Method for recovering active metals from lithium secondary batteries

Abstract

A method for recovering active metals from a lithium secondary battery includes the steps of collecting a positive electrode active material mixture from a positive electrode of a lithium secondary battery, subjecting the positive electrode active material mixture to a reduction reaction to prepare a pre-precursor mixture, forming an aqueous lithium precursor solution from the pre-precursor mixture, and collecting an aluminum-containing material from the aqueous lithium precursor solution using an aluminum-removing resin.

Description

[Technical Field]

[0001] The present invention relates to a method for recovering active metals from lithium secondary batteries, and more particularly to a method for recovering active metals from the positive electrodes of lithium secondary batteries. [Background technology]

[0002] Secondary batteries are capable of repeated charging and discharging, and have been widely used in portable electronic communication devices such as camcorders, mobile phones, and laptops with the development of the information and communication and display industries. Examples of secondary batteries include lithium secondary batteries, nickel-cadmium batteries, and nickel-metal hydride batteries. Among them, lithium secondary batteries have been actively developed and applied due to their high operating voltage and energy density per unit weight, as well as their advantages of fast charging and lightweight design.

[0003] A lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator, and an electrolyte impregnated in the electrode assembly. The lithium secondary battery may further include, for example, a pouch-shaped exterior material that accommodates the electrode assembly and the electrolyte.

[0004] The positive electrode active material of the lithium secondary battery can be a lithium metal oxide, which can further contain a transition metal such as nickel, cobalt, or manganese.

[0005] The lithium metal oxide as the positive electrode active material can be prepared by reacting a lithium precursor with a nickel-cobalt-manganese (NCM) precursor containing nickel, cobalt, and manganese.

[0006] The use of the aforementioned expensive valuable metals in the positive electrode active material results in a significant cost for the production of the positive electrode material. Furthermore, in recent years, growing interest in environmental protection has led to research into methods for recycling positive electrode active materials. To recycle the positive electrode active material, it is necessary to regenerate the lithium precursor from the positive electrode with high efficiency and high purity. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a method for recovering active metals of lithium secondary batteries with high efficiency and high purity. [Means for solving the problem]

[0008] A method for recovering an active metal of a lithium secondary battery according to an embodiment of the present invention includes the steps of collecting a positive electrode active material mixture from a positive electrode of a lithium secondary battery, reducing the positive electrode active material mixture to prepare a pre-precursor mixture, forming an aqueous lithium precursor solution from the pre-precursor mixture, and collecting an aluminum-containing material from the aqueous lithium precursor solution using an aluminum-removing resin.

[0009] In some embodiments, the aluminum removal resin can contain amine and hydroxy groups.

[0010] In some embodiments, the aluminum removal resin can contain two or more hydroxy groups.

[0011] In some embodiments, the aluminum removal resin can include an amphoteric resin.

[0012] In some embodiments, the aluminum-containing material is aluminum hydroxide ions (Al(OH) - ).

[0013] In some embodiments, collecting the aluminum-containing material from the aqueous lithium precursor solution can include passing the aqueous lithium precursor solution through a column packed with the aluminum removal resin.

[0014] In some embodiments, the ratio of the total volume of the aqueous lithium precursor solution to the volume of the aluminum removal resin may be 5-30.

[0015] In some embodiments, after collecting the aluminum-containing material from the aqueous lithium precursor solution, the method can further include charging the aluminum-removal resin with an acid and a metal hydroxide to regenerate the aluminum-removal resin.

[0016] In some embodiments, the reduction reaction can be carried out in a powder state in a fluidized bed reactor.

[0017] In some embodiments, providing the pre-precursor mixture can include supplying a reducing hydrogen gas into the fluidized bed reactor.

[0018] In some embodiments, the pre-precursor mixture can include pre-lithium precursor particles and transition metal-containing particles.

[0019] In some embodiments, the reserve lithium precursor particles can include at least one of lithium hydroxide, lithium oxide, or lithium carbonate.

[0020] In some embodiments, the transition metal-containing particles can include nickel, cobalt, manganese, or oxides thereof. [Effects of the Invention]

[0021] According to the above-mentioned exemplary embodiment, the method for recovering active metals of a lithium secondary battery can include removing aluminum from an aqueous lithium precursor solution using an aluminum-removing resin, thereby removing aluminum from the positive electrode current collector and improving the recovery rate and purity of the lithium precursor.

