KR20210011735A - Preparing method of nickel-cobalt-manganese complex sulphate solution by recycling wasted electrode material - Google Patents

Abstract

The present invention relates to a method for preparing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution by recycling a waste electrode material. The method includes the steps of: (S1) leaching powder of a waste electrode material oxide in an acid leaching bath and filtering the powder; (S2) carrying out selective hydrolysis of the filtrate separated from step (S1) to isolate metallic impurities; (S3) mixing an oxidizing agent with the filtrate isolated from step (S2), and precipitating the solution mixed with the oxidizing agent to isolate manganese (Mn); (S4) hydrolyzing the filtrate separated from step (S3) to isolate lithium, to obtain first cake, and to separate the supernatant; (S5) subjecting the supernatant of step (S4) to a filter press (F/P) process to obtain second cake containing nickel (Ni), cobalt (Co) and manganese (Mn) remaining in the supernatant as micro-powder, and introducing the second cake to the acid leaching bath of step (S1); and (S6) leaching the first cake of step (S4) with an acid, followed by filtering.

Description

Method of manufacturing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution by recycling waste electrode material {PREPARING METHOD OF NICKEL-COBALT-MANGANESE COMPLEX SULPHATE SOLUTION BY RECYCLING WASTED ELECTRODE MATERIAL}

The present invention relates to a method for producing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution by regenerating a waste electrode material, and more particularly, to reduce the loss rate of nickel and cobalt as much as possible, while manganese By removing in advance, it relates to a method for preparing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution having a low manganese content.

As the usage of lithium ion secondary batteries increases with the development of the IT industry, the amount of waste lithium batteries and waste scrap generated in the process is increasing day by day. The positive electrode, which accounts for more than 60% of the cost of such lithium batteries, tends to use ternary oxides (nickel, cobalt, manganese), which have superior battery performance compared to pure materials. All of these high-priced metals depend on imports, and technology to recover metals thrown out as waste is being promoted as a national task.

Due to the explosive demand for lithium-ion secondary batteries and the shortening of the use cycle of small digital home appliances, the amount of lithium-ion secondary batteries has been rapidly increasing, and thus domestic and foreign interest in the treatment and recycling of lithium-ion secondary batteries is increasing. When such a lithium-ion secondary battery is at the end of its life, if the waste materials are used, not only can problems such as environmental pollution be reduced, but also the cost of raw materials in the production of a lithium-ion secondary battery can be reduced. In addition, since defective waste battery scraps generated during the manufacturing process of lithium-ion secondary batteries or lithium-ion secondary battery waste scraps that are disposed of after use contain useful metals such as nickel, cobalt, and manganese, these useful resources are recently recovered and recycled. Technology development for this is actively progressing.

In recent years, by manufacturing and supplying a three-element (nickel, cobalt, manganese) complex sulfate solution (hereinafter referred to as'NCM complex sulfate solution') that can be recycled simultaneously without separating nickel, cobalt, and manganese, the process cost is low and cost reduction. Shows the effect of.

Meanwhile, in relation to the NCM composition of the cathode material precursor, the content ratio (molar ratio) of N, C, and M is from 5:2:3 to 6:2:2, and from 6:2:2 to 8:1:1. It is gradually changing. That is, the content of nickel is gradually increased, but the content of manganese is gradually decreasing. Currently, there are many waste cathode materials with N, C, and M content ratios of 5:2:3 and 6:2:2 that were used in the past, and the NCM complex sulfate solution to be finally delivered is N, There is a high possibility that the content ratio (molar ratio) of C and M becomes a cathode material precursor having a composition of 8:1:1.

Therefore, there is a need to reduce the content of manganese in the waste cathode material, and in particular, it is necessary to develop a process for efficiently removing manganese while reducing the loss rate of nickel and cobalt as much as possible.

An object of the present invention is to prepare a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution having a relatively low manganese content by efficiently removing manganese in advance while reducing the loss rate of nickel and cobalt as much as possible. Is to provide a way to do it.

