JP6610851B2 - Method for producing carbon-containing paste - Google Patents

Description

  The present invention relates to a method for producing a paste containing carbon, and more particularly to a method for producing a paste containing carbon suitable for producing a paste containing carbon used for producing an electrode for a non-aqueous electrolyte secondary battery. is there.

  In recent years, pastes containing carbon having high electronic conductivity have been developed. Such pastes include, for example, battery and capacitor electrode materials, conductive fillers, heat conductive materials, light emitting elements, wiring materials and electrode bonding materials between wirings, reinforcing materials, black pigments, conductive inks, transparent conductive films, etc. It is promising as a material having various functions in various applications.

In particular, as non-aqueous electrolyte secondary batteries, lithium ion secondary batteries have been widely used in various electronic devices such as personal computers and mobile devices. However, as their use has spread to automobiles and household storage batteries, etc. There has been a demand for sophistication, specifically, higher density and larger capacity.
At present, in order to meet the above requirements, the battery has been put into practical use and commercialized in order to use it as an automobile or a household storage battery by increasing the size of the battery.
However, in order to make electric vehicles, etc. (hybrid vehicles (HEV), plug-in hybrid vehicles (PHEV), electric vehicles (EV)) comparable to current gasoline vehicles, the mileage and horsepower increase (battery energy density and battery power) Improvement in power density), improvement in heat resistance of the battery, reduction in cost of the battery, and the like are required. In particular, the heat resistance of a battery is sufficient if it operates at 45 ° C. or lower in conventional applications such as mobile devices. However, in a vehicle-mounted application, heat resistance of 60 ° C. or higher is required.

  Polyvinylidene fluoride (PVDF) is widely used as a binder used for producing such battery electrodes, and is widely used. PVDF is a binder that has high binding properties and excellent battery characteristics. However, since an organic solvent such as N-methylpyrrolidone (NMP) is used as a solvent, it is removed from the viewpoint of manufacturing cost and environment. A solvent is required. In addition, PVDF swells in a high-temperature electrolytic solution and decreases the electronic conductivity of the active material layer, which is one factor that deteriorates the output characteristics and cycle life characteristics of the electrode. Therefore, an electrolyte and a binder that does not easily swell should be selected.

  In recent years, carboxymethyl cellulose (CMC) has attracted attention as a binder that hardly expands even at high temperatures. Although it has not been put into practical use at the positive electrode, it has already been put into practical use at the negative electrode. By using CMC as an electrode binder, water can be selected as a solvent in the paste manufacturing process, and therefore, it is also promising in terms of manufacturing cost and environment (see Non-Patent Documents 1 to 3). However, in the case of using not only CMC but also a binder in which water is dispersed in water or water (aqueous binder), it is extremely difficult to disperse hydrophobic carbon particles added as a conductive additive in the paste kneading step. Therefore, although a small amount of a surfactant is added to achieve uniform dispersion, countless carbon clusters are generated in the active material layer at the micro level even though it appears to be dispersed at the visual level. The effect due to the addition of the agent could not be brought out sufficiently, and a skilled technique was required for dispersion, and much time was required for the dispersion treatment. In addition, since pastes using many water-based binders have higher paste viscosity than those using PVDF binders, it is easy to bite bubbles in the paste and it is difficult to defoam. Further, when such a paste mixed with bubbles is applied to an electrode substrate and dried by heating, there is a problem that voids are formed in the application forming layer.

Thus, as one of the important factors that influence the battery performance, the characteristics of the paste used for manufacturing the electrode for the nonaqueous electrolyte secondary battery can be mentioned.
This paste is obtained by dispersing and mixing a solid content such as a positive electrode active material or a negative electrode active material as a solute, a conductive material, and a binder in a solvent such as water. A positive electrode and a negative electrode are obtained by applying to an aluminum foil or copper foil and then drying by heating.
Specifically, in the paste, a solid content such as a positive electrode active material or a negative electrode active material, a conductive material, a binder, and a solvent such as water are put into a batch type multi-axis mixer as shown in FIG. The solid content is dispersed and mixed (including the dissolution of the soluble solid content), but the carbon used as the conductive material, particularly the aspect ratio (length / diameter) is large. In the case of a substance with poor dispersibility and solubility, such as fibrous carbon powder or CMC (carboxymethylcellulose) used as a binder, it is difficult to obtain a homogeneous paste, or the solid content is dispersed and mixed There are problems that it is difficult to maintain, and that it takes time to disperse and mix the solid content.
In addition, when the batch type multi-axis mixer is used, bubbles are likely to be mixed in and remain in the paste, and when the paste in which such bubbles are mixed is applied to the substrate of the electrode and dried by heating, voids are formed in the coating formation layer. There was a problem of being formed.

By the way, many active materials used for batteries may be subjected to granulation treatment. Granulation is a process of increasing the particle size by agglomeration of powder, molding or particle surface coating, etc., and not only the advantages in handling powder such as the prevention of fine powder scattering and fluidity control, but also the cycle life, It has the effect of improving electrode characteristics such as input / output, high temperature durability, and suppression of self-discharge.
For example, since the positive electrode active material having a polyanion (Li _x MPO ₄ ) has very low electronic conductivity compared to a lithium transition metal oxide having a layered structure such as LiCoO ₂ , Li release from Li _x MPO ₄ , Or the reaction of occlusion of Li to MPO ₄ does not progress easily.
Therefore, Patent Documents 1 to 4 disclose methods for improving the electronic conductivity by coating the active material particle surfaces with carbon.
Patent Document 1 discloses a method for synthesizing a positive electrode material in which a core made of LiMPO ₄ is coated with carbon using thermal decomposition of a mixed gas containing hydrocarbon as a carbon precursor.
In Patent Document 2 and Patent Document 3, a compound composed of an element M source, a lithium source, and a P source is mixed, and a carbon source is thermally decomposed in the presence of a conductive carbon source, and a core made of LiMPO ₄ is coated with carbon. A method for synthesizing the amount of the positive electrode material made is disclosed.
Patent Document 4 discloses a technique for coating the surface of lithium iron oxide with carbon fibers.
The techniques disclosed in Patent Documents 1 to 4 attempt to improve electrode performance by combining an active material and carbon. However, since carbon is hydrophobic, an aqueous binder is used. The paste kneading step lacked dispersibility.
Therefore, the paste manufacturing method using the batch type multi-axis mixer has the following problems.
(1) When an aqueous binder is used, it is difficult to disperse the conductive aid.
(2) The mixing / dispersing process takes time.
(3) Since it is a batch type, it lacks mass productivity.
(4) It is difficult to mix a conductive aid having a large aspect ratio.
(5) It is easy to chew bubbles in the paste and it is difficult to defoam.
(6) When a composite active material is used, mixing is difficult.

US Patent Publication No. 20040157126 Japanese translation of PCT publication No. 2004-509058 JP-T-2004-509447 JP 2004-186075 A

"High output of LiFePO4 positive electrode", Takashi Mukai et al., Abstracts of Battery Discussion 52nd, 128, (2011) “High temperature characteristics of lithium ion battery positive electrode using water-based binder”, Masanori Morishita et al., Abstracts of Annual Meeting of the Electrochemical Society of Japan 79th, 163, (2012) “Development and Safety Design of Positive Electrode for 4V Lithium Ion Batteries Operated at 80 ° C.”, Masanori Morishita et al., Abstracts of Battery Conference 53rd, 16, (2012)

  In view of the problems relating to the production of pastes used in the production of the above-mentioned conventional non-aqueous electrolyte secondary battery electrodes, the present invention provides a homogeneous paste even when containing a substance having poor dispersibility and solubility, such as carbon. A method for producing a carbon-containing paste that can be obtained in a short time, can maintain a state where the solid content is dispersed and mixed for a long time, and can further reduce the mixing and remaining of bubbles in the paste. The purpose is to provide.

