METHOD FOR PRODUCING POSITIVE ACTIVE MATERIAL PRECURSOR AND POSITIVE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERIES, EXHIBITING CONCENTRATION GRADIENT, AND POSITIVE ACTIVE MATERIAL PRECURSOR AND POSITIVE ACTIVE MATERIAL FOR LITHIUM SECONDARY BATTERIES, EXHIBITING CONCENTRATION GRADIENT, PRODUCED BY SAME

Abstract

Disclosed are a method for manufacturing a lithium secondary battery positive active material exhibiting a concentration gradient and a lithium secondary battery positive active material exhibiting a concentration gradient, manufactured by the method, and more particularly, a method for manufacturing a lithium secondary battery positive active material exhibiting a concentration gradient and a lithium secondary battery positive active material exhibiting a concentration gradient, manufactured by the method, the method being characterized by forming a barrier layer so as to maintain a concentration gradient layer even in case of thermal diffusion by a subsequent thermal treatment process.

Claims

1. A method for manufacturing a lithium secondary battery positive active material having a concentration gradient layer, the method comprising: inputting a chelating agent solution into a reactor; continuously inputting a core forming solution, a chelating agent solution, and an alkaline solution into the reactor at the same time and obtaining a spherical precipitate forming a core layer; continuously inputting a barrier layer forming solution, a chelating agent solution, and an alkaline solution into the reactor at the same time and obtaining a spherical precipitate forming a barrier layer; preparing a shell forming solution and continuously mixedly inputting a chelating agent solution, an alkaline solution, the core forming solution, and the shell forming solution into the reactor at the same time and obtaining a precipitate, which forms the concentration gradient layer where concentration of nickel-manganese-cobalt varies gradually and relatively, on a surface of the barrier layer; drying the precipitate; and thermally treating the dried precipitate.

2. The method of claim 1, wherein the barrier layer forming solution includes Ni and Mn.

3. The method of claim 1, wherein the barrier layer forming solution includes Ni and Mn in a mole ratio of 30:70 to 70:30.

4. The method of claim 1, wherein the barrier layer forming solution includes Ni and Mn in a mole ratio of 50:50.

5. The method of claim 1, wherein the core forming solution includes a mole ratio of Ni:Co:Mn=a:b:1−(a+b)(0.7≦a≦1.0, 0≦b≦0.2).

6. The method of claim 1, wherein the shell forming solution includes a mole ratio of Ni:Co:Mn=a:b:1−(a+b)(0.3≦a≦0.6, 0≦b≦0.4).

7. The method of claim 1, wherein the preparing of the shell forming solution and the continuously mixedly inputting of the chelating agent solution, the alkaline solution, the core forming solution, and the shell forming solution into the reactor at the same time comprises: mixing the core forming solution and the shell forming solution in an additional preliminary reactor and continuously inputting the mixed solution into the reactor at the same time.

8. The method of claim 1, further comprising: continuously mixedly putting a shell forming solution, a chelating agent solution, and an alkaline solution into the reactor at the same time and obtaining a spherical precipitate forming a shell layer between the preparing of the shell forming solution and the continuously mixedly putting of the chelating agent solution, the alkaline solution, the core forming solution, and the shell forming solution into the reactor at the same time, and the drying of the precipitate.

9. A lithium secondary battery positive active material precursor, having a concentration gradient layer, manufactured by the method according to claim 1.

10. The lithium secondary battery positive active material precursor of claim 9, wherein a barrier layer has a thickness equal to or larger than 0.01 μm and smaller than 2.0 μm, or equal to or larger than 1% and smaller than 20% of a volume of particles.

11. The lithium secondary battery positive active material precursor of claim 9, wherein a size of a primary particle is reduced in 10 to 40% from a size of a primary particle of a positive active material precursor having the same composition without a barrier layer.

12. A method for manufacturing a lithium secondary battery positive active material having a concentration gradient layer, the method comprising: mixing a lithium secondary battery positive active material precursor having a concentration gradient layer according to claim 9 with a lithium compound; and thermally treating the mixture for 10 to 25 hours in oxidation atmosphere of air or oxygen at 750 to 1000° C.

13. A lithium secondary battery positive active material, having a concentration gradient layer, manufactured by the method according to claim 12.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

[0029] FIG. 1 shows results of taking SEM images of active particles manufactured through comparisons and embodiments according to the inventive concept.

[0030] FIG. 2 shows results of measuring concentrations of transition metals in active particles manufactured through comparisons and embodiments according to the inventive concept.

