Molded body package, molded body carrier, method for manufacturing a molded body, molded body of powder

Abstract

This technology provides an improvement in the production efficiency of powder-molded products. [Solution] A powder molded body package comprising a first base, a second base, a first mold member disposed between the first base and the second base, and a second mold member disposed adjacent to the first mold member between the first base and the second base, wherein a first homogeneous particle portion containing powder, disposed in the space formed by the first base, a first void in the first mold member, a second void in the second mold member, and the second base, is sandwiched between the first surface of the first mold member constituting the first void and the second surface of the second mold member constituting the second void, the first Young's modulus of the material constituting the first mold member is higher than the second Young's modulus of the material constituting the second mold member, and the third Young's modulus, which is the Young's modulus of the material constituting at least one of the first base and the second base, is higher than the first Young's modulus.

Description

[Technical Field]

[0001] The present invention relates to a molded body package, a molded body carrier, a method for manufacturing a molded body, and a molded body made from powder. [Background technology]

[0002] In recent years, with the miniaturization and increased precision of electronic components, there has been a growing need for technologies to manufacture thin powder molded bodies with high yield as part of the components of electronic devices. In particular, thin powder molded bodies are desired for the solid electrolyte layer used in all-solid-state batteries, as thinner layers result in lower resistance and improved battery performance.

[0003] However, thin powder molded bodies are fragile and difficult to mold. Generally, powder molded bodies are manufactured by filling a mold with the material powder and compressing it under pressure, but according to the inventor's research, the molded body often breaks when it is removed from the mold after compression. Typically, thin powder molded bodies are made by first molding them to a thickness, then heat-treating (sintering) them to increase the fixing strength between particles, and finally polishing them. This is inefficient in terms of material usage, and the polishing step makes production very inefficient, as well as raising concerns about contamination due to impurities. In response to this, a technology for directly manufacturing thin powder molded bodies has been proposed (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2012-221887 [Patent Document 1] Japanese Patent Publication No. 2006-128027 [Overview of the project] [Problems that the invention aims to solve]

[0005] Patent Document 1 discloses a technique for equalizing the powder amount distribution filled in a mold. Certainly, when the variation in the powder amount in the mold decreases, the strength unevenness of the molded body during pressure molding decreases, so there is an advantage that cracks are less likely to occur even if the molded body is thin. However, since the strength level of the molded body itself is extremely low, the probability of being broken when removed from the mold is not low.

[0006] Patent Document 2 discloses a technique focusing on the ease of removing a powder molded body from a mold, namely a technique of molding by sandwiching a release film between the upper and lower pressure surfaces of the mold. According to this method, although the releasability between the release film and the mold is enhanced, since the particles on the surface of the powder molded body bite into the release film due to pressure, there is a possibility that the particles on the surface of the powder molded body are peeled off simultaneously with the removal of the release film, and a thin powder molded body is still likely to be damaged.

[0007] An object of the present invention is to provide a technique capable of improving the production efficiency of a powder molded body.

Means for Solving the Problems

[0008] In order to solve the above problems, the molded body package of the present invention is a powder molded body package, comprising a first base, a second base, a first mold member disposed between the first base and the second base, the first mold member having a first void portion penetrating the first mold member in a facing direction in which the first base and the second base face each other a first mold member, a second mold member disposed adjacent to the first mold member between the first base and the second base, the second mold member having a second void portion penetrating the second mold member in the facing direction and communicating with the first void portion a first homogeneous particle portion containing powder, disposed in a space formed by the first base, the first void portion, the second void portion, and the second base, and is provided with The first homogeneous particle portion is sandwiched between both the first surface of the first mold member constituting the first void portion and the second surface of the second mold member constituting the second void portion. The first Young's modulus of the material constituting the first mold member is higher than the second Young's modulus of the material constituting the second mold member. A third Young's modulus, which is the Young's modulus of the material constituting at least one of the first base and the second base, is higher than the first Young's modulus. It is characterized by this.

Effect of the Invention

[0009] According to the present invention, the production efficiency of the powder compact can be improved.

Brief Description of the Drawings

[0010] [Figure 1] It is a flowchart of the method for manufacturing the powder compact of the present invention. [Figure 2] It is an example of the configuration of the molding member of the present invention. [Figure 3] It is an example of the formed body package and the formed body carrier of the present invention. [Figure 4] It is an example of a method for filling powder into the space inside the molding member of the present invention. [Figure 5] It is an example of a method for filling powder into the space inside the molding member of the present invention. [Figure 6] It is an example of a method for filling different powder materials of the present invention. <000​​​​​​​​​​​​This table compares the test results of the examples and comparative examples of the present invention. [Modes for carrying out the invention]

[0011] The embodiments for carrying out this invention will be described in detail below with reference to the drawings, based on examples. However, the dimensions, materials, shapes, and relative arrangements of the components described in these embodiments should be appropriately modified depending on the configuration of the device to which the invention is applied and various conditions. In other words, the scope of this invention is not intended to be limited to the following embodiments. Furthermore, although multiple features are described in the embodiments, not all of these features are necessarily essential to the invention, and the multiple features may be combined arbitrarily. In addition, in the attached drawings, the same or similar components are given the same reference numeral, and redundant explanations are omitted.

[0012] <Embodiment> The method for producing the powder molded article of the present invention will be described step by step.

