Waste battery treatment method

Abstract

The waste battery treatment method comprises a discharging step of discharging a waste battery, a dismounting step of dismounting the discharged waste battery into battery monomer units, a crushing step of crushing the dismounted waste battery, and a roasting step of roasting the crushed waste battery, a pulverization step for pulverizing the roasted waste battery; and a wet process step for extracting and recovering a metal from the pulverized waste battery.

Description

Technical Field

[0001] The present invention relates to a method for processing waste batteries, and more particularly, to a method for recovering metals in the form of compounds from pack-type batteries that have reached the end of their life. Background Art

[0002] Recently, due to the expansion of the battery electric vehicle (BEV) market, the demand for secondary batteries has increased. Secondary batteries cannot be used forever and have a specific life span. Secondary batteries that have reached the end of their life can be discarded, reused or recycled. In recent years, research has been continuously conducted to recover rare metals that are useful resources in batteries through the recycling and reuse of secondary batteries.

[0003] In the past, the development of waste battery processing technology was mainly carried out in the form of small batteries, and therefore, the development of component technology rather than integrated process technology was carried out. However, since most of the recent increasing demand for batteries focuses on medium to large batteries in group units used as power sources for electric vehicles, waste battery processing technology targeting medium to large batteries is required. In addition, instead of developing existing component technologies, it is necessary to develop integrated recycling technologies for complete batteries and final target metal compounds. Summary of the invention

[0004] Technical issues

[0005] The object of the present invention is to provide a method for treating waste batteries which can effectively recover metals in the form of compounds from assembled batteries that have reached the end of their life through a discharge process, a disassembly process, a crushing process, a roasting process, a pulverization process and a wet process.

[0006] Technical Solution

[0007] A method for treating waste batteries according to an embodiment of the present invention comprises: a discharging process for discharging the waste batteries; a disassembling process for disassembling the discharged waste batteries into battery monomer units; a crushing process for crushing the disassembled waste batteries; a roasting process for roasting the crushed waste batteries; a pulverizing process for pulverizing the roasted waste batteries; and a wet process for extracting and recovering metals from the pulverized waste batteries.

[0008] The waste batteries may be battery packs that have reached the end of their lifespan.

[0009] The waste battery treatment method of the present invention can discharge the waste battery through the discharging process so that the voltage of the waste battery reaches 30V or lower.

[0010] The waste battery treatment method of the present invention can break the battery cells of the battery monomer unit into a size of 20 cm or less through the breaking process.

[0011] The method for treating waste batteries of the present invention can omit the step of separating black matter from the crushed waste batteries.

[0012] In the waste battery treatment method of the present invention, the discharging process, the disassembling process, the crushing process, the roasting process and the pulverizing process can be continuously performed by automated facilities.

[0013] In the waste battery treatment method of the present invention, the discharging process, the disassembling process and the crushing process can be performed by an automated facility using a robot.

[0014] In the waste battery treatment method of the present invention, the metal compound can be recovered through the wet process.

[0015] The metal compound may include at least one selected from the group consisting of lithium hydroxide, lithium carbonate, and lithium phosphate.

[0016] The metal compound may include a sulfate selected from the group consisting of nickel, cobalt, and manganese.

[0017] The metal compound may include a nickel-cobalt-manganese system compound in a solution state.

[0018] Effects of the Invention

[0019] According to the present invention, by disassembling discharged waste batteries into battery monomer units and then performing a wet process, the time required to recover metals in the form of compounds from the batteries can be shortened, and the metal recovery rate can be increased by reducing by-products generated during the process operation.

[0020] In particular, the present invention recovers metals through a wet process without going through a process of separating black mass immediately after crushing / pulverizing the battery of the battery unit, thereby minimizing the loss rate of metal components present in the battery pack.

[0021] Furthermore, the present invention can significantly reduce the time required to recover metals in the form of compounds from assembled batteries by automatically performing the discharge process, disassembly process, crushing process, roasting process, and pulverization process in addition to the wet process. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The figure is a flow chart showing the overall process of the waste battery treatment method of the present invention.

