Patent Description:
Recently, as a solid electrolyte material of a lithium battery, a sulfide solid electrolyte material may be used. Patent Document <NUM> describes a method of manufacturing a sulfide solid electrolyte material. In this method, lithium sulfide (Li<NUM>S) powder, diphosphorus pentasulfide (P<NUM>S<NUM>) powder, and red phosphorus (P) powder are mixed with each other in a glove box in an argon atmosphere to obtain a raw material composition. Next, using a planetary ball mill machine, mechanical milling is conducted on the raw material composition to obtain an amorphous ion conductive material. Next, this ion conductive material is heated to obtain a sulfide solid electrolyte material.

[Patent Document <NUM>] <CIT>. <CIT> discloses a process of pulverising coal.

In the manufacturing of the inorganic material such as a sulfide solid electrolyte material, mechanical milling is conducted on plural kinds of inorganic compounds using a crusher such as a planetary ball mill machine. The mechanical milling may be required to reduce contact between the inorganic compound and air.

One example of the objects of the present invention is to reduce contact between an inorganic compound and air during mechanical milling. Another object of the present invention will be clarified from the description of the present specification.

According to one aspect of the present invention,
there is provided an apparatus of manufacturing an inorganic material, the apparatus including:.

According to another aspect of the present invention,
there is provided a method of manufacturing an inorganic material, the method including:.

In the above-described aspects of the present invention, contact between an inorganic compound and air during mechanical milling can be reduced.

Hereinafter, an embodiment of the present invention will be described using the drawings. In all of the drawings, the same components will be represented by the same reference numerals, and the description thereof will not be repeated.

<FIG> is a diagram showing an apparatus <NUM> according to the embodiment. <FIG> is a top view showing a rotating table <NUM> and a plurality of balls <NUM> of a crusher <NUM> shown in <FIG>. <FIG> is a cross-sectional view taken along line A-A' of <FIG>. The apparatus <NUM> manufactures an inorganic material (A) from plural kinds of inorganic compounds (A1). In <FIG>, an upward direction of <FIG> refers to an upward direction with respect to the vertical direction, and a downward direction of <FIG> refers to a downward direction with respect to the vertical direction. For description, <FIG> does not show a presser <NUM>. In <FIG>, a black arrow shows a flow of the plural kinds of inorganic compounds (A1). In <FIG>, a white arrow shows a flow of inert gas.

The summary of the apparatus <NUM> will be described using <FIG>. The apparatus <NUM> includes a blower <NUM>, a crusher <NUM>, a first collector <NUM>, and a system S. The blower <NUM> blows inert gas. The crusher <NUM> repeats vitrifying the plural kinds of inorganic compounds (A1) by mechanical energy and blowing up the plural kinds of vitrified inorganic compounds (A1) by the inert gas blown from the blower <NUM>. At least some of the plural kinds of inorganic compounds (A1) blown up by the inert gas enters into the first collector <NUM>. The first collector <NUM> returns the at least some of the plural kinds of inorganic compounds (A1) to the crusher <NUM>. The system S (for example, a pipe Pa, a buffer tank <NUM>, a pipe Pb, a pipe Pc, and a pipe Pi described below) circulates the inert gas from the blower <NUM> through the crusher <NUM> and the first collector <NUM> to the blower <NUM>.

A structure of the apparatus <NUM> will be described using <FIG>.

The apparatus <NUM> includes the blower <NUM>, the buffer tank <NUM>, the crusher <NUM>, the first collector <NUM>, a first container <NUM>, a second collector <NUM>, a second container <NUM>, a decompressor <NUM>, the pipe Pa, a plurality of pipes Pb, the pipe Pc (second pipe), a pipe Pd, a pipe Pe (first pipe), a pipe Pf (third pipe), a pipe Pg, a pipe Ph (fourth pipe), the pipe Pi, a pipe Pj, a pipe Pk, a pipe Pl, a pipe Pm, a pipe Pn, a pipe Po, a valve Va1, a plurality of valves Vb1, a valve Vc1, a valve Vc2 (second valve), a valve Vc3, a valve Vd1, a valve Ve1 (first valve), a valve Ve2, a valve Vf1 (third valve), a valve Vg1, a valve Vh1, a valve Vh2, a valve Vi1, a valve Vi2, a valve Vj1, a valve Vk1, a valve Vl1, a valve Vm1, a valve Vn1, a valve vo1, a line Le (first line), a line Lh (second line), and an exhaust duct D.

