KR20090087801A - Process for recovering valuable metals from CO, Ni, Mn-containing lithium battery waste - Google Patents

Abstract

Valuable metals such as Mn, Co, Ni, and Li are recovered from the ternary Li metal salt from the lithium battery dregs.

Lithium battery residues containing lithium acid metal salts containing almost equal amounts of Co, Ni and Mn are stirred and leached with a hydrochloric acid solution at a concentration of at least 250 g / l, or heated to 65-80 ° C. with a sulfuric acid solution at a concentration of at least 200 g / l. Stirring leaching or stirring leaching with a solution of a sulfuric acid solution having a concentration of 200 g / l or more and a hydrogen peroxide solution of 20 g / l or more, and acid extraction of at least 98% of the three metals of Mn, Co and Ni to the leaching solution Zero solvent extraction produces a solution containing each metal, and valuable metals such as Mn, Co, Ni, and Li are recovered from these solutions and the residue containing Li after extraction.

Description

Process for recovering valuable metals from CO, Ni, Mn-containing lithium battery residues {METHOD FOR RECOVERING VALUABLE METAL FROM LITHIUM BATTERY WASTE CONTAINING Co, Ni, AND Mn}

The present invention relates to a valuable metal recovery method from Co, Ni, Mn-containing lithium battery waste. Co, Ni, Mn-containing lithium battery waste is a slurry-like substance composed of a ternary Li metal salt and a solvent such as carbon, N-methyl-2-pyrrolidone, polyvinyl alcohol, and the like in the lithium secondary battery manufacturing process. It is the waste which arises for the reason that it cannot load when each material is loaded in a predetermined part. The treatment of lithium metal oxides present in these battery wastes and containing valuable metals is important from the viewpoint of valuable metal recovery.

Patent Document 1: Japanese Patent Laid-Open No. 6-251805 discloses that in 1993 at the time of filing, a lithium secondary battery has not yet been developed, but is prepared for recycling of a lithium secondary battery prior to development. In this method, a used lithium battery is cut by water jet, and the solid separated from the liquid by filtration is sorted by a separator, a current collector, and a positive electrode material. They explain that they can be melted or pulverized and reused depending on the material. In addition, as metals of the metal oxides used as the positive electrode materials, various metals such as Ni, Co, Ti, Fe, V, Mn, Mo, Cr, and W are listed, but not all of these metals are used. The metal is Co.

Patent Document 2: Japanese Unexamined Patent Application Publication No. 2006-331707 proposes a lithium battery recycling method comprising a number of steps, and at the stages before and after the recovery of the positive electrode material, the wound body, the positive electrode, the negative electrode, and the separator are mechanically separated and the positive electrode is acetic acid. It is immersed in aqueous solution, the positive electrode base material (aluminum) and a positive electrode active material are isolate | separated, the positive electrode active material is immersed in a hydrochloric acid solution, and it melt | dissolves, and a solution is filtered and metal ion mixed solutions, such as Li and Ni, are obtained. Subsequently, the respective metals are recovered from the mixed solution using methods such as ion exchange, electrolysis, and precipitation separation.

Patent Document 3: Japanese Patent No. 3450684 is a 1997 application in which a lithium secondary battery is mounted on various electronic devices, and discloses a method for recovering Mo, Co, Ni, Sn, etc. from the positive electrode active material of a used lithium battery. I'm proposing. Specifically, roasting is carried out together with the iron case without disassembling the used lithium battery, and pulverized into a roasted product; Primary magnetic separation; Secondary magnetic screening is conducted for nonmagnetic materials.

Since Co used for a positive electrode is expensive, the technique development which uses the lithium acid metal salt containing nearly equivalent Co, Ni, and Mn as a positive electrode active material is performed in recent years. For example, Japanese Patent Application Laid-Open No. 2007-48692 discloses manganese dioxide, cobalt oxide, nickel oxide and lithium carbonate in a Ni: Mn: Co ratio of 1: 1: 1, and Li: (Ni, Mn , Co) ratio is measured to be 1.06: 1, these compounds are mixed with a polyvinyl alcohol solution, and then granulated, dried and calcined. The calcined ternary metal Li double oxide is mixed with a binder and a solvent to prepare a slurry-like positive electrode active material.

