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WO2025249461A1 - Procédé de traitement de matériau contenant du lithium/nickel/cobalt - Google Patents

Procédé de traitement de matériau contenant du lithium/nickel/cobalt

Info

Publication number
WO2025249461A1
WO2025249461A1 PCT/JP2025/019231 JP2025019231W WO2025249461A1 WO 2025249461 A1 WO2025249461 A1 WO 2025249461A1 JP 2025019231 W JP2025019231 W JP 2025019231W WO 2025249461 A1 WO2025249461 A1 WO 2025249461A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
cobalt
lithium
containing material
leaching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/019231
Other languages
English (en)
Japanese (ja)
Inventor
亮介 佐藤
淳 宮崎
弘樹 村岡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of WO2025249461A1 publication Critical patent/WO2025249461A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B5/00—General methods of reducing to metals
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a method for treating a lithium-nickel-cobalt-containing material, which recovers valuable metals such as lithium, nickel, and cobalt from the lithium-nickel-cobalt-containing material.
  • waste lithium-ion battery powder known as black mass
  • black mass waste lithium-ion battery powder
  • defective products generated during the secondary battery manufacturing process known as black powder
  • the above-mentioned waste lithium-ion battery powder contains metals other than lithium, such as nickel and cobalt, and therefore, techniques for recovering nickel and cobalt from waste lithium-ion battery powder have been proposed.
  • Patent Document 1 proposes a technology for recovering lithium by leaching battery slag containing lithium aluminate obtained by roasting lithium-ion battery waste in an acidic solution, neutralizing the resulting leachate and performing solid-liquid separation to separate the lithium solution from metals such as aluminum, nickel, and cobalt.
  • Patent Document 2 proposes a method in which lithium ion secondary batteries are crushed and classified to obtain an electrode material containing cobalt and nickel, this electrode material is immersed in a treatment solution containing sulfuric acid and hydrogen peroxide to produce a leachate, copper is separated from this leachate to obtain an eluate containing cobalt and nickel, an alkali metal hydroxide is added to this eluate to adjust the pH, a hydrogen sulfide compound is added, and the mixture is stirred and subjected to solid-liquid separation to separate the material into cobalt sulfide and nickel sulfide and a residual solution containing lithium.
  • waste lithium-ion battery powder obtained by firing and pulverizing used lithium-ion batteries contains cobalt and nickel as described above, and may also contain complex compounds that are difficult to dissolve in acid.
  • the method disclosed in Patent Document 1 has a problem in that it is not possible to sufficiently dissolve cobalt and nickel.
  • an electrode material is immersed in a treatment solution containing sulfuric acid and hydrogen peroxide to obtain a leachate. This makes it possible to dissolve cobalt and nickel, but this leachate also contains lithium, which poses a problem in that it is not possible to efficiently recover lithium, nickel, and cobalt, respectively.
  • the present invention was made in consideration of the above-mentioned circumstances, and aims to provide a method for treating lithium-nickel-cobalt-containing materials that can efficiently recover valuable metals such as lithium, nickel, and cobalt from lithium-nickel-cobalt-containing materials that contain lithium, cobalt, and nickel.
  • the method for treating a lithium-nickel-cobalt-containing material of aspect 1 of the present invention is characterized by comprising: a leaching step in which an acidic solution containing an inorganic acid is added to a lithium-nickel-cobalt-containing material containing lithium, nickel, and cobalt to leach lithium, nickel, and cobalt into the acidic solution; a reduction-leaching step in which a reducing agent is added to the acidic solution to reduce at least a portion of the high-valence nickel and cobalt and further leach lithium, nickel, and cobalt; a neutralization step in which a neutralizing agent is added to the leaching step and the lithium-nickel-cobalt leachate obtained in the reduction-leaching step to produce a nickel-cobalt precipitate containing nickel and cobalt; a solid-liquid separation step in which the lithium leachate and the nickel-cobalt precipitate are separated after the neutralization step; and a nickel-cobalt recovery step in which nickel
  • the method for treating a lithium-nickel-cobalt-containing material according to aspect 1 of the present invention includes a leaching step of adding an acidic solution containing an inorganic acid to the lithium-nickel-cobalt-containing material to leach lithium, nickel, and cobalt into the acidic solution, and a reduction-leaching step of adding a reducing agent to the acidic solution to reduce at least a portion of the high-valence nickel and cobalt, thereby further leaching the nickel and cobalt. Therefore, even if a poorly soluble composite oxide is present in the lithium-nickel-cobalt-containing material, lithium, nickel, and cobalt can be stably leached.
