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WO2013172533A1 - Procédé de récupération de métal depuis une solution, système de récupération de métal depuis une solution, et système de récupération de lithium depuis de l'eau salée - Google Patents

Procédé de récupération de métal depuis une solution, système de récupération de métal depuis une solution, et système de récupération de lithium depuis de l'eau salée Download PDF

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Publication number
WO2013172533A1
WO2013172533A1 PCT/KR2013/000353 KR2013000353W WO2013172533A1 WO 2013172533 A1 WO2013172533 A1 WO 2013172533A1 KR 2013000353 W KR2013000353 W KR 2013000353W WO 2013172533 A1 WO2013172533 A1 WO 2013172533A1
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Prior art keywords
electrode
metal
solution
lithium
ions
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Ceased
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English (en)
Korean (ko)
Inventor
윤제용
이재한
김춘수
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SNU R&DB Foundation
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SNU R&DB Foundation
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Priority to US14/401,467 priority Critical patent/US20150129433A1/en
Priority to EP13790312.6A priority patent/EP2851454A4/fr
Publication of WO2013172533A1 publication Critical patent/WO2013172533A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof

Definitions

  • the present invention relates to a method for recovering metal and a system therefor, and more particularly, to a method for recovering metal from a liquid, a system for recovering metal from a solution and a system for recovering lithium from brine. .
  • Lithium is widely used in various industries such as secondary batteries, glass, ceramics, alloys, lubricants, and pharmaceuticals.
  • lithium secondary batteries have recently attracted attention as a major power source for hybrid and electric vehicles.
  • the rechargeable battery is expected to grow into a huge market 100 times larger than the existing small battery market such as mobile phones and laptops.
  • the source of such lithium is mineral, brine or sea water.
  • minerals spodumene, petalite, and lepidolite are relatively high in lithium at about 1 to 1.5%.
  • flotation and high temperature heating are used in order to extract lithium from minerals. Recovery process is complicated because it has to go through the process of crushing, acid mixing, extraction, purification, concentration, precipitation, etc., and it is expensive because of high energy consumption. There is a serious problem.
  • lithium is currently extracted mainly from brine, which is produced in natural salt lakes, and salts such as Mg, Ca, B, Na, and K, including lithium, are dissolved together.
  • the concentration of lithium in the brine is about 0.3 to 1.5 g / L, lithium contained in the brine is mainly extracted in the form of lithium carbonate, the solubility of the lithium carbonate is about 13 g / L, contained in the brine Even if it is assumed that all of the lithium is converted to lithium carbonate, the concentration of lithium carbonate in the brine is 1.59 to 7.95 g / L, which is lower than the solubility of lithium carbonate.
  • the brine in order to extract the brine-containing lithium in the form of lithium carbonate, the brine is pumped from natural salt lake and confined in evaporation ponds in open field, and then naturally evaporated for a long time of one year or more to obtain lithium several times. After concentrating with, a method for recovering lithium by precipitating and removing impurities such as Mg, Ca, and B, and allowing more than lithium carbonate solubility to precipitate is used.
  • Another object of the present invention is to provide a system for implementing a method for recovering various metals from the solution.
  • Yet another object of the present invention is to provide a system for recovering various metals such as lithium from brine as one embodiment of the above objects.
  • a method for recovering metal from a solution is provided.
  • the first electrode containing the metal to be recovered and the second electrode containing a metal different from the metal to be recovered are immersed in a first solution containing ions of the metal to be recovered,
  • the recovery target metal ion is bonded to the first electrode.
  • the first electrode and the second electrode are charged while being immersed in a second solution different from the first solution to separate ions of the metal to be recovered from the first electrode.
  • the metal to be recovered is recovered from the second solution.
  • the coupling of the first electrode to the metal ions to be recovered of the first solution may be performed by electrically connecting a first electrode that is positively charged and a second electrode that is negatively charged to induce a discharge. do.
