NOVEL PRECURSOR PARTICLE FOR PREPARATION OF CATHODE ACTIVE MATERIAL FOR SECONDARY BATTERY AND NOVEL PRECURSOR POWDER CONTAINING SAME

Abstract

Disclosed are novel precursor particles for preparing a cathode active material including transition metal precursor particles containing one or more transition metals, and one or more of an alkali metal and an alkaline earth metal, wherein the alkali metal and the alkaline earth metal are contained in one or more of inner and outer parts of the transition metal precursor particles, and a novel precursor powder including the novel precursor particles.

Claims

1. A novel precursor particle for preparing a cathode active material comprising: a transition metal precursor particle containing one or more transition metals; and one or more of an alkali metal and an alkaline earth metal, wherein the alkali metal and the alkaline earth metal are contained in one or more of inner and outer parts of the transition metal precursor particle.

2. The novel precursor particle according to claim 1, wherein the alkali metal comprises one or more of Li (lithium) and Na (sodium).

3. The novel precursor particle according to claim 1, wherein the novel precursor particle is a secondary granule formed by aggregation between a plurality of primary particles.

4. The novel precursor particle according to claim 1, wherein the novel precursor particle has a spherical shape.

5. The novel precursor particle according to claim 1, wherein the alkali metal or alkaline earth metal is present in at least one of the following states: (a) coating the surface of the primary particles and/or secondary granules; (b) present in the voids between the primary particles; and (c) present in the inner part of primary particles and/or secondary granules.

6. The novel precursor particle according to claim 5, wherein the alkali metal or alkaline earth metal comprises at least one selected from the group consisting of salts, hydroxides and oxides.

7. The novel precursor particle according to claim 5, wherein the novel precursor particle has a composition represented by the following Formula 1:
[(1-x-y)A.sub.2CO.sub.3*xAOH*yA.sub.2O]/[(1-a-b)M(OH).sub.2*aMOOH*bM(OH.sub.1-c).sub.2]  (1) wherein
0≤y≤1,0≤a≤1,0≤b≤1,0<c<1;
A/M(molar ratio)>0; A is at least one alkali metal and/or alkaline earth metal; and M comprises one or more transition metals stable in a tetracoordinate or hexacoordinate structure.

8. The novel precursor particle according to claim 1, wherein the novel precursor particle has a composition of the following Formula 2:
[(1-x-y)A.sub.2CO.sub.3*xAOH*yA.sub.2O]/MO.sub.2-a  (2) wherein
0≤x≤1,0≤y≤1,0≤a≤1;
A/M(molar ratio)>0; A is at least one alkali metal and/or alkaline earth metal; and M comprises one or more transition metals stable in a tetracoordinate or hexacoordinate structure.

9. The novel precursor particle according to claim 7, wherein the molar ratio (A/M) of total alkali metal and/or alkaline earth metal (A) to total transition metal (M) is more than 0 and is not more than 1.5.

10. A novel precursor powder comprising the novel precursor particle for preparing a cathode active material according to claim 1.

11. The novel precursor powder according to claim 10, wherein the novel precursor powder is present as a mixture of the novel precursor particle with a compound and/or mixture containing an alkali metal and/or alkaline earth metal.

12. The novel precursor powder according to claim 10 or 11, wherein the molar ratio (A/M) of total alkali metal and/or alkaline earth metal (A) to total transition metal (M) is more than 0 and is not more than 1.5.

13. A cathode active material prepared by firing the novel precursor powder according to claim 10.

14. A secondary battery comprising the cathode active material according to claim 13.

15. The novel precursor particle according to claim 8, wherein the molar ratio (A/M) of total alkali metal and/or alkaline earth metal (A) to total transition metal (M) is more than 0 and is not more than 1.5.

16. The novel precursor powder according to claim 11, wherein the molar ratio (A/M) of total alkali metal and/or alkaline earth metal (A) to total transition metal (M) is more than 0 and is not more than 1.5.

17. A cathode active material prepared by firing the novel precursor powder according to claim 11.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0058] FIG. 1 is an SEM image of novel precursor particles constituting a novel precursor powder prepared in an embodiment of the present invention;

[0059] FIG. 2 shows the result of mapping analysis based on EDS of novel precursor particles constituting the novel precursor powder prepared in the embodiment of the present invention;

[0060] FIG. 3 is a cross-sectional SEM image of novel precursor particles prepared in Experimental Example 3 of the present invention;

[0061] FIGS. 4 to 7 are spectra and a component assay table illustrating the results of point analysis based on EDS at Point 1, Point 2, and Point 3 in the precursor particles of FIG. 3;

[0062] FIG. 8 is an image showing a comparison in contrast between a novel precursor powder containing Li and a transition metal precursor powder in a bare state in Experimental Example 4 of the present invention; and

[0063] FIGS. 9 to 12 are SEM images showing the surface morphology of the transition metal precursor particles as a function of Li content in Experimental Example 5 of the present invention.

