US20130206607A1 - Lithium Extraction Method, and Metal Recovery Method - Google Patents

Lithium Extraction Method, and Metal Recovery Method Download PDF

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US20130206607A1
US20130206607A1 US13/818,926 US201113818926A US2013206607A1 US 20130206607 A1 US20130206607 A1 US 20130206607A1 US 201113818926 A US201113818926 A US 201113818926A US 2013206607 A1 US2013206607 A1 US 2013206607A1
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lithium
leaching
ion
solution
cobalt
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Yasuko Kojima
Yoshihide Yamaguchi
Masahide Okamoto
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Hitachi Ltd
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Hitachi Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 metal recovery technique for simply recovering metals from batteries.
  • Non Patent Literature 1 features the techniques for recycling lithium ion batteries, and systematically describes the methods for recovering valuable metals constituting lithium ion batteries.
  • spent lithium ion batteries are subjected to mechanical separating such as unsealing, dismantling and shredding, then valuable metals are leached by acid leaching, and from the acid-leached metals, each of the components is separated and made to form precipitates by taking advantage of the differences between the solubility properties of the desired components, or alternatively, each of the desired components is separated and recovered by applying processing such as preferential solvent extraction of each of the desired components.
  • Patent Literature 1 also discloses a technique to recover copper and cobalt by using a leached solution of valuable metals obtained by acid leaching as a catholyte, and by applying diaphragm electrolysis method with a cation exchange membrane as the diaphragm.
  • Patent Literature 1 Japanese Patent No. 3675392
  • Patent Literature 2 Japanese Patent No. 3980526
  • Patent Literature 3 JP-A-11-292533
  • Non Patent Literature 1 Jinqiu Xu et al., “A review of processes and technologies for the recycling of lithium-ion secondary batteries,” Journal of Power Sources, vol. 177, pp. 512 to 527 (2008)
  • Non Patent Literature 1 aims at, with the aid of various contrivances, the establishment of compatibility between the improvement of the yield of valuable substances and the achievement of high purities of the recovered substances; however, there is a large room for improvement in the fact that the steps involved are cumbersome and a huge equipment investment is required for the processing of a large amount of waste batteries.
  • Patent Literature 1 specifically, an apparatus (a diaphragm electrolysis tank shown in FIG. 2 of Patent Literature 1) utilizing the ion selectivity possessed by a cation exchange membrane and a diffusion dialysis apparatus (not shown) utilizing the anion selective properties of an anion selective membrane are used.
  • the main valuable metals can be recovered by the following series of processings: the electrodeposition recovery of copper by diaphragm electrolysis ⁇ pH control ⁇ the electrodeposition recovery of cobalt by diaphragm electrolysis ⁇ pH control ⁇ the precipitation recovery of Fe(OH) 3 and Al(OH) 3 ⁇ the recovery of Li 2 CO 3 by addition of a carbonate.
  • the recovery of about 100 kg of cobalt requires a continuous flow of an electric current of 1 ampere for 100 hours, and preceding the recover of cobalt, a nearly the same quantity of electricity is applied in the electrodeposition of copper, hence the recovery of all the metals only by diaphragm electrolysis requires unexpected time and labor.
  • the multiple stages of pH control increase the liquid quantity at every stage, and hence when Li 2 CO 3 is recovered at the final stage of the series of processings, the Li concentration is decreased and even the addition of a carbonate does not necessarily leads to the increase of the Li yield. This is because the saturated solubility of lithium carbonate is as high as 1.3 wt % at 20° C., and hence the amount of unrecovered component is increased with the increase of liquid quantity.
  • Fe(OH) 3 and Al(OH) 3 each have a tendency to be gelated in a weakly acidic to neutral aqueous solution, and hence the operation in the step of filtrating recovery of Fe(OH) 3 and Al(OH) 3 on the basis of the technique of Patent Literature 1 is not easy.
  • the dilution of the solution for facilitation of the filtration operation results in a decrease of the Li yield. Since the surface of the gel-like precipitation of Fe(OH) 3 or Al(OH) 3 has a characteristic of absorbing Li ion, also from the viewpoint of this absorption, it is difficult to significantly improve the Li yield.