  • the method also includes a neutralization step in which a neutralizing agent is added to the lithium-nickel-cobalt leachate obtained in the leaching step and the reduction leaching step to produce a nickel-cobalt precipitate containing nickel and cobalt, and a solid-liquid separation step in which the lithium leachate is separated from the nickel-cobalt precipitate after the neutralization step.
  • a neutralization step in which a neutralizing agent is added to the lithium-nickel-cobalt leachate obtained in the leaching step and the reduction leaching step to produce a nickel-cobalt precipitate containing nickel and cobalt
  • a solid-liquid separation step in which the lithium leachate is separated from the nickel-cobalt precipitate after the neutralization step.
  • a method for treating a lithium-nickel-cobalt-containing material according to a second aspect of the present invention is characterized in that, in the method for treating a lithium-nickel-cobalt-containing material according to the first aspect of the present invention, the inorganic acid used in the leaching step is one or more of sulfuric acid, hydrochloric acid, and nitric acid.
  • the inorganic acid used in the leaching step is one or more of sulfuric acid, hydrochloric acid, and nitric acid, so that lithium, nickel, and cobalt can be efficiently dissolved to obtain a lithium-nickel-cobalt leachate.
  • a method for treating a lithium-nickel-cobalt-containing material according to Aspect 3 of the present invention is characterized in that, in the method for treating a lithium-nickel-cobalt-containing material according to Aspect 1 or Aspect 2 of the present invention, the neutralizing agent added in the neutralization step is one or more of calcium hydroxide, calcium oxide, and calcium carbonate. According to the method for treating a lithium-nickel-cobalt-containing material of Aspect 3 of the present invention, the neutralizing agent added in the neutralization step is one or more of calcium hydroxide, calcium oxide, and calcium carbonate.
  • fluorine derived from the electrolyte of a lithium ion battery dissolved in the leaching step can be removed as calcium fluoride to obtain a lithium leachate with high lithium purity, and a nickel-cobalt precipitate containing nickel and cobalt can be efficiently produced.
  • a method for treating a lithium-nickel-cobalt-containing material according to Aspect 4 of the present invention is characterized in that, in the method for treating a lithium-nickel-cobalt-containing material according to any one of Aspects 1 to 3 of the present invention, the pH in the leaching step is within the range of 1.5 to 2.0. According to the method for treating a lithium-nickel-cobalt-containing material of Aspect 4 of the present invention, the pH in the leaching step is set within the range of 1.5 or more and 2.0 or less, so that lithium, nickel, and cobalt can be efficiently leached from the lithium-nickel-cobalt-containing material into the acidic solution.
  • a method for treating a lithium-nickel-cobalt-containing material according to Aspect 5 of the present invention is the method for treating a lithium-nickel-cobalt-containing material according to any one of Aspects 1 to 4 of the present invention, characterized in that the reducing agent used in the reduction leaching step is hydrogen peroxide.
  • the reducing agent used in the reduction leaching step is hydrogen peroxide. Therefore, even if a poorly soluble composite oxide is present in the lithium-nickel-cobalt-containing material, lithium, nickel, and cobalt can be reliably leached.
  • a method for treating a lithium-nickel-cobalt-containing material according to a sixth aspect of the present invention is characterized in that, in the method for treating a lithium-nickel-cobalt-containing material according to any one of the first to fifth aspects of the present invention, the leaching step and the reduction leaching step are carried out simultaneously.
