CA3177071C - Method for recovering valuable metal from waste electrode material of lithium secondary battery by using lithium carbonate - Google Patents
Method for recovering valuable metal from waste electrode material of lithium secondary battery by using lithium carbonateInfo
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- CA3177071C CA3177071C CA3177071A CA3177071A CA3177071C CA 3177071 C CA3177071 C CA 3177071C CA 3177071 A CA3177071 A CA 3177071A CA 3177071 A CA3177071 A CA 3177071A CA 3177071 C CA3177071 C CA 3177071C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/77—Aluminium carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/06—Carbonates
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/06—Carbonates
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention relates to a method for recovering a valuable metal and, more specifically, to a method for recovering a valuable metal from a waste electrode material of a lithium secondary battery by using lithium carbonate. The method may: pre-process a positive electrode-negative electrode mixed electrode material that has been separated by draining, crushing, screening, and sorting a waste lithium secondary battery; perform a precipitation step, by using lithium carbonate (Li2CO3), to a metal melt acquired by performing sulfuric acid dissolution using sulfuric acid; recover a valuable metal such as nickel, cobalt, manganese, aluminum, and copper as a residue in the form of a carbonate composite; and recover, as a filtrate, a lithium sulfate (Li2SO4) aqueous solution comprising lithium.
Description
DESCRIPTION TITLE OF INVENTION: METHOD FOR RECOVERING VALUABLE METAL FROM WASTE ELECTRODE MATERIAL OF LITHIUM SECONDARY BATTERY BY USING LITHIUM CARBONATE Technical Field
[1] The present invention relates to a method for recovering valuable metals. More specifically, the present invention relates to a method of recovering valuable metals from a waste electrode material of a lithium secondary battery by using lithium carbonate. With the method, it is possible to easily recover valuable metals such as lithium, nickel, cobalt, manganese, aluminum, and copper from an anode-cathode mixed electrode material obtained from waste lithium secondary batteries as a raw material by discharging, crushing, screening, and classifying the waste lithium secondary batteries. Background Art
[2] As fossil fuels are pointed out as the cause of global warming and environmental pollution around the world, countries are implementing policies to promote the use of electric vehicles.
[3] For this reason, the global supply of electric vehicles is 15 10 15 20 25 Date Recue/Date Received 2023-12-08 expected to increase 25 times from 510,000 units in 2016 to 12.06 million units in 2030.
[4] However, in the case of lithium secondary batteries mounted on electric vehicles, the amount of disposal after the expiration of the service period is also increasing along with the increase in usage.
[5] Globally, the majority of waste lithium secondary batteries were small batteries used for IT devices, and about 200,000 tons were generated in 2018. In 2025, it is expected that a large amount of waste lithium secondary batteries for electric vehicles and electric buses will be generated, and the amount is expected to become about 700,000 tons.
[6] Valuable metals such as about 17 kg of lithium, about 79 kg of nickel, and about 41 kg of cobalt are contained in one ton of waste lithium secondary batteries. In a current situation where it is difficult to gain price competitiveness, the recovery of these metals, which are mostly imported, can be a significant advantage in securing raw materials through recycling of waste resources.
[7] An existing valuable metal recovery method to recycle waste batteries recovers and recycles valuable metals such as nickel and cobalt through sulfuric acid dissolution and solvent extraction processes, but in the case of lithium, the existing method recovers only a small amount of lithium at a low recovery rate and purity in the last stage of the recovery 25 10 15 20 25 Date Recue/Date Received 2023-12-08 processes or does not recover lithium at all. Thus, lithium is discarded as dissolved in wastewater.
[8] Accordingly, in the case of lithium, which is an essential element for the manufacture of a lithium secondary battery, the development of efficient recycling technology for recovering lithium is required in terms of the efficient use of resources and economy. Disclosure Technical Problem
[9] The present invention has been made in view of this need. An objective of the present invention is to provide a method of recovering valuable metals by using lithium carbonate from waste electrode materials of waste lithium secondary batteries, the method being capable of easily recovering valuable metals such as lithium, nickel, cobalt, manganese, aluminum, copper, etc. from the waste electrode materials of the lithium secondary batteries.
