Method for producing material layer and method for producing electrode of solid-state battery

Abstract

To provide a method for producing a material layer which is easy to recycle and is not susceptible to the occurrence of transfer failure.SOLUTION: The method for producing a material layer includes: a first particle arrangement step for arranging first particles on a first adhesion surface of a first base material that has the first adhesion surface; a second particle arrangement step for, while the first particles are remaining on the first adhesion surface, arranging second particles on parts of the first adhesion surface where the first particles are not arranged; and a transfer step for transferring the first particles and the second particles, which are arranged on the first base material, to a second adhesion surface of a second base material that has the second adhesion surface so as to obtain the material layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a method for manufacturing a material layer and a method for manufacturing an electrode for a solid-state battery. [Background technology]

[0002] In recent years, various new manufacturing methods using additive manufacturing technologies have been developed. However, the technology for designing and arranging multiple material particles to create functional structures remains difficult and has not been widely implemented. For example, while the technology for arranging toner particles using electrophotography is widely used, toner particles are made of composite materials that already contain several times the amount of binder as the functional material pigment in order to obtain charging properties. Furthermore, due to the properties of static electricity, positioning individual particles is fundamentally difficult. This phenomenon also applies to electrostatic screen printing, which can pattern particles without using a binder. If functional particles can be placed in the right places, unnecessary particles can be avoided, and greater effects can be achieved, for example, with expensive materials such as battery materials.

[0003] In contrast, Patent Document 1 describes a method for manufacturing a solid-state battery, in which a substrate having a fine uneven pattern formed on its surface is prepared, particles are filled into the recesses of the uneven pattern, and the desired particle pattern is formed by pressing and transferring the pattern onto another substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-137060 Summary of the Invention [Problem to be solved by the invention]

[0005] However, with the advancement of technological development, production efficiency, such as material utilization efficiency, has recently begun to be emphasized. With the recent rise in resource prices, there is a need to improve the yield of formed particle patterns and, in the event that the particle pattern of the product is defective, to recover and recycle the particles that are the raw material for solid-state batteries. In the method for manufacturing a material layer of Patent Document 1, a particle pattern is created using an intaglio plate, and the obtained particle pattern is transferred to the adhesive surface of a substrate equipped with an adhesive. That is, in Patent Document 1, the pattern is directly fixed to the substrate equipped with an adhesive, which makes recycling difficult after the particles are finally fixed to the substrate. Furthermore, the present inventors have recognized that in forming a pattern using an intaglio plate, in the case of a wide pattern, the particles may not be packed sufficiently.

[0006] The present disclosure provides a method for manufacturing a material layer that is easily recycled and less prone to defects, and a method for manufacturing an electrode for a solid-state battery. [Means for solving the problem]

[0007] The present disclosure provides a method for manufacturing a layer of material, comprising: The manufacturing method includes: a first particle arranging step of arranging first particles on a first attachment surface of a first substrate having the first attachment surface; a second particle arranging step of arranging second particles in non-arranged portions of the first particles remaining on the first adhesion surface; a transfer step of transferring the first particles and the second particles arranged on the first substrate to a second attachment surface of a second substrate having a second attachment surface to obtain the material layer; The present invention relates to a method for manufacturing a material layer having the following features.

[0008] The present disclosure also provides a method for manufacturing an electrode for a solid-state battery, comprising: The manufacturing method comprises: obtaining the material layer by the method for manufacturing the material layer; A step of laminating the obtained material layers to obtain a laminate; and a step of heating and degreasing the obtained laminate to remove the second substrate and obtain an electrode; The present invention relates to a method for manufacturing an electrode for a solid-state battery having the above structure. [Effects of the Invention]

[0009] According to the present disclosure, there are provided a method for manufacturing a material layer that is easy to recycle and less prone to transfer defects, and a method for manufacturing an electrode for a solid-state battery. [Brief explanation of the drawings]

[0010] [Figure 1] 1A and 1B are conceptual diagrams illustrating a method for manufacturing a material layer. [Figure 2] FIG. 1 is an explanatory diagram illustrating an embodiment of the present disclosure. [Figure 3] Schematic diagram of a material layer preparation device. [Figure 4] FIG. DETAILED DESCRIPTION OF THE INVENTION

[0011] In the present disclosure, expressions such as "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the upper and lower limits, which are the endpoints, unless otherwise specified. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. Furthermore, in the present disclosure, expressions such as "at least one selected from the group consisting of XX, YY, and ZZ" mean any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.

[0012] As described above, in Patent Document 1, a particle pattern is created using an intaglio plate, and the resulting particle pattern is transferred and fixed to the adhesive surface of a substrate provided with an adhesive. Therefore, after the particles are finally fixed to the substrate, recycling is difficult.

[0013] In contrast, in the present disclosure, first particles and second particles are arranged on a first attachment surface of a first substrate having a first attachment surface, and this is then transferred to a second substrate having a second attachment surface. That is, for example, in the present disclosure, a pattern of material particles including the first particles and the second particles can be completed on the first attachment surface as an intermediate transfer body, and then transferred and fixed to the second substrate, which is the final substrate. Therefore, the pattern can be completed in a state where the particles can be easily recovered on the surface of the first attachment surface as an intermediate transfer body.

[0014] Therefore, if the particle pattern formed on the first attachment surface as an intermediate transfer body does not meet the desired quality, it can be easily recycled by recovering it using a recovery means at that point. Specifically, a weakly adhesive surface, such as silicone rubber, is used as the first attachment surface, and particles are temporarily fixed to the first attachment surface as a pattern without using a fixing material. The quality is inspected in the temporarily fixed state, and if the quality is not satisfactory, the particles can be easily peeled off and recovered from the first attachment surface using a brush or other means.

[0015] The pattern may be determined, for example, by inspecting each time the first particle dispensing step and the second particle dispensing step are performed using a camera, etc. In addition, in a routine mass production system, defects often occur in the initial stage of start-up until the process is stabilized, so that a certain number of processed particles may be completely collected based on prior data.

[0016] The method according to the present disclosure is more effective the more expensive the material particles used and the more difficult the material is to recycle. For example, battery materials are highly effective applications because they are expensive and require many processes for recycling. Typically, recycling Li-ion battery materials requires many processes, such as dissolving, distilling, and sintering, and then further granulation processes such as pulverization and classification. According to the present disclosure, materials can be reused with simpler processing, resulting in increased production efficiency.

[0017] Furthermore, with regard to production efficiency, when using an intaglio plate to form particle patterns, attempting to form a wide pattern can result in insufficient particle filling. In particular, when an intaglio plate lacks particle retention on its surface, attempting to fill a wide pattern relative to the particle diameter makes it difficult for particles to fill the center. This is thought to be because the particles are physically held in place by the uneven surface, and the farther from the edge of the intaglio plate, the less effective the particle movement restriction.

[0018] In contrast, in the present disclosure, the first particles and the second particles are fixed using a first substrate having a first attachment surface, and therefore the arrangement of the particles is dominated by the holding force to the first attachment surface, which increases pattern flexibility and is thought to reduce the likelihood of particle filling defects even in wide patterns, resulting in reduced likelihood of material layer defects.