  • the method for treating a lithium-nickel-cobalt-containing material of Aspect 6 of the present invention by adding a reducing agent to the acidic solution and simultaneously carrying out the leaching step and the reduction-leaching step, lithium, nickel, and cobalt can be leached from the lithium-nickel-cobalt-containing material more efficiently.
  • a method for treating a lithium-nickel-cobalt-containing material according to Aspect 7 of the present invention is the method for treating a lithium-nickel-cobalt-containing material according to any one of Aspects 1 to 6 of the present invention, characterized in that the nickel-cobalt recovery step comprises: a second leaching step of leaching a nickel-cobalt precipitate in an acidic solution containing an inorganic acid to obtain a nickel-cobalt leachate; and a second solid-liquid separation step of separating the nickel-cobalt leachate from a solid component.
  • the nickel-cobalt recovery step includes a second leaching step of leaching the nickel-cobalt precipitate in an acidic solution containing an inorganic acid to obtain a nickel-cobalt leachate, and a second solid-liquid separation step of separating the nickel-cobalt leachate from a solid component, thereby making it possible to recover cobalt and nickel reliably and efficiently.
  • a method for treating a lithium-nickel-cobalt-containing material according to an eighth aspect of the present invention is the method for treating a lithium-nickel-cobalt-containing material according to any one of the first to seventh aspects of the present invention, characterized in that a sulfiding agent is added to the nickel-cobalt leachate obtained in the second solid-liquid separation step to recover nickel-cobalt sulfides.
  • a sulfiding agent is added to the nickel-cobalt leachate obtained in the second solid-liquid separation step to recover nickel-cobalt sulfides, so that cobalt and nickel can be recovered stably and efficiently.
  • a ninth aspect of the present invention is a method for treating a lithium-nickel-cobalt-containing material, which is the method for treating a lithium-nickel-cobalt-containing material according to any one of the first to eighth aspects of the present invention, characterized in that a reducing agent is added after or simultaneously with the second leaching step.
  • a reducing agent is added after or simultaneously with the second leaching step, so that cobalt and nickel can be further leached, and cobalt and nickel can be recovered more efficiently.
  • a tenth aspect of the present invention is a method for treating a lithium-nickel-cobalt-containing material according to the ninth aspect of the present invention, characterized in that heating is not performed when the reducing agent is added in the reduction leaching step, but heating is performed when the reducing agent is added in the second leaching step.
  • the reducing agent is not heated when added in the reduction leaching step, but is heated when added in the second leaching step. This may reduce consumption of the reducing agent in the reduction leaching step and enable efficient separation of nickel-cobalt and lithium.
  • the present invention provides a method for treating lithium-nickel-cobalt-containing materials that can efficiently recover valuable metals such as lithium, nickel, and cobalt from lithium-nickel-cobalt-containing materials containing lithium, cobalt, and nickel.
  • FIG. 1 is a flow diagram showing a method for treating a lithium-nickel-cobalt-containing material according to an embodiment of the present invention.
  • the method for treating a lithium-nickel-cobalt-containing material is for recovering valuable metals such as lithium, nickel, and cobalt from a lithium-nickel-cobalt-containing material that contains lithium, cobalt, and nickel.
  • the lithium-nickel-cobalt-containing material to be treated is waste lithium-ion battery powder (so-called black mass) obtained by firing and/or pulverizing used lithium-ion batteries, or defective products (so-called black powder) generated in the manufacturing process of positive electrode materials for secondary batteries, etc.
  • the above-mentioned waste lithium-ion battery powder (black mass) and defective products (black powder) contain (a) compounds in which lithium is combined with nickel and cobalt (e.g., LiNiO2 , LiCoO2 , etc.), (b) compounds derived from the electrolyte (e.g., Li2CO3 , etc. ), and (c) other compounds (e.g., LiAlO2 , metallic Co, metallic Ni, NiO, CoO, etc.).
