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

Abstract

To provide a method for manufacturing a material layer that contributes to stabilization of manufacturing quality and improvement of the rate of non-defective products.SOLUTION: A method for manufacturing a material layer includes: a first step of forming a mask portion on a portion of a surface of a first substrate; a second step of arranging first particles on the surface of the first substrate; a third step of removing the mask portion from the first substrate; a fourth step of transferring the first particles to a second substrate; and a fifth step of arranging second particles on at least a portion of an area of the surface of the second substrate where the first particles are not arranged.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a material layer and a method for producing a precursor for a solid-state battery. [Background technology]

[0002] In recent years, various new manufacturing methods using additive manufacturing technology have been developed, but the technology for creating functional structures by designing and arranging multiple material particles is difficult and has not been widely realized. In particular, there are not many technologies for designing and arranging particles as they are. For example, electrophotography is a widely used technique for arranging toner particles. However, the ratio of pigments that can function as functional materials in the toner is low, making it difficult to achieve functionality other than color. Electrostatic screen printing is a technique that can pattern particles without using a binder. However, it is difficult to increase resolution because a gap must be created between the plate and the substrate. Furthermore, both techniques make it difficult to create a thin film close to a single particle layer, and it is not possible to increase resolution in the stacking direction.

[0003] In contrast, Patent Document 1 discloses a method for manufacturing a material layer, which includes a first step of arranging first particles in a pattern on a substrate, and a second step of arranging second particles in areas on the substrate where the first particles are not arranged, and is characterized in that the second step includes a step of rubbing a support material carrying the second particles against the substrate on which the first particles are arranged. [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 technology in the world, there is a strong demand not only for improvements in absolute performance but also for manufacturing efficiency, i.e., stabilization of manufacturing quality and improvement of the yield rate. In this regard, the present inventors have reviewed the prior art and found that there are the following problems. In the method for manufacturing a material layer described in Patent Document 1, a particle pattern is created using an intaglio plate, which is then transferred to the adhesive surface of a substrate. However, when creating a pattern of particles 102 on the intaglio plate 101, if unwanted particles 102-1 also adhere to the convex portions, the particles may be deposited in unintended locations (FIG. 1A). Also, when transferring to the second substrate 11, the particles 102-1 on the convex portions of the intaglio plate come into contact with the adhesive portion of the substrate, suppressing the transfer load on the particles inside the intaglio plate (FIG. 1B). As a result, it was found that there are areas for improvement.

[0006] The present disclosure provides a method for manufacturing a material layer that contributes to stabilizing manufacturing quality and improving the yield rate. The present disclosure also provides a method for manufacturing a precursor for a solid-state battery that contributes to stabilizing manufacturing quality and improving the yield rate. [Means for solving the problem]

[0007] The present disclosure provides a method for manufacturing a layer of material, comprising: a first step of forming a mask portion on a part of a surface of a first base material; a second step of disposing first particles on the surface of the first substrate; a third step of removing the mask portion from the first base material; a fourth step of transferring the first particles to a second substrate; and a fifth step of arranging second particles in at least a portion of the area of the surface of the second substrate where the first particles are not arranged.

[0008] The present disclosure also includes a method of making a layer of material of the present disclosure, The present invention provides a method for producing a precursor for a solid-state battery, wherein the second substrate is a resin substrate. [Effects of the Invention]

[0009] According to the present disclosure, a method for manufacturing a material layer that contributes to stabilizing manufacturing quality and improving the yield rate is provided. Also, the present disclosure provides a method for manufacturing a precursor of a solid-state battery that contributes to stabilizing manufacturing quality and improving the yield rate. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is an explanatory diagram illustrating an embodiment of the present disclosure. [Figure 2] 1A and 1B are conceptual diagrams illustrating a method for manufacturing a material layer according to one embodiment of the present disclosure. [Figure 3] FIG. [Figure 4] FIG. 2 is an explanatory diagram of each step according to one embodiment of the present disclosure. [Figure 5] FIG. 2 is an explanatory diagram of each step according to one embodiment of the present disclosure. [Figure 6] FIG. 1 is an explanatory diagram of a laminate according to one embodiment of the present disclosure. 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] The present disclosure relates to a method for manufacturing a material layer. The method for manufacturing a material layer includes a first step of forming a mask portion on a portion of a surface of a first substrate. The method also includes a second step of arranging first particles on the surface of the first substrate. The method further includes a third step of removing the mask portion from the first substrate. The method also includes a fourth step of transferring the first particles to a second substrate. The method also includes a fifth step of arranging second particles in at least a portion of the surface of the second substrate where the first particles are not arranged.