[0013] Figure 1 is a flowchart of the manufacturing process for a powder molded body in an embodiment of the present invention. Figures 2(a) to 2(f) illustrate the configuration of the mold 1 for molding the powder molded body in an embodiment of the present invention. Figure 2(a) is a schematic plan view of the second base 22. Figure 2(b) is a schematic plan view of the second mold member 32. Figure 2(c) is a schematic plan view of the first mold member 31. Figure 2(d) is a schematic plan view of the first base 21. Figure 2(e) is a schematic cross-sectional view showing the stacking order of each member shown in Figures 2(a) to 2(d), and is a cross-sectional view obtained by cutting each member in the stacking direction D. Figure 2(f) is a schematic cross-sectional view showing the state in which the mold 1 is formed by stacking each member shown in Figures 2(a) to 2(d).

[0014] Here, the plan views shown in Figures 2(a) to 2(d) show the planar configuration of each component constituting the mold 1 when viewed in the stacking direction D. Also, the cross-sectional views shown in Figures 2(e) and 2(f) correspond to the cross-sectional views along the α arrow in Figures 2(a) to 2(d). The stacking direction D and the direction along the α arrow are mutually orthogonal directions.

[0015] The mold 1 according to an embodiment of the present invention includes, as necessary components, two bases 21 and 22 (Figures 2(a) and 2(d)), a first mold member 31 (Figure 2(c)), and a second mold member 32 (Figure 2(b)). By stacking these members as shown in Figures 2(e) and 2(f), a void (space) 4 for filling with powder particles to be molded is formed (Figure 1, S101).

[0016] Specifically, the first mold member 31 is stacked on the upper surface 211 of the first base 21. A through hole 311 penetrates the first mold member 31 in the stacking direction D. The inner circumferential surface 312 (first surface) that constitutes the through hole 311 in the first mold member 31 becomes part of the wall surface that forms the void 4. One opening of the through hole 31a in the stacking direction D is blocked by the upper surface 211 of the first base 21. The area on the upper surface 211 of the first base 21 that blocks one opening of the through hole 311 becomes part of the wall surface that forms the void 4.

[0017] The second mold member 32 is stacked on the upper surface of the first mold member 31. The second mold member 32, adjacent to the first mold member 31, also has a through hole 321 that penetrates in the stacking direction D. The inner circumferential surface 322 (second surface) that constitutes the through hole 321 in the second mold member 32 becomes part of the wall surface that forms the void 4. The through hole 311 of the first mold member 31 and the through hole 321 of the second mold member 32 are aligned in the stacking direction D. That is, the other opening of the through hole 311 in the stacking direction D communicates with one opening of the through hole 321. The first mold member 31 is stacked on the upper surface of the second mold member 32. The other opening of the through hole 321 in the stacking direction D is blocked by the lower surface 222 of the second base 22. The area on the lower surface 222 of the second base 22 that blocks the other opening of the through hole 321 becomes part of the wall surface that forms the void 4.

[0018] In other words, the void 4 is formed by the upper surface 211 of the first base 21, the inner circumferential surface 312 of the first mold member 31, the inner circumferential surface 322 of the second mold member 32, and the lower surface 222 of the second base 22. The void 4 is a substantially cylindrical space having a central axis extending in the stacking direction D. The stacking direction D is also the direction in which the first base 21 and the second base 22 face each other.

[0019] In this document, the terms "up" and "down" may be used to describe the stacking direction, with one direction being upward and the other downward, or vice versa. However, this does not necessarily correspond to the vertical direction of gravity. Furthermore, while this embodiment exemplifies a typical shape of the powder molded body 5x as a thin plate with a circular planar shape, it is not limited to this shape.

[0020] Here, the mold 1 according to this embodiment is characterized by having a difference in hardness between the first base 21, the second base 22 and the first mold member 31, the second mold member 32. Specifically, the hardness is arranged in the order of first, second bases 21, 22, first mold member 31, and second mold member 32. As an index of hardness, expressed as Young's modulus, the Young's modulus of the first and second bases 21, 22 is 50 GPa or more, more preferably 100 GPa or more, and even more preferably 200 GPa or more. It is preferable that the pressure is as described above. The first mold member 31 is preferably 50 MPa to 20 GPa, more preferably 1 GPa to 10 GPa. The second mold member 32 is preferably 0.1 MPa to 20 MPa, more preferably 0.5 MPa to 5 MPa. Although it varies depending on the powder material to be molded, it is preferable to have a Young's modulus difference of about 5 times between each member.

[0021] As for specific materials, metal materials can generally be suitably used for the first and second bases 21 and 22. Examples include nichrome, stainless steel, iron and iron alloys, titanium and titanium alloys, copper and copper alloys, aluminum and aluminum alloys. Nichrome and stainless steel are particularly suitable in terms of hardness and workability.

[0022] Furthermore, the difference in hardness between the first base 21 and the second base 22 may be the same hardness as they are made of the same material, or they may be different hardnesses as they are made of different materials, as long as each is harder than the first mold member 31 and the second mold member 32, respectively.

[0023] For the second mold member 32, a resin material is generally preferable. Examples include polyimide, polyester, polypropylene, and polyethylene. Polyester is particularly preferable in terms of hardness and processability.

[0024] Generally, rubber materials are preferably used for the first mold member 31. Examples include silicone rubber, ethylene-propylene-diene rubber, urethane rubber, butyl rubber, nitrile rubber, styrene-butadiene rubber, chloroprene rubber, and natural rubber. Silicone rubber is particularly suitable in terms of hardness selectivity and processability.

[0025] It is desirable to select the appropriate material depending on the powder material to be molded, the desired shape, and the pressure applied during molding.

[0026] In this embodiment, there are no particular restrictions on the shape of the first and second mold members 31 and 32. A thicker form can be adopted as a mold member for forming a thick powder molded body, for example, to obtain sufficient strength for the powder molded body. However, as a configuration in which the effects of the present invention can be more clearly demonstrated, a thin sheet form is preferably used as a mold member for creating a thin powder molded body. Depending on the material, according to the inventor's research, the advantages of the present invention become evident when the thickness of the powder molded body is 1 mm or less, and for example, when using particles with an average particle size of about 5 μm, it can be applied to thicknesses up to about 100 μm.

