JP7448134B2 - Mixing system and material feeding equipment - Google Patents

Description

The present invention relates to a mixing system for mixing a plurality of materials and a material supply device for supplying the materials.

BACKGROUND ART Mixers that mix a plurality of materials, such as a liquid and a powder, can disperse or dissolve the powder added to the liquid, and are used in various fields.

In particular, the fields of application of secondary batteries with high energy density range from power supplies for mobile devices such as smartphones and tablet terminals, to electric vehicles (hybrid vehicles (HEVs), plug-in hybrid vehicles (PHEVs), electric vehicles, etc.) in recent years. (EV)) and power storage. In particular, automobile manufacturers are actively developing and commercializing electric vehicles and the like in order to comply with environmental regulations aimed at reducing automobile exhaust gas and carbon dioxide gas worldwide. The annual production of automotive batteries in 2018 is estimated to be approximately 60 GWh, and is expected to reach approximately 200 GWh by around 2025 (approximately four times the amount for current use in mobile devices).

In fields such as power storage, large power storage systems are required because the amount of power generated fluctuates depending on the environment. Recently, the cost of power generation from renewable energies such as wind and solar power has been reduced to less than half that of coal-fired power generation, and in 2016 they accounted for one-fifth of the world's power generation share. In view of future widespread use, battery production will be required to be more than five times the current level.

In this way, power storage devices such as secondary batteries and capacitors are indispensable for energy conservation, introduction of new energy, clean automobiles, etc., and are positioned as important key devices from the perspective of economic growth.

Conventionally, secondary batteries and capacitors have used electrolytes containing water as a solvent (aqueous electrolytes), such as in nickel-cadmium batteries, nickel-metal hydride batteries, and aluminum capacitors. To achieve this goal, the amount of power storage devices (for example, lithium ion batteries, lithium ion capacitors, etc.) that use non-aqueous electrolytes and have high operating voltages is being used.

A secondary battery or capacitor using a non-aqueous electrolyte is composed of a positive electrode, a negative electrode, a separator, a non-aqueous electrolyte or a non-aqueous electrolyte, and a battery case (storage case).

For example, the electrodes (positive or negative electrodes) used in commercially available lithium-ion batteries are made by slurrying the electrode active material, conductive agent, binder, etc. with a solvent such as N-methylpyrrolidone (NMP), and then coating it on a current collector. After drying, press pressure is adjusted. Generally, electrode active materials are commercially available as powders, conductive aids as powders or dispersions, and binders as powders, emulsions, solutions, etc.

Note that the electrode active material is a material that is directly involved in the transfer of electrons when the battery is charged and discharged. A conductive aid is a material used to increase the conductivity of an electrode active material and reduce electrode resistance. A binder is a material used to bind a powdered active material to a current collector or the like.

As shown in Non-Patent Document 1, it is known that the input/output characteristics and charge/discharge cycle characteristics of secondary batteries and capacitors vary greatly depending on the mixing method of electrode (positive electrode or negative electrode) slurry.

For example, Patent Documents 1 to 4 and Non-Patent Documents 2 to 5 propose mixing devices for uniformly mixing liquid and powder. In this way, it can be seen that powder technology is an important key technology for batteries and capacitors that influences the performance of power storage devices.

Generally, the electric capacity and energy density of a power storage device are determined by the active material provided in the electrode (positive electrode or negative electrode). On the other hand, although the electrolyte is an essential member for the configuration of an electricity storage device, it does not directly and significantly affect the electrical capacity and energy density of the electricity storage device. However, since it is the material that determines the input/output characteristics, cycle characteristics, storage characteristics, etc. of the power storage device, it is important to use a high-quality electrolyte to guarantee the performance of the power storage device with little variation.

An electrolyte is a material that has no electronic conductivity (an insulator), has ionic conductivity, and contains electrodes and reactive species (atoms, molecules, and ions). Examples include electrolytes, polymer electrolytes, gel electrolytes, molten salts, solid electrolytes, and the like.

An electrolytic solution is an electrolyte (supporting salt) dissolved in a solvent. In electricity storage devices that exhibit high operating voltages, such as lithium ion batteries, sodium ion batteries, electric double layer capacitors, and lithium ion capacitors, the use of water as a solvent for the electrolyte narrows the potential window, so operating voltages exceeding 2V cannot be used. However, it is difficult to use it for practical power storage devices.

Therefore, in commercially available power storage devices, an organic or inorganic electrolyte is dissolved in a polar organic solvent to dissociate alkali metal ions and anions, and the resulting liquid is used. The advantage of using a liquid is that the interfacial resistance with the electrode is reduced.

However, the solvent used in the electrolytic solution has a low boiling point, and the electrolyte used in the electrolytic solution is easily decomposed at high temperatures, and many materials are highly reactive with moisture. For example, when lithium hexafluorophosphate (LiPF ₆ ), which is an electrolyte in a typical electrolytic solution, reacts with moisture, it undergoes hydrolysis and generates hydrofluoric acid (HF). According to Non-Patent Document 6, it is suggested that this HF causes deterioration of the power storage device.

A polymer electrolyte (polymer solid electrolyte) is composed of a polar polymer and an electrolyte. The electrolyte can be dissolved in a polymer having a polar functional group in its molecule to form a complex, which is used as an ion conductor.

A gel electrolyte is one in which a polymer electrolyte and an electrolytic solution coexist, or a gelling agent and an electrolytic solution coexist. For example, a gel electrolyte made by dissolving a low-polymer fluororesin in an electrolytic solution to form a gel is used in commercially available lithium ion batteries.

Molten salt is a salt consisting of cations and anions that is in a molten state. In a broad sense, in addition to molten salts that are heated and brought into a molten state, ionic liquids are also positioned in this category. An ionic liquid is a salt that is in a liquid state at 150° C. or lower without containing a solvent, has no boiling point, is flame retardant, and is also called a room temperature molten salt or a room temperature molten salt. Cations can be broadly classified into pyridine-based, alicyclic amine-based, and aliphatic amine-based cations, and ionic liquids using imidazolium and pyridinium are famous.

Solid electrolytes can be broadly classified into the above-mentioned polymer electrolytes and inorganic solid electrolytes. In solid electrolytes, counter anions do not move like in electrolytes, so concentration polarization does not occur, and the transport number of the ionic species responsible for electrical conduction (for example, lithium ions in lithium ion batteries and sodium ions in sodium ion batteries) It becomes almost 1. By selecting an electrolyte with an appropriate potential window, side reactions such as active material dissolution reactions, gas generation due to electrolysis, and precipitation of electrolyte decomposition products can be suppressed, dramatically improving battery stability. It is known that

In addition, unlike conventional lithium-ion batteries that use electrolytes, organic solvents are not used, so there is no possibility of gas or liquid ignition or leakage, and it is expected that the battery will be highly safe. There is. However, since the solid electrolyte is a powdery material with no fluidity, it is difficult to directly apply conventional battery production methods using liquid electrolytes.

Through vigorous research and development to date, solid electrolytes exhibiting high ionic conductivity, such as sulfide-based, oxide-based, hydride-based, and nitride-based solid electrolytes, have been developed. Most of them are amorphous (glass) or crystalline, consisting of alkali metal salts and inorganic derivatives.

Japanese Patent Application Publication No. 2015-35344 Japanese Patent Application Publication No. 2011-233380 JP2016-87560A JP 2019-5696 Publication

Takashi Mukai et al.: Industrial Materials, 63(12), pp. 18-23(2015) Keiichi Asami: Industrial Materials, 66(10), pp. 77-81(2018) Ippei Muneoka: Collection of lecture abstracts from the 54th Battery Symposium, p. 191(2013) Tsumi Ohata: Industrial Materials, 63(12), pp. 49-52(2015) Maiko Kawakubo: Industrial Materials, 66(10), pp. 72-76(2018) Masayuki Morita: Functional Chemistry of Batteries and Ions Series Vol. 3, Chapter 1 Section 5, pp. 116-144, NTS (2003)

Many electrolytes have materials that are highly reactive with water. In particular, a sulfur-based solid electrolyte containing sulfur as a main component easily reacts with water, significantly lowering the ionic conductivity of the solid electrolyte, and further generating hydrogen sulfide gas (H ₂ S) during the reaction.

Hydrogen sulfide gas is a colorless, flammable gas with a rotten egg odor. To the human body, it is a toxic gas that irritates the eyes, skin, and mucous membranes. When the hydrogen sulfide concentration in the air is 1 ppm or more, a faint odor is observed, when it is 3 ppm or more, the odor is noticeable, and when it is 5 ppm or more, an extremely unpleasant odor is felt. If the concentration exceeds 10 ppm, there is a risk of hydrogen sulfide poisoning. The higher the concentration of hydrogen sulfide gas and the longer the exposure time, the more dangerous it becomes to life.

In this application, an electricity storage device includes a secondary battery or a capacitor, and this electricity storage device includes a secondary battery or a capacitor that is constructed by using an electrolyte that is highly reactive with water, a positive electrode, and a negative electrode. It includes a capacitor. A battery using a solid state electrolyte such as a polymer electrolyte or an inorganic solid electrolyte is called an all-solid battery.

Furthermore, in a method for manufacturing a power storage device using a liquid electrolyte, it is common to add an electrolytic solution to a structure with a separator interposed between a positive electrode and a negative electrode, and then seal the structure. However, for all-solid-state batteries, it is difficult to apply conventional battery production methods using liquid electrolytes as they are.

For materials in which the electrolyte is in a solid state, it is important to increase the ionic conductivity between the solid electrolyte and the solid particles of the active material while ensuring the electronic conductivity of the electrode. As described above, many of the electrolytes used in non-aqueous electrolyte power storage devices are materials that are highly reactive with water, and there is a need for a method for producing electrolytes that does not come into contact with water.

Many of the electrode active materials used in non-aqueous electrolyte power storage devices deteriorate when they come into contact with water. Examples of electrode active materials that easily deteriorate upon contact with water include lithium nickelate (LiNiO ₂ ), lithium-excess transition metal oxides (solid solution systems), sulfur-based materials, hard carbon, alkali metals, and activated carbon. It will be done.

Furthermore, although this applies to all electrode active materials, materials with adsorbed water have difficulty in stabilizing their performance as non-aqueous electrolyte power storage devices, and gas is generated inside the power storage device, causing cell swelling. wake up As a countermeasure against this problem, it has been considered preferable to prevent the members used in non-aqueous electrolyte power storage devices from coming into contact with moisture as much as possible, and to perform work in a dry environment.

Lithium ion batteries, which are typical non-aqueous electrolyte power storage devices, are manufactured in a dry environment with a dew point temperature of -60°C or higher and -40°C or lower (moisture content of 10 ppm or lower). Dry room equipment used in the lithium ion battery manufacturing process uses a dehumidifier to lower the humidity in the air and supply dry air with a controlled dew point temperature into the manufacturing area. Specifically, dry air is created by passing air through a dehumidifying agent such as silica gel, zeolite, or alkali metal chloride, and this is supplied into the manufacturing area to create a dry environment. Examples of equipment that create a dry environment include dry rooms, dry booths, and glove boxes.

Dry rooms and dry booths are designed so that workers can enter the work area (indoors) and work, and the dry air flow rate and dew point temperature are set depending on the number of workers entering the room. These dry environments have the advantage of allowing workers to work directly in a dry environment, allowing them to perform precise work, but the moisture generated by the workers can damage battery materials (electrolytes, electrode materials, etc.). ) has the disadvantage of having a high probability of coming into contact with In the manufacturing process of electrolytes and electrodes, if moisture is present in the air around the raw material supply section, the quality of the materials and components obtained will deteriorate because the moisture will be involved in the manufacturing process.

