KR101325176B1 - Method of manufacturing chemical manganese dioxide from trivalent cathode active material, the chemical manganese dioxide manufactured by the method and secondary battery including the chemical manganese dioxide - Google Patents

Abstract

The present invention, (a) a one-stage leaching step of leaching ternary cathode active material powder with a mixture of sulfuric acid and a reducing agent; (b) a two stage leaching step of continuously leaching the one stage leaching solution; And (c) adding Na ₂ S ₂ O ₈ to the two-stage leaching solution to selectively precipitate Mn to prepare chemical manganese dioxide.
According to the present invention, selective separation of Mn from ternary positive electrode active material (Li (Ni _1/3 Mn _1/3 Co _1/3 ) O ₂ ), which is a positive electrode active material of a lithium ion battery used in a mobile phone or an electric vehicle, can be achieved. In order to provide a method for producing chemical manganese dioxide by selectively precipitating only Mn from the sulfuric acid reduction leaching solution using Na ₂ S ₂ O ₈ as an oxidizing agent and the chemical manganese dioxide produced by the manufacturing method.

Description

METHODO OF MANUFACTURING CHEMICAL MANGANESE DIOXIDE FROM TRIVALENT CATHODE ACTIVE MATERIAL, THE CHEMICAL MANGANESE DIOXIDE MANUFACTURED BY THE METHOD AND SECONDARY BATTERY INCLUDING THE CHEMICAL MANGANESE DIOXIDE}

The present invention relates to a method for producing chemical manganese dioxide from a ternary positive electrode active material, and to a secondary battery including chemical manganese dioxide and chemical manganese dioxide prepared by the method, and more particularly, from a ternary positive electrode active material of a lithium ion battery to be discarded. The present invention relates to a method for preparing Chemical Manganese Dioxide (CMD) by selectively precipitating Mn.

 Manganese dioxide is characterized by high capacity and low toxicity, and has a particularly good electrochemical ability. It is a material that is attracting attention as a cathode active material of primary batteries and secondary batteries. Synthetic manganese dioxide has been applied in various manufacturing fields. The most important point of manganese dioxide from a commercial point of view is that it has electrochemical activity, and because of this property, it is widely used as a cathode material of batteries. Another commercial form is ultra high purity manganese dioxide for ferrites and thermistors in the electronics industry. Manganese dioxide is also steadily increasing as an oxidation catalyst used for the decomposition of air pollutants such as the removal of volatile organics and the decomposition of ozone.

Synthetic manganese dioxide can be prepared from manganese salts, solutions containing manganese, or natural ores by chemical processes (chemical manganese dioxide, CMD) or electrochemical methods (electrolytic manganese dioxide, EMD). Chemical manganese dioxide can be prepared by heat treatment of MnCO ₃ and also by oxidation precipitation method using NaClO ₃ from sulfuric acid solution.

In recent years, the demand for lithium ion batteries is increasing and its application range is increasing as a power source for Hybrid Electric Vehicle (HEV) or Electric Vehicle (EV) in the range of being used as energy source of portable electronic devices. In addition, the scope of application is expected to extend to the robot industry, energy storage industry and aerospace industry. Therefore, the usage of cobalt, lithium, nickel, and manganese, which are the main components of lithium ion batteries, is also expected to increase significantly, and the amount of lithium ion batteries discarded after use is expected to increase exponentially. Separation / recovery of rare metals, such as cobalt, nickel, manganese, and lithium, from these waste lithium-ion batteries, and recycling them as metals and metal compounds can provide a stable source of core materials for batteries that depend on imports. Its importance is very high.

In the previous study, a solvent extraction process for cobalt recovery from a lithium ion battery was proposed, but recently, a new lithium-ion battery cathode active material of Co-Mn-Ni, which replaced expensive Co, was developed and commercialized. The content is increasing. Therefore, in order to separate and recover valuable metals, separation of Mn must be preceded.

The present invention has been made to solve the above problems, a three-way cathode active material (Li (Ni _1/3 Mn _1/3 Co _1/3 )) which is a cathode active material of lithium ion batteries used in mobile phones or electric vehicles It is an object of the present invention to provide a method for producing chemical manganese dioxide by selectively precipitating only Mn using an oxidizing agent from a sulfuric acid reduction leaching solution for selective separation of Mn from O ₂ ).

Another object of the present invention is to provide a chemical manganese dioxide produced by the above production method.