[0031] FIG. 3 shows results of measuring charge/discharge characteristics of batteries including active particles manufactured through comparisons and embodiments according to the inventive concept.

[0032] FIG. 4 shows results of measuring residual lithium amounts of batteries including active particles manufactured through comparisons and embodiments according to the inventive concept.

DETAILED DESCRIPTION OF THE INVENTION

[0033] Hereinafter, embodiments of the inventive concept will be described in conjunction with the accompanying drawings, but the inventive concept may not be restrictive to the following embodiments.

Embodiment-1

[0034] After putting distilled water of 20 L and ammonia of 1 kg into a batch reactor (90 L in capacity), a solution of 53 g, which was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 90:10:0, was input thereinto as a core forming solution in concentration of 2.5 M.

[0035] Next, a core forming solution, which was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 90:10:0 and has concentration of 2.5 M, was input into the reactor in a rate of 2.41 L/hour, and continuously an ammonia solution having concentration of 28% was input into the reactor in a rate of 0.29 L/hour. Additionally, for adjusting pH, a sodium hydroxide solution having concentration of 25% was supplied to maintain pH on 11.2. An impeller speed was adjusted to 350 rpm. The prepared core forming solution, ammonia solution, and sodium hydroxide solution were continuously input into the reactor in an amount of 60.5 L. Considering a capacity of the reactor, the reaction proceeded while discharging a supernatant in a specific time.

[0036] Next, after preparing a barrier layer forming solution which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 50:0:50, the barrier layer forming solution was input into the reactor in a rate of 2.41 L/hour and continuously an ammonia solution having concentration of 28% was input into the reactor in a rate of 0.29 L/hour. In this case, an input amount of the barrier layer forming solution, ammonia solution, and sodium hydroxide solution was 3.7 L.

[0037] Next, for adapting a mole ratio of nickel sulfate, cobalt sulfate, and manganese sulfate to 65:15:20, a concentration gradient layer forming solution, which had concentration of 2.5 M where nickel sulfate, cobalt sulfate, and manganese sulfate were mixed in a mole ratio of 19.4:24.3:56.3, was mixed with a core forming solution, which had concentration of 2.5 M where nickel sulfate and cobalt sulfate were mixed in a mole ratio of 90:10, in an additional agitator in addition to the batch reactor. An ammonia solution having concentration of 28% was input in a rate of 0.29 L/hour and a sodium hydroxide solution was maintained in pH of 11.2. In this case, an input amount of the concentration gradient layer forming solution, ammonia solution, and sodium hydroxide solution was 9.91 L.

[0038] Next, as a fifth operation, a shell forming solution, which was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 40:20:40, was input into a batch reactor in a rate of 2.41 L/hour, an ammonia solution was input in a rate of 0.29 L/hour, and a sodium hydroxide solution was input to maintain pH of 11.2. After completing the reaction, a spherical nickel-manganese-cobalt composite hydroxide precipitate was obtained from the batch reactor.

[0039] The precipitated composite metal hydroxide was filtered and washed by water, and then dried through a hot-air blower at 110° C. to obtain a powder.

[0040] Next, as a seventh operation, after mixing the composite metal hydroxide, which was obtained through the sixth operation, with lithium hydroxide, the mixture was thermally treated for 10 to 20 hours at 810° C. to obtain a lithium secondary battery positive active material.

Embodiment-2

[0041] A lithium secondary battery positive active material was obtained in the same manner with Embodiment-1, but first forming a concentration gradient layer and then a barrier layer after forming a core layer.

Embodiment-3

[0042] A lithium secondary battery positive active material was obtained in the same manner with Embodiment-1, but forming a core layer, a concentration gradient layer, and a shell layer, and then forming a barrier layer on the outmost shell of shell layers.

Embodiment-4

[0043] A lithium secondary battery positive active material was obtained in the same manner with Embodiment-1, but forming a barrier layer and a shell layer without forming a concentration gradient layer after forming a core layer.

Embodiment-5

[0044] A lithium secondary battery positive active material was obtained in the same manner with Embodiment-1, but making an average particle composition in Ni:Co:Mn=64:19:17.

Embodiment-6

[0045] A lithium secondary battery positive active material was obtained in the same manner with Embodiment-1, but designing an average particle composition in Ni:Co:Mn=66:17:17 and performing thermal treatment at 920° C.

[0046] <Comparison-1>

[0047] After putting distilled water of 20 L and ammonia of 1 kg into a batch reactor (90 L in capacity), a solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 90:10:0, was input with 53 g.

[0048] The solution was agitated in 350 rpm while maintaining the reactor at temperature of 46° C.