One possible way to prevent moisture absorption from raw materials is to install the entire device in a dry environment, but dehumidifying a large room for a long time not only requires significant running costs, but also requires large-scale equipment to create a dry environment. Become something.

On the other hand, a glove box is an airtight container that is designed so that only hands can enter through gloves, allowing work to be carried out while being isolated from the outside air. . For this reason, running costs can be lowered compared to a dry room or dry booth, but the mixing device must be installed in a glove box, which significantly reduces the maintainability of the device.

The present invention has been made in view of the above-mentioned problems, and its main purpose is to provide a mixing system that suppresses deterioration in the quality of materials that would otherwise be deactivated by moisture in the atmosphere.

In order to achieve the above object, a mixing system according to one aspect of the present invention is a mixing system that mixes a plurality of materials, and includes a mixing mechanism that mixes the plurality of materials, and a powder or liquid injected into the mixing mechanism. a material supply device that supplies a certain first material; the material supply device includes a hopper that includes a material adjustment section that adjusts the material; and a spout section that supplies the first material to the mixing mechanism; a dry gas supply unit that supplies dry gas into the hopper, the material supply device and the mixing mechanism are connected in a state isolated from the outside air, and the dry gas supplied from the dry gas supply unit The dry gas environment has a dew point temperature of -100°C or more and -20°C or less, and an internal pressure (absolute pressure) of 0.01 MPa or more and 10 MPa or less.

According to this configuration, the hopper equipped with the dry gas supply unit and the mixing device are connected in a state isolated from the outside air, so materials such as liquids and powders are mixed without coming into contact with moisture in the outside air. It is possible to do so. Furthermore, since the entire device is not installed in a dry gas environment, the effort and cost for maintenance and management can be reduced.

The hopper has a material adjustment part and a spout part. The material adjustment part is a space for adjusting and storing materials such as liquids and powders, and the spout part is a space for adjusting and storing materials such as liquids and powders. This is for introducing and flowing materials such as powder and powder from the material adjustment section to the mixing mechanism.

The dry gas supply section is not particularly limited as long as it is a mechanism for supplying dry gas into the hopper. For example, dry gas may be supplied via a gas pipe between a cylinder in which dry gas is stored, or between a dry gas generator and a hopper. The dry gas is not particularly limited as long as it is a gas with a dew point temperature of -20°C or lower. Examples include dry air, dry nitrogen gas, dry rare gas, and hydrogen gas.

Further, in this mixing system, the hopper includes a partition between the material adjustment section and the spout, the material adjustment section and the spout are partitioned by the partition, and the partition The portion has an opening through which the first material can pass. According to this configuration, the material adjusted in the material adjustment section can be smoothly moved to the spout section.

Further, in this mixing system, the hopper has a lid that closes the opening, or an opening/closing mechanism that can open and close the opening. Here, the opening/closing mechanism is, for example, a shutter or the like, and may be any mechanism that enables opening and closing of the opening. According to this configuration, during work in the material adjustment section, the opening is blocked by an opening/closing mechanism or the like, thereby preventing the material from flowing into the spout section. Furthermore, after the work is completed, the material can be easily moved to the spout by opening the opening/closing mechanism to expose the opening.

Further, in this mixing system, it is preferable that the material supply device further includes a drying mechanism that dries the first material before the first material passes through the spout of the hopper. According to this configuration, even if the material contains volatile components such as water or an organic solvent, the volatile components can be removed from the material before it passes through the spout of the hopper.

Further, in this mixing system, the drying mechanism exposes the first material to a dry gas environment to remove volatile components in the material, and the material supply device exhausts the removed volatile components to the outside air. It is preferable to further include a discharge mechanism for. By exposing the material to a dry gas environment, volatile components can be efficiently removed from powder materials and the like. Further, by providing a discharge mechanism, the removed volatile components can be exhausted to the outside air.

Further, in this mixing system, it is preferable that the drying mechanism imparts fluidity to the first material and removes volatile components contained in the first material. According to this configuration, since the powder and liquid flow, volatile components contained in the powder can be removed more efficiently.

Further, in this mixing system, it is preferable that the drying mechanism heats the first material to remove volatile components contained in the first material. According to this configuration, since the temperature of the volatile components increases by heating the material such as powder or liquid, the volatile components contained in the material can be removed more efficiently.

Further, in this mixing system, it is preferable that the material supply device further includes a static electricity removing device within the hopper, the dry gas supply section, or between them. According to this configuration, it is possible to suppress powder bridging (a phenomenon in which powder does not move within the apparatus), and material adjustment can be easily performed. The same applies when the liquid material contains solid matter.

Moreover, in this mixing system, the material supply device further includes a transport mechanism, and the transport mechanism moves the material to the mixing mechanism. According to this configuration, bridging of powder can be suppressed.

Further, in this mixing system, the material supply device further includes a glove, and the hopper is a closed container in which work can be performed inside the hopper directly or indirectly via the glove. According to this configuration, materials can be weighed and adjusted like a glove box.

Further, in this mixing system, the material adjustment section has a front chamber, a first opening/closing mechanism that can be opened and closed is interposed between the material adjustment section and the front chamber, and an interior of the material adjustment section and the front chamber is interposed between the material adjustment section and the front chamber. The space communicates through the first opening/closing mechanism, the inner space of the front chamber communicates with the atmosphere through a second opening/closing mechanism, and the front chamber includes a vacuum pump and a dry gas supply unit for gas replacement. connected, and the front chamber has a smaller volume than the material conditioning section.

Here, the material adjustment section having a front chamber includes a configuration in which the front chamber is directly provided in the material adjustment section, and a configuration in which the front chamber is connected to the material adjustment section. According to this configuration, when materials, work tools, etc. are taken in and out of the material adjustment section from the outside, by performing vacuuming and dry gas replacement in the front chamber, material adjustment can be performed without replacing the entire material adjustment section with gas. It can be taken in and out of the unit. Further, from the viewpoint of reducing the work time required for gas replacement and reducing the amount of dry gas used, it is preferable that the volume of the front chamber is smaller than the volume of the material adjustment section.

Further, this mixing system further includes an outlet for discharging the mixed material mixed and discharged by the mixing mechanism, and the outlet is isolated from the outside air. According to this configuration, the mixed material discharged from the mixing mechanism does not come into contact with moisture in the outside air.

Moreover, this mixing system further includes a circulation flow path that circulates the mixed material, which has been mixed and discharged by the mixing mechanism, to the dispersion mixing pump. According to this configuration, the amount of undispersed material present can be reduced.

Further, in this mixing system, at least a portion of the surface of the circulation flow path that contacts the mixed material is coated with a water-repellent material. According to this configuration, the yield of the mixed material discharged from the mixing mechanism is increased.

Further, this mixing system further includes a carbon dioxide gas supply mechanism including a flow path for supplying carbon dioxide gas to the mixing mechanism, and carbon dioxide gas is dispersed in the mixed material discharged from a plurality of materials mixed by the mixing mechanism. or dissolved. According to this configuration, it becomes possible to cause the material to react with carbonic acid.

Further, in this mixing system, the plurality of materials include the first material that is a powder and the second material that is a liquid, and the mixing mechanism causes cavitation in the liquid. A dispersion mixing pump that performs dispersion, dissolution, and mixing of the powder is provided, and the dispersion mixing pump includes a rotor having rotary blades and a stator concentrically forming a constriction flow path inside a cylindrical casing. By rotationally driving the rotor, the liquid and the powder are drawn into the casing, passed through a throttle channel formed in the stator, and then stirred by the rotary blades. .

According to this configuration, it becomes difficult to crush the powder by the mixing mechanism, but uniform dispersion becomes possible. Furthermore, when the internal pressure inside the hopper becomes low, cavitation tends to occur in the liquid. Conversely, if the internal pressure inside the hopper is increased, cavitation becomes less likely to occur. In this way, by adjusting the internal pressure within the hopper, it is possible to adjust the amount of cavitation generated. The internal pressure (absolute pressure) in the hopper is preferably 0.01 MPa or more and 10 MPa or less.

Note that there are two types of pressure: absolute pressure and gauge pressure. Absolute pressure is the pressure measured with a complete vacuum at 0 MPa. Gauge pressure is pressure measured with atmospheric pressure as pressure 0 MPa. Although it is difficult to convert absolute pressure and gauge pressure with high accuracy, it can be converted to absolute pressure by adding standard atmospheric pressure (0.1013 MPa) to gauge pressure. The conversion error in this case is about ±0.003 MPa.

Further, this mixing system is provided with a butterfly valve downstream of the spout of the hopper. According to this configuration, pressure loss when the valve is opened can be reduced.

Further, this mixing system is a mixing system used in a manufacturing process of a non-aqueous electrolyte power storage device, and the first material is a powder forming an electrolyte of the non-aqueous electrolyte power storage device. By using an electrolyte as a material, it is possible to manufacture an electrolyte or an electrolyte solution for a non-aqueous electrolyte power storage device.

Further, this mixing system is a mixing system used in a manufacturing process of a non-aqueous electrolyte power storage device, and the first material is a powder forming an active material of the non-aqueous electrolyte power storage device. By using an active material as a material, it is possible to manufacture an electrode for a non-aqueous electrolyte electricity storage device.

Block diagram illustrating the mixing system Schematic diagram of the hopper Diagram showing a modification of the material supply device in which the front chamber is connected to the hopper Diagram showing an overview of slurry manufacturing equipment Schematic diagram of a distribution system equipped with a centrifugal suction pump mechanism Vertical cross-sectional view showing the main parts of the powder supply device Cross-sectional view taken along the V-V direction in Figure 4 Vertical side view of centrifugal suction pump mechanism Cross-sectional view taken in the VII-VII direction of FIG. 6 Exploded perspective view showing the assembly configuration of the front wall of the main body casing, stator, partition plate, and rotor Schematic diagram of partition board

Hereinafter, one embodiment of the present invention will be described based on the drawings, but the present invention is not limited to the following embodiment. First, a mixing system will be explained focusing on the material supply device of this embodiment, and then an example in which the mixing system of this embodiment is applied to a slurry manufacturing device will be explained.

<1. Mixing system>
FIG. 1A is a block diagram schematically showing a mixing system according to this embodiment. FIG. 1B is a diagram schematically showing a hopper. As shown in FIG. 1A, a mixing system 100 according to this embodiment includes a material supply device 110 and a mixing device 120. The material supply device 110 has a hopper 111, and the hopper 111 and a mixing mechanism 121 constituting the mixing device 120 are connected via a butterfly valve 130 in a state where they are isolated from the outside air.

As shown in FIG. 1B, the inside of the hopper 111 of the material supply device 110 is divided into a material adjustment section 111A and a spout section 111B. The material adjustment section 111A is a space for adjusting or storing materials such as liquids and powders. The spout portion 111B is for supplying material to the mixing mechanism. Note that this configuration is an example of the present embodiment, and the material adjustment section 111A and the spout section 111B may be configured separately and connected to each other while being isolated from the outside air.

Further, in the hopper 111 of this embodiment, a partition plate 111C is disposed between the material adjustment section 111A and the spout section 111B. The partition plate 111C includes an opening 111D through which the material can pass, and a shutter 111E that allows the opening 111D to be opened and closed. The shutter 111E prevents the material from flowing into the spout by blocking the opening during work in the material adjusting section 111A.

After the work, the shutter 111E is opened to expose the opening, and the material is poured into the spout 111B. Note that the shutter 111E that closes the opening is an example of this embodiment, and the shutter 111E only needs to be able to open and close the opening, and may be a lid that closes the opening. Further, the opening and closing of the lid may be configured automatically, or the opening may be manually closed.

Further, the hopper 111 of this embodiment is provided with a globe 111F. Thereby, the operator can insert his/her hand into the glove 111F and work inside the hopper 111 while being shielded from the outside air via the glove 111F.

