Valuable metal reaction product and method for recovering valuable metal comprising same

Abstract

The present invention relates to: a valuable metal reaction product that is recovered by recycling a waste battery; and a method for recovering a valuable metal comprising same. Particularly, the present invention relates to: a valuable metal reaction product that is recovered by performing a hydrogen reduction treatment on a shredded waste battery; and a method for recovering a valuable metal comprising same.

Description

Valuable metal reactant and method for recovering valuable metal containing the same

[0001] The present invention relates to a valuable metal reactant recovered by recycling waste batteries and a method for recovering valuable metals including the same. Specifically, the present invention relates to a valuable metal reactant recovered by performing a hydrogen reduction treatment on crushed waste batteries and a method for recovering valuable metals including the same.

[0002] This application claims priority to Korean Patent Application No. 10-2024-0191900, filed on December 19, 2024, the entire contents of which are incorporated herein by reference.

[0003]

[0004] As global demand for electric vehicles (EVs) intensifies, the issue of disposing of waste batteries generated from these vehicles is emerging as a social concern. Lithium-ion batteries, which serve as the primary raw material for these waste batteries, contain organic solvents, explosive substances, and heavy metals such as Ni, Co, Mn, Fe, and P. However, Ni, Co, Mn, Fe, P, and Li are valuable metals with high scarcity value, making the recovery and recycling processes for lithium-ion batteries after disposal a critical area of ​​research.

[0005] Specifically, the lithium secondary battery comprises copper and aluminum used as current collectors, oxides containing Li, Ni, Co, Mn, Fe, and P constituting the cathode material, and graphite and Si used as the anode material, and includes a separator that separates the cathode material and the anode material, and an electrolyte injected into the separator. The solvent used as the solvent and salt constituting the electrolyte is mainly a mixture of carbonate organic materials such as ethylene carbonate and propylene carbonate, and LiPF6 is used, for example.

[0006] To utilize the aforementioned waste batteries, interest is emerging in waste battery recycling processes that involve crushing the waste batteries to produce intermediate materials such as shredded waste batteries or black powder, followed by subsequent processing to recover valuable metals. Specifically, the major components of waste batteries consist of expensive valuable metal elements such as Ni, Co, Mn, Li, Fe, and P.

[0007] The aforementioned waste batteries are, for example, secondary batteries that have reached the end of their lifespan after being used for a cycle of 5 to 10 years, and recycling the main components of these waste batteries is essential from both environmental and cost perspectives. The waste batteries undergo conventional crushing, grinding, or gravity separation processes to produce a mixture of cathode and anode materials in the form of black powder, which is an intermediate product. The valuable metals essential for battery production are recovered from this generated black powder through wet processes such as leaching, solvent extraction, or crystallization. This ensures a smooth supply of raw materials and enables a significant reduction in battery manufacturing costs.

[0008] As a method to recover the above valuable metals, high-temperature reduction and carbon-based reduction methods have been studied in the past. In the case of high-temperature reduction carried out in an inert atmosphere, high-temperature heat treatment of 1000°C or higher must be performed to sufficiently reduce the valuable metals. Nevertheless, it is difficult to improve the recovery rate of the valuable metals beyond a certain level, and there may be a problem where some of the Li vaporizes due to the high-temperature treatment. In addition, there may be a problem with high energy costs required for reduction. Furthermore, when applying the carbon-based reduction method, there is a problem of CO2 generation due to the oxidation of graphite in the spent battery. Also, because the solubility of Li2CO3 in aqueous solution is low (<3g / L), a large amount of wastewater is generated after the leaching of Li2CO3, and the leaching rate (%) is low at 80% or less, so there are limitations to recovering Li using this method.

[0009] Therefore, there is a need for a valuable metal recovery method that can effectively improve the recovery rate of valuable metals while preventing the loss of Li and the generation of CO2 gas.

[0010]

[0011] The technical problem that the present invention aims to solve is to provide a valuable metal reactant with a high lithium content.

[0012] Another technical problem that the present invention aims to solve is to provide a valuable metal reactant having the aforementioned advantages by hydrogen reduction treatment of crushed waste batteries, and to provide a method for recovering valuable metals with a high lithium recovery rate.

[0013]

[0014] A valuable metal reactant according to one embodiment of the present invention is a valuable metal reactant comprising a valuable metal recovered from a waste battery, comprising a first valuable metal containing a valuable metal; a second valuable metal containing a non-magnetic material; and a carbon compound containing carbon, wherein the first valuable metal containing a valuable metal containing a magnetic material and a first lithium compound attached to the surface of the third valuable metal containing a

[0015] [Equation 1]

[0016] 0.34 ≤ [Li] T / ([Al] T + [P] T )≤ 1.80

[0017] (In Equation 1 above, [Li] T , [Al] T and [P] T represents the weight percent of Li, Al, and P, respectively, based on 100 weight percent of the first valuable metal content.

[0018] In one embodiment, the third valuable metal inclusion within the first valuable metal inclusion may include at least one of nickel, iron, and phosphorus. Specifically, the first valuable metal inclusion may include a magnetic material comprising at least one of nickel, iron, and phosphorus. The first valuable metal inclusion may include a third valuable metal inclusion comprising a magnetic material comprising at least one of nickel, iron, and phosphorus as a core portion.

[0019] In one embodiment, the first lithium compound may be disposed on the surface of a third valuable metal inclusion. Specifically, it may maintain a state of being bonded in a shell form by a reaction between the lithium in the first lithium compound and the magnetic materials in the third valuable metal inclusion.

[0020] When X-ray diffraction analysis (XRD) is performed on the first valuable metal containing material of the valuable metal reactant according to one embodiment of the present invention, at least one peak may occur in each of the intervals where 2theta (2θ) is 15 to 18°, 20 to 25°, 33 to 35°, 55 to 57°, and 66 to 68°.