[0023] Figure 2The figure is an overall flow chart showing the detailed steps of the method for treating waste batteries of the present invention. DETAILED DESCRIPTION

[0024] The waste battery treatment method of the present invention includes a discharge process for discharging the waste batteries, a disassembly process for disassembling the discharged waste batteries into battery monomer units, a crushing process for crushing the disassembled waste batteries, a roasting process for roasting the crushed waste batteries, a crushing process for crushing the roasted waste batteries, and a wet process for extracting and recovering metals from the crushed waste batteries.

[0025] Hereinafter, the present invention will be described with reference to the accompanying drawings. Figure 1 FIG. 2 is a flow chart showing the overall process of the waste battery treatment method of the present invention. Figure 1 As shown in , a waste battery treatment method according to an embodiment of the present invention may include a discharging process S100, a disassembling process S200, a crushing process S300, a roasting process S400, a pulverizing process S500 and a wet process S600.

[0026] Discharge process S100

[0027] The discharge process S100 is to discharge the power accumulated in the waste battery to prevent the waste battery from exploding during the subsequent process. For example, in the discharge process S100, the waste battery can be connected to a discharger to discharge it so that the voltage of the waste battery reaches 30V or less, preferably 0.2V or less. By discharging the waste battery to a voltage within the above numerical range through the discharge process S100, the waste battery can be prevented from exploding in the subsequent disassembly process S200, thereby ensuring stability.

[0028] The waste battery treatment method according to the present invention can be performed on medium to large batteries used in electric vehicles. In this case, the waste batteries discharged by the discharge step S100 can be battery packs that have reached the end of their life.

[0029] The discharge process S100 may be performed by mechanical discharge using a discharger, or brine discharge using brine, etc. Preferably, the discharge process S100 may be performed by mechanical discharge. When mechanical discharge is used, fire and explosion safety can be ensured, the discharge state can be checked, and the discharge time and the associated costs can be reduced.

[0030] Disassembly process S200

[0031] The disassembly process S200 is a process for disassembling the waste batteries in group units into smaller units. In the disassembly process S200 according to the present invention, the waste batteries in group are disassembled into battery monomer units. For example, in the disassembly process S200, the waste batteries in group can be disassembled into battery module units and then disassembled into battery monomer units.

[0032] Although it is convenient to directly use grouped waste batteries for recycling and reuse, there is a problem of increased impurity introduction due to the introduction of BMS (Battery Management System) and various control devices. Therefore, in order to recycle and reuse waste batteries, it is necessary to at least disassemble them into battery module units. The present invention is characterized in that grouped waste batteries are disassembled into battery monomer units rather than battery module units. According to the present invention, unlike the case of disassembling grouped waste batteries into battery module units, the present invention disassembles grouped waste batteries into battery monomer units, which makes it possible to significantly reduce the amount of impurities (for example, Al and Fe) introduced into the recycled metal. In addition, since the amount of aluminum introduced into the recycled metal is quite small, it has the advantage of minimizing the additional process for removing aluminum when recycling the metal.

[0033] On the other hand, if the group-type waste batteries are disassembled only into battery module units, a dry process (roasting process) is performed at a high temperature of at least 1200°C. Therefore, manganese (Mn) is discharged as slag in the form of manganese oxide (MnO), making it difficult to recover manganese. Lithium volatilizes into a gaseous state, which reduces the lithium recovery rate. On the other hand, when the group-type waste batteries are disassembled into battery monomer units as in the present invention, the temperature in the dry process can be set to be relatively low. Therefore, unlike the case where the group-type waste batteries are disassembled into battery module units, manganese can be recovered and the lithium (Li) recovery rate can be significantly improved.