[0013] As a result of investigations by the present inventors, it has been found that the above-mentioned problems can be solved by the method for manufacturing a material layer including the above-mentioned configuration. That is, according to the above process, even if particles adhere to the mask portion 3-1, the adhered particles 102-1 can be removed together with the removal of the mask portion 3-1 (FIGS. 1C and 1D). This means that the amount of unwanted particles that may adhere to areas that are not intended as image areas can be reduced. After the removal of the mask portion 3-1, the patterned first particles 22 remain only on the first substrate 1. Therefore, during transfer, the particle pattern comes into direct contact with the adhesive layer, applying sufficient transfer pressure (FIG. 4F), allowing for stable pattern formation. This is thought to be due to an improved particle transfer rate when transferring the first particles from the first substrate to the second substrate. Furthermore, if the intaglio pattern has a large convex portion, the contact area with the adhesive portion of the substrate also becomes large, which may make peeling after transfer difficult. However, according to the above process, the mask portion is removed and the particle pattern only comes into direct contact with the adhesive layer, making peeling after transfer easy.

[0014] FIG. 2 is a conceptual diagram illustrating a method for manufacturing a material layer according to one embodiment of the present disclosure. FIG. 4 is an explanatory diagram of each step of the present disclosure. A mask layer 3 is attached to a first substrate 1 (FIGS. 4A and 4B). Then, openings 21 (areas where no mask portions are formed) are formed in the mask layer 3 (FIG. 4C). That is, a mask portion 3-1 is formed on a portion of the surface of the first substrate (first step). Then, first particles 22 are filled into the openings 21 (FIG. 4D). That is, the first particles are arranged on the surface of the first substrate (second step). Then, the mask portion is removed from the first substrate (third step, FIG. 4E). Then, a second substrate 11 is pressed against the first particles 22 (FIG. 4F), and the first particles are transferred to the second substrate, transferring the particle pattern (fourth step, FIG. 4G). In addition, second particles are arranged on at least a portion of the surface of the second substrate 11 where the first particles are not arranged (fifth step, FIG. 4H).

[0015] FIG. 3 shows an example of a material layer manufacturing apparatus for carrying out the material layer manufacturing method according to one embodiment of the present disclosure. The material layer production apparatus is centered around a transport device 2 that transports a first substrate 1 between processes, and includes a mask layer application unit consisting of a mask layer supply section 30, a pressure roller 4, and a wet sponge roller 5, a mask production unit (UV laser 6), a mask peeling unit consisting of a first particle supply unit 7, an air blower 8, a peeling roller 9, and a winding device 10, a particle pattern transfer unit consisting of a second substrate (not shown), a pressure roller 12, and a winding device 15, an air blower 14, and a second particle supply unit 13. The method for producing a material layer according to the present disclosure is carried out by sequentially performing processes in these units. In FIG. 3, the material layer manufacturing apparatus is configured to perform each step in a series, but is not limited to this and may be configured to divide each step appropriately.

[0016] Hereinafter, an embodiment of the present disclosure will be described step by step, taking as an example an aspect in which the material layer manufacturing apparatus of FIG. 3 is used. First, the first substrate is not particularly limited, but is preferably a support having a smooth surface. As for a support having a smooth surface, as long as the surface to which the mask layer is attached is smooth, the other surface configurations can be optimized depending on the device. The material of the first substrate may be the same as or different from that of the mask layer. From the viewpoint of improving patterning accuracy, it is preferable that the first substrate is less likely to deform. In particular, if the first substrate deforms when removing the mask, the pattern of the first particles formed will be disturbed, so a high rigidity is desirable. If the rigidity of the first substrate is insufficient, a reinforcing member can be further provided on the back surface of the first substrate (the surface opposite to the side on which the mask portion is formed). Furthermore, it is preferable that the first substrate has high abrasion resistance to the particulate material used, since this allows for repeated use. When the first substrate is worn, the reusability decreases and the abrasion can be contained as impurities in the material layer.

