JP6894948B2 - Manufacturing method of molded film and manufacturing method of all-solid-state lithium-ion battery - Google Patents

Description

The present invention relates to a method for producing a molded film and a method for producing an all-solid-state lithium-ion battery.

Lithium-ion batteries are generally used as a power source for small portable devices such as mobile phones and laptop computers. Recently, in addition to small portable devices, lithium-ion batteries have begun to be used as power sources for electric vehicles and power storage.

Currently commercially available lithium ion batteries use an electrolytic solution containing a flammable organic solvent. On the other hand, a lithium-ion battery in which the electrolyte is changed to a solid electrolyte and the battery is completely solidified (hereinafter, also referred to as an all-solid-state lithium-ion battery) does not use a flammable organic solvent in the battery, and thus is a safety device. It is considered that the manufacturing cost and productivity are excellent because of the simplification of the battery.

In such an all-solid-state lithium-ion battery, a solid electrolyte sheet mainly containing a solid electrolyte material is used as the solid electrolyte layer. The following Patent Documents 1 and 2 describe examples of such a solid electrolyte sheet.

Patent Document 1 (Japanese Unexamined Patent Publication No. 4-133209) describes a solid electrolyte sheet containing a mixture of a lithium ion conductive solid electrolyte and a thermoplastic polymer resin.

According to Patent Document 2 (Japanese Unexamined Patent Publication No. 2008-124011), a crystalline solid electrolyte sheet is produced in which a glass-like lithium ion conductive solid electrolyte is formed into a sheet and then heat-treated, or is formed into a sheet and then heat-treated. The method is described.

Japanese Unexamined Patent Publication No. 4-133209 Japanese Unexamined Patent Publication No. 2008-124011

However, since a binder resin such as a thermoplastic polymer resin has almost no ionic conductivity, if the binder resin is present between the solid electrolyte materials, the ionic conduction between the solid electrolyte materials is hindered. Therefore, the solid electrolyte sheet as described in Patent Document 1 has low lithium ion conductivity, and is not yet satisfactory as a solid electrolyte sheet for an all-solid-state lithium ion battery.
Further, according to the study by the present inventors, it has been clarified that the thickness of the solid electrolyte sheet as described in Patent Document 2 becomes uneven when it is thinned.

The present inventors have diligently studied to provide a molded film having a uniform thickness and a thin thickness. As a result, they have found that a molding film having a uniform thickness and a thin molding film can be obtained by sieving the molding material filled in the voids of the porous body onto the cavity surface of the mold or the surface of the base material. It came to.

That is, according to the present invention.
The step (A) of filling the voids of the porous body with the powdered molding material, and
By sieving the molding material filled in the voids of the porous body onto the cavity surface of the mold or the surface of the base material, the molding material is formed into a film on the cavity surface of the mold or the surface of the base material. Step (B) of depositing in
Including
The base material is a method for producing a molded film that does not contain a conductive resin layer.
Provided is a method for producing a molded film in which the molded film is a solid electrolyte layer, a positive electrode layer, or a negative electrode layer, which is used in an all-solid-state lithium ion battery.

Further, according to the present invention
It is a manufacturing method for manufacturing an all-solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order.
The method for producing a molded film described above provides a method for producing an all-solid-state lithium ion battery, which comprises a step of forming at least one molded film selected from the positive electrode layer, the solid electrolyte layer, and the negative electrode layer. To.

According to the present invention, it is possible to realize a molded film having a uniform thickness and a thin shape.

It is a process cross-sectional view which shows typically an example of the manufacturing process of the molding film of this embodiment. It is a process cross-sectional view which shows typically an example of the manufacturing process of the molding film of this embodiment. It is a process cross-sectional view which shows typically an example of the manufacturing process of the molding film of this embodiment. It is a process cross-sectional view which shows typically an example of the manufacturing process of the molding film of this embodiment. It is sectional drawing which shows typically an example of the structure of the all-solid-state lithium ion battery of this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, similar components are designated by a common reference numeral, and the description thereof will be omitted as appropriate. Moreover, the figure is a schematic view and does not match the actual dimensional ratio.

[Manufacturing method of molded film]
First, a method for producing a molded film according to the present embodiment will be described.
1 to 4 are process cross-sectional views schematically showing an example of a manufacturing process of the molded film 100 of the present embodiment.
The method for producing a molded film according to the present embodiment includes the following steps (A) and (B), and further includes the step (C) if necessary.
(A) Step of filling the voids of the porous body 103 with the powdered molding material 101 (B) The molding material 101 filled in the voids of the porous body 103 is sieved on the cavity surface 107 of the mold 105 or on the surface of the base material. Step of depositing the molding material 101 in the form of a film on the cavity surface 107 of the mold or on the surface of the base material by dropping (C) A step of pressurizing the molding material 101 deposited in the form of a film.

Conventionally, a thin molding film has been produced by directly supplying a powdered molding material onto the cavity surface of a mold or the surface of a base material and then pressing the molding material at a high pressure. However, according to the studies by the present inventors, it has been clarified that the molded film produced by such a method has a non-uniform thickness.
Based on the above findings, the present inventors have diligently studied a method for producing the molded film 100 in order to provide the molded film 100 having a uniform thickness and a thin thickness. As a result, by sieving the molding material 101 filled in the voids of the porous body 103 onto the cavity surface 107 of the mold or the surface of the base material, a molding film 100 having a uniform thickness and a thin thickness can be obtained. The heading led to the present invention.
Although it is not clear why the molding film 100 having a uniform thickness and a thin thickness can be obtained by using the method for producing the molding film 100 of the present embodiment, the present inventors have found that the powdered molding material 101 is a porous body. It is presumed that this is because it is sieved little by little while passing through the opening of 103, so that it can be deposited in a film shape with a uniform thickness on the cavity surface 107 of the mold or on the surface of the base material.
By using the method for producing the molded film 100 of the present embodiment, for example, it is possible to obtain a thin molded film 100 of 100 μm or less with a uniform thickness.
Hereinafter, each step will be described in detail.

First, (A) the powdery molding material 101 is filled in the voids of the porous body 103. The method of filling the voids of the porous body 103 with the powdery molding material 101 is not particularly limited, but for example, the powdery molding material 101 is directly supplied into the voids of the porous body 103 in the air or in an inert atmosphere. Examples thereof include a method in which a powdered molding material 101 is dispersed in a solvent to form a slurry, then the slurry is applied onto the porous body 103, the slurry is allowed to permeate into the voids, and then the solvent is dried. Be done.

