Manufacturing method for electrode structure

Abstract

This manufacturing method for an electrode structure is characterized by comprising: a support step for causing a plurality of prescribed particles to be supported on a rubbing member containing carriers; a first rubbing step for rubbing, at a first rubbing strength, the rubbing member against a sheet-like base material having recesses, and disposing a portion of the plurality of particles in a portion of the recesses; and an N-th rubbing step that is to be performed after the first rubbing step. Said manufacturing method is characterized in that, when an arbitrarily defined rubbing step among the first rubbing step to the N-th rubbing step is defined as an n-th rubbing step, an n-th rubbing strength is higher than an (n-1)-th rubbing strength. (N represents each integer satisfying 2≤N≤M, M represents an integer selected from an integer equal to or greater than 2, and n represents at least one integer selected from the group consisting of the integers represented by N.)

Description

Method for manufacturing an electrode structure

[0001] The present disclosure relates to a method for manufacturing an electrode structure.

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

[0003] In contrast to this, Patent Document 1 proposes a method for manufacturing a material layer, which includes a first step of arranging first particles in a pattern on a substrate, and a second step of arranging second particles in areas on the substrate where the first particles are not arranged, and is characterized in that the second step includes a step of rubbing a support material carrying the second particles against the substrate on which the first particles are arranged.

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

[0005] However, the inventors have found through their studies that the method for manufacturing a material layer of Patent Document 1 has the following problem when the frictional force during rubbing is increased to form a material layer with high density, i.e., when the rubbing strength is high: When the rubbing strength is high, when first particles are arranged on a substrate having an uneven shape, the substrate may be damaged due to friction and wear, resulting in fluctuations in the amount of first particles placed on the substrate or a decrease in placement accuracy. In other words, the reproducibility of the particle pattern may be reduced.

[0006] In addition, secondary batteries generally consist of electrodes (positive and negative electrodes) and an electrolyte, and charge and discharge occur through the movement of ions between the electrodes via the electrolyte. Such secondary batteries are used in a wide range of applications, from small devices such as mobile phones to large devices such as electric vehicles. Therefore, further improvements in the performance of secondary batteries are required. In recent years, research and development of so-called all-solid-state batteries, which use inorganic solid electrolytes as the electrolyte, has been progressing. By replacing conventional organic electrolytes with solid electrolytes, all-solid-state batteries are expected to improve the safety of secondary batteries and establish manufacturing methods that can achieve high capacity and high output.

[0007] Therefore, the present disclosure provides a method for manufacturing an electrode structure that can ensure the reproducibility of particle patterns.

[0008] One aspect of the present disclosure relates to a method for manufacturing an electrode structure, the method comprising: a supporting step of supporting a plurality of particles, including at least one of solid electrolyte particles and active material particles, on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to dispose some of the plurality of particles in some of the recesses; and an Nth rubbing step performed after the first rubbing step, wherein the Nth rubbing step is a step of rubbing the rubbing member against the substrate with an Nth rubbing strength to dispose some of the plurality of particles in the recesses, and wherein when any of the first to Nth rubbing steps is designated as the nth rubbing step, the nth rubbing strength is higher than the (n-1)th rubbing strength. (N represents an integer satisfying 2≦N≦M, M represents an integer selected from integers of 2 or more, and n represents at least one integer selected from the group consisting of integers represented by N.)

[0009] According to the present disclosure, a method for manufacturing an electrode structure that can ensure the reproducibility of particle patterns is provided.

[0010] FIG. 1 is an image illustrating a method for manufacturing an electrode structure according to an embodiment of the present disclosure. FIG. 2 is an explanatory diagram of a first filling device. FIG. 3 is an explanatory diagram illustrating a rubbing process according to an embodiment of the present disclosure. FIG. 4 is an explanatory diagram illustrating a rubbing process according to an embodiment of the present disclosure. FIG. 5 is an explanatory diagram illustrating a rubbing process according to an embodiment of the present disclosure. FIG. 6 is an image illustrating a method for manufacturing an electrode structure according to an embodiment of the present disclosure. FIG. 7 is an explanatory diagram of a third filling device.

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

[0012] The present disclosure relates to a method for manufacturing an electrode structure, the method comprising: a supporting step of supporting a plurality of particles, including at least one of solid electrolyte particles and active material particles, on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to dispose some of the plurality of particles in some of the recesses; and an Nth rubbing step performed after the first rubbing step, wherein the Nth rubbing step is a step of rubbing the rubbing member against the substrate with an Nth rubbing strength to dispose some of the plurality of particles in the recesses, and wherein, when any of the first to Nth rubbing steps is designated as the nth rubbing step, the nth rubbing strength is higher than the n-1th rubbing strength. (N represents an integer satisfying 2≦N≦M, M represents an integer selected from integers equal to or greater than 2, and n represents at least one integer selected from the group consisting of integers represented by N.) In other words, n represents at least one integer satisfying 2≦N≦M.

[0013] Having a first rubbing step and an Nth rubbing step indicates that the manufacturing method of an electrode structure includes the first to Nth rubbing steps. M indicates the number of the first to Nth rubbing steps. And, the nth rubbing strength being higher than the (n-1)th rubbing strength means that the rubbing strength in any rubbing step among the first to Nth rubbing steps is higher than the rubbing strength in the rubbing step immediately preceding that rubbing step. For example, when M is 2, N and n are 2. In this case, the method for manufacturing an electrode structure includes a supporting step of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having a recess with a first rubbing strength and disposing some of the plurality of particles in some of the recesses; and a second rubbing step performed after the first rubbing step, wherein the second rubbing step is a step of rubbing the rubbing member against the substrate with a second rubbing strength and disposing some of the plurality of particles in the recesses, and the second rubbing strength is stronger than the first rubbing strength.

[0014] When M is 3, N is 2 or 3, and n is at least one integer selected from the group consisting of 2 and 3. When n is 2, the method for manufacturing an electrode structure includes a supporting step of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member including a support, a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to dispose some of the plurality of particles in some of the recesses, a second rubbing step performed after the first rubbing step, and a third rubbing step performed after the first rubbing step, wherein the second rubbing step is a step of rubbing the rubbing member against the substrate with a second rubbing strength to dispose some of the plurality of particles in the recesses, and the third rubbing step is a step of rubbing the rubbing member against the substrate with a third rubbing strength to dispose some of the plurality of particles in the recesses, and the second rubbing strength is greater than the first rubbing strength.

[0015] When n is 3, the method for manufacturing an electrode structure includes a supporting step of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to arrange some of the plurality of particles in some of the recesses; a second rubbing step performed after the first rubbing step; and a third rubbing step performed after the first rubbing step, wherein the second rubbing step is a step of rubbing the rubbing member against the substrate with a second rubbing strength to arrange some of the plurality of particles in the recesses, and the third rubbing step is a step of rubbing the rubbing member against the substrate with a third rubbing strength to arrange some of the plurality of particles in the recesses, and the third rubbing strength is a step of rubbing the rubbing member against the substrate with a third rubbing strength to arrange some of the plurality of particles in the recesses, and the third rubbing strength is a step of rubbing the rubbing member against the substrate with a third rubbing strength to arrange some of the plurality of particles in the recesses, and the third rubbing strength is a step of manufacturing an electrode structure.

