Valuable metal recovery alloy and valuable metal recovery composition comprising same

Abstract

The present invention relates to a valuable metal recovery alloy and a valuable metal recovery composition comprising same. Specifically, the present invention relates to a valuable metal recovery alloy obtained by treating an LFP-containing waste battery, and to a valuable metal recovery composition comprising same.

Description

Valuable metal recovery alloy and valuable metal recovery composition containing the same

[0001] The present invention relates to a valuable metal recovery alloy and a valuable metal recovery composition containing the same. Specifically, it relates to a valuable metal recovery alloy obtained by processing LFP-containing waste batteries and a valuable metal recovery composition containing the same.

[0002] The present invention claims priority to Korean Patent Application No. 10-2024-0191921 filed on December 19, 2024, the entire contents of said prior application are incorporated herein by reference.

[0003] The issue of disposing of secondary batteries, such as waste batteries from electric vehicles, is emerging globally. Secondary batteries, particularly lithium-ion batteries, contain explosive materials and heavy metals such as Ni, Co, Mn, and Fe, which pose fire hazards due to organic solvents. In addition to these ternary lithium-ion batteries, LFP-based batteries, which are based on lithium iron phosphate, have recently been gaining attention. LFP-based batteries are cheaper than ternary batteries and have the advantage of being relatively stable against shocks and deformations caused by external factors during use, due to the relatively high chemical stability of the cathode active material.

[0004] LFP batteries consist of copper (Cu) and aluminum (Al) used as the current collector, lithium iron phosphate (LiFePO4) constituting the cathode, and graphite (C) constituting the anode. These components exist in a metallic state within the current collector to ensure electrical conductivity, while they exist in the form of metal-complex oxides within the cathode to ensure chemical stability.

[0005] Various methods, including dry, wet, and direct recycling, have been developed to recycle waste LFP batteries. In the case of dry recycling, oxidative refining methods have been primarily studied to efficiently recover metal components by oxidizing components other than the target metal through the selection of an atmosphere with an appropriate oxygen partial pressure at high temperatures, thereby recovering the target metal in the form of a molten metal. However, since components produced through this dry method have clear limitations in satisfying the purity required for battery-grade materials, in most cases, the purity of the material obtained through the dry method needs to be increased through a wet refining process.

[0006] When utilizing the oxidative refining method among dry methods for recycling LFP-based waste batteries, the graphite derived from the anode material is completely burned and eliminated. This allows metal droplets to combine to form a molten metal, which is advantageous for operating the entire molten metal. However, from the perspective of carbon emission reduction, which has emerged since the Paris Agreement, the graphite removed by combustion is entirely emitted in the form of carbon dioxide. This can act as a factor weakening process price competitiveness, such as carbon taxes, when entering markets like Europe in the future. Meanwhile, the dry oxidative refining method for waste batteries has the disadvantage of not only releasing large amounts of carbon dioxide but also a high likelihood of Li, Fe, and P being lost during the oxidative refining process. In other words, using the oxidative refining method results in high carbon dioxide emissions while having a low recovery rate for valuable metals. Therefore, for the recycling of LFP-based waste batteries, a method is required that can reduce carbon dioxide emissions and improve the recovery rate of valuable metals, in addition to the dry oxidative refining method. In addition, there is a need for valuable metal recovery alloys and compositions in a form that facilitates the separation and recovery of valuable metals.

[0007] The technical problem that the present invention aims to solve is to provide a valuable metal recovery alloy containing a high concentration of valuable metals including lithium, and which facilitates the separation of magnetic and non-magnetic components among the valuable metals.

[0008] The technical problem that the present invention aims to solve is to provide a valuable metal recovery composition that contains a high concentration of valuable metals including lithium and facilitates the separation of magnetic and non-magnetic components among the valuable metals.

[0009] A valuable metal recovery alloy according to one embodiment of the present invention may include a first compound particle comprising an oxide containing Li and P elements; and a second compound particle containing an Fe-P component located on the surface of the first compound particle as a coating particle.

[0010] A valuable metal recovery alloy according to one embodiment of the present invention can satisfy the following Equation 1.

[0011] [Equation 1]

[0012] 5≤[Fe-P] / [Li]≤60

[0013] (In the above Equation 1, [Fe-P] and [Li] represent the weight content of the Fe-P component containing iron (Fe) and phosphorus (P) in the valuable metal recovery alloy and the content of lithium (Li), respectively.)

[0014] A valuable metal recovery alloy according to one embodiment of the present invention may contain 1.5 to 18.5 weight% of lithium (Li) based on 100% of the total weight of the valuable metal recovery alloy. Preferably, the lithium (Li) may contain 3 to 12.5 weight%, 4.5 to 9 weight%, or 6.36 to 8.42 weight%.

[0015] A valuable metal recovery alloy according to one embodiment of the present invention may contain 70 to 95 weight percent of a second compound particle based on 100% of the total weight of the valuable metal recovery alloy.

[0016] In a valuable metal recovery alloy according to one embodiment of the present invention, the second compound particle may be in the form of a semi-sphere metallic drop.

[0017] In a valuable metal recovery alloy according to one embodiment of the present invention, the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 90 or more and 160 or less.

[0018] In a valuable metal recovery alloy according to one embodiment of the present invention, the second compound particles may have an average particle size of 0.1 to 100 μm.

[0019] In a valuable metal recovery alloy according to one embodiment of the present invention, the second compound particles may be aggregated from angular Fe-P containing fine particles having a diameter of 0.1 to 10 μm.

[0020] In a valuable metal recovery alloy according to one embodiment of the present invention, the coating particles are second compound particles formed by connecting Fe-P containing fine particles, and the second compound particles are connected to form a thin film coating layer, and the thickness of the coating layer may be 0.1 to 3 μm.

[0021] In a valuable metal recovery alloy according to one embodiment of the present invention, the area ratio of the coating layer based on the total surface area of ​​the first compound particle may be 20 to 90%.

[0022] In a valuable metal recovery alloy according to one embodiment of the present invention, the first compound particles and the second compound particles may contain at least one of Al, Si, Cu, Ni, Co, Mn, Ti, Zn, Pb, Ca, Mg, B, K, Na, Si, Zr, F, Cr, Nb, and Ta as impurities.

[0023] In a valuable metal recovery alloy according to one embodiment of the present invention, the valuable metal recovery alloy may further include aluminum oxide in the form of Al2O3 or Li-Al-O compound and SiO2 components.