[0034] According to one embodiment, Figure 1 As shown in FIG. 1 , the disassembly process S200 may be performed after the discharge process S100. However, the present invention is not limited thereto. In another embodiment, Figure 1 Different from the situation shown in FIG. 1 , the disassembly process S200 may be performed first, and then the discharge process S100 may be performed.

[0035] Crushing process S300

[0036] The crushing process S300 is a process for crushing the disassembled waste battery. The crushing process S300 can crush the battery monomer unit into a size of 20 cm or less, specifically, 15 cm or less, and more specifically, 10 cm or less. By crushing the waste battery into a size within the above numerical range through the crushing process S300, the crushed waste battery can be more uniformly reduced and roasted in the roasting process S400.

[0037] The crushing step S300 can be carried out in nitrogen (N 2 ) atmosphere to prevent sparks and explosions. After the crushing, the sprayed water and the electrolyte flowing out of the waste battery can be removed. For example, the water and electrolyte can be removed by centrifugation using a rotary barrel.

[0038] The crushing step S300 may include a drying step (not shown) of drying the crushed waste batteries.

[0039] According to the present invention, the discharging process S100, the disassembling process S200, and the crushing process S300 may be performed by automated facilities using robots, thereby significantly reducing the time required to recover metals from waste batteries.

[0040] Calcination process S400

[0041] The roasting step S400 is a step of drying the crushed waste batteries. Specifically, the roasting step S400 may be a step of reducing and roasting the crushed waste batteries in an inert gas atmosphere (IAR: Inert Atmosphere Roaster). For example, in the roasting step S400, the temperature may be 800° C. to 900° C. and nitrogen (N 2 ) atmosphere, the waste batteries that have been broken into 5 cm to 10 cm in size are reduced and roasted for 1 to 3 hours. By roasting the broken waste batteries in an inert gas atmosphere, lithium (Li) can be converted into water-soluble Li 2 CO 3 In the process of reducing and roasting the crushed waste batteries to pre-separate lithium, some advanced oxides (Me 2 O 3 , wherein Me is Ni, Co or Mn) is reduced to lower oxides (MeO, wherein Me is Ni, Co or Mn), which can reduce the amount of auxiliary raw materials (H 2 O 2 , hydrogen peroxide).

[0042] Crushing process S500

[0043] The crushing step S500 is a step of crushing the waste batteries dried by the roasting step S400. For example, in the crushing step S500, the reduction roasted batteries may be classified by a ball mill so that the reduction roasted batteries having a size of 200 mesh or less are 80% or more.

[0044] The crushing step S500 can be carried out in nitrogen (N 2 ) atmosphere to prevent sparks and explosions. After the crushing process, the sprayed water and the electrolyte flowing out of the waste battery can be removed. For example, the water and the electrolyte can be removed by centrifugation using a rotary barrel.

[0045] In the waste battery treatment method of the present invention, an additional process of separating black matter after crushing and pulverizing the battery of the battery unit is omitted. According to the present invention, since metals are recovered through a wet process without going through a process of separating black matter, the loss rate of metal components present in the battery pack can be minimized.

[0046] According to the present invention, the discharging step S100, the disassembling step S200, the crushing step S300, the roasting step S400 and the pulverizing step S500 can be continuously performed by automated facilities. Therefore, an integrated recycling process technology from grouped waste batteries to final target metal compounds can be implemented, which can significantly reduce the time required to recover metals from waste batteries.

[0047] Wet process S600

[0048] The wet process S600 is a process for recovering metals using the pulverized battery. The metals recovered by the wet process S600 may be in the form of compounds. For example, the wet process S600 may recover metals in the form of compounds from the pulverized battery after the pulverization process S500.

[0049] The metal compound recovered by the wet process S600 may include at least one selected from the group consisting of lithium hydroxide, lithium carbonate and lithium phosphate. The wet process S600 of the present invention can produce high-purity lithium carbonate (Li 2 CO 3 ) and high purity lithium hydroxide (LiOH·H 2 O), which shows excellent lithium recovery rate. As described below, lithium hydroxide can be produced by pre-separation step S610, weak acid leaching step S612, post-separation step S614, lithium phosphate manufacturing step S616, lithium sulfate solution manufacturing step S618, lithium carbonate manufacturing step S620, lithium hydroxide solution manufacturing step S622 and ion exchange resin step S624.

