WO2019102765A1 - Procédé de traitement de déchets de batterie lithium-ion - Google Patents

Procédé de traitement de déchets de batterie lithium-ion Download PDF

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Publication number
WO2019102765A1
WO2019102765A1 PCT/JP2018/039199 JP2018039199W WO2019102765A1 WO 2019102765 A1 WO2019102765 A1 WO 2019102765A1 JP 2018039199 W JP2018039199 W JP 2018039199W WO 2019102765 A1 WO2019102765 A1 WO 2019102765A1
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Prior art keywords
electrolytic
lithium ion
copper
alloy
nickel
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PCT/JP2018/039199
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English (en)
Japanese (ja)
Inventor
宏 竹之内
浅野　聡
丹　敏郎
小林　宙
賢二 竹田
Original Assignee
住友金属鉱山株式会社
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Priority claimed from JP2017242907A external-priority patent/JP6798080B2/ja
Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to KR1020207016157A priority Critical patent/KR102427533B1/ko
Priority to US16/765,225 priority patent/US11618959B2/en
Priority to CA3083379A priority patent/CA3083379C/fr
Priority to EP18880919.8A priority patent/EP3715484B1/fr
Priority to CN201880075458.XA priority patent/CN111373062B/zh
Publication of WO2019102765A1 publication Critical patent/WO2019102765A1/fr

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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
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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
    • C22B15/00—Obtaining copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • 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
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • 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 method for treating waste lithium ion batteries, and more particularly to a treatment method for separating and recovering copper, nickel and cobalt contained in waste lithium ion batteries.
  • waste lithium ion batteries contain a large amount of valuable metals such as copper, nickel and cobalt, and waste lithium ion batteries are not recycled as industrial waste as they are, but are recovered and recycled. It is desired to do.
  • waste lithium ion batteries in addition to the above-mentioned valuable metals, such as metals such as iron and aluminum, which are not economically very high even if recovered with much effort, and as they are recovered as plastic parts.
  • valuable metals such as metals such as iron and aluminum
  • a variety of materials are used, such as substances that are difficult to process, and substances that are technically not easy to recover, such as organic electrolytes containing phosphorus and fluorine, and that can not be discarded as they are on an environmental basis. Therefore, it is not easy to separate them efficiently and recover valuable metals.
  • an organic electrolyte used in a lithium ion battery has a high degree of activity, and when used as a battery, the charged charge may remain as it is. Therefore, when the waste lithium ion battery is disassembled carelessly, the positive electrode and the negative electrode of the battery short-circuit, which may cause heat generation or ignition of the electrolyte. As described above, there is also a problem that the handling of the waste lithium ion battery takes care and time.
  • waste lithium ion battery when processing a waste lithium ion battery and recovering valuable metals, first, put the waste lithium ion battery in a furnace and perform processing of melting at a high temperature under high temperature, or process a large amount of waste lithium ion batteries In this case, it is heated (sintered) at a temperature of about 400 ° C. to 600 ° C. necessary for decomposing the electrolytic solution to remove electric charges remaining in the battery and to pretreat the harmless treatment to decompose the organic electrolytic solution. Do as. Next, put the waste lithium ion battery that has been detoxified in an electric furnace etc.
  • a two-stage melting process has been used in which separation is performed to obtain an alloy metal whose main component is copper, nickel, or cobalt.
  • the alloy metal obtained by such a conventional method can be reused as ferronickel which is a stainless steel material, but valuable components such as cobalt and copper other than nickel contained in the alloy metal are useless as a stainless steel material. , It can not be recovered effectively and it will be a waste of resources.
  • nickel contained in a waste lithium ion battery is used as an electrode or a wiring material, it is generally larger than the content of nickel, for example, a method of smelting nickel from nickel oxide ore (nickel oxide ore Of the smelting process) can not be used as it is.
  • Patent Document 1 As a method of separating copper and nickel and cobalt by leaching an alloy metal with an acid, there is a method disclosed in Patent Document 1, for example. In the process of leaching the alloy with acid, this method dissolves valuable metals such as nickel and cobalt in the leaching solution while leaving most of the copper in the solid state, so that the copper dissolved in the solution after leaching It is a method that can simplify or omit the process required for removal, improve the process efficiency, and reduce the process cost.
  • the heating step of heating the lithium ion battery to 450 ° C. to 650 ° C., and the battery powder obtained after the heating step are required to dissolve all the metal components contained in the battery powder.
  • the method disclosed in the patent document 1 and so-called selective leaching method has an advantage that it can be processed efficiently.
  • a gas such as oxygen or air or an oxidant such as hydrogen peroxide.
  • an oxidant such as hydrogen peroxide.
  • the present invention has been proposed in view of such circumstances, and recovers valuable metals copper, nickel, and cobalt from waste lithium ion batteries, and effectively separates copper from nickel and cobalt. Intended to provide a method that can be
  • the inventor of the present invention melts a waste lithium ion battery to obtain an alloy containing copper, nickel and cobalt, and then performs electrolytic treatment in a sulfuric acid solution using the alloy as an anode.
  • the inventors have found that the problems described above can be effectively solved, and have completed the present invention.
