Method for manufacturing a material layer, method for manufacturing a three-dimensional object, material layer, laminate, material layer forming apparatus, and additive manufacturing system

Abstract

The present invention provides a method for manufacturing a material layer in which a desired material is arranged in any pattern and the desired material is contained at a high density. [Solution] A method for manufacturing a material layer, comprising: a first step S101 of arranging first particles P1 in a pattern on a substrate 11; and a second step S102 of arranging second particles in areas on the substrate 11 where the first particles P1 are not arranged, wherein the second step S102 comprises rubbing a support material S2 on which the second particles P2 are supported against the substrate 11 on which the first particles P1 are arranged.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a material layer, a method for manufacturing a three-dimensional object, a material layer, a laminate, a material layer forming apparatus, and an additive manufacturing system. [Background technology]

[0002] Additive manufacturing, a method of creating three-dimensional objects of a desired shape by stacking material layers made of various materials such as metals, ceramics, and resins, is attracting attention. In recent years, the application fields of additive manufacturing have been expanding, and it is now being used not only to create mockups and parts made of a single type of material, but also to create various devices such as batteries, electronic components, and wiring boards made of multiple types of materials.

[0003] Patent Document 1 describes a method for manufacturing an all-solid-state battery using a positive electrode ink containing a positive electrode active material, an electrolyte ink containing a polymer electrolyte, and a negative electrode ink containing a negative electrode active material. In the method described in Patent Document 1, each ink is applied by an inkjet method to form layers in which the desired materials are arranged in a pattern. After drying the resulting layers to form material layers, another material layer is formed on top of the material layer in the same manner. By repeating this process, an all-solid-state battery having a structure in which the positive electrode active material, polymer electrolyte, and negative electrode active material are arranged in an arbitrary three-dimensional pattern is formed. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2005-116248 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In Patent Document 1, by using two types of inks when forming one material layer, a material layer in which two types of materials are arranged in an arbitrary pattern can be formed. However, when applying inks of materials that are components of a battery for a positive electrode, a negative electrode, and an electrolyte by an inkjet method, it is necessary to include unintended materials such as a binder resin, a solvent, and a dispersant in the ink. As a result, there is a problem that the density of the materials that are each component in the formed material layer becomes low.

[0006] Therefore, in the present invention, in view of the above problems, an object is to provide a method for manufacturing a material layer in which a desired material is arranged in an arbitrary pattern and the material layer containing the desired material at a high density can be formed.

Means for Solving the Problems

[0007] A method for manufacturing a material layer according to one aspect of the present invention is a method for manufacturing a material layer having a first step of arranging first particles in a pattern on a substrate and a second step of arranging second particles in a region on the substrate where the first particles are not arranged, wherein the second step includes a step of rubbing a carrier carrying the second particles against the substrate on which the first particles are arranged. A material layer according to one aspect of the present invention includes a first region including a first inorganic material and having a plurality of first particles before sintering arranged therein, and a second region including a second inorganic material and having a plurality of second particles before sintering arranged therein, and includes a pattern layer configured to include the above, and a substrate provided with the pattern layer. In addition, a laminate according to one aspect of the present invention includes a pattern layer including a first region including a first inorganic material and having a plurality of first particles before sintering arranged therein, and a second region including a second inorganic material and having a plurality of second particles before sintering arranged therein, and is characterized in that a plurality of the pattern layers are laminated.

Effects of the Invention

[0008] According to the present invention, it is possible to provide a method for manufacturing a material layer in which a desired material is arranged in an arbitrary pattern and a material layer containing the desired material at a high density can be formed.

Brief Description of Drawings

[0009] [Figure 1] It is a flowchart of a method for manufacturing a material layer. [Figure 2] It is a diagram schematically showing the configuration of a material layer forming apparatus according to the first embodiment. [Figure 3] It is a diagram schematically showing the configuration of a filling apparatus. [Figure 4] It is a diagram schematically showing a filler being conveyed on a first base material. [Figure 5] It is an enlarged view of the vicinity of the surface of the first base material in the filling process by the first filling apparatus. [Figure 6] It is a diagram schematically showing the configuration of a filling apparatus when brush fibers are used as a carrier material and a diagram schematically showing the configuration of a filling apparatus when an elastic material is used as a carrier material. [Figure 7] It is a diagram schematically showing the configuration of a transfer section. [Figure 8] It is an enlarged view of the vicinity of the surface of the second base material in the filling process by the second filling apparatus. [Figure 9] It is a diagram schematically showing the second base material after the first particles are transferred by the transfer section and the second base material after the second particles are transferred by the transfer section. [Figure 10] It is a diagram schematically showing the configuration of a material layer forming apparatus according to the second embodiment. [Figure 11] It is a diagram schematically showing the overall configuration of a laminated manufacturing system according to the third embodiment. [Figure 12] It is a diagram schematically showing the configuration of a lamination unit. [Figure 13] It is a diagram schematically showing the configuration of a removal unit. [Figure 14] It is a diagram schematically showing the structure of a first base material having an uneven pattern formed on its surface. [Figure 15]This figure shows the results of thermogravimetric analysis of a polyester sheet. [Figure 16] The plan view (a) and cross-sectional view (b) show an embodiment comprising a material layer in which a second particle having a smaller average particle size than the first particle is transferred after the first particle has been transferred. [Modes for carrying out the invention]

[0010] The following describes in detail, with reference to the drawings, embodiments for carrying out this invention. However, unless otherwise specifically stated, the dimensions, materials, shapes, relative positions, etc., of each component described in the following embodiments are not intended to limit the scope of this invention to those components alone.

[0011] <First Embodiment> A first embodiment of the present invention, a method for manufacturing a material layer and a material layer forming apparatus, will be described with reference to the drawings.

[0012] Figure 1 is a flowchart of the manufacturing method for the material layer according to the first embodiment.

[0013] The method for manufacturing the material layer according to this embodiment comprises the following steps (1) to (2). Details of each step will be described later. Step (1): A first step (S101) in which first particles are arranged in a pattern on a substrate. Step (2): A second step (S102) in which second particles are placed in areas on the substrate where first particles are not present. Furthermore, the second step S102 includes a step of rubbing the support material on which the second particles are supported against the substrate on which the first particles are arranged.

[0014] In the method for manufacturing a material layer according to this embodiment, after placing first particles on a substrate, a support material bearing second particles is rubbed against the substrate, thereby densely distributing the second particles in areas of the substrate where the first particles are not present. As the second particles are rubbed against the substrate together with the support material, they are constrained by the adhesive force of the substrate surface and the adhesive force of the first and second particles already present on the substrate surface, resulting in a densely distributed material layer. This allows for the arrangement of multiple particles in any desired pattern and the formation of a highly dense material layer.

[0015] Furthermore, "rubbing the support material against the substrate" includes cases where the support material does not directly come into contact with the substrate itself. In other words, the above expression includes cases where a support material bearing the second particles is rubbed against the substrate, and only the second particles come into direct contact with the substrate itself.

[0016] The method for arranging the first particles in a pattern on the substrate in the first step S101 is not particularly limited. For example, a transfer substrate having an uneven pattern formed on its surface may be prepared, a support material bearing the first particles may be rubbed against the transfer substrate to densely arrange the first particles in the recesses of the uneven pattern, and this may be transferred to another substrate to arrange the first particles in a pattern on the substrate. Alternatively, the first particles may be arranged in a pattern on the substrate by applying a liquid in a pattern on the substrate and then attaching a powder containing the first particles to the liquid. The following describes the case in which the first particles are densely arranged in the recesses of the surface of the transfer substrate by rubbing a support material bearing the first particles against the transfer substrate, and then transferred to the substrate.

[0017] Figure 2 is a schematic diagram showing the configuration of the material layer forming apparatus according to this embodiment.

[0018] The material layer forming apparatus 1 according to this embodiment includes a first storage container 21a for storing and supplying a first substrate 11a, a first belt device 22a for transporting the first substrate 11a, and a pattern forming apparatus 23 for forming an uneven pattern on the first substrate 11a. The material layer forming apparatus 1 also includes a first filling device 24a for placing first particles P1 in the recesses of the uneven pattern formed on the first substrate 11a. The material layer forming apparatus 1 also includes a second storage container 21b for storing and supplying a second substrate 11b, and a second belt device 22b for transporting the second substrate 11b. The material layer forming apparatus 1 has a transfer section 25a where the rollers of the first belt device 22a and the second belt device 22b face each other, and the first particles P1 are transferred from the first substrate 11a to the second substrate 11b in the transfer section 25a. Furthermore, the material layer forming apparatus 1 has a second filling apparatus 24b for placing second particles P2 in the non-transfer portion on the second substrate 11b. Note that apparatuses less relevant to explaining the effects of this invention, such as the peeling and recovery apparatus for peeling and recovering the first substrate 11a after transfer from the first belt apparatus 22a, and various cleaning apparatuses, are not shown in the illustrations or detailed descriptions.

[0019] In the material layer forming apparatus 1, the pattern forming apparatus 23, the first filling apparatus 24a, and the transfer section 25a correspond to the first placement means for arranging the first particles P1 in a pattern on the second substrate 11b. The second filling apparatus 24b corresponds to the second placement means for arranging the second particles P2 in areas on the second substrate 11b where the first particles P1 are not present.

[0020] The following describes the method for forming a material layer 12 on a substrate 11 using the material layer forming apparatus 1, following the process flow step by step.

[0021] First, the first base material 11a is supplied from the first containment container 21a to the first belt device 22a by a supply means (not shown).

[0022] The material of the first substrate 11a is not particularly limited, but when an ultraviolet-curable ink is applied by the pattern forming apparatus 23 (described later), it is preferable that at least its surface is made of a material with high wettability to the ultraviolet-curable ink. Furthermore, it is preferable that the surface of the first substrate 11a be smooth. Typically, as the first substrate 11a, a resin sheet such as polyester that has been treated with a hydrophilic or oleophilic treatment according to the ultraviolet-curable ink (water-based or oil-based) used can be used. The first substrate 11a may be a substrate that is cut individually like cut paper, a continuous substrate wound in a roll like roll paper, or a continuous substrate that is folded alternately like continuous paper.

[0023] The first belt device 22a transports the supplied first substrate 11a to the pattern forming position of the pattern forming device 23. The first belt device 22a includes drive rollers 221a, 222a, pressure roller 223a, and a belt-shaped transport member 224a suspended from them. At this time, the pressure roller 223a is driven to rotate.

[0024] The conveying member 224a is preferably made of resin or metal, for example, a polyimide resin belt can be used. The drive rollers 221a and 222a are preferably made of metal, for example, stainless steel rollers can be used. The pressure roller 223a is preferably made of soft roller having an elastic layer on its surface, for example, a soft roller with an elastic layer of silicone rubber on the surface of a stainless steel core can be used.

[0025] In this embodiment, a first belt device 22a is used as a conveying device for transporting the first substrate 11a, but a roller device can also be used instead of a belt device. The same applies to the second belt device 21b, which will be described later.

[0026] The pattern forming apparatus 23 forms a fine uneven pattern on the first substrate 11a that has been transported to the pattern forming position. The method for forming the uneven pattern is not particularly limited, but UV imprinting, thermal imprinting, UV inkjet, printing, laser etching, etc., can be used. When the pattern forming apparatus 23 forms the uneven pattern by UV imprinting, the pattern forming apparatus 23 has a coating means for applying an ultraviolet-curable composition onto the first substrate 11a. The pattern forming apparatus 23 also has an imprinting means for imprinting a mold with an uneven pattern formed on its surface onto the ultraviolet-curable composition on the first substrate 11a, and a light source for irradiating the ultraviolet-curable composition with ultraviolet light. Typically, an ultraviolet-curable liquid silicone rubber (PDMS) or resin can be used as the ultraviolet-curable composition, a film mold can be used as the mold, and a UV lamp can be used as the light source.