[10] The objectives of the present disclosure are not limited to the ones described above, and other objectives will be clearly understood by those skilled in the art from the following description. Technical Solution
[11] In order to accomplish the objective of the present 35 10 15 20 25 Date Recue/Date Received 2023-12-08 invention, there is provided a method of recovering valuable metals from waste electrode materials, the method including: a waste electrode material preparation step of preparing a waste electrode material; a pre-processing step of introducing the waste electrode material into a firing furnace and thermally treating the waste electrode material in the firing furnace; a sulfuric acid dissolution step of adding sulfuric acid to the resulting pre-processed product to cause a reaction; a first filtration step of separating the resulting reaction products produced through the sulfuric acid dissolution step into a pregnant solution and an unreacted residue; a precipitation step of mixing lithium carbonate (Li2CO3) with the pregnant solution and stirring the mixture; and a second filtration step of separating the precipitation result generated through the precipitation step into a precipitation residue and a filtrate. The method recovers an aqueous solution of lithium sulfate from the filtrate and recovers nickel carbonate and cobalt carbonate from the precipitation residue.
[12] In a preferred embodiment, the pre-processing step may be performed at a temperature of 300°C to 500°C for a duration of 30 minutes to 120 minutes.
[13] In a preferred embodiment, in the sulfuric acid dissolution step, the reaction may be performed by stirring at a temperature in a range of 60°C to 100°C for a duration of 60 minutes to 120 minutes at a speed of 250 rpm to 400 rpm. 45 10 15 20 25 Date Recue/Date Received 2023-12-08
[14] In a preferred embodiment, the sulfuric acid dissolution step may further include adding hydrogen peroxide to the preprocessed product.
[15] In a preferred embodiment, in the method, a first washing step of washing the unreacted residue with water may be further performed after the first filtration step, and the precipitation step may be performed by mixing the lithium carbonate with a mixed solution containing a washing solution and the pregnant solution and stirring the mixture.
[16] In a preferred embodiment, in the precipitation step, the reaction may be performed by stirring at a temperature of 40°C to 80°C for a duration of 60 minutes to 180 minutes at a speed of 250 rpm to 400 rpm.
[17] In a preferred embodiment, in the method, a second washing step of washing the precipitation residue with water may be further performed after the second filtration step, and an aqueous solution of lithium sulfate may be recovered from a washing solution obtained through the second washing step. Advantageous Effects
[18] The present invention has the advantages described below.
[19] In the method of recovering valuable metals from waste electrode materials of lithium secondary batteries by using lithium carbonate, the following steps are performed: the lithium secondary batteries are discharged, crushed, sorted, 55 10 15 20 25 Date Recue/Date Received 2023-12-08 and classified to obtain an anode-cathode mixed electrode material; the anode-cathode mixed electrode material is preprocessed; the pre-processed product is dissolved in sulfuric acid to obtain a pregnant solution; the pregnant solution is precipitated by using lithium carbonate (Li2CO3); valuable metals such as nickel, cobalt, manganese, aluminum, and copper are easily recovered from the precipitate; and an aqueous solution of lithium sulfate (Li2SO4) containing lithium is easily recovered from the filtrate.
[20] In addition, with the use of the method of recovering valuable metals by using lithium carbonate from waste electrode materials of lithium secondary batteries, it is possible to recover valuable metals such as lithium, nickel, cobalt, manganese, aluminum, and copper from the waste electrode materials of the waste lithium secondary batteries with a high recovery rate and high purity.
[21] In addition, with the use of the method of recovering valuable metals, by using lithium carbonate, from a waste electrode material of a lithium secondary battery, according to the present invention, a recovered lithium sulfate aqueous solution can be prepared as lithium hydroxide monohydrate through lithium hydroxide conversion and concentration crystallization processes, and a carbonate composite recovered as a residue has the advantage of being used as a raw material for preparing a precursor. 65 10 15 20 25 Date Recue/Date Received 2023-12-08 Description of Drawings
[22] FIG. 1 is a diagram illustrating a method of recovering valuable metals by using lithium carbonate from a waste electrode material of a lithium secondary battery, according to one embodiment of the present invention. Best Mode
[23] As the terms used to describe the present disclosure in the present disclosure, as many general terms as possible are selected. However, in certain cases, terms that are chosen by the inventors of the present disclosure may be used. In such cases, the meanings of the terms should be understood not simply by the name but by the detailed description of the invention.
[24] Hereinafter, the technical aspects of the present disclosure will be described in detail with reference to the preferred embodiments illustrated in the accompanying drawings.
[25] However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like reference numerals refer to like elements throughout the description herein and the drawings.
[26] The term "equivalent" described herein refers to a chemical equivalent which is the amount of a substance that directly or indirectly combines with a hydrogen atomic weight 75 10 15 20 25 Date Recue/Date Received 2023-12-08 of 1 or an oxygen atomic weight of 8. [27]
[28] FIG. 1 is a diagram illustrating a method of recovering valuable metals by using lithium carbonate from a waste electrode material of a lithium secondary battery, according to one embodiment of the present invention.