Still another object of the present invention is to provide a secondary battery including chemical manganese dioxide prepared by the above manufacturing method.

The present invention is to achieve the above object, (a) a one-stage leaching step of leaching the ternary cathode active material powder with a mixture of sulfuric acid and a reducing agent; (b) a two stage leaching step of continuously leaching the one stage leaching solution; And (c) adding Na ₂ S ₂ O ₈ to the two-stage leaching solution to selectively precipitate Mn to prepare chemical manganese dioxide.

In addition, after the step (c) (d) characterized in that it further comprises the step of pickling the chemical manganese dioxide prepared in (c).

In addition, the step (d) is characterized in that the pickling using sulfuric acid.

In addition, in step (c) is characterized in that the addition of at least one equivalent of Na ₂ S ₂ O ₈ .

In addition, the reaction temperature of step (c) is characterized in that more than 90 ℃.

In addition, the reaction time of the step (c) is characterized in that 300 to 400 minutes.

In addition, the reducing agent is characterized in that selected from the group consisting of hydrogen peroxide, H ₂ S, SO ₂ , FeSO ₄ , coal (pyal) and pyrite (Pyrite).

Also, the (a) a ternary positive electrode active material of step powder is a ternary positive electrode of the closed cell active material _{(Li (Ni 1/3 Mn} 1/3 Co 1/3) O 2) Al by a physical separation process from scrap It is characterized in that the separation removed.

In addition, the physical separation step is (a) a ternary positive electrode active material of the closed cell _{(Li (Ni 1/3 Mn} 1/3 Co 1/3) O 2) comprising: the cutting scraps; (B) heat treatment after cutting; (C) pulverizing after the heat treatment; And (d) separating and collecting particles having a size of 40 mesh or less after the pulverization.

The present invention also provides a chemical manganese dioxide produced by the above production method.

The present invention also provides a secondary battery prepared from the ternary cathode active material including the chemical manganese dioxide.

According to the present invention, the portable positive electrode active material is a ternary positive electrode active material of a telephone or a lithium ion battery used in an electric vehicle _{(Li (Ni 1/3 Mn} 1/3 Co 1/3) O 2) optional separation of Mn In order to provide a method for producing chemical manganese dioxide by selectively precipitating only Mn from the sulfuric acid reduction leaching solution using Na ₂ S ₂ O ₈ as an oxidizing agent and the chemical manganese dioxide produced by the manufacturing method.

1 is a schematic diagram of a physical treatment process and waste water reduction continuous leaching process of the three-way cathode active material scrap.
2 is a view showing a reactor for the selective oxidation of Mn from ternary positive electrode active material leaching solution.
Figure 3 is a graph showing the one-step leaching behavior of 2M sulfuric acid solution of the ternary cathode active material scrap sample.
Figure 4 is a graph showing the two-stage leaching behavior of the three-way cathode active material scrap sample.
Figure 5 is a graph showing the pH-Eh diagram of the Mn-SH ₂ O system.
6 to 8 are graphs showing Eh-pH diagrams of Co, Ni, and Li, respectively.
9 is a graph showing the precipitation behavior of Co and Ni, Li coprecipitation behavior according to the reaction time.
10 is a graph showing the precipitation behavior of Mn over time versus reaction temperature.
11 is a graph showing the change in pH and Eh behavior over time.
12 is a graph showing the precipitation behavior of Mn according to the equivalent ratio of the oxidizing agent.
Figure 13 is a graph of the XRD analysis of the Mn precipitate prepared according to the production method of the present invention.
14 is a graph of the TG-DTA analysis of the Mn precipitate prepared according to the production method of the present invention.
15 is a graph of the XRD analysis results according to the heat treatment conditions of the Mn precipitate prepared according to the production method of the present invention.
Figure 16 is a graph showing the average particle size analysis of manganese dioxide prepared according to the production method of the present invention.

The present invention, (a) a one-stage leaching step of leaching ternary cathode active material powder with a mixture of sulfuric acid and a reducing agent; (b) a two stage leaching step of continuously leaching the one stage leaching solution; And (c) adding Na ₂ S ₂ O ₈ to the two-stage leaching solution to selectively precipitate Mn to prepare chemical manganese dioxide.

Hereinafter, with reference to the accompanying drawings, the present invention will be described in detail.

