Method for preparing nickel-cobalt-manganese composite solution

Abstract

An aspect of the present invention is to provide a method for preparing a high-concentration nickel-cobalt-manganese composite solution, and another aspect of the present invention is to provide a method for preparing a high-concentration nickel-cobalt-manganese composite salt. In addition, through the method for preparing a nickel-cobalt-manganese composite solution, sodium sulfate inevitably generated during a solvent extraction process can be reduced, and the scale of equipment required for the process can be reduced.

Description

Method for preparing a nickel-cobalt-manganese complex solution

[0001] The present invention relates to a method for preparing a nickel-cobalt-manganese composite solution. More specifically, the present invention relates to a method for preparing a nickel-cobalt-manganese composite solution from black mass or alloy generated from spent ternary cathode materials of secondary batteries.

[0002] Solvent extraction is widely used to extract specific components from mixtures. For example, it is used to extract a specific metal from a solution containing a mixture of various metal ions, or to extract a specific component from a solution containing a mixture of various substances.

[0003] In particular, as the electric vehicle market grows rapidly, the industry for recovering valuable metals such as lithium, nickel, cobalt, and manganese from spent batteries is gradually developing. To recover valuable metals from spent batteries, it is first necessary to obtain black mass, which is mainly composed of components of positive and negative active materials, through pretreatment processes such as discharge, dismantling, heat treatment, and crushing. Alternatively, the metal components of the negative active material can be obtained in the form of an alloy by heat-treating a large quantity of spent batteries at high temperatures. Subsequently, a solution containing a mixture of various metals can be obtained from the black mass or alloy by using strong acids such as sulfuric acid or hydrochloric acid as leaching agents. Then, the individual valuable metals are separated and recovered through a solvent extraction process using metal extractants such as D2EHPA, PC88A, LIX 984, and Cyanex272.

[0004] Meanwhile, sodium sulfate is generated as a byproduct in the manufacturing of secondary battery materials and the recycling process of waste batteries, and the amount of sodium sulfate generated in these fields is expected to reach approximately 1.2 million tons by 2030. Low-grade sodium sulfate, which is a byproduct, may contain various impurities, making recycling difficult. Although processes to recycle sodium sulfate or produce caustic soda and sulfuric acid through electrolysis are currently under development, there are difficulties in developing economically viable commercial processes due to the low price of sodium sulfate.

[0005] According to one embodiment of the present invention, a method for producing a high concentration nickel-cobalt-manganese complex solution while reducing by-products such as sodium sulfate can be provided.

[0006] The problems of the present invention are not limited to those described above. A person skilled in the art to which the present invention pertains will have no difficulty understanding additional problems of the present invention from the overall contents of this specification.

[0007] A method for preparing a nickel-cobalt-manganese composite solution according to one embodiment of the present invention may include the step of preparing a metal leaching solution; the copper removal step of separating and recovering copper from the metal leaching solution; the iron and aluminum removal step of removing iron and aluminum from the metal leaching solution; and the impurity removal step of removing impurities from the metal leaching solution to obtain a nickel-cobalt-manganese composite solution, wherein the iron and aluminum removal step may use one or more of nickel carbonate (NiCO3), nickel hydroxide (Ni(OH)2), calcium hydroxide (Ca(OH)2), and magnesium hydroxide (Mg(OH)2) as a neutralizing agent.

[0008] The method for preparing the nickel-cobalt-manganese composite solution described above may be characterized in that sodium salts are not used in the copper removal step and the iron and aluminum removal step described above. In this case, the sodium salts may include sodium hydroxide and sodium carbonate.

[0009] The step of preparing the metal leaching solution described above may include a step of obtaining metal powder by crushing a black mass or alloy; and a first atmospheric pressure leaching step of leaching the metal powder.

[0010] In addition, a method for preparing a nickel-cobalt-manganese composite solution according to another embodiment of the present invention may additionally include a second atmospheric pressure leaching step and a pressurized leaching step after the first atmospheric pressure leaching. At this time, the leaching solution used in the second atmospheric pressure leaching has a higher concentration than the leaching solution used in the first atmospheric pressure leaching step, and the pressurized leaching step may be performed under pressurized conditions of oxygen 2 bar or more and 20 bar or less.

[0011] In the copper removal step described above, nickel metal powder or nickel sulfide powder may be added to the metal leaching solution.

[0012] The amount of the nickel metal powder or nickel sulfide powder introduced may be 2 to 8 times the copper equivalent, and the copper removal step may be performed at a temperature range of 50°C to 90°C for a period of 0.5 hours to 5 hours.

[0013] The copper removal step described above may involve adding a LIX-based metal extractant to the metal leaching solution.

[0014] The impurity removal step described above may utilize a solvent extractant pre-loaded with nickel, and the solvent extractant pre-loaded with nickel may be obtained through a step of saponifying the solvent extractant using an aqueous sodium hydroxide solution at a saponification rate of 20% or more and 60% or less; and a step of pre-loading the solvent extractant in an aqueous nickel solution at least once and no more than five times.

[0015] The method for preparing the nickel-cobalt-manganese composite solution described above may additionally include a step of adjusting the amounts of nickel, cobalt, and manganese by adding one or more of nickel, cobalt, and manganese sulfates to the nickel-cobalt-manganese composite solution after the impurity removal step.

[0016] A method for preparing a nickel-cobalt-manganese composite salt according to another embodiment of the present invention may include the step of drying a nickel-cobalt-manganese composite solution prepared according to the above description.

[0017] The drying step described above may include the step of obtaining a solid phase by evaporating the nickel-cobalt-manganese composite solution under reduced pressure; and the step of centrifuging and drying the solid phase to obtain the nickel-cobalt-manganese composite salt, and the nickel-cobalt-manganese composite salt may be nickel-cobalt-manganese sulfate.

[0018] The drying step described above may include the step of adding a precipitating agent and a chelating agent to the nickel-cobalt-manganese composite solution and precipitating to obtain a precipitate; and the step of filtering the precipitate to obtain the nickel-cobalt-manganese composite salt, wherein the precipitating agent may be one or more of sodium carbonate (Na2CO3) and sodium hydroxide (NaOH), the chelating agent may be one or more of NH3H2O ​​and NH4HCO3, and the nickel-cobalt-manganese composite salt may be one or more of nickel-cobalt-manganese carbonate and nickel-cobalt-manganese hydroxide.