[0027] Here, a molded body package 6 is defined as a mold 1 filled with powder material 5. Figures 3(a) to 3(d) show schematic cross-sectional views of various configurations (molded body packages 6a to 6d) of the molded body package 6 according to the embodiment of the present invention. As shown in Figures 3(a) to 3(d), various configurations (molded bodies 1a to 1d) can be adopted for the laminated structure of the mold 1. Note that the molded body package 6a shown in Figure 3(a) has a configuration in which the void portion 4 of the mold 1a, which has the same configuration as the mold 1 shown in Figure 2(f), is filled with powder material 5.

[0028] Furthermore, a distribution configuration in which the molded body package 6 is housed in the sealing member 7 is referred to as the molded body carrier 8, and an example of its configuration is shown in Figure 3(e). Figure 3(e) is a schematic cross-sectional view showing an example of the configuration of the molded body carrier 8 according to an embodiment of the present invention. Figure 3(e) shows an example in which the molded body package 6b is housed in the sealing member 7 to constitute the molded body carrier 8.

[0029] For example, when creating a powder molded body of about 250 μm, the thickness of the first mold member 31 and the second mold member 32 are each about 100 μm thick, and two layers are stacked alternately, as shown in Figure 3(b). It is preferable to have such a configuration.

[0030] A first mold member 31 and a second mold member 32 capable of forming a gap 4 of a desired shape are stacked on the surface of a single base 21. The gap (through holes 311, 321) may be formed on each of the first mold member 31 and the second mold member 32 individually before stacking (Figure 2(e)), or the gap may be created after the first mold member 31 and the second mold member 32 have been stacked in advance. That is, after the first mold member 31 and the second mold member 32 have been stacked on the first base 21, through holes 311, 321 may be formed on each of the first mold member 31 and the second mold member 32 to form the gap 4 (Figure 2(f)).

[0031] The void portion 4 (through holes 311, 321) can be formed using general processing techniques. Specifically, for example, RTV-type silicone rubber can be applied to a predetermined thickness onto a PET film sheet processed to the thickness specified in the design, dried, and then a mold member set with void portions can be created by die cutting or laser processing. The void portion 4 of the molded package 6a shown in Figure 3(a) is a simple circular shape, but is not limited to this and can be any shape, including a square shape. Furthermore, multiple void portions can be provided on the same mold member surface to simultaneously pressure-molde multiple powder molded bodies.

[0032] The thicknesses of the first mold member 31 and the second mold member 32 can be designed arbitrarily, and if a high compression ratio is desired, it is preferable to design the first mold member 31, which is more easily deformed, to be thicker. Also, as shown in Figure 3(b), it is possible to stack multiple layers of the first mold member 31 and the second mold member 32 alternately. According to the inventor's research, it was often easier to remove the powder molded product when there were two or more layers each of the first mold member 31 and the second mold member 32.

[0033] The molding thickness can be easily changed by increasing or decreasing the number of layers of mold members 31 and 32 made of a predetermined thickness. When multiple layers of mold members 31 and 32 are stacked, they may be stacked in pairs of mold members 31 and 32 of the same material and thickness, or in pairs of mold members of different materials and thicknesses. Furthermore, as shown in Figure 3(c), it is also possible to change the shape of the gap for each layer. In addition, the spaces between mold members 31 and 32 and the spaces between mold members 31 and 32 and the bases 21 and 22 may be bonded, or the first mold member 31 may be made surface-adhesive so that it can be fixed simply by stacking them.

[0034] Furthermore, the upper surface 211 of the first base 21 is not perfectly flat. For example, as shown in Figure 3(d), a protrusion 213 projecting in the stacking direction may be provided on the upper surface 211 to create an uneven surface on a part of the surface forming the gap 4.

[0035] The first mold member 31 and the second mold member 32 are stacked on the first base 21, and the void 4 is filled with powder material 5 (Figure 1, S102). In terms of operation of the present invention, the effect does not change regardless of whether the first mold member 31 or the second mold member 32 is on top, but if the second mold member 32 is placed above the opening surface of the void 4, powder adhesion to the mold members is less likely to occur, and filling of the powder material 5 is often easier.

[0036] The powder material 5 can be filled by weighing each portion and filling a fixed weight, but more simply, as shown in Figures 4(a) to 4(d), the powder material 5 can be supplied in excess so that it overflows from the void 4, and then leveled off by a blade member 9 such as a squeegee, thereby filling the void 4 with the powder material 5. If a higher density of filling is desired, as shown in Figures 5(a) to 5(f), a mold member or an applicator equivalent to a mold member can be stacked and leveled off, then removed, and the second base 22 can be stacked on top and pre-pressurized to fill the void 4 with the powder material 5. This allows the powder material 5 to be filled more densely into the void 4.

[0037] The powder material 5 used to fill the void 4 is not limited to any particular type, but it is particularly effective for hard materials where strength is difficult to obtain by pressure molding alone, and is suitably used for battery materials and heat absorption / dissipation materials where thinness affects performance. Powder materials for all-solid-state batteries, which have attracted attention in recent years, are especially suitable. The thinner the battery material, the lower the resistivity can be, and the thinner the heat absorption / dissipation material, the larger the surface area (contact area) per unit area can be. Examples of battery materials include the following:

[0038] Examples of cathode materials include lithium-containing composite metal oxides, chalcogen compounds, and manganese dioxide. Among these, lithium-containing composite metal oxides are preferred.

