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WO2012070193A1 - Solution de lixiviation et procédé de collecte de métal - Google Patents

Solution de lixiviation et procédé de collecte de métal Download PDF

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Publication number
WO2012070193A1
WO2012070193A1 PCT/JP2011/006308 JP2011006308W WO2012070193A1 WO 2012070193 A1 WO2012070193 A1 WO 2012070193A1 JP 2011006308 W JP2011006308 W JP 2011006308W WO 2012070193 A1 WO2012070193 A1 WO 2012070193A1
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Prior art keywords
metal
lithium
recovery method
solution
electrode active
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PCT/JP2011/006308
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English (en)
Japanese (ja)
Inventor
泰子 山田
山口　欣秀
岡本　正英
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Hitachi Ltd
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Hitachi Ltd
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Priority to US13/989,476 priority Critical patent/US20130287654A1/en
Publication of WO2012070193A1 publication Critical patent/WO2012070193A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. 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
    • 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 easily recovering metal from a lithium ion battery.
  • Non-Patent Document 1 features a recycling technology of a lithium ion battery, and systematically describes a method for recovering valuable metals constituting the lithium ion battery.
  • a typical recycling method published in Non-Patent Document 1 for example, a used lithium ion battery is charged with all positive electrode active materials containing valuable metals by acid leaching after mechanical processing such as opening, dismantling, and grinding. Dissolve and use the difference in dissolution characteristics of each desired component to separate and collect each component by precipitation, or separate and collect the desired component by a process such as preferential solvent extraction. .
  • Patent Document 1 discloses a technique for recovering copper and cobalt using a diaphragm electrolysis method in which a solution in which a valuable metal obtained by acid leaching is dissolved is used as a catholyte and a cation exchange membrane is used as a diaphragm.
  • the liquid before the valuable metal treatment is defined as the exudate
  • the liquid after the valuable metal treatment is defined as the solution.
  • Jinquiu Xu et al. “A review of processes and technologies for the recycling of lithium-ion secondary batteries”, Journal of Power Sources, vol. 177, pp. 512-527 (2008)
  • Non-Patent Document 1 aims at improving both the recovery rate of valuable materials and increasing the purity of recovered materials by various devices, but the process is complicated and it is enormous for processing a large amount of waste batteries. There is much room for improvement in terms of capital investment.
  • Patent Document 1 specifically uses the anion selectivity of the anion-selective membrane and the equipment (diaphragm electrolytic cell shown in FIG. 2 of Patent Document 1) using the ion-selective characteristics of the cation exchange membrane. Use the diffusion dialysis equipment (not shown). More specifically, Cu electrodeposition recovery by diaphragm electrolysis ⁇ pH adjustment ⁇ cobalt electrodeposition recovery by diaphragm electrolysis ⁇ pH adjustment ⁇ precipitation recovery of Fe (OH) 3 and Al (OH) 3 ⁇ by carbonate addition The main valuable metals can be recovered by a series of processes called Li2CO3 recovery.
  • Fe (OH) 3 and Al (OH) 3 tend to be gelled in a weakly acidic to neutral aqueous solution
  • Fe (OH) 3 and Al (OH) are based on the technique of Patent Document 1.
  • the operation of the step of collecting 3 by filtration is not easy.
  • the lithium recovery rate is lowered.
  • the surface of the gel-like precipitate of Fe (OH) 3 or Al (OH) 3 also has a property of adsorbing lithium ions, it is difficult to significantly improve the lithium recovery rate from this viewpoint.
  • Lithium is selectively leached from a positive electrode active material containing lithium and a transition metal element using a weakly acidic (pH 4 to 7) exudate, and the transition metal element component that is a non-exudable solid content and the exudate To separate the lithium component.
  • a weakly acidic (pH 4 to 7) exudate the transition metal element component that is a non-exudable solid content and the exudate
  • FIG. 2 is a schematic process flow for recovering valuable metals from the waste lithium battery (hereinafter, waste battery) of this example.
