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

Abstract

Disclosed is a method for producing a material layer which is easy to recycle and is not susceptible to the occurrence of transfer failure. This 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 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.

Description

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

[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.

[0002] While various new manufacturing methods using additive manufacturing have been developed in recent years, the difficulty of designing and arranging multiple material particles to create functional structures has remained limited. For example, while the technique of arranging toner particles using electrophotography is widespread, toner particles are composed of composite materials that contain binders in amounts several times greater than the amount of pigment used as the functional material to achieve electrostatic charging. Furthermore, due to the properties of static electricity, positioning individual particles is fundamentally difficult—a phenomenon that also applies to electrostatic screen printing, which can pattern particles without the use of binders. Arranging functional particles in the right places can avoid unnecessary particle waste, resulting in greater benefits for 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 the substrate onto another substrate and transferring the pattern.

[0004] Japanese Patent Application Laid-Open No. 2019-137060

[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 resulting particle pattern is defective, to recover and recycle the particles that are the raw materials for solid-state batteries. In the method for manufacturing a material layer disclosed in Patent Document 1, a particle pattern is formed using an intaglio plate, and the resulting 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 recognized that when forming a pattern using an intaglio plate, for example, in the case of a wide pattern, particle filling may be insufficient.

[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.

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

[0008] The present disclosure also relates to a method for manufacturing an electrode for a solid-state battery, the method comprising: obtaining a material layer by the above-described method for manufacturing a material layer; stacking the obtained material layers to obtain a laminate; and heating and degreasing the obtained laminate to remove the second base material, thereby obtaining an electrode.

[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.

[0010] Figures 1A and 1B are conceptual diagrams showing a method for manufacturing a material layer. Figures 2A to 2G are explanatory diagrams explaining one embodiment of the present disclosure. Figure 3 is a schematic diagram of a material layer manufacturing apparatus. Figures 4A and 4B are explanatory diagrams of a laminate.

[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 lower and upper 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 at that point using a recovery means. 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 good, the particles can be easily peeled off from the first attachment surface and recovered 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, followed by 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 step by step below. 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: a first particle arrangement step of arranging first particles on a first attachment surface of a first substrate having a first attachment surface; a second particle arrangement step of arranging second particles in areas of the first attachment surface where the first particles are not arranged; and 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 deposition surface and a second step of disposing the first particles in areas of the first deposition surface where the mask is not formed. The second particle disposing step preferably includes a third step of removing the mask from the first deposition surface and a fourth step of disposing second particles in areas of the first deposition surface where the first particles are not disposed.

[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) is prepared having a particle-carrying layer 29 that forms a first attachment surface 21 on the surface of a support 1 (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 method can be used in which a mask layer is separately formed on a support member, patterned to obtain the desired openings 23, and then the mask 22 is transferred from the support member to the first attachment surface 21.

[0023] Then, first particles 24 are placed in the openings 23 of the first attachment surface 21, which are the non-formed portions of the mask 22 (FIG. 2C). This allows the first particles 24 to adhere to the first attachment surface 21. Next, the mask 22 is removed from the first attachment surface 21 (FIG. 2D). By removing the mask, new portions of the first attachment surface where the first particles are not placed are exposed. Second particles 25 are placed in the exposed non-formed portions of the first particles (FIG. 2E). This allows the second particles 25 to adhere to the first attachment surface 21, completing a pattern of the first and second particles. This pattern of the first and second particles is transferred to the 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] 3 shows an example of a material layer production apparatus 100 for carrying out the material layer production method according to one embodiment of the present disclosure. The material layer production apparatus 100 is equipped with processing means for performing 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 the first substrate 20 having the above-described first attachment surface 21.

[0025] The material layer production apparatus 100 is centered around a transport device 2 that drives an intermediate transfer body 1, and includes a mask layer attachment unit including a mask layer supply unit 30 that supplies a mask layer 3 and a pressure roller 4, a mask production unit 6 (UV laser 6), a first particle supply unit 7, and an air blower 8. The material layer production apparatus 100 also includes a mask removal unit including a peeling roller 9 and a winding device 10, a first inspection unit 11, and a first recovery unit 12. The material layer production 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. The material layer production apparatus 100 also includes a particle pattern transfer unit including a second substrate 26, a pressure roller 18, and a winding device 19.