[0039] Lithium-containing composite metal oxides are Li x CoO2, Li x KiO2, Li x MnO2, Li x Co y Ni 1-yO2, Li x Co y Mn 1-y O z , Li x Ni 1-y M y O z , Li x , LiMn2O4 and the like can be mentioned. The composite metal oxide containing lithium further includes Li x Mn 2-y M y O4, LiMPO4, Li2MPO4F, etc. In the formula, M 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. In the formula, x, y, z satisfy 0 < x ≤ 1.2, 0 < y < 0.9, 2.0 ≤ z ≤ 2.3. The composite metal oxide containing lithium further includes LiMeO2 (where Me = MxMyMz: Me and M are transition metals, x + y + z = 1). Specific examples of the composite metal oxide containing lithium include LiCoO2 (LCO: lithium cobaltate), LiNi 0.5 Mn 1.5 O4 (LNMO: lithium nickel manganate), etc. Also, specific examples of the composite metal oxide containing lithium include LiFePO4 (LFP: lithium iron phosphate), Li3V2(PO4)3 (LVP: lithium vanadium phosphate), etc.

[0040] Also, 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, thermal black, etc., conductive fibers such as carbon fiber, carbon nanotube, metal fiber, metal powder such as carbon fluoride, aluminum, conductive whiskers such as zinc oxide, conductive metal oxides such as titanium oxide, and organic conductive materials such as phenylene dielectrics.

[0041] Examples of the electrolyte material include oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes, etc. The oxide-based solid electrolyte is Li1.5 Al 0.5 Ge 1.5 (PO4)3 and Li 1.3 Al 0.3 Ti 1.7 Nasicone-type compounds such as (PO4)3, Li 6.25 La3Zr2Al 0.25 O 12 Examples of garnet-type compounds include Li 0.33 Li 0.55 Examples include perovskite-type compounds such as TiO3. Also, oxide-based solid electrolytes include Li 14 Examples include lithicone-type compounds such as Zn(GeO4)4, and acidic compounds such as Li3PO4, Li4SiO4, and Li3BO3. Specific examples of sulfide-based solid electrolytes include Li2S-SiS2, LiI-Li2S-SiS2, LiI-Li2S-P2S5, LiI-Li2S-P2O5, LiI-Li3PO4-P2S5, and Li2S-P2S5.

[0042] Furthermore, the solid electrolyte may be crystalline or amorphous, and may be glass ceramic. Note that the notation Li2S-P2S5, etc., refers to a sulfide-based solid electrolyte made using raw materials containing Li2S and P2S5.

[0043] Examples of negative electrode materials include metals, metal fibers, carbon materials, oxides, nitrides, silicon, silicon compounds, tin, tin compounds, and various alloy materials. Among these, from the viewpoint of capacity density... Therefore, oxides, carbon materials, silicon, silicon compounds, tin, tin compounds, etc. are preferred.

[0044] Examples of oxides include Li4Ti5O 12 Examples of carbon materials include lithium titanate (LTO). Examples of carbon materials include various types of natural graphite, coke, carbon in the process of graphitization, carbon fibers, spheroidal carbon, various types of artificial graphite, amorphous carbon, etc. Examples of silicon compounds include silicon-containing alloys, silicon-containing inorganic compounds, silicon-containing organic compounds, solid solutions, etc. Examples of tin compounds include SnO b(0 < b < 2), SnO2, SnSiO3, Ni2Sn4, Mg2Sn, etc. can be mentioned.

[0045] In addition, the negative electrode material may contain a conductive aid. Examples of the conductive aid include graphite 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 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.

[0046] Examples of the heat absorption / release material include various alloys such as aluminum and copper, and powder particles such as vanadium oxide (VO2).

[0047] The powder material 5 filled in the void portion 4 may be a single material, a premix of multiple materials, or a surface-treated or surface-coated material.

[0048] Figs. 6(a) to 6(f) are schematic cross-sectional views showing the state when a plurality of powder materials 5a and 5b of different types are filled in one molding die 1. Figs. 6(g) and 6(h) are schematic cross-sectional views showing examples (molded body packages 6e and 6f) of the molded body package 6 filled with a plurality of powder materials of different types. Fig. 6(g) shows the molded die package 6e in which two types of powder materials 5a and 5b are filled in the void portion 4 of the molding die 1e, and Fig. 6(h) shows the molded die package 6f in which three types of powder materials 5a, 5b, and 5c are filled in the void portion 4 of the molding die 1f.

[0049] As shown in Figures 6(g) and 6(h), different materials can be filled into the space and pressure-molded all at once. In this case, using the leveling method described above, multiple types of powder materials 5a and 5b can be efficiently filled in layers by repeatedly stacking the mold material and filling it with powder, as shown in Figures 6(c) and 6(f). Specifically, powder material 5a is filled as the first homogeneous particle portion into the cavity formed by one of the multiple pairs of the first mold member 31 and the second mold member 32. In addition, powder material 5b is filled as the second homogeneous particle portion into the cavity formed by a different pair from the above-mentioned pair. After filling with powder materials, molding is possible even if there are gaps in the voids of the mold members, but molding can be performed more stably if there are no gaps, so the leveling filling method is suitable for the present invention.

[0050] Furthermore, the shape and size of the mold members can be changed depending on the type of powder material to be filled. Figure 7(d) shows a molded package 6h for integrally press-molding the positive electrode layer / solid electrolyte / negative electrode layer of an all-solid-state battery. In the molded package 6h, powder material 5a is the powder that constitutes the solid electrolyte, powder material 5b is the powder of the active material that forms the negative electrode layer, and powder material 5c is the powder of the active material that forms the positive electrode layer. The molded package 6h is an example in which the size of the positive electrode layer (powder material 5c) is designed to be slightly smaller than that of the negative electrode layer (powder material 5b) and the solid electrolyte (powder material 5a) in order to prevent short circuits between the positive electrode layer (powder material 5c) and the negative electrode layer (powder material 5b).

