JP2012074247A - Lithium extraction method and metal recovery method - Google Patents

Lithium extraction method and metal recovery method Download PDF

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JP2012074247A
JP2012074247A JP2010218083A JP2010218083A JP2012074247A JP 2012074247 A JP2012074247 A JP 2012074247A JP 2010218083 A JP2010218083 A JP 2010218083A JP 2010218083 A JP2010218083 A JP 2010218083A JP 2012074247 A JP2012074247 A JP 2012074247A
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lithium
positive electrode
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leaching
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JP5501180B2 (en
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Yasuko Kojima
Masahide Okamoto
Yoshihide Yamaguchi
泰子 小島
欣秀 山口
正英 岡本
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Hitachi Ltd
株式会社日立製作所
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

PROBLEM TO BE SOLVED: To provide a method for recovering lithium from a lithium ion battery using relatively simple equipment and without using a cumbersome process.SOLUTION: In a lithium extraction method for extracting lithium from a positive electrode material of a lithium ion battery containing lithium and cobalt, the positive electrode material is immersed into an acid solution at a temperature of 50°C or less, lithium ions are selectively leached into the acid solution while suppressing the leaching of cobalt ions, and the leaching of lithium ions is stopped while the amount of lithium contained in the positive electrode material is sufficient.

Description

本発明は、電池から金属を簡便に回収する金属回収技術に関する。   The present invention relates to a metal recovery technique for easily recovering metal from a battery.
近年、電子機器の携帯化が進むにつれて2次電池の使用量が急激に増大している。携帯電話や携帯型音楽プレイヤーなどの比較的小電力の機器に限らず、電動工具、電動自転車、電気自動車などの高出力を要する機器へも2次電池の適用が広がるに至り、高エネルギー密度が得られるリチウムイオン電池に注目が集まっている。高出力機器への適用が増えたことにより、使用済み電池からの有価物回収の必要性が高まっており、リチウムイオン電池からの有価金属を回収するためのさまざまな技術が提案されている。   In recent years, the usage amount of secondary batteries has been rapidly increasing as electronic devices have become more portable. Rechargeable batteries are widely used not only for devices with relatively low power, such as mobile phones and portable music players, but also for devices that require high power, such as electric tools, electric bicycles, and electric vehicles, resulting in high energy density. Attention has been focused on the resulting lithium ion battery. Due to the increase in application to high-power devices, the necessity of recovering valuable materials from used batteries is increasing, and various techniques for recovering valuable metals from lithium ion batteries have been proposed.
例えば、非特許文献1には、リチウムイオン電池のリサイクル技術が特集されており、リチウムイオン電池を構成する有価金属類を回収する方法が系統的に説明されている。非特許文献1に掲載された典型的なリサイクル方法によると、例えば、使用済みリチウムイオン電池は開封・解体・粉砕などの機械的な処理の後に、酸滲出によって有価金属を滲出させ、そこから、所望成分毎の溶解特性の差を利用して、成分毎に分別して沈殿形成させる、あるいは所望成分を優先的に溶媒抽出するなどの処理によって所望成分毎に分別回収される。   For example, Non-Patent Document 1 features a lithium ion battery recycling technology, and systematically describes a method of recovering valuable metals that constitute the lithium ion battery. According to a typical recycling method published in Non-Patent Document 1, for example, a used lithium ion battery exudes valuable metals by acid leaching after mechanical processing such as opening, dismantling, and grinding, and from there, Using the difference in solubility characteristics for each desired component, the components are separated and collected for each desired component by a process such as separation for each component to form a precipitate, or solvent extraction of the desired component preferentially.
また、特許文献1には、酸滲出によって得られる有価金属を滲出した液を陰極液とし、陽イオン交換膜を隔膜とする隔膜電解法を用いてCuおよびCoを回収する技術が開示されている。   Patent Document 1 discloses a technique for recovering Cu and Co using a diaphragm electrolysis method in which a liquid obtained by leaching a valuable metal obtained by acid leaching is used as a catholyte and a cation exchange membrane as a diaphragm. .
特許第3675392号公報Japanese Patent No. 3675392 特許第3980526号公報Japanese Patent No. 3980526 特開平11−292533号公報JP 11-292533 A
非特許文献1においては、さまざまな工夫により有価物の回収率向上と回収物の高純度化の両立を目指しているが、工程が煩雑であるうえ、多量の廃電池を処理するには莫大な設備投資が必要という点で改善の余地が大きい。   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.
また、特許文献1は、具体的には、陽イオン交換膜が有するイオン選択特性を利用した設備(特許文献1の図2に示す隔膜電解槽)と陰イオン選択膜の陰イオン選択性を利用した拡散透析設備(説明図なし)を用いる。より具体的に説明すると、隔膜電解によるCuの電析回収→pH調整→隔膜電解によるCoの電析回収→pH調整→Fe(OH)およびAl(OH)の沈殿回収→炭酸塩添加によるLiCO回収という一連の処理により主要有価金属を回収できる。この技術によると、Cu(2価イオン)およびCo(3価イオン)を電気化学的に還元して回収するので高純度な金属を得ることができるが、多量の廃電池を処理する場合には莫大な電気量の印加が必要という点で改善の余地がある。 Further, 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 → Co electrodeposition recovery by diaphragm electrolysis → pH adjustment → precipitation recovery of Fe (OH) 3 and Al (OH) 3 → by adding carbonate Major valuable metals can be recovered by a series of treatments of Li 2 CO 3 recovery. According to this technology, Cu (divalent ions) and Co (trivalent ions) are electrochemically reduced and recovered, so that a high-purity metal can be obtained. However, when treating a large amount of waste batteries, There is room for improvement in that a huge amount of electricity needs to be applied.
