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WO2025038980A1 - Compositions et procédés de recyclage de matériaux de batteries lithium-ion - Google Patents

Compositions et procédés de recyclage de matériaux de batteries lithium-ion Download PDF

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Publication number
WO2025038980A1
WO2025038980A1 PCT/US2024/042813 US2024042813W WO2025038980A1 WO 2025038980 A1 WO2025038980 A1 WO 2025038980A1 US 2024042813 W US2024042813 W US 2024042813W WO 2025038980 A1 WO2025038980 A1 WO 2025038980A1
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WO
WIPO (PCT)
Prior art keywords
lithium
batteries
alternatively
persulfate
instances
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/US2024/042813
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English (en)
Inventor
Zhifeng Ren
Shaowei SONG
Mingchu ZOU
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University of Houston System
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University of Houston System
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Publication of WO2025038980A1 publication Critical patent/WO2025038980A1/fr
Pending legal-status Critical Current
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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
    • 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
    • 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
    • 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
    • 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
    • C22B3/20—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
    • C22B47/00—Obtaining manganese
    • 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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Definitions

  • the present invention relates to compositions and methods for recycling lithium-ion battery materials. More specifically, the present invention relates to acid- and base-free compositions and methods for the recovery of lithium and other valuable materials such as Ni, Co, Mn, Cu, Al, graphite, etc. from lithium-containing battery materials for subsequent purification and reuse.
  • Lithium-ion batteries are widely used and desirable because of their high volumetric energy densities (320-450 Wh L' 1 ), power ouput (over 300 W kg' 1 ) and high cycling stability- (2000 cycles without decreasing).
  • LLBs Lithium-ion batteries
  • power ouput over 300 W kg' 1
  • high cycling stability- 2000 cycles without decreasing.
  • electric vehicles sales increased by from about 750,000 to about 2,900,000.
  • the substantial increase in lithium-ion battery production in recent years has accelerated the consumption of the raw materials worldwide.
  • the limited availability of earth reserves for materials such as Li, Co, and Ni has posed significant sustainability challenges for energy storage development, such as batteries.
  • Pyrometallurgical methods provide some advantages including short process flow, high recovery rates, simple equipment and strong operability. This technology' is the most common recycling method in LIB recycling plants. However, pyrometallurgical methods require high energy inputs (heat treatment at temperatures above 1000 °C), can be responsible for severe air pollution, the product outputs exhibit low purity and the products are metal alloys which cannot be recovered individually.
  • Hydrometallurgical methods are generally more flexible in using various chemical reagents to leach metals, followed by extraction and purification.
  • metal oxides, metal hydroxides, and metal carbonates of a spent battery re solubilized using strong acids or strong bases, followed by separate precipitation of the individual metal salts according to their solubility'.
  • the problems are needing strong acids/bases, elements separating with similar properties, high consumption of water and chemical reagents, complex equipment requirements and high cost of pollution treatment.
  • FIG. 1 is a flowchart illustrating an exemplary method for bulk recovery of active materials from a spent lithium-ion battery in accordance with various aspects of the disclosure.
  • FIG. 2 is a flowchart illustrating an exemplary' method for recovering individual materials (such as lithium and cobalt) from the bulk active materials recovered in an exemplary method as illustrated in FIG. 1 in accordance with various aspects of the disclosure.
  • FIG. 3 is a flowchart illustrating another exemplary' method for bulk recovery of active materials from a spent lithium-ion battery in accordance with various aspects of the disclosure.
  • FIG. 4 is a flowchart illustrating an exemplary method for recovering individual materials (in the form of a metal sulfate salts solution) from the bulk active materials recovered in an exemplary method as illustrated in FIG. 3 in accordance with various aspects of the disclosure.
  • FIG. 5 is a flowchart illustrating an exemplary method for recovering individual materials (in the form of metal oxides or metal hydroxides, and lithium carbonate) from metal sulfate salts recovered in an exemplary' method as illustrated in FIG. 4 in accordance with various aspects of the disclosure.
  • FIG. 6 is a Powder X-Ray Diffraction (PXRD) pattern of a milled and sintered sample produced in Example 1.
  • FIG. 7 is a PXRD patern of a dried raffinate solution obtained in Example 1.
  • FIG. 8 is a PXRD patern of CO3O4 obtained in Example 1.
  • FIG. 9 is an XPS patern showing the elemental composition of the extractive materials of Example 1.
  • FIG. 10 provides a graphical overview of the advantages and shortcomings of prior art methods for the recoven’ of lithium and other metals of interest from spent lithium-ion bateries.
  • ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight.
  • the terms “comprise” (as well as forms, derivatives, or variations thereof, such as “comprising” and “comprises”), “include” (as well as forms, derivatives, or variations thereof, such as “including” and “includes”) and “has” (as well as forms, derivatives, or variations thereof, such as “having” and “have”) are inclusive (i.e., open-ended) and do not exclude additional elements or steps. Accordingly, these terms are intended to not only cover the recited element(s) or step(s), but may also include other elements or steps not expressly recited.
  • FIGS. 1 and 2 are flowcharts illustrating an exemplary method for recovering metals of interest, such as lithium and cobalt, from a spent (or used) lithium-ion battery'. More specifically, FIG. l is a flowchart illustrating an exemplary method for the bulk recovery of active metals from a spent lithium-ion batter ⁇ ' in accordance with various aspects of the disclosure, and FIG. 2 is a flowchart illustrating an exemplar ⁇ ' method for recovering individual active materials (such as lithium and cobalt) from the bulk active materials recovered in an exemplary method as illustrated in FIG. 1 in accordance with various aspects of the disclosure. In some instances, one or more steps may be added or removed from the exemplary method without departing from the scope of this disclosure.
  • An exemplary method according to various aspects of the disclosure can begin at step 105.
  • a spent lithium-ion battery is provided.
  • the type of spent lithium-ion battery is not to be used in the exemplary is not particularly limiting.
  • the lithium ion battery can be, for example, a coin cell battery, a pouch cell battery, a batter ⁇ ' from a portable electronic device (such as a smartphone, tablet, laptop, wireless speaker, and so on), a lithium ion automobile battery, and so on.
  • the composition of the lithium-ion batter ⁇ ' is not particularly limiting.