[0016] When n is 2 or 3, the method for manufacturing an electrode structure includes a supporting step of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to arrange some of the plurality of particles in some of the recesses; a second rubbing step performed after the first rubbing step; and a third rubbing step performed after the first rubbing step, wherein the second rubbing step is a step of rubbing the rubbing member against the substrate with a second rubbing strength to arrange some of the plurality of particles in the recesses, and the third rubbing step is a step of rubbing the rubbing member against the substrate with a third rubbing strength to arrange some of the plurality of particles in the recesses, and the second rubbing strength is higher than the first rubbing strength, and the third rubbing strength is higher than the second rubbing strength.

[0017] The first rubbing step and the Nth rubbing step may be performed multiple times. For example, after the first rubbing step and the second rubbing step are performed, the first rubbing step and the second rubbing step may be further performed.

[0018] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, unless otherwise specified, the dimensions, materials, shapes, relative positions, etc. of each component described in the following embodiments are not intended to limit the scope of the present invention.

[0019] First Embodiment A method for manufacturing an electrode structure according to a first embodiment of the present disclosure will be described with reference to the drawings. FIG. 1 is a conceptual diagram illustrating a method for manufacturing an electrode structure according to one aspect of the present disclosure. The method for manufacturing an electrode structure according to this embodiment includes, for example, the following steps (1) to (4). Details of each step will be described later. Step (1): A supporting step (S101) of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member. Step (2): A first rubbing step (S102) of rubbing the rubbing member against a sheet-like substrate having recesses at a first rubbing strength and disposing some of the plurality of particles in some of the recesses. Step (3): A strength adjusting step (S103) of increasing the rubbing strength. Step (4): A second rubbing step (S104) of rubbing the rubbing member against a sheet-like substrate having recesses at a second rubbing strength higher than the first rubbing strength and disposing some of the plurality of particles in the recesses.

[0020] The method for manufacturing an electrode structure according to this embodiment includes a supporting step (S101) of supporting a plurality of particles, including at least one of solid electrolyte particles and active material particles, on a rubbing member. The supporting step of supporting a plurality of particles on a rubbing member is not particularly limited, and may include, for example, supporting the particles on a rubbing member including a support. Specifically, a method of mixing a support and a plurality of particles, as described below, is exemplified. In this embodiment, the plurality of particles may include first particles P1, and in another embodiment, the plurality of particles may include first particles P1 and second particles P2.

[0021] Next, a first rubbing step (S102) is performed in which the rubbing strength is set to a strength sufficiently small relative to the strength at which the substrate is broken, and the rubbing member is rubbed against a sheet-like substrate having recesses at a first rubbing strength, thereby disposing a portion of the plurality of particles in a portion of the recesses. The first rubbing step (S102) presses the carrier included in the rubbing member against the substrate, and the particles carried by the carrier are pressed into the recesses of the substrate. At this time, the particles are constrained by the force with which the particles are pressed, the adhesive force due to the surface of the substrate, and the adhesive force due to the shape of the recesses on the substrate surface, and the like, and a portion of the plurality of particles is disposed in a portion of the recesses of the substrate. As the rubbing member moves from one end of the recess of the substrate to the other, the carrier also moves, and at that time the carrier sinks into the recesses of the substrate and then climbs up the recesses and moves.

[0022] In this embodiment, an intensity adjustment step (S103) is then performed to increase the friction strength and adjust the friction strength. At this time, the second friction strength, which is the friction strength after the intensity adjustment step, is higher than the first friction strength. That is, the manufacturing method of the electrode structure preferably further includes an intensity adjustment step for adjusting the friction strength between the second friction step and the first friction step. The value of the ratio of the second friction strength to the first friction strength is not particularly limited, but is preferably 1.1 to 10, and more preferably 1.5 to 3.

[0023] The method for adjusting the friction strength in the strength adjustment step is not particularly limited, but examples include at least one of the working distance between the rubbing member and the substrate, the physical properties of the support, the moving speed of the rubbing member relative to the substrate, and the electromagnetic waves applied to the support. The physical properties of the support preferably include magnetism. The electromagnetic waves preferably include a magnetic field. Specifically, the friction strength can be increased by increasing the working distance between the rubbing member and the substrate, increasing the moving speed of the rubbing member relative to the substrate, or increasing the intensity of the electromagnetic waves applied to the support. Furthermore, when electromagnetic waves are used in the rubbing step, the friction strength can be increased by using a support with strong magnetic properties. Conversely, the friction strength can be reduced by reducing the working distance between the rubbing member and the substrate, decreasing the moving speed of the rubbing member relative to the substrate, or decreasing the intensity of the electromagnetic waves applied to the support. Furthermore, when electromagnetic waves are used in the rubbing step, the friction strength can be reduced by using a support with weak magnetic properties. Furthermore, when the physical property of the support includes magnetism, the friction strength can be determined from the magnetic force of the magnet used to rub the support and the distance from the support to the magnet.

[0024] Thereafter, a second rubbing step (S104) is performed in which the rubbing member is rubbed against the substrate at a second rubbing strength to arrange a portion of the plurality of particles in the recesses. The second rubbing strength in the second rubbing step (S104) is higher than the first rubbing strength in the first rubbing step (S102). Therefore, the force with which the particles are pressed in the second rubbing step (S104) is stronger than the force with which the particles are pressed in the first rubbing step (S102). Therefore, in the second rubbing step (S104), the particles are arranged while pushing aside the particles arranged in the first rubbing step (S102). This makes it easier to ensure the reproducibility of the particle pattern.

[0025] At this time, as the carrier moves from one end of the recess of the substrate to the other, it sinks into the recess and then climbs up the recess. However, because the particles arranged in the first rubbing step (S102) are arranged in part of the recess, the amount of sinking of the carrier into the recess is reduced compared to when the second rubbing step is performed without the first rubbing step. Therefore, the force required for the carrier to subsequently climb up from the recess to the protrusion is reduced. This reduces the force applied to the substrate, thereby suppressing damage to the substrate. In this way, reproducibility of the particle pattern is ensured during the manufacture of the electrode structure. Note that the expression "rubbing the rubbing member against the substrate" includes cases where the rubbing member directly contacts the substrate itself, as well as cases where the rubbing member does not directly contact the substrate itself. In other words, the above expression also includes cases where a rubbing member including a carrier carrying particles is rubbed against the substrate, and only the particles directly contact the substrate itself.

[0026] <First filling device> A manufacturing method of an electrode structure according to the first embodiment will be described in detail. FIG. 2 is an explanatory diagram of the first filling device according to this embodiment, and is a diagram schematically illustrating the configuration of the first filling device. FIGS. 3(A) and 3(B) are explanatory diagrams illustrating the rubbing step according to one aspect of the present disclosure, and the configuration of the filler will be described using FIGS. 3(A) and 3(B). The configuration of the first filling device 1a will be described below, but the same applies to the second filling device and second embodiment described below.

[0027] The first filling device 1a has a rubbing unit 10 and a filling unit 20. The rubbing unit 10 has a first substrate 11a, a magnet 12, a rubbing strength adjustment unit 13 that adjusts the rubbing strength, a stage 14 on which the first substrate 11a is positioned, and a drive unit 15 that drives the magnet. The filling unit 20 has a filling container 22 that contains filler 21a, a supply port 23 that supplies the filler, and a stirring screw member 24 that stirs and conveys the filler 21a.

[0028] The filler 21a has first particles P1 and a support S1 that supports the first particles P1. Such a filler 21a can be used as a rubbing member that includes the support S1. More specifically, the filler 21a is a mixture of multiple powders, including a powder composed of multiple first particles P1 and a powder composed of multiple support S1. The filler 21a contained in the filling container 22 is thoroughly mixed when stirred and conveyed by the stirring screw member 24. That is, the support S1 and the multiple first particles P1 are mixed. As a result, the first particles P1 are supported on the surface of the support S1. The force acting between the particles when supported includes electrostatic force due to frictional charging, etc., but also includes van der Waals force, liquid bridging force, etc.