Further, the hopper 111 of this embodiment is sealed, and a dry gas supply section 112 for supplying dry gas inside is connected via piping and a valve. The dry gas supply unit 112 also includes a cylinder 112a that stores dry gas and a static electricity remover 112b. Note that the static electricity removing device is not limited to being provided in the dry gas supply section 112, but may be provided in the hopper 111, or may be provided between the hopper 111 and the dry gas supply section 112.

Furthermore, a carbon dioxide gas supply section 113 is connected to the hopper 111 via piping and a valve. Note that the carbon dioxide gas supply unit 113 of this embodiment is configured so that carbon dioxide gas is supplied to the mixing mechanism via the hopper 111, but the carbon dioxide gas supply unit 113 is connected to the mixing mechanism 121 via piping and a valve. It can also be configured to be directly connected to. Additionally, a vacuum pump 114 is connected to the hopper 111 via piping and a valve, and a pressure gauge 115 is also connected.

Further, a dehumidifier 116 is connected to the hopper 111, which feeds air from which moisture has been removed into the hopper 111, and at the same time discharges existing air within the hopper 111 to the outside. This facilitates drying of the material within the hopper 111.

Note that the dehumidifier 116 is an example of a drying mechanism, and the drying mechanism is not limited to a dehumidifier. The drying mechanism of this embodiment may have a configuration in which a heater is provided in the hopper 111 instead of or in addition to the dehumidifier to heat and dry the material. Alternatively, a structure may be adopted in which a mechanism for supplying gas for stirring the material is provided in the hopper and the material is dried by stirring the gas.

Further, the drying mechanism may be a mechanism in which a screw is provided in the hopper 111 to stir the material, or a structure in which the inside of the hopper 111 is configured to be able to vibrate to vibrate the material. Further, a plurality of these drying mechanisms described above may be provided.

According to the material supply device of this embodiment described above, materials such as liquids and powders can be worked without coming into contact with moisture in the outside air, and can be supplied to the mixer without coming into contact with moisture in the outside air. It is. Furthermore, since the entire device can be operated without being installed in a dry gas environment, maintenance and management efforts and costs can be reduced.

The mixing device 120 also includes a mixing mechanism 121 connected to the hopper 111 via a butterfly valve 130, a tank 122 in which a mixed material obtained by mixing a plurality of materials is temporarily stored, and the mixing mechanism 121 and the tank 122. It includes a circulation flow path 123 and a circulation pump 124. Further, the mixing mechanism 121 is provided with a material supply section (not shown), which supplies materials to the mixing mechanism 121 . The material supplied from this material supply section and the material supplied from the material supply device 110 are mixed by a mixing mechanism 121. Further, the inner wall surface of the circulation channel 123 is coated with a water-repellent material. Note that the detailed structure of the mixing device 120 will be described later.

Further, the material supply device of this embodiment may have a configuration in which a front chamber 117 is further connected to the material adjustment section 111A, as shown in FIG. 1C. In this case, the material adjustment section 111A has an opening/closing mechanism 118 that can open and close the interior space of the front chamber 117, and the material adjustment section 111A and the interior space of the front chamber 117 communicate with each other via the opening/closing mechanism 118.

In addition, the front chamber 117 has an opening and closing mechanism that can be opened and closed between the outside (atmosphere) and the inside of the front chamber 117, in addition to the opening and closing mechanism 118 that can be opened and closed between the interior space of the material adjustment section 111A. 119. By further connecting the vacuum pump 114 and the dry gas supply section 112 to the front chamber 117, it becomes possible to replace the front chamber 117 with gas.

As a result, when materials, work tools, etc. are taken in and out of the material adjustment section 111A from the outside (in the atmosphere), the entire material adjustment section 111A can be replaced with gas by evacuation and dry gas replacement in the front chamber 117. It can be taken in and out of the material adjustment section 111A.

Further, by providing a slide tray inside the front chamber 117, materials, work tools, etc. can be easily taken in and out. Note that the front chamber 117 may be connected directly above, or a plurality of front chambers may be connected to the material adjustment section 111A. Note that, from the viewpoint of shortening the work time required for gas replacement and reducing the amount of dry gas used, it is preferable that the volume of the front chamber 117 is smaller than the volume of the material adjustment section 111A.

<2. Slurry manufacturing equipment>
Next, an example will be described in which a mixing system including the material supply device of the present invention is applied to a slurry manufacturing device that manufactures slurry. The following is an example of a slurry manufacturing apparatus that mixes a first material that is a powder and a second material that is a liquid.

As shown in FIG. 2, the slurry manufacturing apparatus 200 according to the present embodiment includes a material supply device X that supplies a first material that is a powder, and a mixing device Y that mixes the first material and a second material that is a liquid. The main components are:

The material feeding device X includes a hopper 31 as a main component. The inside of the hopper 31 is sealed, and a dry gas supply section 311, a carbon dioxide supply section 312, and a vacuum pump 313 are connected to the hopper 31 via piping and valves. Further, the hopper 31 is connected to a feeder hopper 210 into which material is fed and a feeder 220 having an air vent 211. Further, the hopper 31 has a material adjusting section 31A for adjusting the material and a spout section 31B for introducing the material into the mixing device Y, and these are partitioned by a partition plate having an opening. The containing space is covered with a dry box 230.

The mixing device Y mainly includes a mixing mechanism section 60, which is a mixing mechanism for mixing materials, a recirculation mechanism section 70, a suction pump mechanism section 80, a cooling device 250, a tank 260, and a pressure relief section 270. Prepare as a configuration. Further, the mixing device Y is covered by a dry box 240.

In the slurry manufacturing apparatus 200, slurry F is manufactured in the following manner. Powder P supplied from material supply device X and liquid R (or slurry F) supplied from tank 260 by pump 261 are mixed by mixing mechanism 60 and supplied to suction pump mechanism section 80 .

In the suction pump mechanism section 80, the powder P and the liquid R are dispersed and mixed and sent to the recirculation mechanism section 70. The recirculation mechanism section 70 circulates and supplies liquid R (hereinafter referred to as undissolved slurry Fr) containing powder P that is not completely dissolved to the suction pump mechanism section 80 and sends out the slurry F to the tank 260. Slurry F inside tank 260 is stirred by tank stirring motor M4.

The dry boxes 230 and 240 have an internal space separated from an external space by a panel made of synthetic resin, for example, in order to maintain the atmosphere in a predetermined state only in a limited number of necessary areas. Further, the dry boxes 230 and 240 may be made of various materials having heat insulating properties, metal, etc., as long as they can prevent the powder P from coming into contact with moisture.

Note that the dry boxes 230 and 240 are not essential components, and are used to more reliably prevent the powder P from coming into contact with the outside air. The reason for this is that when the hopper 31 is configured to be sealed, the hopper 31 and the mixing device Y are connected to each other in a manner that is insulated from the outside air, which prevents the powder P from coming into contact with the outside air. .

Further, a dehumidifying unit 233 is attached to the dry box 230, and a dehumidifying unit (not shown) is also attached to the dry box 240. In the present embodiment, the dew point temperature of the inner spaces of the dry boxes 230 and 240 is maintained at −40° C. or lower, and the dew point temperature inside the hopper 31 is maintained at −70° C. or lower. Note that these dew point temperatures are just examples, and are not limited thereto.

As described above, the material supply device X includes the feeder hopper 210, the feeder 220, and the hopper 31. The feeder hopper 210 is a hopper that temporarily stores the powder P that is dry-transported from upstream. The feeder hopper 210 has an air vent 211 connected to a dry box 230 for powder.

The air vent 211 discharges dry air inside the feeder hopper 210 to the powder dry box 230 when the internal pressure of the feeder hopper 210 increases with the introduction of the powder P from upstream. Note that it is preferable that a check valve is provided in the air vent 211 so that the feeder hopper 210 is closed when no pressure is applied to the feeder hopper 210 so that the powder P is not affected by moisture.

Further, the feeder 220 feeds the powder P stored in the feeder hopper 210 into the material adjustment section 31b of the hopper 31 while weighing it. The feeder 220 is, for example, a screw feeder. The spout 31b of the hopper 31 is an inverted cone-shaped member whose diameter decreases from the top to the bottom, and discharges the charged powder P from the bottom opening 31c, and the mixing mechanism 60 supply to

Further, the slurry manufacturing apparatus 200 includes a control section C, which is composed of an arithmetic processing unit including a CPU, a storage section, etc., and controls the overall operation of the slurry manufacturing apparatus 200.

In this embodiment, as shown in FIG. 2, the feeder hopper 210 and feeder 220 of the powder supply device X, and the dry box 230 are stored on a pedestal 280 and arranged above the mixing device Y. There is. Further, the material adjustment section 31a of the hopper 31 is arranged above the pedestal 280. The lower opening 31c of the hopper 31 is arranged below the pedestal 280.

In the slurry manufacturing apparatus 200, it is possible to manufacture slurry F using various types of powder P and liquid R. In particular, the slurry manufacturing apparatus 200 can be suitably used for manufacturing a slurry for manufacturing a positive electrode, a negative electrode, or a solid electrolyte of an all-solid-state battery, that is, a positive electrode active material layer slurry, a negative electrode active material slurry, or a solid electrolyte slurry.

A positive electrode active material slurry is manufactured by dispersing a positive electrode active material, a conductive additive, a binder, etc. in a solvent. A negative electrode active material slurry is manufactured by dispersing a negative electrode active material, a conductive additive, a binder, etc. in a solvent. A solid electrolyte slurry is manufactured by dispersing a solid electrolyte, a conductive agent, a binder, etc. in a solvent. The positive electrode active material slurry may contain a solid electrolyte. The negative electrode active material slurry may contain a solid electrolyte.

The positive electrode active material is not particularly limited as long as it is a positive electrode active material used in non-aqueous electrolyte secondary batteries. Known materials including alkali metal transition metal oxide type, vanadium type, sulfur type, solid solution type (excessive lithium type, excessive sodium type, excessive potassium type), carbon type, organic material type, etc. are used.

For example, alkali metal transition metal oxide systems include, for example, LiCoO ₂ , Li _0.9 Na _0.1 CoO ₂ , LiNiO ₂ , LiNi _0.5 Co _0.5 O ₂ , LiNi _0.33 Mn _0.33 Co _0.33 O ₂ , LiNi _0.5 Mn _0.2 Co _{0 .3} O ₂ , LiNi _0.6 Mn _0.2 Co _0.2 O ₂ , LiNi _0.8 Mn _0.1 Co _0.1 O ₂ , Li(Ni, Co, Al) O ₂ , LiMnO ₂ , LiMn ₂ O ₄ , LiFePO ₄ , LiFe _0.5 Mn _{0.5 PO4} , LiMnPO ₄ , Li ₂ MnSiO ₄ , Li ₂ FeSiO ₄ , Li ₂ (Mn,Fe)SiO ₄ , Li ₂ CoSiO ₄ , Li ₂ MgSiO ₄ , Li ₂ CaSiO ₄ , Li ₂ ZnSiO ₄ , LiNb ₂ O ₅ , LiNb _O2 , _LiFeO2 , _{LiMgO2 , LiCaO2} , _LiTiO2 , LiTiS2, LiCrO2, _{LiRuO2 , LiCuO2} , _LiZnO2 , _LiMoO2 , _LiMoS2 , LiTaO2 _, LiWO2, NaCoO ₂ , NaNiO _{2 ,} NaNi _0.33 Mn _0.33 Co _0.33 O ₂ , NaMnO ₂ , NaMn ₂ O ₄ , NaFePO ₄ , NaFe _0.5 Mn _0.5 PO ₄ , NaMnPO ₄ , Na ₂ MnSiO ₄ , Na ₂ FeSiO ₄ , Na ₂ (Mn,Fe)SiO ₄ , Na _{2 CoSiO4} , _{Na2MgSiO4 , Na2CaSiO4 , Na2ZnSiO4} , _NaNb2O5 , NaNbO2, _{NaFeO2 ,} NaMgO2, _{NaCaO2 , NaTiO2 ,} NaTiS2 _, NaCrO2, NaRu O ₂ , NaCuO _{2 ,} NaZnO _{2 ,} NaMoO ₂ , NaMoS ₂ , NaTaO ₂ , NaWO ₂ , KCoO ₂ , KNiO ₂ , KNi _0.33 Mn _0.33 Co _0.33 O ₂ , KMnO ₂ , KMn ₂ O ₄ , KFePO ₄ , KFe _0.5 Mn _0.5 PO ₄ , KMnPO ₄ , K ₂ MnSiO ₄ , K ₂ FeSiO ₄ , K ₂ (Mn,Fe)SiO ₄ , K ₂ CoSiO ₄ , K ₂ MgSiO ₄ , K ₂ CaSiO ₄ , K ₂ ZnSiO ₄ , KNb ₂ O ₅ , KNbO ₂ , KFeO ₂ , KMg O ₂ , _KCaO2 , KTiO2, _KTiS2 , _KCrO2 , _KRuO2 , _KCuO2 , _KZnO2 , _KMoO2 , _KMoS2 , _{KTaO2 , KWO2,} and the like.

