WO2011049160A1 - Procédé de production de composition d'alliage stockant l'hydrogène - Google Patents

Procédé de production de composition d'alliage stockant l'hydrogène Download PDF

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WO2011049160A1
WO2011049160A1 PCT/JP2010/068558 JP2010068558W WO2011049160A1 WO 2011049160 A1 WO2011049160 A1 WO 2011049160A1 JP 2010068558 W JP2010068558 W JP 2010068558W WO 2011049160 A1 WO2011049160 A1 WO 2011049160A1
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Prior art keywords
negative electrode
electrode main
hydrogen storage
recovered
storage alloy
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PCT/JP2010/068558
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English (en)
Japanese (ja)
Inventor
慎也 蔭井
啓祐 宮之原
秀利 井上
真吾 菊川
祥巳 畑
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三井金属鉱業株式会社
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Priority to CN201080046077.2A priority Critical patent/CN102576919B/zh
Publication of WO2011049160A1 publication Critical patent/WO2011049160A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B7/003—Dry processes only remelting, e.g. of chips, borings, turnings; apparatus used therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/242—Hydrogen storage electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a method for newly producing a hydrogen storage alloy composition from a used waste nickel metal hydride secondary battery.
  • Patent Document 1 As a method of recovering valuable metals such as nickel, cobalt, and rare earth metals from waste nickel metal hydride secondary batteries, for example, after crushing, crushing, and sieving the battery, coarse particles (plastic, iron, nickel substrate, etc.) And fine-grained parts (nickel hydroxide, hydrogen storage alloy), the fine-grained parts are dissolved in sulfuric acid containing alkali metal, impurities are removed from the cobalt-containing nickel solution, and then electrolytically treated to obtain nickel metal And a method for recovering the nickel-cobalt alloy has been proposed (Patent Document 1).
  • the negative electrode mainly recovered material containing a large amount of the negative electrode active material is heat-treated in a hydrogen gas atmosphere, the positive electrode active material, particularly water, contained in the negative electrode active material is slightly contained therein. Since hydroxides such as nickel oxide oxidize rare earths (La, Ce, Pr, Nd, Sm, etc.), it has been gradually found that the recovery rate of rare earths is lower than other hydrogen storage alloy constituent elements.
  • the invention according to Patent Document 3 is a method for recovering a constituent element of a hydrogen storage alloy capable of maintaining a high recovery rate of rare earths, and heat-treats a negative electrode-mainly recovered material containing the constituent element of a hydrogen storage alloy in a reducing atmosphere.
  • Patent Document 4 discloses a method for recovering a useful metal from an alkaline secondary battery using a hydrogen storage alloy as a negative electrode active material, pulverizing and / or disassembling an alkaline secondary battery using a hydrogen storage alloy as a negative electrode active material, The obtained pulverized product and / or dismantled product is thermally decomposed and reduced in the presence of a reducing agent under the condition of 200 ° C. or higher while controlling the dew point to 0 ° C. or lower. From the obtained material, zinc, lithium, potassium A useful metal recovery method that volatilizes and removes highly volatile metals such as the above and their compounds is proposed.
  • a negative electrode mainly recovered material containing a large amount of a negative electrode is recovered from the waste nickel metal hydride secondary battery, and the recovered material is recovered as described above.
  • this is put into a molten metal of the negative electrode active material constituent element (also referred to as “alloy molten metal”), heated and melted, and the obtained molten metal is cast to obtain a new hydrogen storage alloy composition. It is conceivable to produce a product.
  • the negative electrode main body recovered material is actually put into the molten alloy and melted by heating, the problem that the dissolution of the negative electrode main body recovered does not proceed and it is difficult to increase the yield.
  • the present invention provides a new method capable of increasing the melting efficiency when the negative electrode main body recovered from the waste nickel metal hydride battery is charged into the molten alloy of the negative electrode active material constituent element and heated and melted. To do.