[0029] The first particles P1 are particles that fill recesses of the concave-convex pattern formed on the first base material 11a. The first particles P1 include at least one of solid electrolyte particles and active material particles. Preferably, the first particles P1 are a plurality of solid electrolyte particles or a plurality of active material particles.

[0030] The active material particles are not particularly limited, and known active material particles can be used. For example, a composite oxide containing lithium can be used. Specifically, for example, LiCoO ２ Li-Co oxide active material particles such as (lithium cobalt oxide), LiMO ２ (M is an element selected from the group consisting of Ni, Mn, and Co), ４ Oxide-based active material particles, lithium vanadium compounds (Li ３ V ２ (P.O. ４ ) ３ , LiVOPO ４ ), olivine-type phosphate compounds (LiMPO ４ (M is one or more elements selected from the group consisting of Co, Ni, Mn, Fe, Mg, V, Nb, Ti, Al, and Zr). Active material particles that do not contain lithium may also be used. Specifically, for example, metal oxides (MnO ２ , V ２ O ５etc.) and fluorides (FeF ３ , V.F. ３ In the case where the active material particles are a composite oxide containing lithium or a metal oxide as described above, they are difficult to undergo elastic deformation or plastic deformation, and therefore tend to have low transferability in the rubbing step. Even in such cases, the manufacturing method of the electrode structure of the present disclosure can easily ensure the reproducibility of the particle pattern. In particular, Li-Co oxide-based active material particles, Li-PO ４ It is preferable that the negative electrode active material contains oxide-based particles. Alternatively, negative electrode active material particles such as graphite, Si, and lithium titanate (LTO) can also be used.

[0031] The solid electrolyte particles are not particularly limited, and known ones can be used. For example, Li-B oxide-based solid electrolyte particles, Li-Yb oxide-based solid electrolyte particles, Nasicon-type solid electrolyte particles (LiAlTi(PO ４ ) ３ , LiAlGe (PO ４ ) ３ etc.), Li-P-O solid electrolyte particles (Li ３ P.O. ４ , LiPON (Li ３ P.O. ４ Examples of suitable solid electrolyte particles include particles in which some of the O in the above-described metal oxide-based solid electrolyte particles are resistant to elastic deformation or plastic deformation, and therefore tend to have poor transferability in the rubbing step. Even in such cases, the method for manufacturing an electrode structure according to the present disclosure can easily ensure the reproducibility of the particle pattern. Among the above-described solid electrolyte particles, it is preferable to use Li—B oxide-based solid electrolyte particles and Li—Yb oxide-based solid electrolyte particles.

[0032] The support S1 is preferably a magnetic particle (hereinafter also referred to as a magnetic particle). The support S1 is more preferably a particle in which the surface of a resin particle in which ferrite core particles or a magnetic material is dispersed is coated with a resin composition. For example, a standard carrier (Standard Carrier P02 manufactured by the Japan Imaging Society), which is a magnetic particle, can be used. The particle size and material of the support S1 are appropriately selected according to the particle size and material of the first particles P1. This allows the first particles P1 to be stably supported. Furthermore, even if the first particles P1 are small in particle size and prone to agglomeration, the support S1 plays a role in loosening the particles by stirring and transporting them with the support S1. The particle size of the support S1 can be appropriately adjusted by the size (area, width, depth) of the recess. For example, the cumulative 50% particle size (median diameter) based on volume is preferably 50 to 100 μm.

[0033] The magnet 12 is placed facing the filling container 22 via the stage 14. The magnet 12 may be made up of a plurality of magnets, and the type of magnets constituting the magnet is not particularly limited. For example, permanent magnets such as rare earth magnets such as ferrite magnets, neodymium magnets, and samarium-cobalt magnets, plastic magnets, and other magnetic field generating means, such as electromagnets, can be used.

[0034] The friction strength adjustment unit 13 is a member for adjusting the friction strength by changing the distance between the uneven pattern surface formed on the first substrate 11a and the magnet 12. In this embodiment, the distance between the uneven pattern surface formed on the first substrate 11a and the magnet 12 is changed to adjust the friction strength, but the method for adjusting the friction strength is not limited to this. The friction strength may be changed by changing the size, number, or type of the magnet 12, or by changing the reciprocating speed at which the drive unit 15 reciprocates the magnet 12. Furthermore, if the magnet 12 is an electromagnet, the friction strength may be changed by changing the current flowing through the magnet. Furthermore, although the friction strength is adjusted using a magnet and a friction strength adjustment unit in this embodiment, a roller may also be used as the friction member, for example.

[0035] The driving unit 15 is a driving device that drives the magnet 12 to give it a relative speed with respect to the first substrate 11a and causes the filler 21a to rub against the first substrate 11a by the magnetic force of the magnet 12. The driving method of the driving device is not limited, and may be a driving device such as an actuator, a belt conveying device between two pairs of rollers, or the like.

[0036] Next, the process of filling the recesses on the first substrate 11a with the first particles P1 using the first filling device 1a will be described using FIGS. 2 to 4(A) and 4(B). The filler 21a is transported by the stirring screw member 24 and supplied onto the first substrate 11a through the supply port 23 (dotted line a in FIG. 2). At this time, a magnetic field is formed by the magnet 12, and the filler 21a containing the magnetic particle carrier S1 is held on the first substrate 11a by this magnetic field. The drive unit 15 performs reciprocating motion, and the magnet 12 fixed to the drive unit 15 also performs reciprocating motion. The magnetic field changed by the reciprocating motion of the magnet 12 also causes the filler 21a held on the first substrate 11a to perform reciprocating motion (dotted line b in FIG. 2). The reciprocating motion of the filler 21a generates a relative velocity between the first substrate 11a and the filler 21a, resulting in the first rubbing step (S102). In this way, the filler 21a can be used as a rubbing member.

[0037] FIG. 3(A) is an explanatory diagram illustrating the rubbing process according to one embodiment of the present disclosure, and is an enlarged view of the surface vicinity of the first substrate 11a during the reciprocating motion during the sliding process. As shown in FIG. 3(A), a concave-convex pattern 111a is formed on the first substrate 11a. The concave-convex pattern can be formed as a desired pattern, such as a honeycomb pattern or a line pattern. That is, the first substrate preferably has multiple convex portions arranged on the substrate. Furthermore, it is preferable that the concave portions correspond to the gaps between two adjacent convex portions among the multiple convex portions. Methods for forming convex portions on the first substrate 11a include known printing techniques such as applying convex portions using a dispenser and screen printing. Methods for forming concave portions on the first substrate 11a include laser ablation and patterning methods using removal means such as sandblasting or water blasting using a mask. By having convex portions on the first substrate in this way, the concave portions become the gaps between the multiple convex portions.

[0038] The specific material of the first substrate 11a is not particularly limited and may be selected depending on the particles used. Examples include resins such as polyimide resin, polyacetal resin, and polyester resin; metals such as aluminum, stainless steel, and Invar alloy; and glass and ceramics. Among these, polyacetal resin is preferred. The shape of the first substrate 11a is not particularly limited as long as it is a sheet-like material having recesses. For example, a substrate that is individually cut like cut paper may be used, or a continuous substrate wound into a roll like roll paper, or a continuous substrate that is alternately folded like continuous paper, may be used.