  • a system for recovering a metal from a solution includes a first metal, is discharged from a first solution containing ions of the first metal, and binds to ions of the first metal.
  • a second electrode charged in the second solution to release the first anion and a power source for charging the first electrode and the second electrode.
  • the recovery target metal may include lithium
  • the first electrode may include lithium manganese oxide
  • the second electrode may include silver, zinc, copper, mercury, or the like.
  • the first metal comprises lithium manganese oxide and the second metal comprises silver, zinc, copper or mercury.
  • the first electrode comprises LiMn 2 O 4 on the spinel.
  • the first electrode further comprises a carbon electrode, the lithium manganese oxide is coated on the surface of the carbon electrode.
  • the system is capable of repeatedly charging and discharging, and stores the electrical energy generated while the first electrode and the second electrode is discharged, and is connected to the power supply to supply the stored electrical energy It further comprises a battery for.
  • a system for recovering metals from brine includes lithium manganese oxide, is discharged from a brine containing lithium ions and chlorine ions to combine with the lithium ions, and the filling solution different from the brine
  • FIG. 1 is a flow chart illustrating a method for recovering metal from a solution according to an embodiment of the present invention.
  • FIGS. 2 and 3 are conceptual diagrams illustrating a system for recovering metal from a solution according to an embodiment of the present invention.
  • FIG. 4 is a graph showing changes in concentrations of lithium ions and sodium ions remaining in the discharge solution during the charging and discharging processes when lithium is recovered by applying the first embodiment of the present invention.
  • FIG. 5 is a view illustrating changes in concentrations of lithium ions, calcium ions, potassium ions, magnesium ions, and sodium ions remaining in the discharge solution during the charging and discharging process when lithium is recovered by applying the second embodiment of the present invention.
  • FIG. 6 is a graph illustrating a change in concentration of lithium ions remaining in the charging solution during the charging and discharging process when lithium is recovered by applying the second embodiment of the present invention.
  • FIG. 1 is a flow chart illustrating a method for recovering metal from a solution according to an embodiment of the present invention.
  • a first electrode and a second electrode including the recovery target metal are immersed in a first solution containing the recovery target metal ions, and the recovery target metal ions of the first solution are transferred to the first electrode.
  • the first electrode electrically charged with the second electrode and the second electrode charged with negative charge are electrically connected to induce a discharge. .
  • a positive charge is charged to the first electrode, and a negative charge is charged to the second electrode.
  • the recovery target metal is not limited to a specific metal.
  • lithium, sodium, potassium, magnesium, calcium, strontium, manganese, and the like can be used, and lithium is used in this embodiment.
  • the first solution containing the metal ions to be recovered is not limited to a specific source, but may be seawater or high concentration of brine.
  • the first solution may include ions and anions of other metals in addition to the metal ions to be recovered.
  • the first solution may include cations such as sodium, potassium, magnesium, calcium, strontium, and manganese, and anions such as chlorine anion (Cl ⁇ ).
  • the first electrode includes the recovery target metal.
  • the first electrode when the recovery target metal is lithium, the first electrode also includes lithium.
  • the first electrode has selectivity with respect to the metal to be recovered.
  • the first electrode when the recovery target metal is lithium, the first electrode may include lithium manganese oxide.
  • the lithium manganese oxide may include LiMn 2 O 4 , LiMnO 6 , and the like, and each of them may be used alone or in a mixed state.
  • the selectivity for lithium ions of the lithium manganese oxide may vary depending on the phase of the lithium manganese oxide, preferably the lithium manganese oxide has a spinel phase.
  • the second electrode includes a metal different from the recovery target metal.
  • the metal of the second electrode has a greater tendency of ionization than the metal to be recovered. Therefore, when the first electrode and the second electrode are electrically connected, the first electrode serves as a positive electrode and the second electrode serves as a negative electrode.
  • the second electrode may include silver, zinc, copper, mercury, and the like, and may be appropriately selected in consideration of the ionization tendency of the metal to be recovered.