[0051] Once the powder material 5 has been filled into the gaps 4 of the mold members 31 and 32, the second base 22 is placed against it to form the molded body package 6, and pressure is applied in the stacking direction (Figure 1, S103). Any general pressurization method can be applied; specifically, methods such as uniaxial press pressurization or CIP and WIP, which use liquid to pressurize, can be used. When pressurizing with liquid, a waterproof sealing member 7 can be provided on the bases 21 and 22, the first mold member 31, the second mold member 32, and the outer surface of the powder material 5 in the gaps 4 to form a carrier configuration (Figure 3(e)). This carrier configuration offers excellent transportability due to its properties of protecting the powder molded body and blocking outside air, and can be easily transported in this configuration. It can be transported stably both before and after pressurization, so for example, it can be supplied in this state, and the user can pressurize it under any conditions. A high degree of vacuum is preferable inside the sealing member 7, preferably 80% or higher, more preferably 90% or higher, and even more preferably 99% or higher.

[0052] Furthermore, as shown in Figure 8, the mold members 31 and 32, each sealed in the sealing member 7, and the powder material 5 filled in the gaps between them, are held in place by the relatively compatible mold members 31 and 32 when pre-pressurized. Therefore, even when removed from the sealing member 7, they can be handled as a single unit with the mold members 31 and 32, allowing the user to combine them as desired and integrally press-molded as shown in Figure 8. For example, as shown in the molded body package 6i in Figure 8, it is possible to combine the types and number of layers as desired, such as two positive electrode layers (powder material 5b) + one solid electrolyte layer (powder material 5a), and integrally press-molded them to form a molded body.

[0053] Once pressurization is complete, the pressure is released and the powder molded product 5x is removed from the mold 1 (Figure 1, S104). During the pressurization process, the bases 21 and 22, the first mold member 31, the second mold member 32, and the powder material 5 are subjected to the same pressure, and as shown in Figure 9(b), for example, the first and second mold members 31 and 32 deform and reach a stable state. After the pressurization is released, as shown in Figure 9(c), for example, each material recovers its shape according to the properties of its material. That is, because the shrinkage rates of the bases 21 and 22, the first mold member 31, and the second mold member 32 in contact with the powder material 5 are different, a difference in the amount of deformation (recovery) occurs between each material, which improves the peelability with respect to the powder molded product 5x.

[0054] As shown in Figure 10(a), the first homogeneous particle portion, the powder material 5, is held between the inner surface 312 (first surface) of the first mold member 31 and the inner surface 322 (second surface) of the second mold member 32, which constitute the void portion 4. Basically, the lower the hardness, the higher the retention of the powder material 5, so it is important to design the bases 21 and 22, which make contact over the largest area, with high hardness. The holding force differs between the first mold member 31 and the second mold member 32 even on the molded side, making it easier to separate the powder molded body 5x. Furthermore, since the second mold member 32 is generally made of a material in the plastic deformation range, if the material is selected according to the amount of pressure, the deformation during pressure will not return to its original shape, and it will distort as shown in Figure 10(b), making it easier to remove the powder molded body 5x. This phenomenon is more pronounced during uniaxial pressure. Figure 10(c) is an image showing the state when the powder molded body 5x is removed from the mold members 31 and 32.

[0055] Figure 10(d) is a conceptual diagram (schematic cross-sectional view) of a powder molded body 5x formed by the manufacturing method of this embodiment. The powder molded body 5x has a thin plate shape composed of a particle layer containing powder, and has a first flat surface (flat portion) 501 and a second flat surface (flat portion) 502 which is the back surface thereof. The first flat surface 501 and the second flat surface 502 are parallel to each other and are surfaces that extend in a direction perpendicular to the stacking direction D (the opposing direction of the first base 21 and the second base 22). The first flat surface 501 is one end face of the powder molded body 5x in the direction perpendicular to the first flat surface 501 to the second flat surface 502, and the second flat surface 502 is the other end face of the powder molded body 5x in the above direction.

[0056] The side surface of the powder molded body 5x formed by the manufacturing method of this embodiment is as shown in Figure 10(d). A step is formed. That is, the powder molded body 5x is formed in a form in which a first particle layer 51x, whose outer shape (outer part, contour part) is formed by a first mold member 31, and a second particle layer 52x, whose outer shape (outer part, contour part) is formed by a second mold member 32, are stacked. The first particle layer 51x includes a first flat surface 501, and the second particle layer 52x includes a second flat surface 502. In the example shown in Figure 10(d), the first particle layer 51x is formed to have a smaller diameter than the second particle layer 52x, and a step consisting of a large contour part and a small contour part is formed on the side surface of the powder molded body 5x (outer surface with respect to the center line along the stacking direction). That is, the outer edge of the second particle layer 52x is a protruding part 53 that protrudes outward in a direction parallel to the flat surfaces 501 and 502 (planar direction) than the outer edge of the first particle layer 51x. The protruding portion 53 and the outer edge of the first particle layer 51x form a stepped shape. This is formed because the amount of compressive deformation differs between the first mold member 31 and the second mold member 32, so the step is formed according to the number of layers of mold members 31 and 32.

[0057] Although the mechanism has not yet been fully elucidated, it is presumed that this stepped portion also contributes to the ease of removal of the powder molded body. In other words, when there is repeated holding force like perforations, it is thought that both holding and ease of removal are achieved by partially breaking the portion. Just as finer perforations are better, multiple layers of mold members 31 and 32 make removal easier than a single layer, and it has been confirmed that a portion of the side step of the powder molded body 5x after removal remains in the mold, i.e., breaks, which improves the release.