[0017] The specific material of the first substrate is not particularly limited and may be selected depending on the particles to be used, but examples thereof include resins such as polyimide resin, polyacetal resin, and polyester resin, metals such as aluminum, stainless steel, and Invar alloy, as well as glass and ceramics. Glass is particularly preferred because of its high surface smoothness. The shape of the first substrate is not particularly limited as long as it can be in a shape that allows for line contact and pressure application. For example, it may be in the shape of a flat plate, a roller, or a belt. Of these, a flat plate is preferred. In the material layer manufacturing apparatus of FIG. 3, a flat glass plate is used as the first substrate, which is moved horizontally by a conveying device 2.

[0018] In the first step, a mask portion is formed on a part of the surface of the first base material 1. The means for forming the mask portion is not particularly limited, and may include, for example, a step of providing a mask layer 3 on the first base material, and a step of forming an opening 21 in the mask layer 3 to form the mask portion 3-1. The step of providing the mask layer 3 on the first substrate 1 is not particularly limited. For example, The method may include a step of attaching a mask layer 3. There are no particular limitations on the means for attaching the mask layer 3 onto the first substrate 1, and in the material layer preparation device of Figure 3, the mask layer 3 is attached by applying pressure with a pressure roller 4 having an elastic rubber surface. When a smooth mask layer is attached onto the first base material 1, if the mask layer is attached while removing the air layer, it is possible to attach only the first base material 1 and the mask layer 3 by the principle of vacuum adhesion.

[0019] Furthermore, the first step preferably includes a step of increasing the fixing force between the mask layer 3 and the first substrate 1. Such a step is not particularly limited, and a wide range of known techniques can be applied. Examples include a step of forming a water film, a step of heating and pressurizing, a step of using external forces such as static electricity or magnetic force, and a step of providing an adhesive layer on the mask layer. Specifically, these steps are as follows. The material layer preparation apparatus of Fig. 3 has a wet sponge roller 5 for forming a thin water film on the surface of the first substrate 1 prior to attaching the mask layer 3. By providing a liquid layer such as a thin water film between the mask layer 3 and the first substrate 1, the effect of water film adsorption can be obtained. In other words, it is more preferable that the first step includes a step of forming a water film on the surface of the first substrate.

[0020] When the mask is a resin film, the first step preferably includes a step of applying heat and pressure to the mask layer. By applying heat and pressure, the flexibility of the mask layer can be increased, and the adhesive strength with the first substrate can be improved. When the mask layer is made of a magnetic material, magnetic force can also be used. Furthermore, a plurality of mask layers may be stacked in the step of providing the mask layer 3 on the first base material 1. In this case, one type of material for the mask layer may be used alone, or two or more types may be used in combination.

[0021] The thickness of the mask layer 3 is not particularly limited, but can be, for example, 1 to 100 μm or 2 to 50 μm. It is also desirable that the thickness of the mask layer 3 be approximately uniform. The thickness of the mask layer 3 determines the depth of the openings 21, and the openings 21 determine the thickness of the particle layer. Therefore, it is desirable to select the thickness of the mask layer 3 according to the design of the thickness of the particle layer. For example, by using a mask layer with a thickness equivalent to the desired particle diameter, a particle pattern with an approximately single-layer particle layer can be formed. In other words, the thickness of the mask layer is preferably approximately equal to the volume average particle diameter of the first particles, and for example, the thickness (μm) of the mask layer is preferably 0.7 to 1.3 times the volume average particle diameter (μm) of the first particles. The mask layer is preferably flexible for ease of application and removal, and is also preferably easy to drill in order to make the openings finer and improve the planar resolution. For the reasons mentioned above, the thickness of the mask portion is not particularly limited, but can be, for example, 1 to 100 μm, or 2 to 50 μm. It is also desirable that the thickness of the mask portion is approximately uniform.