[0024] A valuable metal recovery composition according to one embodiment of the present invention is a valuable metal recovery composition recovered from a lithium iron phosphate (LFP)-based waste battery using a dry reduction refining method, comprising: a first valuable metal recovery alloy containing a magnetic material; a second valuable metal recovery alloy containing a non-magnetic material; and graphite; wherein the first valuable metal recovery alloy may include a first compound particle having a second compound particle as a coating particle on its surface.

[0025] In a valuable metal recovery composition according to one embodiment of the present invention, the second compound particle included in the first valuable metal recovery alloy may be in the form of a semi-sphere metallic drop, and the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 90 or greater and 160 or less.

[0026] In a valuable metal recovery composition according to one embodiment of the present invention, the lithium (Li) content may be 1 to 20 weight% based on 100 weight% of the total valuable metal recovery composition.

[0027] In a valuable metal recovery composition according to one embodiment of the present invention, the second compound particles are in the form of aggregated angular Fe-P-containing fine particles having a diameter of 0.1 to 10 μm, and the average particle size of the second compound particles may be 0.1 to 100 μm.

[0028] In a valuable metal recovery composition according to one embodiment of the present invention, the average particle size of the first compound particles may be 20 to 220 μm.

[0029] In a valuable metal recovery composition according to one embodiment of the present invention, the valuable metal recovery composition comprises Cu particles, wherein the Cu particles have at least one form among spherical single particles and particles formed by combining two or more spherical single particles, the spherical single particles have a sphericity of 0.85 or higher and 1 or lower, and the Cu particles may have an average particle size of 25 to 70 μm. In the specification of the present invention, the Cu particles refer to particles containing 45 mol% or more of the Cu element based on 100 mol% of the total elements constituting the Cu particles when Electron Backscatter Diffraction (EBSD) is performed. Preferably, the Cu particles may contain 70 mol% or more of the Cu element.

[0030] A valuable metal recovery composition according to one embodiment of the present invention further comprises aluminum oxide in the form of Al2O3 or a Li-Al-O compound, and the average particle size of the aluminum oxide may be 40 to 180 μm. Preferably, the average particle size of the aluminum oxide may be 49 to 170 μm, 60 to 145 μm, or 66 to 131 μm.

[0031] In a valuable metal recovery composition according to one embodiment of the present invention, the first valuable metal recovery alloy comprises Li2O, Li2CO3, Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, Li5FeO4, LiAlO2, LiCuO2, Li2CuO2, Cu2O, CuO, CuO2, Cu2O3, CuO2, Cu3(PO4)2, FeO, Fe2O3, Fe3O4, Fe4O5, Fe5O6, Fe5O7, Fe 25 O 32 , Fe13 O 19 , FePO4, P2O5, P4O 10 It may include at least one of Al2O3 and AlPO4.

[0032] A valuable metal recovery alloy according to one embodiment of the present invention contains a high concentration of valuable metals including lithium and is in a form that facilitates the separation of magnetic and non-magnetic components among the valuable metals, thereby improving the recovery rate of valuable metals.

[0033] A valuable metal recovery composition according to one embodiment of the present invention contains a valuable metal including lithium at a high concentration and is in a form that facilitates the separation of magnetic and non-magnetic components among the valuable metals, thereby improving the recovery rate of the valuable metal.

[0034] Figure 1 illustrates an SEM image of a valuable metal recovery alloy according to one embodiment of the present invention and the angle formed by a tangent line on the surface of an Fe-P alloy.

[0035] Figure 2 shows an SEM image and component analysis results of a valuable metal recovery alloy according to one embodiment of the present invention.

[0036] Figure 3 shows an SEM image and component analysis results of a valuable metal recovery alloy according to one embodiment of the present invention.

[0037] Figure 4 shows the XRD analysis results of a valuable metal recovery alloy according to one embodiment of the present invention.

[0038] Figure 5 shows the mixed enthalpy of Li2O-Al2O3 and Li2O-P2O5 based on 1 mole.

[0039] Figure 6 is an SEM image of a valuable metal recovery composition according to one embodiment of the present invention.

[0040] FIG. 7 is an SEM image of a valuable metal recovery composition according to one embodiment of the present invention.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] Also, unless otherwise specified, % means weight %, and 1 ppm is 0.0001 weight %.

[0046] 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.

[0047] 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.

[0048]

[0049] A valuable metal recovery alloy according to one embodiment of the present invention will be described below.

[0050] 1. Valuable metal recovery alloy

[0051] A valuable metal recovery alloy according to one embodiment of the present invention may include a first compound particle comprising an oxide containing Li and P elements; and a second compound particle containing an Fe-P component located on the surface of the first compound particle as a coating particle.

[0052] In the above-mentioned valuable metal recovery alloy, the first compound particles may include Li3PO4.

[0053] In the above-mentioned valuable metal recovery alloy, the second compound particles may contain an Fe-P alloy component, and preferably, the Fe-P alloy component may be an Fe2P phase.

[0054] When the above-mentioned valuable metal recovery alloy is in the form of having a second compound particle as a coating particle on the surface of a first compound particle, it may be easy to separate magnetic and non-magnetic components from the valuable metal recovery composition. This is because the surface of the first compound particle contains Fe, which is a magnetic component, and since the material can be easily separated in the first step by magnetic separation, the processing speed of the subsequent valuable metal extraction or leaching step can be improved, and the purity or extraction rate of the valuable metal can be simultaneously improved due to the low incorporation of impurities.

[0055] A valuable metal recovery alloy according to one embodiment of the present invention can satisfy the following Equation 1.

[0056] [Equation 1]

[0057] 5≤[Fe-P] / [Li]≤60

[0058] (In the above Equation 1, [Fe-P] and [Li] represent the weight content of the Fe-P component containing iron (Fe) and phosphorus (P) in the valuable metal recovery alloy and the content of lithium (Li), respectively.)

[0059] When the above Equation 1 is satisfied, the valuable metal recovery alloy contains Fe components, making magnetic separation easy and reducing the loss of lithium compounds, so the lithium extraction rate can be improved.

[0060] On the other hand, if the value is below the lower limit of Equation 1 above, the lithium content in the valuable metal recovery alloy may be relatively high, but the Fe-P content may be relatively reduced, resulting in poor formation of second compound particles on the surface of first compound particles, which may lead to a low magnetic separation effect for the valuable metal recovery composition. Consequently, the separation efficiency of the valuable metal may decrease, and an additional refining process is required to increase the extraction rate and purity of the metal. In other words, this may lead to a problem that increases the overall process cost.

