DE112021005103T5 - SEPARATOR WITH LDH-LIKE CONNECTION AND ZINC SECONDARY BATTERY - Google Patents

Abstract

There is provided a hydroxide ion conductive separator which is excellent in alkali resistance and further capable of more effectively suppressing short circuits due to zinc dendrites, which is superior to the LDH separator. This LDH-like compound separator includes a porous substrate made of a polymer material; and a layered double hydroxide-like (LDH-like) compound with which the pores of the porous substrate are clogged. A central region along the thickness of the LDH-like compound separator has a lower average porosity than peripheral regions along the thickness of the LDH-like compound separator.

Description

TECHNICAL AREA

The present invention relates to an LDH-like compound separator and a zinc secondary battery.

STATE OF THE ART

For zinc secondary batteries such. B. nickel-zinc secondary batteries and air-zinc secondary batteries, it is known that during a charging mode, metallic zinc dendrites deposit on the negative electrodes, penetrate voids in the separators, which are made of non-woven fabric, for example, and reach the positive electrodes, resulting in leads to a short circuit. The short circuit caused by such zinc dendrites occurs during repeated charge/discharge operations, and leads to a shortening of the life of zinc secondary batteries.

In order to solve such a problem, there have been proposed zinc secondary batteries containing layered double hydroxide (LDH) separators which selectively permeate hydroxide ions while blocking the penetration of zinc dendrites. For example, Patent Literature 1 ( WO2013/118561 ) a nickel-zinc secondary battery including an LDH separator interposed between a positive electrode and a negative electrode. Patent Literature 2 ( WO 2016/076047 ) discloses a separator structure including an LDH separator fitted into or bonded to a resin frame and having sufficient density to restrict gas and/or water permeation. Patent Literature 2 also discloses that the LDH separator may be a composite having a porous substrate. In addition, Patent Literature 3 discloses ( WO2016/067884 ) various methods of forming a dense LDH membrane on the surface of a porous substrate to obtain a composite material (an LDH separator). These methods include the steps of: uniformly bonding an initiating material capable of initiating crystal growth of LDH to the porous substrate; and then subjecting the porous substrate to hydrothermal treatment in an aqueous raw material solution to form a dense LDH membrane on the surface of the porous substrate.

Meanwhile, Patent Literature 4 ( WO2019/124214 ) an LDH separator comprising a porous substrate made of a polymeric material; and a layered double hydroxide (LDH) with which the pores of the porous substrate are plugged, wherein a central region along the thickness of the LDH separator has a lower mean porosity than peripheral regions along the thickness of the LDH separator.

REFERENCE LIST

PATENT LITERATURE

• Patent Literature 1: WO2013/118561
• Patent Literature 2: WO2016/076047
• Patent Literature 3: WO2016/067884
• Patent Literature 4: WO2019/124214

SUMMARY OF THE INVENTION

In the case where zinc secondary batteries such as nickel-zinc batteries are constructed with an LDH separator as described above, the problem such as B. a short circuit caused by zinc dendrites can be effectively prevented to a certain extent. However, further improvement is desired for a preventive effect of the short circuit caused by the dendrites.

The inventors have now found that by using an LDH-like compound described below as a hydroxide ion-conductive substance instead of conventional LDHs, it is possible to provide a hydroxide ion-conductive separator (LDH-like compound separator) excellent in alkali resistance and further is capable of more effectively suppressing short circuits due to zinc dendrites. The inventors also found that by clogging the pores of a porous polymeric substrate with an LDH-like compound so that a medium region along the thickness of the substrate has a lower mean porosity than peripheral regions along the thickness of the substrate, it is possible to provide an LDH-like compound separator which can more effectively prevent short circuits caused by zinc dendrites.

Accordingly, an object of the present invention is to provide a hydroxide ion conductive separator which is excellent in alkali resistance and capable of suppressing short circuits due to zinc dendrites more effectively, which is superior to the LDH separator.

According to one embodiment of the present invention, there is provided an LDH-like compound separator comprising a porous substrate made of a polymeric material; and a layered double hydroxide-like (LDH-like) compound with which the pores of the porous substrate are plugged, wherein a central region along the thickness of the LDH-like compound separator has a lower mean porosity than peripheral regions along the thickness of the separator with LDH-like connection.

According to another embodiment of the present invention, there is provided a zinc secondary battery including the LDH-like compound separator.

According to another embodiment of the present invention, there is provided a solid-state alkaline fuel cell comprising the LDH-like compound separator.

character list

• 1 Fig. 12 is a conceptual schematic cross-sectional view showing an LDH-like compound separator.
• 2 Fig. 12 is a schematic cross-sectional view of a measuring device used in the dendrite short circuit test in Examples A1 to A4.
• 3A 14 is a conceptual view showing an example system for measuring helium permeability used in Examples A1 to D2.
• 3B is a schematic cross-sectional view of a sample holder and its peripheral configuration used in FIG 3A shown measuring system is used.
• 4 Fig. 12 is a schematic cross-sectional view showing an electrochemical measuring system used in Examples A1 to D2.
• 5A Fig. 12 is a cross-sectional field emission scanning electron microscope (FE-SEM) cross-sectional image of the peripheral portion (the portion at a depth of 1 to 4 µm from the surface) of an LDH separator produced in Example A3. In the drawing, the gray areas correspond to the porous polymer substrate, the white areas to the LDH, and the black areas to the remaining pores.
• 5B Figure 12 is a cross-sectional FE-SEM image of the center portion of the LDH separator produced in Example A3. In the drawing, the gray areas correspond to the porous polymer substrate, the white areas to the LDH, and the black areas to the remaining pores.
• 6A Figure 12 is an SEM image of a surface of an LDH-like compound produced in Example B1.
• 6B is the result of X-ray diffraction of the LDH-like compound separator produced in Example B1.
• 7A Figure 12 is an SEM image of a surface of an LDH-like compound separator produced in Example B2.
• 7B is the result of X-ray diffraction of the LDH-like compound separator produced in Example B2.
• 8A Figure 12 is an SEM image of a surface of an LDH-like compound separator produced in Example B3.
• 8B is the result of X-ray diffraction of the LDH-like compound separator produced in Example B3.
• 9A Fig. 12 is an SEM image of a surface of an LDH-like compound separator produced in Example B4.
• 9B is the result of X-ray diffraction of the LDH-like compound separator produced in Example B4.
• 10A Figure 12 is an SEM image of a surface of an LDH-like compound separator produced in Example B5.
• 10B is the result of X-ray diffraction of the LDH-like compound separator produced in Example B5.
• 11A Fig. 12 is an SEM image of a surface of an LDH-like compound separator produced in Example B6.
• 11B is the result of X-ray diffraction of the LDH-like compound separator produced in Example B6.
• 12 Fig. 12 is an SEM image of a surface of an LDH-like compound separator produced in Example B7.
• 13A Figure 13 is an SEM image of a surface of an LDH separator produced in Example B8 (Comparative).
• 13B is the result of X-ray diffraction of the LDH separator produced in example B8 (comparative).
• 14 Figure 12 is an SEM image of a surface of the LDH-like compound separator produced in Example C1.
• 15 Figure 12 is an SEM image of a surface of the LDH-like compound separator produced in Example D1.
• 16 Figure 12 is an SEM image of a surface of the LDH-like compound separator produced in Example D2.

DETAILED DESCRIPTION OF THE INVENTION

Separator with LDH-like connection

As shown in a schematic cross-sectional view in 1 shown, an LDH-like compound separator 10 of the present invention includes a porous substrate 12 and a layered double hydroxide-like (LDH-like) compound 14. The "LDH-like compound separator" is defined herein as a separator comprising an LDH -like compound and configured to selectively pass hydroxide ions solely using the hydroxide ion conductivity of the LDH-like compound. The "LDH-like compound" is defined herein as a hydroxide and/or an oxide with a layered crystal structure that cannot be referred to as LDH, but is analogous to LDH, and for which no peak assignable to LDH is detected in an X-ray diffraction method . Although individual regions of the LDH-like compound 14 are shown in a two-dimensional cross-section of the LDH-like compound separator 10 in 1 between the top and bottom of the LDH-like compound separator 10 are apparently discontinuous, the areas of the LDH-like compound 14 are in the three-dimensional geometry containing the depth between the top and bottom of the LDH-like compound separator 10 , continuous, which ensures the hydroxide ion conductivity of the separator 10 with LDH-like compound. The porous substrate is made of a polymeric material. The pores of the porous substrate 12 are clogged with the LDH-like compound 14 . In this connection, the pores of the porous substrate 12 are not completely clogged with the LDH-like compound 14, and some pores P which are not clogged with the LDH-like compound remain. From the viewpoint of such remaining pores P, the LDH-like compound separator 10 can be evaluated by an intermediate porosity. A central region 10a along the thickness of the LDH-like compound separator 10 has a lower average porosity than peripheral regions 10b along the thickness of the LDH-like compound separator. In other words, the LDH-like compound separator 10 of the present invention has an uneven distribution of the remaining pores P along the thickness. More specifically, the central area 10a has a high density, while the peripheral areas 10b have a low density. In this way, the pores of the porous polymer substrate 12 are plugged with the LDH-like compound 14 such that the central region 10a along the thickness of the porous substrate 12 has a lower mean porosity than the peripheral regions 10b along the thickness of the porous substrate 12. The LDH-like compound separator 10 can thereby be provided such that short circuits caused by zinc dendrites are prevented more effectively can become. In a conventional separator, the intrusion of zinc dendrites is believed to take place by the following mechanism: (i) zinc dendrites invade voids or defects contained in the separator; (ii) the dendrites grow or spread while expanding the voids or defects in the separator; and (iii) the dendrites eventually penetrate the separator. In contrast, the LDH-like compound separator 10 of the present invention has the central region 10a with high density and the peripheral regions 10b with low density. Thus, the peripheral portions 10b, which have a higher average porosity than the central portion 10a, can serve as buffer layers against the penetration of the zinc dendrites and arrest the growth and spread of the dendrites. As a result, the propagation of the zinc dendrites along the thickness of the LDH-like compound separator 10 (particularly, the penetration of the zinc dendrites through the central portion 10a) can be blocked significantly. In this way, short circuits caused by the zinc dendrites can be prevented more effectively. In particular, by using an LDH-like compound described below as a hydroxide ion conductive substance instead of conventional LDHs, it is possible to provide a hydroxide ion conductive separator (LDH-like compound separator) excellent in alkali resistance and further capable , to effectively suppress short circuits due to zinc dendrites

The LDH-like compound separator 10 of the present invention has excellent flexibility and strength and desired ionic conductivity based on the hydroxide ionic conductivity of the LDH-like compound 14 . The flexibility and the strength are caused by those of the porous polymer substrate of the LDH-like compound separator 10 itself. In other words, the separator 10 is densified with LDH-like compound in such a way that the pores of the porous polymer substrate 12 are sufficiently clogged with the LDH-like compound 14 and the porous polymer substrate 12 and the LDH-like compound 14 are highly in a high quality composite material are integrated, whereby the high rigidity and low ductility caused by the LDH-like compound 14, which is a ceramic material, can be offset or reduced by the high flexibility and high strength of the porous polymer substrate 12.

As described above, a central region 10a along the thickness of the LDH-like compound separator 10 has a smaller average porosity than peripheral regions 10b along the thickness of the LDH-like compound separator. In this specification, the central region 10a refers to the portion located in the center when the LDH-like compound separator 10 is divided into three equal portions in the thickness direction, and the peripheral regions 10b refer to the portions in the vicinity of the faces (i.e., the portions outside the central region 10a) when the LDH-like compound separator 10 is divided into three equal portions in the thickness direction. Preferably, the peripheral portions 10b have an average porosity of 3% or more and the central portion 10a has an average porosity of 2% or less. More preferably, the peripheral portions 10b have an average porosity ranging from 3% to 15%, and the central portion 10a has an average porosity of 1% or less. Even more preferably, the peripheral regions 10b have an average porosity ranging from 5% to 10% and the central region 10a has an average porosity ranging from 0.01% to 1%. The central area 10a and the peripheral areas 10b having intermediate porosities in such areas can better arrest the growth of the zinc dendrites in the peripheral areas 10b. In this way, short circuits caused by the zinc dendrites can be curbed more effectively. A significantly high ion conductivity of the separator 10 with LDH-like compound can be achieved. Thus, the LDH-like compound separator 10 can conduct hydroxide ions well. The mean porosity can be determined by a) polishing a cross-sectional area of the LDH-like compound separator with a cross-sectional polisher (CP), b) taking two frames of a functional layer at a magnification of 50,000x with a field emission scanning electron microscope (FE-SEM ), c) calculating the porosities of the two fields with an image examination software (e.g. HDevelop from MVTec Software) based on the data of the recorded cross-sectional images and d) averaging the calculated porosities.

The LDH-like compound separator 10 has an ionic conductivity of preferably 0.1 mS/cm or more, more preferably 1.0 mS/cm or more, still more preferably 1.5 mS/cm or more, particularly preferably 2.0 mS/cm or more. Such a range allows the LDH-like compound separator to fully function as a hydroxide ion conductive separator. Since higher ionic conductivity is preferred, the LDH-like compound separator may have any upper limit of ionic conductivity, for example, 10 mS/cm. The ionic conductivity is calculated from the resistance, thickness and area of the LDH-like compound separator. The resistance of the LDH-like connection separator 10 is measured in a frequency range from 1 MHz to 0.1 Hz and at an applied voltage of 10 mV using an electrochemical measurement system (potentio-galvanostat frequency response analyzer) for the LDH-like compound separator 10 immersed in a KOH aqueous solution of a predetermined concentration (for example, 5.4 M) submerged is measured and the intersection above the real axis can be determined as the resistance of the separator with LDH-like connection.