[0022] The specific material of the mask layer is not particularly limited, but is desirably selected depending on the particles used and the means for forming the openings used. If the mask layer is to be used repeatedly, metal foil such as aluminum, stainless steel, or invar is preferred, and if the mask layer is to be disposable, a resin film such as polyimide, polyacetal, or polyester is preferred. Polyester resin is particularly suitable because it has good thermal processability and is easy to thin. Furthermore, if the mask layer is to be held in place by magnetic force, a magnetic material is preferred, and a ferromagnetic material is preferred. Therefore, metal foil is preferred. The specific material of the mask portion is also not particularly limited, and the above materials can be used for the same reasons as for the mask layer. The material layer production device shown in Figure 3 uses a roll of polyester resin film. Alternatively, the mask layer can be formed using other methods, such as sheet-cut film or coating with a processing liquid and drying it.

[0023] 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.

[0024] When the first step includes a step of forming the openings 21 in the mask layer 3, the step of forming the openings is not particularly limited, and known techniques can be used. For example, a method can be used in which a mask layer is formed using a photosensitive resin and the openings are formed by photolithography. Alternatively, the step of providing the mask layer 3 on the first substrate and the step of forming the openings 21 in the mask layer 3 can be performed simultaneously. For example, a method can be used in which the mask portion is printed using an ink with high film-forming properties, such as PVA or a vinyl-based material, or a method in which the mask portion is printed by electrophotography or inkjet technology. The material layer production equipment in Figure 3 uses a UV laser 6 as a means of creating openings in the mask. Using a UV laser allows for a high degree of pattern freedom. In addition, by increasing the difference in wavelength absorptivity between the materials of the first substrate and the mask layer, for example by using glass for the first substrate and a resin film for the mask layer, it is possible to remove only the mask layer without damaging the first substrate. When a UV laser is used, the heat generated during processing increases the adhesion of the edges of the mask to the first substrate, reducing unintended peeling of the mask layer.

[0025] 3, the openings are formed after the mask layer is attached to the first base material 1. Alternatively, the mask layer may have openings formed therein in advance, and then the mask layer may be attached to form the mask.

[0026] In the second step, the first particles 22 are disposed on the surface of the first substrate 1. The method for disposing the first particles 22 is not particularly limited and can be selected depending on the particle characteristics of the target particles and the particle density for the pattern. The second step is preferably a step of disposing the first particles 22 in an area of the surface of the first substrate 1 where the mask portion 3-1 is not formed. The area where the mask portion 3-1 is not formed is an image area in the design, and is an area where the first particles 22 are expected to be disposed. Furthermore, the openings 21 can be said to be areas of the surface of the first substrate 1 where the mask portion is not formed. It is also preferable to consider the fixing force of the mask portion to the first substrate. If the shear that can occur when arranging the first particles is excessive, the mask portion may be peeled off. The material layer production device of Figure 3 uses a magnetic particle rubbing means. The magnetic particle rubbing means has the following advantages. Specifically, by controlling the magnetic force of a sliding magnet (not shown) arranged on the back surface of the first substrate (the surface opposite to the side on which the mask layer is provided), the shear during particle arrangement can be easily controlled. According to the present disclosure, excess particles on the mask portion can be removed together with the removal of the mask portion. Therefore, low-shear application methods such as a method using a forward-rotating roller or a vibrating powder flow method can be used effectively as a method for arranging the first particles. Furthermore, the method for arranging the first particles may be used alone or in combination.

[0027] After the first particles are disposed, a step of removing excess first particles may be performed. As described above, in the present disclosure, excess first particles on the mask portion can be removed together with the removal of the mask portion. However, if there are excess particles filled in the openings, the first particles may slide off during the transfer step. This may result in a disruption of the particle pattern or an increase in the amount of unwanted particle adhesion. The material layer production apparatus of FIG. 3 has an air blower 8 as a means for removing excess first particles after the first particles 22 are disposed. Air blowing is preferred for removing excess particles. Other known techniques, such as a soft brush or a weakly adhesive roller, can also be used to remove excess first particles.