  • the present invention relates to a negative electrode-mainly recovered material in a method for producing a hydrogen storage alloy composition by heating and dissolving a negative electrode-mainly recovered material obtained from a waste nickel metal hydride secondary battery to a molten metal composed of a hydrogen storage alloy constituent element.
  • a method for producing a hydrogen storage alloy composition is proposed in which aluminum is added to the molten metal simultaneously or sequentially.
  • a method for producing a hydrogen storage alloy composition as an example of a preferred embodiment of the present invention is a method of deactivating a waste nickel metal hydride battery, if necessary,
  • a composition containing an element, that is, a negative electrode main recovery material containing a large amount of the negative electrode active material (referred to as “this negative electrode main recovery material”) is selected (negative electrode recovery step), and then a polar solution such as water if necessary.
  • the negative electrode mainly recovered material is washed to reduce the alkali metal salt concentration (cleaning step), and further dried as necessary (drying step), and then the positive electrode active material contained in the negative electrode mainly recovered material (Reduction process), and then carbon is removed from the main negative electrode recovery (decarbonization process), and the resulting negative electrode main recovery is combined with aluminum and a molten metal composed of hydrogen storage alloy constituent elements (“alloy melt”).
  • alloy melt aluminum and a molten metal composed of hydrogen storage alloy constituent elements
  • the “negative electrode mainly recovered material” means a recovered material containing a large amount of the negative electrode active material.
  • the negative electrode constituent material is 50% by mass or more, preferably 50% by mass of the negative electrode active material.
  • the recovered material contains 80% by mass or more of the negative electrode active material, and also includes a recovered material made of a negative electrode constituent material.
  • the waste nickel metal hydride battery is deactivated and then disassembled, and the main negative electrode recovered material containing a larger amount of the constituent elements of the hydrogen storage alloy. Can be sorted and recovered.
  • the method for recovering the main negative electrode collection from the nickel metal hydride battery may be performed in the same manner as the conventional method. For example, after the battery is deactivated, it is crushed using a shear crusher, pulverized by a wet method using a pulverizer, and then classified by a predetermined sieve (for example, 24 mesh). As such, the negative electrode mainly recovered material can be selected. In general, after classification, the finer ones contain more negative electrode active material and the coarser ones contain more positive electrode active material. However, the method for recovering the main negative electrode collection material is not limited to this method.
  • the negative electrode active material is a hydrogen storage alloy containing misch metal (also referred to as “Mm”), and is preferably a hydrogen storage alloy containing misch metal and nickel. More specifically, AB 5 type hydrogen storage alloy containing Mm, AB 2 type hydrogen storage alloy containing Mm, among them, for example, containing Ni and Al as B site metals, in addition to Mn, Co, Examples of the alloy include any one of Fe, Ti, Mg, V, Zn, and Zr, or a combination of two or more of these.
  • Misch metal (Mm) is an alloy containing a rare earth element (rare earth). In the AB 5 type hydrogen storage alloy, it is a metal constituting the A site. In the present invention, La, Ce, Nd And an alloy containing one or more of the group consisting of Pr.
  • Activating a battery means preventing it from functioning as a battery.
  • a method of deactivation there are arbitrary methods such as a method of freezing the electrolyte solution with liquid nitrogen or a refrigerator to make it non-functional, or a method of intentionally short-circuiting in an acidic solution.
  • an alkaline solution such as potassium hydroxide (KOH) is obtained by washing the negative electrode main recovery using a polar solution such as water at 0 ° C. to 100 ° C. or a weakly acidic aqueous solution. It is preferred to remove the metal salt. At this time, it is preferable to repeat the washing treatment as necessary. However, other methods may be adopted as long as an alkali metal salt such as potassium hydroxide (KOH) can be removed.
  • KOH potassium hydroxide
  • the K content is preferably less than 0.02%, particularly less than 0.015%, and particularly preferably less than 0.01%. If the amount of K is less than 0.02%, the yield can be further improved, and the surface of the alloy is hardly oxidized due to deliquescence. Therefore, it is necessary to control the dew point of the atmosphere to 0 ° C. or lower in the subsequent hydroxyl group removal step. There is no.
