KR102530619B1 - Method for recoverying lithium and valuable metal from used lithium ion battery - Google Patents

Abstract

The present invention relates to a method for recovering lithium and valuable metals from waste lithium ion batteries. Specifically, according to an embodiment of the present invention, a pre-treatment step of pre-processing a waste lithium ion battery to obtain a lithium pre-treatment material containing at least one of manganese, cobalt, and nickel and lithium; A roasting step of obtaining a lithium intermediate and a metal oxide by heating the lithium pretreatment material; A lithium acquisition step of obtaining lithium from the lithium intermediate; A leaching step of mixing at least one of an acid and hydrogen peroxide (H ₂ O ₂ ) with the metal oxide to obtain a leachate in which the metal oxide is leached; and a recovering step of recovering at least one of manganese, cobalt, and nickel from the leachate obtained in the leaching step, wherein the lithium obtaining step is performed before the leaching step and the recovering step. And a method for recovering the valuable metal may be provided.

Description

Method for recovering lithium and valuable metals from waste lithium ion batteries {METHOD FOR RECOVERYING LITHIUM AND VALUABLE METAL FROM USED LITHIUM ION BATTERY}

The present invention relates to a method for recovering lithium and valuable metals from a waste lithium ion battery.

In recent years, lithium ion batteries have been widely used not only in electronic devices such as smart phones and mobile devices but also in electric vehicles, and the demand for them is increasing exponentially. The demand for lithium ion batteries is expected to further increase in the future as demand for electric vehicles increases as a next-generation means of transportation.

On the other hand, since lithium ion batteries used in electric vehicles require a large electric capacity, they are installed and used in electric vehicles in units of a plurality of battery cells, battery modules, and battery packs. there is. As such, as the capacity and usage of the lithium ion battery increases, the disposal amount of the lithium ion battery also increases.

However, research on the treatment of waste lithium ion batteries has not yet been activated, and recycling of waste lithium ion batteries is still insufficient. For example, there is a problem that pollution occurs due to waste lithium ion batteries that are indiscriminately discarded, and nature is damaged. In addition, lithium, nickel, cobalt, manganese, etc. used to manufacture lithium ion batteries are limited resources on the earth, and if used indiscriminately, the resources may be quickly exhausted. In addition, as the electric vehicle market expands, the demand for lithium-ion batteries is also rapidly increasing, and lithium, nickel, cobalt, and manganese are rapidly depleted. Accordingly, methods for recycling valuable metals such as nickel, cobalt, and manganese and lithium from waste lithium ion batteries are being developed.

In a conventional method for recovering lithium and valuable metals from a waste lithium ion battery, lithium is recovered after recovering valuable metals. However, when lithium is recovered after the valuable metal recovery process, the concentration of recoverable lithium is significantly reduced. In addition, when lithium is recovered after the valuable metal recovery process, the sodium concentration of the mixed solution after the valuable metal recovery process increases due to the sodium introduced in the intermediate process, so it is difficult for the recovered lithium to satisfy the quality standards for use as a battery raw material. .

Therefore, there is a need for a method capable of recovering a large amount of lithium from a waste lithium ion battery and recovering lithium that satisfies quality standards that can be reused as a battery.

One embodiment of the present invention was invented in view of the above background, and a method for recovering lithium and valuable metals from a waste lithium ion battery capable of preventing nature from being damaged by minimizing indiscriminate disposal of the waste lithium ion battery. want to provide

In addition, one embodiment of the present invention is to provide a method for recovering lithium and valuable metals that can be reused as a battery while satisfying quality standards while recovering a large amount of lithium from a waste lithium ion battery.

According to one aspect of the present invention, a pre-treatment step of pre-processing a waste lithium ion battery to obtain a lithium pre-treatment material containing at least one of manganese, cobalt, and nickel and lithium; A roasting step of obtaining a lithium intermediate and a metal oxide by heating the lithium pretreatment material; A lithium acquisition step of obtaining lithium from the lithium intermediate; A leaching step of mixing at least one of an acid and hydrogen peroxide (H ₂ O ₂ ) with the metal oxide to obtain a leachate in which the metal oxide is leached; and a recovering step of recovering at least one of manganese, cobalt, and nickel from the leachate obtained in the leaching step, wherein the lithium obtaining step is performed before the leaching step and the recovering step. And a method for recovering the valuable metal may be provided.

