Material sheet, laminate, material sheet manufacturing method and laminate manufacturing method

Abstract

To provide a manufacturing method for a material layer in which a desired material can be arranged in any pattern to form a material layer containing the desired material at a high density.SOLUTION: A manufacturing method for a material layer comprises: a first process S101 of arranging first particles P1 in a pattern on a base material 11; and a second process S102 of arranging second particles in an area on the base material 11 where the first particles P1 are not arranged. The second process S102 includes a step of sliding a carrier material S2 carrying the second particles P2 onto the base material 11 on which the first particles P1 are arranged.SELECTED DRAWING: Figure 1

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 a laminated manufacturing system.

Background Art

[0002] A laminated manufacturing method has attracted attention, in which a three-dimensional object of a desired shape is formed by stacking material layers formed of various materials such as metals, ceramics, and resins. In recent years, the application fields of the laminated manufacturing method have been expanding, and not only mock-ups and parts made of a single type of material are formed, but also various devices such as batteries, electronic components, and wiring boards made of multiple types of materials are being formed.

[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 separately applied by an inkjet method to form a layer in which a desired material is arranged in a pattern. After drying the obtained layer to form a material layer, a material layer is further formed in the same manner on the material layer. By repeating this, an all-solid-state battery having a structure in which a positive electrode active material, a polymer electrolyte, and a negative electrode active material are three-dimensionally arranged in an arbitrary pattern is formed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[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 has been a problem that the density of the materials that are components in the formed material layer becomes low.

[0006] Therefore, in the present invention, in view of the above-described 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 first region and the second region, 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 the pattern layers are laminated in plurality.

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 the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Figure 11

Figure 12

Figure 13

Figure 14

Figure 15

Figure 16

Mode for Carrying Out the Invention

[0010] Hereinafter, with reference to the drawings, embodiments for carrying out the present invention will be exemplarily described in detail. However, the dimensions, materials, shapes, relative positions, etc. of each member described in the following embodiments are not intended to limit the scope of the present invention only to those, unless otherwise specifically described.

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

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

[0013] The method for manufacturing a material layer according to the present embodiment includes the following steps (1) to (2). Details of each step will be described later. Step (1): First step (S101) of arranging first particles in a pattern on a substrate Step (2): Second step (S102) of arranging second particles in a region on the substrate where the first particles are not arranged Further, the second step S102 includes a step of rubbing a carrier carrying the second particles against the substrate on which the first particles are arranged.

[0014] In the method for manufacturing a material layer according to the present embodiment, after arranging the first particles on a substrate, by rubbing a carrier carrying the second particles on the substrate, the second particles can be densely arranged in the regions on the substrate where the first particles are not arranged. While the second particles are rubbed on the substrate together with the carrier, they are constrained by the adhesion force of the substrate surface and the adhesion force of the first and second particles arranged on the substrate surface, and are densely arranged. Thereby, a plurality of particles can be arranged in an arbitrary pattern, and a material layer with high density can be formed.

[0015] Note that "rubbing the carrier on the substrate" includes the case where the carrier does not directly contact the substrate itself. That is, the above expression includes the case where the carrier carrying the second particles is rubbed on the substrate so that only the second particles directly contact 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 is prepared, and a carrier carrying the first particles is rubbed on the transfer substrate so that the first particles are densely arranged in the concave portions of the uneven pattern, and this is transferred to another substrate, whereby the first particles can be arranged in a pattern on the substrate. Alternatively, after applying a liquid in a pattern on the substrate, a powder containing the first particles may be adhered to the liquid, whereby the first particles can be arranged in a pattern on the substrate. Hereinafter, the case where a carrier carrying the first particles is rubbed on a transfer substrate so that the first particles are densely arranged in the concave portions of the surface of the transfer substrate and then these first particles are transferred to a substrate will be described.

[0017] FIG. 2 is a diagram schematically showing the configuration of a material layer forming apparatus according to the present embodiment.

[0018] The material layer forming apparatus 1 according to the present embodiment includes a first storage container 21a for storing and supplying a first base material 11a, a first belt device 22a for transporting the first base material 11a, and a pattern forming device 23 for forming a concavo-convex pattern on the first base material 11a. The material layer forming apparatus 1 includes a first filling device 24a for arranging first particles P1 in the concave portions of the concavo-convex pattern formed on the first base material 11a. The material layer forming apparatus 1 includes a second storage container 21b for storing and supplying a second base material 11b, and a second belt device 22b for transporting the second base material 11b. The material layer forming apparatus 1 has a transfer portion 25a in which 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 base material 11a to the second base material 11b at the transfer portion 25a. Further, the material layer forming apparatus 1 includes a second filling device 24b for arranging second particles P2 in the non-transfer portion on the second base material 11b. Note that devices with low relevance in explaining the effects of this case, such as a peeling and recovery device for peeling and recovering the first base material 11a after transfer from the first belt device 22a and each cleaning device, etc., are omitted from the illustration and detailed description.

[0019] In the material layer forming apparatus 1, the pattern forming device 23, the first filling device 24a, and the transfer portion 25a correspond to a first arranging means for arranging the first particles P1 in a pattern on the second base material 11b. Also, the second filling device 24b corresponds to a second arranging means for arranging the second particles P2 in a region on the second base material 11b where the first particles P1 are not arranged.

[0020] Hereinafter, a method for forming the material layer 12 on the base material 11 by the material layer forming apparatus 1 will be described along the flow for each process.

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

[0022] The material of the first base material 11a is not particularly limited. However, when the ultraviolet curable ink is applied by a pattern forming device 23 (described later), at least the surface thereof is preferably made of a material having high wettability with respect to the ultraviolet curable ink. Further, the surface of the first base material 11a is preferably smooth. As the first base material 11a, typically, a resin sheet such as polyester which has been subjected to hydrophilic treatment or lipophilic treatment according to the ultraviolet curable ink (aqueous or oil-based) to be used can be used. Note that, as the first base material 11a, a base material separated individually like cut paper may be used, or a continuous base material wound in a roll like roll paper, or a continuous base material folded alternately like continuous paper may be used.

[0023] The first belt device 22a conveys the supplied first base material 11a to the pattern forming position of the pattern forming device 23. The first belt device 22a includes drive rollers 221a and 222a, a pressure roller 223a, and a belt-like conveying member 224a suspended therefrom. At this time, the pressure roller 223a rotates in a driven manner.

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

[0025] In the present embodiment, the first belt device 22a is used as the conveying device for conveying the first base material 11a. However, a roller device can also be used instead of the belt device. The same applies to the second belt device 21b described later.

[0026] The pattern forming device 23 forms a fine concavo-convex pattern on the first substrate 11a conveyed to the pattern forming position. As a method for forming the concavo-convex pattern, there is no particular limitation, but a UV imprint method, a thermal imprint method, a UV inkjet method, a printing method, a laser etching method, etc. can be used. When the pattern forming device 23 forms a concavo-convex pattern by the UV imprint method, the pattern forming device 23 has a coating means for coating an ultraviolet curable composition on the first substrate 11a. Further, the pattern forming device 23 has an imprinting means for imprinting a mold having a concavo-convex 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, as the ultraviolet curable composition, an ultraviolet curable type liquid silicone rubber (PDMS) or resin can be used, as the mold, a film mold can be used, and as the light source, a UV lamp can be used.

[0027] When the first filling device 24a fills the concave portions with the first particles P1 using the carrier S1 carrying the first particles P1, the opening diameter of the concave portions of the concavo-convex pattern on the first substrate 11a is preferably larger than the median diameter of the first particles P1 and smaller than the average size of the carrier S1. Here, the opening diameter of the concave portions of the concavo-convex pattern is preferably the opening diameter in the short side direction of the concave portions, and more preferably the maximum opening diameter in the short side direction of the concave portions. Thereby, the first particles P1 can contact the bottom (typically the bottom surface) of the concave portions of the concavo-convex pattern, and the carrier S1 cannot contact the bottom of the concave portions. Thereby, the first particles P1 contacting the bottom of the concave portions can be captured by the concavo-convex pattern, while the carrier S1 can be prevented from being captured by the concavo-convex pattern. In other words, it is preferable that the first particles P1 can contact the bottom of the concave portions of the concavo-convex pattern and the first carrier S1 cannot contact the bottom of the concave portions of the concavo-convex pattern.

[0028] In the present embodiment, the uneven pattern is formed on the first base material 11a by the pattern forming device 23. However, the present invention is not limited to this, and a base material having an uneven pattern formed on its surface in advance may be used as the first base material 11a. Further, the uneven pattern may be directly formed on the surface of the conveying member 224a of the first belt device 22a by the pattern forming device 23, or a conveying member having an uneven pattern on its surface may be used as the conveying member 224a. In this case, in view of durability, a metal belt such as stainless steel or aluminum is used, and it is preferable to form an uneven pattern on the surface by a microfabrication technique such as laser etching, wet etching, or dry etching.

[0029] The first base material 11a having an uneven pattern formed on its surface is conveyed by the first belt device 22a to the filling position of the first filling device 24a.

[0030] FIG. 3 is a diagram schematically showing the configuration of the filling device according to the present embodiment. Hereinafter, the configuration of the first filling device 24a will be described, but the same applies to the second filling device 24b.

[0031] The first filling device 24a includes a filling container 242a that stores the filler 241a, a stirring screw member 243a that stirs and conveys the filler 241a, a recovery member 244a that recovers the filler, and a magnetic member 247a.

[0032] The filler 241a includes first particles P1 and a carrier S1 that carries the first particles P1. The filler 241a is a mixture of a plurality of powders including a powder composed of a plurality of first particles P1 and a powder composed of a plurality of carriers S1. The filler 241a stored in the filling container 242a is sufficiently mixed and triboelectrically charged when being stirred and conveyed by the stirring screw member 243a. As a result, the first particles P1 are carried on the surface of the carrier S1.

