WO2017221526A1 - Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite - Google Patents

Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite Download PDF

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Publication number
WO2017221526A1
WO2017221526A1 PCT/JP2017/015033 JP2017015033W WO2017221526A1 WO 2017221526 A1 WO2017221526 A1 WO 2017221526A1 JP 2017015033 W JP2017015033 W JP 2017015033W WO 2017221526 A1 WO2017221526 A1 WO 2017221526A1
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Prior art keywords
functional layer
ldh
porous substrate
composite material
hydroxide
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PCT/JP2017/015033
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English (en)
Japanese (ja)
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翔 山本
昌平 横山
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日本碍子株式会社
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Priority to PCT/JP2017/022907 priority Critical patent/WO2017221990A1/fr
Priority to JP2018524148A priority patent/JP6617200B2/ja
Priority to EP17815458.9A priority patent/EP3477741A4/fr
Priority to CN201780037775.8A priority patent/CN109314210A/zh
Publication of WO2017221526A1 publication Critical patent/WO2017221526A1/fr
Priority to US16/227,702 priority patent/US20190126590A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/28—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a functional layer and a composite material containing a layered double hydroxide.
  • LDH Layered double hydroxide
  • LDH is also attracting attention as a material that conducts hydroxide ions, and its addition to the electrolyte of alkaline fuel cells and the catalyst layer of zinc-air cells is also being studied.
  • LDH as a solid electrolyte separator for alkaline secondary batteries such as nickel-zinc secondary batteries and zinc-air secondary batteries
  • an LDH-containing functional layer suitable for such separator applications is provided.
  • Composite materials are known.
  • Patent Document 1 International Publication No. 2015/098610 discloses a composite including a porous substrate and an LDH-containing functional layer that does not have water permeability and is formed on and / or in the porous substrate.
  • the LDH-containing functional layer has a general formula: M 2+ 1-x M 3+ x (OH) 2 A n ⁇ x / n ⁇ mH 2 O (where M 2+ is 2 such as Mg 2+) A valent cation, M 3+ is a trivalent cation such as Al 3+ , A n ⁇ is an n-valent anion such as OH ⁇ , CO 3 2 ⁇ , n is an integer of 1 or more, and x is 0. 1 to 0.4, and m is 0 or more).
  • an alkaline secondary battery for example, a metal-air battery or a nickel-zinc battery
  • LDH low-density diode
  • Patent Document 2 International Publication No. 2016/51934
  • a metal compound containing a metal element for example, Al
  • M 2+ and / or M 3+ is dissolved in an electrolytic solution.
  • an LDH-containing battery that is configured so that erosion of the LDH by the electrolyte is suppressed.
  • the inventors of the present invention have recently found that it is possible to provide an LDH-containing functional layer that is excellent not only in ion conductivity but also in alkali resistance.
  • an object of the present invention is to provide an LDH-containing functional layer that is excellent not only in ion conductivity but also in alkali resistance, and a composite material including the same.
  • a functional layer comprising a layered double hydroxide
  • the layered double hydroxide is immersed in a 5 mol / L potassium hydroxide aqueous solution containing zinc oxide at a concentration of 0.4 mol / L at 70 ° C. for 3 weeks, the surface microstructure and crystal structure change. A functional layer that does not occur is provided.
  • a porous substrate comprising:
  • a battery including the functional layer or the composite material as a separator is provided.
  • FIG. 1 It is a schematic cross section which shows one aspect
  • 2 is a schematic cross-sectional view showing an electrochemical measurement system used in Examples 1 and 2.
  • FIG. It is a disassembled perspective view of the airtight container for measurement used in the denseness determination test of Examples 1 and 2.
  • FIG. 6B is a schematic cross-sectional view of a sample holder used in the measurement system shown in FIG. 6A and its peripheral configuration.
  • 2 is an X-ray diffraction result of a functional layer manufactured in Example 1.
  • FIG. 2 is an SEM image showing a surface microstructure of a functional layer produced in Example 1.
  • 3 is a SEM image showing a cross-sectional microstructure of a functional layer manufactured in Example 1. It is a SEM image which shows the surface microstructure of the functional layer produced in Example 1 before immersion in KOH aqueous solution, after 1 week immersion, and after 3 weeks immersion. It is the X-ray-diffraction result of the functional layer produced in Example 1 before immersion in KOH aqueous solution, after 1 week immersion, and after 3 week immersion.
  • FIG. 6 is a SEM image showing a surface microstructure of a functional layer produced in Example 2.
  • 6 is a SEM image showing a cross-sectional microstructure of a functional layer fabricated in Example 2. It is a SEM image which shows the surface microstructure of the functional layer produced in Example 2 before immersion in KOH aqueous solution, after 1 week immersion, and after 3 weeks immersion. It is the X-ray-diffraction result of the functional layer produced in Example 2 before immersion in KOH aqueous solution, after 1 week immersion, and after 3 weeks immersion. It is a SEM image which shows the surface microstructure of the functional layer produced in Example 3 (comparison).
  • Example 3 It is a SEM image which shows the cross-sectional microstructure of the functional layer produced in Example 3 (comparison). It is a SEM image which shows the surface microstructure of the functional layer of the functional layer produced in Example 3 (comparative) before immersion in KOH aqueous solution and after 1 week immersion. It is the X-ray-diffraction result of the functional layer produced in Example 3 (comparison) before immersion in KOH aqueous solution and after 1 week immersion.
  • the functional layer of the present invention is a layer containing layered double hydroxide (LDH), and this LDH has a concentration of 0.4 mol / L and 5 mol / L of hydroxide containing zinc oxide.
  • LDH layered double hydroxide
  • the surface microstructure and crystal structure do not change.
