Pulverizing device, method for producing inorganic material, and pulverizing method

Abstract

The pulverizing device of the present application includes: a container connected to a discharge pipe; a mill mechanism located inside the container to pulverize an object; a gas feeding mechanism to feed gas into the container; and a wing mechanism to control the discharge amount of gas discharged from the discharge pipe. The wing mechanism has a plurality of wings arranged in a circle, and the discharge amount is controlled by the variation of the gap between adjacent wings.

Description

[0001] This application is a divisional application of an application with the application date of June 11, 2020, the application number of 2020800412166, and the invention name of "Manufacturing method of inorganic material and inorganic material manufacturing apparatus". TECHNICAL FIELD

[0002] The present application relates to a pulverizing apparatus, a manufacturing method of inorganic material, and a pulverizing method. BACKGROUND

[0003] It is known to use, for example, lithium ion batteries as power sources for small portable devices such as portable telephones and notebook computers, and power sources for electric vehicles and electric power storage.

[0004] The lithium ion batteries currently on the market use an electrolyte containing a flammable organic solvent. On the other hand, a lithium ion battery that has been fully solidified by replacing the electrolyte with a solid electrolyte (a fully solidified lithium ion battery) does not use a flammable organic solvent within the battery. Therefore, the fully solidified lithium ion battery achieves simplification of safety devices, and is excellent in manufacturing cost and productivity. As a solid electrolyte material used in such a solid electrolyte, for example, as shown in Patent Literature 1, there is a sulfide-based solid electrolyte material.

[0005] PRIOR ART DOCUMENT

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Publication No. 2016-27545 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] In Patent Literature 1, a method of vitrifying a raw material composition containing constituent components of a sulfide solid electrolyte material by a mechanical grinding method using a planetary ball mill is disclosed.

[0010] However, when the mechanical grinding method using the planetary ball mill is used, the inorganic material after vitrification adheres to the entire inner circumferential surface of the rotating cylinder of the planetary ball mill. Therefore, the mechanical grinding method using the planetary ball mill requires periodic maintenance of the planetary ball mill (scraping off the adhered inorganic material after vitrification from the inner circumferential surface, etc.).

[0011] The present application provides a manufacturing method of inorganic material to obtain an inorganic material after vitrification from a mixed powder of a plurality of inorganic compounds with high manufacturing efficiency.

[0012] TECHNICAL SOLUTION FOR SOLVING THE PROBLEMS

[0013] The manufacturing method of inorganic material of one aspect of the present application includes:

[0014] a vitrification process of subjecting mixed powder of a plurality of inorganic compounds to shearing stress and compressive stress using a planetary mill mechanism, thereby vitrifying at least a part of the mixed powder; and

[0015] a dispersion process of dispersing the vitrified mixed powder after the vitrification process,

[0016] the process combined with the vitrification process and the dispersion process is performed a plurality of times to obtain a powder of the vitrified inorganic material from the mixed powder.

[0017] Further, the inorganic material manufacturing apparatus of one aspect of the present application has:

[0018] a planetary mill mechanism having a plurality of crushing balls, a lower ring rotating around a shaft while holding the plurality of crushing balls, and an upper ring disposed on the side opposite to the lower ring with the plurality of crushing balls interposed therebetween and pressing the plurality of crushing balls toward the lower ring;

[0019] a container in which the planetary mill mechanism is disposed inside and which is formed with a hole in the portion on the upper side compared to the planetary mill mechanism;

[0020] a gas feeding mechanism installed in the container in the portion on the lower side compared to the planetary mill mechanism and feeding gas to the inside on the upper side;

[0021] a cylinder installed in the container and penetrating the hole for flowing the gas outside into the lower ring on the side closer to the shaft than the plurality of crushing balls; and

[0022] a control section controlling the rotation operation of the lower ring and the gas feeding operation of the gas feeding mechanism,

[0023] the inorganic material manufacturing method of one aspect is executed by the control section controlling the rotation operation and the gas feeding operation.

[0024] Effects of the Invention

[0025] The inorganic material manufacturing method of one aspect of the present application can obtain a vitrified inorganic material from mixed powder of a plurality of inorganic compounds with high manufacturing efficiency.

[0026] Further, the inorganic material manufacturing apparatus of one aspect of the present application can manufacture a vitrified inorganic material from mixed powder of a plurality of inorganic compounds with high manufacturing efficiency. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a flowchart showing the inorganic material manufacturing method in the present embodiment (embodiment as an example of the present application).

[0028] Figure 2 FIG. 1 is a cross-sectional view of a mill device used for implementing the manufacturing method of inorganic material of the present embodiment.

[0029] Figure 3A FIG. 2 is a diagram for explaining the vitrification process and the dispersion process in the manufacturing method of inorganic material of the present embodiment.

[0030] Figure 3B FIG. 3 is a diagram (top view) for explaining the posture of the wing mechanism of the mill device in the vitrification process and the dispersion process of the present embodiment.

[0031] Figure 4A FIG. 4 is a diagram (cross-sectional view) for explaining the action of the ring-roller mechanism of the mill device in the vitrification process and the dispersion process of the present embodiment.

[0032] Figure 4B FIG. 5 is a diagram (top view) for explaining the action of the ring-roller mechanism of the mill device in the vitrification process and the dispersion process of the present embodiment.

[0033] Figure 4C FIG. 6 is a diagram (cross-sectional view) for explaining the relationship between the action of the ring-roller mechanism and the behavior of the powder in the vitrification process and the dispersion process of the present embodiment.

[0034] Figure 5A FIG. 7 is a diagram (cross-sectional view) for explaining the discharge process in the manufacturing method of inorganic material of the present embodiment.

[0035] Figure 5B FIG. 8 is a diagram (top view) for explaining the posture of the wing mechanism of the mill device in the discharge process of the present embodiment.

[0036] Figure 6 FIG. 9 is a flowchart showing the manufacturing method of inorganic material in the present embodiment, which is captured from a different angle from the flowchart of FIG. 1. Figure 1 DETAILED DESCRIPTION

[0037] SUMMARY

[0038] Hereinafter, the present embodiment will be described.