[0033] The first particle P1 is a particle filled in the concave portion of the concavo-convex pattern formed on the first base material 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 may be a particulate organic material such as resin particles.

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

[0035] In addition, in order to improve the chargeability and aggregability, particles other than the first particle P1 and the carrier S1 may be added to the filler 241a, or the surface of the first particle P1 may be coated with a resin composition. Further, in order to improve the conductivity of the particle P1, as a conductive aid, a form containing carbon black such as acetylene black, metal, or alloy powder, or a form in which the conductive aid applied to the surface of the first particle P1 is coated is included as a modification example of the present embodiment.

[0036] The recovery member 244a has a roller 245a rotatable in the direction of arrow d2 in the figure, and a magnet 246a disposed inside the roller 245a and fixed to the filling container 242a. Further, the magnetic member 247a is disposed to face the filling container 242a via the conveying member 224a, and has a magnet 248a inside thereof. The magnet 246a has a plurality of N poles and S poles alternately arranged along the rotation direction of the recovery member 244a. The magnet 248a has a plurality of N poles and S poles alternately arranged along the conveying direction of the conveying member 224a. Further, the magnet 246a has a magnetic pole of a different polarity (N1 pole in this embodiment) at a position closest to and facing the most 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 arranged at the most downstream position. Note that the magnet 246a and the magnet 248a may be composed of a plurality of magnets, and the types of magnets constituting the magnet 246a and the magnet 248a are not particularly limited. For example, permanent magnets such as ferrite magnets, neodymium magnets, rare earth magnets such as samarium cobalt magnets, and plastic magnets, or means for generating a magnetic field such as an electromagnet can be used. Note that the magnet 248a may be configured to be movable in the conveying direction of the first base material 11a or the reverse direction thereof.

[0037] Note that a regulating member for regulating the filler 241a on the first base material 11a, or a recovery member for recovering again the filler 241a that cannot be completely recovered by the recovery member 244a, may be provided upstream or downstream of the recovery member 244a in the conveying direction of the conveying member 224a. As the recovery member for recovering again, in addition to a member similar to the recovery member 244a, a recovery member that performs recovery by air blowing from a simple member such as a fixed magnet or a regulating member can be used.

[0038] Next, a process of filling the first particles P1 into the recesses on the first base material 11a by the first filling device 24a will be described with reference to FIGS. 3 to 5.

[0039] When the first conveying member 224a moves in the direction of the solid arrow d1 in FIG. 3, the first base material 11a carried and conveyed by the first conveying member 224a is conveyed and conveyed to the filling position of the first filling device 24a.

[0040] The filler 241a is conveyed by the stirring screw member 243a and supplied onto the first base material 11a (dotted line a in FIG. 3). At this time, a magnetic field is formed by the magnetic member 248a and the recovery member 244a, and the filler 241a containing the carrier S1 which is a magnetic particle forms a plurality of magnetic spikes on the first base material 11a by the magnetic field. The filler 241a supplied onto the first base material 11a is conveyed on the first base material 11a in a state where magnetic spikes are formed as the first base material 11a moves (dotted line b in FIG. 3).

[0041] FIG. 4 is a schematic diagram of the filler 241a conveyed on the first base material 11a. For the sake of explanation, the filler 241a other than the filler forming one magnetic spike is not shown. The filler 241a on the first base material 11a forms magnetic spikes along the magnetic force lines of the formed magnetic field as described above, and is conveyed while changing the shape of the magnetic spikes as shown in FIGS. 4(a), 4(b), and 4(c) as the first base material 11a moves. At this time, since a particularly strong magnetic force acts in the vicinity of the magnet 248a, the conveying speed v2 of the filler 241a is smaller than the moving speed v1 of the first base material 11a when the filler 241a moves away from the magnetic pole, and is larger in the opposite case. That is, the filler 241a on the first base material 11a has a non-zero relative speed with respect to the first base material 11a.

[0042] FIG. 5 is an enlarged view of the vicinity of the surface of the first base material 11a in FIG. 4. Although not shown in FIG. 4, as shown in FIG. 5, an uneven pattern 111a is formed on the first base material 11a. The filler 241a contacts the uneven pattern 111a and is conveyed together with the first base material 11a while having a non-zero relative speed with respect to the first base material 11a while receiving a magnetic force (solid line Fm in the figure) in a direction perpendicular to the surface of the first base material 11a. As a result, the first particles P1 carried on the carrier S1 are conveyed while being rubbed against the uneven pattern 111a on the surface of the first base material 11a. At this time, since the particle size of the first particles P1 is smaller than the opening diameter of the concave portion of the uneven pattern 111a and the particle size of the first carrier S1 is larger than the opening diameter of the concave portion, the first particles P1 can contact the bottom surface (bottom portion) of the concave portion of the uneven pattern 111a, but the carrier S1 cannot contact. That is, only the first particles P1 in the filler 241a selectively contact the bottom surface of the concave portion. The first particles P1 that have contacted the bottom surface of the concave portion are strongly constrained by the physical restraint force due to the structure of the uneven pattern 111a and the electrostatic adhesion force and adhesive force with the first base material 11a and the structural material constituting the uneven pattern 111a, and are detached from the carrier S1.

[0043] Downstream of the magnetic member 247a, as shown in FIG. 3, a recovery member 244a is arranged with a gap from the first conveying member 224a. As the first base material 11a moves, the filler 241a conveyed near the most 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 base material 241a to the recovery member 244a and is recovered (dotted line c in FIG. 3).

[0044] As described above, in the conveying process (dotted lines a, b, c in FIG. 3), the concave portions of the uneven pattern 111a on the surface of the first base material 11a are in sufficient contact with a plurality of fillers 241a. Therefore, the first particles P1 are selectively and densely arranged in the concave portions of the uneven pattern 111a after the fillers 241a are recovered by the recovery member 244a.

[0045] In addition, in FIGS. 4 and 5, all of the first particles P1 are illustrated with the same particle size. However, in reality, there is a particle size distribution, and furthermore, depending on the material, secondary particles formed by aggregation may exist. Even in such a case, only the particles that can contact the bottom surface of the concave portion of the uneven pattern 111a are selectively and densely filled, so that coarse powder, secondary particles, etc. that may have an adverse effect on the formation of the material layer are excluded.

[0046] Thus, the filling amount of the first particles P1 into the concave portion of the uneven pattern 111a can be controlled by the size (area, width, depth) of the concave portion and the particle size of the first particles P1. Specifically, the area of the concave portion becomes the substantially filling area, and the layer thickness of the filled first particles P1 is determined by the depth of the concave portion. For example, in order to obtain a thin layer (single layer) of 50% with respect to the substrate area, the area ratio of the concave portion (the area ratio of the concave portion to the entire uneven pattern) may be controlled to 50%, and the depth of the concave portion may be controlled to be equal to or less than the particle size of the first particles P1. At this time, the opening width of the concave portion is made larger than the median diameter of the first particles P1 and smaller than the average size (here, the average particle size) of the carrier material S1. Note that the first particles P1 may have a broad particle size distribution, but the carrier material S1 preferably has a narrow particle size distribution, and more preferably is monodisperse. Thereby, it is easy to prevent the carrier material S1 from contacting the bottom (or bottom surface) of the concave portion. If the carrier material S1 can contact the bottom of the concave portion, the carrier material S1 may also be restricted and filled in the concave portion.

[0047] Furthermore, the opening width of the concave portion of the concavo-convex pattern 111a is preferably smaller than four times the particle size of the first particles P1. By making the opening width smaller than four times the particle size of the first particles P1, the probability that the first particles P1 come into contact with both the bottom surface and the side wall surface of the concave portion of the concavo-convex pattern 111a can be increased. In this way, the first particles P1 that are in multi-point contact with the concavo-convex pattern 111a are strongly constrained by the concavo-convex pattern 111a, so that the filling efficiency of the first particles P1 into the concavo-convex pattern 111a can be increased. Note that the same applies to the particle size of the second particles P2 described later and the size of the concave portion of the concavo-convex pattern formed by the first particles P1. Also, when brush fibers are used as the carrier, the "average particle size of the carrier" in the above description becomes the "average fiber diameter of the carrier".

[0048] The filler 241a recovered by the recovery member 244a is conveyed by the rotating roller 244a (dotted line d in FIG. 3). The filler 241a conveyed by the roller 244a falls into the filling container 242a under the influence of a magnetic field formed by two like-pole magnetic poles (N1, N2) that are adjacent to each other and repel each other, and gravity (dotted line e in FIG. 3). Thereafter, it is again agitated and conveyed by the agitation screw member 243a, and this is repeated thereafter.

[0049] The weight ratio of the first particles P1 to the carrier S1 in the filler 241a in the filling container 242a is determined by an inductance sensor that measures using magnetic permeability, which is common in electrophotographic devices, a patch density sensor that measures and predicts the reflection density on a substrate, or the like. Then, at least one of the first particles P1 and the carrier S1 is replenished by a replenishing means (not shown) as necessary. Thereby, stable filling over a long period becomes possible.

[0050] Here, a filling device that forms a so-called magnetic brush using magnetic particles as a carrier and fills the concave portion with a particle material has been described, but the type of the filling device is not limited to this. Brush fibers can also be used as the carrier. Alternatively, an elastic material in which at least the surface is made of an elastic body can be used as the carrier.

[0051] FIG. 6(a) is a diagram schematically showing the configuration of the filling device 24c when brush fibers are used as the carrier 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, vinyl chloride, etc. can be used. For the purpose of adjusting the chargeability and rigidity, the surface of the fibers may be surface-treated.

