Reagents for recovering valuable metals, valuable metal scraps, and methods for recovering valuable metals.

Abstract

The invention relates to a valuable metal reactant, a finely ground product containing valuable metals, and a method for recovering valuable metals. The valuable metal reactant under the invention is a valuable metal reactant comprising valuable metals recovered from waste batteries, and comprising a first valuable metal-containing material comprising an alloy or oxide of at least one of iron (Fe) and phosphorus (P), a second valuable metal-containing material comprising a non-magnetic material, and a carbon-containing compound comprising carbon. The first valuable metal-containing material comprises a third valuable metal-containing material comprising a magnetic material and a first lithium compound attached to the surface of the third valuable metal-containing material, and the lithium content of the first lithium compound is 1.5% by mass or more based on the total mass of the first valuable metal-containing material.

Description

Valuable metal reactant, valuable metal scrap, and method for recovering valuable metal

[0001] The present invention relates to waste batteries, and to valuable metal reactants, valuable metal scrap, and a method for recovering valuable metals recovered from waste battery recycling.

[0002] As global demand for electric vehicles grows, the disposal of waste batteries generated from these vehicles is emerging as a social issue. Lithium secondary batteries, the primary raw material for these waste batteries, contain organic solvents, explosive materials, and heavy metals such as nickel, cobalt, manganese, iron, and phosphorus. However, nickel, cobalt, manganese, iron, phosphorus, and lithium are highly valuable metals, making the recovery and recycling of discarded lithium secondary batteries an emerging research area.

[0003] Specifically, a lithium secondary battery is mainly composed of copper and aluminum used as a current collector, oxides containing Li, Ni, Co, Mn, Fe, and P constituting a positive electrode material, and graphite and Si used as a negative electrode material, and includes a separator separating the positive electrode material and the negative electrode 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 substances such as ethylene carbonate and propylene carbonate, and for example, LiPF6 is used.

[0004] To utilize these waste batteries, interest is growing in a waste battery recycling process that involves crushing the waste batteries to produce intermediate materials such as waste battery shreds or black powder, followed by post-processing to recover valuable metals. Specifically, the primary components of waste batteries are comprised of expensive, valuable metal elements such as nickel, cobalt, manganese, lithium, iron, and phosphorus.

[0005] The above-mentioned waste batteries are, for example, secondary batteries that have reached the end of their lifespan after being used for a period of 5 to 10 years. Recycling the main components of these waste batteries is essential for both environmental and cost reasons. These waste batteries undergo conventional crushing, grinding, or gravity sorting processes to produce a mixture of positive and negative electrode materials in the form of a black powder, an intermediate product. The valuable metals essential for battery production are recovered from this black powder through wet processes such as leaching, solvent extraction, or crystallization. This process facilitates the supply of raw materials and significantly reduces battery manufacturing costs.

[0006] In the process of separating a reactant that has been subjected to calcination and heat treatment as a method for recovering waste batteries, a method of first separating graphite and then performing magnetic separation to recover valuable metals was studied. However, when the graphite is separated first, a large amount of lithium compounds of the same fine particles as the graphite and LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4 are mixed, and in the post-processing sorting process for removing the graphite, the lithium compounds are included together, and the lithium content passed on to the subsequent process is lost, which reduces the lithium recovery rate.

[0007] According to one embodiment of the present invention, the valuable metal reactant provides a reactant having a high content of valuable metal, specifically lithium, when recovering valuable metal in a post-process.

[0008] According to another embodiment of the present invention, a valuable metal shredder is produced by shredding a valuable metal reactant having the aforementioned advantages, thereby providing a shredder having a high content of valuable metal.

[0009] According to another embodiment of the present invention, a method for recovering valuable metals provides a method for recovering valuable metals having a high content of valuable metals by producing a valuable metal reactant and a crushed material having the advantages described above.

[0010] According to one embodiment of the present invention, a valuable metal reactant is a valuable metal reactant including a valuable metal recovered from a spent battery, and includes a first valuable metal containing material including an alloy or oxide including at least one of iron (Fe) and phosphorus (P), a second valuable metal containing material including a non-magnetic material, and a carbon compound including carbon, wherein the first valuable metal containing material includes a third valuable metal containing material including a magnetic material and a first lithium compound attached to a surface of the third valuable metal containing material, and a lithium content of the first lithium compound may include lithium (Li) of 1.5% or more by weight in the first valuable metal containing material.

[0011] In one embodiment, the content of the alloy or oxide including at least one of iron (Fe) and phosphorus (P) may be 75.00 to 95.00 wt% based on 100 wt% of the first valuable metal containing material. In one embodiment, the valuable metal reactant may be obtained from a lithium iron phosphate battery.

[0012] In one embodiment, the precious metal reactant may have a content of an alloy or oxide including at least one of iron (Fe) and phosphorus (P) in the first precious metal containing material and a content of lithium (Li) that satisfies the following Equation 1.

[0013] <Formula 1>

[0014] 5.0 ≤ [Fe-P] / [Li] ≤ 60.0

[0015] (In the above formula 1, [Fe-P] and [Li] mean the content of an alloy or oxide containing at least one of iron (Fe) and phosphorus (P) in the first valuable metal content and the content of lithium (Li), respectively.)

[0016] In one embodiment, the first lithium compound may include a lithium compound including at least one of LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4. In one embodiment, the second valuable metal-containing material may include a second lithium compound, and the lithium content of the second lithium compound may include less than 20 wt% of lithium in the second valuable metal-containing material.

[0017] In one embodiment, the second lithium compound may include at least one of LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, and Li5FeO4. In one embodiment, the third valuable metal-containing material may include at least one of iron (Fe) and phosphorus (P).

[0018] In one embodiment, the second valuable metal-containing material may include at least one of a second lithium compound, aluminum, aluminum oxide, aluminum phosphate, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate.

[0019] In another embodiment of the present invention, the valuable metal fragments may be produced by crushing the aforementioned valuable metal reactant. In one embodiment, the valuable metal fragments may have an average particle size of 100 to 4000 μm.

[0020] According to another embodiment of the present invention, a method for recovering valuable metals comprises a high-temperature reduction step of subjecting battery scrap to a high-temperature reduction reaction to obtain a valuable metal reactant, a magnetic separation step of separating the valuable metal reactant into a first valuable metal containing material including an alloy or oxide including at least one of iron (Fe) and phosphorus (P) and a second valuable metal containing material including a non-magnetic material, and a first separation step of separating the second valuable metal containing material into a carbon containing material including carbon and a second lithium compound, wherein the first valuable metal containing material includes a third valuable metal containing material including a magnetic material and a first lithium compound attached to a surface of the third valuable metal containing material, and a lithium content of the first lithium compound may include 1.5% or more of lithium in weight percent within the first valuable metal containing material.