  • Suitable compositions of lithium-ion batteries can include, but are not necessarily limited to, lithium-ion cobalt oxide batteries, lithium-silicon batteries, lithium-ion manganese iron phosphate batteries, lithium-ion manganese-oxide batteries, lithium-ion polymer batteries, lithium-iron-phosphate batteries, lithium-nickel-manganese-cobalt oxides batteries, lithium-nickel-cobalt-aluminum oxides batteries, lithium-sulfur batteries, lithium-selenium batteries, lithium-sulfur/selenium batteries, lithium-nickel oxide batteries, lithium-manganese oxide batteries, lithium iron phosphate batteries, and lithium-titanate batteries.
  • lithium-ion batteries comprising at least lithium and cobalt may be preferred. In other instances, lithium-ion batteries comprising at least lithium, cobalt and nickel may be preferred. In other instances, lithium-ion batteries comprising at least lithium, cobalt, nickel, and manganese may be preferred. In other instances, lithium-ion batteries comprising at least lithium, cobalt, nickel, and aluminum may be preferred.
  • step 110 the spent lithium-ion batten’ is discharged after disabling overcharge protection.
  • the method by which the batten' is discharged is not particularly limiting.
  • the battery can be discharged by, for example immersing the anode and the cathode of the battery in an aqueous sodium chloride solution.
  • the discharged battery is dismantled (or disassembled).
  • the dismantled battery is then immersed in water including a deionized (DI) water bath and allowed to soak in the water bath for a period of time sufficient to allow' for the anode and the cathode/separator to isolated from each other.
  • the length of the soak period may depend on various parameters such as the size and/or surface area of the dismantled battery and the composition of the battery'.
  • the soak period may range from about 15 minutes to about 8 hours, alternatively from about 30 minutes to about 6 hours, alternatively from about 45 minutes to about 4 hours, alternatively from about 1 hour to about 3 hours, and alternatively from about 1.5 hours to about 2.5 hours.
  • the soak period can be about 2 hours.
  • the temperature of the water bath can range from room temperature (20-22 °C) to about 100 °C.
  • step 120 after completion of the soak period, the anode is removed from the water bath and isolated, and the cathode/separator is removed from the water bath and isolated.
  • the isolated anode is then immersed in a second water bath and allowed to soak in the second w ater bath for a period of time sufficient to facilitate separation of individual components of the anode (such as carbon-based materials (e.g.. graphite, activated carbon, carbon black, carbon nanotubes, etc.), copper foil, platinum, zinc, iron, ceramics and so on) and the subsequent isolation and recovery of the individual anode components in step 130.
  • the length of the second w ater bath soak period may depend on various parameters such as the size and/or surface area of the anode and the composition of the anode.
  • the second w ater bath soak period may range from about 1 hour to about 24 hours, alternatively from about 2 hours to about 20 hours, alternatively from about 3 hours to about 16 hours, alternatively from about 4 hours to about 12 hours, alternatively from about 6 hours to about 10 hours, and alternatively from about 7 hours to about 9 hours.
  • the second water bath soak period can be about 8 hours.
  • the temperature of the second water bath can range from room temperature (20-22 °C) to about 100 °C.
  • the temperature of the second water bath can range from about 30 °C to about 100 °C, alternatively from about 40 °C to about 100 °C, alternatively from about 50 °C to about 100 °C, alternatively from about 60 °C to about 100 °C, alternatively from about 70 °C to about 100 °C, alternatively from about 80 °C to about 100 °C, and alternatively from about 90 °C to about 100 °C. In some instances, the temperature of the second water bath can be about 100 °C.
  • step 125 individual components of the anode (such as carbon-based materials (e.g., graphite, activated carbon, carbon black, carbon nanotubes, etc.), copper foil, platinum, zinc, iron, ceramics and so on) can be subjected to additional separation and purification steps, and the purified individual components can be recycled for future use in new batteries or other applications.
  • carbon-based materials e.g., graphite, activated carbon, carbon black, carbon nanotubes, etc.
  • copper foil e.g., platinum, zinc, iron, ceramics and so on
  • step 135 the isolated cathode/separator is then immersed in a third water bath and allowed to soak in the third water bath for a period of time sufficient to facilitate separation of the cathode material from the battery separator.
  • the length of the third water bath soak period may depend on various parameters such as the size and/or surface area of the cathode and battery separator and the compositions of the cathode material and battery separator.
  • the third water bath soak period may range from about 1 hour to about 24 hours, alternatively from about 2 hours to about 20 hours, alternatively from about 3 hours to about 16 hours, alternatively from about 4 hours to about 12 hours, alternatively from about 5 hours to about 10 hours, and alternatively from about 5 hours to about 9 hours.
  • the third water bath soak period can be about 8 hours.
  • the temperature of the third water bath can range from room temperature (20-22 °C) to about 100 °C. In some instances, the temperature of the third water bath can range from about 30 °C to about 100 °C, alternatively from about 40 °C to about 100 °C, alternatively from about 50 °C to about 100 °C, alternatively from about 60 °C to about 100 °C, alternatively from about 70 °C to about 100 °C, alternatively from about 80 °C to about 100 °C, and alternatively from about 90 °C to about 100 °C. In some instances, the temperature of the third water bath can be about 100 °C.
  • step 140 the separator is separated (by, e.g., peeling) from the cathode material, which comprises active materials (such as lithium cobalt, nickel, and so on) and a metal foil (for example, an aluminum foil), and the third water bath.
  • the cathode material now isolated from the battery separator, remains in the third water bath for further processing.
  • step 145 the isolated cathode material is then allowed to continue to soak in the third DI water bath for a period of time sufficient to facilitate separation of active materials from the metal foil.
  • the continued water bath soak period in this step may range from about 15 minutes to about 8 hours, alternatively from about 30 minutes to about 6 hours, alternatively from about 45 minutes to about 4 hours, alternatively from about 1 hour to about 3 hours, and alternatively from about 1.5 hours to about 2.5 hours.
  • the soak period can be about 2 hours.
  • the temperature of the water bath during the soak period in this step can range from room temperature (20-22 °C) to about 100 °C.
  • separation of active materials from the metal foil during the soak period of this step can further be facilitated with the aid of agitation.
  • the agitation can be in the form of stirring with the aid of a mechanical stirring means such as, for example, a magnetic stir bar or a paddle mixer.