[0026] A material layer is manufactured by sequentially performing processes in these units. Although the material layer manufacturing apparatus 100 in Figure 3 is configured to perform each process in a series, the configuration is not limited to this and each process may be divided as appropriate. The following description will be continued using the material layer manufacturing apparatus 100 in Figure 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 utilize adhesive properties as a particle holding force. The first attachment 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 for the final substrate 26 preferably continues to hold and fix the attached particles until the end, and is preferably an adhesive layer that involves 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-carrying layer is within a 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 force was measured using a VPA-3 manufactured by Kyowa Interface Science Co., Ltd. under the following measurement conditions. In the examples described below, the sample size was 20 mm in width and 150 mm in length. Measurement conditions: peel angle 90°, measurement temperature 25°C, peel rate 300 mm / min, target substrate: PET film. From the viewpoint of sufficiently retaining the particles, the adhesive force is preferably 0.2 mN / 20 mm or more. Furthermore, 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 support layer 29 is preferably, for example, 10 to 200 μm, or 40 to 120 μm.

[0033] Specifically, the material of the particle support layer 29 forming the first attachment 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, for example, includes 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 thereto. 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; and, if the support is in the form of a roll or a flat plate, glass, ceramics, and the like.

[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 adhesion force of 0.5 mN / 20 mm, and the first adhesion 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 openings 23 in the mask layer 3 to form a mask 22. The apparatus shown in Figure 3 includes, for example, a supply means for supplying the mask layer 3, a UV laser 6 as a means for forming the openings 23 in the mask layer 3, and a pressure roller 4 as a means for attaching the mask 22 to the first attachment surface.

[0040] There are no limitations on the material of the mask layer 3, but a material that is uniform in thickness and easy to process 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. In the device shown in Figure 3, a polyester resin film with a thickness of 1.5 μm is used.

[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 may be, 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 created 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 repeated uses. This is suitable for cases where there are few pattern changes or when producing large quantities. 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 producing small quantities. 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 a range of not less than the cumulative 10% particle size (D10) in the volumetric particle size distribution of the first particles and not more than the cumulative 90% particle size (D90) in the volumetric particle size distribution of the first particles. The volumetric median diameter D50 of the particles is the cumulative 50% particle size (median diameter: D50) in the volumetric particle size distribution. The particle size 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 member and a mask offers many noteworthy advantages. As mentioned above, compared to the use of an intaglio plate as in Patent Document 1, when a first attachment surface is used, particle fixation is dominated by the holding force on the attachment surface, resulting in greater pattern flexibility and less likely to result in incomplete filling. Furthermore, while intaglio plates require the creation of a step corresponding to the particle diameter in the pattern, attachment via a first attachment surface eliminates the need for a step, allowing the mask to be thinner than the particle diameter of the first particles. The use of a thin mask is advantageous for achieving higher pattern resolution. Conventional shape processing techniques are susceptible to the accuracy of the aspect ratio based on the processing depth, and therefore, thinner masks tend to achieve higher accuracy. Furthermore, when digging grooves as with intaglio plates, processing precision is required in terms of depth, whereas masks allow for through-holes, allowing for more stable processing.

[0045] There are no limitations on the formation of the openings, and it is desirable to select an appropriate method depending on the material of the mask layer and the resolution of the design pattern. If few pattern changes and high resolution are 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 apparatus 100 in Figure 3 is equipped with a UV laser 6.

[0046] Laser processing equipment is easy to adapt to pattern changes. If the mask is made of resin, CO ２ Lasers are suitable, but green lasers and UV lasers have shorter wavelengths and can reduce the spot diameter to accommodate high-definition patterns. ２ Lasers are not suitable, and green lasers or UV lasers are more suitable. One head can be used to create the openings, or multiple heads can be used to process simultaneously. Multiple lasers with different characteristics can also be used in combination. This type of laser is suitable for productivity when the desired pattern contains a mixture of areas that require high precision and areas that do not.

[0047] The shape of the mask portion is not particularly limited, but can be, for example, a stripe shape or a honeycomb shape. In the case of a stripe shape, 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 be made into a highly smooth surface.

[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 flat, or it can be rolled if flexible materials such as polyimide film or SUS foil are used. The technology for machining glass cylinders with high precision is commonplace and is currently produced and utilized in a wide range of industries, making them easily available. In the case of laser machining, the focal length significantly affects accuracy, so a high-precision glass cylinder is also preferred. The mask layer 3 being transported on the pressure roller can be drilled to form openings 23.