[0021] When X-ray diffraction analysis (XRD) is performed on the first valuable metal containing material of the valuable metal reactant according to one embodiment of the present invention, at least one peak may occur in each of the intervals where 2theta (2θ) is 20 to 21°, 32 to 33°, and 35.5 to 36.5°.

[0022] When X-ray diffraction analysis (XRD) is performed on the first valuable metal containing material of the valuable metal reactant according to one embodiment of the present invention, at least one peak may occur in each of the intervals where 2theta (2θ) is 16 to 18°, 23 to 24°, 33 to 35°, 51 to 52°, and 60 to 62°.

[0023] In a valuable metal reactant according to one embodiment of the present invention, the lithium content of the first lithium compound may be 1.5 to 10 weight% based on 100 weight% of the first valuable metal content.

[0024] In a valuable metal reactant according to one embodiment of the present invention, the second valuable metal content comprises a second lithium compound, and the lithium content of the second lithium compound may be less than 30 weight% based on 100 weight% of the second valuable metal content.

[0025] In a valuable metal reactant according to one embodiment of the present invention, based on 100 weight% of the first valuable metal content, the content of an alloy or oxide containing at least one of nickel (Ni), iron (Fe), and phosphorus (P) may be 45.00 to 95.00 weight%.

[0026] In a valuable metal reactant according to one embodiment of the present invention, the waste battery may be one or more selected from lithium nickel-containing batteries and lithium iron phosphate batteries.

[0027] In a valuable metal reactant according to one embodiment of the present invention, the first lithium compound may include at least one of Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4.

[0028] In a valuable metal reactant according to one embodiment of the present invention, the second lithium compound may include a lithium compound comprising at least one of Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4.

[0029] In a valuable metal reactant according to one embodiment of the present invention, the third valuable metal inclusion may include at least one of nickel (Ni), iron (Fe), and phosphorus (P).

[0030] In a valuable metal reactant according to one embodiment of the present invention, the second valuable metal inclusion may include at least one of nickel, nickel oxide, cobalt, cobalt oxide, manganese, manganese oxide, manganese aluminum oxide, aluminum, aluminum oxide, aluminum phosphate oxide, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate oxide.

[0031] A method for recovering valuable metals according to another embodiment comprises: a hydrogen reduction step of obtaining a valuable metal reactant by hydrogen reducing a battery crushed material with a reducing gas; a magnetic separation step of separating the valuable metal reactant into a first valuable metal containing an alloy or oxide containing at least one of nickel (Ni), iron (Fe), and phosphorus (P), and a second valuable metal containing a non-magnetic material; and a first separation step of separating the second valuable metal containing into a carbon containing carbon and a second lithium compound, wherein the first valuable metal containing may include a third valuable metal containing a magnetic material and a first lithium compound attached to the surface of the third valuable metal containing, and may satisfy Formula 2 below.

[0032] [Equation 2] 140≤T*P≤1000

[0033] (In Equation 2 above, T represents the reduction temperature during the hydrogen reduction step and P represents the partial pressure of hydrogen (atm) in the reducing gas during the hydrogen reduction step; the unit of the value in Equation 2 above is not considered.)

[0034] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the partial pressure of hydrogen in the reducing gas may be 0.1 to 1.0 atm.

[0035] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the reduction temperature may be 100 to 1000°C.

[0036] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the reducing gas is H2, C x H y It may include at least one of (1≤x≤10, 3≤y≤22) and NH3.

[0037] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the reducing gas may additionally include at least one of Ar, N2, and He.

[0038] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the valuable metal reactant may satisfy the following Formula 1.

[0039] [Equation 1]

[0040] 0.34 ≤ [Li] T / ([Al] T + [P] T )≤ 1.80

[0041] (In Equation 1 above, [Li] T , [Al] T and [P] T represents the weight percent of Li, Al, and P, respectively, based on 100 weight percent of the first valuable metal content.

[0042] Preferably, Equation 1 is 0.43 ≤ [Li] T / ([Al] T + [P] T )≤ 1.57, 0.59 ≤ [Li] T / ([Al] T + [P] T )≤ 1.17 can be.

[0043] After the first separation step of the valuable metal recovery method according to another embodiment, a second separation step of separating the first valuable metal content into a third valuable metal content and the first lithium compound may be further included.

[0044]

[0045] The valuable metal reactant according to one embodiment of the present invention may have a high lithium content.

[0046] A method for recovering valuable metals according to another embodiment of the present invention can provide a valuable metal reactant with a high lithium content and improve the lithium recovery rate by applying a hydrogen reduction method utilizing a hydrogen-containing gas.

[0047]

[0048] FIG. 1 illustrates a method for recovering valuable metals by a hydrogen reduction process according to one embodiment of the present invention.

[0049]

[0050] Terms such as first, second, and third are used to describe various parts, components, regions, layers, and / or sections, but are not limited thereto. These terms are used solely to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, the first part, component, region, layer, or section described below may be referred to as the second part, component, region, layer, or section without departing from the scope of the present invention.

[0051] The technical terms used herein are for the reference of specific embodiments only and are not intended to limit the invention. The singular forms used herein include plural forms unless phrases clearly indicate otherwise. As used in the specification, the meaning of “comprising” specifies certain characteristics, areas, integers, steps, actions, elements, and / or components, and does not exclude the presence or addition of other characteristics, areas, integers, steps, actions, elements, and / or components.

[0052] When it is stated that one part is "on" or "on" another part, it may be directly on or on the other part, or another part may be involved in between. In contrast, when it is stated that one part is "directly on" another part, no other part is interposed in between.

[0053] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as generally understood by those skilled in the art to which this invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with relevant technical literature and the present disclosure, and are not interpreted in an ideal or highly formal sense unless otherwise defined.