[0019] The precipitation temperature in the step of obtaining the above precipitate may be 30°C or higher and 60°C or lower, and the precipitation pH may be 7.0 or higher and 12.0 or lower.

[0020] In addition, the nickel-cobalt-manganese composite salt obtained according to the above description can be used as a cathode material for lithium-ion batteries.

[0021] The present invention provides a method for preparing a high-concentration nickel-cobalt-manganese composite solution.

[0022] In addition, through the method of preparing the nickel-cobalt-manganese composite solution described above, sodium sulfate, which is inevitably generated during the solvent extraction process, can be reduced, and the process can be simplified by omitting the individual separation process of valuable metals.

[0023] FIG. 1 is a flowchart briefly illustrating a nickel-cobalt-manganese composite solution manufacturing process according to one embodiment of the present invention and a conventional nickel-cobalt-manganese composite solution manufacturing process.

[0024] Figure 2 is a graph showing (a) the copper extraction rate (%) according to pH in the aqueous phase, (b) the copper concentration (g / mL) in the raffinate according to the water at an equilibrium pH of about 1.1 when ion extraction is performed using 14 vol.% LIX973, and (c) the copper extraction rate (%) according to the O / A ratio when ion extraction is performed using 14 vol.% LIX973.

[0025] Figure 3 is a graph showing the McCabe figure during the copper removal step.

[0026] Figure 4 is a graph showing (a) the removal efficiency (%) of aluminum according to pH change and (b) the removal efficiency (%) of iron according to pH change.

[0027] Figure 5 is a graph showing one example of an impurity removal process.

[0028] Figure 6 is a graph showing the change in concentration of nickel and sodium in the organic phase after removing the organic phase sampled over time with an aqueous sulfuric acid solution while operating the Ni pre-extraction process.

[0029] Figure 7 is a graph showing the concentrations (mg / L) of nickel, cobalt, manganese, and sodium in the Raffincate NCM complex solution formed after extraction and removal of impurities.

[0030] Preferred embodiments of the present invention will be described below with reference to the attached drawings. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

[0031] In addition, embodiments of the present invention are provided to more fully explain the present invention to those with average knowledge in the relevant technical field.

[0032] In describing the embodiments of the present invention, if it is determined that a detailed description of known technology related to the present invention may unnecessarily obscure the essence of the present invention, such detailed description will be omitted. Furthermore, the terms described below are defined considering their functions in the present invention, and these may vary depending on the intentions or conventions of the user or operator. Therefore, such definitions should be based on the content throughout this specification. The terms used in the detailed description are merely for describing the embodiments of the present invention and should not be limited in any way. Unless explicitly stated otherwise, expressions in the singular form include the meaning of the plural form.

[0033] In this description, expressions such as “include” or “equipped” are intended to refer to certain characteristics, numbers, steps, actions, elements, parts or combinations thereof, and should not be interpreted to exclude the existence or possibility of one or more other characteristics, numbers, steps, actions, elements, parts or combinations thereof other than those described.

[0034] Unless otherwise specifically defined in the specification of the present invention, % units mean weight %.

[0035] The present invention will be described in detail below through each embodiment or example of the invention. It should be noted that each embodiment or example described in this specification is not limited to a single embodiment or example, but may also be combined with other embodiments or examples. Accordingly, the citation of claims in the patent claims is merely an example of an embodiment, and the technical concept of the present invention should not be interpreted as being limited only to a combination with the cited claims; rather, combinations with various claims are also included within the scope of the technical concept of the present invention.

[0036] In conventional recycling processes, metals are leached from black mass, and a solvent extraction process is applied to extract each metal. In this process, individual metals are extracted and separated, and appropriate metal extractants and organic solvents are used at each extraction step.

[0037] Therefore, when extracting individual metals in this manner, large amounts of the aforementioned metal extractant and organic solvent are used, which leads to a high number of extraction stages and, as a result, may cause problems such as an increased equipment scale.

[0038] In addition, pH-raising agents such as sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) were used in conventional solvent extraction. However, in this case, sodium sulfate (Na2SO4) was inevitably generated, making it difficult to recycle or dispose of the sodium sulfate.

[0039] The inventors have discovered that when a nickel-cobalt-manganese complex solution is prepared from the black mass, the extraction process becomes simpler and the scale of the facility can be reduced compared to the case where each individual metal is extracted. In this case, the nickel-cobalt-manganese complex solution may refer to a solution containing three or more metal ions, including nickel, cobalt, and manganese. In this case, the type of residual solvent included in the solution other than the salts described above is not separately limited in the present invention. However, as an example, the solvent may be an aqueous mixture commonly used in metal leaching and metal extraction processes, and specifically, sulfuric acid may be present. The nickel-cobalt-manganese complex solution may contain unavoidable impurities in addition to the components described above; however, the type and content of such unavoidable impurities are common knowledge in the relevant technical field and are not separately limited in the present invention.

[0040] In addition, the inventors found that if sodium salt is not used as the pH-raising agent, the amount of sodium sulfate generated as a waste product can be reduced. Furthermore, the inventors also discovered that the nickel-cobalt-manganese composite solution prepared according to the above description contains metal components of a high-purity cathode active material and can be usefully used in lithium secondary batteries, etc. Throughout the specification of the present invention, the sodium salt may refer to a water-soluble and basic salt containing sodium, and more specifically, the sodium salt may be sodium hydroxide and sodium carbonate.

[0041] In this regard, a method for preparing a nickel-cobalt-manganese composite solution according to one embodiment of the present invention may include the step of preparing a metal leaching solution; the copper removal step of separating and recovering copper from the metal leaching solution; the iron and aluminum removal step of removing iron and aluminum from the metal leaching solution; and the impurity removal step of removing impurities from the metal leaching solution to obtain a nickel-cobalt-manganese composite solution.

[0042] In addition, as described above, the present invention may be characterized by not using sodium salt in the copper removal step and the iron and aluminum removal step.

[0043] FIG. 1 is a flowchart briefly illustrating a nickel-cobalt-manganese composite solution manufacturing process according to one embodiment of the present invention and a conventional nickel-cobalt-manganese composite solution manufacturing process. As can be seen from FIG. 1, unlike the conventional process, the present invention does not use sodium-based solvents as neutralizing agents and saponifying agents, thereby reducing the generation of sodium sulfate, which is an impurity. As a result, the byproduct removal process and purification process can be omitted, thereby simplifying the process.