[0021] In one embodiment, after the first separation step, a second separation step may be included for separating the first valuable metal-containing material into a third valuable metal-containing material and the first lithium compound. In one embodiment, the second separation step may include a step of detaching the first lithium compound attached to the surface of the third valuable metal-containing material.

[0022] In one embodiment, the second separation step may include crushing the first valuable metal-containing material into particles having an average particle size of 100 to 4000 μm. In one embodiment, the battery waste may be crushed from an iron phosphate battery.

[0023] In one embodiment, the high temperature reduction step may be performed at a temperature of 700 to 1,350° C. In one embodiment, the high temperature reduction step may be performed under conditions of 5 vol % or less of oxygen.

[0024] In one embodiment, the first separation step may be performed through particle size separation. In one embodiment, prior to the high-temperature reduction reaction step, a step of freezing the battery serving as the parent material of the battery shredder may be further included.

[0025] According to one embodiment of the present invention, a valuable metal reactant includes a first valuable metal containing material including an alloy or oxide containing at least one of iron (Fe) and phosphorus (P), and includes lithium (Li) of 1.5% or more in the first valuable metal containing material, thereby providing a reactant having a high content of valuable metal, specifically lithium, and a high recovery rate of lithium when recovering the valuable metal in a post-process.

[0026] According to another embodiment of the present invention, a valuable metal crusher is produced by crushing a valuable metal reactant having the aforementioned advantages, thereby providing a crusher having a high content of valuable metal and a high recovery rate of valuable metal.

[0027] According to another embodiment of the present invention, a method for recovering valuable metals provides a method for recovering valuable metals having an excellent recovery rate of valuable metals by producing a valuable metal reactant and a crushed material having the advantages described above.

[0028] FIG. 1 is a graph of minimum cooling time according to one embodiment of the present invention.

[0029] FIG. 2 is a graph showing the relationship between battery weight, external cooling temperature, and cooling time according to one embodiment of the present invention.

[0030] Figures 3a and 3b are photographs of a comparative example in which a fire occurred when crushing was performed after freezing for a shorter time than the minimum cooling time, and Figures 3c and 3d are photographs of an example in which a fire did not occur when crushing was performed after freezing for a longer time than the minimum cooling time according to the example.

[0031] The terms first, second, and third, etc., are used to describe, but are not limited to, various parts, components, regions, layers, and / or sections. These terms are used only to distinguish one part, component, region, layer, or section from another part, component, region, layer, or section. Accordingly, a first part, component, region, layer, or section described below may be referred to as a second part, component, region, layer, or section without departing from the scope of the present invention.

[0032] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the present invention. As used herein, the singular forms "singular" and "comprising" include plural forms as well, unless the context clearly dictates otherwise. The word "comprising" as used herein specifies a particular feature, region, integer, step, operation, element, and / or component, but does not exclude the presence or addition of other features, regions, integers, steps, operations, elements, and / or components.

[0033] When a part is referred to as being "on" or "over" another part, it can be directly on or over the other part, or there may be other parts intervening. Conversely, when a part is referred to as being "directly on" another part, there are no other parts intervening.

[0034] Although not defined otherwise, all terms, including technical and scientific terms, used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention pertains. Terms defined in commonly used dictionaries are further interpreted to have meanings consistent with the relevant technical literature and the present disclosure, and are not to be construed as ideal or overly formal unless otherwise defined.

[0035] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and the present invention is not limited thereto, and the present invention is defined solely by the scope of the claims set forth below.

[0036] According to one embodiment of the present invention, the valuable metal reactant is a valuable metal reactant including a valuable metal recovered from a spent battery, and may include a first valuable metal containing material including a magnetic material, a second valuable metal containing material including a non-magnetic material, a carbon compound including carbon, and other residual impurities. The valuable metal reactant refers to a reactant obtained by subjecting battery waste to a high-temperature reduction reaction, performing magnetic separation, and then extracting the carbon compound, for example, graphite, from the second valuable metal containing material in the method for recovering valuable metals described below.

[0037] The above-mentioned waste battery may be specifically obtained from a lithium iron phosphate battery. The lithium iron phosphate battery is cheaper, safer, and has a longer lifespan than other lithium ion batteries, making it an excellent battery for use in electric vehicles and power grids. The above-mentioned valuable metal reactant may be produced from the lithium iron phosphate battery and obtained by recycling the lithium iron phosphate battery, which has recently shown a high recovery rate, thereby exhibiting excellent economic efficiency and safety.

[0038] In one embodiment, the first valuable metal-containing material may include a third valuable metal-containing material and a first lithium compound attached to the surface of the third valuable metal-containing material. The valuable metal reactant is a reactant generated in a step before crushing the first valuable metal-containing material in the method for recovering valuable metals described below, and may include the third valuable metal-containing material alone, the third valuable metal-containing material, and the third valuable metal-containing material with the first lithium compound attached to the surface.

[0039] In one embodiment, the third valuable metal content may include Fe: 60 to 95 wt%, P: 5 to 30 wt%, Al: 3 wt% or less, Li: 5 wt% or less, Cu: 0.5 to 30 wt%, C: 7 wt% or less, and the remainder O, based on 100 wt% of the third valuable metal content. Specifically, the Fe content may be 65 to 90 wt%, more specifically, 65 to 75 wt%, and even more specifically, 68 to 73 wt%.

[0040] The P may be 5 to 30 wt%, specifically, 10 to 30 wt%, and more specifically, 18 to 25 wt%. The Al may be 3 wt% or less, specifically, 2 wt% or less, and more specifically, 1.5 wt% or less. The Li may be 5 wt% or less, specifically, 2 wt% or less, and more specifically, 1.5 wt% or less.

[0041] In one embodiment, the third valuable metal containing material within the first valuable metal containing material may include at least one of iron and phosphorus. Specifically, the first valuable metal containing material may include a magnetic material including at least one of iron and phosphorus. The third valuable metal containing material, which includes a magnetic material including at least one of iron and phosphorus, may be included as a core portion among the first valuable metal containing materials.