In order to achieve the above object, according to the present invention, (S1) leaching the waste electrode material oxide powder with acid in an acid leaching tank and filtering it; (S2) separating metallic impurities by selectively hydrolyzing the filtrate separated in step (S1); (S3) mixing an oxidizing agent in the filtrate separated in step (S2), and separating manganese (Mn) by precipitating a solution in which the oxidizing agent is mixed; (S4) hydrolyzing the filtrate separated in step (S3) to separate lithium, obtaining a first cake, and separating the supernatant; (S5) By performing a filter press (F/P) process on the supernatant of step (S4), nickel (Ni), cobalt (Co), and manganese (Mn) remaining as fine powders in the supernatant are removed. After obtaining the second cake containing, the second cake is added to the acid leaching tank of the step (S1); And (S6) leaching the first cake of the step (S4) with acid and filtering the waste electrode material to obtain a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution. A method of making is provided.

Here, in the step (S1), hydrogen peroxide as a reducing agent in the presence of hydrochloric acid may be added to the acid leaching tank and leached at 75° C. to 85° C. for 180 to 300 minutes.

And, the (S2) step, a sodium carbonate aqueous solution in which the content of sodium carbonate (Na ₂ CO ₃ ) is 10% to 25% by weight based on the total weight of the aqueous sodium carbonate solution, and the filtrate separated in the (S1) step It may include a process of mixing.

In addition, the step (S3) may be to adjust the pH of the filtrate separated in the step (S2) to 0.15 to 1.50.

And, in the step (S3), the oxidizing agent is permanganate, and the oxidizing agent is mixed so that the number of moles is 0.3 to 0.7 times the number of moles of manganese contained in the filtrate separated in the step (S2). I can.

And, the step (S4), the sodium carbonate aqueous solution in which the content of sodium carbonate (Na ₂ CO ₃ ) is 10% to 25% by weight based on the total weight of the aqueous sodium carbonate solution, and the filtrate separated in the (S3) step It may include a process of mixing.

And, in the step (S5), in the filter press process, a heavy metal treatment agent is added to the supernatant to precipitate nickel (Ni), cobalt (Co), and manganese (Mn) remaining as fine particles in the supernatant, Through filter press filtration of the precipitated product, nickel (Ni), cobalt (Co), and manganese (Mn) may be additionally recovered.

In addition, the step (S6) may be performing a process of leaching at 50°C to 85°C for 300 to 500 minutes by adding a sulfuric acid solution to the reaction tank in which the first cake is located.

In addition, the nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution may be a precursor of a cathode material having a composition in which the molar ratio of N, C, and M is 8:1:1.

According to the present invention, a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution having a relatively low manganese content can be prepared by efficiently removing manganese in advance while reducing the loss rate of nickel and cobalt as much as possible. I can.

Accordingly, in the manufacturing process of the NCM complex sulfate solution, in the tuning process, which is the final process, the amount of nickel is reduced, thereby making it possible to more economically manufacture the NCM complex sulfate solution.

Furthermore, by performing a filter press process on the supernatant generated after hydrolysis, the recovery rate of nickel, cobalt, and manganese can be further increased.

1 is a flowchart showing a method for preparing an NCM complex sulfate solution according to the prior art.
2 is a flow chart showing a method for preparing an NCM complex sulfate solution according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Therefore, since the configuration described in this specification is only the most preferred embodiment of the present invention and does not represent all the technical spirit of the present invention, there are various equivalents and modifications that can replace them at the time of the present application. It should be understood that you can.

1 is a flowchart showing a method for preparing an NCM complex sulfate solution according to the prior art.

Referring to FIG. 1, a method of preparing a conventional nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution includes the steps of: (a) leaching and filtering waste electrode material oxide powder with acid, (b ) Selectively hydrolyzing the filtrate separated in step (a) to separate metallic impurities, (c) hydrolyzing the filtrate separated in step (b) to separate lithium and obtain a cake , And (d) leaching the cake obtained in step (c) with acid and filtering.

Currently, the amount of cathode materials having a composition ratio (molar ratio) of 8:1:1 of N, C, and M is increasing, and the NCM complex sulfate solution to be finally delivered has a high nickel content and a low manganese content. It is a losing trend. Currently, there are many waste cathode materials with N, C, and M content ratios of 5:2:3 and 6:2:2 that were previously used, so there is a need to lower the manganese content in the waste cathode materials. However, according to the prior art, since the content of manganese cannot be removed in advance, the content of nickel has to be relatively increased in the tuning process, which is the final process, and the process is not economical.