Vanadium-based compounds include, for example, LiV ₂ O ₅ , LiVO ₂ , Li ₃ VO ₄ , Li ₃ V ₂ (PO ₄ ) ₃ , NaV ₂ O ₅ , NaVO ₂ , Na ₃ VO ₄ , Na ₃ V ₂ (PO ₄ ) ₃ , KV ₂ O ₅ , KVO ₂ , K ₃ VO ₄ , K ₃ V ₂ (PO ₄ ) ₃ and the like. Examples of sulfur-based compounds include sulfur, carbon sulfide, polysulfide, carbon polysulfide, sulfur-modified polyacrylonitrile, disulfide compounds, sulfur-modified rubber, sulfur-modified pitch, sulfur-modified anthracene, and metal sulfide. Solid solution systems include, for example, Li ₂ MnO ₃ -LiNiO ₂ , Li ₂ MnO ₃ -LiMnO ₂ , Li ₂ MnO ₃ -LiCoO ₂ , Li ₂ MnO ₃ -Li(Ni,Mn)O ₂ , Li ₂ MnO ₃ - Li(Ni,Co) _O2 , _Li2MnO3 -Li( _Mn ,Co) _O2 , _{Li2MnO3 -} Li( _Ni ,Mn,Co) _O2 , _{Na2MnO3 -} NaNiO2, _{Na2MnO 3} -NaMnO ₂ , Na ₂ MnO ₃ -NaCoO ₂ , Na ₂ MnO ₃ -Na(Ni,Mn)O ₂ , Na ₂ MnO ₃ -Na(Ni,Co)O ₂ , Na ₂ MnO ₃ -Na(Mn, Co)O ₂ , Na ₂ MnO ₃ -Na(Ni,Mn,Co)O ₂ , K ₂ MnO ₃ -KNiO ₂ , K ₂ MnO ₃ -KMnO ₂ , K ₂ MnO ₃ -KCoO ₂ , K ₂ MnO ₃ - K(Ni _, Mn) _O2 , _K2MnO3 -K(Ni,Co) _O2 , K2MnO3 _- K( _Mn ,Co) _{O2 ,} K2MnO3 _- K(Ni,Mn,Co) _O2 , etc. are mentioned.

Examples of carbon-based materials include graphite, soft carbon, hard carbon, and glassy carbon. Organic compounds include rubeanic acid, tetracyanoquinodimethane, triquinoxalinylene, phenazine dioxide, trioxotriangulene, indigo carmine, nitronyl nitroxide radical compounds, radialene compounds, aliphatic cyclic nitroxyl radicals, Examples include benzoquinones.

The above-mentioned positive electrode active materials may be used alone or in combination of two or more, but from the viewpoint of energy density, for example, LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiFePO ₄ , LiFe _0.5 Mn _0.5 PO ₄ , LiMnPO ₄ , LiNi _0.33 Mn _0.33 Co _0.33 O ₂ , LiNi _0.5 Mn _0.2 Co _0.3 O ₂ , LiNi _0.6 Mn _0.2 Co _0.2 O ₂ , LiNi _0.8 Mn _0.1 Co _0.1 O ₂ , Li(Ni, Co , Al)O ₂ , solid solution systems, vanadium systems, and sulfur systems are preferred.

The negative electrode active material is not particularly limited as long as it is a material that can reversibly insert and release alkali metal ions (lithium ions, sodium ions, potassium ions, etc.). For example, Li, Na, K, C, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, At least one element selected from the group consisting of Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, W, Pb and Bi, alloys, composites, oxides, chalcogenides using these elements Alternatively, it may be a halide.

From the viewpoint that the discharge plateau region can be observed within the range of 0 to 1 V (vs. Li ⁺ /Li), Li, Na, K, C, Mg, Al, Si, Ti, Zn, Ge, Fe, Mn, Ag , Cu, In, Sn, and Pb, and allotropes, alloys, or oxides using these elements are preferable.

Furthermore, from the viewpoint of energy density, the elements are preferably Al, Si, Zn, Ge, Ag, Sn, etc., and the alloys are Si-Al, Al-Zn, Si-Mg, Si-La, Al-Ge, Si-Ge, Si-Ag, Si-Sn, Si-Ti, Si-Y, Si-Cr, Si-Ni, Si-Zr, Si-V, Si-Nb, Si-Mo, Zn-Sn, Ge- Combinations of Ag, Ge-Sn, Ge-Sb, Ag-Sn, Ag-Ge, Sn-Sb, etc. are preferred, and oxides include Fe ₂ O ₃ , CuO, MnO ₂ , NiO, Li ₄ Ti ₅ O ₁₂ , H ₂ Ti ₁₂ O ₂₅ , Na ₂ Ti ₃ O ₇ and the like are preferred. The alloy may be a solid solution alloy, a eutectic alloy, a hypoeutectic alloy, a hypereutectic alloy, or a peritectic alloy.

Note that the surfaces of the active material particles of these positive electrode active materials or negative electrode active materials may be coated with a material having excellent electronic conductivity, ceramics, solid electrolyte, or the like. Further, the shape of these active material particles is not particularly limited, and may be spherical, elliptical, faceted, band-shaped, fibrous, flaky, donut-shaped, or hollow.

The electrolyte may be any liquid or solid that can move alkali metal ions from the positive electrode to the negative electrode or from the negative electrode to the positive electrode, and the same electrolyte as used in known non-aqueous electrolyte secondary batteries can be used. Examples include electrolytes, gel electrolytes, solid electrolytes, ionic liquids, and molten salts. Here, the electrolytic solution refers to a state in which an electrolyte is dissolved in a solvent.

Since the electrolyte must contain alkali metal ions, the electrolyte salt is not particularly limited as long as it is used in non-aqueous electrolyte secondary batteries, but lithium salts, sodium salts, potassium salts, etc. Alkali metal salts are preferred. Examples of the alkali metal salt include lithium hexafluorophosphate (LiPF ₆ ), lithium perchlorate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₄ ), and lithium bistrifluoride. Fluoromethanesulfonylimide (LiN(SO ₂ CF ₃ ) ₂ ), Lithium bispentafluoroethanesulfonylimide (LiN(SO ₂ C ₂ F ₅ ) ₂ ), Lithium bisoxalate borate (LiBC ₄ O ₈ ), Hexafluoro Sodium phosphate, sodium perchlorate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate and sodium trifluoromethanesulfonimide, potassium hexafluorophosphate, potassium perchlorate, potassium tetrafluoroborate, potassium trifluoromethanesulfonate At least one member selected from the group consisting of potassium trifluoromethanesulfonic acid imide and potassium trifluoromethanesulfonate imide can be used.

Examples of the electrolyte solvent include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), γ-butyrolactone (GBL), and methyl-γ- Butyrolactone, methyl lactone, 2-methyltetrahydrofuran, 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, furan, dimethyl Furan, tetrahydrofuran (THF), methyltetrahydrofuran (MeTHF), tetrahydropran (THP), dioxane (DIOX), crown ether, dimethoxymethane (DMM), dimethoxyethane (DME), diglyme, triglyme, tetraglyme, methyl acetate (MA), ethyl acetate (EA), propyl acetate, isopropyl acetate, butyl acetate, methyl fluoroacetate, ethyl trifluoroacetate, methyl propionate, ethyl propionate, propyl propionate, methyl formate, ethyl formate, propyl formate, butyric acid Ethyl, propyl butyrate, propyl methyl butyrate, vinyl acetate, methyl cyanoacetate, γ-valerolactone, σ-valerolactone, ε-caprolactone, γ-hexalactone, γ-undecalactone, trimethyl phosphate (TMP), phosphoric acid Triethyl (TEP), tri-n-propyl phosphate, trioctyl phosphate, triphenyl phosphate, N,N-dimethylformamide (DMF), ethylenediamine, pyridine, N-methylimidazole, dimethyl sulfate, dimethyl sulfite, dimethyl Propyl sulfite, ethylene sulfite, dimethyl sulfone, ethyl methyl sulfone, diphenyl sulfone, sulfolane, methyl sulfolane, methyl methanesulfonate, methyl benzenesulfonate, methyl trifluoromethanesulfonate, propane sulfone, butane sulfone, dimethyl sulfoxide, diphenyl disulfide , dimethyl sulfide, diethyl sulfide, acetonitrile, propanenitrile, adiponitrile, valeronitrile, glutanitrile, malononitrile, succinonitrile, pimelonitrile, suberonitrile, isobutyronitrile, biphenyl, succinic anhydride, t-butylbenzene, naphthalene, cyclohexylbenzene , benzotriazole, thiophene, toluene, methyl ethyl ketone, benzene, fluorobenzene, hexafluorobenzene, nitromethane, N,N-dimethylformamide, dimethyl sulfoxide, vinylene carbonate (VC), vinylethylene carbonate (EVC), fluoroethylene carbonate (FEC) , ethylene sulfite (ES).

Ionic liquids and molten salts are classified into pyridine-based, alicyclic amine-based, aliphatic amine-based, etc. based on the type of cation. By selecting the type of anion to be combined with this, various ionic liquids or molten salts can be synthesized. Cations include ammonium-based ions such as imidazolium salts and pyridinium salts, phosphonium-based ions, and inorganic ions. Examples of anions include halogen-based ions such as bromide ions and triflates, boron-based ions such as tetraphenylborate, and hexafluorocarbons. There are phosphorus compounds such as phosphate.

Ionic liquids and molten salts include, for example, cations such as imidazolinium and Br ^- , Cl ^- , BF ₄ ^- , PF ₆ ^- , (CF ₃ SO ₂ ) ₂ N ^- , CF ₃ SO ₃ ^- , FeCl ₄ It can be obtained by known synthetic methods such as combining with anions such as ^- . An ionic liquid or molten salt can function as an electrolyte without adding an electrolyte.

As the solid electrolyte, sulfide-based solid electrolytes, oxide-based solid electrolytes, hydride-based solid electrolytes, etc. used as solid electrolytes for all-solid-state batteries can be used. That is, they are amorphous (glass) and crystalline, which are composed of alkali metal salts and inorganic derivatives.