  In order to achieve the above object, a method for producing a carbon-containing paste according to the present invention comprises a step of dispersing and mixing a solid content by applying a shearing force to a liquid containing carbon as a solid content. It is a manufacturing method of the contained paste, Comprising: The said shear force is provided in the negative pressure state of the range of -0.01--0.10 MPa, It is characterized by the above-mentioned.

  In this case, the liquid may contain a material that absorbs and releases alkali metal ions in the solid content.

  Further, the liquid may use water as a solvent.

  The carbon may contain fibrous carbon powder, and the fibrous carbon powder may have an aspect ratio of 10 to 1000 and an average fiber diameter of 1 to 500 nm.

  Further, in the container provided with the stirring member, the shearing force can be applied by setting the circumferential speed of the stirring member to 6 to 80 m / s.

  Further, the stirring member is a rotor blade, and a rotor provided with the rotor blade is disposed concentrically inside a cylindrical casing, and the rotor provided with the rotor blade is driven to rotate so that a solid content is obtained. And the solvent is sucked into the first introduction chamber formed inside the cylindrical casing through the first supply unit, stirred by the rotary blade, and discharged from the discharge unit through the discharge chamber, The liquid discharged from the discharge part is circulated to the second supply part via the circulation channel, and is partitioned from the second supply part into the cylindrical casing by the first introduction chamber and the partition plate. The air is sucked into the formed second introduction chamber, passed through the throttle channel formed in the stator, stirred by the rotary blade, discharged from the discharge portion through the discharge chamber, and further discharged from the discharge portion. The circulated liquid is circulated to the second supply section via the circulation channel. It is possible to impart the shearing force using a dispersion mixing pump you so that.

  The present invention also provides a carbon-containing paste obtained by the above carbon-containing paste manufacturing method, a non-aqueous electrolyte secondary battery electrode manufactured using the carbon-containing paste, the non-aqueous electrolyte two A non-aqueous electrolyte secondary battery including a secondary battery electrode and a device including the non-aqueous electrolyte secondary battery are targeted.

According to the method for producing a paste containing carbon according to the present invention, the production of a paste containing carbon comprising a step of dispersing and mixing the solid content by applying a shearing force to a liquid containing carbon as a solid content. Even when a material having poor dispersibility or solubility such as carbon is contained by applying the shearing force in a negative pressure state in the range of -0.01 to -0.10 MPa, the method is homogeneous. The paste can be obtained in a short time, and the state in which the solid content is dispersed and mixed can be maintained for a long time. A manufacturing method can be provided.
In particular, according to this manufacturing method, even a paste using an aqueous binder can disperse carbon or the like having a large aspect ratio and continuously obtain a homogeneous paste in a short time.
In addition, the obtained paste can not only maintain the state in which the solid content is dispersed and mixed for a long time, but also can reduce the mixing and remaining of bubbles in the paste, thereby simplifying the defoaming step.
Moreover, the battery using the electrode for nonaqueous electrolyte secondary batteries obtained by this manufacturing method is excellent in output characteristics.

It is explanatory drawing which shows an example of the dispersion | distribution mixing system provided with the dispersion | distribution mixing pump used for the manufacturing method of the paste containing the carbon of this invention. It is a longitudinal cross-sectional view which shows the principal part of a fixed amount supply apparatus. It is sectional drawing in the III-III direction view of FIG. It is explanatory drawing which shows the internal structure of the dispersion | distribution mixing mechanism of a dispersion | distribution mixing pump. It is sectional drawing in the VV direction view of FIG. It is an exploded perspective view which shows the internal structure of the dispersion | distribution mixing mechanism of a dispersion | distribution mixing pump. It is a schematic block diagram of a partition plate. It is explanatory drawing which shows the internal structure of the isolation | separation part of a recirculation mechanism part. It is a top view which shows an example of the batch type multi-axis mixer used for manufacture of the conventional paste. Electron micrographs of electrode surface and electrode cross-section coated with carbon-containing paste ((a) is based on a conventional batch type multi-axis mixer, (b) is based on a method for producing a carbon-containing paste of the present invention) It is. FIG. 4 is a graph showing a relationship between a discharge rate and an average discharge voltage of a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte secondary battery electrode manufactured using the paste according to the method for manufacturing a carbon-containing paste of the present invention. is there. Discharge capacity of the active material of the nonaqueous electrolyte secondary battery provided with the electrode for a nonaqueous electrolyte secondary battery manufactured using the paste according to the method for manufacturing a carbon-containing paste of the present invention, and applying shearing force to the paste It is a graph which shows the relationship with the pressure at the time. It is a graph which shows the high rate discharge curve of the nonaqueous electrolyte secondary battery provided with the electrode for nonaqueous electrolyte secondary batteries manufactured using the paste by the manufacturing method of the paste containing carbon of the present invention. It is a graph which shows the charging / discharging curve of the non-aqueous electrolyte secondary battery of nominal capacity 1100Ah provided with the electrode for non-aqueous electrolyte secondary batteries manufactured using the paste by the manufacturing method of the paste containing carbon of this invention. It is a graph which shows the cycle life characteristic. It is a graph which shows the cycle life characteristic (high temperature durability). FIG. 3 is a graph showing a relationship between a discharge rate and a discharge capacity of a nonaqueous electrolyte secondary battery including a nonaqueous electrolyte secondary battery electrode manufactured using the paste according to the method for manufacturing a carbon-containing paste of the present invention. . FIG. 4 is a graph showing a relationship between a discharge rate and an average discharge voltage of a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte secondary battery electrode manufactured using the paste according to the method for manufacturing a carbon-containing paste of the present invention. is there. It is a graph which shows the high rate discharge curve of the nonaqueous electrolyte secondary battery provided with the electrode for nonaqueous electrolyte secondary batteries manufactured using the paste by the manufacturing method of the paste containing carbon of the present invention.

  Hereinafter, although the embodiment of the manufacturing method of the paste containing carbon of the present invention is described based on a drawing, the present invention is not limited to these embodiments at all.

  1 to 8 show a dispersion mixing system equipped with a centrifugal dispersion mixing pump used in the method for producing a carbon-containing paste of the present invention.

FIG. 1 shows a dispersion mixing system 100 including a centrifugal dispersion mixing pump Y.
This dispersion mixing system 100 uses powder P (solid content) as a dispersoid, uses solvent R as a liquid phase dispersion medium, and disperses and mixes powder P in solvent R (dissolves soluble solid content). The same applies to the following) to produce paste F.
In the present embodiment, for example, as the powder P, a material that occludes and releases alkali metal ions, carbon and CMC (carboxyl methylcellulose), which is a paste material used for manufacturing a non-aqueous electrolyte secondary battery electrode, is used. Water was used as the solvent R.

  As shown in FIG. 1, the dispersion and mixing system 100 includes a quantitative supply device X that supplies powder P in a fixed amount, a solvent supply unit 50 that supplies solvent R in a fixed amount, and a powder P that is supplied in a fixed amount from the quantitative supply device X. And a dispersion and mixing pump Y that disperses and mixes negative pressure of the solvent R that is quantitatively supplied from the solvent supply unit 50 and a powder that is not completely dispersed and mixed from the paste F that is discharged from the dispersion and mixing pump Y A recirculation mechanism unit 70 that circulates and supplies a solvent R containing P (hereinafter referred to as “undispersed paste Fr”) to the dispersive mixing pump Y is configured.