  • the agitation can be in the form of direct or indirect sonication using, for example, an ultrasonic bath, an ultrasonic probe or an ultrasonic hom.
  • the length of the fourth water bath soak period may depend on various parameters such as the size and/or surface area of the cathode and battery separator and the compositions of the cathode and battery separator, the temperature of the water bath and the type and/or intensity of agitation.
  • the metal foil can be recovered, purified and recycled for future use in new batteries or other applications.
  • step 150 the active materials, now removed from the metal foil are isolated and dried. At the end of step 150. a dried mixture of bulk active materials (such as lithium cobalt, nickel, and so on) is produced. Upon completion of step 150, the exemplary method proceeds with steps toward recovery individual active materials of interest from the dried bulk active materials as illustrated in FIG. 2.
  • a dried mixture of bulk active materials such as lithium cobalt, nickel, and so on
  • step 205 the dried bulk active materials are provided.
  • the dried bulk active materials are then mixed with an extraction reagent in step 210.
  • any mixing technique that results in a homogenous or substantially homogenous mixture is sufficient.
  • ball milling is a preferred technique for mixing the dried bulk active materials and the extraction reagent.
  • the mixing may be conducted for a period of time ranging from about 15 minutes to about 8 hours, alternatively from about 30 minutes to about 6 hours, alternatively from about 45 minutes to about 4 hours, alternatively from about 1 hour to about 3 hours, and alternatively from about 1.5 hours to about 2.5 hours.
  • the mixing may be conducted for a period of time of about 2 hours.
  • the extraction reagent is a persulfate (S20s 2 ') salt.
  • the persulfate salt comprises an organic cation.
  • it is preferable that the persulfate salt comprises an organic cation that will volatize during a baking process (step 215, below).
  • Suitable persulfates include, but are not limited to, peroxydisulfuric acid, sodium persulfate, potassium persulfate, calcium persulfate, bis(tetrabutylammonium) peroxydisulfate, benzyltriphenylphosphonium peroxy disulfate, choline peroxy disulfate, ammonium persulfate and combinations thereof. In some instances, the use of ammonium persulfate as the extraction reagent is preferred.
  • the extraction reagent is added to the mixture in a stoichiometric amount relative to the combined molar amount of active materials of interest (for example, lithium, cobalt, nickel, and so on) that are to ultimately be recovered from the dried bulk active materials (step 240, below). In some instances, the extraction reagent is added to the mixture in a stoichiometric excess relative to the combined molar amount of active materials of interest that are to ultimately be recovered from the dried bulk active materials.
  • active materials of interest for example, lithium, cobalt, nickel, and so on
  • the extraction reagent is added to the mixture in an amount that results in the mixture having a dried bulk active materials-to-extraction reagent weightweight ratio ranging from about 5: 1 to about 1:5, alternatively from about 4: 1 to about 1 :4, alternatively from about 3: 1 to about 1:3, alternatively from about 2: 1 to about 1:2, and alternatively about 1 : 1.
  • step 215 the mixture of the dried bulk active matenals and the extraction reagent are sintered (or baked) to formed a sintered composition.
  • the bulk active materials react with the extraction reagent to form corresponding sulfates salts and/or oxides.
  • Sintering can be conducted at a temperature ranging from about 150 °C to about 700 °C, alternatively from about 200 °C to about 650 °C, alternatively from about 300 °C to about 600 °C, alternatively from about 400 °C to about 550 °C, alternatively from about 450 °C to about 550 °C, and alternatively from about 475 °C to about 525 °C.
  • the sintering temperature can be about 500 °C. Sintering can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, and alternatively from about 15 minutes to about 1 hour. In some instances, sintering can be conducted under atmospheric pressure. In some instances, sintering can be conducted in at a pressure less than atmospheric pressure, such as anywhere from 0.01 to 0.99 atm. In some instances, sintering can be conducted in at a pressure greater atmospheric pressure, such as anywhere from 1.01 to about 10 atm. In some instances, sintering can be conducted in an inert gas such as nitrogen or argon. In some instances, sintering can be conducted in a state environment of the inert gas. In some instances, sintering can be conducted under a flow of the inert gas.
  • inert gas such as nitrogen or argon.
  • step 220 the sintered mixture is dispersed in water for a period of time sufficient for sulfate salts of the active materials, and other water-soluble active material-containing compounds formed during sintering in step 215, to completely of substantially completely leach from the sintered composition into the DI water.
  • a dispersion comprising metal oxide solids dispersed in an aqueous active material(s) sulfate salt(s) solution is formed.
  • step 225 the dispersion is filtered, a raffinate (the aqueous active material(s) sulfate salt(s) solution) is recovered in step 230, and a filtrate (the insoluble metal oxide solids) is recovered in step 250.
  • a raffinate the aqueous active material(s) sulfate salt(s) solution
  • a filtrate the insoluble metal oxide solids
  • step 235 the raffinate is heated to evaporate the water solvent and the final active material(s) sulfate salt(s) of interest (for example, sulfate salts of lithium and cobalt) is/are recovered in step 240.
  • the final active material(s) sulfate salt(s) of interest can subsequently be further purified, if necessary, and recycled for future use in new batteries or other applications.
  • the filtrate is sintered (or baked) to volatize or combust organic end products, such as carbon, leaving end products comprising a metal or metals of interest, such as metal oxides, to be recovered in step 260.
  • the end products comprising the metal or metals of interest can subsequently be further purified, if necessary 7 , and recycled for future use in new batteries or other applications.
  • FIGS. 3-5 are flowcharts illustrating various exemplary methods for recovering metals of interest, such as lithium, cobalt nickel and manganese, from a spent (or used) lithium-ion battery.
  • FIG. 3 is a flowchart illustrating another exemplary 7 method for bulk recovery 7 of active materials from a spent lithium-ion battery in accordance with various aspects of the disclosure.
  • FIG. 4 is a flowchart illustrating an exemplary method for recovering individual materials (in the form of a metal sulfate salts solution) from the bulk active materials recovered in an exemplary method as illustrated in FIG. 3 in accordance with various aspects of the disclosure.
  • FIG. 5 is a flowchart illustrating an exemplary 7 method for recovering individual materials (in the form of metal oxides or metal hydroxides, and lithium carbonate) from metal sulfate salts recovered in an exemplary method as illustrated in FIG. 4 in accordance with various aspects of the disclosure. In some instances, one or more steps may be added or removed from the exemplary method without departing from the scope of this disclosure.