  • the presence or absence of changes in the surface microstructure depends on the surface microstructure using an SEM (scanning electron microscope), and the presence or absence of changes in the crystal structure depends on crystal structure analysis using XRD (X-ray diffraction) (for example, (003) derived from LDH) It can be preferably performed depending on whether or not there is a peak shift.
  • Potassium hydroxide is a typical strong alkaline substance, and the composition of the potassium hydroxide aqueous solution corresponds to a typical strong alkaline electrolyte of an alkaline secondary battery. Therefore, it can be said that the above evaluation method of immersing in such a strong alkaline electrolyte at a high temperature of 70 ° C. for a long period of 3 weeks is a severe alkali resistance test.
  • the alkali secondary battery LDH is desired to have a high alkali resistance that hardly deteriorates even in a strong alkaline electrolyte.
  • the functional layer of the present invention has excellent alkali resistance that the surface microstructure and crystal structure are not changed even by such severe alkali resistance tests.
  • the functional layer of the present invention can also exhibit high ionic conductivity suitable for use as a separator for an alkaline secondary battery due to the inherent properties of LDH. That is, according to the present invention, it is possible to provide an LDH-containing functional layer that is excellent not only in ion conductivity but also in alkali resistance.
  • LDH is composed of a plurality of hydroxide base layers and an intermediate layer interposed between the plurality of hydroxide base layers.
  • the hydroxide base layer is mainly composed of metal elements (typically metal ions) and OH groups.
  • the intermediate layer of LDH included in the functional layer is composed of an anion and H 2 O.
  • the anion is a monovalent or higher anion, preferably a monovalent or divalent ion.
  • the anion in LDH comprises OH - and / or CO 3 2- .
  • the composition of LDH in the present invention is not particularly limited as long as the surface microstructure and the crystal structure are not changed by the alkali resistance evaluation described above. Further, as described above, LDH has excellent ionic conductivity due to its inherent properties.
  • the hydroxide base layer of LDH is composed of Ni, Ti, OH groups and possibly inevitable impurities.
  • the intermediate layer of LDH is composed of an anion and H 2 O.
  • the alternate layered structure of the hydroxide basic layer and the intermediate layer itself is basically the same as the generally known alternate layered structure of LDH, but the functional layer of this embodiment is mainly composed of the hydroxide basic layer of LDH as Ni.
  • an element for example, Al
  • Ni in LDH can take the form of nickel ions.
  • the nickel ions in LDH are typically considered to be Ni 2+ , but are not particularly limited because other valences such as Ni 3+ may also exist.
  • Ti in LDH can take the form of titanium ions.
  • the titanium ion in LDH is typically considered to be Ti 4+ , but is not particularly limited because other valences such as Ti 3+ may also exist.
  • Inevitable impurities are optional elements that can be inevitably mixed in the manufacturing process, and can be mixed in LDH, for example, derived from raw materials and base materials.
  • the hydroxide base layer is mainly composed of Ni 2+ , Ti 4+ and OH groups
  • the corresponding LDH has the general formula: Ni 2+ 1-x Ti 4+ x (OH) 2 An - 2x / n ⁇ mH 2 O (wherein, a n-n-valent anion, n is an integer of 1 or more, preferably 1 or 2, 0 ⁇ x ⁇ 1, preferably 0.01 ⁇ x ⁇ 0.5, m is 0 or more, typically greater than 0 or 1 or more real number).
  • the hydroxide base layer of LDH comprises Ni, Al, Ti and OH groups.
  • the intermediate layer is composed of an anion and H 2 O.
  • the alternating layered structure of the hydroxide basic layer and the intermediate layer itself is basically the same as the generally known layered structure of LDH, but the functional layer of this embodiment is configured such that the hydroxide basic layer of LDH is Ni, By comprising a predetermined element or ion containing Al, Ti and OH groups, excellent alkali resistance can be exhibited.
  • Ni in LDH can take the form of nickel ions.
  • the nickel ions in LDH are typically considered to be Ni 2+ , but are not particularly limited because other valences such as Ni 3+ may also exist.
  • Al in LDH can take the form of aluminum ions.
  • Aluminum ions in LDH are typically considered to be Al 3+ , but are not particularly limited because other valences are possible.
  • Ti in LDH can take the form of titanium ions.
  • the titanium ion in LDH is typically considered to be Ti 4+ , but is not particularly limited because other valences such as Ti 3+ may also exist.
  • the hydroxide base layer may contain other elements or ions as long as it contains Ni, Al, Ti and OH groups. However, it is preferable that the hydroxide base layer contains Ni, Al, Ti, and OH groups as main components. That is, the hydroxide base layer is preferably mainly composed of Ni, Al, Ti and OH groups. Therefore, the hydroxide base layer is typically composed of Ni, Al, Ti, OH groups and possibly inevitable impurities.
  • Inevitable impurities are optional elements that can be inevitably mixed in the manufacturing process, and can be mixed in LDH, for example, derived from raw materials and base materials.
  • LDH for example, derived from raw materials and base materials.
  • the hydroxide base layer is mainly composed of Ni 2+ , Al 3+ , Ti 4+ and OH groups
  • the corresponding LDH has the general formula: Ni 2+ 1-xy Al 3+ x Ti 4+ y (OH) 2 A n ⁇ (x + 2y) / n ⁇ mH 2 O
  • a n ⁇ is an n-valent anion
  • n is an integer of 1 or more, preferably 1 or 2, and 0 ⁇ x ⁇ 1, preferably 0.01 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 1, preferably 0.01 ⁇ y ⁇ 0.5, 0 ⁇ x + y ⁇ 1, m is 0 or more, typically 0.
  • the functional layer (particularly LDH contained in the functional layer) preferably has hydroxide ion conductivity.
  • the functional layer preferably has an ionic conductivity of 0.1 mS / cm or more, more preferably 0.5 mS / cm or more, and more preferably 1.0 mS / cm or more.
