WO2019131221A1 - Couche fonctionnelle contenant un hydroxyde double lamellaire, et matériau composite - Google Patents

Couche fonctionnelle contenant un hydroxyde double lamellaire, et matériau composite Download PDF

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WO2019131221A1
WO2019131221A1 PCT/JP2018/046116 JP2018046116W WO2019131221A1 WO 2019131221 A1 WO2019131221 A1 WO 2019131221A1 JP 2018046116 W JP2018046116 W JP 2018046116W WO 2019131221 A1 WO2019131221 A1 WO 2019131221A1
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functional layer
ldh
porous substrate
composite material
layered double
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PCT/JP2018/046116
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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 JP2019563002A priority Critical patent/JP6864758B2/ja
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • 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
    • H01M50/443—Particulate material
    • 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 functional layers and composite materials comprising layered double hydroxides.
  • LDH Layered double hydroxide
  • H 2 O Hydroxide
  • a catalyst or It is used as an adsorbent, a dispersant in polymers for improving heat resistance, and the like.
  • LDH is also attracting attention as a material that conducts hydroxide ions, and addition to the electrolyte of an alkaline fuel cell and the catalyst layer of a zinc-air cell has also been studied.
  • LDH as a solid electrolyte separator for alkaline secondary batteries such as nickel zinc secondary batteries and zinc air secondary batteries has also been proposed, and provided with an LDH-containing functional layer suitable for such separator applications
  • Composite materials are known.
  • Patent Document 1 (WO 2015/098610) discloses a composite comprising a porous substrate and an LDH-containing functional layer formed on and / or in the porous substrate and not having water permeability.
  • the LDH-containing functional layer has the general formula: M 2+ 1 ⁇ x M 3+ x (OH) 2 A n ⁇ x / n ⁇ mH 2 O (wherein M 2+ is Mg 2+, etc. valent cation, M 3+ is a trivalent cation Al 3+, etc., a n-is OH -, CO 3 2- or the like of an n-valent anion, n represents an integer of 1 or more, x is 0. It is stated that it includes LDH represented by 1 to 0.4, and m is 0 or more.
  • the LDH-containing functional layer disclosed in Patent Document 1 is densified so as not to have water permeability, when used as a separator, zinc dendrite which is a barrier to practical use of an alkaline zinc secondary battery Progress and carbon dioxide ingress from the cathode in zinc-air batteries can be prevented.
  • Patent Document 2 WO 2016/051934
  • a metal compound containing a metal element (for example, Al) corresponding to M 2+ and / or M 3+ of the general formula described above is dissolved in an electrolytic solution
  • An LDH-containing battery has been proposed which is configured to suppress the erosion of the LDH by the electrolyte solution.
  • the inventors of the present invention have previously been a Ni that exhibits not only ion conductivity but also good alkali resistance by constituting the hydroxide base layer of LDH with predetermined elements or ions including Ni, Al, Ti and OH groups. It has been found that it can provide a -Al-Ti-LDH containing functional layer. At that time, in the evaluation of the alkali resistance, a potassium hydroxide aqueous solution to which a predetermined amount of zinc oxide was added was used as an electrolytic solution composition assuming practical use to a zinc secondary battery.
  • the alkali resistance of the Ni-Al-Ti-LDH having the above composition may be reduced. Therefore, it is desirable to exhibit alkali resistance to an electrolyte for a high performance battery such as a potassium hydroxide aqueous solution containing no zinc oxide or having a reduced zinc oxide content, that is, an LDH having more excellent alkali resistance.
  • the present inventors have now found that the incorporation of Y into the Ni-Al-Ti-LDH-containing functional layer at a predetermined atomic ratio can provide an LDH-containing functional layer excellent in alkali resistance.
  • an object of the present invention is to provide an LDH-containing functional layer excellent in alkali resistance and a composite material provided with the same.
  • a functional layer comprising layered double hydroxide, wherein the layered double hydroxide comprises Ni, Ti and Al, and the functional layer further comprises Y, and the atomic ratio of Y / Al is 0.5 or more. Is the functional layer.
  • the layered double hydroxide contains Ni, Ti, Al and Y, and / or (ii) the layered double hydroxide contains Ni, Ti and Al, and the functional layer is the layered double hydroxide Item 2.
  • the functional layer according to item 1 comprising a Y compound different from a hydroxide.
  • the functional layer comprises the layered double hydroxide Item 11.
  • the functional layer according to item 10 which comprises different Y compounds.
  • the atomic ratio of Y / Al is 2 to 8.
  • Item 19 Item 19. The composite material according to item 18, wherein the porous substrate is made of a polymeric material, and the functional layer is incorporated throughout the thickness direction of the porous substrate.
  • a battery comprising the functional layer according to any one of Items 1 to 17 or the composite material according to Item 18 or 19 as a separator.
  • FIG. 14 is an exploded perspective view of the measurement-use sealed container used in the denseness determination test of Examples B1 to B6.
  • FIG. 14 is an exploded perspective view of the measurement-use sealed container used in the denseness determination test of Examples B1 to B6.
  • FIG. 7 is a schematic cross-sectional view of a measurement system used in the denseness determination test of Examples B1 to B6. It is a conceptual diagram which shows an example of the He permeability measurement system used in Examples B1 to B6. It is a schematic cross section of the sample holder used for the measurement system shown by FIG. 7A, and its periphery structure. It is a X-ray-diffraction result of the functional layer produced in Example B1 (reference). It is a SEM image which shows the surface microstructure of the functional layer produced in Example B1 (reference). It is a SEM image which shows the cross-section microstructure of the functional layer produced in Example B1 (reference).
  • FIG. 16 is a SEM image showing the cross-sectional microstructure of the functional layer and composite material produced in Example B7.
  • the functional layer of the present invention is a layer containing layered double hydroxide (LDH).
  • This LDH contains Ni, Ti and Al.
  • the functional layer further contains Y, and the atomic ratio of Y / Al is 0.5 or more.