[0039] First, the function and structure of the mill device 10 (an example of inorganic material manufacturing device, refer to FIG. 1) used for implementing the manufacturing method of inorganic material of the present embodiment will be described. Next, the manufacturing method S10 of inorganic material of the present embodiment (refer to FIG. 2) will be described. Next, the effects of the present embodiment will be described. Figure 2 Figure 1

[0040] ​​​In the following description, the same reference numerals are used for the same components having the same functions, and the description thereof is appropriately omitted in the drawings.

[0041] Here, the following describes the details thereof, but the mill device 10 of the present embodiment is provided with: a ring and ball mill mechanism 70 having a plurality of crushing balls 72, a lower ring 76 that rotates around a shaft (around the shaft O) while holding the plurality of crushing balls 72, and an upper ring 74 that is disposed on the side opposite to the lower ring 76 across the plurality of crushing balls 72 and presses the plurality of crushing balls 72 toward the lower ring 76; a container 20 in which the ring and ball mill mechanism 70 is disposed inside and in which a hole 24A is formed on the upper side compared to the ring and ball mill mechanism 70; a gas feeding mechanism 50 that is installed at a position on the lower side compared to the ring and ball mill mechanism 70 in the container 20 and feeds gas to the inside on the upper side; a cylinder 30 (hereinafter, referred to as an injection cylinder 30), which is installed in the container 20 and penetrates the hole 24A, and is used for flowing the gas from the outside into a position on the shaft side compared to the plurality of crushing balls 72 in the lower ring 76; and a control section 90 that controls the rotation operation of the lower ring 76 and the gas feeding operation of the gas feeding mechanism 50, and the manufacturing method of inorganic material of the present embodiment is executed by causing the control section 90 to control the rotation operation and the gas feeding operation (refer to Figure 1 , Figure 2 and the like).

[0042] In addition, the manufacturing method of inorganic material S10 of the present embodiment includes: a vitrification process S12 of vitrifying at least a part of a mixed powder MP made of a powder in which a plurality of inorganic compounds are mixed by applying a shear stress and a compressive stress to the mixed powder MP using the ring and ball mill mechanism 70; and a dispersion process S13 of dispersing the vitrified mixed powder MP after the vitrification process S12, and the process combined by the vitrification process S12 and the dispersion process S13 is performed a plurality of times to obtain a vitrified inorganic material powder from the mixed powder MP (refer to Figure 1 , Figure 3A and the like).

[0043] Function and structure of the mill device

[0044] Hereinafter, the function and the structure of the mill device 10 of the present embodiment will be described mainly with reference to Figure 2

[0045] The mill device 10 of the present embodiment has a function of vitrifying at least a part of a mixed powder MP made of a powder in which a plurality of inorganic compounds are mixed by applying a shear stress and a compressive stress to the mixed powder MP using the ring and ball mill mechanism 70. Figure 4C ​) function of glassifying the mixed powder MP by shearing force and compressive stress. As a result, the mill device 10 of the present embodiment has a function of obtaining (i.e., manufacturing) a powder of the inorganic material after glassification described later from the mixed powder MP in which a plurality of inorganic compounds are mixed.

[0046] As shown in Figure 2 , the mill device 10 of the present embodiment is provided with a container 20, an injection cylinder 30 (an example of a cylinder), a conical cylinder 35, a discharge pipe 40, a gas feeding mechanism 50, a wing mechanism 60, a ring-and-ball mill mechanism 70, a pressurizing mechanism 80, and a control section 90.

[0047] <CONTAINER>

[0048] As shown in Figure 2 , the container 20 is, for example, a cylindrical shape, and has a peripheral wall 22, a top plate 24, and a bottom plate 26. Inside the container 20 (a space surrounded by the peripheral wall 22, the top plate 24, and the bottom plate 26) is arranged a part of the injection cylinder 30, the conical cylinder 35, a part of the discharge pipe 40, the gas feeding mechanism 50, the wing mechanism 60, the ring-and-ball mill mechanism 70, and a part of the pressurizing mechanism 80. A through-hole 24A (hereinafter, referred to as hole 24A) is formed in the top plate 24. From another perspective, the hole 24A is formed in a portion of the container 20 that is on the upper side compared to the ring-and-ball mill mechanism 70. Note that, Figure 2 the reference sign O in Figures 3A-5B indicates an axis of the container 20 (also the same in Figures 3A-5B ). In addition, the reference sign +X indicates the upper side in the vertical direction of the mill device 10, and the reference sign -X indicates the lower side in the vertical direction of the mill device 10 (also the same in

[0049] <INJECTION CYLINDER, CONICAL CYLINDER, AND DISCHARGE PIPE>

[0050] The injection cylinder 30 has a function as an introduction pipe for introducing the mixed powder MP from the outside to the inside of the container 20 before the manufacturing operation of the inorganic material is started, and a function as a flow path for flowing the gas (for example, nitrogen, argon, or the like, non-active gas) outside the container 20 into the inside at the time of the manufacturing operation of the inorganic material.

[0051] As shown in Figure 2As shown, the injection cylinder 30 is arranged in a state of passing through the hole 24A. In a state where the outer periphery of the upper side portion of the injection cylinder 30 in the vertical direction is surrounded by the discharge pipe 40, the upper end portion of the injection cylinder 30 is fixed to the discharge pipe 40. Here, the discharge pipe 40 is embedded in the hole 24A of the top plate 24 of the container 20 and fixed. That is, the injection cylinder 30 is installed in the container 20 via the discharge pipe 40. In addition, the lower end of the injection cylinder 30 is open to the area surrounded by the multiple crushing balls 72 of the ring mill mechanism 70 described later. In addition, the injection cylinder 30 introduces the mixed powder MP into the center side (closer to the axis O side than the multiple crushing balls 72) of the ring mill mechanism 70 before the start of the inorganic material manufacturing operation, and allows external gas to flow in during the inorganic material manufacturing operation.