  • the upper limit is not particularly limited, but is, for example, 10 mS / cm.
  • Such high ionic conductivity is particularly suitable for battery applications.
  • an LDH-containing functional layer having a low resistance can be provided. It is particularly advantageous in the application of LDH as a solid electrolyte separator for secondary batteries.
  • the functional layer is provided on the porous substrate and / or is incorporated into the porous substrate. That is, according to a preferred aspect of the present invention, there is provided a composite material comprising a porous substrate and a functional layer provided on the porous substrate and / or incorporated into the porous substrate.
  • a part of the functional layer 14 may be incorporated in the porous substrate 12 and the remaining part may be provided on the porous substrate 12.
  • the portion of the functional layer 14 on the porous substrate 12 is a film-shaped portion made of an LDH film, and the portion of the functional layer 14 incorporated into the porous substrate 12 is composed of the porous substrate and LDH. It can be said that it is a composite part.
  • the composite part typically has a form in which the pores of the porous substrate 12 are filled with LDH.
  • the functional layer 14 ′ is mainly composed of the porous substrate 12 and LDH. It can be said that.
  • the composite material 10 ′ and the functional layer 14 ′ shown in FIG. 2 are obtained by removing the film-like portion (LDH film) in the functional layer 14 from the composite material 10 shown in FIG. 1 by a known method such as polishing or cutting. Obtainable. 1 and 2, the functional layers 14 and 14 ′ are incorporated only in a part near the surface of the porous base material 12 and 12 ′. However, the functional layer is incorporated in any part of the porous base material. In addition, the functional layer may be incorporated over the whole or the entire thickness of the porous substrate.
  • the porous base material in the composite material of the present invention is preferably capable of forming an LDH-containing functional layer on and / or in it, and the material and the porous structure are not particularly limited.
  • the LDH-containing functional layer is formed on and / or in the porous substrate, but the LDH-containing functional layer is formed on the nonporous substrate, and then nonporous by various known methods.
  • the porous substrate may be made porous.
  • the porous base material has a porous structure having water permeability in that the electrolyte solution can reach the functional layer when incorporated in the battery as a battery separator.
  • the porous substrate is preferably composed of at least one selected from the group consisting of ceramic materials, metal materials, and polymer materials, and more preferably selected from the group consisting of ceramic materials and polymer materials. It is composed of at least one kind. More preferably, the porous substrate is made of a ceramic material.
  • the ceramic material include alumina, zirconia, titania, magnesia, spinel, calcia, cordierite, zeolite, mullite, ferrite, zinc oxide, silicon carbide, and any combination thereof, and more preferable.
  • alumina e.g, yttria stabilized zirconia (YSZ)
  • YSZ yttria stabilized zirconia
  • Preferred examples of the metal material include aluminum, zinc, and nickel.
  • Preferred examples of the polymer material include polystyrene, polyethersulfone, polypropylene, epoxy resin, polyphenylene sulfide, hydrophilic fluororesin (tetrafluorinated resin: PTFE, etc.), cellulose, nylon, polyethylene, and any combination thereof. Is mentioned. Any of the various preferred materials described above has alkali resistance as resistance to the electrolyte of the battery.
  • the porous substrate preferably has an average pore size of at most 100 ⁇ m or less, more preferably at most 50 ⁇ m, for example, typically 0.001 to 1.5 ⁇ m, more typically 0.001. 1.25 ⁇ m, more typically 0.001 to 1.0 ⁇ m, particularly typically 0.001 to 0.75 ⁇ m, and most typically 0.001 to 0.5 ⁇ m.
  • the average pore diameter can be measured by measuring the longest distance of the pores based on the electron microscope image of the surface of the porous substrate.
  • the magnification of the electron microscope image used for this measurement is 20000 times or more. All the obtained pore diameters are arranged in order of size, and the top 15 points and the bottom 15 points are arranged in order from the average value, and 30 points per visual field are combined.
  • the average pore diameter can be obtained by calculating an average value for two visual fields.
  • a length measurement function of SEM software, image analysis software (for example, Photoshop, manufactured by Adobe) or the like can be used for the length measurement.
  • the porous substrate preferably has a porosity of 10 to 60%, more preferably 15 to 55%, still more preferably 20 to 50%. By being within these ranges, it is possible to form an LDH-containing functional layer that is so dense that it does not have water permeability, while ensuring the desired water permeability and strength as a support for the porous substrate.
  • the porosity of the porous substrate can be preferably measured by the Archimedes method.
  • the functional layer does not have air permeability. That is, the functional layer is preferably densified with LDH to such an extent that it does not have air permeability.
  • non-breathable refers to an object to be measured in water when the breathability is evaluated by a “denseness determination test” employed in the examples described later or a method or configuration equivalent thereto. This means that even if helium gas is brought into contact with one surface side (that is, the functional layer and / or the porous substrate) with a differential pressure of 0.5 atm, generation of bubbles due to helium gas is not observed from the other surface side. .
  • the functional layer or the composite material as a whole can selectively pass only hydroxide ions due to its hydroxide ion conductivity, and can exhibit a function as a battery separator.
  • LDH solid electrolyte separator
  • strength can be imparted by a porous substrate. Therefore, the LDH-containing functional layer can be thinned to reduce the resistance.
  • the porous substrate can have water permeability and air permeability, the electrolyte can reach the LDH-containing functional layer when used as a battery solid electrolyte separator.
  • the LDH-containing functional layer and composite material of the present invention are used as solid electrolyte separators applicable to various battery applications such as metal-air batteries (for example, zinc-air batteries) and other various zinc secondary batteries (for example, nickel-zinc batteries). It can be a very useful material.