As a method of directly supplying the powdered molding material 101 into the voids of the porous body 103 in the air or in an inert atmosphere, the molding material 101 is powder-coated on the porous body 103, and the porous body is used by the squeegee 109. Examples thereof include a method of filling the voids with the molding material 101 while removing the excess molding material 101 on the 103.
As a method for applying the slurry, generally known methods such as a doctor blade coating method, a dip coating method, a spray coating method, and a bar coater coating method can be used.
By these methods, the molding material 101 can be continuously filled in the voids of the porous body 103.
Here, in the porous body 103, from the viewpoint of sieving the molding material 101 filled in the voids of the porous body 103 only at a desired position, resin or the like is previously filled in the voids of the portion where the powdered molding material 101 is not desired to be filled. Is preferably embedded so that the powdered molding material 101 is not filled. By doing so, in the step (B), the molding material 101 can be sieved only at a desired position, so that the molding film 100 having a desired size can be obtained more easily.

Subsequently, if necessary, by applying pressure, the voids are filled with the molding material 101 that is attached to the surface of the porous body 103 without being filled in the voids. The method of pressurizing the porous body 103 is not particularly limited, and for example, a roll press or the like can be used. As a result, pressurization can be performed continuously, and productivity can be improved.

Further, as shown in FIG. 2, it is preferable that a space portion 115 for accommodating the molding material 101 is provided on one surface of the porous body 103. In this case, in the step (A), the space portion 115 is also filled with the molding material 101. As a result, the space portion 115 can also be filled with the molding material 101, so that the loading amount of the molding material 101 can be increased.
The space portion 115 is not particularly limited as long as it has a structure capable of filling the molding material 101, but is formed by, for example, providing a support 113 on one surface of the porous body 103 via a spacer 111. Can be mentioned. In this case, the portion surrounded by the porous body 103, the support 113, and the spacer 111 becomes the space portion 115.

The spacer 111 is not particularly limited, and examples thereof include masking tape. The support 113 is not particularly limited, and examples thereof include a resin plate such as a polyethylene terephthalate (PET) plate, a metal plate, and the like. A transparent resin plate is preferable from the viewpoint that the inside can be confirmed.

The size of the space portion 115 is not particularly limited, and is appropriately set according to the filling amount of the molding material 101 and the desired thickness of the molding film 100. The size of the space portion 115 can be adjusted by, for example, the thickness of the spacer 111.

Here, the porous body 103 can fill the voids with the molding material 101.
The shape of the porous body 103 is not particularly limited, but is preferably a sheet shape from the viewpoint of ease of handling.

Examples of the form of the porous body 103 include one or more selected from woven fabrics, non-woven fabrics, mesh cloths, porous membranes, expanding sheets, punching sheets and the like. Among these, mesh cloth is preferable from the viewpoint of excellent filling property of the molding material 101 and excellent performance of sieving the molding material 101.

The materials constituting the porous body 103 include polyesters such as nylon and polyethylene terephthalate (PET), polyethylene, polypropylene, polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer, polyvinylidene chloride, and polyvinylidene chloride. Resin materials such as vinylidene, polyvinyl chloride, polyurethane, vinylon, polybenzimidazole, polyimide, polyphenylene sulfide, polyether ether ketone, cellulose, acrylic resin; natural fibers such as hemp, wood pulp, cotton linter; iron, aluminum, Metallic materials such as titanium, nickel and stainless steel; one or more selected from inorganic materials such as glass and carbon.
Among these, resin materials and natural fibers are preferable, resin materials are more preferable, and nylon is particularly preferable, from the viewpoint of excellent flexibility. The opening of the porous body 103 having excellent flexibility changes slightly when vibration is applied. Therefore, by using the porous body 103 having excellent flexibility, the molding material 101 can be dropped more easily while suppressing clogging, and the molding material 101 can be deposited more uniformly. Is possible.

The porosity of the porous body 103 is preferably 10% or more and 90% or less, more preferably 25% or more and 70% or less, and particularly preferably 30% or more and 55% or less. When the porosity is at least the above lower limit value, the number of molding materials 101 that can be filled in the voids can be increased, so that the productivity of the molding film 100 can be improved.
Further, when the porosity is not more than the above upper limit value, the performance of sieving the molding material 101 can be improved, so that the thickness of the obtained molding film 100 can be made more uniform.
Here, the porosity in the present embodiment differs depending on the form of the porous body 103. For example, a mesh cloth having a regular shape with monotonous voids, an expanding sheet, a punching sheet, or the like means an aperture ratio.
The aperture ratio of the porous body 103 can be calculated according to the following formula for each difference in form. For example, in the case of a punched plate such as a punching sheet, a common name is given according to the difference in the shape and arrangement of holes, and calculation formulas are provided for each. For example, 60 ° staggered type: aperture ratio (%) = 90.6 × D ² / P ² , square staggered type: opening ratio (%) = 157 × D ² / P ² , parallel type: opening ratio (%) ) = 78.5 x D ² / P ² , oval hole zigzag type: aperture ratio (%) = {(2 x W x L)-(0.43 x W ² )} x 100 / (2 x SP x) LP), oval hole parallel type: aperture ratio (%) = {(2 x W x L)-(0.43 x W ² )} x 100 / (2 x SP x LP), square hole staggered type: opening rate ^{(%) = W 2 × 100} / (SP 1 × SP 2), square hole parallel: opening ratio ^{(%) = W 2 × 100} / (SP 1 × SP 2), hexagonal 60 ° staggered: opening Rate (%) = W ² x 100 / P ² , long square hole staggered type: aperture ratio (%) = (W x L x 100) / (SP x LP), long square hole parallel type: aperture ratio (%) = (W x L x 100) / (SP x LP), in the above formula, D is the diameter of the round hole, P is the distance between the centers of the round hole or hexagonal hole, and W is the oblong hole, square hole, hexagonal hole. Or the length of the oblong hole in the short direction, L is the length of the oblong hole or oblong hole in the long direction, SP is the distance between the centers in the short direction of the oblong hole or oblong hole, LP is the oblong hole or long angle. The distance between the centers in the longer direction of the hole, SP ₁ indicates the distance between the centers in the shorter direction of the _{square hole, and SP 2} indicates the distance between the centers in the longer direction of the square hole.
In the case of a plate that has been stretched after making staggered cuts such as an expanding sheet, the aperture ratio (%) = [{SWO × (LWO + B)} / (SW × LW)] × 100 is provided. Here, SWO is the length of the opening in the short direction, LWO is the length of the opening in the long direction, SW is the distance between the centers in the short direction of the mesh, LW is the distance between the centers in the long direction of the mesh, and B is the length of the bond. Is.
Further, in the mesh cloth, the aperture ratio (%) = {A / (A + d)} ² × 100 is provided. Here, A is a mesh opening (mm) and can be calculated by A = (25.4 / M) −d. M is a mesh and d is a wire diameter (mm).
Further, in the case of a woven fabric, a non-woven fabric, or a porous membrane in which the voids have a three-dimensionally complicated shape, the porosity means the ratio of the total volume of the voids to the total volume of the porous body 103. That is, the porosity is expressed by (volume of constituent material in 1-porous body 103 / volume of porous body 103) × 100 (%).