[0027] When the first filling device 24a fills the recesses with the first particles P1 using a support material S1 carrying the first particles P1, it is preferable that the opening diameter of the recesses in the uneven pattern on the first substrate 11a is greater than the median diameter of the first particles P1 and smaller than the average size of the support material S1. Here, it is preferable that the opening diameter of the recesses in the uneven pattern is the opening diameter in the short direction of the recess, and more preferably the maximum opening diameter in the short direction of the recess. As a result, the first particles P1 can come into contact with the bottom (typically the bottom surface) of the recesses in the uneven pattern, while the support material S1 cannot come into contact with the bottom of the recesses. As a result, the first particles P1 that come into contact with the bottom of the recesses can be captured by the uneven pattern, while the support material S1 can not be captured by the uneven pattern. In other words, it is preferable that the first particles P1 can come into contact with the bottom of the recesses in the uneven pattern, and the first support material S1 cannot come into contact with the bottom of the recesses in the uneven pattern.

[0028] In this embodiment, the pattern forming device 23 forms a raised and recessed pattern on the first substrate 11a, but the invention is not limited to this, and a substrate with a raised and recessed pattern already formed on its surface may be used as the first substrate 11a. Alternatively, the pattern forming device 23 may directly form a raised and recessed pattern on the surface of the conveying member 224a of the first belt device 22a, or a conveying member having a raised and recessed pattern on its surface may be used as the conveying member 224a. In this case, considering durability, it is preferable to use a metal belt such as stainless steel or aluminum and to form a raised and recessed pattern on its surface using microfabrication techniques such as laser etching, wet etching, or dry etching.

[0029] The first substrate 11a, which has an uneven surface pattern formed on it, is transported by the first belt device 22a to the filling position of the first filling device 24a.

[0030] Figure 3 is a schematic diagram showing the configuration of the filling apparatus according to this embodiment. The configuration of the first filling apparatus 24a will be described below, but the same applies to the second filling apparatus 24b.

[0031] The first filling device 24a includes a filling container 242a for containing the filler 241a, a stirring screw member 243a for stirring and conveying the filler 241a, a recovery member 244a for recovering the filler, and a magnetic member 247a.

[0032] The filler 241a comprises first particles P1 and a support material S1 that supports the first particles P1. The filler 241a is a mixture of multiple powders, including a powder composed of multiple first particles P1 and a powder composed of multiple support materials S1. When the filler 241a contained in the filling container 242a is stirred and conveyed by the stirring screw member 243a, it is thoroughly mixed and becomes triboelectrically charged. As a result, the first particles P1 are supported on the surface of the support material S1.

[0033] The first particle P1 is a particle that fills the recesses of the uneven pattern formed on the first substrate 11a, and its material is not particularly limited. The first particle P1 may be a particulate inorganic material such as metal particles, ceramic particles, or glass particles, or a particulate organic material such as resin particles.

[0034] The support material S1 is magnetic particles. Preferably, the support material S1 is a particle in which the surface of ferrite core particles or resin particles in which magnetic material is dispersed is coated with a resin composition. The particle size and material of the support material S1 are appropriately selected according to the particle size and material of the first particle P1. This allows the first particle P1 to be stably supported.

[0035] Furthermore, in order to improve electrostatic properties and cohesiveness, particles other than the first particles P1 and the support material S1 may be added to the filler 241a, or the surface of the first particles P1 may be coated with a resin composition. In addition, to improve the conductivity of the particles P1, the embodiment includes variations such as a form containing carbon black such as acetylene black, metal or alloy powder as a conductive additive, or a form in which the surface of the first particles P1 is coated with a conductive additive.

[0036] The recovery member 244a includes a roller 245a that can rotate in the direction of arrow d2 in the figure, and a magnet 246a that is positioned inside the roller 245a and fixed to the filling container 242a. The magnetic member 247a is positioned opposite the filling container 242a via the transport member 224a and has a magnet 248a inside. The magnet 246a has multiple N poles and S poles that are alternately arranged along the rotation direction of the recovery member 244a. The magnet 248a has multiple N poles and S poles that are alternately arranged along the transport direction of the transport member 224a. Furthermore, the magnet 246a has a pole of opposite polarity (N1 pole in this embodiment) at the position closest to and opposite to the downstream magnetic pole (S1 pole in this embodiment) of the magnet 248a, and an N2 pole of the same polarity as the N1 pole is positioned at the downstream position. Magnets 246a and 248a may be composed of multiple magnets, and the types of magnets constituting magnets 246a and 248a are not particularly limited. For example, rare earth magnets such as ferrite magnets, neodymium magnets, and samarium-cobalt magnets, permanent magnets such as plastic magnets, or means of generating a magnetic field such as electromagnets can be used. Magnet 248a may be configured to move in the transport direction of the first substrate 11a or in the opposite direction.

[0037] Furthermore, a restricting member for restricting the filler 241a on the first substrate 11a, or a recovery member for recovering any filler 241a that cannot be recovered by the recovery member 244a, may be provided upstream or downstream of the recovery member 224a in the conveying direction. As the recovery member for recovery, in addition to a member similar to the recovery member 244a, simpler members such as fixed magnets or restricting members, or recovery members that recover by air blowing, may be used.

[0038] Next, the process of filling the recesses on the first substrate 11a with the first particles P1 using the first filling device 24a will be explained with reference to Figures 3 to 5.

[0039] As the first transport member 224a moves in the direction of the solid arrow d1 in Figure 3, the first base material 11a, which is being carried by the first transport member 224a, is transported to the filling position of the first filling device 24a.

[0040] The stirring screw member 243a transports the filler 241a and supplies it onto the first substrate 11a (dotted line a in Figure 3). At this time, a magnetic field is formed by the magnetic member 248a and the recovery member 244a, and the filler 241a, which contains the magnetic particle support S1, forms multiple magnetic spikes on the first substrate 11a due to this magnetic field. The filler 241a supplied onto the first substrate 11a is transported on the first substrate 11a in the state in which it has formed magnetic spikes as the first substrate 11a moves (dotted line b in Figure 3).

[0041] Figure 4 is a schematic diagram of the filler 241a being transported on the first substrate 11a. For explanatory purposes, filler 241a other than the filler forming a single magnetic spike is omitted from the illustration. As described above, the filler 241a on the first substrate 11a forms magnetic spikes along the magnetic field lines of the formed magnetic field, and is transported while changing the shape of the magnetic spikes as shown in Figures 4(a), 4(b), and 4(c) as the first substrate 11a moves. At this time, a particularly strong magnetic force acts near the magnet 248a, so the transport speed v2 of the filler 241a is smaller than the moving speed v1 of the first substrate 11a when the filler 241a moves away from the magnetic pole, and larger in the opposite case. That is, the filler 241a on the first substrate 11a has a non-zero relative speed to the first substrate 11a.

[0042] Figure 5 is an enlarged view of the vicinity of the surface of the first substrate 11a in Figure 4. Although not shown in Figure 4, a textured pattern 111a is formed on the first substrate 11a as shown in Figure 5. The filler 241a comes into contact with this textured pattern 111a and is transported together with the first substrate 11a while having a non-zero relative velocity to the first substrate 11a, while receiving a magnetic force (solid line Fm in the figure) in a direction perpendicular to the surface of the first substrate 11a. As a result, the first particles P1 supported on the support material S1 are transported while being rubbed against the textured pattern 111a on the surface of the first substrate 11a. In this case, the particle size of the first particle P1 is smaller than the opening diameter of the recess in the uneven pattern 111a, and the particle size of the first support material S1 is larger than the opening diameter of the recess. Therefore, the first particle P1 can come into contact with the bottom surface (bottom) of the recess in the uneven pattern 111a, but the support material S1 cannot. In other words, only the first particle P1 selectively comes into contact with the bottom surface of the recess in the filler 241a. The first particle P1 that comes into contact with the bottom surface of the recess is strongly restrained by the physical restraining force due to the structure of the uneven pattern 111a, as well as by the electrostatic adhesion and adhesive force with the first substrate 11a and the structural material constituting the uneven pattern 111a, and detaches from the support material S1.

[0043] Downstream of the magnetic member 247a, as shown in Figure 3, a recovery member 244a is positioned with a gap between it and the first transport member 224a. As the first substrate 11a moves, the filler 241a, which has been transported to the vicinity of the downstream magnetic pole (S1 pole) of the magnet 248a, is affected by the magnetic field formed by the magnet 246a and moves from the first substrate 241a to the recovery member 244a, where it is recovered (dotted line c in Figure 3).

[0044] As described above, during the transport process (dotted lines a, b, c in Figure 3), the recesses of the uneven surface pattern 111a on the first substrate 11a come into sufficient contact with the multiple fillers 241a. Therefore, after the fillers 241a are recovered by the recovery member 244a, the first particles P1 are selectively and densely arranged in the recesses of the uneven surface pattern 111a.

[0045] In Figures 4 and 5, the first particles P1 are all shown with the same particle size, but in reality, there is a particle size distribution, and in some materials, aggregated secondary particles may be formed. Even in such cases, only the particles that can contact the bottom surface of the recesses of the uneven pattern 111a are selectively and densely packed, so coarse powders and secondary particles that could adversely affect material layer formation are excluded.

[0046] Thus, the amount of first particles P1 filling the recesses of the uneven pattern 111a can be controlled by the size (area, width, depth) of the recesses and the particle size of the first particles P1. Specifically, the area of ​​the recesses becomes approximately the filling area, and the thickness of the layer of filled first particles P1 is determined by the depth of the recesses. For example, to obtain a thin layer (single layer) of 50% of the substrate area, the area ratio of the recesses (area ratio of the recesses to the entire uneven pattern) should be controlled to 50%, and the depth of the recesses should be controlled to be less than or equal to the particle size of the first particles P1. In this case, the opening width of the recesses should be larger than the median diameter of the first particles P1 and smaller than the average size (in this case, the average particle size) of the support material S1. The first particles P1 may have a broad particle size distribution, but it is preferable that the support material S1 has a narrow particle size distribution, and more preferably monodisperse. This makes it easier to prevent the support material S1 from coming into contact with the bottom (or bottom surface) of the recesses. If the support material S1 can come into contact with the bottom of the recess, there is a risk that the support material S1 will also be confined and filled into the recess.

[0047] Furthermore, it is preferable that the opening width of the recesses in the uneven pattern 111a is less than four times the particle size of the first particle P1. By making the opening width less than four times the particle size of the first particle P1, the probability of the first particle P1 contacting two locations, the bottom surface and the side wall surface, of the recesses in the uneven pattern 111a can be increased. In this way, the first particle P1 that makes multi-point contact with the uneven pattern 111a is strongly constrained by the uneven pattern 111a, thereby increasing the efficiency of filling the uneven pattern 111a with the first particle P1. The same applies to the particle size of the second particle P2, which will be described later, and the size of the recesses in the uneven pattern formed by the first particle P1. Also, when brush fibers are used as the support material, the "average particle size of the support material" in the above description becomes the "average fiber diameter of the support material."

[0048] The filler 241a recovered by the recovery member 244a is conveyed by the rotating roller 244a (dotted line d in Figure 3). The filler 241a conveyed by the roller 244a falls into the filling container 242a due to the magnetic field created by two adjacent, repelling magnetic poles of the same polarity (N1, N2) and the influence of gravity (dotted line e in Figure 3). Subsequently, it is agitated and conveyed again by the stirring screw member 243a, and this process is repeated thereafter.

[0049] The weight ratio of the first particles P1 to the support material S1 in the filler 241a within the filling container 242a is determined by an inductance sensor that measures magnetic permeability, which is common in electrophotographic devices, or by a patch density sensor that predicts the weight ratio by measuring the reflectance density on a substrate or the like. Then, at least one of the first particles P1 and the support material S1 is replenished as needed by a replenishment means (not shown). This enables stable filling over a long period of time.