[0058] The powder molded bodies 5x removed from the mold members 31 and 32 can be used as devices as is, or after heat treatment (sintering) as needed.

[0059] In this embodiment, an example has been described in which the mold 1 is constructed using two types of mold members, a first mold member 31 and a second mold member 32. However, the mold 1 may also be constructed using three or more types of mold members, such as a third mold member different from the first and second mold members 31 and 32.

[0060] <Examples> Below are examples of the molding of a solid electrolyte powder molded body used in an all-solid-state battery, using the basic method of the present invention, as an embodiment of the present invention.

[0061] (Example 1) On a second mold member 32 (50 μm thick PET: manufactured by Panac Co., Ltd.), a first mold member 31 was prepared by coating a 110 μm thick layer of silicone rubber (KE-1310: manufactured by Shin-Etsu Chemical Co., Ltd.) with a rubber hardness of 40° as the first mold member 31, and curing it into a multilayer sheet. Using a die, circular voids 4 (through holes 311, 321) with a diameter of φ11.0 mm were cut out. On a 125 μm dichrome plate (manufactured by Niraco) prepared as the first base 21, two sheets consisting of the first base material with the voids 4 created and the second base material were stacked with the first mold member 31 side facing down. Next, as the powder material 5, a solid electrolyte LAGP (Li 1.5 Al 0.5 Ge 1.5 (PO4)3 particle size 5μm (manufactured by Toyoshima Seisakusho) was filled into the void 4 of the 60mg type component.

[0062] Next, a nichrome plate similar to that of the first base 21 was placed on the second base 22 to form a molded package 6b in the form shown in Figure 3(b), and a load of 40kN was applied using a hydraulic uniaxial pressurizing device (manufactured by Shimadzu Corporation).

[0063] Next, the pressure was released and the molded package 6b was removed. The first mold member 31 and the second mold member 32 showed visible deformation, holding a portion of the outer circumference of the powder molded body 5x filled in the void 4, while the other portion was separated, allowing for easy demolding. The powder molded body 5x, made of LAGP powder material, was molded to an outer diameter of approximately 11.1 mm and a thickness of 260 μm, and a portion of the side surface was observed by SEM (DX-510: Keyence Corporation). A double layer of unevenness was observed.

[0064] The same process was repeated 19 more times, and all 19 powder molded bodies (5x) could be easily removed without cracking or chipping, just like the first one.

[0065] The molded LAGP powder body 5x was sintered in an electric furnace (Yamato Scientific Co., Ltd.) at 850°C, and its ionic conductivity was measured using an electrochemical analyzer (Solartron 1225: Toyo Technica Co., Ltd.). The ionic conductivity was 2.0 × 10⁻⁶. -4 S cm -1 We confirmed that the values ​​were the same as those in the literature.

[0066] (Comparative Example 1) We attempted to create powder molded bodies 20 times in the same manner as in Example 1, except that we used a commercially available mold (1-6002-15: manufactured by AS ONE Corporation). As a result, not a single good product was produced.

[0067] (Example 2) This document shows an example of a pressurization method different from Example 1 of the present invention, and an example of the transportability of the molded body carrier.

[0068] A molded package of LAGP powder was prepared in the same manner as in Example 1. This molded package was enclosed in a Copack (manufactured by Asahi Kasei Pax Co., Ltd.) as a sealing member 7, and sealed under reduced pressure to 99.9% using a vacuum packaging machine (manufactured by TOSEI Co., Ltd.: V-307G2) to form a molded carrier 8 as shown in Figure 3(e). In this state, the package was wrapped in air packing and packed in a cardboard box, and subjected to random vibrations of 2Hz to 200Hz for 10 minutes using a vibration testing device (G-9117: manufactured by Shinken Co., Ltd.) in accordance with JIS:Z0232 to simulate transport and handling conditions.

[0069] Next, the sample was removed from the molded body carrier 8 and pressure-molded at room temperature under a pressure of 196 MPa using a hot water laminator (Nikkiso Co., Ltd.: WL24-25-200).

[0070] Next, the removed molded body carrier 8 sample was subjected to random vibrations of 2 Hz to 200 Hz for 10 minutes using a vibration testing device to simulate the transport and handling conditions.

[0071] Next, the sealing member 7 of the molded body carrier 8 was opened, the molded body package 6 was removed, and then the powder molded product 5x was removed from the mold 1. Although the deformation of the mold members 31 and 32 was less than in Example 1, the powder molded product 5x could be easily removed from the mold without cracking or chipping. No adverse effects were observed from the vibration tests conducted before and after pressurization. The removed LAGP powder molded product 5x was molded with an outer diameter of 11.03 mm (including a slight error, but slightly larger than the size of the mold member void) and a thickness of 260 μm, and a double layer of unevenness was confirmed on a part of the side surface by SEM observation (DX-510: Keyence Corporation).

[0072] The same process was repeated 19 more times, and all 19 powder molded bodies (5x) could be easily removed without cracking or chipping, just like the first one.

[0073] (Examples 3-6 and Comparative Examples 2-5) This shows the difference in ease of mold removal depending on the combination of bases 21, 22 and mold members 31, 32 in the present invention.

[0074] Following the procedures of Examples 1 and 2, the materials of the bases 21 and 22, the first mold member 31, the second mold member 32, and the pressing method were varied, and 20 pieces of each condition were attempted to be pressure-molded. The results are shown in the table in Figure 11. In the table in Figure 11, the information in parentheses for the bases and mold members indicates the material type. This is the yield rate. The number in parentheses for the yield rate indicates the number of tests. As shown in the table in Figure 11, under the conditions using the mold material of each embodiment of the present invention, molding was possible with a high yield rate in all embodiments.