  • Exemplary methods according to various aspects of the disclosure as illustrated in FIGS. 3-5 utilize extraction reagent.
  • the extraction reagent is a persulfate (S20s 2 ’) salt.
  • the persulfate salt comprises an organic cation.
  • it is preferable that the persulfate salt comprises an organic cation that will volatize during a baking process (step 215, below).
  • Suitable persulfates include, but are not limited to, peroxydisulfuric acid, sodium persulfate, potassium persulfate, calcium persulfate, bis(tetrabutylammonium) peroxydisulfate, benzyltriphenylphosphonium peroxy di sulfate, choline peroxy disulfate, ammonium persulfate and combinations thereof. In some instances, the use of ammonium persulfate as the extraction reagent is preferred.
  • Certain exemplary methods according to various aspects of the disclosure as illustrated in FIGS. 3-5 utilize hydrogen peroxide in addition to the extraction reagent.
  • the hydrogen peroxide may be provided in the form of an aqueous solution containing, for example 20 to 40 %, alternatively 20 to 35 %, or alternatively 25 to 30 % hydrogen peroxide.
  • a spent lithium-ion battery is provided.
  • the type of spent lithium-ion battery is not to be used in the exemplary is not particularly limiting.
  • the lithium ion battery can be, for example, a coin cell battery, a pouch cell battery, a battery from a portable electronic device (such as a smartphone, tablet, laptop, wireless speaker, and so on), a lithium ion automobile battery, and so on.
  • the composition of the lithium-ion battery is not particularly limiting.
  • Suitable compositions of lithium-ion batteries can include, but are not necessarily limited to, lithium-ion cobalt oxide batteries, lithium-silicon batteries, lithium-ion manganese iron phosphate batteries, lithium-ion manganese-oxide batteries, lithium-ion polymer batteries, lithium-iron-phosphate batteries, lithium-nickel-manganese-cobalt oxides batteries, lithium-nickel-cobalt-aluminum oxides batteries, lithium-sulfur batteries, lithium-selenium batteries, lithium-sulfur/selenium batteries, lithium-nickel oxide batteries, lithium-manganese oxide batteries, lithium iron phosphate batteries, and lithium-titanate batteries.
  • lithium-ion batteries comprising at least lithium and cobalt may be preferred. In other instances, lithium-ion batteries comprising at least lithium, cobalt and nickel may be preferred. In other instances, lithium-ion batteries comprising at least lithium, cobalt, nickel, and manganese may be preferred. In other instances, lithium-ion batteries comprising at least lithium, cobalt, nickel, and aluminum may be preferred.
  • step 310 the spent lithium-ion battery is discharged after disabling overcharge protection.
  • the method by which the battery is discharged is not particularly limiting.
  • the battery can be discharged by, for example immersing the anode and the cathode of the battery in an aqueous sodium chloride solution.
  • step 315 the discharged battery is dismantled (or disassembled) remove the battery separator from the anode and cathode materials.
  • the anode and cathode materials are subjected to a thermal treatment to volatize and remove additives contained within the materials such a binders.
  • the thermal treatment can be conducted at a temperature ranging from about 100 °C to about 300 °C, alternatively from about 120 °C to about 250 °C, alternatively from about 140 °C to about 225 °C, alternatively from about 160 °C to about 200 °C, and alternatively from about 170 °C to about 190 °C.
  • the thermal treatment can be conducted at a temperature of about 180 °C.
  • the thermal treatment can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, alternatively from about 15 minutes to about 1 hour, and alternatively about 30 minutes.
  • the thermal treatment time and temperature may vary on the composition and amount of additives to be removed from the anode and cathode materials during the thermal treatment.
  • step 325 the thermally treated anode and cathode materials are subj ected are immersed in DI water and subjected to sonication for a period of time sufficient to separate the active metals from charge collectors (i.e., copper and aluminum foils) of the anode and cathode materials.
  • the sonication can be in the form of direct or indirect sonication using, for example, an ultrasonic bath, an ultrasonic probe or an ultrasonic hom.
  • the sonication period in this step may range from about 1 minute to about 1 hour, alternatively from about 5 minutes to about 45 minutes, alternatively from about 10 minutes to about 30 minutes, alternatively from about 10 minutes to about 15 minutes, and alternatively about 15 minutes.
  • step 330 the charge collectors are removed from the sonicated solution leaving an aqueous solution of the active materials (e.g., Li, Co, Ni, Mn, and so on depending on the battery composition).
  • the active materials e.g., Li, Co, Ni, Mn, and so on depending on the battery composition.
  • step 335 the aqueous solution of the active materials is heated to evaporate the water and result in a dried mixture of bulk active materials.
  • the dried mixture of bulk active materials may be referred to a black mass.
  • the exemplary method proceeds with steps toward recovery individual active materials of interest (in the form of a metal sulfate salts solution) from the dried bulk active materials, or black mass, as illustrated in FIG. 4.
  • FIG. 4 illustrates four separate exemplary pathways for converting the dried bulk active materials, or black mass, to solution comprising sulfate salts of the metals of interest.
  • Each of the four exemplar ⁇ ' pathways may end in a filtration step 450 to recover a raffinate 455 comprising a solution comprising sulfate salts of the metals of interest and a filtrate 460 comprising carbonaceous materials, such a graphite, of the original anode and cathode materials.
  • dried bulk active materials provided in step 405 are mixed with an extraction reagent and then sintered (or baked) in step 410.
  • mixing can be performed using, for example, a ball mill for a period of time ranging from about 30 minutes to about 4 hours, alternatively from about 1 hour to about 3 hours, and alternatively about 2 hours.
  • the dry’ active materials and extraction agent can be mixed in a dried bulk active materials-to-extraction reagent weightweight ratio ranging from about 5: 1 to about 1:5. alternatively from about 4: 1 to about 1 :4, alternatively from about 3: 1 to about 1:3, alternatively from about 2: 1 to about 1:2, and alternatively about 1: 1.
  • the bulk active materials react with the extraction reagent to form corresponding sulfates salts and/or oxides.