[0061] In addition, if the upper limit of Equation 1 above is exceeded, the amount of lithium component loss increases due to the excessive content of Fe-P, so while the magnetic separation effect may be excellent, there may be a problem where the lithium extraction rate is significantly lower. Also, the thickness of the second compound particles present on the surface of the first compound particles becomes excessively thick, so there may be a problem where the subsequent lithium leaching process takes a considerable amount of time or leaching is not easy.

[0062] A valuable metal recovery alloy according to one embodiment of the present invention may contain 1.5 to 18.5 weight% of lithium (Li) based on 100% of the total weight of the valuable metal recovery alloy. Preferably, the lithium (Li) may contain 3 to 12.5 weight%, 4.5 to 9 weight%, or 6.36 to 8.42 weight%.

[0063] A valuable metal recovery alloy according to one embodiment of the present invention may contain 70 to 95 weight percent of a second compound particle based on 100% of the total weight of the valuable metal recovery alloy.

[0064] When the above lithium content and the second compound particle content fall within the aforementioned range, the thickness of the coating layer (hereinafter referred to as the Fe-P containing coating layer) formed by the second compound particles on the surface of the first compound particles in the valuable metal recovery alloy is appropriate, so not only is the magnetic separation effect excellent, but the lithium extraction rate can also be improved during the lithium leaching process.

[0065] In this specification, the coating layer on the surface of the first compound particle, the coating layer containing the second compound particle, and the coating layer containing the first compound particle may include both a coating layer in which the second compound particle containing the Fe-P component exhibits a discontinuous distribution in an island shape and a coating layer in the form of a thin film in which the second compound particle is connected to each other and continuously distributed.

[0066] On the other hand, if the lithium content is below the lower limit of the aforementioned range or the content of the second compound particles exceeds the upper limit of the aforementioned range, it can be understood that a significant amount of lithium metal or lithium compound is lost, resulting in a low lithium content. Furthermore, while an excessive amount of Fe-P may provide excellent magnetic separation effects, the size of the second compound particles present on the surface of the first compound particles or the thickness of the coating layer containing Fe-P components may become excessively thick, potentially causing problems such as requiring a considerable amount of time for the subsequent lithium leaching process or making leaching difficult.

[0067] In addition, if the lithium content exceeds or falls below the upper limit of the aforementioned range, or if the content of the second compound particles is below the lower limit of the aforementioned range, the lithium content in the valuable metal recovery alloy may be relatively high, but the Fe-P content may be relatively reduced, resulting in a failure to properly form a coating layer containing the second compound particles or Fe-P on the surface of the first compound particles, which may lead to a low magnetic separation effect for the valuable metal recovery composition. Consequently, the separation efficiency of the valuable metal may decrease, and an additional refining process is required to increase the extraction rate and purity of the metal. In other words, this may lead to a problem that increases the overall process cost.

[0068] In a valuable metal recovery alloy according to one embodiment of the present invention, the second compound particle may be in the form of a semi-sphere metallic drop.

[0069] When the second compound particles exist on the surface of the first compound particles in the form of hemispherical metallic drops, magnetic separation can be facilitated by the Fe component on the surface. Additionally, since the second compound particles are well distributed in an island shape, a sufficient contact area between the leaching agent and the lithium compound is secured during the subsequent lithium leaching process, thereby improving leaching efficiency. Furthermore, since the solubility of the metallic drops is relatively low in a weak acid environment for lithium (Li) leaching, selective extraction of lithium can also be facilitated. Consequently, lithium can be extracted efficiently, which can improve the lithium extraction rate.

[0070] In the specification of the present invention, the metallic drop refers to a solidified metallic liquid phase generated by a reduction reaction when crushed waste batteries are subjected to high-temperature heat treatment. That is, the metallic drop refers to a solid material whose form and composition are derived from a metallic liquid that is not liquid at room temperature but was liquid in a high-temperature environment. Furthermore, the metallic drop is a form in which Fe-P containing fine particles with a diameter of 0.1 to 10 μm aggregate to exhibit a necking shape. Specifically, the content of the Fe component in the second compound particles of the metallic drop may be 40 to 90 mol% or 43.65 to 79.17 mol%. Specifically, the content of the P component in the second compound particles of the metallic drop may be 5 to 25 mol%, 7 to 23 mol%, or 7.79 to 20.83 mol%.

[0071] As previously mentioned, the second compound particles are in a metallic drop phase at room temperature, and if the size of the Fe-P containing fine particles satisfies the aforementioned range, separation and recovery of Fe and P by subsequent processes may be easy.

[0072] In a valuable metal recovery alloy according to one embodiment of the present invention, the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 90 or more and 160 or less. Preferably, the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 95 or more and 150 or less, 95 or more and 140 or less, or 95 or more and 130 or less. More preferably, the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 96.8 or more and 124.5 or less.

[0073] When the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle satisfies the aforementioned range, the second compound particle has an appropriate contact area with the first compound particle, and the likelihood of forming an island-shaped second compound particle increases. When lithium is leached from the valuable metal recovery alloy, the contact rate between the leaching agent and the lithium compound increases, and lithium ion movement becomes smooth and reactivity is enhanced, thereby improving lithium recovery efficiency. Furthermore, the second compound particle is uniformly distributed, ensuring stability during lithium recovery.

[0074] If the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle is less than the lower limit of the aforementioned range, the second compound particle becomes pointed in shape close to a cone, making it difficult to form a second compound particle with uniform physical properties on the surface of the first compound particle. Consequently, when magnetic separation is performed on the valuable metal recovery composition, it may not be easy to separate the magnetic material from the non-magnetic material. In addition, the degree of wear on the surface of the valuable metal recovery alloy may increase, which may cause the valuable metal in the form of fine particles to be easily lost, and as a result, the recovery rate of the valuable metal may be lowered.

[0075] If the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle exceeds the upper limit of the aforementioned range, the second compound particle may become thinner, and the coverage rate on the surface of the first compound particle may increase excessively. This acts as a weakness during lithium extraction, and there may be a problem where the leaching rate decreases because the contact area between the lithium compound and the leaching agent is very small.

[0076] In a valuable metal recovery alloy according to one embodiment of the present invention, the second compound particles may have an average particle size of 0.1 to 100 μm.