  • LDH contains Ni, Ti, Al and Y
  • LDH contains Ni, Ti and Al
  • the functional layer contains a Y compound different from LDH. . Both the above (i) and (ii) may be satisfied.
  • the functional layer comprises Y as part of the constituent elements of the LDH and / or in the form of a compound separate from the LDH. In other words, the functional layer may contain Y in some form.
  • the functional layer has an atomic ratio of Y / Al of 0.5 or more.
  • Y is incorporated into the Ni-Al-Ti-LDH-containing functional layer at a predetermined atomic ratio (for example, by substituting a part of trivalent Al with trivalent Y), alkali resistance can be obtained.
  • An excellent LDH-containing functional layer can be provided.
  • the Ni-Al-Ti-LDH-containing functional layer exhibits not only ion conductivity but also good alkali resistance.
  • a potassium hydroxide aqueous solution to which a predetermined amount of zinc oxide was added was used as an electrolytic solution composition assuming practical use to a zinc secondary battery.
  • Y is further contained in the functional layer containing Ni—Al—Ti—LDH (for example, in the form of (i) and / or (ii) above) Excellent alkali resistance can also be exhibited for high performance battery electrolytes such as potassium hydroxide aqueous solution containing no zinc oxide or having a reduced zinc oxide content.
  • the LDH contained in the functional layer is immersed in a 6 mol / L aqueous potassium hydroxide solution containing no zinc oxide at 90 ° C. for one week (ie, 168 hours), a change in crystal structure occurs. It is preferable from the viewpoint that alkali resistance is particularly excellent.
  • the presence or absence of the change in the crystal structure can be preferably determined by crystal structure analysis using XRD (X-ray diffraction) (for example, the presence or absence of a shift of the (003) peak derived from LDH).
  • Potassium hydroxide is a representative strongly alkaline substance, and the composition of the potassium hydroxide aqueous solution corresponds to a representative strongly alkaline electrolyte of an alkaline secondary battery.
  • the above-mentioned evaluation method of immersing in such a strong alkaline electrolyte for as long as one week at a high temperature as high as 90 ° C. is a severe alkali resistance test. It is desirable for the LDH for an alkaline secondary battery to have a high degree of alkali resistance that hardly deteriorates even in a strongly alkaline electrolyte. Further, as described above, even if the Ni-Al-Ti-LDH functional layer is judged to be excellent in alkali resistance when it is immersed in a potassium hydroxide aqueous solution to which zinc oxide is added, zinc oxide is included.
  • the functional layer of the present embodiment is particularly excellent in alkali resistance such that no change in the crystal structure occurs even by the above-described severe alkali resistance test using such a potassium hydroxide aqueous solution. . Even so, the functional layer of this embodiment can also exhibit high ion conductivity suitable for use as a separator for an alkaline secondary battery due to the inherent property of LDH. That is, according to this aspect, it is possible to provide an LDH-containing functional layer excellent not only in ion conductivity but also in alkali resistance.
  • the LDH is composed of a plurality of hydroxide basic layers and an intermediate layer interposed between the plurality of hydroxide basic layers.
  • the hydroxide base layer is mainly composed of metal elements (typically metal ions) and OH groups.
  • the intermediate layer of LDH contained in the functional layer is composed of anions and H 2 O.
  • the anion is a monovalent or higher anion, preferably a monovalent or divalent ion.
  • anions in the LDH is OH - containing and / or CO 3 2- and.
  • LDH is required to have a high degree of alkali resistance that hardly deteriorates even in such a strong alkaline electrolyte. Therefore, it is preferable that the LDH in the present invention does not cause a change in the crystal structure by the above-mentioned alkali resistance evaluation. Also, as mentioned above, LDH has excellent ion conductivity due to its inherent properties and the above mentioned composition.
  • the hydroxide base layer of LDH comprises Ni, Al, Ti and OH groups.
  • Y may be contained in the hydroxide base layer, may be contained between the hydroxide base layers, and may be present anywhere in the LDH.
  • Y may be contained in the functional layer as a Y compound different from LDH (for example, yttrium hydroxide) without being contained in LDH.
  • LDH for example, yttrium hydroxide
  • Y may be contained in the LDH and as the Y compound in the functional layer.
  • the intermediate layer is composed of anions and H 2 O as described above.
  • the alternate layered structure itself of the hydroxide basic layer and the intermediate layer is basically the same as the alternate layered structure of generally known LDHs, but the functional layer of this embodiment is formed of Ni, the hydroxide basic layer of the LDH.
  • Excellent alkali resistance can be exhibited by being composed of predetermined elements or ions containing Al, Ti and OH groups, and further containing the above Y compound in the LDH and / or the functional layer. The reason is not necessarily clear, but in the LDH of this embodiment, Al which was conventionally considered to be easily eluted in an alkaline solution becomes difficult to be eluted in an alkaline solution due to any interaction with Ni, Ti and Y. it is conceivable that.
  • Ni in LDH can take the form of nickel ion.
  • the nickel ion in LDH is typically considered to be Ni 2+ but is not particularly limited as it may have other valences such as Ni 3+ .
  • Al in LDH can take the form of aluminum ion.
  • the aluminum ion in LDH is typically considered to be Al 3+ , but is not particularly limited as it may have other valences.
  • 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 as other valences such as Ti 3+ may also be present.
  • Y in LDH can take the form of yttrium ion.
  • Yttrium ion in LDH is typically considered to be Y 3 + , but is not particularly limited as it may have other valences.
  • the hydroxide base layer may contain other elements or ions as long as it contains Ni, Al, Ti and OH groups.
  • the hydroxide base layer may further comprise Zn (typically Zn 2+ ) and / or K (typically K + ).
  • the hydroxide base layer contains Ni, Al, Ti, an OH group, and optionally Y as main components. That is, the hydroxide base layer preferably consists mainly of Ni, Al, Ti, an OH group, and optionally Y.
  • the hydroxide base layer is typically composed of Ni, Al, Ti, OH groups and optionally Y, Zn, K and / or unavoidable impurities.
