Inorganic material manufacturing device

Abstract

This inorganic material manufacturing device is provided with: a lower ring (76), to one surface side of which a material is supplied; a drive mechanism (78) that rotates the lower ring (76); a plurality of recesses (77) formed in the one surface side of the lower ring (76) along a plurality of mutually concentric circumferences; a plurality of balls (72) that are partially fit into the respective recesses (77) and are rotatable; and an upper ring (74) that is located on the opposite side from the lower ring (76) with the plurality of balls (72) therebetween.

Description

Inorganic material manufacturing equipment

[0001] This invention relates to an apparatus for manufacturing inorganic materials.

[0002] Lithium-ion batteries are known to be used as power sources for small portable devices such as mobile phones and laptop computers, as well as for electric vehicles and power storage. Currently available lithium-ion batteries use electrolytes containing flammable organic solvents. On the other hand, lithium-ion batteries that are made entirely solid by replacing the electrolyte with a solid electrolyte (all-solid-state lithium-ion batteries) do not use flammable organic solvents inside the battery. Therefore, all-solid-state lithium-ion batteries allow for the simplification of safety devices and offer advantages in manufacturing cost and productivity. Examples of solid electrolyte materials used in such solid electrolytes include sulfide-based solid electrolyte materials, as shown in Patent Document 1.

[0003] Japanese Patent Publication No. 2016-27545

[0004] One method for manufacturing inorganic materials is mechanical milling using a planetary ball mill. One example of a problem that this invention aims to solve is to improve the efficiency of inorganic material manufacturing in an inorganic material manufacturing apparatus that uses the mechanical milling method.

[0005] The present invention provides an inorganic material manufacturing apparatus as described below: [1] An inorganic material manufacturing apparatus comprising: a lowering ring on which a material is supplied to one side; a drive mechanism for rotating the lowering ring; a plurality of recesses formed on the one side of the lowering ring along the circumferences of a plurality of concentric circles; a plurality of balls, some of which are fitted into each of the recesses and which are rotatable; and an upper ring positioned on the opposite side from the lowering ring, sandwiching the plurality of balls. [2] The inorganic material manufacturing apparatus according to [1], wherein the plurality of balls fitted into at least one of the recesses have a different diameter from the plurality of balls fitted into the other recesses. [3] The inorganic material manufacturing apparatus according to [1] or [2], wherein at least one of the recesses is formed at a higher position than the other recesses. [4] The inorganic material manufacturing apparatus according to [3], wherein a step is formed between at least one of the recesses and the other recesses. [5] The inorganic material manufacturing apparatus according to any one of [1] to [4], wherein the upper ring includes a first upper ring and a second upper ring facing each other with respect to different recesses, and the second upper ring is located outward from the first upper ring. [6] The inorganic material manufacturing apparatus according to [5], further comprising a first pressurizing mechanism for pushing the first upper ring downward and a second pressurizing mechanism for pushing the second upper ring downward. [7] The inorganic material manufacturing apparatus according to any one of [1] to [6], wherein the lower ring includes a first lower ring and a second lower ring having different recesses formed on them, and the second lower ring is located outward from the first lower ring. [8] The inorganic material manufacturing apparatus according to [7], wherein the drive mechanism includes a first drive mechanism for rotating the first lower ring and a second drive mechanism for rotating the second lower ring.[9] An inorganic material manufacturing apparatus comprising: a lowering ring to which material is supplied on one side; a drive mechanism for rotating the lowering ring; a recess formed on the one side of the lowering ring along a circumference concentric with the lowering ring; a plurality of balls, a portion of which are fitted into the recess and which are rotatable; and an upper ring positioned on the opposite side from the lowering ring, sandwiching the plurality of balls, wherein in a cross section passing through the center of the lowering ring, the height of the inner edge of the recess and the height of the outer edge of the recess are different.

[10] The inorganic material manufacturing apparatus according to [9], wherein in a cross section passing through the center of the lowering ring, the height of the inner edge of the recess is lower than the height of the outer edge of the recess.

[11] An inorganic material manufacturing apparatus according to [9] or

[10] , comprising: a first recess along the first circumference; and a second recess along the second circumference surrounding the first circumference, wherein in a cross section passing through the center of the lowering, the height of the outer edge of the first recess is lower than the height of the inner edge of the first recess, and the height of the outer edge of the second recess is higher than the height of the inner edge of the second recess.

[0006] This method can improve the efficiency of inorganic material production in inorganic material manufacturing equipment using the mechanical milling method.

[0007] This is a schematic diagram of the inorganic material manufacturing apparatus according to the first embodiment. This is a diagram showing the general flow of gas within the inorganic material manufacturing apparatus. This is Figure 1 showing the general outline of the wing mechanism. This is Figure 2 showing the general outline of the wing mechanism. This is a diagram showing the general operation of the inorganic material manufacturing apparatus. This is a diagram showing an example of the arrangement of grinding balls in the first embodiment. This is a diagram showing a cross-sectional view of the grinding balls in the first embodiment. This is a flowchart diagram of the operation of the inorganic material manufacturing apparatus. This is Figure 1 showing a cross-sectional view of the grinding balls in the second embodiment. This is Figure 2 showing a cross-sectional view of the grinding balls in the second embodiment. This is a schematic diagram of the inorganic material manufacturing apparatus according to the third embodiment. This is a diagram showing the general flow of gas within the inorganic material manufacturing apparatus according to the third embodiment. This is a diagram showing the general operation of the inorganic material manufacturing apparatus according to the third embodiment. This is a diagram showing an example of the arrangement of grinding balls in the third embodiment. This is Figure 1 showing a cross-sectional view of the grinding balls in the third embodiment. This is Figure 2 showing a cross-sectional view of the grinding balls in the third embodiment.