[0050] Here, we have described a filling device that fills recesses with particle material by forming a so-called magnetic brush using magnetic particles as a support material. However, the filling device is not limited to this method. Brush fibers can also be used as the support material. Alternatively, an elastic material whose surface is composed of an elastic material can also be used as the support material.

[0051] Figure 6(a) schematically shows the configuration of the filling device 24c when brush fibers are used as the support material.

[0052] The filling device 24c has a roller 2410 having brush fibers on its surface. The roller 2410 is a so-called brush roller, with brush fibers implanted on its surface. The material of the fibers constituting the brush fibers of the roller 2410 is not particularly limited, and for example, nylon, rayon, acrylic, vinylon, polyester, polyvinyl chloride, etc., can be used. Surface treatment may be applied to the surface of the fibers for the purpose of adjusting their electrostatic properties and rigidity.

[0053] The filling device 24c has a supply member that supplies the filler 241a to the roller 2410. The filler 241a contains a powder composed of a plurality of first particles P1 and is contained in the filling container 242a. In this example, the filler 241a does not contain a support material S1 which is magnetic particles. The filler 241a is stirred and conveyed by the stirring screw member 243a and supplied to the supply member 249.

[0054] The supply member 249 is a member that supplies the filler 241a to the roller 2410, and its configuration is not particularly limited. For example, the supply member 249 can be a roller in which at least the surface is made of an elastic, porous foam material. Typically, an elastic sponge roller can be used in which a relatively low-hardness polyurethane foam with a foamed skeletal structure is formed on a metal core. In addition to urethane, various rubber materials such as nitrile rubber, silicone rubber, acrylic rubber, hydrin rubber, and ethylene propylene rubber can be used as the material for the foam.

[0055] The supplied filler 241a is filled into the foam on the surface of the supply member 249 and transported to the supply section that contacts the roller 2410. In the supply section, the filler 241a filled into the foam becomes electrically charged by contact with the brush fibers of the roller 2410 and is supported by the brush fibers of the roller 2410. Furthermore, the supply member 249 may also have a function to remove and refresh any filler 241a remaining on the roller 2410. The filler 241a supplied to the roller 2410 comes into contact with the first substrate 11a due to the movement of the brush fibers.

[0056] At this time, the first particles P1 in the filler 241a can come into contact with the bottom surface of the recesses of the uneven pattern 111a on the surface of the first substrate 11a, but the brush fibers cannot. That is, the fiber diameter of the brush fibers is made larger than the opening width of the recesses of the uneven pattern 111a. The fiber diameter of the brush fibers can be measured by placing glass on the surface of the roller 2410 and obtaining an image of the brush fibers through the glass using an optical microscope. At this time, the fiber diameter of about 100 brush fibers is measured, the distribution of fiber diameters is measured, and the average diameter is calculated.

[0057] The movement of the conveying member 224a and / or the rotation of the roller 2410 causes the brush fibers of the roller 2410 to rub against the surface of the first substrate 11a. As a result, the first particles supported on the brush fibers are densely arranged in the recesses of the uneven pattern 111a on the surface of the first substrate 11a.

[0058] Figure 6(b) schematically shows the configuration of the filling device 24d when an elastic material is used as the support material.

[0059] The filling device 24d has a similar configuration to the filling device 24c, but differs in that it uses a roller 2411 having an elastic material instead of a roller 2410 having brush fibers. The roller 2411 is a roller with an elastic layer formed on its surface. The elastic layer is made of an elastic material such as rubber material such as silicone rubber, acrylic rubber, nitrile rubber, urethane rubber, or fluororubber. The surface shape of the elastic layer may be controlled by adding fine particles such as spherical resin. If the elastic layer has protrusions on its surface, the size of the protrusions of the elastic layer should be larger than the size of the recesses of the uneven pattern 111a. The size of the protrusions of the elastic layer can be measured in the same way as the fiber diameter of the brush fibers described above.

[0060] The movement of the conveying member 224a and / or the rotation of the roller 2411 causes the elastic material on the surface of the roller 2411 to rub against the surface of the first substrate 11a. As a result, the first particles supported on the elastic material are densely arranged in the recesses of the uneven pattern 111a on the surface of the first substrate 11a.

[0061] As shown in Figures 6(a) and 6(b), using brush fibers or elastic materials as the support eliminates the need to include magnetic particles in the filler and simplifies the configuration of the filling device. On the other hand, when magnetic particles are used as the support, as shown in Figure 3, there is greater freedom in the size and shape of the support than with brush fibers or elastic materials. Also, with magnetic particles, there is greater freedom in the movement of the support on the substrate. For these reasons, when magnetic particles are used as the support, particles such as the first particle P1 can be supplied to the substrate more efficiently, and the depressions on the substrate can be filled more efficiently. Furthermore, when a magnetic material is used as the support, even if the support deteriorates during the process, the support can be replenished or replaced without stopping the process.

[0062] As in this embodiment, the method of filling recesses with particles by rubbing a support material on which particles are carried allows for a greater supply of dispersed particles to the recesses compared to filling methods using regulating members such as blades, enabling stable and dense filling. This advantage becomes more pronounced as the particle size of the particles being filled decreases, as the particles tend to aggregate more easily.

[0063] The first substrate 11a, in which the first particles 1 have been filled into the recesses of the uneven pattern 111a by the first filling device 24a, is transported to the transfer section 25a by the first belt device 22a.

[0064] Here, as shown in Figure 2, the second belt device 22b, like the first belt device 22a, has drive rollers 221b, 222b, a pressure roller 223b, and a belt-shaped conveying member 224b suspended from them. At this time, the pressure roller 223b is rotated by the drive. In the transfer section 25a, the pressure roller 223a of the first belt device 22a and the pressure roller 223b of the second belt device 22b face each other.

[0065] The second base material 11b is supplied to the second belt device 22b from the second storage container 21b and transported in the direction of the arrow in Figure 2. The supplied second base material 11b is transported in conjunction with the timing when the first base material 11a is transported to the transfer unit 25a. In the transfer unit 25a, the first particles P1 filled in the first base material 11a are transferred to the second base material 11b. In other words, the first base material 11a can be called a transfer base material for transferring the first particles P1 to the second base material 11b. Also, the uneven pattern formed on the surface of the first base material 11a can be called a transfer uneven pattern. The transfer process will be explained below with reference to Figure 7.

[0066] Figure 7 is a schematic diagram showing the configuration of the transfer section 25a. The transfer section 25a consists of the pressure roller 223a and conveying member 224a of the first belt device 22a, and the pressure roller 223b and conveying member 224b of the second belt device 22b. As described above, the pressure rollers 223a and 223b rotate by force, and the two rollers are in contact via the conveying members 224a and 224b. At least one of the pressure rollers 223a and 223b is a soft roller having an elastic layer on its surface, and a nip portion is formed where the two rollers are in contact.

[0067] The first substrate 11a and the second substrate 11b, which have been filled with the first particles P1 by the first filling device 24a, are transported at approximately constant speed by their respective transport members (224a, 224b) and enter the nip portion formed by the contact of the pressure rollers 223a, 223b. In the nip portion, the first particles P1 on the first substrate 11a come into contact with the second substrate 11b and are transferred onto the second substrate 11b.

[0068] The second substrate 11b is a substrate whose adhesion force to the first particle P1 is greater than the adhesion force to the first particle P1 on the first substrate 11a. In other words, the adhesion force of the first particle P1 to the second substrate 11b is greater than the adhesion force of the first particle P1 to the first substrate 11a. As a result, in the nip portion, the first particle P1 on the first substrate 11a is transferred to the second substrate 11b.

[0069] The material of the second base material 11b is not particularly limited, and a base material of the same material as the first base material 11a can be used. The second base material 11b, like the first base material 11a, may be a base material that is individually separated, such as cut paper, or it may be a continuous base material wound in a roll, such as roll paper, or a continuous base material that is folded alternately, such as continuous paper.

[0070] The second substrate 11b is preferably surface-treated to enhance adhesion in order to transfer the first particles P1 that it comes into contact with. For example, the second substrate 11b preferably has an adhesive layer on its surface, to which an adhesive is applied. The adhesive may be an acrylic adhesive, a rubber adhesive, a silicone adhesive, or a thermoplastic resin or photocurable resin whose adhesive strength changes due to disturbances such as heat or light. The adhesive may also be applied to both sides of the second substrate 11b.

[0071] Furthermore, the material layer forming apparatus 1 may have coating means such as a dispenser or an inkjet head for applying an adhesive to the surface of the second substrate 11b while it is being transported.

[0072] The type and amount of adhesive applied are adjusted as appropriate depending on the shape and material of the textured pattern used, the particle size and material of the first particle P1 and the second particle P2, etc., but it is preferable that the adhesive strength of the adhesive is greater than that of the textured pattern 111a. The adhesive strength can be compared using a general method using a nanoindenter.

[0073] In the nip section, the first particle P1 is restrained by the adhesive force generated between it and the second substrate 11b. After passing the nip section, the two transport members 224a and 224b separate, and the first particle P1 that was on the first substrate 11a is transferred to the second substrate 11b.

[0074] The second substrate 11b onto which the first particle P1 has been transferred is transported by the transport member 224b to the filling position of the second filling device 24b.

[0075] The second filling device 24b has the same configuration and function as the first filling device 24a, except that the filling container 242a contains a filling material 241b having second particles P2 and a support material S2 instead of a filling material 241a having first particles P1 and a support material S1.

[0076] The second filling device 24b fills the portions of the second substrate 11b where the first particles P1 are not present with the second particles P2. As described above, the first particles P1 are present on the second substrate 11b after passing through the transfer section 25a, but recesses are formed in the portions where the first particles P1 are not present. The second filling device 24b fills these recesses with the second particles P2 using the same process as the first filling device 24a. Here, we describe the case where magnetic particles are used as the support material, but brush fibers or elastic materials may also be used as the support material, similar to the first filling device 24a.

[0077] The filler 241b comprises second particles P2 and a support material S2 that supports the second particles P2. The filler 241b is a mixture of multiple powders, including a powder composed of a plurality of second particles P2 and a powder composed of a plurality of support materials S2. The material of the second particles P2 is not particularly limited and, like the first particles P1, may be particulate inorganic materials such as metal particles, ceramic particles, or glass particles, or particulate organic materials such as resin particles. Furthermore, the first particles P1 and the second particles P2 may be made of the same material. Similarly, the support material S2 can be the same as the support material S1. It is preferable that the first particles P1 and the second particles P2 are selected from positive electrode materials, solid electrolyte materials, and negative electrode materials for lithium-ion batteries and all-solid-state batteries.

[0078] Figure 8 is an enlarged view of the vicinity of the surface of the second substrate 11b during the filling process by the second filling device 24b. The second substrate 11b has an uneven surface pattern formed thereon, which includes protrusions formed by the placement of the first particles P1 and recesses where the first particles P1 are not placed. The filler 241b comes into contact with this uneven surface pattern and is transported together with the second substrate 11b while having a non-zero relative velocity to the second substrate 11b, under the influence of a magnetic force (solid line Fm in the figure) perpendicular to the surface of the second substrate 11b. As a result, the second particles P2 supported on the carrier S2 are transported while being rubbed against the uneven surface pattern on the second substrate 11b. At this time, the opening width of the recesses in the uneven surface pattern formed on the second substrate 11b is set to a size that allows the second particles P2 to come into contact with the bottom surface of the recess (the second substrate 11b), but the carrier S2 cannot. As a result, only the second particles P2 within the filler 241b selectively come into contact with the bottom surface of the recess (the second substrate 11b). The second particles P2 that come into contact with the bottom surface of the recess are strongly restrained by the physical restraining force due to the structure of the uneven pattern, as well as by the electrostatic adhesion and adhesive force with the second substrate 11b and the structural material constituting the uneven pattern (in this case, the first particles P1), and detach from the support material S2.