Thus, in the present invention, by removing manganese in advance during the manufacturing process of the NCM complex sulfate solution, an NCM complex sulfate solution having a content ratio (molar ratio) of N, C, and M suitable for a composition of 8:1:1 can be prepared. .

Furthermore, with respect to the supernatant generated through hydrolysis, conventionally, it was transferred to a wastewater treatment plant and then discharged, but in the present invention, by performing a filter press process on the supernatant, nickel, cobalt, and manganese remaining as fines in the supernatant. By further recovering, it is possible to further increase the recovery rate of the valuable metal.

2 is a flow chart showing a method for preparing an NCM complex sulfate solution according to the present invention.

With reference to Figure 2, the present invention will be described in more detail.

First, the waste electrode material oxide powder is leached with acid in an acid leaching tank and filtered (S1 step). When the leaching reaction is completed, filtration may be performed to obtain a filtrate.

In step (S1), hydrogen peroxide as a reducing agent in the presence of hydrochloric acid may be added to the acid leaching tank to perform a process of leaching at 75°C to 85°C for 180 to 300 minutes, and after the leaching process, the pH inside the acid leaching tank is 0.8 To 1.8, the amounts of hydrochloric acid and hydrogen peroxide may be adjusted, respectively.

In particular, in this step, the leaching efficiency can be maximized by adjusting the concentration and input rate of hydrogen peroxide in order to remove chemical resistance due to carbon and binder added in the electrode material manufacturing process. In the process of manufacturing an electrode material for a lithium-ion secondary battery, in order to maintain or improve the battery characteristics, a complex process such as sintering, addition of carbon and other metal oxides, and thermal fusion after addition of a binder is carried out. It has chemical resistance, which can act as an inhibitory factor in leaching and recovering valuable metals with acid.

Chemical resistance of the waste electrode material can be eliminated by supplying hydrogen peroxide at a constant concentration and at a constant rate in the process of leaching with acid. In the acid leaching process, hydrogen peroxide not only acts as a reducing agent for reducing metals, but also acts as an oxidizing agent for decomposing organic compounds such as a binder having chemical resistance. For this reason, by adjusting the concentration of hydrogen peroxide in the aqueous solution to 10% by weight to 35% by weight during acid leaching and introducing it in 0.1 to 5 LPM (Liter Per Minute), the recovery rate of valuable metals can be increased. However, a significant amount of the hydrogen peroxide added under high temperature (85±5°C) to maintain the leaching reaction is decomposed into H ₂ O or OH radicals prior to the redox reaction. Therefore, in the introduction of hydrogen peroxide, valuable metals can be recovered with high efficiency only when hydrogen peroxide of a certain concentration is added at a constant rate throughout the acid leaching process.

Subsequently, metallic impurities are separated by selective hydrolysis of the filtrate separated in step (S1) (step S2).

In step (S2), a process of mixing an aqueous sodium carbonate solution in which the content of sodium carbonate (Na ₂ CO ₃ ) is 10% to 25% by weight based on the total weight of the aqueous sodium carbonate solution with the filtrate separated in the step (S1). It may include. At this time, the temperature inside the reaction tank may be 45 ℃ to 75 ℃, the pH of the result of step (S2) may be 4.0 to 6.0, the stirring speed may be 180 to 220 rpm.

In step (S2), at least one selected from the group consisting of metallic impurities aluminum (Al), iron (Fe), and magnesium (Mg) is selectively hydrolyzed to form a hydroxide, which is separated through filtration. Can be removed. In particular, through selective hydrolysis, aluminum is precipitated as Al(OH) ₃ ·nH ₂ O(s) and iron is precipitated as Fe(OH) ₃ ·nH ₂ O(s), and nickel, cobalt, manganese, etc. are present in the solution. It can be selectively separated from the target component of.

Aluminum was used in the process of applying the cathode material powder to an aluminum sheet when constructing a lithium-ion secondary battery, and then in the pretreatment process of removing the cathode material powder from the defective product or waste cathode material sheet, up to 0.5 wt% Since aluminum powder is mixed with the target metal oxide to the maximum extent among impurities, it must be removed through the above process.