[0075] (Example 7) An example of multilayer integrated molding in the present invention is shown.

[0076] A multilayer mold member sheet I was created by applying a 110 μm thick layer of silicone rubber (KE-1310: manufactured by Shin-Etsu Chemical Co., Ltd.) with a rubber hardness of 40° as the first mold member 31 onto a second mold member 32 (50 μm thick PET: manufactured by Panac Co., Ltd.), curing it, and then using a die to cut out circular voids 4 (through holes 311, 321) with a diameter of φ9.0 mm. Furthermore, a multilayer mold member sheet II was created by applying a 40 μm thick layer of silicone rubber (KE-1310: manufactured by Shin-Etsu Chemical Co., Ltd.) with a rubber hardness of 40° as the first mold member 31 onto a second mold member 32 (20 μm thick PET: manufactured by Panac Co., Ltd.), curing it, and then using a die to cut out circular voids 4 (through holes 311, 321) with a diameter of φ11.0 mm.

[0077] On a 125 μm dichrome plate (manufactured by Nilaco) prepared as the first base 21, one mold member sheet I with a φ9 mm void 4 was laminated with the surface of the first mold member 31 facing downwards. Next, as the powder material 5, LCO(Li xA powder material 5, a premix of CoO2 (5μm particle size: manufactured by Cellseed Co., Ltd.) and LBO (Li3BO3 (5μm particle size: manufactured by Toyoshima Seisakusho Co., Ltd.) was filled into the void 4 with a squeegee 9 to form the positive electrode material layer. Next, one mold member sheet II with a φ11mm void 4 was laminated with the surface of the first mold member 31 facing downwards. Next, LAGP (5μm particle size, manufactured by Toyoshima Seisakusho Co., Ltd.) as the powder material 5 was filled into the void 4 with a squeegee 9 to form the solid electrolyte layer. Next, two mold member sheets II with a φ11mm void 4 were laminated with the surface of the first mold member 31 facing downwards. Next, graphite (SGP-5: manufactured by SEC Carbon Co., Ltd.) as the powder material 5 was filled into the void with a squeegee to form the negative electrode layer. Next, a nichrome plate similar to that of the first base 21 was placed on the second base 22 to form a molded package 6h in the form shown in Figure 7(d), and a load of 40kN was applied using a hydraulic uniaxial pressurizing device (SSP-10A: manufactured by Shimadzu Corporation).

[0078] Next, the pressure was released and the molded package 6h was removed. Visible deformation was observed in the first mold member 31 and the second mold member 32, and they were holding a portion of the outer circumference of the powder molded body 5x filled in the void 4, while a portion was separated, making it easy to demold. The powder material 5 filled in the void 4 was a three-layered integral molded body consisting of a positive electrode layer of approximately 130 μm, a solid electrolyte layer of 45 μm, and a negative electrode layer of 130 μm.

[0079] (Example 8) This shows an example of molding of the heat-absorbing / heat-dissipating material powder according to the present invention.

[0080] A first mold member 31, consisting of EPDM with a rubber hardness of 60° (thickness 500 μm, manufactured by Ishizuka Co., Ltd.), was placed on a second mold member 32 (thickness 200 μm PET, manufactured by Panac Co., Ltd.). Using a CO2 laser processing machine VLS2.30 (manufactured by Universal Laser Co., Ltd.), square-shaped voids 4 (through holes 311, 321) with sides of 20 mm were cut out from each. The first mold member 31 and the second mold member 32, with the voids 4 created, were stacked on a 100 μm stainless steel plate (manufactured by Niraco Co., Ltd.) prepared as the first base 21, with the positions of the voids 4 (through holes 311, 321) aligned. Next, VO2 particles (particle size 180 μm or less, manufactured by Kojunkagaku Co., Ltd.), an example of a latent heat material powder that undergoes a solid-solid phase transition, were filled into the voids 4 of the mold members 31 and 32 by the leveling method as the powder material 5.

[0081] Next, a stainless steel plate similar to the first base 21 is placed as the second base 22, as shown in Figure 3(a A molded package 6a in the form shown in () was used, and a load of 60kN was applied using a hydraulic uniaxial pressurizing device (manufactured by Shimadzu Corporation).

[0082] Next, the pressure was released and the molded package 6a was removed. The first mold member 31 and the second mold member 32 showed visible deformation, holding a portion of the outer circumference of the powder molded body 5x filled in the void 4, while the other portion was separated, allowing for easy demolding.

[0083] The powder molded body 5x, made of VO2 powder material 5, was molded to have sides of approximately 19.7 mm and a thickness of 490 μm. SEM observation (DX-510: Keyence Corporation) revealed irregularities on a portion of the side surface.

