JP5572222B2 - Method for producing CMB liquid phase catalyst from lithium ion battery and ternary positive electrode active material - Google Patents

Description

  The present invention relates to a method for recovering cobalt and manganese from waste battery materials, and a method for producing a Co-Mn-Br liquid phase catalyst using the same, and more particularly, to waste lithium ion battery powder and ternary positive electrode active material. Cobalt and manganese recovery, characterized in that cobalt and manganese are recovered by sequentially performing sulfate reduction leaching, neutralization titration, solid-liquid separation, solvent extraction, and water washing on scrap generated in the manufacturing process of The present invention relates to a method and a method for producing a Co—Mn—Br liquid phase catalyst using an extract containing cobalt and manganese obtained by the method.

  Among lithium batteries, a lithium secondary battery whose usage has been increasing rapidly is composed of a positive electrode (cathode), a negative electrode (anode), an organic electrolyte (organic electrolyte), and an organic separator (organic separator). Has been. As a positive electrode active material, lithium cobalt oxide that is excellent in reversibility, has a low self-discharge rate, a high capacity, and a high energy density, and is easily synthesized, has been commercialized.

  In particular, lithium ion batteries are light in weight, and are therefore often used as a power source for small portable equipment. Recently, the demand for mobile terminals has increased in proportion to the explosive increase in the use of mobile terminals. In addition, as the demand for lithium ion batteries increases, the amount of waste lithium ion batteries generated is also increasing rapidly.

  Such waste lithium ion batteries have simple properties and contain a large amount of relatively expensive lithium and valuable metals such as cobalt as the positive electrode active material, and are recognized as economically valuable waste resources and can be recycled. Required. However, in the case of a lithium ion battery that employs lithium cobalt oxide as the positive electrode active material, valuable metals such as cobalt and lithium must be recycled. In addition to efficient metal recovery, hazardous waste generated during the recycling process of waste lithium batteries must be properly treated.

  In particular, among the methods of mechanically treating waste lithium ion batteries, metallic lithium reacts violently with moisture and oxidizes, which can be extremely dangerous, so that cobalt can be efficiently recovered from waste lithium ion batteries It is important to minimize stable mechanical processing and harmful components.

Currently, the trend of commercialization of positive electrode active materials for lithium ion batteries has shifted from LiCoO ₂ to ternary positive electrode active materials, especially as the use of lithium ion batteries has increased in size and diversified (hybrid vehicles, electric The demand for lithium ion batteries using ternary positive electrode active materials, such as automobiles, robots, and energy storage, is expected to increase geometrically, and the development of recycling technology corresponding to this demand is required.
The CMB liquid phase catalyst is a catalyst made of Co—Mn—Br, and is used as a catalyst in a process of producing TPA (terephthalic acid) by oxidizing paraxylene which is one of petrochemical products. TPA is a raw material for polyester fibers, PET (polyethylene terephthalate) bottles, films, paints, and tire cords that are closely related to our daily lives. Korea is a major producer of TPA in 2006. The amount of TPA produced in Korea is 5.5 million tons, accounting for 21% of the world's TPA production capacity (26 million tons), and the CMB catalyst market is extremely large. Therefore, the CMB catalyst can be economically manufactured by recovering Co and Mn from the waste containing Co and Mn discarded in the above-described process and manufacturing the CMB catalyst.

  Here, as a result of diligent efforts to develop an efficient method for recovering cobalt and manganese from scrap generated in the process of producing a waste lithium ion battery and a ternary positive electrode active material, When the sample is subjected to sulfuric acid reduction leaching, impurity removal (neutralization titration and solid-liquid separation), solvent extraction and water washing step by step, high-purity cobalt and manganese from which impurities have been removed are recovered, As a result, it was confirmed that a CMB liquid phase catalyst could be produced using the above-mentioned, and the present invention was completed.

