JP6889607B2 - Solid electrolyte membrane - Google Patents

Description

The present invention relates to a solid electrolyte membrane.

In recent years, as mobile devices have become more multifunctional and lighter in weight, lithium ion secondary batteries having a high output density and a high capacity density have been used as their power sources. As such a separator for a battery, a polyolefin porous membrane is mainly used because the polyolefin porous membrane exhibits excellent electrical insulation and ion permeability (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-76337

While lithium-ion secondary batteries have high output density and capacity density, the separator may be damaged by heat generated by abnormal situations such as short circuit and overcharge, and in the worst case, ignition may occur. Therefore, the separator needs to have heat resistance, and the separator using a polymer is improved in heat resistance by providing an inorganic filler mixed layer as in Patent Document 1. Furthermore, in recent years, the applications of lithium-ion secondary batteries have expanded from conventional portable devices to power devices for in-vehicle and industrial applications, and along with this, the size and capacity of lithium-ion secondary batteries are rapidly increasing. As the size and capacity of the battery increase, the energy generated during abnormal operation also increases, and the amount of heat generated in the battery increases and the temperature rises, so there is a danger that the separator will deform or shrink, causing a short circuit. Increases sex. Therefore, there is a demand for a highly heat-resistant separator that has less dimensional change even at a higher temperature than the current separator and can maintain insulation. Further, in a lithium ion battery, lithium metal is deposited, which may destroy or short-circuit the separator, so a separator having high hardness is desired. As a separator having high heat resistance and high hardness, it is conceivable to use a solid electrolyte made of an inorganic material. Although the solid electrolyte using sulfide has high ionic conductivity, it generates toxic substances such as hydrogen sulfide. There is a possibility and there is a safety issue. A solid electrolyte using an oxide has high safety, but has problems of high grain boundary resistance and low ionic conductivity.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an inorganic solid electrolyte membrane that simultaneously satisfies high heat resistance, high hardness, and high ionic conductivity.

As a result of diligent studies to solve the above problems, the present inventor has found that the above object can be achieved by forming a solid electrolyte membrane made of a specific zeolite on the support without using an organic binder or the like. The heading has led to the completion of the present invention.

That is, the present invention is as follows.
[1]
Is formed in the porous body and is on a support, a solid electrolyte film made of an inorganic solid electrolyte, wherein an inorganic solid electrolyte zeolite, the total content of the carbon element and nitrogen element of the solid electrolyte membrane is 1 Ri wt% less der, the zeolite Ru FAU type zeolite der, the solid electrolyte membrane.
[2]
The solid electrolyte membrane according to the preceding item [1] , wherein the water content of the solid electrolyte membrane is 15% by mass or more with respect to the entire solid electrolyte membrane.
[3]
The solid electrolyte membrane according to the above item [1] or [2] , wherein the cation of the zeolite is lithium or sodium.
[4]
The solid electrolyte membrane according to any one of the preceding items [1] to [3] , which is water-repellent treated on the surface of the solid electrolyte membrane and / or at the interface between the solid electrolyte membrane and the support.
[5]
The solid electrolyte membrane according to any one of the above items [1] to [4] , which has a film thickness of 0.1 to 100 μm.

According to the present invention, it is possible to provide an inorganic solid electrolyte membrane that simultaneously satisfies high heat resistance, high hardness, and high ionic conductivity.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

The solid electrolyte membrane of the present embodiment is a solid electrolyte membrane formed on a support and made of an inorganic solid electrolyte, wherein the inorganic solid electrolyte is zeolite, and the total content of carbon elements and nitrogen elements in the zeolite. Is less than 1% by mass. By having the above-mentioned structure, the solid electrolyte membrane of the present embodiment can simultaneously satisfy high heat resistance, high hardness, and high ionic conductivity. In addition, in this specification, a "solid electrolyte membrane" may be referred to as a "zeolite membrane".

[Support]
The support may have, for example, high heat resistance and high hardness, and may come into contact with a high-temperature strong alkaline aqueous solution when synthesizing a zeolite membrane, so that it is preferable that the support has high alkali resistance. When the alkali resistance is insufficient, corrosion during synthesis of the zeolite membrane can be reduced by treating the surface of the support with water repellent treatment. Examples of the material of the support include a metal plate, a sintered body of metal particles, alumina, silica, a mixture of alumina and silica, a plate of ceramics such as mullite and kaolin, and a sintered body. When a metal is used, stainless steel is preferably used, and SUS304, 316 is more preferable, from the viewpoint of high corrosion resistance. When ceramics are used, it is preferable to use alumina, mullite, or kaolin from the viewpoint of high chemical resistance.