[0022] In some embodiments, the aluminum in the aqueous lithium precursor solution is present in the form of aluminum hydroxide ions (Al(OH) - In this case, removal cannot be achieved by a cation exchange resin, but an excellent removal effect can be achieved by the aluminum removal resin.

[0023] Furthermore, in the case of a cation-removing resin, the lithium ions may be removed, resulting in a decrease in the lithium recovery rate. However, in the case of using the aluminum-removing resin, the decrease in the lithium ion content can be suppressed, thereby preventing a decrease in the recovery rate. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 1 is a schematic flow chart illustrating a method for recovering active metals from a lithium secondary battery according to an exemplary embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0025] An embodiment of the present invention provides a method for recovering active metals with high purity and high yield from the positive electrodes of used lithium secondary batteries.

[0026] Hereinafter, the present invention will be described in detail with reference to the preferred embodiments. However, since the present invention can be modified in various ways and can have various forms, specific embodiments will be illustrated in the drawings and described in detail herein. However, it should be understood that the present invention is not limited to the specific disclosed form, and that all modifications, equivalents, and alternatives within the spirit and technical scope of the present invention are included.

[0027] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which this invention pertains. Terms as defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning they have in the context of the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly defined in this application.

[0028] As used herein, the term "precursor" is used to refer collectively to a compound containing a specific metal to provide the specific metal contained in the electrode active material.

[0029] FIG. 1 is a schematic flow chart illustrating a method for recovering active metals from a lithium secondary battery according to an exemplary embodiment.

[0030] Referring to FIG. 1, a positive electrode active material mixture can be collected from a positive electrode of a lithium secondary battery (eg, step S10).

[0031] The lithium secondary battery may include an electrode assembly including a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and the positive electrode and the negative electrode may include a positive electrode active material layer and a negative electrode active material layer coated on a positive electrode current collector and a negative electrode current collector, respectively.

[0032] For example, the positive electrode active material contained in the positive electrode active material layer may include an oxide containing lithium and a transition metal.

[0033] In some embodiments, the positive electrode active material may include a compound represented by Formula 1:

[0034] [Chemical formula 1] Li x M1 a M2 b M3 c O y

[0035] In Chemical Formula 1, M1, M2, and M3 may be a transition metal selected from Ni, Co, Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, or B. <x≦1.2、2≦y≦2.02、0<a<1、0<b<1、0<c<1、0<a+b+c≦1であってもよい。

[0036] In some embodiments, the active cathode material may be an NCM-based lithium oxide containing nickel, cobalt, and manganese.

[0037] The positive electrode can be recovered by separating it from the lithium secondary battery. The positive electrode may be a used, waste lithium secondary battery or a positive electrode that is damaged or defective during the manufacturing process.

[0038] The positive electrode includes a positive electrode current collector (e.g., aluminum (Al)) and a positive electrode active material layer as described above, and the positive electrode active material layer may include a conductive material and a binder together with the positive electrode active material.

[0039] The conductive material may include, for example, a carbon-based material such as graphite, carbon black, graphene, carbon nanotubes, etc. The binder may include, for example, a resin material such as vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, etc.

[0040] According to an exemplary embodiment, the recovered positive electrode may be pulverized to produce a positive electrode active material mixture. The positive electrode active material mixture may be prepared in powder form. The positive electrode active material mixture may include a lithium-transition metal oxide powder, such as an NCM-based lithium oxide powder (e.g., Li(NCM)O), as described above.

[0041] As used herein, the term "positive electrode active material mixture" may refer to raw materials input into a fluidized bed reaction process, which will be described later, after the positive electrode current collector has been substantially removed from the positive electrode. In one embodiment, the positive electrode active material mixture may include positive electrode active material particles, such as the NCM-based lithium oxide. In one embodiment, the positive electrode active material mixture may partially include a component derived from the binder or the conductive material. In one embodiment, the positive electrode active material mixture may be substantially composed of the positive electrode active material particles.

[0042] In some embodiments, the cathode active material mixture may be heat-treated before being introduced into a fluidized bed reactor, which will be described later. The heat treatment may at least partially remove impurities, such as the conductive material and binder, contained in the cathode active material mixture, and the lithium-transition metal oxide may be introduced into the fluidized bed reactor with high purity.

[0043] The temperature of the heat treatment may be, for example, about 100 to 500° C., preferably about 350 to 450° C. Within this range, the impurities are substantially removed, and decomposition and damage to the lithium-transition metal oxide can be prevented.