In addition, the leaching step may include a first leaching step of leaching the metal oxide by mixing the metal oxide and sulfuric acid (H ₂ SO ₄ ); and a second leaching step of injecting the hydrogen peroxide while the metal oxide and the sulfuric acid are mixed so as to increase the leaching rate of the metal oxide in the first leaching step. A method may be provided.

In addition, a method for recovering lithium and valuable metals from a waste lithium ion battery may be provided, further comprising an impurity removal step of injecting sodium carbonate (Na ₂ CO ₃ ) into the leachate in order to remove impurities contained in the leachate. there is.

In addition, a method of recovering lithium and valuable metals from a waste lithium ion battery, in which the pH of the leachate into which the sodium carbonate is injected in the impurity removal step, is 4 to 5, may be provided.

In addition, a method for recovering lithium and valuable metals from a waste lithium ion battery further comprising a temperature raising step of raising the temperature of the leachate to a predetermined temperature range, wherein the temperature raising step is performed between the impurity removal step and the leaching step. It can be.

In addition, a method for recovering lithium and valuable metals from a waste lithium ion battery may be provided, in which the temperature of the leachate, which has been increased in the temperature raising step, has a temperature in the range of 85° C. to 95° C.

In addition, a mixed solvent providing step of providing a mixed solvent obtained by mixing at least one of P204, C272, and P507 with kerosene, wherein the recovering step is performed by mixing the leachate and the mixed solvent to obtain the manganese, A method for recovering lithium and valuable metals from a waste lithium ion battery by recovering at least one of cobalt and nickel may be provided.

In addition, the step of providing the mixed solvent provides a first mixed solvent obtained by mixing the P204 and the kerosene, and the step of recovering mixes the leachate and the first mixed solvent to obtain the first leachate containing manganese and the cobalt. and a separation step of separating the nickel into a second leachate containing nickel, wherein a method for recovering lithium and valuable metals from a waste lithium ion battery may be provided.

In addition, the step of providing the mixed medium further provides a second mixed medium obtained by mixing the C272 and the kerosene, and the recovering step comprises recovering manganese by mixing the first leachate and the second mixed medium to recover manganese. A method for recovering lithium and valuable metals from a waste lithium ion battery, further comprising the step, may be provided.

In addition, the step of providing the mixed solvent further provides a third mixed solvent obtained by mixing the P507 and the kerosene, and the recovering step comprises a step of recovering cobalt by mixing the second leachate and the third mixed solvent to recover cobalt. A method of recovering lithium and valuable metals from a waste lithium ion battery may be provided, further comprising, wherein the cobalt recovery step is performed after the manganese recovery step.

The recovering step may further include a nickel recovery step of recovering nickel by mixing a third leachate in which the cobalt is recovered from the second leachate and the third mixed solvent, wherein the nickel recovery step is the cobalt recovery step. A method of recovering lithium and valuable metals from a waste lithium ion battery, performed later, may be provided.

In addition, in the recovery step, lithium and valuable metals from a waste lithium ion battery, wherein at least one of the manganese, cobalt, and nickel is recovered using a multi-stage mixer-settler that forms a counter flow. A method of recovering may be provided.

In addition, in the roasting step, lithium sulfate (Li ₂ SO ₄ ) is mixed with ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) with the lithium pretreatment material, and the mixture of the ammonium sulfate and the lithium pretreatment material is heated. A method for recovering lithium and valuable metals from a waste lithium ion battery, obtaining as the lithium intermediate and obtaining the metal oxide, may be provided.

The method further includes a washing step of obtaining an aqueous solution of lithium sulfate by mixing water with the lithium sulfate and the metal oxide, wherein the obtaining of lithium comprises obtaining lithium from the aqueous lithium sulfate solution, and obtaining lithium and lithium from the waste lithium ion battery. A method for recovering valuable metals may be provided.