The opening of the porous body 103 is preferably 40 μm or more and 300 μm or less, and more preferably 50 μm or more and 150 μm or less. When the opening is at least the above lower limit value, the number of molding materials 101 that can be filled in the voids can be increased, so that the productivity of the molding film 100 can be improved.
Further, when the opening is not more than the above upper limit value, the performance of sieving the molding material 101 can be improved, so that the thickness of the obtained molding film 100 can be made more uniform.

The air permeability of the porous body 103 ^{is preferably 1 cm 3} / cm ² / sec or more and 30 cm ³ / cm ² / sec or less, and more preferably 2 cm ³ / cm ² / sec or more and 20 cm ³ / cm ² / sec or less. When the air permeability is equal to or higher than the above lower limit value, the number of molding materials 101 that can be filled in the voids can be increased, so that the productivity of the molding film 100 can be improved. Further, when the air permeability is not more than the above upper limit value, the performance of sieving the molding material 101 can be improved, so that the thickness of the obtained molding film 100 can be made more uniform.
Here, the air permeability of the porous body 103 can be measured according to JIS L1096-A (Frazier method).

The thickness of the porous body 103 is preferably 10 μm or more and 300 μm or less, and more preferably 20 μm or more and 200 μm or less. When the thickness of the porous body 103 is at least the above lower limit value, the number of molding materials 101 that can be filled in the voids can be increased, so that the productivity of the molding film 100 can be improved.
Further, when the thickness of the porous body 103 is not more than the above upper limit value, the unfilled region of the molding material 101 can be reduced, and the performance of sieving the molding material 101 can be improved, so that the obtained molding film 100 can be obtained. The thickness of the can be made even more uniform.

The molding material 101 is not particularly limited as long as it is in the form of powder, and examples thereof include a solid electrolyte material, a positive electrode material, a negative electrode material, and the like used in an all-solid-state lithium ion battery.

_{The average particle size d 50} of the powdered molding material 101 in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 1 μm or more and 40 μm or less, and more preferably 5 μm or more and 20 μm or less.
By setting the average particle size d ₅₀ of the molding material 101 within the above range, good handleability can be maintained and a thinner molding film can be realized.

The solid electrolyte material is not particularly limited as long as it has ionic conductivity and insulating properties, but a material generally used for an all-solid-state lithium ion battery can be used. For example, an inorganic solid electrolyte material such as a sulfide-based solid electrolyte material and an oxide-based solid electrolyte material can be mentioned. Among these, a sulfide-based solid electrolyte material is preferable. As a result, the interfacial resistance between the solid electrolyte materials is further reduced, and the molded film 100 (solid electrolyte membrane or solid electrolyte layer) having more excellent lithium ion conductivity can be obtained.

Examples of the sulfide-based solid electrolyte material include Li ₂ SP ₂ S ₅ material, Li ₂ S-SiS ₂ material, Li ₂ S-GeS ₂ material, Li ₂ S-Al ₂ S ₃ material, and Li ₂ S. -SiS _{2 -Li 3} PO ₄ material, Li ₂ S-P ₂ S _5- GeS ₂ material, Li ₂ S-Li ₂ O-P ₂ S _5- SiS ₂ material, Li ₂ S-GeS _2- P ₂ S Examples thereof include _{5- SiS 2} material, Li ₂ S-SnS _2- P ₂ S _5- SiS ₂ material and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type. _{Among these, the Li 2} SP ₂ S ₅ material is preferable because it has excellent lithium ion conductivity and stability that does not cause decomposition in a wide voltage range. Here, for example, the Li ₂ SP ₂ S ₅ material means a material obtained by mixing and pulverizing a mixture containing at least Li ₂ S (lithium sulfide) and P ₂ S _{5 by mechanochemical treatment or the like.} To do.

Examples of the shape of the solid electrolyte material include particulate matter. _{The particulate solid electrolyte material is not particularly limited, but the average particle size d 50} in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 1 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less. is there.
By setting the average particle size d ₅₀ of the solid electrolyte material within the above range, good handleability can be maintained and lithium ion conductivity can be further improved.

The positive electrode material is used for the positive electrode layer constituting the all-solid-state lithium ion battery, and contains a positive electrode active material as an essential component.

The positive electrode active material is not particularly limited, and a generally known positive electrode active material that can be used for the positive electrode layer of the all-solid-state lithium ion battery can be used. For example, lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganese oxide (LiMn ₂ O ₄ ), solid solution oxide (Li ₂ MnO _3- LiMO ₂ (M = Co, Ni, etc.)). ), Lithium-manganese-nickel oxide (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ), olivine-type lithium phosphorus oxide (LiFePO ₄ ) and other composite oxides; _{molecule; Li 2 S, CuS, Li} -CuS _{compounds, TiS 2, FeS, MoS 2} , Li-MoS _compounds, Li - _TiS compounds, Li _- V _- sulfide cathode active such as S compound Substances; materials using sulfur as an active material, such as acetylene black impregnated with sulfur, porous carbon impregnated with sulfur, and a mixed powder of sulfur and carbon, can be used. These positive electrode active materials may be used alone or in combination of two or more.
Among them, have a higher discharge capacity density, and, from the viewpoint of more excellent cycle characteristics, preferably sulfide-based positive electrode active material, Li-Mo-S compounds, _Li - Ti _- S compound, Li _- V _- S More preferably, one or more selected from the compounds.