  • waste battery waste lithium battery
  • each constituent member obtained by disassembling a waste battery (S101) is sorted for each member (S102), and only an electrode active material containing a valuable metal in a high concentration is taken out.
  • the electrode active material thus taken out is treated with a selective lithium exudate (selective lithium exudation; S103) to obtain a lithium exuded solution.
  • This lithium selective exudate and non-exudate are subjected to solid-liquid separation (S104).
  • Li carbonate can be recovered as lithium carbonate Li2CO3 by mixing carbonate or carbon dioxide with the liquid A containing lithium (S105) (S106).
  • the solid component B (S107) is recovered by the solid-liquid separation.
  • the solid component B is dissolved and separated by filtration by depositing and sedimenting in turn as a hydroxide by a simple operation of adjusting the pH after dissolving the solid component B (S108). Through this series of operations, valuable metals from the waste battery can be recovered.
  • This discharge operation allows the lithium ions dispersed in the battery to be concentrated inside the positive electrode active material, thereby maximizing the amount of lithium recovered.
  • the lithium selectivity in the leaching process is maximized by ensuring that lithium is incorporated in a specific crystal structure.
  • the positive electrode active material is LiCoO22
  • LiCoO2 it is said that Li0.4CoO2 in the fully charged state and LiCoO2 in the fully discharged state, so there is a risk of lithium recovery loss of about 60% at maximum if the discharge treatment is omitted.
  • the safety of the battery disassembly process and the pulverization process can be secured by discharging.
  • a sulfuric acid / ⁇ -butyrolactone mixed solution was used as the conductive liquid containing the electrolyte.
  • the conductivity (reciprocal of the resistance value) can be adjusted by adjusting the sulfuric acid concentration.
  • the electrical resistance of the solution from the right end to the left end of the discharge vessel was measured and found to be 100 k ⁇ . If the resistance value of the solution is too small, the discharge proceeds too rapidly, which is dangerous. On the other hand, if the resistance value is too large, it takes too much time to reduce the practicality.
  • the solution resistance is preferably in the range of about 1 k to 1000 k ⁇ , and the electrolyte concentration may be adjusted so as to fall within this resistance value range.
  • waste battery of the present embodiment in addition to the so-called used battery whose charge capacity has been reduced due to reaching the limit of the predetermined number of times of charge and discharge, half of the battery generated due to problems in the battery manufacturing process, etc. Including old-fashioned inventory items that occur when products and product specifications change.
  • S101 disassemble the waste battery after the discharge treatment.
  • the battery components of the waste battery after discharge such as casing, packing / safety valves, circuit elements, spacers, current collectors, separators, and positive electrode and negative electrode active materials. Sort.
  • waste lithium ion batteries are often filled with gas and are in a pressurized state, and needless to say, work safety considerations are necessary.
  • wet pulverization was performed while cooling in the state of being immersed in a conductive liquid containing the above electrolyte. By adopting wet pulverization under cooling, the gas filled in the battery could be safely crushed without being scattered in the atmosphere.
  • the composition of the conductive liquid containing the electrolyte is adjusted in order to promote separation of the positive electrode active material and the negative electrode active material coated and molded on the current collector surface from the current collector surfaces. Is fine.
  • the conductivity should be noted.
  • the viscosity and the dielectric constant should be noted. Since the required specifications differ between the discharge process and the wet pulverization process, the composition of the conductive liquid used for each process may be changed. In that case, it is necessary to prepare two or more kinds of conductive liquids. In this example, the same composition was used from the viewpoint of simplification and reduction of labor and cost.
  • the wet pulverization method that can be used in this embodiment includes, for example, a ball mill method, but is not necessarily limited thereto.
  • constituent members such as housings, packing / safety valves, circuit elements, spacers, current collectors, separators, and electrode active materials
  • positive electrode active material hereinafter referred to as positive electrode active material
  • negative electrode active material negative electrode active material
  • the slurry obtained by the wet pulverization is separated as it is by a filtering process using a relatively coarse filter. You can also.