[0054] Also, unless otherwise specified, % means weight %, and 1 ppm is 0.0001 weight %.

[0055] In this specification, the term “combination(s) of these” described in the Markush-type expression means one or more mixtures or combinations selected from the group consisting of the components described in the Markush-type expression, and means including any one or more selected from the group consisting of said components.

[0056] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0057]

[0058] A valuable metal reactant according to one embodiment of the present invention will be described below.

[0059] 1. Valuable metal reactants

[0060] A valuable metal reactant according to one embodiment of the present invention is a valuable metal reactant comprising a valuable metal recovered from a waste battery, comprising a first valuable metal containing a valuable metal; a second valuable metal containing a non-magnetic material; and a carbon compound containing carbon, wherein the first valuable metal containing a valuable metal containing a magnetic material and a first lithium compound attached to the surface of the third valuable metal containing a

[0061] [Equation 1]

[0062] 0.34 ≤ [Li] T / ([Al] T + [P] T )≤ 1.80

[0063] (In Equation 1 above, [Li] T , [Al] T and [P] T represents the weight percent of Li, Al, and P, respectively, based on 100 weight percent of the first valuable metal content.

[0064] Preferably, Equation 1 is 0.43 ≤ [Li] T / ([Al] T + [P] T )≤ 1.57, 0.59 ≤ [Li] T / ([Al] T + [P] T )≤ 1.17 can be.

[0065] Specifically, [Li] of Equation 1 above T / ([Al] T + [P] T ) may represent the ratio of the content of the alloy or oxide to the content of LiAlO2 and Li3PO4, etc. contained in the first valuable metal inclusion, and can be interpreted as an indicator of the lithium recovery rate. The aforementioned alloy or oxide may be an alloy or oxide containing at least one of Ni, Fe, and P.

[0066] When the first valuable metal inclusion satisfies the aforementioned Formula 1, a nickel-containing alloy, an Fe-P alloy, or an oxide and a lithium compound can be produced separately. This provides the advantage of being able to recover lithium, the nickel-containing alloy, the Fe-P alloy, and the oxide separately.

[0067] On the other hand, if the above Equation 1 exceeds the upper limit of the aforementioned range, there is a problem in that the lithium compound vaporizes and is lost at high temperatures. If the above Equation 1 exceeds the lower limit of the aforementioned range, as the Al and P content in the composition of the lithium compound increases, the impurity removal process for lithium recovery becomes burdened, and the water leaching rate decreases, resulting in a decrease in the lithium recovery rate.

[0068] In one embodiment, the third valuable metal inclusion within the first valuable metal inclusion may include at least one of nickel, iron, and phosphorus. Specifically, the first valuable metal inclusion may include a magnetic material comprising at least one of nickel, iron, and phosphorus. The first valuable metal inclusion may include a third valuable metal inclusion comprising a magnetic material comprising at least one of nickel, iron, and phosphorus as a core portion.

[0069] In one embodiment, the first lithium compound may be disposed on the surface of a third valuable metal inclusion. Specifically, it may maintain a state of being bonded in a shell form by a reaction between the lithium in the first lithium compound and the magnetic materials in the third valuable metal inclusion.

[0070] When X-ray diffraction analysis (XRD) is performed on the first valuable metal containing material of the valuable metal reactant according to one embodiment of the present invention, at least one peak may occur in each of the intervals where 2theta (2θ) is 15 to 18°, 20 to 25°, 33 to 35°, 55 to 57°, and 66 to 68°.

[0071] The XRD peak occurring in the aforementioned 2theta (2θ) interval is the peak corresponding to the Li2O component.

[0072] If at least one XRD peak occurs in each of the aforementioned 2theta (2θ) intervals, the lithium recovery rate by water leaching may be high.

[0073] When X-ray diffraction analysis (XRD) is performed on the first valuable metal containing material of the valuable metal reactant according to one embodiment of the present invention, at least one peak may occur in each of the intervals where 2theta (2θ) is 20 to 21°, 32 to 33°, and 35.5 to 36.5°.

[0074] The XRD peak occurring in the aforementioned 2theta (2θ) interval is the peak corresponding to the LiOH component.

[0075] If at least one XRD peak occurs in each of the aforementioned 2theta (2θ) intervals, the lithium recovery rate by water leaching may be high.

[0076] When X-ray diffraction analysis (XRD) is performed on the first valuable metal containing material of the valuable metal reactant according to one embodiment of the present invention, at least one peak may occur in each of the intervals where 2theta (2θ) is 16 to 18°, 23 to 24°, 33 to 35°, 51 to 52°, and 60 to 62°.

[0077] The XRD peak occurring in the aforementioned 2theta (2θ) interval is the peak corresponding to the NiO component.

[0078] If at least one XRD peak occurs in each of the aforementioned 2theta (2θ) intervals, the recovery rate of Ni, a valuable metal, in the valuable metal recovery process may be high.

[0079] In a valuable metal reactant according to one embodiment of the present invention, the lithium content of the first lithium compound may be 1.5 to 10 weight% based on 100 weight% of the first valuable metal content.

[0080] When the lithium content of the first lithium compound is included in the first valuable metal inclusion within the aforementioned range, the lithium recovery rate can be increased by having less influence on leaching by graphite in the subsequent process.

[0081] On the other hand, if the lithium content of the first lithium compound is not included within the aforementioned range in the first valuable metal inclusion, there is a problem in that the lithium recovery rate is reduced due to significant influence from leaching by graphite.

[0082] In a valuable metal reactant according to one embodiment of the present invention, the second valuable metal content comprises a second lithium compound, and the lithium content of the second lithium compound may be less than 30 weight% based on 100 weight% of the second valuable metal content.

