JP6685837B2 - Method for producing solid electrolyte particle membrane - Google Patents

Description

  The present invention relates to a method for producing a solid electrolyte particle membrane.

  A solid electrolyte having lithium ion conductivity is a useful compound that is expected to be used as a solid electrolyte for all-ion lithium-ion batteries and lithium-air batteries.

  In particular, when a solid electrolyte is used for a lithium ion battery instead of the electrolytic solution in a conventional lithium ion battery, a lithium ion all-solid battery in which the positive electrode material, the electrolyte and the negative electrode material are all solid can be prepared. The lithium-ion all-solid-state battery has been proposed as a technology with dramatically improved safety because it does not use a flammable electrolyte.

  As a solid electrolyte used for a lithium ion all-solid-state battery, for example, a sulfide-based material having high lithium ion conductivity is known. However, sulfide-based materials have poor chemical stability, and when exposed to the atmosphere, hydrogen sulfide is generated, and when the sulfide-based solid electrolyte and the positive electrode material are directly contacted with each other, lithium does not exist at the boundary surface. There is a problem that a "deficient layer" having a thickness of several nanometers appears and output characteristics are significantly deteriorated.

  In order to solve the above problems, attempts have been made to use a metal oxide material such as a garnet-type oxide or a NASICON-type oxide, which has high lithium ion conductivity and is chemically stable, as a solid electrolyte. However, since an oxide-based material has poor flexibility and is difficult to process, it is difficult to reduce the resistance of the grain boundary and increase the ionic conductivity by applying a pressure like a sulfide-based solid electrolyte. Furthermore, since oxide-based materials are brittle materials, they are inferior in workability, and when incorporated into batteries, short-circuiting is likely to occur and it is difficult to thin the solid electrolyte layer. It was difficult to increase the electric capacity of the battery.

  In order to solve the above problems of the solid electrolyte, there is disclosed a technique of combining the solid electrolyte with a compound having a particle shape and flexibility. Patent Document 1 describes a technique of obtaining a flexible solid electrolyte membrane by arranging solid electrolyte particles in one layer on the same plane, applying a resin solution and forming a film. Patent Document 2 describes a technique of obtaining a flexible solid electrolyte membrane by dispersing particles on an adhesive release film, coating a resin, and peeling the film.

US Patent Application Publication No. 2015/0255767 U.S. Patent Application Publication No. 2015/0079485

  However, in the methods described in Patent Documents 1 and 2, it is necessary to expose the surfaces of the solid electrolyte particles to both surfaces in order to secure lithium ion conductivity between both surfaces of the membrane, and for example, physical treatment by polishing is required. It was necessary to go through complicated processes such as a method of removing the resin to expose the surface of the solid electrolyte particles, a method of removing the resin by chemical etching, and a method of removing the resin by etching with ions. Therefore, any of the methods has problems such as extremely complicated operations and particles falling off from the membrane, and the solid electrolyte membrane having flexibility in which solid electrolyte particles are exposed on both sides of the membrane is easily produced. A method was desired.

  The present invention has been proposed in view of such conventional circumstances, and an object of the present invention is to provide a simple method for producing a membrane in which a part of the solid electrolyte particles is exposed on both sides of the membrane. .

  The present inventors have diligently studied to solve the above problems, and as a result of repeated experiments, the resin particles and the solid electrolyte particles are arranged in a single layer on the same surface and heated to a temperature equal to or higher than the melting point of the resin so that both surfaces of the film are The present invention has been accomplished by finding a manufacturing method for easily obtaining a film in which a part of the solid electrolyte particles is exposed. That is, the present invention is as follows.

[1]
A method for producing a membrane, comprising arranging resin particles and solid electrolyte particles in a single layer on the same surface and heating the resin particles to a temperature equal to or higher than the melting point of the resin to expose a part of the solid electrolyte particles on both surfaces of the membrane.
[2]
The membrane according to item 1, wherein the ratio of the particle size of the resin particles to the particle size of the solid electrolyte particles is 0.3 ≦ (particle size of resin particles / particle size of solid electrolyte particles) ≦ 3.0. Production method.
[3]
Item 2. The method for producing a film according to Item 1, wherein the resin has a molecular weight of 100,000 or more.

It is sectional drawing which shows schematically an example of the film | membrane obtained by the manufacturing method of the film | membrane in this embodiment.

  Hereinafter, modes for carrying out the present invention (hereinafter, simply 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. In addition, the range described by using "to" in the present specification includes the numerical values described before and after the range.