  • the recovery rate may be improved by introducing a continuous treatment from wet pulverization to filtration.
  • the casing, packing / safety valve, current collector (aluminum foil, copper foil), etc. have a larger extensibility than the positive electrode active material (typically LiCoO2) or the negative electrode active material (typically graphite), Therefore, the breaking strength is also large. Because of this characteristic, the crushed material of the electrode active material has a smaller size than the crushed material obtained from other members, and as a result, it can be easily separated and collected by sieving or filtering.
  • the sieving material obtained by the above treatment is leached with a weakly acidic effluent (S103).
  • the positive electrode active material of the waste battery used in this example is a lithium compound mainly composed of LiCoO2, but may include a positive electrode active material of another composition such as iron phosphate, nickel, or manganese.
  • the positive electrode active material was mixed with a weakly acidic leachate and stirred at room temperature for 1 hour to exude lithium.
  • the reaction temperature and reaction time of the lithium selective leaching step are controlled, and before the positive electrode active material is completely dissolved, the leaching process is specifically stopped when the reaction rate becomes 80% or less. From a practical viewpoint, the reaction rate is most preferably about 70 to 75%. If it exceeds 80%, there is an increased risk that the selectivity in the lithium selective leaching reaction will deteriorate, and if it is less than 70%, the recovery rate will decrease and the economy will be impaired.
  • the exudate and the residue are separated (S104).
  • a separation method centrifugation, filtration, or the like can be employed.
  • the separation and recovery were performed by centrifugation at room temperature and 15000 rpm for 15 minutes.
  • the higher the number of revolutions the easier the separation of the exudate and the residue.
  • the Li / Co molar ratio of the obtained solution is shown in FIG.
  • the Li / Co molar ratio of the solution before dialysis when the positive electrode active material is completely leached using a strongly acidic exudate using the method described in Non-Patent Document 1. was about 1.
  • the Li / Co molar ratio is approximately 1.0. This is because the entire composition of lithium cobaltate is dissolved, and even if the dissolution is stopped halfway, the Li / Co molar ratio hardly changes.
  • the Li / Co molar ratio is improved to 4 or more.
  • the weakly acidic exudate may be a buffer solution obtained by adding a substance having a buffering action to pure water.
  • a redox potential adjusting agent is added to the weakly acidic solution, the Li / Co selection ratio is further increased.
  • the Li / Co molar ratio is greatly improved to 335.
  • carbon dioxide is added to ozone water
  • the Li / Co molar ratio is as high as 121.
  • lithium selective exudate of this example an aqueous solution in which ozone, hydrogen peroxide, peracetic acid or the like is dissolved can be used. These solutes act as oxidants.
  • lithium cobaltate is completely dissolved using a high concentration of mineral acid to exude lithium cobaltate.
  • high concentration mineral acid is not used, and the upper limit of the leaching temperature is 30 ° C. If it greatly exceeds 30 ° C., natural decomposition of ozone and hydrogen peroxide is accelerated, and a solute that does not contribute to the dissolution of the positive electrode active material is generated, so that the solute is wasted.
  • the oxidation-reduction potential was 0.3 volts when the hydrogen peroxide solution concentration was 15%, and the oxidation-reduction potential was 0.4 volts when the hydrogen peroxide solution concentration was 20%. It was found that a high Li / Co molar ratio can be obtained in the range of 0.3 to 0.4 volts.
  • the solute (specifically hydrogen peroxide and ozone) used in the exudate spontaneously disappears.
  • Natural extinction means that the concentration of a specific active ingredient is about half or less of the initial concentration without adding chemicals to promote neutralization and decomposition.
  • hydrogen peroxide spontaneously decomposes into water and oxygen molecules
  • ozone naturally decomposes into oxygen molecules.
  • Most of the generated oxygen molecules are discharged out of the solution.