[0052] The conical cylinder 35 is arranged above the ring and ball mill mechanism 70 with its apex (shorter outer circumference) facing downward in the vertical direction and surrounding a portion of the injection cylinder 30 .

[0053] The discharge pipe 40 is a pipe for discharging the manufactured inorganic material. Figure 2 As shown, the discharge pipe 40 has an R-shaped configuration when viewed from the front. Specifically, the discharge pipe 40 includes a cylindrical portion 42 arranged along an axis O and a branch portion 44 connected obliquely to the vertical center of the cylindrical portion 42. The lower end of the cylindrical portion 42 opens into the interior of the container 20, and the injection cylinder 30 is fixed to the upper end of the cylindrical portion 42. The upper end opening of the branch portion 44 is connected to a dust collector (not shown).

[0054] Gas supply mechanism

[0055] like Figure 2 As shown, the gas supply mechanism 50 is installed in the container 20 below the ring and ball mill mechanism 70 and has a function of supplying gas (for example, inert gas such as nitrogen or argon) upward into the container 20 .

[0056] The gas feeding mechanism 50 has, for example, a plurality of gas ejecting portions. Each gas ejecting portion ejects a gas flow toward a gap formed between the inner peripheral surface of the container 20 and the ring and ball mill mechanism 70 (lower ring 76) (see Figure 3A It should be noted that each gas injection portion is connected to a gas cylinder (not shown) disposed outside the container 20 .

[0057] <Wing mechanism>

[0058] like Figure 2 As shown, the wing mechanism 60 is disposed between the top plate 24 and the conical cylinder 35 inside the container 20. Figure 3B and Figure 5BAs shown, the wing mechanism 60 includes a plurality of swinging wings 62 arranged point-symmetrically about the axis O. Each swinging wing 62 is composed of a rotating shaft 62A, a short width plate 62B, and a long width plate 62C. The short width plate 62B and the long width plate 62C are attached to the outer circumference of the rotating shaft 62A, facing in directions intersecting each other and along the axial direction of the rotating shaft 62A.

[0059] And, as Figure 3B As shown, when each swing wing 62 rotates its own rotation axis 62A in the clockwise direction, its own short wide plate 62B contacts the long wide plate 62C of the adjacent swing wing 62, forming a wall extending over the entire circumference. Figure 5B As shown, each swinging blade 62 moves its own rotation axis 62A from Figure 3B When the state is rotated counterclockwise by a predetermined angle, the short wide plate 62B thereof leaves the long wide plate 62C of the adjacent swing wing 62, and a gap is formed between the adjacent swing wings 62.

[0060] It should be noted that Figure 3B The vitrification step S12 and the dispersion step S13 described later (see Figure 1 ) in the posture of the wing mechanism 60. In addition, Figure 5B The discharge step S15 described later (see Figure 1 ) in the posture of the wing mechanism 60. Moreover, the wing mechanism 60 of this embodiment is controlled by the control unit 90 and is set to be in the vitrification step S12 and the dispersion step S13 ( Figure 3B ) is greater than that in the case of the exhaust step S15 ( Figure 5B ) the amount of gas discharged from the branch portion 44 is small.

[0061] <Ring and ball mill mechanism and pressurizing mechanism>

[0062] The ring mill mechanism 70 is pressurized by the pressurizing mechanism 80 to form a mixed powder MP (see Figure 4C ) functions of acting shear and compressive stresses.

[0063] like Figure 2 As shown, the ring and ball mill mechanism 70 is disposed, for example, at the lower side in the vertical direction inside the container 20. The ring and ball mill mechanism 70 includes a plurality of grinding balls 72, a lower ring 76, an upper ring 74, and a drive mechanism 78.

[0064] The plurality of pulverizing balls 72 are made of, for example, ceramics. Here, as the ceramic constituting the plurality of pulverizing balls 72, alumina, stabilized zirconia, silicon nitride, or the like can be used.

[0065] The lower ring 76 is driven by a drive mechanism 78 to rotate about an axis (axis O) while holding the plurality of pulverizing balls 72. The lower ring 76 is, for example, a donut-shaped member with a through-hole formed in the center and is made of ceramic. The upper surface of the lower ring 76 has a plurality of recesses 76A formed therein to hold the plurality of pulverizing balls 72, into which each pulverizing ball 72 fits. Examples of the ceramic material used to form the lower ring 76 include alumina, stabilized zirconia, silicon nitride, and the like.

[0066] The upper ring 74 is positioned opposite the lower ring 76, sandwiching the plurality of crushing balls 72 held by the lower ring 76. The upper ring 74 has its upper surface pressurized by a pressurizing mechanism 80 (described later), pressing the plurality of crushing 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. To hold the plurality of crushing balls 72, a circular recess 74A is formed on the lower surface of the upper ring 74, symmetrically with respect to the axis O, into which each crushing ball 72 is inserted. Examples of the ceramic material constituting the upper ring 74 include alumina, stabilized zirconia, silicon nitride, and the like.

[0067] like Figure 2 As shown, the drive mechanism 78 is arranged below the lower ring 76 while the lower ring 76 is fixed. The drive mechanism 78 rotates about an axis (about the axis O) and can rotate the lower ring 76 at, for example, 25 to 300 rpm, preferably 100 to 140 rpm.

[0068] As described above, the pressurizing mechanism 80 has a ring unit surface area load of 10000 kgf / m 2 ~40000kgf / m 2 The function of pressurizing the upper surface of the upper ring 74 is preferably to pressurize the upper surface of the upper ring 74 with a load per unit surface area of ​​12000 kgf / m 2 ~28000kgf / m 2 Pressurize with the pressure of the pressure.

[0069] <Control Department>

[0070] The control unit 90 has the function of controlling the operation of the mill device 10. Specifically, the control unit 90 controls the rotation of the drive mechanism 78, the gas supply operation of the gas supply mechanism 50, and the like. The control unit 90 also includes a timer 92 for counting the rotation time of the drive mechanism 78. Details of the functions of the control unit 90 will be described later in the description of the inorganic material production method S10 of this embodiment.