<< Method for producing solid electrolyte particle membrane >>
The method for producing a solid electrolyte particle membrane of the present embodiment, the resin particles and the solid electrolyte particles are arranged in a single layer on the same surface, heated above the melting point of the resin, a portion of the solid electrolyte particles on both sides of the membrane. Including exposure to.

  FIG. 1 is a cross-sectional view schematically showing an example of a film obtained by the method for manufacturing a film according to this embodiment. In FIG. 1, the solid electrolyte particles are arranged in a single layer on the same surface, and a part of the solid electrolyte particles is exposed on both surfaces of the membrane. The membrane 100 of FIG. 1 is composed of solid electrolyte particles 110 and a resin 120, and the solid electrolyte particles are arranged in a single layer on the same surface, a part of which is exposed on both surfaces of the membrane and communicates with both surfaces of the membrane. ing.

  In the method for producing a membrane of the present embodiment, the membrane as schematically shown in FIG. 1 can be easily produced by arranging the solid electrolyte particles and the resin particles in one layer on the same plane.

<Solid electrolyte particles>
In the present embodiment, any solid electrolyte can be used as the solid electrolyte particles as long as it is a particulate solid electrolyte. Examples of the solid electrolyte include sulfide-based solid electrolytes and oxide-based solid electrolytes, and oxide-based solid electrolytes are preferable. The oxide-based solid electrolyte is preferable because the particles have sufficient hardness and a short circuit is less likely to occur when incorporated into a battery as a solid electrolyte membrane. Examples of the oxide solid electrolyte include γ-LiPO ₄ type oxide, inverted fluorite type oxide, NASICON type oxide, perovskite type oxide, and garnet type oxide. Examples of the NASICON-type oxide include Li _{1 + x} M _x Ti _2-x (PO ₄ ) ₃ (where M is at least one element selected from Al and rare earths, and x is 0.1 to 1.9). ), As a perovskite type oxide, for example, La _{2 / 3-x} Li _3x TiO ₃ , and as a garnet type oxide, for example, Li ₇ La ₃ Zr ₂ O ₁₂ is preferable. Use of crystalline oxide solid electrolyte particles obtained by substituting and / or doping an element with respect to the above-mentioned basic crystal structure from the viewpoints of enhancing ionic conductivity, chemical stability, and processability. You can also Preferably, the NASICON-type oxide is Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , the garnet-type oxide is Li ₇ La ₃ Zr ₂ O ₁₂ , and the element substitution body Li _6.25 Al. _{0.25 La 3 Zr 2 O 12,} Li 7 La 3 Zr 2-x Nb x O 12 (0 <X <0.95), and _{Li 7 La 3 Zr 2-x} Ta x O 12 (0 <X < 0.95).

  The shape of the solid electrolyte particles is not limited, and for example, a shape close to a sphere is preferable from the viewpoint of obtaining homogeneity when mixed with the resin particles. The particle size of the solid electrolyte particles is, for example, 5 μm to 100 μm, and preferably 20 to 75 μm, although the preferable range varies depending on the particle size of the resin particles to be combined. It is preferable to accurately classify the solid electrolyte particles.To improve the classification accuracy, the solid electrolyte particles are preliminarily dried to remove water, and static electricity is removed by using a static eliminator to prevent the solid electrolyte particles from aggregating due to static electricity. However, it is preferable to perform classification by a sieving vibration, a classification method using an air classifier or the like.

<Resin particles>
Any resin may be used as long as the resin particles are arranged in a single layer on the same surface as the solid electrolyte particles and a film can be formed by heating the resin particles at a temperature higher than the melting point of the resin. Examples of the resin include polyolefin resins represented by polyethylene and polypropylene, polyester resins represented by polyethylene terephthalate and polybutylene terephthalate, polyvinylidene fluoride, polyacrylonitrile, polyamide, and polyamideimide. From the viewpoint of film-forming property and electrochemical stability, polyolefin resin is preferable, and polyethylene and polypropylene are more preferable. It is also preferable to use a resin having lithium ion conductivity for the purpose of increasing the lithium ion conductivity of the film. It is also preferable to use resin particles such as polyethylene oxide, polypropylene oxide, polyvinylidene fluoride, and polyacrylonitrile containing a lithium salt. Examples of the lithium salt include LiBr, LiCl, LiI, LiSCN, LiBF ₄ , LiAsF ₆ , LiClO ₄ , CH ₃ COOLi, CF ₃ COOLi, LiCF ₃ SO ₃ , LiPF ₆ , LiN (CF ₃ SO ₂ ) ₂ , and LiC. _(CF 3 _{SO 2) 3} and the like.