  • those derived from the electrolyte e.g., Li2CO3 , etc.
  • the method for treating a lithium-nickel-cobalt-containing material includes at least a leaching step S01, a reduction leaching step S02, a neutralization step S03, a solid-liquid separation step S04, and a nickel-cobalt recovery step S05, as shown in FIG. 1 .
  • the nickel/cobalt recovery step S05 includes a second leaching step S51 and a second solid-liquid separation step S52.
  • Li-nickel-cobalt-containing material such as waste lithium-ion battery powder is immersed in an acidic solution to leach lithium, nickel, and cobalt into the acidic solution, thereby obtaining a lithium-nickel-cobalt leachate.
  • the acid solution may be, for example, an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid, either singly or in combination.
  • sulfuric acid is used as the acid.
  • the lithium-nickel-cobalt-containing material is mixed with an acidic solution and stirred (stirring time: 1 hour or more and 24 hours or less) to dissolve the lithium, nickel, and cobalt in the lithium-nickel-cobalt-containing material, thereby obtaining a lithium-nickel-cobalt leachate.
  • the pH of the lithium-nickel-cobalt leaching solution in the leaching step S01 is preferably in the range of 1.5 to 2.0.
  • Reduction leaching step S02 In this reduction leaching step S02, a reducing agent is added to the acidic solution to reduce at least a portion of the high-valence nickel and cobalt, and the nickel and cobalt are further leached into the acidic solution.
  • Lithium-nickel-cobalt-containing materials may contain complex compounds containing nickel and cobalt that are difficult to dissolve in acid. In such complex oxides, nickel and cobalt exist in high valence states such as trivalent and tetravalent.
  • a reducing agent to the acidic solution, trivalent and tetravalent nickel and cobalt are reduced to divalent nickel and cobalt, thereby facilitating their leaching into the acidic solution.
  • examples of the reducing agent that can be used include hydrogen peroxide, sulfur dioxide, sodium hydrogen sulfite, etc.
  • hydrogen peroxide is used as the reducing agent.
  • the mixing ratio of the reducing agent to the acidic solution is preferably 0.01 or more and 1.0 or less by mass. By setting the mixing ratio of the reducing agent to the acidic solution to 0.01 or more by mass, nickel and cobalt can be sufficiently leached. Furthermore, by setting the mixing ratio of the reducing agent to the acidic solution to 1.0 or less, it is possible to prevent the added reducing agent from remaining.
  • the mixing ratio of the reducing agent to the acidic solution is more preferably 0.1 or more and 0.5 or less by mass.
  • the leaching step S01 and the reduction leaching step S02 can also be carried out simultaneously.
  • the temperature of the acidic solution during reduction leaching is preferably 50°C or higher and 80°C or lower, and more preferably 60°C or higher and 75°C or lower.
  • a neutralizing agent is added to the lithium-nickel-cobalt leachate obtained in the reduction leaching step S02 to produce a nickel-cobalt precipitate containing nickel and cobalt.
  • the pH in the neutralization step S03 is not particularly limited, but is preferably within the range of 8 or more and 12 or less.
  • Solid-liquid separation step S04 In this solid-liquid separation step S04, the nickel-cobalt precipitate produced in the neutralization step S03 is separated from the lithium leachate.
  • a solid-liquid separation method such as gravity settling, centrifugal separation, or filter cloth filtration using a filter press or the like can be used.
  • Nickel/cobalt recovery step S05 nickel and cobalt are recovered from the nickel-cobalt precipitate separated in the solid-liquid separation step S04.
  • the nickel-cobalt recovery step S05 includes a second leaching step S51 and a second solid-liquid separation step S52.
  • the nickel-cobalt precipitate separated in the solid-liquid separation step S04 is leached in an acidic solution containing an inorganic acid to obtain a nickel-cobalt leachate.