  • the second electrode preferably includes a metal capable of reversibly repeating bonding and dissociation with anions in the charging and discharging process, and more preferably considering such reversibility and harmfulness to the environment. Silver may be used.
  • the discharge means that electrons move from the first electrode to the second electrode.
  • the metal ions to be recovered included in the first solution obtain electrons and bind with the first electrode, and the metal of the second electrode loses electrons and binds with anions contained in the first solution.
  • the first electrode when the first electrode includes LiMn 2 O 4 , the second electrode includes silver, and the first solution includes a lithium cation and a chlorine anion, the first electrode may be represented by the following formula: The reaction of 1 may occur at the second electrode.
  • lithium ions of the first solution combine with lithium manganese oxide of the first electrode, and chlorine ions of the first solution combine with silver of the second electrode to generate silver chloride.
  • concentration of lithium ions and the concentration of chlorine ions in the first solution are lowered.
  • Lithium manganese oxide contained in the first electrode used in the present embodiment has a selectivity for lithium, and thus can selectively separate lithium from the first solution containing different metal ions.
  • the first electrode and the second electrode in order to discharge the first electrode and the second electrode, a method of electrically connecting the first electrode positively charged and the second electrode negatively charged was used, but the first electrode and the The lithium ion of the first solution may be coupled to the first electrode by connecting a power supply to a second electrode, charging a negative charge to the first electrode (supplying electrons), and charging a positive charge to the second electrode. have.
  • the first electrode and the second electrode is charged in a state immersed in a second solution different from the first solution, to separate the ions of the metal to be recovered from the first electrode (S 20).
  • the second solution may be an aqueous solution containing a suitable electrolyte.
  • the first electrode when the first electrode includes LiMn 2 O 4 , and the second electrode includes silver chloride, the first electrode and the second electrode are charged to charge a positive charge to the first electrode.
  • the reaction of Chemical Formula 3 below may occur at the first electrode, and the reaction of Chemical Formula 4 below may occur at the second electrode.
  • the lithium manganese oxide of the first electrode loses lithium ions
  • the silver chloride of the second electrode loses chlorine ions and is reduced to silver.
  • the second solution includes a lithium cation and a chlorine anion.
  • the recovery target metal is recovered from the second solution (S 30).
  • various methods known in the art may be used.
  • the lithium chloride in a solid state can be obtained by heating the solution.
  • Lithium chloride is non-toxic, chemically stable and easy to store and manage. It may also be used directly as an electrolyte of a lithium secondary battery.
  • lithium may be recovered by electrolyzing the second solution containing the lithium cation and the chlorine anion.
  • the discharge in the first solution and the filling in the second solution described above may be repeated to increase the concentration of the metal to be recovered in the second solution.
  • the first electrode charged in the second solution is charged with positive charge
  • the second electrode is charged with negative charge. Accordingly, when the first electrode and the second electrode are taken out of the second solution, immersed in the first solution again, and then electrically connected, the bonding between the lithium ions of the first solution and the first electrode occurs again by discharge. .
  • the concentration of the metal to be recovered in the second solution is increased, the recovery efficiency of the metal to be recovered may be increased.
  • the present invention it is possible to efficiently recover the metal from the solution.
  • it is possible to obtain a high concentration of lithium in a short time compared to the conventional method using the evaporation / concentration of brine and the adsorption from sea water, the process is simple, the risk of environmental pollution This is less.
  • by storing and recycling the electrical energy generated during the discharge process it is possible to minimize the use of energy.
  • the present invention primarily aims to recover metal from seawater or high concentration brine, but may also be used to recover metal from process wastewater and the like.
  • a system for recovering a metal from a solution includes a first electrode including a first metal and a second metal different from the first metal and electrically connected to the first electrode.
  • An electrode The first electrode is discharged in a first solution containing the ions of the first metal to combine with the ions of the first metal, and charged in a second solution different from the first solution to release the ions of the first metal do.
  • the second electrode is discharged from the first solution to combine with the first anion of the first solution, and charged in the second solution to release the first anion.