BEST MODE

[0064] Now, the present invention will be described in more detail with reference to the following examples. These examples should not be construed as limiting the scope of the present invention.

[Example 1]—Wet

[0065] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=5:2:3, a Li compound (Li.sub.2CO.sub.3) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.03, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0066] The prepared novel precursor powder was fired at 940° C. for 13 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Example 2]—Wet

[0067] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=5:2:3, a Li compound (Li.sub.2CO.sub.3) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.03, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0068] The prepared novel precursor powder was fired at 940° C. for 10 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Example 3]—Wet+Dry

[0069] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=5:2:3, a Li compound (Li.sub.2CO.sub.3) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.85, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0070] The dried novel precursor initial powder was charged in a stirrer, and then a Li compound (Li.sub.2CO.sub.3) was further added thereto at a molar ratio of Li to metal of 0.18, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to metal of 1.03.

[0071] The prepared novel precursor final powder was fired at 940° C. for 15 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Example 4]—Wet+Dry

[0072] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=5:2:3, a Li compound (Li.sub.2CO.sub.3) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.5, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0073] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (Li.sub.2CO.sub.3) was further added thereto at a molar ratio of Li to the metal of 0.53, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0074] The prepared novel precursor final powder was fired at 940° C. for 15 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Example 5]—Wet+Dry

[0075] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=5:2:3, a Li compound (Li.sub.2CO.sub.3) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.3, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0076] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (Li.sub.2CO.sub.3) was further added thereto at a molar ratio of Li to the metal of 0.73, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0077] The prepared novel precursor final powder was fired at 940° C. for 15 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Example 6]—Wet+Dry

[0078] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=5:2:3, a Li compound (Li.sub.2CO.sub.3) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.1, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0079] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (Li.sub.2CO.sub.3) was further added thereto at a molar ratio of Li to the metal of 0.93, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0080] The prepared novel precursor final powder was fired at 940° C. for 15 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Comparative Example 1]—Dry

[0081] A transition metal precursor was prepared at a ratio of Ni:Co:Mn=5:2:3 and was dried in an oven at 120° C. for 12 hours to remove moisture to prepare a transition metal precursor powder.

[0082] The dried transition metal precursor powder was mixed with Li.sub.2CO.sub.3 at a molar ratio of Li to the metal of 1.03 in a dry manner to prepare a Li-transition metal mixture precursor powder.

[0083] The prepared Li-transition metal mixture precursor powder was fired at 940° C. for 18 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.5Co.sub.0.2Mn.sub.0.3O.sub.2.

[Example 7]—Wet

[0084] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.03, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0085] The prepared novel precursor powder was fired at 860° C. for 15 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Example 8]—Wet

[0086] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.03, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0087] The prepared novel precursor powder was fired at 860° C. for 12 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Example 9]—Wet+Dry

[0088] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.85, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0089] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.18, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0090] The prepared novel precursor final powder was fired at 860° C. for 18 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Example 10]—Wet+Dry

[0091] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.5, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0092] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.53, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0093] The prepared novel precursor final powder was fired at 860° C. for 18 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Example 11]—Wet+Dry

[0094] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.3, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0095] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.73, followed by stirring, to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0096] The prepared novel precursor final powder was fired at 860° C. for 18 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Example 12]—Wet+Dry

[0097] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.1, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0098] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.93, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0099] The prepared novel precursor final powder was fired at 860° C. for 18 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Comparative Example 2]—Dry

[0100] A transition metal precursor was prepared at a ratio of Ni:Co:Mn=6:2:2 and was dried in an oven at 120° C. for 12 hours to remove moisture to prepare a transition metal precursor powder.

[0101] The dried transition metal precursor powder was mixed with LiOH at a molar ratio of Li to the metal of 1.03 in a dry manner, to prepare a Li-transition metal mixture precursor powder.