The support may be a plate-like body or a porous body, but from the viewpoint that it can be suitably used as a separator for a lithium ion secondary battery, a lithium-air battery, or the like, the support body may be a porous body. preferable.

[Inorganic solid electrolyte membrane]
The inorganic solid electrolyte used for the solid electrolyte membrane of the present embodiment is zeolite. By forming a film on the support, the film thickness can be reduced while maintaining high hardness, and the resistance of the ionic conduction layer can be reduced. As the inorganic solid electrolyte, an oxide-based solid electrolyte such as La-Li-Ti-O can be considered, but these oxide-based solid electrolytes require high-temperature firing at 1000 ° C. or higher, and a film is formed on the support. Even if it is attempted to be formed, cracks and peeling are likely to occur due to the large difference in the coefficient of thermal expansion between the support and the inorganic solid electrolyte, and it is difficult to form a thin film. Therefore, in the present embodiment, a solid electrolyte that simultaneously satisfies thinning, high heat resistance, and high hardness without causing cracks or peeling by forming a zeolite membrane without using an organic binder or the like on the support. A film can be formed. When an organic binder or the like is used, cracks or through holes may occur in the film due to combustion, decomposition, shrinkage, etc. caused by heating.

Even more surprisingly, when the zeolite membrane is grown directly on the support, the zeolite also grows crystals in the direction perpendicular to the membrane surface, and the grain boundaries that must pass when ions are conducted in this direction. Can be reduced, and the grain boundary resistance can be reduced. Furthermore, the present inventors have found that the gaps between crystal grains can be reduced as compared with the compression molding of particles, and high ionic conductivity is exhibited.

The type of zeolite used in this embodiment is not particularly limited, but as the number of cations increases, the number of cations contributing to ionic conduction increases and the ionic conductivity increases. Therefore, zeolites having a low silica / alumina ratio are preferable, and LTA, GIS, and ANA are preferable. , PHI, MOR, FAU type zeolite are more preferable. The larger the pore size of the zeolite and the wider the space in which ions can move, the higher the ionic conductivity. Therefore, the larger the pore size of the zeolite is preferable, and the FAU type zeolite is more preferable.

The type of zeolite cation is not particularly limited, but a cation having a small ionic radius is preferably lithium or sodium from the viewpoint of exhibiting higher ionic conductivity.

The method for forming the zeolite membrane is not particularly limited, and examples thereof include a method of compression molding powdered zeolite on the surface of the support and a method of hydrothermal synthesis directly on the support.

When the powdered zeolite is compression-molded, it is preferable to exchange ions with ions to be conducted in advance in the form of powder because ion exchange is easy. Further, it is preferable that the average particle size of the zeolite is small from the viewpoint that the gaps between the particles are small when the film is formed into a film and the porosity can be reduced. On the other hand, if the average particle size is too small, the crystallinity will decrease. From these viewpoints, the average particle size is preferably 100 nm to 3 μm, more preferably 120 nm to 1.5 μm, and even more preferably 100 to 500 nm. The average particle size of zeolite can be measured, for example, by observing 200 or more zeolite particles with a scanning electron microscope, measuring the particle size of these particles, and calculating the average value thereof.

In the case of hydrothermal synthesis directly on the support, the zeolite film is formed on the surface of the support by putting the support in the zeolite raw material slurry and hydrothermal synthesis. It is preferable to attach the same crystal particles as zeolite to be grown on the surface of the support in advance as seed crystals before hydrothermal synthesis, because the hydrothermal synthesis time can be significantly shortened. When hydrothermal synthesis is performed directly on the support, the crystal growth of the zeolite crystal also proceeds in the direction perpendicular to the surface of the support, so that the grain boundaries can be reduced as compared with the case of forming by compression molding, and ion conduction at the crystal grain boundaries A solid electrolyte film having high ionic conductivity can be obtained because the resistance to the ionic conductivity is reduced. Further, since almost no gaps are generated between the crystal particles, the ionic conductivity can be further increased, which is preferable. When the zeolite membrane is grown directly on the support, it is preferable that the ion exchange for the ions to be conducted is performed after the film formation. This is because ion exchange is possible even after film formation, and the higher the crystallinity of the zeolite membrane, the higher the ionic conductivity. Therefore, zeolite is synthesized with a composition capable of high crystal growth, and ions are formed after film formation. This is because higher ionic conductivity can be obtained by exchanging.