  • the drying method is arbitrary, and it may be naturally dried or may be stored or passed through a drying apparatus and dried.
  • the negative electrode-mainly recovered material is heat-treated in a reducing atmosphere to reduce the positive electrode active material, particularly hydroxides, particularly nickel hydroxide (eg, NiOOH), cobalt hydroxide, etc. contained in the recovered material. It is preferable to do this.
  • the positive electrode active material particularly hydroxides, particularly nickel hydroxide (eg, NiOOH), cobalt hydroxide, etc. contained in the recovered material. It is preferable to do this.
  • heat treatment may be performed in a reducing atmosphere, but heating is preferably performed at 100 ° C. to 350 ° C., preferably 160 ° C. to 240 ° C., more preferably 200 ° C. ⁇ 20 ° C. in a hydrogen atmosphere.
  • the heating temperature is 100 ° C. or higher, the reaction rate is not significantly reduced.
  • the heating temperature is 220 ° C. or less, the oxidation of rare earth can be prevented by about 100%.
  • the hydrogen atmosphere is preferably an atmosphere made of high-purity hydrogen gas with little oxidizing impurities such as moisture and oxygen, but is not particularly limited.
  • the reaction apparatus either a closed type that seals gas or a fluid type that flows gas can be used, but in the case of a closed type, the partial pressure of the reducing gas gradually decreases due to water vapor or the like.
  • the fluid type is preferable.
  • the heating means may be any of electric heating, gas combustion heating, and other heating means.
  • ammonia decomposition gas and other gases can be used as the reducing gas.
  • carbon monoxide cannot reduce Ni and Co at 450 ° C. or lower.
  • Hydrogen gas is particularly preferable because it can be used in a decarbonization step of the next step and can be processed in a common reactor (one furnace).
  • the negative electrode main recovered material reduced as described above is heat-treated in a non-oxidizing atmosphere to remove at least part of the carbon contained in the negative electrode main recovered material by converting it into a hydrocarbon gas. It is preferable to do this.
  • the non-oxidizing atmosphere means an atmosphere in which carbon can be removed by reduction or the like without substantially oxidizing metal or alloy by heating.
  • An inert gas atmosphere, a hydrogen gas atmosphere, a water vapor atmosphere, an inert gas-water vapor It can be appropriately selected from an atmosphere and an inert gas-water vapor-hydrogen gas atmosphere.
  • the inert gas includes argon, nitrogen, helium and the like, and the non-oxidizing atmosphere is particularly preferably a hydrogen gas atmosphere which is a reducing atmosphere.
  • the heating conditions in the decarbonization step are preferably 350 to 1050 ° C. and 5 minutes to 10 hours. At this time, the reaction rate can be increased by heating at 750 ° C. or higher.
  • oxygen, hydrogen, and water vapor contained in the negative electrode main recovery material act reductively or oxidatively, and at least a part of carbon is used as a gas such as hydrocarbon or carbon dioxide. Can be removed.
  • a gas such as hydrocarbon or carbon dioxide.
  • the hydrogen gas atmosphere at least a part of the carbon in the negative electrode mainly recovered product is reduced by hydrogen, converted into lower hydrocarbons, etc., and removed from the recovered product.
  • the carbon concentration can be reduced to 1000 ppm (0.1 mass%) or less, and depending on conditions, to 100 ppm (0.01 mass%) or less.
  • composition preparation so as to obtain a desired composition in the process.
  • aluminum (Al) may be mixed with the negative electrode main recovery material and added to the molten alloy in a mixed state.
  • aluminum may be added to the molten alloy first, and immediately after that, the negative electrode main recovered material may be sequentially added to the molten alloy, or the negative electrode main recovered material may be added to the molten alloy first and immediately thereafter.
  • Aluminum may be sequentially added to the molten metal. In any case, in the molten alloy, it is important that the negative electrode mainly recovered material is present in the vicinity of the aluminum melted in the molten metal.