  • the functional layer or the composite material including the functional layer preferably has a He permeability per unit area of 10 cm / min ⁇ atm or less, more preferably 5.0 cm / min ⁇ atm or less, and even more preferably 1.0 cm / min. It is below min ⁇ atm. It can be said that the functional layer having the He transmittance within such a range has extremely high density. Therefore, the functional layer having a He permeability of 10 cm / min ⁇ atm or less can prevent a high level of passage of substances other than hydroxide ions when applied as a separator in an alkaline secondary battery. For example, in the case of a zinc secondary battery, permeation of zinc ions or zincate ions in the electrolytic solution can be extremely effectively suppressed.
  • the He permeability is measured through a process of supplying He gas to one surface of the functional layer and allowing the He gas to pass through the functional layer, and a process of calculating the He permeability and evaluating the density of the functional layer.
  • the He permeability is expressed by the following formula: F / (P ⁇ S), using the He gas permeation amount F per unit time, the differential pressure P applied to the functional layer when He gas permeates, and the membrane area S through which He gas permeates.
  • H 2 gas is dangerous because it is a combustible gas.
  • He gas permeability index defined by the above-described formula
  • objective evaluation regarding the denseness can be easily performed regardless of differences in various sample sizes and measurement conditions. In this way, it is possible to simply, safely and effectively evaluate whether or not the functional layer has a sufficiently high density suitable for a zinc secondary battery separator.
  • the measurement of the He permeability can be preferably performed according to the procedure shown in Evaluation 5 of Examples described later.
  • LDH includes an aggregate of a plurality of plate-like particles (that is, LDH plate-like particles), and the plurality of plate-like particles are macroscopically such that the plate surface is a layer surface of the functional layer (the fine irregularities of the functional layer can be ignored). It is preferably oriented in a direction perpendicular to or obliquely intersecting the layer surface when observed.
  • a functional layer when a functional layer is provided on a porous base material, a functional layer has a film-like part provided on a porous base material.
  • the LDH constituting the film-like portion includes an aggregate of a plurality of plate-like particles (that is, LDH plate-like particles), and the plate-like particles have a plate surface whose surface is porous (porous). It is preferably oriented in a direction that intersects perpendicularly or obliquely with the surface of the porous base material when the microscopic unevenness due to the structure is macroscopically observed to a negligible extent.
  • grains can exist also in the hole of a porous base material.
  • the film-like part may further contain ceramic particles such as alumina particles as a filler, whereby the adhesion strength between the LDH of the film-like part and the substrate can be increased.
  • the LDH crystal is known to have the form of a plate-like particle having a layered structure as shown in FIG. 3, but the above vertical or oblique orientation is extremely important for an LDH-containing functional layer (for example, an LDH dense film).
  • an LDH-containing functional layer for example, an LDH dense film
  • an oriented LDH-containing functional layer eg, an oriented LDH dense film
  • the conductivity (S / cm) in the orientation direction is one digit higher than the conductivity (S / cm) in the direction perpendicular to the orientation direction. That is, the vertical or oblique orientation in the LDH-containing functional layer of the present invention indicates the conductivity anisotropy that the LDH oriented body can have in the layer thickness direction (that is, the direction perpendicular to the surface of the functional layer or porous substrate). As a result, the conductivity in the layer thickness direction can be maximized or significantly increased.
  • the LDH-containing functional layer has a layer form, lower resistance than that of the bulk form LDH can be realized.
  • the LDH-containing functional layer having such an orientation is easy to conduct hydroxide ions in the layer thickness direction.
  • it is extremely suitable for use in functional membranes such as battery separators (eg, hydroxide ion conductive separators for zinc-air batteries) where high conductivity in the layer thickness direction and denseness are desired. Suitable.
  • the functional layer preferably has a thickness of 100 ⁇ m or less, more preferably 75 ⁇ m or less, still more preferably 50 ⁇ m or less, particularly preferably 25 ⁇ m or less, and most preferably 5 ⁇ m or less. Such thinness can reduce the resistance of the functional layer.
  • the thickness of the functional layer corresponds to the thickness of the film-like portion made of the LDH film.
  • the thickness of the functional layer corresponds to the thickness of the composite portion composed of the porous substrate and LDH.
  • a functional layer when a functional layer is formed over and in a porous base material, it corresponds to the total thickness of a film-like part (LDH film) and a composite part (porous base material and LDH).
  • LDH film film-like part
  • composite part porous base material and LDH
  • the lower limit of the thickness of the LDH alignment film is not particularly limited because it varies depending on the application, but in order to ensure a certain degree of hardness desired as a functional film such as a separator, the thickness is preferably 1 ⁇ m or more. Preferably it is 2 micrometers or more.
  • the manufacturing method of the LDH-containing functional layer and the composite material is not particularly limited, and the LDH-containing functional layer and the composite material are manufactured by appropriately changing various conditions of the known LDH-containing functional layer and composite material manufacturing method (see, for example, Patent Documents 1 and 2). be able to.
  • a porous substrate is prepared, (2) a titanium oxide sol or a mixed sol of alumina and titania is applied to the porous substrate and heat-treated to form a titanium oxide layer or an alumina / titania layer, (3) The porous base material is immersed in a raw material aqueous solution containing nickel ions (Ni 2+ ) and urea, and (4) the porous base material is hydrothermally treated in the raw material aqueous solution to form the LDH-containing functional layer as the porous base material.
  • the LDH-containing functional layer and the composite material can be produced.
  • the raw material of LDH can be provided, but it can also function as a starting point for LDH crystal growth.
  • the LDH-containing functional layer highly densified on the surface can be uniformly formed without unevenness.
  • the presence of urea in the above step (3) raises the pH value due to the generation of ammonia in the solution utilizing the hydrolysis of urea, and the coexisting metal ions form hydroxides. LDH can be obtained. Further, since carbon dioxide is generated in the hydrolysis, LDH in which the anion is carbonate ion type can be obtained.