[0019] An embodiment of the present disclosure will be illustrated below step by step. FIG. 1A is a flowchart of a method for manufacturing a material layer according to the present disclosure. The method for manufacturing a material layer includes the following steps: a first particle arranging step of arranging first particles on a first attachment surface of a first substrate having the first attachment surface; a second particle arranging step of arranging second particles in non-arranged portions of the first particles remaining on the first adhesion surface; a transfer step of transferring the first particles and the second particles arranged on the first substrate to a second attachment surface of a second substrate having a second attachment surface to obtain a material layer; From the viewpoint of adhesion of the second particles, it is preferable that the first particles are patterned.

[0020] The method for forming a particle pattern on the first attachment surface is not limited. Since the first attachment surface as an intermediate transfer member and the particles are held together by the adhesive force at the interface, the particles are basically held together at a thickness equivalent to a monolayer of particles regardless of the patterning method used. A suitable method can be selected depending on the particles used, whether it is a plate-based method such as relief printing or intaglio printing, or a plateless method such as electrophotography. Among these, a patterning method using a mask is preferred.

[0021] 1B is a flowchart of a method for manufacturing a material layer using a mask. The first particle disposing step preferably includes a first step of forming a mask on the first attachment surface, and a second step of disposing the first particles in areas of the first attachment surface where the mask is not formed. It is also preferable that the second particle placement step includes a third step of removing the mask from the first adhesion surface, and a fourth step of placing second particles in the non-placement areas of the first particles remaining on the first adhesion surface.

[0022] 2A to 2G show a specific example of the process of the present disclosure in order of steps. First, a first substrate 20 (intermediate transfer member) having a particle-carrying layer 29 that forms a first attachment surface 21 on the surface of the support 1 is prepared (FIG. 2A). A mask 22 having openings 23 is formed on the first attachment surface 21 of the first substrate 20 (FIG. 2B). There are no particular restrictions on the formation of the mask 22, and known means can be used. For example, a mask layer is separately formed on a support member, and patterned to obtain the desired openings 23, and then the mask is transferred from the support member to the first attachment surface 21. For example, a method of transferring the mask 22 is used.

[0023] Then, first particles 24 are placed in openings 23, which are portions of first attachment surface 21 where mask 22 is not formed (FIG. 2C). This allows first particles 24 to adhere to first attachment surface 21. Next, mask 22 is removed from first attachment surface 21 (FIG. 2D). By removing the mask, new areas on the first attachment surface where the first particles are not located are exposed. Second particles 25 are then placed in the exposed areas where the first particles are not located (FIG. 2E). This allows the second particles 25 to adhere to the first attachment surface 21, completing the pattern of the first and second particles. This pattern of the first and second particles is then transferred to a second attachment surface 27 of a second substrate 26 (final substrate 26) that includes a particle fixing layer 37 having a second attachment surface 27 (FIGS. 2F and 2G), completing the material layer. For example, the second substrate 26 includes at least a support 2 and a particle fixing layer 37.

[0024] Fig. 3 shows an example of a material layer production apparatus 100 for carrying out a material layer production method according to one embodiment of the present disclosure. The material layer production apparatus 100 is equipped with processing means for carrying out the steps shown in Fig. 2, centered around an intermediate transfer body 1 arranged in a belt shape and a transport device that transports the intermediate transfer body 1 between steps. The intermediate transfer body 1 is a first substrate 20 having the above-mentioned first attachment surface 21.

[0025] The material layer manufacturing apparatus 100 is centered around a conveying device 2 that drives an intermediate transfer body 1, and includes a mask layer applying unit that includes a mask layer supply section 30 that supplies a mask layer 3 and a pressure roller 4, a mask manufacturing unit 6 (UV laser 6), a first particle supply unit 7, and an air blower 8. The material layer manufacturing apparatus 100 also includes a mask removing unit configured with a peeling roller 9 and a winding device 10, a first inspection unit 11, and a first recovery unit 12. The material layer manufacturing apparatus 100 also includes a second particle supply unit 13, an air blower 14, a second inspection unit 15, and a second recovery unit 16. Furthermore, the material layer producing apparatus 100 includes a particle pattern transfer unit that is composed of a second substrate 26 , a pressure roller 18 , and a winding device 19 .

[0026] These units are processed sequentially to produce layers of material. 3 is configured to process each step in a series, but is not limited to this and may be configured to divide each step appropriately. Hereinafter, the explanation will be continued using the material layer manufacturing apparatus 100 of FIG. 3 as an example.

[0027] First, the intermediate transfer body 1 must have the property of being able to transfer target particles to the final substrate while retaining them on its surface. To achieve this, the intermediate transfer body 1 has a first attachment surface 21. The outer surface of the intermediate transfer body 1 serves as the first attachment surface 21. For example, the intermediate transfer body 1 has a particle-carrying layer 29 having the first attachment surface 21. The first substrate preferably has a support 1 and a particle-carrying layer 29 laminated on the support 1 to form the first attachment surface 21.

[0028] It is preferable to use adhesive properties as a particle holding force. The first adhesive surface preferably has surface properties that involve elastic deformation. If an adhesive layer that involves plastic deformation is used, the particles may become embedded in the adhesive layer. Conversely, the second attachment surface 27 that can be used as the fixing layer of the final substrate 26 preferably continues to hold and fix the attached particles until the end, and is preferably an adhesive layer that undergoes plastic deformation.

[0029] If the first attachment surface 21 is an elastically deformable surface, a part of the contact surface of the particles can sink, and the holding area is enlarged, so that the particles are sufficiently fixed. In addition, when transferring from the first attachment surface 21 to the second attachment surface, a small shear stress is generated between the particles and the surface of the transfer body by pressure, making the transfer easier.

[0030] The lower the adhesive force of the first adhesive surface 21 as a particle-supporting layer is within the range that allows particles to be retained, the better the transferability. The adhesive force value is greatly affected by the particle size and surface characteristics of the particles used, so it is desirable to select the adhesive force according to the particles used. For example, the adhesive force of the first adhesive surface 21 measured using a peel analysis device is preferably 0.2 to 10 mN / 20 mm, more preferably 0.4 to 5 mN / 20 mm, even more preferably 0.5 to 5 mN / 20 mm, and even more preferably 0.5 to 2 mN / 20 mm.

[0031] The adhesive strength was measured using a VPA-3 manufactured by Kyowa Interface Science Co., Ltd. under the following measurement conditions: In the examples described later, the sample size was 20 mm in width and 150 mm in length; measurement conditions: peel angle 90°, measurement temperature 25°C, peel speed 300 mm / min, target substrate: PET film From the viewpoint of sufficiently holding the particles, the adhesive force is preferably 0.2 mN / 20 mm or more, and from the viewpoint of better transferability and recyclability, the adhesive force is preferably 10 mN / 20 mm or less.

[0032] As for elastic properties, the rubber hardness of the first attachment surface 21 is preferably 10° to 80° (JIS type A), more preferably 15° to 40°, even more preferably 18° to 40°, and still more preferably 18° to 30°. The thickness of the particle-supported layer 29 is, for example, 10 to 200 μm, preferably 40 to 120 μm.