[29] Referring to FIG. 1, according to one embodiment of the present invention, a method of recovering valuable metals, by using lithium carbonate, from a waste electrode material of a lithium secondary battery is a method of recovering a valuable metal from a waste electrode material of a lithium secondary battery. First, a waste electrode material preparation step S100 of preparing a waste electrode material is performed.
[30] Here, the waste electrode material may be an anode-cathode (anode-anode active material and cathode-cathode active material) mixed electrode material obtained by discharging, crushing, screening, and classifying waste lithium secondary batteries to be disposed of or may be a waste cathode material that is poorly processed or unsuitable for use and is generated in a cathode material production process.
[31] The waste electrode material includes at least one selected from lithium nickel cobalt aluminum oxide (LiNiCoA102, NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO?, NCM), lithium iron oxide (LiFePO4, LFP), lithium manganese iron oxide (LiMnFePO4, LMFP), lithium manganese oxide (LiMn204, LMO),5 10 15 20 25 Date Recue/Date Received 2023-12-08 lithium nickel manganese spinel (LiNio.5Mn1.5O4, LNMO), and lithium cobalt oxide (LiCo02, LCO).
[32] Next, a preprocessing step S200 in which the prepared waste electrode material is fired in a firing furnace is performed to thermally treat the prepared waste electrode material.
[33] The pre-processing step S200 is a process for removing an organic binder contained in the waste electrode material. Preferably, the pre-processing step S200 is performed in an air atmosphere at a temperature of 300°C to 500°C for a duration of 30 minutes to 120 minutes to remove the organic binder.
[34] Therefore, moisture and organic binders present in the waste electrode material are removed, and the resulting preprocessed waste electrode material contains a cathode active material and a carbon material as an anode active material.
[35] When the pre-processing step S200 is performed at a temperature higher than 500°C, the carbon material can be removed as well as the organic binder. However, in this case, the cost of the firing process is increased. In addition, such a high pre-processing temperature is not desirable in terms of recycling of the carbon material separated in a sulfuric acid dissolution step S300 described below. Therefore, preferably, the pre-processing step S200 may be performed in a temperature range of 300°C to 500°C.
[36] Next, the sulfuric acid dissolution step S300 is performed 95 10 15 20 25 Date Recue/Date Received 2023-12-08 in which sulfuric acid is added to the pre-processed waste electrode material produced through the pre-processing step S200. In this step, the pre-processed waste electrode material reacts with the sulfuric acid.
[37] The sulfuric acid dissolution step S300 is a process for leaching valuable metals contained in the pre-processed product. In this step, the reaction may be performed with stirring at a temperature of 60°C to 100°C for a duration of 60 minutes to 120 minutes at a speed of 250 rpm to 400 rpm.
[38] In addition, in the sulfuric acid dissolution step S300, sulfuric acid with a purity of 98% may be used, and 0.94 to 1.0 equivalent of the sulfuric acid relative to Li, Ni, Co, Mn, Al and Cu contained in the pre-processed product may be used.
[39] In this case, it is preferable that the solid to liquid ratio of the pre-processed product and the mixture containing the sulfuric acid and water is 300 g/L or more.
[40] In addition, in the sulfuric acid dissolution step S300, while the sulfuric acid is added to the pre-processed product and stirred, hydrogen peroxide may be further added thereto.
[41] In this case, the hydrogen peroxide may have a purity in a range of 30% to 32%, and the amount of hydrogen peroxide that is added may be in a range of 0.5 mole to 0.55 mole relative to the number of moles of Ni, Co, and Mn contained in the preprocessed product.
[42] In the sulfuric acid dissolution step S300, the reason for 105 10 15 20 25 Date Recue/Date Received 2023-12-08 performing the reduction leaching using hydrogen peroxide is that cobalt contained in the pre-processed product is present as Co3+, which causes a low leaching rate. Therefore, in the sulfuric acid dissolution step S300, hydrogen peroxide is added for the reduction of Co3+ to Co2+. This reduction leaching process can also increase the leaching rate of lithium as well as the leaching rate of cobalt.
[43] That is, through the sulfuric acid dissolution step S300, a sulfuric acid solution containing valuable metals such as Li2SO4, NiSO4, C0SO4, MnSO4, A12(SO4)3, and CuSO4 may be obtained.
[44] Next, a first filtration step S400 of separating the dissolved materials in the sulfuric acid solution produced through the sulfuric acid dissolution step S300 into a pregnant solution and an unreacted residue is performed.