  • a first invention according to the present invention comprises an alloy forming step of melting a waste lithium ion battery by charging it into a furnace and heating it to obtain an alloy containing copper, nickel and cobalt; Electrolytic purification process of separating copper contained in the alloy on the cathode and separating it from nickel and cobalt by charging in a sulfuric acid acidic solution as an electrode and subjecting it to electrolytic treatment in which current is applied between the anode and the cathode. And a method of treating a waste lithium ion battery.
  • the copper concentration in the sulfuric acid acidic solution which is an electrolytic solution is in the range of 5 g / L to 50 g / L.
  • the alloy contains phosphorus in a range of 0.5% by weight or more and 2.0% by weight or less, It is a processing method of the waste lithium ion battery which uses the said alloy as an anode in refinement
  • the electrolytic solution after the electrolytic treatment in the electrolytic purification step is supplied to an electrolytic cell, and the electrolysis is carried out using an insoluble anode. It is a processing method of a waste lithium ion battery which further has an electrowinning process of electrodepositing copper which remained in liquid.
  • a sixth aspect of the present invention is the waste lithium according to the fifth aspect, wherein the electrolytic solution discharged from the electrolytic cell through the electrolytic collection step is repeatedly supplied as an electrolytic solution used in the electrolytic purification step. It is a processing method of an ion battery.
  • the seventh invention of the present invention according to the first invention, at least a part of the electrolytic solution obtained after the electrolytic treatment in the electrolytic purification step is recovered, and an oxidizing agent and a neutralizing agent are added to the electrolytic solution.
  • the method further includes an impurity removal step of removing an impurity component by adjusting the redox potential (reference electrode: silver / silver chloride electrode) to be 570 mV or more and the pH to be in the range of 3 to 5 by adding Thereafter, sulfuric acid is added to the filtrate obtained by solid-liquid separation to adjust the pH to 1.5 or less, and the filtrate after pH adjustment is repeatedly supplied as an electrolyte used in the electrolytic purification step, waste lithium ion It is a battery processing method.
  • the redox potential reference electrode: silver / silver chloride electrode
  • the eighth invention of the present invention according to the first invention, at least a part of the electrolytic solution obtained after the electrolytic treatment in the electrolytic purification step is recovered, and the pH of the electrolytic solution is 1.5 or less.
  • An oxidizing agent is added to the electrolytic solution at a stage to adjust the redox potential (reference electrode: silver / silver chloride electrode) to be 570 mV or more, and then an oxidizing agent and a neutralizing agent are further added,
  • the method further comprises an impurity removal step of removing the impurity component by raising the pH to 3 and adjusting the redox potential to be 300 mV or more, and then adding sulfuric acid to the filtrate obtained by solid-liquid separation
  • the pH is adjusted to 1.5 or less, and the filtrate after pH adjustment is repeatedly supplied as an electrolytic solution used in the electrorefining step.
  • valuable metals copper, nickel and cobalt can be recovered from a waste lithium ion battery, and the copper and nickel and cobalt can be effectively separated.
  • the method for treating a waste lithium ion battery according to the present invention is a treatment method for recovering valuable metals copper, nickel and cobalt from waste lithium ion batteries such as used batteries. is there.
  • the term "waste lithium ion battery” is a generic term for scraps such as waste materials generated in the manufacturing process of the above-described used lithium ion battery and lithium ion battery.
  • the waste lithium ion battery is melted by being introduced into a furnace and heated to obtain an alloy forming step S1 for obtaining an alloy containing copper, nickel and cobalt.
  • copper contained in the alloy is electrodeposited on the cathode to obtain nickel and cobalt by subjecting the obtained alloy as an anode to a sulfuric acid solution and subjecting it to an electrolytic treatment in which current is applied between the anode and the cathode.
  • electrorefining step S2 to be separated.
  • an electrolytic method is used to melt the obtained alloy. That is, instead of dissolving the obtained alloy directly with acid or the like, the alloy is used as an anode to conduct electricity and electrolytic treatment is performed to elute copper, nickel and cobalt from the alloy into the electrolytic solution. At the same time, copper on the cathode is electrodeposited on the cathode side on the cathode side.
  • nickel and cobalt can be used, for example, as a battery active material
  • a solution containing nickel and cobalt recovered in a state separated from copper from a waste lithium ion battery can be used as it is. It can be used as a raw material for producing substances.
  • the waste lithium ion battery is put into a furnace and melted to melt it, thereby obtaining an alloy containing copper, nickel and cobalt. That is, in the alloy formation step, it is affirmation to form an alloy containing copper, nickel and cobalt which are valuable metals contained in the waste lithium ion battery.
  • the alloy formation step S1 first, it is put into a roasting furnace of a waste lithium ion battery and roasted at a temperature of, for example, 300 ° C. to 1000 ° C., more preferably 500 ° C. to 900 ° C.
  • the electrolytic solution contained in the waste lithium ion battery can be decomposed, volatilized and removed.
  • the structure including the casing contained in the waste lithium ion battery can be easily separated and removed by controlling the roasting temperature based on the melting point of the material forming the structure.
  • the roasted product (post-baked product) obtained after the roasting treatment is put into a melting furnace such as a graphite crucible or a magnesium crucible, for example, to about 1100 ° C. to 1400 ° C. Melt under high temperature conditions. Such a melting process makes it possible to almost completely melt the roasted product and to form an alloy containing copper, nickel and cobalt.