The positive electrode active material of the nickel-hydride battery is nickel oxyhydroxide (NiOOH), and is not a lithium acid metal which is a positive electrode active material of a lithium battery. Patent Document 5: Japanese Patent Laid-Open No. 10-510878 discloses a method for recovering a metal from such a nickel-hydride battery. That is, (1) the waste battery is shredded with a shredder; (2) Fe and Ni are separated by magnetically screening the obtained scrap; (3) dissolving the nonmagnetic material with sulfuric acid; (4) Fe is separated by pH adjustment; (5) Zn, Cd, Mn, and Al are extracted by extracting the filtrate which isolate | separated Fe by filtration by the organic solvent.

Compared with the positive electrode material, C, Al, Si, etc. included in the negative electrode material together with Li are not valuable metals, and the recovery cost is higher than the raw material cost. However, these negative electrode materials may also be contained in battery waste.

The present applicant has proposed the recovery method described in paragraph No. 0001 in Patent Document 6: Japanese Patent Application No. 2007-74089 (filed March 22, 2007). However, the only metals extracted in the organic solvent by this method were Mn and Co.

<Patent Document 1> Japanese Unexamined Patent Publication No. 6-251805

Patent Document 2: Japanese Unexamined Patent Publication No. 2006-331707

<Patent Document 3> Japanese Patent No. 3450684

Patent Document 4: Japanese Unexamined Patent Publication No. 2007-48692

<Patent Document 5> Japanese Patent Application Laid-open No. 10-510878

<Patent Document 6> Japanese Patent Application No. 2007-74089 (filed March 22, 2007)

Non-Patent Document 1: Resources and Materials, 1997, 12, Vol. 113, Recycling Special Issue, page 941

<Non-Patent Document 2> Lectures / Modern Metallurgical Studies, Refining Part 2, Non-Ferrous Metal Smelting, July 10, 1982, Published by Metal Society, pp. 240-241

Recycling of the battery includes a method of recycling the battery as it is, as in Patent Documents 3 and 5, and a method of decomposing and recovering the battery into respective constituent members or materials, as Patent Documents 1 and 2 suggest. This invention is a recycling method of the slurry-like battery waste containing the said positive electrode material which arises from a battery manufacturing process, and does not belong to any of these.

An object of the present invention is to provide a method for recovering a valuable metal from Co, Ni, and Mn-containing Li acid metal salts contained in battery waste of a lithium battery.

According to the first method of the present invention, a lithium battery residue containing a lithium acid metal salt containing Co, Ni, and Mn is stirred and leached with a hydrochloric acid solution having a concentration of 250 g / l or more, and 98 Mn, Co, and Ni are added to the leaching solution. Solvent extraction with at least% by acid extraction agent to produce three kinds of solutions containing the respective metals, and recovering the metals from these solutions, valuable metal recovery method from Co, Ni, Mn-containing lithium battery waste ,

In the second method, the lithium battery residue containing lithium metal salt containing Co, Ni and Mn is heated and leached with a sulfuric acid solution having a concentration of 200 g / l or more, and 98% or more of Mn, Co and Ni are added to the leach solution. Solvent extraction with an acidic extractant to produce three kinds of solutions containing the respective metals, and recovering the metals from these solutions.

In the third method, lithium flakes containing lithium metal salt containing Co, Ni, and Mn are stirred and leached with a solution obtained by mixing a sulfuric acid solution having a concentration of 200 g / l or more and a hydrogen peroxide solution of 20 g / l or more, Solvent extraction of at least 98% of Mn, Co, and Ni with an acidic extractant to produce three solutions containing the respective metals, and recovering the metals from these solutions. It is a method of recovering valuable metals from waste.