[45] In the first filtration step S400, since the valuable metals leached through the sulfuric acid dissolution step S300 are present in a mixed phase with the unreacted carbon material, the filtration is performed.
[46] Next, a first washing step S500 in which the unreacted residue obtained through the first filtration step S400 is washed with water is further performed.
[47] The first washing step S500 is performed to further recover the metal ions present in the unreacted residue wet with water. Water having a temperature in a range of room temperature and 50°C is added to obtain a washing solution 115 10 15 20 25 Date Recue/Date Received 2023-12-08 resulting from the washing of the unreacted residue.
[48] Next, a precipitation step S600 is performed in which lithium carbonate (Li2CO3) is mixed with the pregnant solution obtained through the first filtration step S400 and stirred.
[49] In addition, when the first washing step S500 is further performed in the precipitation step S600, the lithium carbonate may be mixed with a mixed solution of the pregnant solution obtained through the first filtration step S400 the washing solution obtained through the first washing step S500 and may be stirred.
[50] Here, valuable metals such as Li2SO4, NiSO4, C0SO4, MnS04, AI2(804)3, and CUSO4 are dissolved in the pregnant solution and the washing solution. Among these, to selectively separate lithium and recover other valuable metals in the form of a carbonate composite, lithium carbonate is added and stirred to cause a precipitation reaction.
[51] In addition, in the precipitation step S600, the stirring is performed at a temperature of 40°C to 80°C for a duration of 60 minutes to 180 minutes at a speed of 250 rpm to 400 rpm.
[52] In addition, in the precipitation step S600, the amount of lithium carbonate used is preferably adjusted to minimize the loss of lithium that is finally recovered through the precipitation and separation of metals.
[53] This is because when the amount of lithium carbonate added is increased, the precipitation rates of metal ions such as Ni, 125 10 15 20 25 Date Recue/Date Received 2023-12-08 Co, Mn, Al, and Cu present in the solution are increased, but the overall lithium recovery rate may be reduced due to the presence of unreacted lithium carbonate remaining in the residue.
[54] In the precipitation step S600, metals such as Ni, Co, Mn, Al, and Cu are precipitated in the form of a carbonate composite due to the reaction between the metal ions in the sulfuric acid solution and the lithium carbonate, and lithium is present in the solution in the form of lithium sulfate (Li2SO4).
[55] In addition, in the precipitation step S600, the reaction formulae of lithium carbonate precipitation of major valuable metals are shown below (See Reaction Formulae 1 to 5). [56] (Reaction Formula 1) NiSO4 + Li2CO3 = NiCOs + Li2SO4 [57] (Reaction Formula 2) CoSO4 + Li2CO3 = C0CO3 + Li2SO4 [58] (Reaction Formula 3) MnSO4 + Li2CO3 = MnCOa + Li2SO4 [59] (Reaction Formula 4) A12(SO4)3+ 3Li2CO3 = A12(CO3)3+ 3Li2SO4 [60] (Reaction Formula 5) CuSO4 + Li2CO3 = CuCOa + Li2SO4
[61] Next, a second filtration step S700 of separating the precipitation result generated through the precipitation step S600 into a precipitate and a filtrate is performed.
[62] Through the second filtration step S700, lithium sulfate (Li2SO4) containing lithium is separated as the filtrate, and the remaining useful metals are recovered in the form of a carbonate composite, i.e., the precipitate. 135 10 15 20 25 Date Recue/Date Received 2023-12-08
[63] That is, in the second filtration step S700, an aqueous solution of lithium sulfate is recovered from the filtrate, and nickel carbonate and cobalt carbonate are recovered from the precipitate.
[64] Next, a second washing step S800 in which the precipitate obtained through the second filtration step S700 is washed with water is further performed.
[65] The percentage of water content in the precipitate is about 40% or more, and the precipitate contains a considerably large amount of lithium sulfate ions. The precipitate may be washed with washing water to recover an aqueous solution of lithium sulfate. [66]
[67] Example 1
[68] In order to remove an organic binder and trace moisture present in a waste electrode material of a waste lithium secondary battery, 100 g of the waste electrode material was fired in a firing furnace at 350°C for 60 minutes, and finally, 83.5 g of the pre-processed product was obtained.
[69] The waste electrode material pre-processed by firing was subjected to metal leaching that is performed at a reaction temperature of 80°C and a stirring speed of 300 rpm. When the solid-liquid concentration was 33g/L, 18.4 mL of sulfuric acid (98% concentration) and 81.6 mL of water were added to 33g of the electrode material. 145 10 15 20 25 Date Recue/Date Received 2023-12-08
[70] The sulfuric acid was added as much as 1.0 equivalent to Li, Ni, Co, Mn, Al, Cu of the waste electrode material, and then 10 mL of hydrogen peroxide (30% concentration) was additionally added for reduction leaching.