[0028] In the third step, the mask portion 3-1 is removed from the first base material 1. The method for removing the mask portion 3-1 from the first base material 1 is not particularly limited, but examples thereof include a method of peeling the mask portion 3-1 from the first base material 1. To remove the mask portion 3-1 from the first substrate 1, the material layer production device shown in Figure 3 uses a peeling roller 9 and a winding device 10 to wind up the mask portion 3-1 in the form of a continuous film. Other methods include, for example, in the case of a sheet, sucking up the periphery of the mask by vacuum suction, or providing handles at the ends of the mask beforehand and mechanically lifting them up. Furthermore, since static electricity may be generated when removing a resin mask, which may disrupt the particle pattern, it is preferable to take measures against static electricity depending on the situation.

[0029] In a fourth step, the first particles are transferred to a second substrate. After removing the mask portion 3-1, the first particles 22 remain alone on the first substrate 1 (FIG. 4E). Therefore, by contacting and pressing the first particles with a second substrate having an adhesive layer on its surface, a second substrate having the first particles on its surface can be obtained. The second substrate is not particularly limited and can be freely selected depending on the purpose. For example, the material of the first substrate described above can be used. In the material layer preparation device of FIG. 3, a roll of the second substrate is used, which is a double-sided tape in which adhesive layers have been formed on both sides of the base substrate. In other words, the second substrate may be either an adhesive tape or a double-sided tape. The method for obtaining the second substrate having an adhesive layer is not particularly limited, and for example, a mechanism for applying an adhesive to the surface of the second substrate may be provided within the device. The material used for the adhesive is not particularly limited, and examples thereof include acrylic adhesives, urethane adhesives, and silicone adhesives.

[0030] Furthermore, if the second substrate is made only of an adhesive phase, 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 made of a material that is resistant to stretching and an adhesive layer. Materials that can be used for the base substrate include resin films such as polyester resin, acrylic resin, polypropylene resin, and polyimide resin, and metal foils such as aluminum and copper. Considering that the second substrate will be removed by heating, a resin film is preferred.

[0031] The pressure roller 12 used to transfer the first particles to the second substrate is preferably elastic. An elastic material allows for stable transfer pressure, resulting in a more stable transfer rate. While the material layer production device shown in Figure 3 uses a single elastic roller, other configurations, such as multiple elastic rollers, belt pressure, or batch processing, can also be used. The particles on the first substrate directly contact the surface of the adhesive layer on the second substrate. Therefore, there is little resistance when separating the first and second substrates after transfer, and the shear applied to the second substrate is also small. As a result, the substrate is less likely to stretch or wrinkle.

[0032] In the fifth step, second particles are disposed on at least a part of the area of the surface of the second base material where the first particles are not disposed. The material layer preparation apparatus of FIG. 3 includes a second particle supply unit 13 for supplying second particles to a second substrate on which first particles are disposed. Therefore, the second particles can be disposed in areas where the first particles are not disposed. The first particles are disposed in a portion of the adhesive layer of the second substrate. Therefore, the second particles selectively adhere to exposed portions of the adhesive layer other than the areas on which the first particles are disposed. The means for disposing the second particles can be any of those listed in the first particle column. When preparing a material layer without second particles, the method for preparing a material layer does not need to include the fifth step. That is, the method for preparing a material layer may include the first, second, third, and fourth steps. The second particles may be the same as the first particles, or may be different.

[0033] While the material layer preparation apparatus in Figure 3 illustrates an example using two types of particles, first particles and second particles, the present disclosure also allows for the production of patterns with three or more types of particles. First, first particles 22 on a first substrate are transferred to a second substrate 11 (Figure 5A). In Figure 5, the second substrate comprises a base substrate 23 and an adhesive layer 24 on the base substrate. Then, third particles 25 are placed on another first substrate using the same method as the first particles (Figures 5B and 5C). This is then transferred to the second substrate 11, after which second particles 26 are applied. This results in the second particles 26 selectively adhering to the exposed areas other than the areas where the first particles 22 and third particles 25 are located (Figure 5D). Therefore, by using a mask designed with offset opening patterns, a pattern consisting of more types of particles can be obtained. In other words, it is preferable to perform the first process two or more times, with the shapes of the mask portions formed in each process being different. Here, the third particles can be the same as the first particles described below.

[0034] The material layer preparation apparatus of FIG. 3 can prepare a single-layer particle pattern. Alternatively, this single-layer particle pattern can 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 by the material layer preparation apparatus of FIG. 3, is in the form of a 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 (FIG. 6A). That is, a laminate 601 can be formed by stacking 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 substrates adhere to each other, increasing the strength of the laminate. As a result, slippage 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.

