Cathode active material for lithium secondary battery and method of manufacturing the same
A cathode active material for a lithium secondary battery includes a lithium metal oxide particle and a thio-based compound formed on at least portion of a surface of the lithium metal oxide particle. The thio-based compound has a double bond that contains a sulfur atom. Chemical stability of the lithium metal oxide particle may be improved and surface residues may be reduced by the thio-based compound.
1. A cathode active material for a lithium secondary battery, comprising:
a lithium metal oxide particle; and
a thiosulfate anion (S 2 O 3 2− ) formed on at least portion of a surface of the lithium metal oxide particle,
wherein a content of the thiosulfate anion of the lithium metal oxide particle measured by an ion chromatography analysis is in a range from 100 ppb to 8,000 ppb.
2. The cathode active material for a lithium secondary battery according to claim 1 , wherein the content of the thiosulfate anion is measured using an extraction solution obtained by filtering a solution obtained by mixing the cathode active material for 3 hours at room temperature using a Na 2 CO 3 buffer solution.
3. The cathode active material for a lithium secondary battery according to claim 1 , wherein the content of the thiosulfate anion is in a range from 400 ppb to 5,000 ppb.
4. The cathode active material for a lithium secondary battery according to claim 1 , wherein a surface component represented by General Formula 2 is detected by a Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) analysis on the surface the lithium metal oxide particle:
M1 x C y H z S a O b [General Formula 2]
wherein, in the General Formula 2 above, M1 is an alkali metal or an alkali earth metal, x≥0, y≥0, z≥0, a>0 and b>0.
5. The cathode active material for a lithium secondary battery according to claim 1 , wherein the lithium metal oxide particle includes a nickel-based lithium oxide represented by General Formula 1 below:
L x Ni y M 1-y O 2 [General Formula 1]
wherein, in the General Formula 1 above, 0.95≤x≤1.08, y≥0.5, and M is at least one element selected from a group consisting of Co, Mn, Al, Zr, Ti, B, Mg or Ba.
6. The cathode active material for a lithium secondary battery according to claim 5 , wherein, in the General Formula 1, 0.8≤y≤0.93.
7. The cathode active material for a lithium secondary battery according to claim 1 , wherein the lithium metal oxide particle includes a doping or a coating which contains at least one of Al, Zr or Ti.
8. The cathode active material for a lithium secondary battery according to claim 1 , wherein the thiosulfate anion is directly bonded to the surface of the lithium metal oxide particle.
9. A method of preparing a cathode active material for a lithium secondary battery, comprising:
preparing a preliminary lithium metal oxide particle;
cleaning the preliminary lithium metal oxide particle using a washing solution that includes a thiosulfate anion (S 2 O 3 2− ) salt; and
drying or annealing the washed preliminary lithium metal oxide particle to obtain a lithium metal oxide particle including a thiosulfate anion formed on at least portion of a surface thereof;
wherein a content of the thiosulfate anion of the lithium metal oxide particle including a thiosulfate anion measured by an ion chromatography analysis is in a range from 100 ppb to 8,000 ppb.
10. The method according to claim 9 , wherein an amount of the thiosulfate anion (S 2 O 3 2− ) salt is in a range from about 0.1 wt % to about 2 wt % based on a total weight of the washing solution.
11. The method according to claim 9 , wherein cleaning the preliminary lithium metal oxide particle includes a first washing treatment and a second washing treatment, and an active material cake is formed by the first washing treatment.
12. The method according to claim 11 , wherein the second washing treatment includes providing the washing solution to flow through the active material cake without stirring.
13. The method according to claim 11 , wherein an amount of the thiosulfate anion (S 2 O 3 2− ) salt in the washing solution used in the first washing treatment is greater than an amount of the thiosulfate anion (S 2 O 3 2− ) salt in the washing solution used in the second washing treatment.
14. A lithium secondary battery, comprising:
a cathode including a cathode active material according to claim 1 ;
an anode; and
a separation layer interposed between the cathode and the anode.