  The present invention has been made in view of the above problems, and its object is to provide a method for recovering cobalt and manganese from scrap generated in the process of producing a waste lithium ion battery and a ternary positive electrode active material, An object of the present invention is to provide a method for producing a Co—Mn—Br liquid phase catalyst using an extract containing cobalt and manganese obtained by the method.

  To achieve the above object, the present invention comprises (a) a step of leaching waste battery material using sulfuric acid and a reducing agent, and (b) neutralizing the leaching solution obtained in step (a). Titrating to remove impurities, (c) separating the leaching solution obtained in step (b) into a solution and a residue, and (d) separating the solution from the liquid in step (c). And a step of extracting the solution by adding a solvent, and (e) washing the extract obtained in step (d) with water.

  The present invention further includes (f) adding an HBr solution to the extract obtained by the cobalt and manganese recovery method and back-extracting to obtain a Co-Mn-Br removal solution; and (g) the Co And adding a cobalt salt and a manganese salt to a Mn-Br removal solution to adjust the proper concentration, and a method for producing a Co-Mn-Br liquid phase catalyst using cobalt and manganese recovered from waste battery materials provide.

It is a flowchart for manufacture of a Co-Mn-Br type liquid phase catalyst. It is a recovery simulation test schematic diagram of the main element using 40% soaping solvent of 0.7M Cyanex 272. It is a recovery simulation test schematic diagram of main elements using a 45% soaping solvent of 0.85M Cyanex 272.

  In one aspect, the present invention provides (a) a step of leaching waste battery material using sulfuric acid and a reducing agent, and (b) neutralizing titrating the leaching solution obtained in step (a) to produce impurities. (C) a step of solid-liquid separation of the leaching solution obtained in the step (b) into a solution and a residue, and (d) a solvent in the solution solid-liquid separated in the step (c). And (e) a step of washing the extract obtained in step (d) with water, and a method for recovering cobalt and manganese.

  In the present invention, the waste battery material may be scrap generated in the manufacturing process of the waste lithium ion battery and the ternary positive electrode active material.

  In the present invention, the waste lithium ion battery may be in a powder state, and in the method of the present invention, it is preferable to use a powder of 8 mesh or less.

  The waste lithium ion battery powder can be obtained by a physical processing method described in Korean Patent No. 860972, which is a prior patent of the present inventor.

  In the present invention, the waste battery material may be a cathode material rejected product or a cathode active material powder scrap generated in the process of manufacturing a lithium ion battery cathode material, and is simply separated into a powder form through simple crushing and heat treatment. Then, it may be recovered with a ternary positive electrode active material powder.

The waste battery material contains a large amount of impurities in addition to valuable metals such as cobalt and lithium. Therefore, in the step (a), the waste battery material is leached using sulfuric acid and a reducing agent, and then neutralization titration is performed to remove impurities from the obtained solution.
As the reducing agent, H ₂ , H ₂ S, SO ₂ , FeSO ₄ , coal (Coal), or pyrite (Pyrite) may be used, and preferably H ₂ O ₂ may be used.

In the present invention, the neutralization titration in the step (b) includes a calcium compound selected from the group consisting of CaO, Ca (OH) ₂ and CaCO ₃ , an alkaline solution which is NaOH or NH ₄ OH, and a mixture thereof. The pH may be adjusted to 5.5 to 6.5 with a substance selected from the group consisting of, preferably CaCO ₃ may be used.

  Impurities removed from the leaching solution by neutralization titration are selected from the group consisting of Fe, Cu, Al and mixtures thereof, but impurities other than recyclable valuable metals such as Co, Mn, etc. If so, it is not limited to this.

  In the present invention, the solid-liquid separation in the step (c) can be separated into a solution and a residue using a filter press or filter paper, and the solid-liquid separation means can be easily selected by those skilled in the art.