[0077] Preferably, the second compound particles may have an average particle size of 1 to 100 μm, 5 to 50 μm, 6 to 40 μm, 6 to 32 μm, or 10 to 30 μm.

[0078] If the average particle size of the second compound particles satisfies the aforementioned range, magnetic separation may be facilitated in the subsequent process of separating iron (Fe).

[0079] On the other hand, if the average particle size of the second compound particles is less than the lower limit of the aforementioned range, it may not be easy to separate iron-containing materials by magnetic separation. Furthermore, if the average particle size of the second compound particles exceeds the upper limit of the aforementioned range, the content of fragments of the first compound particles and impurities mixed inside the second compound particles may be high. This is because, in the valuable metal recovery composition according to the present invention, the second compound particles exist in a form surrounding the fragments of the first compound particles. Accordingly, in the subsequent process of separating the valuable metals individually, multi-stage refining is required to separate the second compound particles from the first compound particles, or to separate the second compound particles from impurities, and there may be a problem in that the cost of the waste battery recycling process increases overall.

[0080] In a valuable metal recovery alloy according to one embodiment of the present invention, the second compound particles may be aggregated from angular Fe-P containing fine particles having a diameter of 0.1 to 10 μm.

[0081] As previously mentioned, the second compound particles are in a metallic drop phase at room temperature, and if the size of the Fe-P containing fine particles satisfies the aforementioned range, separation and recovery of Fe and P by subsequent processes may be facilitated. In addition, the second compound particles on the surface of the first compound particles form a coating layer having an appropriate thickness and coverage rate, making it easy to acid-leach lithium in the subsequent stage.

[0082] On the other hand, if the size of the above-mentioned Fe-P-containing fine particles is less than the lower limit of the aforementioned range, it is difficult to form second compound particles that are easy to magnetically separate, so it may not be easy to separate the first valuable metal recovery alloy (containing magnetic material) and the second valuable metal recovery alloy (containing non-magnetic material) by magnetic separation. In addition, if the size of the above-mentioned Fe-P-containing fine particles exceeds the upper limit of the aforementioned range, the content of impurities inside the formed second compound particles may be high. As a result, multi-stage refining is required in the subsequent process of separating the valuable metals individually, and there may be a problem in that the cost of the waste battery recycling process increases overall.

[0083] In a valuable metal recovery alloy according to one embodiment of the present invention, the coating particles are second compound particles formed by connecting Fe-P containing fine particles, and the second compound particles are connected to form a thin film coating layer, and the thickness of the coating layer may be 0.1 to 3 μm.

[0084] In a valuable metal recovery alloy according to one embodiment of the present invention, the area ratio of the coating layer based on the total surface area of ​​the first compound particle may be 20 to 90%.

[0085] When the thickness of the coating layer containing the second compound particles and the ratio of the coating layer's area each satisfy the aforementioned ranges, the separation and recovery of Fe and P by subsequent processes is facilitated, and the recovery rate of Li using a leaching agent can be improved.

[0086] If the thickness of the coating layer and the ratio of the coating layer area are each below the lower limit of the aforementioned range, magnetic separation may not be easy. Since it is difficult to separate magnetic and non-magnetic materials, there is a high possibility that impurities will be mixed in when recovering valuable metals, and an additional refining process may be required, which may lead to an increase in process costs.

[0087] If the thickness of the coating layer and the ratio of the coating layer's area each exceed the upper limit of the aforementioned range, there may be a problem with the lithium extraction rate decreasing.

[0088] In a valuable metal recovery alloy according to one embodiment of the present invention, the first compound particles may not contain C as an impurity.

[0089] If the particles of the first compound do not contain C as an impurity, an additional process of removing carbon during the lithium extraction process is unnecessary, which may provide the advantage of reducing process costs while obtaining high-purity lithium.

[0090] In a valuable metal recovery alloy according to one embodiment of the present invention, the first compound particles and the second compound particles may contain at least one of Al, Si, Cu, Ni, Co, Mn, Ti, Zn, Pb, Ca, Mg, B, K, Na, Si, Zr, F, Cr, Nb, and Ta as impurities.

[0091] In a valuable metal recovery alloy according to one embodiment of the present invention, the valuable metal recovery alloy may further include aluminum oxide in the form of Al2O3 or Li-Al-O compound and SiO2 components.

[0092] In this specification, the valuable metal recovery alloy may correspond to the first valuable metal recovery alloy contained in the valuable metal recovery composition described below.

[0093]

[0094] A valuable metal recovery composition according to one embodiment of the present invention will be described below.

[0095] 2. Valuable metal recovery composition

[0096] A valuable metal recovery composition according to one embodiment of the present invention is a valuable metal recovery composition recovered from a lithium iron phosphate (LFP)-based waste battery using a dry reduction refining method, comprising: a first valuable metal recovery alloy containing a magnetic material; a second valuable metal recovery alloy containing a non-magnetic material; and graphite; wherein the first valuable metal recovery alloy may include a first compound particle having a second compound particle as a coating particle on its surface.

[0097] When the first valuable metal recovery alloy is in the form of having a second compound particle as a coating particle on the surface of a first compound particle, it may be easy to separate magnetic and non-magnetic components from the valuable metal recovery composition. This is because the surface of the first compound particle contains Fe, which is a magnetic component, and since the material can be easily separated in the first step by magnetic separation, the processing speed of the subsequent valuable metal extraction or leaching step can be improved, and the purity or extraction rate of the valuable metal can be simultaneously improved by reducing the incorporation of impurities.

[0098] In a valuable metal recovery composition according to one embodiment of the present invention, the second compound particle included in the first valuable metal recovery alloy may be in the form of a semi-sphere metallic drop, and the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 90 or greater and 160 or less.

[0099] When the second compound particles exist on the surface of the first compound particles in the form of hemispherical metallic drops, magnetic separation can be facilitated by the Fe component on the surface. Additionally, since an island-shaped Fe-P coating layer is formed, a sufficient contact area between the leaching agent and the lithium compound is secured during the subsequent lithium leaching process, thereby improving leaching efficiency. Furthermore, since the solubility of the metallic drops is relatively low in a weak acid environment for lithium (Li) leaching, selective extraction of lithium can also be facilitated. Consequently, lithium can be extracted efficiently, which can improve the lithium extraction rate.

[0100] In the specification of the present invention, the metallic drop refers to the solidification of a metallic liquid phase generated by a reduction reaction when crushed waste batteries are subjected to high-temperature heat treatment. That is, the metallic drop refers to a solid substance whose form and composition are derived from a metallic liquid that is not liquid at room temperature but was liquid in a high-temperature environment.

