Method for manufacturing positive active material, and positive active material and lithium secondary battery using same
A method for preparing a positive electrode active material, a positive electrode active material prepared using the same, and a lithium secondary battery, and in particular, to a method for preparing a positive electrode active material comprising the steps of (a) preparing a coating composition including a precursor of metal-phosphorous-oxynitride; (b) forming a precursor layer on a positive electrode active material with the coating composition of (a) using a solution process; and (c) forming a metal-phosphorous-oxynitride protective layer on the positive electrode active material by heat treating the positive electrode active material having the precursor layer formed thereon. The method for preparing a positive electrode active material uses a solution process, which is advantageous in terms of simplifying the whole process and reducing costs, and high capacity, high stabilization and long lifetime are obtained as well by the formed protective layer having excellent properties.
1. A method for preparing a positive electrode active material comprising:
(a) preparing a coating composition including a precursor of metal-phosphorous-oxynitride;
(b) forming a precursor layer on a positive electrode active material with the coating composition of (a) using a solution process; and
(c) forming a metal-phosphorous-oxynitride protective layer on the positive electrode active material by heat treating the positive electrode active material having the precursor layer formed thereon,
wherein the precursor of metal-phosphorous-oxynitride is prepared by a reaction of a compound comprising a phosphorous-nitrogen bond with a metal salt compound,
wherein the compound comprising the phosphorous-nitrogen bond comprises at least one selected from the compounds represented by the following Chemical Formulae 1 to 3:
wherein each X 1 is the same or different from each other and each independently is OR 1 , F, Cl, Br or I, wherein R 1 is an alkyl group having 1 to 5 carbon atoms;
wherein R 2 and R 3 are the same or different from each other and each independently is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms;
wherein each X 2 is the same or different from each other and each independently is R 4 , OR 5 , NR 6 R 7 , F, Cl, Br or I, wherein R 4 to R 7 are the same or different from each other, and each independently is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms and
n is an integer of 100 to 100,000.
2. The method for preparing a positive electrode active material of claim 1 , wherein the metal salt compound comprises at least one metal selected from the group consisting of lithium, sodium, magnesium, calcium, zinc and aluminum.
3. The method for preparing a positive electrode active material of claim 1 , wherein the coating composition comprises a compound comprising a phosphorous-nitrogen bond, a metal salt compound and an organic solvent.
4. The method for preparing a positive electrode active material of claim 3 , wherein the coating composition comprises, based on a total weight of the composition, the compound comprising the phosphorous-nitrogen bond in an amount of from 0.002 to 27% by weight, the metal salt compound in an amount of from 0.0005 to 12% by weight, and the organic solvent in an amount of from 70 to 99.99% by weight.
5. The method for preparing a positive electrode active material of claim 3 , wherein the coating composition further comprises a chalcogen compound.
6. The method for preparing a positive electrode active material of claim 1 , wherein the positive electrode active material comprises a lithium transition metal oxide.
7. The method for preparing a positive electrode active material of claim 1 , wherein the positive electrode active material has a spherical, an elliptical, a spindle, a scaly, a plate, a fibrous, a rod, a core-shell or an atypical shape.
8. The method for preparing a positive electrode active material of claim 1 , wherein, in step (b), the solution process comprises at least one method selected from the group consisting of spray coating, spin coating, dip coating, inkjet printing, offset printing, reverse offset printing, gravure printing and roll printing.
9. The method for preparing a positive electrode active material of claim 1 , wherein, in step (c), the heat treatment is carried out in a temperature range of 150° C. or higher and lower than 500° C.
10. The method for preparing a positive electrode active material of claim 1 , further comprising, prior to step (c), removing an organic solvent included in the precursor layer formed from step (b).
11. The method for preparing a positive electrode active material of claim 1 , wherein the metal-phosphorous-oxynitride protective layer formed from step (c) comprises amorphous metal-phosphorous-oxynitride.
12. A positive electrode active material prepared using the method of claim 1 .
13. The positive electrode active material of claim 12 , wherein the positive electrode active material comprises a metal-phosphorous-oxynitride protective layer formed on at least a part of the positive electrode active material.
14. The positive electrode active material of claim 13 , wherein the metal-phosphorous-oxynitride protective layer is present in an amount of from 0.01 to 5% by weight based on a total weight of the positive electrode active material.
15. The positive electrode active material of claim 13 , wherein the metal-phosphorous-oxynitride protective layer has a thickness of from 1 to 1000 nm.
16. A lithium secondary battery comprising the positive electrode active material of claim 12 .