[0039] Furthermore, the first substrate 11a is preferably subjected to a surface treatment to enhance adhesive strength in order to hold the first particles P1. For example, the recesses of the first substrate 11a preferably include adhesive bottom surfaces. The method for providing the recesses with adhesive bottom surfaces is not particularly limited, but examples include a method in which an adhesive is applied to the bottom surfaces of the recesses of the first substrate 11a to provide adhesive portions. The adhesive is not particularly limited and may be an acrylic adhesive, a rubber adhesive, or a silicone adhesive, or may be a thermoplastic resin or a photocurable resin whose adhesive strength changes in response to external disturbances such as heat or light.

[0040] In FIG. 3A, the distance from the magnet-side surface of the stage 14 to the magnet 12 is Xa, and the force of the vertical component of the force by which the support S1 is attracted to the first substrate 11a by the magnetic field generated by the magnet 12 is Fa. The filler 21a is in contact with the concave-convex pattern 111a. Furthermore, while receiving the force Fa from the surface of the first substrate 11a, the filler 21a reciprocates horizontally together with the magnet 12 at a non-zero relative speed with respect to the first substrate 11a. This results in a first rubbing step (S102) in which the filler 21a is rubbed against the first substrate 11a having the concave-convex pattern 111a on its surface with a first rubbing strength, thereby disposing a portion of the first particles P1 in a portion of the recesses. The number of reciprocating motions is not limited. For the sake of explanation, in Figure 3 (A) the first particles P1 are supported on the surface of the support S1, but when the filler 21a is stirred, supplied or transported, there may be first particles P1 that are not supported on the support S1.

[0041] In this embodiment, the rubbing process is performed by the reciprocating motion of the magnet 12, but this is not limiting. Furthermore, the rubbing direction during the rubbing process may be continuously driven in one direction, or the drive direction may be reversed and driven in the opposite direction. Alternatively, the magnet 12 may be stationary, and the filler 21a on the first substrate 11a may be stopped, while the first substrate 11a is moved by a separate drive unit, thereby causing the first substrate 11a to have a relative speed with respect to the filler 21a, thereby causing rubbing.

[0042] At this time, the particle size of the first particles P1 is smaller than the opening diameter of the recesses of the uneven pattern 111a, and the particle size of the first support S1 is larger than the opening diameter of the recesses, so the first particles P1 can contact the bottom surfaces (bottoms) and side surfaces of the recesses of the uneven pattern 111a, but the support S1 cannot. In other words, only the first particles P1 in the filler 21a selectively contact the bottom surfaces and side surfaces of the recesses.

[0043] The first particles P1 that contact the bottom surface of the recess are restrained by the force that presses the first particles P1 when the carrier S1 contained in the filler 21a is pressed against the substrate, the force that presses the first particles P1 into the first substrate 11a due to the magnetic field of the magnet 12, the physical restraint force due to the structure of the uneven pattern 111a, and non-electrostatic adhesion forces such as electrostatic adhesion and adhesive forces between the first substrate 11a and the structural material that constitutes the uneven pattern 111a, and are detached from the carrier S1 and placed in a portion of the recess of the first substrate 11a. At this time, the first friction strength is set to a strength that positions the first particles P1 in a portion of the recess. Therefore, the force that the first substrate 11a receives is sufficiently small compared to the strength that would damage the substrate. This allows a portion of the first particles P1 to be placed in a portion of the recess while suppressing damage to the first substrate 11a and the filler 21a.

[0044] After the first rubbing step, an intensity adjustment step (S103) is performed in which the rubbing strength adjustment unit 13 changes the distance between the concave-convex pattern surface formed on the first substrate 11a and the magnet 12 to change the magnetic field and increase the rubbing strength. Increasing the rubbing strength results in a second rubbing strength. At this time, the second rubbing strength is stronger than the first rubbing strength. This makes it easier to ensure the reproducibility of the first particle pattern. The second rubbing step (S104) is performed with the rubbing strength increased. Figure 3(B) is an explanatory diagram illustrating the rubbing step according to one embodiment of the present disclosure, and is an enlarged view of the vicinity of the surface of the first substrate 11a during the reciprocating motion during the rubbing step, similar to Figure 3(A). Since the strength adjustment process (S103) has been performed, when the distance from the magnet-side surface of the stage 14 to the magnet 12 is Xb and the vertical component of the force with which the carrier S1 is attracted to the first substrate 11a by the magnetic field formed by the magnet 12 is Fb, Xb is different from Xa, and Fb is different from Fa.

[0045] The first particles P1 that have come into contact with the recesses in the second rubbing step (S104) are strongly constrained by the force that presses the first particles P1 when the support S1 contained in the filler 21a is pressed against the substrate, the force that presses the first particles P1 into the first substrate 11a due to the magnetic field of the magnet 12, the physical restraint force due to the structure of the uneven pattern 111a, and non-electrostatic adhesion forces such as electrostatic adhesion and adhesive forces between the first substrate 11a and the structural material that constitutes the uneven pattern 111a, and are detached from the support S1 and placed in the recesses of the first substrate 11a. At this time, since the second rubbing strength is stronger than the first rubbing strength, the force that presses the first particles P1 in the second rubbing step is stronger than the force that presses the first particles P1 in the first rubbing step. Therefore, in the second rubbing step, the first particles are arranged while pushing aside the particles arranged in the first rubbing step, which makes it easier to ensure the reproducibility of the particle pattern.

[0046] In the second rubbing step (S104), when the carrier S1 passes through the recesses of the concave-convex pattern 111a of the first substrate 11a, the carrier S1 sinks into the recesses as it moves from one end of the recess to the other end of the first substrate 11a, and then climbs up the recesses and moves. Figure 4(A) is an explanatory diagram illustrating the rubbing step according to one embodiment of the present disclosure, showing the state in which the carrier S1 sinks into the recesses when the second rubbing step is performed without the first rubbing step. When the carrier S1 sinks from the convex surface of the concave-convex pattern 111a of the first substrate 11a, the lowest point of the carrier S1 is La, and the amount of sinking of the carrier S1 is Za. The amount of sinking is the distance between La and a plane including the convex surface of the concave-convex pattern 111a.

[0047] 4B is an explanatory diagram illustrating the rubbing step according to one embodiment of the present disclosure, showing the state in which the support S1 sinks into the recesses of the first substrate 11a during the second rubbing step (S104). When the support S1 sinks from the protruding surface of the uneven pattern 111a of the first substrate 11a as shown in FIG. 4B, the lowest point of the support S1 is Lb, and the amount of sinking of the support S1 is Zb. The amount of sinking is the distance between Lb and a plane including the protruding surface of the uneven pattern 111a.

[0048] Here, when the support S1 is rubbed against the first substrate 11a in the second rubbing step, the presence of the first particles P1 arranged in the first rubbing step results in a sinking amount Zb smaller than Za in FIG. 4(A). This reduces the force required to climb up the recesses, and the force received by the first substrate 11a is smaller than when no particles are arranged. As a result, damage to the substrate can be suppressed. This ensures the reproducibility of the particle pattern.

[0049] 3A, 3B, 4A, and 4B, the first particles P1 are all shown with the same particle size, but in reality there is a particle size distribution, and depending on the material, the particles may form aggregated secondary particles. Furthermore, the particles may not have the spherical shape shown in the drawings. Even in such cases, only particles that can contact the recesses of the concave-convex pattern 111a are selectively and densely packed, so that coarse powder and secondary particles that may adversely affect the particle placement process are easily excluded.