[0050] In addition, the metal compound recovered through the wet process S600 may include copper (II) sulfide (CuS).

[0051] In one embodiment of the present invention, the metal compound recovered by the wet process S600 may include a sulfate selected from the group consisting of nickel, cobalt and manganese. In another embodiment of the present invention, the metal compound recovered by the wet process S600 may include a nickel-cobalt-manganese compound in a solution state, such as an NCM (Ni, Co, Mn) solution.

[0052] As described below, nickel sulfate may be produced through a pre-separation process S610, a weak acid leaching process S612, a post-separation process S614, a two-stage leaching process S626, a first solvent extraction process S628, and a first impurity removal process S630.

[0053] As described below, cobalt sulfate may be produced through a pre-separation process S610, a weak acid leaching process S612, a post-separation process S614, a two-stage leaching process S626, a first solvent extraction process S628, a second solvent extraction process S632, and a second impurity removal process S634.

[0054] As described below, manganese sulfate may be produced through a pre-separation step S610, a weak acid leaching step S612, a post-separation step S614, a two-stage leaching step S626, a first solvent extraction step S628, a second solvent extraction step S632, and a third impurity removal step S636.

[0055] Below, we will refer to Figure 2 Each step of the wet process S600 will be described in more detail. Figure 2 1 is a flow chart showing the wet process step S600 of the waste battery treatment method of the present invention.

[0056] Pre-separation step S610

[0057] The pre-separation process S610 is a process of leaching and separating lithium (Li) by adding water to the calcined and pulverized battery. For example, in the pre-separation process S610, the pulverized battery subjected to the pulverization process S500 may be dissolved in water, and the lithium (Li) solution may be leached at a temperature of 10° C. to 30° C. for 1 to 3 hours to produce lithium carbonate (Li 2 CO 3 ) solution and a separated filter cake. The pre-separation step S610 can reduce the operating cost and auxiliary material cost in the lithium phosphate manufacturing step S616 described below, minimize impurity mixing when manufacturing high-purity lithium hydroxide, and reduce processing costs when manufacturing lithium hydroxide.

[0058] After the pre-separation step S610, a first evaporation and concentration step (not shown) may be performed. The first evaporation and concentration step is to produce lithium carbonate (LiCO) by evaporating and concentrating the lithium (Li) solution (filtrate) produced in the pre-separation step S610. 2 CO 3 ) crystals. The lithium carbonate crystals are produced by the pre-separation step S610 and the first evaporation concentration step. The phosphoric acid (H 3 PO 4) and the amount of sodium hydroxide (NaOH) can be reduced by 50% or more, and the loss of lithium (Li) in the filtrate distributed in the lithium phosphate manufacturing process S616 can be significantly reduced.

[0059] Weak acid leaching process S612

[0060] The weak acid leaching step S612 uses sulfuric acid (H 2 SO 4 ) is a process for leaching the filter cake separated in the pre-separation process S610. Specifically, the weak acid leaching process S612 is a process in which the filter cake produced after lithium pre-separation in the pre-separation process S610 is leached with sulfuric acid and hydrogen peroxide (H2O2) at a temperature of 80° C. to 85° C. 2 O 2 ) is reduced and leached for 1 to 4 hours. Nickel (Ni), cobalt (Co) and manganese (Mn) are dissolved from the filter cake from which lithium (Li) is pre-separated in the pre-separation step S610, so that the amount of auxiliary raw materials used is minimized and stable process management in a continuous process can be achieved.