[Quantitative supply device]
As shown in FIG. 1, the quantitative supply device X includes a hopper 31 that discharges the powder P received from the upper opening 31a from the lower opening 31b, a stirring mechanism 32 that stirs the powder P in the hopper 31, With the upper opening 31a of the hopper 31 open to the atmosphere, the lower opening 31b is absorbed by the negative pressure suction force acting on the lower opening 31b by the suction of the dispersion mixing pump Y connected to the downstream side of the lower opening 31b. And a positive displacement quantitative supply unit 40 for quantitatively supplying the powder P discharged from the liquid to the dispersion mixing pump Y.

  The hopper 31 is formed in an inverted conical shape that is reduced in diameter as it goes from the upper part to the lower part, and its central axis A1 is arranged in a posture along the vertical direction. The cross-sectional shape of each of the upper opening 31a and the lower opening 31b of the hopper 31 is a circular shape centered on the central axis A1 when viewed in the vertical direction of FIG. The inclination angle of the wall surface is approximately 60 degrees with respect to the horizontal plane.

  The stirring mechanism 32 is disposed in the hopper 31 and has a stirring blade 32A for stirring the powder P in the hopper 31, a blade driving motor M1 for rotating the stirring blade 32A around the central axis A1 of the hopper 31, An attachment member 32B that supports the blade drive motor M1 positioned above the upper opening 31a of the hopper 31 and a transmission member 32C that transmits the rotational driving force of the blade drive motor M1 to the stirring blade 32A are configured. .

  The stirring blade 32A is configured by bending a rod-like member into a substantially V-shape, with one side portion being along the inner wall surface of the hopper 31 and the other side portion being at the center axis A1 of the hopper 31. It is coaxially and rotatably supported. Further, the stirring blade 32A has a triangular cross-sectional shape, and is arranged so that a surface forming one side of the triangle is substantially parallel to the inner wall surface of the hopper 31. Thus, the stirring blade 32A is disposed so as to be rotatable around the central axis A1 along the inner wall surface of the hopper 31.

As shown in FIGS. 1 to 3, the positive displacement type quantitative supply unit 40 is a mechanism that quantitatively supplies the powder P supplied from the lower opening 31 b of the hopper 31 to the downstream mixing pump Y by a predetermined amount. is there.
Specifically, the introduction part 41 connected to the lower opening part 31 b of the hopper 31, the casing 43 provided with the supply port 43 a and the discharge port 43 b, and the measuring rotator 44 rotatably disposed in the casing 43. And a metering rotator drive motor M2 that rotationally drives the metering rotator 44.

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

The casing 43 is formed in a substantially rectangular parallelepiped shape, and is connected to the hopper 31 via the introduction portion 41 in a posture inclined by 45 degrees with respect to the horizontal direction (left-right direction in FIG. 1).
As shown in FIGS. 2 and 3, the upper surface of the casing 43 is provided with a slit-shaped supply port 43 a corresponding to the slit-shaped opening of the introduction portion 41, and the powder P from the lower opening 31 b of the hopper 31 is provided. Can be supplied into the casing 43. At the lower part of the lower side surface (right side surface in FIG. 2) of the casing 43 arranged in an inclined manner, the powder P, which is quantitatively supplied by the metering rotator 44, is dispersed and mixed on the downstream side via the expansion chamber 47. A discharge port 43b for discharging to the pump 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 to which the powder P supplied from the supply port 43a to the powder storage chamber 44b of the measuring rotator 44 is supplied in a fixed amount, and is operated by the negative pressure acting from the discharge port 43b. The pressure is maintained at a lower pressure than the supply port 43a. That is, the discharge port 43b is connected to the primary side of the dispersion mixing pump Y so that the negative pressure suction force acts on the expansion chamber 47 and is maintained at a lower pressure than the discharge port 43b. As the measuring rotator 44 rotates, the state of each powder storage chamber 44b is changed to a negative pressure state and a higher pressure state than the negative pressure state.

  The measuring rotator 44 has a disk member 49 disposed on the drive shaft 48 of the measuring rotator driving motor M <b> 2, and a plurality of (e.g., eight) plate-shaped partition walls 44 a radially excluding the central portion of the disk member 49. It is configured to be attached at intervals, and is configured to form a plurality of powder storage chambers 44b (for example, 8 chambers) at equal intervals in the circumferential direction. The powder storage chamber 44 b is configured to open at the outer peripheral surface and the center portion of the measuring rotary body 44. An opening closing member 42 is unevenly distributed in the central direction of the measuring rotating body 44 and is fixedly arranged. The opening on the center side of each powder storage chamber 44b is closed or opened according to the rotation phase. It is configured to be possible. The supply amount of the powder P can be adjusted by changing the number of rotations of the measuring rotator 44 by the measuring rotator driving motor M2 that rotationally drives the measuring rotator 44.

  With the rotation of the measuring rotator 44, each powder storage chamber 44b is opened to the expansion chamber 47, opened to the expansion chamber 47, the first sealed state not communicating with the expansion chamber 47 and the supply port 43a, and opened to the supply port 43a. The supply port is opened and the supply port 43a and the expansion chamber 47 are communicated with each other in the order of the second sealed state. The casing 43 is formed such that the opening on the outer peripheral surface side of the measuring rotator 44 is closed in the first sealed state and the second sealed state, and the opening on the center side of the measuring rotator 44 is the first sealed. The opening closing member 42 is fixedly disposed on the casing 43 so as to be closed in the state, the supply port open state, and the second sealed state.

  Therefore, in the quantitative supply device X, the powder P stored in the hopper 31 is supplied to the quantitative supply unit 40 while being stirred by the stirring blade 32A, and the powder P is discharged from the discharge port 43b by the quantitative supply unit 40. A fixed amount is supplied to the dispersion mixing pump Y through the body discharge pipe 45.

  More specifically, the pressure in the expansion chamber 47 in the casing 43 is in a negative pressure state by the negative pressure suction force from the dispersion mixing pump Y connected to the downstream side of the discharge port 43b of the constant supply unit 40. On the other hand, since the upper opening 31a of the hopper 31 is open to the atmosphere, the inside of the hopper 31 is in a state of about atmospheric pressure. The inside of the introduction part 41 and the vicinity of the lower opening 31b communicating with each other through the gap between the expansion chamber 47 and the metering rotator 44 are in a pressure state between the negative pressure state and the atmospheric pressure state.

  In this state, the powder P in the vicinity of the inner wall surface of the hopper 31 and the lower opening 31b is agitated by the stirring blade 32A of the stirring mechanism 32, whereby the powder P in the hopper 31 is sheared by the stirring blade 32A. On the other hand, the metering rotator 44 is rotated by the metering rotator drive motor M2, so that the empty powder storage chambers 44b are in continuous communication with the supply port 43a. Then, the powder P in the hopper 31 flows down through the introduction portion 41 from the lower opening 31b and is stored in a predetermined amount in the powder storage chamber 44b of the measuring rotary body 44 that is in communication with the supply port 43a one after another. The powder P stored in the powder storage chamber 44b flows down to the expansion chamber 47 and is discharged from the discharge port 43b. Therefore, the fixed amount supply device X can continuously supply the powder P to the first supply unit 11 of the dispersion mixing pump Y continuously by a predetermined amount through the powder discharge pipe 45.

  As shown in FIG. 1, the powder discharge pipe 45 is provided with a shutter valve 46 capable of stopping the supply of the powder P to the first supply unit 11 of the dispersion mixing pump Y.

