WO2021206178A1 - Ｌｉイオン回収部材及びこれを用いたＬｉ回収装置 - Google Patents

Ｌｉイオン回収部材及びこれを用いたＬｉ回収装置 Download PDF

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WO2021206178A1
WO2021206178A1 PCT/JP2021/015099 JP2021015099W WO2021206178A1 WO 2021206178 A1 WO2021206178 A1 WO 2021206178A1 JP 2021015099 W JP2021015099 W JP 2021015099W WO 2021206178 A1 WO2021206178 A1 WO 2021206178A1
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electrode
membrane
ion
ion recovery
selective
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French (fr)
Japanese (ja)
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太 宇都野
聡 勝又
星野　毅
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Idemitsu Kosan Co Ltd
National Institutes For Quantum Science and Technology
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Idemitsu Kosan Co Ltd
National Institutes For Quantum Science and Technology
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Priority to JP2022514139A priority Critical patent/JP7762914B2/ja
Priority to US17/995,663 priority patent/US20230183876A1/en
Publication of WO2021206178A1 publication Critical patent/WO2021206178A1/ja
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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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/468—Apparatus therefor comprising more than two electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/63—Holders for electrodes; Positioning of the electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms
    • 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 Li ion recovery member and a Li recovery device using the Li ion recovery member.
  • Lithium secondary batteries and the like are used as batteries used for the above-mentioned applications, and in recent years, their use in hybrid cars and electric vehicles, which have been developed to comply with carbon dioxide emission regulations, has also been considered. ing. Therefore, there is an urgent need to secure a lithium source more than ever, and as a part of this, a lithium recovery technology by recycling a lithium secondary battery has been developed (see, for example, Patent Document 1). .. Further, as a technique for recovering sodium ions, an ion exchange membrane electrolytic cell using an ion exchange membrane is known (see, for example, Patent Document 2).
  • Patent Document 2 Conventionally, the ion exchange membrane electrolytic cell described in Patent Document 2 is known, but an ion exchange membrane (manufactured by Nafion N-962, DuPont) is used, and lithium ions can be selectively recovered. It wasn't.
  • the technique described in Patent Document 1 recovers metal ions from a stock solution containing metal ions such as lithium by using a selective permeation membrane composed of an ionic conductor.
  • the metal ions there is no ion exchange membrane capable of recovering lithium ions, and an attempt is made to recover lithium ions by using a lithium ion conductor as a selective permeable film as in the technique described in Patent Document 1. ..
  • the selective permeable membrane can be made larger, there is a remarkable problem that as the size of the selective permeable membrane becomes larger, cracks due to movement, damage at the time of mounting on the device, vibration of the device at the time of lithium ion recovery, etc. are likely to occur. It becomes.
  • the enlarged selective permeable membrane itself becomes heavy, so that it is extremely difficult to maintain the device in a state in which water leakage or the like is suppressed during lithium ion recovery.
  • the positional relationship between the selective transmission membrane and the electrode is important in terms of improving the lithium recovery rate, but specific means for arranging the device in the case of a large-sized device, etc. There is no disclosure about. With the increasing demand for lithium, it is required to improve the efficiency of lithium recovery more than ever, and at the same time, it is required to expand the scale of lithium ion recovery. There is a problem that it cannot be done.
  • the present invention has been made in view of such a situation, and even if the size of the Li recovery device is increased, it is possible to suppress the occurrence of damage to the selective permeation membrane and realize stable Li ion recovery for a long period of time. It is an object of the present invention to provide a recovery member and a Li recovery device using the recovery member.
  • a selective permeation membrane containing a Li ion conductor made of an inorganic substance and an electrode are provided.
  • the electrode is provided on at least one main surface side of the selective transmission membrane.
  • At least one of the electrodes comprises a porous electrode or a membrane electrode.
  • the porous electrode or the membrane electrode is sandwiched between the reticulated elastic body and the selective permeable membrane.
  • Li ion recovery member 2.
  • 3. The Li ion recovery member according to 1 or 2 above, further comprising an electrode made of a rigid conductive porous plate. 4.
