WO2022113448A1 - Séparateur de composé de type hydroxyde double lamellaire (de type ldh) et batterie secondaire au zinc - Google Patents

Séparateur de composé de type hydroxyde double lamellaire (de type ldh) et batterie secondaire au zinc Download PDF

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WO2022113448A1
WO2022113448A1 PCT/JP2021/031344 JP2021031344W WO2022113448A1 WO 2022113448 A1 WO2022113448 A1 WO 2022113448A1 JP 2021031344 W JP2021031344 W JP 2021031344W WO 2022113448 A1 WO2022113448 A1 WO 2022113448A1
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ldh
compound
separator
evaluation
compound separator
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PCT/JP2021/031344
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English (en)
Japanese (ja)
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聡太 大河内
昌平 横山
翔 山本
直子 犬飼
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日本碍子株式会社
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Priority to JP2021572068A priority Critical patent/JP7057866B1/ja
Priority to CN202180062519.0A priority patent/CN116325247A/zh
Priority to DE112021005103.2T priority patent/DE112021005103T5/de
Publication of WO2022113448A1 publication Critical patent/WO2022113448A1/fr
Priority to US18/180,276 priority patent/US20230231154A1/en

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/32—Silver accumulators
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an LDH-like compound separator and a zinc secondary battery.
  • Patent Document 1 International Publication No. 2013/118561 discloses that an LDH separator is provided between a positive electrode and a negative electrode in a nickel-zinc secondary battery.
  • Patent Document 2 International Publication No. 2016/076047 discloses a separator structure including an LDH separator fitted or bonded to a resin outer frame, and the LDH separator is gas impermeable and has a gas impermeable property. / Or it is disclosed that it has a high degree of density enough to have water impermeableness.
  • Patent Document 3 International Publication No. 2016/067884 discloses various methods for forming an LDH dense film on the surface of a porous substrate to obtain a composite material (LDH separator).
  • a starting material that can give a starting point for LDH crystal growth is uniformly adhered to the porous base material, and the porous base material is subjected to hydrothermal treatment in an aqueous solution of the raw material to form an LDH dense film on the surface of the porous base material. It includes a step of forming the film.
  • Patent Document 4 International Publication No. 2019/124214 contains a porous base material made of a polymer material and a layered double hydroxide (LDH) that closes the pores of the porous base material, and contains an LDH separator.
  • LDH separator in which the average porosity in the central portion in the thickness direction is smaller than the average porosity in the vicinity of the surface of the LDH separator.
  • the present inventors have excellent alkali resistance and further effect the short circuit caused by zinc dendrite. It was found that a hydroxide ion conduction separator (LDH-like compound separator) that can be suppressed can be provided. Further, by closing the pores of the polymer porous substrate with an LDH-like compound so that the average porosity in the central portion in the thickness direction is smaller than the average porosity in the vicinity of the surface, a short circuit caused by zinc dendrite. It was found that an LDH-like compound separator capable of more effectively suppressing the above can be provided.
  • LDH-like compound separator capable of more effectively suppressing the above can be provided.
  • an object of the present invention is to provide a hydroxide ion conduction separator superior to an LDH separator, which has excellent alkali resistance and can more effectively suppress a short circuit caused by zinc dendrite.
  • the LDH-like compound separator comprising a porous base material made of a polymer material and a layered double hydroxide (LDH) -like compound that closes the pores of the porous base material.
  • LDH layered double hydroxide
  • an LDH-like compound separator in which the average porosity in the central portion in the thickness direction of the LDH-like compound separator is smaller than the average porosity in the vicinity of the surface of the LDH-like compound separator.
  • a zinc secondary battery provided with an LDH-like compound separator is provided.
  • a solid alkaline fuel cell provided with the LDH-like compound separator is provided.
  • FIG. 3 is a schematic cross-sectional view of a sample holder used in the measurement system shown in FIG. 3A and its peripheral configuration. It is a schematic cross-sectional view which shows the electrochemical measurement system used in Examples A1 to D3.
  • 6 is a cross-sectional FE-SEM image of a portion near the surface of the LDH separator produced in Example A3 (a region having a depth of 1 to 4 ⁇ m from the surface).
  • the gray region corresponds to the polymer porous substrate
  • the white region corresponds to LDH
  • the black region corresponds to the residual pores.
  • It is a cross-sectional FE-SEM image of the central part of the LDH separator produced in Example A3.
  • the gray region corresponds to the polymer porous substrate
  • the white region corresponds to LDH
  • the black region corresponds to the residual pores.
  • 6 is a surface SEM image of the LDH-like compound separator prepared in Example B1. It is an X-ray diffraction result of the LDH-like compound separator prepared in Example B1.
  • 6 is a surface SEM image of the LDH-like compound separator prepared in Example B2.
  • 6 is a surface SEM image of the LDH-like compound separator prepared in Example B3. It is an X-ray diffraction result of the LDH-like compound separator prepared in Example B3. 6 is a surface SEM image of the LDH-like compound separator prepared in Example B4. It is an X-ray diffraction result of the LDH-like compound separator prepared in Example B4. 6 is a surface SEM image of the LDH-like compound separator prepared in Example B5. It is an X-ray diffraction result of the LDH-like compound separator prepared in Example B5.
  • 6 is a surface SEM image of the LDH-like compound separator prepared in Example B6. It is an X-ray diffraction result of the LDH-like compound separator prepared in Example B6. 6 is a surface SEM image of the LDH-like compound separator prepared in Example B7. It is a surface SEM image of the LDH separator prepared in Example B8 (comparison). It is an X-ray diffraction result of the LDH separator prepared in Example B8 (comparison). 8 is a surface SEM image of the LDH-like compound separator prepared in Example C1. 6 is a surface SEM image of the LDH-like compound separator prepared in Example D1. 6 is a surface SEM image of the LDH-like compound separator prepared in Example D2.
  • the LDH-like compound separator 10 of the present invention contains a porous substrate 12 and a layered double hydroxide (LDH) -like compound 14. ..
  • LDH-like compound separator is a separator containing an LDH-like compound, and is assumed to selectively pass hydroxide ions by utilizing the hydroxide ion conductivity of the LDH-like compound. Defined.
  • the "LDH-like compound” is a hydroxide and / or oxide having a layered crystal structure similar to LDH, although it cannot be called LDH, and is defined as one in which a peak caused by LDH is not detected by the X-ray diffraction method.
  • the region of the LDH-like compound 14 is drawn so as not to be connected between the upper surface and the lower surface of the LDH-like compound separator 10, because the region is drawn two-dimensionally as a cross section.
  • the region of the LDH-like compound 14 is connected between the upper surface and the lower surface of the LDH-like compound separator 10 three-dimensionally in consideration of the depth, thereby ensuring the hydroxide ion conductivity of the LDH-like compound separator 10.
  • the porous base material 12 is made of a polymer material, and the pores of the porous base material 12 are closed by the LDH-like compound 14. However, the pores of the porous substrate 12 are not completely closed, and there are residual pores P (pores that are not closed by the LDH-like compound). Due to the residual pores P, the LDH-like compound separator 10 can be evaluated by the average porosity. The average porosity of the central portion 10a of the LDH-like compound separator 10 in the thickness direction is smaller than the average porosity of the surface-near portion 10b of the LDH-like compound separator 10.
  • the LDH-like compound separator 10 of the present invention has a sparse distribution of residual pores P in the thickness direction, and specifically, the central portion 10a is dense and the surface vicinity portion 10b is sparse. Is. In this way, zinc is formed by closing the pores of the polymer porous substrate 12 with the LDH-like compound 14 so that the average porosity of the central portion 10a in the thickness direction is smaller than the average porosity of the portion near the surface 10b. It is possible to provide an LDH-like compound separator 10 capable of more effectively suppressing a short circuit caused by dendrites.