  In the present invention, the solvent used in the step (d) is di-2-ethylhexyl phosphate, 2-ethylhexylphosphonic acid, mono-2-ethylhexyl ester, di-2,4,4-trimethylpentylphosphone. Selected from the group consisting of acid, di-2-ethylhexylphosphinic acid, di-2,4,4-trimethylpentyldithiophosphinic acid, and di-2,4,4-trimethylpentylmonothiophosphinic acid Preferably, a di-2-ethylhexyl phosphate solvent may be used.

  The solvent is preferably soaped with an alkaline solution. In this case, a 30 to 60% soaped solvent may be used, and preferably a 40 to 50% soaped solvent is used to obtain cobalt and manganese. The recovery of impurities can be increased and the generation of impurities can be minimized. In addition, when the solvent used in the solvent extraction is soaped, it is possible to prevent pH change during the solvent extraction and increase the efficiency of the solvent extraction.

この際、前記Ｃｙａｎｅｘ ２７２は、分子量２９０、粘度１４２ｃｐ（２５℃）、比重０．９２ｇｍ/ｃｃ（２４℃）及び純度８５%であり、分子式はＣ_１６Ｈ_３４ＰＯ_２Ｈであり、化学式Iのような構造を有する。

反応式（１）の反応が進行するにつれて、ステップ（ｃ）の固液分離された溶液のｐＨが減少するが、ｐＨの減少を抑制するために、溶媒抽出の際に用いる溶媒を、ＮａＯＨ、ＮＨ_４ＯＨ等のようなアルカリ溶液を用いて石鹸化した後（反応式（２））、溶媒抽出において用いた（反応式（３））。

反応式（２）は、溶媒の石鹸化過程を示した反応式であり、溶媒のＨ^＋イオンをＮａ^＋またはＮＨ_４ ^＋イオンで置換し、したがって、反応式（３）のように、溶媒によりコバルトまたはマンガンイオンが抽出されるとき、反応式（２）において置換されたＮａ^＋またはＮＨ_４ ^＋イオンが溶液上に排出されるので、溶液のｐＨ変化を防止することができる。 For example, bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, Cytec Inc., USA) is used as a solvent during solvent extraction, and cobalt and manganese extraction reaction formula (1) is as follows: It is. Here, X is Co or Mn, and R is C ₁₆ H ₃₄ PO ₂ ^— .

At this time, the Cyanex 272 has a molecular weight of 290, a viscosity of 142 cp (25 ° C.), a specific gravity of 0.92 gm / cc (24 ° C.) and a purity of 85%, a molecular formula of C ₁₆ H ₃₄ PO ₂ H, It has such a structure.

As the reaction of reaction formula (1) proceeds, the pH of the solid-liquid separated solution in step (c) decreases. In order to suppress the decrease in pH, the solvent used for solvent extraction is NaOH, After soaping using an alkaline solution such as NH ₄ OH (reaction formula (2)), it was used in solvent extraction (reaction formula (3)).

Reaction formula (2) is a reaction formula showing the process of soaping the solvent, and the H ⁺ ion of the solvent is replaced with Na ⁺ or NH ₄ ⁺ ion. Therefore, the reaction formula (3) depends on the solvent. When cobalt or manganese ions are extracted, Na ⁺ or NH ₄ ⁺ ions substituted in the reaction formula (2) are discharged onto the solution, so that pH change of the solution can be prevented.

  The washing step of step (e) of the present invention is a distillation at a temperature of 50 ° C. to 70 ° C. under the condition that the ratio of O / A (Organic / Aqueous) is 10: 1 to 1:10 with respect to the solvent-extracted extract. It can be washed with water within 1 minute, preferably with distilled water at 60 ° C. under 2: 1 O / A (Organic / Aqueous) conditions.

  In another aspect, the present invention provides (f) adding an HBr solution to the extract obtained by the cobalt and manganese recovery method and back-extracting to obtain a Co-Mn-Br removal solution; And a step of adding a cobalt salt and a manganese salt to the Co—Mn—Br removal solution to adjust the proper concentration, and producing a Co—Mn—Br liquid phase catalyst using cobalt and manganese recovered from waste battery materials Regarding the method.