The pipe Pa communicates to a gas outlet <NUM> of the blower <NUM> and a gas inlet <NUM> of the buffer tank <NUM>. The valve Va1 is provided in the pipe Pa.

Each of the plurality of pipes Pb communicates to each of a plurality of gas outlets <NUM> of the buffer tank <NUM> and each of a plurality of gas inlets <NUM> of the crusher <NUM>. Each of the plurality of valves Vb1 are provided in each of the plurality of pipes Pb. For example, when seen from the top of the rotating table <NUM> (the details will be described below) of the crusher <NUM>, the plurality of pipes Pb are disposed around the rotating table <NUM>. Specifically, the plurality of pipes Pb are arranged in rotational symmetry about the center (rotation axis R described below) of the rotating table <NUM>.

The pipe Pc communicates to a material discharge pipe <NUM> of the crusher <NUM> and a suction port <NUM> of the first collector <NUM>. The valve Vc1, the valve Vc2, and the valve Vc3 are provided in the pipe Pc and are arranged in this order from the material discharge pipe <NUM> of the crusher <NUM> to the suction port <NUM> of the first collector <NUM>.

The pipe Pd communicates to a material supply pipe <NUM> of the crusher <NUM> and a material discharge port <NUM> of the first collector <NUM>. The valve Vd1 is provided in the pipe Pd.

The pipe Pe communicates to the first container <NUM> and a material supply port <NUM> of the first collector <NUM>. The valve Ve1 and the valve Ve2 are provided in the pipe Pe and are arranged in this order from the first container <NUM> to the material supply port <NUM> of the first collector <NUM>. The valve Ve1 is detachably attached to the pipe Pe together with the first container <NUM>. In other words, when the valve Ve1 is detached from the pipe Pe, the first container <NUM> and the valve Ve1 can be integrated. Further, the pipe Pe is connected to the line Le between the valve Ve1 and the valve Ve2. The inside of the pipe Pe can be replaced with a vacuum or inert gas through the line Le. That is, the line Le can reduce the internal pressure of the pipe Pe and can introduce inert gas into the pipe Pe.

The pipe Pf communicates to a portion of the pipe Pc positioned between the valve Vc1 and the valve Vc2 (that is, between the crusher <NUM> and the valve Vc2), and a suction port <NUM> of the second collector <NUM>. The valve Vf1 is provided in the pipe Pf.

The pipe Pg communicates to a portion of the pipe Pc positioned between the valve Vc2 and the valve Vc3, and a gas discharge pipe <NUM> of the second collector <NUM>. The valve Vg1 is provided in the pipe Pg.

The pipe Ph communicates to the second container <NUM> and a material discharge port <NUM> of the second collector <NUM>. The valve Vh1 and the valve Vh2 are provided in the pipe Ph and are arranged in this order from the second container <NUM> to the material discharge port <NUM> of the second collector <NUM>. Further, the pipe Ph is connected to the line Lh between the valve Vh1 and the valve Vh2. The inside of the pipe Ph can be replaced with a vacuum or inert gas through the line Lh. That is, the line Lh can reduce the internal pressure of the pipe Ph and can introduce inert gas into the pipe Ph.

The pipe Pi communicates to a gas discharge port <NUM> of the first collector <NUM> and a gas inlet <NUM> of the blower <NUM>. The valve Vi1 and the valve Vi2 are provided in the pipe Pi, and are arranged in this order from the gas discharge port <NUM> of the first collector <NUM> to the gas inlet <NUM> of the blower <NUM>.

The pipe Pj is connected to a portion of the pipe Pi positioned between the gas discharge port <NUM> of the first collector <NUM> and the valve Vi1 and a portion of the pipe Pi positioned between the gas inlet <NUM> of the blower <NUM> and the valve Vi2. The valve Vj1 is provided in the pipe Pj.

The pipe Pk communicates to an adjustment port <NUM> of the buffer tank <NUM> and an exhaust duct D. The valve Vk1 is provided in the pipe Pk.

The pipe Pl communicates to a gas discharge port <NUM> of the crusher <NUM> and the decompressor <NUM>. The valve Vl1 is provided in the pipe Pl.