[0083] Specifically, the lithium content of the second lithium compound may include 8.0 weight% or less, 6.0 weight% or less, and more specifically, 1.15 weight% or less of lithium in the second valuable metal inclusion. The lithium content of the second lithium compound may exceed 0 weight% in the second valuable metal inclusion. This is because lithium is inevitably mixed in as the second valuable metal inclusion undergoes a classification process after magnetic separation.

[0084] By satisfying the aforementioned range for the lithium content of the second lithium compound within the second valuable metal inclusion, there is an advantage in that the content of the lithium compound lost along with graphite during classification can be reduced. If the lithium content of the second lithium compound within the second valuable metal inclusion deviates from the aforementioned range, there is a problem in that the lithium recovery rate is reduced due to significant leaching by graphite in subsequent processes.

[0085] In a valuable metal reactant according to one embodiment of the present invention, based on 100 weight% of the first valuable metal content, the content of an alloy or oxide containing at least one of nickel (Ni), iron (Fe), and phosphorus (P) may be 45.00 to 95.00 weight%. Specifically, the content of an alloy or oxide containing at least one of nickel (Ni), iron (Fe), and phosphorus (P) may be 50 to 92.5 weight%, more specifically, 55 to 90 weight%.

[0086] If the above content exceeds the upper limit of the aforementioned range, there is a problem in that carbon in the cathode material is oxidized, generating a large amount of carbon dioxide (CO2) gas. If the above content exceeds the lower limit of the aforementioned range, the reduction reaction becomes inferior, and the amount of alloy containing Fe or P produced may decrease. Consequently, separation from lithium-containing compounds may not be easy, and the lithium recovery rate in the wet smelting process may decrease.

[0087] In a valuable metal reactant according to one embodiment of the present invention, the waste battery may be one or more selected from lithium nickel-containing batteries and lithium iron phosphate batteries.

[0088] In a valuable metal reactant according to one embodiment of the present invention, the first lithium compound may include at least one of Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4.

[0089] Based on 100 wt% of the first lithium compound, the first lithium compound may comprise Ni: 0.5 to 20 wt%, Fe: 1 to 35 wt%, P: 1 to 15 wt%, Al: 5 to 35 wt%, Li: 1 to 20 wt%, and the remainder being O. Specifically, the Ni may be 0.7 to 18 wt%, the Fe may be 1 to 15 wt%, more specifically, the Ni may be 0.9 to 16 wt%, the Fe may be 5 to 15 wt%, and even more specifically, the Ni may be 1.1 to 14 wt%, and the Fe may be 5 to 8.5 wt%.

[0090] The above P may be 1 to 15 weight%, specifically 1 to 4 weight%, more specifically 1.5 to 3.0 weight%. The above Al may be 5 to 35 weight%, specifically 20 to 35 weight%, more specifically 28 to 32 weight%. The above Li may be 1 to 20 weight%, specifically 8 to 15 weight%, more specifically 11 to 14.5 weight%.

[0091] In a valuable metal reactant according to one embodiment of the present invention, the second lithium compound may include a lithium compound comprising at least one of Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4.

[0092] In a valuable metal reactant according to one embodiment of the present invention, the third valuable metal inclusion may include at least one of nickel (Ni), iron (Fe), and phosphorus (P).

[0093] In one embodiment, the third valuable metal content may comprise, based on 100 weight% of the third valuable metal content, Ni: 45 to 90 weight%, Fe: 60 to 95 weight%, P: 5 to 30 weight%, Al: 3 weight% or less, Li: 5 weight% or less, Cu: 0.5 to 30 weight%, C: 7 weight% or less, and the remainder being O. Specifically, the Ni may be 48 to 88 weight%, the Fe may be 65 to 90 weight%, more specifically, the Ni may be 50 to 85 weight%, the Fe may be 65 to 75 weight%, and even more specifically, the Ni may be 50 to 85 weight%, and the Fe may be 68 to 73 weight%.

[0094] The above P may be 5 to 30 weight%, specifically 10 to 30 weight%, more specifically 18 to 25 weight%. The above Al may be 3 weight% or less, specifically 2 weight% or less, more specifically 1.5 weight% or less. The above Li may be 5 weight% or less, specifically 2 weight% or less, more specifically 1.5 weight% or less.

[0095] In a valuable metal reactant according to one embodiment of the present invention, the second valuable metal inclusion may include at least one of nickel, nickel oxide, cobalt, cobalt oxide, manganese, manganese oxide, manganese aluminum oxide, aluminum, aluminum oxide, aluminum phosphate oxide, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate oxide.

[0096]

[0097] A method for recovering valuable metals according to another embodiment of the present invention will be described below.

[0098] 2. Method for recovering valuable metals

[0099] FIG. 1 illustrates a method for recovering valuable metals by a hydrogen reduction process according to one embodiment of the present invention.

[0100] Referring to FIG. 1 above, a method for recovering valuable metals according to another embodiment comprises: a hydrogen reduction step of hydrogen reducing a battery crushed material with a reducing gas to obtain a valuable metal reactant; a magnetic separation step of separating the valuable metal reactant into a first valuable metal containing an alloy or oxide containing at least one of nickel (Ni), iron (Fe), and phosphorus (P), and a second valuable metal containing a non-magnetic material; and a first separation step of separating the second valuable metal containing into a carbon containing carbon and a second lithium compound, wherein the first valuable metal containing may include a third valuable metal containing a magnetic material and a first lithium compound attached to the surface of the third valuable metal containing, and may satisfy Formula 2 below.

[0101] [Equation 2] 140≤T*P≤1000

[0102] (In Equation 2 above, T represents the reduction temperature during the hydrogen reduction step and P represents the partial pressure of hydrogen (atm) in the reducing gas during the hydrogen reduction step; the unit of the value in Equation 2 above is not considered.)