[0101] Preferably, the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 95 or more and 150 or less, 95 or more and 140 or less, or 95 or more and 130 or less. More preferably, the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle may be 96.8 or more and 124.5 or less.

[0102] When the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle satisfies the aforementioned range, the second compound particle has an appropriate contact area with the first compound particle, and the likelihood of forming an island-shaped second compound particle increases. When lithium is leached from the first valuable metal recovery alloy, the contact rate between the leaching agent and the lithium compound increases, and lithium ion movement becomes smooth and reactivity is enhanced, thereby improving lithium recovery efficiency. Furthermore, an island-shaped or thin-film Fe-P-containing coating layer is uniformly formed, ensuring stability during lithium recovery.

[0103] If the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle is less than the lower limit of the aforementioned range, the second compound particle becomes pointed in shape close to a cone, making it difficult to form the second compound particle or a coating layer containing the second compound particle on the surface of the first compound particle. Consequently, when magnetic separation is performed on the valuable metal recovery composition, it may not be easy to separate the magnetic material from the non-magnetic material. In addition, the degree of wear on the surface of the first valuable metal recovery alloy may increase, and as a result, the valuable metal in the form of fine particles may be easily lost, which consequently may lead to a lower recovery rate of the valuable metal.

[0104] If the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle exceeds the upper limit of the aforementioned range, the second compound particle may become thinner, and the coverage rate on the surface of the first compound particle may increase excessively. This acts as a weakness during lithium extraction, and there may be a problem in that the contact area between the lithium compound contained in the first compound particle and the leaching agent is very small, resulting in a decrease in the leaching rate.

[0105] In a valuable metal recovery composition according to one embodiment of the present invention, the lithium (Li) content may be 1 to 20 weight% based on 100 weight% of the total valuable metal recovery composition.

[0106] When the above lithium content satisfies the aforementioned range, the lithium recovery rate can be improved by reducing the leaching effect caused by graphite in the valuable metal recovery composition.

[0107] In a valuable metal recovery composition according to one embodiment of the present invention, the second compound particles are in the form of aggregated angular Fe-P-containing fine particles having a diameter of 0.1 to 10 μm, and the average particle size of the second compound particles may be 0.1 to 100 μm.

[0108] Preferably, the second compound particles may have an average particle size of 1 to 100 μm, 5 to 50 μm, 6 to 40 μm, 6 to 32 μm, or 10 to 30 μm.

[0109] If the average particle size of the second compound particles satisfies the aforementioned range, magnetic separation may be facilitated in the subsequent process of separating iron (Fe).

[0110] On the other hand, if the average particle size of the second compound particles is less than the lower limit of the aforementioned range, it may not be easy to separate iron-containing materials by magnetic separation. Furthermore, if the average particle size of the second compound particles exceeds the upper limit of the aforementioned range, the content of fragments of the first compound particles and impurities within the second compound particles may be high. This is because, in the valuable metal recovery composition according to the present invention, the second compound particles exist in a form surrounding fragments of the first compound particles. Consequently, in the subsequent process of separating valuable metals individually, multi-stage refining is required to separate the first compound particles or impurities from the second compound particles, which may lead to an overall increase in the cost of the waste battery recycling process.

[0111] As previously mentioned, the second compound particles are in a metallic drop phase at room temperature, and if the size of the Fe-P-containing fine particles satisfies the aforementioned range, separation and recovery of Fe and P by a subsequent process may be facilitated. In addition, an island-shaped or thin film-shaped coating layer containing the second compound particles on the surface of the first compound particles is formed to have an appropriate thickness and coverage rate, thereby facilitating the acid leaching of lithium in the subsequent stage.

[0112] On the other hand, if the size of the above-mentioned Fe-P-containing fine particles is less than the lower limit of the aforementioned range, it is difficult to form a coating layer containing second compound particles that is easy to magnetically separate, specifically a coating layer containing Fe-P components, so it may not be easy to separate the first valuable metal recovery alloy and the second valuable metal recovery alloy by magnetic separation. In addition, if the size of the above-mentioned Fe-P-containing fine particles exceeds the upper limit of the aforementioned range, the content of impurities within the formed second compound particle coating layer may be high. As a result, multi-stage refining is required in the subsequent process of separating valuable metals individually, and there may be a problem in that the cost of the waste battery recycling process increases overall.

[0113] In a valuable metal recovery composition according to one embodiment of the present invention, the average particle size of the first compound particles may be 20 to 220 μm.

[0114] Preferably, the first compound particles may have an average particle size of 27 to 213 μm, 38 to 130 μm, or 40 to 125 μm.

[0115] If the average particle size of the first compound particle is within the aforementioned range, it is possible to facilitate the separation of the first compound particle and the second compound particle surrounding the surface of the first compound particle.

[0116] On the other hand, if the average particle size of the first compound particles is less than the lower limit of the aforementioned range, it is not easy to separate the second compound particles and the first compound particles in the subsequent process, which may result in high costs for extracting valuable metals. In addition, if the average particle size of the first compound particles exceeds the upper limit of the aforementioned range, the impurity content increases, requiring multi-stage refining in the subsequent process for separating valuable metals individually, which may lead to an overall increase in the cost of the waste battery recycling process.

[0117] In a valuable metal recovery composition according to one embodiment of the present invention, the valuable metal recovery composition comprises Cu particles, wherein the Cu particles have at least one form among spherical single particles and particles formed by combining two or more spherical single particles, the spherical single particles have a sphericity of 0.85 or higher and 1 or lower, and the Cu particles may have an average particle size of 25 to 70 μm. In the specification of the present invention, the Cu particles refer to particles containing 45 mol% or more of the Cu element based on 100 mol% of the total elements constituting the Cu particles when Electron Backscatter Diffraction (EBSD) is performed. Preferably, the Cu particles may contain 70 mol% or more of the Cu element.

[0118] If the sphericity and average particle size of the above Cu particles satisfy the aforementioned range, it may be easy to separate Cu from the valuable metal recovery composition.