The pipe Pm communicates to the decompressor <NUM> and the exhaust duct D. The valve Vm1 is provided in the pipe Pm.

The pipe Pn communicates a portion of the pipe Pl positioned between the gas discharge port <NUM> of the crusher <NUM> and the valve Vl1, and the exhaust duct D. The valve Vn1 is provided in the pipe Pn.

The pipe Po is branched from the pipe Pi and communicates to the exhaust duct D. Specifically, the pipe Pi includes an end portion of the pipe Pj positioned between the valve Vi2 and the gas inlet <NUM> of the blower <NUM>. The pipe Po communicates to a portion of the pipe Pi positioned between the above-described portion and the gas inlet <NUM> of the blower <NUM>, and the exhaust duct D. The valve Vo1 is provided in the pipe Po.

The blower <NUM> sucks gas in the pipe Pj through the gas inlet <NUM> of the blower <NUM>. The blower <NUM> discharges, through the gas outlet <NUM> of the blower <NUM>, the gas sucked through the gas inlet <NUM> of the blower <NUM>. Thus, the blower <NUM> sends the gas to the buffer tank <NUM> through the pipe Pa. The rotation speed of a motor of the blower <NUM> is changeable by an inverter <NUM>, and the flow rate of the gas sent from the blower <NUM> is freely changeable depending on the rotation speed of the motor.

The gas sent from the blower <NUM> through the pipe Pa enters into the gas inlet <NUM> of the buffer tank <NUM>. The gas in the buffer tank <NUM> passes through the plurality of gas outlets <NUM> of the buffer tank <NUM> and is sent to the crusher <NUM> through the plurality of pipes Pb. The pressure of the gas in the buffer tank <NUM> is adjusted by the valve Vk1.

The gas sent from the buffer tank <NUM> through the plurality of pipes Pb enters into the plurality of gas inlets <NUM> of the crusher <NUM>. A material sent from the first container <NUM> through the pipe Pe, the first collector <NUM>, and the pipe Pd enters into the material supply pipe <NUM> of the crusher <NUM>. At least some of the material and at least some of the gas in the crusher <NUM> are discharged through the material discharge pipe <NUM> of the crusher <NUM>. The internal pressure of the crusher <NUM> can be reduced by the decompressor <NUM>. The gas in the crusher <NUM> can be discharged to the exhaust duct D through the pipe Pn.

The first collector <NUM> sucks the material and the gas in the pipe Pc through the suction port <NUM> of the first collector <NUM>. The first collector <NUM> discharges the material sucked through the suction port <NUM> of the first collector <NUM> through the material discharge port <NUM> of the first collector <NUM>. Thus, the first collector <NUM> sends the material to the crusher <NUM> through the pipe Pd. The first collector <NUM> discharges the gas sucked through the suction port <NUM> of the first collector <NUM> through the gas discharge port <NUM> of the first collector <NUM>. Thus, the first collector <NUM> sends the gas to the blower <NUM> through the pipe Pi. The first collector <NUM> is, for example, a dust collector.

The second collector <NUM> sucks the material and the gas in the pipe Pc and the pipe Pf through the suction port <NUM> of the second collector <NUM>. The second collector <NUM> discharges the material sucked through the suction port <NUM> of the second collector <NUM> through the material discharge port <NUM> of the second collector <NUM>. Thus, the second collector <NUM> sends the material to the second container <NUM> through the pipe Ph. The second collector <NUM> discharges the gas sucked through the suction port <NUM> of the second collector <NUM> through the gas discharge pipe <NUM> of the second collector <NUM>. The second collector <NUM> is, for example, a cyclone dust collector.

Next, a structure of the crusher <NUM> will be described using <FIG>.

The crusher <NUM> includes the rotating table <NUM>, the plurality of balls <NUM>, and the presser <NUM>. In the example shown in <FIG>, the number of the plurality of balls <NUM> is seven. However, the number of the plurality of balls <NUM> is not limited to the example shown in <FIG>.