  • Sintering can be conducted at a temperature ranging from about 150 °C to about 700 °C, alternatively from about 200 °C to about 650 °C, alternatively from about 300 °C to about 600 °C, alternatively from about 400 °C to about 550 °C, alternatively from about 450 °C to about 550 °C, and alternatively from about 475 °C to about 525 °C.
  • the sintering temperature can be about 500 °C.
  • Sintering can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, and alternatively from about 15 minutes to about 1 hour.
  • sintering can be conducted under atmospheric pressure.
  • sintering can be conducted in at a pressure less than atmospheric pressure, such as anywhere from 0.01 to 0.99 atm.
  • sintering can be conducted in at a pressure greater atmospheric pressure, such as anywhere from 1.01 to about 10 atm.
  • sintering can be conducted in an inert gas such as nitrogen or argon.
  • sintering can be conducted in a static environment of the inert gas.
  • sintering can be conducted under a flow of the inert gas.
  • step 415 the sintered mixture is dispersed in water for a period of time sufficient for sulfate salts of the active materials, and other water-soluble active material-containing compounds formed during step 410, to completely of substantially completely leach from the sintered composition into the water.
  • the sintered mixture can be dispersed in a water at a sintered mixture-to-water weight: weight ratio of 1 : 10.
  • the relative amounts of water and sintered mixture used in step 415 can be modified as necessary to maximize the leaching process.
  • the dispersion formed in step 415 is then subjected to filtration in step 450 as discussed above for recovery of raffinate 455 and filtrate 460.
  • dry active materials provided in step 405 are mixed with an extraction reagent and then sintered (or baked) in step 420.
  • mixing can be performed using, for example, mechanical vibration for a period of time ranging from about 1 minute to about 1 hour, alternatively from about 5 minutes to about 30 minutes, alternatively from about 5 minutes to about 15 minutes, and alternatively about 10 minutes.
  • the dry active materials and extraction agent can be mixed in a dried bulk active materials-to-extraction reagent weight: weight ratio ranging from about 5: 1 to about 1:5, alternatively from about 4: 1 to about 1:4, alternatively from about 3: 1 to about 1:3, alternatively from about 2: 1 to about 1:2, and alternatively about 1: 1.
  • the bulk active materials react with the extraction reagent to form corresponding sulfates salts and/or oxides.
  • Sintering can be conducted at a temperature ranging from about 150 °C to about 700 °C, alternatively from about 200 °C to about 650 °C, alternatively from about 300 °C to about 600 °C, alternatively from about 400 °C to about 550 °C, alternatively from about 450 °C to about 550 °C, and alternatively from about 475 °C to about 525 °C.
  • the sintering temperature can be about 500 °C.
  • Sintering can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, and alternatively from about 15 minutes to about 1 hour.
  • sintering can be conducted under atmospheric pressure.
  • sintering can be conducted in at a pressure less than atmospheric pressure, such as anywhere from 0.01 to 0.99 atm.
  • sintering can be conducted in at a pressure greater atmospheric pressure, such as anywhere from 1.01 to about 10 atm.
  • sintering can be conducted in an inert gas such as nitrogen or argon.
  • sintering can be conducted in a static environment of the inert gas.
  • sintering can be conducted under a flow of the inert gas.
  • step 425 the sintered mixture is blended vigorously in an aqueous extraction reagent/FbCh solution.
  • the sintered mixture preferably has a temperature ranging from about 220 °C to about 300 °C.
  • the blending process is conducted for a period of time sufficient for sulfate salts of the active materials, and other water-soluble active material-containing compounds formed during step 420, to completely of substantially completely leach from the sintered composition into the aqueous extraction reagent/FbCh solution.
  • the blending process is conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, and alternatively from about 15 minutes to about 1 hour
  • the sintered mixture can be dispersed in a aqueous extraction reagent/tbCh solution having an extraction reagent-to-H2O2 weight: weight ratio of about 1: 10.
  • the relative amounts of water and sintered mixture used in step 425 can be modified as necessary to maximize the leaching process.
  • the reaction solution of step 425 is then subjected to filtration in step 450 as discussed above for recovery of raffinate 455 and filtrate 460.
  • dry active materials provided in step 405 are sintered (or baked) and then subjected to ball milling in step 430.
  • the sintering can be conducted at a temperature ranging from about 100 °C to about 300 °C, alternatively from about 150 °C to about 275 °C, alternatively from about 175 °C to about 250 °C, and alternatively from about 200 °C to about 250 °C.
  • the sintering temperature can be about 220 °C.
  • Sintenng can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, and alternatively from about 15 minutes to about 1 hour.
  • sintering can be conducted under atmospheric pressure.
  • sintering can be conducted in at a pressure less than atmospheric pressure, such as anywhere from 0.01 to 0.99 atm.
  • sintering can be conducted in at a pressure greater atmospheric pressure, such as anywhere from 1.01 to about 10 atm.
  • sintering can be conducted in an inert gas such as nitrogen or argon.
  • sintering can be conducted in a static environment of the inert gas.
  • sintering can be conducted under a flow of the inert gas.
  • the ball milling process can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 30 minutes to about 2 hours, and alternatively about 1 hour.
  • step 435 the sintered and milled product of step 430 is blended with an aqueous extraction reagent solution. Then, an aqueous solution of H2O2 is slowly added and the resulting mixture stirred for period of time ranging from about 15 minutes to about 4 hours, alternatively from about 30 minutes to about 3 hours, alternatively from about 30 minutes to about 2 hours, and alternatively for about 1 hour.
  • step 435 the extraction reagent and sintered and milled product (step 430) are added in amounts that provide an extraction reagent-to-dry active materials mass ratio ranging from about 10: 1 to about 1: 1, alternatively from about 8: 1 to about 1:1, alternatively from about 6: 1 to about 1: 1, alternatively from about 4 : 1 to about 1:1, alternatively from about 3 : 1 to about 1: 1, alternatively from about 3: 1 to about 2: 1, and alternatively from about 2.5: 1 to about 2.3: 1.
  • the extraction reagent and H2O2 are used in amounts that provide a mass (g) of extraction reagent to volume (ml) of H2O2 ratio ranging from about 1 : 1 to about 1 :5, alternatively from about 1: 1 to about 1 :4, alternatively from about 1: 1 to about 1:3, alternatively from about 1 : 1.5 to about 1:2.5, and alternatively about 1:2.