In the present invention, the reducing agent may be selected from the group consisting of hydrogen peroxide, H ₂ S, SO ₂ , FeSO ₄ , coal (Coal) and pyrite (Pyrite). In the present invention, since the addition of a reducing agent during acid leaching of chemically stable manganese oxides has an effect on improving the leaching rate of manganese oxides, in the present invention, the concentration, amount of use, and reaction temperature of the reducing agent can be optimized. And by applying the reaction time, it is possible to improve the recovery of manganese.

In the two-stage leaching step (b), a reducing agent is added to the first leaching solution obtained in step (a) to continuously leach. The reducing agent used herein may be used a reducing agent as exemplified above, it is particularly preferred to use hydrogen peroxide.

In the present invention, the oxidizing agent of step (c) is Na ₂ S ₂ O ₈ , the precipitation reaction of Mn (II) by Na ₂ S ₂ O ₈ is as follows.

MnSO ₄ + Na ₂ S ₂ O ₈ + 2H ₂ O = Na ₂ SO ₄ + MnO ₂ + 2H ₂ SO ₄

2CoSO ₄ + Na ₂ S ₂ O ₈ + 6H ₂ O = Na ₂ SO ₄ + 2Co (OH) ₃ + 3H ₂ SO ₄

2NiSO ₄ + Na ₂ S ₂ O ₈ + 6H ₂ O = Na ₂ SO ₄ + 2Ni (OH) ₃ + 3H ₂ SO ₄

As can be seen from the above equations, it is believed that Co and Ni will partially precipitate together in the precipitation of Mn, and the reaction temperature, reaction time and equivalent of oxidant in the oxidation precipitation step of Mn to minimize co-precipitation of Co and Ni. It is preferable to adjust conditions, such as within a specific range.

In the present invention, the washing water used during the pickling in step (d) may be sulfuric acid, and by washing with pickling water, washing the Co, Ni, Li remaining in the CMD to remove CMD In this case, the wash water after pickling may be reused as the leachate of the first stage leaching.

1 shows a schematic diagram of the physical separation process of the three-way cathode active material scrap and the wastewater reduction continuous leaching process. The physical separation process may be performed in the following process.

(A) a ternary positive electrode active material of the closed cell _{(Li (Ni 1/3 Mn} 1/3 Co 1/3) O 2) comprising: the cutting scraps;

(B) heat treatment after cutting;

(C) pulverizing after the heat treatment; And

(D) separating and collecting particles having a size of 40 mesh or less after the grinding.

In the case of ternary cathode active materials concentrated through the above physical separation, the concentration of impurities is automatically controlled during the first and second stage leaching. The solution thus obtained can be directly added to the separation and purification process for recovery of valuable metals. have.

Using an oxidizing agent which Na ₂ S ₂ O ₈ as the destination of ternary Al removal process and waste reduction-type two-stage removal of the residual Al through continuous leaching solution within the Li, Co, Mn, Ni, etc. through a physical process from an anode active material scrap Mn was selectively precipitated out. FIG. 2 is a view showing a reaction apparatus for selective oxidation precipitation of Mn from a ternary positive electrode active material leaching solution.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the following Example. The following examples are examples for explaining the present invention, and the scope of the present invention is defined by the appended claims below, and is not limited to the exemplary embodiments.

[Example]

Example 1 Continuous Leaching Process with 2M Sulfuric Acid Solution

Leaching experiments were carried out under the conditions of 2M H ₂ SO ₄ , H ₂ O ₂ 5vol%, 60 ° C, 50g / 500ml, 200rpm, 2hr from the concentrated cathode active material through physical treatment from the ternary cathode active material.

Figure 3 is a graph showing the one-step leach behavior of the ternary cathode active material scrap sample by 2M sulfuric acid solution. As can be seen in Figure 3 for the leaching of 2M sulfuric acid leaching for all elements within 60 minutes in the first stage leaching was 95.7% Co, 95.7% Ni, 91.4% Mn, 98.2% Li, 97.1% Al, respectively. In this case, it was confirmed that about 59 mg / L was present in the solution of Al as an impurity.

Two stage leaching experiments were conducted using a single stage leaching solution. Experimental conditions were carried out under the conditions of a single stage leaching solution, 5vol% H ₂ O ₂ , 60 ℃, 50g / 500ml, 200rpm, 4hr.

Figure 4 is a graph showing the two-stage leaching behavior (one-stage leaching solution, 5vol% H ₂ O ₂ , 60 ℃, 50g / 500ml, 200rpm, 4hr) of the three-way cathode active material scrap sample.