  • the system includes a power source for charging the first electrode and the second electrode.
  • FIGS. 2 and 3 are conceptual views illustrating a system for recovering metal from a solution according to an embodiment of the present invention.
  • the first solution 30 is received in the first bath 40.
  • the first electrode 10 and the second electrode 20 are immersed in the first solution 30.
  • the first electrode 10 and the second electrode 20 may be partially immersed in the first solution 30 so that the top is exposed out of the first solution 30, in another embodiment, as a whole It may be immersed.
  • the first solution 30 includes ions of the metal to be recovered.
  • the metal to be recovered is lithium.
  • the first solution 30 may be seawater or high concentration brine, and may further include sodium, potassium, magnesium, calcium, strontium, manganese, and the like, in addition to lithium.
  • the first solution 30 may include an anion.
  • the first solution 30 mainly includes a chlorine anion (Cl ⁇ ).
  • the first electrode 10 includes the recovery target metal.
  • the first electrode 10 when the recovery target metal is lithium, the first electrode 10 also includes lithium.
  • the first electrode 10 has a selectivity to the metal to be recovered.
  • the first electrode 10 when the recovery target metal is lithium, the first electrode 10 may include lithium manganese oxide.
  • the lithium manganese oxide may include LiMn 2 O 4 , LiMnO 6 , and the like, and each of them may be used alone or in a mixed state.
  • the selectivity for lithium ions of the lithium manganese oxide may vary depending on the phase of the lithium manganese oxide, preferably the lithium manganese oxide has a spinel phase.
  • the lithium manganese oxide is relatively low in conductivity. Therefore, the first electrode 10 may further include another material having a relatively high conductivity.
  • the first electrode 10 may include a carbon electrode including graphite, carbon nanotubes, graphene, and the like, and the lithium manganese oxide may be entirely or partially coated on the surface of the carbon electrode.
  • a wire for electrically connecting the first electrode 10 and the second electrode 20 may be connected to the carbon electrode.
  • the first electrode 10 may include a mixture of lithium manganese oxide powder and graphite powder, the mixture may be coated in whole or in part on the surface of the carbon electrode.
  • the cathode material composition including lithium manganese oxide, graphite powder, a binder, and a solvent may be coated on a carbon electrode and then dried to obtain the first electrode 10.
  • the binder may be polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyurethane (PU), and the like, which may be used alone or in combination.
  • the solvent alcohols such as methanol, ethanol, propanol, butanol, and the like may be used, and each of them may be used alone or in combination.
  • the second electrode 20 includes a metal different from the recovery target metal.
  • the metal of the second electrode 20 has a greater tendency to ionize than the metal to be recovered. Therefore, when the first electrode 10 and the second electrode 20 are electrically connected to each other, the first electrode 10 serves as an anode and the second electrode 20 serves as a cathode.
  • the second electrode 20 may include silver, zinc, copper, mercury, and the like. In the present embodiment, the second electrode 20 includes silver.
  • the first electrode 10 and the second electrode 20 are electrically connected through a wire or the like for discharging.
  • the first electrode Positive charge is charged to 10
  • negative charge is charged to the second electrode 20.
  • the first electrode 10 since the first electrode 10 includes LiMn 2 O 4 , the second electrode 20 includes silver, and the first solution includes lithium cation and chlorine anion, When the first electrode 10 and the second electrode 20 are electrically connected, lithium ions of the first solution 30 are combined with lithium manganese oxide of the first electrode 10, and the first solution 30 ) Chlorine ions combine with silver of the second electrode 20 to produce silver chloride. As a result, the concentration of lithium ions and the concentration of chlorine ions in the first solution are lowered.
  • the first electrode 10 and the second electrode 20 are connected to the battery 50.
  • the battery 50 stores electrical energy generated during the discharging process, and may be used as a power source in the charging process to be described later.
  • the battery 50 may be any conventional battery capable of repeating charging and discharging of electrical energy.