  • Carbon dioxide is vaporized and discharged out of the solution. Accordingly, since the solution becomes neutral due to spontaneous disappearance, the neutralization treatment performed after the conventional acid leaching is not required (S105).
  • Non-Patent Document 1 since the valuable metal solution obtained after the leaching treatment is a high-concentration solution of strong acid, a large amount of alkali is recovered prior to recovering lithium as lithium carbonate. So-called pH adjustment to mix the inevitably becomes inevitable. However, the ozone water and the hydrogen peroxide solution used in this example are naturally extinguisher solutions, and the liquidity of the recovered liquid (A) after the lithium cobaltate exudation treatment is weakly alkaline with a pH of 9 to 11.
  • the recovered liquid (A) thus obtained is treated as it is, such as mixing with an alkali metal-free carbonate such as calcium carbonate or carbon dioxide gas without neutralization such as pH adjustment, the alkali-free The precipitate can be recovered as lithium carbonate (S106).
  • an alkali metal-free carbonate such as calcium carbonate or carbon dioxide gas without neutralization such as pH adjustment
  • the transition metal component is recovered from the residue (B) obtained in the Li / transition metal separation in S104 (S107).
  • the residue (B) obtained by the treatment so far contains a small amount of unexuded lithium and cobalt.
  • Separation and recovery can be carried out for each type of transition metal element by treatment using the difference in solubility characteristics of hydroxide, basically pH adjustment ⁇ precipitation recovery (S108).
  • the positive electrode active material contains a lithium compound other than LiCoO2, for example, in the case of an olivine-based positive electrode active material such as LiNiO2, LiMnO2, Li (Ni1 / 3Co1 / 3Mn1 / 3) O2, LiCoPO4, LiFePO4, LiCoPO4F, LiFePO4F, etc.
  • a lithium compound other than LiCoO2 for example, in the case of an olivine-based positive electrode active material such as LiNiO2, LiMnO2, Li (Ni1 / 3Co1 / 3Mn1 / 3) O2, LiCoPO4, LiFePO4, LiCoPO4F, LiFePO4F, etc.
  • the outline of the valuable metal recovery method of this example will be described.
  • the valuable metal recovery method of this example is basically the same as that of Example 1.
  • the difference from the first embodiment is that, in the leaching process in S103 of FIG. 2, an oxidant that spontaneously disappears and a buffer solution that suppresses the rate at which the oxidant spontaneously disappears are used as the weakly acidic exudate. Is a point. This makes it possible to achieve both a high Li / Co molar ratio and a high Li recovery rate in the lithium leaching reaction.
  • the exudate of this example is, for example, an acetic acid buffer solution (0.1 M, pH 4.7) or a phthalate buffer as a buffer solution composed of ozone water having a dissolved ozone concentration of 150 ppm as an oxidizing agent that spontaneously disappears, carboxylic acid, and salts thereof.
  • a mixed solution (0.1 M, pH 4.0) can be used, but the type of oxidizing agent, the type of carboxylic acid, and the concentration thereof are not limited thereto.
  • a positive electrode active material is added to the mixed solution of ozone water and a buffer solution, and the mixture is stirred for about 20 minutes to exude lithium (S103).
  • the exudate and the residue are separated (S104).
  • a separation method centrifugation, filtration, and the like can be adopted.
  • separation and recovery can be performed by treating at 10,000 rpm for 30 seconds at room temperature.
  • the recovered liquid (A) obtained by the above selective leaching is obtained as a lithium concentrate (S105), and the oxidizing agent (ozone) used in the leaching liquid is naturally extinguished.
  • the Li / Co molar ratio of the recovered liquid (A) obtained in this example was 4243 in the case of the acetate buffer solution, and a high Li / Co molar ratio was obtained as in Example 1.
  • the lithium recovery rate is 18% when only ozone water is used as the exudate, whereas it is 28% when ozone water and a phthalate buffer solution are used.
  • a mixture of ozone water and an acetate buffer solution was used, a high value of 98% was obtained.