[0033] Specifically, the material of the particle support layer 29 forming the first adhesion surface 21 preferably includes silicone rubber, urethane rubber, or fluororubber. It may also be a mixture of any of these with other materials. The particle support layer 29 includes, for example, at least one selected from the group consisting of silicone rubber, urethane rubber, and fluororubber, more preferably silicone rubber, and even more preferably silicone rubber. The particle support layer 29 preferably includes 10 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass of at least one selected from the group consisting of silicone rubber, urethane rubber, and fluororubber. The particle support layer 29 preferably includes 10 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 80 to 100% by mass of silicone rubber.

[0034] The first attachment surface of the intermediate transfer body is sufficient as long as it is formed on at least the surface. In particular, when materials having elastic deformation such as those listed as preferred examples are used alone, the material tends to expand and contract, resulting in reduced pattern accuracy. In this case, it is advisable to use a material with low elasticity as the first substrate to maintain the dimensions.

[0035] In the material layer production apparatus 100 of FIG. 3, the intermediate transfer body 1 is in the form of a belt, but is not limited to this. For example, the intermediate transfer body 1 may be in the form of a roller or a flat plate. The support of the intermediate transfer body 1 is not limited, and commercially available materials can be used depending on the application. Examples include plastics such as polyamide resin, polyimide resin, polyacetal resin, and polyester resin, metals such as aluminum, stainless steel (SUS), and Invar alloy, as well as glass and ceramics in the form of a roll or flat plate.

[0036] When the intermediate transfer body 1 is in the form of a belt, the thickness of the support is, for example, 0.01 to 1.0 mm, or 0.05 to 0.5 mm. In the device shown in Figure 3, a 0.1 mm thick Invar support is covered with an 80 μm thick silicone rubber having a rubber hardness of 20° and a surface adhesive force of 0.5 mN / 20 mm, and the first adhesive surface is used.

[0037] The method for forming a particle pattern on the intermediate transfer member is not limited. Since the first adhesion surface and the particles are held together by the adhesive force at the interface, the particles are basically held together at a thickness equivalent to a monolayer of particles regardless of the patterning method used. The method can be suitably selected depending on the particles used, whether it is a plate-based method such as relief printing or intaglio printing, or a plateless method such as electrophotography.

[0038] As mentioned above, a method using a mask is preferred. The surface of the first attachment surface has adhesive strength in a peelable state, which can be used to hold a mask with openings. For example, a mask with a predetermined opening pattern formed on a resin film, metal foil, or the like is attached to the first attachment surface, and then the desired first particles are supplied to the entire surface. The first particles are then fixed to the non-mask-forming portions of the first attachment surface exposed only to the mask openings. By subsequently peeling off the mask, even if unnecessary particles are attached to the mask, they can be removed along with the mask, allowing a particle pattern to be easily obtained.

[0039] The method for manufacturing a material layer includes a first step of forming a mask on a first attachment surface. The means for forming the mask is not particularly limited, and may include, for example, a step of providing a mask layer 3 on the first attachment surface and a step of forming an opening 23 in the mask layer 3 to form a mask 22. The apparatus shown in FIG. 3 includes, for example, a supply means for supplying a mask layer 3, a UV laser 6 as a means for forming openings 23 in the mask layer 3, and a pressure roller 4 as a means for attaching a mask 22 onto the first attachment surface.

[0040] There are no restrictions on the material of the mask layer 3, but a material with a uniform thickness and easy processing is suitable. For example, plastics such as polyimide resin, polyacetal resin, and polyester resin, and metal foils such as aluminum, stainless steel (SUS), and invar alloy are available in high quality on the market, so these are suitable for use. Plastics are preferred. The device in Figure 3 uses a polyester resin film with a thickness of 1.5 μm.

[0041] The thickness of the mask is preferably selected to be equal to or less than the diameter of the particle material used. The arrangement of the first particles is not limited to a thin film equivalent to a particle monolayer, but is particularly suitable for forming a thin film equivalent to a particle monolayer. That is, the thickness of the arranged first particles is, for example, 0.80 to 1.20 times, or 0.90 to 1.10 times the volume-based median diameter D50 of the first particles. The arranged first particles are preferably approximately a monolayer. This is because, in principle, a structure made by stacking two-dimensionally patterned sheets with a thickness equivalent to a particle monolayer offers the greatest degree of freedom in particle pattern arrangement.

[0042] Within this range, the thicker the mask, the greater its durability, making it easier to handle and increasing the number of times it can be reused. This is suitable for cases where there are few pattern changes or when mass production is required. On the other hand, the thinner the mask, the less material is required, making it suitable for cases where there are many pattern changes or when small-scale production is required. The thickness of the mask is preferably 0.05 to 1.10 times, more preferably 0.20 to 1.00 times, and even more preferably 0.20 to 0.50 times the volume-based median diameter D50 of the first particles. Examples of the thickness of the mask layer include 0.5 to 100 μm and 1 to 50 μm.

[0043] The thickness of the mask is also preferably in the range of not less than the cumulative 10% particle size (D10) in the particle size distribution on a volume basis of the first particles and not more than the cumulative 90% particle size (D90) in the particle size distribution on a volume basis of the first particles. The volume-based median particle diameter D50 is the cumulative 50% particle diameter (median diameter: D50) in the particle size distribution on a volume basis. The particle diameter was measured using a laser diffraction / scattering particle size distribution analyzer (LA-960, manufactured by Horiba, Ltd.).

[0044] The particle pattern formation method using a combination of an intermediate transfer medium and a mask has many notable advantages. As described above, in contrast to using an intaglio plate as in Patent Document 1, when the first adhesion surface is used, the fixing of the particles is dominated by the holding force to the adhesion surface, so that the pattern flexibility is increased and filling defects are less likely to occur. Furthermore, in intaglio printing, it is necessary to create a step in the pattern equivalent to the particle diameter, but if the adhesion is by the first adhesion surface, a step is not necessary, so the mask can be thinner than the particle diameter of the first particles. The use of a thin mask is advantageous for achieving high pattern resolution. General shape processing techniques are easily affected by the aspect ratio based on the processing depth, so the thinner the mask, the easier it is to achieve high precision. Furthermore, when digging grooves as in intaglio printing, processing precision is required in terms of depth, but with a mask, through holes are sufficient, allowing for more stable processing.

[0045] There are no limitations on how the openings are formed, and it is desirable to select the appropriate method based on the mask layer material and the resolution of the design pattern. If few pattern changes are required and high resolution is desired, etching metal foil using photolithography is suitable, while if relatively low resolution is sufficient, creating openings in a resin film using a thermal head is suitable. The material layer production device 100 in Figure 3 is equipped with a UV laser 6.

[0046] Laser processing equipment is easy to adapt to pattern changes. When the mask is made of resin material, CO2 lasers are suitable in terms of wavelength, but green lasers and UV lasers have shorter wavelengths and can reduce the spot diameter when dealing with high-resolution patterns. CO2 lasers are unsuitable for metal foils, and green lasers and UV lasers are more suitable. One head can be used to create the openings, or multiple can be used to process simultaneously. It is also possible to use multiple lasers with different characteristics in combination. When the desired pattern contains a mixture of areas that require high resolution and areas that do not, this type of laser is suitable for productivity.