[0071] The above is the description of the function and structure of the grinding device 10 according to the present embodiment.

[0072] 《Methods for producing inorganic materials》

[0073] Next, the manufacturing method S10 of the inorganic material of the present embodiment (hereinafter, referred to as the manufacturing method S10 of the present embodiment) will be described with reference to Figure 1

[0074] The manufacturing method S10 of the present embodiment includes a mixing process S11, a vitrification process S12, a dispersion process S13, a judgment process S14 of judging whether or not a prescribed time T P has elapsed from the start of the vitrification process S12, and a discharge process S15.

[0075] The manufacturing method S10 of the present embodiment, after causing the mixing process S11, the vitrification process S12, and the dispersion process S13 to proceed in the order of the processes as described above, repeatedly proceeds the vitrification process S12 and the dispersion process S13 in the judgment process S14 until the prescribed time T P has elapsed from the start of the vitrification process S12 (that is, as long as the judgment in the judgment process S14 is continuously negative). Also, the manufacturing method S10 of the present embodiment, in the case where the prescribed time T P has elapsed from the start of the vitrification process S12 (that is, in the case where the judgment in the judgment process S14 is positive), proceeds the discharge process S15 and ends. Note that the vitrification process S12, the dispersion process S13, the judgment process S14, and the discharge process S15 are executed by controlling the mill device 10 by the control section 90. Also, the prescribed time T P will be described later.

[0076] Next, the details of each process will be described.

[0077] < Mixing Process >

[0078] The mixing process S11 is a process of mixing the powders of a plurality of inorganic compounds to generate a mixed powder MP. The mixing process S11 is performed using, for example, a mixer (omitted from the drawing).

[0079] Here, an example of the plurality of inorganic compounds in the present embodiment is lithium sulfide, lithium nitride, and diphosphorus pentasulfide.

[0080] Then, when the mixed powder MP is generated by the mixing process S11, the mixed powder MP is introduced from the injection cylinder 30 of the mill device 10 to the inside of the container 20, and the process ends.

[0081] < Vitrification Process and Dispersion Process >

[0082] Next, the vitrification process S12 and the dispersion process S13 will be described with reference to Figure 3A , Figure 3B , Figures 4A-4C ​​

[0083] First, the control section 90 controls the plurality of swing wings 62 of the wing mechanism 60 so that the wing mechanism 60 becomes the state shown in FIG. 4. In addition, the control section 90 starts the drive of the drive mechanism 78 of the ring and ball mill mechanism 70. Along with this, the lower ring 76 is driven by the drive mechanism 78 to rotate around the shaft. In addition, the control section 90 causes the gas to be emitted from the plurality of air emission portions of the gas feeding mechanism 50. In this case, the gas (for example, nitrogen, argon, or the like, which is a non-active gas) is caused to flow from the outside to the inside of the container 20 continuously in the injection cylinder 30. A sulfide, a nitride, a halide, or the like, which easily oxidizes the mixed powder MP or the inorganic material after vitrification, is used to reduce the moisture concentration and the oxygen concentration of the gas. For example, it is preferable that the moisture concentration be 1500 ppm or less and the oxygen concentration be 10% or less, and it is further preferable that the moisture concentration be 400 ppm or less and the oxygen concentration be 1% or less, but the threshold value is appropriately decided in accordance with the properties of the inorganic material. Thus, the gas flow circulation shown in FIG. 4 is caused in the inside of the container 20. In addition, the control section 90 controls the pressurization mechanism 80 to pressurize the upper ring 74. Along with this, the upper ring 74 presses the plurality of crushing balls 72 toward the lower ring 76. Figure 3B Figure 3A Furthermore, the vitrification process S12 and the dispersion process S13 are performed in the state of the gas flow circulation shown in FIG. 4.

[0084] Furthermore, the vitrification process S12 and the dispersion process S13 are performed in the state of the gas flow circulation shown in FIG. 4. Figure 3A

[0085] Note that, along with the start of the drive of the drive mechanism 78, the control section 90 starts the counting of the time by the timer 92. Then, when the timer 92 elapses the prescribed time T P , the control section 90 ends the vitrification process S12 and the dispersion process S13.

[0086] 〔Vitrification Process〕

[0087] The mixed powder MP introduced to the center of the ring and ball mill mechanism 70 is moved to the radially outer side of the lower ring 76 by the centrifugal force along with the rotation of the lower ring 76 (see FIG. 4). As a result, the mixed powder MP enters between each recessed portion 76A of the lower ring 76 and the crushing ball 72 held by the each recessed portion 76A.

[0088] On the other hand, along with the rotation of the lower ring 76, the plurality of crushing balls 72 revolve around the shaft (around the shaft O) (see FIG. 4). In this case, each crushing ball 72 is held by the lower ring 76 and is pressurized by the stationary upper ring 74 while being fitted in each recessed portion 76A of the lower ring 76 rotating around the shaft, whereby each crushing ball 72 revolves while rotating (see FIG. 4). Figure 4B Figure 4A Figure 4B

[0089] ​​​​​Thus, the mixed powder MP between the lower ring 76 and the crushing balls 72 is subjected to pressurization by the crushing balls 72 and the lower ring 76 that are relatively moved with respect to the lower ring 76. As a result, the mixed powder MP is subjected to shearing stress and compressive stress by the crushing balls 72 and the lower ring 76. Also, a part of the mixed powder MP moves to between the crushing balls 72 and the upper ring 74 in a state of being attached to the crushing balls 72. As a result, a part of the mixed powder MP is subjected to shearing stress and compressive stress by the crushing balls 72 and the upper ring 74. In this way, the mixed powder MP moves to the radially outer side of the lower ring 76 under the action of the centrifugal force, and moves to the outer peripheral edge side of the lower ring 76 by being subjected to shearing stress and compressive stress by one or both of the crushing balls 72 and the upper ring 74 and the crushing balls 72 and the lower ring 76. Also, in this state, a part of the mixed powder MP becomes a state after vitrification.