  • the resulting reaction solution is then subjected to filtration in step 450 as discussed above for recovery of raffinate 455 and filtrate 460.
  • dry active materials provided in step 405 are sintered (or baked) in step 440.
  • the sintering can be conducted at a temperature ranging from about 100 °C to about 300 °C. alternatively from about 150 °C to about 275 °C, alternatively from about 175 °C to about 250 °C, and alternatively from about 200 °C to about 250 °C.
  • the sintering temperature can be about 220 °C.
  • Sintering can be conducted for a period of time ranging from about 15 minutes to about 4 hours, alternatively from about 15 minutes to about 3 hours, alternatively from about 15 minutes to about 2 hours, and alternatively from about 15 minutes to about 1 hour.
  • sintering can be conducted under atmospheric pressure. In some instances, sintering can be conducted in at a pressure less than atmospheric pressure, such as anywhere from 0.01 to 0.99 atm. In some instances, sintering can be conducted in at a pressure greater atmospheric pressure, such as anywhere from 1.01 to about 10 atm. In some instances, sintering can be conducted in an inert gas such as nitrogen or argon. In some instances, sintering can be conducted in a static environment of the inert gas. [0057] In step 445. the sintered mixture is blended vigorously in an aqueous extraction reagent/H2O2 solution.
  • the sintered mixture preferably has a temperature ranging from about 180 °C to about 300 °C, even more preferably about 200 °C to about 240 °C, and in some instances about 220 °C.
  • the blending process is conducted for a period of time sufficient for sulfate salts of the active materials, and other water-soluble active materialcontaining compounds formed during step 440, to completely of substantially completely leach from the sintered composition into the aqueous extraction reagent/FbCh solution.
  • the blending is performed for period of time ranging from about 15 minutes to about 4 hours, alternatively from about 30 minutes to about 3 hours, alternatively from about 30 minutes to about 2 hours, and alternatively for about 1 hour.
  • step 445 the extraction reagent and sintered and sintered mixture (step 440) are added in amounts that provide an extraction reagent-to-dry active materials mass ratio ranging from about 1 : 1 to about 10: 1, alternatively from about 1 : 1 to about 9: 1, alternatively from about 1: 1 to about 8:1, alternatively from about 1 : 1 to about 7: 1, and alternatively from about 1: 1 to about 6: 1.
  • the extraction reagent and FhCh are used in amounts that provide a mass (g) of extraction reagent to volume (ml) of H2O2 ratio ranging from about 1 : 1 to about 1:5, alternatively from about 1 : 1 to about 1:4, alternatively from about 1 : 1 to about 1:3, alternatively from about 1: 1.5 to about 1 :2.5, and alternatively about 1:2.
  • step 445 Upon completion of step 445 is then subjected to filtration in step 450 as discussed above for recovery of raffinate 455 and filtrate 460.
  • FIG. 5 is a flowchart illustrating an exemplary method for recovering individual materials (in the form of metal oxides or metal hydroxides, and lithium carbonate) from metal sulfate salts recovered as raffinate 455 in an exemplary method as illustrated in FIG. 4 in accordance with various aspects of the disclosure. As illustrated in FIG. 5, two exemplary pathways may be taken to recover lithium, in the form of lithium carbonate, and other metals of interest in the form of metal oxides or metal hydroxides.
  • a raffinate (from step 455) is provided in a step 505.
  • the raffinate 455 subjected to drying to evaporate water and obtain dried sulfates salts of the metals of interest.
  • step 515 is subjected to sintering (or baking) at elevated temperatures, such as about 800°C, for a period of time to convert the metals of interest (for example Co. N, and Mn) to their corresponding oxides.
  • the metals of interest for example Co. N, and Mn
  • the lithium remain as a soluble sulfate salt.
  • step 520 the sintered mixture is dispersed in water and subjected to filtration to produce a filtrate of the insoluble metal oxides (recovered in step 525) and a raffinate of soluble lithium sulfate (recovered in step 530).
  • step 535 the lithium sulfate is reacted with a suitable carbonate salt, such a NaA'CU to form lithium carbonate.
  • a suitable carbonate salt such as NaA'CU
  • a raffinate (from step 455) is provided in a step 505.
  • urea is added the raffinate 455.
  • the urea reacts with metals of interest (for example Co, N, and Mn), converting them to their corresponding hydroxides.
  • metals of interest for example Co, N, and Mn
  • the lithium remain as a soluble sulfate salt.
  • step 555 the mixture resulting from step 550 is dispersed subjected to filtration to produce a filtrate of the insoluble metal oxides (recovered in step 560) and a raffinate of soluble lithium sulfate (recovered in step 565).
  • step 570 the lithium sulfate is reacted with a suitable carbonate salt, such a Na2COs, to form lithium carbonate.
  • a suitable carbonate salt such as Na2COs
  • PXRD Powder X-Ray Diffraction
  • XPS X-Ray Photoelectron Spectroscopy
  • ICP-OES Inductively coupled plasma optical emission spectroscopy
  • the cathode underwent a similar treatment process as the anode. Following a water bath, the separator was peeled off from the cathode (active materials and Al foil). The cathode was reimmersed into a water bath and the active materials (e.g., lithium-, cobalt-, nickel-containing materials, etc.) gradually fell off the Al foil with the assistance of mechanical agitation. In this experiment, magnetic stirring was used (other forms of mechanical stirring may be more efficient in scaled-up and/or industrial recycling processes). After evaporating the water out, the active materials from the cathode were obtained. Next, APS and collected active materials were mixed, at a 1 : 1 wt: wt ratio, by ball milling for 2 hours.
  • active materials e.g., lithium-, cobalt-, nickel-containing materials, etc.
  • the milled mixture was then sintered at 500 °C for 30 mins in a box furnace. Then, a leaching process was conducted.
  • the sintered materials were mixed with water at a sintered materials-to-water weight ratio of 1/10.
  • the pH value of the leaching solution was observed to be about 6.5.
  • the whole solution was passed through 50 pm filter paper to produce a clear solution (raffinate) containing COSO4 XH2O and Li2SO4 XH2O.
  • the water was from the solution was evaporated, solid COSO4 XH2O and Li2SO4 XH2O remained and were recovered.
  • the filtered insoluble materials were sintered at 800 °C for 30 mins, to obtain pure CO3O4.