例えば、約100kgのCoを回収するためには、1アンペアの電流を約100時間流し続ける必要があるが、その前にCuの電析でもほぼ同等の電気量を印加するのであるから、隔膜電解だけで全ての金属を回収することは案外な手間を要する。さらに、多段のpH調整を経るごとに液量が増大するために一連の処理の最終段階でLiCOを回収する際にはLiの濃度が低下しており、炭酸塩を添加してもLiの回収率は必ずしも高くならないと考えられる。これは、炭酸リチウムの飽和溶解度は20℃で1.3wt%もあるので液量が多くなるほど未回収成分が増えるためである。これを避けるためには濃縮工程を追加するなどの処理が必要である。さらに、Fe(OH)やAl(OH)は弱酸性〜中性の水溶液中でゲル状化しやすい傾向があるため、上記特許文献1の技術に基づいてFe(OH)やAl(OH)を濾別回収する工程の操作は容易ではなく、一方、濾別操作を容易化するために液を希釈するとLiの回収率が低下する。また、Fe(OH)やAl(OH)のゲル状沈殿の表面はLiイオンを吸着する特性もあるので、この観点でもLi回収率を大幅に改善することは難しい。 For example, in order to recover about 100 kg of Co, it is necessary to continue a current of 1 ampere for about 100 hours, but before that, almost the same amount of electricity is applied even in the electrodeposition of Cu. Collecting all the metal by itself alone is an unexpected process. Furthermore, since the amount of liquid increases every time multi-stage pH adjustment is performed, the concentration of Li is reduced when recovering Li 2 CO 3 at the final stage of a series of treatments, and even if carbonate is added. It is considered that the recovery rate of Li does not necessarily increase. This is because the saturated solubility of lithium carbonate is 1.3 wt% at 20 ° C., so that the unrecovered components increase as the liquid amount increases. In order to avoid this, processing such as adding a concentration step is necessary. Further, Fe (OH) 3 and Al (OH) 3 Since there is a tendency to gelled in an aqueous solution of a weakly acidic to neutral, based on the technique of Patent Document 1 Fe (OH) 3 and Al (OH ) The operation of the step of collecting 3 by filtration is not easy. On the other hand, when the liquid is diluted to facilitate the filtration operation, the recovery rate of Li decreases. In addition, since the surface of the gel-like precipitate of Fe (OH) 3 or Al (OH) 3 also has a property of adsorbing Li ions, it is difficult to significantly improve the Li recovery rate from this viewpoint.
本願において開示される発明のうち代表的なものの概要を簡単に説明すれば次のとおりである。   The following is a brief description of an outline of typical inventions disclosed in the present application.
本発明は、リチウムと遷移金属元素とを含む正極材からリチウムを選択的に滲出させ、コバルトに対するリチウムの滲出量の割合が大きいうちに滲出を停止させることを特徴とする。   The present invention is characterized in that lithium is selectively leached from a positive electrode material containing lithium and a transition metal element, and the leaching is stopped while the ratio of the leaching amount of lithium to cobalt is large.
本発明によれば、リチウムイオン電池からリチウムを簡便に高効率に回収する方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the method of collect | recovering lithium from a lithium ion battery simply and efficiently can be provided.
本発明の実施例に係る滲出液の組成および各組成の滲出液のLi/Co比である。It is the composition of the exudate which concerns on the Example of this invention, and Li / Co ratio of the exudate of each composition. 本発明に係る実施例1の有価金属を回収するための工程フロー概略である。It is the process flow outline for collect | recovering valuable metals of Example 1 which concerns on this invention. 酸滲出処理のリチウムイオンと硫酸の濃度比の例である。It is an example of the density | concentration ratio of the lithium ion of a acid leaching process, and a sulfuric acid. 本発明に係る実施例2の有価金属を回収するための工程フロー概略である。It is the process flow outline for collect | recovering valuable metals of Example 2 which concerns on this invention.
以下、本発明を実施するための形態を説明する。なお、図を用いて説明する場合には図面を構成する各部品にはそれぞれ符号を付して説明を施すが、同一機能の場合には符号や説明を省略する場合がある。また、図中に示した各部品の寸法は実際の部品寸法を反映した縮尺には必ずしも一致していない場合がある。   Hereinafter, modes for carrying out the present invention will be described. In the description with reference to the drawings, each component constituting the drawing is provided with a reference numeral, and the description is omitted in the case of the same function. In addition, the dimensions of the parts shown in the drawing may not necessarily match the scale reflecting the actual part dimensions.
本実施例の有価金属回収方法の概略について図2を用いて説明する。図2は、本実施例の廃リチウム電池(以下、廃電池)から有価金属を回収するための概略の工程フローである。まず始めに廃電池を解体(S101)して得られる各構成部材を部材毎に分別(S102)し、有価金属を高濃度で含有する電極活物質のみを取り出す。こうして取り出した電極活物質をLi選択滲出液で処理(Li選択滲出;S103)してLiが滲出した溶液とする。このLi選択滲出液と非滲出分と固液分離する(S104)。Liを含むA液(S105)に炭酸塩を混合すれば炭酸リチウムLiCOとしてLiを回収することができる(S106)。遷移金属が相対的に濃縮されたB(S107)は、まだ固体なので酸溶解させた後にpH調整するだけの簡便な操作により、遷移金属が水酸化物として析出・沈降するのでこれを濾別回収(S108)する。この一連の操作により、廃電池からの有価金属類および過剰の酸をそれぞれ回収することができる。 An outline of the valuable metal recovery method of the present embodiment will be described with reference to FIG. FIG. 2 is a schematic process flow for recovering valuable metals from the waste lithium battery (hereinafter, waste battery) of this example. First, 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 Li selective exudate (Li selective exudation; S103) to obtain a Li exuded solution. This Li selective exudate and non-exudate are separated into solid and liquid (S104). If carbonate is mixed with the liquid A containing Li (S105), Li can be recovered as lithium carbonate Li 2 CO 3 (S106). B (S107), which is relatively concentrated in transition metal, is still solid, so the transition metal precipitates and settles as a hydroxide by simple operation of pH adjustment after acid dissolution. (S108). Through this series of operations, valuable metals and excess acid can be recovered from the waste battery.
以下、図2に示す工程に従って有価金属回収フローをさらに詳しく説明する。   Hereinafter, the valuable metal recovery flow will be described in more detail in accordance with the steps shown in FIG.
廃電池から有価金属を回収するためには、まず電池を解体する必要があるが、解体に先立ち、電池内には電荷が残っている可能性があるので放電する。本実施例では、電解質を含有する導電性液体中に電池を浸漬することによって電池内に残っている電荷を放電させる。   In order to recover valuable metals from the waste battery, it is necessary to first disassemble the battery, but before the disassembly, there is a possibility that electric charge remains in the battery, and thus the battery is discharged. In this embodiment, the charge remaining in the battery is discharged by immersing the battery in a conductive liquid containing an electrolyte.