[0090] The above is a description of the vitrification process S12.

[0091] [Dispersion process]

[0092] Next, a part of the mixed powder MP after vitrification floats to the upper side by the gas ejected from the plurality of gas ejection portions of the gas feeding mechanism 50 (refer to FIG. 6). Figure 4C ) Accompanying this, the mixed powder MP crushed by the ring mill mechanism 70 floats to a position on the upper side compared to the ring mill mechanism 70. In this case, the mixed powder MP is dispersed in the gas. Here, “dispersion” means that the collection of powders that cohere to each other, that is, the mixed powder MP, becomes scattered.

[0093] Next, the mixed powder MP that has been dispersed is guided by the gas flow circulating inside the container 20 and moves again to the center of the ring mill mechanism 70.

[0094] The above is a description of the dispersion process S13.

[0095] Note that in the present specification, the vitrification process S12 and the dispersion process S13 are described as if they are performed separately, with a focus on the movement of the mixed powder MP inside the container 20, but in fact, the vitrification process S12 and the dispersion process S13 are performed simultaneously. Then, when a predetermined time T P passes from the start of the vitrification process S12 and the dispersion process S13, the powder of the inorganic material after vitrification is obtained from the mixed powder MP.

[0096] Here, the inorganic material after vitrification is, for example, an inorganic solid-state electrolyte material. The inorganic solid-state electrolyte material constitutes a solid-state electrolyte layer of a full solid-state lithium ion battery.

[0097] Furthermore, as described above, in this embodiment, the plurality of inorganic compounds are lithium sulfide, lithium nitride, and phosphorus pentasulfide. Therefore, the inorganic solid electrolyte material, which is an example of an inorganic material after vitrification, is a sulfide-based inorganic solid electrolyte material. Specifically, the sulfide-based inorganic solid electrolyte material contains at least one of Li, P, and S as a constituent element.

[0098] It should be noted that the inorganic solid electrolyte material is not particularly limited, and examples thereof include sulfide-based inorganic solid electrolyte materials, oxide-based inorganic solid electrolyte materials, lithium-based inorganic solid electrolyte materials, etc. Among these materials, sulfide-based inorganic solid electrolyte materials are preferred.

[0099] The inorganic solid electrolyte material is not particularly limited, and examples thereof include materials used to constitute a solid electrolyte layer of an all-solid-state lithium-ion battery.

[0100] As sulfide-based inorganic solid electrolyte materials, for example, Li2S-P2S5 materials, Li2S-Si S2 materials, Li2S-GeS2 materials, Li2S-Al2S3 materials, Li2S-SiS2-Li3PO4 materials, Li2S-P2S5-GeS2 materials, Li2S-Li2O-P2S5-SiS2 materials, Li2S-GeS2-P2S5-SiS2 materials, Li2S-SnS2-P2S5-SiS2 materials, Li2S-P2S5-Li3N materials, Li2S 2+X -P4S3 materials, Li2S-P2S5-P4S3 materials, etc.

[0101] Among these materials, Li2S-P2S5 materials and Li2S-P2S5-Li3N materials are preferred because they have excellent lithium ion conductivity and stability without decomposition over a wide voltage range. For example, the Li2S-P2S5 material refers to an inorganic material obtained by mechanically treating an inorganic composition containing at least Li2S (lithium sulfide) and P2S5 to chemically react with each other. Furthermore, the Li2S-P2S5-Li3N material refers to an inorganic material obtained by mechanically treating an inorganic composition containing at least Li2S (lithium sulfide), P2S5, and Li3N to chemically react with each other.

[0102] It should be noted that in this embodiment, lithium sulfide also includes lithium polysulfide.

[0103] Examples of the oxide-based inorganic solid electrolyte materials include NASICON-type (La 0.5+x Li 0.5-3xperovskite type such as TiO3, Li2O-P2O5 materials, Li2O-P2O5-Li3N materials, and the like.

[0104] As the lithium-based inorganic solid electrolyte material, for example, LiPON, LiNbO3, LiTaO3, Li3PO4, LiPO 4- x N x (x is 0 < x < 1), LiN, LiI, LISICON, and the like.

[0105] Further, a glass ceramic obtained by causing crystallization of these inorganic solid electrolyte materials can also be used as the inorganic solid electrolyte material.

[0106] The sulfide-based inorganic solid electrolyte material in the present embodiment preferably contains Li, P, and S as constituent elements.

[0107] <Judgment Step>

[0108] Next, the judgment step S14 will be described. The control section 90 makes a positive judgment and ends the vitrification step S12 and the dispersion step S13 when the time T counted by the timer 92 is the prescribed time T P In the above case, a positive judgment is made and the vitrification step S12 and the dispersion step S13 are ended.

[0109] On the other hand, the control section 90 makes a negative judgment and causes the vitrification step S12 and the dispersion step S13 to continue when the time T counted by the timer 92 is less than the prescribed time T P In the above case, a positive judgment is made and the vitrification step S12 and the dispersion step S13 are ended.

[0110] Here, the prescribed time T P is a time set through experimental research by the inventor of the present application, and is specifically set to a time from the mixed powder MP before the start of the vitrification step S12 and the dispersion step S13 to the time when a certain amount (an amount of approximately 100% or more, such as 98% or more) of the vitrified inorganic material powder is obtained. That is, if the behavior of the mixed powder MP is focused on, the process combining the vitrification step S12 and the dispersion step S13 is performed a plurality of times equivalent to the prescribed time T P In addition, from another perspective, the process combining the vitrification step S12 and the dispersion step S13 is performed a plurality of times by sending the gas from the gas sending mechanism 50 to the inside of the container 20 for the prescribed time T P

[0111] Note that in the present embodiment, the prescribed time T P ​The time required for circulating the mixed powder MP several times (for example, 5 times or more and 15 times or less) in conjunction with circulating the gas stream inside the container 20 in the vitrification process S12 and the dispersion process S13. However, the value of the several times here is based on, for example, the magnitude of the pressure applied to the upper ring 74 by the pressure applying mechanism 80, the rotational speed of the lower ring 76 driven by the driving mechanism 78, the size of the mixed powder MP, and the like.