In addition, a method for recovering lithium and valuable metals from a waste lithium ion battery, wherein the lithium intermediate includes one or more of lithium sulfate, lithium carbonate, and lithium nitrate, may be provided.

In addition, the lithium obtaining step removes impurities including at least one of the manganese, the cobalt, and the nickel before recovering the lithium, and the leaching step mixes the impurities removed in the lithium obtaining step with the metal oxide. After leaching the metal oxide, a method of recovering lithium and valuable metals from a waste lithium ion battery may be provided.

In addition, in the lithium obtaining step, a method of recovering lithium and valuable metals from a waste lithium ion battery may be provided in which the impurities are removed in the form of hydroxide using caustic soda.

One embodiment of the present invention has an effect of preventing damage to nature by minimizing indiscriminate disposal of waste lithium ion batteries.

In addition, an embodiment of the present invention has an effect of recovering a large amount of lithium from a waste lithium ion battery and recovering lithium that satisfies quality standards that can be reused as a battery.

1 is a flowchart sequentially illustrating a method of recovering lithium and valuable metals from a waste lithium ion battery according to an embodiment of the present invention.
FIG. 2 is a flow chart sequentially showing preprocessing steps of FIG. 1 .
FIG. 3 is a flow chart sequentially illustrating the separation step of FIG. 2 .
4 is a flowchart showing the roasting step of FIG. 1 sequentially.
FIG. 5 is a flow chart sequentially illustrating the lithium acquisition step of FIG. 1 .
Figure 6 is a flow chart showing the leaching step of Figure 1 sequentially.
7 is a flow chart sequentially showing the precipitation step of FIG. 1 .
FIG. 8 is a flow chart sequentially illustrating the recovery steps of FIG. 1 .

Hereinafter, specific embodiments for implementing the technical idea of the present invention will be described in detail with reference to the drawings.

In addition, in the description of the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

Terms used in this specification are only used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In addition, terms including ordinal numbers, such as first and second, may be used to describe various components, but the components are not limited by these terms. These terms are only used to distinguish one component from another.

As used herein, the meaning of "comprising" specifies specific characteristics, regions, integers, steps, operations, elements, and/or components, and other specific characteristics, regions, integers, steps, operations, elements, elements, and/or groups. does not exclude the presence or addition of

Hereinafter, a specific configuration of a method (S1) for recovering lithium and valuable metals from a waste lithium ion battery according to an embodiment of the present invention will be described with reference to the drawings.

Hereinafter, referring to FIG. 1 , in a method S1 for recovering lithium and valuable metals from a waste lithium ion battery according to an embodiment of the present invention, lithium can be obtained from a waste lithium ion battery. For example, in the method (S1) for recovering lithium and valuable metals from the waste lithium ion battery, lithium may be recovered in the form of a salt such as carbonate from the waste lithium ion battery. Here, the waste lithium ion battery means a lithium ion battery discarded at the end of its service life. The method (S1) of recovering lithium and valuable metals from the waste lithium ion battery includes a pretreatment step (S100), a roasting step (S200), a washing step (S300), a lithium acquisition step (S400), a leaching step (S500), and precipitation. It may include a step (S600), a step of providing a mixed solvent (S700), and a step of recovering (S800).

Referring to FIG. 2 , in the pretreatment step (S100), a waste lithium ion battery may be pretreated to obtain a lithium pretreated material. For example, the process of pre-treating the waste lithium ion battery in the pre-treatment step (S100) may include discharging, crushing, heat treatment, and separation of the battery. This pretreatment step (S100) may include a discharge step (S110), a crushing step (S120), a heat treatment step (S130) and a separation step (S140).

In the discharging step (S110), the waste lithium ion battery may be physically or chemically discharged. For example, in the discharging step (S110), the waste lithium ion battery may be put into an aqueous solution in which sodium carbonate or the like is dissolved and discharged for a predetermined time.

In the shredding step ( S120 ), the discharged waste lithium ion battery may be disassembled into cell and module units, and then the cell-unit waste lithium ion battery may be shredded. For example, in the shredding step (S120), the waste lithium ion battery may be shredded through a double shaft shredder under a nitrogen atmosphere. In this shredding step (S120), by shredding the waste lithium ion battery under a nitrogen atmosphere, it is possible to prevent fire and explosion from occurring from the electrolyte, which is a flammable solvent.