  • the present invention is characterized in that lithium is selectively leached from the cathode material containing lithium and transition metals, and the leaching is terminated while the ratio of the leached amount of lithium to the leached amount of cobalt is large.
  • a method for recovering lithium in a simple and easy manner and highly efficiently from lithium ion batteries can be provided.
  • FIG. 1 is a table showing compositions of the leaching liquids according to Examples of the present invention and the Li/Co ratios obtained with the leaching liquids.
  • FIG. 2 is a schematic flow chart of the steps of recovering valuable metals in Example 1 according to the present invention.
  • FIG. 3 is a table showing the examples of the concentration ratio of lithium ion to sulfuric acid in the acid leaching treatment.
  • FIG. 4 is a schematic flow chart of the steps of recovering valuable metals in Example 2 according to the present invention.
  • FIG. 2 is a schematic flow chart of the steps of recovering valuable metals from waste lithium batteries (hereinafter, waste batteries) in present Example.
  • the individual constituent members obtained by dismantling the waste batteries (S 101 ) are sorted according to the types of the individual members (S 102 ), and only the electrode active material containing valuable metals in high concentrations is extracted.
  • the electrode active material thus extracted is treated with a Li-selective leachate (Li-selective leaching; S 103 ) to yield a Li-leaching solution.
  • the Li-leaching solution and the non-leached fraction are subjected to solid-liquid separation (S 104 ).
  • the recovery of valuable metals from waste batteries first requires the dismantling of the batteries, however, before the dismantling, the batteries are discharged because charge may remain stored in the batteries.
  • the charge remaining stored in the batteries are discharged by soaking the batteries in an electrolyte-containing conductive liquid.
  • This discharge operation enables the Li ions scattered in each of the batteries to be concentrated within the cathode active material, and enables the Li yield to be maximized.
  • the Li selectivity is maximized.
  • the cathode active material is LiCoO 2
  • the completely charged condition is said to be Li 0.4 CoO 2
  • the completely discharged condition is said to be LiCoO 2 , so that the omission of the discharge treatment results in a risk of the Li recovery loss of at most about 60%.
  • the discharge provides an advantage capable of ensuring the safety.
  • the electrolyte-containing conductive liquid a sulfuric acid/y-butyrolactone mixed solution was used as the electrolyte-containing conductive liquid.
  • sulfuric acid acts as an electrolyte, and hence by regulating the sulfuric acid concentration, the electroconductivity (reciprocal of resistance value) can be regulated.
  • the electric resistance between the right end and the left end of the electrolysis tank was actually measured to be 100 k ⁇ .
  • a too small resistance of the solution leads to a risk of a too rapidly proceeding discharge, and on the contrary, a too large resistance leads to degradation of practicability because of too long discharge time.
  • the waste batteries of present Example include, for example, in addition to so-called spent batteries in which the predetermined limit of the charge-discharge cycle number is reached and the charging capacities are completely decreased, the pre-products occurring due to the failures in the battery production steps, and older-type clearance products in stock occurring due to product specification changes.
  • the waste batteries subjected to discharge treatment are dismantled.
  • the battery constituent members such as cases, packings and safety valves, circuit elements, spacers, current collectors, separators, cathode and anode electrode active materials are dismantled and separated according to the types of the individual members.
  • the interior of the waste batteries is often filled with gas to be in a pressurized condition, and hence, needless to say, consideration of safety in operation is necessary.
  • the waste batteries were elutriated while the waste batteries are being soaked and cooled in the electrolyte-containing conductive liquid. The adoption of the elutriation under cooling enabled the fragmentation to be safely performed without scattering the gas filled in the interior of the batteries in the air.
  • the regulation of the composition of the electrolyte-containing conductive liquid is permissible.
  • the conductivity is the property to be noted
  • the conductive liquid used in the elutriation step the viscosity and the dielectric constant are the properties to be noted.
  • the discharge step and the elutriation step are different in the required specifications, and hence the composition of the conductive liquid may be changed according to the steps.
  • two or more types of conductive liquids are required to be prepared.
  • the compositions of these conductive liquids were set to be the same.
  • Examples of the elutriation methods usable in the present Example include, without necessarily being limited to, a method using a ball mill.