  • the inorganic acid used in the second leaching step S51 can be one or more of sulfuric acid, hydrochloric acid, and nitric acid.
  • Heating is preferably performed in the second leaching step S01.
  • the leaching temperature is preferably 50°C to 80°C, and more preferably 60°C to 75°C.
  • a reducing agent may be added after or simultaneously with the second leaching step S51 to perform reduction leaching. In this case, it is preferable not to heat the reduction leaching step S02 but to heat the second leaching step S51.
  • nickel/cobalt and lithium it is possible to efficiently separate nickel/cobalt and lithium by suppressing consumption of the reducing agent in the reduction leaching step S02.
  • the reason why nickel/cobalt and lithium can be efficiently separated in this case is that in the reduction leaching step S02, in which lithium is leached into an acidic solution, the amount of reducing agent consumed in leaching nickel and cobalt that do not need to be leached is suppressed, and the amounts of nickel and cobalt leached into the lithium leachate are suppressed. Furthermore, more reducing agent can be consumed for leaching nickel and cobalt in the nickel/cobalt recovery step S05.
  • the nickel-cobalt leachate is separated from the solid components, and cobalt and nickel are recovered as the nickel-cobalt leachate.
  • the nickel-cobalt leachate can be separated from the solid components by a solid-liquid separation method such as gravity settling, centrifugation, or filter cloth filtration using a filter press or the like. It is also possible to add a sulfiding agent to the nickel-cobalt leachate to recover nickel-cobalt sulfides.
  • lithium is recovered from the lithium-nickel-cobalt-containing material as lithium leachate, and cobalt and nickel are recovered as nickel-cobalt leachate.
  • the method for treating lithium-nickel-cobalt-containing material of this embodiment includes a leaching step S01 in which an acidic solution containing an inorganic acid is added to leach lithium, nickel, and cobalt into the acidic solution, and a reduction leaching step S02 in which a reducing agent is added to the acidic solution to reduce at least a portion of the high-valence nickel and cobalt, thereby further leaching the nickel and cobalt.
  • the lithium-nickel-cobalt-containing material contains sparingly soluble composite oxides, the trivalent and tetravalent nickel and cobalt, which are difficult to dissolve in the reducing agent, can be converted to divalent form, and lithium, nickel, and cobalt can be stably leached into the acidic solution.
  • the system also includes a neutralization step S03 in which a neutralizing agent is added to the lithium-nickel-cobalt leachate obtained in the leaching step S01 and the reduction leaching step S02 to produce a nickel-cobalt precipitate containing nickel and cobalt, a solid-liquid separation step S04 in which the lithium leachate is separated from the nickel-cobalt precipitate after the neutralization step S03, and a nickel-cobalt recovery step S05 in which nickel and cobalt are recovered from the nickel-cobalt precipitate.
  • This allows the lithium leachate to be separated from the nickel-cobalt precipitate, and lithium can be recovered as the lithium leachate, while nickel and cobalt can be efficiently recovered from the nickel-cobalt precipitate.
  • the inorganic acid used in the leaching step S01 is one or more of sulfuric acid, hydrochloric acid, and nitric acid
  • the lithium, nickel, and cobalt in the lithium-nickel-cobalt-containing material can be dissolved to efficiently produce a lithium-nickel-cobalt leachate.
  • the neutralizing agent added in the neutralization step S03 is one or more of calcium hydroxide, calcium oxide, and calcium carbonate
  • fluorine derived from the electrolyte of the lithium-ion battery dissolved in the leaching step can be removed as calcium fluoride to obtain a lithium leachate with high lithium purity, and a nickel-cobalt precipitate containing nickel and cobalt can be efficiently produced.
  • the pH in the leaching step S01 when the pH in the leaching step S01 is set within the range of 1.5 or higher and 2.0 or lower, lithium, nickel, and cobalt can be efficiently leached from the lithium-nickel-cobalt-containing material into the acidic solution.