As can be seen in Figure 4 it was confirmed that the leaching rate of the valuable metal is kept relatively constant over time, especially in the leaching behavior of all the elements in the leaching time over 10 minutes was confirmed that the equilibrium . The leaching rate of the valuable metals only in the second stage leaching except for the amount of valuable metals leached in the first stage leaching was about 25 to 30% in the case of Co, Ni, and Mn. Observation of the rate could be observed. At this time, the pH of the leaching solution was confirmed to maintain about 5 ~ 5.4 after 10 minutes leaching time. In the case of Al as an impurity, the concentration was reduced to 8 mg / L after 60 minutes of leaching time. Table 1 shows the valuable metal concentrations (mg / L) of the first stage leaching filtrate and the second stage leaching filtrate in 2M sulfuric acid leaching.

Ni Al Li Co Mn pH Eh (mV, SHE) 1st leachate 18800 58.9 7020 17700 16700 0.58 1510.2 2nd leachate 24200 8.1 9470 22000 21600 5.34 763.5

As can be seen in Table 1, about 86% of Al was removed. Concentrations of valuable metals in the leaching filtrate after two stage leaching were 22 g / L for Co, 21.6 g / L for Mn, 24.2 g / L for Ni, and 9.5 g / L for Li and 8 mg / L for Al.

5 is a graph showing the pH-Eh diagram of the Mn-SH ₂ O system. In this graph, it is possible to oxidize and precipitate Mn (II) to Mn (IV) by keeping Eh in the range of 1V or more in the range of pH 5-6. 6 to 8 are graphs showing Eh-pH diagrams of Co, Ni, and Li, respectively. From these, it was judged that selective precipitation of Mn was possible at the conditions of pH 2 or less and Eh 1.5V or more.

Example 2 Precipitation of Mn Using Na ₂ S ₂ O ₈ as an Oxidizer

1. According to the reaction time Mn of Sedimentation behavior  And Co , Ni , Li Reciprocation behavior

Precipitation behavior of Mn was confirmed by using 1 equivalent of oxidant to the concentration of Mn (II) in the leaching solution at a stirring speed of 500 rpm and a temperature of 90 ° C.

9 shows the precipitation behavior of Mn and the coprecipitation behavior of Co, Ni, and Li (500rpm, Na ₂ S ₂ O ₈₎ according to the reaction time. 1 equivalent, 90 ° C., 300 minutes). As can be seen in Figure 9 it can be seen that as the reaction time increases the precipitation rate of Mn increases and at the same time the precipitation rate of Co, Ni, Li also increases to 20%.

2. Reaction temperature and oxidant Equivalence ratio  According to the change Mn of Sedimentation behavior  And Co , Ni , Li's reciprocation behavior

The reaction temperature was changed to 70 ° C., 80 ° C., 90 ° C. and 95 ° C. to investigate the precipitation behavior of Mn and the coprecipitation behavior of Co, Ni, and Li.

10 is a graph showing the sedimentation behavior of Mn according to the reaction temperature (500 ml of ternary two-phase cathode active material, 500 rpm, 1,300 equivalents of Na ₂ S ₂ O ₈ equivalent). As can be seen in FIG. 10, the precipitation rate of Mn was rapidly increased as the reaction temperature was increased. In case of the reaction temperature of 90 ° C. and 95 ° C., the precipitation rate of Mn was slightly different, but both were Mn. It was confirmed that more than 99.5% precipitated.

FIG. 11 is a graph showing the change of pH and Eh over time (500 ml of ternary cathode active material two-stage leachate, 90 ° C., 500 rpm, Na ₂ S ₂ O ₈ equivalent number 1,300 minutes). Looking at the change of Eh and pH according to the reaction time, it was confirmed that Eh was rapidly increased at the beginning of the reaction to maintain 1.4V or more, and in the case of pH, as oxidant was added, as can be seen in the previously described equation As the precipitation reaction proceeded, sulfuric acid was generated, and the pH was confirmed to decrease to 0.5.

Table 2 shows the results of analyzing the valuable metal content (%) of the precipitate produced by each reaction temperature.