[0047] The shape of the mask portion is not particularly limited, but can be, for example, a stripe or honeycomb shape. When the mask portion is stripe-shaped, the width of the opening is not particularly limited, but can be 1 to 200 μm or 2 to 100 μm. The width of the mask portion can be 1 to 200 μm or 2 to 100 μm.

[0048] The mask openings 23 may be formed with the mask attached to the intermediate transfer body 1, but from the viewpoint of protecting the surface of the particle-carrying layer from contamination and damage, it is preferable to form a mask layer 3 separately on a support member, form the openings, and then transfer it to the intermediate transfer body.

[0049] For example, a material with a lower absorption rate for the laser used than the mask layer is suitable for the support member used to form the opening. Specifically, glass is preferable to a thin plastic mask. Plastic has a higher absorption rate for CO2 lasers and UV lasers than glass. Glass is also suitable because it is a material that can easily create a high level of surface smoothness.

[0050] The material layer production apparatus 100 shown in Figure 3 uses a pressure roller 4 as a support member. The pressure roller 4 can be, for example, a glass cylinder. The support member can be a flat plate, or it can be rolled up if flexible materials such as polyimide film or SUS foil are used. The technology for processing glass cylinders with high precision is commonplace and is currently produced and utilized in a wide range of industries, making them easy to obtain. In the case of laser processing, the focal length has a significant effect on accuracy, so a high-precision glass cylinder is also preferred. The mask layer 3 transported on the pressure roller can be drilled to form openings 23.

[0051] In the material layer manufacturing device 100 shown in FIG. 3, a polyester film, which is a material for the mask layer 3 and is wound in a roll, is fed by a pressure roller 4 while being irradiated with a laser 6 according to a design pattern, and holes are formed. The mask is continuously attached to the intermediate transfer body 1, and the subsequent steps from the particle supply step to the mask peeling step are performed in an integrated manner, but the present invention is not limited to this.

[0052] For example, a configuration for batch processing of sheet-like film is also possible. The advantage of using a roller-shaped substrate for creating apertures is that it allows for easier handling during mask transfer because it can utilize the curvature. If the pressure roller is a rigid body such as glass, it may seem unsuitable for attaching a thin film mask to the surface of the intermediate transfer body 1, but if the particle-carrying layer on the surface of the intermediate transfer body 1 is elastic, then attachment pressure can be applied without any problems.

[0053] The laser irradiation method is not limited, and examples include a method in which a mask layer such as a cut thin plastic sheet is attached to a glass cylinder and scanned while rotating. Alternatively, the cylinder may be rotated while a laser head is scanned line by line in the axial direction of the glass cylinder in a plotter-like manner, or multiple processing heads may be lined up to process all at once.

[0054] Following the first step, a second step is carried out in which first particles are placed in the non-mask-forming areas of the first attachment surface. That is, a mask with openings is placed on the intermediate transfer body 1, and then the first particles are placed. There are no particular restrictions on the particles used and the method for supplying the particles, and a wide range of known methods can be applied. In particular, unlike other printing methods, the mask method is advantageous because even if particles remain on the mask, they can be removed along with the mask. Specifically, the particles can be sprinkled by gravity and spread by vibration, attached by spraying, or supplied using a roller, brush, or blade. If it is desired to densely fill the mask openings with particles, it is preferable to apply a rubbing force.

[0055] Generally, to increase the friction force, in the case of the roller supply method, a method of strengthening the nip is used, or a method of achieving a friction force by creating a difference between the feed speed and the roller peripheral speed is used. The friction force can be optimized according to the pattern size and the particles used, so long as it is not enough to peel off the mask.

[0056] Among these, rubbing using magnetic particles is preferred when a mask is used. That is, the first particles are preferably arranged by using magnetic particles as a carrier material to support the first particles and then rubbing the first particles against the first adhesion surface. The first particles can be supported by forming a magnetic brush using magnetic particles as a carrier material. The rubbing force can be easily changed depending on the particles by controlling the magnetic force. Large magnetic particles are a good match because they can be filled while pressing the mask against the transfer body. The first particles may be a single material or a premix of multiple particles. Of course, the particle surface may be subjected to a surface treatment or coating.

[0057] After the second step of disposing the first particles in the non-forming areas of the mask, an excess particle removal step may be performed to remove excess particles. As mentioned above, particles attached to the mask can be removed when the mask is peeled off. However, if there are excessive particles attached to the mask or particles filled in the mask openings, particles that slide off during the mask peeling step or transfer step may disrupt the particle pattern. The apparatus in Figure 3 has an air blower 8 as an excess particle removal means. Air blowing is preferred for removing excess particles. The excess particle removal step makes it easier to form a substantially single layer of particles.

[0058] The method for manufacturing the material layer includes a third step of removing the mask from the first adhesive surface. There are no particular limitations on the means for removing the mask, and any known means may be used. For example, the mask may be peeled off. As a mechanism for peeling the mask from the first substrate, the apparatus shown in FIG. 3 uses a method in which the mask is wound up in the form of a continuous film using a peeling roller 9 and a winding device 10. For example, in the case of a sheet form, the peripheral part of the mask may be picked up by vacuum suction, or the mask edge may be wound up by a method in which the mask is peeled off from the first substrate. A pickup unit may be provided in advance and then mechanically pulled up. Also, when a mask made of a resin material is peeled off, static electricity may be generated, which may disrupt the pattern, so it is preferable to take measures against static electricity depending on the situation.

[0059] It is preferable to perform a first inspection step of inspecting the first particles arranged on the first attachment surface before arranging the second particles in the non-arrangement areas of the first particles. The material layer preparation apparatus 100 of FIG. 3 includes a first inspection unit 11, where the pattern can be inspected. After the mask is removed, the particles on the intermediate transfer body 1 are held by the first adhesion surface, making it difficult for the particles to move. Therefore, it is preferable to inspect the pattern at this point, as there will be little pattern fluctuation thereafter.

[0060] There are no restrictions on the inspection method, and it is desirable to select one based on the particle characteristics and the required measurement accuracy. Generally, methods such as optically capturing image data and comparing the patterns are suitable for determining the surface pattern, while methods such as measuring the film thickness with a distance sensor or creating a 3D map and making a determination based on the three-dimensional information can be used to determine the height pattern. When determining pass / fail based on material composition, infrared or X-ray energy can be irradiated, composition information can be obtained from the recovered information, and a pass / fail determination can be made based on the respective set criteria. Of course, it is also possible to obtain multiple pieces of information using multiple methods and make a comprehensive determination.

[0061] Furthermore, when continuously producing material layers, as with the material layer manufacturing apparatus 100 of Figure 3, the defect rate tends to be high when the apparatus starts operating until each processing unit stabilizes, and if there is data available in advance, it may be possible to set it so that all products are collected up to a certain number of processes without relying on an inspection device. In the material layer manufacturing apparatus 100 of FIG. 3, a thin mask layer is used, so that the particles are arranged in a substantially single layer, and therefore a general camera that optically obtains planar image information is used as the inspection means.