[Thickness of solid electrolyte membrane]
The film thickness of the solid electrolyte membrane is not particularly limited, but is preferably 0.1 to 100 μm, more preferably 0.2 to 80 μm, and even more preferably 0.4 to 60 μm. When the film thickness is within the above range, the resistance of ionic conduction is reduced to obtain high ionic conductivity, and for example, when used in a lithium ion secondary battery, the film is prevented from being destroyed or short-circuited due to Li ion metal precipitation. , It is possible to obtain high hardness in a more balanced manner. The film thickness of the solid electrolyte membrane can be measured by the method described in Examples described later.

[Organic substances contained in the solid electrolyte membrane]
In the present embodiment, the total content of carbon elements and nitrogen elements in the zeolite is less than 1% by mass. The purity of the zeolite in the solid electrolyte membrane is preferably high. In particular, when an organic substance is contained as an impurity, not only the ionic conductivity is lowered, but also decomposition and combustion may occur at a high temperature, and the heat resistance is lowered. Therefore, a small amount is preferable. When the content of organic impurities is the total content of carbon elements and nitrogen elements, it is less than 1% by mass, preferably less than 0.5% by mass, and more preferably less than 0.1% by mass. preferable. The lower limit of the total content of the carbon element and the nitrogen element is not particularly limited, but is, for example, 0% by mass. The total content of carbon element and nitrogen element can be measured by, for example, secondary ion mass spectrometry (SIMS) or CHN analyzer. As will be described later, when the surface of the solid electrolyte membrane and / or the interface between the solid electrolyte membrane and the support is treated with an organic substance to repel water, the composition is distributed in the depth direction using the secondary ion mass analysis method. The amount of organic matter only in the solid electrolyte membrane may be measured. When the surface of the solid electrolyte membrane is water-repellent with an organic substance, CHN analysis of the solid electrolyte membrane may be performed after removing the organic substance on the surface by sputtering with Ar or O plasma.

[Water content of solid electrolyte membrane]
Zeolites usually stably contain about 10 to 30% by mass of water of crystallization, and the zeolite of the solid electrolyte membrane of the present embodiment may also contain water contained in a stable structure. The water content of the solid electrolyte membrane is preferably 15% by mass or more, more preferably 16% by mass or more, and 16.5% by mass or more, based on the entire solid electrolyte membrane (100% by mass). Is even more preferable. If the water content of the solid electrolyte membrane is less than 15% by mass, the ionic conductivity may decrease.

In the present embodiment, the water content of the solid electrolyte membrane is measured by heating to 300 ° C. using a TG-DTA (thermal analyzer) to calculate the weight loss amount, or from the weight loss amount when heated and vacuum dried. It can be calculated by doing so. On the other hand, in these methods, if an organic substance having a boiling point, decomposition temperature, and combustion temperature is present at 300 ° C. or lower, or if it is treated with water repellent, the amount is also counted. -The organic matter content may be measured by an MS device (gas chromatograph mass spectrometer), and the water content may be calculated by subtracting the amount. In addition, when a porous support is used as the support, the adsorbed water on this surface is also detected. Therefore, the water content of only the support is measured in advance, and the water content in the solid electrolyte membrane is calculated by subtracting that amount. It may be calculated.

[Water repellent treatment]
When the solid electrolyte membrane of the present embodiment is used, for example, as a separator for a lithium-air battery, a partition wall between an organic solvent-based electrolyte solution and an aqueous solution-based electrolyte solution, the surface of the solid electrolyte membrane and / or It is preferable that the water repellent treatment is performed at the interface between the solid electrolyte membrane and the support. This tends to reduce the permeation of water through the solid electrolyte membrane. Specific examples of the water-repellent treatment include a surface modification treatment with a silane coupling agent and a water-repellent coating treatment. The thinner the water-repellent layer formed by the water-repellent treatment, the more the decrease in ion conduction can be suppressed. Therefore, from the viewpoint of thinning the water-repellent layer, surface modification with a silane coupling agent is preferable. As the silane coupling agent, hexamethyldisilazane and tetraethyl orthosilicate are preferable, and hexamethyldisilazane is more preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1]
A SUS316 plate having a diameter of 25 mm and a thickness of 0.5 mm was used as a support. A seed crystal slurry in which 0.2% by mass of FAU-type zeolite particles having an average particle diameter of 1 μm were dispersed in ion-exchanged water was added dropwise to a 0.5 cc support, and the mixture was dried at room temperature for 12 hours.