Sulfur-based solid electrolytes are used as sulfides with alkali metal elements. For example, Li ₂ S-SiS ₂ , LiX-Li ₂ S-SiS ₂ , Li ₂ S-GeS ₂ , Li ₁₀ GeP ₂ S ₁₂ , LiX ₂ S ₅ , Li ₂ SP ₂ S ₅ , Li ₃ PS ₄ , Li ₇ P ₃ S ₁₁ , Li ₂ SB ₂ S ₃ , Li ₃ PS ₄ -LiX, Li ₆ PS ₅ X, Li _9.54 Si _1.74 P _1.44 S _11.7 X, and the like. Note that "X" here is a halogen element, and represents F, Cl, Br, I, or the like.

The oxide solid electrolyte is used as an oxide with an alkali metal element. Examples include Li _2.9 PO _3.3 N _0.46 , Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ , Li ₇ La ₃ Zr ₂ O ₁₂ and the like.

The hydride solid electrolyte is used as a hydride with an alkali metal element. For example, LiBH ₄ , LiBH ₄ -LiX, LiNH ₂ -LiBH ₄ , Li ₂ B ₁₀ H ₁₀ , Li ₂ B ₁₂ H ₁₂ , LiCB ₉ H ₁₀ , LiCB ₁₁ H ₁₂ , Li ₂ (CB ₉ H ₁₀ ) (CB ₁₁ H ₁₂ ), Li ₄ Ti ₅ O ₁₂ , LiX-Al ₂ O ₃ , β alumina, β′ alumina, and the like. Note that "X" here is a halogen element, and represents F, Cl, Br, I, or the like.

The conductive aid is not particularly limited as long as it has electronic conductivity, and metals, carbon materials, conductive polymers, conductive glass, etc. can be used. Specifically, acetylene black (AB), Ketjen black (KB), furnace black (FB), thermal black, lamp black, channel black, roller black, disc black, carbon black (CB), carbon fiber (e.g. registered Examples include vapor-grown carbon fiber (trade name: VGCF), carbon nanofiber, carbon nanotube (CNT), carbon nanohorn, graphite, graphene, glassy carbon, amorphous carbon, etc., and one or more of these can be used. You can.

When the total of the active material, binder, and conductive additive contained in the positive electrode and negative electrode is 100% by mass, it is preferable that the conductive additive is contained in an amount of 0 to 20% by mass. That is, the conductive additive is contained as necessary. If it exceeds 30% by mass, the electrode capacity density tends to be low because the proportion of the active material as a battery is small.

As the binder, commonly used binders such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyimide (PI), polyamide, polyamideimide, aramid, polyacrylic, styrene butadiene rubber (SBR), Ethylene-vinyl acetate copolymer (EVA), styrene-ethylene-butylene-styrene copolymer (SEBS), carboxymethyl cellulose (CMC), chitan sun gum, polyvinyl alcohol (PVA), ethylene vinyl alcohol, polyvinyl butyral (PVB), ethylene Vinyl alcohol, polyethylene (PE), polypropylene (PP), polyacrylic acid, lithium polyacrylate, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, methyl polyacrylate, ethyl polyacrylate, polyacrylic acid Amine, polyacrylic acid ester, epoxy resin, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), nylon, vinyl chloride, silicone rubber, nitrile rubber, cyanoacrylate, urea resin, melamine resin, phenolic resin, latex, polyurethane, Silylated urethane, nitrocellulose, dextrin, polyvinylpyrrolidone, vinyl acetate, polystyrene, chloropropylene, resorcinol resin, polyaromatic, modified silicone, methacrylic resin, polybutene, butyl rubber, 2-propenoic acid, cyanoacrylic acid, methyl methacrylate, glycidyl One type of organic material such as methacrylate, acrylic oligomer, 2-hydroxyethyl acrylate, alginic acid, starch, lacquer, sucrose, glue, casein, cellulose nanofiber, etc. may be used alone, or two or more types may be used in combination. .

Alternatively, a mixture of these organic binders and inorganic binders may be used. The inorganic binder may be silicate-based, phosphate-based, sol-based, cement-based, or the like. For example, lithium silicate, sodium silicate, potassium silicate, cesium silicate, guanidine silicate, ammonium silicate, silicofluoride salt, borate, lithium aluminate, sodium aluminate, potassium Aluminate, aluminosilicate, lithium aluminate, sodium aluminate, potassium aluminate, polyaluminum chloride, polyaluminum sulfate, polysulfuric aluminum silicate, aluminum sulfate, aluminum nitrate, ammonium alum, lithium alum, sodium alum, potassium Alum, chrome alum, iron alum, manganese alum, nickel ammonium sulfate, diatomaceous earth, polyzirconoxane, polytantaloxane, mullite, white carbon, silica sol, colloidal silica, fumed silica, alumina sol, colloidal alumina, fumed alumina, zirconia Sol, colloidal zirconia, fumed zirconia, magnesia sol, colloidal magnesia, fumed magnesia, calcia sol, colloidal calcia, fumed calcia, titania sol, colloidal titania, fumed titania, zeolite, silicoaluminophosphate zeolite, sepiolite, montmorinite, kaolin , saponite, aluminum phosphate, magnesium phosphate, calcium phosphate, iron phosphate, copper phosphate, zinc phosphate, titanium phosphate, manganese phosphate, barium phosphate, tin phosphate , low melting point glass, plaster, gypsum, magnesium cement, litharge cement, Portland cement, blast furnace cement, fly ash cement, silica cement, phosphate cement, concrete, solid electrolyte, and other inorganic materials may be used alone. , two or more types may be used in combination.

When the total of the active material, binder, and conductive aid contained in the positive electrode and negative electrode is 100% by mass, it is preferable that the binder content is 0.1 to 60% by mass, and 0.5 to 30% by mass. More preferred. When the binder content is less than 0.1% by mass, the mechanical strength of the electrode is low, so that the active material is likely to fall off during skeleton formation, and the cycle life characteristics of the battery may deteriorate. On the other hand, if it exceeds 60% by mass, the ionic conductivity will be low, the electrical resistance will be high, and the ratio of the active material for the battery will be small, so the electrode capacity density will tend to be low.

Note that the solvent required to liquefy these organic binders and inorganic binders is not particularly limited as long as the binder can be dissolved or dispersed, but water, NMP, tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, xylene, toluene, Examples include alcohols, nitriles, ketones, butyric acid esters, and linear alkanes.

Next, each configuration of the slurry manufacturing apparatus 200 will be explained in more detail.

[Material supply device]
As shown in FIG. 3, the material supply device X includes a hopper 31 that allows the powder P input from the feeder 220 into the material adjustment section 31A to pass through the spout section 31B and be discharged from the lower opening section 31C. A stirring mechanism 32 for stirring the powder P is provided in the spout 31B of the hopper 31. In addition, the material supply device 40.

The spout 31B of the hopper 31 has an inverted conical shape whose diameter decreases from the top to the bottom, and is disposed with its central axis extending in the vertical direction. Further, the inclination angle of the inverted conical inner wall surface of the hopper 31 of this embodiment is approximately 60 degrees with respect to a general horizontal plane. However, the angle of inclination can be changed depending on the properties of the powder. For example, when the powder is carbon black, the angle of inclination can be set to about 45 degrees, for example.

The stirring mechanism 32 includes stirring blades 32A disposed inside the hopper 31 to stir the powder P in the hopper 31, and a drive motor (not shown) that rotates the stirring blades 32A around the central axis of the hopper 31. It consists of

The stirring blade 32A is formed by, for example, bending a rod-shaped member into a roughly V-shaped shape, with one side thereof along the inner wall surface of the hopper 31 and the end of the other side along the central axis of the hopper 31. They are coaxially and rotatably supported. Further, the stirring blade 32A has a triangular cross-sectional shape, and is arranged so that the surface forming one side of the triangle is substantially parallel to the inner wall surface of the hopper 31. Thereby, the stirring blade 32A is arranged along the inner wall surface of the hopper 31 so as to be rotatable around the central axis.

In addition, as shown in FIGS. 3, 4, and 5, the volumetric quantitative supply unit 40 supplies the powder P supplied from the lower opening 31c of the hopper 31 to the mixing device Y on the downstream side in a predetermined amount. It is a mechanism for supplying.

Specifically, an introduction part 41 connected to the lower opening 31C of the hopper 31, a casing 43 including a supply port 43a and a discharge port 43b, and a metering rotary body 44 rotatably disposed within the casing 43. and a metering rotor drive motor M2 that rotationally drives the metering rotor 44.

The introduction part 41 is formed in a cylindrical shape that communicates between the lower opening 31C of the hopper 31 and the supply port 43a formed in the upper part of the casing 43, and has a slit in the same shape as the supply port 43a of the casing 43 at the lowermost end. A shaped opening is formed. This introduction part 41 is formed in a tapered shape that becomes thinner toward the supply hole 43a side of the casing 43. The shape of the slit-shaped opening can be appropriately set depending on the size of the hopper 31, the amount of powder P supplied, the characteristics of the powder P, etc. The dimensions should be set to about 20 to 100 mm, and the width direction dimension should be set to about 1 to 5 mm.

The casing 43 is formed in a generally rectangular parallelepiped shape and is connected to the hopper 31 via the introduction part 41 in an attitude inclined at approximately 45 degrees with respect to the horizontal direction (left-right direction in FIG. 3).

Further, as shown in FIGS. 4 and 5, a slit-shaped supply port 43a corresponding to the slit-shaped opening of the introduction part 41 is provided on the upper surface of the casing 43, and powder from the lower opening 31C of the hopper 31 is provided. It is configured such that the body P can be supplied into the casing 43. At the bottom of the lower side surface (the right side surface in FIG. 5) of the casing 43 arranged in an inclined manner, the powder P supplied in a fixed amount by the metering rotor 44 is passed through the expansion chamber 47 to a mixing device on the downstream side. A discharge port 43b for discharging to Y is provided, and a powder discharge pipe 45 is connected to the discharge port 43b.

The expansion chamber 47 is provided at a position in the casing 43 where the powder P supplied from the supply port 43a to the powder storage chamber 44b of the metering rotary body 44 is supplied in a fixed quantity, and the expansion chamber 47 is provided with a negative pressure suction force acting from the discharge port 43b. Therefore, the pressure is maintained lower than that of the supply port 43a (for example, about -0.06 MPa in gauge pressure).

That is, the discharge port 43b is connected to the primary side of the mixing device Y, so that a negative pressure suction force acts on the expansion chamber 47 to maintain a lower pressure state than that of the supply port 43a. With the rotation of the metering rotary body 44, the state of each powder storage chamber 44b is configured to change between a negative pressure state (for example, about -0.06 MPa in gauge pressure) and a state with a higher pressure than the negative pressure state. ing.

The metering rotary body 44 has a plurality of (for example, eight) plate-shaped partition walls 44a radially arranged on a disk member 49 disposed on the drive shaft 48 of the metering rotary body drive motor M2, excluding the center of the disk member 49. The powder storage chambers 44b are attached at intervals to form a plurality of powder storage chambers 44b (e.g., 8 chambers) at equal intervals in the circumferential direction.

The powder storage chamber 44b is configured to open at the outer circumferential surface and center of the metering rotary body 44. An opening closing member 42 is fixedly disposed at the center of the metering rotary body 44 and unevenly distributed in the circumferential direction, and closes or opens the opening on the center side of each powder storage chamber 44b according to its rotational phase. configured to be possible. Note that the supply amount of the powder P can be adjusted by changing the rotation speed of the metering rotor 44 by the metering rotor drive motor M2 that rotationally drives the metering rotor 44.