この放電操作により、電池内に分散しているLiイオンを正極活物質内部に濃縮させることができるので、Li回収量を最大化できる。また、Liが特定の結晶構造にとりこまれている状態を確保することにより滲出処理におけるLi選択性が最大となる。正極活物質がLiCoOの場合、完全充電状態ではLi0.4CoO、完全放電状態ではLiCoOと言われているので、上記放電処理を省略すると最大で6割程度のLi回収ロスとなる危険性がある。もちろん、放電により安全性が確保できる利点もある。 By this discharging operation, Li ions dispersed in the battery can be concentrated inside the positive electrode active material, so that the amount of recovered Li can be maximized. In addition, by ensuring that Li is incorporated in a specific crystal structure, the Li selectivity in the leaching process is maximized. If the positive electrode active material is LiCoO 2, since it is said that LiCoO 2, a Li recovery loss of about 60% at maximum Omitting the discharging process is Li 0.4 CoO 2, a full discharge state in the fully charged state There is a risk. Of course, there is an advantage that safety can be secured by discharging.
本実施例においては、電解質を含有する導電性液体として硫酸/γブチロラクトン混合溶液を用いた。この混合溶液中では硫酸が電解質として作用するので硫酸濃度を調節することによって導電率(抵抗値の逆数)を調整することができる。本実施例では、放電槽の右端〜左端までの溶液の電気抵抗を実測したところ100kΩであった。溶液の抵抗値が小さすぎると放電が急速に進みすぎて危険であるし、逆に、抵抗値が大きすぎると放電に時間がかかりすぎて実用性が低下する。本実施例では、溶液抵抗が1k〜1000kΩ程度の範囲にあることが望ましく、この抵抗値範囲に入るように電解質濃度を調整すると良い。   In this example, a sulfuric acid / γ-butyrolactone mixed solution was used as the conductive liquid containing the electrolyte. In this mixed solution, since sulfuric acid acts as an electrolyte, the conductivity (reciprocal of the resistance value) can be adjusted by adjusting the sulfuric acid concentration. In this example, when the electrical resistance of the solution from the right end to the left end of the discharge vessel was measured, it was 100 kΩ. 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. In this embodiment, the solution resistance is preferably in the range of about 1 k to 1000 kΩ, and the electrolyte concentration may be adjusted to fall within this resistance value range.
ここで、本実施例の廃電池としては、所定の充放電回数の限界に達して充電容量が低下してしまったいわゆる使用済み電池の他に、電池製造工程内での不具合などで発生する半製品、製品仕様変更に伴って発生する旧型式在庫整理品なども含む。   Here, as the 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にて放電処理後の廃電池を解体する。適当な方法を用いて筐体、パッキン・安全弁、回路素子類、スペーサ、集電体、セパレータ、正極および負極の電極活物質などの放電処理後の廃電池の電池構成部材をそれぞれ部材毎に解体分別する。   In S101, the waste battery after the discharge treatment is disassembled. Using appropriate methods, disassemble 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.
なお、廃リチウムイオン電池は内部にガスが充満して加圧状態になっていることが多いので、作業安全上の配慮が必要であることは言うまでも無い。本実施例では、上記の電解質を含有する導電性液体に浸漬した状態で冷却しながら湿式粉砕した。冷却下での湿式粉砕を採用したことにより、電池内部に充満しているガスを大気中に飛散させることなく安全に破砕することができた。   In addition, since waste lithium ion batteries are often filled with gas and are in a pressurized state, needless to say, work safety considerations are necessary. In this example, 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.
また、集電体表面に塗工・成形された正極活物質および負極活物質をそれぞれの集電体表面からの剥離を促進するために、上記電解質を含有する導電性液体の組成を調整することは差し支えない。尚、放電工程に使用する導電性液体では導電性が留意すべき特性であり、湿式粉砕工程に使用する導電性液体では粘度や誘電率が留意すべき特性である。放電工程と湿式粉砕工程では要求仕様が異なるので、工程毎に使用する導電性液体の組成を換えても良いが、その場合には2種類以上の導電性液体を準備する必要がある。本実施例では、簡便化や手間・コストの抑制の観点から、同一の組成とした。   In addition, 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. In the conductive liquid used in the discharge process, the conductivity should be noted. In the conductive liquid used in the wet grinding process, 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.
本実施例で使用可能な湿式粉砕法としては、例えばボールミルなどの方法があるが、かならずしもこれに限るわけではない。粉砕する前に焙焼工程なしとすると、コバルト酸リチウムとバインダーのポリフッ化ビニリデン(PVDF)が混入せず、リチウムとコバルトを純度よく回収できる。焙焼工程によりPVDFが分解し、正極材を撥水化させるフッ素含有化合物を発生させるからである。正極材が撥水化してしまうと、後述のリチウム抽出工程に影響を与えてしまう。筐体、パッキン・安全弁、回路素子類、スペーサ、集電体、セパレータ、電極活物質などの構成部材のうち、正極の電極活物質(以下正極活物質)と負極の電極活物質(負極活物質)が優先的に破砕する条件で破砕した後に、篩い分け処理を施す。これにより、正極活物質と負極活物質は篩い下、それ以外の部材は篩い上に分別回収される(S102)。   As a wet pulverization method that can be used in the present embodiment, there is a method such as a ball mill, but it is not necessarily limited thereto. If the roasting step is not performed before pulverization, lithium cobalt oxide and the polyvinylidene fluoride (PVDF) binder are not mixed, and lithium and cobalt can be recovered with high purity. This is because PVDF is decomposed by the roasting process to generate a fluorine-containing compound that makes the positive electrode material water repellent. If the positive electrode material becomes water-repellent, it will affect the lithium extraction process described later. Among constituent members such as housings, packing / safety valves, circuit elements, spacers, current collectors, separators, and electrode active materials, a positive electrode active material (hereinafter referred to as positive electrode active material) and a negative electrode active material (negative electrode active material) ) Is preferentially crushed and then sieved. Thereby, the positive electrode active material and the negative electrode active material are separated and recovered on the sieve under the sieve (S102).