  • a method using a ball mill By omitting the roasting step before the shredding is performed, lithium cobalt oxide and polyvinylidene fluoride (PVFD) serving as a binder are not mixed with each other, and lithium and cobalt can be recovered with satisfactory purities.
  • PVFD polyvinylidene fluoride
  • the cathode material made to be water repellent affects the below-described lithium extraction step.
  • the waste batteries are fragmented under the conditions that the electrode active material of the cathode (hereinafter, the cathode active material) and the electrode active material of the anode (hereinafter, the anode active material) are preferentially fragmented among the constituent members such as cases, packings and safety valves, circuit elements, spacers, current collectors, separators and electrode active materials, then the resulting shredded matter is subjected to sieving. In this way, the cathode active material and the anode active material are separated and recovered under the sieve, and the rest of the shredded matter is separated and recovered on the sieve (S 102 ).
  • the yield may also be improved.
  • the members such as cases, packings and safety valves, current collectors (aluminum foil, copper foil) are larger in deferred malleability than the cathode active material (typically, LiCoO 2 ) and the anode active material (typically graphite), and accordingly also larger in strength at fracture. Because of this property, the fragmented matter of the electrode active materials is smaller in size than the fragmented matters obtained from the members other than the electrode active materials, and consequently, the electrode active materials can be easily separated and recovered by sieving or filtrating.
  • the matter under the sieve obtained by the foregoing treatment is subjected to the leaching treatment (S 103 ).
  • the leaching liquids used in present Example are shown as examples in FIG. 1 .
  • the cathode active material of the waste batteries used in the present Examples is a lithium compound mainly composed of LiCoO 2 , and may include the cathode active materials having other compositions including, for example, iron phosphate, nickel and manganese.
  • an acid solution prepared by adding hydrogen peroxide aqueous solution as an oxidation-reduction control agent to concentrated sulfuric acid (90% to 98%) is used.
  • Those mineral acids that contain the alkali metals (sodium, potassium, rubidium and cesium) other than lithium, difficult to be separated from lithium, are not to be used.
  • the mineral acids to be used can be appropriately selected.
  • H 2 SO 4 , LiCoO 2 and H 2 O 2 are allowed to react with each other to produce Li 2 SO 4 , CoO and CoSO 4 .
  • This reaction is divided into two stages. In the first stage, while the crystal structure is being maintained, the lithium ion in the cathode material and the proton in the solution are exchanged. In the second stage, the crystal structure starts to collapse due to the increase of the amount of lithium eluted from the crystal structure of the cathode material. In this case, the ion elution behavior is changed and the elution of cobalt ion is also made easy. Accordingly, it is important that lithium is dissolved before the collapse of the crystal structure and the dissolution reaction is terminated before the crystal structure collapses and the amount of the elution of cobalt becomes large.
  • the present Example when sulfuric acid and hydrogen peroxide are allowed to react with the cathode material, first lithium ion leaches into the solution due to the easiness in reaction based on the reaction energy, and subsequently, cobalt ion leaches.
  • a selective acid dissolution can be performed in such a way that the lithium ion concentration is higher relative to the cobalt ion concentration.
  • the selective acid leaching is performed by controlling the reaction conditions of the Li selective leaching step, and the leaching is terminated within a reaction percentage range of the lithium ion of at most 80% or less (the residual proportion is 20% or more).
  • reaction percentages exceeding 80% enhance the risk of the degradation of the selection ratio in the Li selective leaching reaction, and reaction percentages lower than 70% decrease the yield to impair the economic efficiency.
  • the acid leaching treatment is performed at a temperature of 50° C. or lower.
  • the action of sulfuric acid allows lithium ion to leach as lithium sulfate (Li 2 SO 4 ), and cobalt ion to leach as cobalt sulfate (CoSO 4 ).
  • the activation energy for lithium ion to leach is remarkably smaller than the activation energy for cobalt ion to leach, and consequently, the lithium ion leaches in advance of the cobalt ion.
  • This reaction selectivity appears more remarkably at lower temperatures. This is because at higher temperatures, the thermal energy is abundant and the effect of the magnitude of the activation energy on the reaction selectivity is smaller.