[0102] The prepared Li-transition metal mixture precursor powder was fired at 860° C. for 20 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

[Example 13]—Wet

[0103] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=8.2:1.1:0.7, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.03, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0104] The prepared novel precursor powder was fired at 800° C. for 20 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Example 14]—Wet

[0105] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=8.2:1.1:0.7, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.03, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0106] The prepared novel precursor powder was fired at 800° C. for 18 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Example 15]—Wet+Dry

[0107] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=8.2:1.1:0.7, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.85, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0108] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.18, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0109] The prepared novel precursor final powder was fired at 800° C. for 24 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Example 16]—Wet+Dry

[0110] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=8.2:1.1:0.7, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.5, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0111] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.53, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0112] The prepared novel precursor final powder was fired at 800° C. for 24 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Example 17]—Wet+Dry

[0113] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=8.2:1.1:0.7, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.3, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0114] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.73, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0115] The prepared novel precursor final powder was fired at 800° C. for 24 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Example 18]—Wet+Dry

[0116] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=8.2:1.1:0.7, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 0.1, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor initial powder.

[0117] The dried novel precursor initial powder was charged in a stirrer, and a Li compound (LiOH) was further added thereto at a molar ratio of Li to the metal of 0.93, followed by stirring to prepare a novel precursor final powder as a mixture having a molar ratio of Li to the metal of 1.03.

[0118] The prepared novel precursor final powder was fired at 800° C. for 24 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Comparative Example 3]—Dry

[0119] A transition metal precursor was prepared at a ratio of Ni:Co:Mn=8.2:1.1:0.7 and dried in an oven at 120° C. for 12 hours to remove moisture to prepare a transition metal precursor powder.

[0120] The dried transition metal precursor powder was mixed with LiOH at a molar ratio of Li to the metal of 1.03 in a dry manner, to prepare a Li-transition metal mixture precursor powder.

[0121] The prepared Li-transition metal mixture precursor powder was fired at 800° C. for 26 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.82Co.sub.0.11Mn.sub.0.07O.sub.2.

[Example 19]—Wet

[0122] Along with synthesis by co-precipitation at a ratio of Ni:Co:Mn=6:2:2, a Li compound (LiOH) was added in a wet manner using a circulating filtration apparatus such that the molar ratio of Li to metal was adjusted to 1.21, followed by drying in an oven at 120° C. for 12 hours to remove moisture to prepare a novel precursor powder.

[0123] The prepared novel precursor powder was fired at 860° C. for 15 hours while air was made to flow to prepare a cathode active material of LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2.

Experimental Example 1

[0124] 10 g of the novel precursor powder synthesized in each of Examples 1 to 19 and 10 g of the Li-transition metal mixture precursor powder synthesized in each of Comparative Examples 1 to 3 were charged in a measuring device and a pressure was applied thereto to measure a tap density. The result is shown in Table 1 below.

Experimental Example 2

[0125] The residual amount of Li was measured by titration from the cathode active materials prepared in Examples 1 to 19 and Comparative Examples 1 to 3, and the results are shown in Table 1 below.

Experimental Example 3

[0126] The results of EDS component assay on the novel precursor particles constituting novel precursor powders that had been prepared in the same manner as in Example 18, except that an Al compound (Al.sub.2(SO.sub.4).sub.3) was used instead of the Li compound, are shown in FIGS. 3 and 4 to 7.

[0127] These results showed that Al was contained in the transition metal precursor particles even when Al was used instead of an alkali metal. Both the alkali metal and Al may be used.

Experimental Example 4

[0128] The contrast was compared between the novel precursor initial powder prepared in Example 10 (a), the transition metal precursor powder in a bare state (b), and the novel precursor powder prepared in Example 7 (c), and the result is shown in FIG. 8.

[0129] As can be seen from FIG. 8, the bare-state transition metal precursor powder that does not contain Li (b) was the darkest, and brightness increased as the Li content increased in an ascending order from powder (a) to powder (c).

Experimental Example 5

[0130] SEM images comparing surface morphology between transition metal precursor particles in the bare state (a), novel precursor particles based on Example 10 (b), novel precursor particles based on Example 7 (c), and novel precursor particles based on Example 19 (d) are shown in FIGS. 9 to 12.

[0131] As can be seen from these images, the surface (FIG. 9) of bare-state transition metal precursor particles not containing Li (a) has many pores and is thus very rough, whereas the surfaces (FIGS. 10 to 12) of particles containing Li (b, c, d) decrease in roughness because Li fills the voids as the Li content increases.

Experimental Example 6

[0132] The cathode active material prepared in each of Examples 1 to 19 and Comparative Examples 1 to 3, a conductive agent, and a binder were mixed at a ratio of 95:2:3 (active material: conductive agent: binder), and the resulting mixture was applied onto an Al foil, followed by drying to produce a cathode. Li metal was used as an anode, an electrolyte solution of 1M LiPF.sub.6 in EC/DMC (1:1) was added thereto to produce a secondary battery, and then the discharge capacity was measured at a charge/discharge rate of 0.1C.