[0112] <Discharge Process>

[0113] Next, the discharge process S15 will be described with reference to Figure 5A and Figure 5B

[0114] The discharge process S15 is a process of discharging the powder of the inorganic material obtained through the vitrification process S12 and the dispersion process S13 from the branched portion 44 of the discharge pipe 40 to a dust collector (omitted from the drawing).

[0115] In the discharge process S15, the control section 90 controls the plurality of swing wings 62 of the wing mechanism 60 so that the wing mechanism 60 becomes Figure 5B As a result, the gas sent into the inside of the container 20 from the gas feeding mechanism 50 flows through the inside of the discharge pipe 40 from the gaps formed between the adjacent respective swing wings 62 to each other, and is discharged to the dust collector from the opening of the upper end of the branched portion 44. In conjunction therewith, the inorganic material vitrified in the inside of the container 20 is discharged to the dust collector together with the gas stream.

[0116] Then, the inorganic material vitrified in the inside of the container 20 is discharged from the mill device 10, and the manufacturing method S10 of the present embodiment is ended.

[0117] The above is the description of the manufacturing method S10 of the present embodiment.

[0118] <Effects>

[0119] Next, the effects of the present embodiment will be described with reference to the drawings.

[0120] <First Effect>

[0121] For example, the mixed powder MP can be vitrified by applying a shearing stress and a compressive stress to the mixed powder MP using the planetary ball mill disclosed in Patent Literature 1. However, according to the experimental research by the present inventors, when the mixed powder MP is vitrified using the planetary ball mill, the mixed powder MP vitrified adheres to the inner circumferential surface of the rotating cylinder of the planetary ball mill. Therefore, in the case of the method using the planetary ball mill, it is necessary to periodically perform maintenance of the planetary ball mill (scraping off the inorganic material vitrified adhering to the inner circumferential surface, and the like).

[0122] ​On the other hand, in the case of this embodiment, the ring-and-ball mill mechanism 70 is used (see Figures 4A-4C ).

[0123] like Figure 2 and Figures 4A-4C As shown, the ring-and-sphere mill mechanism 70 includes: a plurality of crushing balls 72; a lower ring 76 that rotates around an axis (around axis O) while holding the plurality of crushing balls 72; and an upper ring 74 that is arranged on the opposite side of the lower ring 76 with the plurality of crushing balls 72 therebetween and presses the plurality of crushing balls 72 toward the lower ring 76.

[0124] Furthermore, in this embodiment, the plurality of pulverizing balls 72, which orbit as the lower ring 76 rotates, are caused to rotate. This causes shear stress and compressive stress to act between the plurality of pulverizing balls 72 and the lower ring 76, and between the plurality of pulverizing balls 72 and the upper ring 74, on the powder mixture MP, which moves from the axial side (axis O side) of the lower ring 76 toward the outer periphery due to the centrifugal force generated by the rotation of the lower ring 76. In this case, since the upper ring 74 is pressurized by the pressurizing mechanism 80, the plurality of pulverizing balls 72 are pressed against the upper and lower rings 74 and 76. Furthermore, in this case, the direction of rotation of each pulverizing ball 72 constantly changes depending on its position during orbital rotation. Therefore, in this embodiment, unlike in the case of a planetary ball mill, even if the pulverized powder mixture MP adheres to the upper and lower rings 74 and 76, it is immediately scraped off by the pulverizing balls 72. In other words, in this embodiment, the pulverized powder mixture MP is less likely to adhere to the recesses 74A of the upper ring 74 and 76A of the lower ring 76. Therefore, in the case of this embodiment, the maintenance required in the case of using the planetary ball mill is unnecessary, or the intervals between regular maintenance are longer than in the case of using the planetary ball mill.

[0125] Therefore, according to the production method S10 of the present embodiment, a vitrified inorganic material can be obtained from the mixed powder MP of a plurality of inorganic compounds at a higher production efficiency than when a planetary ball mill is used.

[0126] <Second Effect>

[0127] In this embodiment, the plurality of pulverizing balls 72, the upper ring 74, and the lower ring 76 are each made of ceramic. Therefore, compared to a case where the plurality of pulverizing balls 72, the upper ring 74, and the lower ring 76 are made of metal, the plurality of pulverizing balls 72, the upper ring 74, and the lower ring 76 in this embodiment are less likely to adhere to the mixed powder MP.

[0128] Therefore, according to this embodiment, compared with a case where the plurality of pulverizing balls 72 , the upper ring 74 , and the lower ring 76 are made of metal, a vitrified inorganic material can be obtained from the mixed powder MP of a plurality of inorganic compounds with higher production efficiency.

[0129] While this effect has been described using a case where the plurality of pulverizing balls 72, the upper ring 74, and the lower ring 76 are made of metal as a comparative example, this comparative example also possesses a structure that achieves the first effect described above. Therefore, even this comparative example falls within the technical scope of the present invention. It should be noted that, compared to this comparative example, this effect can be more easily achieved when at least one of the plurality of pulverizing balls 72, the upper ring 74, and the lower ring 76 is made of ceramic. In other words, even when at least one of the plurality of pulverizing balls 72, the upper ring 74, and the lower ring 76 is made of ceramic, the effect falls within the technical scope of the present invention.

[0130] <Third Effect>

[0131] like Figure 1 As shown, the production method S10 of this embodiment performs a combination of the vitrification step S12 and the dispersion step S13 performed after the vitrification step S12 a plurality of times, thereby obtaining a vitrified inorganic material from the mixed powder MP of a plurality of inorganic compounds.