[0008] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted where appropriate.

[0009] [First Embodiment] First, the inorganic material manufacturing apparatus 10 according to this embodiment will be described with reference to Figure 1. The inorganic material manufacturing apparatus 10 according to this embodiment includes a ring ball mill mechanism 70 having a plurality of grinding balls 72, a lowering ring 76 that rotates around an axis (around axis O) while maintaining the plurality of grinding balls 72, and an upper ring 74 that is positioned on the opposite side of the lowering ring 76 with the plurality of grinding balls 72 in between and presses the plurality of grinding balls 72 against the lowering ring 76, a container 20 in which the ring ball mill mechanism 70 is arranged and a hole 24A is formed in the part above the ring ball mill mechanism 70, and a ring ball mill in the container 20 The invention comprises a gas supply mechanism 50 mounted below the mechanism 70 and supplying gas upward to the interior; a cylinder 30 (hereinafter referred to as the injection cylinder 30) attached to the container 20, passing through the hole 24A and allowing external gas to flow in on the axial side of the plurality of crushing balls 72 in the lowering 76; and a control unit 90 that controls the rotational movement of the lowering 76 and the gas supply movement of the gas supply mechanism 50. The method for manufacturing inorganic materials according to this embodiment is carried out by the control unit 90 controlling the rotational movement and the gas supply movement.

[0010] The inorganic material manufacturing apparatus 10 according to this embodiment has the function of vitrifying a mixed powder MP, which is a mixture of multiple types of inorganic compounds described later, by applying shear force and compressive stress to the mixed powder MP. As a result, the inorganic material manufacturing apparatus 10 of this embodiment has the function of obtaining, i.e., manufacturing, a vitrified inorganic material powder, which is a mixture of multiple types of inorganic compounds, from the mixed powder MP described later.

[0011] <Container 20> As shown in Figure 1, the container 20 is cylindrical in shape, for example, and has a peripheral wall 22, a top plate 24, and a bottom plate 26. Inside the container 20 (the space enclosed by the peripheral wall 22, the top plate 24, and the bottom plate 26), a part of the injection cylinder 30, a conical cylinder 35, a part of the discharge pipe 40, a gas supply mechanism 50, a wing mechanism 60, a ring ball mill mechanism 70, and a part of the pressurizing mechanism 80 are arranged. A through hole 24A (hereinafter referred to as hole 24A) is formed in the top plate 24. In other words, hole 24A is formed in the part of the container 20 above the ring ball mill mechanism 70. Note that the symbol O in Figure 1 indicates the axis of the container 20.

[0012] <Injection cylinder 30, conical cylinder 35, discharge pipe 40> The injection cylinder 30 has two functions: it functions as an introduction pipe for introducing mixed powder MP from outside to inside the container 20 before the start of the inorganic material manufacturing operation, and it functions as an inflow path for introducing gas from outside the container 20 (for example, an inert gas such as nitrogen or argon) into the container 20 during the inorganic material manufacturing operation. As shown in Figure 1, the injection cylinder 30 is positioned so as to penetrate the hole 24A. The injection cylinder 30 is fixed to the discharge pipe 40 at its upper end, with the outer circumference of its upper part surrounded by the discharge pipe 40. Here, the discharge pipe 40 is fitted and fixed into the hole 24A in the top plate 24 of the container 20. In other words, the injection cylinder 30 is attached to the container 20 via the discharge pipe 40. The lower end of the injection cylinder 30 is open toward the area surrounded by the multiple grinding balls 72 of the ring ball mill mechanism 70, which will be described later. Furthermore, the injection cylinder 30 is configured to introduce the mixed powder MP to the central side of the ring ball mill mechanism 70 (towards the axis O side of the multiple grinding balls 72) before the start of the inorganic material manufacturing operation, and to allow external gas to flow in during the inorganic material manufacturing operation.

[0013] The conical cylinder 35 is positioned above the ring ball mill mechanism 70, with its apex (the side with the shorter circumference) facing downwards in the vertical direction, enclosing a portion of the injection cylinder 30.

[0014] The discharge pipe 40 is a pipe for discharging the manufactured inorganic material. As shown in Figure 1, the discharge pipe 40 has an R-shape when viewed from the front. That is, the discharge pipe 40 has a cylindrical portion 42 arranged along axis O and a branch-like portion 44 that is connected diagonally to the central part of the cylindrical portion 42 in the vertical direction. The lower end of the cylindrical portion 42 opens inside the container 20, and an injection cylinder 30 is fixed to the upper end of the cylindrical portion 42. The opening at the upper end of the branch-like portion 44 is connected to a dust collector (not shown).

[0015] <Gas Feeding Mechanism 50> As shown in Figure 1, the gas feeding mechanism 50 is installed below the ring ball mill mechanism 70 in the container 20 and has the function of feeding gas (for example, an inert gas such as nitrogen or argon) upward into the interior of the container 20. The gas feeding mechanism 50 has, for example, a plurality of gas outlets. Each gas outlet is configured to eject a gas flow towards the gap formed between the inner circumferential surface of the container 20 and the ring ball mill mechanism 70 (lowering 76). Each gas outlet is connected to a gas cylinder (not shown) located outside the container 20. Figure 2 shows the gas flow by the gas feeding mechanism 50.