  • the Li ion recovery member according to 3 above wherein the porous electrode or the membrane electrode is provided on one main surface side of the selective permeation film, and the rigid conductive porous plate is provided on the other main surface. 5. The Li ion recovery member according to 3 above, wherein the porous electrode or the membrane electrode and the rigid conductive porous plate are provided on one main surface side of the selective permeation film. 6. 5. The Li ion recovery member according to 5 above, wherein the porous electrode or the membrane electrode and the rigid conductive porous plate are provided on both main surface sides of the selective permeation film. 7. 5. The Li ion recovery member according to 5 or 6, wherein the rigid conductive porous plate is provided so as to sandwich the porous electrode or the membrane electrode and the reticulated elastic body.
  • the selective permeable membrane is composed of a plurality of selective permeable membrane units arranged on the same surface and an adhesive portion.
  • the adhesive portion is provided in a grid shape or a honeycomb shape, and the adhesive portion is provided in a lattice shape or a honeycomb shape.
  • a Li recovery device including the Li ion recovery member according to any one of 1 to 10 above, and a Li ion recovery electrolytic cell that recovers Li ions by electrodialysis.
  • the plurality of Li ion recovery members are provided, and the plurality of Li ion recovery members have a main surface of a selective transmission membrane of one Li ion recovery member and a main surface of a selective transmission membrane of another Li ion recovery member.
  • the Li recovery device according to 11 above which is provided by connecting them so as to face each other.
  • a Li ion recovery member capable of suppressing the occurrence of breakage of the selective permeation membrane and realizing stable Li ion recovery for a long period of time even if the size of the Li recovery device is increased, and a Li recovery device using the Li ion recovery member. Can be provided.
  • the Li ion recovery member and the Li recovery device of one embodiment of the present invention (hereinafter, referred to as “the present embodiment”) will be described.
  • the Li ion recovery member and the Li recovery device according to the embodiment of the present invention are merely one embodiment of the Li ion recovery member and the Li recovery device of the present invention, and the present invention is the embodiment of the present invention. It is not limited to the Li ion recovery member and the Li recovery device.
  • lithium shall mean both lithium and lithium ions, and shall be interpreted as appropriate as long as there is no technical contradiction.
  • the Li ion recovery member of the present embodiment includes a selective transmission film containing a Li ion conductor made of an inorganic substance and an electrode, and the electrode is provided on at least one main surface side of the selective transmission film. At least one of the electrodes is a porous electrode or a membrane electrode, and the porous electrode or the membrane electrode is sandwiched between a reticulated elastic body and the selective permeable film.
  • the Li ion recovery member of the present embodiment adopts a configuration in which the porous body electrode or the membrane electrode is sandwiched between the reticulated elastic body and the selective permeable membrane. According to the Li ion recovery member of the present embodiment, when an increase in size is required, it is possible to cope with the increase in size by combining a plurality of the configurations instead of increasing the size itself. Further, as described above, when the selective permeable membrane is enlarged, there arises a problem of occurrence of breakage due to a decrease in strength.
  • the Li ion recovery member of the present embodiment can stably recover Li ions by one of the above configurations, the arrangement of the selective permeable membrane and the electrode is examined only by combining a plurality of the configurations. It is possible to cope with the increase in size of the device without any problem.
  • the size of the selective permeable membrane can be increased. In any case, it is possible to easily cope with the increase in size, and to suppress the occurrence of damage to the selective permeable membrane, and to realize stable Li ion recovery for a long period of time. Become.
  • the selective permeation membrane used in this embodiment contains a Li ion conductor made of an inorganic substance.
  • a Li ion conductor made of an inorganic substance.
  • the Li ion conductor made of an inorganic substance can be used without particular limitation as long as it is made of an inorganic substance and has the conductivity of Li ions.
  • a super Li ion conductor can be preferably mentioned.
  • the recovery efficiency of Li can be improved by increasing the ion current of Li ions flowing between the electrodes.
  • the Li ions contained in the aqueous solution exist as Li hydrated ions in which water molecules are coordinated around them. Therefore, in order to further increase the ionic current, it is effective to realize a situation in which water molecules can be easily removed on the surface of the selective permeable membrane (the interface between the selective permeable membrane and the stock solution).
  • a Li adsorption layer that adsorbs Li ions (excluding hydrates) in the Li ion extract is formed on the surface of the selective permeation membrane. That is, the selective permeation membrane is preferably one that has been subjected to surface Li adsorption treatment.
  • the Li adsorption layer as described later, those formed by modifying the surface of the material constituting the selective permeation membrane are preferably mentioned.