  The molecular weight of the resin is not limited and may be, for example, a viscosity average molecular weight of 10,000 to 5,000,000. It is preferable to use polyolefin resin particles having a viscosity average molecular weight of 10,000 to 5,000,000, for example, polyethylene resin particles. From the viewpoint of maintaining the fluidity of the resin to such an extent that the surface of the solid electrolyte particles is sufficiently exposed on both sides of the membrane, it is preferable that the viscosity average molecular weight is 10,000 or more, and the resin particles themselves, and the resin particles and the solid electrolyte particles are sufficient. From the viewpoint of obtaining good adhesion, the viscosity average molecular weight is preferably 5,000,000 or less. It is more preferable to use polyolefin resin particles having a viscosity average molecular weight of 100,000 to 3,000,000, for example polyethylene resin particles.

  The shape of the resin particles is not particularly limited, and from the viewpoint of obtaining homogeneity when mixed with the solid electrolyte particles, preferably a shape close to a sphere, more preferably a spherical or grape-like particle can be used. Although the preferable range of the particle size of the resin particles varies depending on the particle size of the solid electrolyte particles to be combined, it is, for example, 5 μm to 100 μm, preferably 20 to 75 μm. It is preferable to classify the resin particles precisely. To improve the classification accuracy, the resin particles are preliminarily dried to remove water, and static electricity is removed using a static eliminator to prevent the resin particles from aggregating due to static electricity. It is preferable to perform classification by a classification method using vibration, a wind force classifier or the like.

<Array>
The method for producing the membrane of the present embodiment includes arranging the resin particles and the solid electrolyte particles in a single layer on the same surface. It is preferable that the resin particles and the solid electrolyte are homogeneously mixed before the arrangement. In order to uniformly mix the resin particles and the solid electrolyte particles, a general particle mixing method can be used, and for example, a container rotary mixer, a mechanical stirring mixer, or the like can be used. From the viewpoint of avoiding a change in particle size distribution due to cracking of particles, it is preferable to mix the particles by a method in which excessive force is not applied to the particles. From the viewpoint of avoiding non-uniformity due to agglomeration of resin particles due to static electricity, it is also preferable to prevent electrification by using a static electricity removing device or the like.

  The ratio between the solid electrolyte particles and the resin particles is not limited, and for example, it is preferable that the volume ratio is 0.2 ≦ (volume of resin particles / volume of solid electrolyte particles) ≦ 10. If 0.2 ≦ (volume of resin particles / volume of solid electrolyte particles), a stronger film is obtained, and if (volume of resin particles / volume of solid electrolyte particles) ≦ 10, solid electrolyte particles It is preferable because the density per unit area is increased and higher ionic conductivity is obtained. More preferably, 0.8 ≦ (volume of resin particles / volume of solid electrolyte particles) ≦ 3. When a membrane in which solid electrolyte particles and resin particles are integrated and used in an all-solid-state battery is used, if dendrite precipitation or the like becomes a problem, it is preferable to increase the resin ratio to increase the strength of the membrane, and as a solid electrolyte membrane. When high ion conductivity is required, it is preferable to increase the lithium ion conductivity by lowering the resin ratio and increasing the ratio of solid electrolyte particles.

  The combination of the solid electrolyte particle size and the resin particle size is such that the resin particles and the solid electrolyte particles are arranged in a single layer on the same surface, and if the film can be formed by heating above the melting point of the resin, any particle size combination is used. be able to. Preferably, 0.3 ≦ (particle size of resin / particle size of solid electrolyte) ≦ 3.0. If 0.3 ≦ (particle size of resin / particle size of solid electrolyte), it becomes easy to expose the surface of the solid electrolyte particles on both surfaces of the membrane, and (particle size of resin / particle size of solid electrolyte) ≦ 3. A value of 0 is preferable because a film having higher strength can be obtained. More preferably, 0.5 ≦ (particle size of resin / particle size of solid electrolyte) ≦ 2.0. In the specification of the present application, the average particle diameter, specifically, the number average particle diameter is used as the particle diameter. The number average particle size can be measured by a wet type particle size measuring device (for example, a laser diffraction / scattering type particle size distribution meter, a dynamic light scattering type particle size distribution meter), a dry type laser diffraction type particle size measuring device, or the like.