Ion-exchanged water, sodium aluminate (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) in a Teflon (registered trademark) container have a mass ratio of Na: Al: H ₂ O = 14: 2: 1500. And stirred at room temperature for 2 hours. Ion-exchanged water and No. 3 water glass (manufactured by Kishida Chemical Co., Ltd.) were _{placed in another container so that the mass ratio was Si: H 2} O = 7: 500, and the mixture was stirred for 30 minutes. These liquids were mixed and mixed at room temperature for 1 hour to obtain a zeolite membrane synthetic raw material liquid (raw material liquid). This raw material solution was placed in an autoclave with a Teflon inner cylinder, the support to which the seed crystals were attached was submerged, and the mixture was allowed to stand in a constant temperature bath at 100 ° C. for 10 days to grow a zeolite membrane.

The obtained zeolite was prepared by using a powder X-ray diffractometer (XRD) "RINT2500 type" (trade name) manufactured by Rigaku Co., Ltd., using an X-ray source Cu tube (40 kV, 200 mA) and a measuring range of 5 to 90 ° (0). The result of analysis under the conditions of .02 ° / step), measurement speed 0.2 ° / min, slit width (scattering, divergence, light reception) 1 °, 1 °, and 0.15 mm was FAU.

The obtained zeolite membrane was placed in 2 liters of a 0.5 N lithium nitrate aqueous solution and stirred at 80 ° C. and 100 rpm for 3 hours for lithium ion exchange. The Li-FAU type zeolite membrane obtained by lithium ion exchange was dried at −120 kPa at 120 ° C. for 24 hours to obtain a Li-FAU type zeolite solid electrolyte membrane (solid electrolyte membrane).

A circular Pt having a diameter of 5 mm was formed on the surface of the obtained solid electrolyte membrane by sputtering to form an electrode, and an ionic conductivity measurement sample was prepared. The AC impedance of this sample was measured at 27 ° C. using an impedance analyzer 12608W (trade name: Solartron, 10μ to 32MHz), and the ionic conductivity was calculated from the resistance value obtained by the Core-Cole plot. It was 7.0 × 10 ^-4 S / cm.

When the composition distribution in the depth direction of the obtained solid electrolyte membrane was measured at a primary ion acceleration voltage of 15 eV using a secondary ion mass spectrometer (SIMS4100: manufactured by ATOMIKA), carbon and nitrogen were detected from the solid electrolyte membrane. Was not done.

When the cross section of the obtained solid electrolyte membrane was observed with a scanning electron microscope (SU-70: manufactured by HITACHI), the film thickness was 10 μm.

In order to evaluate the heat resistance of the obtained solid electrolyte membrane, it was allowed to stand in a constant temperature bath at 200 ° C. and 300 ° C. for 12 hours to perform a high temperature heating test. When the shape of the film was observed with a scanning electron microscope after cooling to room temperature, no particular change was observed compared to before heating, and the film withstood the high-temperature heating test.

[Example 2]
As the support, particles of SUS304 having an average particle diameter of 1 μm were sintered and made porous. The outer diameter was 30 mmφ and the thickness was 2 mm. Seed crystals were attached to this support in the same manner as in Example 1.

Put ion-exchanged water, sodium aluminate (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) in a Teflon container so that the mass ratio is Na: Al: H ₂ O = 29: 2: 600. The mixture was stirred at room temperature for 2 hours. Ion-exchanged water and No. 3 water glass (manufactured by Kishida Chemical Co., Ltd.) were _{placed in another container so that the mass ratio was Si: H 2} O = 10: 200, and the mixture was stirred for 30 minutes. These liquids were mixed and mixed at room temperature for 6 hours to obtain a zeolite membrane synthetic raw material liquid (raw material liquid). This raw material solution was placed in an autoclave with a Teflon inner cylinder, the support to which the seed crystals were attached was submerged, and the mixture was allowed to stand in a constant temperature bath at 100 ° C. for 5 hours to grow a zeolite membrane.