Subsequently, the oxidizing agent is mixed with the filtrate separated in step (S2), and the mixed solution of the oxidizing agent is precipitated to separate manganese (Mn) (step S3). By separating and removing manganese in advance through this step, an NCM complex sulfate solution that can be used in a cathode material precursor having a target content ratio of 8:1:1 of N, C, and M can be prepared.

Here, the result of step (S2), that is, the filtrate after selective hydrolysis, is used to perform this step (S3), while reducing the loss rate of nickel and cobalt, and selectively and effectively removing manganese ions. The optimum pH of the filtrate may be 0.15 to 1.50, preferably 0.5 to 1.0, and most preferably 0.80.

Immediately after the selective hydrolysis, that is, the pH of the resultant product of the (S2) step is about 4.0 to 6.0, and the optimum pH for separation of manganese ions should be 0.15 to 1.50 as described above, so filtration immediately after the selective hydrolysis to lower the pH It may be necessary to add hydrochloric acid to the solution to adjust the pH to the optimum.

The oxidizing agent used in step (S3) is permanganate, and the oxidizing agent may be mixed so that the number of moles is 0.3 to 0.7 times the number of moles of manganese contained in the filtrate separated in step (S2). If the number of moles is less than 0.3 times, the removal rate of manganese ions may decrease, and if it exceeds 0.7 times, the removal rate of manganese is high, but the loss rate of nickel and cobalt increases, which is not preferable.

The permanganate salt has a property that can be removed by precipitating tetravalent manganese ions present in the filtrate after selective hydrolysis as divalent insoluble manganese dioxide. As the permanganate, lithium permanganate (LiMnO ₄ ), sodium permanganate (NaMnO ₄ ), potassium permanganate (KMnO ₄ ), rubidium permanganate (RbMnO ₄ ), cesium permanganate (CsMnO ₄ ), etc. can be used, preferably permanganate Sodium (NaMnO ₄ ) and potassium permanganate (KMnO ₄ ) can be used.

Subsequently, the filtrate separated in the step (S3) is hydrolyzed to separate lithium, a first cake is obtained, and the supernatant is separated (step S4).

Step (S4) is a process of mixing an aqueous sodium carbonate solution in which the content of sodium carbonate (Na ₂ CO ₃ ) is 10% to 25% by weight based on the total weight of the aqueous sodium carbonate solution, and the filtrate separated in the step (S3). It may include. At this time, the temperature inside the reaction tank may be 45° C. to 75° C., the pH may be 6.5 to 8.5, and the stirring speed may be 250 to 350 rpm.

In the (S4) step, lithium is converted to solubilized lithium carbonate (Li ₂ CO ₃ (ℓ)), and nickel, cobalt, and manganese are precipitated nickel carbonate (NiCO ₃ (s)), cobalt carbonate (CoCO ₃ (s)) ), manganese carbonate (MnCO ₃ (s)), and lithium can be obtained by separating nickel, cobalt, and manganese as a solution into a hydroxide cake.

In addition, in addition to the valuable metals of nickel, cobalt, and manganese, the waste electrode material is added for the purpose of improving battery characteristics, or calcium (Ca), magnesium (Mg), iron ( Fe), aluminum (Al), silicon (Si), and other metallic impurities may exist.

Although a significant number of the metallic impurities can be removed through the selective hydrolysis of the step (S2), some impurities such as calcium (Ca), magnesium (Mg), and silicon (Si) are difficult to completely remove.

In addition, calcium, magnesium and sodium contained in the sodium carbonate added in the hydrolysis step should be excluded below the spec in the complex sulfate solution. To this end, in inducing the hydrolysis reaction, while stirring the leaching filtrate at 250 rpm to 350 rpm, sodium carbonate was added to the leaching filtrate at a temperature of room temperature or higher, preferably 45° C. to 75° C., so that sodium carbonate is lithium, nickel, and By quantitatively reacting with cobalt and manganese, a metal component can be precipitated and separated as a carbonate.

Subsequently, by performing a filter press (F/P) process on the supernatant of step (S4), nickel (Ni), cobalt (Co), and manganese (Mn) remaining as fine particles in the supernatant are included. After obtaining the second cake, the second cake is introduced into the acid leaching tank of the step (S1) (step S5).