  • the solubility of lithium sulfate is increased with the decrease of the temperature and the solubility of cobalt sulfate is increased with the increase of the temperature, by performing the treatment at a low temperature of 50° C. or lower, the selective dissolution of lithium can be enhanced. This is because when the dissolution amount of cobalt sulfate is small, the leaching amount of the cobalt ion forming cobalt sulfate is also small. In addition, since the dissolution rate of the ion is slow, the lithium ion which tends to be dissolved stably can be dissolved in advance of the cobalt ion.
  • the sulfuric acid to be used is preferably concentrated sulfuric acid (90% or more). Diluted sulfuric acid acts as a strong acid, and dissolves both lithium and cobalt at fast rates. On the other hand, when concentrated sulfuric acid is used, the content of isolated acid is small so that it does not act as a strong acid. Consequently, when concentrated sulfuric acid is used (also when the 90% sulfuric acid is diluted to some extent), the concentrated sulfuric acid does not act as a strong acid as the diluted sulfuric acid, and hence the dissolution rate of the metal ion becomes slow to facilitate the control of the dissolution rates of lithium and cobalt.
  • the dissolution amount of cobalt sulfate which has a sulfate ion, becomes small in a solution having a small pH to enhance the lithium ion selectivity.
  • FIG. 3 shows the examples of the concentration ratio of lithium ion to sulfuric acid during the acid leaching treatment.
  • Hydrogen peroxide is used as an oxidation-reduction control agent for regulating the electric potential in the acid solution, increased by the dissolution. This is because the electric potential falling out of the predetermined range affects the selective solubility.
  • FIG. 1 shows Li/Co concentration ratios of the acid leachates obtained by dismantling spent lithium ion batteries for use in digital cameras.
  • the spent lithium ion battery was processed as follows.
  • the waste lithium ion battery was subjected to the shredding process and the sieving process to beforehand remove the members such as a case, packing and safety valve, circuit elements, separators and current collectors, and then the valuable metals constituting the lithium ion battery were subjected to acid leaching (dissolving) by using mineral acids.
  • the Li-selective leaching liquids used in the present Example are shown in FIG. 1 .
  • the resulting leachate was stirred at room temperature for 1 hour, subjected to centrifugal separation with a centrifuge separator at 15000 rpm, at 20° C. for 15 minutes, thus a supernatant and a residue were separated to terminate the leaching reaction, and the supernatant was recovered.
  • the centrifugal separation was adopted as the solid-liquid separation to simply terminate the Li leaching reaction from the cathode active material such as lithium cobalt oxide.
  • the acid used in the leaching liquid As the acid used in the leaching liquid, nitric acid, sulfuric acid and hydrochloric acid were used. To these acids, the oxidation-reduction control agent such as methanol or hydrogen peroxide was added. The addition of the oxidation-reduction control agent provides an effect to stabilize the acid leaching and the effect to increase the recovery amount.
  • the leaching time is preferably at the longest 2 hours or less and more preferably about 1 hour. The leaching for a short time significantly less than 1 hour, for example, 15 minutes tends to give a small yield.
  • the crystal structure of the cathode active material from which lithium ion has been removed by leaching is not stable against a strong acid, and accordingly when a leaching treatment for a long time exceeding 2 hours is performed, the crystal of the cathode active material collapses to start the leaching of cobalt. Consequently, the Li selectivity in the acid leaching reaction is degraded.
  • the leaching liquid temperature may not reach the leaching liquid temperature of 80° C. to 90° C. adopted in the nonselective leaching (complete leaching) described in Non Patent Literature 1.
  • the leaching liquid temperature is most preferably room temperature (15° C. to 30° C.), and the highest acceptable temperature is 50° C. or lower. When the leaching liquid temperature significantly exceeded 50° C., the Li selectivity tended to be degraded in the leaching reaction.
  • FIG. 1 shows results obtained by performing the leaching reaction under respective dissolution conditions at 20° C. (exclusive of the case of hot water) for 1 hour.
  • the Li/Co concentration ratio of the acid leachate was about 0.2.
  • the acid leaching liquid was composed only of sulfuric acid
  • the Li/Co concentration ratio was about 1.2
  • the acid leaching liquid was composed only of nitric acid
  • the Li/Co concentration ratio was about 0.8.