本実施例においては篩い分けを用いたが、もともと湿式にて粉砕しているのであるから、湿式粉砕によって得られたスラリーをそのまま比較的目の粗いフィルターを用いて濾別処理にて分別することもできる。湿式粉砕〜濾別の連続処理を導入することにより、回収率が向上する可能性もある。尚、筐体、パッキン・安全弁、集電体(アルミ箔、銅箔)などは、正極活物質(典型的にはLiCoO)や負極活物質(典型的にはグラファイト)よりも延展性が大きく、従って破断強度も大きい。この特性のために、電極活物質の破砕物はそれ以外の部材から得られる破砕物よりもサイズが小さくなり、その結果として、篩い分けあるいは濾別によって容易に分別回収することができる。 In this example, sieving is used, but since it is originally pulverized in a wet manner, 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 process from wet pulverization to filtration. Note that the casing, packing / safety valve, current collector (aluminum foil, copper foil), etc. have a higher spreadability than the positive electrode active material (typically LiCoO 2 ) 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.
上記処理によって得られた篩い下物に滲出処理を行う(S103)。   The sieving material obtained by the above process is subjected to leaching (S103).
本実施例で用いた滲出液は、図1に例示したとおりである。本実施例で使用した廃電池の正極活物質はLiCoOを主成分とするリチウム化合物であるが、リン酸鉄やニッケル、マンガンなど他組成の正極活物質を含んでいても構わない。 The exudate used in this example is as illustrated in FIG. The positive electrode active material of the waste battery used in this example is a lithium compound mainly composed of LiCoO 2 , but may include a positive electrode active material of another composition such as iron phosphate, nickel, or manganese.
本実施例で使用できる鉱酸としては、濃硫酸(90%〜98%)に、酸化還元調節剤として過酸化水素水添加を添加したものを用いる。リチウムとの分離が困難なリチウム以外のアルカリ金属類(ナトリウム、カリウム、ルビジウム、セシウム)を含有する鉱酸は使わないものとする。リチウム化合物の種類や組成、処理量、処理時間、コストなどを考慮して、これらの中から適宜選択できる。   As a mineral acid that can be used in this example, a concentrated sulfuric acid (90% to 98%) to which a hydrogen peroxide solution is added as a redox regulator is used. Mineral acids containing alkali metals other than lithium (sodium, potassium, rubidium, cesium) that are difficult to separate from lithium are not used. In consideration of the type and composition of the lithium compound, the treatment amount, the treatment time, the cost, etc., it can be appropriately selected from these.
酸滲出処理では、HSOとLiCoOとHとが反応することにより、LiSO、CoO、CoSOが生成すると考えられる。この反応は、2段階に分かれている。1段階目では、結晶構造を維持したまま、正極材中のリチウムイオンと溶液中のプロトンがイオン交換される。2段階目では、正極材の結晶構造からのリチウム溶出量が大きくなったために、結晶構造が崩壊し始める。このときにイオン溶出の挙動が変化し、コバルトイオンも溶出しやすくなる。よって、結晶構造が崩壊する前にリチウムを溶解させ、結晶構造が崩壊してコバルトの溶出が大きくなる前に溶解反応を停止するさせることが重要である。 In the acid leaching treatment, it is considered that H 2 SO 4 , LiCoO 2 and H 2 O 2 react to generate Li 2 SO 4 , CoO, and CoSO 4 . This reaction is divided into two stages. In the first stage, the lithium ions in the positive electrode material and the protons in the solution are ion-exchanged while maintaining the crystal structure. In the second stage, since the amount of lithium eluted from the crystal structure of the positive electrode material has increased, the crystal structure starts to collapse. At this time, the behavior of ion elution is changed, and cobalt ions are easily eluted. Therefore, it is important to dissolve lithium before the crystal structure collapses and stop the dissolution reaction before the crystal structure collapses and cobalt elution increases.
本実施例では、正極材に硫酸と過酸化水素を作用させると、反応エネルギーによる反応容易性から、まずリチウムイオンが溶液中に滲出し、その後にコバルトイオンが滲出する。リチウムイオンが滲出し、コバルトイオンが滲出する前に滲出処理を停止すれば、コバルトイオン濃度に対するリチウムイオン濃度が高いように選択酸溶解することができる。本実施例では、Li選択滲出工程の反応条件を制御することにより選択酸滲出させるのであるが、リチウムイオンの反応率は最大で80%以下(残量が20%以上)となる範囲で滲出を停止させる。実用的には誤差を考慮すると、好ましくは、70〜75%程度(残量25〜30%)の反応率でで停止させると、コバルトの溶出を抑えることができる。80%を越えるとLi選択滲出反応における選択比が劣化する危険性が高まり、70%を下回れば回収率が低下して経済性を損なう。   In this embodiment, when sulfuric acid and hydrogen peroxide are allowed to act on the positive electrode material, lithium ions are first leached into the solution and then cobalt ions are leached due to the ease of reaction due to reaction energy. If the leaching process is stopped before lithium ions are leached and cobalt ions are leached, selective acid dissolution can be performed so that the lithium ion concentration relative to the cobalt ion concentration is high. In this example, the selective acid leaching is controlled by controlling the reaction conditions in the Li selective leaching step, but the leaching is performed in a range where the reaction rate of lithium ions is 80% or less (the remaining amount is 20% or more). Stop. Considering errors in practical use, it is preferable to stop elution of cobalt at a reaction rate of about 70 to 75% (remaining amount is 25 to 30%). If it exceeds 80%, the risk of deterioration of the selectivity in the Li selective leaching reaction increases, and if it is less than 70%, the recovery rate decreases and the economy is impaired.
また、温度は50℃以下で行う。硫酸の作用により、リチウムイオンは硫酸リチウム(LiSO)として滲出するとともに、コバルトイオンは硫酸コバルト(CoSO)として滲出する。リチウムイオンが滲出するための活性化エネルギーと、コバルトイオンが滲出するための活性化エネルギーとでは、前者の方が著しく小さいことにより、リチウムイオンが先に滲出する。この反応選択性は、低温のほうが顕著に現れる。高温の場合には、熱エネルギーが豊富であり活性化エネルギーの大小による反応選択性の影響が小さいからである。 The temperature is 50 ° C. or lower. By the action of sulfuric acid, lithium ions are leached as lithium sulfate (Li 2 SO 4 ), and cobalt ions are leached as cobalt sulfate (CoSO 4 ). The activation energy for leaching lithium ions and the activation energy for leaching cobalt ions are significantly smaller in the former, so that the lithium ions are leached first. This reaction selectivity is more apparent at lower temperatures. This is because, when the temperature is high, the heat energy is abundant and the influence of the reaction selectivity due to the magnitude of the activation energy is small.