[0051] 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, thereby performing perforation processing. Then, the mask is continuously attached to the intermediate transfer body 1, and the subsequent processes from the particle supplying process to the mask peeling process 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 films is also possible. The advantage of using a roller-shaped substrate for forming openings is that it can utilize the curvature, making it easier to handle the mask transfer. 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, 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 preferable 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 adhering to the mask can be removed when the mask is peeled off. However, if there are excessive particles adhering to the mask or particles filling the mask openings, particles that slide off during the mask peeling step or transfer step may disrupt the particle pattern. The apparatus shown 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 a material layer includes a third step of removing the mask from the first attachment surface. The means for removing the mask is not particularly limited, and any known means may be employed. For example, the mask may be peeled off. The apparatus shown in FIG. 3 uses a mechanism for peeling the mask from the first substrate, 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-like mask, methods such as vacuum suction may be used to pick up the peripheral portion of the mask, or a pickup portion may be provided at the end of the mask and mechanically pulled up. Furthermore, when a mask is made of a resin material, static electricity may be generated during peeling, 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 to inspect 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 in FIG. 3 is equipped with a first inspection unit 11, which can inspect the pattern. After the mask is peeled off, the particles on the intermediate transfer body 1 are held by the first attachment surface, making them less likely to move. Therefore, it is preferable to inspect the pattern here, as subsequent pattern fluctuations are minimal.

[0060] There are no restrictions on the inspection method, and it is desirable to select it 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 in the material layer production apparatus 100 of Figure 3, the defect rate tends to be high at the start of operation until each processing unit stabilizes, so if there is data in advance, it may be possible to set it so that all processing is carried out up to a certain number of times without relying on an inspection device. In the material layer production apparatus 100 of Figure 3, a thin mask layer is used, so 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 a nylon brush or sponge to the intermediate transfer body in a sliding or rotating manner with moderate pressure.Furthermore, particles can be neatly collected by sliding a flexible, thick blade-shaped member made of rubber such as urethane or EPDM, or a squeegee-shaped member made of 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 shown 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 subject them to a process to separate out any debris that may be mixed in between processes. In the device of this embodiment, the recovered particles are reused after being separated from the debris by a separate airflow classifier that utilizes the Coanda effect.

[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. Since the particle-carrying layer of the intermediate transfer body that was protected by the mask is now exposed, the second particles selectively adhere to this area. The second particles may be the same as or different from the first particles.

[0066] As with the arrangement of the first particles, the supply method is not limited and can be selected according to the particles used. In FIG. 3, the material layer production apparatus 100 includes a second particle supply unit 13. 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 arrangement of the first particles. For example, in FIG. 3, the material layer production apparatus 100 includes an air blower 14.

[0067] In the apparatus shown in FIG. 3, a pattern consisting of two types of particles was formed using one mask, but this is not limiting. 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 process 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 determined to be defective by inspection after the supply of the second particles, the recovered particles will be a mixture of the first particles and the second particles, so it is desirable to separate them until they reach the required state using the air classifier or a classifier using centrifugal force as described above. The apparatus 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 the first recovery unit 12. To reuse the particles, the particles separated using a separate air classifier are reused. 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, separation can be more reliably achieved by passing the particles through the classifier repeatedly.

[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 transfer. After transfer, dirt and remaining particles on the intermediate transfer body can be cleaned by a cleaning means such as a cleaning roller 5.

[0072] In the material layer production apparatus 100 of Figure 3, a second substrate 26 in the form of a "double-sided tape" is used in a roll state, with particle fixing layers having second adhesive surfaces 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. That is, the adhesive force of the second adhesive surface is preferably higher than that of the first adhesive surface. The difference in adhesive force varies depending on the characteristics and size of the particles used, the thickness and deformation amount of the particle fixing layer, but for example, the adhesive force 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 force of the second adhesive surface, which is the side that receives the particles, the better. Therefore, although there is no particular upper limit, for example, a value of 300,000 times or less, or 150,000 times or less is preferred.

[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 the adhesive strength 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-based adhesives.

[0076] In the manufactured material layer, the functional material is the first particles and the second particles, so it is basically 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 used as a functional layer consisting only of the particle pattern, a thin (small in volume) second substrate reduces the load in 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 even transfer pressure. This has the advantage of allowing for lower pressure during transfer and making 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 form at the boundary. When a thin second substrate is transferred and pressed against the intermediate transfer body, the step may follow, causing slight wrinkles or stretching in the second substrate. This can result in slight misalignment of the pattern, or a decrease in the dimensional accuracy of the laminate when the completed material layers are stacked.