  • the penetration of the zinc dendrite in the conventional separator is as follows: (i) the zinc dendrite invades the voids or defects contained in the separator, (ii) the dendrite grows and propagates while expanding the separator, and (ii) finally the dendrite. Is presumed to occur by the mechanism of penetrating the separator.
  • the surface near portion 10b since the central portion 10a is dense and the surface near portion 10b is sparse, the surface near portion 10b having a higher average pore ratio than the central portion 10a buffers dendrite invasion. It can function as a layer to allow the growth and extension of zinc dendrites to stay within the surface vicinity portion 10b.
  • the extension of zinc dendrite in the thickness direction of the LDH-like compound separator 10 can be significantly suppressed, and therefore the short circuit caused by the zinc dendrite can be more effectively suppressed. It can be suppressed.
  • an LDH-like compound described later as a hydroxide ion conductive substance instead of the conventional LDH, water having excellent alkali resistance and capable of more effectively suppressing short circuit due to zinc dendrite.
  • An oxide ion conduction separator (LDH-like compound separator) can be provided.
  • the LDH-like compound separator 10 of the present invention has the desired ionic conductivity required as a separator based on the hydroxide ion conductivity of the LDH-like compound, as well as flexibility and strength. Is also excellent. This is due to the flexibility and strength of the polymer porous base material 12 itself contained in the LDH-like compound separator 10. That is, since the LDH-like compound separator 10 is densified so that the pores of the polymer porous base material 12 are sufficiently closed with the LDH-like compound, the polymer porous base material 12 and the LDH-like compound 14 are combined.
  • the rigidity and brittleness resulting from the LDH-like compound 14, which is a ceramic material, is offset or offset by the flexibility and strength of the polymeric porous substrate 12. It can be said that it will be reduced.
  • the average porosity of the central portion 10a in the thickness direction is smaller than the average porosity of the surface vicinity portion 10b.
  • the central portion 10a means the portion located in the center when the LDH-like compound separator 10 is divided into three equal parts in the thickness direction
  • the surface vicinity portion 10b means the LDH-like compound separator 10 in thickness. It shall mean the portion on the side closer to the surface (that is, the portion on the outer side of the central portion 10a) when divided into three equal parts in the isth direction.
  • the average porosity of the surface vicinity portion 10b is 3% or more, and the average porosity of the central portion 10a is 2% or less, and more preferably, the average porosity of the surface vicinity portion 10b is 3 to 15. %, And the average porosity of the central portion 10a is 1% or less, more preferably, the average porosity of the surface vicinity portion 10b is 5 to 10%, and the average porosity of the central portion 10a is. It is 0.01 to 1%.
  • the central portion 10a and the surface near portion 10b have an average pore ratio within the above range, the growth of the zinc dendrite can be further suppressed in the surface near portion 10b, and therefore the short circuit caused by the zinc dendrite is further effective.
  • the average porosity is measured by a) polishing the cross section of the LDH-like compound separator with a cross section polisher (CP), and b) cross-section of the functional layer at a magnification of 50,000 times with FE-SEM (electron emission scanning electron microscope). Two images were acquired, and c) the pore ratio of each of the two regions was calculated using image inspection software (for example, HDdev, manufactured by MVTecSoftware) based on the image data of the acquired cross-sectional image, and d) the obtained pore ratio. It can be done by finding the average value of.
  • image inspection software for example, HDdev, manufactured by MVTecSoftware
  • the LDH-like compound separator 10 preferably has an ionic conductivity of 0.1 mS / cm or more, more preferably 1.0 mS / cm or more, still more preferably 1.5 mS / cm or more, and particularly preferably 2.0 mS / cm. That is all. Within such a range, the LDH-like compound separator can exhibit a sufficient function as a hydroxide ion conduction separator. The higher the ionic conductivity, the better, so the upper limit thereof is not particularly limited, but is, for example, 10 mS / cm. The ionic conductivity is calculated based on the resistance of the LDH-like compound separator and the thickness and area of the LDH-like compound separator.
  • the resistance of the LDH-like compound separator 10 is determined by using an electrochemical measurement system (potential / galvanostat-frequency response analyzer) for the LDH-like compound separator 10 immersed in a KOH aqueous solution having a predetermined concentration (for example, 5.4 M).
  • the measurement can be performed in a frequency range of 1 MHz to 0.1 Hz and an applied voltage of 10 mV, and the section of the real number axis can be determined as the resistance of the LDH-like compound separator.
  • the LDH-like compound separator 10 is a separator containing a layered double hydroxide (LDH) -like compound 14, and when incorporated into a zinc secondary battery, separates a positive electrode plate and a negative electrode plate so that hydroxide ions can be conducted. It is a thing. That is, the LDH-like compound separator 10 exhibits a function as a hydroxide ion conduction separator.
  • the preferred LDH-like compound separator 10 has gas impermeable and / or water impermeable. In other words, the LDH-like compound separator 10 is preferably densified to have gas impermeableness and / or water impermeableness.
  • "having gas impermeable” in the present specification means that helium gas is brought into contact with one side of an object to be measured in water with a differential pressure of 0.5 atm. However, it means that the generation of bubbles due to helium gas is not observed from the other side.
  • “having water impermeable” means that water in contact with one side of the object to be measured does not permeate to the other side as described in Patent Documents 2 and 3. .. That is, the fact that the LDH-like compound separator 10 has gas impermeableness and / or water impermeableness means that the LDH-like compound separator 10 has a high degree of density so as to be impermeable to gas or water.
  • the LDH-like compound separator 10 selectively passes only hydroxide ions due to its hydroxide ion conductivity, and can exhibit a function as a battery separator. Therefore, the configuration is extremely effective in physically preventing the penetration of the separator by the zinc dendrite generated during charging to prevent a short circuit between the positive and negative electrodes. Since the LDH-like compound separator 10 has hydroxide ion conductivity, it enables efficient transfer of necessary hydroxide ions between the positive electrode plate and the negative electrode plate, and realizes a charge / discharge reaction in the positive electrode plate and the negative electrode plate. can do.
  • the LDH-like compound separator 10 preferably has a He permeability per unit area of 3.0 cm / min ⁇ atm or less, more preferably 2.0 cm / min ⁇ atm or less, still more preferably 1.0 cm / min ⁇ . It is less than or equal to atm.
  • a separator having a He permeability of 3.0 cm / min ⁇ atm or less can extremely effectively suppress the permeation of Zn (typically the permeation of zinc ion or zinc acid ion) in the electrolytic solution.
  • Zn typically the permeation of zinc ion or zinc acid ion
  • the He permeability is determined through a step of supplying He gas to one surface of the separator to allow the Sepa to permeate the He gas, and a step of calculating the He permeability to evaluate the denseness of the hydroxide ion conduction separator. Be measured.
  • the He permeability is determined by the formula of F / (P ⁇ S) using the permeation amount F of the He gas per unit time, the differential pressure P applied to the separator when the He gas permeates, and the film area S through which the He gas permeates. calculate.
  • He gas has the smallest structural unit among the various atoms or molecules that can compose the gas, and its reactivity is extremely low. That is, He constitutes He gas by a single He atom without forming a molecule. In this respect, since hydrogen gas is composed of H 2 molecules, the He atom alone is smaller as a gas constituent unit.
  • H 2 gas is dangerous because it is a flammable gas.
  • the index of He gas permeability defined by the above formula, it is possible to easily perform an objective evaluation of the fineness regardless of the difference in various sample sizes and measurement conditions. In this way, it is possible to easily, safely and effectively evaluate whether or not the separator has sufficiently high density suitable for a zinc secondary battery separator.
  • the measurement of He permeability can be preferably performed according to the procedure shown in Evaluation 5 of Examples described later.
  • the LDH-like compound 14 closes the pores of the porous substrate 12.