[0062] If the particle material is determined to be out of specification, it can be recovered and reused. The material layer production device 100 is equipped with a first recovery unit 12. The recovery means used by the first recovery unit 12 is not particularly limited. The recovery means is preferably a means that can separate the particles under conditions that do not damage the particle-carrying layer on the surface of the intermediate transfer body. Since the particles are appropriately held on the particle-carrying layer, a method that physically removes the particles is preferred.

[0063] For example, particles can be collected by applying moderate pressure to a nylon brush or sponge in a sliding or rotating manner against the intermediate transfer body.Also, particles can be neatly collected by sliding a flexible, thick blade-shaped rubber material such as urethane or EPDM, or a squeegee-shaped material such as polyester, polyacetal, polypropylene, or fluororesin over the intermediate transfer body at a counter angle.

[0064] Of course, it is also possible to use multiple means in combination. The recovery mechanism in the device in Figure 3 is configured to slide parallel to a brush made of nylon thread with a wire diameter of 150 μm and a polyurethane microporous sponge (Ruby Cell, manufactured by Toyo Polymer Co., Ltd.). The recovered particles can basically be used as is, but it is desirable to perform a process to separate out any debris that may have been mixed in during the process. In the device in this example, the recovered particles are passed through a separate airflow classifier that uses the Coanda effect to separate out the debris, and then returned to the device for reuse.

[0065] Next, a fourth step is performed in which second particles are placed in the non-placement areas of the first particles remaining on the first adhesion surface. That is, the second particles are placed in the mask-removed areas. The particle-carrying layer of the intermediate transfer body, which was protected by the mask, is now exposed, and the second particles selectively adhere to this exposed area. The second particles may be the same as the first particles, or may be different.

[0066] As with the arrangement of the first particles, the supply method is not limited and can be selected according to the particles to be used. In FIG. The second particle supply unit 13 may be the same as the first particle supply unit 7. After the second particles are supplied, excess particles may be removed in the same manner as after the placement of the first particles. For example, in FIG. 3, the material layer preparation apparatus 100 includes an air blower 14.

[0067] In the device shown in Figure 3, a pattern consisting of two types of particles was formed using one mask, but this is not limited to this. For example, if two masks are used, offset from one another, a pattern consisting of three types of particles can be obtained by repeating the same process.

[0068] Also, pattern inspection can be performed at this point. That is, after disposing the second particles, a second inspection step may be performed to inspect the first particles and the second particles disposed on the first attachment surface. For example, the material layer preparation apparatus 100 includes a second inspection unit 15 and a second recovery unit 16. The second inspection unit 15 and the second recovery unit 16 may be the same as the first inspection unit 11 and the first recovery unit 12, respectively.

[0069] If the second particles are found to be defective by inspection after the supply, the recovered particles will be a mixture of the first and second particles, so it is desirable to separate them until they reach the required state using the air classifier or a classifier that utilizes centrifugal force, as described above. The device in Figure 3 is equipped with a camera-based inspection device and a particle recovery device using brushes and sponges, the same as the first inspection unit 11 and first recovery unit 12. To reuse the particles, the particles are separated using a separate air classifier. In the air classifier, the classification conditions are optimized by factors such as air flow velocity and Coanda blade shape, and if a single pass is insufficient, repeated passage through the classifier can ensure more reliable separation.

[0070] Next, a transfer step is performed in which the first particles and second particles arranged on the first substrate are transferred to a second attachment surface of a second substrate 26 having a second attachment surface 27 to obtain a material layer. That is, after the particle pattern is completed on the intermediate transfer body, the particles are transferred to the second substrate 26 as the final substrate. The second substrate 26 can be freely selected depending on the purpose.

[0071] For example, the material layer production apparatus 100 includes a particle pattern transfer unit composed of a second substrate 26, a pressure roller 18, and a winding device 19. While the second substrate 26 is unwound and wound by the winding device 19, the pressure roller 18 brings the second adhesion surface of the second substrate 26 into contact with the first particles and second particles arranged on the first substrate, thereby allowing the transfer to occur. After the transfer, the intermediate transfer body can be cleaned of dirt and remaining particles by a cleaning means such as a cleaning roller 5 .

[0072] In the material layer production apparatus 100 of FIG. 3, a second substrate 26 in the form of a "double-sided tape" is used in a roll state, in which particle fixing layers having second adhesive surfaces are formed on both sides of the base substrate 2 (support 2). However, this is not limiting. For example, a mechanism for applying an adhesive to the surface of the base substrate 2 as the second adhesive surface may be provided within the apparatus. The second adhesive surface may be formed on at least one side of the second substrate. The second substrate preferably has a support and a particle fixing layer 37 laminated on the support to form the second adhesive surface 27.

[0073] The particle fixing layer 37 forming the second adhesive surface preferably has a stronger adhesive force than the first adhesive surface in the particle carrying layer on the surface of the intermediate transfer body in order to receive the particle pattern from the intermediate transfer body. In other words, the adhesive force of the second adhesive surface is preferably higher than that of the first adhesive surface. The difference in adhesive strength varies depending on the characteristics and size of the particles used and the thickness and deformation amount of the particle fixing layer, but for example, the adhesive strength of the second adhesive surface is at least three times, preferably at least five times, and more preferably at least ten times that of the first adhesive surface. From the viewpoint of transferability, the higher the adhesive strength of the second adhesion surface that receives the particles, the better. Therefore, although there is no particular upper limit, it is preferably, for example, 300,000 times or less, or 150,000 times or less.

[0074] As described above, from the viewpoint of transferability, the adhesive strength of the second adhesive surface 27 is only required to be higher than that of the first adhesive surface, and the range is not particularly limited. For example, the adhesive strength of the second adhesive surface 27 measured using a peel analysis device is preferably 0.5 to 30 N / 20 mm, more preferably 1.2 to 20 N / 20 mm, and even more preferably 2 to 20 N / 20 mm. The adhesive strength is measured as described above.

[0075] Since the particles are not released after being transferred to the particle fixing layer, it is desirable that the particle fixing layer be an adhesive layer capable of plastic deformation. That is, it is preferable that the particle fixing layer contains an adhesive, and the second attachment surface is preferably the surface of the adhesive. Furthermore, if the particle support layer is an adhesive layer that undergoes elastic deformation, good transferability can often be obtained even with a small difference in adhesive strength. For example, the second substrate may be an adhesive tape or a double-sided tape. Specific examples of adhesive materials include acrylic adhesives, urethane adhesives, and silicone adhesives.

[0076] In the manufactured material layer, the functional material is the first particles and the second particles, so it is generally desirable that the second substrate, which does not contribute to the function, is thin. Also, even if the functional layer is ultimately removed by heating or other means and is used as a functional layer consisting only of the particle pattern, a thin (small volumetric) second substrate reduces the load during the removal process and reduces the volume change during removal, making the particle pattern less likely to collapse.

[0077] The particle pattern on the intermediate transfer body is aligned in a nearly single layer, making it easy to apply transfer pressure evenly. This has the advantage of lowering the pressure applied during transfer and also makes it easier to use a thin second substrate. If there are areas on the intermediate transfer body where particles exist and areas where they do not, a step will be created at the boundary. When the thin second substrate is transferred and pressed against the intermediate transfer body, the second substrate may follow this step, causing slight wrinkles or stretching. This can cause slight misalignment in the pattern, or reduce the dimensional accuracy of the laminate when using completed material layers stacked together.