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

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

[0055] The supplied filler 241a is filled into the foam material on the surface of the supply member 249 and conveyed to the supply part that contacts the roller 2410. At the supply part, the filler 241a filled into the foam material is charged by contact with the brush fibers of the roller 2410 and carried by the brush fibers of the roller 2410. Further, the supply member 249 may also have a function of scraping off and refreshing the filler 241a remaining on the roller 2410. The filler 241a supplied to the roller 2410 contacts the first base material 11a due to the movement of the brush fibers.

[0056] At this time, the first particles P1 in the filler 241a can contact the bottom surface of the recess of the concavo-convex pattern 111a on the surface of the first base material 11a, but the brush fibers are prevented from contacting. That is, the fiber diameter of the brush fibers is made larger than the opening width of the recess of the concavo-convex pattern 111a. The fiber diameter of the brush fibers can be measured from an image of the brush fibers obtained through glass by applying glass to the surface of the roller 2410 and using an optical microscope. At this time, the fiber diameters of about 100 brush fibers are measured, the fiber diameter distribution is measured, and the average diameter is calculated.

[0057] Due to the movement of the conveying member 224a and / or the rotation of the roller 2410, the brush fibers of the roller 2410 are rubbed against the surface of the first base material 11a. As a result, the first particles carried by the brush fibers are densely arranged in the recesses of the concavo-convex pattern 111a on the surface of the first base material 11a.

[0058] FIG. 6(b) is a diagram schematically showing the configuration of the filling device 24d when an elastic material is used as the carrier.

[0059] The filling device 24d has the same configuration as the filling device 24c, but is different in that a roller 2411 having an elastic material is used instead of a roller 2410 having brush fibers. The roller 2411 is a roller having an elastic layer formed on its surface. The elastic layer is formed of a material having elasticity such as a rubber material such as silicone rubber, acrylic rubber, nitrile rubber, urethane rubber, fluororubber. The elastic layer may be formed by adding fine particles such as spherical resin to control the surface shape. When the elastic layer has convex portions on its surface, the size of the convex portions of the elastic layer is made larger than the size of the concave portions of the uneven pattern 111a on the surface of the first base material 11a. The size of the convex portions of the elastic layer can be measured in the same manner as the fiber diameter of the above-described brush fibers.

[0060] By the movement of the transport member 224a and / or the rotation of the roller 2411, the elastic material on the surface of the roller 2411 is rubbed against the surface of the first base material 11a. As a result, the first particles carried by the elastic material are densely arranged in the concave portions of the uneven pattern 111a on the surface of the first base material 11a.

[0061] By using brush fibers or an elastic material as the carrier as shown in FIGS. 6(a) and 6(b), it is not necessary to include magnetic particles in the filler, and the configuration of the filling device can be simplified. On the other hand, when using magnetic particles as the carrier as shown in FIG. 3, the degree of freedom in the size and shape of the carrier is higher than in the case of brush fibers or an elastic material. Also, in the case of magnetic particles, the degree of freedom in the movement of the carrier on the base material is high. For these reasons, when using magnetic particles as the carrier, particles such as the first particles P1 can be supplied more efficiently onto the base material and filled more efficiently into the concave portions on the base material. Also, when using a magnetic material as the carrier, even if the carrier deteriorates during the process, the carrier can be replenished or replaced without stopping the process.

[0062] According to the method of filling the recesses with particles by rubbing the carrier material carrying the particles as in this embodiment, compared with the filling method using a regulating member such as a blade, more dispersed particles can be supplied to the recesses, and filling can be performed stably and densely. This advantage becomes more prominent as the particle size of the particles to be filled becomes smaller because the particles are more likely to aggregate.

[0063] The first base material 11a filled with the first particles 1 in the recesses of the concavo-convex pattern 111a by the first filling device 24a is conveyed to the transfer portion 25a by the first belt device 22a.

[0064] Here, as shown in FIG. 2, the second belt device 22b has drive rollers 221b and 222b, a pressure roller 223b, and a belt-like conveying member 224b suspended therefrom, similar to the first belt device 22a. At this time, the pressure roller 223b is rotating in a driven manner. In the transfer portion 25a, the pressure roller 223a of the first belt device 22a and the pressure roller 223b of the second belt device 22b are opposed to each other.

[0065] The second base material 11b is supplied to the second belt device 22b from the second storage container 21b and conveyed in the direction of the arrow in FIG. 2. The supplied second base material 11b is conveyed in accordance with the timing when the first base material 11a is conveyed to the transfer portion 25a. In the transfer portion 25a, the first particles P1 filled in the first base material 11a are transferred to the second base material 11b. That is, the first base material 11a can also be referred to as a transfer base material for transferring the first particles P1 to the second base material 11b. Further, the concavo-convex pattern formed on the surface of the first base material 11a can also be referred to as a transfer concavo-convex pattern. Hereinafter, this transfer process will be described with reference to FIG. 7.

[0066] FIG. 7 is a diagram schematically showing the configuration of the transfer unit 25a. The transfer unit 25a is composed of a pressure roller 223a and a conveying member 224a of the first belt device 22a, and a pressure roller 223b and a conveying member 224b of the second belt device 22b. As described above, the pressure rollers 223a and 223b rotate passively, 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 the surface layer, and a nip portion is formed at the portion where the two rollers are in contact.

[0067] The first substrate 11a filled with the first particles P1 by the first filling device 24a and the second substrate 11b are conveyed at substantially the same speed by their respective conveying members (224a, 224b), and enter the nip portion formed by the contact of the pressure rollers 223a and 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 having an adhesive force to the first particles P1 greater than the adhesive force of the first substrate 11a to the first particles P1. In other words, the adhesive force of the first particles P1 to the second substrate 11b is greater than the adhesive force of the first particles P1 to the first substrate 11a. Thereby, in the nip portion, the first particles P1 on the first substrate 11a are transferred onto the second substrate 11b.

[0069] The material of the second substrate 11b is not particularly limited, and a substrate having the same material as the first substrate 11a can be used. Note that the second substrate 11b may also be a substrate individually cut off like cut paper, similar to the first substrate 11a, or a continuous substrate wound in a roll like roll paper, or a continuous substrate alternately folded like continuous paper.

[0070] The second substrate 11b is preferably subjected to a surface treatment for enhancing the adhesive force in order to transfer the contacted first particles P1. For example, the second substrate 11b preferably has an adhesive layer with an adhesive applied to its surface. The adhesive may be an acrylic adhesive, a rubber-based adhesive, a silicone-based adhesive, or may be a thermoplastic resin or a photocurable resin whose adhesive force changes due to external disturbances such as heat or light. Note that the adhesive may be applied to both surfaces of the second substrate 11b.

[0071] Further, the material layer forming apparatus 1 may have an application means such as a dispenser or an inkjet head for applying an adhesive to the surface of the second substrate 11b during conveyance.

[0072] The type and application amount of the adhesive are appropriately adjusted according to the shape and material of the uneven pattern to be used, the particle diameters and materials of the first particles P1 and the second particles P2, etc., but it is preferable that the adhesive force of the adhesive is greater than that of the uneven pattern 111a. The comparison of the adhesive force can be measured by a general method using a nanoindenter.

[0073] In the nip portion, the first particles P1 are constrained by the adhesive force generated between the first particles P1 and the second substrate 11b. When the two conveying members 224a and 224b are separated after passing through the nip portion, the first particles P1 on the first substrate 11a are transferred to the second substrate 11b.

[0074] The second substrate 11b onto which the first particles P1 are transferred is conveyed by the conveying 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 a filler 241b having the second particles P2 and the carrier S2 is accommodated in the filling container 242a instead of the filler 241a having the first particles P1 and the carrier S1.

[0076] The second filling device 24b fills the portion on the second substrate 11b where the first particles P1 are not disposed with the second particles P2. As described above, although the first particles P1 are disposed on the second substrate 11b that has passed through the transfer portion 25a, a recess is formed, so to speak, in the portion where the first particles P1 are not disposed. The second filling device 24b fills this recess with the second particles P2 by the same process as the first filling device 24a. Here, the case where magnetic particles are used as the carrier is described, but similar to the first filling device 24a, brush fibers or elastic materials may be used as the carrier.

[0077] The filler 241b includes the second particles P2 and a carrier S2 that carries the second particles P2. The filler 241b is a mixture of a plurality of powders including a powder composed of a plurality of second particles P2 and a powder composed of a plurality of carriers S2. The material of the second particles P2 is not particularly limited, and similar to the first particles P1, it may be a particulate inorganic material such as metal particles, ceramic particles, or glass particles, or it may be a particulate organic material such as resin particles. Also, the first particles P1 and the second particles P2 may be of the same material. Also, for the carrier S2, the same one as the carrier S1 can be used. Note that the first particles P1 and the second particles P2 are preferably selected from a positive electrode material of a lithium ion battery or an all-solid-state battery, a material including a solid electrolyte, and a negative electrode material.

[0078] FIG. 8 is an enlarged view of the vicinity of the surface of the second substrate 11b in the filling process by the second filling device 24b. On the second substrate 11b, a concavo-convex pattern having convex portions formed by arranging the first particles P1 and concave portions where the first particles P1 are not arranged is formed. The filler 241b contacts this concavo-convex pattern and has a non-zero relative velocity with respect to the second substrate 11b while receiving a magnetic force (solid line Fm in the figure) in a direction perpendicular to the surface of the second substrate 11b, and is conveyed together with the second substrate 11b. As a result, the second particles P2 carried on the carrier S2 are conveyed while being rubbed against the concavo-convex pattern on the surface of the second substrate 11b. At this time, the opening width of the concave portion of the concavo-convex pattern formed on the second substrate 11b is set to a size such that the second particles P2 can contact the bottom surface (second substrate 11b) of the concave portion, but the carrier S2 cannot contact it. Thereby, only the second particles P2 in the filler 241b selectively contact the bottom surface (second substrate 11b) of the concave portion. The second particles P2 that have contacted the bottom surface of the concave portion are strongly constrained by the physical restraint force due to the structure of the concavo-convex pattern and the electrostatic adhesion force and adhesive force with the second substrate 11b and the structural material (here, the first particles P1) constituting the concavo-convex pattern, and detach from the carrier S2.