[0044] In an exemplary embodiment, the cathode active material mixture may be subjected to a reduction reaction in a fluidized bed reactor 100 to form a pre-precursor mixture 80 (eg, step S20).

[0045] As used herein, the term "fluidized bed reactor" may refer to a reactor in which a fluid (gas or liquid) is passed through an injected positive electrode active material mixture to fluidize the positive electrode active material mixture.

[0046] In an exemplary embodiment, the positive electrode active material mixture may be injected into fluidized bed reactor 100 through inlet 102 located at the top of fluidized bed reactor 100 .

[0047] In an exemplary embodiment, the cathode active material mixture injected into fluidized bed reactor 100 may undergo a reduction reaction to form pre-precursor mixture 80 .

[0048] In some embodiments, the reduction reaction may be a hydrogen reduction reaction or a carbon reduction reaction.

[0049] In some embodiments, the hydrogen reduction reaction can be carried out by injecting a reducing gas containing hydrogen (H 2 ) into the reactor body 110 of the fluidized bed reactor 100 through the gas inlet 104.

[0050] For example, the reducing gas can be a mixture of hydrogen and a non-reactive gas, and the volume ratio of hydrogen to the total volume of the mixture gas can be 5 to 40%, and the volume ratio of the non-reactive gas can be 60 to 95%.

[0051] For example, the non-reactive gas may include at least one selected from the group consisting of helium (He), nitrogen (N2), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).

[0052] In some embodiments, an expansion section 120 may be located at the top of the fluidized bed reactor 100. The expansion section 120 reduces the flow rate of the reducing gas injected from the bottom of the fluidized bed reactor 100, thereby preventing the cathode active material mixture from leaking out during the process of fluidizing the cathode active material mixture inside the fluidized bed reactor 100.

[0053] In some embodiments, the reducing gas is supplied from the lower part of the fluidized bed reactor 100 and contacts the cathode active material mixture, and the cathode active material mixture moves to the upper part of the fluidized bed reactor 100 and reacts with the reducing gas to be converted into a pre-precursor.

[0054] The hydrogen reduction reaction in the reactor main body 130 can be carried out at a temperature of about 400 to 700° C., preferably 450 to 550° C. Within this reaction temperature range, the reduction reaction can be promoted without causing re-aggregation or recombination of the preliminary lithium precursor and the transition metal / transition metal oxide.

[0055] In some embodiments, the reduction reaction may be a carbo-reduction reaction. In this case, the carbo-reduction reaction may be carried out by reacting the positive electrode active material mixture with a carbon-based compound. For example, the positive electrode active material mixture may be added with a carbon-based compound and heated to 400 to 800°C to be carbo-reduced. For example, the carbon-based compound may include carbon black powder or activated carbon.

[0056] In some embodiments, lithium-transition metal oxides can be hydrogen- or carbon-reduced to produce, for example, pre-lithium precursors including lithium hydroxide (LiOH), lithium oxides (e.g., LiO), lithium carbonate (LiCO), and transition metal or transition metal oxides. For example, the reductive reaction can produce Ni, Co, NiO, CoO, and MnO along with the lithium oxides.

[0057] For example, a preliminary precursor mixture 80 including preliminary lithium precursor particles 60 and transition metal-containing particles 70 (e.g., the transition metal or transition metal oxide) can be formed in the reactor body 110. The preliminary lithium precursor particles 60 can include, for example, lithium hydroxide, lithium oxide, and / or lithium carbonate. From the viewpoint of the charge / discharge characteristics, life characteristics, high-temperature stability, etc. of the lithium secondary battery, the lithium precursor can include lithium hydroxide.

[0058] In some embodiments, a preliminary precursor mixture 80 including preliminary lithium precursor particles 60 and transition metal-containing particles 70 can be collected via an outlet 106 connected to the reactor body 110.

[0059] In an exemplary embodiment, an aqueous lithium precursor solution may be formed from the pre-precursor mixture 80 (eg, step S30).

[0060] For example, the pre-precursor mixture 80 formed from the reduction reaction described above can be reacted with the leachate and the lithium precursor collected.

[0061] For example, the pre-precursor mixture 80 may react with the leachate to form an aqueous lithium precursor solution in which the lithium precursor is dissolved and a precipitate in which the transition metal precursor is precipitated.

[0062] For example, preliminary lithium precursor particles 60 in the form of lithium oxide and lithium carbonate may react with the leachate to form lithium hydroxide, which may dissolve in the leachate.