[71] Most of the metals were leached within an hour after the addition of hydrogen peroxide. Since hydrogen peroxide comes into contact with sulfuric acid, a sudden exothermic reaction occurs. Therefore, the rate of addition of hydrogen peroxide was regulated, and oxygen (O2) generated as a byproduct was discharged.
[72] The filtrate was recovered through filtration after dissolving the waste electrode material in sulfuric acid, and the residue was washed with water.
[73] The filtrate of the leachate recovered through the sulfuric acid dissolution from the waste electrode material was mixed with the washing solution recovered through the residue washing, and the mixture of the filtrate of the leachate and the washing solution was reacted with lithium carbonate (purity: 98% to 99%) to obtain a precipitate.
[74] The precipitation products were separated through filtration. After washing the precipitate with water, the washing solution was obtained.
[75] An aqueous solution of high purity lithium sulfate was then recovered from the washing solution and the filtrate, and a metal carbonate composite including nickel carbonate, cobalt 155 10 15 20 Date Recue/Date Received 2023-12-08 carbonate, etc. was selectively recovered from the precipitate that was washed. [76]
[77] Experiment Example 1: Composition analysis of preprocessed product
[78] Composition analysis of the pre-processed product of the waste electrode material obtained in Example 1 was performed, and the results are shown in Table 1. [79] [Table 1] Elements Li (%) Ni (%) Co (%) Mn (%) Al (%) Cu (%) Content 4.02 11.68 10.0 9.52 2.86 2.05
[80] As shown in Table 1, it was confirmed that the preprocessed product contained lithium in an amount of 4.02%, nickel in an amount of 11.68%, cobalt in an amount of 10.00%, manganese in an amount of 8.52%, aluminum in an amount of 2.86%, and copper in an amount of 2.05%.
[81] Experiment Example 2: Metal leaching rate of waste electrode material
[82] Using the mixture of the washing solution obtained through the first washing step of Example 1 and the pregnant solution, the metal leaching rate was determined. The results are shown in Table 2 below. [83] [Table 2] 165 10 15 20 Date Recue/Date Received 2023-12-08 Li leaching rate (%) Ni leaching rate (%) Co leaching rate (%) Mn leaching rate (%) Al leaching rate (%) Cu leaching rate (%) 99.8 99.7 99.6 99.7 99.1 99.8
[84] As shown in Table 2, through the sulfuric acid dissolution step, 99% or more of the valuable metals present in the waste electrode material were leached.
[85] Experimental Example 3: Lithium recovery rate according to precipitation reaction time and temperature [86] 8.0% by weight of lithium carbonate was added to the mixture of the filtrate of the leachate and the washing solution of Example 1, and a precipitation reaction was carried out at 60°C for 1 to 3 hours. Next, the reaction products underwent filtration, so that the filtrate and the precipitate were recovered. The recovery rate of each valuable metal is shown in Table 3 below.
[87] In addition, 8.0% by weight of lithium carbonate was added to the mixture of the filtrate of the leachate and the washing solution, a precipitation reaction was carried in a reaction temperature range of 25°C to 60°C for 1 hour. Next, the filtrate and the precipitate were recovered through filtration. The recovery rate of each valuable metal is shown in Table 3 below. 17[88] [Table 3] Classification Li recovery rate (%) Ni recovery rate (%) Co recovery rate (%) Mn recovery rate (%) Al recovery rate (%) Cu recovery rate (%) Reaction time (temperature 60°C) lhr 96.4 99.9 99.9 99.8 99.9 99.9 2hr 96.6 99.9 99.9 99.8 99.9 99.9 3hr 96.7 99.9 99.9 99.9 99.9 99.9 Reaction temperature (time lhr) 25°C 92.2 77.4 78.6 83.1 97.2 99.6 40°C 96.1 99.9 99.8 99.8 99.8 99.9 60°C 96.4 99.9 99.9 99.8 99.9 99.9