By the way, both the use of Co-based compounds as positive electrode active materials for batteries of electronic devices and the use of lithium acid metal salts (hereinafter referred to as "ternary Li metal salts") containing almost equal amounts of Mn, Co and Ni are available on the market. We can fully think that the state will continue. In this case, the relative amount of Co of the lithium battery waste increases. Such battery residues can also be acid leached by the present invention, followed by solvent extraction to recover valuable metals. However, in the following description, the treatment of ternary Li metal salt is mainly described.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The battery residue is a slurry-like substance composed of a ternary Li metal salt and a solvent such as carbon, N-methyl-2-pyrrolidone, polyvinyl alcohol, or the like, and is a residue generated in a lithium secondary battery manufacturing process. The metal composition is generally 10-12 mass% Co, 10-12 mass% Ni, 10-12 mass% Mn, and 4-5 mass% Li.

The present inventors leached the battery debris of the ternary Li metal salt under the following conditions, and as a result, the sulfuric acid solution, the hydrochloric acid solution, and the sulfuric acid and hydrogen peroxide mixed solution were found to be effective for all leaching of Co, Ni, Mn, and Li.

(A) Battery residues: those described in paragraph No. 0005; 200 g.

(B) Leachate: Various acids of concentration shown in Table 1; Capacity 2000 mL.

(C) leaching time: 4h to 8h

(D) Temperature: Heating to room temperature or 65 to 80 ℃.

(E) Stirring: Yes.

The results of the test are shown in Table 1.

Acid solution Leaching Method Co (g / l) Ni (g / l) Mn (g / l) Li (g / l) Co leaching rate (%) Ni leaching rate (%) Mn leaching rate (%) Li leaching rate (%) 150g / l sulfuric acid 70-80 ° C heating + stirring (8h) 10.5 10.7 9.8 4.3 95 97 89 100  200g / l sulfuric acid 70-80 degreeC heating + stirring (8h) 11.0 11.0 11.0 4.3 100 100 100 100  300g / l sulfuric acid 70-80 degreeC heating + stirring (6h) 11.0 11.0 11.0 4.3 100 100 100 100 300g / l sulfuric acid 65-70 degreeC heating + stirring (8h) 11.0 11.0 11.0 4.3 100 100 100 100 500g / l sulfuric acid 70-80 degreeC heating + stirring (4h) 11.0 11.0 11.0 4.3 100 100 100 100 1000g / l sulfuric acid Stirring (4h) 2.8 2.9 2.8 2.2 25 26 25 51 200 g / l hydrochloric acid Stirring (8h) 10.0 10.0 10.0 4.3 91 91 91 100 250 g / l hydrochloric acid Stirring (4h) 11.0 11.0 11.0 4.3 100 100 100 100 200g / l sulfuric acid 20g / l hydrogen peroxide Stirring (4h) 11.0 11.0 11.0 4.3 100 100 100 100

The leaching of the binary Li metal salt was as follows.

(1) If it is 8 hours stirring leaching, heating at 70-80 degreeC, 100% of Co, Ni, Mn, and Li can be leached also with 200 g / l sulfuric acid aqueous solution. Leaching is possible even at a temperature of 80 ° C. or higher, but a purification facility for evaporated sulfuric acid is required. In addition, if it is 300 g / l sulfuric acid aqueous solution, the same leaching rate can be achieved by performing sulfuric acid leaching at 65-70 degreeC for 8 hours.

(2) In leaching only with stirring, the leaching rate is 100 for Co, Ni, Mn, and Li if the aqueous solution of hydrochloric acid at a concentration of 250 g / l or more and a mixed aqueous solution of sulfuric acid at a concentration of 200 g / l or more and hydrogen peroxide at a concentration of 20 g / l or more. %to be.

As described above, when the sulfuric acid aqueous solution having a concentration of 200 g / l or more is subjected to heat leaching, the leaching rate of 100% can be achieved.