[0119] On the other hand, if the sphericity and average particle size of the above Cu particles are below the lower limit of the aforementioned range, the ease of separating Cu from the valuable metal recovery composition may decrease, which may lead to an increase in the cost of the waste battery recycling process. Furthermore, if the average particle size of the above Cu particles exceeds the upper limit of the aforementioned range, separation may be easy, but there may be a problem of increased energy costs due to the long high-temperature reduction treatment time required to achieve the said average particle size. In addition, due to excessive reduction reactions during the process, a problem may occur where lithium compounds such as LiAlO2 are reduced and lost as Li(g). Consequently, a problem may arise where the lithium recovery rate is low.

[0120] A valuable metal recovery composition according to one embodiment of the present invention further comprises aluminum oxide in the form of Al2O3 or a Li-Al-O compound, and the average particle size of the aluminum oxide may be 40 to 180 μm. Preferably, the average particle size of the aluminum oxide may be 49 to 170 μm, 60 to 145 μm, or 66 to 131 μm.

[0121] Specifically, the aluminum oxide in the form of the Li-Al-O compound may include at least one of LiAlO2, Li5AlO4, and LiAl5O8. Additionally, the aluminum oxide may simultaneously include both Al2O3 and the Li-Al-O compound.

[0122] If the average particle size of the aluminum oxide falls within the aforementioned range, it may be easy to separate and recover the aluminum oxide.

[0123] On the other hand, if the average particle size of the aluminum oxide is less than the lower limit of the aforementioned range, Al2O3 may exist in the form of fine particles, which may reduce the ease of separation. Consequently, the recovery rate of Al may be significantly lowered. In addition, it may be difficult for the average particle size of the aluminum oxide to exceed the upper limit of the aforementioned range.

[0124] In a valuable metal recovery composition according to one embodiment of the present invention, the first valuable metal recovery alloy comprises Li2O, Li2CO3, Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, Li5FeO4, LiAlO2, LiCuO2, Li2CuO2, Cu2O, CuO, CuO2, Cu2O3, CuO2, Cu3(PO4)2, FeO, Fe2O3, Fe3O4, Fe4O5, Fe5O6, Fe5O7, Fe 25 O 32 , Fe 13 O 19 , FePO4, P2O5, P4O 10 It may include at least one of Al2O3 and AlPO4.

[0125] The metal compounds included in the valuable metal recovery composition of the present invention may include other types in addition to those described above, and the present invention is not limited to the aforementioned types.

[0126]

[0127] 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.

[0128] Example 1

[0129] (Preparation and Charging Steps) 25 kg of lithium iron phosphate (LFP) batteries were cooled at -70 ℃ 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 long axis among the width, length, and height. After preparing the crushed battery material, it was placed into a heating furnace.

[0130] (Heating step) Next, a mixed gas was injected into the furnace. At this time, the mixed gas was a mixture of oxygen (O2), hydrogen (H2), and nitrogen (N2), and the mixture of hydrogen and oxygen was first saturated inside the furnace. Subsequently, oxygen was injected into the furnace by applying a negative pressure of -10 kPa to the furnace flue gas facility so that the volume fraction of oxygen in the mixed gas was maintained at 2 vol%. After a reducing gas atmosphere was established, the temperature inside the furnace was raised to 1100 ℃ and maintained for 5 hours to produce a valuable metal recovery composition.

[0131] After the (step of obtaining a valuable metal recovery composition), a negative pressure of -10 kPa was applied to the flue gas facility to discharge the flue gas and obtain a valuable metal recovery composition.

[0132] (Classification step after magnetic separation) A magnetic field of strength of 0.3T was applied to the obtained valuable metal recovery composition to separate and classify it into a first valuable metal recovery alloy containing a magnetic material and a second valuable metal recovery alloy containing a non-magnetic material.

[0133] Example 2

[0134] A valuable metal recovery composition was produced using the same process as in Example 1, except that in the heating step above, the temperature condition was changed to 1000 ℃.

[0135] Comparative Example 1

[0136] A valuable metal recovery composition was produced using the same process as in Example 1, except that the temperature condition in the heating step was changed to 600 ℃ and the classification step after magnetic separation was performed first followed by magnetic separation.

[0137] Comparative Example 2

[0138] A valuable metal recovery composition was produced using the same process as in Example 2, except that the temperature condition in the heating step was changed to 1500 ℃ and the classification step after magnetic separation was performed first followed by magnetic separation.

[0139]

[0140] Experimental Example 1 - Analysis of Valuable Metal Reduction Rate and Lithium Compound Content

[0141] The recovery rate of lithium was calculated from the manufactured valuable metal recovery alloy (the first valuable metal recovery alloy among the valuable metal recovery compositions).

[0142] Classification Process Condition Result Refining Method Magnetic Separation Time Heating Furnace Internal Temperature (°C) Presence of Coating Layer Containing Second Compound Particles on the Surface of First Compound Particles Size of the Angle Formed by Intersecting Any Two Tangents on the Surface of Second Compound Particles (°) Li Recovery Rate (%) Example 1 Classification after Dry Reduction Magnetic Separation 1100 O 124.588 Example 2 Classification after Dry Reduction Magnetic Separation 1000 O 96.884 Comparative Example 1 Magnetic Separation after Dry Reduction Classification 600 X 63.475 Comparative Example 2 Magnetic Separation after Dry Reduction Classification 1500 X 17 1.663

[0143] Table 1 above describes the manufacturing process conditions of the first valuable metal recovery alloy, whether a coating layer containing the second compound particles is included on the surface of the first compound particles, the size of the angle formed by the intersection of any two tangents on the second compound particles (hereinafter referred to as 'angle size'), and the lithium recovery rate. According to Table 1 above, in Examples 1 and 2, where the internal temperature of the furnace was 1000 ℃ and 1100 ℃, it was confirmed that a coating layer containing the second compound particles was formed on the surface of the first compound particles. It was confirmed that the reduction reaction of the metal components contained in the LFP battery crushed material proceeded well, and a coating layer of the second compound particles containing Fe-P was formed. However, in the case of Example 1, where the internal temperature of the furnace was somewhat lower at 600 ℃, it can be understood that a large amount of metals in an oxide state that were not reduced existed, or even if reduction occurred, the particle size of the second compound particles containing Fe-P was too small, making it difficult to form a coating layer. On the other hand, in Comparative Example 2, where the internal temperature of the furnace is somewhat high at 1500 ℃, the reduction reaction of the metal would have proceeded actively; however, since lithium (Li) can vaporize at temperatures above 1300 ℃, it may be difficult to form first compound particles containing lithium compounds. Consequently, it may also be difficult to form a valuable metal recovery alloy in which the second compound is attached to the surface of the first compound particles. Thus, results as shown in Table 1 above may occur. Furthermore, when measuring the size of the angle formed by the intersection of any two tangents drawn on the surface of the second compound particles, it can be confirmed that the angle in the Comparative Example is too small or too large compared to the Example. A small angle indicates that the second compound particles have a somewhat narrow and pointed shape. If the second compound has such a shape, the magnetic separation effect decreases, and the lithium recovery rate in the subsequent process may decrease somewhat. Conversely, a large angle can cause the particles of the second compound to become excessively thin, which reduces the magnetic separation effect and may hinder contact between the particles of the first compound and the lithium leaching agent.This may lead to a problem where the lithium recovery rate decreases significantly.