(Solvent supply unit)
As shown in FIG. 1, the solvent supply unit 50 is configured to continuously supply the solvent R stored in the storage and mixing tank 51 to the first supply unit 11 of the dispersion mixing pump Y at a set flow rate. Yes.
Specifically, the solvent supply unit 50 stores and mixes a solvent R, a storage and mixing tank 51 that sends out the solvent R, a supply pipe 52 that interposes a delivery pump 52P that sends out the solvent R from the storage and mixing tank 51, and storage and mixing. A flow rate adjusting valve (not shown) that adjusts the flow rate of the solvent R sent from the tank 51 to the supply pipe 52 to a set flow rate, and a powder that is quantitatively supplied from the quantitative supply unit 40 with the solvent R adjusted to the set flow rate. And a mixing mechanism 60 that is mixed with P and supplied to the first supply unit 11.
Here, as will be described later, the storage and mixing tank 51 is configured such that the paste F in a state where the powder P is dispersed and mixed from the discharge path 22 is introduced together with the bubbles contained in the paste F.
For this reason, the storage and mixing tank 51 is provided with a stirring mechanism 51K and connected with an air (gas) G discharge pipe 51G and a manufactured paste F discharge path 53.

As shown in FIG. 4, the mixing mechanism 60 includes a mixing member 61 that connects the powder discharge pipe 45 and the supply pipe 52 to the first supply unit 11.
The mixing member 61 is configured to have a smaller diameter than the cylindrical first supply unit 11, and is inserted into the first supply unit 11 so as to form an annular slit 63 between the first supply unit 11. An annular flow path forming portion 65 is provided which forms an annular flow path 64 in the outer peripheral portion of the first supply portion 11 in a state where it communicates with the cylindrical portion 62 and the annular slit 63 disposed over the entire circumference. It is configured.
The powder discharge pipe 45 is connected to the mixing member 61 in a state of communicating with the cylindrical portion 62, and the supply pipe 52 is connected to supply the solvent R to the annular flow path 64 in the tangential direction. .
The powder discharge pipe 45, the cylindrical portion 62 of the mixing member 61, and the first supply portion 11 have an angle 45 with respect to an inclined posture (horizontal plane (left-right direction in FIG. 1)) with the axis A <b> 2 facing downward. It is arranged so as to be inclined.

That is, the powder P discharged from the discharge port 43b of the fixed amount supply unit 40 to the powder discharge tube 45 is introduced into the first supply unit 11 along the axis A2 through the cylindrical portion 62 of the mixing member 61. . On the other hand, since the solvent R is supplied to the annular flow path 64 from the tangential direction, the solvent R is in a state of a hollow cylindrical vortex without a break through the annular slit 63 formed on the inner peripheral side of the annular flow path 64. It is supplied to the first supply unit 11.
Therefore, the powder P and the solvent R are uniformly premixed by the cylindrical first supply unit 11, and the premixed mixture Fp is sucked and introduced into the first introduction chamber 13 of the dispersion mixing pump Y.

[Dispersed mixing pump]
The dispersion mixing pump Y will be described with reference to FIGS. 1 and 4 to 8.
As shown in FIG. 4, the dispersive mixing pump Y includes a casing 1 having a cylindrical outer peripheral wall portion 4 whose both end openings are closed by a front wall portion 2 and a rear wall portion 3. The rotor 5 is concentrically provided in a freely rotatable manner, the cylindrical stator 7 is provided concentrically within the casing 1 and fixedly disposed on the front wall 2, and the pump drive motor that rotationally drives the rotor 5. M3 etc. are provided.

As shown in FIG. 5, on the radially outer side of the rotor 5, a plurality of rotor blades 6 project to the front side (the left side in FIG. 4) which is the front wall 2 side, and in the circumferential direction, etc. It is provided integrally with the rotor 5 in a state of being arranged at intervals.
The cylindrical stator 7 is provided with a plurality of through-holes 7a and 7b, which are throttle channels, arranged side by side in the circumferential direction. The stator 7 rotates on the front side of the rotor 5 (left side in FIG. 4) and rotates. A rotating blade 6 that also serves as a discharge chamber and circulates between the stator 7 and the outer peripheral wall portion 4 of the casing 1 is positioned on the inner side in the radial direction of the blade 6 and fixed to the front wall portion 2. An annular blade chamber 8 is formed.

As shown in FIGS. 4 to 6, a first supply unit that sucks and introduces a premixed mixture Fp, in which the powder P and the solvent R are premixed by the mixing mechanism 60, into the casing 1 by the rotation of the rotor blades 6. 11 is provided at a position shifted from the center axis of the front wall portion 2 (axial center A3 of the casing 1) to the outer peripheral side.
As shown in FIGS. 4 and 6, an annular groove 10 is formed on the inner surface of the front wall portion 2 of the casing 1, and a first supply portion 11 is provided in communication with the annular groove 10.
As shown in FIGS. 4 and 5, the cylindrical discharge portion 12 that discharges the paste F generated by mixing the powder P and the solvent R is the circumferential direction of the cylindrical outer peripheral wall portion 4 of the casing 1. 1 is provided in a state extending in the tangential direction of the outer peripheral wall 4 and communicating with the blade chamber 8.

As shown in FIGS. 1, 4, and 8, in this embodiment, the paste F discharged from the discharge unit 12 is supplied to the recirculation mechanism unit 70 through the discharge path 18, and the recirculation mechanism unit 70 is separated. The undispersed paste Fr from which bubbles have been separated in a cylindrical container 71 as a part is circulated and supplied into the casing 1 through a circulation flow path 16 with a circulation pump 16P rotated by a pump drive motor M4. The 2nd supply part 17 to perform is provided in the center part (concentric with axial center A3) of the front wall part 2 of the casing 1. As shown in FIG.
Moreover, as shown in FIGS. 4-6, the partition plate 15 which divides the inner peripheral side of the stator 7 into the 1st introduction chamber 13 by the side of the front wall part 2, and the 2nd introduction chamber 14 by the side of the rotor 5 is provided. In addition to being provided in a state of rotating integrally with the rotor 5 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. A plurality of scraping blades 9 are concentrically provided at equal intervals in the circumferential direction (four in FIG. 6), and each of the scraping blades 9 enters the annular groove 10 in the state where each of the scraping blades 9 enters the annular groove 10. And are arranged so as to be able to circulate integrally.

The first introduction chamber 13 and the second introduction chamber 14 are configured to communicate with the blade chamber 8 through the plurality of through holes 7 a and 7 b of the stator 7, and the first supply unit 11 is the first supply portion 11. The second supply unit 17 communicates with the introduction chamber 13 and communicates with the second introduction chamber 14.
Specifically, the first introduction chamber 13 and the blade chamber 8 are a plurality of first introduction chambers 13 arranged at equal intervals in the circumferential direction at a portion facing the first introduction chamber 13 in the stator 7. The second introduction chamber 14 and the blade chamber 8 communicate with each other through the through-holes 7a, and the second introduction chamber 14 and the blade chamber 8 are arranged at equal intervals in the circumferential direction on the portion of the stator 7 facing the second introduction chamber 14. It communicates with a through hole 7b on the introduction chamber 14 side.

Each part of the dispersion mixing pump Y will be described.
As shown in FIG. 4, the rotor 5 is configured to have a shape in which the front surface swells substantially in a truncated cone shape, and is arranged at equal intervals on the outer peripheral side with a plurality of rotor blades 6 protruding forward. Is provided. In FIG. 5, ten rotating blades 6 are arranged at equal intervals in the circumferential direction. Further, the rotor blade 6 is formed to project from the outer periphery side of the rotor 5 to the inner periphery side so as to incline backward in the rotation direction from the inner periphery side toward the outer periphery side. The inner diameter is slightly larger than the outer diameter of the stator 7.
The rotor 5 is connected to a drive shaft 19 of a pump drive motor M3 inserted through the rear wall 3 and inserted into the casing 1 in a state of being concentrically positioned with the casing 1 in the casing 1, and the pump It is rotationally driven by the drive motor M3.
Then, the rotor 5 is rotationally driven in a direction in which the tip end portion of the rotor blade 6 is the front side when viewed in the axial direction (viewed in the direction VV in FIG. 4 as shown in FIG. 5). A so-called local boiling (cavitation) occurs on the surface (back surface) 6a which is the rear side in the rotation direction.