[0063] In some embodiments, the leachate may include water, in which case pre-precursor mixture 80 may be washed with water, which may cause pre-precursor mixture 80 to react with water to form an aqueous lithium precursor solution in which lithium hydroxide is dissolved in water.

[0064] In some exemplary embodiments, the leachate may further include dimethyl carbonate or diethyl carbonate.

[0065] For example, dimethyl carbonate or diethyl carbonate can promote the reaction of the pre-precursor mixture 80 with water, thereby improving the separation efficiency of the lithium precursor.

[0066] In some embodiments, the precipitate may comprise a slurry containing the pre-precursor mixture 80 .

[0067] For example, the slurry may be formed by dispersing the transition metal-containing particles 70, which are insoluble in the leachate, in the leachate, and by separating the slurry from the solution containing the dissolved lithium precursor, an aqueous lithium precursor solution can be obtained.

[0068] In some embodiments, the precipitated transition metal-containing particles 70 can be collected to form a transition metal precursor. For example, the transition metal-containing particles 70 can be reacted with an acid solution to form a transition metal precursor.

[0069] In an exemplary embodiment, the acid solution may be sulfuric acid, and the transition metal precursor may include a transition metal sulfate, such as NiSO4, MnSO4, or CoSO4.

[0070] In an exemplary embodiment, an aluminum (Al) removal resin can be applied to the resulting aqueous lithium precursor solution to remove aluminum-containing materials from the aqueous lithium precursor solution (eg, step S40).

[0071] For example, the lithium precursor may be substantially in the form of lithium hydroxide, and thus, an aqueous lithium precursor solution in which lithium hydroxide is dissolved in water may be a basic solution.

[0072] For example, the lithium precursor aqueous solution may contain an aluminum-containing material derived from the positive electrode current collector included in the positive electrode. In this case, since the lithium precursor aqueous solution is a basic solution, the aluminum-containing material is converted into aluminum hydroxide ions (Al(OH)4 - ) may be dissolved in the lithium precursor aqueous solution. Therefore, when a cation exchange resin is used, the aluminum hydroxide ions, which are anions, cannot be removed, and instead lithium ions (Li + ) may be removed, reducing the recovery rate of active metals.

[0073] According to an exemplary embodiment of the present invention, a separate aluminum removal resin can be used in the aqueous lithium precursor solution to remove aluminum hydroxide ions.

[0074] In some embodiments, the aluminum removal resin can include an amine group and a hydroxy group, where the hydroxy group can bind with the aluminum element of an aluminum hydroxide ion to remove the aluminum.

[0075] In some embodiments, the aluminum removal resin may contain an amine group and two or more hydroxy groups, in which case two hydroxy groups bind to the aluminum element of the aluminum hydroxide ion, allowing the aluminum element to be more stably bound to the resin and removed.

[0076] In some embodiments, the aluminum removal resin can comprise an amphoteric resin having both acidic and basic exchange groups, which allows selective collection of anionic aluminum hydroxide ions while not collecting lithium cations, for example, depending on the pH of the solution.

[0077] In some embodiments, the aluminum removal resin may be a resin containing methylglucosylamine groups, such as AmberLite UP7530 from DuPont, which is a resin containing methylglucosylamine groups.

[0078] For example, the volume of aluminum removal resin required to remove aluminum may vary depending on the aluminum content in the aqueous lithium precursor solution, and in this case, the ratio of the volume of aluminum removal resin to the total volume of the aqueous lithium precursor solution may vary.

[0079] In some embodiments, the ratio of the total volume of the aqueous lithium precursor solution to the volume of the aluminum removal resin may be 5-30.

[0080] For example, when the above-mentioned volume ratio is satisfied, aluminum contained in the aqueous lithium precursor solution can be sufficiently removed while preventing a decrease in the purity of the final recovered lithium precursor due to excessive addition of resin.

[0081] Furthermore, the aluminum-removing resin selectively removes aluminum-containing substances contained in the lithium precursor aqueous solution, which is a basic solution, without substantially removing lithium ions, thereby increasing the recovery rate in the active metal recovery step.

[0082] For example, in some embodiments, after the aluminum removal step (e.g., S40), the aluminum content of the aluminum-removed aqueous lithium precursor solution may be 20 ppm or less based on the total weight of the aqueous lithium precursor solution, thereby significantly reducing the aluminum content of the aqueous lithium precursor solution and increasing the recovery rate of the transition metal.