  • Evaluation 1 Identification of functional layer
  • the crystal phase of the functional layer was measured with an X-ray diffractometer (RINT TTR III manufactured by Rigaku Corporation) under the measurement conditions of voltage: 50 kV, current value: 300 mA, measurement range: 10 to 70 °.
  • an XRD profile was obtained.
  • JCPDS card NO. Identification was performed using a diffraction peak of LDH (hydrotalcite compound) described in 35-0964.
  • Evaluation 2 Observation of microstructure
  • the surface microstructure of the functional layer was observed with a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL) at an acceleration voltage of 10 to 20 kV. Further, after obtaining a cross-sectional polished surface of a functional layer (a film-shaped portion made of an LDH film and a composite portion made of LDH and a base material) with an ion milling device (manufactured by Hitachi High-Technologies Corporation, IM4000) The structure was observed by SEM under the same conditions as the observation of the surface microstructure.
  • Evaluation 3 Elemental analysis evaluation (EDS) Polishing was performed with a cross section polisher (CP) so that the cross-section polished surface of the functional layer (a film-like portion made of an LDH film and a composite portion made of LDH and a substrate) could be observed.
  • FE-SEM ULTRA55, manufactured by Carl Zeiss
  • a cross-sectional image of the functional layer was obtained in one field of view at a magnification of 10,000 times.
  • Evaluation 4 Evaluation of alkali resistance Zinc oxide was dissolved in a 6 mol / L potassium hydroxide aqueous solution to obtain a 5 mol / L potassium hydroxide aqueous solution containing zinc oxide at a concentration of 0.4 mol / L. 15 ml of the aqueous potassium hydroxide solution thus obtained was placed in a Teflon (registered trademark) sealed container. A composite material having a size of 1 cm ⁇ 0.6 cm was placed on the bottom of the sealed container so that the functional layer faced upward, and the lid was closed. The composite material was then removed from the sealed container after holding at 70 ° C. (Examples 1 and 2) or 30 ° C. (Example 3) for 1 week (ie, 168 hours) or 3 weeks (ie, 504 hours). The removed composite material was dried overnight at room temperature. The obtained sample was observed for microstructure by SEM and crystal structure by XRD.
  • Evaluation 5 Measurement of ion conductivity
  • the conductivity of the functional layer in the electrolytic solution was measured as follows using an electrochemical measurement system shown in FIG.
  • the composite material sample S porous substrate with LDH film
  • the composite material sample S was sandwiched from both sides by a 1 mm thick silicone packing 40 and incorporated into a PTFE flange type cell 42 having an inner diameter of 6 mm.
  • As the electrode 46 a # 100 mesh nickel wire mesh was incorporated into the cell 42 in a cylindrical shape having a diameter of 6 mm so that the distance between the electrodes was 2.2 mm.
  • As the electrolytic solution 44 a 6 M KOH aqueous solution was filled in the cell 42.
  • the frequency range is 1MHz to 0.1Hz
  • the applied voltage is 10mV
  • the real axis intercept was defined as the resistance of the composite material sample S (porous substrate with LDH film).
  • the same measurement as described above was performed only on the porous substrate without the LDH film, and the resistance of only the porous substrate was also obtained.
  • the difference between the resistance of the composite material sample S (porous substrate with LDH film) and the resistance of only the substrate was defined as the resistance of the LDH film.
  • the conductivity was determined using the resistance of the LDH film and the film thickness and area of the LDH.
  • Evaluation 6 Denseness determination test A denseness determination test was performed as follows in order to confirm that the functional layer does not have air permeability. First, as shown in FIGS. 5A and 5B, an acrylic container 130 without a lid and an alumina jig 132 having a shape and size that can function as a lid for the acrylic container 130 were prepared.
  • the acrylic container 130 is formed with a gas supply port 130a for supplying gas therein.
  • the alumina jig 132 is formed with an opening 132a having a diameter of 5 mm, and a sample placement recess 132b is formed along the outer periphery of the opening 132a.
  • An epoxy adhesive 134 was applied to the depression 132b of the alumina jig 132, and the functional layer 136b side of the composite material sample 136 was placed on the depression 132b to adhere to the alumina jig 132 in an airtight and liquid-tight manner. Then, the alumina jig 132 to which the composite material sample 136 is bonded is adhered to the upper end of the acrylic container 130 in a gas-tight and liquid-tight manner using a silicone adhesive 138 so as to completely close the open portion of the acrylic container 130. A measurement sealed container 140 was obtained.
  • the measurement sealed container 140 was placed in a water tank 142, and the gas supply port 130 a of the acrylic container 130 was connected to a pressure gauge 144 and a flow meter 146 so that helium gas could be supplied into the acrylic container 130.
  • Water 143 was put into the water tank 142 and the measurement sealed container 140 was completely submerged.
  • the inside of the measurement sealed container 140 is sufficiently airtight and liquid tight, and the functional layer 136b side of the composite material sample 136 is exposed to the internal space of the measurement sealed container 140, while the composite material sample
  • the porous substrate 136 a side of 136 is in contact with the water in the water tank 142.
  • helium gas was introduced into the measurement sealed container 140 into the acrylic container 130 via the gas supply port 130a.
  • the pressure gauge 144 and the flow meter 146 are controlled so that the differential pressure inside and outside the functional layer 136a becomes 0.5 atm (that is, the pressure applied to the side in contact with the helium gas is 0.5 atm higher than the water pressure applied to the opposite side). Whether or not helium gas bubbles were generated in the water from the composite material sample 136 was observed. As a result, when generation
  • He permeation measurement A He permeation test was performed as follows to evaluate the denseness of the functional layer from the viewpoint of He permeation.