[0044] Below, each step of the method for preparing a nickel-cobalt-manganese composite solution according to one embodiment of the present invention will be described in detail.

[0045] First, according to a method for preparing a nickel-cobalt-manganese composite solution according to one example of the present invention, a metal leaching solution can be prepared.

[0046] More specifically, the step of preparing the metal leaching solution may include the step of crushing a black mass or alloy to obtain metal powder; and the step of leaching the metal powder.

[0047] That is, the present invention can obtain metal powder by crushing black mass or alloy.

[0048] At this time, the black mass may refer to a material obtained through pretreatment processes such as discharge, dismantling, heat treatment, and crushing of waste batteries, and may include, as an example, one or more positive active materials among NCM batteries, NCA batteries, LCO batteries, LFP batteries, LMO batteries, LNMO batteries, and SIB (Sodium Ion Battery).

[0049] In addition, the above alloy may refer to the metal component of an anode active material in the form of an alloy obtained by heat-treating a large amount of waste batteries at a high temperature.

[0050] As a method for crushing the black mass or alloy, the present invention may adopt a milling method. Furthermore, after crushing, the Dmax of the metal powder may be 500 μm or less. Here, the Dmax of the metal powder may refer to the largest particle size when the metal powder is measured with a particle size meter.

[0051] The present invention allows for more efficient leaching of valuable metals by making the Dmax of the metal powder 500 μm or less.

[0052] Next, a manufacturing method according to one embodiment of the present invention may include a first atmospheric pressure leaching step for leaching the metal powder.

[0053] In addition, if the leaching is insufficient with only the first atmospheric pressure leaching step, the manufacturing method of the present invention may additionally include a second atmospheric pressure leaching step after the first atmospheric pressure leaching step.

[0054] In the first atmospheric pressure leaching step and the second atmospheric pressure leaching step, a strong acid may be used as the leaching solution, and as a non-limiting example, the strong acid used as the leaching solution may be one or more of an aqueous sulfuric acid solution and an aqueous hydrochloric acid solution.

[0055] Meanwhile, the leaching solution used in the second atmospheric pressure leaching step may have a higher concentration than the leaching solution used in the first atmospheric pressure leaching step. By making the leaching solution used in the first atmospheric pressure leaching step more concentrated than the second atmospheric pressure leaching, the present invention allows for the reuse of process water in the first atmospheric pressure leaching and enables additional leaching of metal that was not leached into the residue in the second atmospheric pressure leaching.

[0056] More specifically, the first atmospheric pressure leaching step can be carried out using an aqueous sulfuric acid solution of 10% by weight or more and 20% by weight or less, at a temperature range of 60°C or more and 80°C or less, for a period of 4 hours or more and 8 hours or less.

[0057] The above second atmospheric pressure leaching step can be carried out using an aqueous sulfuric acid solution of 20% by weight or more and 30% by weight or less, at a temperature range of 70°C or more and 100°C or less, for a period of 7 hours or more and 10 hours or less.

[0058] In addition, if the metal in the residue is not completely dissolved even after the first atmospheric pressure leaching step and the second atmospheric pressure leaching step are performed, the present invention may additionally include an oxygen pressurized leaching step.

[0059] In this way, when leaching is performed under oxygen pressurization conditions, there may be an advantage of increasing the recovery rate by leaching out all valuable metals contained in the black mass or alloy.

[0060] In the above oxygen pressurized leaching step, a strong acid may be used as the leaching solution, similar to the leaching solution in the first atmospheric pressure leaching step and the second atmospheric pressure leaching step described above, and as a non-limiting example, one or more of an aqueous sulfuric acid solution and an aqueous hydrochloric acid solution may be used.

[0061] The oxygen pressurized leaching step used above may involve leaching using an aqueous sulfuric acid solution of 5% by weight or more and 20% by weight or less under oxygen pressurized conditions of 2 bar or more and 20 bar or less.

[0062] Thus, after preparing a metal leaching solution, a method for preparing a nickel-cobalt-manganese composite solution according to one example of the present invention may include a copper removal step for separating and recovering copper from the metal leaching solution.

[0063] Specifically, the copper removal step can be performed through cementation or solvent extraction.

[0064] According to the above cementation, the copper removal step may precipitate copper by adding nickel metal (Ni) powder or nickel sulfide (Ni3S2) powder to the metal leaching solution. Through the above cementation, nickel, a relatively highly reactive metal, can reduce copper, a metal ion in the solution. As a result, the present invention can precipitate the reduced copper in a solid form. As an example, the amount of the nickel metal powder or nickel sulfide powder added may be between 2 and 8 times the copper equivalent.

[0065] According to a manufacturing method according to a non-limiting example of the present invention, the nickel metal powder or nickel sulfide powder may be added to the metal leaching solution and stirred while heating for a certain period of time. More specifically, the stirring may be performed at a temperature range of 50°C or higher and 90°C or lower for a period of 0.5 hours or longer and 5 hours or shorter. By doing so, the present invention can appropriately induce a cementation reaction due to the difference in redox potential between copper and nickel.

[0066] As copper is precipitated by the aforementioned cementation reaction and some nickel is dissolved in the metal leaching solution, the copper concentration in the metal leaching solution may decrease and the nickel concentration may increase. Additionally, the solid phase separated by solid-liquid separation contains a mixture of precipitated copper and unreacted nickel powder or nickel sulfide powder.

[0067] As a non-limiting example of the present invention, the solid phase can be reused in a cementation reaction. The number of reuses depends on the copper content of the metal leaching solution and the equivalent amount of nickel added, but generally, the lower the copper content and the higher the nickel equivalent amount, the more times it can be reused.

[0068] According to an alternative method of solvent extraction, the copper removal step can be performed by adding a LIX-based metal extractant to the metal leaching solution.

[0069] As an example, the above LIX-based metal extractant can be used by diluting it in kerosene.

[0070] To explain the solvent extraction described above in more detail, the present invention can separate the metal leaching solution in the aqueous phase from the metal extractant in the organic phase by adding and mixing a LIX-based metal extractant to the metal leaching solution and stirring for a certain period of time. Thereby, the present invention can selectively extract copper from the aqueous phase to the organic phase.

[0071] As a non-limiting example, the present invention may repeat the solvent extraction process described above until all the copper contained in the metal leaching solution is removed.