[0035] Furthermore, by utilizing the difference in properties between the particles used and the second substrate, the second substrate can be removed to obtain a patterned laminate (three-dimensional object 602) consisting only of particles (Figure 6B). That is, a three-dimensional object can 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 made from the material layer at high temperature. 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.

[0036] The conditions for high-temperature degreasing are not particularly limited, but it is preferable to heat at a temperature equal to or higher than the thermal decomposition temperature of the second base material, and preferably at a temperature 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. It is preferable to maintain the sintering temperature for 30 minutes or longer, more preferably 1 hour or longer. The upper limit is not particularly limited, but it may be, for example, 3 hours or shorter, or 2 hours or shorter. For example, it is preferable to maintain the sintering temperature for 30 minutes to 3 hours, or 1 hour to 2 hours. The thermal decomposition temperature is the temperature at which a material begins to lose weight 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, its weight can be reduced, and the second substrate can be removed from the laminate.

[0037] The present invention can be applied to a wide range of functional materials, but is particularly suitable for battery modules. Battery materials are designed to functionally arrange the materials in the electrode layer and efficiently arrange the paths of ions and electrons. This is expected to lead to improved performance, and all-solid-state batteries in particular do not use electrolyte, so the functional arrangement of positive and negative electrode materials and solid electrolyte materials is highly effective.

[0038] 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. 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.

[0039] 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.

[0040] The solid electrolyte is not particularly limited, and known solid electrolytes can be used. Examples include Li-B oxide-based solid electrolyte particles, 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.

[0041] The second particles are not particularly limited, and can be any desired resin particles, inorganic particles, etc., similar to the first particles. 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 particles preferably include 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.

[0042] 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 surface-treated or coated.

[0043] 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 method for manufacturing a precursor for a solid-state battery includes a first step of forming a mask portion on a portion of the surface of a first substrate, a second step of arranging first particles on the surface of the first substrate, a third step of removing the mask portion from the first substrate, a fourth step of transferring the first particles to a second substrate, and a fifth step of arranging second particles on at least a portion of the surface of the second substrate where the first particles are not arranged. Here, the obtained material layer corresponds to a precursor for a solid-state battery. By using the method for manufacturing a material layer according to the present disclosure as a method for manufacturing a precursor for a solid-state battery, the amount of unnecessary particle adhesion is reduced, the particle transfer rate when transferring the first particles to the second substrate is improved, and the fluctuation range of the electrical resistance value described below is narrowed. A solid-state battery without second particles can be manufactured using the method for manufacturing a material layer according to the present disclosure. In the case of producing a precursor, the method for producing a precursor of a solid state battery does not need to include step 5. That is, the method for producing a precursor of a solid state battery may be a method for producing a precursor of a solid state battery that includes the above-mentioned steps 1, 2, 3, and 4.

[0044] 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.

[0045] Furthermore, a vibration absorber can be obtained by using at least one of strong elastic particles and weak elastic particles as the first particles and the other of strong elastic particles and weak elastic particles as the second particles. The obtained vibration absorber has specificity with respect to the vibration direction.

[0046] 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 material layers for a solid-state battery are stacked. 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 may include the steps of obtaining a material layer by the above-described manufacturing method, stacking the obtained material layers to obtain a laminate, and thermally degreasing the obtained laminate to remove the second substrate to obtain an electrode. When the solid-state battery is a single layer, a method for manufacturing an electrode for a solid-state battery may include the steps of obtaining a material layer by the above-described manufacturing method, and thermally degreasing the material layer to remove the second substrate to obtain an electrode.

[0047] That is, an electrode for a solid-state battery can be obtained by removing the second substrate from the laminate. 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]

[0048] 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.