Conventionally, the supernatant was directly transferred to a wastewater treatment plant and then discharged, but in the present invention, by performing a filter press process on the supernatant, nickel, cobalt, and manganese remaining as fine powders in the supernatant are additionally recovered, and thus nickel and cobalt The loss rate of can be further minimized.

At this time, in the filter press process, a heavy metal treatment agent such as an aqueous sodium sulfide solution is added to the supernatant to precipitate nickel (Ni), cobalt (Co), and manganese (Mn) remaining as fine particles in the supernatant, and then the result of precipitation It is characterized in that nickel (Ni), cobalt (Co), and manganese (Mn) are additionally recovered through filter press filtration. The pH of the first supernatant is 7 to 8, and the pH of the supernatant is adjusted to 9 to 10 by adding a heavy metal treatment agent such as an aqueous sodium sulfide solution to precipitate nickel, cobalt, and manganese, and then recovered as a second cake and reused.

Then, the first cake of the step (S4) is leached with acid and filtered (step S6). When the leaching reaction is completed, filtration may be performed to obtain a filtrate.

Nickel (Ni)-cobalt (Co) that can be used to prepare a cathode material precursor by performing a process of leaching for 300 to 500 minutes at 50°C to 85°C by adding a sulfuric acid solution to the reaction tank where the first cake is located -Manganese (Mn) complex sulfate solution can be prepared.

When one or more of nickel sulfate, cobalt sulfate, manganese sulfate, and the like are appropriately further mixed with the final composite sulfate solution, the composition of nickel, cobalt, and manganese can be adjusted as desired. In particular, in the present invention, it is possible to prepare a sulfate precursor of a cathode material having a composition ratio of N, C, and M of 8:1:1.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples.

1. Prepare filtrate (mother liquor) after acid leaching and hydrolysis of waste cathode material

Of the ternary cathode materials of nickel, cobalt and manganese as waste cathode materials, a cathode material having a composition of 622 (molar ratio of nickel, comalt, and manganese is 6:2:2) was prepared.

150 g of the waste cathode material was placed in a Pyrex 2 liter reactor filled with 400 ml of pure water, and 455 ml of hydrochloric acid corresponding to 1 mol was slowly added while stirring at 300 rpm. After adding hydrochloric acid, the reaction temperature was increased to 50° C. due to a self-exothermic reaction, and thereafter, it was maintained at 85±5° C. using a hot plate. The reaction tank was placed on a hot plate to adjust the temperature. The reaction time was maintained for 180 minutes to perform leaching.

After the addition of hydrochloric acid, hydrogen peroxide, which is a reducing agent, was constantly added at a rate of 1 ml/min for 100 minutes. As hydrogen peroxide, a total amount of 100 ml was used by adding 60 ml of pure water to 40 ml of a 35% by weight aqueous hydrogen peroxide solution to increase the leaching efficiency. After completion of the reaction, the pH was measured to be 1.20.

The leachate was placed in a 2 liter Pyrex reaction tank and the temperature was maintained at 50±5° C., and 42 ml of a 15% by weight aqueous sodium carbonate solution, which was 1.3 times the equivalent of impurities (aluminum, iron), was slowly added and maintained for 30 minutes. After filtration and the residue was washed with pure water, 900 ml of a filtrate including a washing solution was obtained.

As above, after acid leaching (hydrochloric acid and hydrogen peroxide) of the waste cathode material for lithium ion secondary batteries, metal impurities such as Al and Fe were separated and removed through selective hydrolysis, and then filtered to prepare a mother liquor for removing manganese ions.

Table 1 below shows the results of analysis of the filtrate after acid leaching and selective hydrolysis using a high frequency inductively coupled plasma (ICP-MS).

ingredient Li Ni Co Mn Mg Ca Zn Cu Fe Na Al Si Content (mg/kg) 5,279 23,910 8,247 8,084 5 5 0 0 0 1,449 0 6

2. Remove manganese ions according to the pH of the filtrate (mother liquor) after hydrolysis

After the acid leaching and hydrolysis, hydrochloric acid was added to 300 g of the filtrate (mother liquor, pH 5.85), and the pH was adjusted differently to 0.10, 0.80, 1.50, 5.85 (pH finely adjusted) to remove manganese ions. The molar ratio of potassium permanganate (99.3%) was added at 1.0 times (7.0 g) compared to the number of moles of manganese present in the mother liquor, and the reaction time was 1 hour, the reaction temperature was 40 ℃, and the stirring speed was fixed at 250 rpm. I did. After the reaction was completed, the concentration of the filtrate was shown in Table 2 (unit: mg/kg), and the removal rates of nickel, cobalt, and manganese were shown in Table 3 below.