As a result of examining the structure of the solid electrolyte membrane by the same method as in Example 1, it was a FAU-type zeolite, and the film thickness was 8 μm.

Lithium ion exchange was carried out in the same manner as in Example 1 to obtain a Li-FAU type zeolite membrane, and further dried in the same manner as in Example 1 to obtain a Li-FAU type zeolite solid electrolyte membrane (solid electrolyte membrane). An electrode was formed on the surface of this solid electrolyte film by the same method as in Example 1, and the ionic conductivity was measured and found to be 4.8 × 10 ^-4 S / cm.

When the composition distribution in the depth direction was measured by the same method as in Example 1, carbon and nitrogen were not detected from the solid electrolyte membrane.

When the heat resistance was evaluated by the same method as in Example 1, no particular change was observed as compared with that before heating, and it withstood the high temperature heating test.

[Example 3]
As a support, a mullite hollow tube (manufactured by Nikkato) having an outer diameter of 12 mmφ, an inner diameter of 9 mmφ, and a length of 100 mm was used, and a solid electrolyte was used in the same manner as in Example 2 except that a FAU-type zeolite having a particle size of 400 nm was used as a seed crystal. A membrane was obtained.

As a result of examining the structure of the solid electrolyte membrane by the same method as in Example 1, it was a FAU-type zeolite, and the film thickness was 6 μm.

When the composition distribution in the depth direction was measured by the same method as in Example 1, carbon and nitrogen were not detected from the solid electrolyte membrane.

When the heat resistance was evaluated by the same method as in Example 1, no particular change was observed as compared with that before heating, and it withstood the high temperature heating test.

[Example 4]
A solid electrolyte membrane was obtained by the same method as in Example 2 except that an alumina hollow tube having an outer diameter of 10 mmφ, an inner diameter of 8 mmφ, and a length of 100 mm was used for the support and FAU-type zeolite having a particle size of 100 nm was used for the seed crystal.

As a result of examining the structure of the solid electrolyte membrane by the same method as in Example 1, it was a FAU-type zeolite, and the film thickness was 3 μm.

When the composition distribution in the depth direction was measured by the same method as in Example 1, carbon and nitrogen were not detected from the solid electrolyte membrane.

When the heat resistance was evaluated by the same method as in Example 1, no particular change was observed as compared with that before heating, and it withstood the high temperature heating test.

[Example 5]
The solid electrolyte membrane obtained by the same method as in Example 3 was placed in 300 cc of toluene containing 1% by mass of hexamethyldisilazane and heated at 85 ° C. for 2 hours in a nitrogen atmosphere while refluxing to modify the surface (water repellent treatment). did.

When the composition distribution in the depth direction was measured by the same method as in Example 1, carbon and nitrogen were not detected from the solid electrolyte membrane. Since carbon from the methyl group due to surface modification of the surface of the solid electrolyte film was not detected, only the surface-modified solid electrolyte film and support, and the Murite support were used as a CHN analyzer manufactured by J-Science Lab, "MICRO". CHN analysis was performed using "CORDER JM10" (trade name), and the carbon and nitrogen contents detected from the Murite support were subtracted from the carbon and nitrogen contents detected from the surface-modified solid electrolyte membrane and support. When the contents of carbon and nitrogen from the surface-modified methyl group were measured, it was found that C = 0.005% by mass and N = 0.000% by mass, and the solid electrolyte membrane did not contain carbon and nitrogen. , It turned out that carbon is present only on the surface.

When the heat resistance was evaluated by the same method as in Example 1, no particular change was observed as compared with that before heating, and it withstood the high temperature heating test.
[Comparative Example 1]
A Na-FAU type zeolite having an average particle size of 1 μm was placed in 2 liters of a 0.5 N lithium nitrate aqueous solution, and the mixture was stirred at 80 ° C. and 100 rpm for 3 hours to exchange lithium ions. The lithium ion-exchanged Li-FAU type zeolite membrane was dried at −120 kPa at 120 ° C. for 24 hours to obtain a powdered Li-FAU type zeolite solid electrolyte.