[0042] In one embodiment, the first lithium compound may be disposed on the surface of the third valuable metal-containing material. Specifically, the first lithium compound may be maintained in a shell-like state by a reaction between lithium in the first lithium compound and magnetic materials in the third valuable metal-containing material. The first lithium compound may be a composition including a lithium compound including at least one of LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, and Li3Fe5O8, Li5FeO4.

[0043] The first lithium compound may include Fe: 1 to 35 wt%, P: 1 to 15 wt%, Al: 5 to 35 wt%, Li: 1 to 20 wt%, and the remainder O, based on 100 wt% of the first lithium compound. Specifically, the Fe may be 1 to 15 wt%, more specifically, 5 to 15 wt%, and even more specifically, 5 to 8.5 wt%.

[0044] The P may be 1 to 15 wt%, specifically, 1 to 4 wt%, and more specifically, 1.5 to 3.0 wt%. The Al may be 5 to 35 wt%, specifically, 20 to 35 wt%, and more specifically, 28 to 32 wt%. The Li may be 1 to 20 wt%, specifically, 8 to 15 wt%, and more specifically, 11 to 14.5 wt%.

[0045] In one embodiment, the second valuable metal-containing material may include at least one of a second lithium compound, aluminum, aluminum oxide, aluminum phosphate oxide, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate oxide.

[0046] The third valuable metal containing material and the first lithium compound and the second valuable metal containing material in the first valuable metal containing material may include the aforementioned type of material. The aforementioned type of material may be a characteristic that appears because it is obtained from a lithium iron phosphate battery.

[0047] In one embodiment, the content of the alloy or oxide including at least one of iron (Fe) and phosphorus (P) may be 75.00 to 95.00 wt% based on 100 wt% of the first valuable metal content. Specifically, the content of the alloy or oxide including at least one of iron (Fe) and phosphorus (P) may be 80 to 92.5 wt%, and more specifically, 85 to 90 wt%.

[0048] If the content exceeds the upper limit of the aforementioned range, there is a problem that the carbon in the negative electrode material is oxidized, generating a large amount of carbon dioxide (CO2) gas. If the content exceeds the lower limit of the aforementioned range, the reduction reaction is poor, the amount of alloy containing Fe or P produced is reduced, and the separation from lithium-containing compounds is poor, resulting in a problem that the lithium recovery rate in the wet smelting process is reduced.

[0049] In one embodiment, the lithium content of the first lithium compound may include at least 1.5% by weight of lithium within the first valuable metal containing material. Specifically, the lithium content of the first lithium compound may include from 1.1% to 9.5% by weight of lithium within the first valuable metal containing material, and more specifically from 6.36% to 8.42% by weight of lithium within the first valuable metal containing material.

[0050] When the lithium content of the first lithium compound is within the above-mentioned range within the first valuable metal-containing material, the lithium recovery rate can be increased due to less influence of leaching by graphite in the post-process. When the lithium content of the first lithium compound is not within the above-mentioned range within the first valuable metal-containing material, there is a problem in that the lithium recovery rate is reduced due to a significant influence of leaching by graphite.

[0051] In one embodiment, the content of the alloy or oxide including at least one of iron (Fe) and phosphorus (P) and the content of lithium (Li) in the first valuable metal content may satisfy the following equation 1.

[0052] <Formula 1>

[0053] 5.0 ≤ [Fe-P] / [Li] ≤ 60.0

[0054] (In the above formula 1, [Fe-P] and [Li] mean the content of an alloy or oxide containing at least one of iron (Fe) and phosphorus (P) in the first valuable metal content and the content of lithium (Li), respectively.)

[0055] The above formula 1 is a ratio of the content of an alloy or oxide containing either iron or phosphorus to lithium in the first valuable metal containing material, and may be an indicator of a lithium recovery rate. The above formula 1 may satisfy a ratio of 5.0 to 60.0, specifically, 8.0 to 25.0, more specifically, 8.0 to 20.0, more specifically, 9.0 to 15.0, and more specifically, 10.0 to 14.0.

[0056] Since the above formula 1 satisfies the above-mentioned range, there is an advantage in that the Fe-P alloy or oxide and the lithium compound are produced separately, and thus lithium and the precious metal Fe-P can be recovered separately. If the above formula 1 exceeds the upper limit of the above-mentioned range, there is a problem in that the carbon in the negative electrode material is oxidized and a large amount of carbon dioxide (CO2) gas is generated. If the above formula 1 exceeds the lower limit of the above-mentioned range, the reduction reaction is poor, so that the amount of alloy containing Fe or P produced is reduced, and the separation from the lithium-containing compound is poor, so that there is a problem in that the lithium recovery rate in the wet refining process is reduced.

[0057] In one embodiment, the lithium content of the second lithium compound may include less than 20% by weight of lithium within the second valuable metal containing material. Specifically, the lithium content of the second lithium compound may include 8.0% or less, 6.0% or less, and more specifically, 1.15% or less by weight of lithium within the second valuable metal containing material. The lithium content of the second lithium compound may be greater than 0% within the second valuable metal containing material. This is because lithium is bound to be mixed in as the second valuable metal containing material undergoes a classification process after magnetic separation.

[0058] There is an advantage in that the lithium content of the second lithium compound within the second valuable metal-containing material satisfies the aforementioned range, thereby reducing the content of the lithium compound lost together with graphite during classification. If the lithium content of the second lithium compound within the second valuable metal-containing material exceeds the aforementioned range, there is a problem in that the lithium recovery rate is lowered due to significant influence of leaching by graphite in the subsequent process.

[0059] According to another embodiment of the present invention, the precious metal fragment may be produced by crushing the precious metal reactant described above. Specifically, the precious metal fragment may be produced by a crushing step performed to separate a third precious metal containing substance having a first lithium compound disposed on the surface of the first precious metal containing substance of the above-described precious metal reactant.

[0060] More specifically, the valuable metal fragment may include a crushed third valuable metal-containing material and a first lithium compound. In one embodiment, the valuable metal fragment may have an average particle size of 100 to 4000 μm. By having an average particle size within the aforementioned range, the valuable metal fragment may easily obtain the first lithium compound within the first valuable metal-containing material, thereby increasing the lithium recovery rate.

[0061] Specific descriptions and contents of the third valuable metal containing material and the first lithium compound may be referred to in the description of the valuable metal reactant.