[0079] Figure 9(a) is a schematic diagram of the second substrate 11b after the first particles P1 have been transferred by the transfer unit 25a, and is a view of the second substrate 11b from a direction perpendicular to the substrate surface. As shown in Figure 9(a), a honeycomb pattern is formed on the second substrate 11b, in which arrangement regions in which the first particles P1 are arranged in a regular hexagonal shape are aligned. The first particles P1 are densely arranged within these regular hexagonal regions, and the first particles P1 are not arranged in the other parts (the white areas in Figure 9(a)), and the surface of the second substrate 11b is exposed. The regular hexagonal regions in which the first particles P1 are held can be rephrased as the first pattern region, and the honeycomb pattern regions in which the second particles P2 are held and which correspond to the gaps in the first pattern region can be rephrased as the second pattern region.

[0080] Figure 9(b) is a schematic diagram showing the second substrate 11b after it has been filled with the second particles P2 by the second filling device 24b, and is a view of the second substrate 11b from a direction perpendicular to the substrate surface. As shown in Figure 9(b), the second particles P2 are densely arranged in the areas where the first particles P1 were not previously present. Furthermore, the first particles P1 and the second particles P2 are densely arranged at the boundary between the areas where the first particles P1 are present and the areas where the second particles P2 are present. It should be noted that particles can also be filled into the small gaps between the first particles P1 in the same manner. In this case, it is possible to fill the gaps using a filler containing particles with a particle size corresponding to the gaps between the first particles P1 in the same manner as described above, thereby forming an even denser thin film.

[0081] Figures 16(a) and (b) show a plan view and a cross-sectional view of an embodiment having a first pattern section and a second pattern section in which first and second particle groups P1 and P2, exhibiting different average particle sizes, are laid out on a substrate 11b. The cross-sectional view shown in Figure 16(b) corresponds to the cross-sectional view of the BB section shown in Figure 16(a).

[0082] As shown in Figure 16(a), the first and second pattern sections, corresponding to the first particle group P1 and the second particle group P2, have equal repetition periods L / 5 in the x-direction. Similarly, the first and second pattern sections also have equal repetition periods L / 5 in directions rotated by +1 / 3π radians (+60 degrees) and -1 / 3π radians (-60 degrees), respectively, with respect to the x-direction.

[0083] In this embodiment, as shown in Figure 16(b), the first and second pattern sections are filled with particle groups P1 and P2 having different average particle sizes. Therefore, the surface density of the particle groups held in each pattern section differs between the first and second pattern sections. In this embodiment, the surface density of the first particle group P1 in the first pattern section is lower than the surface density of the second particle group P2 in the second pattern section.

[0084] In addition, in the present embodiment, the second particle group P2 is stacked not only on the portion in contact with the base material 11 but also in the thickness direction (z direction) of the base material 11 of the base material 11 and is filled in the second pattern portion. When the first particle group P1 and the second particle group P2 are selected as functional elements of the secondary battery, they may be selected as a combination of the same materials such as positive electrode active materials, negative electrode active materials, and electrolytes, or different materials such as a positive electrode active material and an electrolyte, and a negative electrode active material and an electrolyte may be selected.

[0085] In addition, in the present embodiment, as shown in FIG. 16(b), the first particle group P1 and the second particle group P2 are held on the base material 11b by the adhesive layer 15. The form in which the particles are held on the base material depends on the layer thickness t of the adhesive layer 15 and the particle diameter Φ of the particles. In the present embodiment, the first particle group P1 (Φ1>t) is in contact with the adhesive layer 15 at a part on the side of the base material 11b. The second particle group P2 (Φ2<t) has a portion where a part of the first-layer particle group and the second-layer particle group located on the base material 11b side is in contact with the adhesive layer 15. When the layer thickness t of the adhesive layer 13 is larger than the average particle diameter of each of the first particle group P1 and the second particle group P2, the first particle group P1 and the second particle group P2 may be in a form of being buried in the adhesive layer 13 (not shown).

[0086] In addition, the adhesive layer 15 does not need to continuously maintain adhesiveness as long as it maintains the form in which the first particle group P1 and the second particle group P2 are held on the base material 11b, and the adhesive force may decrease. Therefore, the adhesive layer 15 may be referred to as a holding layer 15. The holding layer 15 (adhesive layer 15) includes a form in which the adhesive force decreases over time and a form in which the adhesive force decreases by post-treatment. The actions of the decrease in the adhesive force over time include drying, crosslinking, etc., and the post-treatment includes heat curing treatment, photo-curing treatment, etc. The decrease in the adhesive force of the holding layer 15 (adhesive layer 15) is preferable in terms of reducing the adhesion of dust, contaminants, etc. from the environment and maintaining the purity of the material layer 12 by decreasing after the first particle group P1 and the second particle group P2 are held on the base material 11b.

[0087] Thus, according to the material layer forming apparatus 1 of this embodiment, a material layer can be formed on the second substrate 11b in which the first particles P1 and the second particles P2 are densely arranged in a pattern. Specifically, according to this embodiment, the coverage rate of the substrate by particles can be made 80% or more in each material layer. The coverage rate of the substrate by particles can be measured by photographing the area in which the material layer is formed from the vertical direction of the substrate with an optical microscope and calculating the area ratio of particles within that area using image processing software.

[0088] In this embodiment, the case in which the material layer forming apparatus 1 forms a material layer using two types of particle materials has been described, but the invention is not limited to this, and the material layer may be formed using one type of particle material, or using three or more types of particle materials.

[0089] When forming a material layer with one type of particle material, the same particle material can be used to fill both the first filling device 24a and the second filling device 24b. This allows for the formation of a material layer in which the single type of material is more densely arranged. In this case, the first particles P1 in the first filling device 24a and the second particles P2 in the second filling device 24b may be made of the same material but have different particle sizes. For example, by using particles with a smaller particle size than the first particles P1 as the second particles P2, an even denser material layer can be formed.

[0090] On the other hand, when forming a material layer with three or more types of particle materials, a third filling device can be added to the upstream side of the first filling device 24a or the second filling device 24b. In this case, it is preferable that the particle diameter of the particles filled in the upstream filling device be larger than the particle diameter of the particles filled in the downstream filling device. It is also preferable to provide multiple recesses of different sizes on the substrate, so that the particles filled in the upstream filling device come into contact only with the bottom of some of these recesses. This makes it possible to form a material layer in which the particles of three or more types of particle materials are densely arranged in a pattern.

[0091] Alternatively, although the configuration becomes more complex, multiple first belt devices 22a may be provided, and different particles may be transferred from each device onto the second substrate 11b. Or, a third belt device having a third filling device may be provided, and in the transfer section formed by the second belt device 22b and the third belt device, the first and second particles may be transferred from the second substrate 11b, where the first and second particles are placed, onto the third substrate. After that, if the third particles are filled with third particles by the third filling device into the parts of the third substrate where neither the first nor the second particles are placed, a material layer can be formed with three or more types of particle materials.

[0092] As described above, the method for manufacturing the material layer according to this embodiment is a dry process that allows for the dense arrangement of particles on a substrate in any pattern and can be carried out under atmospheric pressure. This eliminates the need for solvent management, air conditioning equipment, and vacuum level adjustments that were essential in conventional wet processes (e.g., coating methods, inkjet methods) and vapor phase growth methods, making it a method that can be implemented in a simple configuration and environment. Furthermore, the method for manufacturing the material layer according to this embodiment has the advantage that the thickness of the material layer can be easily adjusted by adjusting the particle size of the particles used, the depth of the recesses in the uneven pattern, or by laminating multiple substrates.

[0093] Thus, according to the material layer forming apparatus 1 of this embodiment, one or more types of particles can be arranged on the substrate 11b in any pattern, and a material layer in which these particles are densely arranged can be formed.

[0094] (Method for determining the structure of an uneven pattern) In this embodiment, it is preferable that the uneven pattern 111a allows the first particles P1 to come into contact with the surface of the substrate 11a (the bottom surface of the recesses of the uneven pattern 111a), while the support material S1 that carries the first particles P1 cannot come into contact with it.

[0095] The structure of the uneven pattern can be determined using an AFM (Nano-I manufactured by Pacific Nanotechnology). If the uneven pattern is formed on the surface of a component such as a roller, a replica of the uneven pattern can be created on a smooth substrate using UV-curing resin or thermoplastic resin, and this replica can be used to determine the structure.

[0096] When determining the structure of a surface irregularity pattern, two cantilevers (probes) are used for the AFM: Cantilever A, which has a hemispherical tip corresponding to the particle size r of the first particle P1, and Cantilever B, which has a hemispherical tip corresponding to the particle size rc of the supporting material S1. The surface irregularity pattern is measured using these two types of cantilevers. If the first particle P1 can contact the bottom surface of a recess in the surface irregularity pattern, the surface irregularity structure is observed by measurement using Cantilever A, and typically a flat surface of the recess is observed. On the other hand, if the supporting material S1 cannot contact the bottom surface of a recess in the surface irregularity pattern, the depth of the recess in the surface irregularity pattern is measured to be smaller by measurement using Cantilever B than by measurement using Cantilever A. In this way, by measuring the depth of the recess in the surface irregularity pattern using two types of cantilevers and comparing the results, it is possible to determine whether or not contact with the bottom surface of the surface irregularity pattern is possible.

[0097] According to the first embodiment, it is possible to provide a material layer having a pattern layer provided on a desired substrate.

[0098] The pattern layer comprises, for example, a first region comprising a first inorganic material and containing a plurality of first particles before sintering, and a second region comprising a second inorganic material and containing a plurality of second particles before sintering.

[0099] (Inorganic materials) Examples of the first inorganic material include at least one of a positive electrode material, an electrolyte material, and a negative electrode material. Specifically, examples of the positive electrode material include, for example, composite metal oxides containing lithium, chalcogen compounds, manganese dioxide, and the like. The composite metal oxide containing lithium is a metal oxide containing lithium and a transition metal, or a metal oxide in which a part of the transition metal in the metal oxide is substituted with a different element. Here, examples of the different element include, for example, Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, B, and the like. The different element may be one kind or two or more kinds. Among these, a composite metal oxide containing lithium is preferable. The composite metal oxide containing lithium is Li x CoO2, Li x NiO2, Li x MnO2, Li x Co y Ni 1-y O2, Li x Co y Mn 1-y O z , Li x Ni 1-y M y O z , Li x Mn2O4, etc. The composite metal oxide containing lithium further includes Li x Mn 2-y MyO4, LiMPO4, Li2MPO4F, etc. M in the formula is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, V, and B. x, y, z in the formula are 0 < x ≤ 1.2, 0 < y < 0.9, 2.0 ≤ z ≤ 2.3. The composite metal oxide containing lithium further includes LiMeO2 (Me in the formula is Me = MxMyMz: Me and M are transition metals, x + y + z = 1). Specific examples of the composite metal oxide containing lithium are LiCoO2 (LCO: lithium cobaltate), LiNi 0.5 Mn 1.5O4 (LNMO: lithium nickel manganese oxide) is one example. Specific examples of lithium-containing composite metal oxides include LiFePO4 (LFP: lithium iron phosphate) and Li3V2(PO4)3 (LVP: lithium vanadium phosphate). The above cathode material may also contain a conductive additive. Examples of conductive additives include graphite such as natural graphite and artificial graphite, and carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black. Other conductive additives include conductive fibers such as carbon fibers, carbon nanotubes, and metal fibers, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene dielectrics.

[0100] Examples of electrolyte materials include oxide-based solid electrolytes, sulfide-based solid electrolytes, and complex hydride-based solid electrolytes. Oxide-based solid electrolytes include Li 1.5 Al 0.5 Ge 1.5 (PO4)3 and Li 1.3 Al 0.3 Ti 1.7 Nasicone-type compounds such as (PO4)3, Li 6.25 La3Zr2Al 0.25 O 12 Examples of garnet-type compounds include Li 0.33 Li 0.55 Examples include perovskite-type compounds such as TiO3. Also, oxide-based solid electrolytes include Li 14Examples of the silicon-type compounds include Zn(GeO4)4, and examples of the acid compounds include Li3PO4, Li4SiO4, and Li3BO3. Specific examples of the sulfide-based solid electrolytes include Li2S-SiS2, LiI-Li2S-SiS2, LiI-Li2S-P2S5, LiI-Li2S-P2O5, LiI-Li3PO4-P2S5, and Li2S-P2S5. The solid electrolyte may be crystalline, amorphous, or glass-ceramics. Note that the description of Li2S-P2S5, etc. means a sulfide-based solid electrolyte formed using raw materials containing Li2S and P2S5.