Next, about leaching only by stirring, the leaching rate of 100% can be achieved if it is the aqueous solution of hydrochloric acid of 250 g / l or more concentration, and the mixed aqueous solution of sulfuric acid of 200 g / l or more concentration and hydrogen peroxide of 20 g / l or more concentration.

In addition, in the case of leaching these aqueous hydrochloric acid solutions or leaching sulfuric acid / hydrogen peroxide mixed solution, the heating of the leaching liquid does not interfere.

In Table 1, the leaching rate is 100% in the laboratory. In the practice on an industrial scale, in the case of recycling the battery residue at 100 tons / month or more, a leaching rate of 98 to 100% can be achieved by adding a measurement error. The leachate produced as a result of leaching contains ternary metal ions, and the residue consists mainly of organic or inorganic carbon. Such carbon is poorly soluble to sulfuric acid and hydrochloric acid and remains as a solid, but since carbon and the like are not recoverable, the residue after leaching is disposed of or incinerated.

Stirring can be performed by arbitrary means, such as a rotating blade, so that a slurry battery residue may be disperse | distributed uniformly in a leach liquid.

In recovering Co, Ni, Mn, and Li contained in the liquid after leaching, Li is separated by solvent extraction of three metals of Mn, Co, and Ni. As an extractant which solvent-extracts these, For example, Nonpatent literature 1: a resource and a material, 1997, 12, Vol. 113, "Recycling Great Special Issue", page 941, Table 1 can be used a known acidic extractant.

It is preferable to use D2EHPA manufactured by LANXESS Corporation as the Mn extractant, and PC-88A manufactured by Daihachi Chemical Co., Ltd. as the extractant of Co and Ni. D2EHPA is di2-ethylhexyl phosphoric acid and is a Mn extractant known from Non-Patent Document 1. PC-88A is a 2-ethylhexyl 2-ethylhexyl hosehonate system, the information of which can be obtained from 1202884345093_1.pdf.

About the metal recovery method from the solution after extraction, it collect | recovers by the actual method described below, or it is sold as a valuable metal containing resource, and it processes as a subsidiary raw material in the well-known wet refining process which collects these metals, and a metal It is possible to recover.

About Co: Electrolytic Sampling of Co Chloride.

About Mn: Electrolytic Sampling of Mn Sulfate.

For Ni: Ni electrolysis by chlorine leaching.

As another method of metal recovery, a method of precipitating a metal salt by neutralizing a sulfuric acid acid solution, which is a liquid extracted back after solvent extraction, and employing a method of recovering the metal salt as a solid by filtration. Subsequently, such a metal salt may be sold to a metal refining company as a metal raw material. Alternatively, if the concentration of the metal salt is concentrated several times higher than the concentration in the liquid after extraction of the solvent, and then recovered by electrolytic collection, recycling from battery waste to metal regeneration can be performed consistently. Electrolytic sampling of Ni, Co, and Mn is, for example, nonpatent literature 2: lectures and modern metallurgy, refining piece 2, nonferrous metal smelting, the conditions described in the July 10, 1982 edition of the Metal Society, pp. 240-241. This can be done.

Subsequently, a method of solvent extraction of Mn, Co, and Ni by DE2HPA and PC-88A will be described in detail with reference to FIGS. 1, 2, and 3, respectively.

Extraction of Mn

Solvent extraction is performed by mixing a kerosene (kerosene) mixed solution of DE2HPA with a Co-Ni-Mn-Li solution (i.e., after leaching, see FIG. 1), a site flow and a separatory tank equipped with a stirrer. Caustic soda is added to adjust the pH to 2-3.

Thereafter, extraction with a solvent is carried out again, whereby only Co-Ni-Li remains in the solution. The solvent flows into the extraction 3, extraction 2 and extraction 1 in the reverse direction to the solution (countercurrent multistage extraction). Among the solvents after extraction Mn because it contains also some Co by 10g / l H ₂ S0 ₄ Co is cleaned.