[0103] The above Equation 2 may preferably be 300≤T*P≤1000, 350≤T*P≤1000, 400≤T*P≤1000, 500≤T*P≤1000, and 500≤T*P≤900.

[0104] When the above Equation 2 is satisfied, there is an advantage in improving the reduction rate of the battery crushed material and the water leaching rate of the first lithium compound. Accordingly, the lithium recovery rate can be improved.

[0105] On the other hand, if the above Equation 2 is below the lower limit value, the reduction rate is significantly low, so a large amount of metal oxide components that were not reduced may exist in the valuable metal reactants, and it may not be easy to separate magnetic and non-magnetic materials by magnetic separation.

[0106] In addition, if the above Equation 2 exceeds the upper limit, the reduction rate may be high, but water leaching may not be easy because a large amount of LiAlO2 component is contained in the valuable metal reactant. Consequently, a problem may arise in which the lithium recovery rate decreases.

[0107] The above-mentioned battery shredder refers to a material that serves as the base material for the battery shredder, or the material itself after the shredding process is completed. The base material of the above-mentioned battery shredder may include batteries that have reached the end of their lifespan, waste batteries, and waste materials generated within the manufacturing process of lithium-ion batteries. Specifically, the waste batteries may include positive electrode materials such as scrap, jelly rolls, and slurries constituting the waste batteries, defective products generated during the manufacturing process, residues within the manufacturing process, and generated debris. The base material of the above-mentioned battery shredder may subsequently undergo a shredding process to be manufactured into a battery shredder. Specifically, as previously mentioned, the waste batteries may be nickel-containing lithium secondary batteries or lithium iron phosphate batteries.

[0108] The aforementioned crushed material itself may be the crushed product itself, such as black powder. In this way, recycling waste batteries to manufacture crushed battery material offers eco-friendly and economic advantages.

[0109] The above hydrogen reduction step may be a step of heat treatment in which a reducing gas containing hydrogen atoms is introduced into the furnace after the battery crushed material is fed into the furnace without undergoing a melting step.

[0110] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the partial pressure of hydrogen in the reducing gas may be 0.1 to 1.0 atm. Preferably, the partial pressure of hydrogen in the reducing gas may be 0.2 to 1.0 atm, 0.5 to 1.0 atm, 0.2 to 0.9 atm, 0.5 to 0.9 atm, 0.7 to 1.0 atm, or 0.7 to 0.9 atm.

[0111] When the partial pressure of hydrogen in the above-mentioned reducing gas falls within the aforementioned range, there is an advantage of improving the lithium recovery rate in the valuable metal recovery process while simultaneously reducing CO2 emissions.

[0112] On the other hand, if the hydrogen partial pressure in the reducing gas is below the lower limit of the aforementioned range, the reduction rate of valuable metals may be significantly low. Consequently, there is a problem with the recovery rate of valuable metals such as lithium and nickel being low. In addition, if the hydrogen partial pressure in the reducing gas exceeds the upper limit of the aforementioned range, the risk of explosion caused by hydrogen gas may increase somewhat, and the safety of the process may be low.

[0113] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the reduction temperature may be 100 to 1000°C. Preferably, the reduction temperature may be 200 to 1000°C, 300 to 1000°C, 400 to 1000°C, 500 to 1000°C, 200 to 900°C, 300 to 900°C, 300 to 800°C, or 500 to 900°C.

[0114] When the above reduction temperature falls within the aforementioned range, there is an advantage in that the water leaching rate and lithium recovery rate of lithium compounds are improved in the valuable metal recovery process, while CO2 emissions are also reduced.

[0115] On the other hand, if the above reduction temperature is below the lower limit of the aforementioned range, the reduction rate of valuable metals may be significantly low. Consequently, there is a problem with a low recovery rate of valuable metals such as lithium and nickel. Furthermore, if the above reduction temperature exceeds the upper limit of the aforementioned range, a large amount of LiAlO2, which is difficult to leach out with water, may be generated among the lithium compounds, leading to a problem with a low lithium recovery rate.

[0116] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the reducing gas is H2, C x H y It may include at least one of (1≤x≤10, 3≤y≤22) and NH3.

[0117] Specifically, in the present invention, the reducing gas may be a gas containing hydrogen atoms, and the present invention is not limited to the types of reducing gases mentioned above. It may also include the application of other reducing gases suitable for the present invention in addition to the types mentioned above.

[0118] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the reducing gas may additionally include at least one of Ar, N2, and He.

[0119] In the method for recovering valuable metals according to the present invention, inert gases such as Ar, N2, and He may be utilized to adjust the hydrogen partial pressure of the reducing gas. However, the present invention is not limited thereto, and may also include the application of other inert gases in addition to the aforementioned types to appropriately adjust the hydrogen partial pressure.

[0120] In the hydrogen reduction step of the valuable metal recovery method according to another embodiment, the valuable metal reactant may satisfy the following Formula 1.

[0121] [Equation 1]

[0122] 0.34 ≤ [Li] T / ([Al] T + [P] T )≤ 1.80

[0123] (In Equation 1 above, [Li] T , [Al] T and [P] T represents the weight percent of Li, Al, and P, respectively, based on 100 weight percent of the first valuable metal content.

[0124] Preferably, Equation 1 is 0.43 ≤ [Li] T / ([Al] T + [P] T )≤ 1.57, 0.59 ≤ [Li] T / ([Al] T + [P] T )≤ 1.17 can be.

[0125] Specifically, [Li] of Equation 1 above T / ([Al] T + [P] T ) may represent the ratio of the content of the alloy or oxide to the content of LiAlO2 and Li3PO4, etc. contained in the first valuable metal inclusion, and can be interpreted as an indicator of the lithium recovery rate. The aforementioned alloy or oxide may be an alloy or oxide containing at least one of Ni, Fe, and P.