The LDH-like compound separator 10 contains a layered double hydroxide-like compound (LDH-like compound) 14 and can insulate a positive electrode plate from a negative electrode plate and ensures hydroxide ion conductivity between them in a zinc secondary battery. The LDH-like compound separator 10 functions as a hydroxide ion conductive separator. The preferred LDH-like compound separator 10 exhibits gas impermeability and/or water impermeability. In other words, the LDH-like compound separator 10 is preferably densified to a degree that it exhibits gas impermeability and/or water impermeability. The term "gas impermeability" throughout the specification indicates that no bubbling of helium gas is observed on one side of a sample when helium gas is contacted with the other side in water at a differential pressure of 0.5 atm, as in the patent literature 2 and 3 is described. In addition, the term “waterproofness” throughout the specification indicates that water in contact with one side of the sample does not permeate to the other side as described in Patent Literature 2 and 3. As a result, the LDH-like compound separator 10 having gas impermeability and water impermeability indicates that it has a density to a degree that gas or water does not permeate, and that it has no porous membrane or other porous material that exhibits gas impermeability or water impermeability. Accordingly, due to its hydroxide ion conductivity, the LDH-like compound separator 10 can selectively permeate only hydroxide ions and serve as a battery separator. The LDH-like compound separator 10 thus has a physical configuration that prevents zinc dendrites generated during a charging mode from penetrating through the separator, thereby preventing a short circuit between positive and negative electrodes. Since the LDH-like compound separator 10 has hydroxide ion conductivity, the ionic conductivity allows a necessary amount of hydroxide ions to move efficiently between the positive electrode plate and the negative electrode plate, thereby achieving a charge/discharge reaction on the positive electrode plate and the negative electrode plate can be.

The LDH-like compound separator 10 preferably has a helium 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·atm Or less. A separator having a helium permeability of 3.0 cm/min·atm or less can significantly control the permeation of Zn (typically, the permeation of zinc ion or zinc ion) in the electrolytic solution. Thus, it is in principle conceivable that the separator of the present embodiment can effectively restrain the growth of zinc dendrites when used in zinc secondary batteries because Zn permeation is significantly suppressed. The helium permeability is measured by the following steps: supplying helium gas to one side of the separator to allow the helium gas to permeate into the separator; and calculating helium permeability to evaluate the density of the hydroxide ion conductive separator. The helium permeability is calculated from the expression F/(P×S), where F is the volume of helium gas permeated per unit time, P is the differential pressure acting on the separator as helium gas permeates therethrough, and S is the area of the membrane, through which helium gas permeates. Evaluating the permeability of helium gas in this way can determine the density extremely accurately. As a result, a high degree of density which permeates substances other than hydroxide ions (particularly zinc, which causes deposition of dendritic zinc) as little as possible (or only in trace amounts) can be effectively evaluated. Helium gas is suitable for this evaluation because helium gas has the smallest constitutional unit among the various atoms or molecules that can make up the gas and its reactivity is extremely low. That is, helium does not form molecules, and helium gas exists in atomic form. In this regard, since hydrogen gas is in molecular form (H ₂ ), atomic helium in the gaseous state is smaller than molecular H ₂ . Basically, the gas H ₂ is flammable and dangerous. By using the helium gas permeability defined by the above expression as an index, the density can be evaluated precisely and easily regardless of differences in sample size and measurement conditions. Thus, whether the separator has a sufficiently high density suitable for separators of zinc secondary batteries can be easily, safely and effectively evaluated. The helium permeability can be preferably measured in accordance with the procedure shown in Evaluation 5 in Examples described later.

1. (a) ein Hydroxid und/oder ein Oxid mit einer geschichteten Kristallstruktur, das enthält: Mg; und eines oder mehrere Elemente, die wenigstens Ti enthalten, ausgewählt aus der Gruppe, die aus Ti, Y und AI besteht, oder
2. (b) ein Hydroxid und/oder ein Oxid mit einer geschichteten Kristallstruktur, das (i) Ti, Y und optional Al und/oder Mg und (ii) wenigstens ein additives Element M, ausgewählt aus der Gruppe, die In, Bi, Ca, Sr und Ba enthält, umfasst, oder
3. (c) ein Hydroxid und/oder ein Oxid mit einer geschichteten Kristallstruktur, das Mg, Ti, Y und optional Al und/oder In umfasst, wobei in (c) die LDH-ähnliche Verbindung in Form einer Mischung mit In(OH)₃ vorhanden ist.

In the LDH-like compound separator 10 , the pores of the porous substrate 12 are filled with the LDH-like compound 14 . Preferably, the LDH-like compound is:

1. (a) a hydroxide and/or an oxide having a layered crystal structure containing: Mg; and one or more elements containing at least Ti selected from the group consisting of Ti, Y and Al, or
2. (b) a hydroxide and/or an oxide with a layered crystal structure containing (i) Ti, Y and optionally Al and/or Mg and (ii) at least one additive element M selected from the group consisting of In, Bi, Ca , Sr and Ba contains, comprises, or
3. (c) a hydroxide and/or an oxide with a layered crystal structure comprising Mg, Ti, Y and optionally Al and/or In, wherein in (c) the LDH-like compound is in the form of a mixture with In(OH) ₃ is available.

According to a preferred embodiment (a) of the present invention, the LDH-like compound 14 is a hydroxide and/or an oxide having a layered crystal structure and containing: Mg; and one or more elements containing at least Ti selected from the group consisting of Ti, Y and Al. Accordingly, LDH-like compound 14 is typically a compound hydroxide and/or oxide of Mg, Ti, optionally Y, and optionally Al. The foregoing elements may be substituted with other elements or ions to a degree that does not affect the basic properties of the LDH-like compound 14, but preferably the LDH-like compound 14 is free of Ni. For example, the LDH-like compound 14 may further contain Zn and/or K. This can further improve the ion conductivity of the LDH-like compound separator 10 .

The LDH-like compound 14 can be identified by X-ray diffraction. Specifically, the LDH-like compound separator 10 has a peak derived from the LDH-like compound detected in the range of typically 5°≦2θ≦10°, more typically 7°≦2θ≦10° when at its Surface X-ray diffraction is performed. As described above, an LDH is a substance having an alternating laminated structure in which exchangeable anions and H ₂ O exist as an interlayer between stacked basic hydroxide layers. In view of this, when the LDH is measured by X-ray diffraction, a peak attributed to the crystal structure of the LDH (ie, the (003) peak of the LDH) is originally detected at a position of 2θ=11° to 12°. In contrast, when the LDH-like compound 14 is measured by X-ray diffraction, a peak is typically detected in such a portion that is shifted to the low-angle side from the peak position of the LDH. Further, the interlayer spacing in the layered crystal structure can be determined by Bragg's equation using 2θ corresponding to the peaks in X-ray diffraction derived from the LDH-like compound. The interlayer spacing in the layered crystal structure constituting the LDH-like compound 14 thus determined is typically in the range of 0.883 to 1.8 nm, more typically in the range of 0.883 to 1.3 nm.

The LDH-like compound separator 10 according to embodiment (a) above preferably has an atomic ratio Mg/(Mg + Ti + Y + Al) in the LDH-like compound 14, as determined by energy dispersive X-ray spectroscopy (EDS), in the range from 0.03 to 0.25, more preferably in the range of 0.05 to 0.2. Further, an atomic ratio of Ti/(Mg + Ti + Y + Al) in the LDH-like compound 14 is preferably in the range of 0.40 to 0.97, more preferably in the range of 0.47 to 0.94. Further, an atomic ratio Y/(Mg + Ti + Y + Al) in the LDH-like compound 14 is preferably in the range of 0 to 0.45, more preferably in the range of 0 to 0.37. Further, an atomic ratio Al/(Mg + Ti + Y + Al) in the LDH-like compound 14 is preferably in the range of 0 to 0.05, more preferably in the range of 0 to 0.03. Further, within such a range, the alkali resistance is excellent, and the effect of suppressing short circuits due to zinc dendrites (ie, the dendrite resistance) can be more effectively achieved. Meanwhile, the LDHs known for LDH separators can be expressed by a basic composition of this formula: M ²⁺ _1-x ,M ³ + _x (OH) ₂ A ⁿ _{x/n M} H ₂ O (in the formula, M ²⁺ a divalent cation, M ³⁺ is a trivalent cation, A ⁿ - is an n-valent anion, n is an integer of 1 or greater, x ranges from 0.1 to 0.4, and m is 0 or greater ). In contrast, the above atomic ratios in the LDH-like compound 14 generally differ from those in the above formula of LDH. Therefore, it can be said that the LDH-like compound 14 in the present embodiment generally has compositional ratios (atomic ratios) different from those of such a conventional LDH. The EDS analysis is preferably performed by 1) taking an image with an acceleration voltage of 20 kV and a magnification of 5,000 times, 2) performing an analysis at three points at intervals of about 5 µm in the point analysis mode, 3) repeating the above once Procedures 1) and 2), and 4) calculating an average of the total six points using an EDS analyzer (e.g. X-act, manufactured by Oxford Instruments).

According to a further embodiment (b), the LDH-like compound 14 can be a hydroxide and/or an oxide with a layered crystal structure containing (i) Ti, Y and optionally Al and/or Mg and (ii) an additive element M . Therefore, the LDH-like compound 14 is typically a complex hydroxide and/or a complex oxide with Ti, Y, the additive element M, and optionally Al and optionally Mg. The additive element M is In, Bi, Ca, Sr, Ba or one combination of them. The elements described above may be replaced with other elements or ions to a degree that does not impair the basic properties of the LDH-like compound 14, and the LDH-like compound is preferably free of Ni.

The LDH-like compound separator 10 according to the above embodiment (b) preferably has an atomic ratio of Ti/(Mg+Al+Ti+Y+M) in the LDH-like compound 14 in the range of 0.50 to 0.85 , as determined by energy dispersive X-ray spectroscopy (EDS), and preferably has an atomic ratio in the range of 0.56 to 0.81. An atomic ratio of Y/(Mg + Al + Ti + Y + M) in the LDH-like compound is 14, preferably in the range of 0.03 to 0.20, and more preferably in the range of 0.07 to 0.15. An atomic ratio of M/(Mg + Al + Ti + Y + M) in the LDH-like compound 14 is preferably in the range of 0.03 to 0.35, and more preferably 0.03 to 0.32. An atomic ratio of Mg/(Mg + Al + Ti + Y + M) in the LDH-like compound 14 is preferably in the range of 0 to 0.10, and more preferably in the range of 0 to 0.02. In addition, the atomic ratio of Al/(Mg + Al + Ti + Y + M) in the LDH-like compound 14 is preferably in the range of 0 to 0.05, and more preferably in the range of 0 to 0.04. The ratios within the above ranges make it possible to obtain more excellent alkali resistance and an effect of inhibiting short circuits caused by zinc dendrites (ie, dendrite resistance) more efficiently. Incidentally, an LDH conventionally known in relation to an LDH separator can be represented by the basic composition of the formula M ²⁺ _1-x M ³⁺ _x (OH) ₂ A ^n- _x/n · mH ₂ O, where M ²⁺ is a divalent cation, M ³⁺ is a trivalent cation, A ^n- is an n-valent anion, n is an integer of 1 or greater, x is in the range of 0.1 to 0.4 and m is an integer of 0 or greater. In contrast, the above atomic ratio in the LDH-like compound 14 generally deviates from that of the above formula of LDH. Therefore, it can be generally said that the LDH-like compound 14 in the present embodiment has a different composition ratio (atomic ratio) from conventional LDH. The EDS analysis is preferably performed with an EDS analyzer (e.g. X-act, manufactured by Oxford Instruments) by 1) taking an image at an accelerating voltage of 20 kV and a magnification of 5,000 times, 2) performing a trio -point analysis at intervals of about 5 µm in a point analysis mode, 3) repeating the above steps 1) and 2) once, and 4) calculating an average value from a total of 6 points.

According to yet another embodiment (c), the LDH-like compound 14 may be a hydroxide and/or an oxide with a layered crystal structure comprising Mg, Ti, Y and optionally Al and/or In, the LDH-like compound 14 is present in the form of a mixture with In(OH) ₃ . The LDH-like compound of the present embodiment is a hydroxide and/or an oxide with a layered crystal structure containing Mg, Ti, Y, and optionally Al and/or In. Therefore, the typical LDH-like compound is a complex hydroxide and/or a complex oxide with Mg, Ti, Y, optionally Al and optionally In. Here, In, which may be contained in the LDH-like compound, may not only be intentionally added but also inevitably be integrated into the LDH-like compound, and result from the formation of In(OH) ₃ or the like. The elements described above may be replaced with other elements or ions to a degree that the basic properties of the LDH-like compound are not impaired, and the LDH-like compound is preferably free of Ni. Incidentally, an LDH conventionally known in relation to an LDH separator can be represented by the basic composition of the formula M ²⁺ _1-x M ³⁺ _x (OH ) ₂ A ^n- _x/n mH ₂ O, wherein M ²⁺ is a divalent cation, M ³⁺ is a trivalent cation, A ^n- is an n-valent anion, n is an integer of 1 or greater, x ranges from 0.1 to 0.4, and m is 0 or greater. In contrast, the atomic ratio in the LDH-like compound generally deviates from that of the above formula of LDH. Therefore, it can be generally said that the LDH-like compound in the present embodiment has a different composition ratio (atomic ratio) from conventional LDH.

The mixture according to embodiment (c) above contains not only the LDH-like compound but also In(OH) ₃ (typically consisting of the LDH-like compound and In(OH) ₃ . The contained In(OH) ₃ effectively improves the alkali resistance and the dendrite resistance of the LDH-like compound separator 10 . The content ratio of In(OH) ₃ in the mixture is preferably an amount that can improve alkali resistance and dendrite resistance without impairing the hydroxide ion conductivity of the LDH-like compound separator 10, and is not limited to a specific amount. In(OH) ₃ can have a cubic crystal structure and can be in a configuration where its crystals are surrounded by the LDH-like compounds. The In(OH) ₃ can be identified by X-ray diffraction; and the X-ray diffraction measurement is preferably performed according to the method described in the following example.

As described above, the LDH-like compound separator 10 comprises the LDH-like compound 14 and the porous substrate 12 (typically consists of the porous substrate 12 and the LDH-like compound) 14, and the LDH-like compound 14 plugs the Pores in the porous substrate 12 so that the LDH-like compound separator 10 exhibits hydroxide ion conductivity and gas impermeability (thus serving as an LDH-like compound separator exhibiting hydroxide ion conductivity). In particular, the LDH-like compound 14 is preferably integrated throughout the thickness of the porous substrate 12 made of a polymeric material. The LDH-like compound separator preferably has a thickness in the range of 3 to 80 µm, more preferably 3 µm to 60 µm, still more preferably 3 to 40 µm.