[0079] FIG. 9(a) is a diagram schematically showing the second substrate 11b after the first particles P1 are transferred by the transfer portion 25a, and is a view of the second substrate 11b seen from a direction perpendicular to the substrate surface. As shown in FIG. 9(a), on the second substrate 11b, a honeycomb pattern in which arrangement regions where the first particles P1 are arranged in a regular hexagonal shape are aligned is formed. The first particles P1 are densely arranged within this regular hexagonal region, and the first particles P1 are not arranged in the other portions (the white portions in FIG. 9(a)), and the surface of the second substrate 11b is exposed. The regular hexagonal region where such first particles P1 are held is the first pattern portion, and the region of the honeycomb pattern where the second particles P2 are held and which corresponds to the gap between the first pattern portions is the second pattern portion.

[0080] FIG. 9(b) is a diagram schematically showing a second base material 11b after filling with second particles P2 by a second filling device 24b, and is a view of the second base material 11b as seen from a direction perpendicular to the base material surface. As shown in FIG. 9(b), the second particles P2 are densely arranged in the region where the first particles P1 are not arranged. Also, the first particles P1 and the second particles P2 are densely arranged at the boundary between the region where the first particles P1 are arranged and the region where the second particles P2 are arranged. Note that particles can be filled in a similar manner even in the slight gaps between the first particles P1. In this case, it is possible to fill using a filler containing particles having a particle size corresponding to the gaps between the first particles P1 by the same method as described above, and a denser thin film can be formed.

[0081] FIGS. 16(a) and (b) show a plan view and a cross-sectional view of an embodiment having a first pattern portion and a second pattern portion in which first and second particle groups P1 and P2 having different average particle sizes are spread on a base material 11b. The cross-sectional view shown in FIG. 16(b) corresponds to a cross-sectional view taken along the B-B section shown in FIG. 16(a).

[0082] As shown in FIG. 16(a), the first pattern portion and the second pattern portion corresponding to the first particle group P1 and the second particle group P2 have the same repetition period L / 5 as each other in the x direction. Similarly, in the directions rotated by +1 / 3π radians (+60 degrees) and -1 / 3π radians (-60 degrees) with respect to the x direction, the first pattern portion and the second pattern portion also have the same repetition period L / 5 as each other.

[0083] In the present embodiment, as shown in FIG. 16(b), since the particle groups P1 and P2 having different average particle sizes are spread on the first pattern portion and the second pattern portion, the surface densities of the particle groups held in each pattern portion are different between the first pattern portion and the second pattern portion. In the present embodiment, the surface density at which the first particle group P1 is arranged in the first pattern portion is lower than the surface density of the second particle group P2 in the second pattern portion.

[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 base material thickness direction (z direction) 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 combinations 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 the present embodiment, a material layer in which the first particles P1 and the second particles P2 are densely arranged in a pattern can be formed on the second base material 11b. Specifically, according to the present embodiment, in each of the material layers, the coverage rate of the base material by the particles can be set to 80% or more. The coverage rate of the base material by the particles can be measured by photographing the region where the material layer is formed from the vertical direction of the base material with an optical microscope and calculating the area ratio of the particles in the region by image processing software.

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

[0089] When forming a material layer with one type of particle material, the first filling device 24a and the second filling device 24b may be filled with particle materials of the same material. Thereby, a material layer in which one type of material is more densely arranged can be formed. At this time, for the first particles P1 in the first filling device 24a and the second particles P2 in the second filling device 24b, particles of the same material but different particle sizes may be used. For example, by using particles having a smaller particle size than the first particles P1 as the second particles P2, a more dense 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 may be added on the downstream side of the first filling device 24a or the second filling device 24b with respect to the upstream side. At this time, it is preferable that the particle size of the particles filled in the upstream filling device is larger than the particle size of the particles filled in the downstream filling device. Further, it is preferable to provide a plurality of recesses of different sizes on the base material so that the particles filled in the upstream filling device contact only the bottom of a part of the recesses. Thereby, a material layer in which each particle is densely arranged in a pattern can be formed using three or more types of particle materials.

[0091] Also, although the structure becomes complicated, a plurality of first belt devices 22a may be provided, and different particles may be transferred onto the second base material 11b from each device. Alternatively, a third belt device having a third filling device may be provided, and in a transfer portion formed by the second belt device 22b and the third belt device, the particles may be transferred from the second base material 11b on which the first and second particles are arranged onto the third base material. Then, if the third particles are filled by the third filling device in a portion where neither the first nor the second particles are arranged on the third base material, a material layer can be formed of three or more types of particle materials.

[0092] As described above, the method for manufacturing a material layer according to the present embodiment is a dry process capable of densely arranging particles on a base material in an arbitrary pattern and can be performed in the atmosphere. Thereby, there is no need for management of solvents, adjustment of air conditioning equipment and vacuum degree, etc., which are essential in conventional wet processes (e.g., coating method, inkjet method) and vapor deposition methods, and it is a method that can be realized with an easy configuration and environment. Further, in the method for manufacturing a material layer according to the present embodiment, there is also an 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 concave portion of the uneven pattern, or laminating a plurality of base materials.

[0093] Thus, according to the material layer forming apparatus 1 of the present embodiment, a single type or a plurality of types of particles can be arranged on the base material 11b in an arbitrary pattern, and a material layer in which these particles are densely arranged can be formed.

[0094] (Method for determining the structure of the uneven pattern) In the uneven pattern 111a in the present embodiment, it is preferable that the first particle P1 can contact the surface of the base material 11a (the bottom surface of the concave portion of the uneven pattern 111a), and the carrier S1 carrying the first particle P1 cannot contact.

[0095] The determination of the structure of the concavo-convex pattern can be carried out using an AFM (Nano-I manufactured by Pacific nanotechnology). When the concavo-convex pattern is formed on the surface of a member such as a roller, a replica of the concavo-convex pattern may be produced using an ultraviolet curable resin, a thermoplastic resin, etc. on a smooth base material, and the replicated concavo-convex pattern may be used for the determination of the structure.

[0096] When determining the structure of the concavo-convex pattern, as the AFM cantilever (probe), a cantilever A having a hemispherical tip corresponding to the particle diameter r of the first particle P1 and a cantilever B having a hemispherical tip corresponding to the particle diameter rc of the supporting material S1 to be supported are used. The measurement of the target concavo-convex pattern is performed using each of these two types of cantilevers. When the first particle P1 can contact the bottom surface of the concave portion of the concavo-convex pattern, the concavo-convex structure is observed by the measurement using the cantilever A, and typically, a flat surface of the concave portion is observed. On the other hand, when the supporting material S1 cannot contact the bottom surface of the concave portion of the concavo-convex pattern, the depth of the concave portion of the concavo-convex pattern is measured to be smaller by the measurement using the cantilever B than the measurement result using the cantilever A. Thus, by measuring and comparing the depth of the concave portion of the concavo-convex pattern using two types of cantilevers, it is possible to determine whether or not the bottom surface of the concavo-convex pattern can be contacted.

[0097] According to the first embodiment, it becomes possible to provide a material layer in which a pattern layer is provided on a desired base material.

[0098] The pattern layer includes, for example, a first region including a first inorganic material and in which a plurality of first particles before sintering treatment are arranged, and a second region including a second inorganic material and in which a plurality of second particles before sintering treatment are arranged.

[0099] (Inorganic material) 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 1.5Examples include O4 (LNMO: lithium nickel manganate). Specific examples of the composite metal oxide containing lithium include LiFePO4 (LFP: lithium iron phosphate) and Li3V2(PO4)3 (LVP: lithium vanadium phosphate). Further, the above positive electrode material may contain a conductive aid. Examples of the conductive aid include graphite such as natural graphite and artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Further, examples of the conductive aid 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 the electrolyte material include oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes, etc. Oxide-based solid electrolytes include 1.5 Al 0.5 Ge 1.5 (PO4)3 and Li 1.3 Al 0.3 Ti 1.7 (PO4)3 and other NASICON-type compounds, Li 6.25 La3Zr2Al 0.25 O 12 and other garnet-type compounds. Further, oxide-based solid electrolytes include Li 0.33 Li 0.55 TiO3 and other perovskite-type compounds. Further, oxide-based solid electrolytes include Li 14Examples of the silicon-type compounds include Zn(GeO4)4, and examples of the oxygen 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, and solid solutions. 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 different materials. In the first region, a plurality of types of particles may be mixed.

[0103] As a preferable combination of the first inorganic material and the second inorganic material, in the case of a base material for an electrode, it is preferable that the first inorganic material is a positive electrode material or a negative electrode material, and the second inorganic material is an electrolyte material. In the case of a base material for an electrolyte, the first inorganic material and the second inorganic material may be the same electrolyte material or different electrolyte materials.

[0104] The particle diameters (average particle diameters) of the first and second particles are, for example, 0.05 μm or more and 100 μm or less (large range), preferably 0.1 μm or more and 50 μm or less (medium range), and more preferably 0.5 μm or more and 25 μm or less (small range). From the viewpoint of denseness, it is preferable to make the particle size smaller, but the lower limit is set due to material cost and deterioration of cohesiveness. The upper limit is set due to a decrease in denseness. The average particle diameter is measured, for example, by a laser diffraction / scattering type particle size distribution measuring device.

