KR100541871B1 - Method for producing cobalt compound, and method for producing cathode active material using the cobalt compound - Google Patents

Abstract

Disclosed is a method of preparing a cobalt, a valuable metal, in the form of a cobalt salt from a cobalt sulfate solution, and manufacturing a cathode active material for a high performance lithium secondary battery using the same. The method for preparing a cobalt compound from a cobalt sulfate solution includes adding a precipitant selected from the group consisting of oxalic acid, lithium hydroxide, ammonium hydroxide and mixtures thereof to the cobalt sulfate solution for reaction; And filtering and drying the precipitate produced in the reaction. In addition, the method of manufacturing a cathode active material for a lithium secondary battery includes mixing the cobalt compound and a lithium compound, followed by heat treatment.

Lithium secondary battery, positive electrode material, lithium / cobalt oxide, oxalic acid, cobalt sulfate

Description

Method for producing cobalt compound and method for manufacturing cathode active material for secondary battery using same {Method for producing cobalt compound, and method for producing cathode active material using the cobalt compound}             

1A to 1D are scanning electron micrographs of lithium / cobalt oxides prepared according to embodiments of the present invention, respectively.

Figure 2 is a graph showing the X-ray diffraction analysis pattern of the lithium / cobalt oxide prepared in accordance with an embodiment of the present invention.

3 is a graph illustrating the evaluation of the constant current charge and discharge characteristics of a secondary battery including lithium / cobalt oxide prepared according to an embodiment of the present invention.

The present invention relates to a method for preparing a cobalt compound from a cobalt sulfate solution and a method for producing a cathode active material for a secondary battery using the same. More specifically, from the cobalt sulfate solution, cobalt, a valuable metal, is prepared in the form of a cobalt salt and used therein. The present invention relates to a method for manufacturing a high performance lithium secondary battery positive electrode active material economically and environmentally friendly.

Recently, with the development of the portable, information and communication equipment industry, the lithium secondary battery industry capable of charging and discharging is rapidly developing. The global market for lithium secondary batteries was $ 1.1 billion in 1996 and $ 3.2 billion in 2001. Comparing the battery size of cell phones with those installed in electric vehicles, the market for lithium secondary batteries is expected to reach more than $ 20 billion by 2010 when electric vehicles become commercially available. Lithium secondary battery is not only a large market but also a high value-added product, and the production of lithium secondary battery is active in Korea, and accordingly, secondary batteries such as CoC ₂ O ₄ , CoCO ₃ and Co (OH) ₂ are Imports of constituent raw materials are surging. Cobalt compounds such as CoC ₂ O ₄ , CoCO ₃ , and Co (OH) ₂ are used as raw materials for lithium / cobalt oxide, which is a cathode material for commercial lithium secondary batteries. However, they require high recycling costs due to high cost and low resources.

The present inventors have found that a cobalt compound in a crystalline form can be obtained from a cobalt sulfate solution containing a cobalt metal, and it can be used to prepare a cathode active material for a lithium secondary battery with good physical properties, thereby completing the present invention.

Accordingly, an object of the present invention is to provide a method for producing a cobalt compound using a cobalt sulfate solution as a raw material.

It is another object of the present invention to provide a method of manufacturing lithium / cobalt oxide (LiCoO ₂ ), which is a cathode active material for a lithium secondary battery, using the cobalt compound prepared above, economically and environmentally.

Still another object of the present invention is to provide a method of reducing the process energy of the lithium / cobalt oxide manufacturing process by reducing the average particle diameter of the lithium / cobalt oxide in a simple process.

In order to achieve the above object, the present invention comprises the steps of reacting by adding a precipitating agent selected from the group consisting of oxalic acid, lithium hydroxide, ammonium hydroxide and mixtures thereof to a cobalt sulfate solution; And it provides a method for producing a cobalt compound comprising the step of filtering and drying the precipitate produced in the reaction. The present invention also provides a method of manufacturing a cathode active material for a lithium secondary battery, including the step of heat treatment after mixing the cobalt compound and the lithium compound. Here, it is preferable to perform the precipitation reaction while applying ultrasonic waves to the reaction solution of the precipitation reaction, the frequency of the ultrasonic wave is preferably 10 to 40 kHz.

Hereinafter, the present invention will be described in detail.

In order to prepare a cobalt compound from a cobalt sulfate solution according to the present invention, as shown in Schemes 1 and 2, oxalic acid (H ₂ C ₂ O ₄ ), lithium hydroxide (LiOH) in a liquid cobalt sulfate (CoSO ₄ ) solution And cobalt compounds such as cobalt oxalate (CoC ₂ O ₄ ) and cobalt hydroxide (Co (OH) ₂ ) are prepared by adding a precipitant such as ammonium hydroxide (NH ₄ OH) and a mixture thereof.