[0126] When the first valuable metal inclusion satisfies the aforementioned Formula 1, a nickel-containing alloy, an Fe-P alloy, or an oxide and a lithium compound can be produced separately. This provides the advantage of being able to recover lithium, the nickel-containing alloy, the Fe-P alloy, and the oxide separately.

[0127] On the other hand, if the above Equation 1 exceeds the upper limit of the aforementioned range, there is a problem in that the lithium compound vaporizes and is lost at high temperatures. If the above Equation 1 exceeds the lower limit of the aforementioned range, as the Al and P content in the composition of the lithium compound increases, the impurity removal process for lithium recovery becomes burdened, and the water leaching rate decreases, resulting in a decrease in the lithium recovery rate.

[0128] After the first separation step of the valuable metal recovery method according to another embodiment, a second separation step of separating the first valuable metal content into a third valuable metal content and the first lithium compound may be further included.

[0129] Specifically, the second separation step may include applying a physical (mechanical) external force to the first valuable metal inclusion to crush it to a particle size range of 100 to 4000 μm, more specifically to a range of 100 to 1000 μm. By crushing the first valuable metal inclusion to the aforementioned range, the first lithium compound attached to the surface of the third valuable metal inclusion may be detached. At this time, the third valuable metal inclusion may be an alloy or oxide containing at least one of nickel, iron, and phosphorus, and the first lithium compound may be a lithium compound such as LiOH, LiOH·H2O, LiAlO2, Li3PO4, etc.

[0130] In the second separation step above, when separating the third valuable metal inclusion and the first lithium compound by a physical external force, there is an advantage in that the recovery rate of lithium, as well as valuable metals such as nickel, iron, and phosphorus, can be improved together.

[0131] In the second separation step, if crushing is performed outside the upper limit of the particle size range, the size of the nickel-containing alloy or Fe-P-containing alloy produced during high-temperature heat treatment of the crushed material increases, which causes a problem of increased leaching time in the subsequent wet process. In the second separation step, if crushing is performed outside the lower limit of the range, the size of the alloy produced during high-temperature heat treatment of the crushed material of 100 μm or less decreases, so graphite is separated together during magnetic separation, and the process is delayed due to interference problems with graphite that is not dissolved in acid during the leaching process.

[0132] In one embodiment, the second separation step, which crushes the first valuable metal inclusion to separate it into a third valuable metal inclusion and a first lithium compound, may be performed after the magnetic separation step, which separates the valuable metal inclusion into a first valuable metal inclusion containing a magnetic material and a second valuable metal inclusion containing a non-magnetic material, after the aforementioned high-temperature reduction reaction. The second separation step may be performed, for example, between the aforementioned magnetic separation step and the aforementioned graphite separation step, or after the aforementioned magnetic separation step and the aforementioned graphite separation step. The advantage of the second separation step being performed after the aforementioned magnetic separation step is that it prevents the aggregation of lumps such as flakes.

[0133] In one embodiment, after a high-temperature reduction reaction, the method may further include a step of removing impurities prior to a magnetic separation step for separating the valuable metal contents into a first valuable metal contents containing a magnetic material and a second valuable metal contents containing a non-magnetic material. The impurities may be, for example, impurities such as flakes. Specifically, the impurities may be, for example, materials derived from aluminum or copper.

[0134] In one embodiment, the step of removing the impurities may be performed using any one of magnetic separation, particle size separation, and specific gravity separation. In the case of magnetic separation, it may be performed using a magnetic material having a magnetic field strength capable of separating impurities, such as flakes, from valuable metal inclusions, including nickel-containing alloys or Fe-P alloys. Particle size separation may separate iron fragments through particle size control. Specifically, the particle size may be an average particle diameter, and particle size separation may be performed based on a range of, for example, 5 to 10 mm or more.

[0135] By first removing impurities prior to the aforementioned magnetic separation, there is an advantage in that impurities that may affect magnetic separation are removed, thereby increasing the recovery rate of valuable metals.

[0136]

[0137] The following describes embodiments, comparative examples, and experimental examples of the present invention. However, the following examples are merely preferred embodiments of the present invention, and the present invention is not limited by the following examples. Furthermore, it is possible to implement the invention with various modifications within the scope of the claims, the detailed description of the invention, and the attached drawings, and such modifications may also fall within the scope of the present invention.

[0138] Example 1

[0139] (Hydrogen reduction step) 25 kg of lithium iron phosphate (LFP) batteries were cooled to -70°C for 7 hours and then crushed to prepare crushed battery material. At this time, the size of the crushed battery material was set to 10 to 20 mm based on the major axis among the width, length, and height. After preparing the crushed battery material, it was introduced into a furnace. Then, a reducing gas was injected into the furnace. At this time, the reducing gas was a mixed gas of hydrogen (H2) and nitrogen (N2), and the partial pressure of the hydrogen was set to 1.0 atm. After the reducing gas atmosphere was established, the temperature inside the furnace was raised to 300°C and maintained for 5 hours to produce valuable metal reactants.

[0140] (Magnetic separation step) The above valuable metal reactants were separated by magnetic separation to separate a first valuable metal containing a magnetic material and a second valuable metal containing a non-magnetic material.

[0141] (1st separation step) The second valuable metal-containing material was crushed and classified to extract graphite.

[0142] (Second separation step) The first valuable metal content was crushed so that its average particle size was 500 μm, and separated into the third valuable metal content and the first lithium compound.

[0143] Example 2

[0144] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 400 ℃.

[0145] Example 3

[0146] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 500 ℃.

[0147] Example 4

[0148] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 700 ℃.

[0149] Example 5

[0150] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 800 ℃.

[0151] Example 6

[0152] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 4, except that the hydrogen partial pressure was changed to 0.2 atm.

[0153] Example 7

[0154] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 4, except that the hydrogen partial pressure was changed to 0.5 atm.