[0061] Post-separation process S614

[0062] The post-separation process S614 is a process for neutralizing the leached filtrate generated in the weak acid leaching process S612 to separate the lithium (Li) solution from the nickel-cobalt-manganese filter cake (hereinafter referred to as the NCM filter cake). Specifically, in the post-separation process S614, the leached filtrate obtained in the weak acid leaching process S612 is neutralized with sodium hydroxide (NaOH) (pH 10 to pH 12) and reacted at a temperature of 70° C. to 85° C. for 4 to 8 hours, so that nickel (Ni), cobalt (Co) and manganese (Mn) can be recovered by precipitation, and lithium (Li) can be separated by distributing it as a filtrate. In the post-separation process S614, the precipitation rate of nickel (Ni), cobalt (Co) and manganese (Mn) can be 99.9% or more.

[0063] In addition, in the post-separation process S614, the filtered NCM filter cake can be repulped twice or more to remove residual sodium salt (Na Salt). For example, the sodium (Na) content in the NCM filter cake can be removed by 3.43% to 0.4%. In this specification, the repulping process refers to a process of repulping the solid filter cake with water to wash the filtrate component (e.g., residual sodium salt) present in the filter cake.

[0064] Lithium phosphate manufacturing process S616

[0065] The lithium phosphate manufacturing step S616 is to prepare phosphoric acid (H 3 PO 4) and sodium hydroxide (NaOH) are added to the lithium (Li) solution separated in the post-separation step S614 to produce lithium phosphate (Li 3 PO 4 ) filter cake. Specifically, phosphoric acid (H 3 PO 4 ) is added to the lithium (Li) solution separated in the post-separation step S614 and reacted at a temperature of 70° C. to 85° C. for 1 to 4 hours to precipitate and recover lithium phosphate (Li 3 PO 4 ) in the form of lithium (Li). In addition, sodium hydroxide (NaOH) may be added to neutralize the lithium (Li) solution to pH 10.0 to pH 12.0.

[0066] Lithium sulfate solution manufacturing process S618

[0067] The lithium sulfate solution manufacturing step S618 is to dissolve the solution (lithium carbonate (Li 2 CO 3 ) solution) is evaporated and concentrated to recover lithium carbonate (Li 2 CO 3 ) crystals and the lithium phosphate (Li 3 PO 4 ) filter cake to produce lithium sulfate (Li 2 SO 4 For example, in the lithium sulfate solution manufacturing process S618, the temperature is 60° C. to 80° C., the reaction time is 0.5 hour to 3 hours, and the pH is 2.0 or lower.

[0068] After the lithium sulfate solution manufacturing process S618, a second evaporation concentration process (not shown) may be performed. The second evaporation concentration process is to evaporate and concentrate the lithium sulfate solution generated in the lithium sulfate solution manufacturing process S618 to obtain lithium sulfate (Li 2 SO 4 ) crystals and phosphoric acid (H 3 PO 4 ) filtrate separation process. Phosphoric acid (H 3 PO 4 ) The filtrate can be recycled and reused in the lithium phosphate manufacturing process S616 to be used as a lithium precipitation auxiliary material. The evaporation condensate produced in the second evaporation concentration process can be recycled and reused as a process solution in the lithium (Li) pre-separation process S610. Thus, the amount of wastewater discharged to the outside of the system and the amount of fresh water introduced into the system can be reduced.

[0069] The first phosphorus removal step (not shown) is to remove the lithium sulfate (Li2 SO 4 ) crystals were dissolved in pure water and then treated with aluminum sulfate (Al 2 (SO 4 ) 3 ) and caustic soda (NaOH) to remove phosphorus (P). For example, aluminum sulfate (Al 2 (SO 4 ) 3 ) is added to the solution generated in the lithium sulfate solution manufacturing step S618, the pH is adjusted to 5.0 to 6.0, and the reaction is carried out at a temperature of 50° C. to 70° C. for 4 to 8 hours. Thus, most of phosphorus (P) can be removed by precipitation, and iron (Fe) and other impurities can also be co-precipitated.