[0133] The results of measurement of Experimental Examples 1 to 19 described above are shown in Table 1 below.

[0134] In general, the productivity (yield) increases as the weight per unit volume increases upon a single firing and the firing time decreases. Here, the unit of weight per volume, that is, the density unit, is g/cc, which is measured as a tap density, and the firing time means the total time from the time at which a firing vessel enters a firing furnace to the time at which the firing vessel passed through the firing furnace and was then cooled. Therefore, the production amount may be converted in accordance with the following formulas.

[00001]$\mathrm{Productivity}\left(\%\right)=A\times B\times 100$$A=\frac{\mathrm{Actual}\left(\mathrm{measured}\right)\mathrm{tap}\mathrm{density}\left(g/\mathrm{cc}\right)}{\mathrm{Refe}\mathrm{rence}\mathrm{tap}\mathrm{density}\left(g/\mathrm{cc}\right)}$$B=2-\left(\frac{\mathrm{Actual}\left(\mathrm{measured}\right)\mathrm{firing}\mathrm{time}}{Refe\mathrm{rence}\mathrm{firing}\mathrm{time}}\right)$

[0135] Based on this, as shown in Table 1 below, the productivity of Examples 1 to 6 was evaluated relative to Comparative Example 1 as 100%, the productivity of Examples 7 to 12 and Example 19 was evaluated relative to Comparative Example 2 as 100%, and the productivity of Examples 13 to 18 was evaluated relative to Comparative Example 3 as 100%.

TABLE-US-00001 TABLE 1 Li/Metal Tap Firing Firing Li Discharge Production Li/Me Li/Me ratio density time temperature byproduct capacity amount Type Item (wet) (dry) (Total) (g/cc) (hour) (° C.) (Li.sub.2CO.sub.3) (mAh/g) (Productivity) NCM Example 1   1.03 0   1.03  2.00 13 940 0.108 171.3 154% 523 Example 2   1.03 0   1.03  2.00 10 940 0.117 170.8 175% Example 3   0.85  0.18 1.03  1.91 15 940 0.115 169.7 134% Example 4  0.5  0.53 1.03  1.85 15 940 0.119 169.6 129% Example 5  0.3  0.73 1.03  1.77 15 940 0.121 169.4 124% Example 6  0.1  0.93 1.03  1.71 15 940 0.124 169.3 120% Comparative 0    1.03 1.03  1.65 18 940 0.128 169.2 100% Example 1  NCM Example 7   1.03 0   1.03  1.80 15 860 0.273 181.0 156% 622 Example 8   1.03 0   1.03  1.80 12 860 0.275 180.8 175% Example 9   0.85  0.18 1.03  1.67 18 860 0.282 180.7 128% Example 10 0.5  0.53 1.03  1.63 18 860 0.291 180.4 125% Example 11 0.3  0.73 1.03  1.58 18 860 0.298 179.9 119% Example 12 0.1  0.93 1.03  1.47 18 860 0.304 179.8 113% Comparative 0    1.03 1.03  1.43 20 860 0.312 179.8 100% Example 2  NCM Example 13  1.03 0   1.03  1.90 20 800 0.785 204.9 152% 821107 Example 14  1.03 0   1.03  1.90 18 800 0.794 204.5 162% Example 15  0.85  0.18 1.03  1.81 24 800 0.816 204.0 127% Example 16 0.5  0.53 1.03  1.77 24 800 0.837 203.8 124% Example 17 0.3  0.73 1.03  1.69 24 800 0.864 203.7 118% Example 18 0.1  0.93 1.03 1.6 24 800 0.920 203.3 112% Comparative 0    1.03 1.03  1.54 26 800 0.970 203.2 100% Example 3  NCM Example 19  1.21 0   1.21  1.52 15 860 0.516 175.3 132% 622

[0136] As can be seen from Table 1, the novel precursor powders (Examples 1 to 19) according to the present invention exhibited high productivity and improved secondary battery characteristics in various transition metal compositions.

[0137] Specifically, the novel precursor powders exhibit a high packing density because lithium is contained in the precursor, and improve the diffusion of lithium into the precursor during firing, thereby shortening the reaction time and thus remarkably increasing productivity.

[0138] In addition, the reactivity improvement of lithium reduces the residual amount of lithium, thereby improving the performance of the secondary battery.

[0139] Moreover, when the content of lithium with respect to the transition metal in the novel precursor particles constituting the novel precursor powders is 1 or more (Examples 1, 2, 7, 8, 13, 14, 19), firing can be performed immediately without adding a separate lithium compound/mixture, thus omitting a mixing process and significantly improving productivity.

[0140] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.