  • a melting furnace such as a graphite crucible or a magnesium crucible
  • the roasted product can be treated, for example, by being introduced together with an oxide-based flux.
  • the flux is not particularly limited, and calcium oxide, magnesium oxide, silicon oxide and the like can be mentioned.
  • iron may also be contained in the alloy obtained by the melting process.
  • lithium ion batteries may use an electrolyte containing phosphorus in addition to fluorine such as hexafluorophosphoric acid, among which fluorine is easily volatilized and removed by roasting treatment.
  • fluorine such as hexafluorophosphoric acid
  • fluorine is easily volatilized and removed by roasting treatment.
  • Part of the phosphorus may be distributed to the alloy. Therefore, the alloy obtained by the melting process may contain a part of phosphorus, and is alloyed with copper and exists as phosphorus-containing copper or a form similar thereto.
  • passivation of the anode can be made difficult to occur, and the electrolytic treatment is carried out at a high current density to make the electrolytic solution It can be dissolved in it.
  • the obtained alloy (an alloy containing copper, nickel and cobalt) is charged as an anode in a sulfuric acid acidic solution to carry out electrolytic treatment.
  • an alloy containing copper, nickel, and cobalt is used as an anode, and a stainless steel plate or the like is used as a cathode, and the anode and the cathode are charged face to face in an electrolytic cell. Then, it is subjected to an electrolytic treatment by energizing between the anode and the cathode.
  • the electrolytic solution a sulfuric acid acidic solution is used, and the concentration of sulfuric acid is not particularly limited. For example, it is preferable to use a solution in a concentration range of 1% by mass to 70% by mass.
  • the sulfuric acid concentration of the electrolytic solution composed of a sulfuric acid acidic solution is the sulfuric acid concentration of the initial electrolytic solution at the start of energization.
  • the concentration of sulfuric acid in the electrolytic solution is less than 1% by mass, the concentrations of soluble copper, nickel, and cobalt may not increase and productivity may be reduced.
  • the electric conductivity is lowered and the voltage is increased, resulting in a loss.
  • the concentration of copper that can be dissolved is not high, the electrodeposition of copper on the cathode is not smooth and tends to be powdery or granular, and it is not preferable because nickel and cobalt are entrapped in the electrodeposition gaps, leading to a decrease in separability. .
  • an electrolyte solution it is preferable to adjust the pH to the range of 0 or more and 1.5 or less, and to perform an electrolysis process.
  • copper, nickel, and cobalt can be more efficiently dissolved from the alloy, and only copper can be electrodeposited more selectively thereafter. If the pH of the electrolytic solution is less than 0, the acid may be too strong and the electrodeposited copper may be easily redissolved. On the other hand, when the pH of the electrolyte exceeds 1.5, not only copper but also nickel and cobalt may tend to be electrodeposited.
  • the anode current density is not particularly limited, it is preferable to 3A / m 2 or more 3000A / m 2 or less in the range, and more preferably to 100A / m 2 or more 2000A / m 2 or less.
  • the production efficiency may be degraded, for example, by requiring an extra facility.
  • the current density of the anode exceeds 3000 A / m 2 , passivation tends to occur on the anode side, and the liquid resistance by the electrolyte between the anode and the cathode increases, so the process The overall power cost increases and efficient processing can not be performed.
  • the heat generation of the electrolytic treatment increases, which may cause problems in terms of material and safety.
  • it is not preferable that components other than copper are easily electrodeposited on the cathode.
  • the current density of the cathode is preferably equal to or lower than the above-mentioned range of the anode current density.
  • copper eluted from the anode can be deposited more efficiently on the cathode.
  • copper eluted from the anode is electrodeposited on the cathode, while nickel and cobalt are kept dissolved to separate copper from nickel and cobalt. From this fact, if the electrodeposition of copper is not efficiently performed, it will be a loss from the viewpoint of electric power, which is not preferable.
  • a cathode having a structure in which the electrode area of the cathode is larger than the electrode area of the anode may be used.
  • the inventor has found that the pH of the electrolyte is in the range of 0 to 1.2 between the pH of the electrolyte from which an electrodeposit having a nickel grade of less than 0.1% by weight is obtained and the cathode current density (Dk).
  • Equation 1 Found that the relationship that That is, by performing electrolytic purification at a current density equal to or lower than the current density calculated by the above-mentioned formula 1 for a predetermined pH, the quality of nickel deposited on the cathode can be suppressed to less than 0.1% by weight. it can.
  • the electrolytic treatment in the electrolytic refining step S2 copper, nickel, cobalt, iron and the like are dissolved in the electrolytic solution from the alloy used as the anode, and then the dissolved copper is preferentially electrodeposited on the cathode Although it will come out, it is preferable to adjust so that the copper concentration in the electrolyte solution at this time may be maintained in the range of 5 g / L to 50 g / L.
  • the concentration of copper dissolved in the electrolyte is less than 5 g / L, nickel and cobalt dissolved in the electrolyte also tend to be electrodeposited on the cathode, and can not be effectively separated from copper There is sex.
  • copper ions in the electrolytic solution become insufficient, water is electrolyzed at the cathode to generate hydrogen gas, and as a result, the pH of the electrolytic solution is increased to promote the tendency of nickel and cobalt to be electrodeposited.