As shown in FIGS. 4, 6, and 7, the partition plate 15 is configured in a generally funnel shape having an outer diameter slightly smaller than the inner diameter of the stator 7. Specifically, the funnel-shaped partition plate 15 includes a funnel-shaped portion 15b opened at a central sliding portion of a cylindrical sliding contact portion 15a projecting in a cylindrical shape, and the funnel-shaped portion 15b. In the outer peripheral part of this, it is comprised in the shape provided with the cyclic | annular flat plate part 15c used as the state orthogonal to the axial center A3 of the casing 1 in the front surface and the rear surface.
As shown in FIGS. 4 and 5, the partition plate 15 has a plurality of locations spaced at equal intervals in the circumferential direction with the top cylindrical sliding contact portion 15 a facing the front wall portion 2 side of the casing 1. It is attached to the attachment portion 5a on the front surface of the rotor 5 via the spacing members 20 arranged in (four places in this embodiment).

  As shown in FIG. 5 and FIG. 7 (c), when the partition plate 15 is attached to the rotor 5 via the spacing member 20 at each of a plurality of locations, the stirring blade 21 is placed on the rear wall 3 side of the casing 1. The four agitating blades 21 are configured to rotate integrally with the rotor 5 when the rotor 5 is driven to rotate by being integrally assembled to the partition plate 15 in a posture to face.

  As shown in FIGS. 4 and 6, in this embodiment, the cylindrical second supply portion 17 is concentric with the casing 1 and is provided at the center of the front wall portion 2 of the casing 1. The second supply part 17 is formed with a throttle part 14a having a smaller diameter than the inner diameter of the circulation flow path 16 and smaller than the cylindrical sliding contact part 15a of the partition plate 15 and a smaller flow area. By rotating the rotor blade 6 of the rotor 5, the paste F is discharged through the discharge unit 12, and the undispersed paste Fr is introduced through the throttle unit 14 a of the second supply unit 17. The inside of the dispersion mixing pump Y is depressurized.

  As shown in FIG. 4 to FIG. 6, the first supply unit 11 is a casing in which the opening (inlet portion) that opens into the casing 1 includes a part of the annular groove 10 in the circumferential direction inside. 1 is provided on the front wall portion 2 so as to be located laterally of the opening of the second supply portion 17 with respect to the interior of the first supply portion 17. The first supply unit 11 has a horizontal axis that is parallel to the axis A3 of the casing 1 and orthogonal to the axis A3 of the casing 1 in plan view (up and down direction in FIGS. 1 and 4). When viewed from the direction (viewed from the front and back of the paper in FIGS. 1 and 4), the front wall portion of the casing 1 is in a downward inclined posture that approaches the shaft center A3 of the casing 1 as the shaft center A2 approaches the front wall portion 2 of the casing 1. 2 is provided. Incidentally, the downward inclination angle of the first supply unit 11 with respect to the horizontal direction (left-right direction in FIGS. 1 and 4) is about 45 degrees as described above.

  As shown in FIGS. 4 and 6, the stator 7 is attached to the inner surface of the front wall portion 2 of the casing 1 (surface facing the rotor 5), and the front wall portion 2 of the casing 1 and the stator 7 are integrated. It is fixed to become. In the stator 7, the plurality of first introduction chamber side through-holes 7 a disposed in the portion facing the first introduction chamber 13 are formed in a substantially circular shape and are larger than the flow path area of the first introduction chamber 13. The total flow passage area of the plurality of first introduction chamber side through holes 7a is set to be small, and the plurality of introduction chamber side through holes 7b disposed in the portion facing the second introduction chamber 14 Is formed in a substantially elliptical shape, and is set so that the total flow area of the plurality of first introduction chamber side through holes 7 b is smaller than the flow area of the second introduction chamber 14. By rotating the rotor blades 6 of the rotor 5, the paste F is discharged through the discharge unit 12, and the preliminary mixture Fp is supplied through the first introduction chamber side through hole 7 a of the first introduction chamber 13. At the same time, since the undispersed paste Fr is introduced through the second supply unit 17, the inside of the dispersion mixing pump Y is decompressed.

  As shown in FIGS. 6 and 7, in this embodiment, each scraping blade 9 is formed in a rod shape, and the rod-like scraping blade 9 is viewed in the radial direction of the rotor 5 (viewed from the front and back in FIG. 7B). The tip side of the ejector blade 9 is located closer to the front wall 2 side, and the tip side of the rod-shaped scraping blade 9 is closer to the front side of the rotor 5 as viewed in the axial direction of the rotor 5 (viewed from the front and back in FIG. 7A). The base end portion 9B of the rod-shaped scraping blade 9 is fixed so as to rotate integrally with the rotor 5 in an inclined posture located on the radially inner side of the rotor 5, and the rotor 5 is viewed in the axial direction (see FIG. 7 (a), the tip of the scraping blade 9 is rotationally driven in a direction (the direction indicated by an arrow in FIGS. 4 to 7).

The scraping blade 9 will be described with reference to FIGS.
The scraping blade 9 is a base end portion 9B fixed to the partition plate 15, an intermediate portion 9M that is exposed to the first introduction chamber 13, and a tip end that is fitted (that is, enters) the annular groove 10. The portion 9T is configured in a rod shape provided in a series from the proximal end to the distal end.

As shown in FIGS. 5, 6, and 7 (b), the base end portion 9 </ b> B of the scraping blade 9 is generally formed in a rectangular plate shape.
As shown in FIGS. 5, 6, 7 (a) and 7 (b), the intermediate portion 9 </ b> M of the scraping blade 9 is configured in a substantially triangular prism shape with a substantially triangular cross-sectional shape (particularly, (See FIG. 5). Further, by providing the scraping blade 9 in the inclined posture as described above, one side surface 9m (hereinafter referred to as “a dissipating surface”) facing the front side in the rotational direction of the rotor 5 among the three side surfaces of the triangular columnar intermediate portion 9M. ) Is a front-falling shape that is inclined toward the front side in the rotational direction of the rotor 5, and is directed radially outward with respect to the radial direction of the rotor 5 (hereinafter referred to as “obliquely outward”). (In particular, see FIGS. 6 and 7).

  That is, the bar-shaped scraping blade 9 is provided in the inclined posture as described above, so that the intermediate portion 9M exposed to the first introduction chamber 13 of the scraping blade 9 is inserted into the annular groove 10 from the tip portion 9T. Is also located on the radially outer side of the rotor 5, and the radiating surface 9 m facing the front side in the rotational direction of the intermediate portion 9 </ b> M is in a forwardly descending shape inclined toward the front side in the rotational direction of the rotor 5. It is inclined obliquely outward with respect to the radial direction. As a result, the preliminary mixture Fp scraped from the annular groove 10 by the tip portion 9T of the scraping blade 9 is disposed in the first introduction chamber 13 by the diffusion surface 9m of the intermediate portion 9M of the scraping blade 9. Guided to flow radially outward.