Here, the Li-Mo-S compound contains Li, Mo, and S as constituent elements, and is usually obtained by mixing and pulverizing molybdenum sulfide and lithium sulfide, which are raw materials, by mechanochemical treatment or the like. be able to.
Further, the Li-Ti-S compound contains Li, Ti, and S as constituent elements, and is usually obtained by mixing and pulverizing titanium sulfide and lithium sulfide, which are raw materials, by mechanochemical treatment or the like. Can be done.
The Li-VS compound contains Li, V, and S as constituent elements, and can be obtained by mixing and pulverizing vanadium sulfide and lithium sulfide, which are usually raw materials, by mechanochemical treatment or the like. ..

_{The positive electrode active material is not particularly limited, but the average particle size d 50} in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 0.5 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less. Is.
_{By setting the average particle size d 50} of the positive electrode active material within the above range, good handleability can be maintained and a higher density positive electrode can be produced.

The positive electrode material is not particularly limited, but may contain one or more materials selected from, for example, a solid electrolyte material, a binder, a conductive additive, and the like as components other than the positive electrode active material.
The mixing ratio of various materials in the positive electrode material is appropriately determined according to the intended use of the battery and the like, and is not particularly limited, and can be set according to generally known information.

The negative electrode material is used for the negative electrode layer constituting the all-solid-state lithium ion battery, and contains a negative electrode active material as an essential component.

The negative electrode active material is not particularly limited, and a generally known negative electrode active material that can be used for the negative electrode layer of the all-solid-state lithium ion battery can be used. For example, carbonaceous materials such as natural graphite, artificial graphite, resin charcoal, carbon fiber, activated charcoal, hard carbon, soft carbon; tin, tin alloy, silicon, silicon alloy, gallium, gallium alloy, indium, indium alloy, aluminum, aluminum. Metal-based materials mainly composed of alloys and the like; conductive polymers such as polyacene, polyacetylene and polypyrrole; metallic lithium; lithium titanium composite oxides (for example, Li ₄ Ti ₅ O ₁₂ ) and the like can be mentioned. These negative electrode active materials may be used alone or in combination of two or more.

Examples of the shape of the negative electrode active material include a particle shape and a foil shape.
The particulate negative particle active material according to the present embodiment is not particularly limited, but the average particle size d ₅₀ in the weight-based particle size distribution measured by the laser diffraction / scattering particle size distribution measurement method is preferably 1 μm or more and 50 μm or less, more preferably. It is 5 μm or more and 30 μm or less.
_{By setting the average particle size d 50} of the negative electrode active material within the above range, good handleability can be maintained and a higher density negative electrode can be produced.

The negative electrode material is not particularly limited, but may contain one or more materials selected from, for example, a solid electrolyte material, a binder, a conductive auxiliary agent, and the like as components other than the negative electrode active material.
The mixing ratio of various materials in the negative electrode material is appropriately determined according to the intended use of the battery and the like, and is not particularly limited, and can be set according to generally known information.

Next, (B) the molding material 101 filled in the voids of the porous body 103 is sieved onto the cavity surface 107 of the mold 105 or the surface of the base material, so that the molding material 101 is placed on the cavity surface 107 of the mold or on the surface of the base material. The molding material 101 is deposited in the form of a film. Here, the molding material 101 filled in the voids of the porous body 103 is sieved onto the cavity surface 107 of the mold 105 or the surface of the base material until a desired thickness is obtained.
Since the molding material 101 is screened off little by little by the opening of the porous body 103, it can be deposited in a film shape with a uniform thickness on the cavity surface 107 of the mold or on the surface of the base material.

As a method of sieving the molding material 101 onto the cavity surface 107 of the mold 105 or the surface of the base material, for example, by vibrating the porous body 103, the molding material 101 filled in the voids of the porous body 103 is molded into the mold. Examples thereof include a method of sieving on the cavity surface 107 of 105 or on the surface of the base material.

Further, as shown in FIG. 2, when a space portion 115 for accommodating the molding material 101 is provided on one surface of the porous body 103, the voids of the porous body 103 and the molding material 101 filled in the space portion 115 are molded into a mold. By sieving on the cavity surface 107 of the 105 or on the surface of the base material, the molding material 101 is deposited in a film form on the cavity surface 107 of the mold 105 or on the surface of the base material. As a result, the molding material 101 can be continuously screened off, so that the productivity of the molding film 100 can be further improved.

Further, as shown in FIG. 3, in the step (B), the molding material 101 deposited in the form of a film is vibrated to cause the powdered molding material 101 to flow, and the molding material 101 deposited in the form of a film is densely formed. It is preferable to further include a step of converting. The thickness of the molded film 100 thus obtained can be made even more uniform. Examples of the method of vibrating include vibration with a small amplitude such as ultrasonic vibration and light impact by a hammer.

Examples of the base material include a positive electrode layer, a negative electrode layer, a metal foil, a plastic film, carbon and the like.
When the molding material 101 is a solid electrolyte material, the base material is preferably, for example, a positive electrode layer, a negative electrode layer, a metal foil, a plastic film, or the like.
When the molding material 101 is a positive electrode material or a negative electrode material, examples of the base material include a metal foil, a plastic film, carbon, a solid electrolyte layer, and the like. In particular, a metal foil that can be used as a current collector and a solid electrolyte layer are preferable.
The metal foil is not particularly limited, and for example, copper foil, aluminum foil, stainless steel foil and the like can be used.

Then, if necessary, as shown in FIG. 4, (C) the molding material 101 deposited in the form of a film is pressed. As a result, the molding film 100 has a certain strength due to the anchor effect between the molding materials 101. Here, when the powdered molding material 101 is deposited on the surface of the base material, the base material may be pressurized in a laminated state, or the base material may be peeled off and then pressurized.
When pressure is applied, the molding materials 101 are bonded to each other, and the strength of the obtained molding film 100 is further increased. As a result, the chipping of the molding material 101 and the cracking on the surface of the molding material 101 can be further suppressed.
The method of pressurizing the molding material 101 is not particularly limited. For example, when the molding material 101 is deposited on the cavity surface 107 of the mold 105, it is pressed by a mold and a stamping die, and the powdered molding material 101 is used as a base. When deposited on the surface of the material, a press using a die and a pressing die, a roll press, a flat plate press, or the like can be used.
The pressure for pressurizing the molding material 101 is, for example, 10 MPa or more and 500 MPa or less.