[0049] [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 used as the cathode material: lithium cobalt oxide (manufactured by Nippon Chemical Industry Co., Ltd.; average particle size 5 μm). The second particles were used as the solid electrolyte: lithium borate (manufactured by Toshima Manufacturing Co., Ltd.; particle size target 5 μm). The first substrate was borosilicate glass (manufactured by Hoya Corporation; 5 mm thick). The mask layer was made of polyester film (manufactured by Toray Industries, Inc.; Lumirror 5 μm thick). A UV laser processing machine (manufactured by Kokyo Co., Ltd.; fine UV laser marker). The second substrate was made of double-sided tape (manufactured by Nitto Denko Corporation; No. 5600). The particle supply unit was made of magnetic particles (Japan Imaging Society; P02). The material layer fabrication apparatus shown in Figure 3 was used to perform the above-described steps 1 to 5 to fabricate a cathode material layer for an all-solid-state battery. The mask aperture pattern was a 10 μm line-and-space stripe pattern, i.e., the aperture was 10 μm wide and the mask portion was a 10 μm wide stripe pattern with a 20 μm pitch.

[0050] The prepared positive electrode material layers were stacked on an aluminum foil (20 μm thick) in five layers, with the stacking angle shifted by 90 degrees. Then, the layers were heated at 500°C for 1 hour in an electric furnace (MMF-1 manufactured by AS ONE Corporation). The laminate was heated and degreased, and the second substrate was removed to prepare a positive electrode material layer laminate (thickness: approximately 25 μm) for an all-solid-state battery.

[0051] The material layer and the laminate were evaluated by measuring the following three items. <Unwanted particle adhesion amount> The area ratio of the first particles adhering to the non-image areas (areas where the masked areas were removed) was optically observed immediately before the transfer of the particle pattern (after the third process). Then, the area ratio of the first particles in the non-image areas was calculated using image processing software (Adobe Systems: Photoshop (registered trademark)). A total of 10 similar material layers were fabricated, and the arithmetic mean value of the area ratios of the first particles obtained was taken as the amount of unwanted particle adhesion. The amount of unwanted particle adhesion was 0 area %.

[0052] <Particle transfer rate> The mass of the first particles attached to the second substrate after transfer and the mass of the first particles held on the first substrate immediately before transfer were each measured using an electronic balance manufactured by AS ONE Corporation. Both values were rounded to the nearest fourth decimal place. The values were then calculated using the following formula: Mass (g) of the first particle attached to the second substrate after transfer / Mass (g) of the first particle held on the first substrate immediately before transfer × 100 A total of 10 similar material layers were fabricated, and the arithmetic mean value of the values obtained by the above formula was taken as the particle transfer rate, which was 99.2%.

[0053] <Variation Range of Electrical Resistance in the Thickness Direction of the Positive Electrode Material Layer Laminate> The fluctuation range of the electrical resistance value in the thickness direction of the obtained positive electrode material layer laminate was measured. A Solartron 1255WB model was used as the electrochemical device. A total of 10 similar laminates were produced, and the electrical resistance value of each was measured using the electrochemical device, and the arithmetic mean value of the obtained electrical resistance values was calculated. Then, among the electrical resistance values of the total 10 laminates, the electrical resistance value A that was the most different from the obtained arithmetic mean value and the arithmetic mean value were used to calculate the fluctuation range of the electrical resistance value according to the following formula. |Electrical resistance value A (Ω) - arithmetic mean value of electrical resistance (Ω)| / arithmetic mean value of electrical resistance (Ω) x 100 The fluctuation range of the electrical resistance value was 1.75%.

[0054] According to the above evaluation, no transfer defects were observed in the produced material layers, and the quality of the produced laminates was stable.

[0055] [Comparative Example 1] An all-solid-state battery positive electrode material layer was produced under the same conditions as in Example 1, except that no first substrate or mask layer was used, and instead a glass intaglio plate was used that was prepared by patterning borosilicate glass (HOYA: 5 mm thick) with photoresist and then dry etching to the same pattern (plate depth 5 μm) as in Example 1. A positive electrode material layer laminate for an all-solid-state battery was also produced under the same conditions as in Example 1. Evaluations were then performed in the same manner as in Example 1. The evaluation results are shown in Table 1. [Table 1]