  As a method for arranging the resin particles and the solid electrolyte particles in one layer, for example, by placing the particles on the adhesive layer and removing the particles not fixed to the adhesive layer, a structure in which the particles are arranged in one layer is obtained. be able to. As the pressure-sensitive adhesive layer, for example, a pressure-sensitive adhesive tape or a base material coated with grease that can be easily removed can be used. As a method of removing particles that are not fixed to the adhesive layer, by inversion with the adhesive layer on which the particles are placed, a method of dropping and removing the particles that are not fixed, and fixing to the adhesive layer by jetting gas, etc. It is possible to use a method in which unremoved particles are blown off and removed. The above operation is preferably performed by removing static electricity by using a static eliminator or the like in order to prevent the solid electrolyte particles and the resin particles from being non-uniformly dispersed by the aggregation of particles due to static electricity.

<heating>
The solid electrolyte and the resin particles arranged in a single layer on the same surface can be integrated by heating above the melting point of the resin to form a film.

  The heating temperature may be equal to or higher than the melting point of the resin, and is preferably from the melting point of the resin to (a temperature 100 ° C. higher than the melting point of the resin). When the temperature is equal to or higher than the melting point, proper viscosity of the resin is obtained, the resin particles are firmly adhered to each other and the resin particles and the solid electrolyte particles are sufficiently fixed, and sufficient film strength is obtained, which is 100 ° C. higher than the melting point of the resin. When the temperature is lower than the temperature, the resin is not easily denatured, and the fluidity of the resin can be maintained to the extent that the surfaces of the solid electrolyte particles are sufficiently exposed on both surfaces of the membrane, which is preferable. More preferably, it is from the melting point of the resin to (a temperature higher than the melting point of the resin by 80 ° C.), and further preferably from the melting point of the resin to a temperature (60 ° C. higher than the melting point of the resin).

  The heating time is not limited and is preferably 10 seconds to 1 hour. If the time is 10 seconds or more, the resin particles and the resin particles and the solid electrolyte particles are sufficiently fixed to each other, and sufficient membrane strength can be obtained. The fluidity of the resin can be maintained to the extent that the surfaces of the electrolyte particles are sufficiently exposed on both sides of the membrane, and sufficient strength of the membrane can be maintained. More preferably, the heating time is 1 minute to 30 minutes. For heating, the adhesive layer used to fix the resin particles and the solid electrolyte particles, and if the removable grease does not deteriorate, deform, or denature at the heating temperature, the adhesive layer and the base material on which the grease is placed are heated. It is preferable. If problems such as deterioration, deformation, and modification of the adhesive layer and grease occur when heating the base material together, heat the adhesive layer and grease with radiant heat from the surface where no grease is present to deteriorate, deform, or modify the adhesive layer and grease. Is preferably suppressed.

<Other>
After heating the solid electrolyte and resin particles arranged in a single layer on the same surface, the membrane composed of the integrated solid electrolyte particles and resin is separated from the base material, and the residual adhesive layer, residual grease, etc. of the membrane are removed. It can be used by removing it with a solvent or the like.

  In the membrane produced by the method for producing a membrane of the present embodiment, some solid electrolyte particles are exposed on both sides of the membrane. Confirmation that part of the solid electrolyte particles is exposed on both sides of the membrane can be confirmed by observing using an optical microscope, a laser microscope, a scanning electron microscope (Scanning Electron Microscope, SEM), or the like. .

  The embodiments for carrying out the present invention have been described above, but the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the gist thereof.

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

[Example 1]
Using polyethylene particles as the resin particles and LATP (Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ ) particles that are NASICON-type solid electrolytes as the solid electrolyte particles, the solid particles were solidified by the following procedure. The electrolyte particles were arranged in one layer on the same surface, and a part of the solid electrolyte particles was exposed on both surfaces of the film to form a film.

<Classification of resin particles and solid electrolyte particles>
As polyethylene particles, MIPELON KM-220 (particle shape: spherical, viscosity molecular weight: 2710,000) manufactured by Mitsui Chemicals, Inc. was dried at 110 ° C. for 2 hours. Then, the particles were classified using a stainless steel sieve having openings of 20 μm and openings of 53 μm while continuing the static electricity removing operation of the dry resin particles by a static eliminator (STABLO-EX) manufactured by Shimadzu to obtain polyethylene particles of 20 μm to 53 μm. Obtained. The number average particle diameter of the polyethylene particles was 38 μm as determined by Microtrac Particle Size Analyzer manufactured by Nikkiso Co., Ltd., and the melting point of the polyethylene particles was 136 ° C. when TG-DTA measurement was performed.