  • the material of the Li ion conductor composed of the inorganic substance constituting the selective permeation membrane body for example, the following Li-containing oxides, oxynitrides and the like are preferably mentioned. That is, the selective permeation membrane preferably contains the following Li-containing oxides, oxynitrides, and the like.
  • these materials can be obtained, for example, as a sintered body in which particles composed of this material are mixed with a sintering aid or the like and sintered at a high temperature (1000 ° C. or higher).
  • the surface of the Li selective permeable membrane can be formed as a porous body in which fine particles composed of LLTO are bonded (sintered), so that the effective area of the surface of the Li selective permeable membrane body is effective. Can be raised. The same applies not only to LLTO but also to other oxides containing Li and oxynitrides described later.
  • Examples of the super-Li ion conductor that can be used as a material constituting the main body of the selective permeable film include Li-containing oxides such as LLTO and LLZO described above, as well as, for example, Li-substituted NASICON (Na Super Ionic Controller).
  • Li-containing oxynitride examples include lithium phosphate oxynite (Li 3 PON, hereinafter also referred to as “LiPON”), LLTO nitride (LLTON), LLZO nitride (LLZON), and LASiPTIGeO nitride (LASiPTIGeON).
  • LiPON lithium phosphate oxynite
  • LLTON LLTO nitride
  • LLZON LLZO nitride
  • LASiPTIGeON LASiPTIGeON
  • the above-mentioned super-Li ion conductors such as Li-containing oxides and oxynitrides contain Li as one of its constituent elements, and the extra-crystal Li ions move between Li sites in the crystal to form ions. Conductivity develops. Li ions flow through the body of the Li selective permeable membrane, but sodium ions cannot flow through the Li selective permeable membrane. At this time, it is the Li ion (Li + ) that conducts in the crystal, and the hydrate ion of Li that exists in the stock solution together with the Li ion cannot enter the Li site, so that it does not conduct in the crystal. In this respect, it is the same as the Li selective permeation membrane described in WO2015 / 022121.
  • Li adsorption layer if a large amount of only Li ions are adsorbed on the surface of the selective permeable membrane body by the Li adsorption layer, water molecules of Li hydrated ions are removed at the time of adsorption and only Li ions are formed.
  • the conduction efficiency of Li ions (ion current flowing through the selective permeation membrane body) from the stock solution side (one main surface side) to the recovery solution side (the other main surface side) can be increased.
  • the selective permeable membrane may be formed by one selective permeable membrane, or may be formed as an aggregate of a plurality of selective permeable membranes.
  • the aggregate of the plurality of selective permeable membranes includes, for example, the form shown in (3-1) of FIG. 3, that is, the plurality of selective permeable membrane units 21 arranged on the same surface and the adhesive portion 22. It is preferable that the adhesive portions are provided in a grid pattern, and the plurality of selective permeable membrane units are arranged in a region partitioned by the lattice-like adhesive portions and are bonded to each other by the adhesive portions. Further, although the case of a grid shape is shown in FIG.
  • the shape is not limited to the grid shape, and may be, for example, a streak shape, a honeycomb shape, or the like, and the honeycomb shape is shape-stable. It is preferable from the viewpoint of sex.
  • the adhesive used for the above-mentioned adhesive portion include an epoxy resin, a silicone resin, and a ceramics-containing adhesive having resistance to alkalinity.
  • the adhesive portion 22 is provided with the current collector 23. ..
  • the electrode can be reliably energized while effectively utilizing the surface of the selective transmission membrane.
  • the size of the selective permeable membrane unit is usually 10 cm or more and 3000 cm or less in length and 10 cm or more and 2000 cm or less in width, preferably 30 cm or more and 2800 cm or less in length and 30 cm or more and 1800 cm or less in width.
  • the thickness of the selective permeable membrane unit is usually 0.1 cm or more and 10 cm or less, preferably 1 cm or more and 6 cm or less.
  • the current collector is preferably provided on at least one main surface side of the selective transmission membrane, and more preferably provided on both main surface sides.
  • the material constituting the current collector it is preferable to use a material having high electrical conductivity, and since it is assumed that the material is used in an alkaline atmosphere, it is preferable to use a material having resistance to alkalinity.