Further, if necessary, the molding material 101 deposited in the form of a film may be pressurized and heated. When heat and pressure are applied, the molding materials 101 are fused and bonded to each other, and the strength of the obtained molding film 100 is further increased. As a result, the chipping of the molding material 101 and the cracking on the surface of the molding material 101 can be further suppressed.
The temperature at which the molding material 101 is heated is, for example, 40 ° C. or higher and 500 ° C. or lower.

The thickness of the molded film 100 is, for example, 100 μm or less, preferably 70 μm or less, and more preferably 50 μm or less. According to the method for producing the molded film 100 of the present embodiment, it is possible to obtain such a thin molded film 100 with a uniform thickness.

The molded film 100 is not particularly limited, but is, for example, a solid electrolyte layer, a positive electrode layer, or a negative electrode layer used in an all-solid-state lithium ion battery. According to the method for producing the molded film 100 of the present embodiment, the obtained solid electrolyte layer, positive electrode layer, or negative electrode layer can be thinned, so that the impedance of the solid electrolyte layer, positive electrode layer, or negative electrode layer can be lowered. As a result, the charge / discharge characteristics of the obtained all-solid-state lithium-ion battery can be further improved.
However, the method for producing the molded film 100 of the present embodiment is not limited to these, and can be applied to the production of a molded film that requires a thin and uniform thickness.

The solid electrolyte layer can be obtained, for example, from the solid electrolyte material described above.
The solid electrolyte layer may contain a binder, but the content of the binder is preferably less than 0.5% by mass, more preferably less than 0.5% by mass, assuming that the entire solid electrolyte layer is 100% by mass. It is 0.1% by mass or less, more preferably 0.05% by mass or less. Further, it is more preferable that the solid electrolyte layer according to the present embodiment contains substantially no binder, and it is particularly preferable that the solid electrolyte layer does not contain a binder.
As a result, the contact property between the solid electrolyte materials is improved, and the interfacial contact resistance of the solid electrolyte layer can be further reduced. As a result, the lithium ion conductivity of the solid electrolyte layer can be further improved.
In addition, "substantially free of binder" means that the binder may be contained to the extent that the effect of the present invention is not impaired.

The binder refers to a binder generally used in a lithium ion battery for binding the electrode active materials to each other and the electrode active material to the current collector. For example, polyvinyl alcohol or polyacrylic. Water-based binders such as acids, carboxymethyl cellulose, polytetrafluoroethylene (PTFE) fine particles, and styrene-butadiene rubber fine particles; solvent-based binders such as polytetrafluoroethylene, polyvinylidene fluoride, and polyimide.

The positive electrode layer can be obtained from, for example, the above-mentioned positive electrode material. The negative electrode layer can be obtained from, for example, the negative electrode material described above.
The thickness and density of the positive electrode layer and the negative electrode layer are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.

[Manufacturing method of all-solid-state lithium-ion battery]
Next, a method for manufacturing the all-solid-state lithium-ion battery 200 of the present embodiment will be described.
First, the all-solid-state lithium-ion battery 200 will be described. FIG. 5 is a cross-sectional view schematically showing an example of the structure of the all-solid-state lithium-ion battery 200. The all-solid-state lithium-ion battery 200 is a lithium-ion secondary battery, but may be a lithium-ion primary battery.

The all-solid-state lithium-ion battery 200 is formed by laminating a positive electrode layer 210, a solid electrolyte layer 220, and a negative electrode layer 230 in this order. Then, at least one selected from the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 is produced by using the method for producing the molded film 100 of the present embodiment.
The shape of the all-solid-state lithium-ion battery 200 is not particularly limited, and examples thereof include a cylindrical type, a coin type, a square type, a film type, and any other shape.

The positive electrode layer 210 is not particularly limited, and a positive electrode generally used for an all-solid-state lithium ion battery can be used. The positive electrode layer 210 is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming the above-mentioned positive electrode material on a current collector such as aluminum foil.
The thickness and density of the positive electrode layer 210 are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
Further, the positive electrode layer 210 may be manufactured by using the method for manufacturing the molded film 100 of the present embodiment.

The solid electrolyte layer 220 is not particularly limited, and a solid electrolyte layer generally used for all-solid-state lithium-ion batteries can be used. The solid electrolyte layer 220 is not particularly limited, but can be produced according to a generally known method. For example, it can be obtained by forming the above-mentioned solid electrolyte material on the positive electrode layer or the negative electrode layer.
The thickness and density of the solid electrolyte layer 220 are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
Further, the solid electrolyte layer 220 is preferably manufactured by using the method for manufacturing the molded film 100 of the present embodiment.

The negative electrode layer 230 is not particularly limited, and those generally used for all-solid-state lithium ion batteries can be used. The negative electrode layer 230 is not particularly limited, but can be manufactured according to a generally known method. For example, it can be obtained by forming a negative electrode active material layer containing a negative electrode active material on a current collector such as copper.
The thickness and density of the negative electrode active material layer are appropriately determined according to the intended use of the battery and the like, and are not particularly limited, and can be set according to generally known information.
Further, the negative electrode layer 230 may be manufactured by using the manufacturing method of the molded film 100 of the present embodiment.

The manufacturing method of the all-solid-state lithium-ion battery 200 forms at least one molded film 100 selected from the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 by the manufacturing method of the molded film 100 of the present embodiment. Includes steps.

The method for manufacturing the all-solid-state lithium-ion battery 200 according to the present embodiment includes a step of obtaining a laminate in which the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 are laminated in this order, and the laminate. It is preferable to include a step of integrating the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 by pressing. As a result, the all-solid-state lithium-ion battery 200 has a certain strength due to the anchor effect between the layers.
The pressure for pressurizing the laminate is, for example, 40 MPa or more and 500 MPa or less.
The method of pressurizing the laminate is not particularly limited, and for example, a flat plate press, a roll press, or the like can be used.