The porous substrate 12 is made of a polymeric material. The porous polymer substrate 12 has the following advantages; (1) high flexibility (difficult to tear even when thinned), (2) high porosity, (3) high conductivity (small thickness with high porosity), and (4) good manufacturability and handleability. The porous polymeric substrate has another advantage; (5) Easy folding and sealing of the LDH-like compound separator containing the porous substrate made of the polymer material based on the advantage (1): high flexibility. Preferred examples of the polymeric material include polystyrene, poly(ether sulfone), polypropylene, epoxy resin, poly(phenylene sulfide), fluorocarbon resin (tetrafluorinated resin such as PTFE), cellulose, nylon, polyethylene, and any combination thereof. More preferred examples are polystyrene, poly(ether sulfone), polypropylene, epoxy resin, poly(phenylene sulfide), fluorocarbon resin (tetrafluorinated resin such as PTFE), nylon, polyethylene and any combination thereof from the viewpoint of a thermoplastic resin suitable for hot pressing. All of the various preferred materials described above have alkali resistance to resist the electrolyte solution of batteries. More preferred polymer materials are polyolefins such as. B. Polypropylene and polyethylene, with polypropylene and polyethylene being most preferred from the viewpoint of excellent hot water resistance, acid resistance and alkali resistance and their low material cost. In a case where the porous substrate consists of the polymeric material, the LDH-like compound is particularly preferably embedded over the entire thickness of the porous substrate (e.g. most of the pores or substantially all of the pores are within the porous substrate with the LDH-like connection filled). A commercially available polymeric microporous membrane can be preferably used as such a porous polymeric substrate.

production process

The method for producing the LDH-like compound separator 10 is not specifically limited, and the LDH-like compound separator can be produced by suitably changing various conditions (particularly, the composition of the LDH starting material) in the already known methods (see, for example, Patent Literature 1 to 4) for producing an LDH-containing functional layer and a composite material. For example, a functional layer containing an LDH-like compound and a composite material (i.e., an LDH-like compound separator) can be produced by (1) preparing a porous substrate, (2) applying a solution containing titanium dioxide sol ( or further contains yttrium sol and/or alumina sol) onto the porous substrate, followed by drying to form a titania-containing layer, (3) immersing the porous substrate in an aqueous starting material solution containing magnesium ions (M ^{2 +} ) and urea (or further contains yttrium ions (Y ³⁺ )), and (4) hydrothermally treating the porous substrate in the aqueous starting material solution to form a functional layer containing an LDH-like compound on the porous substrate and /or to form in the porous substrate. It is considered that the presence of urea in step (3) generates ammonia in the solution through hydrolysis of urea to raise the pH and that coexisting metal ions form a hydroxide and/or an oxide, so that the LDH -like connection can be obtained.

In particular, in the case of producing a composite material (i.e., an LDH-like compound separator) in which the porous substrate 12 is made of a polymer material and the LDH-like compound 14 is integrated over the entire thickness direction of the porous substrate, the mixed sol - the solution in step (2) above is preferably applied to the substrate by a technique that allows the mixed sol solution to permeate all or most of the interior of the substrate. This allows most or almost all of the pores within the porous substrate to eventually be filled with the LDH-like compound. Preferred examples of application technology are dip coating and filtration coating, with dip coating being particularly preferred. Adjusting the number of deposits, such as B. the dip coating, allows adjustment of the application amount of the mixed sol solution. The substrate coated with the mixed sol solution by dip coating or the like may be dried and then subjected to the above steps (3) and (4).

When the porous substrate 12 is made of a polymer material, an LDH-like compound separator obtained by the above-described method or the like is preferably pressed. This enables an LDH-like compound separator further excellent in density to be obtained. The pressing technique is not specifically limited and may be, for example, roll pressing, uniaxial pressing, CIP (cold isotropic pressing) or the like, but is preferably roll pressing. This pressing is preferably carried out under heating since the porous polymer substrate is softened so that the pores of the porous substrate can be sufficiently filled with the LDH-like compound. In order to achieve sufficient softening, the heating temperature is preferably in the range of 60 to 200°C, for example in the case of polypropylene or polyethylene. By pressing such. B. roll pressing, in such a temperature range, the residual pores in the separator with LDH-like compound can be significantly reduced. As a result, the LDH-like compound separator can be extremely densified, and short circuits due to zinc dendrites can thus be further effectively suppressed. Appropriately adjusting the roll gap and the roll temperature during roll pressing makes it possible to control the morphology of the residual pores, thereby making it possible to obtain an LDH-like compound separator with the desired density.

Zinc Secondary Batteries

The LDH-like compound separator of the present invention is preferably applied to zinc secondary batteries. According to a preferred embodiment of the present invention, there is provided a zinc secondary battery comprising the LDH-like compound separator. A typical zinc secondary battery contains a positive electrode, a negative electrode and an electrolytic solution, and insulates the positive electrode from the negative electrode with the LDH-like compound separator therebetween. The zinc secondary battery of the present invention may be of any type containing a zinc negative electrode and an electrolytic solution (typically an aqueous alkali metal hydroxide solution). Accordingly, examples of the zinc secondary battery include nickel-zinc secondary batteries, silver oxide-zinc secondary batteries, manganese oxide-zinc secondary batteries, zinc-air secondary batteries, and other various alkaline-zinc secondary batteries. For example, the zinc secondary battery may preferably be a nickel-zinc secondary battery whose positive electrode contains nickel hydroxide and/or nickel oxyhydroxide. Alternatively, the zinc secondary battery may be a zinc-air secondary battery whose positive electrode is an air electrode.

Alkaline Solid State Fuel Cells

The LDH-like compound separator 10 of the present invention can be applied to a solid-state alkaline fuel cell. By using the LDH-like compound separator containing the porous polymer substrate whose pores are clogged with the LDH-like compound so that the central portion along the thickness of the substrate has a lower average porosity than the peripheral portions along the thickness of the substrate, it is possible to provide a solid-state alkaline fuel cell which can effectively restrain a reduction in electromotive force caused by permeation of a fuel (e.g., transfer of methanol) into an air electrode. The hydroxide ion conductivity of the LDH-like compound separator can effectively restrain the permeation of a fuel such as methanol through the thickness of the LDH-like compound separator. Thus, another preferred embodiment of the present invention provides a solid-state alkaline fuel cell containing the LDH-like compound separator. A typical solid-state alkaline fuel cell contains an air electrode that collects oxygen, a Fuel electrode accommodating a liquid and/or gaseous fuel and LDH-like compound separator interposed between the fuel electrode and the air electrode.

Other batteries

The LDH-like compound separator of the present invention can be used not only in nickel-zinc batteries or solid-state alkaline fuel cells but also in nickel-hydrogen batteries, for example. In this case, the LDH-like compound separator serves to block nitride pendulum (movement of nitrate groups between electrodes) which is a factor of self-discharge in the battery. The LDH-like compound separator of the present invention can also be used in, for example, lithium batteries (batteries having a negative electrode made of lithium metal), lithium ion batteries (batteries having a negative electrode made of carbon, for example) or lithium-air batteries are applied.

EXAMPLES

The invention is described in more detail by the following examples.

[Examples A1 to A6

Examples A1 to A6 shown below are reference examples or comparative examples of LDH separators, but the experimental procedures and results in these examples are also generally applicable to LDH-like compound separators. The following procedures were used to evaluate the LDH separator produced in these examples.

Evaluation 1: Identification of the LDH separator

The crystalline phase of the LDH separator was measured with an X-ray diffractometer (RINT TTR III, manufactured by Rigaku Corporation) at a voltage of 50 kV, a current of 300 mA and a measuring range of 10° to 70° to obtain an XRD profile create. The resultant XRD profile was identified with the diffraction peaks of LDH (hydrocalcite compound) described in JCPDS card NO.35-0964.

Evaluation 2: measurement of the thickness

The thickness of each LDH separator was measured with a micrometer. The thickness was measured at three points on the LDH separator. The average of these measurements was calculated and defined as the thickness of the LDH separator.

Evaluation 3: Calculation of the average aspect ratio

A cross-sectional face of each LDH separator was polished with a cross-sectional polisher (CP). Two image fields of the cross-sectional area of the LDH separator were acquired with an FE-SEM (ULTRA55, available from Carl Zeiss) at a magnification of 50,000x. Based on the image data, the porosities of the pores observed on the two fields were calculated using image analysis software (HDevelop, available from MVTec Software). The average of the porosities was defined as mean porosity. The average porosity was determined in the peripheral areas of the LDH separator (the areas at a depth of 1 to 4 µm from the faces of the LDH separator) and in the central area of the LDH separator.

Evaluation 4: Continuous charging test

A device 210 was made as in 2 shown assembled and an accelerated test was performed to continuously grow zinc dendrites. Specifically, a rectangular container 212 made of ABS resin in which a zinc electrode 214a and a copper electrode 214b face each other with a gap of 0.5 cm was prepared. The zinc electrode 214a is a metallic zinc plate, and the copper electrode 214b is a metallic copper plate. In addition, an LDH separator structure including the LDH separator 216 was constructed such that an epoxy resin-based adhesive was applied along the outer peripheral surface of the LDH separator, and the LDH separator was bonded to a jig made of ABS resin, the had an opening in the middle. To At this point, the bonded area between the device and the LDH separator was sufficiently sealed with the adhesive to ensure liquid tightness. The LDH separator structure was then placed in the container 212 to isolate a first section 215a containing the zinc electrode 214a from a second section 215b containing the copper electrode 214b, creating a different liquid connection than the region of the LDH separator 216 was prevented. In this configuration, three outer edges of the LDH separator structure (or three outer edges of the device made of ABS resin) were bonded to the inner wall of the container 212 with an epoxy resin adhesive to ensure liquid tightness. In other words, the bonded area between the separator structure containing the LDH separator 216 and the container 212 was sealed to prevent liquid communication. 5.4 mol/L KOH aqueous solution as the alkaline aqueous solution 218 was poured into the first portion 215a and the second portion 215b together with ZnO powders equivalent to a saturated solubility. The zinc electrode 214a and the copper electrode 214b were connected to a negative terminal and a positive terminal, respectively, of the constant current power supply, and a voltmeter was also connected in parallel to the constant current power supply. The liquid level of the aqueous alkaline solution 218 was determined below the level of the LDH separator structure (which contains the device) so that the entire area of the LDH separator 216 in both the first section 215a and the second section 215b falls into the aqueous alkaline solution 218 was immersed. In the measuring device 210 having such a configuration, a constant current of 20 mA/cm ² was applied between the zinc electrode 214a and the copper electrode 214b for up to 200 hours. During the application of the constant current, the voltage between the zinc electrode 214a and the copper electrode 214b was monitored with a voltmeter to check whether there was a short circuit (a large voltage drop) between the zinc electrode 214a and the copper electrode 214b caused by zinc dendrites. No short for more than 100 hours (or for more than 200 hours) was determined as "(short) not found" and a short for less than 100 hours (or less than 200 hours) was determined as "(short) found". certainly.

Evaluation 5: Helium permeability

A helium permeation test was conducted to evaluate the density of the LDH separator from the viewpoint of helium permeability. That in the 3A and 3B The helium permeability measurement system 310 shown was constructed. The helium permeability measurement system 310 was configured to supply helium gas from a gas cylinder filled with helium gas via the pressure gauge 312 and a flow meter 314 (digital flow meter) into a sample holder 316 and the gas by permeation from side to side of that held by the sample holder 316 LDH separator 318 derives.

The sample holder 316 had a structure including a gas supply port 316a, a sealed space 316b and a gas exhaust port 316c, and was assembled as follows: An adhesive 322 was applied along the outer peripheral surface of the LDH separator 318 and bonded to a jig 324 (manufactured made of ABS plastic) which had a central opening. Gaskets or sealing members 326a, 326b made of butyl rubber were placed at the top and bottom of the device 324, respectively, and then the outsides of the members 326a, 326b were fitted with support members 328a, 328b (made of PTFE), each having a flange with an opening contained, held. Thus, 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 tightly fastened to each other with fasteners 330 with screws to prevent helium gas from leaking from portions other than the gas discharge port 316c. A gas supply line 334 was connected to the gas supply port 316a of the sample holder 316 assembled as above through a connector 332 .

Then, helium gas was supplied to the helium permeability measurement system 310 via the gas supply line 334 , and then the gas was permeated through the LDH separator held in the sample holder 316 . A gas supply pressure and flow rate were then monitored with a pressure gauge 312 and a flow meter 314 . After permeating helium gas for one to thirty minutes, the helium permeability was calculated. The helium permeability was calculated from the expression F/(P×S), where F (cm ³ /min) was the volume of helium gas permeated per unit time, P (atm) was the differential pressure acting on the separator when helium gas permeated therethrough , and S (cm ² ) was the area of the membrane through which helium gas permeated. The permeation rate F (cm ³ /min) of the helium gas was read directly from the flow meter 314 . The measured pressure read off the pressure gauge 312 was taken as the differential pressure P is used. Helium gas was supplied so that the differential pressure P was in the range of 0.05 to 0.90 atm.

Evaluation 6: Measurement of ionic conductivity The ionic conductivity of the LDH separator in the electrolytic solution was measured with an in 4 measured electrochemical measuring system shown. An LDH separator sample S was sandwiched between two silicone gaskets 440 having a thickness of 1 mm and installed in a flange-type PTFE cell 442 having an inner diameter of 6 mm. Electrodes 446 of 100 mesh nickel wire mesh were formed into a cylindrical shape with a diameter of 6 mm and installed in the cell 442, and the distance between the electrodes was 2.2 mm. The cell 442 was filled with 5.4 M KOH aqueous solution as an electrolytic solution 444 . Using the electrochemical measurement system (potentio-galvanostat frequency response analyzers 1287A and 1255B manufactured by Solartron), the sample was measured under the conditions of a frequency range of 1 MHz to 0.1 Hz and an applied voltage of 10 mV, and the resistance of the LDH Separator Sample S was determined from the intersection across a real number axis. Conductivity was calculated from the resistivity, thickness and area of the LDH separator.

Example A1 (comparison)

(1) Preparation of a porous polymer substrate

A commercially available polypropylene microporous membrane having a porosity of 50%, an average pore size of 0.1 µm and a thickness of 20 µm was cut out as a porous polymer substrate in a size of 2.0 cm × 2.0 cm.

(2) Coating of alumina/titania sol on the porous polymer substrate

An amorphous alumina solution (AI-ML15, manufactured by Taki Chemical Co., Ltd.) and a titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) were prepared in a Ti/Al molar ratio of 2 mixed to obtain a mixed sol. The mixed sol was allowed to permeate into the substrate prepared in process (1) by dip coating. In the dip coating, the substrate was immersed in 100 ml of the mixed sol, pulled up vertically and dried in a drier at 90°C for 5 minutes.