[0072] The method for preparing the nickel-cobalt-manganese composite solution of the present invention does not use sodium salts such as sodium hydroxide and sodium carbonate, whether by the cementation or the solvent extraction. Therefore, according to the copper removal step of one example of the present invention, copper can be effectively removed from the metal leaching solution without the incorporation of sodium.

[0073] After removing copper from the metal leaching solution as described above, the method for preparing a nickel-cobalt-manganese composite solution according to one example of the present invention may include an iron and aluminum removal step for removing iron and aluminum from the metal leaching solution.

[0074] In one example, the present invention may utilize a neutralization precipitation method to remove iron and aluminum. The neutralization precipitation method may refer to a method of precipitating specific components by adjusting the pH of a solution in a chemical process.

[0075] Conventional neutralization precipitation methods generally used sodium-based neutralizing agents such as NaOH or Na2CO3 to raise the pH of the solution and form precipitates of iron and aluminum, but this had the disadvantage that the amount of byproducts such as sodium sulfate increased as the sodium content in the solution increased.

[0076] However, the iron and aluminum removal step of the present invention does not use a sodium-based neutralizing agent as a neutralizing agent, so the generation of sodium sulfate, which is a byproduct of the waste battery recycling process, can be reduced, and as a result, the byproduct removal process and purification process can be omitted, thereby simplifying the process.

[0077] As an example, the present invention may use one or more of nickel carbonate (NiCO3), nickel hydroxide (Ni(OH)2), calcium hydroxide (Ca(OH)2) and magnesium hydroxide (Mg(OH)2) as the neutralizing agent, and more preferably, one or more of nickel carbonate (NiCO3) and nickel hydroxide (Ni(OH)2) may be used.

[0078] Accordingly, the present invention can raise the pH of a solution by using the aforementioned neutralizing agent, and thereby cause iron and aluminum in the solution to precipitate. As an example, the present invention can raise the pH until all iron and aluminum in the solution are removed, and the precipitate generated by the precipitation can be removed through solid-liquid separation.

[0079] Next, a method for preparing a nickel-cobalt-manganese composite solution according to one embodiment of the present invention may include an impurity removal step of removing impurities from the metal leaching solution to obtain a nickel-cobalt-manganese composite solution.

[0080] As described above, the metal leaching solution, having undergone the copper removal step and the aluminum and iron removal step, contains trace amounts of impurity elements in addition to the target metal ions, namely nickel, cobalt, and manganese. For example, the impurity elements may include Al, Fe, Ca, Mg, and Zn. Since these impurity elements can affect the performance of the cathode material, they need to be removed.

[0081] As an example, the removal of the aforementioned impurity elements can be achieved through a solvent extraction process.

[0082] In the conventional solvent extraction process, a solvent extractant loaded with sodium was obtained through a saponification process using sodium hydroxide (NaOH) and used for the extraction of a target metal.

[0083] However, as a non-limiting example, the present invention may further react a sodium-loaded solvent extractant with an aqueous nickel hydroxide (NiOH) solution to substitute sodium and nickel, thereby obtaining a nickel-pre-loaded solvent extractant. Subsequently, by using the nickel-pre-loaded solvent extractant during the impurity solvent extraction process, the incorporation of sodium ions into the final extraction solution is prevented, and at the same time, a solution in which impurities are removed and only valuable metals remain is obtained. Therefore, the present invention can achieve the effect of the saponification process by using nickel hydroxide (NiOH) while reducing the amount of sodium sulfate, which is a waste product.

[0084] To achieve the above-mentioned effect, the present invention can remove impurities using a solvent extractant pre-loaded with nickel, and the solvent extractant pre-loaded with nickel can be obtained through the steps of: saponifying the solvent extractant using an aqueous sodium hydroxide solution at a saponification rate of 20% or more and 60% or less; and pre-loading the solvent extractant into an aqueous nickel solution at least once and no more than five times.

[0085] Below, the preparation of the solvent extractant obtained by pre-extracting the above nickel is described in detail.

[0086] First, the present invention allows a solvent extractant to be saponified using an aqueous sodium hydroxide solution at a saponification rate of 20% or more and 60% or less. One or more of a single solvent extractant and a mixed solvent extractant may be used as the solvent extractant.

[0087] The above single solvent extractant may be bis(2-ethylhexyl)phosphate (D2EHPA). In this case, the concentration of the bis(2-ethylhexyl)phosphate (D2EHPA) single solvent extractant may be 1 vol% to 40 vol% and may be used by diluting it in kerosene.

[0088] As the above mixed solvent extractant, any one selected from 2-hydroxy-5-nonyllacetophenone oxime (LIX 984 NC), neodecanoic acid (Versatic acid), mono-2-ethylhexyl(2-ethylhexyl)phosphonate (PC88A), bis(2,4,4-trimethylpentyl)phosphinic acid (Ion quest 290), tri-n-butyl phosphate (TBP), tertiary amine (Alamine 336), and trioctylmethylammonium chloride (Aliquat 336) is used as bis-(2-ethyl There may be a mixed solvent extractant mixed with hexyl phosphate (Bis(2-ethylhexyl) phosphate, D2EHPA). In this case, the concentration of the added solvent may be 1 vol% to 5 vol%.

[0089] As such, when saponifying the solvent extractant using an aqueous sodium hydroxide solution, the saponification rate may be 20 to 60% as described above. Subsequently, the present invention can produce a solvent extractant in which sodium is substituted with nickel at a substitution rate (%) close to 100% by pre-loading the sodium-loaded solvent extractant into an aqueous nickel solution one to five times. As a result, the present invention can obtain a pre-extracted nickel solvent extractant with a saponification rate of 20 to 60%. In this way, by securing a pre-extracted nickel solvent extractant having the saponification rate described above, the present invention can prevent a decrease in pH of the aqueous phase and the incorporation of sodium during the extraction process.

[0090] In the present invention, when the solvent extractant from which nickel has been pre-extracted is mixed with a metal leaching solution from which iron and aluminum have been removed, the pre-loaded nickel (Ni) is exchanged with impurity metal ions present in the aqueous phase, thereby allowing impurity elements to be extracted into the organic phase.

[0091] When solvent extraction is performed using the solvent extractant that pre-extracted the nickel, the ratio of the organic phase to the aqueous phase (O / A) may be 0.5 to 2.0. In addition, as a non-limiting example, the solvent extraction method may be a countercurrent multi-stage method, and the number of solvent extractions may be 1 to 15 times. Furthermore, the pH of the metal leaching solution during solvent extraction may be about 2 to 3.0.