[0083] For example, the lithium removal rate obtained by subtracting the lithium content relative to the total weight of the lithium precursor aqueous solution after aluminum removal from the lithium content relative to the total weight of the lithium precursor aqueous solution before the addition of the aluminum-removing resin may be 0.08 wt % or less.

[0084] In some embodiments, collecting aluminum-containing materials from the aqueous lithium precursor solution can include passing the aqueous lithium precursor solution through a column packed with the aluminum removal resin.

[0085] For example, an aluminum-removing column packed with the aluminum-removing resin described above can be prepared, and then an aqueous lithium precursor solution can be passed through the column to remove aluminum-containing substances.

[0086] In some embodiments, the aluminum removal resin can be regenerated by adding an acid and a metal hydroxide to the used aluminum removal resin. For example, the acid added can include at least one of sulfuric acid and hydrochloric acid. For example, the metal of the metal hydroxide added can include at least one of lithium (Li), sodium (Na), and potassium (K). This allows the aluminum removal resin to be reused, thereby reducing the cost of recovering the lithium precursor.

[0087] According to an exemplary embodiment, the lithium hydroxide dissolved in the lithium precursor aqueous solution from which aluminum has been removed can be subjected to a crystallization process or the like to obtain a lithium precursor substantially composed of lithium hydroxide.

[0088] Specific examples are presented below to aid in understanding the present invention, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications can be made to these examples within the scope and technical spirit of the present invention, and it is natural that these changes and modifications also fall within the scope of the appended claims.

[0089] Example 1 1 kg of the cathode material separated from the waste lithium secondary battery was heat-treated at 450°C for 1 hour. The heat-treated cathode material was cut into small units and pulverized by milling to obtain a sample of the Li-Ni-Co-Mn oxide cathode active material mixture (step S10).

[0090] A 0.2 kg sample of the collected cathode active material mixture was fluidized in the fluidized bed reactor by injecting a 20 vol% hydrogen / 80 vol% nitrogen mixed gas (reducing gas) through a gas inlet located at the bottom of the reactor for 4 hours to react with the hydrogen gas, forming a pre-precursor mixture containing lithium hydroxide. The internal temperature of the fluidized bed reactor was maintained at 460°C (step S20).

[0091] Water and nitrogen gas were added to the pre-precursor mixture collected from the reactor outlet to form a slurry of the pre-precursor mixture, which was then collected. Water was then added to the collected slurry of the pre-precursor mixture, which was then washed with water to obtain an aqueous lithium precursor solution (step S30).

[0092] The lithium precursor aqueous solution and DuPont's AmberLite UP7530 resin were mixed in a volume ratio of 6:1 and stirred for 2 hours to obtain a lithium precursor aqueous solution from which impurities had been removed, followed by a crystallization process to obtain a lithium precursor essentially composed of lithium hydroxide.

[0093] Example 2 An aqueous lithium precursor solution was obtained in the same manner as in Example 1, except that AmberLite UP7530 resin was not added to the aqueous lithium precursor solution and an aluminum removal column was used.

[0094] Specifically, a 75 ml aluminum removal column made of SUS was filled with the same amount of AmberLite UP7530 resin as in Example 1, and the lithium precursor aqueous solution was then passed through the aluminum removal column so that the ratio of the volume of the aluminum removal resin to the total volume of the lithium precursor aqueous solution was 8, thereby obtaining an aluminum-removed lithium precursor aqueous solution. A crystallization step was then performed to obtain a lithium precursor essentially composed of lithium hydroxide.

[0095] Example 3 An aqueous lithium precursor solution and a lithium precursor were obtained in the same manner as in Example 2, except that the aqueous lithium precursor solution was passed through the aluminum removal column so that the ratio of the total volume of the aqueous lithium precursor solution to the volume of the aluminum removal resin was 15.

[0096] Example 4 An aqueous lithium precursor solution and a lithium precursor were obtained in the same manner as in Example 2, except that the aqueous lithium precursor solution was passed through the aluminum removal column so that the ratio of the total volume of the aqueous lithium precursor solution to the volume of the aluminum removal resin was 23.

[0097] Example 5 An aqueous lithium precursor solution and a lithium precursor were obtained in the same manner as in Example 2, except that the aqueous lithium precursor solution was passed through the aluminum removal column so that the ratio of the total volume of the aqueous lithium precursor solution to the volume of the aluminum removal resin was 31.