[0016] <Wing mechanism 60> As shown in Figure 1, the wing mechanism 60 is located inside the container 20, between the top plate 24 and the conical cylinder 35.

[0017] Figures 3 and 4 show the wing mechanism 60 in a top view. As shown in Figures 3 and 4, the wing mechanism 60 has a plurality of swing wings 62 arranged point-symmetrically with respect to axis O. Each swing wing 62 consists of a rotation axis 62A, a short plate 62B, and a long plate 62C. The short plate 62B and the long plate 62C are attached to the outer surface of the rotation axis 62A, respectively, while facing in directions that intersect each other and are aligned with the axial direction of the rotation axis 62A.

[0018] As shown in Figure 3, when each oscillating wing 62 rotates its axis of rotation 62A clockwise, it brings its own short plate 62B into contact with the long plate 62C of the adjacent oscillating wing 62, forming a wall that extends around its entire circumference. In contrast, as shown in Figure 4, when each oscillating wing 62 rotates its axis of rotation 62A counterclockwise by a predetermined angle from the state shown in Figure 3, it separates its own short plate 62B from the long plate 62C of the adjacent oscillating wing 62, forming a gap between adjacent oscillating wings 62.

[0019] Furthermore, the wing mechanism 60 in this embodiment is controlled by the control unit 90 so that the amount of gas discharged from the branch portion 44 in the case of Figure 3 is less than the amount of gas discharged from the branch portion 44 in the case of Figure 4.

[0020] <Ring Ball Mill Mechanism 70 and Pressurization Mechanism 80> As shown in Figure 5, the ring ball mill mechanism 70 is pressurized by the pressurization mechanism 80 and has the function of applying shear force and compressive stress to the mixed powder MP, which is a mixture of multiple types of inorganic compounds.

[0021] As shown in Figure 1, the ring ball mill mechanism 70 is, for example, located on the lower side in the vertical direction inside the container 20. The ring ball mill mechanism 70 has a plurality of grinding balls 72, a lowering ring 76, an upper ring 74, and a drive mechanism 78. The plurality of grinding balls 72 are, for example, made of ceramic. Here, alumina, stabilized zirconia, silicon nitride, etc. can be used as the ceramic constituting the plurality of grinding balls 72.

[0022] The lowering ring 76 is driven by a drive mechanism 78 to rotate around an axis (around axis O) while maintaining a plurality of crushing balls 72. The lowering ring 76 is, for example, a donut-shaped member with a through hole formed in the center and is made of ceramic. On one side (the top side) of the lowering ring 76, a plurality of recesses 77A are formed into which each crushing ball 72 is fitted in order to maintain the plurality of crushing balls 72. Here, alumina, stabilized zirconia, silicon nitride, etc. can be used as the ceramic that makes up the lowering ring 76.

[0023] The upper ring 74 is positioned on the opposite side of the lower ring 76, sandwiching the multiple grinding balls 72 that are maintained by the lower ring 76. The upper surface of the upper ring 74 is pressurized by a pressurizing mechanism 80, which will be described later, to press the multiple grinding balls 72 against the lower ring 76. The upper ring 74 is, for example, a donut-shaped member with a through hole formed in the center, and is made of ceramic. On the lower surface of the upper ring 74, a circular recess is formed that is point-symmetric with respect to the axis O, into which each grinding ball 72 fits, in order to maintain the multiple grinding balls 72. Here, alumina, stabilized zirconia, silicon nitride, etc., can be used as the ceramic that makes up the upper ring 74.

[0024] As shown in Figure 1, the drive mechanism 78 is positioned below the lowering ring 76 while the lowering ring 76 is fixed. The drive mechanism 78 rotates around the axis (around axis O) and can rotate the lowering ring 76 at a speed of 25 rpm to 300 rpm, for example, preferably at 100 rpm to 140 rpm.

[0025] As described above, the pressurizing mechanism 80 applies a ring-unit surface area load of 0.1 kgf / cm² to the upper surface of the upper ring 74, for example. ２ The above 5.0 kgf / cm² ２ It has the function of applying pressure at a pressure of 0.01 MPa or more and 0.5 MPa or less, preferably a ring unit surface area load of 1.0 kgf / cm². ２ The above 5.0 kgf / cm² ２Pressurize with a pressure of 0.1 MPa or more and 0.5 MPa or less, more preferably a ring unit surface area load of 2.0 kgf / cm². ２ The above is 4.0 kgf / cm². ２ The following pressure should be applied: (0.2 MPa or more and 0.4 MPa or less).

[0026] <Control Unit 90> The control unit 90 has the function of controlling the operation of the inorganic material manufacturing apparatus 10. Specifically, the control unit 90 controls the rotational operation of the drive mechanism 78, the gas supply operation of the gas supply mechanism 50, etc. The control unit 90 also has a timer 92 that counts the rotation time of the drive mechanism 78. Details of the functions of the control unit 90 will be explained later in the description of the inorganic material manufacturing method S10 of this embodiment.

[0027] Next, the ring ball mill mechanism 70 and the pressurizing mechanism 80 will be described in more detail using Figures 6 and 7. Figure 6 is a top view of the ring ball mill mechanism 70. Figure 7 is an enlarged view of the ring ball mill mechanism 70 in Figure 1.

[0028] As shown in Figures 6 and 7, in this embodiment, the crushed balls 72 are arranged in multiple rows. In other words, the multiple crushed balls 72 are arranged along multiple concentric circles. Here, being arranged along a circle does not mean that the centers of each crushed ball are strictly aligned on the circumference, but may be offset to some extent.