  In the present invention, the “extract” may be mixed with “extract solvent extracted by Cyanex 272” or “extract solvent” and used in the method for producing the Co—Mn—Br liquid phase catalyst. As the solvent, the extract obtained in step (d) or step (e) of the cobalt and manganese recovery method may be used as the starting solvent.

  In the present invention, the waste battery material may be scrap generated in the manufacturing process of the waste lithium ion battery and the ternary positive electrode active material.

  In the present invention, the waste lithium ion battery may be in a powder state, and in the method of the present invention, it is preferable to use a powder of 8 mesh or less.

  The Co—Mn—Br removal solution obtained in the back extraction (desorption) step of the present invention does not have an appropriate amount for each component to be used as a Co—Mn—Br liquid phase catalyst. Therefore, after obtaining a removal solution with an HBr solution, an appropriate concentration of a cobalt salt and a manganese salt is additionally mixed with the removal solution, and the component ratio of the Co-Mn-Br liquid phase catalyst has an appropriate content. Can be made.

In the step (g), the cobalt salt and the manganese salt may be CoBr ₂ (cobalt bromide), MnBr ₂ (manganese bromide), and Mn (OAc) ₂ (manganese acetate), and Co—Mn— The amount added to the stripping solution to produce the Br liquid phase catalyst is such that the CMB liquid phase catalyst components Co, Mn and Br are 0.51M, 1.09M and 1.91M respectively. Can be determined by the contents of cobalt, manganese and bromine in the Co-Mn-Br removal solution obtained.

  Hereinafter, the present invention will be described in more detail through examples. These examples are merely for explaining the present invention more specifically, and it is a technical field to which the present invention belongs that the scope of the present invention is not limited by these examples due to the gist of the present invention. It will be obvious to those with ordinary knowledge in

Example 1: For the solvent extraction feed solution scrap generated in the manufacturing process of manufacturing waste lithium ion batteries powder and ternary positive electrode active material, a reducing agent H ₂ SO ₄ solution of 2M as a leachate 5~6vol Using a mixed solution of% H ₂ O ₂ as a leachate, a reaction temperature of 60 ° C., a stirring speed of 200 to 250 rpm, a solid-liquid ratio of 1:10, and a reaction time of 1 hr, 8 mesh waste lithium ion battery powder and ternary system Scrap generated during the production process of the positive electrode active material was leached with sulfuric acid reduction.

  At this time, the waste lithium ion battery powder is obtained by physical treatment disclosed in Korean Patent No. 860972, and scrap generated in the manufacturing process of the ternary positive electrode active material is subjected to simple fracture and heat treatment. The powder was separated into simple powders and used in a powder state.

In order to produce the sulfuric acid leaching solution as a solvent extraction feed solution, 150 mL of 50% CaCO ₃ solution and 25 mL of 4M NaOH solution are added to 500 mL of the leaching solution, neutralized with stirring at 400 rpm at room temperature, and then the pH is set to 5. After 5 to 6, solid-liquid separation with a filter press is performed to remove the residue containing impurities, a solvent extraction feed solution is produced, and finally the solvent extraction feed solution obtained by adjusting the pH of the leachate As a result of component analysis, it was confirmed that Cu, Fe, and Al as impurities were completely removed (Table 1).

Example 2: Solvent extraction of Co and Mn from waste lithium ion battery The soap extraction degree and washing were performed on the solvent extraction feed solution obtained from the leachate of waste lithium ion battery powder of Example 1 using Cyanex 272 solvent. In order to select the optimum Co and Mn selective extraction conditions including the number of times, the following experiment was conducted.
2-1. Extraction of Co and Mn with 40% and 50% soaped solvent of 0.7M Cyanex 272 To the solvent extraction feed solution derived from the waste lithium ion battery obtained in Example 1, NaOH was used. 0.7M bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, Cytec Inc., USA) soaped at 40% and 50% with respect to the organic phase, O / A (Organic / Aqueous) = 2: 1 (40 ml: 20 ml) was mixed and extracted once with stirring at 25 ° C. for 5 minutes.