[0062] According to another embodiment of the present invention, a method for recovering valuable metals comprises a step of subjecting battery waste to a high-temperature reduction reaction, a magnetic separation step of separating the generated reaction product after the high-temperature reduction reaction into a first valuable metal-containing material including a magnetic material and a second valuable metal-containing material including a non-magnetic material, and a first separation step of separating a carbon-containing material containing carbon from the valuable metal-containing material obtained after the magnetic separation step.

[0063] The above battery shredder refers to a material that serves as a parent material for battery shredder, or the material itself that has been shredded. The parent material for the battery shredder may include batteries that have reached the end of their useful life, waste batteries, and waste materials generated during the manufacturing process of lithium ion batteries. Specifically, the waste batteries may include positive electrode materials such as scrap, jelly rolls, and slurry that constitute the waste batteries, defective products generated during the manufacturing process, residues within the manufacturing process, and generated debris. The parent material for the battery shredder may then be manufactured into battery shredder through a shredding process. Specifically, the waste batteries may be lithium iron phosphate batteries, as described above.

[0064] The shredded material itself can be a shredded product, such as a black powder. In this way, recycling waste batteries to produce shredded battery material offers environmentally friendly and economical benefits.

[0065] The step of subjecting the battery shreds to a high-temperature reduction reaction is a step of placing the battery shreds into a heating furnace capable of raising the temperature to a temperature higher than the melting point of the battery shreds. The step of subjecting the battery shreds to a high-temperature reduction reaction may involve heat treatment conditions that perform a high-temperature reduction reaction without going through a melting step.

[0066] In one embodiment, the step of subjecting the battery shreds to a high-temperature reduction reaction may be performed at a temperature range of 700 to 1,350°C. In one embodiment, the step of subjecting the battery shreds to a high-temperature reduction reaction may be performed under conditions of 5 vol% or less oxygen. By performing the high-temperature reduction reaction under these conditions, there is the advantage of improved lithium recovery and reduced CO2 emissions.

[0067] After the high-temperature reduction reaction, the magnetic separation step of separating the generated reactant into a first valuable metal containing material including a magnetic material and a second valuable metal containing material including a non-magnetic material is a step of separating the first valuable metal containing material including a magnetic material and a second valuable metal containing material including a non-magnetic material, specifically a material without magnetism, through magnetic separation. The magnetic separation can be performed, for example, by separating particles through contact with a magnetic material using a magnetic material, and various types of magnetic separation methods can be applied.

[0068] When the above magnetic separation is performed, a first valuable metal containing substance including a magnetic material such as iron can be selected and separated, and a substance not including a magnetic material other than the first valuable metal containing substance can be separated as a second valuable metal containing substance.

[0069] The first valuable metal containing material may include a third valuable metal containing material and a first lithium compound attached to the surface of the third valuable metal containing material. Specifically, the first valuable metal containing material may be included as a containing material itself, including an alloy or oxide containing at least one of iron (Fe) and phosphorus (P).

[0070] In one embodiment, at least a portion of the first valuable metal containing material may be comprised of the third valuable metal containing material and the first lithium compound disposed on the surface of the third valuable metal containing material. Specifically, the first valuable metal containing material may be comprised of the third valuable metal containing material alone or the first valuable metal containing material and the first valuable metal containing material having the first lithium compound disposed on the surface thereof. In this way, through magnetic separation, the first valuable metal containing material having the first lithium compound disposed on the surface thereof is preferentially selected, thereby preventing the lithium compound from being detached from the first valuable metal containing material in a subsequent particle size separation, thereby having the advantage of increasing the lithium recovery rate.

[0071] The second valuable metal containing material may include at least one of aluminum, aluminum oxide, aluminum phosphate, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate. The second valuable metal containing material may include a non-magnetic material, such as LiAlO2, Cu, CuO, Cu2O, FeO, Fe2O3, Fe3O4, P2O5, and FePO4.

[0072] In one embodiment, the third valuable metal-containing material may include an alloy or oxide containing at least one of iron (Fe) and phosphorus (P). In one embodiment, the first lithium compound may be, for example, lithium aluminum oxide, LiAlO2. Specific contents of the third valuable metal-containing material and the first lithium compound may be referred to the above.

[0073] The first separation step of separating a carbon-containing material and a second lithium compound from the second valuable metal-containing material obtained after the magnetic separation step includes a step of separating a carbon-containing material, specifically graphite, from the second valuable metal-containing material including a non-magnetic material obtained after the magnetic separation step. In one embodiment, the step of separating the graphite may be performed through either particle size separation or gravity separation.

[0074] In one embodiment, either particle size separation or gravity separation may be achieved using a means such as a cyclone or a flotator. Specifically, the separation of graphite may be performed with a particle size of approximately 100 μm as a reference. The graphite may be separated through particle size separation in the region of 100 μm or less.

[0075] In this way, after the magnetic separation step, the obtained second valuable metal content is subjected to a classification process to separate the graphite, thereby resolving the problem of lithium loss due to inclusion of fine lithium compounds in the process of removing and sorting graphite, compared to the case where the process of separating the graphite is performed in advance, thereby increasing the amount of lithium added in the subsequent process.

[0076] As described above, in the reactant obtained by separately classifying and separating graphite after magnetic separation, the lithium content of the first lithium compound may include 1.5% or more of lithium by weight in the first valuable metal-containing material. Specifically, the lithium content of the first lithium compound may include 6% or more of lithium by weight in the first valuable metal-containing material.

[0077] As described above, the magnetic separation step is performed in advance of the classification step, so that the third valuable metal containing material having the first lithium compound disposed on the surface within the first valuable metal containing material is simultaneously recovered, thereby reducing the influence of leaching by graphite in the subsequent process, thereby providing an advantage in that the recovery rate of lithium can be increased.

[0078] In one embodiment, the lithium content of the second lithium compound may include less than 20 wt% of lithium in the second valuable metal containing material. Specifically, the lithium content of the second lithium compound may include less than 17 wt%, more specifically less than 9 wt%, more specifically less than 6.0 wt%, more specifically less than 5.0 wt%, and more specifically less than 1.15 wt% of lithium in the second valuable metal containing material.

[0079] As described above, after the magnetic separation step, the obtained second valuable metal content is subjected to a classification process to separate the graphite, thereby resolving the problem of lithium loss due to inclusion of fine lithium compounds in the process of removing and sorting graphite, compared to the case where the process of separating the graphite is performed in advance, thereby increasing the amount of lithium added in the subsequent process.

[0080] The above second lithium compound can prevent the problem of the lithium recovery rate of the second lithium compound being lowered in the subsequent process by containing a large amount of lithium compound in the additional selection process for removing the graphite.