As the metering rotary body 44 rotates, each powder storage chamber 44b is in an expansion chamber open state in which it is opened to the expansion chamber 47, a first sealed state in which it is not in communication with the expansion chamber 47 and the supply chamber 43a, and an open state in which it is opened to the supply chamber 43a. The state is configured such that the state changes repeatedly in the order of the supply port open state and the second closed state in which there is no communication with the supply port 43a and the expansion chamber 47. Note that the casing 43 is formed such that the opening on the outer peripheral surface side of the metering rotary body 44 is closed in the first sealed state and the second sealed state, and the opening on the center side of the metering rotary body 44 is closed in the first sealed state. An opening closing member 42 is fixedly disposed on the casing 43 so as to be closed in the supply port open state and the second closed state.

Therefore, in the material supply device A fixed amount is supplied to the mixing mechanism 60 of the mixing device Y through the discharge pipe 45.

[Mixing device]
(solvent supply section)
As shown in FIGS. 2 and 3, the tank 260 is configured to continuously supply the liquid R in the tank 260 to the supply port 11 of the mixing device Y at a set flow rate. Therefore, tank 260 functions as a solvent supply source that supplies liquid R to mixing device Y. Further, slurry F is supplied to the tank 260 from the recirculation mechanism section 70 via the discharge path 22. Therefore, tank 260 functions as a slurry recovery source that recovers slurry F.

The tank 260 includes a solvent supply pipe 52 that connects the tank 260 and the mixing mechanism 60 and through which the liquid R passes, and a solvent supply pipe 52 that is provided in the solvent supply pipe 52 and connects the tank 260 and the mixing mechanism 60 to the mixing mechanism 60 through the solvent supply pipe 52. A pump 261 that sends liquid R to the solvent supply pipe 52, and a flow rate adjustment valve (not shown) that adjusts the flow rate of the liquid R sent from the tank 260 to the solvent supply pipe 52 to a set flow rate.

The mixing mechanism 60 mixes the liquid R adjusted to a set flow rate with the powder P supplied in a fixed quantity from the fixed quantity supply section 40 and supplies the mixture to the supply rotor 11 . As shown in FIG. 6, the mixing mechanism 60 includes a mixing member 61 that connects the powder discharge pipe 45 and the solvent supply pipe 52 to the supply chamber 11.

This mixing member 61 is. A cylindrical portion 62 configured to have a smaller diameter than the cylindrical supply port 11 and inserted into the supply port 11 to form an annular slit 63 between the cylindrical portion 62 and the annular slit. The supply port 11 is provided with an annular flow path forming portion 65 that forms an annular flow path 64 on the outer periphery of the supply port 11 in communication with the supply port 63 over the entire circumference.

A powder discharge pipe 45 is connected to the mixing member 61 so as to communicate with the cylindrical portion 62 , and a solvent supply pipe 52 is connected to the mixing member 61 so as to supply the liquid R to the annular flow path 64 in a tangential direction. Ru.

The powder discharge pipe 45, the cylindrical portion 62 of the mixing member 61, and the supply port 11 are arranged so that their axis A2 is inclined at an angle of about 45 degrees with respect to the inclined posture in which the supply direction is downward. There is.

That is, the powder P discharged from the discharge port 43b of the quantitative supply section 40 to the powder discharge pipe 45 is introduced into the supply port 11 along the axis A2 through the cylindrical portion 62 of the mixing member 61. On the other hand, since the liquid R is supplied to the annular flow path 64 from the tangential direction, it flows through the annular slit 63 formed on the inner circumferential side of the annular flow path 64 in the state of an unbroken hollow cylindrical vortex flow. It is supplied to the supply port 11. Therefore, the powder P and the liquid R are evenly premixed through the cylindrical supply port 11, and the premix Fp is suctioned into the supply chamber 13 of the suction pump mechanism Y.

(Suction pump mechanism)
The suction pump mechanism section 80 will be explained based on FIGS. 3 and 6 to 9. As shown in FIG. 6, the suction pump mechanism section 80 includes a main body casing 1 including a cylindrical outer peripheral wall 4 whose openings at both ends are closed by a front wall 2 and a rear wall 3. A rotor 5 is provided concentrically inside the body casing 1 and can be freely rotated, a cylindrical stator 7 is concentrically provided inside the main body casing 1 and fixed to the front wall 2, and the rotor 5 is rotatably driven. The pump drive motor M3 is configured to include a pump drive motor M3 and the like.

As shown in FIG. 7, on the radially outward side of the rotor 5, a plurality of rotary blades 6 protrude toward the front side (the left side in FIG. 6), which is the front wall portion 2 side, and are arranged at equal intervals in the circumferential direction. They are integrally provided with the rotor 5 in a state where they are lined up.

The cylindrical stator 7 is provided with a plurality of through holes 7a and 7b arranged in the circumferential direction, and the stator 7 is located on the front side of the rotor 5 (on the left side in FIG. 6) and on the inside of the rotor blade 6 in the radial direction. An annular blade chamber 8 in which a rotor blade 6 revolves is formed between the stator 7 and the outer peripheral wall 4 of the main casing 1 .

As shown in FIGS. 6 to 8, a supply port 11 is configured to suck and introduce a premix Fp, in which powder P and liquid R are premixed in a mixing mechanism 60, into the main body casing 1 by rotation of a rotor 6. , is provided at a position shifted toward the outer circumferential side with respect to the central axis of the front wall portion 2 (axis center A3 of the main body casing 1).

As shown in FIGS. 6 and 8, an annular groove 10 is formed on the inner surface of the front wall 2 of the main casing 1, and a supply port 11 is provided in communication with the annular groove 10. As shown in FIGS. 6 and 7, a cylindrical discharge portion 12 that discharges slurry F generated by mixing powder P and liquid R is arranged around the cylindrical outer peripheral wall portion 4 of the main body casing 1. It is provided at one location in the direction so as to extend in the tangential direction of the outer peripheral wall portion 4 and communicate with the blade chamber 8 .

As shown in FIGS. 3 and 6, in this embodiment, the slurry F discharged from the discharge section 12 is supplied to the recirculation mechanism section 70 through the discharge path 18, and the slurry F is supplied to the recirculation mechanism section 70 at the separation section of the recirculation mechanism section 70. An inlet 17 that circulates the undissolved slurry Fr from which air bubbles have been separated in the cylindrical container 71 into the main casing 1 through the circulation path 16 is connected to the center of the front wall 2 of the main casing 1 (axis center A3). It is located concentrically with the

Further, as shown in FIGS. 6 to 8, a partition plate 15 that partitions the inner peripheral side of the stator 7 into a supply chamber 13 on the front wall 2 side and an introduction chamber 14 on the rotor 5 side is located on the front side of the rotor 5. A scraping blade 9 is provided on the front wall 2 side of the partition plate 15 so as to rotate integrally with the rotor 5 . A plurality of scraping blades 9 (four in FIG. 8) are provided concentrically at equal intervals in the circumferential direction, and each scraping blade 9 is connected to the rotor 5 with its tip 9T entering the annular groove 10. It is arranged so that it can be rotated integrally.

The supply chamber 13 and the introduction chamber 14 are configured to communicate with the blade chamber 8 through a plurality of through holes 7a and 7b of the stator 7, with the supply chamber 11 communicating with the supply chamber 13 and the introduction port 17 communicating with the blade chamber 8. It is configured to communicate with the chamber 14.

Specifically, the supply chamber 13 and the blade chamber 8 are communicated with each other through a plurality of supply chamber-side through holes 7a arranged at equal intervals in the circumferential direction in the portion of the stake 7 facing the supply chamber 13, and the introduction chamber 14 and the blade chamber 8 are communicated with each other through a plurality of introduction chamber side through holes 7b arranged at equal intervals in the circumferential direction in a portion of the stator 7 facing the introduction chamber 14.

Each part of the suction pump mechanism section Y will be explained. As shown in FIG. 6, the rotor 5 has a front surface that bulges out in the shape of a truncated cone, and a plurality of rotary blades 6 are arranged at equal intervals on the outer circumferential side of the rotor 5 and protrude forward. It is being In addition, in FIG. 7, ten rotary blades 6 are arranged at equal intervals in the circumferential direction. Further, the rotor blade 6 is formed to protrude from the outer circumference side of the port 5 toward the inner circumference side so as to be inclined rearward in the rotational direction as it goes from the inner circumference side to the outer circumference side. The inner diameter of the tip is slightly larger than the outer diameter of the stator 7.

This rotor 5 is connected to a drive shaft 19 of a pump drive motor M3 inserted into the main casing 1 through the rear wall 3 while being located concentrically with the main casing 1 within the main casing 1. , is rotationally driven by its pump drive motor M3.

The rotor 5 is rotationally driven in a direction in which the tip of the rotor blade 6 faces forward when viewed in the axial direction (as seen in the VII-VII direction in FIG. 6 as shown in FIG. 7), so that the rotor blade 6 The rear surface (back surface) 6a in the rotational direction is configured so that so-called cavitation occurs.

As shown in FIGS. 6, 8, and 9, the partition plate 15 is generally funnel-shaped and has an outer diameter slightly smaller than the inner diameter of the stator 7. As shown in FIGS. Specifically, this funnel-shaped partition plate 15 is provided with a funnel-shaped part 15b opened at a cylindrical sliding contact part 15a whose top protrudes in a cylindrical shape in the center thereof, and the funnel-shaped part 15b The main body casing 1 is configured to have an annular flat plate portion 15c on the outer peripheral portion thereof, both of the front and rear surfaces being orthogonal to the axis A3 of the main body casing 1.

As shown in FIGS. 6 and 7, this partition plate 15 has a plurality of partition plates arranged at equal intervals in the circumferential direction, with the cylindrical sliding contact part 15a at the top facing the front wall 2 side of the main body casing 1. It is attached to the attachment portion 5a on the front surface of the rotor 5 via the spacing members 20 arranged at locations (four locations in this embodiment).

As shown in FIGS. 7 and 9(c), when attaching the partition plate 15 to the rotor 5 via the spacing members 20 at a plurality of locations, the fastening blades 21 It is assembled integrally with the partition plate 15 in an attitude facing to the side, and is configured so that when the rotor 5 is rotationally driven, the four fastening blades 21 rotate integrally with the rotor 5.

As shown in FIGS. 6 and 8, in this embodiment, a cylindrical inlet 17 is concentric with the main casing 1 and provided at the center of the front wall 2 of the main casing 1. The introduction port 17 is formed with a constricted portion 14a having a diameter smaller than the inner diameter of the circulation path 16 and smaller in diameter than the cylindrical sliding contact portion 15a of the partition plate 15, and having a smaller flow path area. As the rotary blades 6 of the rotor 5 rotate, the slurry F is discharged through the discharge section 12, and the undissolved slurry Fr is introduced through the constriction section 14a of the inlet 17, so that the suction pump mechanism The pressure inside section Y is reduced.

As shown in FIGS. 6 to 8, the supply chamber 11 has an opening (inlet portion) opening into the main casing 1 that includes a part of the annular groove 10 in the circumferential direction. It is provided in the front wall part 2 so as to be located on the lateral side of the opening of the inlet 17 to the inside.

In addition, the supply rotor 11 has an axial center A2 parallel to the axial center A3 of the main body casing 1 in a plan view (vertical view in FIGS. 3 and 6), and a horizontal direction perpendicular to the axial center A3 of the main casing 1. In the view (viewed from the front and back of the paper in FIGS. 3 and 6), the front of the main body casing 1 is tilted downward so that the closer the axis A2 is to the front wall 2 of the main casing 1, the closer it is to the axis A3 of the main body casing 1. It is provided on the wall part 2. Incidentally, the downward inclination angle of the supply port 11 with respect to the horizontal direction (left-right direction in FIGS. 3 and 6) is about 45 degrees, as described above.