[0132] Here, as described above, the dispersion step S13 disperses the mixed powder MP that has been at least partially vitrified in the vitrification step S12. Specifically, the mixed powder MP that has been partially vitrified is floated upward by the gas injected from the plurality of gas injection portions of the gas feeding mechanism 50 (see Figure 4C ). In this case, the mixed powder MP is dispersed in the gas. That is, the aggregates of the powders that have agglomerated with each other in the mixed powder MP are dispersed in the gas. Then, due to the structure of the mill device 10 of this embodiment, the dispersed mixed powder MP is guided by the airflow circulating inside the container 20 and moves again to the center of the ring mill mechanism 70. Then, after a predetermined time T has passed since the start of the vitrification step S12, P Before this, the mixed powder MP is repeatedly subjected to the vitrification step S12 and the dispersion step S13 ( Figure 1 14 in the flowchart of FIG. 1 ).

[0133] As described above, in the manufacturing method S10 of this embodiment, the mixed powder MP undergoing the vitrification step S12 is dispersed in the gas in the immediately preceding dispersion step S13. Specifically, in the vitrification step S12, the mixed powder MP, subjected to shear and compressive stresses by the ring-and-ball mill mechanism 70, is loosened by the immediately preceding dispersion step S13. Therefore, according to the manufacturing method S10 of this embodiment, the mixed powder MP is efficiently vitrified.

[0134] Therefore, the manufacturing method S10 of the present embodiment achieves an effect better than the first effect by performing a combination of the vitrification step S12 and the dispersion step S13 following the vitrification step S12 a plurality of times.

[0135] <Fourth Effect>

[0136] like Figure 2 As shown, the milling device 10 of this embodiment includes a ring mill mechanism 70, a container 20, a gas supply mechanism 50, an injection cylinder 30, and a control unit 90. The control unit 90 controls the opening and closing of the wing mechanism 60, the rotation of the lower ring 76, and the gas supply of the gas supply mechanism to execute the manufacturing method S10 of this embodiment (see Figure 1 、 Figures 3A-5B ).

[0137] That is, when the mill apparatus 10 of this embodiment is used to produce a vitrified inorganic material from a mixed powder MP of multiple inorganic compounds, the first and third effects described above are achieved. Furthermore, from another perspective, the mill apparatus 10 of this embodiment allows the combination of the vitrification step S12 and the subsequent dispersion step S13 to be performed multiple times through simple control.

[0138] <Fifth Effect>

[0139] like Figure 2 As shown, the mill device 10 of this embodiment includes a wing mechanism 60. In addition, in this embodiment, the amount of gas discharged from the branch portion 44 can be adjusted by changing the posture of the plurality of swing wings 62 of the wing mechanism 60 (see Figure 3A 、 Figure 3B 、 Figure 5A and Figure 5B Specifically, when the process consisting of the combination of the vitrification process S12 and the dispersion process S13 is performed, the control unit 90 controls the wing mechanism 60 so that the wing mechanism 60 becomes Figure 3B On the other hand, when the discharge process S15 is performed, the control unit 90 controls the wing mechanism 60 so that the wing mechanism 60 becomes Figure 5B status.

[0140] Incidentally, if the wing mechanism 60 maintains Figure 5B If the vitrification step S12 is performed in a state where the mixed powder MP is pulverized once and then discharged immediately after the first grinding, most of the mixed powder MP that has floated upward in the container 20 by the gas supply mechanism 50 is discharged from the branch portions 44 by the airflow without returning to the vitrification step S12. That is, the mill apparatus 10 of this embodiment can also be used as a conventional mill apparatus that pulverizes powder once and then discharges the powder immediately.

[0141] Therefore, according to the mill device 10 of this embodiment, by controlling the postures of the plurality of swing wings 62 of the wing mechanism 60 , it is possible to implement the manufacturing method S10 of this embodiment and the pulverizing operation of the above-described conventional mill device.

[0142] The above is the description of the effects of this embodiment.

[0143] As described above, the present invention has been described using the above embodiment as an example, but the present invention is not limited to the above embodiment. The technical scope of the present invention also includes the following aspects (modifications), for example.

[0144] For example, in the manufacturing method S10 of the present embodiment, the dispersion step S13 (see FIG. 1 ) is performed after the vitrification step S12 from the viewpoint of the movement of the powder constituting the mixed powder MP (microscopic viewpoint). Figure 1 ). However, from a macroscopic point of view, the vitrification step S12 and the dispersion step S13 can be performed simultaneously. Figure 6 Captured as a flowchart Figure 1 In this case, the vitrification step S12, the dispersion step S13 and the determination step S14 of this embodiment can be replaced by a process that is performed for a predetermined time T P Step S12A is a combination of a vitrification step and a dispersion step.

[0145] In addition, the manufacturing method S10 of this embodiment (see Figure 1 ) as a mill device 10 using this embodiment (refer to Figure 2 However, if the vitrification step S12 can be performed using the ring-and-sphere mill mechanism 70 and a process consisting of the vitrification step S12 and the dispersion step S13 following the vitrification step S12 can be repeatedly performed, the manufacturing method S10 of this embodiment can be performed without using the mill device 10 of this embodiment.

[0146] In this embodiment, the vitrified inorganic material is described as an inorganic solid electrolyte material, for example. However, the vitrified inorganic material may also be a positive electrode active material.

[0147] Here, as an example of a positive electrode active material, a positive electrode active material that can be used for the positive electrode layer of a lithium ion battery can be cited. Specifically, lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), lithium manganese oxide (LiMn2O4), solid solution oxide (Li2MnO3-LiMO2 (M=Co, Ni, etc.)), lithium-manganese-nickel oxide (LiNi 1 / 3 Mn 1 / 3 Co 1 / 3O2), olivine-type lithium phosphorous oxide (LiFePO4), and the like; CuS, Li-Cu-S compounds, TiS2, FeS, MoS2, V2S5, Li-Mo-S compounds, Li-Ti-S compounds, Li-V-S compounds, Li-Fe-S compounds, and the like; and sulfide-based positive electrode active materials, and the like. Note that, among these, from the viewpoint of having a higher discharge capacity density and more excellent cycle characteristics, sulfide-based positive electrode active materials are preferable, and Li-Mo-S compounds, Li-Ti-S compounds, and Li-V-S compounds are more preferable.