[0144]

[0145] Classification of Valuable Metal Recovery Alloys Magnetic Separation Time Point Fe-P[wt%]Li[wt%]C[wt%] After Leaching Lithium Recovery Rate (%) Formula 1([Fe-P] / [Li]) Comparative Example 1 1st Valuable Metal Recovery Alloy After Classification Magnetic Separation 97.69 0.71 1.675 137.59 Comparative Example 2 1st Valuable Metal Recovery Alloy 96.52 1.38 2.16 369.94 Comparative Example 1 2nd Valuable Metal Recovery Alloy 2.07 8.638 9.317 0.24 Comparative Example 2 2nd Valuable Metal Recovery Alloy 1.32 11.088 7.612 0.12 Example 1 1st Valuable Metal Recovery Alloy After Magnetic Separation Classification 87.28 8.42 4.388 10.37 Example 2 1st Valuable Metal Recovery Alloy 88.14 6.36 5.58 41 3.86 Example 1 Second valuable metal recovery alloy 2.37 1.23 96.41 31.93 Example 2 Second valuable metal recovery alloy 1.75 1.15 97.19 1.52

[0146] Table 2 above lists the magnetic separation treatment time, material content, lithium recovery rate, and the value of Equation 1 for the first valuable metal recovery alloy and the second valuable metal recovery alloy included in the valuable metal recovery composition prepared according to each example and comparative example. When comparing the first valuable metal recovery alloys of the examples and comparative examples in Table 2, it was confirmed that the [Fe-P] / [Li] value of the comparative example was significantly higher than that of the example, and the lithium recovery rate was lower. This is believed to be because the first valuable metal recovery alloy of the comparative example contained an excessive amount of Fe-P components while the content of Li was relatively lower. In the case of the comparative example, it can be understood that the size of the first compound particles containing lithium compounds is small, while the second compound particles containing Fe-P are formed to be relatively hypertrophic. Due to this shape, the movement of lithium ions is hindered during lithium leaching in the subsequent process, which may lead to a problem where the lithium recovery rate decreases.

[0147] Experimental Example 2 - SEM and EBSD Analysis

[0148] SEM images of the manufactured valuable metal recovery composition were taken, and the components of alloys and metal compounds having specific shapes were analyzed using an Electron Back Scatter Diffraction (EBSD) analyzer mounted on the SEM.

[0149] The particle size (average particle diameter) of each alloy or metal compound was measured using the Image J program on the captured SEM images. For 20 particles, the particle size was measured by selecting two points that formed the longest length when connected along the perimeter of particles of the same or similar composition, and the average value was calculated.

[0150] Classification Average Particle Size (㎛) Standard Deviation (㎛) Minimum Particle Size (㎛) Maximum Particle Size (㎛) Compound 2 Particles (Containing Fe-P) 15.35 65.35 76.37 31.8 44 Cu drop 45.37 57.6 28.49 859.9 11 Compound 1 Particles (Containing Li3PO4) 94.37 435.8 47.0 82 212.89 Aluminum Oxide (Al2O3) 98.44 132.38 49.6 29 168.1 33

[0151] Table 3 above shows the results of measuring the particle size of the alloy or metal compound forming the valuable metal recovery composition using SEM images and the Image J program. In the case of Cu, it existed in the form of spherical particles and had high particle uniformity. The particles of the second compound containing Fe-P, the particles of the first compound, and aluminum oxide (Al2O3) were close to amorphous, and it was confirmed that the size of the formed particles was similar, except for Cu. Figure 1 illustrates the SEM image of the valuable metal recovery alloy according to one embodiment of the present invention and the angle formed by the tangent on the surface of the Fe-P alloy.

[0152] The size of the above angle can be measured by referring to Fig. 1.

[0153] According to Figure 1 above, it was confirmed that the hemispherical second compound particle forms an island-shaped coating layer on the surface of the first compound particle.

[0154] Figure 2 shows an SEM image and component analysis results of a valuable metal recovery alloy according to one embodiment of the present invention.

[0155] Figure 3 shows an SEM image and component analysis results of a valuable metal recovery alloy according to one embodiment of the present invention.

[0156] According to Figures 2 and 3 above, it was confirmed that the high-brightness portion within the valuable metal recovery alloy contains significantly high levels of Fe and P and is a second compound particle (particle containing Fe-P alloy components) containing C and / or Cu as impurities. Conversely, it was inferred that the low-brightness, dark portion within the valuable metal recovery alloy is a phosphate-based component with low Fe content and high levels of P and O, and when combined with the XRD analysis (see Figure 4) and enthalpy analysis (see Figure 5) described later, it was confirmed that it is a first compound particle (a lithium compound containing Li3PO4 components).

[0157] Figure 6 is an SEM image of a valuable metal recovery composition according to one embodiment of the present invention.

[0158] FIG. 7 is an SEM image of a valuable metal recovery composition according to one embodiment of the present invention.

[0159] From the above Figures 6 and 7, the types of components of the valuable metal recovery composition, the particle size of each component, and the structural form could be confirmed.

[0160]

[0161] Experimental Example 3 - XRD Analysis

[0162] The manufactured valuable metal recovery composition was classified after magnetic separation to obtain a first valuable metal recovery alloy, and XRD analysis was performed on the first valuable metal recovery alloy.

[0163] Figure 4 shows the XRD analysis results of a valuable metal recovery alloy according to one embodiment of the present invention.

[0164] According to FIG. 4 above, the valuable metal recovery alloy according to one embodiment of the present invention is a first compound particle containing a Li3PO4 component In addition to the second compound particles containing an Fe-P alloy represented as Fe2P, it was confirmed that they further contained aluminum oxide and SiO2 components in the form of Al2O3 or Li-Al-O compounds.