The rotating table <NUM> is rotatable about the rotation axis R. The rotation axis R of the rotating table <NUM> passes through the center of the rotating table <NUM> in a height direction (thickness direction) of the rotating table <NUM>. The height direction (thickness direction) of the rotating table <NUM> is along the vertical direction. The plurality of balls <NUM> are arranged around the rotation axis R of the rotating table <NUM>. Specifically, the plurality of balls <NUM> are arranged in rotational symmetry about the rotation axis R. The plurality of balls <NUM> rotate together with the rotation of the rotating table <NUM>. Each of the plurality of balls <NUM> is individually rotatable about rotation axis R1 rotating together with the rotation of the rotating table <NUM>. The rotation axis R1 of each ball <NUM> passes through the center of the ball <NUM> in the height direction (thickness direction) of the ball <NUM>. The height direction (thickness direction) of the ball <NUM> is along the vertical direction. The presser <NUM> presses the plurality of balls <NUM> to the rotating table <NUM> from a side opposite to the rotating table <NUM>.

Next, an example of a method of manufacturing the inorganic material (A) from the plural kinds of inorganic compounds (A1) using the apparatus <NUM> will be described using <FIG>.

The valve Ve1 and the valve Ve2 are closed, and the plural kinds of inorganic compounds (A1) are contained in the first container <NUM>. Specifically, first, the first container <NUM> is detached from the pipe Pe together with the valve Ve1. Next, the plural kinds of inorganic compounds (A1) are contained in the first container <NUM>. The containing of the plural kinds of inorganic compounds (A1) is implemented in an atmosphere (for example, in a glove box) controlled by the inert gas. Next, the first container <NUM> and the valve Ve1 are attached to the pipe Pe with the valve Ve1 being closed. In this case, even if the first container <NUM> and the valve Ve1 are exposed to the atmosphere, the closed valve Ve1 can prevent the plural kinds of inorganic compounds (A1) in the first container <NUM> from being exposed to the atmosphere (air). When the first container <NUM> is attached, the atmosphere in the pipe Pe can be replaced with the inert gas through the line Le connected to the pipe Pe. Thus, when the inorganic compounds (A1) pass through the pipe Pe, the inorganic compounds (A1) can be prevented from being exposed to the atmosphere (air). Next, the valve Ve1, the valve Ve2, and the valve Vd1 are opened, and the plural kinds of inorganic compounds (A1) are sent from the first container <NUM> to the crusher <NUM> through the pipe Pe, the first collector <NUM>, and the pipe Pd. That is, the first container <NUM> contains the plural kinds of inorganic compounds (A1) supplied to the crusher <NUM>.

Further, the valve Ve1, the valve Ve2, the valve Vf1, the valve Vg1, the valve Vh1, the valve Vh2, the valve Vj1, the valve Vl1, the valve Vm1, the valve Vn1, and the valve vo1 are closed, and the valve Va1, the valves Vb1, the valve Vc1, the valve Vc2, the valve Vc3, the valve Vd1, the valve Vi1, and the valve Vi2 are opened, and the inert gas is supplied to a portion of the pipe Pi positioned between the valve Vi1 and the valve Vi2. Next, the blower <NUM> is operated while adjusting the internal pressure of the buffer tank <NUM> using the valve Vk1. Thus, the system S, that is, the system from the blower <NUM> through the pipe Pa, the buffer tank <NUM>, the pipe Pb, the crusher <NUM>, the pipe Pc, the first collector <NUM>, and the pipe Pi to the blower <NUM> circulates the inert gas and is closed from the outside (that is, the system S is not exposed to the atmosphere (air)).

The supply of the inert gas to the portion of the pipe Pi positioned between the valve Vi1 and the valve Vi2 may be conducted before or after supplying the plural kinds of inorganic compounds (A1) from the first container <NUM> to the crusher <NUM> or may be conducted while supplying the plural kinds of inorganic compounds (A1) from the first container <NUM> to the crusher <NUM>. The position where the inert gas is supplied does not need to be the portion of the pipe Pi positioned between the valve Vi1 and the valve Vi2 and may be any portion in the system S. The inert gas may be supplied to a plurality of portions in the system S (including the portion of the pipe Pi positioned between the valve Vi1 and the valve Vi2).