上記した過程で抽出された溶媒に対して、さらに洗浄過程を経ることにより、抽出率がどのくらい向上するかを観察した。前記抽出された溶媒の洗浄条件は、Ｏ/Ａ＝２：１（４０ｍｌ：２０ｍｌ）の条件で、６０℃の蒸溜水を用いて１分間撹拌し、これを３回繰り返して実施した。 As a result, Co, Ni, Li, Mn, and Cu components are extracted with raffinate as shown in Table 3 due to different degrees of soaping with respect to the components of the initial solvent extraction feed solution of Table 2, As a result, the extraction ratios of Co and Mn with a soaping degree of 0.7M Cyanex 272 are 68.7% and 93.2% respectively at 40% soaping conditions, and 80.7% at 50% soaping conditions. %, 94.5% (Table 4). In addition, Cu and Al, which are impurities, showed an extremely high extraction rate, but the content in the solution is about 1 to 2 ppm, so there is no significant meaning.

It was observed how much the extraction rate was improved by further washing the solvent extracted in the above process. The extracted solvent was washed under the condition of O / A = 2: 1 (40 ml: 20 ml), stirred for 1 minute using distilled water at 60 ° C., and this was repeated three times.

As a result, it was confirmed that the remaining Ni and Li were completely removed through washing three times for all of the extraction solvents using 40% and 50% soaped solvents (Tables 5 and 6).

2-2. Preparation of removal solution using HBr solution To the extraction solvent extracted with 0.7M Cyanex 272 soaped in Example 2-1, the 2M HBr solution has a mixing ratio of O / A = 4: 1. And then removed once with stirring for 5 minutes. As a result, the removal efficiency of Co and Mn from the extraction solvent obtained under the 40% soap condition was 79.3% and 85.3%, respectively. The removal efficiency of Co and Mn was confirmed to be 85.2% and 79.4% (Tables 7 and 8).

Example 3: Solvent extraction of Co and Mn from waste ternary positive electrode active material leachate Using Cyanex 272 solvent for the solvent extraction feed solution obtained from the waste ternary positive electrode active material leachate of Example 1 In order to select the optimum Co and Mn selective extraction conditions including the degree of soaping and the number of washings, the following experiment was conducted.

Extraction of Co and Mn using 40%, 45% and 50% soaped solvent of 3-1.0.85M Cyanex272 Into the solvent extraction feed solution derived from the waste ternary positive electrode active material leachate obtained in Example 1 In contrast, 0.85M bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272, Cytec Inc., USA) soaped at 40%, 45% and 50% with NaOH was added to the organic phase. Phase / phase was mixed at a ratio of O / A (Organic / Aqueous) = 2: 1 (40 ml: 20 ml), and extracted once with stirring at 25 ° C. for 5 minutes.

As a result, as shown in Table 10, Co, Ni, Li, Mn, and Cu components were extracted as Raffinate with different degrees of soaping with respect to the components of the initial solvent extraction feed solution of Table 9, resulting in 0 The extraction ratio of Co and Mn according to the soaping degree of .85M Cyanex 272 is 56.7%, 78.8% under the 40% soaping condition, 62.1%, 84.6% under the 45% soaping condition. And 50% soaping conditions indicate 77.4% and 94.6%, and the extraction rate of Co and Mn increases with increasing soaping degree. confirmed. However, in the case of Li as an impurity, 4% is extracted under 40% soaping conditions, 3.5% is extracted under 45% soaping conditions, and 11.7% is extracted together under 50% soaping conditions. (Table 11).