  • a lithium recovery method with a high lithium recovery rate and a high Li / Co molar ratio could be established.
  • both the lithium recovery rate and the Li / Co molar ratio in the recovered components are higher, and the former is preferably close to 100%.
  • the high lithium recovery rate can be realized by the oxidant and the buffer solution that disappear spontaneously will be described in detail below.
  • Phthalic acid is dissociated in aqueous solution according to the following chemical formulas 1 and 2.
  • the acid dissociation index (logarithm of the reciprocal of the dissociation constant) pKa of Chemical Formula 1 is 2.94
  • the pKa of Chemical Formula 2 is 5.41.
  • the equilibrium of chemical formula 1 is almost completely biased to the right side, and chemical formula 2 is biased to the left side or to the right side depending on the pH.
  • this pH-dependent equilibrium reaction keeps the pH within a suitable range and suppresses the decomposition of ozone, improving the lithium recovery rate from 18% to 28%. did.
  • phthalic acid has many dissociated components.
  • C6H4 (COOH) COO 2 ⁇ the electron density on the carboxyl group increases. Since the carboxy ion is an electron donating group, the electron density of the aromatic ring is increased as a result.
  • phthalic acid since phthalic acid has an aromatic ring which is a weak electron-withdrawing group in the molecular structure, it tends to increase the electron density.
  • the electron density on the aromatic ring is high, electrons are easily taken away by the oxidizing agent. For this reason, when dissociated phthalate ions coexist with ozone as an oxidizing agent, ozone may oxidize part of the phthalate ions.
  • the acetate buffer solution can maintain the buffering action in the reaction solution, even if a dissolution reaction of the positive electrode active material occurs, the liquidity of the reaction solution does not become alkaline. Natural extinction can be suppressed, and as a result, ozone is effectively used for the leaching reaction of LiCoO 2 and a high lithium recovery rate can be realized.
  • the result of measuring the change in the dissolved ozone concentration during the leaching reaction of LiCoO 2 is shown in FIG. From FIG. 5, when the positive electrode active material is dissolved only with ozone water, the dissolved ozone concentration rapidly decreases in the first few minutes, and when the leaching time is 10 minutes, the dissolved ozone concentration decreases to about 5 ppm. On the other hand, when the acetic acid buffer solution is added to the ozone water, the dissolved ozone concentration at the same time is 50 ppm, which indicates that the decrease in the dissolved ozone concentration is suppressed.
  • the concentration can be maintained by suppressing the decrease in the dissolved ozone concentration by adding an acetic acid buffer solution to the ozone water. And it is possible to perform the leaching reaction of lithium from a positive electrode active material efficiently by maintaining the dissolved ozone concentration high over a long period of time.
  • acetic acid is not limited to acetic acid, and any carboxylic acid having a carboxyl group that does not contain an aromatic ring may be used.
  • acetic acid buffer solution results with an acetic acid buffer solution were shown.
  • aliphatic monocarboxylic acids such as propionic acid, butanoic acid and pentanoic acid can be used. If the number of carbon atoms constituting the carbon chain is larger than this, the solubility in water will be low, which is not suitable for practical use.
  • the buffer concentration is generally about 0.1 mol / L, and is preferably at least 0.001 mol / L.
  • the solubility of the substance having a small carbon number (value at 20 ° C .; the solute mass soluble in 100 g of water and the molar concentration at that time) is 37 g / 100 g water (0.005 mol / L) for propionic acid and 0.005 mol / L for butanoic acid, respectively.
  • 5.6 g / 100 g water (0.032 mol / L) and pentanoic acid are 2.4 g / 100 g water (0.075 mol / L).
  • the oxidative decomposition rate of the aliphatic monocarboxylic acid is butanoic acid> propionic acid> acetic acid.
  • oxalic acid succinic acid, tartaric acid, citric acid, malic acid, and malonic acid can be used in consideration of pKa and solubility.
  • general glycine can also be used as a buffer solution.