[0070] Lithium carbonate manufacturing process S620

[0071] The lithium carbonate manufacturing process S620 is to convert sodium carbonate (Na 2 CO 3 ) is added to the lithium sulfate (Li 2 SO 4 ) and lithium carbonate (Li 2 CO 3 ) precipitation process. For example, in the lithium carbonate production process S620, sodium carbonate (Na 2 CO 3 ) is added to the filtrate generated in the first phosphorus removal step, and the reaction can be carried out at a temperature of 80° C. to 85° C. for 1 hour to 6 hours to precipitate lithium carbonate.

[0072] Preferably, a repulping process may be performed to remove residual sodium (Na) salts in the filter cake left in the lithium carbonate production process S620. In this case, the repulping may be performed at a temperature of 80° C. to minimize the loss of lithium (Li). The filtrate obtained in the lithium carbonate production process S620 may be recycled and reused in the lithium phosphate production process S616.

[0073] Lithium hydroxide solution manufacturing process S622

[0074] The lithium hydroxide solution manufacturing process S622 is a process for dissolving the lithium carbonate filter cake generated in the lithium carbonate manufacturing process into pure water, and then adding calcium oxide (CaO) to manufacture a lithium hydroxide (LiOH) solution. For example, calcium oxide (CaO) and water may be added to the lithium carbonate filter cake generated in the lithium carbonate manufacturing process S620, and may be reacted at a temperature of 80°C to 100°C for 3 hours or less, and then reacted at a temperature of 80°C to 100°C for 2 hours or less to manufacture a lithium hydroxide (LiOH) solution. Preferably, a repulping process may be performed to recover the calcium carbonate (CaCO) generated in the lithium hydroxide solution manufacturing process S622. 3 ) Lithium contained in the residue.

[0075] Ion exchange resin process S624

[0076] The ion exchange resin step S624 is a step of removing calcium (Ca) and magnesium (Mg), which are impurities contained in the lithium hydroxide (LiOH) solution generated as described above.

[0077] The third evaporation and concentration step (not shown) is a step of evaporating and concentrating the lithium hydroxide (LiOH) solution generated in the lithium hydroxide solution manufacturing step S622 and / or the ion exchange resin treatment solution from which impurities have been removed in the ion exchange resin step S624 to produce lithium hydroxide (LiOH) crystals. Specifically, in the third evaporation and concentration step, the lithium hydroxide (LiOH) solution and / or the ion exchange resin treatment solution can be evaporated and concentrated to produce LiOH·H 2 O product.

[0078] Two-stage leaching process S626

[0079] The two-stage leaching process S626 uses sulfuric acid and hydrogen peroxide (H 2 O 2 ) is a process for leaching the weak acid leaching process cake generated in the weak acid leaching process S612 and the NCM filter cake generated in the post-separation process S614. For example, in the two-stage leaching process S626, sulfuric acid (H2SO4) may be used at a temperature of 60° C. to 80° C. 2 SO 4 ) dissolves the filter cake from the weak acid leaching process and separates the NCM filter cake from lithium for 2 to 4 hours. In order to improve the dissolution rate of the NCM filter cake, a small amount of reducing agent can be added. In this case, hydrogen peroxide (H 2 O 2 ) as a reducing agent.

[0080] Preferably, an impurity removal process may be performed to remove impurities from the filtrate generated in the two-stage leaching process S626. In this case, the impurity removal process may include a first copper removal process and a first aluminum and phosphorus removal process. The first copper removal process (not shown) is a process of adding NaSH to remove copper (Cu) as an impurity from the filtrate generated in the two-stage leaching process S626. The first aluminum and phosphorus removal process (not shown) is a process of adding caustic soda (NaOH) and oxygen (O 2 ) is a process for removing additional impurities such as aluminum (Al) and phosphorus (P) from the filtrate generated in the first copper removal process.