In the heat treatment step (S130), the waste lithium ion battery may be thermally decomposed by heat treatment at a predetermined temperature in order to remove the electrolyte and adhesive of the waste lithium ion battery. For example, in the heat treatment step (S130), the waste lithium ion battery may be heat treated at a temperature of 400° C. to 600° C. for 1 hour to 3 hours. As a more specific example, when the waste lithium ion battery is heated to less than 400° C. in the heat treatment step (S130), the electrolyte and adhesive of the waste lithium ion battery may remain without being completely removed. In addition, when the waste lithium ion battery is heated to a temperature exceeding 600° C. in the heat treatment step (S130), excessive energy and cost may be consumed.

Meanwhile, in the heat treatment step (S130), the waste lithium ion battery may be indirectly heated through a rotary kiln rotary furnace. As such, by heating the waste lithium ion battery through the rotary kiln rotary furnace, the waste lithium ion battery can be heat treated through accurate temperature control, and the shredded waste lithium ion battery can be effectively heat treated.

In this heat treatment step (S130), the waste lithium ion battery may be heat treated to remove organic materials such as electrolyte and adhesives in the waste lithium ion battery. In this case, organic substances and moisture in the waste lithium ion battery are removed, and the waste lithium ion battery may be decomposed into active materials and residual materials.

In the present specification, the active material may include a positive electrode active material and a negative electrode active material. For example, the cathode active materials include lithium nickel cobalt manganese metal oxide (LiNiCoMnO ₂ , NCM), lithium cobalt metal oxide (LiCoO ₂ , LCO), lithium nickel cobalt aluminum metal oxide (LiNiCoAlO ₂ , NCA) and lithium manganese metal oxide (LiMn). ₂ O ₄ , LMO). In addition, the anode active material may include at least one of silicon, graphite, and a silicon mixture. In addition, the residual material may include one or more of copper, iron, and aluminum. Also, the valuable metal may include one or more of nickel, cobalt, and manganese. Here, the active material may be a concept including a valuable metal.

Referring to FIG. 3 , in the separation step (S140), the waste lithium ion battery that has undergone the heat treatment step (S130) can be separated into an active material and a residual material using a vibrating screen. For example, in the separation step (S140), the active material and the remaining material may be separated by configuring the vibrating screen in two stages. This separation step (S140) may include a primary separation step (S141), a grinding step (S142) and a secondary separation step (S143).

In the first separation step (S141), the waste lithium ion battery may be separated into an active material and a residual material through a vibrating screen. For example, the vibrating screen may have a mesh of 100 to 200, and when the waste lithium ion battery passes through the vibrating screen, the residual material may remain on the upper side of the body and the active material may be placed on the lower side of the body. The active material placed on the lower side of the body in the first separation step (S141) may be used in the roasting step (S200).

In the crushing step (S142), the residual material filtered on the upper side of the sieve may be crushed through the vibrating screen. For example, in the pulverizing step (S142), the residual material may be pulverized into a predetermined size through a fine pulverizer. The residual material pulverized in the crushing step (S142) may be separated into a residual material and an active material once more in a secondary separation step (S143).

In the secondary separation step (S143), the residual material pulverized in the crushing step (S142) may be separated into a residual material and an active material through a vibrating screen.

As such, the active material obtained in the first separation step (S141) and the second separation step (S143) may be named a lithium pretreatment material.

Referring to FIG. 4 , in the roasting step (S200), the lithium intermediate and the metal oxide may be obtained by heating the lithium pretreatment material. For example, in the roasting step (S200), the lithium pretreatment material obtained in the separation step (S140) is mixed with ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), and the mixture is heated to obtain lithium sulfate (Li ₂ SO ₄ ) and metal oxides can be obtained. In the present specification, the mixture means a mixture of lithium pretreatment material and ammonium sulfate. In addition, the lithium intermediate may be lithium sulfate, but this is only an example and may be lithium carbonate or lithium nitrate depending on the material mixed with the lithium pretreatment material. As a more detailed example, lithium carbonate and a metal oxide may be obtained when the lithium pretreatment material is mixed with carbon dioxide and heated. In addition, when the lithium pretreatment material is mixed with nitric acid and heated, lithium nitrate may be obtained. This roasting step (S200) may include an analysis step (S210), a mole number determination step (S220), a mixing step (S230), and a heating step (S240).