  • Unavoidable impurities are optional elements that can be inevitably mixed in the manufacturing method, and may be mixed into LDH derived from, for example, a raw material or a base material.
  • LDH derived from, for example, a raw material or a base material.
  • the hydroxide base layer is mainly composed of Ni 2+ , Al 3+ , Ti 4+ , Y 3+ and OH groups
  • the corresponding LDH has the general formula: Ni 2+ 1 ⁇ x ⁇ y Al 3 + 1- ⁇ Y 3 + ⁇ ) x Ti 4 + y (OH) 2 A n- (x + 2 y) / n ⁇ mH 2 O
  • a n- is an n-valent anion
  • n is an integer of 1 or more, It is preferably 1 or 2, 0 ⁇ x ⁇ 1, preferably 0.01 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 1, preferably 0.01 ⁇ y ⁇ 0.5, 0 ⁇ x + y ⁇ 1, 0 ⁇ ⁇ 1, preferably 0.3 ⁇ ⁇ ⁇ 0.9, more preferably 0.6 ⁇ ⁇ 0.9, preferably m is 0 or more, typically more than 0 or 1 or more real number It can be expressed by the basic composition of
  • the functional layer has a Y / Al atomic ratio of 0.5 or more, preferably 1 or more, more preferably 1 to 9, still more preferably 2 to 8, and particularly preferably 3 to 8.
  • the atomic ratio of Y / Al is preferably determined by energy dispersive X-ray analysis (EDS).
  • the functional layer preferably has a Ti / (Y + Al) atomic ratio of 0.1 to 8, more preferably 0.2 to 7, and still more preferably 0.2 to 5. Within the above range, both alkali resistance and ion conductivity can be improved.
  • the atomic ratio of Y / Al is preferably determined by energy dispersive X-ray analysis (EDS).
  • the functional layer preferably has a Ti / (Ni + Ti + Al + Y) atomic ratio of 0.10 to 0.90, more preferably 0.20 to 0.80, still more preferably 0.25 to 0.70, Preferably, it is 0.30 to 0.61. Within the above range, both alkali resistance and ion conductivity can be improved.
  • the atomic ratio of Ti / (Ni + Ti + Al + Y) is preferably determined by energy dispersive X-ray analysis (EDS).
  • the functional layer may further contain titania.
  • titania can be expected to increase the hydrophilicity and improve the wettability with the electrolytic solution (that is, the conductivity is improved).
  • the functional layer contains titania
  • the LDH contained in the functional layer may not contain Ti.
  • the functional layer (in particular, LDH contained in the functional layer) preferably has hydroxide ion conductivity.
  • the functional layer preferably has an ion 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, and is, for example, 10 mS / cm.
  • Such high ionic conductivity is particularly suitable for battery applications.
  • the functional layer is provided on a porous substrate and / or incorporated in the porous substrate. That is, according to a preferred embodiment 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 in the porous substrate.
  • the functional layer 14 may be partially incorporated in the porous substrate 12 and the remaining portion may be provided on the porous substrate 12.
  • a portion of the functional layer 14 on the porous substrate 12 is a film-like portion made of an LDH film, and a portion of the functional layer 14 to be incorporated into the porous substrate 12 is a porous substrate and LDH.
  • the composite part is typically in a form in which the inside of the pores of the porous substrate 12 is filled with LDH.
  • the functional layer 14 ' is mainly composed of the porous substrate 12 and the 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 and cutting. You can get it.
  • LDH film film-like portion
  • the functional layers 14 and 14 ' are incorporated only in part of the vicinity of the surface of the porous substrates 12 and 12', the functional layers may be incorporated anywhere on the porous substrate.
  • the functional layer 14 ' may be incorporated throughout the entire thickness of the porous substrate 12 as in the composite material 10' 'shown in FIG. 3, for example. That is, the LDH may block the pores of the porous substrate 12 to form a functional layer 14 ′ ′ as a whole over the entire thickness or the entire thickness of the porous substrate 12.
  • the functional layer of the present invention does not require supporting by a porous substrate, but is a self-standing functional layer 14 ′ ′ ′ of a form not involving a porous substrate as shown in FIG. It goes without saying that it is also good.
  • Such a self-supporting functional layer 14 ′ ′ ′ is removed by a known method such as polishing, cutting, etc. (ii) after producing the composite material 10 as shown in FIG. It can be produced by leaving a filmy part (LDH film).
  • the porous substrate in the composite material of the present invention is preferably one capable of forming an LDH-containing functional layer thereon and / or therein, and the material and the porous structure thereof are not particularly limited. Although it is typical to form an LDH-containing functional layer on and / or in a porous substrate, the LDH-containing functional layer is formed on a nonporous substrate, and then nonporous by a known method.
  • the quality substrate may be made porous. In any case, it is preferable that the porous substrate has a porous structure having water permeability in that the electrolytic solution can reach the functional layer when it is incorporated in a 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, more preferably selected from the group consisting of ceramic materials and polymer materials It consists of at least one type.
  • the porous substrate is more preferably composed of a ceramic material.
  • preferable examples of 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, polyether sulfone, polypropylene, epoxy resin, polyphenylene sulfide, hydrophilized fluorocarbon resin (tetrafluorinated resin: such as PTFE), cellulose, nylon, polyethylene and any combination thereof Can be mentioned. All the various preferable materials mentioned above have alkali resistance as resistance with respect to the electrolyte solution of a battery.
  • the porous substrate be composed of a polymeric material.
  • the porous polymer substrate has 1) flexibility (therefore, it is difficult to be broken even if it is thin), 2) it is easy to increase the porosity, 3) it is easy to increase the conductivity (the thickness is increased while the porosity is increased) To be thin) and 4) easy to manufacture and handle.
  • Particularly preferable polymer materials are polyolefins such as polypropylene and polyethylene in that they are excellent in hot water resistance, acid resistance and alkali resistance and are low in cost, and most preferably polypropylene.