(3) Preparation of the raw material aqueous solution

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 Corporation) were provided as starting materials. Nickel nitrate hexahydrate was weighed to 0.015 mol/l and placed in a beaker. Ion-exchanged water was added to a total volume of 75 mL. After stirring the solution, the weighed urea was added in a urea/NO ₃ - molar ratio of 16 and further stirred to obtain a raw material aqueous solution.

(4) Membrane formation by hydrothermal treatment

The aqueous starting material solution and the dip-coated substrate were sealed in a Teflon™ autoclave (internal volume: 100 ml, covered with a stainless steel jacket). The substrate was fixed horizontally off the bottom of the Teflon™ autoclave so that the solution was in contact with both surfaces of the substrate. Then, an LDH was formed on the surface and inside of the substrate by a hydrothermal treatment at a temperature of 120°C for 24 hours. After a predetermined period of time, the substrate was taken out of the autoclave, washed with ion-exchanged water, and dried at 70°C for ten hours to form the LDH in the pores of the porous substrate and obtain an LDH-containing composite material.

(5) Compaction by roller pressing

The composite material containing the above LDH is sandwiched between two PET films (Lumirror™ manufactured by Toray Industries, Inc., with a thickness of 40 µm) and then at a rotation speed of 3 mm/s, a roller temperature of 110 ° C and a nip of 60 microns to obtain an LDH separator

(6) Results of evaluation

The resulting LDH separator was evaluated according to Evaluations 1-6. As a result of evaluation 1, this LDH separator was identified as LDH (hydrocalcite compound). The results of evaluations 2 to 6 are as shown in Table 1. As shown in Table 1, in Evaluation 4, zinc dendrites did not cause a short circuit after continuous charging up to 100 hours, but caused a short circuit after continuous charging for less than 200 hours.

Examples A2 and A3 (reference)

Each LDH separator was produced and evaluated as in Example A1, except that the drying temperature after immersion in alumina/titania sol was varied to the values shown in Table 1 in Process (2). As a result of evaluation 1, the LDH separators in these examples were identified as LDH (hydrocalcite compound). Table 1 shows the results of evaluations 2 to 6. As shown in Table 1, the zinc dendrites in Examples A2 to A3 did not cause a short circuit even after being charged continuously for 200 hours or more. The 5A and 5B show FE-SEM cross-sectional images recorded in evaluation 3 of the peripheral area and the central area of the LDH separator according to example A3.

Example 4 (comparison)

An LDH separator was produced and evaluated as in Example A1, except that compaction by roller pressing in process (5) was not performed. The results of Evaluation 1 indicated that the LDH separator of this example was identified as LDH (Hydrocalcite Compoundy).

Table 1 shows the results of Evaluations 2 to 6. As shown in Table 1, in Evaluation 4, zinc dendrites caused a short circuit after being continuously charged for less than 100 hours.

Examples A5 and A6 (reference)

• a) Die Trocknungstemperatur nach dem Eintauchen in Aluminiumoxid/Titanoxid-Sol wurde auf die in Tabelle 1 angegebenen Werte im Prozess (2) variiert
• b) Magnesiumnitrathexahydrat (Mg(NO₃)₂-6H₂O hergestellt von Kanto Chemical Co., Ltd.) wurde anstelle des Nickelnitrathexahydrats in Prozess (3) verwendet, auf 0,03 mol/l eingewogen und in ein Becherglas gegeben. ionenausgetauschtes Wasser wurde bis zu einem Gesamtvolumen von 75 ml hinzugefügt. Nach dem Rühren der resultierenden Lösung wurde der eingewogene Harnstoff in einem molaren Verhältnis von Harnstoff/NO₃- von 8 hinzugefügt und weiter gerührt, um eine wässrige Ausgangsmateriallösung zu erhalten.
• b) Die hydrothermale Temperatur in Prozess (4) war 90°C.

An LDH separator was produced and evaluated as in Example A1, except for the following conditions a) to c).

• a) The drying temperature after immersion in alumina/titania sol was varied to the values given in Table 1 in process (2).
• b) Magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ -6H ₂ O manufactured by Kanto Chemical Co., Ltd.) was used instead of nickel nitrate hexahydrate in process (3), weighed to 0.03 mol/L and placed in a beaker. ion exchanged water was added to a total volume of 75 ml. After stirring the resultant solution, the weighed urea was added thereto in a urea/NO ₃ - molar ratio of 8 and further stirred to obtain a raw material aqueous solution.
• b) The hydrothermal temperature in process (4) was 90°C.

As a result of evaluation 1, this LDH separator was identified as LDH (hydrotalcite compound). The results of evaluations 2 to 6 are shown in Table 1. As shown in Table 1, the zinc dendrites in Examples A5 and A6 did not cause a short circuit even after being continuously charged for 200 hours or more. [Table 1] Table 1 Composition of the LDH separator production conditions Evaluations of the LDH separator Drying temperature after immersion in alumina/titania sol (°C) roller temp. (ºC) Thickness (µm) average porosity (%) Helium permeability (cm/min × atm) Ionic Conductivity (mS/cm) Continuous load test peripheral area (area at a depth of 1 to 4 µm from the surface) middle area Short circuit over continuous charging time up to 100 hours Short circuit over continuous charging time up to 200 hours E.g. A1* Ni-Al,Ti 90 110 13 1 1 0.0 3.0 No Found Ex. A2 ^# Ni-Al,Ti 70 110 13 5 1 0.0 3.0 No No Ex. A3 ^# Ni-Al,Ti 50 110 13 10 1 0.0 3.1 No No E.g. A4* Ni-Al,Ti 90 - 16 20 20 100 3.2 Found - Ex. A5 ^# Mg-Al,Ti 70 110 13 6 1 0.0 3.0 No No Ex. A6 ^# Mg-Al ,Ti 50 110 14 12 1 0.0 3.1 No No
^# indicates a reference example.
* indicates a comparative example.

[Examples B1 to B8]

Examples B1 to B7 shown below are reference examples of LDH-like compound separators, while Example B8 shown below is a comparative example of an LDH separator. The LDH-like compound separators and the LDH separator are collectively referred to as hydroxide ion conductive separators. The method for evaluating the hydroxide ion-conductive separators produced in the following examples was as follows.

Evaluation 1: Observation of the surface microstructure

The surface microstructure of the hydroxide ion conductive separator was observed using a scanning electron microscope (SEM, JSM-6610LV, manufactured by JEOL Ltd.) at an acceleration voltage of 10 to 20 kV.

Evaluation 2: STEM analysis of the layered structure

The layered structure of the hydroxide ion conductive separator was observed using a scanning transmission electron microscope (STEM) (product name: JEM-ARM200F, manufactured by JEOL Ltd.) at an acceleration voltage of 200 kV.

Evaluation 3: Evaluation of the elemental analysis (EDS)

A surface of the hydroxide ion conductive separator was subjected to compositional analysis using an EDS analyzer (device name: X-act, manufactured by Oxford Instruments) to calculate the compositional ratio (atomic ratio) Mg:Ti:Y:Al. This analysis was performed by 1) taking an image with an acceleration voltage of 20 kV and a magnification of 5,000 times, 2) performing analysis at three points at intervals of about 5 µm in the point analysis mode, 3) repeating the above procedures 1 once ) and 2), and 4) calculating an average of the total of six points.

Evaluation 4: X-ray diffraction measurement

Using an X-ray diffractometer (RINT TTR III, manufactured by Rigaku Corporation), the crystalline phase of the hydroxide ion conductive separator was measured under the measurement conditions of voltage: 50 kV, current: 300 mA, and measurement range: 5 to 40° to obtain an XRD profile . Further, the interlayer distance in the layered crystal structure was determined by Bragg's equation using 2θ corresponding to the peaks derived from the LDH-like compound.

Evaluation 5: He permeation measurement

In order to evaluate the density of the hydroxide ion conductive separator in terms of He permeation, a He permeation test was carried out according to the same procedure as in Evaluation 5 of Examples A1 to A8.

Evaluation 6: Measurement of the ionic conductivity

The conductivity of the hydroxide ion conductive separator in the electrolytic solution was measured using the in 11 measured using the electrochemical measuring system shown as follows. A hydroxide ion conductive separator sample S was sandwiched between 1 mm thick silicone gaskets 440 and installed in a PTFE flange type cell 442 with an inner diameter of 6 mm. As the electrodes 446, in the cell 442, 100 mesh nickel wire meshes were assembled into a cylindrical shape having a diameter of 6 mm so that the distance between the electrodes was 2.2 mm. The cell 442 was filled with 5.4 M KOH aqueous solution as an electrolytic solution 444 . Using electrochemical measurement systems (potentiostat/galvanostat frequency response analyzers Type 1287A and Type 1255B manufactured by Solartron Metrology), the measurement was carried out under the conditions of a frequency range of 1 MHz to 0.1 Hz and an applied voltage of 10 mV, and the cut point of the real axis was taken as the resistance of the hydroxide ion conductive separator sample S. The same measurement as above was performed without the hydroxide ion conductive separator sample S to determine a blank resistance. The difference between the resistance of the hydroxide ion conductive separator sample S and the blank resistance was taken as the resistance of the hydroxide ion conductive separator. The conductivity was determined using the obtained resistance of the hydroxide ion conductive separator and the thickness and area of the hydroxide ion conductive separator.

Evaluation 7: Evaluation of alkali resistance

A 5.4M KOH aqueous solution containing zinc oxide at a concentration of 0.4M was prepared. 0.5 ml of the prepared KOH aqueous solution and a hydroxide ion conductive separator sample having a size of 2 cm square were placed in a closed container made of Teflon®. Thereafter, it was kept at 90°C for one week (ie, 168 hours), and then the hydroxide ion conductive separator sample was taken out from the closed container. The extracted hydroxide ion conductive separator sample was dried overnight at room temperature. For the sample obtained, the He permeability was calculated in the same manner as in Evaluation 5 to determine whether or not the He permeability changed before and after the alkali immersion.

Evaluation 8: Evaluation of dendrite resistance (cycle test)

• - Es traten keine Kurzschlüsse auf: Während des Ladens wurden selbst nach 300 Zyklen keine plötzlichen Spannungsabfälle wie vorstehend beschrieben beobachtet.
• - Es traten Kurzschlüsse auf: Plötzliche Spannungsabfälle wie vorstehend beschrieben wurden während des Ladens in weniger als 300 Zyklen beobachtet.

In order to evaluate the effect of suppressing short circuits due to zinc dendrites (dendrite resistance) of the hydroxide ion conductive separator, a cycle test was carried out as follows. First, the positive electrode (containing nickel hydroxide and/or nickel oxyhydroxide) and the negative electrode (containing zinc and/or zinc oxide) were each wrapped with a non-woven fabric, and the current extraction terminal was welded thereto. The positive electrode and negative electrode thus prepared were positioned opposite to each other via the hydroxide ion conductive separator and sandwiched between laminated sheets provided with current outlets, and three sides of the laminated sheets were heat-sealed. An electrolytic solution (a solution in which 0.4M zinc oxide was dissolved in a 5.4M KOH aqueous solution) was added into the thus obtained open-topped cell container, and the positive electrode and the negative electrode were made sufficient by vacuum or the like impregnated with the electrolyte solution. Thereafter, the remaining one side of the laminate sheets was heat sealed to form a simple sealed cell. Using a charge/discharge device (TOSCAT3100, manufactured by TOYO SYSTEM CO., LTD.), the chemical conversion simple sealed cell was charged at 0.1C and discharged at 0.2C. Thereafter, a 1C charge/discharge cycle was performed. During the repetition of the charge/discharge cycle under the same conditions, the voltage between the positive and negative electrodes was monitored with a voltmeter, and the presence or absence of sudden voltage drops (especially voltage drops of 5 mV or more from the voltage recorded immediately before) as Succession of short circuits due to zinc dendrites between the positive and negative electrodes was examined and evaluated according to the following criteria.

• - No short-circuiting occurred: During charging, even after 300 cycles, no sudden voltage drops as described above were observed.
• - Short circuits occurred: Sudden voltage drops as described above were observed during charging in less than 300 cycles.

Example B1 (reference)

(1) Preparation of a porous polymer substrate

A commercially available microporous polyethylene membrane having a porosity of 50%, an average pore size of 0.1 μm and a thickness of 2θ μm was prepared as a porous polymer substrate and cut out into a size of 2.0 cm×2.0 cm.

(2) Titanium dioxide sol coating on the porous polymer substrate

The substrate prepared by the above procedure (1) was coated with a titanium oxide sol solution (M6, manufactured by Taki Chemical Co.) by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of the sol solution and pulling it out vertically, followed by drying at room temperature for 3 hours.

(3) Production of the raw material aqueous solution

As starting materials, magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O manufactured by KANTO CHEMICAL CO., INC.) and urea ((NH ₂ ) ₂ CO manufactured by Sigma-Aldrich Corporation) were prepared. The magnesium nitrate hexahydrate was weighed to 0.015 mol/L and placed in a beaker and deionized water was added so that the total was 75 mL. After stirring the obtained solution, urea weighed in a urea/NO ₃ - ratio (molar ratio) of 48 was added to the solution, followed by further stirring to obtain a raw material aqueous solution.

(4) Membrane formation by hydrothermal treatment

The raw material aqueous solution and the dip-coated substrate were sealed together in a Teflon®-made closed container (autoclave container, capacity: 100 ml, with a stainless steel outer jacket). At this point, the substrate was lifted from the bottom of the closed container made of Teflon® and fixed and installed vertically so that the solution was in contact with both sides of the substrate. Thereafter, an LDH-like compound was formed on the surface and inside of the substrate by applying hydrothermal treatment at a temperature of 120°C for 24 hours. After a lapse of a predetermined time, the substrate was taken out of the closed container, washed with deionized water, and dried at 70°C for 10 hours to form an LDH-like compound in the pores of the porous substrate. Thus, an LDH-like compound separator was obtained.

(5) Compaction by roller pressing

The LDH-like compound separator was sandwiched between two PET films (Lumirror®, manufactured by Toray Industries, Inc., with a thickness of 40 μm) and heated at a roller rotation speed of 3 mm/s and a roller heating temperature of 70°C at a nip of 70 µm to obtain an LDH-like compound separator which was further densified.