In the present embodiment, the inert gas is nitrogen gas. The nitrogen gas is supplied, for example, from a nitrogen gas container through a nitrogen purifier. In this example, the impurity concentration (for example, the water concentration or the oxygen concentration) in the nitrogen gas can be reduced. For example, the water concentration in the nitrogen gas may be <NUM> ppm or less, preferably <NUM> ppm or less, and more preferably <NUM> ppm or less, and the oxygen concentration in the nitrogen gas may be <NUM> ppm or less, preferably <NUM> ppm or less, and more preferably <NUM> ppm or less. The inert gas may be, however, gas other than nitrogen gas, such as argon gas.

Further, the crusher <NUM> is operated. Specifically, the rotating table <NUM> is rotated about the rotation axis R, each of the balls <NUM> is rotated about the rotation axis R1, and the plurality of balls <NUM> are pressed to the rotating table <NUM> by the presser <NUM>. The operation of the crusher <NUM> may start before or after supplying the plural kinds of inorganic compounds (A1) from the first container <NUM> to the crusher <NUM> or may start while supplying the plural kinds of inorganic compounds (A1) from the first container <NUM> to the crusher <NUM>. The crusher <NUM> repeats vitrifying the plural kinds of inorganic compounds (A1) using mechanical energy and blowing up the plural kinds of vitrified inorganic compounds (A1) by the inert gas blown from the blower <NUM>, as below.

First, as indicated by the black arrow extending from the material supply pipe <NUM> to the rotating table <NUM> in <FIG>, the plural kinds of inorganic compounds (A1) supplied from the first container <NUM> arrive at the center of the rotating table <NUM> or the periphery thereof (the rotation axis R and the periphery thereof) through the material supply pipe <NUM>.

Next, as indicated by two black arrows extending from the periphery of the center (rotation axis R) of the rotating table <NUM> to both sides in <FIG>, The plural kinds of inorganic compounds (A1) move from the center (rotation axis R) of the rotating table <NUM> to the balls <NUM> due to a centrifugal force generated by the rotation of the rotating table <NUM>, and enters into a gap between the rotating table <NUM> and the balls <NUM>. The plural kinds of inorganic compounds (A1) in the gap between the rotating table <NUM> and the balls <NUM> are vitrified by mechanical energy. Specifically, shearing stress and compressive stress are applied to the plural kinds of inorganic compounds (A1) in the gap between the rotating table <NUM> and the balls <NUM> due to the rotation of the balls <NUM> and the press of the balls <NUM> to the rotating table <NUM> by the presser <NUM>. The plural kinds of inorganic compounds (A1) are vitrified by the shearing stress and the compressive stress. That is, mechanical milling is conducted on the plural kinds of inorganic compounds (A1).

As indicated by two white arrows positioned on both sides of the rotating table <NUM>, the plurality of balls <NUM>, and the presser <NUM> in <FIG>, the inert gas flows from the lower side to the upper side of the crusher <NUM> outside of the rotating table <NUM>. This flow is generated by the inert gas sent from the blower <NUM> through the gas inlets <NUM> of the crusher <NUM>. As indicated by two black arrows positioned on both sides of the plurality of balls <NUM> and the presser <NUM> in <FIG>, the plural kinds of vitrified inorganic compounds (A1) are blown up by the inert gas. At this time, the rotation speed of the motor of the blower <NUM> is reduced by the inverter <NUM>. Thus, the flow rate of the inert gas sent from the blower <NUM> to the crusher <NUM> is reduced, and the inorganic compounds (A1) are prevented from exiting from the material discharge pipe <NUM>.

As indicated by two black arrows extending from the outside of the rotating table <NUM> to the center of the rotating table <NUM> on the presser <NUM> in <FIG>, some of the plural kinds of inorganic compounds (A1) blown up by the inert gas moves from the outside of the rotating table <NUM> to the center of the rotating table <NUM> above the presser <NUM>. As in the plural kinds of inorganic compounds (A1) supplied from the material supply pipe <NUM>, the plural kinds of inorganic compounds (A1) arrive at the center of the rotating table <NUM> or the periphery thereof (the rotation axis R and the periphery thereof). Then, mechanical milling is conducted on the plural kinds of inorganic compounds (A1) in the same manner as that described above.