[0081] First solvent extraction step S628

[0082] The first solvent extraction step S628 is a step of extracting cobalt from the filtrate generated in the two-stage leaching step S626 and / or the filtrate generated in the above-mentioned impurity removal step using an extractant.

[0083] Preferably, the filtrate generated in the first solvent extraction step S628 may be subjected to a nickel hydroxide production step and a nickel weak acid leaching step. For example, the nickel hydroxide production step (not shown) may be a step of adding caustic soda (NaOH) to the filtrate generated in the first solvent extraction step S628 to produce nickel hydroxide (Ni(OH) 2 ) process. The nickel weak acid leaching process (not shown) may be a process in which water, sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ) is added to the filter cake generated in the nickel hydroxide manufacturing process to dissolve the filter cake.

[0084] First impurity removal process S630

[0085] The first impurity removal process S630 is a process for removing impurities from the filtrate generated in the first solvent extraction process S628 and / or the filtrate generated in the nickel hydroxide production process and the nickel weak acid leaching process. Specifically, the first impurity removal process S630 may include a second copper removal process and a first aluminum removal process. For example, the second copper removal process may be a process for adding sodium hydrosulfide (NaSH) to remove copper (Cu) as an impurity from the filtrate generated in the nickel weak acid leaching process. The first aluminum removal process is a process for adding caustic soda (NaOH) and oxygen (O 2 ) is added to the filtrate generated in the second copper removal process to remove aluminum (Al) as an additional impurity.

[0086] The fourth evaporation and concentration step (not shown) is to evaporate and concentrate the solution generated in the first impurity removal step S630 to produce nickel sulfate (NiSO4 )Crystal process.

[0087] Second solvent extraction step S632

[0088] The second solvent extraction step S632 is a step of extracting manganese from the stripping liquid generated in the first solvent extraction step S628 using an extractant.

[0089] Preferably, the filtrate generated in the second solvent extraction step S632 may be subjected to a first cobalt extraction step (not shown). The first cobalt extraction step is a step of extracting cobalt from the filtrate generated in the second solvent extraction step S632 using an extractant.

[0090] Second impurity removal process S634

[0091] The second impurity removal process S634 is a process for removing impurities from the filtrate generated in the second solvent extraction process S632 and / or the filtrate generated in the first cobalt extraction process. Specifically, the second impurity removal process S634 may include a third copper removal process (not shown) and a second aluminum removal process (not shown). For example, the third copper removal process is a process for adding sodium hydrosulfide (NaSH) to remove copper (Cu) as an impurity from the stripping solution generated in the first cobalt extraction process. The second aluminum removal process is a process for adding caustic soda (NaOH) and oxygen (O 2 ) is a process for removing aluminum (Al) as an additional impurity from the filtrate generated in the third copper removal process.

[0092] The fifth evaporation concentration step (not shown) is to produce cobalt sulfate (CoSO 4 )Crystal process.

[0093] Third impurity removal process S636

[0094] The third impurity removal process S636 is a process for removing impurities from the stripping solution generated in the second solvent extraction process S632. Specifically, the third impurity removal process S636 may include a fourth copper removal process (not shown) and a third aluminum removal process (not shown). The fourth copper removal process is a process for adding sodium hydrosulfide (NaSH) to remove copper (Cu) from the stripping solution generated in the second solvent extraction process S632. The third removal process is a process for adding caustic soda (NaOH) and oxygen (O 2 ) is a process for removing aluminum (Al) as an additional impurity from the filtrate generated in the fourth copper removal process.

[0095] The sixth evaporation and concentration step (not shown) is to produce manganese sulfate (MnSO) by evaporating and concentrating the filtrate generated in the third impurity removal step S636. 4 )Crystal process.

[0096] Hereinafter, the present invention will be described in detail by comparing the embodiment and the comparative example. In the embodiment, valuable metals are recovered from waste batteries through the above process. On the other hand, in the comparative example, the valuable metals are recovered by disassembling the grouped waste batteries into battery module units in the same manner as in the embodiment, but in the disassembly process S200.