  As a solid electrolyte particle, a Toshima Seisakusho LATP plate was roughly crushed using an agate mortar and pestle, and then crushed by an automatic crusher at 100 rpm for 10 minutes. The obtained powder is dried at 150 ° C. for 2 hours, particles are classified using a stainless steel sieve with openings of 20 μm and openings of 53 μm, and static electricity removal operation is continued by a static eliminator (STABLO-EX) manufactured by Shimadzu. Meanwhile, LATP particles of 20 μm to 53 μm were obtained. The number average particle diameter of LATP particles was 30 μm as determined by a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.

<Film formation using resin particles and solid electrolyte particles>
1.2 g of the classified resin particles and 3.8 g of the classified LATP particles were weighed and sufficiently mixed using a container rotary mixer to obtain a homogeneous particle mixture. Since the number average particle diameter of polyethylene was 38 μm and the number average particle diameter of LATP particles was 30 μm, the ratio of the resin particle diameter / the solid electrolyte particle diameter was 1.3. Since the specific gravity of polyethylene particles was 0.94 g / cm ³ and the specific gravity of LATP particles was 2.94 g / cm ³ , the ratio of volume of polyethylene particles / volume of LATP particles was 0.99.

  Apply a thin coat of Dow Corning heat-resistant grease to a central area of 2 cm x 2 cm of an aluminum plate having a size of 4 cm x 4 cm and a thickness of 0.2 mm, place the particle mixture on the grease, and invert the base material together. Then, the excess particles not fixed on the substrate were removed. The operation of removing the surplus particles by further placing the particle mixture on the base material and inverting the mixture was repeated several times, so that the polyethylene particles and the LATP particles were arranged in a single layer. The operation of removing the excess particles was performed by a static eliminator (STABLO-EX) manufactured by Shimadzu while continuing the operation of removing static electricity.

  The base material on which the particles were placed was placed on a flat plate block heater heated to 190 ° C., and heating was continued for 30 minutes. Then, it was cooled for 15 minutes, and the membrane in which the resin and the solid electrolyte particles were integrated was separated from the substrate. Then, the grease remaining on the membrane was removed with hexane to obtain a membrane in which the resin and the solid electrolyte particles were integrated. When both surfaces of the film were observed using a SEM at a magnification of × 1000, it was confirmed that part of the particle surface was exposed on both surfaces.

SEM observation condition Device: VE-9800 manufactured by KEYENCE
Accelerating voltage: 1.2KV
Spot diameter: 6 (set value of the device)
Degree of vacuum: 3 Pa
Detector: Secondary electron detector

[Example 2]
The same operation as in Example 1 was carried out except that 4.2 g of LATP particles were used, 0.7 g of polyethylene particles were used, and the resin particle volume / solid electrolyte particle volume ratio was 0.52. An integrated film was obtained. As a result of SEM observation, the solid electrolyte particles were partially exposed on both sides of the membrane.

[Example 3]
The polyethylene particles were classified using a sieve having a mesh opening of 53 μm and a sieve having a mesh opening of 100 μm to obtain polyethylene particles having a particle diameter of 53 to 100 μm. The number average particle diameter of the polyethylene particles was measured and found to be 75 μm, and the ratio of the particle diameter of the polyethylene particles / the particle diameter of the solid electrolyte particles was 0.7. A membrane in which the solid electrolyte and the resin were integrated was obtained by the same method as in Example 1 except that the polyethylene particles were used as the resin particles. As a result of SEM observation, the solid electrolyte particles were partially exposed on both sides of the membrane.

[Example 4]
By grinding Toshima Seisakusho solid electrolyte _{LLZO (Li 7 La 3 Zr 2} O 12) plate-like target material, except that to obtain a particle size 20~50μmLLZO particles do in the same manner as in Example 1, the solid electrolyte A film in which the particles and the resin are integrated was obtained. At this time, the number average particle size of the LLZO particles was 31 μm, and the ratio of the particle size of the resin / the particle size of the solid electrolyte was 1.27. Since the specific gravity of the LLZO particles was 4.85 g / cm ³ , the ratio of the volume of polyethylene particles / the volume of LATP particles was 1.63. As a result of SEM observation of the obtained membrane, the solid electrolyte particles were partially exposed on both sides of the membrane.