[0050] In this way, the amount of the first particles P1 filling the recesses of the concave-convex pattern 111a can be controlled by the size (area, width, height) of the concave-convex pattern and the particle size of the first particles P1. Specifically, the area of ​​the recesses is approximately the filling area, and the layer thickness of the filled first particles P1 is determined by the height of the convex portions. The pitch of the convex portions is not particularly limited, but is preferably, for example, 1.0 to 20 μm, and more preferably 2.0 to 15 μm. The height of the convex portions is not particularly limited, but is preferably, for example, 0.1 to 20.0 μm, and more preferably 1.0 to 10.0 μm. The area ratio of the concave portions (the ratio of the concave portions to the area of ​​the concave-convex pattern) is not particularly limited, but is preferably, for example, 50% or more, and more preferably 70% or more.

[0051] For example, to obtain a thin layer (single layer) that accounts for 50% of the area of ​​the substrate, the area ratio of the recesses (the area ratio of the recesses to the entire concave-convex pattern) should be 50%, and the depth of the recesses should be equal to or less than the particle size of the first particles P1. In this case, the opening width of the recesses should be greater than the median diameter of the first particles P1 and smaller than the average size (here, the average particle size) of the support S1.

[0052] The first particles P1 may have a wide particle size distribution (broad particle size distribution), but the support S1 preferably has a narrow particle size distribution, and is more preferably monodisperse. This makes it easier to prevent the support S1 from contacting the bottom (or bottom surface) or side surface of the recess. If the support S1 can contact the bottom or side surface of the recess, there is a risk that the support S1 will also be restrained and filled in the recess.

[0053] Furthermore, the opening width of the recesses of the uneven pattern 111a is preferably smaller than four times the particle diameter of the first particles P1. By making the opening width smaller than four times the particle diameter of the first particles P1, the probability that the first particles P1 will contact two points, the bottom and side surfaces of the recesses of the uneven pattern 111a, can be increased. In this way, the first particles P1 that make multiple contacts with the recesses of the uneven pattern 111a are strongly constrained by the uneven pattern 111a, thereby increasing the efficiency of filling the uneven pattern 111a with the first particles P1. The same applies to the particle diameter of the second particles P2 (described later) and the size of the recesses of the uneven pattern formed by the first particles P1 on the second substrate. Furthermore, when brush fibers are used as the carrier, the "average particle diameter of the carrier" in the above description becomes the "average fiber diameter of the carrier."

[0054] The mass ratio of the first particles P1 to the carrier S1 in the filler 21a in the filling container 22 is determined by an inductance sensor that measures magnetic permeability, a patch density sensor that measures and predicts the reflection density on a substrate, or the like, which are common in electrophotographic devices. At least one of the first particles P1 and the carrier S1 is replenished by a replenishment means (not shown) as needed. This allows stable filling over a long period of time.

[0055] The content (mass %) of the first particles P1 in the filler 21a (the proportion of the mass of the first particles P1 to the total mass of the filler 21a) is expressed by the following formula (1) using the coverage s1 of the first particles P1 with respect to the surface area of ​​the support: Content (mass %) of the first particles P1 in the filler 21a=(400×ρP1×rP1×s1) / (100×ρc×rc+4×ρP1×rP1×s1) Formula (1) (In formula (1), ρP1 is the true density (g / cm) of the first particles P1.３ ), rP1 represents the particle size (μm) of the first particles P1, and ρc represents the true density (g / cm ３ ), rc represents the particle size (μm) of the support, and s1 represents the coverage (area %) of the first particles P1 with respect to the surface area of ​​the support.) The content (mass %) of the first particles P1 in the filler 21a is not particularly limited, but is preferably in the range of 5 to 40 mass %, or 10 to 30 mass %.

[0056] The coverage s1 in the formula (1) is preferably 30 to 200 area %, more preferably 50 to 100 area %. The particle sizes of the first particles P1 and the support S1 can be determined by laser diffraction / scattering particle size distribution measurement. The true densities of the first particles P1 and the support S1 can be determined by a pycnometer method.

[0057] While the filling device described here uses magnetic particles as a carrier to form a magnetic brush, filling the recesses with particulate material, the filling device's method is not limited to this. Brush fibers can also be used as the carrier. Alternatively, an elastic material, at least the surface of which is made of an elastic material, can be used as the carrier. The direction of these velocity vectors can be changed by changing the position of the substrate in each rubbing process and the driving direction of the driving unit.

[0058] <Second Filling Device> As described above, the first filling device 1a fills the first substrate 11a with the first particles P1. The first substrate 11a can be used as a transfer substrate for transferring the first particles P1 to a second substrate. For example, at a nip formed by contact between the pressure rollers, 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. In the second substrate 11b on which the first particles P1 are arranged, a recess is formed in a portion where the first particles P1 are not arranged. The second filling device fills the recess with the second particles P2 using a process similar to that of the first filling device 1a.

[0059] The second substrate 11b has a stronger adhesive force to the first particles P1 than the first substrate 11a. In other words, the adhesive force of the first particles P1 to the second substrate 11b is stronger than the adhesive force of the first particles P1 to the first substrate 11a. As a result, the first particles P1 on the first substrate 11a are transferred to the second substrate 11b at the nip portion.

[0060] The material of the second substrate 11b is not particularly limited, and a substrate of the same material as the first substrate 11a can be used. Note that, like the first substrate 11a, the second substrate 11b may be a substrate that is individually cut like cut paper, a continuous substrate that is wound into a roll like roll paper, or a continuous substrate that is alternately folded like continuous paper.

[0061] The second substrate 11b is preferably subjected to a surface treatment to enhance adhesive strength in order to transfer the contacted first particles P1. For example, the second substrate 11b preferably has an adhesive layer coated with an adhesive on its surface. The adhesive may be an acrylic adhesive, a rubber adhesive, or a silicone adhesive, or may be a thermoplastic resin or a photocurable resin whose adhesive strength changes in response to external disturbances such as heat or light. The adhesive may be coated on both sides of the second substrate 11b.

[0062] Furthermore, the method for forming the uneven pattern using the first particles P1 on the second substrate 11b is not limited to the transfer method of transferring the first particles P1 from the first substrate 11a to the second substrate 11b as described above.

[0063] The following description will be given of the case where magnetic particles are used as the carrier, but brush fibers or an elastic material may also be used as the carrier, as in the first filling device 1a. The second filling device has the same configuration and function as the first filling device 1a, except that a filler 21b having second particles P2 and carrier S2 is contained in the filling container 22 instead of the filler 21a having first particles P1 and carrier S1.

[0064] The second filling device fills the second particles P2 into the areas of the second substrate 11b where the first particles P1 are not arranged. Even in such a case, since the reproducibility of the pattern of the first particles P1 is ensured, the reproducibility of the pattern of the second particles P2 is also easily ensured. The filler 21b has second particles P2 and a support S2 that supports the second particles P2. Such a filler 21b can be used as a rubbing member including the support S2. More specifically, the filler 21b is a mixture of multiple powders including a powder composed of multiple second particles P2 and a powder composed of multiple supports S2.

[0065] The second particles P2 include at least one of solid electrolyte particles and active material particles. Specifically, the active material particles and solid electrolyte particles described in the description of the first particles above can be used. That is, the second particles P2 are preferably a plurality of solid electrolyte particles or a plurality of active material particles. Furthermore, the first particles P1 and the second particles P2 may be made of the same material or different materials. Furthermore, the support S2 can be made of the same material as the support S1.