[0148] Further, the inorganic material after vitrification can be a mixed powder in which the above-described positive electrode active material, inorganic solid-state electrolyte material, and conductive aid are combined at an arbitrary ratio. As an example of the conductive aid, carbon black, Ketjen black, and the like can be given.

[0149] In addition, the inorganic material after vitrification can also be a negative electrode active material.

[0150] Here, as an example of the negative electrode active material, a negative electrode active material that can be used for a negative electrode layer of a lithium ion battery can be given. Specifically, metal-based materials mainly including lithium alloys, tin alloys, silicon alloys, gallium alloys, indium alloys, aluminum alloys, and the like, lithium titanium composite oxides (for example, Li4Ti5O 12 ), graphite-based materials, and the like can be given.

[0151] Further, the inorganic material after vitrification can be a mixed powder in which the above-described negative electrode active material, inorganic solid-state electrolyte material, and conductive aid are combined at an arbitrary ratio. As an example of the conductive aid, carbon black, Ketjen black, and the like can be given.

[0152] This application claims priority based on Japanese Patent Application No. 2019-110875, filed on June 14, 2019, and incorporates all of its disclosures herein.

[0153] BRIEF DESCRIPTION OF DRAWINGS

[0154] 10: mill device (example of inorganic material manufacturing device)

[0155] 20: container

[0156] 22: peripheral wall

[0157] 24: top plate

[0158] 24A: through hole (hole)

[0159] 26: bottom plate

[0160] 30: injection cylinder

[0161] 35: conical cylinder

[0162] 40: discharge pipe

[0163] 42: cylindrical portion

[0164] 44: branched portion

[0165] 50: gas feeding mechanism

[0166] 60: wing mechanism

[0167] 62: oscillating wing

[0168] 62A: rotation axis

[0169] 62B: short wide plate

[0170] 62C: long wide plate

[0171] 70: ring and ball type mill mechanism

[0172] 72: pulverizing ball

[0173] 74: upper ring

[0174] 74A: recess

[0175] 76: lower ring

[0176] 76A: recess

[0177] 78: drive mechanism

[0178] 80: pressurizing mechanism

[0179] 90: control section

[0180] 92: timer

[0181] O: shaft

[0182] S10: method for producing inorganic material

[0183] S11: mixing step

[0184] S12: vitrification step

[0185] S13: dispersion step

[0186] S14: determination step

[0187] S15: discharge step

[0188] T P : prescribed time

Claims

1. A crushing device, wherein: include: a container connected to a discharge pipe; a grinding mechanism, located inside the container, for crushing the object; A gas feeding mechanism for feeding gas into the container; as well as a wing mechanism for controlling the discharge amount of the gas discharged from the discharge pipe, A control unit controls the grinding mechanism, the gas feeding mechanism, and the wing mechanism to perform the second step after the first step. The wing mechanism includes a plurality of wings arranged on a circumference, and the discharge amount is controlled by changing the gap between adjacent wings. In the wing mechanism, the discharge amount is controlled by switching between a first state in which adjacent wings contact each other to form a circumferential wall extending over the circumference and a second state in which gaps are formed between adjacent wings. The object is a mixed powder obtained by mixing powders of multiple inorganic compounds. The mill mechanism is a ring and ball mill mechanism, In the first step, the control unit maintains the wing aircraft in the first state and performs the following control: driving the mill mechanism to vitrify at least a portion of the mixed powder by applying shear stress and compressive stress to the mixed powder; feeding gas from the gas feeding mechanism into the interior of the container to disperse the vitrified mixed powder; In the second step, the control unit maintains the wing mechanism in the second state and performs the following control: Gas is fed into the container from the gas feeding mechanism to discharge the inorganic material obtained by vitrifying the mixed powder from the discharge pipe.

2. The pulverizing device according to claim 1, wherein: Each of the plurality of wings has a rotation shaft and a plate whose end is fixed to the rotation shaft. The gap between the adjacent wings is controlled by rotating the rotation shaft.

3. The pulverizing device according to claim 2, wherein: By rotating the rotating shaft in a first direction, the first state can be switched to the second state. By rotating the rotation shaft in a second direction opposite to the first direction, the second state can be switched to the first state.

4. The pulverizing device according to any one of claims 1 to 3, wherein The pulverizing device is configured to perform a plurality of steps of vitrifying at least a portion of the mixed powder and dispersing the vitrified mixed powder in the first step, thereby obtaining a vitrified inorganic material powder from the mixed powder.

5. The pulverizing device according to any one of claims 1 to 3, wherein The vitrified inorganic material is an inorganic solid electrolyte material, a positive electrode active material or a negative electrode active material.

6. The pulverizing device according to claim 5, wherein: The vitrified inorganic material is the inorganic solid electrolyte material, The inorganic solid electrolyte material constitutes the solid electrolyte layer of the all-solid-state lithium-ion battery.

7. The pulverizing device according to claim 5, wherein: The vitrified inorganic material is the inorganic solid electrolyte material, The inorganic solid electrolyte material at least includes a sulfide-based inorganic solid electrolyte material.

8. The pulverizing device according to claim 7, wherein: The sulfide-based inorganic solid electrolyte material contains at least one of Li, P, and S as a constituent element.

9. A method for producing an inorganic material, comprising using the pulverizing device according to any one of claims 1 to 3 to produce the inorganic material. in, include: a vitrification step of applying shear stress and compressive stress to the mixed powder using a ring and ball mill mechanism, thereby vitrifying at least a portion of the mixed powder; and a dispersion step, after the vitrification step, dispersing the vitrified mixed powder; The process consisting of the vitrification process and the dispersion process is performed multiple times to obtain a vitrified inorganic material powder from the mixed powder. The method further comprises: a discharge step of discharging the inorganic material from the discharge pipe after performing the combined steps multiple times; In the discharging step, the wing mechanism is set to the second state, and in the combining step, the wing mechanism is set to the first state.

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