As indicated by two black arrows extending to the upper side of the presser <NUM> above the presser <NUM> in <FIG>, some other of the plural kinds of inorganic compounds (A1) blown up by the inert gas may enter into the material discharge pipe <NUM> without returning to the rotating table <NUM>. For example, the plural kinds of inorganic compounds (A1) having a small particle size are likely to enter into the material discharge pipe <NUM> without returning to the rotating table <NUM>. The plural kinds of inorganic compounds (A1) in the material discharge pipe <NUM> are sent to the first collector <NUM> through the pipe Pc, are sent from the first collector <NUM> to the material supply pipe <NUM> of the crusher <NUM> through the pipe Pd, and return to the rotating table <NUM>. Accordingly, mechanical milling by the crusher <NUM> can be conducted on even the plural kinds of inorganic compounds (A1) in the material discharge pipe <NUM>.

While conducting mechanical milling of the crusher <NUM>, as described above, the system S, that is the system from the blower <NUM> through the pipe Pa, the buffer tank <NUM>, the pipe Pb, the crusher <NUM>, the pipe Pc, the first collector <NUM>, and the pipe Pi to the blower <NUM> circulates the inert gas and is closed from the outside. Accordingly, contact between the plural kinds of inorganic compounds (A1) and air can be reduced.

By conducting mechanical milling on the plural kinds of inorganic compounds (A1) by the crusher <NUM>, the plural kinds of inorganic compounds (A1) are vitrified, and the inorganic material (A) is manufactured from the plural kinds of inorganic compounds (A1).

Next, an example of a method of removing the inorganic material (A) from the apparatus <NUM> will be described.

The valve Vc2 is closed, the valve Vf1 and the valve Vg1 are opened, and the inverter <NUM> connected to the motor of the blower <NUM> is controlled to increase the rotation speed of the motor of the blower <NUM>, and the flow rate of the inert gas sent to the gas inlets <NUM> of the crusher <NUM> increases (at this stage, the valve Vh1 and the valve Vh2 are closed). By increasing the flow rate of the inert gas sent to the gas inlets <NUM> of the crusher <NUM>, the inorganic material (A) blown up by the inert gas in the crusher <NUM> is sent into the material discharge pipe <NUM> without substantially or completely returning to the rotating table <NUM>. The inorganic material (A) sent into the material discharge pipe <NUM> enters into the suction port <NUM> of the second collector <NUM> through the pipe Pc and the pipe Pf. Thus, the inorganic material (A) is collected by the second collector <NUM>. Next, the valve Vh1 and the valve Vh2 are opened. Thus, the inorganic material (A) collected by the second collector <NUM> enters into the second container <NUM> through the pipe Ph. Next, the valve Vh1 and the valve Vh2 are closed. Next, the second container <NUM> is detached from the pipe Ph. In this case, the inside of the pipe Ph can be prevented from being exposed to the atmosphere (air) by the closed valve Vh1 and valve Vh2. When the second container <NUM> is attached to the pipe Ph again, the atmosphere in the pipe Ph can be replaced with the inert gas through the line Lh connected to the pipe Ph. Thus, when the inorganic material (A) passes through the pipe Ph, the inorganic material (A) can be prevented from being exposed to the atmosphere (air).

Next, an example of the operation of the decompressor <NUM> will be described.

The inside of the crusher <NUM> may be exposed to the atmosphere (air), for example, when an internal component (for example, the rotating table <NUM>, the balls <NUM>, or the presser <NUM>) of the crusher <NUM> is cleaned. In this case, the air in the crusher <NUM> can be removed by reducing the internal pressure of the crusher <NUM> using the decompressor <NUM>. For example, the decompressor <NUM> can be operated with the plurality of valves Vb1, the valve Vc1, the valve Vd1, and the valve Vn1 closed, and with the valve Vl1 and the valve Vm1 opened.

By heating the inorganic material (A), an inorganic material (B) having improved crystallinity can be formed. The inorganic material (B) is not particularly limited, and examples thereof include an inorganic solid electrolyte material, a positive electrode active material, a negative electrode active material, and the like.

The inorganic solid electrolyte material is not particularly limited, and examples thereof include a sulfide-based inorganic solid electrolyte material, an oxide-based inorganic solid electrolyte material, and other lithium-based inorganic solid electrolyte materials. Among these, a sulfide-based inorganic solid electrolyte material is preferable. The inorganic solid electrolyte material is not particularly limited, and examples thereof include an inorganic solid electrolyte material used for a solid electrolyte layer forming an all-solid-state lithium ion battery.