[0155] Example 8

[0156] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 4, except that the hydrogen partial pressure was changed to 0.8 atm.

[0157] Example 9

[0158] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the hydrogen partial pressure was changed to 0.5 atm and the temperature inside the furnace was changed to 1000 ℃.

[0159] Example 10

[0160] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the hydrogen partial pressure was changed to 0.8 atm and the temperature inside the furnace was changed to 1000 ℃.

[0161] Example 11

[0162] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the hydrogen partial pressure was changed to 0.9 atm and the temperature inside the furnace was changed to 1000 ℃.

[0163] Example 12

[0164] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 1000 ℃.

[0165] Comparative Example 1

[0166] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 100°C.

[0167] Comparative Example 2

[0168] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 1, except that the temperature inside the furnace was changed to 1100 ℃.

[0169] Comparative Example 3

[0170] In the hydrogen reduction step, the process of generating valuable metal reactants and recovering valuable metals was carried out in the same manner as in Example 4, except that the hydrogen partial pressure was changed to 0.1 atm.

[0171]

[0172] Experimental Example 1 - Analysis of Valuable Metal Reduction Rate and Lithium Compound Content

[0173] The reduction rate of nickel or iron-containing oxides from the valuable metal reactants generated after the above hydrogen reduction step was measured, and the content of lithium compounds contained in the valuable metal reactants was analyzed.

[0174] Experimental Example 2 - XRD Analysis

[0175] XRD analysis was performed on the first valuable metal content obtained after magnetic separation of the valuable metal reactants.

[0176] Classification Process Condition Result Reduction Temperature Hydrogen Partial Pressure Equation 2 Value T*P Reduction Rate Li2OL LiOH Li3PO4 Li2CO3 LiAlO2 Water Leaching Rate Equation 1 Value [Li] T / ([Al] T +[P] T)Reduction rate (%) * Water leaching rate (%) [℃][atm][%][Weight %][%] Example 1 300 1300 8 11.5 2 11.6 0 3 1.9 6 2 7.7 6 17.1 5 4 3.0 3 1.3 6 3 4 4.2 Example 2 400 400 2 4 10.4 5 12.9 2 3 2.4 5 2 5.3 3 18.8 5 4 1.3 0 1.2 8 9 9 1.2 Example 3 500 500 5 6 7.2 5 15.2 5 3 2.7 8 2 3.9 12 0.8 1 3 9.3 7 1.1 6 2 2 0 4.7 Example 4 700 700 6 8 5.9 6 10.2 6 3 5.5 0 2 3.1 8 2 5.1 0 3 3.1 4 0.9 5 2 2 5 3.5 Example 5800800843.687.6436.4223.0329.2328.610.812403.2 Example 67000.21402810.3121.704.3534.0229.6156.031.571568.8 Example 70.5350643.365.205.0833.9052.4634.820.682228.5 Example 80.8560802.214.695.3630.1157.6330.300.592424.0 Example 910000.5500718.7915.134.8834.1837.0148.881.173470.5 Example 100.8800855.4911.415.0734.3843.6442.720.913631.2 Example 110.9900903.946.305.0934.7749.9037.030.733332.7 Example 12110001001.214.036.0917.7670.9118.920.431892.0 Comparative Example 11001100414.1813.8134.2129.198.6148.541.81194.2 Comparative Example 21100111001000.231.063.1812.1083.4310.840.331084.0 Comparative Example 37000.1701611.6722.614.1236.1225.4859.751.88956.0

[0177] Table 1 shows the reduction rate of the valuable metal reactant, the content of each type of lithium compound, the water leaching rate of the lithium compound, and the values ​​of Equation 1 according to the conditions of the valuable metal recovery process. Regarding the contents described in Table 1, referring to Examples 1 to 5, 12 and Comparative Example 2, it was confirmed that the reduction rate increases as the reduction temperature increases. An increase in the reduction rate can be understood as an improvement in the magnetic separation performance of the first valuable metal content and the second valuable metal content within the valuable metal reactant. In other words, it may be easier to separate magnetic and non-magnetic components. However, it was confirmed that the water leaching rate decreases as the reduction temperature increases. In particular, it was confirmed that when the reduction temperature is 1000 ℃ or higher, the decrease in the water leaching rate is greater than when it is below 1000 ℃. The aforementioned decrease in the water leaching rate is due to an increase in the content of Li3PO4 and LiAlO2 among the lithium compounds, which inhibit water leaching. Specifically, when the reduction temperature is below 1000 ℃, the content of LiAlO2 is less than 30 wt%, but when it is above 1000 ℃, the content of LiAlO2 exceeds 70 wt%, making water leaching more difficult. Furthermore, in the temperature range below 1000 ℃, as the reduction temperature increases, the content of Li3PO4 also increases to a range of 30 wt% or more, resulting in a decrease in the water leaching rate. A decrease in the water leaching rate may lead to a lower lithium recovery rate in subsequent processes. Additionally, referring to Examples 6 to 8 and Examples 9 to 12, it was confirmed that when controlled at the same reduction temperature, the reduction rate increases as the hydrogen partial pressure increases. As with Examples 1 to 5, it was confirmed that the water leaching rate actually decreases as the hydrogen partial pressure increases. This is because, within the same temperature range, as the hydrogen partial pressure increases, the content of both Li3PO4 and LiAlO2, which inhibit water leaching, increases.