In the analysis step (S210), the amount of lithium in the lithium pretreatment material may be analyzed. For example, in the analysis step (S210), the amount of lithium in the lithium pretreated material may be analyzed using an inductively coupled plasma-optical emission spectroscopy (ICP-OES).

In the step of determining the number of moles (S220), the number of moles of ammonium sulfate to be mixed with the lithium pretreatment material may be determined. In other words, in the step of determining the number of moles (S220), the number of moles of ammonium sulfate to be mixed may be determined in response to the amount of lithium analyzed in the analysis step (S210). For example, when the amount of lithium in the lithium pretreatment material is large, a large amount of ammonium sulfate may be mixed with the lithium pretreatment material. As a more detailed example, in the step of determining the number of moles (S220), the number of moles of ammonium sulfate may be determined such that the mole ratio of ammonium sulfate to lithium in the lithium pretreatment material is 0.8 to 1.2. However, if the molar ratio of ammonium sulfate to lithium in the lithium pretreatment material is out of the range of 0.8 to 1.2, the sulfuration rate of lithium may be insufficient or not only lithium sulfuration but also valuable metals may be sulfurized. In other words, lithium may be insufficiently recovered in the washing step (S300) and the lithium acquisition step (S400), and not only lithium but also valuable metals are leached and recovered, resulting in a low recovery rate of lithium. This is related to the characteristics of the lithium pretreatment material, and it is desirable to set the optimal ratio through experiments when it is out of the usual range.

In the mixing step (S230), the ammonium sulfate of the mole number determined in the mole determination step (S220) may be mixed with the lithium pretreatment material. In this mixing step (S230), ammonium sulfate and the lithium pretreatment material may be stirred and mixed at 1 rpm to 60 rpm for 10 to 50 minutes using a stirrer.

In the heating step (S240), the mixture may be heated to obtain lithium sulfate and a metal oxide. For example, in the heating step (S240), the mixture may be heated at a temperature of 500°C to 800°C for 1 hour to 4 hours. As a more detailed example, if the mixture is heated for less than 1 hour in the heating step (S240), the sulfuration rate of lithium may be insufficient or not only lithium but also valuable metals may be sulfurized. In addition, when heating the mixture for more than 4 hours in the heating step (S240), excessive energy and cost may be consumed.

Meanwhile, in the heating step (S240), the mixture may be indirectly heated through a rotary kiln rotary furnace. In addition, when the mixture is subjected to a heating step (S240), lithium sulfate and a metal oxide may be obtained. As a more detailed example, when the lithium pretreatment material is NCM, lithium sulfate and a metal oxide may be obtained according to the following chemical formula.

(NH ₄ ) ₂ SO ₄ + Li(NCM)O ₂ → Li ₂ SO ₄ + (NCM)O ₂

Here, the metal oxide may be (NCM)O ₂ , but this is only an example and the metal oxide may vary depending on the type of lithium pretreatment material. In addition, ammonium ions before the reaction are discharged in the form of gaseous ammonia when lithium sulfate and metal oxide are obtained.

In the water washing step (S300), water may be mixed with the lithium sulfate and the metal oxide obtained in the roasting step (S200). In this case, lithium sulfate is dissolved in water to become an aqueous lithium sulfate solution, and metal oxides may be precipitated without being dissolved in water. As such, in the water washing step (S300), lithium sulfate is dissolved through water rather than acid, thereby having an effect of selectively leaching only lithium rather than metal oxide.

Referring to FIG. 5, in the lithium acquisition step (S400), lithium may be obtained from a lithium intermediate. For example, in the lithium acquisition step (S400), some of the lithium sulfate aqueous solution obtained in the washing step (S300) may be recovered, and lithium may be obtained from the recovered lithium sulfate aqueous solution. This lithium acquisition step (S400) may include a pH adjustment step (S410) and a lithium carbonate acquisition step (S420).