Further, the laminate may be pressurized and heated as needed. When heat and pressure are applied, the molding materials 101 are fused and bonded to each other, and the strength of each obtained layer is further increased. As a result, the chipping of each material and the cracking on the surface of each layer can be further suppressed.
The temperature at which the laminate is heated is, for example, 150 ° C. or higher and 500 ° C. or lower.

Examples of the method for manufacturing the all-solid-state lithium-ion battery 200 according to the present embodiment include Examples 1 to 4 below.

(Example 1)
Example 1 is a case where the solid electrolyte layer 220 is formed by the method for producing the molded film 100 of the present embodiment.
First, the solid electrolyte layer 220 is formed in the mold 105 by using the method for producing the molding film 100 of the present embodiment. Next, either the positive electrode layer 210 or the negative electrode layer 230 is superposed on the solid electrolyte layer 220. Next, the other one of the positive electrode layer 210 and the negative electrode layer 230 is laminated on the opposite surface to obtain a laminated body. Next, a stamp is inserted and pressure is applied to integrate the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230. As a result, the all-solid-state lithium-ion battery 200 can be obtained.
In Example 1, the solid electrolyte layer 220 was formed first, but either the positive electrode layer 210 or the negative electrode layer 230 was arranged in advance in the mold 105, and the molding film 100 of the present embodiment was formed on the solid electrolyte layer 220. The solid electrolyte layer 220 may be formed by using the production method.

(Example 2)
Example 2 is a case where the positive electrode layer 210 or the negative electrode layer 230 and the solid electrolyte layer 220 are formed by the method for producing the molded film 100 of the present embodiment.
First, the solid electrolyte layer 220 is formed in the mold 105 by using the method for producing the molding film 100 of the present embodiment. Next, using the method for producing the molded film 100 of the present embodiment, either the positive electrode layer 210 or the negative electrode layer 230 is formed on the solid electrolyte layer 220 produced in the mold 105. Next, the other one of the positive electrode layer 210 and the negative electrode layer 230 is laminated on the opposite surface to obtain a laminated body. Next, a stamp is inserted and pressure is applied to integrate the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230. As a result, the all-solid-state lithium-ion battery 200 can be obtained.
In Example 2, the solid electrolyte layer 220 was formed first, but the positive electrode layer 210 or the negative electrode layer 230 may be formed first.

(Example 3)
Example 3 is a case where the positive electrode layer 210 or the negative electrode layer 230 is formed by the method for producing the molded film 100 of the present embodiment.
First, either the positive electrode layer 210 or the negative electrode layer 230 is formed in the mold 105 by using the method for producing the molding film 100 of the present embodiment. Next, the solid electrolyte layer 220 is overlaid on the positive electrode layer 210 or the negative electrode layer 230. Next, the other one of the positive electrode layer 210 and the negative electrode layer 230 is laminated on the solid electrolyte layer 220 to obtain a laminated body. Next, a stamp is inserted and pressure is applied to integrate the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230. As a result, the all-solid-state lithium-ion battery 200 can be obtained.
In Example 3, the positive electrode layer 210 or the negative electrode layer 230 was formed first, but the solid electrolyte layer 220 was arranged in advance in the mold 105, and the method for producing the molded film 100 of the present embodiment was used on the solid electrolyte layer 220. The positive electrode layer 210 or the negative electrode layer 230 may be formed.

(Example 4)
Example 4 is a case where the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 are formed by the method for producing the molded film 100 of the present embodiment.
First, the solid electrolyte layer 220 is formed in the mold 105 by using the method for producing the molding film 100 of the present embodiment. Next, using the method for producing the molded film 100 of the present embodiment, either the positive electrode layer 210 or the negative electrode layer 230 is formed on the solid electrolyte layer 220 produced in the mold 105. Next, the remaining one of the positive electrode layer 210 and the negative electrode layer 230 is formed on the opposite surface by using the method for producing the molded film 100 of the present embodiment to obtain a laminated body. Next, a stamp is inserted and pressure is applied to integrate the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230. As a result, the all-solid-state lithium-ion battery 200 can be obtained.
In Example 4, the solid electrolyte layer 220 was formed first, but the positive electrode layer 210 or the negative electrode layer 230 may be formed first.

(Example 5)
Example 5 is a case where the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230 are formed by the method for producing the molded film 100 of the present embodiment.
First, the solid electrolyte layer 220 is formed in the mold 105 by using the method for producing the molding film 100 of the present embodiment. Next, using the method for producing the molding film 100 of the present embodiment, the positive electrode layer 210 is formed in the separately prepared mold 105, and the positive electrode layer 210 is taken out. Further, using the method for producing the molding film 100 of the present embodiment, the negative electrode layer 230 is formed in the mold 105 using the positive electrode layer 210 or in the mold 105 prepared separately, and the negative electrode layer 230 is taken out. Next, either the positive electrode layer 210 or the negative electrode layer 230 is superposed on the solid electrolyte layer 220. Next, the other one of the positive electrode layer 210 and the negative electrode layer 230 is laminated on the opposite surface to obtain a laminated body. Next, a stamp is inserted and pressure is applied to integrate the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230. As a result, the all-solid-state lithium-ion battery 200 can be obtained.