[0078] In particular, if the second substrate is made only of a particle fixing layer, it may stretch due to the force applied during handling, such as when peeling it off from the intermediate transfer body. Therefore, it is desirable for the second substrate to have a multilayer structure consisting of a base substrate 2 (support 2) made of a material that is resistant to stretching and an adhesive layer serving as the particle fixing layer. Plastic films such as polyester, acrylic, polypropylene, and polyimide, as well as metal foils such as aluminum and copper, can also be used as materials for the base substrate. Considering that the second substrate will be removed by heating or the like, a plastic film is preferred.

[0079] The material layer production device of FIG. 3 can produce a substantially single-layer particle pattern. On the other hand, this substantially single-layer particle pattern can also be laminated to form a laminate. That is, a laminate may be manufactured by a process of laminating material layers to obtain a laminate. The second substrate on which a particle pattern is formed, produced by the material layer production device of FIG. 3, is in the form of a double-sided tape. Therefore, sheets can be laminated using the adhesive layer on the opposite side of the layer on which the particle pattern is formed (FIG. 4A). That is, a laminate 401 can be formed by laminating multiple second substrates on which particle layers are formed. Here, by having an adhesive layer on the opposite side of the layer on which the particle pattern is formed, the substrate can be easily adhered. The materials adhere to each other, increasing the strength of the laminate. As a result, it is possible to suppress misalignment between the substrates. Furthermore, the particle layer between the substrates is sandwiched between the upper and lower adhesive layers, which prevents misalignment during storage, etc. The number of layers in the laminate is not particularly limited.

[0080] Alternatively, after obtaining a laminate, the second substrate can be removed by utilizing the difference in properties between the particles used and the second substrate to obtain a patterned laminate (three-dimensional object 402) consisting only of particles (Figure 4B). That is, a three-dimensional object may be manufactured by removing the second substrate from the laminate and molding a three-dimensional object containing particles. The method for removing the second substrate is not particularly limited. For example, a patterned laminate consisting only of particles can be obtained by forming a material layer on the second substrate using a resin material and then degreasing the laminate produced from the material layer at high temperature.

[0081] When the second substrate is finally removed, a material with high removability can be selected depending on the removal method. The removal method can be selected depending on the characteristics of the particles used. For example, one method involves dissolving and removing the substrate using a solvent, but the conditions should be selected so that the fluidity of the liquid does not disrupt the pattern. Another method involves using a photodegradable photosensitive material, but the conditions must be selected because some particle materials may block the light. If the particle material is resistant to high temperatures, removal by heating can be selected. This method can be relatively easily reproduced by selecting the materials for the base substrate and particle fixing layer of the second substrate. For example, using a polyester film or the like for the base substrate of the final substrate and an acrylic adhesive for the particle fixing layer can achieve both thinness and thermal removability.

[0082] Furthermore, by using a second substrate having ceramic particles and particles that can be degreased by heating, the internal porosity of the ceramic structure can be controlled.

[0083] The conditions for high-temperature degreasing are not particularly limited, but heating is preferably performed at a temperature equal to or higher than the thermal decomposition temperature of the second substrate, and preferably lower than the thermal decomposition temperature of each particle layer in the pattern laminate. The temperature to which the laminate is heated is preferably 200°C or higher and 1000°C or lower, more preferably 400°C or higher and 800°C or lower, particularly preferably 450°C or higher and 800°C or lower, and even more preferably 450°C or higher and 650°C or lower. The sintering temperature is preferably maintained for 30 minutes or longer, more preferably 1 hour or longer. The upper limit is not particularly limited, but may be, for example, 3 hours or shorter, or 2 hours or shorter. For example, the sintering temperature is preferably maintained for 30 minutes to 3 hours, or 1 hour to 2 hours. The thermal decomposition temperature is the temperature at which the weight of a material begins to decrease when the temperature is gradually increased in a heating atmosphere in a sintering treatment device. Therefore, by heating the laminate at a temperature equal to or higher than the thermal decomposition temperature of the second substrate, the second substrate in the laminate can be decomposed to reduce its weight, and the second substrate can be removed from the laminate.

[0084] This disclosure is widely applicable to functional materials, but battery modules are particularly suitable. Battery materials are expected to achieve higher performance by functionally arranging electrode layer materials and efficiently arranging ion and electron paths. All-solid-state batteries, in particular, do not use electrolytes, so positive and negative electrode materials and solid electrolyte materials can be functionally arranged according to optimized patterns. Furthermore, because battery materials are expensive particles and contain rare earths and other scarce substances, the ability to recycle unnecessary materials is economically and environmentally significant.

[0085] The first particles are not particularly limited, and desired resin particles, inorganic particles, etc. can be used. Examples of resin particles include (meth)acrylic resin particles, urethane resin particles, and ester resin particles. Metal particles such as copper particles may also be used. When the method for producing a material layer according to the present disclosure is used as a method for producing a precursor for a solid-state battery, it is preferable that the first particles contain at least one of active material particles and solid electrolyte particles, for example.

[0086] The active material particles are not particularly limited, and known active material particles can be used. For example, lithium-containing composite oxides can be used. Specific examples include Li-Co oxide active material particles such as LiCoO2 (lithium cobalt oxide), LiMO2 (where M is an element selected from the group consisting of Ni, Mn, and Co), Li-PO4 oxide active material particles, lithium vanadium compounds (Li3V2(PO4)3, LiVOPO4), and olivine-type phosphate compounds (LiMPO4 (where M is one or more elements selected from the group consisting of Co, Ni, Mn, Fe, Mg, V, Nb, Ti, Al, and Zr)). Active material particles that do not contain lithium can also be used. Specific examples include metal oxides (MnO2, V2O5, etc.) and fluorides (FeF3, VF3, etc.). Among these, it is preferable to include Li-Co oxide-based active material particles and Li-PO4 oxide-based active material particles. Furthermore, negative electrode active material particles such as graphite, Si, and lithium titanate (LTO) can also be used.

[0087] The solid electrolyte is not particularly limited, and known solid electrolytes can be used. Examples include Li-B oxide-based solid electrolyte particles such as lithium borate, Li-Yb oxide-based solid electrolyte particles, Nasicon-type solid electrolyte particles (LiAlTi(PO4)3, LiAlGe(PO4)3, etc.), and Li-PO-based solid electrolyte particles (Li3PO4, LiPON (particles in which part of the O in Li3PO4 is replaced with N), etc.). Among the above solid electrolyte particles, it is preferable to use Li-B oxide-based solid electrolyte particles and Li-Yb oxide-based solid electrolyte particles.

[0088] The second particles are not particularly limited, and as with the first particles, desired resin particles, inorganic particles, etc. can be used. When the method for manufacturing a material layer of the present disclosure is used as a method for manufacturing a precursor for a solid-state battery, the second particles preferably include, for example, at least one of active material particles and solid electrolyte particles. Specifically, the active material particles and solid electrolyte particles described above as the first particles can be used.