  It was observed how much the extraction rate was improved by further washing the solvent extracted in the above process. The extracted solvent was washed under the condition of O / A = 2: 1 (40 ml: 20 ml), stirred for 1 minute using distilled water at 60 ° C., and this was repeated three times.

As a result, it was confirmed that the remaining Ni and Li were relatively completely removed through washing three times with respect to the extraction solvent using the 40% soaped solvent, and the 45% and 50% soaped solvents were removed. It was confirmed that the impurities were removed through the washing three times (Table 12, Table 13 and Table 14).

3-2. Preparation of removal solution using HBr solution 2M HBr solution has a mixing ratio of O / A = 4: 1 with respect to the extraction solvent extracted by 0.85M Cyanex 272 soaped in Example 3-1. Then, it was removed once with stirring for 5 minutes. As a result, the removal efficiency of Co and Mn was shown to be 97% and 84.4% at 40% soaping condition, respectively, and 86.9% and 100.7% at 45% soaping condition, In addition, in the removal reaction under 50% soaping conditions, complete removal is not performed in the first stage removal, and the second stage removal proceeds to obtain a removal liquid. Co and Mn in the second stage removal are obtained. The removal efficiency was confirmed to be 100% and 92.2% (Tables 15 and 16).

Example 3 Preparation of CMB liquid phase catalyst from removal solution In order to prepare a CMB liquid phase catalyst from the removal solution prepared in Examples 2-2 and 3-2 (Co-Mn-Br removal solution), CMB liquid was prepared. The components of the phase catalyst (CMB spec.) And the components of the prepared removal solution were measured using ion chromatography and ICP (Table 17).

As a result, each component contained in the removal solution is insufficient to constitute the CMB liquid phase catalyst, so that the CMB liquid phase catalyst is produced from the removal solution that is an intermediate product of the CMB liquid phase catalyst. In addition, cobalt bromide, manganese bromide, and manganese acetate were added. The amount of addition necessary to produce the CMB liquid phase catalyst varies depending on the extraction conditions. Were added at the concentrations in Table 18 to produce a CMB liquid phase catalyst.

Experimental example 1: Co and Mn extraction efficiency simulation test according to the degree of soaping of the solvent 1-1. Co and Mn extraction efficiency simulation from waste lithium ion battery 0.7M Cyanex 272 (Cytec Inc., USA) solvent soap for solvent extraction feed solution obtained from leachate of waste lithium ion battery powder of Example 1 Co and Mn extraction efficiency simulation tests were performed according to the degree of conversion. All solvent extraction and removal processes were carried out at O / A = 2: 1 (40 ml: 20 ml) at 25 ° C. with a stirring time of 5 minutes.

As a result of 2 step count-current extraction simulation extraction using a 40M soaped solvent of 0.7M cyanex 272, it was confirmed that the extraction rate of Co was 99.6% and Mn was 93.3%. It was. In the case of one-stage extraction, Co is 6.9%, Mn is 79.9%, and in the case of Li and Ni, all indicate a (-) extraction rate, so it is confirmed that no extraction is performed. It was done. The amounts of Co and Mn that finally escaped as raffinate were 89.3 mg / L and 0.542 mg / L, respectively (Table 19 and Table 20, FIG. 2).

1-2. Simulation of Co and Mn extraction efficiency from waste ternary positive electrode active material leachate For the solvent extraction feed solution obtained from the waste ternary positive electrode active material leachate of Example 1, 0.85M Cyanex 272 (Cytec Inc., USA) Co and Mn extraction efficiency simulation tests were conducted according to the degree of soaping of the solvent. All solvent extraction and removal processes were performed at O / A = 2: 1 (40:20 ml) at 25 ° C. with a stirring time of 5 minutes.