[0084] The disclosure of embodiments of the present invention includes the following configurations. (Composition 1) A molded package for powder, The first base and, The second base, A first mold member disposed between the first base and the second base, the first mold member having a first void portion that penetrates the first mold member in the opposing direction in which the first base and the second base face each other, A second mold member is positioned adjacent to the first mold member between the first base and the second base, and the second mold member has a second void that penetrates the second mold member in the opposing direction and communicates with the first void, A first homogeneous particle portion containing powder is disposed in the space formed by the first base, the first void, the second void, and the second base, Equipped with, The first homogeneous particle portion is sandwiched between the first surface of the first mold member constituting the first void and the second surface of the second mold member constituting the second void. The first Young's modulus of the material constituting the first mold member is higher than the second Young's modulus of the material constituting the second mold member. The third Young's modulus, which is the Young's modulus of the material constituting at least one of the first base and the second base, is higher than the first Young's modulus. A molded powder package characterized by the following features. (Configuration 2) The powder molded package according to configuration 1, wherein the first Young's modulus is 20 GPa or less. (Composition 3) The powder molded package according to configuration 1 or 2, wherein the second Young's modulus is 20 MPa or less. (Composition 4) The third Young's modulus is 50 GPa or more, and the powder molded package is according to any one of the configurations 1 to 3. (Composition 5) A powder molded body package according to any one of configurations 1 to 4, further comprising a second homogeneous particle portion containing powder, which is arranged in the aforementioned space. (Composition 6) The powder is a molded powder package according to any one of configurations 1 to 5, comprising powder of at least one of the active material and solid electrolyte. (Composition 7) The powder is a molded powder package according to any one of configurations 1 to 6, which includes a powder of a latent heat material that undergoes a solid-solid phase transition. (Composition 8) A molded powder package according to any one of configurations 1 to 7, The sealing member that seals the molded package inside, A molded body carrier equipped with a molded body carrier. (Composition 9) A first step is to prepare a molded package according to one of the configurations 1 to 7, A second step involves applying pressure to the molded package to pressurize the homogeneous particle portion, By doing so, A method for manufacturing a molded body, characterized by obtaining a molded body of the powder in the aforementioned space. (Composition 10) The method for manufacturing a molded article according to configuration 9, characterized in that, in the second step, at least a portion of the end of the molded article of the powder is released from the first mold member and the second mold member. (Composition 11) A molded body made of powder, A particle layer containing powder, comprising a first particle layer having a first outer casing, A second particle layer laminated on the first particle layer, having a second outer portion larger than the first outer portion, and the second outer portion forming a protrusion that protrudes in a direction perpendicular to the lamination direction of the particle layer compared to the first outer portion, A molded powder body characterized by having [a certain characteristic]. (Composition 12) The powder molded body according to configuration 11, wherein the first particle layer is one end face of the powder molded body in the stacking direction and includes a first flat surface extending in a direction perpendicular to the stacking direction. (Composition 13) The powder molded body according to configuration 12, wherein the second particle layer is the other end face of the powder molded body in the stacking direction and includes a second flat surface extending in a direction perpendicular to the stacking direction. (Composition 14) The powder is a molded body of the powder according to any one of the configurations 11 to 13, comprising powder of at least one of the active material and the solid electrolyte. (Composition 15) The powder is a molded body of the powder according to any one of the configurations 11 to 13, which includes a powder of a latent heat material that undergoes a solid-solid phase transition. [Explanation of symbols]

[0085] 1…Molding mold, 21…First base, 22…Second base, 31…First mold member, 32…Second mold member, 4…Void, 5…Powder material, 6…Molded body package

Claims

1. A molded package for powder, The first base and, The second base, A first mold member disposed between the first base and the second base, the first mold member having a first void portion that penetrates the first mold member in the opposing direction in which the first base and the second base face each other, A second mold member is positioned adjacent to the first mold member between the first base and the second base, and the second mold member has a second void that penetrates the second mold member in the opposing direction and communicates with the first void, A first homogeneous particle portion containing powder is disposed in the space formed by the first base, the first void, the second void, and the second base, Equipped with, The first homogeneous particle portion is sandwiched between the first surface of the first mold member constituting the first void and the second surface of the second mold member constituting the second void. The first Young's modulus of the material constituting the first mold member is higher than the second Young's modulus of the material constituting the second mold member. The third Young's modulus, which is the Young's modulus of the material constituting at least one of the first base and the second base, is higher than the first Young's modulus. A molded powder package characterized by the following features.

2. The powder molded body package according to claim 1, wherein the first Young's modulus is 20 GPa or less.

3. The powder molded body package according to claim 1, wherein the second Young's modulus is 20 MPa or less.

4. The powder molded body package according to claim 1, wherein the third Young's modulus is 50 GPa or more.

5. The powder molded body package according to claim 1, further comprising a second homogeneous particle portion containing powder, which is arranged in the aforementioned space.

6. The powder molded package according to claim 1, wherein the powder comprises at least one of the active material and the solid electrolyte.

7. The powder molded package according to claim 1, wherein the powder comprises a powder of a latent heat material that undergoes a solid-solid phase transition.

8. A molded powder package according to claim 1, The sealing member that seals the molded package inside, A molded body carrier equipped with a molded body carrier.

9. A first step of preparing the molded package according to claim 1, A second step involves applying pressure to the molded package to pressurize the homogeneous particle portion, By doing so, A method for manufacturing a molded body, characterized by obtaining a molded body of the powder in the aforementioned space.

10. The method for manufacturing a molded article according to claim 9, characterized in that, in the second step, at least a portion of the end portion of the molded article of the powder is released from the first mold member and the second mold member.

11. A molded body made of powder, A particle layer containing powder, comprising a first particle layer having a first outer casing, A second particle layer laminated on the first particle layer, having a second outer portion larger than the first outer portion, and the second outer portion forming a protrusion that protrudes in a direction perpendicular to the lamination direction of the particle layer compared to the first outer portion, A molded powder body characterized by having [a certain characteristic].

12. The powder molded body according to claim 11, wherein the first particle layer is one end face of the powder molded body in the stacking direction and includes a first flat surface extending in a direction perpendicular to the stacking direction.

13. The powder molded body according to claim 12, wherein the second particle layer is the other end face of the powder molded body in the stacking direction and includes a second flat surface extending in a direction perpendicular to the stacking direction.

14. The powder molded body according to claim 11, wherein the powder comprises at least one of the active material and the solid electrolyte.

15. The powder molded body according to claim 11, wherein the powder includes a powder of a latent heat material that undergoes a solid-solid phase transition.

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