  • the LDH-like compound is (A) A hydroxide and / or oxide having a layered crystal structure containing Mg and at least one element containing at least Ti selected from the group consisting of Ti, Y and Al, or (b) (i). ) Ti, Y, and optionally Al and / or Mg, and (ii) a layered crystal structure comprising at least one additive element M selected from the group consisting of In, Bi, Ca, Sr and Ba.
  • Hydroxides and / or oxides or (c) hydroxides and / or oxides of a layered crystal structure containing Mg, Ti, Y, and optionally Al and / or In, said (c).
  • the LDH-like compound is present in the form of a mixture with In (OH) 3 .
  • the LDH-like compound 14 is hydroxylated in a layered crystal structure containing Mg and at least one element containing Ti selected from the group consisting of Ti, Y and Al. It can be an object and / or an oxide.
  • a typical LDH-like compound 14 is a composite hydroxide and / or composite oxide of Mg, Ti, optionally Y and optionally Al.
  • the element may be replaced with another element or ion to the extent that the basic properties of the LDH-like compound 14 are not impaired, but the LDH-like compound 14 preferably does not contain Ni.
  • LDH-like compound 14 may further contain Zn and / or K. By doing so, the ionic conductivity of the LDH-like compound separator 10 can be further improved.
  • LDH-like compound 14 can be identified by X-ray diffraction. Specifically, when X-ray diffraction is performed on the surface of the LDH-like compound separator 10, the LDH-like compound separator 10 is typically in the range of 5 ° ⁇ 2 ⁇ ⁇ 10 °, and more typically 7 ° ⁇ 2 ⁇ ⁇ . Peaks derived from LDH-like compounds are detected in the range of 10 °. As described above, LDH is a substance having an alternating laminated structure in which exchangeable anions and H2O are present as an intermediate layer between the stacked hydroxide basic layers.
  • the interlayer distance of the layered crystal structure can be determined by the Bragg equation using 2 ⁇ corresponding to the peak derived from the LDH-like compound in X-ray diffraction.
  • the interlayer distance of the layered crystal structure constituting the LDH-like compound 14 thus determined is typically 0.883 to 1.8 nm, and more typically 0.883 to 1.3 nm.
  • the LDH-like compound separator 10 has an atomic ratio of Mg / (Mg + Ti + Y + Al) in LDH-like compound 14 determined by energy dispersive X-ray analysis (EDS) of 0.03 to 0.25. Is preferable, and more preferably 0.05 to 0.2.
  • the atomic ratio of Ti / (Mg + Ti + Y + Al) in the LDH-like compound 14 is preferably 0.40 to 0.97, more preferably 0.47 to 0.94.
  • the atomic ratio of Y / (Mg + Ti + Y + Al) in the LDH-like compound 14 is preferably 0 to 0.45, more preferably 0 to 0.37.
  • the atomic ratio of Al / (Mg + Ti + Y + Al) in the LDH-like compound 14 is preferably 0 to 0.05, more preferably 0 to 0.03. Within the above range, the alkali resistance is further excellent, and the effect of suppressing a short circuit caused by zinc dendrite (that is, dendrite resistance) can be more effectively realized.
  • LDH conventionally known for LDH separators has a general formula: M 2+ 1-x M 3+ x (OH) 2 Ann- x / n ⁇ mH 2 O (in the formula, M 2+ is a divalent cation, M.
  • LDH-like compound 14 generally has a composition ratio (atomic ratio) different from that of the conventional LDH.
  • an EDS analyzer for example, X-act, manufactured by Oxford Instruments
  • X-act for example, X-act, manufactured by Oxford Instruments
  • the LDH-like compound 14 contains (i) Ti, Y, and optionally Al and / or Mg, and (ii) an additive element M in a layered crystal structure. It can be a hydroxide and / or an oxide of.
  • a typical LDH-like compound 14 is a composite hydroxide and / or composite oxide of Ti, Y, additive element M, optionally Al and optionally Mg.
  • the additive element M is In, Bi, Ca, Sr, Ba or a combination thereof.
  • the element may be replaced with another element or ion to the extent that the basic properties of the LDH-like compound 14 are not impaired, but the LDH-like compound 14 preferably does not contain Ni.
  • the LDH-like compound separator 10 has an atomic ratio of Ti / (Mg + Al + Ti + Y + M) in the LDH-like compound 14 determined by energy dispersive X-ray analysis (EDS) of 0.50 to 0.85. Is preferable, and more preferably 0.56 to 0.81.
  • the atomic ratio of Y / (Mg + Al + Ti + Y + M) in LDH-like compound 14 is preferably 0.03 to 0.20, more preferably 0.07 to 0.15.
  • the atomic ratio of M / (Mg + Al + Ti + Y + M) in LDH-like compound 14 is preferably 0.03 to 0.35, more preferably 0.03 to 0.32.
  • the atomic ratio of Mg / (Mg + Al + Ti + Y + M) in LDH-like compound 14 is preferably 0 to 0.10, more preferably 0 to 0.02.
  • the atomic ratio of Al / (Mg + Al + Ti + Y + M) in the LDH-like compound 14 is preferably 0 to 0.05, more preferably 0 to 0.04.
  • the alkali resistance is further excellent, and the effect of suppressing a short circuit caused by zinc dendrite (that is, dendrite resistance) can be more effectively realized.
  • LDH conventionally known for LDH separators has a general formula: M 2+ 1-x M 3+ x (OH) 2 Ann- x / n ⁇ mH 2 O (in the formula, M 2+ is a divalent cation, M. 3+ is a trivalent cation, An- is an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is 0 or more).
  • M 2+ is a divalent cation
  • M. 3+ is a trivalent cation
  • An- is an n-valent anion
  • n is an integer of 1 or more
  • x is 0.1 to 0.4
  • m is 0 or more
  • the atomic ratio of LDH-like compound 14 generally deviates from the above general formula of LDH. Therefore, it can be said that the LDH-like compound 14 in this embodiment generally has a composition ratio (atomic ratio) different from that of the conventional LDH.
  • an EDS analyzer for example, X-act, manufactured by Oxford Instruments
  • X-act for example, X-act, manufactured by Oxford Instruments
  • the LDH-like compound 14 is a hydroxide and / or oxide having a layered crystal structure containing Mg, Ti, Y, and optionally Al and / or In.
  • the LDH-like compound 14 may be present in the form of a mixture with In (OH) 3 .
  • the LDH-like compound of this embodiment is a hydroxide and / or oxide having a layered crystal structure containing Mg, Ti, Y, and optionally Al and / or In.
  • typical LDH-like compounds are composite hydroxides and / or composite oxides of Mg, Ti, Y, optionally Al, and optionally In.
  • LDH-like compound The In that can be contained in the LDH-like compound is not only intentionally added to the LDH-like compound, but is inevitably mixed in the LDH-like compound due to the formation of In (OH) 3 and the like. It may be a compound.
  • the above elements may be replaced with other elements or ions to the extent that the basic properties of the LDH-like compound are not impaired, but the LDH-like compound preferably does not contain Ni.
  • LDH conventionally known for LDH separators has a general formula: M 2+ 1-x M 3+ x (OH) 2 Ann- x / n ⁇ mH 2 O (in the formula, M 2+ is a divalent cation, M.
  • LDH-like compound in this embodiment generally has a composition ratio (atomic ratio) different from that of the conventional LDH.
  • the mixture according to the above aspect (c) contains not only an LDH-like compound but also In (OH) 3 (typically composed of an LDH-like compound and In (OH) 3 ).
  • the inclusion of In (OH) 3 can effectively improve the alkali resistance and dendrite resistance of the LDH-like compound separator 10.
  • the content ratio of In (OH) 3 in the mixture is preferably an amount capable of improving alkali resistance and dendrite resistance without impairing the hydroxide ion conductivity of the LDH-like compound separator 10, and is not particularly limited.
  • In (OH) 3 may have a cube-shaped crystal structure, or the crystal of In (OH) 3 may be surrounded by an LDH-like compound.