[0081] In one embodiment, after the step of separating the carbon-containing material and the second lithium compound from the valuable metal-containing material obtained after the magnetic separation step, a second separation step may be included of separating the first valuable metal-containing material from the third valuable metal-containing material and the first lithium compound.

[0082] The second separation step is a step of separating the third valuable metal containing material and the first lithium compound from the first valuable metal containing material by a mechanical or physical external force, and can separate an alloy or oxide including at least one of iron and phosphorus and a lithium compound, for example, LiAlO2, etc., disposed on the surface of the valuable metal containing material from the valuable metal containing material.

[0083] The second separation step may be performed by applying an external force, such as crushing, to separate the first valuable metal-containing material from the third valuable metal-containing material and the first lithium compound, thereby separating the third valuable metal-containing material and the first lithium compound. The second separation step is not limited to the crushing method described above, and various methods may be utilized as long as the third valuable metal-containing material and the first lithium compound can be separated by an external force. In this way, by separating the 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 iron and phosphorus, can be increased.

[0084] In one embodiment, the second separation step of crushing the first valuable metal-containing material into a third valuable metal-containing material and a first lithium compound may include a step of crushing the first valuable metal-containing material into particles having an average particle size ranging from 100 to 4000 μm. Specifically, the crushing step may include a step of crushing into particles having an average particle size ranging from 100 to 1000 μm. By performing the crushing step in the above-described range, there is an advantage in that the lithium content of the first lithium compound attached to the surface of the third valuable metal-containing material including Fe-P is high.

[0085] The second separation step has a problem that if the crushing is performed outside the upper limit of the above range, the size of the Fe-P containing alloy produced during the high-temperature heat treatment of the crushed material increases, which increases the leaching time in the subsequent wet process. The second separation step has a problem that if the crushing is performed outside the lower limit of the above range, the size of the alloy produced during the high-temperature heat treatment of the crushed material of 100 ㎛ or less decreases, which causes graphite to be separated together during magnetic separation, and the process is delayed due to interference problems of graphite that does not dissolve in acid during the leaching process.

[0086] In one embodiment, the second separation step of crushing the first valuable metal-containing material into a third valuable metal-containing material and a first lithium compound may be performed after the magnetic separation step of separating the generated reactant into the first valuable metal-containing material including a magnetic material and the second valuable metal-containing material including a non-magnetic material after the high-temperature reduction reaction described above. The second separation step may be performed, for example, between the magnetic separation step described above and the graphite separation step described above, or may be performed after the magnetic separation step described above and the graphite separation step described above. The second separation step is advantageous in that it can prevent lumps such as flakes from agglomerating by being performed after the magnetic separation step described above.

[0087] In one embodiment, after the high-temperature reduction reaction, the method may further include a step of removing impurities before a magnetic separation step of separating the generated reactant into a first valuable metal containing material comprising a magnetic material and a second valuable metal containing material comprising a non-magnetic material. The impurities may be, for example, impurities such as flakes. Specifically, the impurities may be, for example, materials produced from aluminum or copper.

[0088] In one embodiment, the step of removing the impurities may be performed by any one of magnetic separation, particle size separation, and gravity separation. The magnetic separation may be performed using a magnetic body having a magnetic field strength capable of separating impurities such as flakes from the valuable metal containing Fe-P. The particle size separation may be performed by controlling the particle size to separate iron pieces. Specifically, the particle size separation may be performed based on an average particle diameter, for example, a range of 5 to 10 mm or more.

[0089] By first removing impurities before the aforementioned magnetic separation, there is an advantage in that the recovery rate of valuable metals can be increased by removing impurities that may affect magnetic separation.

[0090] In one embodiment, prior to the step of subjecting the battery shreds to a high-temperature reduction reaction, the battery shreds may be subjected to a step of freezing the batteries and a step of crushing the frozen batteries. By freezing the battery shreds prior to crushing, the battery ignition during the crushing process can be prevented.

[0091] The step of freezing the battery is performed at a temperature sufficient to freeze the electrolyte contained within the battery. Specifically, the step of freezing may be performed at a temperature range of, for example, -150 to -20°C. More specifically, the temperature range may be -150 to -50°C, and even more specifically, -80 to -60°C.

[0092] When the battery is frozen in the above temperature range, the voltage remaining slightly inside the battery, for example, about 2 V to 3 V, is lowered to close to 0 V, and even if a short circuit occurs in which the positive and negative electrodes are in direct contact, no battery reaction occurs, so the battery temperature does not increase, and gas generation and combustion of the electrolyte do not occur. In addition, since the electrolyte is in a frozen state or in a state in which vaporization is suppressed, the mobility of lithium ions is very low, so that the conduction characteristics according to the movement of lithium ions can be significantly reduced, and since vaporization of the electrolyte does not occur, flammable gases such as ethylene, propylene, and hydrogen can not be generated.

[0093] If the above freezing process is outside the above temperature range, for example, if it cools to a temperature higher than -60℃, the voltage remaining inside the battery will not be lowered to 0 V, so a battery reaction due to a short circuit may occur, and the electrolyte will not be completely frozen, which is not appropriate. In addition, if it is cooled to -150℃, the electrolyte is sufficiently frozen, and the voltage inside the battery will also be lowered to 0 V, so there is no need to lower the temperature below this. In this way, the battery processing method has the advantage of preventing the risk of fire that may occur during the battery crushing process by including a freezing step before crushing a battery such as a lithium secondary battery.

[0094] The step of shredding the frozen battery may refer to a process of applying shock or pressure to the battery so that a portion of the battery detaches from the battery. In one embodiment, the step of shredding the battery may refer to a process of crushing the battery, a process of cutting the battery, a process of compressing the battery, or a combination thereof. Specifically, the step of shredding may include any process that can destroy the battery to obtain small-sized shredded materials.

[0095] In one embodiment, the step of crushing the battery may include any process that destroys the battery by compressing the frozen battery or applying an external force, such as a shear force or tensile force. The step of crushing the battery may be performed, for example, using a crusher.

[0096] In one embodiment, the step of crushing the battery may be performed at least once. Specifically, the step of crushing may be performed at least once, either continuously or discontinuously.