  • lithium, nickel, and cobalt when hydrogen peroxide is used as the reducing agent in the reduction leaching step S02, lithium, nickel, and cobalt can be reliably leached even if insoluble composite oxides are present in the lithium-nickel-cobalt-containing material.
  • lithium, nickel, and cobalt can be leached even more efficiently from the lithium-nickel-cobalt-containing material.
  • the nickel-cobalt recovery process S05 includes a second leaching process S51 in which the nickel-cobalt precipitate is leached in an acidic solution containing an inorganic acid to obtain a nickel-cobalt leachate, and a second solid-liquid separation process S52 in which the nickel-cobalt leachate is separated from the solid components, cobalt and nickel can be reliably and efficiently recovered from the nickel-cobalt precipitate.
  • the reducing agent is not heated when added in the reduction leaching step S02, but is heated when added in the second leaching step S51, it may be possible to reduce consumption of the reducing agent in the reduction leaching step S02 and efficiently separate nickel-cobalt and lithium.
  • Example 1 47 vol % sulfuric acid was added to 80 g of the black mass shown in Table 1 until the pH reached 2 or less (leaching step). Next, while adding the hydrogen peroxide solution, 47 vol% sulfuric acid was added at room temperature (20°C to 30°C, 25°C in this example) so that the pH was 2 or less (reductive leaching step). The mixing ratio of hydrogen peroxide solution (reducing agent) to sulfuric acid (acidic solution) was 0.6 by mass. Next, an aqueous calcium hydroxide solution was added to adjust the pH to 9.5 or higher, thereby obtaining a slurry (neutralization step). This slurry was subjected to solid-liquid separation (solid-liquid separation step).
  • the resulting lithium leachate and nickel-cobalt precipitate were subjected to elemental analysis by ICP.
  • 47 vol % sulfuric acid was added to the nickel-cobalt precipitate at room temperature to adjust the pH to 2.0 or less (second leaching step).
  • the slurry obtained in the second leaching step was subjected to solid-liquid separation (second solid-liquid separation step).
  • the obtained nickel-cobalt leachate and solid components were subjected to elemental analysis by ICP.
  • the leaching rate (%) of Li was calculated from the results of the above elemental analysis using the following formula: The calculation results are shown in Table 1.
  • Li leaching rate (%) [amount of Li leached in the first leaching step (g) / (amount of Li leached in the first leaching step (g) + amount of Li leached in the second leaching step (g) + amount of Li in the residue of the second leaching step (g))] ⁇ 100
  • Co leaching rate (%) [amount of Co leached in the second leaching step (g) / (amount of Co leached in the first leaching step (g) + amount of Co leached in the second leaching step (g) + amount of Co in the residue of the second leaching step (g))] ⁇ 100
  • Ni leaching rate (%) [amount of Ni leached in the second leaching step (g) / (amount of Ni leached in the first leaching step (g) + amount of Ni leached in the second leaching step (g) + amount of Ni in the residue of the second leaching step (g))] ⁇ 100
  • Example 2 47 vol % sulfuric acid was added to 80 g of the black mass shown in Table 2 until the pH reached 2 or less (leaching step). Next, while adding the hydrogen peroxide solution, the temperature was set to 60°C, and 47 vol% sulfuric acid was added so that the pH was 2 or less (reduction leaching step). Note that the mixing ratio of the hydrogen peroxide solution (reducing agent) to the sulfuric acid (acidic solution) was 0.4 by mass. Next, an aqueous calcium hydroxide solution was added to adjust the pH to 9.5 or higher, thereby obtaining a slurry (neutralization step). This slurry was subjected to solid-liquid separation (first solid-liquid separation step).
  • the resulting lithium leachate and nickel-cobalt precipitate were subjected to elemental analysis by ICP.
  • the temperature of the nickel-cobalt precipitate was set to 60° C., and then 47 vol % sulfuric acid was added to the precipitate to adjust the pH to 2.0 or less (second leaching step).
  • the slurry obtained in the second leaching step was subjected to solid-liquid separation (second solid-liquid separation step).