As a result of 2 step count-current extraction simulation extraction using a 45% soaped solvent of 0.85M cyanex 272, the extraction rate of Co was 99.8% and Mn was extracted 100%. In the case of one-stage extraction, Co is −14.1% and Mn is 55.2%. In the case of Ni as an impurity, (−) extraction rate is shown, so it is confirmed that no extraction has been performed. However, in the case of Li, it was confirmed that 0.3% was extracted. The amounts of Co and Mn that finally escaped as Raffinate were 17.48 mg / L and 1.179 mg / L, respectively, and the total amount of Li extracted was confirmed to be 18 mg / L (Table 21 and Table 22, FIG. 3).

  In conclusion, in the case of a pH adjustment solution of waste lithium ion battery leachate, selective extraction of Co and Mn is possible under the condition of 40% soaping of 0.7M cyanex 272, and the extraction rate is 99. It was confirmed that 6% and Mn were extremely high at 93.3%. In addition, Co and Mn must be extracted under the condition of 45% soaping of 0.85M cyanex 272 of waste ternary positive electrode active material leachate, and the extraction rates are 99.8% and 100%, respectively. there were.

  The specific part of the content of the present invention has been described in detail above. However, for those having ordinary skill in the art, such a specific technique is merely a preferred embodiment, and the scope of the present invention is thereby limited. It will be clear that it is not limited. Accordingly, the substantial scope of the present invention may be defined by the appended claims and their equivalents.

  According to the present invention, cobalt and manganese are recovered from scrap generated in the manufacturing process of a waste lithium ion battery and a ternary positive electrode active material. By increasing the removal rate and recovery rate of impurities, high purity cobalt and manganese are recovered. The recovered liquid is useful for use as a raw material for producing a CMB liquid phase catalyst.

Claims (7)

Leaching the waste battery material with sulfuric acid and a reducing agent;
Neutralizing titrating the leaching solution obtained in step (a) to remove impurities;
(C) separating the leaching solution obtained in step (b) into a solution and a residue;
(D) extracting by adding a solvent to the solution solid-liquid separated in the step (c);
Washing the extract obtained in step (d) with water (e);
Including
The solvent used in the solvent extraction in the step (d) is a 40-50% saponified solvent with an alkali solution, a solvent containing di-2-ethylhexyl phosphoric acid, a solvent containing 2-ethylhexyl phosphonic acid the solvent containing the mono-2-ethylhexyl ester, a solvent containing a di-2,4,4-trimethyl pentyl phosphinic acid, solvent containing di-2-ethylhexyl phosphinic acid, di-2,4,4-trimethyl pentyl dithiophosphinic the solvent containing the acid, a solvent containing a di-2,4,4-trimethylpentyl monothioglycolate phosphinic acid, and cobalt and method for recovering manganese from waste battery material, characterized in that it is selected from the group consisting of mixtures.   The method according to claim 1, wherein the waste battery material is scrap generated in the manufacturing process of the waste lithium ion battery powder or the ternary positive electrode active material. The neutralization titration in the step (b) is performed from a group consisting of a calcium compound selected from the group consisting of CaO, Ca (OH) ₂ and CaCO ₃ , an alkali solution which is NaOH or NH ₄ OH, and a mixture thereof. The method according to claim 1, wherein the pH is adjusted to 5.5 to 6.5 depending on a substance selected.   The method of claim 1, wherein the impurities in step (b) are selected from the group consisting of Fe, Cu, Al, and mixtures thereof. (F) adding an HBr solution to the extract obtained from claim 1 and back-extracting to obtain a Co-Mn-Br removal solution;
(G) adding a cobalt salt and a manganese salt to the Co—Mn—Br removal solution to adjust an appropriate concentration;
A method for producing a Co—Mn—Br liquid phase catalyst using cobalt and manganese recovered from a waste battery material.   6. The method for producing a Co—Mn—Br liquid phase catalyst according to claim 5, wherein the waste battery material is scrap generated in the production process of waste lithium ion battery powder or ternary positive electrode active material.   The extract obtained from claim 1 in step (f) is obtained in step (d) or step (e) according to claim 1, and is Co-. A method for producing a Mn—Br liquid phase catalyst.

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