  • the He permeability measurement system 310 is a function in which He gas from a gas cylinder filled with He gas is supplied to the sample holder 316 via the pressure gauge 312 and the flow meter 314 (digital flow meter), and is held in the sample holder 316.
  • the layer 318 was configured to be transmitted from one surface to the other surface and discharged.
  • the sample holder 316 has a structure including a gas supply port 316a, a sealed space 316b, and a gas discharge port 316c, and was assembled as follows. First, an adhesive 322 was applied along the outer periphery of the functional layer 318 and attached to a jig 324 (made of ABS resin) having an opening at the center. Support members 328a and 328b (made of PTFE) provided with gaskets made of butyl rubber as sealing members 326a and 326b at the upper and lower ends of the jig 324 and further provided with openings formed from flanges from the outside of the sealing members 326a and 326b. ).
  • the sealed space 316b was partitioned by the functional layer 318, the jig 324, the sealing member 326a, and the support member 328a.
  • the functional layer 318 is in the form of a composite material formed on the porous substrate 320, but the functional layer 318 is disposed so that the functional layer 318 side faces the gas supply port 316a.
  • the support members 328a and 328b were firmly fastened to each other by fastening means 330 using screws so that He gas leakage did not occur from a portion other than the gas discharge port 316c.
  • the gas supply pipe 34 was connected to the gas supply port 316a of the sample holder 316 assembled in this way via a joint 332.
  • He gas was supplied to the He permeability measurement system 310 via the gas supply pipe 334 and permeated through the functional layer 318 held in the sample holder 316.
  • the gas supply pressure and the flow rate were monitored by the pressure gauge 312 and the flow meter 314.
  • the He permeability was calculated. The calculation of the He permeability is based on the permeation amount of He gas per unit time F (cm 3 / min), the differential pressure P (atm) applied to the functional layer during He gas permeation, and the membrane area S (cm 2 ) and calculated by the formula of F / (P ⁇ S).
  • the permeation amount F (cm 3 / min) of He gas was directly read from the flow meter 314. Further, as the differential pressure P, the gauge pressure read from the pressure gauge 312 was used. The He gas was supplied so that the differential pressure P was in the range of 0.05 to 0.90 atm.
  • Example 1 A functional layer and a composite material containing Ni and Ti-containing LDH were prepared and evaluated by the following procedure.
  • porous substrate 70 parts by weight of a dispersion medium (xylene: butanol 1: 1) and binder (polyvinyl butyral: Sekisui Chemical) with respect to 100 parts by weight of alumina powder (AES-12, manufactured by Sumitomo Chemical Co., Ltd.) BM-2 manufactured by Kogyo Co., Ltd. 11.1 parts by weight, 5.5 parts by weight of a plasticizer (DOP: manufactured by Kurokin Kasei Co., Ltd.), and 2.9 parts by weight of a dispersant (Rheodor SP-O30 manufactured by Kao Corporation)
  • a dispersant Rosodor SP-O30 manufactured by Kao Corporation
  • the slurry was molded into a sheet shape on a PET film using a tape molding machine so that the film thickness after drying was 220 ⁇ m to obtain a sheet molded body.
  • the obtained molded body was cut out to have a size of 2.0 cm ⁇ 2.0 cm ⁇ thickness 0.022 cm and fired at 1300 ° C. for 2 hours to obtain an alumina porous substrate.
  • the porosity of the porous substrate was measured by the Archimedes method by a technique using image processing, and it was 40%.
  • the average pore diameter of the porous substrate was measured, it was 0.3 ⁇ m.
  • the average pore diameter was measured by measuring the longest distance of the pores based on an electron microscope (SEM) image of the surface of the porous substrate. The magnification of the electron microscope (SEM) image used for this measurement is 20000 times. All obtained pore diameters are arranged in order of size, and the top 15 points and the bottom 15 points are arranged in order from the average value. An average value for two visual fields was calculated at 30 points to obtain an average pore diameter. For length measurement, the length measurement function of SEM software was used.
  • Titanium oxide sol coat on porous substrate 0.2 ml of titanium oxide sol (M-6, manufactured by Taki Chemical Co., Ltd.) was applied onto the alumina porous substrate obtained in (1) above by spin coating. did.
  • the titanium oxide sol was dropped onto the substrate rotated at 8000 rpm, and after 5 seconds, the rotation was stopped. The substrate was allowed to stand on a hot plate heated to 100 ° C. and dried for 1 minute. Thereafter, heat treatment was performed at 200 ° C. in an electric furnace.
  • the titanium oxide layer thus formed had a thickness of about 100 nm.
  • Nickel nitrate hexahydrate Ni (NO 3 ) 2 ⁇ 6H 2 O, manufactured by Kanto Chemical Co., Inc.
  • urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich)
  • Nickel nitrate hexahydrate was weighed so as to be 0.015 mol / L, put into a beaker, and ion-exchanged water was added thereto to make a total volume of 75 ml.
  • Urea weighed in a ratio of urea / NO 3 ⁇ (molar ratio) 16 was added thereto, and further stirred to obtain a raw material aqueous solution.
  • the substrate was taken out from the sealed container, washed with ion-exchanged water, dried at 70 ° C. for 10 hours, and a part of the functional layer containing LDH was incorporated into the porous substrate. Got in shape.
  • the thickness of the obtained functional layer was about 5 ⁇ m (including the thickness of the portion incorporated in the porous substrate).
  • Evaluation results Evaluations 1 to 7 were performed on the obtained functional layers or composite materials. The results were as follows.
  • -Evaluation 1 The XRD profile shown in FIG. 7 was obtained. From this XRD profile, it was identified that the functional layer was LDH (hydrotalcite compound). FIG. 7 also shows a peak derived from alumina constituting the porous substrate.