  • the functional layer is incorporated throughout the thickness direction of the porous substrate (for example, most or almost all pores inside the porous substrate are filled with LDH) Is particularly preferred.
  • the preferable thickness of the porous polymer substrate in this case is 5 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 5 to 30 ⁇ m.
  • a microporous film commercially available as a lithium battery separator can be preferably used.
  • the porous substrate preferably has an average pore size of at most 100 ⁇ m or less, more preferably at most 50 ⁇ m or less, eg 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.
  • an LDH-containing functional layer so dense that it does not have water permeability while securing desired permeability and strength as a support on the porous substrate.
  • the measurement of the average pore diameter can be performed by measuring the longest distance of 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, and all the pore diameters obtained are arranged in order of size, and the upper 15 points and lower 15 points in order of closeness from the average value
  • An average pore diameter can be obtained by calculating an average value for two fields of view.
  • a length measurement function of software of SEM, image analysis software (for example, Photoshop, manufactured by Adobe), or the like can be used.
  • the porous substrate preferably has a porosity of 10 to 60%, more preferably 15 to 55%, still more preferably 20 to 50%. By setting the content in these ranges, it is possible to form an LDH-containing functional layer so dense that it does not have water permeability while securing desired permeability and strength as a support on the porous substrate.
  • the porosity of the porous substrate can be preferably measured by the Archimedes method. However, when the porous substrate is composed of a polymer material and the functional layer is incorporated throughout the thickness direction of the porous substrate, the porosity of the porous substrate is preferably 30 to 60%, more preferably Preferably, it is 40 to 60%.
  • the functional layer preferably does not have breathability. That is, it is preferable that the functional layer be densified with LDH to such an extent that it does not have air permeability.
  • “does not have air permeability” means the object to be measured in water when the air permeability is evaluated by the “fineness determination test” adopted in the examples described later or a method or configuration according thereto. Even if helium gas is brought into contact with one side of the functional layer and / or porous substrate at a differential pressure of 0.5 atm, this means that generation of bubbles due to the helium gas is not seen from the other 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 for batteries
  • strength can be imparted by the porous substrate Therefore, it is possible to reduce the resistance by thinning the LDH-containing functional layer.
  • the porous substrate can have water permeability and air permeability, the electrolyte can reach the LDH-containing functional layer when it is used as a battery solid electrolyte separator.
  • the LDH-containing functional layer and the composite material of the present invention can be used as solid electrolyte separators applicable to various battery applications such as metal-air batteries (for example, zinc-air batteries) and various other zinc secondary batteries (for example, nickel-zinc batteries). It can be a very useful material.
  • the functional layer or the composite material provided with the same preferably has a He permeability of 10 cm / min ⁇ atm or less per unit area, more preferably 5.0 cm / min ⁇ atm or less, still more preferably 1.0 cm / It is less than min ⁇ atm. It can be said that the functional layer having the He permeability in such a range is extremely high in compactness. Therefore, the functional layer having a He permeability of 10 cm / min ⁇ atm or less can prevent passage of substances other than hydroxide ions at a high level when applied as a separator in an alkaline secondary battery.
  • the permeation of Zn (typically, the permeation of zinc ions or zincate ions) can be extremely effectively suppressed in the electrolytic solution.
  • the Zn permeation is remarkably suppressed, and it is theoretically considered that the growth of zinc dendrite can be effectively suppressed when it is used in a zinc secondary battery.
  • the He permeability is measured through the steps of supplying He gas to one surface of the functional layer to allow He gas to permeate through the functional layer, and calculating the He permeability to evaluate the compactness of the functional layer. Ru.
  • the He permeability is expressed by the formula of F / (P ⁇ S) using the permeation amount F of He gas per unit time, the differential pressure P applied to the functional layer at the time of He gas permeation, and the membrane area S at which He gas permeates.
  • He gas has the smallest structural unit among a wide variety of atoms or molecules that can constitute the gas, and the reactivity is extremely low. That is, He forms He gas with He atoms alone without forming molecules. In this respect, since hydrogen gas is composed of H 2 molecules, a single He atom is smaller as a gas constituent unit. First of all, H 2 gas is dangerous because of flammable gas. And, by adopting the indicator of He gas permeability defined by the above-mentioned equation, objective evaluation regarding compactness can be simply performed regardless of various sample sizes and differences in measurement conditions. Thus, it can be simply, safely and effectively evaluated whether the functional layer has a sufficiently high compactness suitable for a zinc secondary battery separator.
  • the measurement of the He permeability can be preferably performed according to the procedure shown in Evaluation 8 of Examples described later.
  • 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 realize low 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 made of the porous substrate and the LDH.
  • the functional layer When the functional layer is formed on and in the porous substrate, it corresponds to the total thickness of the membrane part (LDH film) and the composite part (porous substrate and LDH).
  • the thickness when the thickness is as described above, a desired low resistance suitable for practical use in battery applications and the like can be realized.
  • the lower limit of the thickness of the LDH film is not particularly limited because it varies depending on the application, but in order to secure a certain degree of rigidity desired as a functional film such as a separator, the thickness is preferably 1 ⁇ m or more, more preferably Is 2 ⁇ m or more.
  • the method for producing the LDH-containing functional layer and the composite material is not particularly limited, and the LDH-containing functional layer and the composite material are produced by appropriately changing the conditions of the known methods for producing the LDH-containing functional layer and the composite material (see, for example, Patent Documents 1 and 2) be able to.
  • a porous substrate is prepared, (2) a mixed sol of alumina, titania and yttria is applied to the porous substrate and heat treated to form an alumina-titania-yttria layer, (3) The porous base material is immersed in a raw material aqueous solution containing nickel ions (Ni 2+ ) and urea, (4) the porous base material is hydrothermally treated in the raw material aqueous solution, and the LDH-containing functional layer is formed on the porous base Alternatively, LDH-containing functional layers and composite materials can be produced by forming in a porous substrate.