[89] As shown in Table 3, it was confirmed that the metal precipitation was effectively performed only within a reaction 5 time of 1 hour. In the case of Li, the recovery rate was marginally increased. In addition, it was found that the metal precipitation reaction was somewhat insufficient at a reaction temperature of 25°C. When the reaction temperature was above 40°C, the metal recovery rate was high, and most of the 10 reactions were effective. [90]
[91] Experimental Example 4: Valuable metal precipitation separation efficiency according to amount of input of lithium carbonate 15 [92] 8.0% by weight of lithium carbonate was added to the mixture of the filtrate of the leachate and the washing 18 Date Recue/Date Received 2023-12-08solution obtained in Example 1, and a precipitation reaction was performed at a reaction temperature of 60°C for 1 hour. Next, a filtration step and a second washing step were performed to obtain the filtrate, the washing solution, and the 5 precipitate. The precipitation step, the second filtration step, and the second washing step were formed in the same manner as in Example 1, except that the amount of input of lithium carbonate was varied to be 7.5% by weight, 9.0% by weight, and 10.0% by weight. 10 [93] Next, valuable metal content analysis for each of the filtrates obtained by varying the amount of input of lithium carbonate input was performed, and the results are shown in Table 4 below. The valuable metal recovery rate for each amount of input of lithium carbonate was determined, and the 15 results are shown in Table 5 below. For the case where the amount of input of lithium carbonate was added 8.0% by weight, the content of a metal carbonate composite finally obtained was analyzed, and the results are shown in Table 6 below. [94] [Table 4] Input of lithium carbonate (wt.%) Li (mg/L) Ni (mg/L) Co (mg/L) Mn (mg/L) Al (mg/L) Cu (mg/L) 7.5 24152 28.1 32.7 19.0 0.2 0.4 8.0 24892 14.5 11.6 9.7 0.2 0.6 9.0 25121 6.2 5.6 5.7 0.1 0.5 10.0 27350 2.8 4.0 1.8 0.1 0.5 19 Date Recue/Date Received 2023-12-08[95] [Table 5] Input of lithium carbonate (wt.%) Li recovery rate (%) Ni recovery rate (%) Co recovery rate (%) Mn recovery rate (%) Al recovery rate (%) Cu recovery rate (%) 7.5 97.4 99.8 99.7 99.8 99.9 99.9 8.0 96.4 99.9 99.9 99.8 99.9 99.9 9.0 95.2 99.9 99.9 99.9 99.9 99.9 10.0 91.6 99.9 99.9 99.9 99.9 99.9 [96] [Table 6] Input of lithium carbonate (wt.%) Ni (mg/L) Co (mg/L) Mn (mg/L) Al (mg/L) Cu (mg/L) 8.0 158563 134264 132297 39574 30235 5
[97] As shown in Tables 4 to 6, as the amount of input of lithium carbonate increased, the content of Li in the precipitation filtrate increased, and the contents of Ni, Co, Mn, Al, and Cu decreased. In addition, when observing the 10 metal recovery rate according to the amount of input of lithium carbonate, when the amount of input of lithium carbonate was 8.0% by weight, 99% of Ni, Co, Mn, Al, and Cu were effectively precipitated in the form of a metal carbonate composite. It was found that Li recovery rate decreased as the amount of 15 input of lithium carbonate increased. This is because the 20 Date Recue/Date Received 2023-12-085 10 15 20 25 Date Recue/Date Received 2023-12-08 unreacted lithium carbonate is contained in the precipitate residue. Therefore, when lithium carbonate is added in an optimum amount, Li can be recovered at a high recovery rate, and a high-purity aqueous lithium sulfate solution can be obtained as a filtrate. In addition, a metal carbonate composite with high purity can be obtained at a high recovery rate as a precipitate.
[98] As described above, the method of recovering valuable metals from a waste electrode material of a lithium secondary battery by using lithium carbonate, according to the present invention, has an advantage of recovering valuable metals with high purity at high recovery rates from waste an electrode material of a lithium secondary battery by pre-processing the waste electrode material, dissolving the pre-processed waste electrode material with sulfuric acid to obtain a pregnant solution, and adding an optimum amount of lithium carbonate (Li2CO3) to the pregnant solution so that the metals can be precipitated.