また、硫酸リチウムは、低温になるにつれ溶解度が大きくなり、硫酸コバルトは高温になるにつれ溶解度が大きくなるので、50℃以下の低温で処理を行うことによりリチウムの選択溶解を高めることができる。硫酸コバルトの溶解量が小さければ、それを形成するコバルトイオンの滲出量も少ないからである。また、イオンの溶解速度が遅いので、安定して溶解しやすいリチウムイオンを先に溶解させることができる。   Moreover, since lithium sulfate becomes more soluble as the temperature becomes lower, and cobalt sulfate becomes more soluble as the temperature becomes higher, the selective dissolution of lithium can be enhanced by performing the treatment at a low temperature of 50 ° C. or lower. This is because if the dissolution amount of cobalt sulfate is small, the leaching amount of cobalt ions forming the cobalt sulfate is also small. In addition, since the ion dissolution rate is low, lithium ions that are easily dissolved stably can be dissolved first.
用いる硫酸としては、濃硫酸(90%以上)であることが望ましい。希硫酸は強酸として働くので、リチウムとコバルトとをともに速い速度で溶解させる。一方で濃硫酸は、遊離する酸の量が少なく、強酸としては働かない。そのため、濃硫酸を用いた場合(90%硫酸を用いて若干の希釈をした場合も)、希硫酸ほどの強酸としての働きがないため、金属イオンの溶解速度が遅くなり、リチウムとコバルトの溶解速度を制御しやすい。   The sulfuric acid used is preferably concentrated sulfuric acid (90% or more). Since dilute sulfuric acid works as a strong acid, both lithium and cobalt are dissolved at a high rate. On the other hand, concentrated sulfuric acid has a small amount of free acid and does not work as a strong acid. Therefore, when concentrated sulfuric acid is used (even when diluted slightly with 90% sulfuric acid), it does not act as a strong acid as dilute sulfuric acid, so the dissolution rate of metal ions is slow, and lithium and cobalt dissolve. Easy to control speed.
また、希硫酸であっても、pHの小さい溶液に対しては、硫酸イオンを有する硫酸コバルトの溶解量が小さくなり、リチウムイオンの選択溶解性が高くなる。特に、酸滲出処理中のリチウムイオンと硫酸の濃度比が7以下となるように、硫酸の濃度、量、リチウムの添加量を調整することが望ましい。この濃度比の範囲では、選択溶解性が高いからである。図3に酸浸出処理中のリチウムイオンと硫酸の濃度比の例を記す。比較例1(特許文献2)及び比較例2(特許文献3)のように酸浸出処理中のリチウムイオンと硫酸の濃度比が、本実施例と比較して桁違いに大きな値である場合には、Li/Co比は低い値をとる。   Moreover, even if it is a dilute sulfuric acid, with respect to a solution with low pH, the dissolution amount of cobalt sulfate having sulfate ions is reduced, and the selective solubility of lithium ions is increased. In particular, it is desirable to adjust the concentration and amount of sulfuric acid and the amount of lithium added so that the concentration ratio of lithium ions and sulfuric acid during the acid leaching process is 7 or less. This is because the selective solubility is high in this concentration ratio range. FIG. 3 shows an example of the concentration ratio between lithium ions and sulfuric acid during the acid leaching process. As in Comparative Example 1 (Patent Document 2) and Comparative Example 2 (Patent Document 3), when the concentration ratio of lithium ions and sulfuric acid during the acid leaching process is an extremely large value compared to this example. Has a low Li / Co ratio.
過酸化水素は、溶解により上がった酸溶液中の電位を調整するために、酸化還元調整剤として用いる。電位が所定の範囲から外れてしまうと、選択溶解性に影響を与えてしまうからである。   Hydrogen peroxide is used as a redox regulator in order to adjust the potential in the acid solution raised by dissolution. This is because if the potential deviates from the predetermined range, the selective solubility is affected.
また、電池解体の焙焼工程を経ずに滲出工程を行うと、前述のようにバインダーのPVDFに起因する物質により正極材表面が撥水化して、選択溶解が起こらないという事態を回避できる。   In addition, when the leaching step is performed without passing through the battery disassembly roasting step, it is possible to avoid a situation where the surface of the positive electrode material becomes water repellent due to the PVDF as a binder and selective dissolution does not occur as described above.
本実施例では使用済みデジタルカメラ用リチウムイオン電池を解体して得られた酸滲出液のLi/Co濃度比を図1に示す。処理は以下のように行った。   In this embodiment, the Li / Co concentration ratio of the acid exudate obtained by disassembling a used lithium ion battery for a digital camera is shown in FIG. The treatment was performed as follows.
まず、廃リチウムイオン電池に粉砕および篩い分け処理を施して、筐体、パッキン・安全弁、回路素子類、セパレータ、集電体などをあらかじめ除去した後に、鉱酸を用いてリチウムイオン電池を構成している有価金属類を酸滲出(溶解)する。本実施例で用いたLi選択滲出液を図1に示す。室温で、1時間攪拌した後、遠心分離機で、15000rpm、20℃、15分間、遠心分離して上澄みと残渣に分けて滲出反応を停止させ、上澄み液を回収する。   First, waste lithium ion batteries are crushed and sieved to remove the casing, packing / safety valves, circuit elements, separators, current collectors, etc., and then make up the lithium ion batteries using mineral acid. Acid leaching (dissolving) valuable metals. The Li selective exudate used in this example is shown in FIG. After stirring at room temperature for 1 hour, the mixture is centrifuged at 15000 rpm, 20 ° C. for 15 minutes in a centrifuge to separate the supernatant and the residue to stop the exudation reaction, and the supernatant is recovered.
本実施例では、コバルト酸リチウム等の正極活物質からのLi滲出反応を簡便に停止させるための固液分離処理として、遠心分離を使用した。   In this example, centrifugation was used as a solid-liquid separation process for easily stopping the Li leaching reaction from the positive electrode active material such as lithium cobaltate.