[0089] The first particles and the second particles may each be of one type, or a combination of multiple types. When multiple types are combined, multiple types of particles may be premixed in advance. The particle surfaces may be subjected to a surface treatment or coating.

[0090] The method for manufacturing a material layer according to the present disclosure can be used as a method for manufacturing a precursor for a solid-state battery. That is, the material layer is preferably a precursor for a solid-state battery. As described above, materials for solid-state batteries are expensive, so using the method for manufacturing a material layer as a method for manufacturing a precursor for a solid-state battery is effective in suppressing transfer failures and improving recyclability.

[0091] When the method for manufacturing a material layer according to the present disclosure is used as a method for manufacturing a precursor for a solid-state battery, the second substrate is preferably a resin substrate. Furthermore, it is preferable that the first particles include at least one of active material particles and solid electrolyte particles, and the second particles include at least one of active material particles and solid electrolyte particles. More preferably, the first particles include at least one of active material particles and solid electrolyte particles, and the second particles include the other of active material particles and solid electrolyte particles. Even more preferably, the first particles include active material particles, and the second particles include solid electrolyte particles.

[0092] Furthermore, an anisotropic conductive material layer can be obtained by using at least one of metal particles and resin particles as the first particles and the other of metal particles and resin particles as the second particles.

[0093] An example of a precursor for a solid-state battery is a material layer for a solid-state battery. A material layer for a solid-state battery can be used as a precursor for a solid-state battery to obtain a material laminate in which the material layers for the solid-state battery are laminated. The precursor for a solid-state battery is preferably a material layer for an electrode of a solid-state battery. Therefore, a method for manufacturing an electrode for a solid-state battery includes the steps of obtaining a material layer by the above-described manufacturing method, laminating the obtained material layers to obtain a laminate, and heating and degreasing the obtained laminate to remove the second substrate and obtain an electrode.

[0094] That is, an electrode for a solid-state battery can be obtained by removing the second substrate from the laminate and forming a three-dimensional object containing the particles. The above-mentioned processes can be used for the process of obtaining the laminate and the process of forming the three-dimensional object. The electrode may be a positive electrode or a negative electrode. The number of layers in the laminate is not particularly limited and can be changed depending on the purpose of the electrode to be manufactured. For example, three or more layers can be used. [Example]

[0095] The present disclosure will be specifically described below with reference to examples, but these examples are not intended to limit the present disclosure in any way. In the following formulations, parts are by mass unless otherwise specified.

[0096] Example 1 An example of producing a positive electrode material layer for an all-solid-state battery using the material layer production device of Figure 3 will be shown. The first particles were made of a positive electrode material: lithium cobalt oxide (Nippon Chemical Industry Co., Ltd.: volumetric median diameter D50: 5 μm), and the second particles were made of a solid electrolyte: lithium borate (Toshima Manufacturing Co., Ltd.: volumetric median diameter D50: 5 μm). The intermediate transfer belt used was a 0.1 mm thick Invar support with a 80 μm thick silicone rubber (Dow Toray Industries: SE9186) coated as a particle-carrying layer having a first adhesive surface. The first adhesive surface had a rubber hardness of 20° and a surface adhesion of 0.5 mN / 20 mm. Additionally, a polyester film (1.5 μm thick, Mitsubishi Chemical: K-917) was used as the mask layer, and a UV laser processing machine (Kokyo: fine UV laser marker) was used to create the mask openings. Double-sided tape (Nitto Denko: No. 5600) was used as the second substrate, and magnetic particles (Japan Imaging Society: P02) were used for particle supply units 7 and 13. Then, using the material layer preparation device shown in FIG. 3, the above-mentioned steps were carried out to prepare a positive electrode material layer for an all-solid-state battery. The mask openings were in a 10 μm stripe pattern with lines and spaces, i.e., the openings were in a stripe pattern with a width of 10 μm. The adhesive strength of the second adhesive surface was 1.3 N / 20 mm, which was 34 times that of the first adhesive surface.

[0097] The prepared positive electrode material layers were stacked three times on an aluminum foil (20 μm thick) with a stacking angle of 90° to obtain a laminate. The obtained laminate was degreased by heating at 500 °C for 1 hour in an electric furnace (MMF-1 manufactured by AS ONE Corporation), and the second substrate was removed to obtain a positive electrode material layer laminate (thickness: approximately 15 μm) for an all-solid-state battery.

[0098] This positive electrode material laminate was used to prepare a prototype battery under the following conditions. A sintered body was obtained by processing and molding the solid electrolyte LAGP (Toshima Manufacturing Co., Ltd.) to a thickness of 250 μm and then sintering it at 850°C. The cathode material laminate and 50 μm thick indium metal foil as the anode material were layered on both sides of the sintered body, and each was connected to an extraction electrode, vacuum-packed in an aluminum laminate sheet, and finally pressurized at 200 MPa in a CIP device to obtain a prototype battery.

[0099] The prototype battery was able to be charged and discharged normally, and the charge capacity when charged and discharged at a charge / discharge rate of 0.1C was 86% of the theoretical value (measured using an electrochemical device (Solartron 1255WB model)).

[0100] Example 2 During the manufacturing process of Example 1, the first particles were forcibly collected from the intermediate transfer body using the first recovery unit 12. The mass of the first particle pattern was determined by subtracting the mass of the intermediate transfer body from the total mass of the intermediate transfer body and the first particle pattern. The mass ratio of the first particles that were recovered based on the mass of the first particle pattern, i.e., the recovery ratio, was calculated to be 93.3 mass%. The first recovery unit 12 has a recovery mechanism in which a brush made of nylon thread with a wire diameter of 150 μm and a polyurethane microporous sponge (Ruby Cell, manufactured by Toyo Polymer Co., Ltd.) slide in parallel.

[0101] Example 3 During the manufacturing process of Example 1, the second recovery unit 16 was used to forcibly recover the mixture of the first particles and the second particles from the intermediate transfer member. The recovery ratio of the first particles and the second particles was calculated in the same manner as in Example 2, and was found to be 95.1% by mass.

[0102] (Comparative Example 1) In Example 1, the second substrate on which the first particles were fixed was attached to the intermediate transfer member support material, and an attempt was made to recover the first particles under the same conditions as in Example 2, but recovery of the particles was impossible.

[0103] (Comparative Example 2) In Comparative Example 1, the first recovery unit 12 was changed to a polyacetal blade with higher particle peeling ability, and recovery was attempted, but particle recovery was impossible. Furthermore, when the blade pressure was increased, the tip of the blade became trapped in the particle fixed layer and could not move.