[99] Although the present invention has been described with reference to the preferred example, the ordinarily skilled in the art will appreciate that the present invention is not limited to the example described above and can be diversely changed and modified without departing from the scope of the spirit of the present invention. 21Industrial ^Applicability
[100] In the method of recovering valuable metals from a waste electrode material of a lithium secondary battery by using lithium carbonate, according to the present invention, valuable 5 metals such as nickel, cobalt, manganese, aluminum, and copper are recovered as a residue in the form of a carbonate composite, and an aqueous solution of lithium sulfate (Li2SO4), which contains lithium, is recovered as a filtrate. The recovered valuable metals can be used as raw materials for 10 manufacturing a lithium secondary battery. 22 Date Recue/Date Received 2023-12-08
Claims (7)
- CLAIMS 1. A method of recovering valuable metals by using a waste electrode material, the method comprising: a waste electrode material preparation step of preparing a waste electrode material; a pre-processing step of thermally processing the waste electrode material in a firing furnace at a temperature range of 300°C to 500°C for a duration of 30 minutes to 120 minutes; a sulfuric acid dissolution step, after the pre-processing step, of adding sulfuric acid to the waste electrode material so that the waste electrode material reacts with the sulfuric acid; a first filtration step of separating the resulting product obtained through the sulfuric acid dissolution step into a pregnant solution and an unreacted residue; a precipitation step of mixing lithium carbonate (U2CO3) with the pregnant solution and stirring the resulting mixture; and a second filtration step of separating the resulting product obtained through the precipitation step into a precipitate and a filtrate, wherein an aqueous solution of lithium sulfate is recovered from the filtrate, and nickel carbonate and cobalt carbonate are recovered from the precipitate.
- 2. The method of claim1, wherein the sulfuric acid dissolution step is performed by stirring in a temperature range of 60°C to 100°C for a duration of 60 minutes to 120 minutes at a stirring speed of 250 rpm to 400 rpm.
- 3. The method of claim 2, wherein the sulfuric acid dissolution step further comprises adding hydrogen peroxide to the waste electrode material.
- 4. The method of claim1 , further comprising a first washing step of washing the unreacted residue with water, the first washing step following the first filtration step, wherein the precipitation step is performed by mixing the lithium carbonate with a mixture containing a washing solution obtained through the first washing step and the pregnant solution, and then stirring the mixture. 23 Date re?ue/Date received 2024-04-195.
- The method of claim 1, wherein in the precipitation step, a reaction is performed by stirring in a temperature range of 40°C to 80°C for a duration of 60 minutes to 180 minutes at a stirring speed of 250 rpm to 400 rpm.
- 6. The method of claim 1, further comprising a second washing step of washing the precipitate with water, the second washing step following the second filtration step, wherein an aqueous solution of lithium sulfate is recovered from a washing solution obtained through the second washing step.
- 7. The method of claim 1, wherein the waste electrode material comprises at least one selected from among lithium nickel cobalt aluminum oxide (LiNiCoAIO2, NCA), lithium nickel cobalt manganese oxide (LiNiCoMnO2, NCM), lithium iron oxide (LiFePO4, LFP), lithium manganese iron oxide (LiMnFePO4, LMFP), lithium manganese oxide (LiMn2O4, LMO), lithium nickel manganese spinel (LiNio.5Mn1.5O4, LNMO), and lithium cobalt oxide (LiCoO2, LCO). 24 Date re?ue/Date received 2024-04-19
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| KR1020200063069A KR102205442B1 (en) | 2020-05-26 | 2020-05-26 | Method for recovering valuable metals using lithium carbonate from waste electrode materials of lithium-ion batteries |
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| PCT/KR2021/006364 WO2021241944A1 (en) | 2020-05-26 | 2021-05-21 | Method for recovering valuable metal from waste electrode material of lithium secondary battery by using lithium carbonate |
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| WO2022183243A1 (en) * | 2021-03-02 | 2022-09-09 | The University Of Queensland | Precipitation of metals |
| CN113117637A (en) * | 2021-04-19 | 2021-07-16 | 重庆大学 | Method for preparing carbon dioxide adsorbing material by using waste lithium cobaltate battery as raw material |