[0029] As shown in Figure 6, the lowering ring 76 has multiple recesses formed along a concentric circumference. Preferably, these recesses are also concentric with the lowering ring 76. Multiple crushing balls 72 are rotatably and movably fitted into each of these multiple recesses. In the example shown in this figure, the recesses of the lowering ring 76 are double-layered, but these recesses may be triple or more. In the following description, the inner circumference will be referred to as the first circumference S1, and the circumference surrounding the first circumference (in other words, the outer circumference) will be referred to as the second circumference S2. The recess along the first circumference S1 will be referred to as the first recess 77A, and the recess along the second circumference S2 will be referred to as the second recess 77B. The crushing ball 72 fitted into the first recess 77A will be referred to as the first crushing ball 72A, and the crushing ball 72 fitted into the second recess 77B will be referred to as the second crushing ball 72B. When the second crushing balls 72B are arranged so that the distances (gaps) between them are all equal, the distance W1 between the centers of adjacent second crushing balls 72B is, for example, 20 mm to 40 mm. Also, when the second crushing balls 72B are arranged so that the distances between them are all equal, the distance (gaps) W2 between adjacent second crushing balls 72B is, for example, 1.5 mm to 3.5 mm. Also, when the first crushing balls 72A are arranged so that the distances (gaps) between them are all equal, the distance W3 between the centers of adjacent first crushing balls 72A is, for example, 20 mm to 40 mm. Also, when the first crushing balls 72A are arranged so that the distances between them are all equal, the distance (gaps) W4 between adjacent first crushing balls 72A is, for example, 1.5 mm to 3.5 mm. Furthermore, when all the second crushing balls 72B are connected, the distance between the centers of the second crushing balls 72B at both ends is, for example, 80 mm to 90 mm. Furthermore, when all the first crushing balls 72A are connected, the distance between the centers of the first crushing balls 72A at both ends is, for example, 55 mm or more and 65 mm or less.

[0030] The inorganic material manufacturing apparatus 10 according to this embodiment can improve the efficiency of inorganic material manufacturing by having multiple rows of pulverizing balls 72 as described above. This is because, by having multiple rows of pulverizing balls 72, the time that the mixed powder MP remains between the pulverizing balls 72 is increased, which increases the time that pressure is applied to the mixed powder MP (in other words, the energy applied to the mixed powder MP), and thus promotes the reaction.

[0031] Furthermore, as shown in Figure 7, the height of the center of the first grinding ball 72A and the height of the center of the second grinding ball 72B may be different. For example, the height of the center O1 of the first grinding ball 72A may be higher than the height of the center O2 of the second grinding ball 72B. In this case, the mixed powder MP will move outward more easily, and the manufacturing process will be smoother. Although not shown in the figure, the height of the center O1 of the first grinding ball 72A may also be lower than the height of the center O2 of the second grinding ball 72B. In this case, the mixed powder MP will not flow outward as easily, the time that pressure is applied to the mixed powder MP will increase, and the reaction will be promoted.

[0032] Furthermore, as shown in Figure 7, the height of the center of the first depression 77A and the height of the center of the second depression 77B may be different from each other. For example, the height of the center of the first depression 77A may be higher than the height of the center of the second depression 77B. In this case, the mixed powder MP will move outward more easily, and the manufacturing process will be smoother. Although not shown in the figure, the height of the center of the first depression 77A may also be lower than the height of the center of the second depression 77B. In this case, the mixed powder MP will not flow outward as easily, the time that pressure is applied to the mixed powder MP will increase, and the reaction will be promoted. The center of the depression is the area located directly below the center of the grinding ball 72 when the grinding ball 72 is fitted into the depression.

[0033] Furthermore, as shown in Figures 6 and 7, the diameter R1 of the first grinding ball 72A and the diameter R2 of the second grinding ball 72B may be different from each other. This allows different shear forces and compressive stresses to be applied to the mixed powder MP. As shown in the figure, the diameter R1 of the first grinding ball 72A may be larger than the diameter R2 of the second grinding ball 72B, or the diameter R1 of the first grinding ball 72A may be smaller than the diameter R2 of the second grinding ball 72B.

[0034] Furthermore, as shown in Figures 6 and 7, the lowering ring 76 may include a first lowering ring 76A and a second lowering ring 76B, each having different indentations. In Figures 6 and 7, the second lowering ring 76B is located outside the first lowering ring 76A. The drive mechanism 78 may also include a first drive mechanism 78A for rotating the first lowering ring 76A and a second drive mechanism 78B for rotating the second lowering ring. This allows the first crushing ball 72A and the second crushing ball 72B to be rotated under different conditions.

[0035] Furthermore, as shown in Figures 6 and 7, the upper ring 74 may include a first upper ring 74A and a second upper ring 74B facing each other in different recesses. In Figures 6 and 7, the second upper ring 74B is located outside the first upper ring 74A. The pressurizing mechanism 80 may also include a first pressurizing mechanism that pushes the first upper ring 74A downward and a second pressurizing mechanism that pushes the second upper ring 74B downward. This allows the first crushed ball 72A and the second crushed ball 72B to be pressurized under different conditions.

[0036] [Method for Manufacturing Inorganic Materials] Next, a method for manufacturing inorganic materials according to this embodiment will be described. Figure 8 is a flowchart showing an example of a method for manufacturing inorganic materials according to this embodiment.

[0037] As shown in Figure 8, the method for manufacturing an inorganic material consists of a mixing step S11, a vitrification step S12, a dispersion step S13, and a predetermined time T from the start of the vitrification step S12. Ｐ The process includes a determination step S14 to determine whether the required time has elapsed, and a discharge step S15.