As shown in FIGS. 6, 7 (a) and 7 (b), the tip end portion 9 </ b> T of the scraping blade 9 has a substantially quadrangular prism shape with a substantially rectangular cross-sectional shape, and the axial view of the rotor 5 ( 7A, the outward side surface 9o facing the radially outward side of the rotor 5 among the four side surfaces is an inwardly facing inner surface facing the radially inward side of the inner surface of the annular groove 10. The inward side surface 9i is configured in an arc shape along the outward inner surface facing the radially outer side of the inner surface of the annular groove 10 on the radially inner side of the rotor 5 among the four side surfaces. .
Of the four side surfaces of the quadrangular columnar tip portion 9T, the scraped surface 9f facing the front side in the rotational direction of the rotor 5 is in a front-falling shape inclined toward the front side in the rotational direction of the rotor 5, and the diameter of the rotor 5 It is configured to face radially outward with respect to the direction (hereinafter, sometimes referred to as “obliquely outward”).
Thereby, the preliminary mixture Fp scraped from the annular groove 10 by the tip portion 9T of the scraping blade 9 is directed radially outward of the rotor 5 by the scraping surface 9f of the tip portion 9T of the scraping blade 9. It is discharged into the first introduction chamber 13.
Further, the tip surface 9t of the tip portion 9T of the scraping blade 9 is configured to be parallel to the bottom surface of the annular groove 10 in a state where the tip portion 9T is fitted in the annular groove 10.

  Further, when the rotor 5 is rotationally driven in a direction in which the tip of the scraping blade 9 is the front side when viewed from the axial direction (viewed from the front and back of the paper in FIG. 7A), the base end portion of the scraping blade 9 A surface (back surface) 9a which is the rear side in the rotation direction is formed on each of 9B, the intermediate portion 9M, and the tip portion 9T. The rear surface 9a is configured such that so-called local boiling (cavitation) occurs when the scraping blade 9 rotates.

  The four scraped wings 9 configured in the above-described shape are arranged in the circumferential direction at intervals of 90 degrees at the central angle in the inclined posture as described above, and the base end portions 9B are respectively arranged. It is fixed to the annular flat plate portion 15 c of the partition plate 15.

As shown in FIG. 4, the partition plate 15 provided with the scraping blades 9 is attached to the attachment portion 5 a on the front surface of the rotor 5 in a state of being separated from the front surface of the rotor 5 by the interval holding member 20. 5 is disposed in the casing 1 in a state in which the cylindrical sliding contact portion 15a of the partition plate 15 is fitted in the second supply portion 17 so as to be capable of sliding contact rotation.
As a result, a tapered second introduction chamber 14 having a smaller diameter toward the front wall 2 side of the casing 1 is formed between the bulging front surface of the rotor 5 and the rear surface of the partition plate 15. The supply unit 17 is configured to communicate with the second introduction chamber 14 via the cylindrical sliding contact portion 15 a of the partition plate 15.
An annular first introduction chamber 13 communicating with the first supply unit 11 is formed between the front wall 2 of the casing 1 and the front surface of the partition plate 15.

  Then, when the rotor 5 is driven to rotate, the partition plate 15 rotates integrally with the rotor 5 in a state where the cylindrical sliding contact portion 15 a is in sliding contact with the second supply portion 17. Even in a state where the plate 15 rotates, the state where the second supply unit 17 communicates with the second introduction chamber 14 via the cylindrical sliding contact portion 15a of the partition plate 15 is maintained.

[Recirculation mechanism]
The recirculation mechanism part (an example of a separation part) 70 is configured to separate the dissolved liquid by specific gravity in the cylindrical container 71, and as shown in FIG. 1, from the discharge part 12 of the dispersion mixing pump Y to the discharge path 18. A state in which the powder P is almost completely dispersed and mixed in the circulation channel 16 from the paste F supplied through the uncirculated paste Fr in a state in which the powder P may not be completely dispersed and mixed. The paste F is separated into the discharge path 22 together with the bubbles contained in the paste F. 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 storage and mixing tank 51 from a discharge part 73 formed at the upper part of the cylindrical container 71.
Here, as shown in FIG. 8, the recirculation mechanism unit 70 is provided with an introduction pipe 72 to which the discharge passage 18 is connected so as to protrude from the bottom surface of the cylindrical container 71 to the upper part of the cylindrical container 71. A discharge part 73 connected to the discharge path 22 is provided, a circulation part 74 connected to the circulation flow path 16 is provided at the lower part, and the flow of the paste F discharged from the introduction pipe 72 is provided at the upper discharge end of the introduction pipe 72. A twist plate 75 to be swiveled is arranged. Thereby, the bubbles of the solvent R are separated from the paste F, and the bubbles of the solvent R are separated from the undispersed paste Fr circulated and supplied to the circulation flow path 16 and supplied to the second introduction chamber 14. Can do.

(Control part)
Although not shown, the control unit provided in the dispersion mixing system 100 includes a known arithmetic processing device including a CPU, a storage unit, and the like. The fixed amount supply device X, the dispersion mixing pump Y, and the solvent supply that constitute the dispersion mixing system 100 The operation of each device such as the unit 50 is configured to be controllable.
In particular, the control unit is configured to be able to control the peripheral speed of the rotor blade 6 (the number of rotations of the rotor 5), and the pressure in the first introduction chamber 13 and the second introduction chamber 14 is in a predetermined negative pressure state. As described above, by setting the peripheral speed of the rotor blade 6 (rotation speed of the rotor 5) and rotating the rotor blade 6 at the set peripheral speed (rotation speed of the rotor 5), at least the first speed of the stator 7 is reached. The region in the blade chamber 8 immediately after passing through the through-hole 7a on the introduction chamber 13 side and the through-hole 7b on the second introduction chamber 14 side is continuously spread over the entire circumference in the blade chamber 8. The microbubbles (microbubbles) can be formed as a microbubble region where a large number of microbubbles are generated.

  Here, the pressure in the first introduction chamber 13 and the second introduction chamber 14 (in this embodiment, the pressure in the first introduction chamber 13 (here, the first introduction chamber 13 and the second introduction chamber 13). A pressure gauge 80 is provided for measuring the pressure of the chamber 14 when the shutter valve 46 is closed.

[Operation of distributed mixing system]
Next, the operation of the dispersion mixing system 100 will be described.
First, the quantitative supply device X is stopped, the shutter valve 46 is closed, and the suction of the powder P through the powder discharge pipe 45 is stopped, and only the solvent R is supplied from the storage and mixing tank 51 of the solvent supply unit 50. While rotating the rotor 5, the operation of the dispersion mixing pump Y is started. When the predetermined operating time has elapsed and the inside of the dispersion mixing pump Y is in a negative pressure state, the shutter valve 46 is opened. As a result, the expansion chamber 47 of the quantitative supply device X is brought into a negative pressure state, and the inside of the introduction part 41 and the vicinity of the lower opening 31b of the hopper 31 are brought into a pressure state between the negative pressure state and the atmospheric pressure state.

Then, the quantitative supply device X is operated, and the powder P stored in the hopper 31 is quantitatively supplied from the lower opening 31b of the hopper 31 by the stirring action of the stirring blade 32A and the negative pressure suction force of the dispersion mixing pump Y. Through the expansion chamber 47 of the section 40, a predetermined amount is continuously supplied in a predetermined amount to the mixing member 61 of the mixing mechanism 60. In parallel, the delivery pump 52P of the solvent supply unit 50 is operated, and the solvent R is continuously supplied in a predetermined amount to the mixing member 61 of the mixing mechanism 60 by the negative pressure suction force of the dispersion mixing pump Y.
From the mixing member 61 of the mixing mechanism 60, the powder P is supplied to the first supply unit 11 through the cylindrical part 62 of the mixing member 61, and the solvent R passes through the annular slit 63 and has a hollow cylindrical shape without a break. The powder P and the solvent R are premixed by the first supply unit 11 in the state of the vortex flow, and the preliminary mixture Fp is introduced into the annular groove 10.