[0178] In addition, when the values ​​of Equation 1 and Equation 2 in Table 1 above are controlled within a predetermined range, it can be said that a preferred valuable metal reactant of the present invention is formed. The control range of the value of Equation 1 may be 0.34 to 1.80, preferably 0.43 to 1.57. The control range of the value of Equation 2 may be 140 to 1000, preferably 350 to 1000, or 500 to 1000. Furthermore, considering the aspect of simultaneous improvement of the reduction rate of the valuable metal and the lithium recovery rate, when the product of the reduction rate and the water leaching rate (reduction rate * water leaching rate) is 1568.8 to 3631.2 (preferably 1892.0 to 3631.2, or 2204.7 to 3631.2), which is significantly higher than that of the comparative example, it can be understood that a valuable metal reactant is formed that facilitates magnetic separation and simultaneously has an excellent lithium recovery rate.

[0179]

[0180] The present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art will understand that the invention can be implemented in other specific forms without changing the technical concept or essential features of the invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A valuable metal reactant comprising a valuable metal recovered from a waste battery, First valuable metal inclusion; A second valuable metal inclusion comprising a non-magnetic material; and It includes carbon compounds containing carbon, and The first valuable metal inclusion comprises a third valuable metal inclusion containing a magnetic material and a first lithium compound attached to the surface of the third valuable metal inclusion, and The above first valuable metal inclusion satisfies Formula 1 below, Precious metal reactants: [Equation 1] 0.34 ≤ [Li] T / ([Al] T + [P] T ≤ 1.80 (In Equation 1 above, [Li] T , [Al] T and [P] T represents the weight percent of Li, Al, and P, respectively, based on 100 weight percent of the first valuable metal content.

2. In Paragraph 1, When X-ray diffraction analysis (XRD) is performed on the first valuable metal inclusion, at least one peak occurs in each interval where 2theta (2θ) is 15 to 18°, 20 to 25°, 33 to 35°, 55 to 57°, and 66 to 68°. Precious metal reactants.

3. In Paragraph 1, When X-ray diffraction analysis (XRD) is performed on the first valuable metal inclusion, at least one peak occurs in each interval where 2theta (2θ) is 20 to 21°, 32 to 33°, and 35.5 to 36.5°, Precious metal reactants.

4. In Paragraph 1, When X-ray diffraction analysis (XRD) is performed on the first valuable metal inclusion, at least one peak occurs in each interval where 2theta (2θ) is 16 to 18°, 23 to 24°, 33 to 35°, 51 to 52°, and 60 to 62°, Precious metal reactants.

5. In Paragraph 1, The lithium content of the first lithium compound is 1.5 to 10 weight% based on 100 weight% of the first valuable metal content, Precious metal reactants.

6. In Paragraph 1, The above second valuable metal inclusion comprises a second lithium compound, The lithium content of the second lithium compound is less than 30 weight% based on 100 weight% of the second valuable metal content, Precious metal reactants.

7. In Paragraph 1, Based on 100 weight% of the first valuable metal content, the content of the alloy or oxide containing at least one of nickel (Ni), iron (Fe), and phosphorus (P) is 45.00 to 95.00 weight%, Precious metal reactants.

8. In Paragraph 1, The above waste battery is one or more types selected from lithium nickel-containing batteries and lithium iron phosphate batteries, Precious metal reactants.

9. In Paragraph 1, The first lithium compound comprises a lithium compound including at least one of Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4. Precious metal reactants.

10. In Paragraph 6, The second lithium compound above comprises a lithium compound including at least one of Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4. Precious metal reactants.

11. In Paragraph 1, The above third valuable metal inclusion comprises at least one of nickel (Ni), iron (Fe), and phosphorus (P). Precious metal reactants.

12. In Paragraph 1, The second valuable metal inclusion comprises at least one of nickel, nickel oxide, cobalt, cobalt oxide, manganese, manganese oxide, manganese aluminum oxide, aluminum, aluminum oxide, aluminum phosphate oxide, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate oxide. Precious metal reactants.

13. A hydrogen reduction step for obtaining a valuable metal reactant by hydrogen reducing battery fragments with a reducing gas; A magnetic separation step for separating the above valuable metal reactants into a first valuable metal containing an alloy or oxide comprising at least one of nickel (Ni), iron (Fe), and phosphorus (P), and a second valuable metal containing a non-magnetic material; and The above second valuable metal inclusion includes a first separation step of separating into a carbon inclusion containing carbon and a second lithium compound, and The first valuable metal inclusion comprises a third valuable metal inclusion containing a magnetic material and a first lithium compound attached to the surface of the third valuable metal inclusion, and Satisfying Equation 2 below, Method for recovering valuable metals: [Equation 2] 140≤T*P≤1000 (In Equation 2 above, T represents the reduction temperature during the hydrogen reduction step and P represents the partial pressure of hydrogen (atm) in the reducing gas during the hydrogen reduction step; the units of the values ​​in Equation 2 above are not considered.) 14. In Paragraph 13, In the above hydrogen reduction step, the partial pressure of hydrogen in the reducing gas is 0.1 to 1.0 atm, Method for recovering valuable metals.

15. In Paragraph 13, In the above hydrogen reduction step, the reduction temperature is 100 to 1000℃, Method for recovering valuable metals.

16. In Paragraph 13, In the above hydrogen reduction step, the reducing gases are H2 and C x H y (1≤x≤10, 3≤y≤22) and at least one of NH3, Method for recovering valuable metals.

17. In Paragraph 16, In the above hydrogen reduction step, the reducing gas further comprises at least one of Ar, N2, and He. Method for recovering valuable metals.

18. In Paragraph 13, In the above hydrogen reduction step, The above valuable metal reactant satisfies Formula 1 below, Method for recovering valuable metals. [Equation 1] 0.34 ≤ [Li] T / ([Al] T + [P] T ≤ 1.80 (In Equation 1 above, [Li] T , [Al] T and [P] T represents the weight percent of Li, Al, and P, respectively, based on 100 weight percent of the first valuable metal content.

19. In Paragraph 13, After the first separation step above, A second separation step further comprising separating the first valuable metal content into a third valuable metal content and the first lithium compound, Method for recovering valuable metals.

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