(6) Evaluation results

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B1 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 6A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg und Ti, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg und Ti auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 1 gezeigt.
• - Auswertung 4: 6B zeigt das in Beispiel B1 erhaltene XRD-Profil. In dem erhaltenen XRD-Profil wurde ein Peak um 2θ = 9,4 ° beobachtet. Im Allgemeinen wird die Position des (003)-Peaks von LDH bei 2θ = 11 bis 12° beobachtet, und daher wird davon ausgegangen, dass der Peak der (003)-Peak von LDH ist, der zur Seite des niedrigen Winkels verschoben ist. Daher kann der Peak nicht als der von LDH bezeichnet werden, sondern es ist naheliegend, dass er ein Peak ist, der von einer Verbindung ähnlich LDH (d. h. einer LDH-ähnlichen Verbindung) herrührt. Zwei im XRD-Profil beobachtete Peaks bei 20 < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren. Ferner war der Zwischenschichtabstand in der geschichteten Kristallstruktur der LDH-ähnlichen Verbindung 0,94 nm.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90°C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

The obtained LDH-like compound separator was subjected to evaluations 1 to 8. The results were as follows.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B1 (before roll pressing) was as in FIG 6A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg and Ti, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg and Ti on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 1.
• - Evaluation 4: 6B shows the XRD profile obtained in Example B1. In the XRD profile obtained, a peak was observed around 2θ=9.4°. In general, the position of the (003) peak of LDH is observed at 2θ=11 to 12°, and therefore the peak is considered to be the (003) peak of LDH shifted to the low angle side. Therefore, the peak cannot be said to be that of LDH, but it stands to reason that it is a peak originating from a compound similar to LDH (ie, an LDH-like compound). Two peaks observed in the XRD profile at 20 < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate. Further, the interlayer distance in the layered crystal structure of 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B2 (reference)

An LDH-like compound separator was produced and evaluated in the same manner as in Example B1 except that the raw material aqueous solution was produced as in the above procedure (3) and the temperature for the hydrothermal treatment in the above procedure (4 ) was changed to 90 °C.

(Production of raw material aqueous solution)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B2 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 7A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg und Ti, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg und Ti auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 2 gezeigt.
• -Auswertung 4: 7B zeigt das in Beispiel B2 erhaltene XRD-Profil. In dem erhaltenen XRD-Profil wurde ein Peak um 2θ = 7,2° beobachtet. Im Allgemeinen wird die Position des (003)-Peaks von LDH bei 2θ = 11 bis 12° beobachtet, und daher wird davon ausgegangen, dass der Peak der (003)-Peak von LDH ist, der zur Seite des niedrigen Winkels verschoben ist. Daher kann der Peak nicht als der von LDH bezeichnet werden, sondern es ist naheliegend, dass er ein Peak ist, der von einer Verbindung ähnlich LDH (d. h. einer LDH-ähnlichen Verbindung) herrührt. Zwei im XRD-Profil beobachtete Peaks bei 2θ < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren. Ferner war der Zwischenschichtabstand in der geschichteten Kristallstruktur der LDH-ähnlichen Verbindung 1,2 nm.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90 °C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

As starting materials, magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O manufactured by KANTO CHEMICAL CO., INC.) and urea ((NH ₂ ) ₂ CO manufactured by Sigma-Aldrich Corporation) were prepared. The magnesium nitrate hexahydrate was weighed to 0.03 mol/L and placed in a beaker and deionized water was added so that the total amount was 75 mL. After stirring the obtained solution, urea weighed in a ratio of urea/NO ₃ - (molar ratio) of 8 was added to the solution, followed by further stirring to obtain a raw material aqueous solution.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B2 (before roll pressing) was as in FIG 7A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg and Ti, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg and Ti on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 2.
• -Evaluation 4: 7B shows the XRD profile obtained in example B2. In the obtained XRD profile, a peak was observed around 2θ=7.2°. In general, the position of the (003) peak of LDH is observed at 2θ=11 to 12°, and therefore the peak is considered to be the (003) peak of LDH shifted to the low angle side. Therefore, the peak cannot be said to be that of LDH, but it stands to reason that it is a peak originating from a compound similar to LDH (ie, an LDH-like compound). Two peaks observed in the XRD profile at 2θ < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate. Further, the interlayer distance in the layered crystal structure of 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B3 (reference)

An LDH-like compound separator was produced and evaluated in the same manner as in Example B1, except that the porous polymer substrate was coated with titania and yttria sols instead of that of the above procedure (2) as follows.

(titania yttria sol coating on the porous polymer substrate)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B3 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 8A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg, Ti, und Y, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, Ti, und Y auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 2 gezeigt.
• -Auswertung 4: 8B zeigt das in Beispiel B3 erhaltene XRD-Profil. In dem erhaltenen XRD-Profil wurde ein Peak um 2θ = 8,0° beobachtet. Im Allgemeinen wird die Position des (003)-Peaks von LDH bei 2θ = 11 bis 12° beobachtet, und daher wird davon ausgegangen, dass der Peak der (003)-Peak von LDH ist, der zur Seite des niedrigen Winkels verschoben ist. Daher kann der Peak nicht als der von LDH bezeichnet werden, sondern es ist naheliegend, dass er ein Peak ist, der von einer Verbindung ähnlich LDH (d. h. einer LDH-ähnlichen Verbindung) herrührt. Zwei im XRD-Profil beobachtete Peaks bei 2θ < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren. Ferner war der Zwischenschichtabstand in der geschichteten Kristallstruktur der LDH-ähnlichen Verbindung 1,1 nm.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90 °C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

A titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) and an yttrium sol were mixed in a Ti/Y molar ratio of 4. The substrate prepared in the above procedure (1) was coated with the obtained mixed solution by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of the mixed solution and pulling it up vertically, followed by drying at room temperature for 3 hours.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B3 (before roll pressing) was as in FIG 8A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg, Ti, and Y, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg, Ti, and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 2.
• -Evaluation 4: 8B shows the XRD profile obtained in example B3. In the obtained XRD profile, a peak was observed around 2θ=8.0°. In general, the position of the (003) peak of LDH is observed at 2θ=11 to 12°, and therefore the peak is considered to be the (003) peak of LDH shifted to the low angle side. Therefore, the peak cannot be said to be that of LDH, but it stands to reason that it is a peak originating from a compound similar to LDH (ie, an LDH-like compound). Two peaks observed in the XRD profile at 2θ < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate. Further, the interlayer distance in the layered crystal structure of 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B4 (reference)

An LDH-like compound separator was produced and evaluated in the same manner as in Example B1, except that the porous polymer substrate was coated with titania, yttria and alumina sols instead of the above procedure (2) as follows.

(titania-yttria-alumina sol coating on the porous polymer substrate)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B4 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 9A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg, AI, Ti, und Y, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, und Y auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 2 gezeigt.
• -Auswertung 4: 9B zeigt das in Beispiel B4 erhaltene XRD-Profil. In dem erhaltenen XRD-Profil wurde ein Peak um 2θ = 7,8° beobachtet. Im Allgemeinen wird die Position des (003)-Peaks von LDH bei 2θ = 11 bis 12° beobachtet, und daher wird davon ausgegangen, dass der Peak der (003)-Peak von LDH ist, der zur Seite des niedrigen Winkels verschoben ist. Daher kann der Peak nicht als der von LDH bezeichnet werden, sondern es ist naheliegend, dass er ein Peak ist, der von einer Verbindung ähnlich LDH (d. h. einer LDH-ähnlichen Verbindung) herrührt. Zwei im XRD-Profil beobachtete Peaks bei 2θ < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren. Ferner war der Zwischenschichtabstand in der geschichteten Kristallstruktur der LDH-ähnlichen Verbindung 1,1 nm.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90 °C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

A titania sol solution (M6, manufactured by Taki Chemical Co., Ltd.), an yttrium sol and an amorphous alumina solution (AI-ML15, manufactured by Taki Chemical Co., Ltd.) were used in a molar ratio Ti/(Y+Al) of 2 and a molar ratio Y/Al of 8. The substrate prepared in the above procedure (1) was coated with the mixed solution by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of the mixed solution and pulling it up vertically, followed by drying at room temperature for 3 hours.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B4 (before roll pressing) was as in FIG 9A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg, Al, Ti, and Y, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg, Al, Ti, and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 2.
• -Evaluation 4: 9B shows the XRD profile obtained in Example B4. In the obtained XRD profile, a peak was observed around 2θ=7.8°. In general, the position of the (003) peak of LDH is observed at 2θ=11 to 12°, and therefore the peak is considered to be the (003) peak of LDH shifted to the low angle side. Therefore, the peak cannot be said to be that of LDH, but it stands to reason that it is a peak originating from a compound similar to LDH (ie, an LDH-like compound). Two peaks observed in the XRD profile at 2θ < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate. Further, the interlayer distance in the layered crystal structure of 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B5 (reference)

An LDH-like compound separator was produced and evaluated in the same manner as in Example B1, except that instead of the above procedure (2), the porous polymer substrate was coated with titania and yttria sols as follows and the raw material aqueous solution was produced in the above procedure (3) as follows.

(titania yttria sol coating on the porous polymer substrate)

A titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) and an yttrium sol were mixed in a Ti/Y molar ratio of 18. The substrate prepared in the above procedure (1) was coated with the obtained mixed solution by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of the mixed solution and pulling it up vertically, followed by drying at room temperature for 3 hours.

(Production of raw material aqueous solution)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B5 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 10A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg, Ti, und Y, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, Ti, und Y auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 2 gezeigt.
• -Auswertung 4: 10B zeigt das in Beispiel B5 erhaltene XRD-Profil. In dem erhaltenen XRD-Profil wurde ein Peak um 2θ = 8,9° beobachtet. Im Allgemeinen wird die Position des (003)-Peaks von LDH bei 2θ = 11 bis 12° beobachtet, und daher wird davon ausgegangen, dass der Peak der (003)-Peak von LDH ist, der zur Seite des niedrigen Winkels verschoben ist. Daher kann der Peak nicht als der von LDH bezeichnet werden, sondern es ist naheliegend, dass er ein Peak ist, der von einer Verbindung ähnlich LDH (d. h. einer LDH-ähnlichen Verbindung) herrührt. Zwei im XRD-Profil beobachtete Peaks bei 2θ < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren. Ferner war der Zwischenschichtabstand in der geschichteten Kristallstruktur der LDH-ähnlichen Verbindung 0,99 nm.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90 °C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

As starting materials, magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ -6H ₂ O manufactured by KANTO CHEMICAL CO., INC.) and urea ((NH ₂ ) ₂ CO manufactured by Sigma-Aldrich Corporation) were prepared. The magnesium nitrate hexahydrate was weighed to 0.0075 mol/L and placed in a beaker and deionized water was added so that the total was 75 mL. Then the obtained solution was stirred. Urea weighed in a ratio of urea/NO ₃ - (molar ratio) = 96 was added to the solution, followed by further stirring to obtain a raw material aqueous solution.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B5 (before roll pressing) was as in FIG 10A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg, Ti, and Y, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg, Ti, and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 2.
• -Evaluation 4: 10B shows the XRD profile obtained in Example B5. In the obtained XRD profile, a peak was observed around 2θ=8.9°. In general, the position of the (003) peak of LDH is observed at 2θ=11 to 12°, and therefore the peak is considered to be the (003) peak of LDH shifted to the low angle side. Therefore, the peak cannot be said to be that of LDH, but it stands to reason that it is a peak originating from a compound similar to LDH (ie, an LDH-like compound). Two peaks observed in the XRD profile at 2θ < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate. Further, the interlayer distance in the layered crystal structure of 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B6 (reference)

An LDH-like compound separator was produced and evaluated in the same manner as in Example B1, except that the porous polymer substrate was coated with titania and alumina sols instead of the above procedure (2) as follows and the raw material aqueous solution was produced in the above procedure (3) as follows.

(titania-alumina sol coating on the porous polymer substrate)

A titanium oxide sol solution (M6, manufactured by Taki Chemical Co., Ltd.) and an amorphous alumina solution (AI-ML15, manufactured by Taki Chemical Co., Ltd.) were mixed in a Ti/Al molar ratio of 18 . The substrate prepared in the above procedure (1) was coated with the mixed solution by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of the mixed solution and pulling it out vertically, followed by drying at room temperature for 3 hours.

(Production of raw material aqueous solution)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B6 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 11A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg, AI, Ti, und Y, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, und Y auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 2 gezeigt.
• -Auswertung 4: 11B zeigt das in Beispiel B6 erhaltene XRD-Profil. In dem erhaltenen XRD-Profil wurde ein Peak um 2θ = 7,2° beobachtet. Im Allgemeinen wird die Position des (003)-Peaks von LDH bei 2θ = 11 bis 12° beobachtet, und daher wird davon ausgegangen, dass der Peak der (003)-Peak von LDH ist, der zur Seite des niedrigen Winkels verschoben ist. Daher kann der Peak nicht als der von LDH bezeichnet werden, sondern es ist naheliegend, dass er ein Peak ist, der von einer Verbindung ähnlich LDH (d. h. einer LDH-ähnlichen Verbindung) herrührt. Zwei im XRD-Profil beobachtete Peaks bei 20 < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren. Ferner war der Zwischenschichtabstand in der geschichteten Kristallstruktur der LDH-ähnlichen Verbindung 1,2 nm.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90°C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

As starting materials, magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O manufactured by KANTO CHEMICAL CO., INC.), yttrium nitrate n-hydrate (Y(NO ₃ ) _{3 ·} nH ₂ O manufactured by FUJIFILM Wako Pure Chemical Corporation), and urea ((NH ₂ ) ₂ CO, manufactured by Sigma-Aldrich Corporation). The magnesium nitrate hexahydrate was weighed out to 0.0015 mol/l and placed in a beaker. Further, the yttrium nitrate n-hydrate was weighed to 0.0075 mol/L and placed in the beaker, and deionized water was added so that the total amount was 75 mL. Then the obtained solution was stirred. Urea weighed in a ratio of urea/NO ₃ - (molar ratio) = 9.8 was added to the solution, followed by further stirring to obtain a raw material aqueous solution.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B6 (before roll pressing) was as in FIG 11A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg, Al, Ti, and Y, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg, Al, Ti, and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 2.
• -Evaluation 4: 11B shows the XRD profile obtained in example B6. In the obtained XRD profile, a peak was observed around 2θ=7.2°. In general, the position of the (003) peak of LDH is observed at 2θ=11 to 12°, and therefore the peak is considered to be the (003) peak of LDH shifted to the low angle side. Therefore, the peak cannot be said to be that of LDH, but it stands to reason that it is a peak originating from a compound similar to LDH (ie, an LDH-like compound). Two peaks observed in the XRD profile at 20 < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate. Further, the interlayer distance in the layered crystal structure of 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B7 (reference)

An LDH-like compound separator was produced and evaluated in the same manner as in Example B6, except that the starting material aqueous solution was produced as follows in the above procedure (3).