  • In (OH) 3 can be identified by X-ray diffraction. The X-ray diffraction measurement can be preferably performed according to the procedure shown in the examples described later.
  • the LDH-like compound separator 10 contains the LDH-like compound 14 and the porous substrate 12 (typically composed of the porous substrate 12 and the LDH-like compound 14), and the LDH-like compound separator 10 is hydroxylated.
  • the LDH-like compound closes the pores of the porous substrate so as to exhibit ionic conductivity and gas impermeableness (hence to function as an LDH-like compound separator exhibiting hydroxide ionic conductivity). It is particularly preferable that the LDH-like compound 14 is incorporated over the entire area of the polymer porous substrate 12 in the thickness direction.
  • the thickness of the LDH-like compound separator is preferably 3 to 80 ⁇ m, more preferably 3 to 60 ⁇ m, and even more preferably 3 to 40 ⁇ m.
  • the porous base material 12 is made of a polymer material.
  • the polymer porous substrate 12 has 1) flexibility (hence, it is hard to break even if it is thinned), 2) easy to increase the porosity, and 3) easy to increase the conductivity (increasing the porosity). However, it has the advantages of being easy to manufacture and handle) (because the thickness can be reduced). Further, taking advantage of the flexibility of 1) above, there is also an advantage that the LDH-like compound separator containing a porous substrate made of a polymer material can be easily bent or sealed and bonded. be.
  • Preferred examples of the polymer material include polystyrene, polyether sulfone, polypropylene, epoxy resin, polyphenylene sulfide, fluororesin (tetrafluororesin: PTFE, etc.), cellulose, nylon, polyethylene and any combination thereof. .. More preferably, from the viewpoint of a thermoplastic resin suitable for heat pressing, polystyrene, polyether sulfone, polypropylene, epoxy resin, polyphenylene sulfide, fluororesin (tetrafluororesin: PTFE, etc.), nylon, polyethylene and any of them. Examples include the combination of the above. All of the various preferred materials described above have alkali resistance as resistance to the electrolytic solution of the battery.
  • Particularly preferable polymer materials are polyolefins such as polypropylene and polyethylene, and most preferably polypropylene or polyethylene, because they are excellent in heat resistance, acid resistance and alkali resistance and are low in cost.
  • the porous substrate is composed of a polymer material, LDH-like compounds are incorporated over the entire thickness direction of the porous substrate (for example, most or almost all the pores inside the porous substrate are LDH-like. It is particularly preferable that it is filled with a compound).
  • a commercially available polymer microporous membrane can be preferably used as such a polymer porous substrate.
  • the production method of the LDH-like compound separator 10 is not particularly limited, and various conditions (particularly LDH raw material composition) of the already known LDH-containing functional layer and composite material production method (see, for example, Patent Documents 1 to 4) are appropriately used. It can be produced by changing it. For example, (1) a porous substrate is prepared, and (2) a solution containing titania sol (or further yttrium sol and / or alumina sol) is applied to the porous substrate and dried to form a titania-containing layer.
  • a solution containing titania sol or further yttrium sol and / or alumina sol
  • the pH value rises due to the generation of ammonia in the solution by utilizing the hydrolysis of urea, and the coexisting metal ions are hydroxide and / or oxidized. It is considered that an LDH-like compound can be obtained by forming a substance.
  • the porous base material 12 is composed of a polymer material and the LDH-like compound 14 is incorporated over the entire thickness direction of the porous base material (that is, an LDH-like compound separator) is produced.
  • the preferred coating method include a dip coat, a filtration coat and the like, and a dip coat is particularly preferable. By adjusting the number of times of application of the dip coat or the like, the amount of adhesion of the mixed sol solution can be adjusted.
  • the base material coated with the mixed sol solution by dip coating or the like may be dried and then the above steps (3) and (4) may be carried out.
  • the porous base material 12 is made of a polymer material
  • the pressing method may be, for example, a roll press, a uniaxial pressure press, a CIP (cold isotropic pressure pressurization), or the like, and is not particularly limited, but is preferably a roll press. It is preferable to perform this press while heating because the pores of the porous substrate can be sufficiently closed with the LDH-like compound by softening the polymer porous substrate.
  • a temperature for sufficient softening for example, in the case of polypropylene or polyethylene, it is preferable to heat at 60 to 200 ° C.
  • a press such as a roll press in such a temperature range
  • the residual pores of the LDH-like compound separator can be significantly reduced.
  • the LDH-like compound separator can be extremely highly densified, and therefore short circuits caused by zinc dendrites can be suppressed even more effectively.
  • the morphology of the residual pores can be controlled by appropriately adjusting the roll gap and the roll temperature, whereby an LDH-like compound separator having a desired density can be obtained.
  • Zinc secondary battery The LDH-like compound separator of the present invention is preferably applied to a zinc secondary battery. Therefore, according to a preferred embodiment of the present invention, a zinc secondary battery provided with an LDH-like compound separator is provided.
  • a typical zinc secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution, and the positive electrode and the negative electrode are separated from each other via an LDH-like compound separator.
  • the zinc secondary battery of the present invention is not particularly limited as long as it is a secondary battery using zinc as a negative electrode and using an electrolytic solution (typically, an aqueous alkali metal hydroxide solution).
  • the positive electrode contains nickel hydroxide and / or nickel oxyhydroxide, whereby the zinc secondary battery forms a nickel-zinc secondary battery.
  • the positive electrode may be an air electrode, whereby the zinc secondary battery may be a zinc air secondary battery.
  • the LDH-like compound separator of the present invention can also be applied to a solid alkaline fuel cell. That is, by using an LDH-like compound separator in which the pores of the polymer porous substrate are closed with an LDH-like compound so that the average porosity in the central portion in the thickness direction is smaller than the average porosity in the vicinity of the surface. It is possible to provide a solid alkaline fuel cell capable of effectively suppressing a decrease in electromotive force due to permeation of fuel to the air electrode side (for example, crossover of methanol).
  • a solid alkaline fuel cell with an LDH-like compound separator there is provided a solid alkaline fuel cell with an LDH-like compound separator.
  • a typical solid alkaline fuel cell according to this embodiment has an air electrode to which oxygen is supplied, a fuel electrode to which a liquid fuel and / or a gaseous fuel is supplied, and an LDH-like intervening between the fuel electrode and the air electrode. It is equipped with a compound separator.
  • the LDH-like compound separator of the present invention can be used not only for nickel-zinc batteries and solid alkaline fuel cells, but also for nickel-metal hydride batteries, for example.
  • the LDH-like compound separator functions to block the nitride shuttle (movement of nitric acid groups between electrodes), which is a factor of self-discharge of the battery.
  • the LDH-like compound separator of the present invention can also be used for a lithium battery (a battery having a negative electrode of lithium metal as a negative electrode), a lithium ion battery (a battery having a negative electrode of carbon or the like), a lithium air battery or the like.
  • Examples A1 to A8 shown below are reference examples or comparative examples regarding LDH separators, but the experimental procedures and results in these examples are generally applicable to LDH-like compound separators as well.
  • the evaluation method of the LDH separator produced in the following example was as follows.
  • Evaluation 1 Identification of LDH separator
  • the crystal phase of the LDH separator was measured by an X-ray diffractometer (Rigaku, RINT TTR III) under the measurement conditions of voltage: 50 kV, current value: 300 mA, and measurement range: 10 to 70 °. The measurement was performed to obtain an XRD profile. Regarding the obtained XRD profile, JCPDS card No. Identification was performed using the diffraction peak of LDH (hydrotalcite compound) described in 35-0964.
  • Evaluation 2 Measurement of thickness The thickness of the LDH separator was measured using a micrometer. The thickness was measured at three points, and the average value thereof was adopted as the thickness of the LDH separator.
  • Evaluation 3 Average porosity measurement
  • Cross-section polishing of LDH separator by cross-section polisher (CP), and acquisition of 2 cross-sectional images of LDH separator at 50,000 times magnification by FE-SEM (ULTRA55, manufactured by Carl Zeiss) did.