  • the negative electrode main body recovered material is sequentially added to the molten metal “immediately after that”, or the negative electrode main body recovered material is first added to the molten metal, and “immediately thereafter” the molten aluminum material is molten. “Immediately” in the case of sequentially adding to each other means that any of them added first will float on the molten metal for a certain period of time, so that they are preferably added within the floating range while they are floating It is.
  • An apparatus for performing heating and melting is arbitrary.
  • heat melting can be performed using a high frequency melting furnace or a low frequency melting furnace.
  • the molten alloy to which the present negative electrode mainly recovered material is added may be a molten metal composed of a hydrogen storage alloy constituent element, and the composition thereof can be adjusted as appropriate.
  • Even a molten metal obtained by melting the negative electrode active material may be a molten metal made of a mother alloy for producing the negative electrode active material.
  • the dissolution efficiency of the main negative electrode recovery material can be remarkably increased.
  • the reason why the dissolution efficiency is increased has not been investigated, it can be inferred as follows. That is, it is considered that the negative electrode mainly recovered material is added to the molten alloy and melted, not simply being melted by heat, but the oxides on the surface are reduced and dissolved in the molten metal.
  • Aluminum has a relatively low melting point among the constituent elements of hydrogen storage alloys. In addition, when dissolved, it has the property of reducing the metal oxide with high reaction heat.
  • the viscosity of the molten metal is reduced by the aluminum melted in the high-temperature molten metal, and the main negatively recovered material in the mixed state is reduced by the heat of reaction at the time of melting, and the dissolution efficiency of the negatively recovered material is dramatically increased. Can be inferred. *
  • the aluminum added to the molten alloy together with the negative electrode main body recovered may be metal aluminum or an aluminum alloy. From the viewpoint of the effect, metal aluminum is more preferable.
  • the aluminum to be added to the molten alloy together with the recovered material of the negative electrode main body is preferably in the form of particles or powders. Among them, the aluminum particles are classified using a sieve having a particle size of 2 to 10 mm, that is, a mesh size of 2 to 10 mm. Preferably there is. At this time, the amount of aluminum to be added is preferably 10% by mass or more, particularly 20% by mass or more, particularly 30% by mass or more of the negative negative electrode main body recovery material from the viewpoint of increasing the dissolution rate of the main negative electrode main body recovery material. .
  • this negative electrode mainly recovered material and aluminum are mixed and added to the molten alloy in a mixed state, it may be poured directly into the molten alloy in the mixed state. However, when it is poured into the molten metal as it is, the mixture floats on the molten metal. It is even more preferable to bundle the mixture into a molten metal with a member composed of one or more of hydrogen-absorbing alloy constituent elements such as aluminum, nickel, and magnesium. .
  • the shape of the member for bundling the negative electrode mainly collected material is not particularly limited, and may be, for example, a bag shape, a cylindrical shape, a string shape, a band shape, a ribbon shape, or other shapes, such as a net or a foil. You may make it wrap. Specifically, the mixture may be wrapped in aluminum foil and poured into the molten metal.
  • the temperature at which the negative electrode mainly recovered material is melted in other words, the molten metal temperature of the molten alloy is preferably 1200 to 1600 ° C., more preferably 1300 to 1550 ° C., and particularly preferably 1400 to 1500 ° C. Moreover, it is preferable to perform a melt
  • the element amount of the negative electrode main recovery material is analyzed in advance, the element amount of the negative electrode main recovery material, the amount of Al added together with the negative electrode main recovery material, The composition and amount of the molten alloy, the amount of Al added together with the main negative electrode recovery, and the input amount of the main negative electrode recovery so that the total value of the element amount of the molten alloy is the target product composition Is preferably adjusted.
  • the element amount of the member when bundled with a member consisting of one or more hydrogen storage alloy elements and put into the molten metal, it is preferable to analyze the element amount of the member to be bundled and adjust the total element amount added thereto. .
  • a hydrogen storage alloy constituent element such as Ni or Co is further added to adjust the target composition. Good.