[0104] Example 4 An example of producing an anisotropic conductive rubber laminate using the material layer producing device of FIG. 3 will be described. The first particles were copper particles (in-house prototype: granulated by disk atomization and then sieved, volumetric median diameter D50: 30 μm), and the second particles were elastic resin particles: crosslinked polyacrylic ester (Sekisui Chemical Co., Ltd.: ARX-30, volumetric median diameter D50: 30 μm). The intermediate transfer belt used consisted of a 0.1 mm thick Invar support and an 80 μm thick silicone rubber (Dow Toray: SE9186) coating as a particle-carrying layer with a first adhesive surface. The first adhesive surface had a rubber hardness of 20° and a surface adhesion of 0.5 mN / 20 mm. In addition, SUS430 (30 μm thick) was used as the mask layer, and a UV laser processing machine (Kokyo: fine UV laser marker) was used to create the mask opening. Double-sided tape (Nitto Denko: No. 5600) was used as the second substrate, and a forward-rotating roller unit with a urethane rubber roller (rubber hardness 70 degrees) was used for particle supply units 7 and 13. Then, using the material layer creation device of Figure 3, each of the above-mentioned steps was performed to create an anisotropic conductive rubber material layer. The mask opening was a 100 μm stripe pattern with lines and spaces.

[0105] In addition, from the mask attachment step to the mask peeling step, a magnet was placed on the rear surface of the intermediate transfer body, and the mask was held in place by magnetic force. The anisotropic conductive rubber material laminate obtained by stacking 20 layers of the anisotropic conductive rubber material layers in the same stacking direction was able to be manufactured with stable quality as an anisotropic conductive rubber laminate with low resistance in the stripe direction.

[0106] Example 5 During the manufacturing process of Example 4, the second recovery unit 16 was used to forcibly recover the mixture of the first particles and the second particles from the intermediate transfer member. The recovery ratio of the first particles and the second particles was calculated in the same manner as in Example 2, and was found to be 96.6% by mass. In addition, the collected particles were processed twice using an air classifier that utilizes the Coanda effect, and the separation rate for the first particles was 85.4% and for the second particles was 91.1%, which was satisfactory.

[0107] Table 1 shows the particle recovery rates in the examples and comparative examples. [Table 1]

[0108] The present disclosure relates to the following methods: (Method 1) 1. A method for manufacturing a material layer, comprising: The manufacturing method includes: a first particle arranging step of arranging first particles on a first attachment surface of a first substrate having the first attachment surface; a second particle arranging step of arranging second particles in non-arranged portions of the first particles remaining on the first adhesion surface; a transfer step of transferring the first particles and the second particles arranged on the first substrate to a second attachment surface of a second substrate having a second attachment surface to obtain the material layer; 10. A method for manufacturing a material layer, comprising: (Method 2) The first particle arrangement step includes a first step of forming a mask on the first attachment surface, and a second step of arranging the first particles in a portion of the first attachment surface where the mask is not formed. the second particle placement step includes a third step of removing the mask from the first deposition surface; and a fourth step of disposing second particles in non-disposed areas of the first particles remaining on the first adhesion surface. Method for producing a layer of material according to method 1. (Method 3) The thickness of the mask is 0.10 to 1 times the volume-based median diameter D50 of the first particles. A method for manufacturing a material layer according to method 2, wherein the thickness is 0.10 times. (Method 4) The method for manufacturing a material layer according to Method 2 or 3, further comprising a step of removing excess particles after the second step. (Method 5) 5. The method for producing a material layer according to any one of methods 1 to 4, wherein the second adhesive surface has a higher adhesive strength than the first adhesive surface. (Method 6) 6. The method for producing a material layer according to any one of Methods 1 to 5, wherein the adhesive strength of the first adhesive surface measured by a peel analysis device is 0.2 to 10 mN / 20 mm. (Method 7) the first substrate has a support and a particle-carrying layer laminated on the support to form the first attachment surface; 7. The method for producing a material layer according to any one of methods 1 to 6, wherein the particle-supported layer contains at least one selected from the group consisting of silicone rubber, urethane rubber, and fluororubber. (Method 8) the first particles include at least one of active material particles and solid electrolyte particles, The method for producing a material layer according to any one of Methods 1 to 7, wherein the second particles include at least one of active material particles and solid electrolyte particles. (Method 9) The method for producing a material layer according to Method 8, wherein the material layer is a precursor for a solid-state battery. (Method 10) A method for manufacturing a material layer described in any of methods 1 to 9, comprising a step of inspecting the first particles arranged on the first attachment surface before arranging the second particles in the non-arrangement portions of the first particles. (Method 11) 11. The method for producing a material layer according to any one of Methods 1 to 10, further comprising a step of obtaining a laminate by laminating a plurality of the obtained material layers. (Method 12) A method for manufacturing an electrode for a solid-state battery, comprising: The manufacturing method comprises: obtaining a material layer by the method for producing a material layer according to method 8 or 9; A step of laminating the obtained material layers to obtain a laminate; and a step of heating and degreasing the obtained laminate to remove the second substrate and obtain an electrode; A method for manufacturing an electrode for a solid-state battery, comprising:

Claims

1. 1. A method for manufacturing a material layer, comprising: The manufacturing method includes: a first particle arranging step of arranging first particles on a first attachment surface of a first substrate having the first attachment surface; a second particle arranging step of arranging second particles in non-arranged portions of the first particles remaining on the first adhesion surface; a transfer step of transferring the first particles and the second particles arranged on the first substrate to a second attachment surface of a second substrate having a second attachment surface to obtain the material layer; 10. A method for manufacturing a material layer, comprising:

2. The first particle arrangement step includes a first step of forming a mask on the first attachment surface, and a second step of arranging the first particles in a portion of the first attachment surface where the mask is not formed. the second particle placement step includes a third step of removing the mask from the first deposition surface; and a fourth step of disposing second particles in non-disposed areas of the first particles remaining on the first adhesion surface. A method for producing the material layer of claim 1 .

3. 3. The method for manufacturing a material layer according to claim 2, wherein the thickness of the mask is 0.10 to 1.10 times the volume-based median diameter D50 of the first particles.

4. The method for manufacturing a material layer according to claim 2 , further comprising the step of removing excess particles after the second step.

5. The method for manufacturing a material layer according to claim 1 , wherein the second adhesive surface has a higher adhesive strength than the first adhesive surface.

6. The method for manufacturing a material layer according to claim 1, wherein the adhesive strength of the first adhesive surface measured by a peel analysis device is 0.2 to 10 mN / 20 mm.

7. the first substrate has a support and a particle-carrying layer laminated on the support to form the first attachment surface; The method for manufacturing a material layer according to claim 1 , wherein the particle-carrying layer contains at least one selected from the group consisting of silicone rubber, urethane rubber, and fluororubber.

8. the first particles include at least one of active material particles and solid electrolyte particles, 8. The method for manufacturing a material layer according to claim 1, wherein the second particles include at least one of active material particles and solid electrolyte particles.

9. The method for manufacturing a material layer according to claim 8 , wherein the material layer is a precursor for a solid-state battery.

10. The method for manufacturing a material layer according to claim 1 , further comprising a step of inspecting the first particles disposed on the first attachment surface before disposing the second particles on the non-disposed portions of the first particles.

11. The method for manufacturing a material layer according to claim 1 , further comprising a step of stacking a plurality of the obtained material layers to obtain a laminate.

12. A method for manufacturing an electrode for a solid-state battery, comprising: The manufacturing method comprises: A step of obtaining the material layer by the method for manufacturing a material layer according to claim 8; A step of laminating the obtained material layers to obtain a laminate; and a step of heating and degreasing the obtained laminate to remove the second substrate and obtain an electrode; A method for manufacturing an electrode for a solid-state battery, comprising:

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