[0105] The average particle diameter of the first particle group and the average particle diameter of the second particle group can also be made different from each other. For example, when the first region is formed first and then the second region is formed, the relationship between the particle diameters of the particle groups arranged in both regions should be such that the average particle diameter of the first particle group ≥ the average particle diameter of the second particle group. The second particle group fills the voids and gaps where the first particle group is not arranged on the base material 11b. The reason why the second particle group is arranged and filled on the base material 11b is due to the adhesion force on the surface of the base material 11b and the restraint force by the uneven pattern formed by the first particle group on the base material 11b. Therefore, in order to fill stably and densely, it is desirable that the average particle diameter of the second particle group is 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 (in a large range, it is desirable that the packing density be high, and since it is difficult to define the upper limit at present, only the lower limit is described), preferably 50% or more, and more preferably 70% or more. This packing density is measured, for example, by subjecting an image obtained by photographing the substrate with an optical microscope or an electron microscope to binarization processing of the presence or absence of particles in the first region on the substrate using image processing software, and calculating the ratio (%) of the total number of pixels of the particle images to the total number of pixels of the entire 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, when the first region is formed first and then the second region is formed, the second region (the second pattern portion) can be made to have a higher packing density than the first region (the first pattern portion) by selective particle patterning using the particle size difference.

[0108] In addition, the plurality of first particles before being sintered are sintered by firing at a predetermined sintering temperature or higher.

[0109] In addition, the particles arranged in the first and second regions are not necessarily limited to inorganic materials, and the materials (such as metal materials and organic materials) described in this embodiment, other embodiments, or examples can be appropriately used according to the application.

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

[0111] The pattern included in the pattern layer is a pattern including a first region and a second region (there may be another region in some cases). For example, a honeycomb pattern in the shape of a honeycomb can be mentioned. In addition to the honeycomb pattern, a hole pattern in which circles are repeatedly arranged in the in-plane direction, a square pattern in which squares are arranged, a triangular pattern in which triangles are arranged, and patterns that are repeatedly arranged other than the shape are included. Also, the same applies to the case of a line pattern in which vertical, horizontal, diagonal, or a mixture of them are repeatedly arranged with respect to a pattern in which each isolated shape like a pattern is arranged in the plane.

[0112] Examples of the pattern aspect include, for example, a repeating pattern having a repeating structure in the in-plane direction of the substrate, a random pattern, or a gradation. The repeating pattern having a repeating structure in the in-plane direction of the substrate is equivalently referred to as a repeating pattern having a repeating structure within the pattern layer.

[0113] Furthermore, in addition to the basic period of the pattern, a configuration in which patterns of other periods are mixed can also be used. Whether such a pattern exists can be determined, for example, by acquiring an in-plane image on the substrate, extracting feature points of the image by image processing, performing Fourier analysis, etc., and acquiring the spatial frequency spectrum.

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

[0115] In addition, the height variation in the first region (and / or the second region) where the pattern is formed is such that the height range is 3 times or less, preferably 2 times or less, and more preferably equal to or less than the average particle diameter of the first particles P1. Here, the height range is the difference between the maximum value and the minimum value of the height in the first region.

[0116] (Substrate) The substrate is preferably configured to have different thermal decomposability or solubility in a solvent from the first and second regions that constitute the sheet-like pattern layer. For example, the first and second regions can be mainly composed of an inorganic material, and the substrate can be composed of an organic material.

[0117] As the substrate, for example, polyethylene terephthalate, polyester, etc. can be used.

[0118] In addition, 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] (Laminate) A plurality of substrates provided with a pattern layer can be laminated to form a structure, and by thermally decomposing or dissolving the substrate from the structure with a solvent, a laminate in which a plurality of pattern layers are laminated can be formed.

[0120] A laminate can be provided that includes a pattern layer including a first region and a second region and in which a plurality of the pattern layers are laminated.

[0121] Here, the in-plane pattern composed of the first region and the second region can also be configured to include a portion where the phases are not aligned between the pattern layers 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, or in the case of a line pattern, the phases can be shifted in the same manner, or the line angles between the pattern layers can be shifted, so as to include a portion where the phases are not aligned. As a result, the particle positions between the pattern layers are shifted, which has the effect of improving the compactness of the particles during stacking. Further, when the laminate forms a part of all-solid-state battery, for example, in the case of an electrode, the following effects can be expected due to the shift of the particle positions between the pattern layers. That is, due to the shift of the particle positions between the pattern layers, it becomes easier for the electrode active material and the solid electrolyte to come into contact in the stacking direction, and the amount of electrode active material that cannot contact the solid electrolyte and is isolated within the electrode decreases, improving the capacity. Also, with respect to the volume change of the electrode active material accompanying charge and discharge, it becomes easier to contact the solid electrolyte or the conductive assistant that relaxes it, so that the cycle characteristics are improved.

[0122] The material layer obtained according to the present embodiment has a pattern layer and a base material on which the pattern layer is provided. Such a pattern layer includes a first region including a first inorganic material and in which a plurality of first particles before sintering are arranged, and a second region including a second inorganic material and in which a plurality of second particles before sintering are arranged.

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

[0124] FIG. 10 is a diagram schematically showing the configuration of a material layer forming apparatus 2 according to the present embodiment. The same parts as those of the material layer forming apparatus 1 are denoted by the same reference numerals, and the description thereof will be omitted as appropriate.

[0125] The material layer forming apparatus 2 is an apparatus for forming a material layer 12 on a base material 11, and includes a storage container 21 for storing and supplying the base material 11 and a belt apparatus 22 for transporting the base material 11. Further, the material layer forming apparatus 2 includes a liquid application apparatus 201 for disposing a liquid in a pattern on the base material 11, and a powder application apparatus 202 for applying a powder containing first particles P1 onto the base material 11 on which the liquid is disposed in a pattern. Furthermore, the material layer forming apparatus 2 has a filling apparatus 24 having the same configuration as the second filling apparatus 24b of the first embodiment.

[0126] In the material layer forming apparatus 2, the liquid application apparatus 201 and the powder application apparatus 202 correspond to a first arranging means for arranging the first particles P1 in a pattern on the base material 11. Further, the filling apparatus 24 corresponds to a second arranging means for arranging second particles P2 in a region on the base material 11 where the first particles P1 are not arranged.

[0127] The liquid application device 201 arranges a liquid in a pattern on the substrate 11 to form a liquid pattern L1 on the substrate 11. As the liquid application device 201, typically an inkjet device can be used, but it is not limited thereto, and a plate-making method such as a flexographic plate can also be applied. For example, when forming a large number of patterns of the same shape, it may be more efficient to use a plate. Note that the liquid application device 201 may be configured to apply a gel instead of a liquid as long as the gel has fluidity for ejection. Considering the drying speed of the pattern L1 arranged in a pattern, the affinity with the substrate 11, the stability of fixing the particles P1, etc., the viscosity of the ejection fluid is appropriately adjusted. That is, the liquid application device 201 can be equivalently referred to as the fluid application device 201. The liquid application device 201 of the present embodiment is different from the patterning device using an inkjet described in the background art in that it does not eject the materials of the positive electrode, negative electrode, and electrolyte, which are functional components of the secondary battery, onto the substrate 11. The liquid application device 201 of the present embodiment is different from the patterning device using an inkjet described in the background art in that it patterns a holding layer for holding the materials of the positive electrode, negative electrode, and electrolyte, which are functional components of the secondary battery, as particles on the substrate 11. Such a holding layer can be made into a form that is not an element constituting the secondary battery by giving physical properties different from those of the particles as functional materials.

[0128] As the inkjet device applicable as the liquid application device 201, various types of inkjet devices such as thermal type, piezo type, electrostatic type, and continuous type can be used. The inkjet device is not particularly limited as long as it can eject a liquid. There is also no particular limitation on the number of nozzles (ejection ports) of the inkjet device. It may be single like a dispenser or plural like a line head, but in terms of productivity, it is preferable that the inkjet device has a plurality of nozzles.

[0129] The liquid applied by the liquid application device 201 is not particularly limited as long as it is a material capable of adhering the first particles P1, and it may be an aqueous liquid (for example, aqueous ink) or an oily liquid (for example, oil-based ink). Further, the liquid application device 201 may form the pattern L1 with a plurality of types of liquids. For example, the liquid application device 201 may apply two types of liquid materials that react on the base material 11 to enhance adhesiveness.

[0130] The powder application device 202 applies powder containing the first particles P1 to the base material 11 on which the liquid is arranged in a pattern. Thereby, the first particles P1 are fixed by the liquid on the base material 11, and the first particles P1 are fixed in a pattern corresponding to the pattern L1.

[0131] The means for applying the powder by the powder application device 202 is not particularly limited, and means for spraying the powder toward the base material 11 or means for sprinkling can be used. The powder application device 202 may further include means for removing the first particles P1 that were not fixed on the base material 11 by the liquid by means such as vibration, blowing, or suction.

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

[0133] Further, the material layer forming device 2 may further include heating means for heating the base material 11 to which the first particles P1 are applied by the powder application device 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 type method of irradiating infrared rays or microwaves may be used. In addition, it is also possible to heat by scanning an energy ray such as a laser beam. Note that the heating means may be provided on the back side of the belt 224 of the belt device 22, or may be provided on the front side (the side on which the base material 11 is supported).

[0134] According to this embodiment, the first particles P1 can be arranged in a pattern on the base material 11 by the liquid application device 201 and the powder application device 202. Then, the base material 11 on which the first particles P1 are arranged in a pattern is conveyed to the filling position of the filling device 24 by the belt device 22. The filling device 24 fills the portion on the base material 11 where the first particles P1 are not arranged with the second particles P2. Since the filling of the second particles P2 by the filling device 24 is the same as that in the first embodiment (the second filling device 24b), the following description is omitted.