[0165]

[0166] Experimental Example 4 - Enthalpy Analysis

[0167] The manufactured valuable metal recovery composition was classified after magnetic separation to obtain a first valuable metal recovery alloy, and enthalpy analysis was performed on the first valuable metal recovery alloy. Specifically, the enthalpies of Li2O-P2O5 and Li2O-Al2O3 bonds were measured according to the Li2O mole fraction.

[0168] Figure 5 shows the mixed enthalpy of Li2O-Al2O3 and Li2O-P2O5 based on 1 mole.

[0169] According to Figure 5 above, since the Li-P bond is more stable than the Li-Al bond, a valuable metal recovery alloy in which the second compound particles are coated on the surface of the first compound particles can be easily formed. Additionally, the Al component contained therein is highly likely to exist within the valuable metal recovery alloy in the form of aluminum oxide particles in the form of Al2O3 or Li-Al-O compounds independent of the first compound particles. Since the two elements can form a thermodynamically more stable phase as the mixing enthalpy for the chemical reaction between the two elements has a negative value, as shown in the graph of Figure 5, at a temperature of 1100 ℃, Li2O-Al2O3 has the lowest negative value of -40,000 J / mol, whereas Li2O-P2O5 has -250,000 J / mol; therefore, in a high-temperature reaction, Li2O can easily form a stable phase such as Li3PO4 by reacting with P2O5.

[0170]

[0171] 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 first compound particle comprising an oxide containing elements Li and P; and A second compound particle containing an Fe-P component located on the surface of the first compound particle and comprising the second compound particle as a coating particle. Precious metal recovery alloy.

2. In Paragraph 1, Satisfying Equation 1 below, Precious metal recovery alloy: [Equation 1] 5≤[Fe-P] / [Li]≤60 (In the above Equation 1, [Fe-P] and [Li] represent the weight content of the Fe-P component containing iron (Fe) and phosphorus (P) in the valuable metal recovery alloy and the content of lithium (Li), respectively.) 3. In Paragraph 1, A alloy containing 1.5 to 18.5 weight percent of lithium (Li) based on 100% of the total weight of the above-mentioned valuable metal recovery alloy, Precious metal recovery alloy.

4. In Paragraph 1, A second compound particle comprising 70 to 95 weight percent based on 100% of the total weight of the above valuable metal recovery alloy, Precious metal recovery alloy.

5. In Paragraph 1, The above second compound particle is a semi-sphere-shaped metallic drop phase, Precious metal recovery alloy.

6. In Paragraph 1, The size of the angle formed by the intersection of any two tangents on the surface of the second compound particle is 90 to 160 degrees. Precious metal recovery alloy.

7. In Paragraph 1, The second compound particles have an average particle size of 0.1 to 100 μm, Precious metal recovery alloy.

8. In Paragraph 1, The second compound particles are aggregated from angular Fe-P-containing fine particles having a diameter of 0.1 to 10 μm, Precious metal recovery alloy.

9. In Paragraph 1, The above coating particles are second compound particles formed by connecting Fe-P containing fine particles, and The above-mentioned second compound particles are connected to form a thin film coating layer, and The thickness of the coating layer is 0.1 to 3 μm, Precious metal recovery alloy.

10. In Paragraph 9, The area ratio of the coating layer based on the total surface area of ​​the first compound particle is 20 to 90%, Precious metal recovery alloy.

11. In Paragraph 1, The first compound particles and the second compound particles contain at least one of Al, Si, Cu, Ni, Co, Mn, Ti, Zn, Pb, Ca, Mg, B, K, Na, Si, Zr, F, Cr, Nb, and Ta as impurities, Precious metal recovery alloy.

12. In Paragraph 1, A valuable metal recovery alloy further comprising aluminum oxide in the form of Al2O3 or Li-Al-O compounds and SiO2 components, Precious metal recovery alloy.

13. A valuable metal recovery composition recovered from lithium iron phosphate (LFP)-based waste batteries using a dry reduction refining method, A first valuable metal recovery alloy containing a magnetic material; A second valuable metal recovery alloy containing a non-magnetic material; and Includes graphite; The above-mentioned first valuable metal recovery alloy comprises first compound particles having second compound particles as coating particles on the surface, Valuable metal recovery composition.

14. In Paragraph 13, The above second compound particle is in the form of a semi-sphere metallic drop, and Comprising that the size of the angle formed by the intersection of any two tangents on the surface of the second compound particle is 90 to 160 degrees. Valuable metal recovery composition.

15. In Paragraph 13, Based on 100 weight% of the total valuable metal recovery composition, the lithium (Li) content is 1 to 20 weight%, Valuable metal recovery composition.

16. In Paragraph 13, The second compound particles are in the form of aggregated angular Fe-P-containing fine particles having a diameter of 0.1 to 10 μm, and The average particle size of the second compound particles is 0.1 to 100 μm, Valuable metal recovery composition.

17. In Paragraph 13, The average particle size of the first compound particles is 20 to 220 μm, Valuable metal recovery composition.

18. In Paragraph 13, The above valuable metal recovery composition includes Cu particles, and The above Cu particles have at least one form among spherical single particles and particles formed by combining two or more spherical single particles, and The above-mentioned spherical single particle has a sphericity of 0.85 or higher and 1 or lower, and The above Cu particles have an average particle size of 25 to 70 μm, Valuable metal recovery composition.

19. In Paragraph 13, The above valuable metal recovery composition includes aluminum oxide in the form of Al2O3 or Li-Al-O compounds, and The above aluminum oxide has an average particle size of 40 to 180 μm, Valuable metal recovery composition.

20. In Paragraph 13, The above-mentioned first valuable metal recovery alloy is Li2O, Li2CO3, Li2O, Li2CO3, LiOH, LiOH·H2O, LiAlO2, Li5AlO4, LiAl5O8, Li2CO3, LiF, Li3PO4, Li4P2O7, LiPO3, Li2SiO3, Li4SiO4, Li2Si2O5, LiFeO2, LiFe5O8, Li3Fe5O8, Li5FeO4, LiAlO2, LiCuO2, Li2CuO2, Cu2O, CuO, CuO2, Cu2O3, CuO2, Cu3(PO4)2, FeO, Fe2O3, Fe3O4, Fe4O5, Fe5O6, Fe5O7, Fe 25 O 32 , Fe 13 O 19 , FePO4, P2O5, P4O 10 , comprising at least one of Al2O3 and AlPO4, Valuable metal recovery composition.

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