  • a material having high electrical conductivity in addition to SUS, Ti, Ti—Ir alloy and the like which can be used as an electrode described later, nickel, nickel alloy, carbon felt and the like can also be used.
  • Electrode At least one of the electrodes used in the present embodiment is a porous electrode or a membrane electrode.
  • the porous body electrode is an electrode composed of a porous body having pores, and specific examples thereof include carbon felt, carbon sheet, metal non-woven fabric, and metal mesh body.
  • a metal commonly used as an electrode can be used without limitation, but it is preferable to use a metal material that does not cause an electrochemical reaction and is resistant to alkalinity.
  • SUS, Ti, Ti—Ir alloy and the like are preferably mentioned.
  • the porous electrode is not particularly limited as long as it is composed of a porous body having pores, and the pores usually have an opening area of about 0.05 to 1.0 mm 2 , preferably 0. .1 to 0.5 mm 2 .
  • the ratio of the total pored area to the surface area of the porous body is preferably 10% or more, more preferably 20% or more, and the upper limit is preferably 50% or less, more preferably 40% or less. Since the porous electrode has the pores, it becomes easy to make the current flow uniform, it comes into surface contact with the selective permeable membrane, and it is flexible, so that local stress and the like can be suppressed. Further, when the selective permeable membrane is increased in size, it is easy to increase the size of the porous electrode such as a metal non-woven fabric.
  • the selective permeable membrane is a partition between the stock solution and the recovered liquid when Li ions are recovered, pressure is applied to prevent water leakage, but the pressure applied to the selective permeable membrane is non-uniform. It may be damaged if there are any or hard protrusions. Therefore, by using a porous electrode and further installing the porous electrode on both sides of the selective permeable membrane so that both sides of the selective permeable membrane have the same structure, the pressure received from both sides over the entire surface of the selective permeable membrane is made equal. As a result, it is possible to prevent the selective permeable membrane from being damaged due to local force being applied, so that it becomes easy to realize stable Li ion recovery for a long period of time.
  • the contact points between the selective permeable membrane and the porous electrode are increased on both sides of the selective permeable membrane, and uniform and large electrolysis can be performed in the plane of the selective permeable membrane. Therefore, improvement in the recovery rate of Li ions can be expected.
  • the membrane electrode is a membrane-like electrode, and examples thereof include a metal film made of a metal forming the above-mentioned porous electrode.
  • the thickness of the metal film may be appropriately determined according to the desired performance, size, etc., and cannot be unequivocally determined because it differs depending on the film forming method. Is usually about 1 to 5000 nm, preferably 10 to 3500 nm, more preferably 50 to 2500 nm, and even more preferably 100 to 2000 nm.
  • a liquid composition containing a metal for forming an electrode is applied and formed, it is usually about 0.1 to 100 ⁇ m, preferably 0.5 to 70 ⁇ m, more preferably 1 to 50 ⁇ m, and further preferably 5 to 20 ⁇ m. Is.
  • the porous electrode or the membrane electrode may be used as either an anode or a cathode. Further, both the porous electrode and the membrane electrode may be used alone or in combination of two or more.
  • an electrode made of a rigid conductive porous plate may be further provided.
  • the conductive perforated plate By making the conductive perforated plate a rigid body, parallelism between a plurality of selective permeable membranes can be maintained, and since it is a rigid body, it is possible to uniformly apply pressure to the selective permeable membrane at a higher pressure. Therefore, it becomes easy to suppress the occurrence of breakage of the selective permeation membrane and realize stable Li ion recovery for a long period of time.
  • a metal plate having an opening such as an expanded metal or a punched metal is preferably mentioned.
  • Examples of the metal constituting the expanded metal, punched metal, etc. include those exemplified as the metal that can be used for the electrode.
  • the ratio of the area of the opening to the whole is preferably 5 to 50%, more preferably 10 to 45%, still more preferably 20 to 35%.
  • the ratio of the openings is within the above range, local stress can be suppressed, so that the occurrence of breakage of the selective permeable membrane can be suppressed, and stable Li ion recovery for a long period of time can be easily realized.
  • the reticulated elastic body used in the present embodiment is provided to fix the porous electrode or the membrane electrode, which is at least one electrode, to the selective permeable membrane. These electrodes are sandwiched between a reticulated elastic body and a selective permeable membrane, and by using a reticulated elastic body that can be easily increased in size, even if the device is enlarged, the selective permeable membrane is particularly enlarged. Even when the size of the device is increased, it is possible to fix these electrodes so as to be surely in contact with the selective permeable membrane while suppressing the occurrence of damage to the electrodes such as the porous electrode and the membrane electrode.