滲出液に用いる酸としては硝酸、硫酸、塩酸を用いた。これらの酸に、メタノール、過酸化水素などの酸化還元電位調節剤を添加した。酸化還元電位調節剤を添加しておくことにより、酸滲出が安定し、回収量が増大する効果がある。滲出時間は、最長でも2時間以下が望ましく、さらに好ましくは、約1時間程度である。1時間を大きく下回る短時間、たとえば15分間の滲出では、回収率が少なくなりやすい。リチウムイオンが滲出除去された正極活物質の結晶構造は、強酸に対して安定ではないため、2時間を超えた長時間の滲出処理を行うと、正極活物質の結晶が崩壊して、コバルトの滲出が始まる。その結果として、酸滲出反応におけるLi選択性が低下する。また、非特許文献1に記載された非選択滲出(完全滲出)で採用されている80℃〜90℃に到達しないように滲出液の温度を十分に注意する。本実施例では、室温(15℃〜30℃)が最も好ましいが、最高でも50℃以下とする。50℃を大きく超えると滲出反応においてLi選択性が低下しやすくなる傾向があった。   Nitric acid, sulfuric acid, and hydrochloric acid were used as the acid used in the exudate. To these acids, a redox potential regulator such as methanol and hydrogen peroxide was added. By adding the oxidation-reduction potential regulator, there is an effect that acid leaching is stabilized and the recovery amount is increased. The leaching time is desirably 2 hours or less at the longest, and more preferably about 1 hour. In the case of leaching for a short time that is significantly less than 1 hour, for example, 15 minutes, the recovery rate tends to decrease. Since the crystal structure of the positive electrode active material from which lithium ions have been leached and removed is not stable against strong acids, if the leaching process for a long time exceeding 2 hours is performed, the crystal of the positive electrode active material collapses and cobalt Exudation begins. As a result, the Li selectivity in the acid leaching reaction is reduced. In addition, the temperature of the exudate is sufficiently taken care of so as not to reach 80 ° C. to 90 ° C., which is employed in the non-selective exudation (complete exudation) described in Non-Patent Document 1. In this example, room temperature (15 ° C. to 30 ° C.) is most preferable, but the maximum is 50 ° C. or less. When the temperature greatly exceeds 50 ° C., the Li selectivity tends to decrease in the exudation reaction.
図1は、各溶解条件で、20℃(温水除く)1時間滲出反応を行った結果である。図1に示すように、正極材(LiCoO2)を完全に滲出させた場合(完全溶解)の酸滲出液のLi/Co濃度比は約0.2であった。硫酸のみの場合は、Li/Co濃度比は約1.2、硝酸のみの場合はLi/Co濃度比は約0.8となる。硫酸:過酸化水素=1:1を酸滲出液として選択滲出させたとき、Li/Co濃度比は約1.7となる。上記の選択滲出によって得られる回収液(A)には、Liの他、酸滲出の際に過剰に添加した酸も同時に回収されている。 FIG. 1 shows the results of an exudation reaction for 1 hour at 20 ° C. (excluding hot water) under each dissolution condition. As shown in FIG. 1, when the positive electrode material (LiCoO 2 ) was completely leached (complete dissolution), the Li / Co concentration ratio of the acid exudate was about 0.2. In the case of only sulfuric acid, the Li / Co concentration ratio is about 1.2, and in the case of only nitric acid, the Li / Co concentration ratio is about 0.8. When selective leaching is performed using sulfuric acid: hydrogen peroxide = 1: 1 as the acid leaching solution, the Li / Co concentration ratio is about 1.7. In addition to Li, the acid added excessively at the time of acid leaching is simultaneously recovered in the recovery liquid (A) obtained by the above selective leaching.
本実施例では、上記の滲出処理が終了した後の残渣は、負極活物質および正極活物質のうちの遷移金属成分である。酸性溶液、負極活物質、正極活物質は、比重が異なることを利用すれば容易に分離できる(図2(S104))。具体的には、滲出液を遠心分離することで分離回収できる。本実施例では、遠心分離法を採用して、15000rpmで、15分処理することにより分離回収したが、回転数はさらに高い方が上澄みの酸性溶液(回収液、Li)、負極活物質(C:カーボン)、正極活物質(Co)の分離が容易である。また、比重差の利用以外で分離回収する方法として、滲出液をろ過することで、上澄み液と残渣(負極活物質及び正極活物質)とに分離回収できる。この場合、さらに残渣を負極活物質と正極活物質とに分離する工程を行うこととなる。   In this example, the residue after the above leaching process is a transition metal component of the negative electrode active material and the positive electrode active material. The acidic solution, the negative electrode active material, and the positive electrode active material can be easily separated by utilizing the fact that the specific gravity is different (FIG. 2 (S104)). Specifically, the exudate can be separated and recovered by centrifuging. In this example, the centrifugal separation method was adopted, and separation and recovery were performed by treating at 15000 rpm for 15 minutes. However, the higher the number of revolutions, the higher the acidic solution (recovered liquid, Li), the negative electrode active material (C : Carbon) and the positive electrode active material (Co) are easily separated. Further, as a method of separating and collecting other than using the specific gravity difference, the exudate can be filtered and separated and recovered into a supernatant and a residue (a negative electrode active material and a positive electrode active material). In this case, a step of further separating the residue into the negative electrode active material and the positive electrode active material is performed.
Liを含有する上澄み液は、陰イオン交換膜を用いた拡散透析処理や、圧力透析処理、イオン交換樹脂、などの処理を単独、または組み合わせて、または多段階で実施し、さらにLi、Coを分離してもよい。また、陰イオン選択透過膜を用いた透析処理や、溶媒抽出法、アシッドリターデーション法などを用いてさらにLiとCoを分離することもできる。これらの残液から、それぞれの元素毎に分離回収するにはさまざまな方法が使用できるが、隔膜電解法、中和(pH=6〜9)による水酸化物沈殿回収、あるいはこれらを組み合わせた方法を用いることができる。これらの方法を行えば、さらにLi/Coの濃度比を高くすることができる。   The supernatant liquid containing Li is subjected to diffusion dialysis treatment using an anion exchange membrane, pressure dialysis treatment, treatment of ion exchange resin, etc., alone or in combination, or in multiple stages, and further Li, Co. It may be separated. Further, Li and Co can be further separated by dialysis using an anion selective permeation membrane, solvent extraction method, acid retardation method and the like. Various methods can be used for separating and recovering each residual element from these residual liquids. However, a diaphragm electrolysis method, hydroxide precipitation recovery by neutralization (pH = 6 to 9), or a combination of these methods. Can be used. By performing these methods, the Li / Co concentration ratio can be further increased.
上記のようにして得たLiの含有割合が大きい回収液(A)をナトリウムを含まない炭酸塩で中和処理すれば、高純度なLiが回収できる(S105)。   Highly pure Li can be recovered by neutralizing the recovered liquid (A) having a large Li content ratio as described above with a carbonate not containing sodium (S105).