  • the molten metal obtained by heating and melting the main negative electrode recovered material can be poured into a mold as necessary and cast into a desired shape.
  • the casting process can be omitted.
  • the production purpose of this embodiment is not to produce a mother alloy, that is, a hydrogen storage alloy that can be used as a negative electrode active material as it is, but a hydrogen storage alloy is manufactured by adjusting the composition by appropriately adding components later.
  • an alloy as an intermediate material referred to as “mother alloy”
  • it can be cast as described above, or once the molten alloy of the mother alloy is manufactured, The composition can be appropriately casted to prepare a hydrogen storage alloy composition, and then cast as described above.
  • the hydrogen storage alloy composition produced in the present embodiment can be made into a hydrogen storage alloy composition that can be used as a negative electrode active material of a nickel-metal hydride battery by the above-described composition preparation. It can also be set as the hydrogen storage alloy composition which can be utilized as a mother alloy for negative electrode active materials.
  • a hydrogen storage alloy composition that can be used as a negative electrode active material of a nickel metal hydride battery
  • appropriate components such as La, Ce, Nd, Pr, Ni, Al, Mn, Co, Fe, Ti, V, Zn, Mg, Cu, Y, Rb, Gd, Tm, Lu, Zr, etc., or a combination of two or more of these is added and melted to produce an alloy. What is necessary is just to manufacture the hydrogen storage alloy composition which can be utilized as.
  • the raw material recovered from the waste nickel metal hydride battery is used as a starting material.
  • a member composed of one or more hydrogen storage alloy elements and a hydrogen storage alloy layer is selectively extracted. If possible, it is not limited to the raw material taken out from the waste nickel metal hydride battery.
  • storage devices for natural energy such as solar and wind power, hydrogen storage devices, actuators, fuel cells, etc.
  • a member consisting of one or more hydrogen storage alloy elements and a hydrogen storage alloy layer is selected. It can be used as a starting material if it can be taken out.
  • the “hydrogen storage alloy” means an AB 5 type alloy represented by LaNi 5 , an AB 2 type alloy represented by ZrV 0.4 Ni 1.5 , an AB type alloy or an A 2 B type ( A variety of alloys such as alloys including A 2 B 7 are included.
  • the “hydrogen storage alloy constituent element” means an element composed of one or a combination of two or more of the elements constituting the hydrogen storage alloy.
  • an AB 5 type hydrogen storage alloy having a CaCu 5 type crystal structure specifically, Mm (Misch metal), which is a rare earth-based mixture, is used at the A site, and metal elements such as Ni, Al, Mn, and Co are used at the B site.
  • the “hydrogen storage alloy composition” is a composition composed of a hydrogen storage alloy constituent element, and the shape thereof may be any of a block shape, a molded body shape, and a powder shape.
  • X to Y means “X or more and Y or less” unless otherwise specified, and “preferably larger than X and larger than Y”. It includes the meaning of “small”. Furthermore, when “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number) is described, it is “preferably greater than X” or “preferably less than Y”. The intention of
  • ⁇ Quantitative elemental analysis> Put 0.2 g of a measurement sample (hydrogen storage alloy composition) in a 250 ml beaker, add 10 ml of nitric acid to dissolve it with heating, add 10 ml of hydrochloric acid to completely dissolve it, and then transfer it to a 100 ml volumetric flask. Water was added to obtain 100 ml of an aqueous solution. The aqueous solution was diluted 50 times, and each element was quantified using an ICP emission spectrometer (model SPS-3100 manufactured by SII Nanotech).
  • the carbon concentration of the measurement sample (hydrogen storage alloy composition) was measured on a sample weighed to 0.5 g.
  • the measurement of the negative electrode mainly collected material was performed on a sample weighed to 0.2 g because the sample board was damaged due to a rapid exothermic reaction during sample combustion.
  • the analyzer and measurement conditions are as follows.