[0092] However, when performing solvent extraction of impurities under these conditions, a problem of partial co-extraction may occur because the content of the metals to be recovered, such as cobalt or nickel, is high relative to the impurities. Therefore, the method for preparing a nickel-cobalt-manganese composite solution according to an example of the present invention may additionally include a washing process capable of recovering the co-extracted cobalt and nickel.

[0093] The concentration of sulfuric acid (H2SO) used in the above cleaning process may be 0.01 M to 1 M, and the ratio of organic phase to aqueous phase (O / A) during cleaning may be 1 to 10. In addition, the equilibrium pH may be 1 to 3. However, considering that as the pH increases, the cleaning rate of nickel and cobalt can be maintained at 70 to 100% while the cleaning rate of impurity elements can be reduced, a more desirable equilibrium pH range during cleaning may be 2 to 2.5.

[0094] The present invention allows for the omission of a separate pH adjustment process through the aforementioned pre-loading solvent extraction method. Furthermore, the present invention provides a process for producing a nickel (Ni)-cobalt (Co)-manganese (Mn) composite solution while preventing the incorporation of sodium (Na), an impurity, into the organic solvent and aqueous solution phases during the solvent extraction process. Thus, unlike conventional solvent extraction methods that sequentially recover each metal individually, the present invention simplifies the process and simultaneously reduces the amount of wastewater, such as sodium sulfate, generated during the process. Through the aforementioned impurity removal step, the present invention can extract and remove impurities (Mg, Ca, Zn, Zr) and obtain a nickel, cobalt, and manganese (Ni, Co, Mn) composite solution with a higher nickel (Ni) concentration.

[0095] After removing such impurities, the method for preparing a nickel-cobalt-manganese composite solution according to one embodiment of the present invention may additionally include a step of adjusting the amounts of nickel, cobalt, and manganese by adding one or more of nickel, cobalt, and manganese sulfates to the nickel-cobalt-manganese composite solution.

[0096] More specifically, the present invention can adjust the ratio of nickel-cobalt-manganese in the nickel-cobalt-manganese composite solution by adding one or more of nickel, cobalt, and manganese sulfates to match the ratio of the cathode material to be manufactured.

[0097] Next, a method for preparing a nickel-cobalt-manganese complex salt according to another embodiment of the present invention may additionally include a step of drying the complex solution prepared according to the above.

[0098] At this time, the nickel-cobalt-manganese complex salt may refer to a mixture of three or more salts containing nickel, cobalt, and manganese and unavoidable impurities.

[0099] Specifically, the drying step can be achieved through crystallization or co-precipitation.

[0100] The crystallization described above may comprise the steps of: obtaining a solid phase by evaporating the nickel-cobalt-manganese complex solution under reduced pressure; and obtaining the nickel-cobalt-manganese complex salt by centrifuging and drying the solid phase. At this time, the nickel-cobalt-manganese complex salt may be a nickel-cobalt-manganese sulfate.

[0101] In addition, the above co-precipitation may comprise the steps of: adding a precipitating agent and a chelating agent to the nickel-cobalt-manganese composite solution and precipitating to obtain a precipitate; filtering the precipitate to obtain a precursor; and calcining the precursor at a temperature of 500°C or higher and 800°C or lower to obtain the nickel-cobalt-manganese composite salt.

[0102] At this time, the precipitating agent may be one or more of sodium carbonate (Na2CO3) and sodium hydroxide (NaOH), and the chelating agent may be one or more of NH3H2O ​​and NH4HCO3.

[0103] Since the precipitating agent is one or more of sodium carbonate (Na2CO3) and sodium hydroxide (NaOH), the resulting nickel-cobalt-manganese complex salt may be one or more of nickel-cobalt-manganese carbonate and nickel-cobalt-manganese hydroxide.

[0104] During the above precipitation, the precipitation temperature may be 30°C or higher and 60°C or lower, and the precipitation pH may be 7.0 or higher and 12.0 or lower. Accordingly, in one embodiment of the present invention, a nickel-cobalt-manganese composite salt can be obtained by adding a precipitating agent and a chelating agent while stirring the composite solution under the said conditions, and by filtering, washing, and drying the formed precipitate. The nickel-cobalt-manganese composite salt prepared according to the above description is useful in that it can be used as a cathode material for lithium-ion batteries.

[0105] The present invention will be described in detail below through examples. However, it should be noted that the examples described below are intended merely to illustrate and embody the present invention and are not intended to limit the scope of the present invention. This is because the scope of the present invention is determined by the matters described in the patent claims and matters reasonably inferred therefrom.

[0106] 1. Preparation of metal powder

[0107] First, the present invention obtained an alloy containing nickel, cobalt, and manganese by smelting waste batteries. Next, the present invention prepared a metal powder by crushing the alloy using a cup milling method. At this time, the cup milling was performed for less than 5 minutes, and the Dmax particle size of the metal powder, measured by a Malvern particle size meter, was 500 μm.

[0108] 2. Leaching of metal powder

[0109] Examples 1 to 3 were obtained by leaching the metal powder obtained by the above-described method under each condition.

[0110] (1) Example 1

[0111] The above metal powder was added to an aqueous sulfuric acid solution with a concentration of 17.5 wt.% to obtain a slurry with a concentration of 100 g / L, which was reacted at 80°C for 6 hours and then leached to obtain a metal leaching solution. Next, the leaching rate (%) of each metal in the metal leaching solution was measured using an inductively coupled plasma emission spectrometer (ICP-OES) from PerkinElmer and is shown in Table 1 below. At this time, the concentration of the slurry was 100 g / L.

[0112] The leaching rate (%) of each metal can be derived by the following Equation 1. In the following equation, C L Concentration of target metal in silver metal leaching solution (mg / L), V LTotal volume of silver metal leaching solution (L), M F represents the concentration of the target metal in the black mass (mg / g), and m represents the amount of black mass (g) added to the leaching reaction.