  • the alumina-titania-yttria layer on the porous substrate in the above step (2), not only the raw material of LDH is given, but it is made to function as a starting point of LDH crystal growth on the surface of the porous substrate A highly densified LDH-containing functional layer can be formed uniformly without unevenness.
  • the pH value is raised by the generation of ammonia in the solution by utilizing the hydrolysis of urea, and the coexisting metal ions form a hydroxide.
  • LDH can be obtained by
  • the hydrolysis involves the generation of carbon dioxide, it is possible to obtain a carbonate ion LDH as the anion.
  • the application of the mixed sol to the substrate is preferably carried out in such a way that the mixed sol penetrates into the whole or most of the interior of the substrate. In this way, most or almost all pores inside the porous substrate can be finally filled with LDH.
  • preferred coating techniques include dip coating, filtration coating and the like, with dip coating being particularly preferred.
  • the adhesion amount of the mixed sol can be adjusted by adjusting the number of times of application such as dip coating.
  • the base on which the mixed sol is applied by dip coating or the like may be dried, and then the steps (3) and (4) may be performed.
  • LDH does not contain Ti
  • the functional layer contains titania
  • the layered double hydroxide contains Ni and Al
  • the functional layer further contains Y and titania
  • the atomic ratio of Y / Al is 0.5 or more.
  • LDH may contain Ni, Al and Y.
  • the LDH may include Ni and Al
  • the functional layer may include a Y compound different from the layered double hydroxide. Both the above (i) and (ii) may be satisfied. Therefore, the explanations regarding the functional layer and the composite material, which have already been described in detail, apply to this modification, except that the LDH contains Ti and the functional layer contains titania.
  • the functional layer or the composite material of the present invention can be used, for example, in nickel hydrogen batteries as well as alkaline secondary batteries such as zinc air batteries and nickel zinc batteries.
  • the functional layer or the composite material functions to block the nitride shuttle (the movement of the nitrate group between the electrodes), which is a factor of the self-discharge of the battery.
  • the functional layer or the composite material of the present invention can also be used for lithium batteries (lithium metal is a negative electrode battery), lithium ion batteries (negative electrode is a battery such as carbon) or lithium air battery.
  • dispersant Leodol SP-O30 manufactured by Kao Corporation
  • This slurry was formed into a sheet on a PET film using a tape forming machine so that the film thickness after drying became 220 ⁇ m, to obtain a sheet molded body.
  • the obtained molded product was cut out so as to have a size of 2.0 cm ⁇ 2.0 cm ⁇ thickness 0.022 cm, and fired at 1100 ° C. for 2 hours to obtain a zirconia-made porous base material.
  • the average pore size of the porous substrate was 0.2 ⁇ m.
  • the measurement of the average pore diameter was performed by measuring the longest distance of 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, and all the obtained pore diameters are arranged in order of size, and the upper 15 points and lower 15 points in order of closeness from the average value
  • the average pore diameter was calculated by calculating the average value for two fields of view at 30 points.
  • the length measurement function of SEM software was used for length measurement.
  • Alumina-titania-yttria sol coating on a porous substrate A commercially available amorphous alumina solution, a commercially available titanium oxide sol solution, and a commercially available yttrium oxide sol have Y / Al atomic ratio and Ti / (Y + Al) atomic ratio
  • the mixed sols were prepared by mixing so as to have the atomic ratios shown in Table 1 respectively.
  • 0.2 ml of the mixed sol was applied by spin coating onto the zirconia porous substrate obtained in (1) above. In spin coating, the rotation was stopped 5 seconds after the mixed sol was dropped on the substrate rotated at 8,000 rpm, and the substrate was allowed to stand on a hot plate heated to 100 ° C. and dried for 1 minute. 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. and urea ((NH 2) 2 CO, manufactured by Sigma-Aldrich)
  • Nickel nitrate hexahydrate was weighed into a beaker so as to be 0.015 mol / L, and ion-exchanged water was added there to make the total amount 75 ml.
  • the substrate is removed from the closed container, washed with ion-exchanged water, allowed to stand at 70 ° C. for 10 hours, and dried to partially convert the functional layer containing LDH into a porous substrate. Obtained in incorporated form.
  • the thickness of the obtained functional layer (including the thickness of the part incorporated into the porous substrate) was about 5 ⁇ m. (5) Evaluation The evaluation described below was performed on the obtained functional layer or composite material.
  • Evaluation 1 Identification of functional layer
  • the crystal phase of the functional layer is measured under the measurement conditions of voltage: 50 kV, current value: 300 mA, measurement range: 10 to 70 ° with an X-ray diffractometer (RINT TTR III manufactured by Rigaku Corporation)
  • the XRD profile was obtained.
  • JCPDS card NO. Using the diffraction peak of LDH (hydrotalcite compounds) described in 35-0964, TiO 2 described in 01-071-1169, and ⁇ -Ni (OH) 2 described in 00-014-0117 Identification was done.
  • LDH hydrotalcite compounds
  • Evaluation 2 Evaluation of alkali resistance 1.5 ml of a 6 mol / L potassium hydroxide aqueous solution not containing zinc oxide and a sample of 2 cm ⁇ 2 cm in size are placed in a Teflon (registered trademark) closed container, and one week at 90 ° C. After holding for 168 hours, the sample was removed from the closed vessel. The removed sample was allowed to dry at room temperature overnight. About the obtained sample, the crystal structure observation by XRD was performed similarly to the above, and the presence or absence of the change of the crystal phase before and behind immersion was confirmed.
  • Teflon registered trademark
  • the Y / Al ratio is 0.5 or more, the change in the crystal phase is significantly reduced and the alkali resistance is improved, and when it is 2 or more, the change in the crystal phase is eliminated and the alkali resistance is further improved.
  • the Y / Al ratio and the Ti (Y + Al) ratio described in Table 1 above are atomic ratios in the mixed sol, but are considered to be the same atomic ratios also in the finally obtained functional layer.
  • LDH is considered to include Ni, Ti, Al and Y.