When the rotor 5 is driven to rotate and the partition plate 15 rotates integrally with the rotor 5, the scraping blade 9 provided concentrically on the partition plate 15 is fitted into the annular groove 10 with the tip portion 9 </ b> T. Circulate in a state.
As a result, as shown by solid arrows in FIGS. 4 and 5, the preliminary mixture Fp that flows through the first supply unit 11 and is introduced into the annular groove 10 is inserted into the annular groove 10 and scraped around. The preliminary mixture Fp scraped out by the tip portion 9T of the blade 9 is roughly divided into the front surface of the funnel-shaped portion 15b of the partition plate 15 and the annular flat plate portion 15c in the first introduction chamber 13. It flows in the rotational direction of the rotor 5 along the front surface, further passes through the first introduction chamber side through hole 7a of the stator 7 and flows into the blade chamber 8, and the rotation direction of the rotor 5 in the blade chamber 8 And is discharged from the discharge unit 12.

The preliminary mixture Fp introduced into the annular groove 10 undergoes a shearing action when it is scraped by the tip 9T of the scraping blade 9. In this case, between the outward side surface 9o of the tip portion 9T of the scraping blade 9 and the inward inner surface of the inner annular groove 10, and the inward side surface 9i of the tip portion 9T of the scraping blade 9 and the inner annular groove. A shearing action acts between the ten outwardly facing inner surfaces. At the same time, the so-called local boiling (cavitation) occurs on the rear surface 9a on the rear side in the rotational direction of the scraping blade 9 as the scraping blade 9 rotates. Further, when passing through the first introduction chamber side through hole 7 a of the stator 7, a shearing action works.
That is, since a shearing force can be applied to the preliminary mixture Fp in the first introduction chamber 13 and local boiling can be generated, the preliminary mixture Fp to be scraped out is on the scraping blade 9 and the first introduction chamber side. While being mixed by receiving a shearing action from the through-hole 7a, the powder P is more favorably dispersed in the solvent R due to local boiling (cavitation) generated on the back surface 9a of the scraping blade 9. Therefore, such a preliminary mixture Fp can be supplied, and good dispersion of the powder P with respect to the solvent R in the blade chamber 8 can be expected.

  The paste F discharged from the discharge unit 12 is supplied to the recirculation mechanism unit 70 through the discharge path 18, and in the recirculation mechanism unit 70, the undispersed paste Fr including the powder P that is not completely dispersed and mixed. And the paste P in which the powder P is almost completely dispersed and mixed, and the bubbles of the solvent R are separated, and the undispersed paste Fr is rotated by a pump drive motor M4. It is supplied again to the second supply section 17 of the dispersion mixing pump Y through the circulation flow path 16 with 16P interposed, and the paste F is supplied to the storage and mixing tank 51 through the discharge path 22.

  The undispersed paste Fr is introduced into the second introduction chamber 14 in a state where the flow rate is restricted via the throttle portion 14a of the second supply portion 17. In the second introduction chamber 14, it is subjected to a shearing action by a plurality of rotating stirring blades 21, and is further finely crushed. Further, it is also subjected to a shearing action when passing through the introduction chamber side through hole 7 b. It will be crushed. At this time, the air is introduced into the blade chamber 8 in a state where the flow rate is limited via the introduction chamber side through hole 7b. Then, in the blade chamber 8, the paste F, which is crushed by the shearing action by the rotating blade 6 rotating at a high speed and further reduced in the aggregate (dama) of the powder P, is discharged from the first introduction chamber 13. It is mixed with the paste F and discharged from the discharge part 12.

Here, the control unit is configured to be able to control the peripheral speed of the rotor blade 6 (the number of rotations of the rotor 5), and the pressure in the first introduction chamber 13 and the second introduction chamber 14 is in a predetermined negative pressure state. Thus, by setting the peripheral speed (rotation speed of the rotor 5) of the rotor blade 6 and rotating the rotor blade 6 at the set peripheral speed (rotation speed of the rotor 5), at least the first speed of the stator 7 is reached. The region in the blade chamber 8 immediately after passing through the through hole 7a on the first introduction chamber 13 side and the through hole 7b on the second introduction chamber 14 side is continuously spread over the entire circumference in the blade chamber 8. It can be formed as a fine bubble region where a large number of R fine bubbles (microbubbles) are generated.
As a result, the solvent R penetrating into the aggregate (so-called lumps) of the powder P is foamed over the entire circumference of the blade chamber 8 to promote the crushing of the aggregate. Dispersion of the powder P is further promoted by the impact force when the bubbles are pressurized and disappeared in the blade chamber 8, and as a result, almost the entire paste F existing around the entire periphery of the blade chamber 8 is covered. A high-quality paste F in which the dispersion of the powder P in the solvent R is good can be produced.

When the supply of a predetermined amount of the powder P from the hopper 31 of the fixed amount supply device X is finished, the fixed amount supply device X is stopped and the shutter valve 46 provided in the powder discharge pipe 45 is closed to close the powder. The suction of the powder P through the discharge pipe 45 is stopped.
Thereby, when the powder P is not supplied, it is possible to prevent the powder discharge pipe 45 inside the upstream side of the shutter valve 46 from being wetted and blocked, and at the same time, the first of the dispersion mixing pump Y. It is possible to prevent air from being sucked from the supply unit 11.

In this state, the operation of the dispersion mixing pump Y is continued for a predetermined time.
At this time, the paste F replaced with the solvent R is supplied from the storage and mixing tank 51 of the solvent supply unit 50.
When the powder P is not supplied, air is not sucked from the first supply unit 11, so that the inside of the dispersion mixing pump Y, that is, the first introduction chamber 13 and the second introduction chamber. 14 (the first introduction chamber 13 and the second introduction chamber 14 have substantially the same pressure when the shutter valve 46 is closed), so that the set peripheral speed (rotor 5), the blade chamber immediately after passing through the through hole 7a on the first introduction chamber 13 side and the through hole 7b on the second introduction chamber 14 side of the stator 7 at least. The region in 8 can be formed continuously as a fine bubble region in which many fine bubbles (microbubbles) of the solvent R are generated over the entire circumference in the blade chamber 8.
As a result, the solvent R penetrating into the aggregate (so-called lumps) of the powder P is foamed over the entire circumference of the blade chamber 8 to promote the crushing of the aggregate. Dispersion of the powder P is further promoted by the impact force when the bubbles are pressurized and disappeared in the blade chamber 8, and as a result, almost the entire paste F existing around the entire periphery of the blade chamber 8 is covered. Thus, it is possible to more reliably produce a high-quality paste F in which the powder P is well dispersed in the solvent R.
The generated high-quality paste F is stored in the storage and mixing tank 51.

Thereafter, the operation of the dispersion mixing pump Y is stopped.
The generated high-quality paste F stored in the storage and mixing tank 51 is supplied to the subsequent process through the discharge path 53 of the paste F.

[Electrode for non-aqueous electrolyte secondary battery]
Next, the manufacturing method of the electrode for nonaqueous electrolyte secondary batteries of this invention is demonstrated.
Hereinafter, in the present invention, the electrode for a non-aqueous electrolyte secondary battery will be described by taking a lithium ion battery electrode as an example, but it may be a sodium ion battery, a magnesium ion battery, a calcium ion battery, a capacitor, or the like.