Examples of the sulfide-based inorganic solid electrolyte material include a Li<NUM>S-P<NUM>S<NUM> material, a Li<NUM>S-SiS<NUM> material, a Li<NUM>S-GeS<NUM> material, a Li<NUM>S-Al<NUM>S<NUM> material, a Li<NUM>S-SiS<NUM>-Li<NUM>PO<NUM> material, a Li<NUM>S-P<NUM>S<NUM>-GeS<NUM> material, a Li<NUM>S-Li<NUM>O-P<NUM>S<NUM>-SiS<NUM> material, a Li<NUM>S-GeS<NUM>-P<NUM>S<NUM>-SiS<NUM> material, a Li<NUM>S-SnS<NUM>-P<NUM>S<NUM>-SiS<NUM> material, a Li<NUM>S-P<NUM>S<NUM>-Li<NUM>N material, a Li<NUM>S<NUM>+X-P<NUM>S<NUM> material, a Li<NUM>S-P<NUM>S<NUM>-P<NUM>S<NUM> material, and the like. Among these, the Li<NUM>S-P<NUM>S<NUM> material and the Li<NUM>S-P<NUM>S<NUM>-Li<NUM>N material are preferable from the viewpoint that they have excellent lithium ionic conductivity and has stability to the extent that decomposition or the like does not occur in a wide voltage range. Here, for example, the Li<NUM>S-P<NUM>S<NUM> material refers to an inorganic material obtained by a chemical reaction of an inorganic composition including at least Li<NUM>S (lithium sulfide) and P<NUM>S<NUM> by mechanical energy, and the Li<NUM>S-P<NUM>S<NUM>-Li<NUM>N material refers to an inorganic material obtained by a chemical reaction of an inorganic composition including at least Li<NUM>S (lithium sulfide), P<NUM>S<NUM>, and Li<NUM>N by mechanical energy. Here, in the present embodiment, examples of the lithium sulfide include lithium polysulfide.

Examples of the oxide-based inorganic solid electrolyte material include: a NASICON type such as LiTi<NUM>(PO<NUM>)<NUM>, LiZr<NUM>(PO<NUM>)<NUM>, or LiGe<NUM>(PO<NUM>)<NUM>; a perovskite type such as (La<NUM>+xLi<NUM>-3x)TiO<NUM>; a Li<NUM>O-P<NUM>O<NUM> material; a Li<NUM>O-P<NUM>O<NUM>-Li<NUM>N material; and the like.

Examples of the other lithium-based inorganic solid electrolyte material include LiPON, LiNbO<NUM>, LiTaO<NUM>, Li<NUM>PO<NUM>, LiPO<NUM>-xNx (x satisfies <NUM> < x ≤ <NUM>), LiN, LiI, LISICON, and the like. A glass ceramic obtained by precipitating crystal of the inorganic solid electrolytes may also be used as the inorganic solid electrolyte material.

The sulfide-based inorganic solid electrolyte material includes Li, P, and S as constituent elements. From the viewpoint of further improving the lithium ionic conductivity, the electrochemical stability, the stability and the handling properties in water or air, and the like, a molar ratio (Li/P) of the content of Li to the content of P in the solid electrolyte material is preferably <NUM> or higher and <NUM> or lower, more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, and still more preferably <NUM> or higher and <NUM> or lower. A molar ratio (S/P) of the content of S to the content of P is preferably <NUM> or higher and <NUM> or lower, more preferably <NUM> or higher and <NUM> or lower, more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, still more preferably <NUM> or higher and <NUM> or lower, and still more preferably <NUM>. Here, the contents of Li, P, and S in the solid electrolyte material can be obtained, for example, by ICP optical emission spectroscopy or X-ray photoelectron spectroscopy.

Examples of the shape of the sulfide-based inorganic solid electrolyte material include a particle shape. The inorganic solid electrolyte material having a particle shape is not particularly limited, and an average particle size d<NUM> in a weight-based particle size distribution measured using a laser-diffraction scattering method particle size distribution measurement is preferably <NUM> or more and <NUM> or less, more preferably <NUM> or more and <NUM> or less, still more preferably <NUM> or more and <NUM> or less. When the average particle size d<NUM> of the inorganic solid electrolyte material is in the above-described range, the lithium ionic conductivity of the obtained solid electrolyte membrane can be further improved while maintaining excellent handling properties.