  • the Li/Co concentration ratio was about 1.7.
  • the recovery solution (A) obtained by the selective leaching in addition to Li, the acid added excessively at the time of the acid leaching is simultaneously recovered.
  • the residue left after the completion of the leaching treatment is composed of the transition metal component of the anode active material and the cathode active material.
  • the acidic solution, the anode active material and the cathode active material can be easily separated from each other by taking advantage of the different specific gravities thereof ((S 104 ) in FIG. 2 ). Specifically, these can be separated from each other by performing centrifugal separation of the leachate.
  • the separation and recovery were performed by adopting centrifugal separation and treating at 15000 rpm for 15 minutes, a more larger frequencies of rotation facilitates the mutual separation of the supernatant acidic solution (recovery solution, Li), the anode active material (C: carbon) and the cathode active material (Co).
  • the leachate can be separated into the supernatant and the residue (the anode active material and the cathode active material) to be recovered.
  • a step of further separating the residue into the anode active material and the cathode active material is to be performed.
  • the Li-containing supernatant may be subjected to further separation of lithium and cobalt by performing the treatments such as a diffusion dialysis treatment or a pressure dialysis treatment using an anion exchange resin, and an ion exchange resin treatment, each alone or in combinations, or in multi-stages,.
  • lithium and cobalt can be further separated, for example, by using a dialysis treatment using an anion permselective membrane, a solvent extraction method or an acid retardation method.
  • High-purity lithium can be recovered (S 105 ) by neutralizing the recovery solution (A) having a large content proportion of lithium obtained as described above with a carbonate containing no sodium.
  • lithium can be recovered by precipitation as lithium carbonate by adding calcium carbonate or a carbonate containing no sodium. Additionally, for example, there is a method in which CO 2 gas is made to blow in while the electrodialysis is being performed.
  • the transition metal component (B) can be separated and recovered from the Li-containing solution (A) by the centrifugal separation step taking advantage of the specific gravity difference (S 106 ).
  • the cathode active material is recovered (S 107 ). Then, the cathode material is soaked in an acidic solution and cobalt ion is leached (or eluted). To the solution in which cobalt ion is leached, a precipitation recovery method in which cobalt is precipitated and recovered as hydroxide by pH control can be used (S 108 ).
  • the transition metal component (B) is dissolved in an acid, then by a treatment utilizing the solubility property difference between the hydroxides of the individual metal elements, basically by repeating a cycle of pH control and recovery by precipitation, each of the transition metal elements can be separated and recovered.
  • the cathode active material contains lithium compounds other than LiCoO 2
  • the cathode active material is LiNiO 2 , LiMnO 2 , Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2
  • one of olivine-based cathode materials such as LiCoPO 4 , LiFePO 4 , LiCoPO 4 F and LiFePO 4 F, Co, Ni, Mn and Fe can be separated as hydroxides and recovered by precipitation by the pH control of the solution.
  • FIG. 4 shows a flow chart of the metal recovery method in Example 2.
  • S 201 and 5202 are the same as S 101 and S 102 in Example 1, respectively.
  • the cathode material is subjected to acid leaching in the same manner as in Example 1, and then the resulting leachate is separated into a supernatant and a residue.
  • the supernatant is an acidic solution in which lithium ion and cobalt ion are leached and the Li/Co ratio is high, and the residue is the cathode active material left after the leaching of the anode active material and ions.
  • a method such as centrifugal separation or filtration, these are separated into the supernatant and the residue.
  • the lithium ion and the cobalt ion in the supernatant obtained in S 203 are separated.
  • Examples of the separation method include the following.
  • lithium ion and cobalt ion can be separated.
  • the anion permselective membrane is a membrane allowing anions to permeate, however, although lithium ion is a cation, a phenomenon occurs in which lithium ion permeates the anion permselective membrane. Consequently, when the acidic solution in which ions were leached in S 203 is made to flow on one side of the anion permselective membrane, and a recovery liquid (for example, pure water) for recovering lithium ion is made to flow on the other side, lithium ion permeates the dialysis membrane and transfers from the acidic solution into the recovery liquid. In this case, cobalt ion does not permeate the dialysis membrane and stays in the acidic solution. In this way, the lithium ion can be separated into the recovery liquid, and the cobalt ion can be separated in the acidic solution.