  • the copper concentration in the electrolytic solution exceeds 50 g / L, the copper concentration in the electrolytic solution may be excessive, and the separation from nickel and cobalt may be insufficient.
  • the alloy obtained through the alloy formation step S1 may contain phosphorus derived from the electrolyte solution of the waste lithium ion battery.
  • a phosphorus-containing alloy as the anode, passivation of the anode can be less likely to occur, and electrolytic treatment can be performed at a high current density.
  • the concentration of phosphorus in the alloy is not particularly limited, but is preferably in the range of, for example, 0.5% by weight or more and 2.0% by weight or less.
  • Phosphorus is considered to be present in the form of copper phosphide (CuP), nickel phosphide (NiP), etc. in the alloy serving as the anode, but as copper, nickel, and cobalt are eluted from the alloy during electrolysis, Phosphorus is concentrated in the deposit formed as slime on the anode surface.
  • the phosphorus concentration in the alloy is less than 0.5% by weight, it is difficult to obtain the above-described effect of suppressing passivation of the anode.
  • the phosphorus concentration is more than 2.0% by weight, the time for slime treatment and the time for partially removing the phosphorus eluted in the electrolytic solution are increased.
  • purifying the electrolyte solution from which nickel and cobalt were leached by electrolytic refining the effort which removes the phosphorus as an impurity will increase.
  • the concentration of phosphorus in the anode slime tends to proceed as the acid concentration of the electrolytic solution is lower and the anode current density is smaller. Therefore, the total amount of phosphorus in the alloy does not elute in the electrolytic solution in the range of the preferred acid concentration in the treatment in the electrolytic purification step S2 and the range of the anode current density as described above. Since it is necessary to separate and remove from the electrolytic solution (separate and remove in the impurity removing step described later) when reusing a part of the electrolytic solution in the electrolytic purification step S2, the phosphorus eluted in the electrolytic solution needs time and effort In consideration of this, it is preferable that the proportion of phosphorus distributed to the anode slime be 20% or more.
  • the alloy containing copper, nickel and cobalt obtained in the alloy formation step S1 is used as an anode, and is inserted into the electrolyte of a sulfuric acid acidic solution And electrolytic treatment. Then, copper, nickel, and cobalt contained in the alloy are dissolved in the electrolytic solution, and only copper is preferentially deposited on the cathode and recovered, whereby copper, nickel, and cobalt are effectively removed. And efficiently separate.
  • valuable metals such as copper, nickel and cobalt can be effectively recovered from the waste lithium ion battery by a simple method of electrolytic treatment, and copper and nickel and cobalt are separated. It can be collected in the state.
  • the elution amount of the metal component eluted in the electrolytic solution by the electrolytic treatment can be controlled by the amount of electricity supplied between the anode and the cathode.
  • the electrolytic treatment since blowing of an oxidizing agent and air is unnecessary, power and motive power for air supply are unnecessary other than the power for electrolysis, and the acid-containing mist is There is no environmental deterioration such as scattering around, and stable operation can be performed.
  • electrolytic solution after the electrolytic treatment in the electrolytic refining step S2 may be supplied to the electrolytic cell to carry out the electrolytic treatment, and the electrolytic collection step S3 may be carried out to cause the copper remaining in the electrolytic solution to be electrodeposited.
  • the amount of copper dissolved in the electrolytic solution fluctuates according to the amount of copper in the alloy, the amount of electrification in the electrolytic treatment in the electrolytic refining step S2, etc., and the amount of copper electrodeposited on the cathode also changes.
  • an electrolytic collection step S3 is performed in which the electrolytic treatment is performed using the electrolytic solution after the electrolytic treatment in the electrolytic purification step S2 (the electrolytic solution in which copper remains), whereby the copper remaining in the electrolytic solution is electrodeposited.
  • the electrolytic solution after the electrolytic treatment in the electrolytic purification step S2 is supplied to a predetermined electrolytic cell, and copper remaining in the electrolytic solution is electrodeposited using an insoluble anode.
  • copper in the electrolytic solution recovered through the electrolytic refining step S2 can be deposited and recovered, and separated from nickel and cobalt contained in the electrolytic solution with high separation property, Highly pure solutions of nickel and cobalt can be obtained.
  • the electrolytic solution to be subjected to electrolytic collection is preferably adjusted to pH 1.5 or less, more preferably pH 1.0 or less.
  • the cathode current density is preferably in the range of 1 A / m 2 to 2000 A / m 2 , more preferably in the range of 1 A / m 2 to 1500 A / m 2 .
  • the insoluble anode one in which a platinum group oxide is coated on the electrode surface as a catalyst is generally used, and among them, one of the kind called oxygen generation type may be used preferable.
  • electrolytic solution obtained through the electrowinning step S3 can be used as a treatment start solution for extracting and separating nickel and cobalt as described above, at least a part thereof is electrorefining step S2 It may be repeatedly used as an electrolytic solution in
  • the electrolytic solution after the electrolytic treatment in the electrolytic refining step S2 or the electrolytic solution after the electrolytic treatment in the electrolytic collection step S3 is a solution in which mainly nickel and cobalt are dissolved.
  • the electrolytic solution containing nickel and cobalt obtained by separating it from copper by electrolytic treatment is then subjected to known purification treatment such as solvent extraction treatment to thereby obtain high purity of nickel and cobalt respectively. It can be recovered as a solution containing it.