The positive electrode active material is not particularly limited, and examples thereof include a positive electrode active material that can be used for a positive electrode layer of a lithium ion battery. Examples of the positive electrode active material include a composite oxide such as a lithium cobalt oxide (LiCoO<NUM>), a lithium nickel oxide (LiNiO<NUM>), a lithium manganese oxide (LiMn<NUM>O<NUM>), a solid solution oxide (Li<NUM>MnO<NUM>-LiMO<NUM> (M = Co, Ni, or the like)), lithium-manganese-nickel oxide (LiNi<NUM>/<NUM>Mn<NUM>/<NUM>Co<NUM>/<NUM>O<NUM>), or an olivine-type lithium phosphorus oxide (LiFePO<NUM>); a sulfide-based positive electrode active material such as CuS, a Li-Cu-S compound, TiS<NUM>, FeS, MoS<NUM>, V<NUM>S<NUM>, a Li-Mo-S compound, a Li-Ti-S compound, a Li-V-S compound, or a Li-Fe-S compound; and the like. Among these, from the viewpoints of higher discharge capacity density and higher cycle characteristics, a sulfide-based positive electrode active material is preferable, and a Li-Mo-S compound, a Li-Ti-S compound, or a Li-V-S compound is more preferable. Here, the Li-Mo-S compound includes Li, Mo, and S as constituent elements and can be typically obtained by a chemical reaction of an inorganic composition including molybdenum sulfide and lithium sulfide as raw materials by mechanical energy. The Li-Ti-S compound includes Li, Ti, and S as constituent elements and can be typically obtained by a chemical reaction of an inorganic composition including titanium sulfide and lithium sulfide as raw materials by mechanical energy. The Li-V-S compound includes Li, V, and S as constituent elements and can be typically obtained by a chemical reaction of an inorganic composition including vanadium sulfide and lithium sulfide as raw materials by mechanical energy.

The negative electrode active material is not particularly limited, and examples thereof include a negative electrode active material that can be used for a negative electrode layer of a lithium ion battery. Examples of the negative electrode active material include: a metal material mainly formed of a lithium alloy, a tin alloy, a silicon alloy, a gallium alloy, an indium alloy, or an aluminum alloy; a lithium titanium composite oxide (for example, Li<NUM>Ti<NUM>O<NUM>), a graphite material, and the like.

Examples of the plural kinds of inorganic compounds (A1) include a material to be the inorganic material (B) by mechanical milling and heating. For example, the plural kinds of inorganic compounds (A1) include Li.

<FIG> is a diagram showing a modification example of <FIG>.

The crusher <NUM> further includes a cover portion <NUM>. The cover portion <NUM> is positioned above the presser <NUM>. As indicated by white arrows extending along the cover portion <NUM> in <FIG>, the cover portion <NUM> directs the flow of the inert gas blowing up the plural kinds of inorganic compounds (A1), to the center of the crusher <NUM> (the rotation axis R of the rotating table <NUM>) and a downward direction of the crusher <NUM>. In this case, as compared to when the cover portion <NUM> is not provided, the amount of the plural kinds of inorganic compounds (A1) blown up by the inert gas to enter into the material discharge pipe <NUM> can be reduced, and the amount of the plural kinds of inorganic compounds (A1) blown up by the inert gas to return to the rotating table <NUM> can be increased. Accordingly, as compared to when the cover portion <NUM> is not provided, the efficiency of mechanical milling of the crusher <NUM> can be improved.

Hereinafter, the embodiment of the present invention has been described with reference to the drawings. However, the embodiment is merely an example of the present invention, and various configurations other than the above-described configurations may also be adopted.

Claim 1:
An apparatus of manufacturing an inorganic material, the apparatus comprising:
a blower blowing inert gas;
a crusher repeating vitrifying plural kinds of inorganic compounds to be the inorganic material by mechanical energy and blowing up the plural kinds of vitrified inorganic compounds by the inert gas blown from the blower;
a first collector into which at least some of the plural kinds of inorganic compounds blown up by the inert gas enters, the first collector returning the at least some of the plural kinds of inorganic compounds to the crusher; and
a system circulating the inert gas from the blower through the crusher and the first collector to the blower,
wherein the system is closed from the outside.