[0078] In particular, if the second substrate is formed only from 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 a 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 preparation apparatus of Figure 3 can prepare a substantially monolayer particle pattern. On the other hand, this substantially monolayer particle pattern can also be stacked to form a laminate. That is, a laminate may be manufactured by a process of stacking material layers to obtain a laminate. The second substrate on which a particle pattern is formed, prepared using the material layer preparation apparatus of Figure 3, is in the form of double-sided tape. Therefore, sheets can be stacked using the adhesive layer on the opposite side of the layer on which the particle pattern is formed (Figure 4A). That is, a laminate 401 can be formed by stacking multiple second substrates on which a particle layer is formed. Here, by having an adhesive layer on the opposite side of the layer on which the particle pattern is formed, the substrates adhere to each other, increasing the strength of the laminate. As a result, misalignment between the substrates can be suppressed. Furthermore, by sandwiching the particle layer between the substrates between the upper and lower adhesive layers, misalignment during storage, etc., can be suppressed. 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 (FIG. 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 at a temperature equal to or higher than the thermal decomposition temperature of the second substrate is preferred, and heating at a temperature lower than the thermal decomposition temperature of each particle layer in the pattern laminate is preferred. The temperature to which the laminate is heated is preferably 200°C to 1000°C, more preferably 400°C to 800°C, particularly preferably 450°C to 800°C, and even more preferably 450°C to 650°C. The sintering temperature is preferably maintained for 30 minutes or more, more preferably 1 hour or more. The upper limit is not particularly limited, but may be, for example, 3 hours or less, or 2 hours or less. 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 the material begins to decrease when the temperature is gradually increased in the heating atmosphere in the 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, allowing the second substrate to 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 any 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.

[0086] The active material particles are not particularly limited, and known active material particles can be used. For example, a composite oxide containing lithium can be used. Specifically, for example, LiCoO ２ Li-Co oxide active material particles such as (lithium cobalt oxide), LiMO ２ (M is an element selected from the group consisting of Ni, Mn, and Co), ４ Oxide-based active material particles, lithium vanadium compounds (Li ３ V ２ (P.O. ４ ) ３ , LiVOPO ４ ), olivine-type phosphate compounds (LiMPO ４ (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 may also be used. Specifically, for example, metal oxides (MnO ２ , V ２ O ５ etc.) and fluorides (FeF ３ , V.F. ３Among them, Li-Co oxide-based active material particles, Li-PO ４ It is preferable that the negative electrode active material contains oxide-based particles. Alternatively, 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. For example, Li-B oxide-based solid electrolyte particles such as lithium borate, Li-Yb oxide-based solid electrolyte particles, and Nasicon-type solid electrolyte particles (LiAlTi(PO ４ ) ３ , LiAlGe (PO ４ ) ３ etc.), Li-P-O solid electrolyte particles (Li ３ P.O. ４ , LiPON (Li ３ P.O. ４ and the like) in which part of O is substituted with N. Among the above solid electrolyte particles, Li—B oxide-based solid electrolyte particles and Li—Yb oxide-based solid electrolyte particles are preferred.

[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 of 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.

[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: This example shows the fabrication of a positive electrode material layer for an all-solid-state battery using the material layer fabrication apparatus shown in Figure 3. The first particles were a positive electrode material: lithium cobalt oxide (Nippon Chemical Industry Co., Ltd.: volume-based median diameter D50: 5 μm), and the second particles were a solid electrolyte: lithium borate (Toshima Manufacturing Co., Ltd.: volume-based median diameter D50: 5 μm). The intermediate transfer belt used was a 0.1 mm thick Invar support, coated with an 80 μm thick silicone rubber (Dow Toray Industries: SE9186) 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. A polyester film (1.5 μm thick, Mitsubishi Chemical: K-917) was used as the mask layer, and a UV laser processing machine (Hikarikyo: Fine UV Laser Marker) was used to fabricate 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 of 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 the adhesive strength of the first adhesive surface.

[0097] Three of the prepared positive electrode material layers were laminated on an aluminum foil (20 μm thick) with a 90° offset in the lamination angle to obtain a laminate. The resulting 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 cathode material laminate was used to prepare a prototype battery under the following conditions: A 250 μm thick sintered body was obtained by processing and molding a solid electrolyte LAGP (Toshima Manufacturing Co., Ltd.) and sintering it at 850°C. The cathode material laminate and a 50 μm thick indium metal foil were stacked on both sides of the sintered body, and an extraction electrode was connected to each. The battery was then vacuum-packed with an aluminum laminate sheet and finally pressurized at 200 MPa using a CIP device to obtain a prototype battery.

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

[0100] Example 2 During the manufacturing process of Example 1, first particles were forcibly recovered 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 recovered first particles 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 configured to slide 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.) in parallel.