[0049] Next, as a second operation, a first precursor solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 90:10:0, was input into the reactor in a rate of 2.41 L/hour and continuously an ammonia solution having concentration of 28% was input into the reactor in a rate of 0.29 L/hour. Additionally, for adjusting pH, a sodium hydroxide solution having concentration of 25% was supplied to maintain the pH on 11.2. An impeller speed was adjusted to 350 rpm. The prepared first precursor solution, ammonia solution, and sodium hydroxide solution were continuously input into the reactor in an amount of 63.87 L.

[0050] Next, as a third operation, for adapting a mole ratio of nickel sulfate, cobalt sulfate, and manganese sulfate to 65:15:20, after preparing a concentration gradient layer forming solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 19.4:24.3:56.3, and measuring 8.016 kg of a solution which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 90:10:0 in an additional agitator in addition to the batch reactor during the second operation, the solution of the second operation was input as a concentration gradient layer forming solution of the third operation. An ammonia solution having concentration of 28% was input in a rate of 0.29 L/hour and a sodium hydroxide solution was maintained on pH of 11.2. In this case, an input amount of a precursor solution, ammonia solution, and sodium hydroxide solution was 10.06 L.

[0051] As a fourth operation, a fourth precursor solution, which is mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 40:20:40, was input into a batch reactor in a rate of 2.41 L/hour, an ammonia solution having concentration of 28% was input in a rate of 0.29 L/hour, and a sodium hydroxide solution was input to maintain pH of 11.2. In this case, an input amount of a precursor solution, ammonia solution, and sodium hydroxide solution was 11.07 L.

[0052] Comparison 2 and Comparison 3 manufactured active materials in the same manner with Comparison 1, but setting temperature of thermal treatment at 810° C. and 790° C., respectively.

[0053] <Comparison-4>

[0054] After putting distilled water of 20 L and ammonia of 1 kg into a batch reactor (90 L in capacity), a solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 80:10:10, was input in 80.6 g.

[0055] The solution was agitated in 400 rpm while maintaining the reactor at temperature of 46° C.

[0056] Next, as a second operation, a first precursor solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 80:10:10, was input into the reactor in a rate of 2.41 L/hour and continuously an ammonia solution having concentration of 28% was input into the reactor in a rate of 0.29 L/hour. Additionally, for adjusting pH, a sodium hydroxide solution having concentration of 25% was supplied to maintain the pH in 11.4˜11.5. An impeller speed was adjusted to 300˜400 rpm. The prepared first precursor solution, ammonia solution, and sodium hydroxide solution were continuously input into the reactor in an amount of 77.22 L.

[0057] <Comparison-5>

[0058] After putting distilled water of 20 L and ammonia of 1 kg into a batch reactor (90 L in capacity), a solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 60:20:20, was input in 80.6 g.

[0059] The solution was agitated in 400 rpm while maintaining the reactor at temperature of 46° C.

[0060] Next, as a second operation, a first precursor solution, which had concentration of 2.5 M and was mixed with nickel sulfate, cobalt sulfate, and manganese sulfate in a mole ratio of 60:20:20, was input into the reactor in a rate of 2.41 L/hour and continuously an ammonia solution having concentration of 28% was input into the reactor in a rate of 0.29 L/hour. Additionally, for adjusting pH, a sodium hydroxide solution having concentration of 25% was supplied to maintain the pH in 11.4˜11.5. An impeller speed was adjusted to 400˜450 rpm. The prepared first precursor solution, ammonia solution, and sodium hydroxide solution were continuously input into the reactor in an amount of 77.22 L. Considering the capacity of the reactor, the reaction proceeded while discharging a supernatant in a specific time.

[0061] Compositions of the particles manufactured through the aforementioned embodiments and comparisons are summarized Table 1 as follows.

TABLE-US-00001 TABLE 1 <Experimental example> Monitoring by SEM Bulk composition, Barrier layer applied Calcination mol % Thickness, Volume, temperature No Ni Co Mn Al Position Ni/Mn μm % (° C.) Comparison- 80 12 8 — — — — — 790 1 Comparison- 80 12 8 — — — — — 810 2 Comparison- 80 12 8 — — — — — 790 3 Comparison- 80 10 10 — — — — — 750 4 Comparison- 60 20 20 — — — — — 850 5 Embodiment- 79 11 10 — Core- 50/50 0.10 4.0 810 1 grad Embodiment- 79 11 10 — Grad- 50/50 0.10 5.0 810 2 shell Embodiment- 79 11 10 — Shell 50/50 0.10 5.0 810 3 end Embodiment- 80 10 10 — Core- 50/50 0.20 10.0 810 4 shell Embodiment- 64 19 17 — Core- 50/50 0.25 8.0 900 5 grad Embodiment- 66 17 17 — Core- 50/50 0.25 10.0 920 6 grad Embodiment- 78 11 11 — Core- 30/70 0.10 4.0 810 7 grad Embodiment- 79 11 10 — Grad- 60/40 0.15 7.0 810 8 shell

[0062] FIG. 1 shows results of taking Scanning Electron Microscope (SEM) images from the active particles manufactured through Embodiment-1, Embodiment-2, and Comparison-2.