  • a lead storage battery, a mercury battery, a lithium ion battery, a lithium polymer battery, and the like may be used. Can be used as.
  • the first electrode 10 and the second electrode 20 are immersed in the second solution 60 accommodated in the second bath 70.
  • the first electrode 10 and the second electrode 20 are charged to charge the first electrode 10 with positive charges, and the second electrode 20 with negative charges, the first electrode 10 is charged.
  • the lithium manganese oxide of) loses lithium ions
  • silver chloride of the second electrode 20 loses chlorine ions and is reduced to silver.
  • the second solution 60 includes a lithium cation and a chlorine anion.
  • the first electrode 10 and the second electrode 20 are connected to a suitable power source.
  • the power source may be connected to the battery 50, and by using electrical energy stored in the battery 50, energy efficiency may be increased.
  • the first bath 20 and the second bath 70 separated from each other are described as an example, but are not limited to this configuration of the present invention.
  • the present invention compared with the conventional method of using the evaporation / concentration of brine and the method of adsorption from sea water, it is possible to obtain a high concentration of lithium in a short time, the process is simple, the risk of environmental pollution little. In addition, by storing and recycling the electrical energy generated during the discharge process, it is possible to minimize the use of energy.
  • Silver electrodes of about 3 ⁇ 3 cm size and graphite electrodes of the same size were prepared.
  • Lithium manganese oxide (LiMn 2 O 4 ) powder, Super-P (trade name, Timcal, Switzerland) as a graphite powder, PVDF as a binder resin in a mixture of about 80: 10: 8 by weight of the mixture was dispersed in ethanol to disperse the graphite electrode After coating, the mixture was dried to prepare a lithium recovery electrode.
  • the lithium recovery electrode and the silver electrode were immersed in a filling solution containing about 25 mM of lithium chloride and having a volume of about 90 ml, spaced at an interval of about 1 cm, and then connected to a power source, and a voltage of about 1.2 V. Was charged for about 20 minutes, and the lithium recovery electrode was charged with a positive charge, and the silver electrode was charged with a negative charge.
  • the lithium recovery electrode and the silver electrode are immersed in a discharge solution containing about 25 mM of lithium chloride and about 25 mM of sodium chloride and having a volume of about 90 ml, and then the lithium recovery electrode and the silver electrode are wired. Connected and discharged for about 30 minutes.
  • the charging and discharging process was repeated three times, and each time one cycle (one charge and one discharge) was completed, approximately 1 ml of the sample was extracted from the discharge solution, and the ion chromatography apparatus DX-120 ( Trade name, DIONEX) was used to measure the concentration change of lithium ions and sodium ions, and are shown in Figure 4 respectively.
  • Silver electrodes of about 3 ⁇ 3 cm size and graphite electrodes of the same size were prepared.
  • PVDF weight average molecular weight: ⁇ 534,000, glass transition temperature: -38 °C, density: 25 °C
  • a mixture of 1.74 g / mL, Sigma Aldrich, USA) in a weight ratio of about 80:10:10 was dispersed in ethanol, applied to the graphite electrode, and dried to prepare a lithium recovery electrode.
  • the lithium recovery electrode and the silver electrode were immersed in a filling solution containing about 30 mM of lithium chloride and having a volume of about 80 ml, spaced at an interval of about 1 cm, and then connected to a power source, and the voltage of about 1.2 V. Was charged for about 20 minutes, and the lithium recovery electrode was charged with a positive charge, and the silver electrode was charged with a negative charge.
  • the lithium recovery electrode and the silver electrode were connected by wire to discharge for about 40 minutes.
  • the charge and discharge process was repeated four times, each time one cycle (one charge and one discharge) was completed, about 1 ml of the sample was extracted from the discharge solution, and the ion chromatography apparatus DX-120 ( Brand name, DIONEX) to measure the change in concentration of lithium ions, potassium ions, calcium ions, magnesium ions and sodium ions, extract the same amount of sample from the filling solution to measure the change in the concentration of lithium ions 5 and 6, respectively.