[0066] 5A is an explanatory diagram illustrating the rubbing process according to one embodiment of the present disclosure, and is an enlarged view of the vicinity of the surface of the second substrate 11b during the reciprocating motion of the second filling device during the sliding process. As shown in FIG. 5A, a concave-convex pattern is formed on the second substrate 11b, having convex portions formed by the first particles P1 and concave portions where the first particles P1 are not arranged. Furthermore, let Xc be the distance from the magnet-side surface of the stage 14 to the magnet 12, and let Fc be the vertical component of the force by which the carrier S2 is attracted to the second substrate 11b by the magnetic field generated by the magnet 12.

[0067] The filler 21b is in contact with the concave-convex pattern 111b. Furthermore, like the filler 21a, the filler 21b receives a force Fc against the surface of the second substrate 11b, and reciprocates horizontally with the magnet 12 at a non-zero relative speed relative to the second substrate 11b. This results in a first rubbing step (S102) in which the filler 21b is rubbed against the second substrate 11b having the concave-convex pattern 111b on its surface with a first rubbing strength, thereby disposing a portion of the second particles P2 in a portion of the recesses. The number of reciprocating motions is not limited. For illustrative purposes, FIG. 5(A) shows the second particles P2 supported on the surface of the support S2. However, during the agitation, supply, or transport of the filler 21b, there may be second particles P2 that are not supported on the support S2.

[0068] During the first rubbing step (S102), when the carrier S2 passes through the recess of the uneven pattern 111b of the second substrate 11b, the carrier S2 sinks into the recess as it moves from one end of the recess of the second substrate 11b to the other end, and then climbs up the recess and moves.

[0069] At this time, the particle diameter of the second particles P2 is smaller than the opening diameter of the recesses of the uneven pattern 111b, and the particle diameter of the second support S2 is larger than the opening diameter of the recesses, so the second particles P2 can contact the bottom surfaces (bottoms) of the recesses of the uneven pattern 111b, but the support S2 cannot. In other words, only the second particles P2 in the filler 21b selectively contact the bottom surfaces of the recesses (second substrate 11b).

[0070] The second particles P2 that contact the bottom surface of the recess are strongly constrained by the force that presses the second particles P2 when the carrier S2 contained in the filler 21b is pressed against the substrate, the force that presses the second particles P2 into the second substrate 11b due to the magnetic field of the magnet 12, the physical constraining force due to the structure of the uneven pattern 111b, and the electrostatic adhesion and adhesive force between the second substrate 11b and the structural material (here, the first particles P1) that constitutes the uneven pattern 111b, and are detached from the carrier S2 and placed in a portion of the recess of the second substrate 11b. At this time, the first friction strength is set to a strength that positions the second particles P2 in a portion of the recess. Therefore, the force that the second substrate 11b receives is sufficiently small compared to the strength that would damage the substrate. This allows a portion of the second particles P2 to be placed in a portion of the recess while suppressing damage to the second substrate 11b and the filler 21b.

[0071] After the first rubbing step, an intensity adjustment step (S103) is performed in which the rubbing strength adjustment unit 13 changes the distance between the concave-convex pattern surface formed on the second substrate 11b and the magnet 12 to change the magnetic field and increase the rubbing strength. Increasing the rubbing strength results in a second rubbing strength. At this time, the second rubbing strength is higher than the first rubbing strength. This makes it easier to ensure the reproducibility of the second particle pattern. The second rubbing step (S104) is performed with the rubbing strength increased. Figure 5(B) is an explanatory diagram illustrating the rubbing step according to one embodiment of the present disclosure, and is an enlarged view of the vicinity of the surface of the second substrate 11b during the reciprocating motion during the rubbing step, similar to Figure 5(A). Since the strength adjustment process (S103) has been performed, when the distance from the magnet-side surface of the stage 14 to the magnet 12 is Xd and the vertical component of the force with which the carrier S2 is attracted to the second substrate 11b by the magnetic field formed by the magnet 12 is Fd, Xd is different from Xc, and Fd is different from Fc.

[0072] The second particles P2 that have come into contact with the recesses in the second rubbing step (S104) are strongly constrained by the force that presses the second particles P2 when the carrier S2 contained in the filler 21b is pressed against the substrate, the force that presses the second particles P2 into the second substrate 11b due to the magnetic field of the magnet 12, the physical restraint force due to the structure of the uneven pattern 111b, and non-electrostatic adhesion forces such as electrostatic adhesion and adhesive forces between the second substrate 11b and the structural material that constitutes the uneven pattern 111b, and are detached from the carrier S2 and placed in the recesses of the second substrate 11b. At this time, since the second rubbing strength is stronger than the first rubbing strength, the force that presses the second particles P2 in the second rubbing step is stronger than the force that presses the second particles P2 in the first rubbing step. Therefore, in the second rubbing step, the second particles are placed while pushing aside the particles placed in the first rubbing step, which makes it easier to ensure the reproducibility of the particle pattern.

[0073] As with the arrangement of the first particles, in the second rubbing step (S104), when the carrier S2 passes through the recesses of the concave-convex pattern 111b of the second substrate 11b, i.e., between the arranged first particles, the carrier S2 sinks into the recesses as it moves from one end of the recess of the first substrate 11a to the other, and then climbs up the recesses and moves. FIG. 6(A) is an explanatory diagram illustrating the rubbing step according to one embodiment of the present disclosure, showing the state in which the carrier S2 sinks into the recesses when the second rubbing step is performed without the first rubbing step. When the carrier S2 sinks from the first particle P1, which is the convex portion of the concave-convex pattern 111b of the second substrate 11b, the lowest point of the carrier S2 is Lc, and the sinking amount of the carrier S2 is Zc. The sinking amount is the distance between Lc and a plane including the apex of the convex portion of the concave-convex pattern 111b.

[0074] 6B is an explanatory diagram illustrating the rubbing step according to one embodiment of the present disclosure, showing the state in which the support S2 sinks into the recesses of the second substrate 11b during the second rubbing step (S104). When the support S2 sinks from the surface of the protrusions of the concave-convex pattern 111b of the second substrate 11b as shown in FIG. 6B, the lowest point of the support S1 is Ld, and the amount of sinking of the support S2 is Zd. The amount of sinking is the distance between Ld and a plane including the apexes of the protrusions of the concave-convex pattern 111b.

[0075] Here, when the support S2 is rubbed against the second substrate 11b in the second rubbing step, the second particles P2 arranged in the first rubbing step are present, so the sinking amount Zd is smaller than Zc in FIG. 6A. This reduces the force required to climb up the recesses, suppresses the movement of the first particles P1 on the second substrate 11b, and makes it easier to ensure pattern reproducibility. As described above, the reproducibility of the particle pattern is ensured when manufacturing the electrode structure.

[0076] Second Embodiment The second embodiment differs from the first embodiment in the flowchart of the substrate arrangement method. FIG. 7 is an image diagram illustrating a method for manufacturing an electrode structure according to one aspect of the present disclosure, and is a flowchart of the substrate arrangement method. In the second embodiment, when a plurality of particles including at least one of solid electrolyte particles and active material particles are arranged on a first substrate, a rubbing step and a strength adjustment step are repeatedly performed. That is, the method for manufacturing an electrode structure includes the supporting step described in the description of the first embodiment, the first rubbing step described in the description of the first embodiment, and an Nth rubbing step performed after the first rubbing step. The Nth rubbing step is a step of rubbing a rubbing member with an Nth rubbing strength to arrange a portion of the plurality of particles in a recess. When any of the first to Nth rubbing steps is designated as the nth rubbing step, the nth rubbing strength is preferably higher than the n-1th rubbing strength. Here, N represents an integer satisfying 2≦N≦M, M represents an integer selected from integers equal to or greater than 3, and n represents an integer represented by N. That is, n represents an integer satisfying 2≦n≦M. The nth rubbing step may be a step performed after the (n-1)th rubbing step. Furthermore, the manufacturing method of the electrode structure preferably further includes an intensity adjustment step for adjusting the rubbing strength between the nth rubbing step and the (n-1)th rubbing step. As the intensity adjustment step, the steps described in the description of the first embodiment can be used.