具体的には、炭酸カルシウムをナトリウムを含まない炭酸塩として添加して炭酸リチウムとして沈殿回収できる。他に電気透析しながらCOガスを吹き込む、などの方法がある。本実施例では遷移金属成分(B)は上記比重差を活用した遠心分離工程によって、Li含有液(A)から分離回収できる(S106)。 Specifically, calcium carbonate can be added as a carbonate containing no sodium and precipitated and recovered as lithium carbonate. Other methods include blowing CO 2 gas while electrodialyzing. In this embodiment, the transition metal component (B) can be separated and recovered from the Li-containing liquid (A) by the centrifugal separation process utilizing the above specific gravity difference (S106).
一方でCoが選択分離された酸滲出液からのCo回収には、まず、S104で分離したものから正極活性材を回収する(S107)。そして、正極材を酸性溶液に浸漬し、コバルトイオンを滲出(または溶出)させる。コバルトイオンが滲出した溶液に、pH調整によって水酸化物としてコバルトを沈殿させ回収する沈殿回収法が使用できる(S108)。遷移金属成分(B)をそれぞれの金属種類別に分別回収するためには、遷移金属成分(B)を酸溶解した後にそれぞれの金属元素の水酸化物の溶解特性差を利用する処理、基本的にはpH調整→沈殿回収の繰り返しによって遷移金属元素種類毎に分別回収できる。正極活物質がLiCoO以外のリチウム化合物を含有する場合、例えば、LiNiO、LiMnO、Li(Ni1/3Co1/3Mn1/3)O、LiCoPO、LiFePO、LiCoPOF、LiFePOF等のオリビン系正極材などの場合も液のpH調整によってCo、Ni、Mn、Feを水酸化物として分別して沈殿回収できる。 On the other hand, for recovering Co from the acid exudate from which Co has been selectively separated, first, the positive electrode active material is recovered from the one separated in S104 (S107). Then, the positive electrode material is immersed in an acidic solution to exude (or elute) cobalt ions. A precipitation recovery method can be used in which cobalt is precipitated and recovered as a hydroxide by pH adjustment in a solution from which cobalt ions have exuded (S108). In order to separate and recover the transition metal component (B) for each metal type, a treatment using the difference in the dissolution characteristics of the hydroxides of the respective metal elements after the transition metal component (B) is acid-dissolved, basically Can be recovered separately for each type of transition metal element by repeated pH adjustment and precipitation recovery. When the positive electrode active material contains a lithium compound other than LiCoO 2 , for example, LiNiO 2 , LiMnO 2 , Li (Ni 1/3 Co 1/3 Mn 1/3 ) O 2 , LiCoPO 4 , LiFePO 4 , LiCoPO 4 F In the case of an olivine-based positive electrode material such as LiFePO 4 F, Co, Ni, Mn, and Fe can be fractionated as hydroxides by adjusting the pH of the liquid and precipitated and recovered.
図4に、実施例2における金属回収方法のフローチャートを示す。   In FIG. 4, the flowchart of the metal collection | recovery method in Example 2 is shown.
S201〜S202は、実施例1のS101〜S102と同じである。S203において、実施例1と同様に正極材を酸滲出を行った後、上澄み液と残渣に分ける。上澄み液は、リチウムイオンとコバルトイオンとが滲出しLi/Coの比が高い酸性溶液であり、残渣は、負極活性材とイオンが滲出した正極活性材である。これらを遠心分離や濾過などの方法により、上澄み液と残渣に分離する。   S201 to S202 are the same as S101 to S102 of the first embodiment. In S203, the positive electrode material is subjected to acid leaching in the same manner as in Example 1, and then divided into a supernatant and a residue. The supernatant is an acidic solution in which lithium ions and cobalt ions are leached and the ratio of Li / Co is high, and the residue is a negative electrode active material and a positive electrode active material from which ions are leached. These are separated into a supernatant and a residue by a method such as centrifugation or filtration.
S204において、残渣をさらに酸性溶液に溶解させることにより、残渣中の正極活性材に含まれているコバルト及びリチウムをイオン化させて酸性溶液中に溶解させる。ここで目的となるのはコバルトとリチウムであるので、炭素からなる負極活性材は溶解前に取り除き、正極活性材のみを溶解させてもよい。こうして、Li/Coの比が低い酸性溶液が生成する。   In S204, the residue is further dissolved in an acidic solution, whereby cobalt and lithium contained in the positive electrode active material in the residue are ionized and dissolved in the acidic solution. Here, since the target is cobalt and lithium, the negative electrode active material made of carbon may be removed before dissolution, and only the positive electrode active material may be dissolved. Thus, an acidic solution with a low Li / Co ratio is produced.
S205においては、S203で得られた上澄み液のリチウムイオンとコバルトイオンとを分離する。分離の方法としては、以下のものがある。   In S205, the lithium ions and cobalt ions in the supernatant obtained in S203 are separated. Examples of the separation method include the following.
陰イオン選択透過膜(透析膜)を用いることにより、リチウムイオンとコバルトイオンとを分離することができる。陰イオン選択透過膜は陰イオンを透過させる膜であるが、リチウムイオンは陽イオンであるにもかかわらず陰イオン選択透過膜を透過する現象が起こる。そのため、陰イオン選択透過膜の面の一方にS203にてイオンを滲出させた酸性溶液を流し、他方の面にリチウムイオンを回収するための回収液(例えば純水)を流すと、酸性溶液からリチウムイオンが透析膜を透過して回収液中に移動する。このとき、コバルトイオンは透析膜を透過せず、酸性溶液中に留まる。このようにして、リチウムイオンを回収液中に、コバルトイオンを酸性溶液中に分離することができる。   By using an anion selective permeable membrane (dialysis membrane), lithium ions and cobalt ions can be separated. An anion selective permeable membrane is a membrane that allows anions to pass therethrough, but a phenomenon occurs in which lithium ions are transmitted through the anion selective permeable membrane even though they are cations. Therefore, when an acidic solution in which ions are leached in S203 is flowed to one of the surfaces of the anion selective permeation membrane and a recovery solution (for example, pure water) for recovering lithium ions is flowed to the other surface, the acidic solution Lithium ions permeate through the dialysis membrane and move into the recovered solution. At this time, cobalt ions do not permeate the dialysis membrane and remain in the acidic solution. In this way, lithium ions can be separated into the recovered solution and cobalt ions into the acidic solution.