[0101] Examples of the negative electrode material include metals, metal fibers, carbon materials, oxides, nitrides, silicon, silicon compounds, tin, tin compounds, and various alloy materials. Among these, from the viewpoint of the capacity density, oxides, carbon materials, silicon, silicon compounds, tin, tin compounds, etc. are preferable. Examples of the oxides include Li4Ti5O 12 (LTO: lithium titanate), etc. Examples of the carbon materials include various natural graphites (graphite), coke, carbon in the process of graphitization, carbon fibers, spherical carbon, various artificial graphites, and amorphous carbon. Examples of the silicon compounds include silicon-containing alloys, silicon-containing inorganic compounds, silicon-containing organic compounds, solid solutions, etc. Examples of the tin compounds include SnO b (0 < b < 2), SnO2, SnSiO3, Ni2Sn4, Mg2Sn, etc. Further, the above negative electrode material may contain a conductive assistant. Examples of the conductive assistant include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Other examples of the conductive assistant include conductive fibers such as carbon fibers, carbon nanotubes, and metal fibers, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene derivatives.

[0102] The first inorganic material and the second inorganic material can be the same material, or they can be different materials. Multiple types of particles may be mixed in the first region.

[0103] A preferred combination of the first inorganic material and the second inorganic material is, in the case of an electrode substrate, a positive electrode material or a negative electrode material as the first inorganic material and an electrolyte material as the second inorganic material. In the case of an electrolyte substrate, the first inorganic material and the second inorganic material may be the same electrolyte material or different electrolyte materials.

[0104] The particle size (average particle size) of the first and second particles is, for example, 0.05 μm to 100 μm (large range), preferably 0.1 μm to 50 μm (medium range), and more preferably 0.5 μm to 25 μm (small range). From the viewpoint of density, it is preferable to reduce the particle size further, but the lower limit is set by material cost and deterioration of cohesiveness. The upper limit is set by the decrease in density. The average particle size is measured, for example, by a laser diffraction / scattering particle size distribution analyzer.

[0105] The average particle size of the first particle group and the average particle size of the second particle group can be made different from each other. For example, if the first region is formed first and then the second region is formed, it is desirable that the relationship between the particle sizes of the particle groups placed in both regions be such that the average particle size of the first particle group ≥ the average particle size of the second particle group. The second particle group fills the voids and gaps on the substrate 11b where the first particle group is not placed. The reason why the second particle group is placed and filled on the substrate 11b is due to the adhesive force on the surface of the substrate 11b and the restraining force created by the uneven pattern formed by the first particle group on the substrate 11b. For this reason, in order to fill stably and densely, it is desirable that the average particle size of the second particle group be smaller than that of the first particle group.

[0106] The packing density of the first particles in the first region is, for example, 30% or more (a wide range is desirable, and since it is currently difficult to specify an upper limit, only a lower limit is stated), preferably 50% or more, and more preferably 70% or more. This packing density is measured by, for example, taking an image of the substrate with an optical microscope or electron microscope, and using image processing software to binarize the presence or absence of particles within the first region on the substrate, and then determining the ratio (%) of the total number of pixels of the particle image to the total number of pixels of the image.

[0107] The packing density of the first particles in the first region and the packing density of the second particles in the second region can also be made different from each other. For example, if the first region is formed first and then the second region is formed, selective particle patterning utilizing the particle size difference can be used to create a configuration in which the second region (second patterned area) has a higher packing density than the first region (first patterned area).

[0108] Furthermore, the multiple first particles before the sintering process are sintered by firing them at a predetermined sintering temperature or higher.

[0109] Furthermore, the particles placed in the first and second regions are not necessarily limited to inorganic materials; materials (metallic materials, organic materials, etc.) described in this embodiment or other embodiments or examples can be used as appropriate depending on the application.

[0110] (Pattern layer) The pattern layer is a repeating pattern in which a plurality of first regions are repeatedly arranged in the in-plane direction of the substrate at a predetermined period, and it can also be configured so that second regions are provided between the first regions.

[0111] The pattern of a pattern layer is a pattern composed of a first region and a second region (and possibly other regions). For example, a honeycomb pattern is a honeycomb shape. In addition to honeycomb patterns, other patterns include hole patterns in which circles are repeatedly arranged in the direction of the plane, square patterns in which squares are arranged, triangular patterns in which triangles are arranged, and patterns in which shapes other than shapes are repeated. The same applies to line patterns in which vertical, horizontal, diagonal, or mixed lines are repeatedly arranged, as opposed to patterns in which each isolated shape is arranged in the plane.

[0112] Examples of pattern types include repeating patterns having a repeating structure in the in-plane direction of the substrate, random patterns, and gradients. A repeating pattern having a repeating structure in the in-plane direction of the substrate can be rephrased as a repeating pattern having a repeating structure within the layers of the pattern layer.

[0113] Furthermore, configurations can be used in which patterns of other periods are mixed in with the basic period of the pattern. Whether or not such a pattern exists can be determined, for example, by acquiring an in-plane image of the substrate, extracting feature points from the image using image processing, performing Fourier analysis, etc., and obtaining a spatial frequency spectrum.

[0114] Furthermore, the manufacturing method shown in this embodiment is effective when the size of the pattern provided on the substrate in the first or second region (for example, the size in the in-plane direction of the first region) is small. For example, it is preferable that the minimum width of the first region on the substrate is greater than the average particle size of the first particle P1 and less than four times the average particle size. Here, the minimum width is the diameter of the largest circle that fits within the first region. That is, in the case of a honeycomb pattern, it is the diameter of the largest circle that fits within the hexagon; in the case of a hole pattern, it is the diameter of the largest circle that fits within the circle; and the same applies to square and triangular patterns. In the case of a line pattern, it is the diameter of the largest circle that fits within the line, that is, the length of the shorter side of the line.

[0115] Furthermore, the height variation in the first region (and / or second region) forming the pattern is such that the height range is 3 times or less the average particle size of the first particle P1, preferably 2 times or less the average particle size, and more preferably less than or equal to the average particle size. Here, the height range is the difference between the maximum and minimum heights in the first region.

[0116] (base material) It is preferable that the substrate is configured to have different thermal decomposition properties or solubility in solvents from the first and second regions that constitute the sheet-like pattern layer. For example, the first and second regions may be mainly composed of inorganic materials, while the substrate may be composed of organic materials.

[0117] For example, polyethylene terephthalate and polyester can be used as the base material.

[0118] Furthermore, the coverage rate of the substrate in the first region and / or the second region is 80% or more, preferably 85% or more, and more preferably 90% or more.

[0119] (Laminated structure) A structure can be formed by stacking multiple substrates equipped with pattern layers, and then by thermally decomposing the substrates from the structure or dissolving them with a solvent, a laminate with multiple pattern layers can be formed.

[0120] A laminate can be provided that comprises a pattern layer comprising a first region and a second region, and wherein a plurality of such pattern layers are stacked.

[0121] Here, the in-plane pattern composed of the first and second regions can be configured to include areas where the phases of the pattern layers are not aligned when viewed in the stacking direction. For example, in the case of a honeycomb pattern, the phases between the pattern layers can be deliberately shifted, and in the case of a line pattern, the phases can be similarly shifted, or the line angles between the pattern layers can be shifted to include areas where the phases are not aligned. This causes a shift in the particle positions between the pattern layers, which has the effect of improving the density of the particles during stacking. Furthermore, in the case of a part of the stacked material that forms an all-solid-state battery, such as an electrode, the shift in particle positions between the pattern layers can be expected to have the following effects. That is, the shift in particle positions between the pattern layers makes it easier for the electrode active material and the solid electrolyte to come into contact in the stacking direction, reducing the amount of electrode active material that is isolated within the electrode without contact with the solid electrolyte, thus improving capacity. In addition, it is easier for the electrode active material to come into contact with the solid electrolyte and conductive additives that mitigate volume changes in the electrode due to charging and discharging, thus improving cycle characteristics.

[0122] The material layer obtained by this embodiment comprises a pattern layer and a substrate on which the pattern layer is provided. The pattern layer comprises a first region comprising a first inorganic material and on which a plurality of first particles are arranged before sintering, and a second region comprising a second inorganic material and on which a plurality of second particles are arranged before sintering.

[0123] <Second Embodiment> A second embodiment of the present invention, a method for manufacturing a material layer and a material layer forming apparatus, will be described with reference to the drawings. In this embodiment, in the first step S101, the first particles are arranged in a pattern on the substrate by applying a liquid in a pattern on the substrate and then attaching a powder containing the first particles to the liquid.

[0124] Figure 10 is a schematic diagram showing the configuration of the material layer forming apparatus 2 according to this embodiment. Parts identical to those of the material layer forming apparatus 1 are denoted by the same reference numerals, and explanations are omitted as appropriate.

[0125] The material layer forming apparatus 2 is an apparatus for forming a material layer 12 on a substrate 11, and includes a storage container 21 for storing and supplying the substrate 11, and a belt device 22 for conveying the substrate 11. The material layer forming apparatus 2 also includes a liquid dispensing device 201 for arranging a liquid in a pattern on the substrate 11, and a powder dispensing device 202 for dispensing a powder containing first particles P1 onto the substrate 11 on which the liquid is arranged in a pattern. Furthermore, the material layer forming apparatus 2 has a filling device 24 having the same configuration as the second filling device 24b of the first embodiment.

[0126] In the material layer forming apparatus 2, the liquid dispensing device 201 and the powder dispensing device 202 correspond to a first arrangement means for arranging the first particles P1 in a pattern on the substrate 11. The filling device 24 corresponds to a second arrangement means for arranging the second particles P2 in areas on the substrate 11 where the first particles P1 are not present.

[0127] The liquid application device 201 arranges liquid in a pattern on the substrate 11 to form a liquid pattern L1 on the substrate 11. Typically, an inkjet device can be used as the liquid application device 201, but it is not limited to this, and plate-based methods such as flexographic plates can also be applied. For example, when forming a large number of patterns of the same shape, using a plate may be more efficient. The liquid application device 201 may also be configured to apply gel instead of liquid within a range that has fluidity for dispensing. The viscosity of the discharged fluid is adjusted as appropriate, taking into consideration the drying speed of the pattern L1 arranged in a pattern, affinity with the substrate 11, and stability of fixation of particles P1. In other words, the liquid application device 201 can be replaced with a fluid application device 201. The liquid application device 201 of this embodiment differs from the inkjet-based patterning device described in the background art in that it does not discharge the materials of the positive electrode, negative electrode, and electrolyte, which are functional components of a secondary battery, onto the substrate 11. The liquid application apparatus 201 of this embodiment differs from the inkjet-based patterning apparatus described in the background art in that it patterns a retaining layer for holding the materials of the positive electrode, negative electrode, and electrolyte, which are functional components of a secondary battery, as particles on the substrate 11. By giving such a retaining layer different physical properties from the particles as functional materials, it can be made into a form that does not constitute an element of the secondary battery.

[0128] Various types of inkjet devices can be used as the liquid dispensing device 201, including thermal, piezo, electrostatic, and continuous inkjet devices. The inkjet device is not particularly limited as long as it is capable of dispensing liquid. The number of nozzles (dispensing ports) of the inkjet device is also not particularly limited; it may be a single nozzle like a dispenser, or multiple nozzles like a dryhead, however, from a productivity standpoint, it is preferable for the inkjet device to have multiple nozzles.