The concentration of the precipitant used in the reaction may vary depending on the type of precipitant, but is preferably about 1 to 20% by weight solution, and the concentration of the cobalt sulfate solution is preferably about 1 to 30% by weight. Therefore, the molar ratio of the precipitant to cobalt sulfate that can express the optimum yield is in the range of 1.3 to 2.0 with respect to the solution, but this may vary depending on the type of precipitant and the reaction conditions.

The reaction temperature of the precipitant is usually 25 to 100 ° C., the reaction time is usually 10 to 60 minutes, and when the precipitation reaction is performed while applying ultrasonic waves to the reaction solution of the precipitation reaction, compared with the case where no ultrasonic waves are applied. Cobalt compounds in the form of fine powder having an average particle diameter of about 1/40 can be obtained, which is preferable. At this time, if the reaction temperature is less than 25 ℃ or the reaction time is less than 10 minutes, the precipitation reaction does not occur sufficiently, if the reaction temperature exceeds 100 ℃, or if the reaction time exceeds 60 minutes, the precipitate is dissolved again to yield There is a disadvantage of deterioration. In addition, the frequency of the ultrasonic wave used is preferably 10 to 40 kHz. If the frequency is less than 10 kHz, the dispersion force is weak. If the frequency exceeds 40 kHz, the finely dispersed particles are reaggregated to have an uneven particle size. There is a problem of precipitation. By filtering and drying the precipitate thus produced, cobalt oxalate (CoC ₂ O ₄ 2H ₂ O), cobalt hydroxide (Co (OH), which is a high-purity cobalt compound in the form of raw materials, which can produce lithium cobalt oxide economically and environmentally friendly ) ₂ ) can be obtained.

In order to manufacture a cathode active material for a secondary battery using the cobalt compound thus obtained, as shown in Schemes 3 and 4, the cobalt compound, lithium hydroxide (LiOH), lithium oxide (Li ₂ O), and lithium carbonate (Li ₂ A lithium compound such as CO ₃ ) is uniformly mixed in an alcohol, preferably an ethanol solution, and then heat-treated to prepare a cathode active material for a lithium secondary battery.

Preferably, the heat treatment is performed twice, wherein the first heat treatment is performed at 100 to 600 ° C., preferably at 200 to 500 ° C. for 2 to 18 hours, more preferably at 300 to 500 ° C. for 3 to 10 hours. , Secondary heat treatment is carried out at 600 to 1100 ℃ 6 to 36 hours, preferably at 800 to 1000 ℃ for 10 to 24 hours. A high purity lithium / cobalt oxide can be prepared by such a high temperature solid phase reaction method (K. Mizushima, P. C. Jones, P. J. Jones, J. B. Goodenough, Mat. Res. Bull., 15, 783 (1980)).

In the secondary battery, in order to minimize the electrochemical energy loss due to concentration polarization, it is desirable to secure a uniform particle size distribution and a fine average particle diameter. Generally, commercially available lithium / cobalt oxides have an average particle diameter of about 15 μm. . However, the lithium / cobalt oxide produced by the method of the present invention exhibits a uniform particle size distribution, and is a fine powder having an average particle diameter of about 1 to 2 μm, and thus a concentration causing electrochemical energy loss in the secondary battery positive electrode material. By minimizing polarization, it is possible not only to construct a high rate secondary battery system, but also in terms of economic and environmental aspects. In addition, the cobalt salt obtained from the cobalt sulfate solution according to the present invention is controlled by the ultrasonic process, thereby reducing the process energy of the LiCoO ₂ manufacturing process of lithium / cobalt oxide, and reducing the particle size of the final product lithium / cobalt oxide. It can be controlled smaller.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited by the following examples.

Example 1

Cobalt sulfate solution was added to a 10 wt% aqueous solution of oxalic acid (H ₂ C ₂ O ₄ · 2H ₂ O) at 25 ° C. at a rate of 20 ml / min, and the reaction mixture was mixed at 500 rpm and maintained for 2 hours. The solid and liquid were separated using a microfilter. After separation, the filter residue was dried at 100 ° C. for 24 hours to obtain cobalt oxalate (CoC ₂ O ₄ · 2H ₂ O) powder in a yield of 99%. During the reaction, ultrasonication was performed using an ultrasonic disperser of 20 kHz to refine the precipitated particles.

Example 2

An aqueous cobalt sulfate solution was added at a rate of 20 ml / min at 25 ° C. to a lithium hydroxide (LiOH.H 2 O) aqueous solution or an ammonium hydroxide (NH ₄ OH) aqueous solution having a concentration of 10% by weight, and cobalt hydroxide (Co) was used in the same manner as in Example 1. (OH) ₂ ) A powder was prepared.