  • a preferable buffer solution is preferably a buffer solution made of a substance having a carbon number of 1 to 4 (excluding carboxyl group carbon) and an acid dissociation index of 4 ⁇ pH ⁇ 7 from the viewpoint of solubility.
  • Patent Document 2 discloses a method for recovering lithium and cobalt using an organic acid such as citric acid, succinic acid, malic acid or the like as an exudate of the positive electrode active material.
  • an organic acid such as citric acid, succinic acid, malic acid or the like
  • the pH is low.
  • the pH of a solution having a concentration of 1.25 mol / L of citric acid described in Example 1 of Patent Document 2 is 1 or less. For this reason, all LiCoO2 dissolves, and the recovered lithium and cobalt are of low purity, and a separation operation is required to recover only lithium.
  • the exudate is suitable for weak acidity, and by exuding with weak acidity, only lithium is selectively exuded from the positive electrode active material, and the exudation residue By leaving only cobalt therein, the resulting metal can be highly purified.
  • buffer solution other buffer solutions can be used as long as they are not only carboxylic acids but also buffer solutions exhibiting acidity (4 ⁇ pH ⁇ 7).
  • a buffer solution other than carboxylic acid for example, a buffer solution of phosphoric acid and its salt can be used.
  • phosphoric acid and its salt can be used.
  • the composition is not limited to this salt, and other compositions can be used. In this case, if phosphorus is recovered after recovering Li from the acidic solution in which Li is selectively dissolved, phosphorus can be reused as the solute of the buffer solution.
  • separation operations such as dialysis membrane separation, acid retardation and ion exchange resin.
  • ozone is used as an oxidant that spontaneously disappears, but hydrogen peroxide can be used instead.
  • LiCoO2 was used as the positive electrode active material.
  • olivine-based positive electrode actives such as LiNiO2, LiMnO2, Li (NiCoMn) O2, LiCoPO4, LiFePO4, LiCoPO4F, and LiFePO4F are used.
  • precipitation can be recovered by separating Co, Ni, Mn, and Fe as hydroxides by adjusting the pH of the liquid.
  • the transition metal recovery operation is performed in the same manner as S107 and S108 in the first embodiment, and the method is the same as in the first embodiment.
  • a recovery method could be provided.

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Abstract

La présente invention a pour but de proposer un procédé de collecte de métal de valeur pour recueillir un métal à partir d'une batterie lithium-ion à l'aide d'une installation relativement simple sans employer de procédé compliqué. Dans la présente invention, pour atteindre le but, du lithium est sélectivement lixivié à partir d'une matière active d'électrode positive comprenant un oxyde composite de lithium et d'un élément métal de transition à l'aide d'une solution faiblement acide ayant une valeur de pH de 4-7 d'une manière telle que le rapport de sélection Li/Co est augmenté et qu'un rapport élevé de collecte de Li peut être atteint et du lithium est ensuite recueilli à partir d'une solution de lixiviation. En ce qui concerne la solution acide obtenue après la lixiviation de lithium, toute étape de neutralisation pour la solution acide peut être éliminée et la quantité des déchets de la solution acide peut être réduite à l'aide d'un soluté qui peut générer un gaz ou similaire afin de permettre à l'acidité de la solution acide de disparaître naturellement.
PCT/JP2011/006308 2010-11-25 2011-11-11 Solution de lixiviation et procédé de collecte de métal Ceased WO2012070193A1 (fr)

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US13/989,476 US20130287654A1 (en) 2010-11-25 2011-11-11 Leaching solution and metal recovery method

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JP2010-261905 2010-11-25
JP2010261905 2010-11-25
JP2011-128806 2011-06-09
JP2011128806A JP5618913B2 (ja) 2010-11-25 2011-06-09 滲出液および金属回収方法

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CN109346741A (zh) * 2018-11-30 2019-02-15 成都尤尼瑞克科技有限公司 一种锂电池废旧正极材料再利用的方法
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