[0129] The liquid applied by the liquid application device 201 is not particularly limited and can be any material to which the first particles P1 can adhere, and may be an aqueous liquid (e.g., water-based ink) or an oil-based liquid (e.g., oil-based ink). Furthermore, the liquid application device 201 may form the pattern L1 with multiple types of liquids. For example, the liquid application device 201 may apply two types of liquid materials that react on the substrate 11 to increase its tackiness.

[0130] The powder dispensing device 202 dispenses powder containing the first particles P1 onto the substrate 11, on which the liquid is arranged in a pattern. As a result, the first particles P1 are fixed by the liquid on the substrate 11, and the first particles P1 are fixed in a pattern corresponding to the pattern L1.

[0131] The means by which the powder is applied by the powder application device 202 are not particularly limited, and means such as blowing or sprinkling the powder toward the substrate 11 can be used. The powder application device 202 may further include means for removing the first particles P1 that were not fixed on the substrate 11 by the liquid by means of vibration, air blowing, suction, etc.

[0132] The material layer forming apparatus 2 may further include a drying apparatus that evaporates at least a portion of the liquid applied by the liquid application apparatus 201 to control the amount of liquid on the substrate 11, the thickness of the pattern L1, and so on. This drying apparatus may be provided downstream of the liquid application apparatus 201 and upstream of the powder application apparatus 202.

[0133] Furthermore, the material layer forming apparatus 2 may further include a heating means for heating the substrate 11 to which the first particles P1 have been applied by the powder application apparatus 202. The heating method of the heating means is not particularly limited; for example, a contact-type heat roller may be used, or a non-contact method of irradiating with infrared rays or microwaves may be used. Alternatively, heating can be performed by scanning with an energy beam such as laser light. The heating means may be provided on the back side of the belt 224 of the belt apparatus 22, or on the front side (the side on which the substrate 11 is supported).

[0134] According to this embodiment, the liquid dispensing device 201 and the powder dispensing device 202 can arrange the first particles P1 in a pattern on the substrate 11. The substrate 11 with the first particles P1 arranged in a pattern is then transported by the belt device 22 to the filling position of the filling device 24. The filling device 24 fills the portions of the substrate 11 where the first particles P1 are not present with the second particles P2. The filling of the second particles P2 by the filling device 24 is the same as in the first embodiment (second filling device 24b), so the following explanation is omitted.

[0135] As described above, according to the material layer forming apparatus 2 of this embodiment, similar to the first embodiment, one or more types of particles are arranged on the substrate 11 in an arbitrary pattern, and a material layer is formed in which the particles are densely arranged.

[0136] <Third Embodiment> A third embodiment of the present invention, a method for manufacturing a three-dimensional object and an additive manufacturing system, will be described with reference to the drawings.

[0137] Figure 11 is a schematic diagram showing the overall configuration of the additive manufacturing system 100 according to the third embodiment.

[0138] The additive manufacturing system 100 according to this embodiment includes a control unit U1, a material layer formation unit U2, a stacking unit U3, a removal unit U4, and a post-processing unit U5. The control unit U1 is responsible for controlling each part of the additive manufacturing system 100. The material layer formation unit U2 forms a material layer 12 on a substrate 11. The stacking unit U3 stacks multiple substrates 11, each with a material layer 12 formed by the material layer formation unit U2, to form a laminate 13 containing multiple material layers 12 and multiple substrates 11. The removal unit U4 removes the substrates 11 from the laminate 13 formed by the stacking unit U3 to form a three-dimensional object 14. The post-processing unit U5 performs post-processing on the three-dimensional object 14 formed by the removal unit U4. Note that the unit configuration shown in Figure 11 is merely an example, and other configurations may be adopted. The configuration and operation of each unit will be described below.

[0139] [Control Unit] The control unit U1 is responsible for controlling various parts of the additive manufacturing system 100, specifically the material layer formation unit U2, the layering unit U3, the removal unit U4, and the post-processing unit U5.

[0140] The control unit U1 may include a 3D shape data input unit that accepts input of 3D shape data of a three-dimensional object (hereinafter sometimes referred to as "object to be manufactured") to be formed by the additive manufacturing system 100 from an external device (e.g., a personal computer). As 3D shape data, data created and output by 3D CAD, 3D modeler, 3D scanner, etc., can be used. The file format is not limited, but for example, the STL (StereoLithography) file format can be preferably used.

[0141] The control unit U1 may include a slice data calculation unit that slices the 3D shape data at a predetermined pitch to calculate the cross-sectional shape of each layer, and generates image data (referred to as "slice data") to be used for image formation in the material layer formation unit U2 based on that cross-sectional shape. Furthermore, the slice data calculation unit may analyze the 3D shape data or the slice data of the upper and lower layers to determine the presence or absence of overhangs (parts that float in mid-air), and add images for support material to the slice data as needed.

[0142] As will be described in more detail later, the material layer formation unit U2 of this embodiment can use multiple types of materials and form material layers with each material patterned. Therefore, slice data corresponding to the image of each material may be generated. As for the file format of the slice data, for example, multi-level image data (each value representing the type of material) or multi-plane image data (each plane corresponding to the type of material) can be used.

[0143] Although not shown in the diagram, the control unit U1 also includes an operation unit, a display unit, and a storage unit. The operation unit is responsible for receiving instructions from the user. For example, it can input commands such as turning the power on / off, various device settings, and operation instructions. The display unit is responsible for presenting information to the user. For example, it can display various setting screens, error messages, and operating status. The storage unit is responsible for storing 3D shape data, slice data, and various setting values.

[0144] The control unit U1 can be configured, in hardware terms, as a computer equipped with a CPU (Central Processing Unit), memory, auxiliary storage devices (hard disk, flash memory, etc.), input devices, display devices, and various interfaces. Each of the above functions is realized by the CPU reading and executing programs stored in auxiliary storage devices, etc., and controlling the necessary devices. However, some or all of the above functions may be configured with circuits such as ASICs or FPGAs, or they may be executed by other computers using technologies such as cloud computing or grid computing.

[0145] [Material layer formation unit] The material layer forming unit U2 is a unit that forms a material layer 12 on the substrate 11. As the material layer forming unit U2, the material layer forming apparatus 1 of the first embodiment or the material layer forming apparatus 2 of the second embodiment described above can be used.

[0146] The additive manufacturing system 100 may have multiple material layer formation units U2. This allows for the simultaneous formation of material layers 12 on the substrate 11, further improving the throughput of forming the laminate and three-dimensional objects. Furthermore, when there are many types of materials constituting the three-dimensional object, a material layer formation unit U2 can be provided for each material type or group of material types, eliminating the need to switch between material types or processes within the material layer formation unit U2. This enables the continuous manufacturing of three-dimensional objects.

[0147] The following describes a case in which the material layer forming unit U2 forms a material layer 12 on the substrate 11 by a method that combines filling the recesses of the uneven pattern with material and transferring the filled material to the substrate.

[0148] [Laminated Unit] The lamination unit U3 is a unit that stacks multiple substrates 11, each having a material layer 12 formed on it by the material layer formation unit U2, to form a laminate 13 that includes multiple material layers 12 and multiple substrates 11.

[0149] Figure 12 is a schematic diagram showing the configuration of the lamination unit U3. The lamination unit U3 includes a transport device 31 for transporting a substrate 11 on which a material layer 12 is formed, and a stage 32 that can be moved relative to another in the vertical direction by an actuator (not shown).

[0150] The conveying device 31 receives the substrate 11 on which the material layer 12 has been formed from the lamination unit U2 and conveys it to the stage 32. The conveying device 31 is not particularly limited as long as it is a device capable of conveying the substrate 11, and may be a belt conveyor, rollers, or a robotic arm.

[0151] When the substrate 11 is transported to the stage 32 by the transport device 31, the stage 32 moves vertically by the thickness of the substrate 11 and the material layer 12. By repeating the transport by the transport device 31 and the movement of the stage 32, multiple substrates 11, each with a material layer 12 formed on it, are stacked to form a laminate 13.

[0152] The lamination unit U3 may further include a transport device 33 for transporting the formed laminate 13 to a removal unit U4 or the like, and a pressurizing device (not shown) for pressurizing the laminate 13 in the lamination direction. The transport device 33 may have the same configuration as the transport device 31.

[0153] [Removal Unit] The removal unit U4 is a unit that removes the base material 11 from the laminate 13 formed by the lamination unit U3 to form a three-dimensional object 14.

[0154] The method by which the removal unit U4 removes the substrate 11 from the laminate 13 is not particularly limited. The removal unit U4 may remove the substrate 11 by heating the laminate 13, by dissolving the substrate 11 with a solvent, or by mechanically removing the substrate 11 with air pressure or water pressure. When mechanically removing the substrate 11, the substrate 11 may be made brittle by heating or a solvent, and then the brittle substrate 11 may be mechanically removed. Among these, it is preferable for the removal unit U4 to remove the substrate 11 by heating the laminate 13. With removal by heating, the force applied to the upper and lower material layers of the substrate to be removed during removal can be reduced, making it easier to maintain the structure of the material layers. In addition, since heat can be applied to the inside of the laminate, the substrate inside the laminate can also be easily removed, making it easier to increase the removal rate of the substrate. The following describes the case in which the removal unit U4 removes the substrate 11 by heating.

[0155] Figure 13 is a schematic diagram showing the configuration of the removal unit U4. The removal unit U4 includes a transport device 41 for transporting the laminate 13 and a heating furnace 42 for heating the laminate 13.

[0156] The conveying device 41 receives the laminated body 13 from the stacking unit U3 and conveys it to the heating furnace 42. The conveying device 41, like the conveying device 31, is not particularly limited as long as it is capable of conveying the laminated body 13, and may be a belt conveyor, rollers, or a robotic arm.

[0157] The heating furnace 42 is a furnace for heating the laminate 13. The heating furnace 42 includes a heating means 421, a pressurizing means 422, and an atmosphere adjustment means 423. As the heating furnace 42, a firing furnace used for firing ceramics and the like can be used. The pressurizing means 422 pressurizes the laminate 13 being heated in the heating furnace 42, or pressurizes the laminate 13 before and after heating. Preferably, the pressurizing part of the pressurizing means 422 that pressurizes the laminate 13 is made of a porous material that allows gas to pass through easily. The atmosphere adjustment means 423 includes an atmosphere gas supply means 423a and a depressurizing means 423b, and adjusts the atmosphere gas in the processing space of the heating furnace 42.

[0158] The removal unit U4 heats the laminate 13 at a temperature above the thermal decomposition temperature of the substrate 11, but below the thermal decomposition temperature of each material layer in the laminate 13. This selectively decomposes the substrate in the laminate 13 and removes it. If the laminate 13 contains multiple types of substrates 11 made of different materials, the heating temperature of the removal unit U4 should be set to a temperature above the highest thermal decomposition temperature among the thermal decomposition temperatures of the multiple substrates.

[0159] In this specification, the thermal decomposition temperature is the temperature at which the weight of the material begins to decrease when the temperature is gradually increased under the heating atmosphere of the removal unit U4. Therefore, by heating the laminate at a temperature above the thermal decomposition temperature of the substrate 11, the substrate 11 in the laminate can be decomposed and its weight reduced, and the substrate 11 can be removed from the laminate. The heating temperature in the removal process is preferably above the thermal decomposition temperature of the substrate 11, but it is even more preferable to heat at a temperature higher than the thermal decomposition temperature. Specifically, it is preferable to heat at a temperature above the temperature at which the weight becomes 70% of the initial weight when thermogravimetric analysis is performed by raising the temperature from room temperature (25°C) at a rate of 5°C / min under the heating atmosphere (typically air) of the removal unit U4. Furthermore, it is more preferable to heat at a temperature above the temperature at which the weight becomes 50% of the initial weight when similar thermogravimetric analysis is performed, and even more preferable to heat at a temperature above the temperature at which the weight becomes 20% of the initial weight. This makes it possible to shorten the time required to remove the substrate 11 and to increase the removal rate of the substrate 11.