In the pH adjusting step (S410), the pH of the lithium sulfate aqueous solution may be adjusted. In order to adjust the pH of the aqueous lithium sulfate solution, caustic soda may be added to the aqueous lithium sulfate solution. For example, the pH of the lithium sulfate aqueous solution into which caustic soda is added may be 8 to 11. In this case, impurities in the lithium sulfate aqueous solution can be removed by caustic soda. Here, the impurity in the lithium sulfate aqueous solution may be at least one of a small amount of sulfated nickel, cobalt, and manganese. These impurities can be removed in the form of hydroxide by caustic soda.

In the lithium carbonate obtaining step (S420), lithium carbonate may be obtained through the lithium sulfate aqueous solution whose pH is adjusted in the pH adjusting step (S410). In the lithium carbonate recovery step (S420), lithium carbonate may be obtained by injecting carbon dioxide or sodium carbonate (Na ₂ CO ₃ ) into an aqueous solution of lithium sulfate whose pH is adjusted.

The lithium acquisition step (S400) may be performed before the leaching step (S500), the precipitation step (S600), the mixed solvent providing step (S700), and the recovery step (S800).

Referring to FIG. 6 , in the leaching step ( S500 ), the metal oxide may be leached by mixing the metal oxide with at least one of an acid and hydrogen peroxide (H ₂ O ₂ ). For example, in the leaching step (S500), the metal oxide may be leached by mixing sulfuric acid (H ₂ SO ₄ ) with the metal oxide. This leaching step (S500) may include a first leaching step (S510) and a second leaching step (S520).

In the first leaching step (S510), the metal oxide may be leached by mixing the metal oxide and sulfuric acid. For example, in the first leaching step (S510), the metal oxide precipitated in the washing step (S300) and the impurities removed in the pH adjusting step (S410) may be mixed and then sulfuric acid is injected to leach the metal oxide. Here, the impurities removed in the pH adjusting step (S410) may be one or more of a small amount of sulfated nickel, cobalt, and manganese. As such, there is an effect of further improving the recovery rate of valuable resources by mixing the removed impurities again.

In the second leaching step (S520), hydrogen peroxide may be injected into a mixture of metal oxide and sulfuric acid. Here, hydrogen peroxide can improve the leaching rate of metal oxides. This secondary leaching step (S520) may be performed sequentially or simultaneously with the primary leaching step (S510). In other words, even in the first leaching step (S510), sulfuric acid and hydrogen peroxide may be simultaneously injected according to circumstances.

As such, cobalt, manganese, and nickel may be reduced and leached through the first leaching step (S510) and the second leaching step (S520). In addition, the solution in which the metal oxide is leached through the leaching step (S500) may be referred to as a leachate.

Referring to FIG. 7 , in the precipitation step (S600), the temperature of the leachate may be raised to a predetermined temperature range, and impurities included in the leachate may be removed. This precipitation step (S600) may include a temperature raising step (S610) and an impurity removal step (S620).

In the temperature raising step (S610), the leachate may be heated to a predetermined temperature range. For example, in the temperature raising step (S610), the leachate may be heated to a temperature in the range of 85°C to 95°C.

In the impurity removal step (S620), impurities in the leachate, which has been heated to a predetermined temperature range through the temperature raising step (S610), may be removed. For example, in the impurity removal step (S620), impurities in the leachate may be removed by injecting sodium carbonate (Na ₂ CO ₃ ) into the leachate. In addition, the pH of the leachate injected with sodium carbonate may be 4 to 5. Meanwhile, the impurities removed in the impurity removal step (S620) may be one or more of copper, iron, and aluminum.