[0098] Comparative Example 1 An aqueous lithium precursor solution was prepared in the same manner as in Example 1, except that AmberLite UP7530 resin was not added.

[0099] Comparative Example 2 An aqueous lithium precursor solution was obtained in the same manner as in Example 1, except that the aqueous lithium precursor solution and the cation exchange resin were mixed in a volume ratio of 6:1 without adding AmberLite UP7530 resin.

[0100] Experimental example (1) Measurement of the lithium content in the lithium precursor solution before and after aluminum removal The lithium precursor aqueous solutions prepared in the above examples and comparative examples before and after aluminum removal were measured using an ICP (Inductivity Coupled Plasma) method to measure the lithium content in the lithium precursor aqueous solutions before and after aluminum removal.

[0101] (2) Measurement of the aluminum content in the lithium precursor solution before and after aluminum removal The lithium precursor aqueous solutions prepared in the above examples and comparative examples before and after aluminum removal were measured using an ICP (Inductivity Coupled Plasma) method to measure the lithium contents in the aluminum precursor aqueous solutions before and after aluminum removal.

[0102] The measurement results are shown in Table 1 below.

[0103] [Table 1]

[0104] Referring to Table 1, in the examples in which an aluminum removal resin (DuPont's AmberLite UP7530) was added to the aqueous lithium precursor solution recovered after the reduction process and water washing treatment, or in which the resin was prepared in a column and the aqueous lithium precursor solution was passed through, a significant aluminum removal effect was achieved overall compared to the comparative example in which the resin was not added, and the decrease in lithium content after aluminum removal was suppressed, thereby preventing a decrease in the lithium recovery rate.

[0105] However, among the above examples and comparative examples in which the aluminum content in the lithium precursor aqueous solution was 110 ppm, in the case of Example 5 in which a lithium precursor aqueous solution with a volume 30 times or more the volume of the aluminum removal resin packed in the column was passed through the column, the aluminum removal effect was slightly reduced.

Claims

1. collecting a positive electrode active material mixture from a positive electrode of a lithium secondary battery; preparing a pre-precursor mixture by subjecting the positive electrode active material mixture to a reduction reaction; forming an aqueous lithium precursor mixture from the pre-precursor mixture; collecting aluminum-containing materials from the aqueous lithium precursor solution using an aluminum removal resin; a ratio of the total volume of the lithium precursor aqueous solution to the volume of the aluminum removal resin is 5 to 30.

2. 2. The method for recovering active metals from lithium secondary batteries according to claim 1, wherein the aluminum-removing resin contains an amine group and a hydroxyl group.

3. 2. The method for recovering active metals from a lithium secondary battery according to claim 1, wherein the aluminum-removing resin contains two or more hydroxy groups.

4. The method for recovering active metals from a lithium secondary battery according to claim 1 , wherein the aluminum-removing resin comprises an amphoteric resin.

5. The aluminum-containing material contains aluminum hydroxide ions (Al(OH) ４ － 2. The method for recovering active metals from a lithium secondary battery according to claim 1, comprising:

6. 2. The method for recovering active metals of lithium secondary batteries according to claim 1, wherein the step of collecting the aluminum-containing material from the aqueous lithium precursor solution comprises a step of passing the aqueous lithium precursor solution through a column packed with the aluminum-removing resin.

7. 2. The method for recovering active metals of lithium secondary batteries according to claim 1, further comprising, after the step of collecting the aluminum-containing material from the lithium precursor aqueous solution, the step of adding an acid and a metal hydroxide to the aluminum-removing resin to regenerate the aluminum-removing resin.

8. The method for recovering active metals from a lithium secondary battery according to claim 1 , wherein the reduction reaction is carried out in a powder state in a fluidized bed reactor.

9. 9. The method for recovering active metals of a lithium secondary battery according to claim 8, wherein the step of preparing the preliminary precursor mixture includes the step of supplying reducing hydrogen gas into the fluidized bed reactor.

10. 2. The method for recovering active metals of a lithium secondary battery according to claim 1, wherein the preliminary precursor mixture comprises preliminary lithium precursor particles and transition metal-containing particles.

11. 11. The method for recovering active metals of a lithium secondary battery according to claim 10, wherein the preliminary lithium precursor particles include at least one of lithium hydroxide, lithium oxide, or lithium carbonate.

12. The method for recovering an active metal from a lithium secondary battery according to claim 10, wherein the transition metal-containing particles contain nickel, cobalt, manganese, or an oxide thereof.

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