[0056] [Example 2] An example of producing a vibration-absorbing rubber material layer using the material layer production device of Figure 3 will be described. The first particles were strong-elastic particles: cross-linked polyacrylate ester (Sekisui Chemical Co., Ltd.: ARX-30), the second particles were weak-elastic particles: cross-linked acrylic monodisperse particles (Soken Chemical & Engineering Co., Ltd.: MX-3000), the first substrate was borosilicate glass (HOYA: 5 mm thick), and the mask layer was SUS430 (30 μm thick). A CO2 laser processing machine (Kokyosha) was used to create the mask openings, double-sided tape (Nitto Denko: No. 5600) was used for the second substrate, and a forward-rotating roller unit equipped with a urethane rubber roller (rubber hardness 70°) was used as the particle supply unit. Steps 1 to 5 were then performed using the material layer preparation device shown in Figure 3 to prepare the vibration-absorbing rubber material layer. The opening pattern of the mask was a 100 μm stripe pattern with lines and spaces, that is, the openings were 100 μm wide and the mask portion was a stripe pattern with a 100 μm wide pattern and a 200 μm pitch. In addition, during the first to third steps, a magnet was placed on the back surface of the intermediate transfer body to hold the mask layer and mask portion in place with magnetic force.

[0057] The material layer was evaluated by evaluating the amount of unwanted particle adhesion and the particle transfer rate. The results are shown in Table 2. No transfer defects were observed in the produced material layer, and stable quality was obtained. Furthermore, a vibration-absorbing rubber material laminate was obtained by repeatedly stacking 150 layers of the vibration-absorbing rubber material in the order of 0°, 0°, and 90°. This laminate was able to be manufactured with stable quality as a vibration absorber with specificity in the vibration direction. Here, specificity in the vibration direction means that the amount of deformation when the laminate is subjected to vibration is not isotropic. Specifically, the amount of deformation in the longitudinal direction of the stripe pattern relative to the vibration direction was small, while the amount of deformation in the transverse direction relative to the vibration direction was large.

[0058] Comparative Example 2 A vibration-absorbing rubber material layer was produced under the same conditions as in Example 2, except that a first substrate and a mask layer were not used, and a PDMS intaglio plate (produced in-house) was used, which was produced by casting a master mold processed on a precision lathe into the same pattern (plate depth 30 μm) as in Example 2. Evaluations were also carried out in the same manner as in Example 2. The evaluation results are shown in Table 2. [Table 2]

[0059] The present disclosure includes the following methods. [Method 1] 1. A method for manufacturing a material layer, comprising: a first step of forming a mask portion on a part of a surface of a first base material; a second step of disposing first particles on the surface of the first substrate; a third step of removing the mask portion from the first base material; a fourth step of transferring the first particles to a second substrate; and a fifth step of arranging second particles in at least a portion of the area of the surface of the second base material where the first particles are not arranged. [Method 2] The method for manufacturing a material layer according to Method 1, wherein the first step includes a step of providing a mask layer on the first substrate and a step of forming an opening in the mask layer to form the mask portion. [Method 3] The method for manufacturing a material layer according to Method 1 or 2, wherein the second step is a step of arranging first particles in an area of the surface of the first substrate where the mask portion is not formed. [Method 4] the first particles include at least one of active material particles and solid electrolyte particles, 4. The method for producing a material layer according to any one of Methods 1 to 3, wherein the second particles include at least one of active material particles and solid electrolyte particles. [Method 5] a method for producing a layer of material according to method 4, The method for producing a precursor of a solid state battery, wherein the second substrate is a resin substrate.

Claims

1. 1. A method for manufacturing a material layer, comprising: a first step of forming a mask portion on a part of a surface of a first substrate; a second step of disposing first particles on the surface of the first substrate; a third step of removing the mask portion from the first base material; a fourth step of transferring the first particles to a second substrate; and a fifth step of arranging second particles in at least a portion of the area of the surface of the second base material where the first particles are not arranged.

2. The method for manufacturing a material layer according to claim 1 , wherein the first step includes the steps of providing a mask layer on the first substrate and forming an opening in the mask layer to form the mask portion.

3. The method for manufacturing a material layer according to claim 1 or 2, wherein the second step is a step of arranging first particles in an area of the surface of the first base material where the mask portion is not formed.

4. the first particles include at least one of active material particles and solid electrolyte particles, 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.

5. A method for producing a layer of material according to claim 4, The method for manufacturing a precursor of a solid state battery, wherein the second substrate is a resin substrate.

Images