[0038] The manufacturing method of the inorganic material according to this embodiment performs the mixing step S11, the vitrification step S12, and the dispersion step S13 in this order of description. Then, in the determination step S14, until the predetermined time T Ｐ elapses from the start of the vitrification step S12, that is, as long as the negative determination continues in the determination step S14, the vitrification step S12 and the dispersion step S13 are repeated. And the manufacturing method S10 of this embodiment is the predetermined time T Ｐ from the start of the vitrification step S12. When it has elapsed, that is, when an affirmative determination is made in the determination step S14, the discharge step S15 is performed and the process ends. The vitrification step S12, the dispersion step S13, the determination step S14, and the discharge step S15 are executed by the control unit 90 controlling the inorganic material manufacturing apparatus 10. Also, the predetermined time T Ｐ will be described later. Hereinafter, the details of each step will be described.

[0039] <Mixing Step> The mixing step S11 is a step of mixing powders of a plurality of types of inorganic compounds to generate a mixed powder MP. The mixing step S11 is performed, for example, using a mixer (not shown). Here, an example of the plurality of types of inorganic compounds in this embodiment is lithium sulfide, lithium nitride, and diphosphorus pentasulfide. And when the mixed powder MP is generated by the mixing step S11, the mixed powder MP is introduced into the container 20 from the injection cylinder 30 of the inorganic material manufacturing apparatus 10, and this step ends.

[0040] <Vitrification and Dispersion Processes> First, the control unit 90 controls the multiple oscillating wings 62 of the wing mechanism 60 to bring the wing mechanism 60 into the state shown in Figure 3. The control unit 90 also starts driving the drive mechanism 78 of the ring ball mill mechanism 70. Accordingly, the lowering ring 76 is driven by the drive mechanism 78 and rotates around its axis. The control unit 90 also injects gas from the multiple air outlets of the gas supply mechanism 50. In this case, gas (for example, an inert gas such as nitrogen or argon) is continuously flowed from the outside into the container 20 through the injection cylinder 30. Sulfides, nitrides, halides, etc., which are easily oxidized when used as mixed powder MP or vitrified inorganic materials, are used with reduced water and oxygen concentrations in the gas. For example, a water concentration of 1,500 ppm or less and an oxygen concentration of 10% or less is preferred, and a water concentration of 400 ppm or less and an oxygen concentration of 1% or less is even more preferred, but the thresholds are appropriately determined according to the properties of the inorganic material. As described above, a gas flow as shown in Figure 2 circulates inside the container 20. The control unit 90 also controls the pressurizing mechanism 80 to pressurize the upper ring 74. Consequently, the upper ring 74 presses the multiple crushed balls 72 against the lower ring 76. The vitrification process S12 and the dispersion process S13 are then carried out with the air flow circulating as shown in Figure 2. The control unit 90 starts counting time using the timer 92 when the drive mechanism 78 starts to operate. The control unit 90 then stops counting time using the timer 92 once the timer 92 has set to a predetermined time T Ｐ Once the time has elapsed, the vitrification process S12 and the dispersion process S13 are terminated.

[0041] [Vitrification Process] The mixed powder MP introduced into the center of the ring ball mill mechanism 70 is subjected to centrifugal force as the lowering ring 76 rotates and moves radially outward from the lowering ring 76. As a result, the mixed powder MP gets trapped between each depression in the lowering ring 76 and the grinding balls 72 held in each depression. Meanwhile, as the lowering ring 76 rotates, the multiple grinding balls 72 revolve around an axis (around axis O). In this case, each grinding ball 72 rotates while revolving because it is fitted into each depression in the lowering ring 76 which rotates around the axis and is held in place by the lowering ring 76, and is also pressed by the stationary upper ring 74. Therefore, the mixed powder MP trapped between the lowering ring 76 and the grinding balls 72 is pressed by the grinding balls 72 and the lowering ring 76, which are moving relative to the lowering ring 76. As a result, the mixed powder MP is subjected to shear force and compressive stress by the grinding balls 72 and the lowering ring 76. Then, some of the mixed powder MP remains attached to the grinding balls 72 and moves between the grinding balls 72 and the upper ring 74. As a result, some of the mixed powder MP is subjected to shear force and compressive stress by the grinding balls 72 and the upper ring 74. In this way, the mixed powder MP moves radially outward of the lower ring 76 due to centrifugal force, and is subjected to shear force and compressive stress by either or both between each grinding ball 72 and the upper ring 74, and between each grinding ball 72 and the lower ring 76, as it moves to the outer edge of the lower ring 76. In this state, some of the mixed powder MP becomes vitrified.

[0042] [Dispersion Process] Next, the partially vitrified mixed powder MP is suspended upward by the gas emitted from multiple gas outlets of the gas supply mechanism 50. Consequently, the mixed powder MP that has been pulverized by the ring ball mill mechanism 70 is suspended above the ring ball mill mechanism 70. In this case, the mixed powder MP is dispersed in the gas. Here, "dispersion" means that the mixed powder MP, which is an aggregate of powder particles that were previously agglomerated together, becomes separated. Next, the dispersed mixed powder MP is guided by the gas flow circulating inside the container 20 and moves back to the center of the ring ball mill mechanism 70.