  • the electrolytic solution obtained through such an electrolytic process can be repeatedly used again as an electrolytic solution of the electrolytic process in the electrolytic purification step S2.
  • the copper remaining in the electrolytic solution can be electrodeposited on the cathode by the treatment in the electrolytic refining step S2 repeatedly used to enhance the copper recovery rate, and also enhance the separation of nickel and cobalt.
  • the alloy to be subjected to the treatment in the electrolytic refining step S2 that is, the alloy containing copper, nickel, and cobalt obtained by melting the waste lithium ion battery in the alloy forming step S1
  • the alloy containing copper, nickel, and cobalt obtained by melting the waste lithium ion battery in the alloy forming step S1 May contain iron.
  • the phosphorus derived from the electrolyte solution of a waste lithium ion battery may be contained.
  • These components such as iron and phosphorus are eluted in the electrolytic solution by the electrolytic treatment in the electrolytic purification step S2 using the alloy as an anode.
  • the electrolyte is a solution containing iron and phosphorus together with nickel and cobalt.
  • the impurity component contained in the electrolytic solution prior to supplying the electrolytic cell in the electrolytic purification step S2 Is separated and removed (impurity removal step).
  • Patent Document 2 discloses a method of separating phosphorus. Specifically, a nickel compound containing a phosphorus compound and a cobalt component as impurities is dissolved in an inorganic acid to form a nickel solution containing the phosphorus compound and the cobalt component, and an oxidizing agent is added to the nickel solution. The phosphorus compound is precipitated as a phosphate by precipitation, and this is removed by solid-liquid separation, and a nickel oxide (Ni 2 O 3 ), which is a substance different from the oxidizing agent, is added to the nickel solution.
  • a cobalt removing step is disclosed, which comprises oxidizing and then neutralizing and precipitating the cobalt component and removing it by solid-liquid separation.
  • the cobalt removal step is carried out after the phosphorus removal step, or the phosphorus removal step and the cobalt removal step are carried out simultaneously to carry out the oxidation of the cobalt component by nickel oxide after the oxidation of the phosphorus compound by the oxidizing agent. It is something to do.
  • the concentration at which phosphorus can be separated by this method is shown to be about 5 mg / L according to the example of Patent Document 2, and the separation effect is further enhanced for use as a battery application. Is desired.
  • the electrolytic solution obtained after the electrolytic treatment in the electrolytic purification step S2 is recovered, and the oxidizing agent and the neutralizing agent are added to the electrolytic solution.
  • the redox potential (ORP) using a silver / silver chloride electrode as a reference electrode is adjusted so as to be in the range of 570 mV or more and the pH in the range of 3 to 5.
  • ORP redox potential
  • the separation and removal of the precipitate containing the impurity component can be performed by solid-liquid separation of the electrolytic solution after the treatment with the oxidizing agent and the neutralizing agent as described later.
  • the oxidizing agent and the neutralizing agent are not particularly limited as long as the ORP and the pH can be adjusted to the above-mentioned ranges, respectively.
  • the oxidizing agent hydrogen peroxide water, oxygen gas, ozone gas or the like can be used as appropriate.
  • the temperature condition is room temperature or higher, but if it exceeds 60 ° C., the phosphorus concentration in the electrolytic solution after dephosphorization Is preferably 60.degree. C. or less, because it may increase.
  • the removal of impurities such as phosphorus it may be processed as follows. That is, first, at least a part of the electrolytic solution obtained after the electrolytic treatment in the electrolytic purification step S2 is recovered, and an oxidizing agent is added in a pH state where the pH of the electrolytic solution is 1.5 or less. Adjust the (ORP) to 570 mV or more, then add a neutralizer to raise the pH to 3, and add an oxidant to adjust the ORP to 300 mV or more.
  • iron and phosphorus which are impurity components contained in the electrolytic solution may be precipitated simultaneously or selectively.
  • the electrolyte after treatment with the oxidizing agent and the neutralizing agent is subjected to solid-liquid separation, and sulfuric acid is added to the obtained filtrate to adjust the pH to 1.5 or less.
  • the solid-liquid separation treatment is performed on the electrolytic solution containing the precipitate.
  • the precipitate which is solid content is separated and removed.
  • the filtrate obtained after solid-liquid separation is recovered, and sulfuric acid is added to the filtrate to obtain a sulfuric acid solution having a pH of 1.5 or less.
  • the filtrate after pH adjustment is a sulfuric acid acidic solution after pH adjustment with sulfuric acid, and a solution after separation and removal of impurity components such as iron and phosphorus. Therefore, by supplying the solution (filtrate) obtained by such treatment to the electrolytic cell in the electrolytic purification step S2, it can be effectively used as an electrolytic solution of electrolytic treatment without bringing iron, phosphorus, etc. .
  • the electrolytic solution obtained in the electrolytic collection step S3 after the electrolytic purification step S2 is also obtained.
  • a solution (filtered solution after treatment) from which the impurity component has been separated and removed can be used as an electrolytic solution in the electrolytic purification step S2.
  • Example 1 (Alloy formation process) First, the waste lithium ion battery was put in a roasting furnace and roasted at a temperature of 500 ° C. to decompose and volatilize and remove the electrolytic solution contained in the waste lithium ion battery to obtain a roasted product. Subsequently, the obtained roasted product was placed in a furnace made of a graphite crucible and heated to 1100 ° C. to be completely melted to obtain an alloy.