[0077] For example, if M is 3, then N is 2 and 3, and n is 2 and 3. In this case, the method for manufacturing an electrode structure according to this embodiment includes a supporting step of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to dispose some of the plurality of particles in some of the recesses; a second rubbing step performed after the first rubbing step; and a third rubbing step performed after the first rubbing step, wherein the second rubbing step is a step of rubbing the rubbing member against the substrate with a second rubbing strength to dispose some of the plurality of particles in the recesses, and the third rubbing step is a step of rubbing the rubbing member against the substrate with a third rubbing strength to dispose some of the plurality of particles in the recesses, and the third rubbing strength is a step of rubbing the rubbing member against the substrate with a third rubbing strength to dispose some of the plurality of particles in the recesses, and the third rubbing strength is higher than the second rubbing strength, and the second rubbing strength is higher than the first rubbing strength. Here, the Nth rubbing step can use the method described in the description of the second rubbing step.

[0078] By performing the rubbing process while changing the rubbing strength in M ​​stages, the force applied to the substrate is further reduced, and damage to the substrate can be suppressed, even when the particles are made of a material that is more likely to damage the uneven pattern of the substrate than in the first embodiment. As a result, the reproducibility of the particle pattern is more easily ensured.

[0079] In the first and second embodiments, the movement direction of the rubbing member relative to the substrate in the n-1th rubbing step is defined as the n-1th velocity vector, and the movement direction of the rubbing member relative to the substrate in the nth rubbing step is defined as the nth velocity vector. When the nth velocity vector is decomposed, it is preferable that the nth velocity vector has a directional component parallel to the n-1th velocity vector. Here, n preferably represents at least one integer selected from the group consisting of integers represented by N, and more preferably represents each integer represented by N. That is, n preferably represents at least one integer satisfying 2≦n≦M, and more preferably represents each integer satisfying 2≦n≦M. M represents an integer selected from integers equal to or greater than 2. It is also more preferable that the nth velocity vector is parallel or anti-parallel to the n-1th velocity vector. As a result, the direction of the nth rubbing step is aligned with the direction of the (n-1)th rubbing step, making it easier to achieve the effect of suppressing damage to the substrate and more easily ensuring the reproducibility of the particle pattern.

[0080] In addition, the directional component of the nth velocity vector parallel to the n-1th velocity vector may be in the same direction as the n-1th velocity vector, or may be in the opposite direction, but is preferably in the same direction. If the directional component is in the same direction, the substrate surface subjected to rubbing and the vector of rubbing received by the substrate are in the same direction, which results in the effect of more easily ensuring the reproducibility of the particle pattern. Furthermore, if the directional component is in the opposite direction, when the nth rubbing step is performed after the n-1th rubbing step, the nth rubbing step can be performed without moving the rubbing member between each rubbing step, which makes it easier to improve transfer efficiency. The direction of these velocity vectors can be changed depending on the placement position of the substrate in each rubbing step and the driving direction of the drive unit.

[0081] The filling device used in the second embodiment can be the first filling device or the second filling device described in the description of the first embodiment. That is, the second embodiment can be used to place first particles on a first substrate, or to place second particles on a second substrate. In addition, materials such as fillers can be used that are described in the description of the first embodiment.

[0082] Third Embodiment This embodiment illustrates a method for manufacturing an electrode structure using brush fibers as the carrier. FIG. 8 is an explanatory diagram of a third filling device, schematically illustrating the configuration of a third filling device 1c when brush fibers are used as the carrier. Compared to the filling device 1a of FIG. 2, the filling device 1c differs from the filling device 1a of FIG. 2 in that the filler 21a is a filler 21c that does not contain the carrier S1 and in that a roller 121 having brush fibers on its surface is used as the rubbing member. The material of the fibers constituting the brush fibers is not particularly limited, and examples thereof include nylon, rayon, acrylic, vinylon, polyester, and vinyl chloride. Surface treatment may be applied to the fiber surface to adjust the chargeability and rigidity.

[0083] The filling unit 20 has a function of supplying the filler 21c to the roller 121. The filler 21c contains a powder composed of a plurality of first particles and is contained in the filling unit 20. As described above, the filler 21c in this example does not contain the carrier S1. The filler 21c is agitated by the agitating screw member 24 and transported from the supply port 23 to the roller 121. The filler 21c is charged by contact with the brush fibers of the roller 121 and is carried by the brush fibers, which serve as the carrier, of the roller 121. In this manner, a carrying step (S101) is performed in which a plurality of particles are carried by the rubbing member.

[0084] Next, the roller is reciprocated by the drive unit 15, causing the first substrate 11a and the filler 21c to rub against each other. In this way, a first rubbing step (S102) is performed in which the rubbing member is rubbed against the sheet-like substrate having recesses at a first rubbing strength, and a portion of the plurality of particles is disposed in a portion of the recesses. At this time, the first rubbing strength is set to a strength that disposes the first particles in a portion of the recesses. Therefore, the force applied to the first substrate 11a is sufficiently small compared to the strength that would damage the first substrate 11a or the filler 21a.

[0085] At this time, the first particles in the filler 21c can contact the bottom surfaces of the recesses of the uneven pattern 111a on the surface of the first substrate 11a, but the brush fibers cannot. That is, the fiber diameter of the brush fibers is set to be larger than the opening width of the recesses of the uneven pattern. The fiber diameter of the brush fibers can be measured by placing glass on the surface of the roller 121 and taking an image of the brush fibers through the glass using an optical microscope.

[0086] After the first rubbing step, an intensity adjustment step (S103) is performed in which the rubbing strength adjustment unit 13 changes the distance between the roller 121 and the uneven pattern surface formed on the first substrate 11a to change the contact force and increase the rubbing strength. Increasing the rubbing strength results in a second rubbing strength. At this time, the second rubbing strength is stronger than the first rubbing strength. This makes it easier to ensure the reproducibility of the first particle pattern. The second rubbing step (S104) is performed with the increased rubbing strength. The first particles that contact the recesses in the second rubbing step (S104) are strongly constrained by the force of the brush fibers pressing the first particles, the physical constraining force due to the uneven pattern structure, and non-electrostatic adhesive forces such as electrostatic adhesion and adhesive forces between the first substrate 11a and the structural material that constitutes the uneven pattern, and are detached from the roller 121 and placed in the recesses of the first substrate 11a.

[0087] At this time, since the second rubbing strength is stronger than the first rubbing strength, the force pushing the first particles in the second rubbing process is stronger than the force pushing the first particles in the first rubbing process. Therefore, in the second rubbing process, the first particles are arranged while pushing aside the particles arranged in the first rubbing process. At this time, for the same reason as in the first embodiment, the force applied to the first substrate 11a in the second rubbing process is smaller than when no particles are arranged. As a result, damage to the substrate can be suppressed. This ensures the reproducibility of the particle pattern.

[0088] The third filling device used in the third embodiment can be used like the second filling device described in the description of the first embodiment. That is, the third embodiment may be used to arrange first particles on a first substrate, or to arrange second particles on a second substrate. Furthermore, materials such as fillers can be used that are described in the description of the first embodiment. Furthermore, using the third filling device used in the third embodiment, the rubbing process and the strength adjustment process may be repeated when arranging first particles on a first substrate or when arranging second particles on a second substrate, as in the second embodiment.