Subsequently, back-extraction is performed with 50 g / l sulfuric acid aqueous solution, and Mn is concentrated in sulfuric acid aqueous solution ("Mn solution"). Back extraction is carried out in two steps, and the solvent is reused in extraction 3. Caustic soda or sodium carbonate is added to the Mn solution for neutralization, and the liquid and precipitation after neutralization are filtered to recover Mn as Mn (OH) ₂ and MnCO ₃ . The washing liquid is added to the Co-Ni-Mn-Li solution before extraction.

Extraction of Co

Solvent extraction is carried out by mixing a kerosene (kerosene) mixed solution of PC-88A with a Co-Ni-Li solution (i.e., a solution after Mn extraction, see FIG. 2), a site flow and a stirrer. Caustic soda is added to adjust the pH to 4-5.

Thereafter, extraction with a solvent is carried out again, whereby only Ni remains in the solution. The solvent flows in the reverse direction from the solution to extraction 3, extraction 2 and extraction 1 (countercurrent multistage extraction). Because it also contains some Ni during Co solvent after extraction by 10g / l H ₂ SO ₄ Ni is cleaned.

Subsequently, back extraction is performed with 50 g / l sulfuric acid aqueous solution, and Co is concentrated in sulfuric acid aqueous solution ("Co solution"). Back extraction is carried out in two steps, and the solvent is reused in extraction 3. Caustic soda or sodium carbonate is added to the Co solution for neutralization, and the liquid and precipitation after neutralization are filtered and Co is recovered as Co (OH) ₂ and CoC0 ₃ . The cleaning liquid is added to the Co-Ni-Li solution before extraction.

Extraction of Ni

Solvent extraction is carried out by mixing a kerosene (kerosene) mixture of PC-88A with a Ni-Li solution (i.e., after Co extraction, see Fig. 3), a site flow, and a separator with a stirrer. Caustic soda is added to adjust the pH to 6-7.

Thereafter, extraction with a solvent is performed again, thereby leaving only Li in the solution. The solvent flows into extraction 3, extraction 2 and extraction 1 in the reverse direction to the solution (countercurrent multistage extraction). Li is washed by 10 g / l H ₂ SO ₄ because some Li is included in the solvent after Ni extraction.

Subsequently, back extraction is performed with 50 g / l sulfuric acid aqueous solution, and Ni is concentrated in sulfuric acid aqueous solution ("Ni solution"). Back extraction is carried out in two stages, and the solvent is reused in extraction 3. Caustic soda or sodium carbonate is added to the Ni solution for neutralization, and the liquid and precipitation after neutralization are filtered to recover Ni as Ni (OH) ₂ and NiCO ₃ . The cleaning liquid is added to the Ni-Li solution before extraction.

Table 2 shows the general ranges of Co, Ni, Mn, and Li concentrations obtained by the above solvent extraction and the concentrations of the examples. Metal may each number Mn (OH) ₂ or MnCO ₃ and, Co (OH) ₂ or CoCO ₃ and, Ni (OH) ₂ or NiC0 ₃ and, Li (OH) ₂ or a LiCO ₃ by neutralization.

Co concentration (g / l) Ni concentration (g / l) Mn concentration (g / l) Li concentration (g / l) Mn-containing solution <0.01 <0.01 44 <0.01 Co-containing solution 35 <0.01 <0.01 <0.01 Ni-containing solution <0.01 32 <0.01 <0.01 Li-containing solution <0.01 <0.01 <0.01 2.9

In the above point, preferable embodiment of this invention is as follows.

(1) A method of acidic solvent extraction of Mn, Co and Ni.

(2) A method of separating metals as solids by precipitating and filtering Mn, Co, Ni and Li by adjusting the pH of the solution after back extraction and the solution containing Li after recovering Co, Ni, and Mn.

(3) The method of (2), wherein the solid metal is redissolved in the electrolytic solution and electrolytically collected.

(1) Since the ternary metal Li salt-based positive electrode active material can be recycled in a slurry state, energy for solidifying lithium battery waste is unnecessary. In addition, since the ternary metal Li salt in the slurry is in a particulate state, the contact area with the leach liquid is large and the leach efficiency is high.