2 g of epoxy resin (EP106NL: manufactured by Cemedine Co., Ltd.) and 25 g of tetrahydrofuran were mixed and stirred at 40 ° C. for 3 hours to dissolve and dilute. 5 g of this mixed solution was added to 10 g of Li-FAU type zeolite and mixed until uniform. This mixed solution was applied onto a metal plate and evacuated while heating at 60 ° C. to remove the solvent, and then a metal plate was placed on the upper part and sandwiched, and compressed and stretched to a thickness of 500 μm. .. It was peeled off from a metal plate, and the obtained membrane was cured while vacuum drying at 120 ° C. for 24 hours to obtain a zeolite membrane using an epoxy resin as a binder.

When the ionic conductivity was measured by the same method as in Example 1 except that electrodes were formed on both sides, it was 1.6 × 10 ^-6 S / cm.

When the composition distribution in the depth direction was measured by the same method as in Example 1, 2.50% by mass of carbon and 0.010% by mass of nitrogen were detected from the solid electrolyte membrane.

When the heat resistance was evaluated by the same method as in Example 1, some cracks were generated when heated at 200 ° C., and the cracks were further expanded when heated at 300 ° C. Did not withstand the heating test.

[Comparative Example 2]
A mixed solution of Li-FAU type zeolite powder and epoxy resin-tetrahydrofuran was prepared by the same method as in Comparative Example 1, applied to the same SUS plate as in Example 1, desolvated and then compressed and stretched to 100 μm. The epoxy resin was cured by the same method as in Comparative Example 1 to obtain a SUS plate support and a zeolite membrane using the epoxy resin as a binder.

When the electrode was formed by the same method as in Example 1 and the ionic conductivity was measured, it was 4.2 × 10 ^-5 S / cm.

When the composition distribution in the depth direction was measured by the same method as in Example 1, 2.18% by mass of carbon and 0.005% by mass of nitrogen were detected from the solid electrolyte membrane.

When the heat resistance was evaluated by the same method as in Example 1, some tears and peeling occurred when heated to 200 ° C., and peeling further expanded when heated to 300 ° C. Did not withstand the heating test.

[Comparative Example 3]
Ultra-high molecular weight polyethylene with a viscosity average molecular weight (Mv) of 1 million 20.0% by mass, high-density polyethylene with an Mv of 200,000 10.0% by mass, dioctyl phthalate (DOP) 50% by mass, fine silica powder 20% by mass. After mixed granulation, the mixture was melt-kneaded with a twin-screw extruder equipped with a T-die at the tip, extruded, rolled with heated rolls from both sides, and formed into a sheet having a thickness of 80 μm. DOP and fine silica powder were extracted and removed from the molded product to prepare an extraction film. Two of the extraction films were laminated, stretched 6 times to MD at a stretching temperature of 125.0 ° C., stretched 2 times to TD at 120 ° C., and finally heat-treated at 136.0 ° C. to relax 10% stretching. A microporous membrane was obtained. This film was brought into close contact with the same SUS304 support as in Example 2 by heating and pressing at 120 ° C.

When the heat resistance of this film was evaluated by the same method as in Example 1, when it was heated to 200 ° C, it shrank as compared with that before heating, and some peeling was observed, and when it was heated to 300 ° C, it shrank further. Peeling and tearing were observed, and it did not withstand the high temperature heating test.

The solid electrolyte of the present invention can be used for electrochemical elements such as primary batteries, secondary batteries and capacitors.

Claims (5)

Is formed in the porous body and is on a support, a solid electrolyte film made of an inorganic solid electrolyte, wherein an inorganic solid electrolyte zeolite, the total content of the carbon element and nitrogen element of the solid electrolyte membrane is 1 Ri wt% less der, the zeolite Ru FAU type zeolite der, the solid electrolyte membrane. The water content of the solid electrolyte membrane, the entire solid electrolyte film was, at 15 mass% or more, a solid electrolyte membrane according to claim 1. The solid electrolyte membrane according to claim 1 or 2 , wherein the zeolite cation is lithium or sodium. The solid electrolyte membrane according to any one of claims 1 to 3 , which is water-repellent treated on the surface of the solid electrolyte membrane and / or at the interface between the solid electrolyte membrane and the support. The solid electrolyte membrane according to any one of claims 1 to 4 , wherein the film thickness is 0.1 to 100 μm.