As shown in FIGS. 6 and 8, the stator 7 is attached to the inner surface of the front wall 2 of the main casing 1 (the surface facing the rotor 5), and the front wall 2 of the main casing 1 and the stake 7 are connected to each other. fixed to be one piece. In the stator 7, the plurality of supply chamber side through holes 7a arranged in the portion facing the supply chamber 13 are formed in a generally circular shape, and the plurality of supply chamber side through holes 7a are larger than the flow path area of the supply chamber 13. The total flow path area is set to be small, and the plurality of introduction chamber side through holes 7b arranged in the portion facing the introduction chamber 14 are formed in a roughly elliptical shape, and the flow path of the introduction chamber 14 is set to be small. The total flow path area of the plurality of introduction chamber side through holes 7b is set to be smaller than the area.

As the rotary blades 6 of the rotor 5 rotate, the slurry F is discharged through the discharge section 12, and the premix Fp is supplied through the supply chamber-side through hole 7a of the supply chamber 13, and the inlet port 17 is supplied with the premix Fp. Since the undissolved slurry Fr is introduced through the suction pump mechanism 80, the pressure inside the suction pump mechanism 80 is reduced.

As shown in FIGS. 8 and 9, in this embodiment, each scraping blade 9 is formed into a rod shape, and when viewed in the radial direction of the rotor 5 (as viewed from the front and back of the paper in FIG. 9(b)), the rod-shaped scraping blade 9 is The tip side of the blade 9 is located closer to the front wall portion 2, and the tip side of the rod-shaped scraping blade 9 is located closer to the front wall portion 2 side when viewed in the axial direction of the rotor 5 (as viewed from the front and back of the paper in FIG. 9(a)). In an inclined position located on the radially inward side of the rotor 5, the base end portion 9B of the rod-shaped scraping blade 9 is fixed so as to rotate integrally with the rotor 5, and the rotor 5 is rotated in the axial direction (see FIG. 9). The tip of the scraping blade 9 is driven to rotate in a direction in which the tip of the scraping blade 9 faces the front side as viewed from the front and back of the page (a).

The scraping blade 9 will be explained based on FIGS. 7 to 9. The scraping blade 9 has a base end 9B fixed to the partition plate 15, a middle part 9M exposed to the supply chamber 13, and a distal end 9T fitted into the annular groove 10 from the base to the distal end. It is constructed in the form of a series of rods.

As shown in FIG. 7, FIG. 8, and FIG. 9(b), the base end portion 9B of the scraping blade 9 is formed into a generally rectangular plate shape. As shown in FIGS. 7, 8, 9(a) and 9(b), the intermediate portion 9M of the scraping blade 9 has a generally triangular prism shape with a generally triangular cross-sectional shape.

By providing the scraping blades 9 in the above-mentioned inclined position, one side 9m (hereinafter referred to as a dissipation surface) of the three sides of the triangular prism-shaped intermediate portion 9M faces toward the front in the rotational direction of the rotor 5. ) has a forward-sloping shape that is inclined toward the front side in the rotational direction of the rotor 5, and also faces radially outward with respect to the radial direction of the rotor 5 (hereinafter sometimes referred to as diagonally outward). ) (see especially FIGS. 8 and 9).

That is, by providing the rod-shaped scraping blade 9 in the above-mentioned inclined position, the intermediate portion 9M of the scraping blade 9 exposed to the supply chamber 13 is closer to the rotor 5 than the tip portion 9T fitted into the annular groove 10. The dissipation surface 9m, which is located radially outward and faces the front in the rotational direction of the intermediate portion 9M, has a forward-sloping shape that is inclined toward the front in the rotational direction of the coder 5, and is diagonally outward in the radial direction of the rotor 5. It is tilted in the direction. As a result, the premix Fp scraped out from the annular groove 10 by the tip portion 9T of the scraping blade 9 is transferred to the outside of the rotor 5 in the radial direction within the supply chamber 13 by the dispersion surface 9m of the intermediate portion 9M of the scraping blade 9. It is guided so that it flows in one direction.

As shown in FIGS. 8, 9(a) and 9(b), the distal end portion 9T of the scraping blade 9 has a generally rectangular columnar shape with a generally rectangular cross-sectional shape, and when viewed in the axial direction of the rotor 5 ( In FIG. 9A (viewed from the front and back of the paper), an outward facing side surface 9o facing radially outward of the rotor 5 out of the four sides is an inward facing surface 9o facing radially inward on the inner surface of the annular groove 10. The inward side surface 9i is formed in an arc shape along the inner surface of the annular groove 10 on the radially inward side of the rake 5 and along the outer surface of the annular groove 10. .

Further, among the four side surfaces of the square columnar tip portion 9T, the scraping surface 9f facing the front side in the rotational direction of the rotor 5 has a forward-sloping shape that is inclined toward the front side in the rotational direction of the rotor 5, and has a diameter of the rotor 5. It is configured to face radially outward (hereinafter sometimes referred to as diagonally outward) with respect to the direction.

As a result, the premix Fp scraped out from the annular groove 10 by the tip 9T of the scraping blade 9 is directed toward the outside in the radial direction of the rotor 5 by the scraping surface 9f of the tip 9T of the scraping blade 9. It will be discharged into the supply chamber 13. Further, the distal end surface 9t of the distal end portion 9T of the scraping blade 9 is configured to be parallel to the bottom surface of the annular groove 10 when the distal end portion 9T is fitted into the annular groove 10.

Further, when the rotor 5 is rotationally driven in such a direction that the tips of the scraping blades 9 face forward when viewed in the axial direction (viewed from the front and back of the page in FIG. 9(a)), the proximal end of the scraping blades 9 9B, the intermediate portion 9M, and the tip portion 9T are each formed with a surface (back surface) 9a that is on the rear side in the rotational direction.

The four scraping blades 9 configured in the above-described shape are arranged in the circumferential direction at intervals of 90 degrees at the center angle in the tilted posture as described above, and each of the four scraping blades 9 has the base end portion 9B. It is fixed to the annular flat plate portion 15c of the partition plate 15.

As shown in FIG. 6, the partition plate 15 provided with the scraping blades 9 is attached to the mounting portion 5a on the front surface of the rotor 5 with a distance from the front surface of the rotor 5 by the spacing member 20. 5 is disposed within the main casing 1, with the cylindrical sliding contact portion 15a of the partition plate 15 being slidably and rotatably fitted into the introduction port 17.

Then, a tapered introduction chamber 14 is formed between the bulging front surface of the rotor 5 and the rear surface of the partition plate 15, and the diameter becomes smaller toward the front wall 2 of the main body casing 1, and the introduction port 17 is connected to the partition plate 15. It is configured to communicate with the introduction chamber 14 via 15 cylindrical sliding contact parts 15a. Further, an annular supply chamber 13 communicating with the supply port 11 is formed between the front wall portion 2 of the main body casing 1 and the front surface of the partition plate 15 .

Then, when the rotor 5 is rotationally driven, the partition plate 15 rotates integrally with the rotor 5 with the cylindrical sliding contact portion 15a in sliding contact with the introduction port 17, and the coder 5 and the partition plate 15 rotate. Even in the rotating state, the introduction port 17 is configured to maintain communication with the introduction chamber 14 via the cylindrical sliding contact portion 15a of the partition plate 15.

(Recirculation mechanism)
The recirculation mechanism section (an example of a separation section) 70 is configured to separate the solution based on specific gravity in a cylindrical container 71, and as shown in FIG. From the slurry F supplied through 18, the undissolved slurry Fr, which may contain powder P that is not completely dissolved, is sent to the circulation path 16, and the slurry F, in which the powder P is almost completely dissolved, is sent to the circulation path 16. The discharge passages 22 are configured to be separated from each other. The discharge path 18 and the circulation path 16 are each connected to the lower part of the cylindrical container 71, and the discharge path 22 is connected to the upper part of the cylindrical container 71 and the tank 260 to which the slurry F is supplied.

Although not shown, the recirculation mechanism section 70 has an introduction pipe to which the discharge passage 18 is connected protruding from the bottom surface of the cylindrical container 71 inward, and a discharge passage 22 connected to the upper part of the cylindrical container 71. It has a discharge part connected thereto, a circulation part connected to the circulation path 16 at the lower part, and a twisting plate for swirling the flow of slurry F discharged from the introduction pipe at the discharge upper end of the introduction pipe. It is configured. Thereby, the bubbles of the liquid R can be separated from the slurry F, and the bubbles of the liquid R can be supplied into the introduction chamber 14 in a separated state from the undissolved slurry Fr that is circulated and supplied to the circulation path 16.

(control unit)
In particular, the control unit C is configured to be able to control the rotation speed of the rotor 5 (rotor blade 6), and the pressure in the outlet area of the supply chamber side through hole 7a and the introduction chamber side through hole 7b (throttle through hole) of the stator 7 is controlled. The rotation speed of the rotor blade 6 is set so that the saturated vapor pressure of the liquid R (3.169 kPa in the case of water at 25° C.) is lower than or equal to the entire circumference of the outlet area, and the rotor blade 6 rotates at the set rotation speed. By rotating the blades 6, at least the region within the blade chamber 8 immediately after passing through the supply chamber side through hole 7a and the introduction chamber side through hole 7b of the stator 7 is continuous over the entire circumference within the blade chamber 8. The structure is such that a large number of microbubbles of the liquid R can be formed as a microbubble region.

[Operation of slurry manufacturing equipment]
Next, the operation of this slurry manufacturing apparatus 200 will be explained. First, the dry boxes 230 and 240 are operated to lower the dew point temperature, and the cooling device 250 is also operated. In addition, by adjusting the dehumidification unit 233, the air pressure inside the hopper 31 is set to positive pressure (approximately 2 to 3 Pa higher than the outside air pressure), and the air pressure in the dry box 230 is set to negative pressure (approximately 2 to 3 Pa lower than the outside air pressure). do.

Next, with the shack valve 46 closed and suction of the powder P through the powder discharge pipe 45 stopped, the rotor 5 is rotated, and then the pump 261 is operated to supply only the liquid R from the tank 260. , the operation of the suction pump mechanism section 80 is started. By supplying the liquid R to the suction pump mechanism section 80 after rotating the rotor 5, the mechanical seal on the back surface of the rotor 5 comes into close contact with the rotor 5, and liquid leakage from the back surface of the rotor 5 can be prevented.

Due to the negative pressure suction force of the suction pump mechanism section 80, the liquid R is continuously supplied in a predetermined amount to the mixing member 61 of the mixing mechanism 60.

When a predetermined operating time has elapsed and the inside of the suction pump mechanism section 80 becomes a negative pressure state (for example, a vacuum state of about -0.06 MPa in gauge pressure), the shack valve 46 is opened. As a result, the expansion chamber 47 of the material supply device to a pressure state between.

Then, the material supply device X is operated to supply the powder P from the feeder 220 to the material adjustment section 31A of the hopper 31. At this time, if the powder P needs to be adjusted, the operator adjusts the material in the hopper 31 through the glove 31D. Thereafter, the powder P stored in the hopper 31 is moved to the pouring spout 31B side, and is quantified from the lower opening 31C of the hopper 31 by the stirring action of the stirring blade 32A and the negative pressure suction force of the suction pump mechanism 80. A predetermined amount is continuously supplied to the mixing member 61 of the mixing mechanism 60 via the expansion chamber 47 of the supply section 40 .

In this case, depending on the properties of the powder, a predetermined amount of the powder may be directly supplied from the feeder 220 to the mixing mechanism 60 via the hopper 31 without using the quantitative supply section 40. At this time, the supply speed of the feeder 220 is controlled so as not to exceed the powder processing capacity of the mixing mechanism 60, and the powder is supplied to the mixing mechanism 60.