  • the reticular elastic body can be used without particular limitation as long as the electrodes can be fixed so as to be in contact with the selective permeable membrane so as not to damage the electrodes such as the porous electrode and the membrane electrode and the selective permeable membrane.
  • a conductive or insulating elastic mat is preferable. If the pressure applied to the selective permeable membrane is non-uniform, or if there are hard protrusions, it may be damaged. It is easy to suppress the occurrence of breakage and realize stable Li ion recovery for a long period of time.
  • wire mesh in which metal wires such as plain woven wire mesh, flat tatami woven wire mesh, twill woven wire mesh, twill woven wire mesh, cedar woven wire mesh, and knitted woven wire mesh are woven by various methods, and these wire meshes are crimped.
  • a crimped wire mesh, an aggregate of metal wool, and the like are preferably mentioned, and among them, a knitted woven wire mesh is preferable.
  • flexible materials such as springs (metal coil bodies) can also be used. When a spring is used, it may be provided so that its expansion / contraction direction is parallel to the main surface of the selective transmission membrane.
  • the process difference between the peaks and valleys of the crimp is usually about 1 to 40 mm, preferably 2 to 30 mm.
  • the reticulated elastic body has elasticity, and is easy to fix the electrode in contact with the selective permeable membrane to the extent that the electrode and the selective permeable membrane are not damaged, and from the viewpoint of further suppressing local stress, the following properties It is preferable to have.
  • the following properties are common to both the case where the reticulated elastic body is the wire mesh and the case where the reticulated elastic body is a spring (metal coil body).
  • the repulsive force when the reticulated elastic body is compressed and deformed by 50% in the thickness direction is preferably 30 to 50 g / cm 2 , and more preferably 35 to 45 g / cm 2 .
  • the repulsive force when the reticulated elastic body is compressed and deformed by 20% in the thickness direction is preferably 10 to 30 g / cm 2 , and more preferably 15 to 25 g / cm 2 .
  • the spring elasticity is not particularly limited as long as it has the above-mentioned repulsive force, but the deformation width in the thickness direction in which the spring constant shows a constant value is preferably 1 to 30 mm, preferably 2 to 20 mm. More preferably.
  • the porosity when the reticulated elastic body is used is preferably 20% or more, more preferably 30% or more.
  • the material constituting the reticulated elastic body is not particularly limited, but considering that it can be used as a current collector from the viewpoint of recovering Li ions more efficiently, it is preferable to use a material having high electrical conductivity. Moreover, since it is assumed that it is used in an alkaline atmosphere, it is preferable to use a material having resistance to alkalinity. As such a material, in addition to the SUS, Ti, Ti—Ir alloy and the like exemplified as the material that can be used as the electrode, carbon steel, nickel, nickel alloy and the like can also be used. Considering the cost, for example, carbon steel or a material obtained by nickel-plating SUS is preferable.
  • the insulating elastic mat is preferably a material having a certain strength or higher, permeating an aqueous solution containing recovered ions, and having chemical stability with respect to the aqueous solution, and a non-woven fabric, a separator, or the like is preferable.
  • the non-woven fabric is preferably vegetable fiber, animal fiber, mineral fiber or chemical fiber
  • the chemical fiber is preferably rayon, nylon, polyester, acrylic fiber or aramid fiber
  • the separator is a polyolefin-based fiber having fine pores.
  • a urethane-based resin is preferable.
  • the recovery member such as a stack type or a cylindrical type, it can also serve as a spacer for passing the stock solution and the recovery solution.
  • the elastic mat may be a single layer of the above elastic mats or a plurality of the same or different materials.
  • the above-mentioned insulating elastic mat may be used alone, the conductive elastic mat may be used alone, or a plurality of insulating elastic mats may be used in combination, or a plurality of conductive elastic mats may be used in combination.
  • an insulating and conductive elastic mat may be used in combination.
  • FIGS. 1 and 2 Installation position relationship
  • the electrode 3 of the porous electrode or the membrane electrode needs to be provided on at least one main surface side of the selective transmission film 2, and these electrodes are sandwiched between the reticulated elastic body 4 and the selective transmission film 2. It takes that.