[0043] Here, the vitrified inorganic material is, for example, an inorganic solid electrolyte material. The inorganic solid electrolyte material constitutes the solid electrolyte layer of an all-solid-state lithium-ion battery. Furthermore, as mentioned above, in this embodiment, the multiple inorganic compounds are lithium sulfide, lithium nitride, and diphosphorus pentasulfide, so the inorganic solid electrolyte material, which is an example of a vitrified inorganic material, is a sulfide-based inorganic solid electrolyte material. That is, the sulfide-based inorganic solid electrolyte material contains at least one of Li, P, and S as constituent elements.

[0044] While the inorganic solid electrolyte material is not particularly limited, examples include sulfide-based inorganic solid electrolyte materials, oxide-based inorganic solid electrolyte materials, and lithium-based inorganic solid electrolyte materials. Among these, sulfide-based inorganic solid electrolyte materials are preferred. Furthermore, while the inorganic solid electrolyte material is not particularly limited, examples include those used in the solid electrolyte layer constituting an all-solid-state lithium-ion battery.

[0045] Examples of sulfide-based inorganic solid electrolyte materials include Li ２ S-P ２ S ５ Material, Li ２ S-SiS ２ Material, Li ２ S-GeS ２ Material, Li ２ S-Al ２ S ３ Material, Li ２ S-SiS ２ -Li ３ PO ４ Material, Li ２ S-P ２ S ５ -GeS ２ Material, Li ２ S-Li ２ O-P ２ S ５ -SiS ２ Material, Li ２ S-GeS ２ -P ２ S ５ -SiS ２ Material, Li ２ S-SnS ２ -P ２S ５ -SiS ２ Material, Li ２ S-P ２ S ５ -Li ３ N material, Li ２ S ２＋Ｘ -P ４ S ３ Material, Li ２ S-P ２ S ５ -P ４ S ３ Materials are among them. Among these, Li is chosen because it has excellent lithium-ion conductivity and stability that does not decompose over a wide voltage range. ２ S-P ２ S ５ Materials and Li ２ S-P ２ S ５ -Li ３ N material is preferred. Here, for example, Li ２ S-P ２ S ５ The material is at least Li ２ S (lithium sulfide) and P ２ S ５ It refers to an inorganic material obtained by chemically reacting inorganic compositions containing Li with each other through mechanical processing. ２ S-P ２ S ５ -Li ３ N material is defined as at least Li ２ S (lithium sulfide) and P ２ S ５ and Li ３ This refers to an inorganic material obtained by chemically reacting inorganic compositions containing N with each other through mechanical treatment. In this embodiment, lithium sulfide also includes lithium polysulfide.

[0046] Examples of the oxide-based inorganic solid electrolyte materials mentioned above include LiTi ２ (PO ４ ) ３ LiZr ２ (PO ４ ) ３ LiGe ２ (PO ４ ) ３NASICON type such as, (La ０．５＋ｘ Li ０．５－３ｘ )TiO ３ Perovskite type such as, Li ２ O - P ２ O ５ materials, Li ２ O - P ２ O ５ -Li ３ N materials and the like. Examples of the lithium-based inorganic solid electrolyte material include, for example, LiPON, LiNbO ３ , LiTaO ３ , Li ３ PO ４ , LiPO ４－ｘ N ｘ (x is 0 < x ≤ 1), LiN, LiI, LISICON and the like. Furthermore, glass ceramics obtained by precipitating crystals of these inorganic solid electrolyte materials can also be used as inorganic solid electrolyte materials.

[0047] The sulfide-based inorganic solid electrolyte material in the present embodiment preferably contains Li, P, and S as constituent elements.

[0048] <Judgment step> Next, the judgment step S14 will be described. When the time T counted by the timer 92 is equal to or greater than the determined time T Ｐ , the control unit 90 makes an affirmative judgment and ends the vitrification step S12 and the dispersion step S13. On the other hand, when the time T counted by the timer 92 is less than the determined time T Ｐ , the control unit 90 makes a negative judgment and continues the vitrification step S12 and the dispersion step S13.

[0049] Here, the determined time T Ｐ is the time set by the test research of the inventors of the present application. Specifically, it is set to the time until a certain amount (an amount of almost 100% such as 98% or more) of the powder of the vitrified inorganic material is obtained from the mixed powder MP before the start of the vitrification step S12 and the dispersion step S13. That is, focusing on the behavior of the mixed powder MP, the step combining the vitrification step S12 and the dispersion step S13 is the determined time T ＰThis is performed multiple times. Alternatively, from another perspective, the gas is supplied from the gas supply mechanism 50 to the inside of the container 20 for a predetermined time T. Ｐ By supplying gas, the process combining the vitrification process S12 and the dispersion process S13 is performed multiple times. In this embodiment, a predetermined time T Ｐ This refers to the time required for the mixed powder MP to circulate multiple times (for example, 5 to 15 times) as the gas flow circulates inside the container 20 during the vitrification process S12 and the dispersion process S13. However, the number of times referred to here depends on factors such as the magnitude of the pressure applied when the pressurizing mechanism 80 pressurizes the upper ring 74, the rotational speed of the lower ring 76 driven and rotated by the drive mechanism 78, and the size of the mixed powder MP.

[0050] <Discharge Process> The discharge process S15 is a process in which the inorganic material powder obtained in the vitrification process S12 and the dispersion process S13 is discharged from the branch-shaped portion 44 of the discharge pipe 40 to a dust collector (not shown). In the discharge process S15, the control unit 90 controls the multiple swinging wings 62 of the wing mechanism 60 to bring the wing mechanism 60 into the state shown in Figure 4. As a result, the gas sent into the container 20 from the gas supply mechanism 50 flows through the gaps formed between adjacent swinging wings 62 inside the discharge pipe 40 and is discharged to the dust collector from the opening at the upper end of the branch-shaped portion 44. Accordingly, the vitrified inorganic material inside the container 20 is discharged to the dust collector along with this gas flow. Then, the vitrified inorganic material inside the container 20 is discharged from the inorganic material manufacturing apparatus 10, and the method for manufacturing inorganic material according to this embodiment is completed.