Reaction temperature Ni Li Co Mn 70 ℃ 0.1 0.005 0.5 58.4 80 ℃ 0.1 0.003 1.2 86.1 90 ° C 0.1 0.001 1.8 99.7 95 ℃ 0.1 0.002 2.4 99.9

As can be seen in Table 2, as the reaction temperature increases, the precipitation rate of Mn was also rapidly increased, and it was confirmed that more than 99.7% of the precipitation was performed at 90 ° C. or higher. In addition, Co, Ni, Li can be seen that the precipitation is rarely precipitated selectively can be seen that the selective precipitation. However, in the case of Co, the precipitation rate increased from 0.5% to 2.4% as the reaction temperature was increased, and it was found that additional treatment was required for Co precipitated after the precipitation reaction.

3. oxidizer In equivalence  Following Mn of Sedimentation behavior  And Co , Ni , Li Reciprocation behavior

The precipitation ratio of Mn and the coprecipitation behavior of Co, Ni, and Li were investigated by increasing the equivalent ratio of oxidant to 1, 1.1, 1.2 at the temperature of 90 ° C.

12 is a graph showing the precipitation behavior of Mn according to the equivalent ratio of oxidant. As can be seen in Figure 12, as the equivalent ratio of the oxidizing agent increases, the precipitation rate of Mn also increases, and it was confirmed that most of Mn precipitated in a reaction time of 300 minutes or more under 1 equivalent or more. Table 3 shows the precipitation rate (%) of valuable metals according to the oxidant equivalent ratio change.

Oxidizer Equivalence Ratio Ni Li Co Mn 0.9 0.2 0.005 1.4 93.5 One 0.1 0.002 1.8 99.4 1.1 0.2 0.06 2.9 99.9 1.2 0.3 0.02 3.9 99.9

Based on the precipitate analysis results of Table 2 and Table 3, it could be confirmed that the contents of Co, Li, and Ni which are co-precipitated during Mn precipitation are insignificant. However, it was confirmed that the concentration of these valuable metals in the solution was reduced by about 20% during Mn oxidation precipitation. This is because the surface potential of the produced manganese dioxide has a negative value, so that cations in the solution are adsorbed on the surface of manganese dioxide. Therefore, to recover the produced manganese dioxide, the manganese dioxide obtained after solid-liquid separation was washed with water, and the adsorbed Ni, Co, Li ions were washed and examined for the content of recoverable Ni, Co, Li through this process.

Table 4 shows the precipitation rates (%) obtained from the final solution for the 500 ml initial solution and the mass balance calculation for the precipitate.

Ni Li Co Mn Sedimentation rate (%)-based on final solution 20.8 23.4 20.3 100.0 Sedimentation Rate (%)-Sediment Basis 0.3 0.074 2.7 99.5

As can be seen in Table 4, the calculation of the precipitation rate of valuable metals according to each precipitation rate standard shows that the solution-based precipitation rate is about 23 to 29% except for Mn.

In addition, in the case of precipitation based precipitation, almost no precipitation occurred in Ni and Li except for Mn, and Co showed a precipitation rate of about 2.7%.

Since some valuable metals are adsorbed on the surface of the sediment during the precipitation process, it is necessary to wash them to recover them.After washing, it is important to reuse the cleaning solution containing valuable metals to recover valuable metals. Judging.

[ Example  3: remove impurities in the produced precipitate]

In order to remove Co, Ni, and Li contained in the resulting precipitate 4M H ₂ SO ₄ , 10g / 100ml, 80 ℃, 500rpm, was carried out for 2 hours washing experiment. Table 5 shows the percentage removal of impurities in the precipitate through pickling.

Co Mn Li Ni % Residue before cleaning 2.1 61.5 0.001 0.2 % Residue after washing 1.6 67.8 0.001 0.1 Final wash solution (mg / L) 341.2 714 5.74 70.72 Impurity Removal Rate (%) 24.8 - - 45.6

As can be seen in Table 5, the removal rate of Co was 24.8% and Ni was 45.6%. In the case of Li, since there was little change in the content before and after pickling, it was judged that there was little amount of adsorption on the surface of the prepared precipitate. From the above results it can be confirmed that the pickling having a purity of 98% or more through pickling.

[Experiment result]

The chemical crystal form was analyzed using XRD on the precipitate with fine impurities. Figure 13 is a graph of the XRD analysis of the prepared Mn precipitate. As can be seen in Figure 13 it was confirmed that the chemical crystal form of the precipitate is γ-MnO ₂ .

Thermogravimetric analysis was carried out on the precipitates and the weight loss behaviors of the precipitates were investigated.