  • the lithium ion and the cobalt ion can be separated.
  • the acid retardation is known in which when an acidic solution is made to pass through the ion-exchange resin, first a salt of the acid is eluted, and subsequently the acid is eluted.
  • the lithium ion and the cobalt ion are contained as the salts of the acid, first the cobalt ion is eluted and subsequently the lithium ion is eluted, and finally the acid is eluted.
  • the solution eluted first is large in the cobalt ion concentration
  • the solution eluted subsequently is large in the lithium ion concentration, and thus, the lithium ion and the cobalt ion can be separated.
  • the supernatant can be separated into the Li concentrated solution having a high Li/Co concentration ratio and the Co concentrated solution having a low Li/Co concentration ratio.
  • Example 2 in this way, lithium and Co are recovered. As compared to Example 1, in addition to the step of separating lithium and Co, the obtained Li concentrated solution and the Co concentrated solution are respectively collected and recovered, and thus the yields of lithium and Co are improved.

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US20150247216A1 (en) * 2012-10-10 2015-09-03 Rockwood Lithium GmbH Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells
US20150267277A1 (en) * 2012-10-10 2015-09-24 Rockwood Lithium GmbH Method for the hydrometallurgical recovery of lithium from the fraction of used galvanic cells containing lithium, iron and phosphate
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US20150247216A1 (en) * 2012-10-10 2015-09-03 Rockwood Lithium GmbH Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells
US20150267277A1 (en) * 2012-10-10 2015-09-24 Rockwood Lithium GmbH Method for the hydrometallurgical recovery of lithium from the fraction of used galvanic cells containing lithium, iron and phosphate
US9677153B2 (en) * 2012-10-10 2017-06-13 Rockwood Lithium GmbH Method for the hydrometallurgical recovery of lithium from the fraction of used galvanic cells containing lithium, iron and phosphate
US9702024B2 (en) * 2012-10-10 2017-07-11 Rockwood Lithium GmbH Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells
EP3459138B1 (fr) 2016-05-20 2023-11-01 Hydro-Québec Procédé pour le recyclage de matériaux d'électrode de batterie au lithium
CN107022683A (zh) * 2017-03-29 2017-08-08 华南师范大学 一种锂离子电池钴酸锂正极材料的回收方法
WO2019121086A1 (en) * 2017-12-19 2019-06-27 Basf Se Battery recycling by treatment of the leach with metallic nickel
US12018350B2 (en) 2018-01-30 2024-06-25 Dusenfeld Gmbh Method for recycling lithium batteries
CN108878866A (zh) * 2018-06-28 2018-11-23 山东理工大学 利用废旧锂离子电池三元正极材料制备三元材料前驱体及回收锂的方法
TWI729543B (zh) * 2018-10-31 2021-06-01 日商Ｊｘ金屬股份有限公司 鋰離子二次電池之正極活性物質廢棄物之處理方法
CN109837392A (zh) * 2019-01-25 2019-06-04 宁波行殊新能源科技有限公司 锂离子电池正极材料废料的回收及再生方法
US11476510B2 (en) 2019-05-07 2022-10-18 Chang Dong Methods and green reagents for recycling of lithium-ion batteries
CN112310499A (zh) * 2019-07-31 2021-02-02 中国科学院过程工程研究所 一种废旧磷酸铁锂材料的回收方法、及得到的回收液
WO2022119565A1 (en) * 2020-12-02 2022-06-09 U.S. Borax Inc. A lithium extraction process and apparatus
US11873540B2 (en) 2020-12-02 2024-01-16 Us Borax Inc. Lithium extraction process and apparatus
CN114606386A (zh) * 2022-03-31 2022-06-10 东北大学 一种废弃锂电池磨浸回收钴和锂的工艺
DE102022004722A1 (de) 2022-12-15 2024-06-20 Tadios Tesfu Mehrstufiges Recyclingverfahren
EP4400616A2 (de) 2022-12-15 2024-07-17 Tesfu Tadios Mehrstufiges recyclingverahren

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