  • -Evaluation 2 The SEM images of the surface microstructure and the cross-sectional microstructure of the functional layer were as shown in FIGS. 8A and 8B, respectively. As shown in FIG. 8B, it was found that the functional layer was composed of a film-shaped portion made of an LDH film and a composite portion made of LDH and a porous substrate located under the film-shaped portion.
  • the LDH constituting the film-like portion is composed of an aggregate of a plurality of plate-like particles, and the plurality of plate-like particles have their plate surfaces on the surface of the porous substrate (fine irregularities due to the porous structure). It was oriented in a direction perpendicular to or obliquely intersecting the surface of the porous substrate when observed macroscopically to a negligible extent.
  • the composite part constituted a dense layer by filling the pores of the porous substrate with LDH.
  • -Evaluation 3 As a result of EDS elemental analysis, LDH constituent elements C, Ti, and Ni were detected in both LDH contained in the functional layer, that is, the LDH film on the substrate surface and the LDH portion in the substrate. .
  • Example 2 A functional layer and a composite material containing Ni, Al, and Ti-containing LDH were prepared and evaluated by the following procedure.
  • porous substrate 70 parts by weight of a dispersion medium (xylene: butanol 1: 1) and binder (polyvinyl butyral: Sekisui Chemical Co., Ltd.) with respect to 100 parts by weight of zirconia powder (manufactured by Tosoh Corporation, TZ-8YS) 11.1 parts by weight of BM-2 manufactured by Co., Ltd., 5.5 parts by weight of a plasticizer (DOP: manufactured by Kurokin Kasei Co., Ltd.), and 2.9 parts by weight of a dispersant (Rheodor SP-O30 manufactured by Kao Corporation)
  • a dispersant Roslurry was obtained by mixing and defoaming the mixture by stirring under reduced pressure.
  • the slurry was molded into a sheet shape on a PET film using a tape molding machine so that the film thickness after drying was 220 ⁇ m to obtain a sheet molded body.
  • the obtained molded body was cut out to have a size of 2.0 cm ⁇ 2.0 cm ⁇ thickness 0.022 cm and baked at 1100 ° C. for 2 hours to obtain a zirconia porous substrate.
  • the porosity of the porous substrate was measured by the Archimedes method and found to be 40%.
  • the average pore diameter of the porous substrate was measured, it was 0.2 ⁇ m.
  • the average pore diameter was measured by measuring the longest distance of the pores based on an electron microscope (SEM) image of the surface of the porous substrate. The magnification of the electron microscope (SEM) image used for this measurement is 20000 times. All obtained pore diameters are arranged in order of size, and the top 15 points and the bottom 15 points are arranged in order from the average value. An average value for two visual fields was calculated at 30 points to obtain an average pore diameter. For length measurement, the length measurement function of SEM software was used.
  • Alumina / titania sol coating on porous substrate Amorphous alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.) and titanium oxide sol solution (M-6, manufactured by Taki Chemical Co., Ltd.) was mixed to make a mixed sol.
  • 0.2 ml of the mixed sol was applied onto the zirconia porous substrate obtained in (1) above by spin coating. In spin coating, the mixed sol was dropped onto the substrate rotated at 8000 rpm, and the rotation was stopped 5 seconds later. The substrate was allowed to stand on a hot plate heated to 100 ° C. and dried for 1 minute. Thereafter, heat treatment was performed at 300 ° C. in an electric furnace. The thickness of the layer thus formed was about 1 ⁇ m.
  • Nickel nitrate hexahydrate Ni (NO 3 ) 2 ⁇ 6H 2 O, manufactured by Kanto Chemical Co., Inc.
  • urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich)
  • Nickel nitrate hexahydrate was weighed so as to be 0.015 mol / L, put into a beaker, and ion-exchanged water was added thereto to make a total volume of 75 ml.
  • Urea weighed in a ratio of urea / NO 3 ⁇ (molar ratio) 16 was added thereto, and further stirred to obtain a raw material aqueous solution.
  • the substrate was taken out from the sealed container, washed with ion-exchanged water, dried at 70 ° C. for 10 hours, and a part of the functional layer containing LDH was incorporated into the porous substrate. Got in shape.
  • the thickness of the obtained functional layer was about 5 ⁇ m (including the thickness of the portion incorporated in the porous substrate).
  • Evaluation results Evaluations 1 to 7 were performed on the obtained functional layers or composite materials. The results were as follows.
  • -Evaluation 1 The XRD profile shown in FIG. 11 was obtained. From this XRD profile, it was identified that the functional layer was LDH (hydrotalcite compound). FIG. 11 also shows zirconia-derived peaks constituting the porous substrate.
  • -Evaluation 2 The SEM images of the surface microstructure and the cross-sectional microstructure of the functional layer were as shown in FIGS. 12A and 12B, respectively. As shown in FIG. 12B, it was found that the functional layer was composed of a film-shaped portion made of an LDH film and a composite portion made of LDH and a porous substrate located under the film-shaped portion.
  • the LDH constituting the film-like portion is composed of an aggregate of a plurality of plate-like particles, and the plurality of plate-like particles have their plate surfaces on the surface of the porous substrate (fine irregularities due to the porous structure). It was oriented in a direction perpendicular to or obliquely intersecting the surface of the porous substrate when observed macroscopically to a negligible extent.
  • the composite part constituted a dense layer by filling the pores of the porous substrate with LDH.
  • -Evaluation 3 As a result of EDS elemental analysis, LDH constituent elements C, Al, Ti, and Ni are detected in the LDH contained in the functional layer, that is, the LDH film on the substrate surface and the LDH portion in the substrate.
  • Example 3 (Comparison) A functional layer and a composite material containing Mg and Al-containing LDH were prepared and evaluated by the following procedure.
  • porous substrate made of alumina was produced in the same manner as in step (1) in Example 1.