[Example 5]
The same LATP ground particles as in Example 1 were classified with a sieve having an opening of 20 μm to obtain LATP particles having a particle diameter of 20 μm or less. When the number average particle diameter of the LATP particles was measured, it was 11 μm. The same polyethylene particles as in Example 1 were classified using a sieve having a mesh opening of 53 μm and a sieve having a mesh opening of 100 μm to obtain polyethylene particles having a particle diameter of 53 to 100 μm. The number average particle diameter of the polyethylene particles was measured and found to be 74 μm. The ratio of the particle diameter of polyethylene particles / the particle diameter of solid electrolyte particles was 7.5. The same operation as in Example 1 was carried out except that the above-mentioned polyethylene particles and solid electrolyte particles were used to obtain a membrane in which the solid electrolyte particles and the resin were integrated, but the membrane had low strength and cracked, and separation was difficult. there were.

[Example 6]
A film in which the solid electrolyte particles and the resin were integrated was obtained by using the same method as described in Example 1 except that CREOREX K4125P manufactured by Asahi Kasei Co., Ltd. having a viscosity molecular weight of 85,000 was used as the resin particles. During the separation operation, the strength of the film was low and many cracks were generated in the film, making it difficult to isolate the film.

[Example 7]
Using the same method as in Example 1, except that 4.7 g of LATP particles and 0.3 g of polyethylene particles were used and the ratio of the volume of resin particles / the volume of solid electrolyte particles was 0.20. Although a film in which the particles and the resin were integrated was obtained, it was difficult to isolate the particles in the form of a film because the particles fell off during the separation.

[Comparative Example 1]
In Example 1, the same operation was performed except that the particle mixture was placed on the substrate during the film formation with the resin particles and the solid electrolyte particles, and the operation of reversing was not performed and the particles were not arranged in one layer. Tried to obtain an integrated membrane. When the obtained composite was observed by SEM, the particles were not arranged in one layer on the same plane, so that the particles became a composite in which a plurality of layers were integrated, and one solid electrolyte particle was exposed on both sides of the membrane. There wasn't.

  Table 1 shows the film forming conditions and the results of Examples and Comparative Examples. As is clear from Table 1, in Example 5 in which the particle size of the resin particles and the particle size of the solid electrolyte particles were large, it was difficult to separate the membrane in which the solid electrolyte and the resin were integrated. On the other hand, in Examples 1 to 4 in which the ratio of the particle size of the resin to the particle size of the solid electrolyte is in the preferable range, the membrane in which the solid electrolyte particles and the resin were integrated was more easily obtained. In Example 6 in which particles of resin having a low viscosity molecular weight were used, it was difficult to separate the membrane in which the solid electrolyte and the resin were integrated, whereas in Examples 1 to 4 in which a viscosity molecular weight in a preferable range was used. In, it was easier to obtain a membrane in which the solid electrolyte and particles were integrated. In addition, in Example 7, it was difficult to separate the membrane in which the solid electrolyte and the resin were integrated, whereas in Examples 1 to 4 in which the ratio of the volume of the resin to the volume of the solid electrolyte was in a preferable range. In, it was easier to obtain a membrane in which the solid electrolyte particles and the resin were integrated.

  The method of the present invention makes it possible to easily obtain a membrane in which a part of the solid electrolyte particles is exposed on both sides of the membrane. The membrane in which a part of the solid electrolyte particles is exposed on both sides of the membrane can be widely applied to an electrolyte membrane of a lithium ion all-solid battery, a lithium ion separation membrane because it selectively permeates lithium ions, and the like.

100 Solid Electrolyte Membrane 110 Solid Electrolyte Particles 120 Resin

Claims (3)

By removing the pressure-sensitive adhesive layer disposed on the substrate and the resin particles carrying the mixture of solid electrolyte particles, the said resin particles which are not fixed to the adhesive layer and the solid electrolyte particles, the said resin particles and it is arranged more on the same surface of the solid electrolyte particles,
And heating above the melting point of the resin,
A method for producing a membrane , comprising removing the base material after heating to above the melting point of the resin to expose a part of the solid electrolyte particles on both sides of the membrane.   The membrane according to claim 1, wherein the ratio of the particle size of the resin particles to the particle size of the solid electrolyte particles is 0.3 ≦ (particle size of resin particles / particle size of solid electrolyte particles) ≦ 3.0. Manufacturing method.   The method for producing a film according to claim 1, wherein the resin has a molecular weight of 100,000 or more.

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