[0051] [Second Embodiment] Next, an inorganic material manufacturing apparatus 10 according to the second embodiment will be described. This embodiment is the same as the first embodiment, except for the points described below.

[0052] Figure 9 shows a schematic diagram of the inorganic material manufacturing apparatus 10 according to this embodiment. As shown in Figure 9, in this embodiment, the ring ball mill mechanism 70 has different heights for the outer edge and the inner edge of the depressions. In the example shown in Figure 9, the height T1 of the inner edge 1a of the first depression 77A is higher than the height T2 of the outer edge 1b of the first depression 77A. Also, the height T3 of the inner edge 1c of the second depression 77B is higher than the height T4 of the outer edge 1d of the second depression 77B. As a result, the mixed powder MP flows more easily from the inside to the outside of the grinding balls 72, accelerating the manufacturing process.

[0053] Furthermore, it is preferable that a step is formed between at least one depression and the other depressions. In the example shown in Figure 9, a step 73 is formed between the first depression 77A and the second depression 77B, which increases the time that the mixed powder MP remains inside the grinding ball 72 and promotes the reaction.

[0054] Alternatively, as shown in Figure 10, the height T1 of the inner edge 1a of the first depression 77A may be lower than the height T2 of the outer edge 1b of the first depression 77A. Furthermore, the height T3 of the inner edge 1c of the second depression 77B may be lower than the height T4 of the outer edge 1d of the second depression 77B. In this case, the time that the mixed powder MP remains inside the grinding ball 72 can be increased, thereby promoting the reaction.

[0055] Furthermore, although not shown in the diagram, the height T1 of the inner edge 1a of the first depression 77A may be higher than the height T2 of the outer edge 1b of the first depression 77A, and the height T3 of the inner edge 1c of the second depression 77B may be lower than the height T4 of the outer edge 1d of the second depression 77B. This makes it easier for the mixed powder MP to flow from the center to the outside of the first grinding ball 72A, while making it more difficult for it to flow to the outside of the second grinding ball 72B. This allows the mixed powder MP to remain inside the grinding ball 72 for a longer period of time.

[0056] As described above, in this embodiment as well, the manufacturing of inorganic materials can be made more efficient. Furthermore, according to this embodiment, the flow of the mixed powder MP can be further adjusted by adjusting the height of the edge of the recess.

[0057] [Third Embodiment] Next, an inorganic material manufacturing apparatus 10 according to the third embodiment will be described. This embodiment is the same as the first embodiment, except for the points described below.

[0058] Figure 11 shows an overview of the inorganic material manufacturing apparatus 10 according to this embodiment. In this embodiment, the crushing balls 72 are arranged in a single row. Also, there is only one depression formed in the lowering ring 76.

[0059] Figure 12 shows the gas flow by the gas feeding mechanism 50 in this embodiment. The gas flow is the same as the gas flow in the first embodiment shown in Figure 2. Figure 13 shows an overview of the operation of the ring ball mill mechanism 70 in this embodiment. The ring ball mill mechanism 70 in this embodiment, like the ring ball mill mechanism 70 in the first embodiment shown in Figure 5, has the function of being pressurized by the pressurizing mechanism 80 and applying shear force and compressive stress to the mixed powder MP, which is a mixture of multiple types of inorganic compounds.

[0060] Next, the ring ball mill mechanism 70 and the pressurizing mechanism 80 will be described in more detail using Figures 14 and 15. Figure 14 is a top view of the ring ball mill mechanism 70. Figure 15 is an enlarged view of the ring ball mill mechanism 70 in Figure 11.

[0061] As shown in Figures 14 and 15, in this embodiment, the grinding balls 72 are arranged along the circumference. Here, being arranged along the circumference does not mean that the centers of each grinding ball are strictly aligned on the circumference, but may be offset to some extent. When the grinding balls 72 are arranged so that the distance (gap) between them is all equal, the distance W1 between the centers of adjacent grinding balls 72 is, for example, 20 mm to 40 mm. Also, when the grinding balls 72 are arranged so that the distance (gap) between them is all equal, the distance (gap) W2 between adjacent grinding balls 72 is, for example, 1.5 mm to 3.5 mm. When all the grinding balls 72 are connected, the distance between the centers of the grinding balls 72 at both ends is, for example, 80 mm to 90 mm.

[0062] As shown in Figure 15, in this embodiment, the ring ball mill mechanism 70 has different heights T1 for the inner edge 1a of the depression and T2 for the outer edge 1b of the depression. In the example shown in Figure 15, the height T1 for the inner edge 1a of the first depression 77A is higher than the height T2 for the outer edge 1b of the first depression 77A. This makes it easier for the mixed powder MP to flow from the inside to the outside of the grinding ball 72, thereby improving the efficiency of the manufacturing process.

[0063] Alternatively, as shown in Figure 16, the height T1 of the inner edge 1a of the first recess 77A may be lower than the height T2 of the outer edge 1b of the first recess 77A. In this case, the time that the mixed powder MP remains inside the grinding ball 72 is increased, which may improve the efficiency of vitrification of the mixed powder MP.

[0064] As described above, the manufacturing of inorganic materials can be made more efficient in this embodiment as well.