[0063] From FIG. 1, it may be seen that while Comparison-2 without a barrier layer in an positive active material shows about 0.6 to 0.7 μm as a result of measuring a longitudinal average width value of primary particles, Embodiment-1 employing a barrier layer on the surface of the layer and Embodiment-2 employing a barrier layer on the surface of a concentration gradient layer show about 0.4 to 0.5 μm as results of measuring longitudinal average width values of primary particles. Therefore, it may be known that the barrier layer contributes to restraining the growth of primary particles.

<Experimental Example> Monitoring by EDX

[0064] FIG. 2 shows results of measuring, by Energy Dispersion X-ray spectroscopy (EDX), concentration of transition metals in particles of an active material manufactured through Embodiment-2, Embodiment-5, and Comparison-2 and comparing them with practically designed concentration.

[0065] For Comparison-2 having a positive active material without a barrier layer, there was an apparent difference between a practical concentration gradient (the dotted line) and a designed concentration gradient (the solid line) due to metallic diffusion after thermal treatment. Differently, it could be seen that for Embodiment-2 employing a barrier layer after forming a concentration gradient layer and Embodiment-5 employing a barrier layer after forming a core layer, metallic diffusion was restrained by a small difference between a designed concentration gradient (the solid line) and a practical concentration gradient (the dotted line).

<Experimental Example> Evaluating Charge/Discharge Characteristics

[0066] FIG. 3 shows results of using positive active materials. The positive active materials were manufactured through the aforementioned Embodiments and Comparisons, as positive electrodes, manufacturing respective coin cells by using a lithium metal as a negative electrode, and performing a charge/discharge experiment between 3˜4.3 V in charge and discharge rates of C/10 (1C=150 mA/g).

[0067] Embodiment-1 employing a barrier layer on the surface of a core layer had higher firing temperature than that of Comparison-1 without a barrier layer but had the same lifetime. Differently, Comparison-2, which performed thermal treatment at the same temperature with Embodiment-1, without a barrier layer, was greatly degraded in lifetime. Embodiment-1 was better in lifetime than Comparison-4 having a composition of NCM811 without a concentration gradient.

<Experimental Example> Measuring Unreacted Lithium

[0068] Measuring unreacted lithium was performed with an amount of 0.1 M of HCl which was used until pH reaches 4. First, after putting a positive active material of 5 g into distilled water of 100 ml, agitating the solution for 15 minutes, filtering the solution, and taking the filtered solution of 50 ml, HCl of 0.1 M was added to the filtered solution and a consumption amount of HCl dependent on pH variation was measured to determine Q1 and Q2. The unreacted LiOH and Li.sub.2CO.sub.3 were calculated based on the following equations.

M1=23.94(LiOH molecular weight)

M2=73.89(Li.sub.2CO.sub.3 molecular weight)

SPL size=(Sample weight×Solution weight)/Water weight

LiOH(wt %)=[(Q1−Q2)×C×M1×100]/(SPL size×1000)

Li.sub.2CO.sub.3(wt %)=[2×Q2×C×M2/2×100]/(SPL size×1000)

[0069] FIG. 4 shows results of measuring concentration of the unreacted LiOH and Li.sub.2CO.sub.3 from an NCA series lithium oxide composite manufactured through the aforementioned Embodiments and Comparisons by the method described above.

[0070] Embodiment-1 employing a barrier layer on the surface of a core layer has smaller residual lithium because optimum temperature of thermal treatment is higher than that of Comparison-1 without a barrier layer.

[0071] As described above, a positive active material and a lithium secondary battery positive active material precursor exhibiting a concentration gradient according to embodiments of the inventive concept may be useful for industrial applicability in the points that a barrier layer is included between a shell part showing a concentration gradient and a core having uniform concentration, and the manufactured positive active material has a continuous concentration distribution, which is desired from design, appearing even at an interface where the core meets an outer shell even though a transition metal is diffused between a shell and the core.