From the mixing member 61 of the mixing mechanism 60, the powder P is supplied to the supply port 11 through the cylindrical part 62 of the mixing member 61, and the liquid R passes through the annular slit 63 in a continuous hollow cylindrical vortex state. The powder P and the liquid R are premixed through the supply port 11, and the premix Fp is introduced into the annular groove 10.

When the supply of a predetermined amount of powder P is completed, the powder discharge port 221 and the shack valve 46 are closed to stop suction of the powder P through the powder discharge pipe 45, and the powder P is transferred from the material supply device X to the mixing device Y. Stop supplying powder. Then, the operation of the dry box 230 is stopped. Dry box 240 continues to operate.

When the rotor 5 is rotationally driven and the partition plate 15 rotates integrally with the rotor 5, the tip portion 9T of the scraping blade 9 provided concentrically on the partition plate 15 is fitted into the annular groove 10. Rotate around in the same position.

Then, as shown by solid line arrows in FIGS. 6 and 7, the premix Fp flowing through the supply port 11 and introduced into the annular groove 10 reaches the tip of the scraping blade 9 that is fitted into the annular groove 10 and circulates. The scraped premix Fp is scraped out by the section 9T, and the scraped premix Fp is roughly passed through the rotor 5 while moving inside the supply chamber 13 along the front surface of the funnel-shaped section 15b and the front surface of the annular flat plate section 15c in the partition plate 15. It flows in the rotational direction of the rotor 5, further passes through the supply chamber side through hole 7a of the stake 7, flows into the blade chamber 8, flows in the blade chamber 8 in the rotational direction of the rotor 5, and is discharged from the discharge part 12. be done.

The premix Fp introduced into the annular groove 10 is subjected to a shearing action when being scraped out by the tip portion 9T of the scraping blade 9. In this case, between the outward facing side surface 9o of the tip part 9T of the scraping blade 9 and the inward facing inner surface of the inner annular groove 10, and between the inward facing side surface 9i of the tip part 9T of the scraping blade 9 and the inner annular groove A shearing action is exerted between the outer surface and the outer inner surface of 10. In addition, a shearing action occurs when passing through the supply chamber side through-hole 7a of the stator 7.

In other words, since a shearing force can be applied to the premix Fp in the supply chamber 13, the premix Fp scraped out is mixed by receiving the shearing action from the scraping blades 9 and the through holes 7a on the supply chamber side. As a result, the powder P is better dispersed in the liquid R. Therefore, such a premix Fp can be supplied, and good dispersion of the powder P in the liquid R in the blade chamber 8 can be expected.

The slurry F discharged from the discharge section 12 is supplied to the recirculation mechanism section 70 through the discharge path 18, and in the recirculation mechanism section 70 it is mixed with undissolved slurry Fr containing powder P that is not completely dissolved. The liquid R is separated into a slurry F in which the body P is almost completely dissolved, and the bubbles of the liquid R are separated, and the undissolved slurry Fr is again supplied to the inlet 17 of the suction pump mechanism 80 through the circulation path 16. Slurry F is supplied to tank 260 through discharge path 22.

The undissolved slurry Fr is introduced into the introduction chamber 14 through the constriction part 14a of the introduction port 17 in a state where the flow rate is restricted. In the introduction chamber 14, it is subjected to a shearing action by a plurality of rotating stirring blades 21, and is further crushed into fine pieces, and is also subjected to a shearing action and crushed when passing through the introduction chamber side through hole 7b. . At this time, the air is introduced into the blade chamber 8 through the introduction chamber side through-hole 7b in a state where the flow rate is restricted.

Then, in the blade chamber 8, the powder P is crushed by the shearing action of the rotor blade 6 rotating at high speed and the generation of cavitation on the rear side (back surface) 6a of the rotor blade 6 in the rotational direction. Slurry F containing even fewer aggregates (clumps) is mixed with slurry F from supply chamber 13 and discharged from discharge section 12 .

Here, the control unit causes the pressure in the blade chamber 8, which is the outlet area of the supply chamber side through hole 7a and the introduction chamber side through hole 7b of the stator 7, to be equal to or lower than the saturated vapor pressure of the liquid R over the entire circumference. The rotational speed of the rotary blade 6 is set as follows, and the rotary blade 6 is rotated at the set rotational speed.

As a result, by setting the rotational speed of the rotary blade 6, the pressure in the blade chamber 8, which is the exit area, is equal to or lower than the saturated vapor pressure of the liquid R (3.169 kPa in the case of water at 25° C.) throughout its entire circumference. Therefore, at least in the region within the blade chamber 8 immediately after passing through the supply chamber side through hole 7a and the introduction chamber side through hole 7b of the stake 7, the generation of microbubbles due to vaporization of the liquid R is promoted. , the region is formed as a micro-bubble region in which a large number of micro-bubbles are continuously generated over the entire circumference of the blade chamber 8 .

The expansion and contraction of the bubbles due to the cavitation generated here promotes the disintegration of the aggregates of the powder P. As a result, a high-quality slurry F in which the powder P is well dispersed in the liquid R can be generated over almost the entire slurry F existing around the entire circumference in the blade chamber 8.

<3. Other embodiments>
In addition to the configuration of the above embodiment, a configuration for monitoring the amount of powder P introduced into the hopper 31 may be added. For example, a sensor A capable of detecting the powder P is provided below the hopper 31 at a predetermined position from the lowest end. The sensor A can detect that the powder P is being charged into the hopper 31 from the lowest end of the hopper 31 to a predetermined position. When the sensor A detects the powder P, a control section (not shown) slows down the supply speed of the powder P from the feeder 220 to the hopper 31. This prevents the powder P from being excessively supplied to the hopper 31, and prevents the hopper 31 from clogging with the powder P.

Further, a sensor B may be provided near the top end of the hopper 31 for detecting that the powder P has accumulated almost entirely in the hopper 31. When the sensor B detects the powder P, a control section (not shown) stops supplying the powder P from the feeder 220 to the hopper 31. Thereby, overflowing of the powder P from the hopper 31 can be suppressed. Further, in the above embodiment, the dry box 230 that covers the hopper 31 is provided, but a configuration may be adopted in which the dry box 230 is not provided.

Note that the configuration disclosed in the above-described embodiment can be applied in combination with the configuration disclosed in other embodiments as long as no contradiction occurs. Further, the embodiments disclosed in this specification are illustrative, and the embodiments of the present invention are not limited thereto, and can be modified as appropriate without departing from the purpose of the present invention.

100: Mixing system 110: Material supply device 111: Hopper 111A: Material adjustment section 111B: Spout section 111C: Partition plate 111D: Opening 111E: Shutter 111F: Glove 112: Dry gas supply section 112a: Cylinder 112b: Static electricity removal device 113 : Carbon dioxide supply section 114: Vacuum pump 115: Pressure gauge 116: Dehumidifier 117: Front chamber 118: Opening/closing mechanism 119: Opening/closing mechanism 120: Mixing device 130: Butterfly valve 1: Main body casing 2: Front wall 3: Rear wall Part 4: Outer peripheral wall 5: Rotor 5a: Mounting part 6: Rotating blade 7: Stator 7a: Supply chamber side through hole 7b: Introducing chamber side through hole 8: Blade chamber 9: Scraping blade 9B: Base end portion 9M: Intermediate portion 9T: Tip portion 9a; Back surface 9f: Scraping surface 9i: Inward side surface 9m: Diffusion surface 9o: Outward side surface 9t: Tip surface 10: Annular groove 11: Supply hole 12: Discharge portion 13: Supply chamber 14: Introduction Chamber 14a: Squeezing section 15: Division plate 15a: Cylindrical sliding contact section 15b: Funnel section 15c: Annular flat plate section 16: Circulation path 17: Inlet 18: Discharge path 19: Drive shaft 20: Spacing member 21: Stirring Blade 22: Discharge path 31: Hopper 31A: Material adjustment section 31B: Spout section 31C: Lower opening 31D: Globe 32: Stirring mechanism 32A: Stirring blade 40: Quantitative supply section 41: Introduction section 42: Opening closing member 43: Casing 43a: Supply chamber 43b: Discharge port 44: Measuring rotary body 44a: Plate partition wall 44b: Powder storage chamber 45: Powder discharge pipe 46: Shack valve 47: Expansion chamber 48: Drive shaft 49: Disk member 52: Solvent Supply pipe 60: Mixing mechanism 61: Mixing member 62: Cylindrical portion 63: Slit 64: Annular channel 65: Annular channel forming section 70: Recirculation mechanism section 71: Cylindrical container 80: Suction pump mechanism section 200: Slurry Manufacturing equipment 210: Feeder hopper 211: Air vent 220: Feeder 221: Powder discharge port 230: Powder dry box 231: Outer box 232: Inner box 233: Dehumidification unit 240: Main body dry box 250: Cooling device 260 : Tank 261: Pump 270: Pressure relief section 271: Filter 280: Frame C: Control section F: Slurry Fp: Premix Fr: Undissolved slurry M2: Measuring rotor drive motor M3: Pump drive motor M4: Tank stirring motor P : Powder R: Liquid V: Outline X: Material supply device Y: Mixing device

Claims (9)

A mixing system that mixes a plurality of materials, comprising a mixing mechanism that mixes the plurality of materials, and a material supply device that supplies a first material that is a powder or a liquid to the mixing mechanism,
The material supply device includes a hopper that includes a material adjustment section that adjusts the material and a spout section that supplies the first material to the mixing mechanism, and a hopper that is provided in the hopper and that is cut off from outside air. and a dry gas supply unit that supplies dry gas into the hopper,
The material supply device and the mixing mechanism are connected to each other while being isolated from the outside air via a valve attached to the outlet of the spout, and the dry gas supplied from the dry gas supply unit is used to cool the hopper. A dry gas environment with an internal dew point temperature of -100°C or more and -20°C or less and an internal pressure (absolute pressure) of 0.01 MPa or more and 10 MPa or less,
The hopper includes a partition section between the material adjustment section and the spout section, the partition section partitions the material adjustment section and the spout section, and the partition section separates the material adjustment section from the spout section. It has an opening through which the material can pass , and a lid that blocks the opening to prevent the material from flowing into the spout, or an opening/closing mechanism that can open and close the opening ,
The material adjustment section includes a front chamber, and the material adjustment section and the front chamber are provided with a first opening/closing mechanism that can be opened and closed to take in and take out the material , and an inner space between the material adjustment section and the front chamber is connected to the front chamber. communicates through a first opening/closing mechanism, the inner space of the front chamber communicates with the atmosphere through a second opening/closing mechanism, and a vacuum pump and a dry gas supply unit for gas replacement are connected to the front chamber, A mixing system, wherein the front chamber has a smaller volume than the material adjustment section. The material supply device further includes a drying mechanism that dries the first material before the first material passes through the spout of the hopper.
A mixing system according to claim 1 . The drying mechanism exposes the first material to a dry gas environment to remove volatile components in the material,
The material supply device further includes an exhaust mechanism for exhausting the removed volatile components to the outside air.
A mixing system according to claim 2 . The drying mechanism imparts fluidity to the first material and removes volatile components contained in the first material.
Mixing system according to claim 2 or 3 . The drying mechanism heats the first material to remove volatile components contained in the first material,
A mixing system according to any one of claims 2 to 4 . The material supply device further includes a static electricity removing device within the hopper, the dry gas supply section, or between them.
A mixing system according to any one of claims 1 to 5 . Further comprising a discharge port for discharging the mixed material mixed and discharged by the mixing mechanism,
the outlet is isolated from the outside air;
A mixing system according to any one of claims 1 to 6 . A mixing system used in the manufacturing process of non-aqueous electrolyte energy storage devices.
A mixing system according to any one of claims 1 to 7 . A material supply device used in connection with the mixing mechanism of the mixing system according to any one of claims 1 to 8 .

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