[0097] In one embodiment, the step of crushing the battery can be performed under conditions of supplying an inert gas, carbon dioxide, nitrogen, water, or a combination thereof, or under vacuum conditions of 100 torr or less. For example, when the process of freezing the battery is performed by cooling it in a temperature range of -60 to -20°C, when performed under the above-described conditions, the supply of oxygen can be suppressed, preventing the electrolyte from reacting with oxygen, thereby preventing an explosion caused by this, and the vaporization of the electrolyte can be suppressed, thereby preventing the generation of flammable gases such as ethylene, propylene, or hydrogen.

[0098] In one embodiment, the step of crushing the battery may be performed so that the maximum size of the battery shreds is 100 mm or less. Specifically, the size of the battery shreds may be performed so that the size of the battery shreds is 50 mm or less. If the maximum size of the battery shreds is 100 mm or more, the temperature of the heat generated due to instability as the battery shreds are crushed may rise to a temperature range of 120°C, which is the average vaporization temperature of the electrolyte, which may cause safety issues such as fire.

[0099] In one embodiment, the step of freezing the battery may satisfy the following equation 2.

[0100] <Formula 2>

[0101] Minimum cooling time (Hr) = A × (W 0.33 )

[0102] (A = 4 × e(-0.02×dT), W = battery weight (Kg), dT= │external cooling temperature - target temperature│, ││ represents the absolute value)

[0103] The minimum cooling time in the above equation 2 refers to the weight of the battery, for example, the weight of a battery pack, a single battery, or a combination thereof. The minimum cooling time refers to the external cooling temperature, which is the cooling temperature applied to the battery, for example, the target temperature for cooling the electrolyte within the battery.

[0104] The step of freezing the battery has the advantage of allowing the electrolyte inside the battery to be cooled for a period longer than the minimum cooling time, thereby stably performing subsequent processes. However, if the step of freezing the battery is performed for a period shorter than the minimum cooling time, the electrolyte may not be cooled, which may lead to a risk of fire when crushed.

[0105] Hereinafter, preferred embodiments and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

[0106] <Experimental Example>

[0107] <Battery internal temperature according to minimum freezing time>

[0108] The battery pack used in the examples was shredded without refrigeration using the same shredder as in the examples. During the shredding process, a flame occurred due to a short circuit, as shown in Figures 3a and 3b. The battery used in this case was a ferric phosphate (LFP) battery.

[0109] In this way, through examples and comparative examples, it can be confirmed that by including a step of freezing a battery pack including the battery before crushing the battery, no short circuit occurs and no flame is generated in the battery crushing step, resulting in excellent stability.

[0110] Figure 1 shows the change in voltage of a battery according to cooling temperature according to one embodiment of the present invention.

[0111] Referring to Fig. 1, when the battery is frozen to -80°C and the battery voltage is measured, the battery pack shows almost the same voltage at a high temperature of about 40°C, room temperature, and up to -60°C, confirming that the battery characteristics are not lost. Next, when the temperature decreases from -60°C to -70°C, the voltage drops rapidly, and below -70°C, the voltage becomes 0. In this way, it was confirmed that a short circuit does not occur when the battery is frozen to -60 to -150°C.

[0112] FIG. 2 is a graph showing the relationship between battery weight, external cooling temperature, and cooling time according to one embodiment of the present invention.

[0113] Referring to FIG. 2, it can be confirmed that a battery processing method according to one embodiment of the present invention can derive a minimum cooling time for cooling the battery during the battery freezing step. Specifically, it can be confirmed that the minimum cooling time is related to the battery weight, the external cooling temperature, and the target temperature.

[0114] More specifically, when the target temperature is set to -70℃ and the battery weights are 2.5 kg (A), 10 kg (B), 20 kg (C), and 50 kg (D), the external cooling temperature and minimum cooling time are shown. When cooling the battery, it can be confirmed that the electrolyte of the battery begins to cool after a certain period of time and the voltage becomes 0. Through this, it can be confirmed that a minimum maintenance time is required to sufficiently cool the inside, specifically the electrolyte, when cooling the battery.

[0115] Specifically, in a heat transfer situation for cooling where heat is lost to the outside, considering the specific heat of the battery itself, it can be confirmed that the battery weight and cooling time are required. Thus, the present invention can determine the minimum time required for cooling by using the external cooling temperature for refrigeration, the target temperature, and the battery weight.

[0116] Table 1 below lists the minimum cooling time based on battery weight and external cooling temperature.

[0117] Battery weight [kg] External cooling temperature [℃] Target temperature [℃] Formula 2Minimum cooling time [h]A_12.5-120-701.91.9A_22.5-100-702.92.9A_32.5-80-704.44.4B_110-120-703.13.1B_210-100-704.64.6B_310-80-707.07.0C_120-120-703.93.9C_220-100-705.85.8C_320-80-708.88.8D_150-120-705.35.3D_250-100-707.97.9D_350-80-7011.911.9

[0118] Looking at Table 1 above, it can be confirmed that the smaller the battery weight, the shorter the minimum cooling time required for the battery to be cooled. In addition, it can be confirmed that when the value of Equation 2 derived from the relationship according to the battery weight, external cooling temperature, and target temperature is cooled with the minimum cooling time, the battery, specifically, the electrolyte of the battery, is cooled. In addition, when the battery is cooled for a time longer than the value of Equation 2, a fire does not occur in the post-process, that is, the battery crushing process. FIGS. 3a and 3b are photographs showing a fire that occurred when crushing was performed after freezing for a shorter minimum cooling time than the minimum cooling time according to a comparative example of the present invention, and FIGS. 3c and 3d are photographs showing an example in which a fire did not occur when crushing was performed after freezing for a longer minimum cooling time than the embodiment of the present invention.

[0119] Referring to Figures 3a and 3b, the fire occurrence status of shredded material was tested when the battery was frozen for a time shorter than the minimum cooling time required for cooling. In the experiment, when the battery weight was 25 kg, the external cooling temperature was -95°C, and the target freezing temperature was -70°C, the experiment was conducted for 5 hours, which is lower than the value of Equation 2, when the value of Equation 2 below was 7 hours.

[0120] <Formula 2>

[0121] Minimum cooling time = A × (W 0.33 )

[0122] (In the above equation 2, A = 4 × e(-0.02×dT), W = battery weight (Kg), dT = │external cooling temperature - target temperature│, ││ represents an absolute value)

[0123] Referring to Figures 3c and 3d, the fire occurrence status of shredded material was tested when the battery was frozen for a period exceeding the minimum freezing time required for cooling. The above experiment was conducted under the same battery weight as Figures 3a and 3b, the external cooling temperature, and the minimum freezing time of 7 hours or more.