division Li Ni Co Mn Mg Ca Zn Cu Fe Na Al Si Feed 5,279 23,910 8,247 8,084 5 5 0 0 0 1,449 0 6 pH 0.15 4,438 15,870 4,291 199 4 4 One 0 0 1,172 0 6 pH 0.80 4,414 20,189 6,598 53 4 4 One 0 0 1,155 0 5 pH 1.50 4,141 16,380 5,086 45 4 4 One 0 One 1.103 0 4 pH 5.85 4,371 12,510 20 4 4 4 One 0 One 1.164 0 4

division element Theoretical metal amount (g) Concentration (mg/kg) Weight(g) Actual amount (g) Removal rate (%) pH 0.15 Ni 7.17 15,870 297 4.71 34.4 Co 2.47 4,291 1.27 48.6 Mn 2.43 199 0.06 97.6 pH 0.80 Ni 7.17 20,189 312 6.29 12.3 Co 2.47 6,598 2.06 16.9 Mn 2.43 53 0.02 99.3 pH 1.50 Ni 7.17 16,380 335 5.48 23.6 Co 2.47 5,086 1.70 31.2 Mn 2.43 45 0.02 99.4 pH 5.85 Ni 7.17 12,510 320 4.00 44.3 Co 2.47 20 0.01 99.7 Mn 2.43 4 0.001 99.9

Referring to Tables 2 and 3, it is determined that the optimum pH for minimizing the loss rate of nickel and cobalt and efficiently removing manganese ions is 0.80. It was confirmed that manganese could be efficiently removed while reducing the loss rate of nickel and cobalt compared to the case. Therefore, the results of this experiment suggest that it is necessary to lower the pH in advance when removing manganese ions.

3. Removal of manganese ions according to the amount of potassium permanganate input

As shown in Table 1, a reaction equation for separating remaining manganese ions into manganese dioxide by adding potassium permanganate to the mother liquor in which manganese is leached is shown below.

2MnCl ₂ + 2KMnO ₄ → 4MnO ₂ + 2KCl + Cl ₂

The molar ratio of potassium permanganate (99.3%) to 300 g of the filtrate (mother liquor) after acid leaching and hydrolysis was 0.3 times (2.1 g), 0.5 times (3.5 g), 0.7 times ( 4.9 g) and 1.0 times (7.0 g) were added. After hydrolysis, the pH of the filtrate (mother liquor) was adjusted to 0.80 by adding hydrochloric acid, the reaction time was 1 hour, the reaction temperature was 40 ℃, the stirring speed was fixed at 250 rpm, and the concentration of the filtrate after the reaction was completed. Is shown in Table 4 (unit: mg/kg), and the removal rates of nickel, cobalt, and manganese are shown in Table 5 below.

division Li Ni Co Mn Mg Ca Zn Cu Fe Na Al Si Feed 5,279 23,910 8,247 8,084 5 5 0 0 0 1,449 0 6 0.3 times 4,277 21,650 7,219 3,140 2 2 0 0 0 1,159 0 4 0.5 times 4,253 20,990 7,133 1,240 2 2 0 0 0 1,152 0 4 0.7 times 4,414 20,611 6,939 243 2 2 0 0 0 1.210 0 4 1.0 times 4,414 20,189 6,598 53 4 4 One 0 0 1.155 0 5

division element Theoretical metal amount (g) Concentration (mg/kg) Weight(g) Actual amount (g) Removal rate (%) 0.3 times Ni 7.17 21,650 320 6.93 3.4 Co 2.47 7,219 2.31 6.6 Mn 2.43 3,140 1.00 58.6 0.5 times Ni 7.17 20,990 318 6.68 6.9 Co 2.47 7,133 2.27 8.3 Mn 2.43 1,240 0.39 83.7 0.7 times Ni 7.17 20,611 316 6.52 9.1 Co 2.47 6,939 2.19 11.3 Mn 2.43 243 0.08 96.8 1.0 times Ni 7.17 20,189 312 6.29 12.3 Co 2.47 6,598 2.06 16.9 Mn 2.43 53 0.02 99.3