[0135] As described above, according to the material layer forming device 2 of this embodiment, similar to the first embodiment, single or multiple types of particles can be arranged on the base material 11 in an arbitrary pattern, and a material layer in which those particles are densely arranged can be formed.

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

[0137] FIG. 11 is a diagram schematically showing the overall configuration of a laminated manufacturing system 100 according to the third embodiment.

[0138] The laminated manufacturing system 100 according to this embodiment includes a control unit U1, a material layer forming unit U2, a lamination unit U3, a removal unit U4, and a post-processing unit U5. The control unit U1 is responsible for controlling each part of the laminated manufacturing system 100. The material layer forming unit U2 forms a material layer 12 on the base material 11. The lamination unit U3 laminates a plurality of base materials 11 on which the material layers 12 are respectively formed, and forms a laminate 13 including a plurality of material layers 12 and a plurality of base materials 11. The removal unit U4 removes the base material 11 from the laminate 13 formed by the lamination 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 FIG. 11 is merely an example, and other configurations may be adopted. Hereinafter, the configuration and operation of each unit will be described.

[0139] [Control Unit] The control unit U1 is responsible for controlling each part of the additive manufacturing system 100, specifically, the material layer forming unit U2, the lamination unit U3, the removal unit U4, and the post-processing unit U5, etc.

[0140] The control unit U1 may be provided with a 3D shape data input unit that receives input of 3D shape data of a three-dimensional object (hereinafter sometimes referred to as a "modeling target object") to be formed by the additive manufacturing system 100 from an external device (such as a personal computer, etc.). As the 3D shape data, data created and output by a 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 be provided with 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") for use in image formation by the material layer forming unit U2 based on the cross-sectional shape. Further, 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 an overhang portion (a portion floating in the air), and add an image for the support material to the slice data as necessary.

[0142] As will be described in detail later, the material layer forming unit U2 of the present embodiment uses a plurality of types of materials and can form a material layer in which each material is patterned. Therefore, data corresponding to the images of each material may be generated as the slice data. As the file format of the slice data, for example, multi-value image data (each value represents the type of material) or multi-plane image data (each plane corresponds to the type of material) can be used.

[0143] Also, although not shown in the figure, the control unit U1 also includes an operation unit, a display unit, and a storage unit. The operation unit is a function for receiving instructions from the user. For example, it is possible to input power on / off, various settings of the device, operation instructions, etc. The display unit is a function for presenting information to the user. For example, it is possible to present various setting screens, error messages, operation status, etc. The storage unit is a function for storing three-dimensional shape data, slice data, various setting values, etc.

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

[0145] [Material layer forming unit] The material layer forming unit U2 is a unit for forming a material layer 12 on the base material 11. As the material layer forming unit U2, the material layer forming device 1 of the above-described first embodiment or the material layer forming device 2 of the second embodiment can be used.

[0146] The additive manufacturing system 100 may have a plurality of material layer forming units U2. Thereby, the formation of the material layer 12 on the base material 11 can be performed simultaneously in parallel, and the throughput of forming the laminate and the three-dimensional object can be further improved. Also, when there are a large number of types of materials constituting the three-dimensional object, by providing the material layer forming unit U2 for each material type or for each group of material types, it is also possible to omit the switching of the material type and the process within the material layer forming unit U2. Thereby, the manufacturing of the three-dimensional object can be performed continuously.

[0147] Hereinafter, a case will be described in which the material layer forming unit U2 forms the material layer 12 on the base material 11 by a method that combines filling the recesses of the concavo-convex pattern with the material and transferring the filled material to the base material.

[0148] [Laminating Unit] The laminating unit U3 is a unit that laminates a plurality of base materials 11 on each of which the material layer 12 is formed by the material layer forming unit U2 to form a laminate 13 including a plurality of material layers 12 and a plurality of base materials 11.

[0149] FIG. 12 is a diagram schematically showing the configuration of the laminating unit U3. The laminating unit U3 includes a transfer device 31 that transfers the base material 11 on which the material layer 12 is formed, and a stage 32 that can be relatively moved in the vertical direction by an actuator (not shown).

[0150] The transfer device 31 receives the base material 11 on which the material layer 12 is formed from the material layer forming unit U2 and transfers it to the stage 32. The transfer device 31 is not particularly limited as long as it is a device capable of transferring the base material 11, and may be a belt conveyor, a roller, or a robot arm.

[0151] When the base material 11 is transferred to the stage 32 by the transfer device 31, the stage 32 moves in the vertical direction by the thickness of the base material 11 and the material layer 12. By repeating the transfer by the transfer device 31 and the movement of the stage 32, a plurality of base materials 11 on each of which the material layer 12 is formed are laminated to form the laminate 13.

[0152] The laminating unit U3 may further include a transfer device 33 that transfers the formed laminate 13 to the removal unit U4 or the like, and a pressing device (not shown) that presses the laminate 13 in the laminating direction. The transfer device 33 may have the same configuration as the transfer 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 laminating unit U3 to form a three-dimensional object 14.

[0154] The method for the removal unit U4 to remove the base material 11 from the laminate 13 is not particularly limited. The removal unit U4 may remove the base material 11 by heating the laminate 13, may dissolve and remove the base material 11 with a solvent, or may mechanically remove the base material 11 by wind pressure or water pressure. When mechanically removing the base material 11, after making the base material 11 brittle by heating or a solvent, the brittle base material 11 may be mechanically removed. Among these, it is preferable for the removal unit U4 to remove the base material 11 by heating the laminate 13. According to the removal by heating, the force applied to the upper and lower material layers of the base material to be removed during removal can be reduced, and the structure of the material layer is easy to maintain. Also, since heat can be applied to the inside of the laminate, the base material inside the laminate is also easy to remove, and the removal rate of the base material is easy to increase. Hereinafter, the case where the removal unit U4 removes the base material 11 by heating will be described.

[0155] FIG. 13 is a diagram schematically showing the configuration of the removal unit U4. The removal unit U4 includes a transfer device 41 for transferring the laminate 13 and a heating furnace 42 for heating the laminate 13.

[0156] The transfer device 41 receives the laminate 13 from the lamination unit U3 and transfers it to the heating furnace 42. The transfer device 41 is not particularly limited as long as it is a device capable of transferring the laminate 13, and may be a belt conveyor, a roller, or a robot arm, similar to the transfer device 31.

[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 adjusting means 423. As the heating furnace 42, a firing furnace used for firing ceramics or 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. Note that the pressing means 422 preferably has a pressing portion for pressing the laminate 13 formed of a porous body that allows gas to pass through easily. The atmosphere adjusting means 423 includes an atmosphere gas supply means 423a and a decompression means 423b, and adjusts the atmosphere gas in the processing space of the heating furnace 42.

[0158] The removal unit U4 performs heating at a temperature equal to or higher than the thermal decomposition temperature of the base material 11 in the laminate 13 and lower than the thermal decomposition temperature of each material layer in the laminate 13. Thereby, the base material in the laminate 13 can be selectively decomposed and removed. When the laminate 13 contains a plurality of types of base materials 11 made of different materials, the heating temperature by the removal unit U4 may be set to a temperature equal to or higher than the highest thermal decomposition temperature among the thermal decomposition temperatures of the plurality of base materials.

[0159] Note that in this specification, the thermal decomposition temperature refers to the temperature at which the weight loss of the material starts when the temperature is gradually increased under the atmosphere during heating by the removal unit U4. Therefore, by heating the laminate at a temperature equal to or higher than the thermal decomposition temperature of the base material 11, the base material 11 in the laminate can be decomposed and its weight can be reduced, and the base material 11 can be removed from the laminate. The heating temperature in the removal step is preferably equal to or higher than the thermal decomposition temperature of the base material 11, but more preferably heated at a temperature higher than the thermal decomposition temperature. Specifically, when performing thermogravimetric analysis by increasing the temperature from room temperature (25 °C) at a rate of 5 °C / min under the atmosphere (typically air) during heating by the removal unit U4, it is preferable to heat at a temperature equal to or higher than the temperature at which the weight becomes 70% of the initial weight. Similarly, when performing thermogravimetric analysis, it is more preferable to heat at a temperature equal to or higher than the temperature at which the weight becomes 50% of the initial weight, and even more preferable to heat at a temperature equal to or higher than the temperature at which the weight becomes 20% of the initial weight. Thereby, the time required for removing the base material 11 can be shortened or the removal rate of the base material 11 can be increased.

[0160] That is, when the removal unit U4 removes the base material 11 by heating, the first particles P1 and the second particles P2 are preferably made of a material having a thermal decomposition temperature higher than that of the base material 11. Generally, since inorganic materials tend to have a higher thermal decomposition temperature than organic materials, the materials of the first particles P1 and the second particles P2 are preferably inorganic materials, and the material of the base material 11 is preferably an organic material such as resin. Further, when the removal unit U4 removes the base material 11 by heating, the first particles P1 and the second particles P2 are preferably materials having a softening point temperature higher than the thermal decomposition temperature of the base material 11. Also, as described above, as the first particles P1 and the second particles P2, it is preferable to use particles made of a material selected from the positive electrode materials of lithium ion batteries and all-solid-state batteries, materials containing solid electrolytes, and negative electrode materials. Thereby, all-solid-state batteries, electrode sheets such as positive electrode sheets and negative electrode sheets, and solid electrolyte sheets can be manufactured.

[0161] The removal unit U4 preferably causes 90% by weight or more of the base material in the laminate 13 to disappear by heating, more preferably 95% by weight or more, and even more preferably 97% by weight or more. At this time, it is preferable that the base material burns or gasifies and is released to the outside as a gas. Note that by using a base material formed of an organic material such as resin as the base material, the removal of the base material by heating can be facilitated. As the material constituting the base material, polyethylene (PE), polypropylene (PP), polyesters such as polyethylene terephthalate (PET), polyamides such as nylon, and the like can be used. Among them, from the viewpoints of the decomposition temperature and the low toxicity of the gas generated during thermal decomposition, it is preferable to use PET.