[0065] The embodiments of the present invention have been described above with reference to the drawings, but these are merely examples of the present invention, and various other configurations can also be adopted.

[0066] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way to the descriptions of these examples.

[0067] As an example, an inorganic material was manufactured using the inorganic material manufacturing apparatus 10 according to this embodiment. As a comparative example, an inorganic material was manufactured using a conventional inorganic material manufacturing apparatus in which crushed balls 72 were arranged in a single row, and the properties of the inorganic materials were compared.

[0068] The manufacturing conditions for the ring ball mill mechanism 70 and pressurizing mechanism 80 of the example and comparative example are shown below. <Example> ・Diameter of the first circumference S1: 13.4 cm ・Diameter of the second circumference S2: 21.4 cm ・Diameter of the first grinding ball 72A: 3.81 cm ・Diameter of the second grinding ball 72B: 2.54 cm ・Number of first grinding balls 72A: 10 ・Number of second grinding balls 72B: 24 ・Rotation speed: 120 rpm ・Ring unit surface area load: 0.11 kgf / cm ２<Comparative Example> ・Circumference diameter of the circle where the crushing balls 72 are arranged: 21.4 cm ・Diameter of the crushing ball 72: 2.54 cm ・Number of crushing balls 72: 24 ・Rotation speed: 120 rpm ・Ring unit surface area load: 0.18 kgf / cm ２

[0069] As the mixed powder MP, a mixed powder was used that was manufactured by mixing raw materials mainly consisting of lithium sulfide and phosphorus pentasulfide using a mixer.

[0070] The vitrification process S12 and dispersion process S13 described above were carried out for 24 hours, 48 ​​hours, and 90 hours, respectively, and the ionic conductivity of the obtained inorganic materials was measured. Ionic conductivity is an indicator of the progress of the mechanical milling synthesis reaction of the mixed powder MP; the higher the value, the higher the proportion of the inorganic material that has undergone the mechanical milling synthesis reaction. The measured results are shown in Table 1. In Table 1, the ionic conductivity of the comparative example is set to 1.00, and the ionic conductivity of the example is expressed as a relative value.

[0071]

[0072] As shown in Table 1, it was confirmed that the inorganic material manufacturing apparatus 10 according to this embodiment can more efficiently vitrify the mixed powder MP when the vitrification process S12 and dispersion process S13 are performed for the same amount of time, thereby improving the efficiency of inorganic material manufacturing.

[0073] This application claims priority based on Japanese Patent Applications No. 2024-195929 and No. 2024-195930, filed on 8 November 2024, and incorporates all of their disclosures herein.

[0074] 20 Container 30 Injection cylinder 35 Conical cylinder 40 Discharge pipe 50 Gas feeding mechanism 60 Wing mechanism 70 Ring ball mill mechanism 80 Pressurization mechanism 90 Control unit

Claims

1. An inorganic material manufacturing apparatus comprising: a lowering ring on which material is supplied to one side; a drive mechanism for rotating the lowering ring; a plurality of recesses formed on the one side of the lowering ring along the circumferences of a plurality of concentric circles; a plurality of balls, partly fitted into each of the recesses and rotatable; and an upper ring positioned on the opposite side from the lowering ring, sandwiching the plurality of balls.

2. The inorganic material manufacturing apparatus according to claim 1, wherein the plurality of balls fitted into at least one of the recesses have a different diameter from the plurality of balls fitted into the other recesses.

3. The inorganic material manufacturing apparatus according to claim 1 or 2, wherein at least one of the recesses is formed at a higher position than the other recesses.

4. An inorganic material manufacturing apparatus according to claim 3, wherein a step is formed between at least one of the recesses and the other recesses.

5. The inorganic material manufacturing apparatus according to claim 1 or 2, wherein the upper ring includes a first upper ring and a second upper ring facing each other in different recesses, the second upper ring being located outward from the first upper ring.

6. The inorganic material manufacturing apparatus according to claim 5, further comprising a first pressurizing mechanism for pushing the first upper ring downward and a second pressurizing mechanism for pushing the second upper ring downward.

7. The inorganic material manufacturing apparatus according to claim 1 or 2, wherein the lowering ring includes a first lowering ring and a second lowering ring having different recesses formed on each other, the second lowering ring being located outward from the first lowering ring.

8. The inorganic material manufacturing apparatus according to claim 7, wherein the drive mechanism comprises a first drive mechanism for rotating the first lowering ring and a second drive mechanism for rotating the second lowering ring.

9. An inorganic material manufacturing apparatus comprising: a lowering ring on which material is supplied to one side; a drive mechanism for rotating the lowering ring; a recess formed on the one side of the lowering ring along a circumference concentric with the lowering ring; a plurality of balls, some of which are fitted into the recess and which are rotatable; and an upper ring positioned on the opposite side from the lowering ring, sandwiching the plurality of balls, wherein in a cross section passing through the center of the lowering ring, the height of the inner edge of the recess and the height of the outer edge of the recess are different.

10. The inorganic material manufacturing apparatus according to claim 9, wherein in a cross section passing through the center of the lowering, the height of the inner edge of the depression is lower than the height of the outer edge of the depression.

11. An inorganic material manufacturing apparatus according to claim 9 or 10, comprising: a first recess along the first circumference; and a second recess along the second circumference surrounding the first circumference, wherein in a cross section passing through the center of the lowering, the height of the outer edge of the first recess is lower than the height of the inner edge of the first recess, and the height of the outer edge of the second recess is higher than the height of the inner edge of the second recess.

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