Example 3-6

Cobalt oxide synthesized in Examples 1 and 2 and 5% excess of lithium carbonate (Li ₂ CO ₃ ) in an equivalent ratio evenly mixed in ethanol, the first heat treatment for 5 hours at 450 ℃, at 800 or 900 ℃ Secondary heat treatment for 10 hours to produce lithium / cobalt oxide. Using the obtained lithium / cobalt oxide to prepare a lithium ion secondary battery according to a conventional secondary battery manufacturing method, the charge and discharge characteristics experiments were performed, the results are shown in Table 1 below. In addition, scanning electron micrographs of the obtained lithium / cobalt oxide are shown in Figs. 1A to 1D, respectively. The charge-discharge characteristic evaluation experiment was performed under constant current conditions of 0.2 C rate in the region of 3.0 to 4.3V.

division Cobalt compounds Secondary heat treatment temperature Characteristics Particle size and shape I (003) / I (104) Lattice constant Initial discharge capacity a (Å) c (Å) c / a Example 3 CoC ₂ O ₄ 800 ℃ Figure 1a 1.6 2.81 14.11 5.02 150 mAh / g Example 4 900 ℃ 1b 1.5 2.81 14.13 5.03 143 mAh / g Example 5 Co (OH) ₂ 800 ℃ Fig 1c 1.48 2.82 14.11 5.00 135 mAh / g Example 6 900 ℃ Fig 1d 1.46 2.82 14.13 5.00 130 mAh / g

From Table 1, it can be seen that all of the lithium / cobalt oxide synthesized by the present invention has excellent positive electrode active material properties, as shown in Figure 1a to 1d, lithium / cobalt oxide synthesized at the heat treatment temperature 800 ℃ It can be seen that this smaller particle diameter and the initial discharge capacity is also higher. The initial discharge capacity of the battery of each of the above examples is 150 mAh / g (2.5-4.3 V) (T. Ohzuku, A. Ueda, J. Electrochem. Soc., 141, 2972, which is a documented value for a cell containing the same component sample). 1994).

Also, according to Ohzuku et al., The relative peak intensity ratio of (003) peak to (104) peak, I (003) / I (104), was calculated as a method for evaluating the electrochemical reactivity of lithium / cobalt oxide. The larger the value of, the less contamination by other phases and the better the electrochemical reactivity. In addition, when the intensity ratio is 1.2 or less, the reversible capacity is greatly reduced, and below 1.0, the electrochemical reactivity is reported to be lost. X-ray diffraction analysis results of the positive electrode active material used in Example 3-6 are shown in FIG. 2. It can be seen that the I (003) / I104 values calculated from FIG. 2 are all 1.4 or more, and thus the electrochemical reactivity of the lithium / cobalt oxide prepared according to the present invention is excellent. That is, it was confirmed from the peak relative strength ratio value that the degree of phase contamination in which the transition metal atom was distributed in the lithium (Li) layer was small.

In addition, it was shown in FIG. 3 by evaluating the constant current charge / discharge characteristics of the battery of Example 3 showing the highest initial charge and discharge capacity, and it can be seen from FIG. 3 that the battery of Example 3 has excellent charge and discharge characteristics.

As described above, lithium / cobalt oxides, which are cathode active materials for lithium secondary batteries, synthesized according to the present invention, all have excellent layered structure crystallinity and excellent battery characteristics. In other words, lithium / cobalt oxide prepared using a cobalt compound obtained from a cobalt sulfate solution according to the present invention is not only economical and environmentally friendly, but also has an advantage of having excellent electrochemical reactivity and battery characteristics.

Claims (6)

Reacting by adding a precipitant selected from the group consisting of oxalic acid, lithium hydroxide, ammonium hydroxide and mixtures thereof to the cobalt sulfate solution; And Filtrating the precipitate produced in the reaction, and the method of producing a cobalt compound comprising the step of drying. The method of claim 1, wherein the precipitation reaction is performed while applying ultrasonic waves to the reaction solution of the precipitation reaction. The method of claim 2, wherein the frequency of the ultrasonic wave is 10 to 40 kHz. The method of claim 1, wherein the reaction temperature of the precipitation reaction is 25 to 100 ℃, the reaction time is 10 to 60 minutes. Reacting by adding a precipitant selected from the group consisting of oxalic acid, lithium hydroxide, ammonium hydroxide and mixtures thereof to the cobalt sulfate solution; Filtering the precipitate produced in the reaction and drying to obtain a cobalt compound; And After mixing the cobalt compound and the lithium compound, a method of manufacturing a positive electrode active material for a lithium secondary battery comprising the step of heat treatment. The method of claim 5, wherein the heat treatment is a secondary lithium heat treatment step consisting of a first heat treatment step of heat treatment for 2 to 18 hours at 100 to 600 ℃ and a second heat treatment step of heat treatment for 6 to 36 hours at 600 to 1100 ℃ Method for producing a positive electrode active material for batteries.

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