(Example 6)
Example 6 is a case where the positive electrode layer 210 and the solid electrolyte layer 220 are formed by the method for producing the molded film 100 of the present embodiment.
First, the solid electrolyte layer 220 is formed in the mold 105 by using the method for producing the molding film 100 of the present embodiment. Next, using the method for producing the molding film 100 of the present embodiment, the positive electrode layer 210 is formed in the separately prepared mold 105, and the positive electrode layer 210 is taken out. Next, either the positive electrode layer 210 or the negative electrode layer 230 is superposed on the solid electrolyte layer 220. Next, the other one of the positive electrode layer 210 and the negative electrode layer 230 is laminated on the opposite surface to obtain a laminated body. Next, a stamp is inserted and pressure is applied to integrate the positive electrode layer 210, the solid electrolyte layer 220, and the negative electrode layer 230. As a result, the all-solid-state lithium-ion battery 200 can be obtained.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.
Hereinafter, an example of the reference form will be added.
1. 1.
The step (A) of filling the voids of the porous body with the powdered molding material, and
By sieving the molding material filled in the voids of the porous body onto the cavity surface of the mold or the surface of the base material, the molding material is formed into a film on the cavity surface of the mold or the surface of the base material. Step (B) of depositing in
A method for producing a molded film including.
2.
1. 1. In the method for producing a molded film described in 1.
A method for producing a molded film, further comprising a step (C) of pressurizing the molding material deposited in the form of a film.
3. 3.
1. 1. Or 2. In the method for producing a molded film described in 1.
The step (B) further includes a step of causing the powdered molding material to flow by vibrating the molding material deposited in the form of a film to densify the molding material deposited in the form of a film. Manufacturing method.
4.
1. 1. To 3. In the method for producing a molded film according to any one of them,
A space for accommodating the molding material is provided on one surface of the porous body.
In the step (A), a method for producing a molding film in which the molding material is also filled in the space.
5.
4. In the method for producing a molded film described in 1.
In the step (B), the molding material filled in the voids and the space of the porous body is sieved onto the cavity surface of the mold or the surface of the base material, thereby forming the cavity surface of the mold. Alternatively, a method for producing a molding film in which the molding material is deposited in the form of a film on the surface of the base material.
6.
1. 1. To 5. In the method for producing a molded film according to any one of them,
A method for producing a molded film in which the molding material is a solid electrolyte material, a positive electrode material, or a negative electrode material, which is used in an all-solid-state lithium-ion battery.
7.
1. 1. To 6. In the method for producing a molded film according to any one of them,
A method for producing a molded film in which the molded film is a solid electrolyte layer, a positive electrode layer, or a negative electrode layer, which is used in an all-solid-state lithium-ion battery.
8.
1. 1. To 7. In the method for producing a molded film according to any one of them,
A method for producing a molded film in which the porosity of the porous body is 10% or more and 90% or less.
9.
1. 1. ~ 8. In the method for producing a molded film according to any one of them,
A method for producing a molded film in which the opening of the porous body is 40 μm or more and 300 μm or less.
10.
1. 1. ~ 9. In the method for producing a molded film according to any one of them,
_{A method for producing a molding film in which the average particle size d 50} of the powdery molding material is 1 μm or more and 40 μm or less in a weight-based particle size distribution measured by a laser diffraction / scattering type particle size distribution measurement method.
11.
1. 1. To 10. In the method for producing a molded film according to any one of them,
A method for producing a molded film in which the porous body is in the form of a sheet.
12.
11. In the method for producing a molded film described in 1.
A method for producing a molded film, wherein the porous body is one or more selected from a woven fabric, a non-woven fabric, a mesh cloth, a porous film, an expanding sheet, and a punching sheet.
13.
1. 1. To 12. In the method for producing a molded film according to any one of them,
A method for producing a molded film having a thickness of 100 μm or less.
14.
It is a manufacturing method for manufacturing an all-solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order.
1. 1. To 13. An all-solid-state lithium-ion battery comprising a step of forming at least one molded film selected from the positive electrode layer, the solid electrolyte layer, and the negative electrode layer by the method for producing a molded film according to any one of the above. Production method.
15.
14. In the method for manufacturing an all-solid-state lithium-ion battery described in 1.
A step of obtaining a laminate in which the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are laminated in this order.
A step of integrating the positive electrode layer, the solid electrolyte layer, and the negative electrode layer by pressurizing the laminate.
A method for manufacturing an all-solid-state lithium-ion battery including.

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

[1] Measurement method First, the measurement methods in the following examples and comparative examples will be described.

(1) Particle Size Distribution The particle size distribution of the solid electrolyte material used in Examples and Comparative Examples was measured by a laser diffraction method using a laser diffraction scattering type particle size distribution measuring device (Mastersizer 3000 manufactured by Malvern). _{From the measurement results, the particle size (D 50} , average particle size) at 50% cumulative in the weight-based cumulative distribution was determined for each positive electrode active material.

(2) Thickness variation Using a micrometer, the thickness at 10 points was measured from the obtained solid electrolyte membrane, and the (arithmetic) average value and standard deviation of the thickness were obtained. Those having a standard deviation of 6.7 or less were defined as having a uniform thickness, and those having a standard deviation of more than 6.7 were defined as having a non-uniform thickness.

[2] Materials Next, the materials used in the following Examples and Comparative Examples will be described.

(1) Solid electrolyte material (Li ₁₁ P ₃ S ₁₂ )
As raw materials, Li ₂ S (manufactured by Sigma-Aldrich, purity 99.9%) and P ₂ S ₅ (reagent manufactured by Kanto Chemical Co., Inc.) were used. Li ₃ N was prepared by the following procedure.
First, a stainless steel net (150 mesh) was pressure-bonded to Li foil (purity 99.8%, thickness 0.5 mm) manufactured by Honjo Metal Co., Ltd. in a glove box having a nitrogen atmosphere. The Li foil began to change to black-purple from the opening of the net, and when left as it was at room temperature for 24 hours, all of the Li foil changed to _{black-purple Li 3 N.} Li ₃ N was pulverized in an agate mortar and then sieved with a stainless steel sieve, and a powder of 25 μm or less was recovered and used as a raw material for a solid electrolyte material.
Next, each raw material was precisely weighed in an argon glove box so that Li ₂ S: P ₂ S ₅ : Li ₃ N = 67.5: 22.5: 10.0 (mol%), and these powders were added. Mix in agate mortar for 20 minutes. Next, 2 g of the mixed powder was weighed, placed in _{an Al 2} O ₃ ball mill pot (internal volume 400 mL) together with 500 g _{of a φ10 mm ZrO 2} ball, and mixed and pulverized at 120 rpm for 200 hours. The powder after mixing and crushing was placed in a carbon boat and heat-treated in an argon air stream at 330 ° C. for 2 hours to obtain _{Li 11} P ₃ S _12. The average particle size D ₅₀ was 10 μm.

(2) Porous body As the porous body, nylon mesh cloth (13XX-100 manufactured by Sanjiro Tanaka Shoten Co., Ltd., thickness 105 μm, porosity 36%, opening 100 μm) was used.