[0101] Example 3 During the manufacturing process of Example 1, a mixture of the first particles and the second particles was forcibly collected from the intermediate transfer body using the second collection unit 16. The collection 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 body support material, and an attempt was made to recover the first particles under the same conditions as in Example 2, but particle recovery was impossible.

[0103] Comparative Example 2: In Comparative Example 1, the first recovery unit 12 was replaced with a polyacetal blade with a higher particle peeling ability, but particle recovery was not possible. Furthermore, when the blade pressure was increased, the tip of the blade became trapped in the particle fixing layer and could not move.

[0104] Example 4: This example shows the fabrication of an anisotropic conductive rubber laminate using the material layer fabrication device shown in Figure 3. The first particles were copper particles (in-house prototype: granulated by disk atomization and then sieved, volume-based median diameter D50: 30 μm), and the second particles were elastic resin particles: cross-linked polyacrylic ester (Sekisui Chemical Co., Ltd.: ARX-30, volume-based 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 Industries: 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. The mask layer was made of SUS430 (30 μm thick), and a UV laser processing machine (Hikarikyo: Fine UV Laser Marker) was used to fabricate the mask openings. 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 production device of FIG. 3, the above-mentioned steps were carried out to produce an anisotropic conductive rubber material layer. The mask openings were formed into a 100 μm stripe pattern with lines and spaces.

[0105] Furthermore, from the mask application step to the mask peeling step, a magnet was placed on the back surface of the intermediate transfer body, and the mask was held in place by magnetic force. An anisotropically conductive rubber material laminate obtained by laminating 20 of the anisotropically conductive rubber material layers in the same lamination direction was able to be manufactured with stable quality as an anisotropically conductive rubber laminate with low resistance in the stripe direction.

[0106] Example 5 During the manufacturing process of Example 4, a mixture of first particles and second particles was forcibly collected from the intermediate transfer body using the second collection unit 16. The collection ratio of the first particles and the second particles was calculated as in Example 2 and was found to be 96.6% by mass. Furthermore, the collected particles were separately treated twice with an air flow classifier utilizing the Coanda effect to separate the particles, resulting in a good separation rate of 85.4% for the first particles and 91.1% for the second particles.

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

[0108] The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible without departing from the spirit and scope of the present disclosure. Therefore, the following claims are appended to clarify the scope of the present disclosure. This application claims priority based on Japanese Patent Application No. 2024-019964, filed February 14, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A method for manufacturing a material layer, comprising: a first particle arrangement step of arranging first particles on a first adhesion surface of a first substrate having a first adhesion surface; a second particle arrangement step of arranging second particles in areas of the first adhesion surface where the first particles are not arranged; and a transfer step of transferring the first particles and the second particles arranged on the first substrate to a second adhesion surface of a second substrate having a second adhesion surface to obtain the material layer.

2. A method for manufacturing a material layer according to claim 1, wherein the first particle arrangement step comprises a first step of forming a mask on the first attachment surface, and a second step of arranging the first particles in areas of the first attachment surface where the mask is not formed, and the second particle arrangement step comprises a third step of removing the mask from the first attachment surface, and a fourth step of arranging second particles in areas of the first attachment surface where the first particles are not arranged.

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 or 3, further comprising a step of removing excess particles after the second step.

5. The method for manufacturing a material layer according to any one of claims 1 to 4, wherein the adhesive strength of the second adhesive surface is higher than the adhesive strength of the first adhesive surface.

6. The method for manufacturing a material layer according to any one of claims 1 to 5, wherein the adhesive strength of the first adhesive surface measured by a peeling analysis device is 0.2 to 10 mN / 20 mm.

7. The method for producing a material layer according to any one of claims 1 to 6, wherein the first base material has a support and a particle-carrying layer laminated on the support to form the first attachment surface, and the particle-carrying layer comprises at least one selected from the group consisting of silicone rubber, urethane rubber, and fluororubber.

8. The method for manufacturing a material layer according to any one of claims 1 to 7, wherein 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.

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

10. A method for manufacturing a material layer described in any one of claims 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-arranged portions of the first particles.

11. A method for producing a material layer according to any one of claims 1 to 10, further comprising a step of laminating a plurality of the obtained material layers to obtain a laminate.

12. A method for manufacturing an electrode for a solid-state battery, the method comprising the steps of: obtaining the material layer by the method for manufacturing a material layer according to claim 8 or 9; stacking the obtained material layers to obtain a laminate; and heating and degreasing the obtained laminate to remove the second base material and obtain an electrode.

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