[0113] [Relationship 1]

[0114] Elemental NiCoMnCuLiAlFeSiCaMgZnZr Leaching Rate (%) 40.9 44.1 39.9 1.8 94.2 100.3 41.5 21.6 38.1 81.3 38.9 29.6

[0115] (2) Example 2

[0116] The above metal powder was added to an aqueous sulfuric acid solution with a concentration of 17.5 wt.% to obtain a slurry with a concentration of 100 g / L, which was reacted at 80°C for 6 hours and then leached to obtain a leaching solution and a residue. An aqueous sulfuric acid solution with a concentration of 22.5 wt.% was added to the residue to obtain a slurry with a concentration of 100 g / L, and additional leaching was performed by reacting this at 90°C for 8 hours. Subsequently, the leaching solutions obtained from each leaching were mixed, and the leaching rate (%) of each metal in the mixture was measured and is shown in Table 2 below.

[0117] The leaching rate (%) of each metal in the above mixture was measured in the same way as in Example 1.

[0118] Element NiCoMnCuLiAlFeSiCaMgZnZr Primary + Secondary Leaching Rate (%) 57.35 9.75 6.66 94.81 02.64 9.42 7.93 8.18 4.75 2.954

[0119] (3) Example 3

[0120] The above metal powder was added to an aqueous sulfuric acid solution with a concentration of 11.4 wt.% to obtain a slurry with a concentration of 250 g / L, and after reacting at a temperature of 80°C for 6 hours, a first atmospheric pressure leaching was performed to obtain a leaching solution and a residue. An aqueous sulfuric acid solution with a concentration of 25 wt.% was added to the residue to obtain a slurry with a concentration of 100 g / L, and a second atmospheric pressure leaching was performed by reacting at a temperature of 90°C for 8 hours. Next, pressurized leaching was carried out on the residue obtained from the second atmospheric pressure leaching under conditions of sulfuric acid concentration of 7.8 wt.%, slurry concentration of 200 g / L, temperature of 180°C, reaction time of 7 hours, and oxygen of 0.2 MPa.

[0121] The leaching rates (%) of each metal in the first atmospheric pressure leaching, the second atmospheric pressure leaching, and the pressurized leaching are shown in Table 3 below, and the concentration (g / L) of each metal after the pressurized leaching is shown in Table 4 below.

[0122] The leaching rate (%) of each of the above metals was measured in the same manner as in Example 1, and the concentration (g / L) of each metal was also measured using an inductively coupled plasma emission spectrometer (ICP-OES) from PerkinElmer.

[0123] Classification Leaching rate of each metal (%) NiCoMnCuLiAlFeSiCaMgZnZr 1st After atmospheric pressure leaching 19.26 20.27 17.76 0.0 19 2.48 81.67 27.95 17.56 75.22 76.07 18.64 2.19 2nd After atmospheric pressure leaching 52.49 54.29 50.5 10.0 499.629 2.0 849.61 31.0 590.438 8.75 0.57 48.69 After pressurized leaching 99.64 99.46 99.58 100 100 99.0999.6299.66 100 99.58 99.85 99.57

[0124] Concentration of each metal (g / L) NiCoMnCuLiAlFeSiCaMgZnZr Alloy Metal Leaching Solution 5 1.8 15.6 16.5 6.6 0.0 9 30.9 5 0.9 40.0 10.0 78 0.1 5 0.1 5 0.0 3

[0125] (4) Sintering

[0126] Looking at Tables 1 to 3 above, it can be seen that the leaching rate of each metal can be secured higher when performing the first and second atmospheric pressure leaching compared to when performing the first atmospheric pressure leaching. In particular, in Example 3, by additionally performing pressurized leaching, all metal elements present in the metal powder could be leached with a leaching rate of 99% or higher.

[0127] 3. Copper removal

[0128] (1) Cementation

[0129] An experiment was conducted to precipitate copper under the conditions of Table 5 by adding the cementation agent of Table 5 below to the metal leaching solution of Example 3 above. After precipitating copper, the copper removal efficiency (%) was measured and shown in Table 5 below.

[0130] The above copper removal efficiency (%) can be derived by the following relationship 2.

[0131] [Relationship 2]

[0132]

[0133] Cementation Preparation Copper Input Equivalent Temperature (°C) Time (h) Copper Removal Efficiency (%) Ni5853100Ni3S25853100

[0134] (2) Solvent extraction

[0135] Solvent extraction was performed using the metal extractant LIX973 in the metal leaching solution of Example 3 above. Figure 2(a) shows the copper extraction rate (%) according to pH in the aqueous phase during the copper removal step. Looking at Figure 2(a), it can be seen that in this experiment, when 14 vol.% LIX973 (O / A ratio=2) in twice the volume of the metal leaching solution was used, copper ions were extracted with an extraction rate of 83.0% at pH 1.0 and 94.9% at pH 1.5. At pH 2 or higher, nickel precipitation occurs, which is undesirable. Figure 2(b) is a graph showing the copper concentration (g / mL) in the raffinate according to the number of stages when ion extraction is performed using 14 vol.% LIX973 as described above with an O / A ratio of 2, and Figure 2(c) is a graph showing the copper extraction rate (%) according to the O / A ratio during the same ion extraction. Through measurements in Figures 2(b) and (c), it was found that the maximum copper extraction amount of 14 vol.% LIX973 was 7.80 g / L, and the maximum copper extraction rate was 96.3%.

[0136] The extraction rate of copper ions can be measured by the following Equation 3. As described above, the concentration (g / L) of each metal in the metal leaching solution from which copper was removed was measured and is shown in Table 6 below.

[0137] [Relationship 3]

[0138]

[0139] Concentration of metal (g / L) NiCoMnCuLiAlFeCaMgNa After copper removal (using LIX-973) 54.5 216.7 218.8 500.2 13.0 5.00.10.0 61-

[0140] Meanwhile, Figure 3 is a graph showing the McCabe figure during the copper removal step. As can be seen in Figure 3, when the ratio of the organic phase to the aqueous phase was set to 2 (O / A=2), almost all of the 6.6 g / L of copper ions contained in the alloy metal leaching solution could be extracted over four stages.

[0141] 4. Removal of iron and aluminum

[0142] As described above, in a metal leaching solution from which copper has been removed by cementation or solvent extraction, a sodium-free neutralizing agent, NiCO₃ 3, Neutralization precipitation was carried out using Ca(OH)2 or Mg(OH)2. Each neutralizing agent was added to a solution of the same composition from which copper had been removed to remove aluminum and iron by precipitation. Simultaneously, for each neutralizing agent, the removal efficiency (%) of aluminum and iron according to pH change in the pH range of 3.5–4.5, which is the main precipitation range for aluminum and iron, was measured and is shown in Fig. 4. Fig. 4 (a) is a graph showing the removal efficiency (%) of aluminum according to pH change, and Fig. 4 (b) is a graph showing the removal efficiency (%) of iron according to pH change. At this time, the removal efficiency (%) of aluminum and iron was calculated using the same method as the removal efficiency (%) of copper in Equation 2 above, and the pH change was measured using a pH meter from DKK TOA CORPORATION. The reaction temperature for this neutralization precipitation reaction was 55℃. In the leaching solution from which iron and aluminum had been removed as described above, the concentration (g / L) of each metal was measured and is shown in Table 7 below. The concentration of each metal (g / L) was measured using an inductively coupled plasma emission spectrometer (ICP-OES) from PerkinElemr, as in '3. Copper Removal'.