  • magnesium nitrate hexahydrate (Mg (NO 3) 2 ⁇ 6H 2 O, manufactured by Kanto Chemical Co., Inc.), aluminum nitrate nonahydrate (Al (NO 3) 3 ⁇ 9H 2 O, manufactured by Kanto Chemical Co., Ltd.) and urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich) were prepared.
  • Mg (NO 3) 2 ⁇ 6H 2 O manufactured by Kanto Chemical Co., Inc.
  • Al (NO 3) 3 ⁇ 9H 2 O manufactured by Kanto Chemical Co., Ltd.
  • urea ((NH 2 ) 2 CO, manufactured by Sigma-Aldrich)
  • ion exchange water was added to make a total volume of 70 ml.
  • the substrate was taken out from the sealed container, washed with ion-exchanged water, dried at 70 ° C. for 10 hours, and a part of the functional layer containing LDH was incorporated into the porous substrate. Got in shape.
  • the thickness of the functional layer obtained was about 3 ⁇ m (including the thickness of the portion incorporated in the porous substrate).
  • Evaluation results Evaluations 1 to 7 were performed on the obtained functional layers or composite materials. The results were as follows. -Evaluation 1: From the obtained XRD profile, it was identified that the functional layer was LDH (hydrotalcite compound). -Evaluation 2: The SEM images of the surface microstructure and the cross-sectional microstructure of the functional layer were as shown in FIGS. 15A and 15B, respectively. In almost the same manner as the functional layers obtained in Examples 1 and 2, a functional layer composed of a film-shaped portion made of an LDH film and a composite portion made of LDH and a porous substrate located under the film-shaped portion is provided. Observed.
  • -Evaluation 3 As a result of EDS elemental analysis, LDH constituent elements C, Mg, and Al were detected in both the LDH contained in the functional layer, that is, the LDH film on the substrate surface and the LDH portion in the substrate. . That is, Mg and Al are constituent elements of the hydroxide basic layer, while C corresponds to CO 3 2 ⁇ which is an anion constituting the intermediate layer of LDH.
  • -Evaluation 4 The SEM image which image

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Abstract

L'invention concerne : une couche fonctionnelle comprenant un hydroxyde double stratifié (LDH), ladite couche fonctionnelle présentant non seulement une excellente conductivité ionique, mais également une excellente résistance aux alcalis; et un matériau composite pourvu de ladite couche fonctionnelle. La couche fonctionnelle comprend un LDH et présente une conductivité ionique d'hydroxyde. Lorsque le LDH est immergé dans une solution aqueuse d'hydroxyde de potassium à 5 mol/L comprenant de L'oxyde de zinc à une concentration de 0,4 mol/L, pendant trois semaines à 70 °C, aucune modification ne se produit dans la microstructure de surface et la structure cristalline.
PCT/JP2017/015033 2016-06-24 2017-04-12 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite WO2017221526A1 (fr)

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PCT/JP2017/022907 WO2017221990A1 (fr) 2016-06-24 2017-06-21 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
JP2018524148A JP6617200B2 (ja) 2016-06-24 2017-06-21 層状複水酸化物を含む機能層及び複合材料
EP17815458.9A EP3477741A4 (fr) 2016-06-24 2017-06-21 Couche fonctionnelle comprenant un hydroxyde double stratifié, et matériau composite
CN201780037775.8A CN109314210A (zh) 2016-06-24 2017-06-21 包含层状双氢氧化物的功能层及复合材料
US16/227,702 US20190126590A1 (en) 2016-06-24 2018-12-20 Functional layer including layered double hydroxide, and composite material

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CN114041233A (zh) * 2019-06-19 2022-02-11 日本碍子株式会社 氢氧化物离子传导隔板及锌二次电池

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JP2005089277A (ja) * 2003-09-19 2005-04-07 Toda Kogyo Corp ハイドロタルサイト類化合物粒子粉末及び該ハイドロタルサイト類化合物粒子粉末を含有する水系分散体
JP2013201056A (ja) * 2012-03-26 2013-10-03 Osaka Prefecture Univ 金属−空気二次電池用空気極触媒層
WO2016088673A1 (fr) * 2014-12-02 2016-06-09 日本碍子株式会社 Batterie rechargeable zinc-air
WO2016098513A1 (fr) * 2014-12-17 2016-06-23 日本碍子株式会社 Film d'hydroxyde double lamellaire et matériau composte contenant un hydroxyde double lamellaire
JP2016115540A (ja) * 2014-12-15 2016-06-23 日本碍子株式会社 水酸化物イオン伝導性セラミックスセパレータを用いた二次電池

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JP2005089277A (ja) * 2003-09-19 2005-04-07 Toda Kogyo Corp ハイドロタルサイト類化合物粒子粉末及び該ハイドロタルサイト類化合物粒子粉末を含有する水系分散体
JP2013201056A (ja) * 2012-03-26 2013-10-03 Osaka Prefecture Univ 金属−空気二次電池用空気極触媒層
WO2016088673A1 (fr) * 2014-12-02 2016-06-09 日本碍子株式会社 Batterie rechargeable zinc-air
JP2016115540A (ja) * 2014-12-15 2016-06-23 日本碍子株式会社 水酸化物イオン伝導性セラミックスセパレータを用いた二次電池
WO2016098513A1 (fr) * 2014-12-17 2016-06-23 日本碍子株式会社 Film d'hydroxyde double lamellaire et matériau composte contenant un hydroxyde double lamellaire

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CN114041233A (zh) * 2019-06-19 2022-02-11 日本碍子株式会社 氢氧化物离子传导隔板及锌二次电池
CN114041233B (zh) * 2019-06-19 2024-03-29 日本碍子株式会社 氢氧化物离子传导隔板及锌二次电池

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