(Production of raw material aqueous solution)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B7 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) war wie in 12 gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg, AI, Ti, und Y, die Bestandteile der LDH-ähnlichen Verbindung waren, auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, und Y auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 2 gezeigt.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und es wurde bestätigt, dass sich die He-Permeabilität auch nach dem einwöchigen Eintauchen in Alkali bei einer hohen Temperatur von 90 °C nicht veränderte, was angibt, dass die Alkalibeständigkeit ausgezeichnet war.
• -Auswertung 8: Wie in Tabelle 2 gezeigt wurde bestätigt, dass selbst nach 300 Zyklen keine Kurzschlüsse aufgrund von Zinkdendriten auftraten, was angibt, dass die Dendritenbeständigkeit ausgezeichnet war.

As starting materials, magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O manufactured by KANTO CHEMICAL CO., INC.), yttrium nitrate n-hydrate (Y(NO ₃ ) ₃ ·nH ₂ O manufactured by FUJIFILM Wako Pure Chemical Corporation), and urea ((NH ₂ ) ₂ CO, manufactured by Sigma-Aldrich Corporation). The magnesium nitrate hexahydrate was weighed out to 0.0075 mol/l and placed in a beaker. Further, the yttrium nitrate n-hydrate was weighed to 0.0075 mol/L and placed in the beaker, and deionized water was added so that the total amount was 75 mL. Then the obtained solution was stirred. Urea weighed in a ratio of urea/NO ₃ - (molar ratio) of 25.6 was added to the solution, followed by further stirring to obtain a raw material aqueous solution.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example B7 (before roll pressing) was as in FIG 12 shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg, Al, Ti, and Y, which were components of the LDH-like compound, were detected on the surface of the LDH-like compound separator. Further, the composition ratio (atomic ratio) of Mg, Al, Ti, and Y on the surface of the LDH-like compound separator calculated by EDS elemental analysis was 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, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and it was confirmed that the He permeability improved even after the alkali immersion for one week at a high temperature of 90°C did not change, indicating that the alkali resistance was excellent.
• -Evaluation 8: As shown in Table 2, it was confirmed that short circuits due to zinc dendrites did not occur even after 300 cycles, indicating that the dendrite resistance was excellent.

Example B8 (comparison)

An LDH separator was produced and evaluated in the same manner as in Example B1 except that the alumina sol coating was carried out as follows instead of the above procedure (2).

(Alumina sol coating on the porous polymer substrate)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel B8 erhaltenen LDH-Separators (vor dem Walzenpressen) war wie in 13A gezeigt.
• - Auswertung 2: Aus dem Ergebnis, dass geschichtete Plaids beobachtet werden konnten, wurde bestätigt, dass der Abschnitt LDH-Separators, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden Mg und AI, die Bestandteile der LDH waren, auf der Oberfläche des LDH-Separators detektiert. Ferner war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg und Al auf der Oberfläche des LDH-Separators wie in Tabelle 2 gezeigt.
• -Auswertung 4: 13B zeigt das in Beispiel B8 erhaltene XRD-Profil. Anhand eines Peaks um 2θ = 11,5° in dem erhaltenen XRD-Profil wurde der in Beispiel B8 erhaltene LDH-Separator als ein LDH (Hydrotalcit-Verbindung) identifiziert. Diese Identifizierung wurde unter Verwendung Beugungspeaks des LDH (Hydrotalcit-Verbindung), der in der JCPDS-Karte Nr. 35-0964 beschrieben ist, ausgeführt. Zwei im XRD-Profil beobachtete Peaks bei 20 < 2θ° < 25 sind Peaks, die von Polyethylen, das das poröse Substrat bildet, herrühren.
• - Auswertung 5: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die He-Permeabilität 0,0 cm/min × atm war, was angibt, dass die Dichte extrem hoch war.
• -Auswertung 6: Wie in Tabelle 2 gezeigt wurde bestätigt, dass die lonenleitfähigkeit hoch war.
• - Auswertung 7: Als ein Ergebnis des einwöchigen Eintauchens in Alkali bei einer hohen Temperatur von 90°C war die He-Permeabilität, die bei Auswertung 5 0,0 cm/min × atm war, über 10 cm/min × atm, was eine schlechte Alkalibeständigkeit erkennen lässt.
• - Auswertung 8: Wie in Tabelle 2 gezeigt traten Kurzschlüsse aufgrund von Zinkdendriten in weniger als 300 Zyklen auf, was erkennen lässt, dass die Dendritenbeständigkeit schlecht war.

[Tabelle 2] Tabelle 2 LOH-ähnliche Verbindung oder Zusammensetzung von LDH Auswertung eines hydroxidionenleitfähigen Separators Zusammensetzungsverhältnis (Atomverhältnis) He Permeation (cm/ min × atm) Ionenleitfähigkeit (mS/cm) Alkalibeständigkeit Dendritenbeständigkeit Vorhandensein/Fehlen einer Veränderung der He-Permeabilität- Vorhandensein oder Fehlen von Kurzschlüssen Beispiel B1^# Mg-Ti-LOH-ähnlich Mg:Ti=6:94 0,0 3,0 fehlt fehlt Beispiel B2^# Mg-Ti-LOH-ähnlich Mg:Ti=20:80 0,0 2,0 fehlt fehlt Beispiel B3^# Mg-(Ti, Y)-LOH-ähnlich Mg:Ti:Y=5:83:12 0,0 3,0 fehlt fehlt Beispiel B4^# Mg (Ti,Y,Al)-LDH-ähnlich Mg:AI:Ti:Y=7:3:79:12 0,0 3,1 fehlt fehlt Beispiel B5^# Mg-(Ti,Y)-LOH-ähnlich Mg:Ti:Y=6:88:6 0,0 3,0 fehlt fehlt Beispiel B6^# Mg-(Ti,Y,Al)-LDH-ähnlich Mg:AI:Ti:Y=5:2:67:25 0,0 3,1 fehlt fehlt Beispiel B7^# Mg-(Ti,Y,Al)-LDH-ähnlich Mg:Al:Ti:Y=15:1:47:37 0,0 2,9 fehlt fehlt Beispiel B8* Mg-Al-LDH Mg:AI=67:32 0,0 2,7 vorhanden vorhanden
Das Symbol # repräsentiert ein Referenzbeispiel.
Das Symbol * repräsentiert ein Vergleichsbeispiel.The substrate prepared in the above procedure (1) was coated with an amorphous alumina sol (AI-M15, manufactured by Taki Chemical Co.) by dip coating. The dip coating was carried out by immersing the substrate in 100 ml of the amorphous alumina sol and pulling it up vertically, followed by drying at room temperature for 3 hours.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH separator obtained in Example B8 (before roll pressing) was as in FIG 13A shown.
• - Evaluation 2: From the result that layered plaids could be observed, 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 the EDS elemental analysis, Mg and Al, which were components of the LDH, were detected on the surface of the LDH separator. Further, the composition ratio (atomic ratio) of Mg and Al on the surface of the LDH separator calculated by EDS elemental analysis was as shown in Table 2.
• -Evaluation 4: 13B shows the XRD profile obtained in Example B8. From a peak around 2θ=11.5° in the obtained XRD profile, the LDH separator obtained in Example B8 was identified as an LDH (hydrotalcite compound). This identification was carried out using diffraction peaks of LDH (hydrotalcite compound) described in JCPDS card No. 35-0964. Two peaks observed in the XRD profile at 20 < 2θ° < 25 are peaks originating from polyethylene constituting the porous substrate.
• - Evaluation 5: As shown in Table 2, it was confirmed that the He permeability was 0.0 cm/min·atm, indicating that the density was extremely high.
• -Evaluation 6: As shown in Table 2, it was confirmed that the ionic conductivity was high.
• - Evaluation 7: As a result of immersing in alkali at a high temperature of 90°C for one week, the He permeability, which was 0.0 cm/min·atm in evaluation 5, was over 10 cm/min·atm, which was a shows poor alkali resistance.
• - Evaluation 8: As shown in Table 2, short circuits due to zinc dendrites occurred in less than 300 cycles, showing that the dendrite resistance was poor.

[Table 2] Table 2 LOH-like compound or composition of LDH Evaluation of a hydroxide ion conductive separator Composition Ratio (Atomic Ratio) He permeation (cm/min × atm) Ionic Conductivity (mS/cm) alkali resistance dendrite resistance Presence/absence of a change in He permeability Presence or absence of short circuits Example B1 ^# Mg-Ti-LOH-like Mg:Ti=6:94 0.0 3.0 is missing is missing Example B2 ^# Mg-Ti-LOH-like Mg:Ti=20:80 0.0 2.0 is missing is missing Example B3 ^# Mg-(Ti,Y)-LOH-like Mg:Ti:Y=5:83:12 0.0 3.0 is missing is missing Example B4 ^# Mg(Ti,Y,Al)-LDH-like Mg:AI:Ti:Y=7:3:79:12 0.0 3.1 is missing is missing Example B5 ^# Mg-(Ti,Y)-LOH-like Mg:Ti:Y=6:88:6 0.0 3.0 is missing is missing Example B6 ^# Mg-(Ti,Y,Al)-LDH-like Mg:AI:Ti:Y=5:2:67:25 0.0 3.1 is missing is missing Example B7 ^# Mg-(Ti,Y,Al)-LDH-like Mg:Al:Ti:Y=15:1:47:37 0.0 2.9 is missing is missing Example B8* Mg-Al-LDH Mg:AI=67:32 0.0 2.7 available available
The # symbol represents a reference example.
The symbol * represents a comparative example.

[Examples C1 to C9]

Examples C1 to C9 shown below are reference examples of LDH-like compound separators. The method for evaluating the LDH-like compound separators produced in the following examples is the same as in Examples B1 to B8, except that the composition ratio (atomic ratio) of Mg:Al:Ti:Y: additive element M in Evaluation 3 was calculated.

Example C1 (reference)

(1) Preparation of the porous polymer substrate

A commercially available microporous polyethylene membrane having a porosity of 50%, an average pore diameter of 0.1 μm and a thickness of 2θ μm was prepared as a porous polymer substrate and cut out to a size of 2.0 cm×2.0 cm.

(2) Coating of Titanium Oxide. yttria. Alumina sol on the porous polymer substrate

A titania sol solution (M6, manufactured by Taki Chemical Co., Ltd.), an yttrium sol, and an amorphous alumina solution (Al-ML15, manufactured by Taki Chemical Co., Ltd.) were mixed so that Ti /(Y+Al) (molar ratio)=2 and Y/Al (molar ratio)=8. The substrate prepared in (1) above was coated with the mixed solution by dip coating. The dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling up the coating substrate vertically and drying at room temperature for 3 hours.

(3) Preparation of raw material aqueous solution (I)

Magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O manufactured by Kanto Chemical Co, Inc.) and urea ((NH ₂ ) ₂ CO manufactured by Sigma-Aldrich Co. LLC) were prepared as starting materials. Magnesium nitrate hexahydrate was weighed to 0.015 mol/L and placed in a beaker, and ion-exchanged water was added thereto to make the total amount 75 mL. After stirring the obtained solution, the weighed urea in a ratio of urea/NO ₃ - (molar ratio) = 48 was added to the solution, and the mixture was further stirred to obtain an aqueous starting material solution (I).

(4) Membrane formation by hydrothermal treatment

Both the aqueous starting material solution (I) and the dip-coated substrate were sealed in an airtight Teflon® container (100 ml autoclave container with a stainless steel outer jacket). At this point, a substrate was floated from the bottom of the Teflon® airtight container and installed vertically so that the solution was in contact with both sides of the substrate. Thereafter, an LDH-like compound was formed on the surface and inside of the substrate by subjecting it to hydrothermal treatment at a hydrothermal temperature of 120°C for 22 hours. With the lapse of a predetermined time, the substrate was taken out of the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to form an LDH-like compound in the pores of the porous substrate.

(5) Preparation of raw material aqueous solution (II)

Indium sulfate n-hydrate (In ₂ (SO ₄ ) ₃ ·nH ₂ O, manufactured by FUJIFILM Wako Pure Chemical Corporation) was prepared as a starting material. The indium sulfate n-hydrate was weighed to 0.0075 mol/L and placed in a beaker, to which ion-exchanged water was added to make the total volume 75 mL. The resulting solution was stirred to obtain an aqueous starting material solution (II).

(6) Addition of indium by immersion treatment

In an airtight Teflon® container (autoclave container with a capacity of 100 ml and an outer jacket made of stainless steel), the starting material aqueous solution (II) and the LDH-like compound separator obtained in (4) above were sealed together. At this point, a substrate was floated from the bottom of the Teflon® airtight container and placed vertically so that the solution was in contact with both sides of the substrate. Thereafter, indium was added on the substrate by subjecting it to dip treatment at 30°C for 1 hour. With the lapse of a predetermined time, the substrate was taken out from the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to obtain an indium-added LDH-like compound separator thereon.

(7) Compaction by roller pressing

The LDH-like compound separator was sandwiched between two PET films (Lumiler®, manufactured by Toray Industries, Inc., thickness 40 µm) and pressed at a roller rotation speed of 3 mm/s, a roller heating temperature of 70°C and a nip of 70 µm roll pressed to obtain a further densified separator with LDH-like compound.

(8) Evaluation result

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel C1 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) wurde in 14 gezeigt.
• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich AI, Ti, Y und In, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von AI, Ti, Y und In auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min. atm bestätigt.
• - Auswertung 6: Wie in Tabelle 3 gezeigt wurde die hohe Ionenleitfähigkeit bestätigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb auch nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt wurde die ausgezeichnete Dendritenbeständigkeit dadurch bestätigt, dass selbst nach 300 Zyklen kein Kurzschluss aufgrund von Zinkdendriten auftrat.

Various evaluations were made for the obtained LDH-like compound separators. The results were as follows.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example C1 (before roll pressing) was obtained in 14 shown.
• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Al, Ti, Y and In, were detected. In addition, the composition ratio (atomic ratio) of Al, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was demonstrated by a He permeability of 0.0 cm/min. ATM confirmed.
• - Evaluation 6: As shown in Table 3, the high ionic conductivity was confirmed.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week of alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, the excellent dendrite resistance was confirmed that no short circuit due to zinc dendrites occurred even after 300 cycles.