[0089] The method for manufacturing an electrode structure according to the present disclosure can be used as a method for manufacturing an electrode or a precursor of an active material layer of a solid-state battery. That is, the electrode structure may be, for example, a precursor of an electrode of a solid-state battery or a precursor of an active material layer. The electrode structure according to the present disclosure contributes to improving battery performance.

[0090] An electrode structure can be used as a precursor for an electrode of a solid-state battery to obtain a material laminate in which the electrode structure is stacked. The obtained material laminate is then thermally degreased to obtain an electrode for a solid-state battery. That is, a method for manufacturing an electrode for a solid-state battery may include the steps of obtaining an electrode structure by the above-described manufacturing method, stacking the obtained electrode structures to obtain a laminate, and thermally degreasing the obtained laminate to remove the second substrate and obtain an electrode. When the solid-state battery is a single layer battery, a method for manufacturing an electrode for a solid-state battery may include the steps of obtaining an electrode structure by the above-described manufacturing method and thermally degreasing the electrode structure to remove the second substrate and obtain an electrode.

[0091] That is, an electrode for a solid-state battery can be obtained by removing the second substrate from the laminate. Known methods can be used for the process of obtaining the laminate and the process of forming the three-dimensional object. The electrode may be a positive electrode or a negative electrode. The number of layers in the laminate is not particularly limited and can be changed depending on the purpose of the electrode to be manufactured. For example, three or more layers can be used.

[0092] The present disclosure will be specifically described below with reference to examples, but these examples are not intended to limit the present disclosure in any way. In the following formulations, parts are by mass unless otherwise specified.

[0093] Example 1 This shows an example of fabricating an electrode structure using the filling device of FIG. 2 . The filler used lithium cobalt oxide (LCO) as the first particles and magnetic particles as the carrier. A neodymium magnet was used as the magnet, a height adjustment stage was used as the friction strength adjustment unit, and an actuator was used as the drive unit. The substrate was made of polyacetal resin, and a concave-convex pattern was processed using a CO2 laser. Next, a resin solution prepared by dissolving a water-soluble thermoplastic resin in a solvent was applied as an adhesive only to the concave portions of the concave-convex pattern. After drying the applied resin solution, the substrate was heated to 60°C to soften the water-soluble thermoplastic resin. In this state, the drive unit was driven, and a magnet mounted on the height adjustment stage mounted on the drive unit was driven and moved back and forth to rub the filler on the substrate, thereby performing a rubbing process. The number of reciprocations was 100. Here, the first rubbing process and the second rubbing process were each repeated once, for a total of 50 times. The second rubbing strength, which is the strength of the second rubbing step, was set to be higher than the first rubbing strength, which is the strength of the first rubbing step. It was confirmed that the reproducibility of the uneven pattern created in the first rubbing step and the uneven pattern created in the tenth rubbing step maintained a predetermined reproducibility. The reproducibility of the particle pattern was evaluated by performing spatial frequency analysis of each of the first particle development patterns after the Nth development of the recessed pattern of the plate, and evaluating the effect of decreasing high-frequency components and increasing low-frequency components.

[0094] [Comparative Example 1] The reproducibility of the particle pattern was confirmed in the same manner as in Example 1, except that the reciprocating motion was performed 100 times at the second rubbing strength in Example 1. As a result, compared to Example 1, the reproducibility of the pattern maintained a predetermined performance in the concave-convex pattern created the first time, but a decrease in the reproducibility of the particle pattern was observed in the concave-convex pattern created the 10th time.

[0095] As described above, according to the present disclosure, it is possible to provide a manufacturing method for an electrode structure that can ensure the reproducibility of particle patterns.

[0096] The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible without departing from the spirit and scope of the present invention. Therefore, the following claims are appended to clarify the scope of the present disclosure. This application claims priority based on Japanese Patent Application No. 2024-045593, filed March 21, 2024, the entire contents of which are incorporated herein by reference.

[0097] 1a: first filling device, 1c: third filling device, 10: rubbing section, 11a: first substrate, 11b: second substrate, 12: magnet, 13: rubbing strength adjustment section, 14: stage, 15: drive section, 20: filling section, 21a: filler, 22: filling container, 23: supply port, 24: stirring screw member, 111a: uneven pattern, 111b: uneven pattern, 121: roller, P1: first particle, P2: second particle, S1: support, S2: support

Claims

1. A method for manufacturing an electrode structure, comprising: a supporting step of supporting a plurality of particles including at least one of solid electrolyte particles and active material particles on a rubbing member including a support; a first rubbing step of rubbing the rubbing member against a sheet-like substrate having recesses with a first rubbing strength to dispose some of the plurality of particles in some of the recesses; and an Nth rubbing step performed after the first rubbing step, wherein the Nth rubbing step is a step of rubbing the rubbing member against the substrate with an Nth rubbing strength to dispose some of the plurality of particles in the recesses, and wherein when any of the first to Nth rubbing steps is designated as the nth rubbing step, the nth rubbing strength is higher than the (n-1)th rubbing strength. (N represents an integer satisfying 2≦N≦M, M represents an integer selected from integers of 2 or more, and n represents at least one integer selected from the group consisting of integers represented by N.) 2. The method for manufacturing an electrode structure according to claim 1, wherein M is any one of 2 to 4.

3. The method for manufacturing an electrode structure according to claim 1 or 2, wherein n represents an integer represented by N.

4. A method for manufacturing an electrode structure according to any one of claims 1 to 3, wherein the substrate has a plurality of protrusions arranged on the substrate, and the recessed portion corresponds to a gap between two adjacent protrusions among the plurality of protrusions.

5. A method for manufacturing an electrode structure according to any one of claims 1 to 4, wherein the recess includes a bottom surface having adhesive properties.

6. A method for manufacturing an electrode structure according to any one of claims 1 to 5, further comprising an intensity adjustment step between the nth rubbing step and the (n-1)th rubbing step for adjusting the friction strength, wherein the intensity adjustment step is a step for adjusting the friction strength by at least one of the operating distance between the rubbing member and the substrate, the physical properties of the carrier, the moving speed of the rubbing member relative to the substrate, and the electromagnetic waves acting on the carrier.

7. The method for manufacturing an electrode structure according to claim 6, wherein the physical property includes magnetism and the electromagnetic wave includes a magnetic field.

8. The method for manufacturing an electrode structure according to any one of claims 1 to 7, wherein the direction of movement of the rubbing member relative to the substrate in the (n-1)th rubbing step is defined as the (n-1)th velocity vector, the direction of movement of the rubbing member relative to the substrate in the nth rubbing step is defined as the nth velocity vector, and when the nth velocity vector is resolved, the nth velocity vector has a directional component parallel to the (n-1)th velocity vector (n represents at least one integer selected from the group consisting of integers represented by N).

9. The method for manufacturing an electrode structure according to claim 8, wherein the nth velocity vector is parallel or anti-parallel to the n-1th velocity vector.

10. The method for manufacturing an electrode structure according to any one of claims 1 to 9, wherein the support is a particle having magnetic properties.

11. The method for manufacturing an electrode structure according to any one of claims 1 to 10, wherein the plurality of particles are a plurality of active material particles or a plurality of solid electrolyte particles.

12. The method for manufacturing an electrode structure according to any one of claims 1 to 11, wherein the substrate includes a resin substrate.

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