  • Example 1 A used waste nickel metal hydride battery is frozen and deactivated with liquid nitrogen, dry crushed using a biaxial shear crusher, then crushed by a wet method using a crusher, and then washed with water. Plastic, paper, and the like were removed, and then classified with a sieve (28 mesh), and the non-classified material on the sieve was magnetically sorted with 2000 to 3000 gauss to remove the negative electrode Fe substrate.
  • the classified product under the sieve was a negative electrode active material-based recovered material (negative electrode-based recovered material) in which the negative electrode hydrogen storage alloy was concentrated.
  • the ratio of the negative electrode active material was 88 mass%, the remainder was mixed with the positive electrode active material, and the Co concentration was 9.6 mass%.
  • the mass% of each element amount is: Mm: 30.6%, Ni: 52.7% , Mn: 4.4%, Al: 1.5%, Co: 9.6%, C: 1.2%.
  • the oxygen concentration was 5.0%.
  • Mm is a misch metal that is a rare earth mixture of La, Ce, Nd, and Pr, and the amount of each component in Mm (mass% in the recovered material) is La: 10.3%, Ce: 14. The results were 3%, Nd: 4.5%, and Pr: 1.5%.
  • the negative electrode mainly recovered material (recycle raw material) obtained in this way was used in a high-purity hydrogen atmosphere (H 2 99.9999999%, O 2 ⁇ 0.02 ppm, H 2 O (dew point)) using a fluid rotary furnace (1 rpm). After heat treatment at 200 ° C. for 3 hours at ⁇ 80 ° C. and CO 2 ⁇ 0.01 ppm) to reduce the positive electrode active material mixed in the negative electrode main body recovered material, subsequently continue to 900 ° C. in the hydrogen atmosphere. The carbon was removed by heat treatment for 1 hour to obtain a treated negative electrode main body recovered material. The obtained treated negative electrode main product had a carbon concentration of 0.03% and an oxygen concentration of 4.0%.
  • molten alloy was prepared as follows using a high-frequency induction furnace chamber. That is, the mass ratio of each element is Mm (Mm is a misch metal that is a rare earth mixture of La, Ce, Nd, and Pr, etc.), and the amount of each component in Mm (in the recovered material) %), La: 11.0%, Ce: 15.4%, Nd: 5.0%, Pr: 1.6%): 33.12%, Ni: 59.7%, Mn : Each elemental metal was weighed and mixed so as to be 5.2% (the balance was Al added).
  • Mm is a misch metal that is a rare earth mixture of La, Ce, Nd, and Pr, etc.
  • the obtained mixture is put in a crucible and fixed in a high-frequency induction furnace, and after reducing the pressure to 10 ⁇ 4 to 10 ⁇ 5 Torr, argon gas is introduced and the alloy is heated and melted at 1400 ° C. in an argon gas atmosphere. A molten metal was prepared.
  • the above-mentioned mixture wrapped with aluminum foil from the above-mentioned raw material charging vessel was charged into the molten metal surface of the alloy melt thus prepared, and heated and dissolved in an argon gas atmosphere.
  • About 9 kg of the obtained molten metal was poured at a rate of 4 kg / second into a water-cooled copper mold having a total mass of 200 kg and cooled to room temperature (casting).
  • the obtained alloy lump was roughly crushed with a jaw crusher and then pulverized and classified with a disk mill to produce a product (hydrogen storage alloy composition).
  • Example 1 a product (hydrogen storage alloy composition) was obtained in the same manner as in Example 1 except that granular aluminum was not mixed in the treated negative electrode main body recovered material (aluminum foil was naturally used).
  • Example 2-6 Comparative Example 2
  • the dissolution rate (mass%) of the treated negative electrode main body recovered in Table 2 below is a value calculated by the following formula.
  • Co dissolution rate (%) (Co content in the hydrogen storage alloy composition after casting / Co content in the recycled material) ⁇ 100
  • the amount of aluminum to be added is preferably 10% by mass or more, particularly 20% by mass or more, and particularly preferably 30% by mass or more with respect to the recovered material mainly composed of the negative electrode active material.
  • the liquid nitrogen was used for deactivation. However, it has been confirmed that the same effect can be obtained when the deactivation is performed by freezing in a refrigerator at ⁇ 150 ° C.