  • the possibility that the LDH contains Ni, Ti and Al and the functional layer further contains a Y compound different from the LDH can not be denied. In any case, it does not change that the functional layer contains Y.
  • Examples B1 to B7 In order to help demonstrate the basic performance of the functional layer and the composite material of the present invention, the functional layer composition of the present invention containing Y is not identical to the functional layer composition of the present invention except that Y is not contained. Or, examples of preparation and evaluation of functional layers having similar compositions are shown below. Specifically, reference examples relating to functional layers and composite materials containing Ni, Al and Ti-containing LDH (but not Y), and functions containing Mg and Al-containing LDH (but not Y) as comparative examples It shows below with the comparative example regarding a layer and a composite material. In addition, the evaluation method of the functional layer and composite material which are produced by the following example was as follows.
  • Evaluation 1 Identification of functional layer
  • the crystal phase of the functional layer is measured under the measurement conditions of voltage: 50 kV, current value: 300 mA, measurement range: 10 to 70 ° with an X-ray diffractometer (RINT TTR III manufactured by Rigaku Corporation)
  • the XRD profile was obtained.
  • JCPDS card NO. Identification was performed using the diffraction peak of LDH (hydrotalcite-like compound) described in 35-0964.
  • Evaluation 2 Observation of Microstructure The surface microstructure of the functional layer was observed at an acceleration voltage of 10 to 20 kV using a scanning electron microscope (SEM, JSM-6610 LV, manufactured by JEOL). In addition, after obtaining a cross-sectional polished surface of a functional layer (a composite layer comprising a film-like portion made of an LDH film, an LDH, and a base material by IM4000 manufactured by Hitachi High-Technologies Corp.), The structure was observed by SEM under the same conditions as the observation of surface microstructure.
  • SEM scanning electron microscope
  • Evaluation 3 Elemental Analysis Evaluation (EDS) I Polishing was carried out using a cross section polisher (CP) so that the cross-sectional polished surface of the functional layer (the film-like portion made of the LDH film and the composite portion made of the LDH and the base material) could be observed.
  • FE-SEM ULTRA 55, manufactured by Carl Zeiss
  • a cross-sectional image of a functional layer was acquired in one field of view at a magnification of 10000 times.
  • Elemental analysis of the LDH film on the substrate surface and the LDH part inside the substrate (point analysis) of this cross-sectional image was carried out using an EDS analyzer (NORAN System SIX, manufactured by Thermo Fisher Scientific) under conditions of an acceleration voltage of 15 kV. went.
  • EDS analyzer NORAN System SIX, manufactured by Thermo Fisher Scientific
  • Evaluation 4 Elemental Analysis Evaluation (EDS) II
  • EDS Elemental Analysis Evaluation
  • Evaluation 5 Evaluation of alkali resistance Zinc oxide was dissolved in a 6 mol / L aqueous potassium hydroxide solution to obtain a 5 mol / L aqueous potassium hydroxide solution containing zinc oxide at a concentration of 0.4 mol / L. 15 ml of the potassium hydroxide aqueous solution thus obtained was placed in a Teflon (registered trademark) closed container. A composite of 1 cm ⁇ 0.6 cm in size was placed at the bottom of the closed container with the functional layer facing up and the lid closed. Then, after holding at 70 ° C. (Examples B1 to B5) or 30 ° C.
  • Example B6 for 1 week (ie 168 hours), 3 weeks (ie 504 hours) or 7 weeks (1176 hours) I took it out.
  • the removed composite was allowed to dry overnight at room temperature.
  • the obtained sample was subjected to microstructure observation by SEM and crystal structure observation by XRD.
  • crystal structure observation by XRD the crystal structure becomes significant when a shift of peak position (2 ⁇ ) exceeding 0.25 ° occurs with respect to the (003) peak of LDH before and after immersion in aqueous potassium hydroxide solution. I judged that it had changed.
  • the conductivity of the functional layer in the electrolytic solution was measured as follows using the electrochemical measurement system shown in FIG.
  • the composite material sample S (a porous base material with an LDH film) was sandwiched from both sides by a silicone gasket 40 with a thickness of 1 mm, and was incorporated into a PTFE flange type cell 42 with 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 with a diameter of 6 mm so that the distance between the electrodes was 2.2 mm.
  • As the electrolyte solution 44 6 M KOH aqueous solution was filled in the cell 42.
  • Evaluation 7 Fineness determination test
  • an acrylic container 130 without a lid, and an alumina jig 132 having a shape and a size that can function as a lid of the acrylic container 130 were prepared.
  • the acrylic container 130 is formed with a gas supply port 130a for supplying a gas therein.
  • an opening 132a having a diameter of 5 mm is formed in the alumina jig 132, and a recess 132b for placing a sample is formed along the outer periphery of the opening 132a.
  • the epoxy adhesive 134 was applied to the recess 132b of the alumina jig 132, and the functional layer 136b side of the composite material sample 136 was mounted on the recess 132b, and was adhered 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 an airtight and liquid tight manner using the silicone adhesive 138 so as to completely close the opening of the acrylic container 130, The measurement sealed container 140 was obtained.
  • the measurement airtight container 140 was placed in the water tank 142, and the gas supply port 130a of the acrylic container 130 was connected to the pressure gauge 144 and the flow meter 146 so that helium gas could be supplied into the acrylic container 130.
  • the water 143 was put in the water tank 142, and the measurement sealed container 140 was completely submerged. At this time, the inside of the measurement sealed container 140 is sufficiently airtight and liquid tight, and the functional layer 136 b side of the composite material sample 136 is exposed to the internal space of the measurement sealed container 140, while the composite material sample is 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 acrylic container 130 through the gas supply port 130 a into the measurement sealed container 140.
  • the pressure gauge 144 and the flow meter 146 are controlled so that the pressure difference between the inside and the outside of the functional layer 136a is 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).
  • bubbles of helium gas were generated from the composite material sample 136 in water.
  • the functional layer 136 b had such a high density as to have no air permeability.