  • the porosity of each of the two fields was calculated using image inspection software (HDdevrop, manufactured by MVTecSoftware), and the average value thereof was taken as the average porosity of the LDH separator.
  • the average porosity was measured in the vicinity of the surface of the LDH separator (a region having a depth of 1 to 4 ⁇ m from the surface) and in the center of the LDH separator.
  • Evaluation 4 Continuous charge test An accelerated test was conducted in which a measuring device 210 as shown in FIG. 2 was constructed to continuously grow zinc dendrites. Specifically, a rectangular parallelepiped container 212 made of ABS resin was prepared, and zinc poles 214a and copper poles 214b were arranged in the container 212 so as to be separated from each other by 0.5 cm and face each other.
  • the zinc pole 214a is a metal zinc plate
  • the copper pole 214b is a metal copper plate.
  • the LDH separator was coated with an epoxy resin adhesive along the outer periphery thereof and attached to a jig made of ABS resin having an opening in the center to form an LDH separator structure containing the LDH separator 216.
  • the jig and the LDH separator were sufficiently sealed with the above adhesive so as to ensure liquidtightness at the joint.
  • the LDH separator structure is arranged in the container 212 so that the first compartment 215a containing the zinc pole 214a and the second compartment 215b containing the copper pole 214b do not allow liquid communication with each other at a place other than the LDH separator 216. Isolated on.
  • an epoxy resin-based adhesive was used to bond the three outer edges of the LDH separator structure (that is, the three outer edges of the ABS resin jig) to the inner wall of the container 212 so as to ensure liquidtightness.
  • the joint portion between the separator structure containing the LDH separator 216 and the container 212 was sealed so as not to allow liquid communication.
  • a 5.4 mol / L KOH aqueous solution as an alkaline aqueous solution 218 was placed in the first compartment 215a and the second compartment 215b together with ZnO powder corresponding to the saturated solubility.
  • the zinc pole 214a and the copper pole 214b were connected to the negative electrode and the positive electrode of the constant current power supply, respectively, and a voltmeter was connected in parallel with the constant current power supply.
  • the water level of the alkaline aqueous solution 218 is such that the entire region of the LDH separator 216 is immersed in the alkaline aqueous solution 218, and the height of the LDH separator structure (including the jig) is high. It was set to the extent that it did not exceed the limit.
  • a constant current of 20 mA / cm 2 was continuously passed between the zinc pole 214a and the copper pole 214b for a maximum of 200 hours.
  • the value of the voltage flowing between the zinc pole 214a and the copper pole 214b was monitored with a voltmeter to confirm the presence or absence of a zinc dendrite short circuit (rapid voltage drop) between the zinc pole 214a and the copper pole 214b.
  • a short circuit does not occur for 100 hours or more (or 200 hours or more), it is determined as "no short circuit", and if a short circuit occurs in less than 100 hours (or less than 200 hours), it is determined as "with a short circuit”. did.
  • the He permeation test was performed as follows. First, the He permeability measuring system 310 shown in FIGS. 3A and 3B was constructed. In the He permeability measuring system 310, the He gas from the gas cylinder filled with the He gas is supplied to the sample holder 316 via the pressure gauge 312 and the flow meter 314 (digital flow meter), and the LDH held in the sample holder 316. The separator 318 was configured to be permeated from one surface to the other surface and discharged.
  • the sample holder 316 has a structure including a gas supply port 316a, a closed space 316b, and a gas discharge port 316c, and was assembled as follows. First, the adhesive 322 was applied along the outer circumference of the LDH separator 318 and attached to a jig 324 (made of ABS resin) having an opening in the center. Packing made of butyl rubber is arranged as sealing members 326a and 326b at the upper and lower ends of the jig 324, and support members 328a and 328b (manufactured by PTFE) having openings made of flanges from the outside of the sealing members 326a and 326b. ).
  • the sealed space 316b was partitioned by the LDH separator 318, the jig 324, the sealing member 326a, and the support member 328a.
  • the support members 328a and 328b were fastened tightly to each other by the fastening means 330 using screws so that the Hegas did not leak from the portion other than the gas discharge port 316c.
  • a gas supply pipe 334 was connected to the gas supply port 316a of the sample holder 316 thus assembled via a joint 332.
  • He gas was supplied to the He permeability measuring system 310 via the gas supply pipe 334, and was permeated through the LDH separator 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 permeation was calculated.
  • the calculation of He permeability is performed by the permeation amount F (cm 3 / min) of He gas per unit time, the differential pressure P (atm) applied to the LDH separator when the He gas permeates, and the film area S (cm) through which the He gas permeates. It was calculated by the formula of F / (P ⁇ S) 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, 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.
  • the ionic conductivity of the LDH separator in the electrolytic solution was measured as follows using the electrochemical measurement system shown in FIG.
  • the LDH separator sample S was sandwiched between both sides with a 1 mm thick silicone packing 440 and incorporated into a PTFE flange type cell 442 having an inner diameter of 6 mm.
  • As the electrodes 446 a nickel wire mesh of # 100 mesh was incorporated into the cell 442 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 444 a 5.4 M aqueous solution of KOH was filled in the cell 442.
  • the measurement was performed under the conditions of a frequency range of 1 MHz to 0.1 Hz and an applied voltage of 10 mV, and a section of the real number axis. was taken as the resistance of the LDH separator sample S.
  • the conductivity was determined using the resistance of the obtained LDH separator and the thickness and area of the LDH separator.
  • Example A1 (comparison) (1) Preparation of Polymer Porous Substrate A commercially available polyethylene microporous membrane having a porosity of 50%, an average pore diameter of 0.1 ⁇ m and a thickness of 20 ⁇ m was prepared as the polymer porous substrate, and 2.0 cm ⁇ 2. It was cut out to a size of 0 cm.
  • Alumina-titania sol coating on polymer porous substrate Atypical alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.) and titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) are mixed with Ti / Al (M6, manufactured by Taki Chemical Co., Ltd.).
  • the mixed sol was impregnated into the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed sol, pulling it up vertically, and drying it in a dryer at 90 ° C. for 5 minutes.
  • 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
  • the substrate was taken out of the closed container, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to form LDH in the pores of the porous substrate.
  • a composite material containing LDH was obtained.
  • Evaluation Results Evaluations 1 to 6 were performed on the obtained LDH separator. As a result of Evaluation 1, it was identified that the LDH separator of this example is LDH (hydrotalcite compound). The results of evaluations 2 to 6 were as shown in Table 1. As shown in Table 1, zinc dendrite short circuit did not occur in the continuous charging time up to 100 hours, but zinc dendrite short circuit occurred in the continuous charging time less than 200 hours.
  • Examples A2 and A3 (reference) LDH separators were prepared in the same manner as in Example A1 except that the drying temperature after impregnation with alumina / titaniasol in (2) was changed to the values shown in Table 1, and evaluated in the same manner.
  • LDH separator of this example is LDH (hydrotalcite compound).
  • the results of evaluations 2 to 6 were as shown in Table 1.
  • zinc dendrite short circuit did not occur even in the continuous charging time of 200 hours or more.
  • FIGS. 5A and 5B show cross-sectional FE-SEM images of the LDH separator obtained in the evaluation 3 of Example A3 near the surface and in the center, respectively.
  • Example A4 (comparison) The LDH separator was prepared and evaluated in the same manner as in Example A1 except that the densification was not performed by the roll press in (5) above. As a result of Evaluation 1, it was identified that the LDH separator of this example is LDH (hydrotalcite compound). The results of evaluations 2 to 6 were as shown in Table 1. As shown in Table 1, in Rating 4, a zinc dendrite short circuit occurred with a continuous charge time of less than 100 hours.