[0162] The removal unit U4 preferably exhausts the released gas to the outside of the heating furnace 42 by the decompression means 423b. By setting the inside of the heating furnace 42 to an oxidizing atmosphere, that is, an atmosphere containing oxygen gas such as air, by the atmosphere gas supply means 423a or the like, the base material can be burned and removed.

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

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

[0165] The type of post-treatment performed by the post-treatment unit U5 is not particularly limited. For example, a process of further heating and firing the three-dimensional object 14 can be mentioned. When the post-treatment unit U5 performs a heat treatment as a post-treatment, the removal unit U4 may also serve this function. By firing the three-dimensional object 14, the materials such as the particle materials in each material layer can be sintered together.

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

[0167] Further, the post-processing unit U5 may perform a process of removing at least one type of material constituting the three-dimensional object 14 from the three-dimensional object 14. For example, when the three-dimensional object 14 is formed of the first particle material P1 and the second particle material P2, after fixing or integrating only the first particle materials P1 by sintering or the like, only the second particle material P2 may be selectively removed by air blowing or the like. At this time, the second particle material P2 functions as a so-called support material in the additive manufacturing method and has a function of supporting the first particle material P1 during lamination. Thereby, a three-dimensional object can be formed using the first particle material P1. When only the first particle materials P1 are fixed to each other, for example, a material having a sintering temperature higher than that of the first particle material P1 is used as the second particle material P2, and heating is performed at a temperature equal to or higher than the sintering temperature of the first particle material P1 and lower than the sintering temperature of the second particle material P2.

[0168] As described above, according to the present embodiment, the throughput when manufacturing a three-dimensional object by additive manufacturing can be improved.

[0169] According to the present embodiment, by forming a material layer on a substrate using a material including a positive electrode material, a negative electrode material, or a solid electrolyte of a lithium ion battery or an all-solid-state battery, an electrode sheet such as a positive electrode sheet or a negative electrode sheet or a solid electrolyte sheet can be manufactured. According to the present embodiment, since the particulate materials can be densely arranged in an arbitrary pattern, it is possible to provide an electrode sheet or a solid electrolyte sheet having high electrochemical characteristics. Further, when manufacturing the electrode sheet, by patterning a material including a solid electrolyte in addition to the positive electrode material or the negative electrode material, a good interface can be formed between the positive electrode material or the negative electrode material and the material including the solid electrolyte. Further, an all-solid-state battery can also be manufactured by forming a three-dimensional object using a positive electrode material, a negative electrode material, and a material including a solid electrolyte.

Example

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

[0171] In the first belt device 22a and the second belt device 22b, a resin belt made of polyimide was used as the conveying member 224. Further, stainless steel metal rollers were used as the driving rollers 221 and 222, and a soft roller in which a silicone rubber elastic layer was provided on a stainless steel core was used as the pressing roller 223.

[0172] As the first base material 11a, a sheet made of polyester (PET) was used. On the first base material 11a, a honeycomb pattern-shaped concavo-convex pattern was formed by the pattern forming device 23. First, an ultraviolet curable resin (ultraviolet curable liquid silicone rubber, PDMS, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto the first base material 11a. Then, a film mold (standard mold, manufactured by Soken Chemical & Engineering Co., Ltd.) having a honeycomb pattern-shaped concavo-convex pattern on its surface corresponding to the concavo-convex pattern to be formed was pressed against the ultraviolet curable resin on the first base material 11a. With the film mold pressed against it, ultraviolet rays were irradiated by a UV lamp to cure the ultraviolet curable resin, and the film mold was demolded.

[0173] The structure of the first base material 11a having the concavo-convex pattern 111a formed on its surface is shown in FIG. 14. FIG. 14(a) is a top view of the first base material 11a, and FIG. 14(b) is a cross-sectional view taken along the line A-A of FIG. 14(a). As shown in FIG. 14, on the surface of the first base material 11a, a honeycomb pattern-shaped concavo-convex pattern having hexagonal frame-shaped convex portions is formed. Here, as shown in FIG. 14(b), let the interval between adjacent convex portions (that is, the width of the concave portion) be k (μm), the pitch between adjacent convex portions be s (μm), and the height of the convex portion (that is, the depth of the concave portion) be d (μm). In the following examples, the shape measurement of the concavo-convex pattern was performed using a non-contact surface / layer cross-sectional shape measurement system (VertScan 2.0 manufactured by Rhika System Co., Ltd.).

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

[0175] The first particle P1 and the second particle P2 are made of any one of 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 (hereinafter referred to as LLZ), Li3BO3 (hereinafter referred to as LBO), or graphite. Note that lithium cobalt oxide LCO is a cathode material, lithium aluminum germanium phosphate LAGP, LLZ, and lithium borate LBO are materials containing a solid electrolyte, and graphite is an anode material. Note that lithium cobalt oxide LiCoO2 can be the one manufactured by Nippon Chemical Industry Co., Ltd. Similarly, Li 1.5 Al 0.5 Ge 1.5 P3O 12 can be used. Also, Li 6.75 La3Zr 1.75 Nb 0.25 O 12 can be the one manufactured by Toyoshima Seisakusho Co., Ltd. In some cases, the abbreviation LLZ may be replaced with LLZNb. Also, lithium borate Li3BO3 can be the one manufactured by Toyoshima Seisakusho Co., Ltd. Graphite can be SGP-5 manufactured by SEC Carbon Co., Ltd.

[0176] Also, as the carrier S1 and the carrier S2, either a standard carrier (standard carrier P02 manufactured by the Japan Society for Imaging Science and Technology) which is a magnetic particle or an in-house carrier (manufactured by Canon) was used. Note that the in-house carrier is a particle in which pores of porous ferrite particles are filled with resin. When forming the material layer 1, the ratio of the first particle P1 in the filler 241a was 17% by weight, and the ratio of the second particle P2 in the filler 241b was 45% by weight.

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

[0178]

Table 1

[0179] In addition, the particle size of each particle in the filler used when forming each material layer was as shown in Table 2. In Table 2, the particle size (r10, r50, r90) of each particle is the particle size of the cumulative distribution in the particle size distribution based on volume, r10 is the cumulative 10%, r50 is the cumulative 50%, and r90 is the cumulative 90% particle size. That is, r50 is the median diameter. The particle size was measured using a laser diffraction scattering type particle size distribution measuring device (LA-960 manufactured by Horiba, Ltd.).

[0180]

Table 2

[0181] The density of the formed material layers 1 to 9 was evaluated by the following method. Specifically, the second base material 11b on which each material layer was formed was photographed from the material layer side with an optical microscope, and the coverage rate of the particles in the observation region was measured by image processing software (Adobe Systems' Photoshop (registered trademark)). The evaluation was A when the coverage rate was 85% or more, B when the coverage rate was less than 85% and 80% or more, and C when the coverage rate was less than 80%. When the coverage rate is less than 80%, it is difficult to form a sufficiently dense material layer even if post-treatment such as sintering treatment is performed on the formed material layer.

[0182] As shown in Table 2, it was found that for all of the material layers 1 to 9, the coverage rate was 80% or more, indicating that a dense material layer could be formed. For material layers 2 and 4, the size of the second particles P2 is larger than that in the case of other material layers. In the case of material layer 2, since the median diameter r50 of the second particles P2 is larger than the concave portions of the uneven pattern formed by the first particles P1, the ratio of the particles among the second particles P2 that can contact the bottom of the concave portions is small. Also, in material layer 4, although the median diameter r50 of the second particles P2 is smaller than the concave portions of the uneven pattern formed by the first particles P1, the difference is small, and the ratio of the particles among the second particles P2 that can contact the bottom of the concave portions is small compared to the case of other material layers. Therefore, it is considered that the coverage rate of material layers 2 and 4 is slightly lower than that of other material layers.

[0183] (Examples 10 to 20) Next, a three-dimensional object was formed using the above-described laminated manufacturing system 100. Specifically, the material layer forming apparatus 1 shown in FIG. 2 was used as the material layer forming unit U2 to form a material layer on a substrate, the substrates on which the material layers were formed were laminated, and the substrate was removed from the laminate by heating to form an electrode sheet, an electrolyte sheet, and a all-solid-state battery, which are three-dimensional objects.

[0184] Second substrates 11b on which each material layer was formed in the same manner as in Examples 1 to 9 were laminated in a plurality as shown in Table 3 to form a laminate. Then, the laminate was transferred to a heating furnace and heated in the heating furnace. The weights of the laminate before and after heating were measured respectively, and the weight ratio (wt%) of the substrate before and after heating was evaluated. Further, the upper and lower surfaces of the laminate after heating were sputtered with gold, and a tester was applied to the upper and lower surfaces to investigate whether or not there was leakage. Those with leakage were designated as B, and those without leakage were designated as A. The results are shown in Table 3. Note that those with leakage can be evaluated to have a resistance value of approximately 10 Ω or less.

[0185]

Table 3

[0186] Figure 15 shows the thermogravimetric analysis results of a sheet made of polyester (PET) which is the second substrate 11b. The thermogravimetric analysis was performed using a differential thermal balance (TG-DTA manufactured by Rigaku Corporation), and the temperature was raised from room temperature (25 °C) at a rate of 5 °C / min in air. From Figure 15, the temperature when it reached 50% of the initial weight was about 400 °C, and the temperature when it reached 20% of the initial weight was about 500 °C. Also, for all of LCO, LAGP, LLZ, LBO, and graphite, the thermal decomposition temperature was 510 °C or higher.