Referring to Tables 4 and 5, it is determined that the optimal amount of potassium permanganate for removing manganese ions is 0.3 to 0.7 times the number of moles of manganese in the mother liquid. If it is less than 0.3 times, the removal rate of manganese ions is very low, and if it exceeds 0.7 times, that is, if 1.0 times potassium permanganate is added in this experiment, more than 99% manganese ions are removed, but the loss rate of nickel and cobalt is also As it increased, it was evaluated as undesirable.

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will understand that the present invention may be implemented in a modified form within the scope not departing from the essential characteristics of the present invention. I will be able to. Therefore, the disclosed embodiments and experimental examples should be considered from a descriptive point of view rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (9)

(S1) leaching and filtering the waste electrode material oxide powder with acid in an acid leaching tank;
(S2) separating metallic impurities by selectively hydrolyzing the filtrate separated in step (S1);
(S3) mixing an oxidizing agent in the filtrate separated in step (S2), and separating manganese (Mn) by precipitating a solution in which the oxidizing agent is mixed;
(S4) hydrolyzing the filtrate separated in step (S3) to separate lithium, obtaining a first cake, and separating a supernatant;
(S5) By performing a filter press (F/P) process on the supernatant of step (S4), nickel (Ni), cobalt (Co), and manganese (Mn) remaining as fine powders in the supernatant are removed. After obtaining a second cake containing, the second cake is added to the acid leaching tank of the step (S1); And
(S6) Regenerating the waste electrode material comprising the step of leaching and filtering the first cake of the step (S4) with acid to prepare a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution How to. The method of claim 1,
In the step (S1), hydrogen peroxide is added to the acid leaching tank as a reducing agent in the presence of hydrochloric acid and leached at 75° C. to 85° C. for 180 minutes to 300 minutes. A method of preparing a (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution. The method of claim 1,
In the step (S2), a sodium carbonate aqueous solution having a content of sodium carbonate (Na ₂ CO ₃ ) of 10% to 25% by weight based on the total weight of the aqueous sodium carbonate solution is mixed with the filtrate separated in the step (S1). A method for producing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution by regenerating a waste electrode material comprising a process. The method of claim 1,
In the step (S3), the pH of the filtrate separated in the step (S2) is adjusted to 0.15 to 1.50, and the waste electrode material is regenerated to obtain nickel (Ni)-cobalt (Co)-manganese (Mn). ) A method of preparing a complex sulfate solution. The method of claim 1,
In the step (S3), the oxidizing agent is a permanganate salt, and the oxidizing agent is mixed so that the number of moles is 0.3 to 0.7 times the number of moles of manganese contained in the filtrate separated in the step (S2). A method for producing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution by regenerating the waste electrode material. The method of claim 1,
In the step (S4), a sodium carbonate aqueous solution in which the content of sodium carbonate (Na ₂ CO ₃ ) is 10% to 25% by weight based on the total weight of the aqueous sodium carbonate solution is mixed with the filtrate separated in the (S3) step. A method for preparing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution by regenerating a waste electrode material comprising a process. The method of claim 1,
In the step (S5), in the filter press process, a heavy metal treatment agent is added to the supernatant to precipitate nickel (Ni), cobalt (Co), and manganese (Mn) remaining as fine powders in the supernatant, and then the result of precipitation Nickel (Ni), cobalt (Co), and manganese (Mn) are additionally recovered through filter press filtration of the waste electrode material to recover nickel (Ni)-cobalt (Co)-manganese (Mn). ) A method of preparing a complex sulfate solution. The method of claim 1,
In the step (S6), a sulfuric acid solution is added to the reaction tank in which the first cake is placed and leached at 50° C. to 85° C. for 300 to 500 minutes. A method of preparing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution. The method of claim 1,
The nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution is a precursor of a positive electrode material having a composition of 8:1:1 in molar ratios of N, C, and M, by regenerating a waste electrode material. A method of preparing a nickel (Ni)-cobalt (Co)-manganese (Mn) complex sulfate solution.

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