[0143] Concentration of each metal (g / L) NiCo MnCuLiAlFeCaMgNa After removal of iron and aluminum (neutralization precipitation @pH4) 57.3 15.3 18.3 00.2 10.0 90.1 50.0 80.0 61-

[0144] Referring to Figures 4(a) and 4(b), iron and aluminum were removed from a copper-removed feed solution (Al 3 g / L, Fe 5 g / L, Ni 54.52 g / L, Co 16.72 g / L, Mn 18.85 g / L) using pH-raising agents: 10% NaOH, 15% Mg(OH)2, 10% Ca(OH)2, and 20% NiCO3. The 10% Ca(OH)2 and 20% NiCO3 solutions exhibited higher iron and aluminum removal rates in the pH range of 3.5–4.25, which is lower than that of the 10% NaOH and 15% Mg(OH)2 solutions.

[0145] In addition, Table 8 below shows the removal rate (%) of each metal at each neutralization pH when using a 20% NiCO3 solution. As shown in Table 8 below, when neutralization precipitation was performed at pH 3.5, pH 4.0, and pH 4.5 using a 20% NiCO3 solution, iron and aluminum were removed by 97% at pH 4.0, while the co-precipitation rates of other metals were low, indicating that pH 4.0 is the most appropriate condition for neutralization precipitation.

[0146] Through the above results, it was confirmed that even when using a neutralizing agent that does not contain sodium, aluminum and iron can be sufficiently removed at a pH of 4.0, while simultaneously reducing the possibility of by-products caused by sodium.

[0147] Removal rate of each metal (%) NiCoMnLiAlFeNaCaMgZnZrpH 3.53%0%0%10%24%61%8%7%5%2%0%pH 4.06%2%3%26%97%97%13%11%6%12%83%pH 4.513%6%1%13%99%94%12%6%14%37%98%

[0148] 5. Removal of impurities

[0149] The impurity removal process conditions are shown in Fig. 5. Bis(2-ethylhexyl) phosphate (D2EHPA) was diluted in kerosene to a concentration of 30 vol.%. The prepared solvent extractant was mixed with an aqueous sodium hydroxide (NaOH) solution and saponified to a saponification rate of 40%. The sodium-loaded solvent extractant was reacted with a 0.3 M aqueous nickel hydroxide (NiOH) solution at pH 6.42 to obtain a pre-loaded nickel solvent extractant through a substitution reaction between nickel and sodium. The nickel pre-extraction process was carried out in five stages. Fig. 6 is a graph showing the changes in the concentrations of nickel and sodium in the organic phase, obtained by stripping the organic phase sampled over time with an aqueous sulfuric acid solution while operating the nickel pre-extraction process. Through this, it was found that as the nickel pre-extraction operation proceeded, sodium ions bound to the solvent extractant were replaced by nickel, and nickel was loaded onto the solvent extractant. As a result, the incorporation of sodium into the NCM complex solution could be minimized.

[0150] Subsequently, the metal leaching solution from which iron and aluminum had been removed and the solvent extractant pre-loaded with nickel (Ni) were mixed at an organic phase / aqueous phase volume ratio (O / A) of 0.9. At this time, the solvent extraction was carried out five times in a countercurrent multi-stage manner, and the pH was maintained at approximately 2 to 3.0. Through this process, the metal concentration of the impurity-removed Raffinate is shown in Fig. 7. As shown in Fig. 7, a nickel-cobalt-manganese composite solution with minimized sodium incorporation was obtained by carrying out the continuous impurity solvent extraction process.

[0151] The concentrations (g / L) of each metal in the nickel-cobalt-manganese complex solution from which impurities had been removed were measured and are shown in Table 9 below. The concentrations (g / L) of each metal were measured using an inductively coupled plasma emission spectrometer (ICP-OES) from PerkinElmer, as in '3. Copper Removal'.

[0152] Concentration of each metal (g / L) NiCo MnCuLiAlFeCaMgNa After impurity removal (g / L) 36.3 10.25.5 0.0000.21 0.0000.0000.0000.06 20.45

[0153] Looking at Table 9 above, it can be seen that, according to the method described above, the present invention can remove elements other than nickel-cobalt-manganese through a series of processes without using sodium salts in the process, and can finally produce a mixed solution with a high concentration of nickel-cobalt-manganese remaining.

[0154] 6. Concentration Control and Crystallization in Nickel-Cobalt-Manganese Complex Solution

[0155] After removing impurities, nickel, cobalt, and manganese sulfates were added to adjust the nickel-cobalt-manganese ratio of the solution to 6:2:2. After adjustment, the solution was evaporated under reduced pressure, and the resulting solid phase was centrifuged and dried to produce nickel-cobalt-manganese sulfate. In addition, the purity (%) of each element in the finally obtained nickel-cobalt-manganese sulfate was measured and is shown in Table 10 below.

[0156] The purity (%) of each element can be measured by the following relationship 4.

[0157] [Relationship 4]

[0158]

[0159] Classification NiCoMn Purity (%) 99.999.999.9

[0160] 7. Cell Evaluation

[0161] Additionally, during the process of producing the nickel-cobalt-manganese composite salt obtained through the present invention, cell performance was evaluated when the composite solution, prior to crystallization, was incorporated into the cathode material raw material. The composite solution was prepared by mixing commercial nickel sulfate, cobalt sulfate, and manganese sulfate salts from Merck in deionized water at mass ratios of 5% and 30%, respectively, and the experiment was conducted by adjusting the nickel-cobalt-manganese ratio to 6:2:2. The cathode material for cell evaluation was prepared by forming a precursor through co-precipitation with ammonia water and sodium hydroxide, in the same manner as a general process, followed by a calcination process.