(2) Co, Ni, Mn, and Li can be leached entirely. On the other hand, carbon etc. other than this become a residue and isolate | separates from the said 4 types of metal.

(3) Since dilute sulfuric acid or dilute hydrochloric acid is used, the burden on the environment is small.

(4) Li is dissolved in the leachate, but can be separated from other valuable metals by extracting and separating other valuable metals (they remain in the liquid even after Ni is extracted from the Ni solution). After Mn, Co, and Ni are separated in the solvent extraction, Li remains in the filtrate and is separated.

Leaching and solvent extraction were performed for 100 g of ternary metal Li salt-containing paste (co 11%, Ni 11%, Mn 11%, Li 4.3% or less, simply referred to as "paste"). In the test described below, extraction time was stirred for 10 minutes, back extraction time was stirred for 10 minutes, and washing was performed for 10 minutes with stirring.

(1) leaching

The paste was put into 1000 L of 300 g / l sulfuric acid aqueous solution, stirred for 4 hours while heating to 70 to 80 ° C., and then filtered. Thereafter, 10 g of residue remained in the dried state. The metal concentration in 1000 L of filtrate was shown in the following table, and 100% of the leaching was possible.

Filtrate Co Ni Mn Li Concentration (g / l) 11 11 11 4.3 Distribution rate (%) 100 100 100 100

(2) Mn extraction

After neutralization with a 25% NaOH solution to the filtrate, solvent extraction of Mn was performed. The solution after neutralization was 1290L. The solvent extractant was 1290 L of a kerosene solution of D2EHPA manufactured by LANXESS, which was stirred with a solution after neutralization and adjusted to pH = 2.5 with a 25% NaOh solution (O / A ratio = 1/1). As a result of the solvent extraction, 1290 L of Mn extract and 1340 L of Co-Ni-Li solution were obtained. The Mn extract (containing some Co) is washed with 10 g / l H ₂ SO ₄ , then back extracted with an aqueous 50 g / l sulfuric acid solution to concentrate Mn in an aqueous sulfuric acid solution (Mn solution). 1340 L of Co-Ni-Li solution (metal concentration is shown in Table 4) and 250 L of Mn solution (metal concentration are shown in Table 5) were obtained.

Co-Ni-Li Solution Co Ni Mn Li Concentration (g / l) 8.0 8.1 <0.01 3.1 Distribution rate (%) 99 100 0 100

Mn solution Co Ni Mn Li Concentration (g / l) <0.01 <0.01 44 <0.01 Distribution rate (%) 0 0 99 0

Solvent extraction of Co was performed with respect to Co, Ni, and Li solution shown in Table 4. The solvent extractant was 1340L of a kerosene solution from Daihachi Chemical Co., Ltd. PC-88A, which was stirred with a solution after neutralization and adjusted to pH = 4.2 with a 25% NaOH solution (O / A ratio = 1/1). As a result of the solvent extraction, 1340L of Co extract and 1390L of Ni-Li solution were obtained. The Co extract (containing some Ni) is washed with 10 g / l H ₂ SO ₄ , and then back extracted with an aqueous 50 g / l sulfuric acid solution to concentrate Co in the aqueous sulfuric acid solution (Co solution). 1390 L of Ni-Li solution (metal concentration is shown in Table 6) and 250 L of Co solution (metal concentration are shown in Table 7) were obtained.

Ni-Li solution Co Ni Mn Li Concentration (g / l) <0.01 7.8 <0.01 3.0 Distribution rate (%) 0 99 0 100

Co solution Co Ni Mn Li Concentration (g / l) 43 <0.01 <0.01 <0.01 Distribution rate (%) 98 0 0 0

Solvent extraction of Ni was performed with respect to the Ni and Li solutions shown in Table 6. The solvent extracting agent was 1390L of the kerosene solution of Daihachi Chemical Co., Ltd. PC-88A, which was stirred with the solution after neutralization and adjusted to pH = 6.5 with 25% NaOH solution (O / A ratio = 1/1). As a result of the solvent extraction, 1390L of Ni extract and 1410L of Li solution were obtained. The Ni extract (containing a little Li) is washed with 10 g / l H ₂ SO ₄ , and then back extracted with an aqueous 50 g / l sulfuric acid solution to concentrate Ni in the aqueous sulfuric acid solution (Ni solution). 1410 L of Li solution (metal concentration is shown in Table 8) and Ni solution 250 L (metal concentration are shown in Table 9) were obtained.