  • the obtained nickel-cobalt leachate and solid components were subjected to elemental analysis by ICP.
  • the leaching rates (%) of Li, Co, and Ni were calculated in the same manner as in Example 1. The calculation results are shown in Table 2.
  • Example 1 in which the reduction leaching step was carried out, the leaching rates of Li, Co, and Ni were improved compared to the comparative example in which the reduction leaching step was not carried out, and it was confirmed that lithium, nickel, and cobalt could be efficiently separated and recovered from the lithium-nickel-cobalt-containing material containing lithium, cobalt, and nickel. Furthermore, in Example 2, in which the temperature during leaching was set to 60°C, it was confirmed that the leaching rates of Li, Co, and Ni were further improved compared to Example 1.
  • the present invention can provide a method for treating lithium-nickel-cobalt-containing materials that can efficiently recover valuable metals such as lithium, nickel, and cobalt from lithium-nickel-cobalt-containing materials containing lithium, cobalt, and nickel.
  • the present invention makes it possible to provide a method for processing lithium-nickel-cobalt-containing materials that enables the efficient recovery of valuable metals such as lithium, nickel, and cobalt from lithium-nickel-cobalt-containing materials.

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Abstract

L'invention concerne un procédé de traitement d'un matériau contenant du lithium/nickel/cobalt, qui comprend une étape de lixiviation (S01) consistant à ajouter une solution acide qui contient un acide inorganique à un matériau contenant du lithium/nickel/cobalt pour lixivier le lithium, le nickel et le cobalt dans la solution acide, une étape de lixiviation par réduction (S02) consistant à ajouter un agent réducteur à la solution acide pour lixivier plus de lithium, de nickel et de cobalt, une étape de neutralisation (S03) consistant à ajouter un composé de calcium au lixiviat de lithium/nickel/cobalt pour générer un précipité de nickel/cobalt qui comprend du nickel et du cobalt, une étape de séparation solide/liquide (S04) consistant à séparer le précipité de nickel/cobalt et le lixiviat de lithium, et une étape de récupération de nickel/cobalt (S05) consistant à récupérer le nickel et le cobalt à partir du précipité de nickel/cobalt.
PCT/JP2025/019231 2024-05-31 2025-05-28 Procédé de traitement de matériau contenant du lithium/nickel/cobalt Pending WO2025249461A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012072488A (ja) * 2010-08-30 2012-04-12 Jx Nippon Mining & Metals Corp 正極活物質の浸出方法
JP2016003353A (ja) * 2014-06-16 2016-01-12 住友金属鉱山株式会社 廃ニッケル水素電池からの有価金属の回収方法
WO2020045596A1 (fr) * 2018-08-31 2020-03-05 Ｊｘ金属株式会社 Procédé de production de carbonate de lithium
JP2022042982A (ja) * 2020-09-03 2022-03-15 三菱マテリアル株式会社 コバルトおよびニッケルの分離方法
JP2023174586A (ja) * 2022-05-27 2023-12-07 ツー－シックス デラウェア インコーポレイテッド 合理化されたリチウムイオン電池廃棄物のリサイクル

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012072488A (ja) * 2010-08-30 2012-04-12 Jx Nippon Mining & Metals Corp 正極活物質の浸出方法
JP2016003353A (ja) * 2014-06-16 2016-01-12 住友金属鉱山株式会社 廃ニッケル水素電池からの有価金属の回収方法
WO2020045596A1 (fr) * 2018-08-31 2020-03-05 Ｊｘ金属株式会社 Procédé de production de carbonate de lithium
JP2022042982A (ja) * 2020-09-03 2022-03-15 三菱マテリアル株式会社 コバルトおよびニッケルの分離方法
JP2023174586A (ja) * 2022-05-27 2023-12-07 ツー－シックス デラウェア インコーポレイテッド 合理化されたリチウムイオン電池廃棄物のリサイクル

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