  • FIG. 4 is a graph showing a change in concentration of lithium ions and sodium ions remaining in the discharge solution during the charging and discharging process in the first embodiment of the present invention
  • Figure 5 is a charge in a second embodiment of the present invention
  • Figure 6 is a graph showing the change in concentration of lithium ions, calcium ions, potassium ions, magnesium ions and sodium ions remaining in the discharge solution during the repeated discharge process
  • Figure 6 is a charge and discharge process in a second embodiment of the present invention It is a graph showing the change in concentration of lithium ions remaining in the filling solution during the repetition.
  • lithium ions can be selectively recovered from a mixture with sodium ions using a method and system for recovering metal from a solution according to one embodiment of the present invention.
  • lithium ions in the second embodiment of the present invention, as the charge and discharge processes are repeated, the concentration of lithium ions is continuously decreased, whereas the concentrations of calcium ions, potassium ions, and sodium ions are maintained without being substantially reduced. And the concentration of magnesium ions remained substantially undecreased after decreasing in the first cycle.
  • lithium ions were continuously increased in the charging solution while the charging and discharging processes were repeated.
  • Sodium ions and magnesium ions are ions contained in seawater and high concentration brine, which are the source of lithium. Especially, magnesium is solubility similar to that of lithium, which makes it difficult to separate by evaporation. In view of the above, it can be seen that lithium can be effectively recovered from seawater and high concentration brine using a method and system for recovering metal from a solution according to one embodiment of the present invention.
  • a method for recovering metals from a solution according to the invention a system for recovering metals from a solution and a system for recovering lithium from brine can be used to recover metals such as lithium from seawater and high concentration brine.

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PCT/KR2013/000353 2012-05-16 2013-01-17 Procédé de récupération de métal depuis une solution, système de récupération de métal depuis une solution, et système de récupération de lithium depuis de l'eau salée Ceased WO2013172533A1 (fr)

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Application Number Priority Date Filing Date Title
US14/401,467 US20150129433A1 (en) 2012-05-16 2013-01-17 Method for recovering a metal from solution, system for recovering a metal from solution, and system for recovering lithium from salt water
EP13790312.6A EP2851454A4 (fr) 2012-05-16 2013-01-17 Procédé de récupération de métal depuis une solution, système de récupération de métal depuis une solution, et système de récupération de lithium depuis de l'eau salée

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KR1020120051834A KR101361836B1 (ko) 2012-05-16 2012-05-16 용액으로부터 금속을 회수하기 위한 방법, 용액으로부터 금속을 회수하기 위한 시스템 및 염수로부터 리튬을 회수하기 위한 시스템
KR10-2012-0051834 2012-05-16

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FI124088B (fi) 2012-06-05 2014-03-14 Outotec Oyj Menetelmä ja laitteisto puhtaan litiumpitoisen liuoksen valmistamiseksi
KR101455093B1 (ko) * 2013-04-17 2014-10-27 서울대학교산학협력단 폐전지로부터 금속을 회수하기 위한 방법
KR101509134B1 (ko) * 2014-05-22 2015-04-07 이이알앤씨 주식회사 브라인폐수 처리 및 금속 회수 시스템
KR101710283B1 (ko) * 2015-11-11 2017-03-08 고려대학교 산학협력단 마그네슘이온 선택적 회수장치와 이를 이용한 마그네슘이온 선택적 회수방법
KR102129313B1 (ko) * 2018-08-13 2020-07-08 명지대학교 산학협력단 니켈망간산화물을 이용한 리튬회수방법
KR102133790B1 (ko) * 2018-08-13 2020-07-21 명지대학교 산학협력단 니켈코발트망간산화물을 이용한 리튬회수방법
SG11202102646QA (en) * 2018-10-26 2021-04-29 Nat Univ Singapore A lithium ion battery materials recycling method
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KR20130128079A (ko) 2013-11-26
US20150129433A1 (en) 2015-05-14

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