また、イオン交換樹脂を用いることにより、リチウムイオンとコバルトイオンとを分離することができる。酸性溶液をイオン交換樹脂に通すと、先に酸の塩が溶出し、その後に遅れて酸が溶出するアシッドリターデーションが知られている。このとき、酸の塩としてリチウムイオンとコバルトイオンとを含む場合、最初にコバルトイオンが溶出し、その後にリチウムイオンが溶出し、最後に酸が溶出する。溶出する液体を時間ごとに分ければ、最初に溶出した溶液はコバルトイオン濃度が大きく、その後に溶出した溶液はリチウムイオンが大きくなり、リチウムイオンとコバルトイオンの分離をすることができる。   Moreover, lithium ion and cobalt ion can be separated by using an ion exchange resin. Acid retardation is known in which when an acidic solution is passed through an ion exchange resin, an acid salt elutes first, and then an acid elutes later. At this time, when lithium ions and cobalt ions are contained as an acid salt, cobalt ions are eluted first, lithium ions are then eluted, and acid is finally eluted. If the liquid to be eluted is divided by time, the solution eluted first has a large cobalt ion concentration, and the solution eluted thereafter has a large lithium ion, so that lithium ions and cobalt ions can be separated.
このようにして、上澄み液を、Li/Coの濃度比が高いLi濃縮液と、Li/Coの濃度比が低いCo濃縮液とに分離することができる。   In this way, the supernatant can be separated into a Li concentrate having a high Li / Co concentration ratio and a Co concentrate having a low Li / Co concentration ratio.
S206においては、S204で得られた酸性溶液のリチウムイオンとコバルトイオンとを分離し、Li濃縮液とCo濃縮液とを得る。分離の方法としては、S205と同様の方法を適用可能である。   In S206, the lithium ion and cobalt ion of the acidic solution obtained in S204 are separated to obtain a Li concentrated solution and a Co concentrated solution. As a separation method, the same method as in S205 can be applied.
S207においては、S204及びS205で得られたLi濃縮液を回収する。S208においては、S106と同様な方法で、Li濃縮液からリチウムを回収する。   In S207, the Li concentrate obtained in S204 and S205 is recovered. In S208, lithium is recovered from the Li concentrate by the same method as in S106.
S209においては、S204及びS205で得られたCo濃縮液を回収する。S208においては、S108と同様な方法で、Li濃縮液からリチウムを回収する。   In S209, the Co concentrate obtained in S204 and S205 is recovered. In S208, lithium is recovered from the Li concentrate by the same method as in S108.
実施例2では、このようにして、リチウム及びCoを回収する。実施例1に対して、リチウムとCoを分離する工程を加え、得られたLi濃縮液とCo濃縮液とをそれぞれ集めて回収することで、リチウム及びCoの回収率が向上する。   In Example 2, lithium and Co are recovered in this way. A recovery step of lithium and Co is improved by adding a step of separating lithium and Co to Example 1 and collecting and collecting the obtained Li concentrated solution and Co concentrated solution.

Claims (7)

  1. リチウムとコバルトを含むリチウムイオン電池の正極材からリチウムを抽出するリチウム抽出方法において、
    前記正極材を、酸性溶液に50℃以下で浸漬して前記溶液中にリチウムイオンを滲出させる工程と、
    前記正極材のリチウムの含有量が前記滲出工程前の前記正極材のリチウムの含有量の30%以上のときに、前記リチウムイオンの滲出を止める工程とを含むことを特徴とするリチウム抽出方法。
    In a lithium extraction method for extracting lithium from a positive electrode material of a lithium ion battery containing lithium and cobalt,
    Immersing the positive electrode material in an acidic solution at 50 ° C. or less to exude lithium ions in the solution;
    And a step of stopping leaching of the lithium ions when the lithium content of the positive electrode material is 30% or more of the lithium content of the positive electrode material before the leaching step.
  2. 請求項1において、
    前記酸性溶液は、硫酸を含むことを特徴とするリチウム抽出方法。
    In claim 1,
    The method for extracting lithium, wherein the acidic solution contains sulfuric acid.
  3. 請求項2において、
    前記酸性溶液は、濃硫酸であることをことを特徴とするリチウム抽出方法。
    In claim 2,
    The method for extracting lithium, wherein the acidic solution is concentrated sulfuric acid.
  4. 請求項1または請求項2において、
    前記酸性溶液は、酸化還元調整剤を有していることを特徴とするリチウム抽出方法。
    In claim 1 or claim 2,
    The said acidic solution has a redox regulator, The lithium extraction method characterized by the above-mentioned.
  5. 請求項4において、
    前記酸化還元調整剤は、過酸化水素であることを特徴とするリチウム抽出方法。
    In claim 4,
    The method of extracting lithium, wherein the redox regulator is hydrogen peroxide.
  6. 請求項1乃至5のいずれかに記載のリチウム抽出方法で得られた前記リチウムイオンが滲出した溶液からリチウムを回収する工程と、
    請求項1乃至5のいずれかに記載のリチウム抽出方法に用いた正極材からCoを回収する工程とを含む金属回収方法。
    A step of recovering lithium from the lithium ion leached solution obtained by the lithium extraction method according to any one of claims 1 to 5;
    A metal recovery method including a step of recovering Co from the positive electrode material used in the lithium extraction method according to claim 1.
  7. 請求項6において、
    前記リチウムイオンが滲出した溶液を、さらにリチウムイオンの含有割合が大きい溶液とCoイオンの含有割合が大きい溶液とに分離する工程を含み、
    当該分離されたリチウムイオンの含有割合が大きい溶液からリチウムを回収することを特徴とする金属回収方法。
    In claim 6,
    Separating the lithium ion exuded solution into a solution having a higher lithium ion content and a solution having a higher Co ion content,
    A metal recovery method comprising recovering lithium from a solution having a large content of separated lithium ions.
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KR101601918B1 (en) * 2013-09-17 2016-03-09 울산과학기술원 Lithium secondary battery and lithium secondary battery system
JP2016069706A (en) * 2014-09-30 2016-05-09 Jx金属株式会社 Method for leaching metal and method for recovering metal using the same
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CN112143897A (en) * 2020-09-11 2020-12-29 威海广泰空港设备股份有限公司 Method for extracting noble metal from waste lithium battery in airport service vehicle

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