<Example 1>
A polyethylene terephthalate (PET) plate was prepared by attaching a polyethylene terephthalate (PET) plate to one surface of a nylon mesh cloth via a spacer having a thickness of 75 μm (a masking tape having a thickness of 60 μm and a baseless double-sided tape having a thickness of 15 μm). The nylon mesh cloth was filled with a resin at openings other than 25 mm × 25 mm so that the powder could pass through only 25 mm × 25 mm.
_{Next, a powdered solid electrolyte material (Li 11} P ₃ S) was used in the space provided between the nylon mesh cloth and the PET plate (the space secured by the spacer) and the opening (void) of the nylon mesh cloth using a squeegee. ₁₂ ) was filled.
Next, the nylon mesh cloth filled with the powdered solid electrolyte material is inverted and placed on the press die, and the PET plate is hit with a mallet and vibrated to cause the solid electrolyte on the cavity surface of the press die. By sieving 60 mg of the material, the solid electrolyte material was deposited in a film on the cavity surface of the press die. Here, the solid electrolyte material was deposited in a film shape with a uniform thickness in the cavity (25 mm × 25 mm) of the press die.
Next, after the press die is placed in the press die, each side surface of the press die is hit with a titanium hammer to vibrate the powdery solid electrolyte material in the press die, and the film-like solid electrolyte is applied. The material was densified.
Then, a solid electrolyte membrane was obtained by pressing at 160 MPa using a hydraulic flat plate press.
The produced solid electrolyte membrane had an average thickness of 70 μm and a standard deviation of 5.1. Further, in the obtained solid electrolyte membrane, the solid electrolyte material was not chipped or the surface was not cracked. That is, the solid electrolyte membrane obtained in Example 1 could be thinned and had a uniform thickness.

<Comparative example 1>
A squeegee was used to powder coat 60 mg of a powdered _{solid electrolyte material (Li 11} P ₃ S ₁₂ ) into the cavity (25 mm × 25 mm) of the press die.
Next, after the press die is placed in the press die, each side surface of the press die is hit with a titanium hammer to vibrate the powdered solid electrolyte material in the press die to make the solid electrolyte material dense. I made it.
Then, a solid electrolyte membrane was obtained by pressing at 160 MPa using a hydraulic flat plate press.
The produced solid electrolyte membrane had an average thickness of 70 μm and a standard deviation of 9.2. That is, the solid electrolyte membrane obtained in Comparative Example 1 had a non-uniform thickness. Further, in the obtained solid electrolyte membrane, the solid electrolyte material was chipped and the surface was cracked. That is, it was difficult to thin the solid electrolyte membrane obtained in Comparative Example 1.

<Comparative example 2>
_{90 mg of powdered solid electrolyte material (Li 11} P ₃ S ₁₂ ) was powder coated into the cavity (25 mm x 25 mm) of the press die using a squeegee.
Next, after the press die is placed in the press die, each side surface of the press die is hit with a titanium hammer to vibrate the powdered solid electrolyte material in the press die to make the solid electrolyte material dense. I made it.
Then, a solid electrolyte membrane was obtained by pressing at 160 MPa using a hydraulic flat plate press.
The produced solid electrolyte membrane had an average thickness of 105 μm and a standard deviation of 8.8.
That is, the solid electrolyte membrane obtained in Comparative Example 2 was difficult to thin and had a non-uniform thickness.

100 Molding film 101 Molding material 103 Porous 105 Mold 107 Surface 109 Squeegee 111 Spacer 113 Support 115 Space 200 All-solid-state lithium-ion battery 210 Positive electrode layer 220 Negative electrode layer 230 Solid electrolyte layer

Claims (13)

The step (A) of filling the voids of the porous body with the powdered molding material, and
By sieving the molding material filled in the voids of the porous body onto the cavity surface of the mold or the surface of the base material, the molding material is formed into a film on the cavity surface of the mold or the surface of the base material. Step (B) of depositing in
Including
The base material is a method for producing a molded film that does not contain a conductive resin layer.
A method for producing a molded film in which the molded film is a solid electrolyte layer, a positive electrode layer, or a negative electrode layer, which is used in an all-solid-state lithium-ion battery . In the method for producing a molded film according to claim 1,
A method for producing a molded film, further comprising a step (C) of pressurizing the molding material deposited in the form of a film. In the method for producing a molded film according to claim 1 or 2.
A space for accommodating the molding material is provided on one surface of the porous body.
In the step (A), a method for producing a molding film in which the molding material is also filled in the space. In the method for producing a molded film according to claim 3,
In the step (B), the molding material filled in the voids and the space of the porous body is sieved onto the cavity surface of the mold or the surface of the base material, thereby forming the cavity surface of the mold. Alternatively, a method for producing a molding film in which the molding material is deposited in the form of a film on the surface of the base material. In the method for producing a molded film according to any one of claims 1 to 4.
A method for producing a molded film in which the molding material is a solid electrolyte material, a positive electrode material, or a negative electrode material, which is used in an all-solid-state lithium-ion battery. In the method for producing a molded film according to any one of claims 1 to 5,
A method for producing a molded film in which the porosity of the porous body is 10% or more and 90% or less. In the method for producing a molded film according to any one of claims 1 to 6,
A method for producing a molded film in which the opening of the porous body is 40 μm or more and 300 μm or less. In the method for producing a molded film according to any one of claims 1 to 7.
_{A method for producing a molding film in which the average particle size d 50} of the powdery molding material is 1 μm or more and 40 μm or less in a weight-based particle size distribution measured by a laser diffraction / scattering type particle size distribution measurement method. In the method for producing a molded film according to any one of claims 1 to 8.
A method for producing a molded film in which the porous body is in the form of a sheet. In the method for producing a molded film according to claim 9,
A method for producing a molded film, wherein the porous body is one or more selected from a woven fabric, a non-woven fabric, a mesh cloth, a porous film, an expanding sheet, and a punching sheet. In the method for producing a molded film according to any one of claims 1 to 10.
A method for producing a molded film having a thickness of 100 μm or less. It is a manufacturing method for manufacturing an all-solid-state lithium ion battery in which a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are laminated in this order.
An all-solid state including a step of forming at least one molded film selected from the positive electrode layer, the solid electrolyte layer, and the negative electrode layer by the method for producing a molded film according to any one of claims 1 to 11. Manufacturing method of type lithium ion battery. In the method for manufacturing an all-solid-state lithium-ion battery according to claim 12.
A step of obtaining a laminate in which the positive electrode layer, the solid electrolyte layer, and the negative electrode layer are laminated in this order.
A step of integrating the positive electrode layer, the solid electrolyte layer, and the negative electrode layer by pressurizing the laminate.
A method for manufacturing an all-solid-state lithium-ion battery including.

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