Figure 14 is a graph of the TG-DTA analysis of the prepared Mn precipitate. As can be seen in Figure 14 it was confirmed that the weight loss occurs at 502.08 ℃, 590.02 ℃, 756.84 ℃. Therefore, in order to observe the phase change according to the weight loss, the precipitates were heat-treated under the conditions of 250 ° C., 500 ° C., 620 ° C. and 780 ° C., respectively, and XRD analysis was performed.

15 is a graph of the XRD analysis results according to the heat treatment conditions of the prepared Mn precipitate. As can be seen in FIG. 15, it was confirmed that the sample had a crystalline form of γ-MnO _{2 up} to 500 ° C. heat-treated samples, but it was confirmed that it had a crystalline form of Mn ₂ O ₃ at higher temperature conditions. Table 6 shows the chemical composition analysis results (%) of the heat treated samples.

Co Mn Li Al Ni Na Raw materials 1.0 65.1 0.05 0.008 0.2 0.3 250 ℃ 1.0 66.8 0.05 0.006 0.2 0.3 500 ℃ 1.0 69.5 0.04 0.004 0.2 0.3 620 ℃ 1.1 74.3 0.06 0.006 0.2 0.3 800 ° C 1.1 77.8 0.05 0.004 0.2 0.3

As can be seen in Table 6, the Mn content of the raw material was confirmed to have a composition of MnO ₂ to 65.1%, and it was confirmed that the Mn content increased to 77.8% as the heat treatment temperature was increased. At this time, it was confirmed that the main impurity contained Co about 1 to 1.1% of the impurity.

16 is a graph showing the average particle size analysis of the prepared manganese dioxide. As can be seen in Figure 16 it was confirmed through the particle size analyzer analysis that manganese dioxide having an average particle diameter of 10.7㎛ was prepared.

From the above results, the following three-way cathode active material recycling process can be proposed. In the situation where the content of Mn in the positive electrode active material used in the lithium ion battery is continuously increasing, when it is separated and recovered by the wet smelting method, first, Mn is selectively prepared as CMD using the oxidative precipitation method and then recovered in the filtrate. Co, Ni, Li recovers Co using solvent extraction. Ni and Li remaining in raffinate recover Ni through another solvent extraction. Li solution generated after the second solvent extraction is carbonate using sodium carbonate. It can be recovered as lithium carbonate through precipitation.

Claims (11)

(a) leaching the ternary cathode active material (Li (Ni _1/3 Mn _1/3 Co _1/3 ) O ₂ ) powder containing Al, Co, Ni, Li, and Mn with a mixture of sulfuric acid and a reducing agent; Removing one step, and leaching Co, Ni, Li and Mn;
(b) a two stage leaching step of continuously leaching the one stage leaching solution; and
(c) adding at least one equivalent of Na ₂ S ₂ O ₈ to the two-stage leaching solution and reacting at a temperature above 90 ° C. for 300 to 400 minutes to selectively precipitate Mn from the leaching solution of Co, Ni, Li, and Mn. Steps to Prepare Manganese Dioxide
Method of manufacturing manganese dioxide from the ternary cathode active material comprising a.
The method of claim 1,
(d) pickling the chemical manganese dioxide prepared in (c) above
Method of manufacturing manganese dioxide from the ternary cathode active material, characterized in that it further comprises.
3. The method of claim 2,
Method of producing manganese dioxide from the ternary cathode active material, characterized in that the pickling using sulfuric acid in the step (d). delete delete delete The method of claim 1,
The reducing agent is hydrogen peroxide, H ₂ S, SO ₂ , FeSO ₄ , coal (coal) and pyrite (Pyrite) method for producing a chemical manganese dioxide from the ternary cathode active material, characterized in that selected from the group consisting of.
The method of claim 1,
(A) the ternary positive electrode active material of step powder is a ternary positive electrode of the closed cell active material _{(Li (Ni 1/3 Mn} 1/3 Co 1/3) O 2) separating the Al by a physical separation process from scrap Method of producing manganese dioxide from the ternary cathode active material, characterized in that removed.
The method of claim 8,
The physical separation process
(A) a ternary positive electrode active material of the closed cell _{(Li (Ni 1/3 Mn} 1/3 Co 1/3) O 2) comprising: the cutting scraps;
(B) heat treatment after cutting;
(C) pulverizing after the heat treatment; And
(D) separating and collecting particles having a size of 40 mesh or less after the grinding.
Method of producing manganese dioxide from ternary positive electrode active material, characterized in that it comprises a.
delete delete

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