[0124] Table 2 below compares the fire occurrence status of the examples and comparative examples according to the same battery weight, external cooling temperature, and minimum freezing time according to 3a to 3d. The fire occurrence status was determined as "O" if fire occurrence was observed after crushing the battery, and "X" if not.

[0125] Battery weight [Kg] External cooling temperature [℃] Target temperature [℃] Formula 2 Actual cooling time [h] Fire occurrence Comparative example 25- 95- 707.05 O Example 25- 95- 707.07 X

[0126] Examining Table 2 above, it can be seen that if the battery is cooled to a value lower than the value in Equation 2, which corresponds to the minimum cooling time, the electrolyte will not be cooled, resulting in a fire after the battery is shredded. Thus, it can be confirmed that if the battery is cooled using the value in Equation 2 as the minimum cooling time, the shredded material can be reliably utilized without a fire after the battery is shredded.

[0127] <Battery shredder calcination heat treatment>

[0128] The step of calcining and heat treating the above-mentioned battery shreds was performed by dry heat treatment under conditions of 5 vol% or less of oxygen in a temperature range of 700 to 1,350°C. Specifically, the calcining and heat treatment of this experiment was performed by dry heat treatment in a temperature range of 900 to 1,200°C, specifically, about 1,100°C, under conditions of about 3 vol% or less of oxygen.

[0129] After dry heat treatment, the size of the manufactured battery shreds is 10 to 20 mm in the long axis among width, length, and height, the graphite content is 5% or more, and the impurity content of plastic or iron pieces such as Al covers and PCB substrates in the shreds is less than 5%.

[0130]

[0131] <Control of the recovery method of valuable metal reactants>

[0132] After the high-temperature reduction reaction, the components contained in the manufactured product include Fe-P alloy, lithium compounds, graphite, and other residual impurities such as copper and aluminum.

[0133]

[0134] Comparative Examples 1 and 2

[0135] After a high-temperature reduction reaction, the produced product was classified to extract graphite, and then magnetic separation was performed. Comparative Examples 1 and 2 each report values ​​measured twice.

[0136]

[0137] Examples 1 and 2

[0138] After the high-temperature reduction reaction, the manufactured product is subjected to magnetic separation, separating the valuable metal-containing material containing magnetic substances from the valuable metal-containing material containing non-magnetic substances. Further crushing and separation are performed, taking into account the composition of each magnetic and non-magnetic substance. Graphite is then extracted through classification. Examples 1 and 2 each describe values ​​measured twice.

[0139] Table 3 below shows the lithium content in graphite according to the graphite classification and magnetic separation order.

[0140] Sorting procedure Graphite lithium content [%] Lithium recovery rate during leaching [%] Comparison Pre-sorting and magnetic sorting 6.1831 Example Pre-sorting and magnetic sorting 0.4782

[0141] Looking at Table 3 above, it was confirmed that when the magnetic separation step was performed before the classification step as in the example, the first lithium compound in the first valuable metal containing material was recovered simultaneously with the third valuable metal containing material disposed on the surface, which was advantageous for lithium recovery. As in the comparative example, when the classification step was performed before the magnetic separation step, it was confirmed that the first lithium compound contained in the first valuable metal containing material was separated together with graphite, making lithium recovery difficult. In the case of graphite, since it does not dissolve when leached in acid, a separate separation process is required, and at this time, lithium is also separated together, which causes a problem in that the lithium recovery rate is lowered during the leaching process. Table 4 below shows the contents of reactants recovered according to the order of graphite classification and magnetic separation according to magnetic separation.

[0142] Experimental example Magnetic classification Classification Fe-P [wt%] Li [wt%] C [wt%] Lithium recovery rate after leaching (%) Formula 1 ([Fe-P] / [Li]) Comparative example 1 First valuable metal containing material Classification after magnetic separation 97.69 0.71 1.67 5 13 7.59 Comparative example 2 First valuable metal containing material 96.5 2 1.38 2.16 36 9.94 Comparative example 1 Second valuable metal containing material 2.0 7 8.63 89.3 17 0.24 Comparative example 2 Second valuable metal containing material 1.3 2 11.0 8 8 7.6 1 2 0.12 Example 1 First valuable metal containing material Classification after magnetic separation 87.2 8 8.4 2 4.38 8 10.37 Example 2 First valuable metal Contains 88.146.365.58413.86 Example 1 Second valuable metal containing 2.371.2396.4131.93 Example 2 Second valuable metal containing 1.751.1597.191.52

[0143] Looking at Table 4 above, it was confirmed that the composition ratio of the input crushed material components, Fe-P, Li, and C, after high-temperature reaction differed as shown in Table 4 depending on whether magnetic separation was performed after classification as in Comparative Examples 1 and 2 or magnetic separation was performed before classification as in Examples 1 and 2. As in Comparative Examples, when classification was performed first, it was confirmed that the lithium content in the first valuable metal-containing material of Comparative Examples 1 and 2 was about 0.7 to 1.4 wt%, specifically 0.71 wt% and 1.38 wt%, respectively. In contrast, when magnetic separation was performed first as in the examples, the lithium content in the first valuable metal containing materials of examples 1 and 2 was about 6 to 9 wt%, specifically, 6.36 wt% and 8.42 wt%, and when classification was performed after magnetic separation, it was confirmed that the loss of lithium compounds was small and the lithium content in the first valuable metal containing material was as high as 1.5 wt% or more. Specifically, it was confirmed that the lithium content in the second valuable metal containing material of example 1 or 2 was about 8 to 11 wt%, and that it was about 0.7 to 1.4 wt%, specifically, 0.71 wt% and 1.38 wt%, which was about 6 to 16 times lower than that in the second valuable metal containing material of comparative example 1 or 2.

[0144] It was confirmed that the content of Fe-P in the second metal-containing material of the comparative example and the example was at a similar level of 0.5 to 3 wt%.

[0145] In contrast, the content of graphite in the second precious metal-containing compound of the comparative example was found to be approximately 10% lower than in the example. This is believed to be due to the detachment and dispersion of some of the Li compound attached to the magnetic body during classification. As can be seen in Table 4, in the case of lithium compounds mixed with graphite, the lithium recovery rate may be lowered due to the reduced leaching efficiency caused by the high graphite content during the acid leaching process.