  • FIG. 6 is a PXRD pattern of a sample of the milled mixture after sintered at 500 °C for 30 mins.
  • the PXRD pattern indicates that carbon (C), CO3O4 and Li2Co(SC>4)2 are the major compositional constituents of the sintered mixture. Without be bound to any particular theory’, it is believed that the reaction occurring during the ball milling and sintering steps is as shown in Equation 1:
  • Equation 3 the CoSO4 and Li2SC>4 were obtained as CoSO4 XH2O and Li2SC>4 XH2O.
  • the final product exhibited a light pink color, which is indicative of C0SO4 H2O.
  • FIG. 7 is a PXRD pattern of a sample of the final dried product obtained from the raffinate.
  • the method exemplified by this example is an improvement over pyrometallurgy and hydrometallurgy methods in the art because 1) it is strong acid-and strong base-free, 2) the entire method is marked by low potential hazard and minimal waste generation due to the use of water and extractive reagents that are free of heavy and toxic metals, and 3)the method requires low energy’ consumption, particularly with respect to the temperature (thermal input) requirements of numerous steps of the method, compared to similar pyrometallurgical and/or hydrometallurgical methods.
  • the black mass may contain one or more cathode materials.
  • the black mass component obtained by disassembling an iPhone battery is a mixture of LiCoCh and graphite. If you disassemble batteries from both iPhone and Hewlett Packard (HP) laptops, the black mass will contain LiCoCh, LiNiCh, Li(NisCoiMm)O2, and graphite.
  • Example 2 the black mass of Example 2 was subjected to an extraction process using APS as the extraction reagent.
  • APS power and black mass (1 : 1 weight ratio) were mixed by ball milling for 2 hours, then sintered at 500 °C for 30 mins in the box furnace.
  • the sintered materials were mixed with water at a material-to-water weight ratio of 1/10.
  • the solution was filtered using 50 pm filter paper.
  • the filtered solution (raffinate) was a metal sulfate solution, and the remaining solid (filtrate) was graphite which can be directly recovered.
  • the leaching efficiency of the main recovered elements are listed in Table 1.
  • the sintering temperature of this example is raised to 600 °C and the sintering time is increased to 120 min. Under these conditions, graphite can be completely removed and filtered to obtain a metal sulfate solution and an iron phosphate solid.
  • Example 2 the black mass of Example 2 was subjected to an extraction process using APS as the extraction reagent in conjunction with H2O2.
  • APS power and black mass (1:1 weight ratio) were mixed by mechanical vibration for 10 min, then sintered at 500 °C for 30 mins in a box furnace.
  • the sintered materials were directly added to a vigorously stirring blender while the black mass was still hot (around 220 to 300 °C).
  • In the blender was a solution of APS and H2O2 a having an APSiFLCh weight ratio of 1/10. After 30 minutes of stirring and leaching, the solution was filtered using 50 pm filter paper.
  • the filtered solution (raffinate) is a metal sulfate solution, and the remaining solid (filtrate) is graphite which can be directly recovered.
  • the leaching efficiency of the main recovered elements are listed in Table 2. The efficiency of extraction was calculated as described in Example 3.
  • the sintering temperature in this example is raised to 600 °C and the sintering time is increased to 120 min. Under these conditions, graphite can be completely removed and filtered to obtain a metal sulfate solution and an iron phosphate solid. If the black mass contains LiFePO4 and any one or more other cathode materials (LiCoCh, Li(Ni8CoiMm)O2, Li(NisCoiAli)O2, LiNiCh, LiMnCh), it should be sintered under 600 °C for 120 min to completely remove graphite and then ball milled for 60 min.
  • LiCoCh Li(Ni8CoiMm)O2
  • Li(NisCoiAli)O2 LiNiCh, LiMnCh
  • the sintered black mass can then be added to an APS solution at a black mass/solution weight ratio of 1/20, and then H2O2 is slowly added. After 60 min stirring, the solution will be filtered using 50 pm filter paper.
  • the filtered solution (raffinate) is a metal sulfate solution, and the remaining solid (filtrate) is LiFePO4.
  • the LiFePOi can then be added to a new APS solution at 60 °C for 60 min and filtered by 50 gm filter paper.
  • the resulting filtered solution (raffinate) is lithium sulfate solution and remaining solid (filtrate) is iron phosphate.
  • the black mass of Example 2 was subjected to an extraction process using APS as the extraction reagent in conjunction with H2O2.
  • the black mass was sintered at 220 °C for 30 mins in a box furnace and the ball milled for 60 minutes.
  • the sintered black mass was then added to an APS solution at 60°C with a black mass/solution weight ratio of 1/20, and is then H2O2 (25 % solution) is slowly added until a mass (g) to volume (ml) ratio of APS to H2O2 of 1:2 is reached.
  • the solution was filtered using 50 pm filter paper.
  • the filtered solution (raffinate) is a metal sulfate solution, and the remaining solid (filtrate) is graphite which can be directly recovered.
  • the optimal mass ratio of APS to black mass is 2.4: 1.
  • the leaching efficiency of the main recovered elements are listed in Table 3. The efficiency of extraction was calculated as described in Example 3.
  • the sintering temperature in this example is raised to 600 °C and the sintering time is increased to 120 min, and the resulting sintered product is ball milled for 60 minutes. Under these conditions, graphite can be completely removed after sintering. After that, the remaining material is added to an APS solution at 60 °C for 60 min without H2O2 and then filtered by 50 pm filter paper. The resulting solution is a lithium sulfate solution and the remaining solid is iron phosphate.
  • the black mass contains LiFePOi and any one or more other cathode materials (LiCoCh, Li(Ni8CoiMm)O2, LitNisCoiAlijCh, LiNiCh, LiMnCh), it should be sintered under 600 °C for 120 min to completely remove graphite and then ball milled for 60 min.
  • the sintered black mass can then be added to an APS solution with a solid-liquid ratio of 1/20, and then added H2O2 slowly. After 60 minutes of stirring, the solution is filtered using 50 pm filter paper.
  • the filtered solution (raffinate) is a metal sulfate solution, and the remaining solid (filtrate) is LiFePOi.
  • the LiFePOi is then added to a new APS solution at 60 °C for 60 min and filtered by 50 pm filter paper.
  • the resulting filtered solution (raffinate) is lithium sulfate solution and remaining solid (filtrate) is iron phosphate.