  • Evaluation 8 He permeation measurement
  • the He permeability measurement system 310 shown in FIGS. 7A and 7B was constructed.
  • the He gas from the 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 the function held by the sample holder 316 It was configured to permeate from one side of the layer 318 to the other side for drainage.
  • the sample holder 316 has a structure provided with a gas supply port 316a, a sealed space 316b and a gas discharge port 316c, and was assembled as follows.
  • the 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.
  • Packing made of butyl rubber is disposed as sealing members 326a and 326b at the upper and lower ends of the jig 324, and support members 328a and 328b (made of PTFE are provided with openings made of flanges from the outside of the sealing members 326a and 326b) It was pinched by).
  • the sealed space 316b is defined by the functional layer 318, the jig 324, the sealing member 326a and the support member 328a.
  • the functional layer 318 is a form of the composite material formed on the porous base material 320, it arrange
  • the support members 328a and 328b were tightly tightened with each other by means of fastening means 330 using a screw so that no He gas leaked from portions other than the gas outlet 316c.
  • the gas supply pipe 334 was connected to the gas supply port 316 a of the sample holder 316 thus assembled via the joint 332.
  • He gas was supplied to the He permeability measurement system 310 through the gas supply pipe 334, and permeated to the functional layer 318 held in the sample holder 316.
  • the gas supply pressure and flow rate were monitored by the pressure gauge 312 and the flow meter 314.
  • the He permeability was calculated.
  • the He permeability is calculated by the amount of He gas permeation F (cm 3 / min) per unit time, the differential pressure P (atm) applied to the functional layer during He gas permeation, and the membrane area S (cm) through which He gas permeates. It calculated by the formula of F / (PxS) using 2 ).
  • the permeation amount F (cm 3 / min) of He gas was read directly from the flow meter 314. Further, as the differential pressure P, a gauge pressure read from the pressure gauge 312 was used. The He gas was supplied such that the differential pressure P was in the range of 0.05 to 0.90 atm.
  • Evaluation 9 Identification of Titania
  • STEM scanning transmission electron microscope
  • JEM-ARM200F product name: JEM-ARM200F, manufactured by JEOL
  • FFT fast Fourier transform
  • Examples B1 to B5 (informative) Functional layers and composite materials containing Ni, Al and Ti-containing LDH were prepared and evaluated according to the following procedure.
  • dispersant Leodol SP-O30 manufactured by Kao Corporation
  • This slurry was formed into a sheet on a PET film using a tape forming machine so that the film thickness after drying became 220 ⁇ m, to obtain a sheet molded body.
  • the obtained molded product was cut out so as to have a size of 2.0 cm ⁇ 2.0 cm ⁇ thickness 0.022 cm, and fired at 1100 ° C. for 2 hours to obtain a zirconia-made porous base material.
  • the average pore size of the porous substrate was 0.2 ⁇ m.
  • the measurement of the average pore diameter was performed by measuring the longest distance of 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, and all the obtained pore diameters are arranged in order of size, and the upper 15 points and lower 15 points in order of closeness from the average value
  • the average pore diameter was calculated by calculating the average value for two fields of view at 30 points.
  • the length measurement function of SEM software was used for length measurement.
  • Alumina-titania sol coating on a porous substrate Amorphous alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.) and titanium oxide sol solution (M6 manufactured by Taki Chemical Co., Ltd.) It mixed so that it might become Al atomic ratio, and prepared the mixed sol.
  • 0.2 ml of the mixed sol was applied by spin coating onto the zirconia porous substrate obtained in (1) above. In spin coating, the rotation was stopped 5 seconds after the mixed sol was dropped on the substrate rotated at 8,000 rpm, and 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. and urea ((NH 2) 2 CO, manufactured by Sigma-Aldrich)
  • Nickel nitrate hexahydrate was weighed into a beaker so as to be 0.015 mol / L, and ion-exchanged water was added there to make the total amount 75 ml.
  • the substrate was removed from the closed vessel, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to partially incorporate the LDH-containing functional layer into the porous substrate. Obtained in the form.
  • the thickness of the obtained functional layer (including the thickness of the part incorporated into the porous substrate) was about 5 ⁇ m.
  • Evaluation results were performed on the obtained functional layer or composite material. Evaluation 9 was also performed only for Example B4. The results were as follows.
  • Evaluation 1 The functional layers obtained in Examples B1 to B5 were identified as LDH (hydrotalcite compounds) from the obtained XRD profiles.
  • FIG. 8 shows the XRD profile obtained in Example B1.
  • the peak derived from the zirconia which comprises a porous base material is also collectively shown by FIG.
  • Evaluation 2 SEM images of surface microstructure and cross-sectional microstructure of the functional layer obtained in Example B1 were as shown in FIGS. 9A and 9B, respectively. As shown in FIG. 9B, it was found that the functional layer was composed of a film-like portion made of an LDH film, and a composite portion made of LDH and a porous base material located below the film-like portion.
  • LDH which comprises a film-like part is comprised by the aggregate
  • the pores of the porous substrate were filled with LDH to constitute a dense layer.
  • the surface microstructure and cross-sectional microstructure of the functional layer obtained in Examples B2 to B5 were also substantially the same as in Example B1.
  • Example B1-B5 The XRD results obtained for Examples B1-B5 were as shown in Table 2.
  • Table 2 and FIG. 11 the X-ray diffraction results of the functional layer of Example B1 before, after one week and after three weeks immersion in the KOH aqueous solution were as shown in FIG.
  • Table 2 and FIG. 11 no significant change was observed in the crystal structure in any of Examples B1 to B5 after immersion for 3 weeks in a 70 ° C. aqueous potassium hydroxide solution.
  • Table 2 in which the Ti / (Ni + Ti + Al) ratio is high, there is a significant change in the crystal structure even after immersion for 7 weeks in a 70 ° C.
  • Evaluation 6 The ionic conductivity of the functional layer of Examples B1 to B5 was 2.0 to 2.5 mS / cm, which was at the same level as Example B6 which is a comparative example described later.