The mixed solvent providing step (S700) is P204 (Di (2-ethylhexyl) phosphoric acid (D2EPHA)), C272 (Bis-2,4,4-trimethylpentyl phosphinic acid) and P507 (2-Ethylhexyl-2-Ethylhexyl phosphate) A mixed solvent in which one or more and kerosene is mixed may be provided. Here, the mixed solvent may include a first mixed solvent of P204 and kerosene, a second mixed solvent of C272 and kerosene, and a third mixed solvent of P507 and kerosene. The first mixed solvent provided in the step of providing the mixed solvent (S700) can be used in the separation step (S810) to be described later, the second mixed solvent can be used in the manganese recovery step (S820) to be described later, and the third mixed solvent can be used in the step of recovering manganese (S820). may be used in the cobalt recovery step (S830) and the nickel recovery step (S840) to be described later.

Referring to FIG. 8, in the recovery step (S800), at least one of manganese, cobalt, and nickel is recovered by mixing the leachate from which impurities are removed in the impurity removal step (S620) and the mixed solvent provided in the mixed solvent providing step (S700). can For example, in the recovery step (S800), one or more of the manganese, cobalt, and nickel may be recovered using a multi-stage mixer-settler forming a counter flow. This recovery step (S800) may include a separation step (S810), a manganese recovery step (S820), a cobalt recovery step (S830), and a nickel recovery step (S840).

In the separation step (S810), cobalt, nickel, and manganese may be separated by mixing the leachate from which impurities are removed in the impurity removal step (S620) and the first mixed solvent. That is, in the separation step (S810), the leachate may be separated into a first leachate containing manganese and a second leachate containing cobalt and nickel. For example, in the separation step (S810), the mixture of the leachate and the first mixed solvent may be separated into the first leachate and the second leachate using a multi-stage mixer-settler.

In the manganese recovery step (S820), manganese may be recovered by mixing the first leachate separated in the separation step (S810) and the second mixed solvent. Here, the first leachate may include not only manganese, but also calcium (Ca), copper (Cu), and the like, and when the second mixed solvent is mixed with the first leachate, manganese may be separated from calcium and copper. In other words, after copper is removed by mixing the second mixed solvent with the first leachate, manganese can be separated from calcium by mixing the second mixed medium with the first leachate from which copper is removed. For example, in the manganese recovery step (S820), manganese may be extracted from the mixture of the first leachate and the second mixed solvent using a multi-stage mixer-settler.

In the cobalt recovery step (S820), cobalt may be recovered by mixing the second leachate separated in the separation step (S810) and the third mixed solvent. For example, in the cobalt recovery step (S830), cobalt may be extracted from the mixture of the second leachate and the third mixed solvent using a multi-stage mixer-settler.

In the nickel recovery step (S840), nickel may be recovered by mixing the third leachate in which cobalt is removed from the second leachate through the separation step (S810) and the cobalt recovery step (S830) and the third mixed solvent. For example, in the nickel recovery step (S840), nickel may be extracted from a mixture of the third leachate from which manganese and cobalt are removed and the third mixed solvent using a multi-stage mixer-settler.

As such, the method (S1) for recovering lithium and valuable metals from a waste lithium ion battery according to an embodiment of the present invention has an effect of recycling lithium by recovering lithium from a waste lithium ion battery.

In addition, the method (S1) for recovering lithium and valuable metals from a waste lithium ion battery has an effect of recovering a larger amount of lithium by recovering lithium before the step of recovering manganese, cobalt, and nickel.

Although the embodiments of the present invention have been described as specific embodiments, this is merely an example, and the present invention is not limited thereto, and should be construed as having the widest scope according to the technical spirit disclosed herein. A person skilled in the art may implement a pattern of a shape not indicated by combining/substituting the disclosed embodiments, but this also does not deviate from the scope of the present invention. In addition, those skilled in the art can easily change or modify the disclosed embodiments based on this specification, and it is clear that such changes or modifications also fall within the scope of the present invention.