  • Example 2 the black mass of Example 2 was subjected to an extraction process using APS as the extraction reagent in conjunction with H2O2.
  • the black mass was sintered under 220 °C for 30 min and then directly added to a vigorously stirring blender while the black mass was still hot (220 °C).
  • In the blender was the solution of APS and H2O2 (mass (g) to volume (ml) ratio of APS to H2O2 of 1:2).
  • the solid-liquid ratio of black mass to APS-H2O2 solution was 1/20.
  • the strong shear of the stirring paddles and the high temperature of the powder were utilized to significantly increase the reaction rate.
  • the filtered solution was a metal sulfate solution, and the remaining solid was graphite which can be directly recovered.
  • the black mass only contains LiFePCh and graphite, it should be sintered under 600 °C for 120 min and then ball milled for 60 min and then directly added to a vigorously stirring blender while the black mass was still hot (around 220 to 300 °C).
  • a vigorously stirring blender In the blender was the solution of APS and H2O2.
  • the solid-liquid ratio of black mass to APS-H2O2 solution was 1/20.
  • the solution is then filtered through 50 pm filter paper.
  • the filtered solution (raffinate) is a lithium sulfate solution, and the remaining solid (filtrate) is FePOi
  • the black mass contains LiFcPOi and any one or more other cathode materials (LiCoCh. LifNisCoiMnijOz, LifNisCoiAlijCh, LiNiCh, LiMnCh), it should be sintered under 600 °C for 120 min to completely remove graphite and then directly added to a vigorously stirring blender while the black mass is still hot (for example, around 220 °C).
  • a vigorously stirring blender In the blender is a solution of APS and H2O2 as described above in this example. After stirring for 60 min, the solution is filtered through 50 pm filter paper.
  • the filtered solution (raffinate) is a metal sulfate solution, and the remaining solid (filtrate) is LiFePCL which can be directly recovered. After that, the LiFePCL is added to APS solution at 60 °C for 60 min without H2O2 and then filtered by 50 pm filter paper. The resulting solution (raffinate) is a lithium sulfate solution and remaining solid (filtrate) is iron phosphate.
  • raffinates containing sulfate salts of metals on interest were obtained.
  • a method is provided to separate the individual metal elements.
  • a raffinate solution containing sulfate salts of metals on interest was evaporated to produce a powder.
  • the powder was sintered in a box furnace at 800 °C for up to 30 mins and then dispersed into DI water.
  • the dispersion was then filtered, to produce an insoluble filtrate of metal oxides (e.g., CO3O4, NiO, and MnCh) and a raffinate solution of lithium sulfate.
  • Excess sodium carbonate was then added to the lithium sulfate solution and heated to 90 °C to produce solid lithium carbonate, which was recovered by hot filtration.
  • sintering temperature should be above 600 °C and below 860 °C in view of the decomposition temperature of certain transition metal sulfates formed during the process (around 600 °C) and the decomposition temperature of lithium sulfate (around 860 °C). Lower sintering temperatures require longer sintering times. The sintering time at 600 °C should be around 120 min.
  • the type of metal oxide(s) obtained will depend on the composition of the black mass. If the black mass contains only a single ty pe of anode material, then the resulting metal oxide is a single component material. If the black contains more than one anode material, then a mixture of metal oxides will be present.
  • Examples 3-6 raffinates containing sulfate salts of metals on interest (Li, Co, Ni and Mn) were obtained. In this example, another method is provided to separate the individual metal elements.
  • metal hydroxides e.g., Co(OH)2, Ni(0H)2 and Mn(0H)4
  • Lithium carbonate precipitate is obtained by adding excess sodium carbonate to the filtered solution containing lithium hydroxide, which could be recovered by filtration.
  • FIG. 10 provides a graphical overview of the advantages and shortcomings of prior art methods for the recovery' of lithium and other metals of interest from spent lithium-ion batteries. Compared with these methods, some notable advantages of the novel and inventive compositions and methods described herein are as follows: [00102] Low temperature treatment, low energy consumption and low cost

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Abstract

L'invention concerne des compositions et des procédés de recyclage de matériaux de batteries lithium-ion. Plus particulièrement, l'invention concerne des compositions exemptes d'acides et de bases et des procédés de récupération de lithium et d'autres matériaux valorisables tels que le Ni, le Co, le Mn, le Cu, l'Al, le graphite, etc. présents dans des matériaux de batteries contenant du lithium pour une purification et une réutilisation ultérieures. Certains procédés de récupération de lithium à partir d'une batterie lithium-ion consistent à isoler un matériau en vrac d'une cathode ou de la cathode et d'une anode d'une batterie lithium-ion, le matériau en vrac comprenant du lithium, à faire réagir le matériau en vrac avec un composé persulfate pour former du sulfate de lithium ou un hydrate de celui-ci, et à récupérer le sulfate de lithium ou l'hydrate de celui-ci.
PCT/US2024/042813 2023-08-16 2024-08-16 Compositions et procédés de recyclage de matériaux de batteries lithium-ion Pending WO2025038980A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190207275A1 (en) * 2016-05-20 2019-07-04 HYDRO-QUéBEC Process for the recycling of lithium battery electrode materials
US20220009793A1 (en) * 2020-07-10 2022-01-13 Hatch Ltd. Process and method for producing crystallized metal sulfates
WO2022026530A1 (fr) * 2020-07-31 2022-02-03 Refined Technologies, Inc. Procédés d'oxydation pour catalyseurs autochauffants et pyrophoriques contenant des sulfures métalliques actifs, et atténuation des mécanismes de fissuration par corrosion sous contrainte d'halogénure et d'acide polythionique dans un équipement de traitement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190207275A1 (en) * 2016-05-20 2019-07-04 HYDRO-QUéBEC Process for the recycling of lithium battery electrode materials
US20220009793A1 (en) * 2020-07-10 2022-01-13 Hatch Ltd. Process and method for producing crystallized metal sulfates
WO2022026530A1 (fr) * 2020-07-31 2022-02-03 Refined Technologies, Inc. Procédés d'oxydation pour catalyseurs autochauffants et pyrophoriques contenant des sulfures métalliques actifs, et atténuation des mécanismes de fissuration par corrosion sous contrainte d'halogénure et d'acide polythionique dans un équipement de traitement

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