  • Evaluation 7 It was found that the functional layers and composites of Examples B1 to B5 have a high density so as not to have breathability.
  • Evaluation 8 The He permeability of the functional layers and composite materials of Examples B1 to B5 was 0.0 cm / min ⁇ atm.
  • Evaluation 9 For the functional layer of Example B4, the BF-STEM image and the FFT analysis pattern shown in FIG. 14 were obtained. The lattice constant which can be read from this FFT analysis pattern is substantially in agreement with the result of the electronic analysis simulation of the anatase type titanium oxide shown in FIG. 14, and it was confirmed that it contains titania.
  • Example B6 (comparison) Functional layers and composite materials containing Mg and Al containing LDH were prepared and evaluated according to the following procedure.
  • This slurry was formed into a sheet on a PET film using a tape forming machine so that the film thickness after drying became 220 ⁇ m, to obtain a sheet molded body.
  • the obtained molded product was cut out so as 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 base material.
  • the average pore diameter of the porous substrate was 0.3 ⁇ m.
  • the measurement of the average pore diameter was performed by measuring the longest distance of 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, and all the obtained pore diameters are arranged in order of size, and the upper 15 points and lower 15 points in order of closeness from the average value
  • the average pore diameter was calculated by calculating the average value for two fields of view at 30 points.
  • the length measurement function of SEM software was used for length measurement.
  • 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)
  • the mixture was placed in a beaker, and ion exchange water was added thereto to make the total volume 70 ml.
  • the substrate was removed from the closed vessel, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to partially incorporate the LDH-containing functional layer into the porous substrate. Obtained in the form.
  • the thickness of the obtained functional layer (including the thickness of the part incorporated into the porous substrate) was about 3 ⁇ m.
  • Evaluation results were performed on the obtained functional layer or composite material. The results were as follows. -Evaluation 1: From the obtained XRD profile, it was identified that the functional layer is LDH (hydrotalcite compound). Evaluation 2: SEM images of surface microstructure and cross-sectional microstructure of the functional layer were as shown in FIGS. 15A and 15B, respectively. In substantially the same manner as the functional layer obtained in Example B1, a functional layer composed of a film-like portion made of an LDH film and a composite portion made of LDH and a porous base material located below the film-like portion is observed.
  • the -Evaluation 3 As a result of EDS elemental analysis, C, Mg, and Al which are LDH constituent elements were detected in LDH contained in the functional layer, that is, in both 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 5 SEM images of the surface microstructure of the functional layer before and after immersion in a KOH aqueous solution were as shown in FIG. As can be seen from FIG. 16, even after immersion for 1 week in the aqueous potassium hydroxide solution at 30 ° C. lower than 70 ° C.
  • the shift of the (003) peak may suggest that Al contained in LDH is eluted in a KOH aqueous solution to degrade LDH.
  • the functional layer of Example B6 is inferior to the functional layer of Example B1 in alkali resistance, that is, the functional layer of Example B1 which is a reference example is superior in alkali resistance to the functional layer of Comparative Example B6.
  • Evaluation 6 The conductivity of the functional layer was 2.0 mS / cm.
  • -Evaluation 7 It was confirmed that the functional layer and the composite material have high density so as not to have air permeability.
  • Evaluation 8 The He permeability of the functional layer and the composite material was 0.0 cm / min ⁇ atm.
  • Example B7 (Informative) Using a polymeric porous substrate, functional layers and composite materials containing Ni, Al and Ti-containing LDH were prepared and evaluated according to the following procedure.
  • Alumina-titania sol coating on polymeric porous substrate Amorphous alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.) and titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.)
  • the mixed sol was applied by dip coating to the substrate prepared in (1) above. The dip coating was performed by immersing the substrate in 100 ml of the mixed sol, pulling it vertically, and drying it in a dryer at 90 ° C. for 5 minutes.
  • Evaluation results were performed on the obtained functional layer or composite material. The results were as follows. -Evaluation 1: From the obtained XRD profile, it was identified that the functional layer is LDH (hydrotalcite compound). Evaluation 2: The SEM image of the cross-sectional microstructure of the functional layer or the composite material is as shown in FIG. As can be seen from FIG. 18, it was observed that the functional layer was incorporated throughout the thickness direction of the porous substrate, that is, the pores of the porous substrate were uniformly filled with LDH.

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Abstract

L'invention concerne : une couche fonctionnelle contenant du LDH qui présente une excellente résistance aux alcalis ; et un matériau composite qui est pourvu de cette couche fonctionnelle contenant du LDH. Cette couche fonctionnelle contient un hydroxyde double lamellaire ; l'hydroxyde double lamellaire contient Ni, Ti et Al ; la couche fonctionnelle contient en outre Y ; et le rapport atomique Y/Al est supérieur ou égal à 0,5.
PCT/JP2018/046116 2017-12-27 2018-12-14 Couche fonctionnelle contenant un hydroxyde double lamellaire, et matériau composite WO2019131221A1 (fr)

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CN115461923B (zh) * 2020-05-11 2024-02-06 日本碍子株式会社 Ldh隔板及锌二次电池
JP7441308B2 (ja) 2020-05-11 2024-02-29 日本碍子株式会社 Ｌｄｈセパレータ及び亜鉛二次電池
JP7441309B2 (ja) 2020-05-11 2024-02-29 日本碍子株式会社 Ｌｄｈセパレータ及び亜鉛二次電池
JP7037002B1 (ja) * 2020-11-30 2022-03-15 日本碍子株式会社 層状複水酸化物様化合物を用いた電池
WO2022113433A1 (fr) * 2020-11-30 2022-06-02 日本碍子株式会社 Batterie utilisant un composé de type hydroxyde double lamellaire
WO2023058268A1 (fr) * 2021-10-06 2023-04-13 日本碍子株式会社 Séparateur ldh, procédé de fabrication de celui-ci, et batterie rechargeable au zinc

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