Example C2 (reference)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich AI, Ti, Y und In, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von AI, Ti, Y und In auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb auch nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C1, except that the time of the dipping treatment was changed to 24 hours upon addition of indium by the above dipping treatment of (6).

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Al, Ti, Y and In, were detected. In addition, the composition ratio (atomic ratio) of Al, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week of alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming excellent dendrite resistance.

Example C3 (reference)

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C1, except that the titania-yttria sol coating was performed as follows instead of in (2) above.

(2) Coating of titania-yttria sol on the porous polymer substrate)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich Ti, Y und In, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Ti, Y und In auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb auch nach einer Woche Eintauchen in Alkali bei einer erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

A titania sol solution (M6, manufactured by Taki Chemical Co., Ltd.) and an yttrium sol were mixed so that Ti/Y (molar ratio)=2. The substrate prepared in (1) above was coated with the obtained mixed solution by dip coating. The dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling up the coating substrate vertically and drying at room temperature for 3 hours.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Ti, Y and In, were detected. In addition, the composition ratio (atomic ratio) of Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week of alkali immersion at an elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming excellent dendrite resistance.

Example C4 (reference)

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C1, except that the above preparation of the starting material aqueous solution (II) in (5) was carried out as follows and bismuth was treated by immersion treatment as follows instead of was added to (6) above.

(5) Preparation of raw material aqueous solution (II))

Bismuth nitrate pentahydrate (Bi(NO ₃ ) ₃ ·5H ₂ O) was prepared as the starting material. The bismuth nitrate pentahydrate was weighed to 0.00075 mol/L and placed in a beaker, to which ion-exchanged water was added to make the total volume 75 mL. The resulting solution was stirred to obtain an aqueous starting material solution (II).

(adding bismuth by immersion treatment)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich Mg, AI, Ti, Y und Bi, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, Y und Bi auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

In an airtight Teflon® container (autoclave container with a capacity of 100 ml and an outer jacket made of stainless steel), the starting material aqueous solution (II) and the LDH-like compound separator obtained in (4) were sealed together. At this time, a substrate was floated from the bottom of the Teflon® airtight container and placed vertically so that the solution was in contact with both sides of the substrate. Thereafter, bismuth was added onto the substrate by subjecting it to a dip treatment at 30°C for 1 hour. Upon the lapse of the predetermined time, the substrate was taken out of the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to obtain a bismuth-added LDH-like compound separator thereon.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Mg, Al, Ti, Y and Bi, were detected. In addition, the composition ratio (atomic ratio) of Mg, Al, Ti, Y and Bi on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming excellent dendrite resistance.

Example C5 (reference)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich Mg, AI, Ti, Y und Bi, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, Y und Bi auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C4, except that the time of the immersion treatment was changed to 12 hours when bismuth was added by the immersion treatment described above.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Mg, Al, Ti, Y and Bi, were detected. In addition, the composition ratio (atomic ratio) of Mg, Al, Ti, Y and Bi on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming excellent dendrite resistance.

Example C6 (reference)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich Mg, AI, Ti, Y und Bi, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, Y und Bi auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt, wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C4, except that the time of the immersion treatment was changed to 24 hours when bismuth was added by the immersion treatment described above.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Mg, Al, Ti, Y and Bi, were detected. In addition, the composition ratio (atomic ratio) of Mg, Al, Ti, Y and Bi on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming excellent dendrite resistance.

Example C7 (reference)

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C1 except that the above preparation of the starting material aqueous solution (II) in (5) was carried out as follows and calcium was treated by immersion treatment instead of the above ( 6) has been added as follows.

(Preparation of Aqueous Starting Material Solution (II))

Calcium nitrate tetrahydrate (Ca(NO ₃ ) ₂ ·4H ₂ O) was prepared as the starting material. The calcium nitrate tetrahydrate was weighed to 0.015 mol/L and placed in a beaker, to which ion-exchanged water was added to make the total volume 75 mL. The resulting solution was stirred to obtain an aqueous starting material solution (II).

(adding calcium by immersion treatment)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich Mg, AI, Ti, Y und Ca, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, Y und Ca auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt, trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

In an airtight Teflon® container (autoclave container with a capacity of 100 ml and an outer jacket made of stainless steel), the starting material aqueous solution (II) and the LDH-like compound separator obtained in (4) were sealed together. At this point, a substrate was floated from the bottom of the Teflon® airtight container and placed vertically so that the solution was in contact with both sides of the substrate. Thereafter, calcium was added on the substrate by subjecting it to a dip treatment at 30°C for 6 hours. Upon the lapse of the predetermined time, the substrate was taken out of the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to obtain a calcium-added LDH-like compound separator.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Mg, Al, Ti, Y and Ca, were detected. In addition, the composition ratio (atomic ratio) of Mg, Al, Ti, Y and Ca on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming the excellent dendrite resistance.

Example C8 (reference)

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C1 except that the above preparation of the starting material aqueous solution (II) in (5) was carried out as follows and strontium was added by immersion treatment instead of the above ( 6) has been added as follows.

(Preparation of Aqueous Starting Material Solution (II))

Strontium nitrate (Sr(NO ₃ ) ₂ ) was prepared as the starting material. The strontium nitrate was weighed to 0.015 mol/L and placed in a beaker, to which ion-exchanged water was added to make the total volume 75 mL. The resulting solution was stirred to obtain an aqueous starting material solution (II).

(adding strontium by immersion treatment)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich Mg, AI, Ti, Y und Sr, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, Y und Sr auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

In an airtight Teflon® container (autoclave container with a capacity of 100 ml and an outer jacket made of stainless steel), the starting material aqueous solution (II) and the LDH-like compound separator obtained in (4) above were sealed together. At this point, a substrate was floated from the bottom of the Teflon® airtight container and placed vertically so that the solution was in contact with both sides of the substrate. Thereafter, strontium was added on the substrate by subjecting it to a dip treatment at 30°C for 6 hours. Upon the lapse of the predetermined time, the substrate was taken out of the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to obtain a strontium-added LDH-like compound separator.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Mg, Al, Ti, Y and Sr, were detected. In addition, the composition ratio (atomic ratio) of Mg, Al, Ti, Y and Sr on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming excellent dendrite resistance.

Example C9 (reference)

An LDH-like compound separator was prepared and evaluated in the same manner as in Example C1, except that the above preparation of the aqueous starting material rial solution (II) in (5) was carried out as follows and barium was added by immersion treatment instead of the above (6) as follows.

(Preparation of Aqueous Starting Material Solution (II))

Barium nitrate (Ba(NO ₃ ) ₂ ) was prepared as a starting material. The barium nitrate was weighed to 0.015 mol/L and placed in a beaker, to which ion-exchanged water was added to make the total volume 75 mL. The resulting solution was stirred to obtain an aqueous starting material solution (II).

(adding barium by immersion treatment)

• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Abschnitt des Separators mit LDH-ähnlicher Verbindung, der nicht das poröse Substrat war, eine Verbindung mit einer geschichteten Kristallstruktur war.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung, nämlich AI, Ti, Y und Ba, detektiert. Außerdem war das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von AI, Ti, Y und Ba auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung wie in Tabelle 3 gezeigt.
• - Auswertung 5: Wie in Tabelle 3 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe Ionenleitfähigkeit wurde bestätigt, wie in Tabelle 3 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 3 gezeigt trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

[Tabelle 3] Tabelle 3 LOH-ähnliche Verbindung oder LDH-Zusammensetzung Zusammensetzungsverhältnis (Atomverhältnis bezogen auf 100 der Gesamtmenge von Mg+Al+Ti+Y+M) M/(Mg+Al +Ti+Y+M) Auswertung eines hydroxidionenleitfähigen Separators He-Permeabilität (cm/min × atm) lonenleitfähigkeit (mS/cm) Alkalibeständigkeit Dendritenbeständigkeit Vorhandensein oder Fehlen einer Veränderung der He-Permeabilität Vorhandensein oder Fehlen eines Kurzschlusses Beispiel C1^# Al,Ti,Y,In-LDH-ähnlich Mg:0, AI:2, Ti:78, Y:8, In:12 0,12 (M=ln) 0,0 3,1 fehlt fehlt Beispiel C2^# Al,Ti,Y,In-LDH-ähnlich Mg:0, AI:1, Ti:56, Y:11, In:32 0,32 (M=ln) 0,0 3,1 fehlt fehlt Beispiel C3^# Ti,Y,ln-LDH-ähnlich Mg:0, AI:0, Ti:78, Y:8, In:14 0,14 (M=ln) 0,0 3,0 fehlt fehlt Beispiel C4^# Mg,AI,Ti,Y,Bi-LDH-ähnlich Mg:2, Al:2, Ti:81, Y:12, Bi:3 0,03 (M=Bi) 0,0 2,9 fehlt fehlt Beispiel C5^# Mg,AI,Ti,Y,Bi-LDH-ähnlich Mg:2, AI:2, Ti:72, Y:10, Bi:14 0,14 (M=Bi) 0,0 2,8 fehlt fehlt Beispiel C6^# Mg,Al,Ti,Y,Bi-LDH-ähnlich Mg:1, Al:1, Ti:66, Y:7, Bi:25 0,25 (M=Bi) 0,0 2,8 fehlt fehlt Beispiel C7^# Mg,Al,Ti,Y,Ca-LDH-ähnlich Mg:1, Al:3, Ti:73, Y:15, Ca:8 0,08 (M=Ca) 0,0 2,8 fehlt fehlt Beispiel C8^# Mg,Al,Ti,Y,Sr-LDH-ähnlich Mg:1, Al:3, Ti:74, Y:14, Sr:8 0,08 (M=Sr) 0,0 3,0 fehlt fehlt Beispiel C9^# Al,Ti,Y, Ba-LOH-ähnlich Mg:0, Al:4, Ti:71, Y:14, Ba:11 0,11 (M=Ba) 0,0 2,8 fehlt fehlt Beispiel B8* Mg,Al-LDH Mg:68 AI:32 0 0,0 2,7 vorhanden vorhanden
Das Symbol # repräsentiert ein Referenzbeispiel.
Das Symbol * repräsentiert ein Vergleichsbeispiel.In an airtight Teflon® container (autoclave container with a capacity of 100 ml and an outer jacket made of stainless steel), the starting material aqueous solution (II) and the LDH-like compound separator obtained in (4) were sealed together. At this point, a substrate was floated from the bottom of the Teflon® airtight container and placed vertically so that the solution was in contact with both sides of the substrate. Thereafter, barium was added on the substrate by subjecting it to a dip treatment at 30°C for 6 hours. Upon the lapse of the predetermined time, the substrate was taken out from the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to obtain a barium-added LDH-like compound separator thereon.

• - Evaluation 2: From the observation result of layered lattice fringes, 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 the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound, namely Al, Ti, Y and Ba, were detected. In addition, the composition ratio (atomic ratio) of Al, Ti, Y and Ba on the surface of the LDH-like compound separator calculated by EDS elemental analysis was as shown in Table 3.
• - Evaluation 5: As shown in Table 3, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 3.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 3, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming the excellent dendrite resistance.

[Table 3] Table 3 LOH-like compound or LDH composition Composition ratio (atomic ratio based on 100 of the total amount of Mg+Al+Ti+Y+M) M/(Mg+Al+Ti+Y+M) Evaluation of a hydroxide ion conductive separator He permeability (cm/min × atm) ionic conductivity (mS/cm) alkali resistance dendrite resistance Presence or absence of a change in He permeability Presence or absence of a short circuit Example C1 ^# Al,Ti,Y,In-LDH-like Mg:0, Al:2, Ti:78, Y:8, In:12 0.12 (M=ln) 0.0 3.1 is missing is missing Example C2 ^# Al,Ti,Y,In-LDH-like Mg:0, Al:1, Ti:56, Y:11, In:32 0.32 (M=ln) 0.0 3.1 is missing is missing Example C3 ^# Ti,Y,ln-LDH-like Mg:0, AI:0, Ti:78, Y:8, In:14 0.14 (M=ln) 0.0 3.0 is missing is missing Example C4 ^# Mg,Al,Ti,Y,Bi-LDH-like Mg:2, Al:2, Ti:81, Y:12, Bi:3 0.03 (M=Bi) 0.0 2.9 is missing is missing Example C5 ^# Mg,Al,Ti,Y,Bi-LDH-like Mg:2, AI:2, Ti:72, Y:10, Bi:14 0.14 (M=Bi) 0.0 2.8 is missing is missing Example C6 ^# Mg,Al,Ti,Y,Bi-LDH-like Mg:1, Al:1, Ti:66, Y:7, Bi:25 0.25 (M=Bi) 0.0 2.8 is missing is missing Example C7 ^# Mg,Al,Ti,Y,Ca-LDH-like Mg:1, Al:3, Ti:73, Y:15, Ca:8 0.08 (M=Ca) 0.0 2.8 is missing is missing Example C8 ^# Mg,Al,Ti,Y,Sr-LDH-like Mg:1, Al:3, Ti:74, Y:14, Sr:8 0.08 (M=Sr) 0.0 3.0 is missing is missing Example C9 ^# Al,Ti,Y, Ba-LOH-like Mg:0, Al:4, Ti:71, Y:14, Ba:11 0.11 (M=Ba) 0.0 2.8 is missing is missing Example B8* Mg,Al-LDH Mg:68 AI:32 0 0.0 2.7 available available
The # symbol represents a reference example.
The symbol * represents a comparative example.

[Examples D1 and D2]

Examples D1 and D2 shown below are reference examples of LDH-like compound separators. The method for evaluating the LDH-like compound separators produced in the following examples was 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 became.

Example D1 (reference)

(1) Preparation of a porous polymer substrate

A commercially available polyethylene microporous membrane having a porosity of 50%, an average pore diameter of 0.1 μm and a thickness of 20 μm was prepared as a porous polymer substrate and cut out to a size of 2.0 cm×2.0 cm.

(2) Coating of Titanium Oxide. yttria. Alumina sol on the porous polymer substrate

A titania sol solution (M6, manufactured by Taki Chemical Co., Ltd.), an yttrium sol and an amorphous alumina solution (AI-ML15, manufactured by Taki Chemical Co., Ltd.) were mixed so that Ti/(Y + Al) (molar ratio)=2 and Y/Al (molar ratio)=8. The substrate prepared in (1) above was coated with the mixed solution by dip coating. The dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling up the coating substrate vertically and drying at room temperature for 3 hours.