| KR102650913B1 (en) * | 2021-09-07 | 2024-03-22 | 국립부경대학교 산학협력단 | METHOD FOR SELECTIVE RECOVERY OF LiTHIUM FROM LiFePO4 |
| KR102627665B1 (en) * | 2021-09-09 | 2024-01-23 | 국립부경대학교 산학협력단 | METHOD FOR SELECTIVE RECOVERY OF LiTHIUM FROM LiMnFePO4 |
| KR102715086B1 (en) * | 2021-10-14 | 2024-10-10 | 에너지머티리얼즈 주식회사 | Method for recoverying lithium from used lithium ion battery |
| KR102672210B1 (en) | 2021-12-01 | 2024-06-05 | 단국대학교 천안캠퍼스 산학협력단 | Method for separating and recovering electrode materials using supercritical dispersion |
| KR102813073B1 (en) | 2022-07-25 | 2025-05-27 | 단국대학교 천안캠퍼스 산학협력단 | Method for separating ionomer and catalyst from defective membrane-electrode assembly |
| CN115051056B (en) * | 2022-04-18 | 2025-10-14 | 福州华复新能源科技有限公司 | A method for industrially separating electrode materials in the process of regenerating waste electrode sheets |
| KR102525088B1 (en) * | 2022-06-09 | 2023-04-24 | 한국선별기 주식회사 | Method For Producing High Purity Lithium Sulfate From Waste Saggar |
| KR102789642B1 (en) * | 2022-08-29 | 2025-04-01 | 주식회사 에코프로이노베이션 | Method for recovering valuable metals using carbonate from waste cathode material manufacturing crucible |
| KR102806372B1 (en) * | 2022-08-31 | 2025-05-12 | 에너지머티리얼즈 주식회사 | Method for recoverying valuable metal from used battery, inlcuding process pretreating used battery |
| KR102769864B1 (en) * | 2022-12-07 | 2025-02-21 | 주식회사 플랜텍 | Mixing tank for extraction |
| EP4649536A1 (en) * | 2023-01-10 | 2025-11-19 | Ignis Lithium Inc. | Melt process involving a direct use of a metal sulfate precursor for preparing a lithium metal phosphate cathode material |
| CN116179857B (en) * | 2023-02-22 | 2026-02-17 | 百杰瑞(荆门)新材料有限公司 | Method for extracting lithium from waste lithium molecular sieve |
| US20250051877A1 (en) * | 2023-08-09 | 2025-02-13 | Ascend Elements, Inc. | Curing process for surface defects of cathode material |
| KR102874902B1 (en) | 2023-04-05 | 2025-10-23 | 주식회사 지엠텍 | Recovery method of lithium from waste lithium battery |
| CN116855762B (en) * | 2023-05-25 | 2024-07-30 | 中铝郑州有色金属研究院有限公司 | Method for recovering lithium from aluminum electrolysis waste cathode |
| WO2025029646A1 (en) * | 2023-07-28 | 2025-02-06 | The Trustees Of Columbia University In The City Of New York | In situ electrochemical hydrogen peroxide generation for hydrometallurgical lithium-ion battery recycling |
| JP7738608B2 (en) * | 2023-08-03 | 2025-09-12 | プライムプラネットエナジー＆ソリューションズ株式会社 | Battery material manufacturing method |
| GB202312756D0 (en) * | 2023-08-21 | 2023-10-04 | Watercycle Tech Ltd | Method |
| WO2025127521A1 (en) * | 2023-12-14 | 2025-06-19 | 주식회사 천보 | Method for recovering lithium compound from cathode material waste crucible |
| KR102917898B1 (en) * | 2023-12-28 | 2026-01-27 | 주식회사 코솔러스 | An organic phosphoric acid extraction composition for selective manganese recovery from metal mixture and a selective recovery method of manganese therewith |
| WO2025143804A1 (en) * | 2023-12-28 | 2025-07-03 | 주식회사 코솔러스 | Organic phosphoric acid extractant capable of selectively recovering manganese from metal mixture and manganese recovery method using same |
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| JP4099057B2 (en) * | 2002-12-27 | 2008-06-11 | 三井金属鉱業株式会社 | Cobalt recovery method and cobalt recovery system in lithium ion battery |
| JP4892925B2 (en) * | 2005-10-25 | 2012-03-07 | 住友金属鉱山株式会社 | Method for recovering valuable metals from lithium-ion batteries |
| KR101220149B1 (en) * | 2011-02-17 | 2013-01-11 | 한국지질자원연구원 | Method for making sulfate solution of valuable metal from used battery and for making cathode active material |
| KR101568216B1 (en) * | 2014-01-17 | 2015-11-11 | 경상대학교산학협력단 | Method of manufacturing electrode active material and cathod active material manufactured by the method |
| US10246343B2 (en) * | 2016-11-11 | 2019-04-02 | Rocher Manganese, Inc. | Processing of cobaltous sulpha/dithionate liquors derived from cobalt resource |
| US10308523B1 (en) * | 2017-11-07 | 2019-06-04 | Rocher Manganese, Inc. | Processing of cobaltous sulphate/dithionate liquors derived from cobalt resource |
| CN108767353B (en) * | 2018-05-25 | 2020-08-04 | 北京矿冶科技集团有限公司 | Method for producing lithium-rich clean liquid from anode active material of waste lithium ion battery |
| CN110668506B (en) * | 2019-09-29 | 2021-01-22 | 昆明理工大学 | A method for recycling and regenerating lithium cobalt oxide from waste lithium ion battery |
| CN111115662B (en) * | 2019-12-31 | 2021-03-09 | 清华四川能源互联网研究院 | Lithium battery material recovery method |
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