  • the obtained alloy was cast into a plate-like anode.
  • the anode a portion to be an electrode surface is 50 mm long ⁇ 50 mm wide, and 10 mm thick.
  • the composition of the anode was copper: 65% by weight, nickel: 15% by weight, cobalt: 15% by weight, iron: 2% by weight, and phosphorus: 1% by weight.
  • the side which does not face an other party electrode with the anode and the cathode was insulated with the masking tape.
  • a sulfuric acid solution having a sulfuric acid concentration of 10% by mass was used as an electrolytic solution (electrolytic initial solution), and self circulation was performed by extracting it from one end of the electrolytic cell with a pump and supplying the other end.
  • the temperature of the electrolyte was 30 ° C. (room temperature).
  • electrolytic treatment was performed at an anode current density of 300 A / m 2 .
  • the alloy used as the anode was easily dissolved, and powdery copper having a purity of 99.9% or more was deposited on the cathode.
  • valuable metals copper, nickel and cobalt can be recovered from the waste lithium ion battery, and in particular, copper and nickel and cobalt can be separated and recovered.
  • Example 2 The polarization of the anode surface was measured by a potential scanning method using a commercially available potentiostat using an electrolyte of the same composition and the same anode as in Example 1.
  • Comparative Example 1 In Comparative Example 1, the waste lithium ion battery was roasted in the same manner as in Example 1, and then the roasted product was melted to obtain an alloy.
  • the obtained alloy was dropped into water while being melted to obtain a water splitting shot, and the obtained water splitting shot was further crushed. Thereafter, a shot after grinding was placed in a sulfuric acid solution having a sulfuric acid concentration of 20% by mass, and a method of dissolving while heating to a temperature of 60 ° C. to 70 ° C. was tried. However, the whole amount could not be dissolved.
  • Example 3 In the same manner as in Example 1, the waste lithium ion battery is roasted and subjected to a dry treatment to melt the roasted product, and copper: 65% by weight, nickel: 15% by weight, cobalt: 15% by weight, iron: An alloy having a composition of 2% by weight and phosphorus: 1% by weight was obtained. Thereafter, the obtained alloy was cast on a plate-like anode, and electrolytic treatment was performed using a sulfuric acid solution having a sulfuric acid concentration of 10% by mass as an electrolytic solution. The anode current density was 300 A / m 2, and the temperature of the electrolyte was 30 ° C. (room temperature).
  • the electrolyte and the slime attached to the anode surface were respectively recovered and analyzed to determine the distribution of phosphorus.
  • the distribution ratio of phosphorus from the alloy used as the anode to slime was 34%. This result greatly exceeds the target value of 20% of the distribution ratio of phosphorus to slime, and therefore, the elution of phosphorus contained in the alloy into the electrolyte can be suppressed and it can be effectively separated from nickel and cobalt.
  • Example 4 Using the alloy and equipment having the same composition as in Example 3, an electrolytic treatment was performed using a sulfuric acid solution with a sulfuric acid concentration of 20% by mass as the electrolytic solution and an anode current density of 2000 A / m 2 .
  • the distribution ratio of phosphorus from the alloy used as the anode to slime was 30%. This result greatly exceeds the target value of 20% of the distribution ratio of phosphorus to slime, and therefore, the elution of phosphorus contained in the alloy into the electrolyte can be suppressed and it can be effectively separated from nickel and cobalt.
  • Comparative Example 2 Using the alloy and equipment having the same composition as in Example 3, an electrolytic treatment was performed using a sulfuric acid solution with a sulfuric acid concentration of 40% by mass as the electrolytic solution and an anode current density of 4000 A / m 2 .
  • Example 5 Comparative Example 3
  • the waste lithium ion battery was roasted in the same manner as in Example 1, and the resulting roasted product was subjected to a dry treatment to obtain an alloy having the same composition as that in Example 1. Thereafter, the obtained alloy was cast on a plate-like anode, and electrolytic treatment was performed using a sulfuric acid solution having a sulfuric acid concentration of 20% by mass as an electrolytic solution. In addition, pH of the electrolyte solution before an electrolytic treatment (before electricity supply) was 0.
  • Table 1 below shows the analysis results of copper electrodeposited on the cathode in the relation between the cathode current density and the electrolyte pH.
  • the notation “o” in Table 1 indicates that the copper was electrodeposited with high purity without the nickel being electrodeposited. Also, the notation “ ⁇ 0.1” indicates that although only slight electrodeposition of nickel was confirmed, the nickel grade was less than 0.1% by weight. The expressions “0.1” and “0.3” indicate that the nickel grade was 0.1% by weight and 0.3% by weight, respectively. Further, the notation “NG” indicates that nickel was electrodeposited and the nickel grade exceeded 0.3% by weight.
  • Example 6 The waste lithium ion battery was roasted in the same manner as in Example 1, and the resulting roasted product was subjected to a dry treatment to obtain an alloy having the same composition as that in Example 1. Thereafter, the obtained alloy was cast into a plate-like anode, and electrolytic treatment was performed using a titanium plate as a cathode and a sulfuric acid solution having a sulfuric acid concentration of 20% by mass as an electrolytic solution. The pH of the electrolyte was adjusted to 1. Further, the temperature of the electrolytic solution was set to 30 ° C. (room temperature).