(3) Preparation of the raw material aqueous solution

As starting materials, magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O manufactured by KANTO CHEMICAL CO., INC.), indium sulfate n-hydrate (In(SO ₄ ) ₃ ·nH ₂ O manufactured by FUJIFILM Wako Pure Chemical Corporation), and urea ((NH ₂ ) ₂ CO, manufactured by Sigma-Aldrich Corporation). Magnesium nitrate hexahydrate, indium sulfate n-hydrate, and the urea were weighed to adjust their concentrations to 0.0075 mol/L, 0.0075 mol/L, and 1.44 mol/L, respectively, and placed in a beaker, to which ion-exchanged water was added was added to obtain a total volume of 75 ml. The resulting solution was stirred to obtain a raw material aqueous solution.

(4) Membrane formation by hydrothermal treatment

Both the aqueous starting material solution and the dip-coated substrate were sealed in an airtight Teflon® container (100 ml autoclave container with a stainless steel outer jacket). At this time, a substrate was floated from the bottom of the Teflon® airtight container and installed vertically so that the solution was in contact with both sides of the substrate. Thereafter, an LDH-like compound was formed on the surface and inside of the substrate by subjecting it to hydrothermal treatment at a hydrothermal temperature of 120°C for 22 hours. When the predetermined time elapsed, the substrate was taken out of the airtight container, washed with ion-exchanged water, and dried at 70°C for 10 hours to allow a functional layer containing an LDH-like compound and In(OH ) ₃ contains could form. Thus, an LDH-like compound separator was obtained.

(5) Compaction by roller pressing

The LDH-like compound separator was sandwiched between two PET films (Lumiler®, manufactured by Toray Industries, Inc., thickness 40 µm) and pressed at a roller rotation speed of 3 mm/s, a roller heating temperature of 70°C and a nip of 70 µm roll pressed to obtain a further densified separator with LDH-like compound.

(6) Evaluation result

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel D1 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) wurde in 15 gezeigt. Wie in 15 gezeigt, wurde bestätigt, dass kubische Kristalle auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung beobachtet wurden. Die nachstehend beschriebenen Ergebnisse der EDS-Elementaranalyse und der Röntgenbeugungsmessung zeigen, dass es sich bei diesen kubischen Kristallen vermutlich um In(OH)₃ handelt.
• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Separator mit LDH-ähnlicher Verbindung eine Verbindung mit einer geschichteten Kristallstruktur enthält.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung oder von In(OH)₃, nämlich Mg, AI, Ti, Y und In, detektiert. Außerdem wurde in den kubischen Kristallen auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung In, das ein Bestandteil von In(OH)₃ war, detektiert. Das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, AI, Ti, Y und In auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung ist wie in Tabelle 4 gezeigt.
• -Auswertung 4: Die Peaks im erhaltenen XRD-Profil identifizierten, dass In(OH)₃ in dem Separator mit LDH-ähnlicher Verbindung vorhanden war. Diese Identifizierung wurde unter Verwendung der Beugungspeaks von In(OH)₃, die in der JCPDS-Karte Nr. 01-085-1338 aufgeführt sind, durchgeführt.
• - Auswertung 5: Wie in Tabelle 4 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Wie in Tabelle 4 gezeigt wurde die hohe Ionenleitfähigkeit bestätigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 4 gezeigt, wurde die ausgezeichnete Dendritenbeständigkeit dadurch bestätigt, dass selbst nach 300 Zyklen kein Kurzschluss aufgrund von Zinkdendriten auftrat.

Evaluations 1 to 8 were carried out for the obtained LDH-like compound separators. The results were as follows.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example D1 (before roll pressing) was obtained in 15 shown. As in 15 shown, it was confirmed that cubic crystals were observed on the surface of the LDH-like compound separator. The results of the EDS elemental analysis and the X-ray diffraction measurement described below show that these cubic crystals are probably In(OH) ₃ .
• - Evaluation 2: From the observation result of layered lattice fringes, it was confirmed that the LDH-like compound separator contains a compound having a layered crystal structure.
• - Evaluation 3: As a result of the EDS elemental analysis, the components of the LDH-like compound or In(OH) ₃ , namely Mg, Al, Ti, Y and In, were detected on the surface of the LDH-like compound separator. In addition, In, which was a component of In(OH) ₃ , was detected in the cubic crystals on the surface of the LDH-like compound separator. The composition ratio (atomic ratio) of Mg, Al, Ti, Y and In on the surface of the LDH-like compound separator calculated by EDS elemental analysis is as shown in Table 4.
• -Evaluation 4: The peaks in the obtained XRD profile identified that In(OH) ₃ was present in the LDH-like compound separator. This identification was performed using the diffraction peaks of In(OH) ₃ listed in JCPDS card No. 01-085-1338.
• - Evaluation 5: As shown in Table 4, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: As shown in Table 4, the high ionic conductivity was confirmed.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 4, the excellent dendrite resistance was confirmed that no short circuit due to zinc dendrites occurred even after 300 cycles.

Example D2 (reference)

An LDH-like compound separator was prepared and evaluated in the same manner as in Example D1, except that the titania-yttria sol coating was performed as follows instead of in (2) above.

(2) Coating of titania-yttria sol on the porous polymer substrate)

• - Auswertung 1: Das SEM-Bild der Oberflächenmikrostruktur des in Beispiel D2 erhaltenen Separators mit LDH-ähnlicher Verbindung (vor dem Walzenpressen) ist wie in 16 gezeigt. Wie in 16 gezeigt wurde bestätigt, dass kubische Kristalle auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung beobachtet wurden. Die nachstehend beschriebenen Ergebnisse der EDS-Elementaranalyse und der Röntgenbeugungsmessung zeigen, dass es sich bei diesen kubischen Kristallen vermutlich um In(OH)₃ handelt.
• - Auswertung 2: Aus dem Beobachtungsergebnis von geschichteten Gitterstreifen wurde bestätigt, dass der Separator mit LDH-ähnlicher Verbindung eine Verbindung mit einer geschichteten Kristallstruktur enthält.
• - Auswertung 3: Als ein Ergebnis der EDS-Elementaranalyse wurden auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung die Bestandteile der LDH-ähnlichen Verbindung oder von In(OH)₃, nämlich Mg, Ti, Y und In, detektiert. Außerdem wurde in den kubischen Kristallen auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung In, das ein Bestandteil von In(OH)₃ ist, detektiert. Das durch EDS-Elementaranalyse berechnete Zusammensetzungsverhältnis (Atomverhältnis) von Mg, Ti, Y und in auf der Oberfläche des Separators mit LDH-ähnlicher Verbindung ist wie in Tabelle 4 gezeigt.
• -Auswertung 4: Die Peaks im erhaltenen XRD-Profil identifizierten, dass In(OH)₃ in dem Separator mit LDH-ähnlicher Verbindung vorhanden war. Diese Identifizierung wurde anhand der Beugungspeaks von In(OH)₃, die in der JCPDS-Karte Nr. 01-085-1338 aufgeführt sind, durchgeführt.
• - Auswertung 5: Wie in Tabelle 4 gezeigt wurde die extrem hohe Dichte durch eine He-Permeabilität von 0,0 cm/min × atm bestätigt.
• - Auswertung 6: Die hohe lonenleitfähigkeit wurde bestätigt, wie in Tabelle 4 gezeigt.
• -Auswertung 7: Die He-Permeabilität nach dem Eintauchen in Alkali war 0,0 cm/min × atm, wie in Auswertung 5, und die He-Permeabilität blieb selbst nach einer Woche Eintauchen in Alkali bei der erhöhten Temperatur von 90 °C unverändert, was die ausgezeichnete Alkalibeständigkeit bestätigt.
• - Auswertung 8: Wie in Tabelle 4 gezeigt, trat selbst nach 300 Zyklen kein durch Zinkdendriten verursachter Kurzschluss auf, was die ausgezeichnete Dendritenbeständigkeit bestätigt.

[Tabelle 4] Tabelle 4 Beschaffenheit der funktionalen Schicht Zusammensetzungsverhältnis (Atomverhältnis bezogen auf 100 der Gesamtmenge von Mg+Al+Ti+Y+In) In/(Mg+Al+ Ti+Y+In) Auswertung des hydroxidionenleitfähigen Separators He-Permeabilität (cm/min × atm) lonenleitfähigkeit (mS/cm) Alkalibeständigkeit Dendritenbeständigkeit Vorhandensein oder Fehlen einer Veränderung der He-Permeabilität Vorhandensein oder Fehlen eines Kurzschlusses Beispiel D1^# LDH-ähnlich+ In(OH)₃ Mg:7, AI:1, Ti:24, Y:3, In:65 0,65 0,0 2,7 fehlt fehlt Beispiel D2^# LDH-ähnlich +In(OH)₃ Mg:6, AI:0, Ti:17, Y:3, In:74 0,74 0,0 2,8 fehlt fehlt Beispiel B8* LDH Mg:68, Al:32 0 0,0 2,7 vorhanden vorhanden
Das Symbol # repräsentiert ein Referenzbeispiel.
Das Symbol * repräsentiert ein Vergleichsbeispiel.A titania sol solution (M6, manufactured by Taki Chemical Co., Ltd.) and an yttrium sol were mixed so that Ti/Y (molar ratio)=2. The substrate prepared in (1) above was coated with the obtained mixed solution by dip coating. The dip coating was performed by immersing the substrate in 100 ml of the mixed solution, pulling up the coating substrate vertically and drying at room temperature for 3 hours.

• - Evaluation 1: The SEM image of the surface microstructure of the LDH-like compound separator obtained in Example D2 (before roll pressing) is as in FIG 16 shown. As in 16 as shown, it was confirmed that cubic crystals were observed on the surface of the LDH-like compound separator. The results of the EDS elemental analysis and the X-ray diffraction measurement described below show that these cubic crystals are probably In(OH) ₃ .
• - Evaluation 2: From the observation result of layered lattice fringes, it was confirmed that the LDH-like compound separator contains a compound having a layered crystal structure.
• - Evaluation 3: As a result of the EDS elemental analysis, on the surface of the LDH-like compound separator, the components of the LDH-like compound or In(OH) ₃ , namely Mg, Ti, Y and In, were detected. In addition, In, which is a component of In(OH) ₃ , was detected in the cubic crystals on the surface of the LDH-like compound separator. The composition ratio (atomic ratio) of Mg, Ti, Y and m on the surface of the LDH-like compound separator calculated by EDS elemental analysis is as shown in Table 4.
• -Evaluation 4: The peaks in the obtained XRD profile identified that In(OH) ₃ was present in the LDH-like compound separator. This identification was made from the diffraction peaks of In(OH) ₃ listed in JCPDS card No. 01-085-1338.
• - Evaluation 5: As shown in Table 4, the extremely high density was confirmed by a He permeability of 0.0 cm/min·atm.
• - Evaluation 6: The high ionic conductivity was confirmed as shown in Table 4.
• -Evaluation 7: The He permeability after the alkali immersion was 0.0 cm/min·atm as in the evaluation 5, and the He permeability remained unchanged even after one week alkali immersion at the elevated temperature of 90°C , which confirms the excellent alkali resistance.
• - Evaluation 8: As shown in Table 4, no short circuit caused by zinc dendrites occurred even after 300 cycles, confirming the excellent dendrite resistance.

[Table 4] Table 4 Structure of the functional layer Composition ratio (atomic ratio based on 100 of the total amount of Mg+Al+Ti+Y+In) In/(Mg+Al+Ti+Y+In) Evaluation of the hydroxide ion conductive separator He permeability (cm/min × atm) ionic conductivity (mS/cm) alkali resistance dendrite resistance Presence or absence of a change in He permeability Presence or absence of a short circuit Example D1 ^# LDH-like+ In(OH) ₃ Mg:7, Al:1, Ti:24, Y:3, In:65 0.65 0.0 2.7 is missing is missing Example D2 ^# LDH-like +In(OH) ₃ Mg:6, Al:0, Ti:17, Y:3, In:74 0.74 0.0 2.8 is missing is missing Example B8* LDH Mg:68, Al:32 0 0.0 2.7 available available
The # symbol represents a reference example.
The symbol * represents a comparative example.

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• WO 2013118561 [0003, 0004]
• WO 2016076047 [0003, 0004]
• WO 2016067884 [0003, 0004]
• WO 2019124214 [0004]

Claims (11)

An LDH-like compound separator comprising a porous substrate made of a polymer material; and a layered double hydroxide-like (LDH-like) compound with which the pores of the porous substrate are plugged, wherein a central region along the thickness of the LDH-like compound separator has a lower mean porosity than peripheral regions along the thickness of the separator with LDH-like connection. Separator with LDH-like compound claim 1 wherein the LDH-like compound is: (a) a hydroxide and/or an oxide having a layered crystal structure containing: Mg; and one or more elements containing at least Ti selected from the group consisting of Ti, Y and Al, or (b) a hydroxide and/or an oxide having a layered crystal structure containing (i) Ti, Y and optionally Al and/or Mg and (ii) at least one additive element M selected from the group consisting of In, Bi, Ca, Sr and Ba, or (c) a hydroxide and/or an oxide having a layered crystal structure comprising Mg, Ti, Y and optionally Al and/or In, wherein in (c) the LDH-like compound is present in the form of a mixture with In(OH) ₃ . Separator with LDH-like compound claim 1 or 2 , wherein the peripheral areas have an average porosity of 3% or more and the central area has an average porosity of 2% or less. Separator with LDH-like connection according to one of Claims 1 until 3 wherein the peripheral regions have an average porosity in the range of 3% to 15% and the central region has an average porosity of 15% or less. Separator with LDH-like connection according to one of Claims 1 until 4 , where the LDH-like compound is integrated throughout the thickness of the porous substrate. Separator with LDH-like connection according to one of Claims 1 until 5 having a helium permeability per unit area of 3.0 cm/atm·min or less. Separator with LDH-like connection according to one of Claims 1 until 6 which has an ionic conductivity of 2.0 mS/cm or more. Separator with LDH-like connection according to one of Claims 1 until 7 wherein the polymeric material is selected from the group consisting of polystyrene, poly(ether sulfone), polypropylene, epoxy resin, poly(phenylene sulfide), fluorocarbon resin, cellulose, nylon and polyethylene. Separator with LDH-like connection according to one of Claims 1 until 8th , which consists of the porous substrate and the LDH-like compound. Zinc secondary battery using the LDH-like compound separator according to any of the Claims 1 until 9 includes. A solid-state alkaline fuel cell using the LDH-like compound separator according to any one of Claims 1 until 9 includes.

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