[0097] The amount of impurities introduced into the materials recovered in the embodiments and comparative examples is shown in Table 1 below. The amount of impurities introduced is calculated by the following method. Specifically, the amount of NCM622 waste batteries processed per day is 285.7 tons (tons) based on the battery pack, 205.5 tons based on the module without other components after disassembling the battery pack, and 168.2 tons based on the battery monomer unit without other components after disassembling the module. At this time, the amount of impurities introduced is calculated by deriving the ratio of aluminum (Al) and iron (Fe) in the materials recovered from the waste battery module.

[0098] Table 1

[0099]

[0100] As shown in Table 1, it can be seen that in the embodiment where the waste battery pack is disassembled into battery monomer units, the amount of aluminum (Al) and iron (Fe) introduced is significantly reduced compared to the comparative example. Specifically, compared to the comparative example, the amount of aluminum (Al) introduced in the embodiment is reduced by 82.4%, and the amount of iron (Fe) introduced is reduced by 100%.

[0101] On the other hand, the recovery rates of individual valuable metals among the materials recovered in the Examples and Comparative Examples are shown in the following Table 2. The recovery rate of individual valuable metals refers to a value calculated by excluding the loss in the process of recovering the target metal (e.g., Li) in a commercial form (e.g., LiOH). At this time, the weight of the raw material (and slag) containing the target metal is measured using a scale, and the concentration of the leached metal in the form of a compound is measured using ICP-AES spectroscopic analysis, thereby calculating the recovery rate of the individual metal.

[0102] Table 2

[0103]

[0104] As shown in Table 2, it can be seen that the recovery rate of lithium (Li) in the example is significantly improved compared to the comparative example. In addition, it can be noted that unlike the comparative example, it is possible to recover manganese (Mn) in the example.

[0105] Although the present invention has been described with reference to some embodiments in this specification, it should be understood that the present invention may be deformed and modified without departing from the spirit and scope of the present invention as understood by those skilled in the art. In addition, such deformation and modification shall fall within the scope of the invention claimed in this specification.

Claims

1. A method for treating waste batteries, characterized in that: include: Discharging process, discharging the waste battery; A disassembly step of disassembling the discharged waste battery into battery monomer units; A crushing process, crushing the disassembled waste batteries; A roasting step, roasting the crushed waste batteries; A crushing step, crushing the waste batteries after roasting; as well as The wet process extracts and recovers metals from the crushed waste batteries.

2. The method for treating waste batteries according to claim 1, characterized in that: The waste batteries are grouped batteries that have reached the end of their lifespan.

3. The method for treating waste batteries according to claim 1, characterized in that: The waste battery is discharged through the discharging process so that the voltage of the waste battery reaches 30V or less.

4. The method for treating waste batteries according to claim 1, characterized in that: The battery cells of the battery single unit are broken into a size of 20 cm or less through the breaking process.

5. The method for treating waste batteries according to claim 1, characterized in that: The step of separating black matter from the pulverized waste batteries is omitted.

6. The method for treating waste batteries according to claim 1, characterized in that: The discharge process, the disassembly process, the crushing process, the roasting process, and the pulverization process are continuously performed by automated facilities.

7. The method for treating waste batteries according to claim 1, characterized in that: The discharging process, the disassembling process, and the crushing process are performed by an automated facility using a robot.

8. The method for treating waste batteries according to claim 1, characterized in that: The metal compounds are recovered through the wet process.

9. The method for treating waste batteries according to claim 8, characterized in that: The metal compound includes at least one selected from the group consisting of lithium hydroxide, lithium carbonate and lithium phosphate.

10. The method for treating waste batteries according to claim 8, characterized in that: The metal compound includes a sulfate selected from the group consisting of nickel, cobalt, and manganese.

11. The method for treating waste batteries according to claim 8, characterized in that: The metal compound includes a nickel-cobalt-manganese compound in a solution state.

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