Li solution Co Ni Mn Li Concentration (g / l) <0.01 <0.01 <0.01 2.9 Distribution rate (%) 0 0 0 99

Ni solution Co Ni Mn Li Concentration (g / l) <0.01 32 <0.01 <0.01 Distribution rate (%) 0 98 0 0

As described above, all of Mn, Co, Ni, and Li could be separated. Moreover, although the example of sulfuric acid leaching was demonstrated, since the whole metal can be leached also in hydrochloric acid leaching, subsequent solvent extraction will have the same result.

In the prior art, there was no recycling method for battery residues using a ternary metal Li salt as a positive electrode active material, but storage and the like were carried out in a warehouse. However, when the battery residues are leached with sulfuric acid or hydrochloric acid according to the present invention, valuable metals can be recovered. do. The same test was conducted using Co, Ni, and Mn-containing lithium battery waste not in slurry form, but the same result was obtained. Moreover, since the solvent extraction method is employ | adopted as the method of this invention, even if a Co type positive electrode active material mixes in a battery waste, valuable metals can be recovered without a problem, and it is easy to develop a recycling business.

1 is a flow chart showing a solvent extraction process of Mn.

2 is a flowchart illustrating a solvent extraction process of Co.

3 is a flowchart showing a solvent extraction process of Ni;

Claims (7)

Lithium battery residues containing lithium acid metal salts containing Co, Ni and Mn were stirred and leached with a hydrochloric acid solution having a concentration of 250 g / l or more, and 98% or more of Mn, Co and Ni were solvent-extracted with the acid extractant to the leaching solution. A method for recovering valuable metals from Co, Ni, and Mn-containing lithium battery wastes, wherein three kinds of solutions containing respective metals are produced and the metals are recovered from these solutions. Lithium battery residues containing lithium acid metal salts containing Co, Ni and Mn were heated and leached with sulfuric acid solution having a concentration of 200 g / l or more, and solvent extraction with at least 98% of Mn, Co and Ni was performed with an acidic extractant. To produce three kinds of solutions containing the respective metals, and recovering the metals from these solutions. The method for recovering valuable metals of Co, Ni, and Mn-containing lithium battery wastes. Lithium battery residues containing lithium acid metal salts containing Co, Ni and Mn were stirred and leached with a solution of a sulfuric acid solution having a concentration of 20Og / l or more and a hydrogen peroxide solution of 20g / l or more, and Mn, Co and Valuable metals from Co, Ni, and Mn-containing battery scraps characterized by solvent extraction of at least 98% of Ni with an acidic extractant to produce three solutions containing the respective metals and recovering the metals from these solutions. Recovery method. The method for recovering valuable metals from Co, Ni, and Mn-containing battery scraps according to any one of claims 1 to 3, wherein Mn, Co, and Ni are solvent-extracted with an acidic extractant. 5. The method for recovering valuable metals from Co, Ni, and Mn-containing lithium battery scraps according to claim 4, wherein Mn, Co, and Ni are recovered as a solid by precipitating and adjusting pH after solvent extraction. The method for recovering valuable metals from Co, Ni, and Mn-containing lithium battery wastes according to claim 5, wherein the solids are redissolved in an electrolytic solution and electrolytically collected. The valuable metal from Co, Ni, Mn-containing lithium battery wastes according to claim 4, wherein the remaining liquid from which Co, Ni, and Mn are extracted by solvent extraction is recovered as a solid by precipitating Li and filtering by adjusting the pH. Recovery method.

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