  • Table 3 shows the results of examining the dissolution rate of Mm for Example 2-6 and Comparative Example 2.
  • the dissolution rate (%) of Ce and La was calculated as follows.
  • Ce dissolution rate (%) (Ce content in the hydrogen storage alloy composition after casting / Ce content in the recycled material) ⁇ 100
  • La dissolution rate (%) (La content in hydrogen storage alloy composition after casting / La content in recycled material) ⁇ 100

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Abstract

La présente invention concerne un procédé qui peut augmenter l'efficacité de dissolution au cours de la dissolution thermique d'un matériau actif d'une électrode négative ou d'une composition composée principalement de matériau actif d'électrode négative qui a été collecté à partir d'une batterie nickel-hydrogène mise au rebut, en introduisant le matériau actif d'électrode négative ou la composition dans un produit en fusion d'un alliage d'un élément constituant le matériau actif d'électrode négative. On peut augmenter considérablement l'efficacité de dissolution du matériau actif d'électrode négative ou de la composition composée principalement de matériau actif d'électrode négative en ajoutant de l'aluminium au produit en fusion de l'alliage simultanément ou consécutivement à l'addition d'un produit de collecte principale de l'électrode négative.
PCT/JP2010/068558 2009-10-23 2010-10-21 Procédé de production de composition d'alliage stockant l'hydrogène WO2011049160A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2017204732A1 (fr) * 2016-05-25 2017-11-30 Nilar International Ab Procédé pyrométallurgique de recyclage de batteries ni-mh
SE1751459A1 (en) * 2017-11-28 2019-05-29 Nilar Int Ab Milling of recovered negative electrode material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103146957B (zh) * 2013-02-18 2015-02-25 先进储能材料国家工程研究中心有限责任公司 一种利用失效镍氢电池制备储氢合金的方法
CN103555954A (zh) * 2013-11-04 2014-02-05 湖南格瑞普新能源有限公司 从废旧镍氢电池中回收稀土元素的方法
WO2015145884A1 (fr) * 2014-03-26 2015-10-01 三井金属鉱業株式会社 Alliage de stockage d'hydrogène
WO2018123752A1 (fr) * 2016-12-26 2018-07-05 三井金属鉱業株式会社 Alliage de stockage d'hydrogène

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JPH09117749A (ja) * 1995-10-26 1997-05-06 Mitsui Mining & Smelting Co Ltd 電気自動車用２次電池からの有価物の回収方法
JP2000067935A (ja) * 1998-08-25 2000-03-03 Mitsui Mining & Smelting Co Ltd 廃ニッケル・水素二次電池からの有価物回収方法
WO2000025382A1 (fr) * 1998-10-27 2000-05-04 Mitsui Mining & Smelting Co., Ltd. Procede et systeme de recuperation de metal precieux a partir de batteries mises au rebut
JP2005113226A (ja) * 2003-10-09 2005-04-28 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金構成元素の回収方法

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JPH09117749A (ja) * 1995-10-26 1997-05-06 Mitsui Mining & Smelting Co Ltd 電気自動車用２次電池からの有価物の回収方法
JP2000067935A (ja) * 1998-08-25 2000-03-03 Mitsui Mining & Smelting Co Ltd 廃ニッケル・水素二次電池からの有価物回収方法
WO2000025382A1 (fr) * 1998-10-27 2000-05-04 Mitsui Mining & Smelting Co., Ltd. Procede et systeme de recuperation de metal precieux a partir de batteries mises au rebut
JP2005113226A (ja) * 2003-10-09 2005-04-28 Mitsui Mining & Smelting Co Ltd 水素吸蔵合金構成元素の回収方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017204732A1 (fr) * 2016-05-25 2017-11-30 Nilar International Ab Procédé pyrométallurgique de recyclage de batteries ni-mh
SE1751459A1 (en) * 2017-11-28 2019-05-29 Nilar Int Ab Milling of recovered negative electrode material

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