[0162] The cathode material produced through the above process was used as the cathode of a lithium-ion battery cell, and its performance is shown in Table 11 below. Charging and discharging were performed under conditions of a cut-off of 3.0 to 4.3 V at a 0.1 C-rate and 25℃.

[0163] Classification Composite Solution Mass Ratio (wt.%) 0 wt.% 5 wt.% 30 wt.% Discharge Capacity (mAh / g) 184.53 181.95 180.89 Coulomb Efficiency (%) 94.58 93.99 94.18 Capacity Retention Rate (%) 98.40 97.67 999.20

[0164] From the results of Table 11 above, it was confirmed that when using the nickel-cobalt-manganese composite salt produced in the present invention, it can partially replace existing expensive cathode materials and the performance of the cathode material is formed at a similar level.

[0165] 8. Experimental Results

[0166] Through the experiment described above, it can be seen that according to the method for preparing the nickel-cobalt-manganese composite solution of the present invention, the present invention can provide a high concentration nickel-cobalt-manganese composite solution, and furthermore, a high concentration nickel-cobalt-manganese composite salt.

[0167] In this case, compared to the case of separating metal elements individually, there are advantages such as reducing the organic solvents and metal extractants used, simplifying the manufacturing process, and reducing the land required for the facility.

[0168] In particular, the present invention has an eco-friendly effect in that it prevents sodium from being mixed into the solution and reduces sodium by-products such as sodium sulfate by not using sodium salts in the step of removing copper, iron, aluminum, and impurities.

Claims

1. Step of preparing the metal leaching solution; A copper removal step for separating and recovering copper from the above metal leaching solution; An iron and aluminum removal step for removing iron and aluminum from the metal leaching solution; and It includes an impurity removal step to obtain a nickel-cobalt-manganese composite solution by removing impurities from the metal leaching solution, The above iron and aluminum removal step is a method for preparing a nickel-cobalt-manganese complex solution using one or more of nickel carbonate (NiCO3), nickel hydroxide (Ni(OH)2), calcium hydroxide (Ca(OH)2) and magnesium hydroxide (Mg(OH)2) as a neutralizing agent.

2. In Paragraph 1, A method for preparing a nickel-cobalt-manganese complex solution in which sodium salt is not used in the copper removal step and the iron and aluminum removal step.

3. In Paragraph 2, A method for preparing a nickel-cobalt-manganese complex solution, wherein the sodium salts are sodium hydroxide and sodium carbonate.

4. In Paragraph 1, A method for preparing a nickel-cobalt-manganese composite solution, comprising the step of preparing the metal leaching solution, the step of crushing a black mass or alloy to obtain a metal powder; and the first atmospheric pressure leaching step of leaching the metal powder.

5. In Paragraph 4, After the first atmospheric pressure leaching step, the method additionally includes a second atmospheric pressure leaching step and a pressurized leaching step, The leaching solution used in the second atmospheric pressure leaching step is of a higher concentration compared to the leaching solution used in the first atmospheric pressure leaching step, and A method for preparing a nickel-cobalt-manganese composite solution, wherein the above-mentioned pressurized leaching step involves leaching under pressurized conditions of oxygen at 2 bar or more and 20 bar or less.

6. In Paragraph 1, A method for preparing a nickel-cobalt-manganese composite solution, wherein the copper removal step involves adding one or more of nickel metal powder and nickel sulfide powder to the metal leaching solution.

7. In Paragraph 6, The amount of the nickel metal powder or nickel sulfide powder added is at least 2 times and no more than 8 times the copper equivalent, and A method for preparing a nickel-cobalt-manganese composite solution, wherein the copper removal step is performed at a temperature range of 50°C or higher and 90°C or lower for a duration of 0.5 hours or longer and 5 hours or shorter.

8. In Paragraph 1, The copper removal step described above is a method for preparing a nickel-cobalt-manganese complex solution by adding a LIX-based metal extractant to the metal leaching solution.

9. In Paragraph 1, The above impurity removal step utilizes a solvent extractant pre-loaded with nickel, and the solvent extractant pre-loaded with nickel A step of saponifying a solvent extractant using an aqueous sodium hydroxide solution at a saponification rate of 20% or more and 60% or less; and A method for preparing a nickel-cobalt-manganese complex solution obtained by pre-loading the above solvent extractant into a nickel aqueous solution one to five times.

10. In Paragraph 1, A method for preparing a nickel-cobalt-manganese complex solution, comprising, after the impurity removal step, an additional step of adjusting the amounts of nickel, cobalt, and manganese by adding one or more of nickel, cobalt, and manganese sulfates to the nickel-cobalt-manganese complex solution.

11. A method for preparing a nickel-cobalt-manganese complex salt comprising the step of drying a nickel-cobalt-manganese complex solution prepared according to claim 1.

12. In Paragraph 11, The drying step above is a step of obtaining a solid phase by evaporating the nickel-cobalt-manganese composite solution under reduced pressure; and The method includes the step of centrifuging the above solid phase and drying it to obtain the nickel-cobalt-manganese complex salt, A method for preparing a nickel-cobalt-manganese complex salt, wherein the nickel-cobalt-manganese complex salt is a nickel-cobalt-manganese sulfate.

13. In Paragraph 11, The drying step above comprises adding a precipitating agent and a chelating agent to the nickel-cobalt-manganese composite solution and precipitating to obtain a precipitate; A step of obtaining a precursor by filtering the above-mentioned precipitate; and The method includes the step of obtaining the nickel-cobalt-manganese composite salt by calcining the above precursor at a temperature of 500°C or higher and 800°C or lower, and The above precipitating agent is one or more of sodium carbonate (Na2CO3) and sodium hydroxide (NaOH), and the chelating agent is one or more of NH3H2O ​​and NH4HCO3, and A method for preparing a nickel-cobalt-manganese complex salt, wherein the nickel-cobalt-manganese complex salt is one or more of nickel-cobalt-manganese carbonate and nickel-cobalt-manganese hydroxide.

14. In Paragraph 13, A method for producing a nickel-cobalt-manganese complex salt, wherein the precipitation temperature in the step of obtaining the above precipitate is 30°C or higher and 60°C or lower, and the precipitation pH is 7.0 or higher and 12.0 or lower.

15. A method for manufacturing a nickel-cobalt-manganese composite salt, wherein the nickel-cobalt-manganese composite salt manufactured according to any one of claims 11 to 14 is used as a cathode material for a lithium-ion battery.

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