[0187] As shown in Table 3, when laminates were formed by changing the material layer, the number of laminated sheets, and the heating conditions, three-dimensional objects could be formed in all examples. Also, when the heat treatment temperature was increased or the heating time was lengthened, the removal rate of the substrate could be further increased (Examples 10 to 20). Note that for the laminates 1 and 2 of Examples 10 and 11, the substrate remained in an amount greater than 10% by weight after the heat treatment in the heating furnace. Therefore, when the substrate was thermally decomposed by heating, gasification was insufficient and the substrate remained as soot in the laminate, and it is considered that the laminate had a lower resistance. On the other hand, for the laminates 3 to 11 of Examples 12 to 20, the remaining rate of the substrate after the heat treatment in the heating furnace was 10% by weight or less, and no leakage was confirmed in the leakage test.

[0188] (Examples 21 to 23) Next, a plurality of second substrates 11b each having a material layer formed thereon were laminated to form a laminate. Then, the laminate was transferred to a heating furnace and heated in the heating furnace. Further, the laminate was transferred to a firing furnace and heated and fired in the firing furnace. Thereby, an all-solid-state battery was manufactured.

[0189] (Example 21) On a Si substrate with gold sputtered on its surface, 4 sheets of material layer 9 (graphite), 2 sheets of material layer 5 (LAGP), and 2 sheets of material layer 1 (LCO + LAPG) were laminated in order together with the substrate. Then, the formed laminate was placed in a heating furnace and heated in the heating furnace at 500 °C for 30 minutes in air (atmosphere) to disappear the substrate. Thereafter, it was heated at 700 °C for 1 hour in a sintering furnace under vacuum. Thereby, an all-solid-state battery 1 was manufactured.

[0190] (Example 22) On the graphite compact, two material layers 5 (LAGP) and two material layers 1 (LCO + LAPG) were sequentially laminated together with the substrate. Then, the formed laminate was placed in a heating furnace and heated in the heating furnace at 500 °C for 30 minutes under air (atmosphere) to remove the substrate. Thereafter, it was heated in a sintering furnace at 700 °C for 1 hour under vacuum. Thereby, the all-solid-state battery 2 was fabricated. The graphite compact was formed by pressing graphite powder at 250 MPa using a hydraulic press.

[0191] (Example 23) Under the LLZ compact, four material layers 9 (graphite) were laminated together with the substrate, and on the LLZ compact, two material layers 7 (LCO + LBO) were laminated together with the substrate. Then, the formed laminate was placed in a heating furnace and heated in the heating furnace at 500 °C for 30 minutes under air (atmosphere) to remove the substrate. After removing the substrate, the laminate was pressed and then heated in a sintering furnace at 700 °C for 1 hour under vacuum. Thereby, the all-solid-state battery 3 was fabricated. The LLZ compact was formed by pressing LLZ powder at 250 MPa using a hydraulic press and then firing it at 1150 °C for 36 hours under atmosphere. Also, the upper and lower surfaces of the formed LLZ compact were polished with sandpaper.

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

[0193]

Table 4

[0194] The evaluation of each all-solid-state battery was performed by a charge-discharge test using an electrochemical device (Solartron 1255WB type). Specifically, it was rated as A when the charge capacity was 10 mAh / g or more and the discharge capacity was 1 / 10 or more of that. It was confirmed that charge and discharge were performed for all the all-solid-state batteries and they operated as secondary batteries.

[0195] As described above, according to this embodiment, it was possible to manufacture the electrode sheet and electrolyte sheet of the battery, as well as the all-solid-state battery. Since patterning of the particles constituting each of them was possible, a battery having a three-dimensional structure in which the particles were patterned in the plane direction and the stacking direction could be manufactured.

Claims

1. A first step of disposing first particles in a pattern on a substrate; and a second step of disposing second particles in areas on the substrate where the first particles are not disposed, the method comprising the steps of: The method for manufacturing a material layer, wherein the second step includes a step of rubbing a support material carrying the second particles against the base material on which the first particles are disposed.

2. The method for manufacturing a material layer according to claim 1 , wherein the support material is any one of magnetic particles, brush fibers, and an elastic material.

3. the substrate has a concave-convex pattern formed by the first particles, a median diameter of the second particles is smaller than an opening diameter of a concave portion of the concave-convex pattern; 3. The method for manufacturing a material layer according to claim 1, wherein an average diameter of the support material is larger than an opening diameter of the recesses of the uneven pattern.

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

5. The method for manufacturing a material layer according to claim 1 , wherein the base material has an adhesive layer on a surface thereof.

6. The first step includes: A step of arranging the first particles in a pattern on a transfer substrate different from the substrate; The method for manufacturing a material layer according to claim 1 , further comprising the step of: transferring the first particles from the transfer substrate to the substrate.

7. The transfer base material has a transfer concavo-convex pattern formed on a surface thereof, 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 a step of rubbing a second support material carrying the first particles against the transfer concave-convex pattern.

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

9. a median diameter of the first particles is smaller than an opening diameter of a recess of the concave-convex pattern to be transferred; 9. The method for manufacturing a material layer according to claim 7, wherein an average diameter of the second support material is larger than an opening diameter of the recesses of the concave-convex pattern to be transferred.

10. A method for manufacturing a material layer described in 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 includes: depositing a liquid onto the substrate in a pattern; The method for manufacturing a material layer according to any one of claims 1 to 5, further comprising a step of applying the first particles onto 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 , wherein the step of disposing the liquid in a pattern on the base material is a step of applying the liquid onto the base material by an inkjet method.

13. 13. The method for manufacturing a material layer according to claim 11, further comprising the step of removing the first particles that have not adhered to the liquid after the step of applying the first particles.

14. a material layer forming step of forming a material layer on a substrate; a lamination step of laminating a plurality of the base materials each having the material layer formed thereon to form a laminate; a removing step of removing the plurality of base materials from the laminate, The material layer forming step includes: A first step of disposing first particles in a pattern on a substrate; and a second step of disposing second particles in areas of the substrate where the first particles are not disposed, A method for manufacturing a three-dimensional object, characterized in that the second step includes a step of rubbing a support material carrying the second particles against the base material on which the first particles are arranged.

15. The method for manufacturing a three-dimensional object according to claim 14, wherein the removing step removes the base material by heating.

16. At least one of the first particles and the second particles is a solid electrolyte material; The method for manufacturing a three-dimensional object according to claim 14 or 15, wherein 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, wherein the three-dimensional object is an electrode sheet.

18. the material layer forming step includes a step of forming a material layer including a solid electrolyte material, and a step of forming a material layer including a positive electrode material or a negative electrode material, The method for manufacturing a three-dimensional object according to claim 14 or 15, wherein 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 second disposing means for disposing second particles in an area on the substrate where the first particles are not disposed, A material layer forming apparatus characterized in that the second placement means is configured to rub a support material carrying the second particles against the substrate on which the first particles are placed.

20. a material layer forming unit for forming a material layer on a substrate; a lamination unit for laminating the plurality of base materials, each having the material layer formed thereon, to form a laminate; a removal unit for removing the plurality of base materials from the laminate, The material layer forming unit includes: A first arrangement means for arranging first particles in a pattern on a substrate; and a second disposing means for disposing second particles in areas on the substrate where the first particles are not disposed, An additive manufacturing system, characterized in that the second placement means is configured to rub a support material carrying the second particles against the substrate on which the first particles are placed.

21. A material layer comprising: a pattern layer including a first region comprising a first inorganic material and in which a plurality of first particles are arranged before being sintered; and a second region comprising a second inorganic material and in which a plurality of second particles are arranged before being sintered; and a substrate on which the pattern layer is provided.

22. The material layer of claim 21 , wherein the first inorganic material includes at least one of a positive electrode material, an electrolyte material, and a negative electrode material.

23. 23. The material layer according to claim 21, wherein the first inorganic material and the second inorganic material are different from each other.

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

25. 25. The material layer of claim 21, wherein the substrate has different thermal decomposition or solubility properties 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 made of an organic material.

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

28. 30. The layer of material of claim 27, wherein the pattern has a predetermined repeat period within the layer.

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

30. The material layer according to any one of claims 27 to 29, characterized in that the pattern portion has 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, the first group of particles and the second group of particles differ in average particle size, and the first pattern portion and the second pattern portion differ in held areal density.

31. 31. The material layer of claim 30, wherein the first particle group and the second particle group having different average particle sizes include at least any combination of lithium cobalt oxide and lithium cobalt oxide, lithium aluminum substituted germanium phosphate and lithium aluminum substituted germanium phosphate, LLZ and LLZ, and graphite and graphite.

32. 32. The material layer according to claim 30 or 31, wherein the first pattern portion and the second pattern portion have the same repeat period within the pattern layer.

33. The material layer according to any one of claims 27 to 29, characterized in that the pattern portion has a first pattern portion in which a first group of particles is held and a third pattern portion in which a third group of particles is held, and the first group of particles and the third group of particles have different compositions.

34. 34. The material layer of claim 33, wherein the first particle group and the third particle group having different compositions include at least any combination of lithium cobalt oxide and lithium aluminum substituted germanium phosphate, lithium cobalt oxide and LLZ, and lithium cobalt oxide and lithium borate.

35. A laminate comprising a plurality of material layers each including the pattern layer according to any one of claims 21 to 34 and the base material.

36. A laminate comprising a pattern layer including a first region containing a first inorganic material and in which a plurality of first particles are arranged before being sintered, and a second region containing a second inorganic material and in which a plurality of second particles are arranged before being sintered, the pattern layer being stacked in multiple layers.

37. The laminate described in claim 35 or 36, characterized in that the pattern layer composed of the first region and the second region includes a portion where the phase is not matched between the pattern layers when viewed in the stacking direction.

Images