[0146]

[0147] <Crushing stage of the first valuable metal content>

[0148] The first valuable metal containing material of Example 1 was magnetically separated, and the first valuable metal containing material was crushed into a particle size range of 500 to 1000 μm through an Attrition Mill, thereby separating the Fe-P alloy and the lithium compound LiAlO2 attached to the surface of the Fe-P alloy. Thereafter, the composition ratios of the Fe-P alloy and the lithium compound are shown in Table 5 below.

[0149] First valuable metal containing material After crushing and separation, LiFePAlO total [wt%] [wt%] [wt%] [wt%] [wt%] [wt%] particle size 500-1000 ㎛ First lithium compound 13.447.612.1531.6845.12100 Third valuable metal containing material 1.2471.023.71.42.65100

[0150] Looking at Table 5 above, when the first valuable metal-containing material is crushed to a particle size of 500 to 1000 ㎛, the weight % of the main components is shown. In the crushing step, when crushing to a particle size of 500 to 1000 ㎛, it was confirmed that the Li content of the first lithium compound attached to the surface of the third valuable metal-containing material including Fe-P was high. Through this, it can be confirmed that the Li content of the reactant included in the post-process will increase when separating the first lithium compound after crushing the first valuable metal-containing material. In addition, when applied to the post-process, the first lithium compound is mixed with only a small amount of graphite, so a separate graphite sorting step is not required, and therefore, the processing process is shortened, which is judged to be economical.

[0151] Although the preferred embodiments have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concepts defined in the following claims also fall within the scope of the present invention.

Claims

1. A valuable metal reactant containing valuable metal recovered from a waste battery, A first precious metal containing alloy or oxide comprising at least one of iron (Fe) and phosphorus (P); A second valuable metal containing non-magnetic material; and Containing a carbon compound containing carbon, The first metal-containing material comprises a third metal-containing material including a magnetic material and a first lithium compound attached to the surface of the third metal-containing material, The lithium content of the first lithium compound is a lithium (Li) reactant comprising at least 1.5% by weight of lithium (Li) in the first valuable metal containing material.

2. In paragraph 1, A metal reactant having a content of an alloy or oxide including at least one of iron (Fe) and phosphorus (P) of 75.00 to 95.00 wt% based on 100 wt% of the first metal-containing substance.

3. In paragraph 1, The valuable metal reactant is a valuable metal reactant obtained from a lithium iron phosphate battery.

4. In paragraph 1, A metal reactant in which the content of an alloy or oxide containing at least one of iron (Fe) and phosphorus (P) in the first metal-containing substance and the content of lithium (Li) satisfy the following formula 1. <Formula 1> 5.0 ≤ [Fe-P] / [Li] ≤ 60.0 (In the above formula 1, [Fe-P] and [Li] mean the content of an alloy or oxide containing at least one of iron (Fe) and phosphorus (P) in the first valuable metal content and the content of lithium (Li), respectively.) 5. In paragraph 1, The above first lithium compound is LiAlO 2 , Li 5 AlO 4 , LiAl 5 O 8 , Li 2 CO 3 , LiF, Li 3 PO 4 , Li 4 P 2 O 7 , LiPO 3 , Li 2 SiO 3 , Li 4 SiO 4 , Li 2 Si 2 O 5 , LiFeO 2 , LiFe 5 O 8 , Li 3 Fe 5 O 8 , and Li 5 FeO 4 A precious metal reactant comprising a lithium compound comprising at least one of:

6. In paragraph 1, The second metal-containing material comprises a second lithium compound, A lithium content of the second lithium compound is less than 20 wt% of lithium in the second valuable metal reactant.

7. In paragraph 6, The second lithium compound is LiAlO 2 , Li 5 AlO 4 , LiAl 5 O 8 , Li 2 CO 3 , LiF, Li 3 PO 4 , Li 4 P 2 O 7 , LiPO 3 , Li 2 SiO 3 , Li 4 SiO 4 , Li 2 Si 2 O 5 , LiFeO 2 , LiFe 5 O 8 , Li 3 Fe 5 O 8 , and Li 5 FeO 4 A precious metal reactant comprising a lithium compound comprising at least one of:

8. In paragraph 1, The third valuable metal containing substance is a valuable metal reactant containing at least one of iron (Fe) and phosphorus (P).

9. In paragraph 1, The second valuable metal containing substance is a valuable metal reactant comprising at least one of a second lithium compound, aluminum, aluminum oxide, aluminum phosphate, copper, copper oxide, iron, iron oxide, phosphorus, phosphorus oxide, iron phosphate, and iron phosphate oxide.

10. A precious metal fragment produced by crushing any one of the precious metal reactants of clauses 1 to 9.

11. In Article 10, A metal fragment having an average particle size of 100 to 4000 ㎛.

12. A high-temperature reduction step for obtaining a valuable metal reactant by subjecting battery waste to a high-temperature reduction reaction; A magnetic separation step for separating the above metal reactant into a first metal-containing material including an alloy or oxide including at least one of iron (Fe) and phosphorus (P) and a second metal-containing material including a non-magnetic material; and The second metal-containing material comprises a first separation step of separating the second metal-containing material into a carbon-containing material and a second lithium compound, The first metal-containing material comprises a third metal-containing material including a magnetic material and a first lithium compound attached to the surface of the third metal-containing material. A method for recovering a valuable metal, wherein the lithium content of the first lithium compound comprises at least 1.5% by weight of lithium in the first valuable metal containing material.

13. In paragraph 12, After the first separation step above, A method for recovering a valuable metal, comprising a second separation step of separating the first valuable metal containing material into a third valuable metal containing material and the first lithium compound.

14. In paragraph 13, A method for recovering a precious metal, wherein the second separation step comprises a step of detaching the first lithium compound attached to the surface of the third precious metal-containing material.

15. In paragraph 14, A method for recovering precious metals, wherein the second separation step comprises a step of crushing the first precious metal-containing material into particles having an average particle size of 100 to 4,000 ㎛.

16. In paragraph 12, The above battery scrap is a method for recovering valuable metals scraped from iron phosphate batteries.

17. In paragraph 12, A method for recovering valuable metals, wherein the high temperature reduction step is performed at a temperature of 700 to 1,350°C.

18. In paragraph 12, A method for recovering valuable metals, wherein the above high temperature reduction step is performed under conditions of oxygen of 5 vol % or less.

19. In paragraph 12, A method for recovering valuable metals, wherein the first separation step is performed through particle size separation.

20. In paragraph 12, Prior to the above high temperature reduction reaction step, A method for recovering valuable metals further comprising the step of freezing a battery that serves as a parent material of the above battery shreds.

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