  • FIGS. 1 (1-1), (1-2) and the like is preferably mentioned.
  • the electrode 3 of the porous electrode or the membrane electrode is provided on one main surface side of the selective permeable membrane 2, and is sandwiched between the reticulated elastic body 4 and the selective permeable membrane 2. It is also possible that the selective permeable membrane 2 is provided on both main surface sides and is sandwiched between the reticulated elastic body 4 and the selective permeable membrane 2. As shown in these drawings, the electrode 3 of the porous electrode or the membrane electrode is preferably provided on the main surface of the selective transmission film 2 (provided so as to be in contact with the main surface).
  • the electrodes when the electrodes are provided on both main surface sides of the selective permeable membrane, the electrode on one main surface side is sandwiched between the reticulated elastic body and the selective permeable membrane. However, it is preferable that the electrodes 3 provided on both main surface sides as shown in (1-2) of FIG. 1 are sandwiched between the reticulated elastic body 4 and the selective permeable membrane 2, respectively. Since the selective permeable membrane is composed of an inorganic substance as described above, it is more likely to be damaged than an ion exchange membrane composed of an organic substance. , The pressure applied to the selective permeable membrane can be made uniform over the entire surface of the selective permeable membrane regardless of the current collector structure.
  • the electrode has a porous electrode or an electrode other than the membrane electrode, which is at least one of the electrodes, and an electrode made of a rigid conductive porous plate
  • the selective permeable film shown in FIG. 2 (2-1) is provided.
  • An embodiment in which an electrode 3 of a porous body electrode or a film electrode is provided on one main surface side of 2 and an electrode 5 of a rigid conductive porous plate is provided on the other main surface side can be mentioned.
  • the rigid conductive porous plate 5 is provided so as to sandwich the porous electrode or the membrane electrode 3 and the reticulated elastic body 4, that is, the porous electrode when viewed from one main surface of the selective transmission film 2.
  • the membrane electrode 3, the reticulated elastic body 4, and the rigid conductive perforated plate 5 are provided in this order.
  • the rigid conductive porous plate 5 is provided so as to sandwich the porous electrode or membrane electrode 3 and the reticulated elastic body 4, that is, the porous electrode or membrane electrode when viewed from one main surface of the selective transmission film 2. 3. It is preferable that the reticulated elastic body 4 and the rigid conductive perforated plate 5 are provided in this order.
  • the Li recovery device of the present embodiment has the above-mentioned Li ion recovery member of the present embodiment, and includes a Li ion recovery electrolytic cell that recovers Li ions by electrodialysis.
  • the Li recovery device can recover Li ions from the undiluted solution containing Li ions by the Li ion recovery electrolytic cell having the Li ion recovery member of the present embodiment described above.
  • the Li ion recovery electrolytic cell used in the present embodiment includes, for example, a treatment tank for storing a stock solution containing Li ions and a recovery liquid for recovering Li ions from the stock solution, and a Li ion recovery member of the present embodiment. , The undiluted solution and the recovered solution are partitioned by a Li ion recovery member and stored, and Li ions are transferred from the undiluted solution to the recovered solution through the selective permeation film of the Li ion recovery member to become the recovered solution.
  • An electrolytic cell that recovers Li ions is preferable.
  • the undiluted solution tank and the recovered solution for storing the undiluted solution are stored by partitioning one treatment tank by the Li ion recovery member. It may be divided into a recovery liquid tank to be used, or a separate stock solution tank and a recovery liquid tank may be connected so as to be separated by a Li ion recovery member. Further, when the stock solution and the recovery liquid are separated by the Li ion recovery member, the Li ion recovery member stores the stock solution on one main surface side of the selective permeable membrane and the recovery liquid on the other main surface side. It means that it is provided so as to. As a result, Li ions in the undiluted solution are recovered in the recovery solution via the selective permeation membrane of the Li ion recovery member.
  • the stock solution may be pH controlled.
  • the pH of the stock solution is a value of 8.5 or more and less than 9.5 for pH 9 of pH 9 or more and 15 or less.
  • PH 15 is assumed to include a value of 14.5 or more and less than 15.5, which means that it is substantially in the range of 8.5 or more and less than 15.5.