  • Examples A5 and A6 (reference) LDH separators were prepared and evaluated in the same manner as in Example A1 except for the following a) to c).
  • a) The drying temperature after impregnation with alumina / titaniasol in (2) above was changed to the value shown in Table 1.
  • LDH separator of this example is LDH (hydrotalcite compound).
  • the results of evaluations 2 to 6 were as shown in Table 1. As shown in Table 1, in each of Examples A5 and A6, zinc dendrite short circuit did not occur even in the continuous charging time of 200 hours or more.
  • Example B1 to B8 Examples B1 to B7 shown below are reference examples relating to LDH-like compound separators, while Example B8 is a comparative example relating to LDH separators.
  • LDH-like compound separators and LDH separators are collectively referred to as hydroxide ion conduction separators.
  • the evaluation method of the hydroxide ion conduction separator produced in the following example was as follows.
  • Evaluation 1 Observation of surface microstructure The surface microstructure of the hydroxide ion conduction separator was observed with an acceleration voltage of 10 to 20 kV using a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL Ltd.).
  • Evaluation 2 STEM analysis of layered structure The layered structure of the hydroxide ion conduction separator was observed at an acceleration voltage of 200 kV using a scanning transmission electron microscope (STEM) (product name: JEM-ARM200F, manufactured by JEOL).
  • STEM scanning transmission electron microscope
  • Evaluation 3 Elemental analysis evaluation (EDS) The composition of the surface of the hydroxide ion conduction separator was analyzed using an EDS analyzer (device name: X-act, manufactured by Oxford Instruments), and the composition ratio of Mg: Ti: Y: Al (atomic ratio). ) was calculated. In this analysis, 1) an image is captured at an acceleration voltage of 20 kV and a magnification of 5,000 times, 2) three-point analysis is performed at intervals of about 5 ⁇ m in the point analysis mode, and 3) 1) and 2) above are performed once more. It was repeated, and 4) it was performed by calculating the average value of a total of 6 points.
  • EDS Elemental analysis evaluation
  • Evaluation 4 X-ray diffraction measurement With an X-ray diffractometer (Rigaku, RINT TTR III), a hydroxide ion conduction separator under measurement conditions of voltage: 50 kV, current value: 300 mA, and measurement range: 5 to 40 °. The crystal phase of was measured to obtain an XRD profile. In addition, the interlayer distance of the layered crystal structure was determined by the Bragg's formula using 2 ⁇ corresponding to the peak derived from the LDH-like compound.
  • Evaluation 5 He Permeation Measurement A He permeation test was performed in the same procedure as in Evaluation 5 of Examples A1 to A6 in order to evaluate the denseness of the hydroxide ion conduction separator from the viewpoint of He permeability.
  • the measurement was performed under the conditions of a frequency range of 1 MHz to 0.1 Hz and an applied voltage of 10 mV, and a section of the real number axis.
  • a frequency range of 1 MHz to 0.1 Hz and an applied voltage of 10 mV was taken as the resistance of the hydroxide ion conduction separator sample S.
  • the same measurement as above was performed with the configuration without the hydroxide ion conduction separator sample S, and the blank resistance was also determined.
  • the difference between the resistance of the hydroxide ion conduction separator sample S and the blank resistance was taken as the resistance of the hydroxide ion conduction separator.
  • the conductivity was determined using the resistance of the obtained hydroxide ion conductive separator and the thickness and area of the hydroxide ion conductive separator.
  • Evaluation 7 Alkali resistance evaluation A 5.4 M KOH aqueous solution containing zinc oxide at a concentration of 0.4 M was prepared. 0.5 mL of the prepared KOH aqueous solution and a hydroxide ion conduction separator sample having a size of 2 cm square were placed in a closed container made of Teflon (registered trademark). Then, after holding at 90 ° C. for 1 week (that is, 168 hours), the hydroxide ion conduction separator sample was taken out from the closed container. The removed hydroxide ion conduction separator sample was dried overnight at room temperature. For the obtained sample, the He permeability was calculated by the same method as in Evaluation 5, and it was determined whether or not there was a change in the He permeability before and after the alkali immersion.
  • Evaluation 8 Evaluation of dendrite resistance (cycle test) A cycle test was conducted as follows to evaluate the short-circuit suppression effect (dendrite resistance) caused by zinc dendrite of the hydroxide ion conduction separator. First, each of the positive electrode (containing nickel hydroxide and / or nickel oxyhydroxide) and the negative electrode (containing zinc and / or zinc oxide) was wrapped in a non-woven fabric, and the current extraction terminal was welded. The positive electrode and the negative electrode thus prepared were opposed to each other via a hydroxide ion conduction separator, sandwiched between the laminated films provided with current extraction ports, and the three sides of the laminated film were heat-sealed.
  • An electrolytic solution (a solution in which 0.4 M zinc oxide is dissolved in a 5.4 M KOH aqueous solution) is added to the cell container with an open top thus obtained, and the electrolytic solution is sufficiently applied to the positive electrode and the negative electrode by vacuuming or the like. Infiltrated. Then, the remaining one side of the laminated film was also heat-sealed to form a simple sealed cell.
  • a charging / discharging device TOSCAT3100 manufactured by Toyo System Co., Ltd.
  • chemical conversion was carried out for a simple sealed cell by 0.1C charging and 0.2C discharging. Then, a 1C charge / discharge cycle was carried out.
  • Example B1 (reference) (1) Preparation of Polymer Porous Substrate A commercially available polyethylene microporous membrane having a porosity of 50%, an average pore diameter of 0.1 ⁇ m and a thickness of 20 ⁇ m was prepared as the polymer porous substrate, and 2.0 cm ⁇ 2. It was cut out to a size of 0 cm.
  • Titania sol coating on a polymer porous substrate A titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of a sol solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • the substrate was taken out of the closed container, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to form LDH-like compounds in the pores of the porous substrate.
  • an LDH-like compound separator was obtained.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B1 was as shown in FIG. 6A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg and Ti, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator.
  • the composition ratios (atomic ratios) of Mg and Ti on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 2.
  • Figure 6B shows the XRD profile obtained in Example B1.
  • the two peaks observed at 20 ⁇ 2 ⁇ ° ⁇ 25 in the XRD profile are peaks derived from polyethylene constituting the porous substrate.
  • the interlayer distance of the layered crystal structure in the LDH-like compound was 0.94 nm.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and excellent alkali resistance that the He permeability does not change even after alkali immersion at a high temperature of 90 ° C for one week. Was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B2 (reference) Preparation and evaluation of LDH-like compound separator in the same manner as in Example B1 except that the raw material aqueous solution of (3) above was prepared as follows and the temperature of the hydrothermal treatment in (4) above was set to 90 ° C. Was done.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B2 was as shown in FIG. 7A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg and Ti, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator.
  • the composition ratios (atomic ratios) of Mg and Ti on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 2.
  • Figure 7B shows the XRD profile obtained in Example B2.
  • the two peaks observed at 20 ⁇ 2 ⁇ ° ⁇ 25 in the XRD profile are peaks derived from polyethylene constituting the porous substrate.
  • the interlayer distance of the layered crystal structure in the LDH-like compound was 1.2 nm.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and excellent alkali resistance that the He permeability does not change even after alkali immersion at a high temperature of 90 ° C for one week. Was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B3 (reference) LDH-like compound separators were prepared and evaluated in the same manner as in Example B1 except that titania-itriasol coating on a polymer porous substrate was performed as follows instead of (2) above.
  • Titanium oxide sol solution M6, manufactured by Taki Chemical Co., Ltd.
  • the obtained mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B3 was as shown in FIG. 8A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Ti and Y, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator.
  • the composition ratios (atomic ratios) of Mg, Ti and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 2.
  • Figure 8B shows the XRD profile obtained in Example B3.
  • the two peaks observed at 20 ⁇ 2 ⁇ ° ⁇ 25 in the XRD profile are peaks derived from polyethylene constituting the porous substrate.