[0160] In other words, when the removal unit U4 removes the substrate 11 by heating, it is preferable that the first particles P1 and the second particles P2 are made of materials having a higher thermal decomposition temperature than the substrate 11. Generally, inorganic materials tend to have higher thermal decomposition temperatures than organic materials, so it is preferable that the materials of the first particles P1 and the second particles P2 are inorganic materials, and the material of the substrate 11 is an organic material such as resin. Furthermore, when the removal unit U4 removes the substrate 11 by heating, it is preferable that the first particles P1 and the second particles P2 are made of materials having a softening point temperature higher than the thermal decomposition temperature of the substrate 11. In addition, as described above, it is preferable to use particles made of materials selected from positive electrode materials, solid electrolyte materials, and negative electrode materials for lithium-ion batteries and all-solid-state batteries as the first particles P1 and the second particles P2. This makes it possible to manufacture all-solid-state batteries, electrode sheets such as positive electrode sheets and negative electrode sheets, solid electrolyte sheets, etc.

[0161] The removal unit U4 preferably removes 90% or more by weight of the substrate in the laminate 13 by heating, more preferably 95% or more by weight, and even more preferably 97% or more by weight. At this time, it is preferable that the substrate is burned or gasified and released to the outside as a gas. By using a substrate made of an organic material such as resin as the substrate, the removal of the substrate by heating can be facilitated. As materials constituting the substrate, polyesters such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and polyamides such as nylon can be used. Among these, PET is preferred from the viewpoint of decomposition temperature and the low toxicity of the gas generated during thermal decomposition.

[0162] The removal unit U4 preferably exhausts the released gas to the outside of the heating furnace 42 using the depressurization means 423b. By maintaining an oxidizing atmosphere inside the heating furnace 42 using the atmosphere gas supply means 423a, etc., the substrate can be burned and removed.

[0163] When the substrate material is gasified and released as a gas from the laminate 13 by thermal decomposition, the individual material layers within the laminate 13 may be pushed up, causing a change in shape. Therefore, when heating in the heating furnace 42, it is preferable to pressurize the laminate 13 with the pressurizing means 422 before, during, or after heating, or during cooling or heat dissipation.

[0164] [Post-processing unit] The post-processing unit U5 is a unit that performs post-processing on the three-dimensional object 14 formed by the removal unit U4.

[0165] The type of post-processing performed by the post-processing unit U5 is not particularly limited, but one example is further heating and firing of the three-dimensional object 14. If the post-processing unit U5 performs heat treatment as a post-processing step, the removal unit U4 may also perform that function. By firing the three-dimensional object 14, the granular materials and other materials within each material layer can be sintered together.

[0166] The post-processing unit U5 may also have pressurizing means for heating the three-dimensional object 14, similar to the removal unit U4. The post-processing unit U5 may pressurize the three-dimensional object 14 by the pressurizing means before or during heating as a post-processing step, or during cooling or heat dissipation after heating.

[0167] Furthermore, the post-processing unit U5 may perform a process to remove at least one type of material that constitutes the three-dimensional object 14 from the three-dimensional object 14. For example, when the three-dimensional object 14 is formed with a first particle material P1 and a second particle material P2, the first particle materials P1 may be sintered together to fix or integrate them, and then only the second particle material P2 may be selectively removed by air blowing or the like. In this case, the second particle material P2 functions as a so-called support material in additive manufacturing and has the function of supporting the first particle material P1 during layering. This makes it possible to fabricate a three-dimensional object using the first particle material P1. When fixing only the first particle materials P1 together, for example, a material with a higher sintering temperature than the first particle material P1 may be used as the second particle material P2, and it may be heated at a temperature above the sintering temperature of the first particle material P1 but below the sintering temperature of the second particle material P2.

[0168] As described above, this embodiment makes it possible to improve the throughput when manufacturing three-dimensional objects by additive manufacturing.

[0169] According to this embodiment, electrode sheets such as positive electrode sheets and negative electrode sheets, and solid electrolyte sheets can be manufactured by forming a material layer on a substrate using a material containing a positive electrode material, negative electrode material, or solid electrolyte for lithium-ion batteries or all-solid-state batteries. According to this embodiment, particulate materials can be densely arranged in any pattern, making it possible to provide electrode sheets and solid electrolyte sheets with high electrochemical properties. Furthermore, when manufacturing electrode sheets, a good interface can be formed between the positive electrode material or negative electrode material and the material containing the solid electrolyte by patterning a material containing a solid electrolyte in addition to the positive electrode material or negative electrode material. In addition, all-solid-state batteries can be manufactured by forming a three-dimensional object using a material containing a positive electrode material, a negative electrode material, and a solid electrolyte. [Examples]

[0170] (Examples 1-9) Material layers 1 to 9 were formed using the material layer forming apparatus 1 described above.

[0171] In the first belt device 22a and the second belt device 22b, a polyimide resin belt was used as the conveying member 224. In addition, stainless steel metal rollers were used as the drive rollers 221 and 222, and a soft roller with a stainless steel core and an elastic layer of silicone rubber was used as the pressure roller 223.

[0172] A polyester (PET) sheet was used as the first substrate 11a. A honeycomb pattern of uneven surfaces was formed on the first substrate 11a using a pattern forming device 23. First, an ultraviolet-curable resin (ultraviolet-curable liquid silicone rubber, PDMS, manufactured by Shin-Etsu Chemical Co., Ltd.) was coated onto the first substrate 11a. Then, a film mold (standard mold, manufactured by Soken Chemical Co., Ltd.) having a honeycomb pattern of uneven surfaces corresponding to the desired uneven surface pattern was pressed onto the ultraviolet-curable resin on the first substrate 11a. With the film mold pressed in place, ultraviolet light was irradiated with a UV lamp to cure the ultraviolet-curable resin, and the film mold was released.

[0173] Figure 14 shows the structure of the first substrate 11a having a surface uneven pattern 111a formed thereon. Figure 14(a) is a top view of the first substrate 11a, and Figure 14(b) is a cross-sectional view AA of Figure 14(a). As shown in Figure 14, a honeycomb-like uneven pattern with hexagonal frame-shaped protrusions is formed on the surface of the first substrate 11a. Here, as shown in Figure 14(b), the distance between adjacent protrusions (i.e., the width of the recess) is k (μm), the pitch between adjacent protrusions is s (μm), and the height of the protrusions (i.e., the depth of the recess) is d (μm). In the following embodiment, the shape measurement of the uneven pattern was performed using a non-contact surface / layer cross-sectional shape measurement system (VertScan2.0 manufactured by Ryoka Systems Co., Ltd.).

[0174] As the second base material 11b, a polyester (PET) sheet with an acrylic adhesive applied to its surface was used.

[0175] The first particle P1 and the second particle P2 are LiCoO2 (hereinafter referred to as LCO), Li 1.5 Al 0.5 Ge 1.5 P3O 12 (hereinafter referred to as LAGP), Li 6.75 La3Zr 1.75 Nb 0.25 O 12 Li(LLZ), Li3BO3 (LBO), or graphite were used. Lithium cobaltate (LCO) is the positive electrode material, aluminum-substituted lithium germanium phosphate (LAGP), LLZ, and lithium borate (LBO) are materials containing a solid electrolyte, and graphite is the negative electrode material. Lithium cobaltate (LiCoO2) manufactured by Nippon Chemical Industrial Co., Ltd. can be used. Similarly, Li 1.5 Al 0.5 Ge 1.5 P3O 12 Li can be used. 6.75 La3Zr 1.75 Nb 0.25 O 12It is possible to use lithium borate manufactured by Toyoshima Seisakusho Co., Ltd., and the abbreviation may be LLZNb instead of LLZ. Lithium borate (Li3BO3) manufactured by Toyoshima Seisakusho Co., Ltd. is also possible. Graphite (SGP-5) manufactured by SEC Carbon Co., Ltd. is also possible.

[0176] Furthermore, as the support material S1 and support material S2, either a standard carrier (standard carrier P02 manufactured by the Image Society of Japan) or a proprietary carrier (manufactured by Canon) was used, which are magnetic particles. The proprietary carrier is a particle in which resin is filled into the pores of porous ferrite particles. When forming material layer 1, the proportion of the first particle P1 in filler 241a was set to 17% by weight, and the proportion of the second particle P2 in filler 241b was set to 45% by weight.

[0177] Material layers 1 to 9 were formed on the second substrate 11b based on the first embodiment, by changing the size (spacing k, pitch s, depth d) of the uneven pattern 111a formed on the first substrate 11a and the filler, as shown in Table 1. When forming material layer 8, a polyester sheet was used as the first substrate 11a, and OP-4003 manufactured by DIC Corporation was used as the UV-curable resin.

[0178] [Table 1]

[0179] The particle sizes of each particle in the filler used to form each material layer are shown in Table 2. In Table 2, the particle sizes (r10, r50, r90) represent the cumulative particle size distribution in the volume-based particle size distribution, where r10 is the particle size at 10% cumulative, r50 is at 50% cumulative, and r90 is at 90% cumulative. In other words, r50 is the median diameter. The particle size was measured using a laser diffraction scattering particle size distribution analyzer (LA-960, manufactured by Horiba, Ltd.).

[0180] [Table 2]

[0181] The density of the formed material layers 1 to 9 was evaluated using the following method. Specifically, the second substrate 11b on which each material layer was formed was photographed from the material layer side using an optical microscope, and the particle coverage rate in the observation area was measured using image processing software (Adobe Photoshop®). The evaluation was as follows: A if the coverage rate was 85% or more, B if the coverage rate was between 80% and 85% and B, and C if the coverage rate was less than 80%. If the coverage rate is less than 80%, it is difficult to form a sufficiently dense material layer even if post-processing such as sintering is applied to the formed material layer.

[0182] As shown in Table 2, all of material layers 1 to 9 achieved a coverage rate of 80% or more, indicating the formation of dense material layers. However, for material layers 2 and 4, the size of the second particles P2 is larger compared to the other material layers. In the case of material layer 2, the median diameter r50 of the second particles P2 is larger than the recesses in the uneven pattern formed by the first particles P1, so the proportion of second particles P2 that can contact the bottom of the recesses is small. Similarly, in material layer 4, although the median diameter r50 of the second particles P2 is smaller than the recesses in the uneven pattern formed by the first particles P1, the difference is small, resulting in a smaller proportion of second particles P2 that can contact the bottom of the recesses compared to the other material layers. Therefore, it is considered that the coverage rate for material layers 2 and 4 was slightly lower than that of the other material layers.

[0183] (Examples 10-20) Next, three-dimensional objects were formed using the additive manufacturing system 100 described above. Specifically, a material layer forming apparatus 1 shown in Figure 2 was used as a material layer forming unit U2 to form a material layer on a substrate, the substrates with the material layers formed on them were stacked, and the substrates were removed from the stack by heating to form three-dimensional objects: electrode sheets, electrolyte sheets, and all-solid-state batteries.

[0184] A second substrate 11b, each with its respective material layer formed in the same manner as in Examples 1-9, was stacked in multiple layers as shown in Table 3 to form a laminate. The laminate was then transferred to a heating furnace and heated. The weight of the laminate was measured before and after heating, and the weight ratio (wt%) of the substrate before and after heating was evaluated. In addition, the top and bottom surfaces of the heated laminate were sputtered with gold, and a tester was applied to the top and bottom surfaces to check for leaks. Those that leaked were designated as B, and those that did not leak were designated as A. The results are shown in Table 3. Those that leaked can be evaluated as having a resistance value of approximately 10Ω or less.

