclosure provides a preparing method of a positive electrode additive for a lithium secondary battery capable of reducing the amount of Li-based byproduct and unreacted lithium oxide generated in a preparing process, thereby significantly reducing the amount of gas generated when the electrode is operated.
1. A method for preparing a positive electrode additive of a lithium secondary battery, comprising
mixing a lithium raw material, a nickel raw material, and a raw material of an element M, and heat treating them under an atmosphere of an inert gas to produce a lithium nickel oxide of Chemical Formula 1 below,
wherein the heat treating comprises first heat treating at 300° C. to 500° C., and second heat treating at 550° C. to 800° C. after the first heat treating, and the first heat treating is performed for 30% or more and less than 50of a total duration of the heat treating,
wherein the positive electrode additive comprises the lithium nickel oxide of Chemical Formula 1,
wherein the positive electrode additive further comprises less than 11 wt % NiO and 1 wt % or less Li 2 O based on a total weight of the positive electrode additive, wherein a total amount of the NiO and the Li 2 O is less than or equal to 11 wt % based on a total weight of the positive electrode additive, and,
after being charged at 0.1 C to 3.8 V at 25° C. and then being analyzed using X-ray diffraction, the positive electrode additive has a peak intensity ratio of d1/d2=0, when a peak intensity appearing at 2θ=30° to 35° is d1 and a peak intensity appearing at 2θ=15° to 20° is d2:
Li 2 Ni 1-x M x O 2 [Chemical Formula 1]
wherein, in Chemical Formula 1, M is a transition metal, an amphoteric element, P, F, or B, wherein M is not nickel, and 0<x<1.
2. The method of claim 1 , wherein the first heat treating is performed for 35% to 45% of the total duration of the heat treating at 330° C. to 450° C.
3. The method of claim 1 , wherein the first heat treating comprises a temperature rising step of heating to a temperature of 300° C. to 500° C. at a rate of 2° C./min to 7° C./min, and a maintaining step of maintaining the heated temperature for 40% to 80% of the total duration of the first heat treating.
4. The method of claim 1 , wherein the second heat treating is performed at 600° C. to 800° C.
5. The method of claim 1 , wherein the second heat treating comprises a temperature rising step of heating to a temperature of 550° C. to 800° C. at a rate of 2° C./min to 7° C./min and a maintaining step of maintaining the heated temperature for 60% to 90% of the total duration of the second heat treating.
6. The method of claim 1 , wherein the lithium raw material is used in an amount such that a mole ratio of lithium:(nickel+element M) is 2:1 when mixing the lithium raw material, the nickel raw material, and the raw material of the element M.
7. The method of claim 1 , wherein the lithium raw material comprises any one or a mixture of two or more selected from the group consisting of a lithium-containing oxide, a hydroxide, an oxyhydroxide, a sulfate, a nitrate, an acetate, a carbonate, an oxalate, a citrate, a halide, and hydrates thereof.
8. The method of claim 1 , wherein the raw material of the element M comprises any one or a mixture of two or more selected from the group consisting of an oxide, a hydroxide, an oxyhydroxide, a sulfate, a nitrate, an acetate, a carbonate, an oxalate, a citrate, a halide, a phosphate, and hydrates thereof that contain the element M.
9. The method of claim 1 , wherein the Ni raw material comprises NiO.
10. The method of claim 1 , wherein the element M is selected from the group consisting of W, Ti, Zr, Al, P, F, and B.
11. A positive electrode additive for a lithium secondary battery, comprising a lithium nickel oxide of Chemical Formula 1, wherein the positive electrode additive further comprises less than 11 wt % NiO and 1 wt % or less Li 2 O based on the total weight of the positive electrode additive, wherein a total amount of the NiO and the Li 2 O is less than or equal to 11 wt % based on a total weight of the positive electrode additive, and after being charged at 0.1 C to 3.8 V at 25° C. and then being analyzed using X-ray diffraction, the positive electrode additive has a peak intensity ratio of d1/d2=0, when a peak intensity appearing at 2θ=30° to 35° is d1 and a peak intensity appearing at 2θ=15° to 20° is d2, and
wherein the positive electrode additive is prepared by the method of claim 1 :
Li 2 Ni 1-x M x O 2 [Chemical Formula 1]
wherein, in Chemical Formula 1, M is a transition metal, an amphoteric element, P, F, or B, wherein M is not nickel, and 0<x<1.
12. A positive electrode for a lithium secondary battery comprising the positive electrode additive of claim 11 .
13. A lithium secondary battery comprising: a positive electrode comprising the positive electrode additive of claim 11 ; an electrolyte; and a negative electrode.