Claims (17)

A pretreatment step of preprocessing the waste lithium ion battery to obtain a lithium pretreatment material containing at least one of manganese, cobalt, and nickel and lithium;
Lithium sulfate (Li ₂ SO ₄ ) is obtained as a lithium intermediate by mixing ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) with the lithium pretreatment material and heating the mixture of the ammonium sulfate and the lithium pretreatment material, A roasting step of obtaining a metal oxide including at least one of lithium nickel cobalt manganese metal oxide, lithium cobalt metal oxide, lithium nickel cobalt aluminum metal oxide and lithium manganese metal oxide by extracting a lithium intermediate;
A lithium acquisition step of obtaining lithium from the lithium intermediate;
A leaching step of mixing at least one of an acid and hydrogen peroxide (H ₂ O ₂ ) with the metal oxide to obtain a leachate in which the metal oxide is leached; and
And a recovery step of recovering at least one of manganese, cobalt and nickel from the leachate obtained in the leaching step,
The lithium acquisition step is performed before the leaching step and the recovery step,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 1,
The leaching step is
A first leaching step of leaching the metal oxide by mixing the metal oxide and sulfuric acid (H ₂ SO ₄ ); and
And a second leaching step of injecting the hydrogen peroxide while the metal oxide and the sulfuric acid are mixed so that the leaching rate of the metal oxide is improved in the first leaching step.
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 1,
Further comprising a precipitation step including an impurity removal step of injecting sodium carbonate (Na ₂ CO ₃ ) into the leachate in order to remove at least one impurity of sulfated nickel, cobalt, and manganese contained in the leachate;
The impurity removal step is performed after the leaching step,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 3,
In the impurity removal step, the pH of the leachate into which the sodium carbonate is injected is 4 to 5,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 3,
The precipitation step is
Further comprising a temperature raising step of raising the temperature of the leachate to a predetermined temperature range,
The temperature raising step is performed after the leaching step and before the impurity removal step,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 5,
In the temperature raising step, the temperature of the leachate has a temperature in the range of 85 ° C to 95 ° C,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 1,
Further comprising a mixed solvent providing step of providing a mixed solvent in which at least one of P204, C272 and P507 and kerosene are mixed,
The recovery step is
Recovering at least one of the manganese, cobalt, and nickel by mixing the leachate and the mixed solvent;
The step of providing the mixed solvent is performed before the step of recovering,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 7,
In the step of providing the mixed solvent, a first mixed solvent obtained by mixing the P204 and the kerosene is provided,
The recovering step includes a separation step of mixing the leachate and the first mixed solvent and separating the first leachate containing the manganese and the second leachate containing the cobalt and the nickel,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 8,
In the step of providing the mixed solvent, a second mixed solvent obtained by mixing the C272 and the kerosene is further provided,
The recovery step is
Further comprising a manganese recovery step of recovering the manganese by mixing the first leachate and the second mixed solvent,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 9,
In the step of providing the mixed solvent, a third mixed solvent obtained by mixing the P507 and the kerosene is further provided,
The recovery step is
Further comprising a cobalt recovery step of recovering cobalt by mixing the second leachate and the third mixed solvent;
The cobalt recovery step is performed after the manganese recovery step,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 10,
The recovery step is
Further comprising a nickel recovery step of recovering nickel by mixing the third leachate in which the cobalt is recovered from the second leachate and the third mixed solvent,
The nickel recovery step is performed after the cobalt recovery step,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 7,
The recovery step is
Recovering at least one of the manganese, cobalt and nickel using a multi-stage mixer-settler forming a counter flow,
A method for recovering lithium and valuable metals from waste lithium ion batteries. delete According to claim 1,
Further comprising a water washing step of mixing the lithium sulfate and the metal oxide with water to obtain an aqueous lithium sulfate solution;
The lithium obtaining step is to obtain the lithium from the lithium sulfate aqueous solution,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 1,
The lithium intermediate includes at least one of lithium sulfate, lithium carbonate and lithium nitrate,
A method for recovering lithium and valuable metals from waste lithium ion batteries. According to claim 1,
The lithium obtaining step removes impurities including at least one of the manganese, the cobalt, and the nickel before recovering the lithium,
The leaching step mixes the impurities removed in the lithium obtaining step with the metal oxide and then leaches the metal oxide.
A method for recovering lithium and valuable metals from waste lithium ion batteries. 17. The method of claim 16,
The lithium obtaining step is to remove the impurities in the form of hydroxide using caustic soda,
A method for recovering lithium and valuable metals from waste lithium ion batteries.

Images