  • the interlayer distance of the layered crystal structure in the LDH-like compound was 1.1 nm.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is less than 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B4 (reference) The LDH-like compound separator was prepared and evaluated in the same manner as in Example B1 except that the titania-itria-alumina sol coat was applied to the polymer porous substrate instead of the above (2) as follows.
  • the mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B4 was as shown in FIG. 9A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti and Y, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator.
  • the two peaks observed at 20 ⁇ 2 ⁇ ° ⁇ 25 of the XRD profile are peaks derived from polyethylene constituting the porous substrate.
  • the interlayer distance of the layered crystal structure in the LDH-like compound was 1.1 nm.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B5 (reference) Examples except that the titania-itria sol coating on the polymer porous substrate instead of the above (2) was performed as follows, and the raw material aqueous solution of the above (3) was prepared as follows. LDH-like compound separators were prepared and evaluated in the same manner as in B1.
  • Titanium oxide sol solution M6, manufactured by Taki Chemical Co., Ltd.
  • the obtained mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B5 was as shown in FIG. 10A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Ti and Y, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator.
  • the composition ratios (atomic ratios) of Mg, Ti and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 2.
  • Figure 10B shows the XRD profile obtained in Example B5.
  • the two peaks observed at 20 ⁇ 2 ⁇ ° ⁇ 25 in the XRD profile are peaks derived from polyethylene constituting the porous substrate.
  • the interlayer distance of the layered crystal structure in the LDH-like compound was 0.99 nm.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B6 (reference) Example B1 except that the titania-alumina sol coat was applied to the polymer porous substrate instead of the above (2) as follows, and the raw material aqueous solution of the above (3) was prepared as follows.
  • the LDH-like compound separator was prepared and evaluated in the same manner as above.
  • Ti / Al (molar ratio) 18.
  • the mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • magnesium nitrate hexahydrate Mg (NO 3 ) 2.6H 2 O , manufactured by Kanto Chemical Co., Ltd.
  • yttrium nitrate n hydrate Y (NO 3 ) 3. nH 2 O, Fujifilm Wako Jun Yaku Co., Ltd.
  • urea ((NH 2 ) 2CO , manufactured by Sigma Aldrich) were prepared.
  • Magnesium nitrate hexahydrate was weighed to 0.0015 mol / L and placed in a beaker.
  • yttrium nitrate n hydrate was weighed to 0.0075 mol / L and placed in the beaker, ion-exchanged water was added thereto to make the total volume 75 ml, and the obtained solution was stirred.
  • Urea weighed at a ratio of urea / NO 3- ( molar ratio) 9.8 was added to this solution, and the mixture was further stirred to obtain an aqueous raw material solution.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B6 was as shown in FIG. 11A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti and Y, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator.
  • the two peaks observed at 20 ⁇ 2 ⁇ ° ⁇ 25 in the XRD profile are peaks derived from polyethylene constituting the porous substrate.
  • the interlayer distance of the layered crystal structure in the LDH-like compound was 1.2 nm.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B7 (reference) The LDH-like compound separator was prepared and evaluated in the same manner as in Example B6 except that the raw material aqueous solution of (3) was prepared as follows.
  • magnesium nitrate hexahydrate Mg (NO 3 ) 2.6H 2 O , manufactured by Kanto Chemical Co., Ltd.
  • yttrium nitrate n hydrate Y (NO 3 ) 3. nH 2 O, Fujifilm Wako Jun Yaku Co., Ltd.
  • urea ((NH 2 ) 2CO , manufactured by Sigma Aldrich) were prepared.
  • Magnesium nitrate hexahydrate was weighed to 0.0075 mol / L and placed in a beaker.
  • yttrium nitrate n hydrate was weighed to 0.0075 mol / L and placed in the beaker, ion-exchanged water was added thereto to make the total volume 75 ml, and the obtained solution was stirred.
  • Urea weighed at a ratio of urea / NO 3- ( molar ratio) 25.6 was added to this solution, and the mixture was further stirred to obtain an aqueous raw material solution.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll press) obtained in Example B7 was as shown in FIG. -Evaluation 2: From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti and Y, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Mg, Al, Ti and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 2.
  • -Evaluation 5 As shown in Table 2, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 2, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 2, excellent dendrite resistance was confirmed, in which there was no short circuit due to zinc dendrite even after 300 cycles.
  • Example B8 (comparison) The LDH separator was prepared and evaluated in the same manner as in Example B1 except that the alumina sol coat was applied instead of the above (2) as follows.
  • Alumina sol coating on polymer porous substrate Amorphous alumina sol (Al-ML15, manufactured by TAKI CHEMICAL CO., LTD.) was applied to the substrate prepared in (1) above by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of amorphous alumina sol, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH separator (before roll press) obtained in Example B8 was as shown in FIG. 13A.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg and Al, which are LDH constituent elements, were detected on the surface of the LDH separator. The composition ratios (atomic ratios) of Mg and Al on the surface of the LDH separator calculated by EDS elemental analysis are as shown in Table 2.
  • -Evaluation 4 Figure 13B shows the XRD profile obtained in Example B8.
  • Examples C1 to C9 shown below are reference examples relating to LDH-like compound separators.
  • the method for evaluating the LDH-like compound separator produced in the following example is, except that the composition ratio (atomic ratio) of Mg: Al: Ti: Y: additive element M was calculated in evaluation 3, Examples B1 to B8. It was the same as.
  • Example C1 (reference) (1) Preparation of Polymer Porous Substrate A commercially available polyethylene microporous membrane having a porosity of 50%, an average pore diameter of 0.1 ⁇ m and a thickness of 20 ⁇ m was prepared as the polymer porous substrate, and 2.0 cm ⁇ 2. It was cut out to a size of 0 cm.
  • the mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 1 The SEM image of the surface microstructure of the LDH-like compound separator (before roll pressing) obtained in Example C1 was as shown in FIG. -Evaluation 2: From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Al, Ti, Y and In, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Al, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and excellent alkali resistance that the He permeability does not change even after alkali immersion at a high temperature of 90 ° C for one week. Was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C2 (reference) In the addition of indium by the dipping treatment of (6) above, LDH-like compound separators were prepared and evaluated in the same manner as in Example C1 except that the dipping treatment time was changed to 24 hours.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Al, Ti, Y and In, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Al, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and excellent alkali resistance that the He permeability does not change even after alkali immersion at a high temperature of 90 ° C for one week. Was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C3 (reference) LDH-like compound separators were prepared and evaluated in the same manner as in Example C1 except that titania-itria sol coat was applied instead of (2) above.
  • Titanium oxide sol solution M6, manufactured by Taki Chemical Co., Ltd.
  • the obtained mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Ti, Y and In, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is less than 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C4 Same as Example C1 except that the raw material aqueous solution (II) of (5) was prepared as follows, and bismuth was added by dipping treatment instead of (6) as follows. LDH-like compound separators were prepared and evaluated.
  • the substrate was taken out of the closed container, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to obtain an LDH-like compound separator to which bismuth was added.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti, Y and Bi, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Mg, Al, Ti, Y and Bi on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C5 (reference) LDH-like compound separators were prepared and evaluated in the same manner as in Example C4, except that the time of the dipping treatment was changed to 12 hours in the addition of bismuth by the dipping treatment.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti, Y and Bi, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Mg, Al, Ti, Y and Bi on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in evaluation 5, and excellent resistance to change in He permeability even after alkali immersion at a high temperature of 90 ° C for one week. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C6 (reference) In the addition of bismuth by the above dipping treatment, LDH-like compound separators were prepared and evaluated in the same manner as in Example C4, except that the dipping treatment time was changed to 24 hours.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti, Y and Bi, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Mg, Al, Ti, Y and Bi on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in evaluation 5, and excellent resistance to change in He permeability even after alkali immersion at a high temperature of 90 ° C for one week. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C7 Same as Example C1 except that the raw material aqueous solution (II) of (5) was prepared as follows, and calcium was added by dipping treatment instead of (6) as follows. LDH-like compound separators were prepared and evaluated.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti, Y and Ca, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Mg, Al, Ti, Y and Ca on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in evaluation 5, and excellent resistance to change in He permeability even after alkali immersion at a high temperature of 90 ° C for one week. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C8 (reference) Same as Example C1 except that the raw material aqueous solution (II) of (5) was prepared as follows, and strontium was added by dipping treatment instead of (6) as follows. LDH-like compound separators were prepared and evaluated.