  • the cathode current density was set to 1500 A / m 2 and current was supplied, the alloy of the anode was easily dissolved.
  • the copper grade was 99.9% by weight or more.
  • the electrolytic solution after copper is separated and collected add an aqueous solution of hydrogen peroxide to the electrolytic solution after electrolytic treatment (the electrolytic solution after copper is separated and collected), and refer to the silver / silver chloride electrode for the redox potential (ORP) of the electrolytic solution.
  • ORP redox potential
  • the potential was adjusted to 570 mV at the potential of the electrode, and at the same time, the pH was adjusted to 4 by adding sodium hydroxide.
  • the electrolyte after adjusting the ORP and pH was subjected to solid-liquid separation, and the obtained filtrate was subjected to chemical analysis.
  • the iron concentration in the filtrate was 2 mg / L or less, and the phosphorus concentration could be reduced to 1 mg / L.
  • Comparative Example 4 In Comparative Example 4, the filtrate obtained by solid-liquid separation was treated in the same manner as in Example 6 except that the pH of the electrolytic solution after the electrolytic treatment was adjusted to 2, and the chemical analysis was performed.
  • the iron concentration in the filtrate was 2000 mg / L
  • the phosphorus concentration was 500 mg / L
  • iron and phosphorus were contained at a significantly higher concentration than in Example 6.
  • the phosphorus in the electrolyte could not be reduced to the target of 5 mg / L or less.
  • Example 7 An alloy having the same composition as in Example 1 was used as an anode, and electrolytic processing was performed under the same conditions to dissolve the alloy, and copper was electrodeposited on the cathode.
  • the electrolytic solution from which copper was separated and recovered after the electrolytic treatment had a Ni concentration of 20 g / L, a Co concentration of 20 g / L, and a Cu concentration of 10 g / L.
  • the pH of the solution after the elution was 1.
  • electrolytic collection processing was performed by using the obtained post-electrolytic solution as an electrolytic starting solution. Specifically, using an oxygen-generating insoluble anode coated on the electrode surface with a platinum group oxide catalyst as the anode, using a titanium plate as the cathode, and using a cathode current density of 1500 A / m 2 for electrowinning treatment went. This electrolytic treatment was performed until the copper concentration of the electrolytic solution was reduced to 1 g / L, and then the power was cut off to recover and analyze the copper deposited on the cathode.
  • the grade of copper electrodeposited on the cathode was 99.9% by weight. Further, when the electrolytic final solution after separation and recovery of copper was analyzed, it was found that the concentrations of nickel and cobalt did not change before and after electrolysis, and from this point as well, nickel and cobalt co-deposition did not occur.
  • Example 8 After the electrowinning treatment performed in Example 7, the cathode current density was set to 300 A / m 2 , and electrowinning was continued until the copper concentration of the electrolytic solution became 0.5 g / L.
  • the grade of copper electrodeposited on the cathode was 99.0% by weight. Further, when the electrolytic final solution after separation and recovery of copper was analyzed, it was found that the concentrations of nickel and cobalt did not change before and after electrolysis, and from this point as well, nickel and cobalt co-deposition did not occur.
  • Comparative Example 5 The pH of the solution after electrolytic elution was adjusted to 3, and using the solution after pH adjustment as the electrolyte starting solution, the electrolytic extraction treatment was performed under the conditions of a cathode current density of 3000 A / m 2, and Example 7 and It processed similarly.
  • the copper grade of the deposited material electrodeposited on the cathode was 82% by weight, nickel eutectic was confirmed, and copper could not be separated and recovered in a high purity state.
  • the electrolytic final solution after separating and collecting copper was analyzed, the concentration of nickel fluctuated before and after the electrolysis, and from this point also, the co-precipitation of nickel was confirmed.
  • Table 2 shows the measurement results of the conditions of the electrowinning in Examples 7 and 8 and Comparative Example 5 and the concentrations of the respective components of the electrolytic initial solution and the electrolytic final solution.

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Abstract

L'invention concerne un procédé de traitement grâce auquel il devient possible de récupérer du cuivre, du nickel et du cobalt, qui sont des métaux de valeur, contenus dans des déchets de batterie lithium-ion et de séparer efficacement le cuivre, le nickel et le cobalt. Un procédé de traitement de déchets de batterie au lithium-ion selon la présente invention comprend : une étape de production d'alliage S1 consistant à introduire les déchets de batterie lithium-ion dans un four, puis à faire fondre les déchets de batterie lithium-ion par chauffage, ce qui permet de produire un alliage contenant du cuivre, du nickel et du cobalt ; et une étape de purification électrolytique S2 consistant à soumettre l'alliage à un tel traitement électrolytique de sorte que l'alliage soit chargé en tant qu'anode dans une solution d'acide sulfurique, puis à faire passer de l'électricité entre l'anode et une cathode pour déposer par électrolyse du cuivre contenu dans l'alliage sur la cathode, ce qui permet de séparer le nickel et le cobalt l'un de l'autre.