  • the means thereof is not particularly limited, but for example, an alkaline aqueous solution may be added to the undiluted solution.
  • the pH control of the stock solution may be performed when recovering Li ions in the recovery solution, that is, Li ions may be recovered in the recovery solution while controlling the pH of the stock solution, or Li ions may be collected in the recovery solution. It may be done in advance before collection.
  • alkaline component of the alkaline aqueous solution used for adjusting the pH of the undiluted solution examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, and tetraethyl hydroxide.
  • Preferable examples include ammonium, calcium hydroxide, barium hydroxide, europium hydroxide (II), talium hydroxide (I), guanidine and the like.
  • These alkaline components may be used alone or in combination of two or more.
  • sodium hydroxide is more preferable from the viewpoint that the pH of the lithium ion extract can be adjusted quickly.
  • FIGS. 4 to 6 show a preferable example showing a specific embodiment of the Li ion recovery electrolytic cell.
  • the Li ion recovery electrolytic cell 10 shown in FIG. 4 shows a cross section of one cell (unit cell) of the multipolar electrolyte, and a plurality of the cells may be used in combination.
  • the Li ion recovery electrolytic cell 10 shown in FIGS. 5 and 6 is shown to have a plurality of Li ion recovery members 1. For example, by combining a plurality of cells having one Li ion recovery member 1 shown in FIG. 4, or by incorporating a plurality of Li ion recovery members 1 in one cell, each selective permeation membrane becomes smaller.
  • the Li ion recovery electrolytic cell 10 shown in FIGS. 4 to 6 can be used by either a unipolar type or a double pole type.
  • FIG. 4 shows a cross section of the electrolytic cell 10 having the Li ion recovery member 1 of the present embodiment shown in FIG. 2 (2-4), and is an electrode (porous electrode) of the selective transmission film 2 and 1.
  • Packing 13, and ribs 14a and 14b, and the two electrolytic cell frames 11a and 11b are combined via the packing 13 and the selective transmission film 2 to form a Li ion recovery electrolytic cell (one cell). doing.
  • it has an anode chamber 6a as a stock solution tank for storing the stock solution and a cathode chamber 6b as a recovery liquid tank for storing the recovery liquid.
  • FIGS. 5 and 6 show a cross section of the Li ion recovery electrolytic cell 10 having a plurality of Li ion recovery members 1 shown in FIGS. 1 and 2 (FIG. 6 shows Li ions in the Li ion recovery electrolytic cell 10). Only the portion of the recovery member 1 is shown.), The plurality of Li ion recovery members 1 are provided, and the plurality of Li ion recovery members 1 are the main surface of the selective permeation film of one Li ion recovery member, and the like. The configuration is shown in which the main surface of the selective permeable film of the Li ion recovery member of No. 1 is connected so as to face each other.
  • FIG. 5 shows an electrolytic cell 10 in which a plurality of Li ion recovery electrolytic cells 10 shown in FIG.
  • the Li ion recovery electrolytic cell 10 shown in FIG. 5 has a preferable configuration because a constant capacity can be secured in the anode chamber 6a and the cathode chamber 6b by the two electrodes (rigid conductive porous plate) 5. Further, as shown in FIG. 6, a plurality of Li ion recovery members 1 in FIG. 4 may be provided via a reticulated elastic body.
  • the plurality of Li ion recovery members are fixed by ribs 14 so that the members at both ends thereof are surrounded by the electrolytic cell frame 11 and the back partition wall 12.
  • the undiluted solution and the recovered solution are held in the portion of the reticulated elastic body 4 surrounded by the selective permeable membrane 2.
  • the electrolytic cell frame 11 can be said to be a frame of one cell, it is also called a unit cell frame, and may be made of a metal such as carbon steel, or a stock solution containing Li ions to be processed in the electrolytic cell. Since it is assumed that it is used in an alkaline atmosphere, it may be made of reinforced plastic or the like having resistance to alkalinity.
  • the back partition wall 12 is provided to partition from the adjacent cell when a plurality of electrolytic cells shown in FIG. 4 are used in combination, and is formed of a metal such as Ti as a material having resistance to alkalinity. ..
  • the portion partitioned by the electrolytic cell frame 11b, the back partition wall 12b, and the selective transmission membrane 2 becomes the cathode chamber 6b, and the electrodes 3 and 5 existing in the cathode chamber 6b function as the cathode.