  • Strontium nitrate (Sr (NO 3 ) 2 ) was prepared as a raw material.
  • Strontium nitrate was weighed to 0.015 mol / L and placed in a beaker, and ion-exchanged water was added thereto to make the total volume 75 ml. The obtained solution was stirred to obtain a raw material aqueous solution (II).
  • the substrate was taken out of the closed container, washed with ion-exchanged water, and dried at 70 ° C. for 10 hours to obtain an LDH-like compound separator to which strontium was added.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti, Y and Sr, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Mg, Al, Ti, Y and Sr on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Example C9 Same as Example C1 except that the raw material aqueous solution (II) of (5) was prepared as follows, and barium was added by dipping treatment instead of (6) as follows. LDH-like compound separators were prepared and evaluated.
  • -Evaluation 2 From the result that layered plaids could be confirmed, it was confirmed that the portion of the LDH-like compound separator other than the porous substrate was a compound having a layered crystal structure.
  • -Evaluation 3 As a result of EDS elemental analysis, Al, Ti, Y and Ba, which are constituent elements of the LDH-like compound, were detected on the surface of the LDH-like compound separator. The composition ratios (atomic ratios) of Al, Ti, Y and Ba on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 3.
  • -Evaluation 5 As shown in Table 3, it was confirmed that the He permeability was 0.0 cm / min ⁇ atm, which was extremely high density.
  • -Evaluation 6 As shown in Table 3, high ionic conductivity was confirmed.
  • -Evaluation 7 The He permeability after alkali immersion is 0.0 cm / min ⁇ atm as in Evaluation 5, and the He permeability does not change even after alkaline immersion at a high temperature of 90 ° C for one week, which is an excellent resistance. Alkaline was confirmed.
  • -Evaluation 8 As shown in Table 3, excellent dendrite resistance was confirmed, with no short circuit due to zinc dendrite even after 300 cycles.
  • Examples D1 and D2 shown below are reference examples regarding LDH-like compound separators.
  • the method for evaluating the LDH-like compound separator produced in the following example is the same as in Examples B1 to B8 except that the composition ratio (atomic ratio) of Mg: Al: Ti: Y: In was calculated in evaluation 3. And said.
  • Example D1 (reference) (1) Preparation of Polymer Porous Substrate A commercially available polyethylene microporous membrane having a porosity of 50%, an average pore diameter of 0.1 ⁇ m and a thickness of 20 ⁇ m was prepared as the polymer porous substrate, and 2.0 cm ⁇ 2. It was cut out to a size of 0 cm.
  • the mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • magnesium nitrate hexahydrate Mg (NO 3 ) 2.6H 2 O , manufactured by Kanto Chemical Co., Ltd.
  • indium sulfate n hydrate In 2 (SO 4 ) 3 . nH 2 O, manufactured by Fujifilm Wako Junyaku Co., Ltd.
  • urea ((NH 2 ) 2 CO, manufactured by Sigma Aldrich) were prepared.
  • the substrate is taken out of the closed container, washed with ion-exchanged water, dried at 70 ° C. for 10 hours, and the LDH-like compound and In (OH) 3 containing functional layer are contained in the pores of the porous substrate. Was formed. Thus, an LDH-like compound separator was obtained.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Al, Ti, Y and In, which are constituent elements of the LDH-like compound or In (OH) 3 , were detected on the surface of the LDH-like compound separator. In addition, In, which is a constituent element of In (OH) 3 , was detected in the cube-shaped crystals existing on the surface of the LDH-like compound separator.
  • the composition ratios (atomic ratios) of Mg, Al, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 4.
  • -Evaluation 4 From the peak of the obtained XRD profile, it was identified that In (OH) 3 was present in the LDH-like compound separator.
  • Example D2 (reference) LDH-like compound separators were prepared and evaluated in the same manner as in Example D1 except that titania-itria sol coat was applied instead of (2) above.
  • Titanium oxide sol solution M6, manufactured by Taki Chemical Co., Ltd.
  • the obtained mixed solution was applied to the substrate prepared in (1) above by dip coating. Dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling it up vertically, and drying it at room temperature for 3 hours.
  • -Evaluation 3 As a result of EDS elemental analysis, Mg, Ti, Y and In, which are constituent elements of the LDH-like compound or In (OH) 3 , were detected on the surface of the LDH-like compound separator. In addition, In, which is a constituent element of In (OH) 3 , was detected in the cube-shaped crystals existing on the surface of the LDH-like compound separator.
  • the composition ratios (atomic ratios) of Mg, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis are as shown in Table 4.
  • -Evaluation 4 From the peak of the obtained XRD profile, it was identified that In (OH) 3 was present in the LDH-like compound separator.

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Abstract

L'invention concerne un séparateur conducteur d'ions hydroxyde qui présente une excellente résistance aux alcalis, et peut supprimer plus efficacement un court-circuit provoqué par une dendrite de zinc et qui est supérieur aux séparateurs de type LDH. Ce séparateur de composé de type LDH comprend : un substrat poreux qui est constitué d'un matériau polymère ; et un composé de type hydroxyde double lamellaire (LDH) qui remplit les pores du substrat poreux. La porosité moyenne de la section centrale du séparateur de composé de type LDH dans la direction de l'épaisseur est inférieure à la porosité moyenne de la section à proximité de la surface du séparateur de composé de type LDH.
PCT/JP2021/031344 2020-11-30 2021-08-26 Séparateur de composé de type hydroxyde double lamellaire (de type ldh) et batterie secondaire au zinc WO2022113448A1 (fr)

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JP2021572068A JP7057866B1 (ja) 2020-11-30 2021-08-26 Ｌｄｈ様化合物セパレータ及び亜鉛二次電池
CN202180062519.0A CN116325247A (zh) 2020-11-30 2021-08-26 类ldh化合物隔板及锌二次电池
DE112021005103.2T DE112021005103T5 (de) 2020-11-30 2021-08-26 Separator mit ldh-ähnlicher verbindung und zink-sekundärbatterie
US18/180,276 US20230231154A1 (en) 2020-11-30 2023-03-08 Ldh-like compound separator and zinc secondary battery

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019124214A1 (fr) * 2017-12-18 2019-06-27 日本碍子株式会社 Séparateur ldh et batterie secondaire au zinc
WO2020255856A1 (fr) * 2019-06-19 2020-12-24 日本碍子株式会社 Séparateur conducteur d'ions hydroxyde et batterie secondaire au zinc

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019124214A1 (fr) * 2017-12-18 2019-06-27 日本碍子株式会社 Séparateur ldh et batterie secondaire au zinc
WO2020255856A1 (fr) * 2019-06-19 2020-12-24 日本碍子株式会社 Séparateur conducteur d'ions hydroxyde et batterie secondaire au zinc

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GÁBOR VARGAA, MÁRTON SZABADOSA, ÁKOS KUKOVECZ, ZOLTÁN KÓNYA, TAMÁS VARGA, PÁL SIPOS, ISTVÁN PÁLINKÓ: "Layered double alkoxides a novel group of layered double hydroxides without water content.", MATERIALS RESEARCH LETTERS., vol. 8, no. 2, pages 68 - 74, XP055934985, ISSN: 2166-3831, DOI: 10.1080/21663831.2019.1700199 *

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