[0185] [Table 3]

[0186] Figure 15 shows the results of thermogravimetric analysis of the second substrate 11b, a polyester (PET) sheet. Thermogravimetric analysis was performed using a differential thermobalance (TG-DTA, Rigaku Corporation) in air, with the temperature increased at a rate of 5°C / min from room temperature (25°C). From Figure 15, the temperature at which the initial weight was reduced to 50% was approximately 400°C, and the temperature at which the initial weight was reduced to 20% was approximately 500°C. In addition, the thermal decomposition temperature for LCO, LAGP, LLZ, LBO, and graphite was 510°C or higher.

[0187] As shown in Table 3, when laminates were formed by changing the material layers, the number of layers, and the heating conditions, three-dimensional objects could be formed in all examples. Furthermore, when the heating temperature was increased or the heating time was extended, the removal rate of the base material could be further increased (Examples 10-20). In Examples 10 and 11, laminates 1 and 2 had a base material residue of more than 10% by weight after heating in the furnace. Therefore, it is thought that when the base material was thermally decomposed by heating, gasification was insufficient, and the base material remained in the laminate as soot, resulting in a low resistance of the laminate. On the other hand, in Examples 12-20, laminates 3-11 had a base material residue rate of 10% by weight or less after heating in the furnace, and no leaks were detected in the leak test.

[0188] (Examples 21-23) Next, multiple second substrates 11b, each with its own material layer, were stacked to form a laminate. The laminate was then transferred to a heating furnace and heated in the furnace. Furthermore, the laminate was transferred to a firing furnace and heated and fired in the firing furnace. This completed the fabrication of an all-solid-state battery.

[0189] (Example 21) On a Si substrate sputtered with gold on its surface, four material layers 9 (graphite), two material layers 5 (LAGP), and two material layers 1 (LCO+LAPG) were sequentially layered, each layer attached to the substrate. The formed laminate was then placed in a heating furnace and heated at 500°C for 30 minutes under air (atmosphere) to remove the substrate. Subsequently, it was heated in a sintering furnace under vacuum at 700°C for 1 hour. This process fabricated an all-solid-state battery 1.

[0190] (Example 22) Two material layers 5 (LAGP) and two material layers 1 (LCO+LAPG) were sequentially laminated onto a graphite molded body, along with the substrate. The formed laminate was then placed in a heating furnace and heated at 500°C for 30 minutes under air (atmosphere) to remove the substrate. Subsequently, it was heated in a sintering furnace at 700°C for 1 hour under vacuum. This produced all-solid-state battery 2. The graphite molded body was formed by pressurizing graphite powder with a hydraulic press at 250 MPa.

[0191] (Example 23) Four layers of material layer 9 (graphite), along with the substrate, were laminated beneath the LLZ molded body, and two layers of material layer 7 (LCO+LBO), along with the substrate, were laminated on top of the LLZ molded body. The formed laminate was then placed in a heating furnace and heated in the furnace under air (atmosphere) at 500°C for 30 minutes to remove the substrate. After the substrate was removed, the laminate was pressurized and then heated in a sintering furnace under vacuum at 700°C for 1 hour. This produced the all-solid-state battery 3. The LLZ molded body was formed by pressurizing LLZ powder with a hydraulic press at 250 MPa, and then firing it under air at 1150°C for 36 hours. The top and bottom surfaces of the formed LLZ molded body were polished with sandpaper.

[0192] Table 4 shows the evaluation results for all-solid-state batteries in Examples 21-23.

[0193] [Table 4]

[0194] Each solid-state battery was evaluated by performing charge-discharge tests using an electrochemical apparatus (Solartron 1255WB model). Specifically, a battery was rated A if its charge capacity was 10 mAh / g or higher and its discharge capacity was 1 / 10 or more of that. All solid-state batteries were confirmed to be able to charge and discharge and function as secondary batteries.

[0195] In summary, according to this embodiment, it was possible to manufacture electrode sheets and electrolyte sheets for batteries, as well as all-solid-state batteries. Because the particles constituting each of these components could be patterned, it was possible to manufacture batteries having a three-dimensional structure in which the particles were patterned in both the planar and stacking directions.

Claims

1. A first step of arranging first particles in a pattern on a substrate, A method for manufacturing a material layer, comprising a second step of arranging second particles in a region on the substrate where the first particles are not arranged, A method for manufacturing a material layer, characterized in that the second step involves rubbing a support material on which the second particles are supported against the substrate on which the first particles are arranged.

2. The method for manufacturing a material layer according to claim 1, characterized in that the supporting material is one of magnetic particles, brush fibers, and an elastic material.

3. The substrate has an uneven pattern formed by the first particles, The median diameter of the second particle is smaller than the opening diameter of the recess in the uneven pattern. The method for manufacturing a material layer according to claim 1 or 2, characterized in that the average diameter of the support material is larger than the opening diameter of the recess of the uneven pattern.

4. A method for manufacturing a material layer according to any one of claims 1 to 3, characterized in that, in a region on the substrate where the first particles are not arranged, the second particles can come into contact with the substrate, and the support material cannot come into contact with the substrate.

5. The method for manufacturing a material layer according to any one of claims 1 to 4, characterized in that the substrate has an adhesive layer on its surface.

6. The first step described above is, A step of arranging the first particles in a pattern on a transfer substrate different from the aforementioned substrate, A method for manufacturing a material layer according to any one of claims 1 to 5, comprising the step of transferring the first particles from the transfer substrate to the substrate.

7. The transfer substrate has a transfer-oriented uneven pattern formed on its surface. The method for manufacturing a material layer according to claim 6, characterized in that the step of arranging the first particles in a pattern on the transfer substrate includes the step of rubbing a second support material on which the first particles are supported against the transfer uneven pattern.

8. The method for manufacturing a material layer according to claim 7, characterized in that the second support material is any of magnetic particles, brush fibers, and an elastic material.

9. The median diameter of the first particle is smaller than the opening diameter of the recess of the transfer pattern. The method for manufacturing a material layer according to claim 7 or 8, characterized in that the average diameter of the second support material is greater than the opening diameter of the recess of the transfer pattern.

10. A method for manufacturing a material layer according to any one of claims 7 to 9, characterized in that the first particles can contact the bottom of the recesses of the transfer pattern, and the second support material cannot contact the bottom of the transfer pattern.

11. The first step described above is, A step of arranging the liquid in a pattern on the substrate, A method for manufacturing a material layer according to any one of claims 1 to 5, comprising the step of applying first particles to the substrate on which the liquid is arranged in a pattern, such that the first particles adhere to the liquid.

12. The method for manufacturing a material layer according to claim 11, characterized in that the step of arranging the liquid in a pattern on the substrate is a step of applying the liquid to the substrate by an inkjet method.

13. A method for manufacturing a material layer according to claim 11 or 12, further comprising the step of removing the first particles that did not adhere to the liquid after the step of applying the first particles.

14. A material layer formation process in which a material layer is formed on a substrate, A lamination step of stacking a plurality of substrates on which the material layers are each formed to form a laminate, The process includes a removal step of removing the plurality of substrates from the laminate, The aforementioned material layer formation step is, A first step of arranging first particles in a pattern on a substrate, The process includes a second step of placing second particles in areas on the substrate where the first particles are not present, A method for manufacturing a three-dimensional object, characterized in that the second step involves rubbing a support material on which the second particles are supported against the substrate on which the first particles are arranged.

15. The method for manufacturing a three-dimensional object according to claim 14, characterized in that the removal step involves removing the substrate by heating.

16. At least one of the first particles and the second particles is a solid electrolyte material. The method for producing a three-dimensional object according to claim 14 or 15, characterized in that the three-dimensional object is a solid electrolyte sheet.

17. At least one of the first particles and the second particles is a material for forming an electrode. The method for manufacturing a three-dimensional object according to claim 14 or 15, characterized in that the three-dimensional object is an electrode sheet.

18. The material layer formation step comprises the steps of forming a material layer containing a solid electrolyte material and forming a material layer containing a positive electrode material or a negative electrode material. The method for manufacturing a three-dimensional object according to claim 14 or 15, characterized in that the three-dimensional object is an all-solid-state battery.

19. A first arrangement means for arranging first particles in a pattern on a substrate, A material layer forming apparatus having a second arrangement means for arranging second particles in a region on the substrate where the first particles are not arranged, A material layer forming apparatus characterized in that the second arrangement means is configured to rub a support material on which the second particles are supported against the substrate on which the first particles are arranged.

20. A material layer forming unit that forms a material layer on a substrate, A lamination unit that stacks the plurality of substrates on which the material layers are each formed to form a laminate, The laminate includes a removal unit for removing the plurality of substrates from the laminate, The aforementioned material layer forming unit is A first arrangement means for arranging first particles in a pattern on a substrate, The system includes a second arrangement means for arranging second particles in areas on the substrate where the first particles are not present, The additive manufacturing system is characterized in that the second arrangement means is configured to rub a support material carrying the second particles against the substrate on which the first particles are arranged.

21. A material layer comprising: a pattern layer comprising: a first region comprising a first inorganic material and having a plurality of first particles arranged therein before sintering; a second region comprising a second inorganic material and having a plurality of second particles arranged therein before sintering; and a substrate on which the pattern layer is provided.

22. The material layer according to claim 21, characterized in that the first inorganic material comprises at least one of a positive electrode material, an electrolyte material, and a negative electrode material.

23. The material layer according to claim 21 or 22, characterized in that the first inorganic material and the second inorganic material are composed of different materials from each other.

24. The material layer according to any one of claims 21 to 23, wherein the pattern layer has a repeating pattern in which a plurality of the first regions are repeatedly arranged in the in-plane direction of the substrate at a predetermined period, and the second regions are provided between the first regions.

25. The material layer according to any one of claims 21 to 24, characterized in that the substrate has different thermal decomposition properties or solubility from the first region and the second region.

26. The material layer according to any one of claims 21 to 25, wherein the substrate is composed of an organic material.

27. A material layer comprising a sheet-like pattern layer having a pattern portion exhibiting a repeating pattern within the layer, and a material layer in which a plurality of particles are held in the pattern portion, wherein the particles include at least one of a positive electrode material, a solid electrolyte, and a negative electrode material.

28. The material layer according to claim 27, characterized in that the pattern has a predetermined repeating period within the layer.

29. The material layer according to claim 27 or 28, characterized in that the pattern layer differs from the particles in terms of solubility in a solvent or thermal decomposition.

30. The material layer according to any one of claims 27 to 29, wherein the pattern portion comprises a first pattern portion in which a first group of particles is held and a second pattern portion in which a second group of particles is held, and the first group of particles and the second group of particles differ in average particle size, and the surface density of the held particles differs between the first pattern portion and the second pattern portion.

31. The material layer according to claim 30, characterized in that the first group of particles and the second group of particles with different average particle sizes include at least one combination of lithium cobaltate and lithium cobaltate, aluminum-substituted lithium germanium phosphate and aluminum-substituted lithium germanium phosphate, LLZ and LLZ, and graphite and graphite.

32. The material layer according to claim 30 or 31, characterized in that the first pattern portion and the second pattern portion have the same repeating period within the pattern layer.

33. The material layer according to any one of claims 27 to 29, wherein the patterned portion comprises a first patterned portion that holds a first group of particles and a third patterned portion that holds a third group of particles, and the composition of the first group of particles and the third group of particles are different.

34. The material layer according to claim 33, characterized in that the first group of particles and the third group of particles with different compositions include at least one combination of lithium cobalt oxide and aluminum-substituted lithium germanium phosphate, lithium cobalt oxide and LLZ, and lithium cobalt oxide and lithium borate.

35. A laminate characterized in that a plurality of material layers are laminated, each layer comprising the pattern layer and the substrate described in any one of claims 21 to 34.

36. A laminate characterized by comprising a pattern layer comprising a first region comprising a first inorganic material and having a plurality of first particles arranged therein before being sintered, and a second region comprising a second inorganic material and having a plurality of second particles arranged therein before being sintered, wherein a plurality of such pattern layers are stacked.

37. The laminate according to claim 35 or 36, characterized in that the pattern layer composed of the first region and the second region includes portions where the phases of the pattern layers are not aligned when viewed in the stacking direction.

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