PCT/JP2018/039199 2017-11-24 2018-10-22 Procédé de traitement de déchets de batterie lithium-ion WO2019102765A1 (fr)

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KR1020207016157A KR102427533B1 (ko) 2017-11-24 2018-10-22 리튬 이온 폐전지의 처리 방법
US16/765,225 US11618959B2 (en) 2017-11-24 2018-10-22 Method for treating lithium ion battery waste
CA3083379A CA3083379C (fr) 2017-11-24 2018-10-22 Procede de traitement de dechets de batterie lithium-ion
EP18880919.8A EP3715484B1 (fr) 2017-11-24 2018-10-22 Procédé de traitement de déchets de batterie lithium-ion
CN201880075458.XA CN111373062B (zh) 2017-11-24 2018-10-22 废锂离子电池的处理方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110541077A (zh) * 2019-09-30 2019-12-06 中国矿业大学 一种从废旧钴酸锂电池正极片中回收有价组分的方法
WO2023099401A1 (fr) 2021-11-30 2023-06-08 Umicore Lixiviation sélective
BE1030447B1 (nl) * 2022-10-14 2023-11-10 Umicore Nv Additief-vrije Cu Elektrowinning
JP7487509B2 (ja) 2020-03-25 2024-05-21 住友金属鉱山株式会社 有価金属を回収する方法及びマグネシア耐火物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114875240A (zh) * 2022-04-06 2022-08-09 湖南邦普循环科技有限公司 处理废旧锂电池铜钴合金的方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003157913A (ja) * 2001-08-20 2003-05-30 Ind Technol Res Inst 廃リチウムイオン電池中金属の回収方法
US7169206B2 (en) * 2004-04-19 2007-01-30 Umicore Battery recycling
JP2013091826A (ja) * 2011-10-25 2013-05-16 Sumitomo Metal Mining Co Ltd 有価金属回収方法
JP2017036489A (ja) 2015-08-13 2017-02-16 Ｊｘ金属株式会社 リチウムイオン電池の処理方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB539006A (en) * 1940-05-01 1941-08-25 Clarence Bailey White Process for recovery of metals from alloys and metallurgical residues
JPS59156486A (ja) * 1983-02-28 1984-09-05 Sumitomo Metal Mining Co Ltd シアン錯塩を含むメツキ廃水の処理方法
RU2098498C1 (ru) * 1993-09-30 1997-12-10 Калужский филиал Московского государственного технического университета им.Н.Э.Баумана Способ утилизации кеков очистки промывных вод гальваноцехов
JP3526983B2 (ja) * 1995-09-05 2004-05-17 三井金属鉱業株式会社 ニッケル・水素吸蔵合金二次電池からの有効成分の回収方法
CN103370427B (zh) * 2011-11-28 2015-07-01 住友金属矿山株式会社 有价金属的回收方法
CN103526035B (zh) * 2013-10-31 2015-08-05 长沙矿冶研究院有限责任公司 从废旧锂离子电池和/或其材料中回收有价金属的方法
CN103628088B (zh) * 2013-12-13 2017-01-18 深圳市新昊青科技有限公司 从含钴合金分离钴的方法及硫酸钴产品
CN105274563A (zh) * 2014-05-28 2016-01-27 北京有色金属研究总院 一种制备高纯钴的方法
CN104037468B (zh) * 2014-06-05 2016-06-22 浙江工业大学 一种从废旧锂离子电池中回收锰和铜资源的方法
CN104611566B (zh) * 2014-12-29 2017-02-22 长沙矿冶研究院有限责任公司 废旧锂离子电池中有价金属回收的方法
KR101528507B1 (ko) * 2015-01-13 2015-06-12 한국지질자원연구원 리튬계 전지로부터 코발트 및 망간의 동시 회수 방법
CN105063349B (zh) * 2015-08-17 2017-07-07 长沙矿冶研究院有限责任公司 从熔炼合金中浸出铜钴镍的方法
CN107012332A (zh) * 2017-04-18 2017-08-04 中科过程（北京）科技有限公司 一种含镍、钴废电池和含铜电子废弃物协同回收金属的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003157913A (ja) * 2001-08-20 2003-05-30 Ind Technol Res Inst 廃リチウムイオン電池中金属の回収方法
US7169206B2 (en) * 2004-04-19 2007-01-30 Umicore Battery recycling
JP2013091826A (ja) * 2011-10-25 2013-05-16 Sumitomo Metal Mining Co Ltd 有価金属回収方法
JP2017036489A (ja) 2015-08-13 2017-02-16 Ｊｘ金属株式会社 リチウムイオン電池の処理方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3715484A4

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110541077A (zh) * 2019-09-30 2019-12-06 中国矿业大学 一种从废旧钴酸锂电池正极片中回收有价组分的方法
JP7487509B2 (ja) 2020-03-25 2024-05-21 住友金属鉱山株式会社 有価金属を回収する方法及びマグネシア耐火物
WO2023099401A1 (fr) 2021-11-30 2023-06-08 Umicore Lixiviation sélective
BE1030447B1 (nl) * 2022-10-14 2023-11-10 Umicore Nv Additief-vrije Cu Elektrowinning
WO2024078938A2 (fr) 2022-10-14 2024-04-18 Umicore Extraction électrolytique de cu sans additif
WO2024078938A3 (fr) * 2022-10-14 2024-06-20 Umicore Extraction électrolytique de cu sans additif

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