  • the recovered solution is stored in the cathode chamber 6b, applied to the electrodes and electrodialyzed, so that the Li ions contained in the undiluted solution move from the undiluted solution to the recovered solution via the selective permeation membrane, and Li ions are transferred to the recovered solution.
  • the anode chamber 6a can be referred to as a stock solution tank
  • the cathode chamber 6b can be referred to as a recovery liquid tank.
  • the stock solution and the recovery liquid are supplied to the anode chamber 6a and the cathode chamber 6b through pipes, respectively, and the Li ions in the stock solution are recovered in the recovery liquid via the selective permeation membrane 2 of the Li ion recovery member. Will be done. Further, if necessary, as shown in FIG. 6, a pipe for recovering the undiluted solution and the recovered solution from the anode chamber 6a and the cathode chamber 6b, respectively, may be provided.
  • the Li recovery device of the present embodiment is not particularly limited as long as it includes a Li ion recovery electrolytic cell having a Li ion recovery member having the above configuration.
  • the Li ion recovery electrolytic cell has an anode thereof. Piping that supplies undiluted solution to the chamber, piping that drains undiluted solution from the anode chamber, discharge piping that exhausts gases such as oxygen generated by electrodialysis, and piping that supplies recovered liquid (newly supplied water, etc.) to the cathode chamber, It is preferable that the recovery liquid from which Li ions have been recovered is connected by a pipe for draining the liquid from the cathode chamber, a recovery pipe for recovering a gas such as hydrogen generated by electrodialysis, or the like.
  • the Li recovery device of the present embodiment includes a stock solution storage tank and a recovery liquid storage tank for supplying to the Li ion recovery electrolytic cell, a stock solution waste liquid tank when the stock solution is drained, and recovery when the recovery liquid is drained.
  • a stock solution waste liquid tank when the stock solution is drained
  • recovery when the recovery liquid is drained in addition to a liquid waste liquid tank, an extraction and crystallization device for recovering Li from a recovery liquid containing Li ions recovered from the undiluted solution, these devices and a Li ion recovery electrolytic cell are connected by the above pipes and the like. Is preferable.
  • each of the above-mentioned stock solution and recovery liquid storage tanks has a stirrer. By stirring the undiluted solution and the recovered solution circulating through the above pipes with a stirrer in each storage tank, Li ions can be recovered more efficiently.
  • the Li recovery device of the present embodiment may include means for circulating the undiluted solution and the recovered solution. It becomes possible to recover Li ions more efficiently.
  • the stock solution is supplied to the anode chamber of the Li ion recovery electrolytic cell via the stock solution storage tank, the stock solution is circulated from the anode chamber, and the recovery liquid storage tank is used.
  • a means for supplying the recovered liquid to the cathode chamber of the Li ion recovery electrolytic cell and circulating the recovered liquid for draining the recovered liquid obtained by recovering Li ions from the cathode chamber can be adopted.
  • the circulation can be performed, for example, by manually or automatically turning the pump on and off using a pump, and may be continuously operated to be a distribution type or intermittently operated to be a batch type. From the viewpoint of improving work efficiency, it is preferable to operate automatically.
  • a means for adding an alkaline aqueous solution to the undiluted solution may be provided.
  • the means may be a means that allows the addition to be performed continuously or intermittently, manually or automatically, and may be provided, for example, in a stock solution storage tank. From the viewpoint of work efficiency, it is preferable to provide means that can be performed automatically.
  • Examples of the undiluted solution used in the Li recovery device include a Li ion extract extracted from a processing member of a lithium secondary battery.
  • the Li ion extract is not particularly limited as long as it is extracted from the processing member, but for example, a Li ion extract extracted from the processing member of the lithium secondary battery containing a sulfide-based solid electrolyte, that is, a sulfide-based solid electrolyte is used.
  • Examples include Li ion extracts containing.
  • the Li recovery device of the present embodiment may be provided with a solid-liquid separation device or the like for separating Li and water or the like generated by extraction and crystallization of Li from the recovery liquid, if necessary. Further, a drying device for drying Li (for example, the above-mentioned lithium carbonate and lithium hydroxide monohydrate) separated by a solid-liquid separation device or the like may be provided.
  • a drying device for drying Li for example, the above-mentioned lithium carbonate and lithium hydroxide monohydrate

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