As a method for producing an electrode for a nonaqueous electrolyte secondary battery (positive electrode or negative electrode) according to the invention, an active material, a binder, and a conductive additive are mixed, and a paste is applied to a current collector. An example is a method of obtaining an electrode by performing heat treatment after temporary drying.
The temporary drying is not particularly limited as long as the solvent in the paste can be volatilized and removed, and examples thereof include a method of performing a heat treatment in the air at a temperature of 50 to 400 ° C.
Said heat processing can be performed by hold | maintaining at 50-400 degreeC under reduced pressure for 0.5 to 50 hours.

The positive electrode of the lithium secondary battery obtained using the electrode of the present invention is LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiNi _0.33 Mn _0.33 Co _0.33 O ₂ , LiMn ₂ O ₄ , LiFePO ₄ , LiFe _{0. .5 Mn 0.5 PO 4, LiMnPO 4} , MnO 2, LiV 2 O 5, LiVO 2, LiNb 2 O 5, LiNbO 2, LiFeO 2, LiMgO 2, LiCaO 2, LiTiO 2, LiTiS 2, LiCrO 2, LiRuO ₂ , a known electrode containing a lithium transition metal oxide such as LiCuO ₂ , LiZnO ₂ , LiMoO ₂ , LiMoS ₂ , LiTaO ₂ or LiWO ₂ is used. The positive electrode active materials described above may be used alone or in combination of two or more.
In the case of a sodium ion battery, a magnesium ion battery, or a calcium ion battery, sodium, magnesium, or calcium may be substituted for the alkali metal site of the lithium transition metal oxide described above.
In the case of a capacitor, a material having a large specific surface area having micropores, nanopores, etc., such as activated carbon, carbon nanotubes, carbon nanofibers, graphite, hard carbon, soft carbon, and graphene.

The current collector used for the positive electrode is not particularly limited as long as it is a material having electronic conductivity and capable of supplying current to the held positive electrode active material. For example, conductive materials such as C, Ti, Cr, Ni, Cu, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, and Al, and alloys containing two or more of these conductive materials ( For example, stainless steel) can be used. Note that these electronically conductive materials may be carbon-coated materials.
The positive electrode current collector is preferably C, Ti, Cr, Ni, Cu, Au, Al, stainless steel, etc. from the viewpoint of high electrical conductivity and good stability in the electrolyte solution, and further oxidation resistance. From the viewpoint of material cost, C, Al, stainless steel and the like are preferable.
The shape of the current collector includes linear, rod-like, plate-like, foil-like, net-like, woven fabric, non-woven fabric, expanded, porous body or foam, among which the packing density can be increased and the output characteristics are good. Therefore, an expand, a porous body or a foam is preferable.

The negative electrode of the lithium secondary battery obtained by using the electrode of the present invention is not particularly limited as long as it is a material capable of reversibly inserting and extracting lithium. For example, Li, Na, C, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, At least one element selected from the group consisting of Mo, Pd, Ag, Cd, In, Sn, Sb, W, Pb, and Bi, and an alloy, oxide, chalcogenide, or halide using these elements. That's fine.
Further, from the viewpoint of energy density, the element is preferably Al, Si, Zn, Ge, Ag, Sn, or the like, and the alloy is Si—Al, Al—Zn, Si—Mg, Al—Ge, Si—Ge, Each combination of Si—Ag, Si—Sn, Zn—Sn, Ge—Ag, Ge—Sn, Ge—Sb, Ag—Sn, Ag—Ge, Sn—Sb, and the like is preferable. SnO, SnO ₂ , SnC ₂ O ₄ , Li ₄ Ti ₅ O _{12 and the} like are preferable. As the chalcogenide, SnS, SnS _{2 and the} like are preferable. As the halide, SnF ₂ , SnCl ₂ , SnI ₂ , SnI _{4 and the} like are preferable. Is preferred.
In addition, the above-described negative electrode active materials may be used alone or in combination of two or more.
The same applies to sodium ion batteries, magnesium ion batteries, and calcium ion batteries.
In the case of a capacitor, a material having a large specific surface area having micropores, nanopores, etc., such as activated carbon, carbon nanotubes, carbon nanofibers, graphite, hard carbon, soft carbon, and graphene.

The current collector used for the negative electrode is not particularly limited as long as it is a material that has electronic conductivity and can conduct electricity to the held positive electrode active material. For example, it contains conductive materials such as C, Ti, Cr, Ni, Cu, Mo, Ru, Rh, Ta, W, Os, Ir, Pt, Au, Al, and Fe, and two or more of these conductive materials. An alloy (eg, stainless steel) may be used. In addition, the material of the multilayer structure which coat | covered these electronic conductive materials may be sufficient.
The current collector used for the negative electrode is preferably C, Ti, Cr, Ni, Cu, Au, Al, stainless steel, etc. from the viewpoint of high electrical conductivity and good stability in the electrolyte. From the viewpoint of reduction resistance and material cost, C, Cu, Ni, stainless steel and the like are preferable. The shape of the negative electrode current collector may be linear, rod-like, plate-like, foil-like, net-like, woven fabric, non-woven fabric, expanded, porous body or foam, among which the packing density can be increased and the output characteristics are good Therefore, an expand, a porous body or a foam is preferable.

  The binder used for the electrode for the nonaqueous electrolyte secondary battery (positive electrode or negative electrode) is usually used, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyimide (PI), polyamide, Polyamideimide, polyethylene (PE), polypropylene (PP), styrene butadiene rubber (SBR), styrene-ethylene-butylene-styrene copolymer (SEBS), methylcellulose, methylethylcellulose, ethylcellulose, microcrystalline cellulose, hydroxyethylcellulose, hydroxybutyl Methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose stearoxyte Carboxymethyl hydroxyethyl cellulose, alkyl hydroxyethyl cellulose, nonoxynyl hydroxyethyl cellulose, carboxymethyl cellulose (CMC), cellulose sulfate, methyl cellulose ether, methyl ethyl cellulose ether, ethyl cellulose ether, low nitrogen hydroxyethyl cellulose dimethyl diallyl ammonium chloride (polyquaternium-4), Chloride- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-10), Chloride- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-24), starch , Polyacrylate, polyvinyl alcohol (PVA), polyvinyl buty Lumpur (PVB), alginate, may be used a material such as an acrylic acid ester alone or in combination of two or more. Among these, it is preferable to use an aqueous binder (a binder using water as a solvent or a binder used by dispersing in water). An electrode using an aqueous binder absorbs an electrolytic solution in a high-temperature environment and hardly swells, and the high-temperature durability is improved as compared with a conventional non-aqueous electrolyte secondary battery using PVDF.

The conductive substance (conductive auxiliary agent) is not particularly limited as long as it has electronic conductivity, but conductive metals, conductive glasses, conductive polymers, conductive ceramics, etc. may react with the electrolyte, Since there exists a possibility of reacting with lithium, it is preferable to use a carbon material.
There is no particular limitation on the type (structure, etc.) of the carbon material as the conductive material. For example, acetylene black (AB), ketjen black (KB), furnace black, channel black, thermal black, graphite, activated carbon, hard carbon, soft carbon, carbon fiber (VGCF), carbon nanotube (CNT), graphene, amorphous Carbon materials such as carbonaceous materials may be used alone or in combination of two or more. More preferably, those capable of forming a conductive three-dimensional network structure in the composite powder (for example, flaky conductive material (graphene, etc.), carbon fiber, carbon nanotube, amorphous carbon, etc.) are preferable. If a conductive three-dimensional network structure is formed, a current collecting effect sufficient as an electrode material for a nonaqueous electrolyte secondary battery can be obtained.

In the active material layer of the electrode, for example, when the total amount of the electrode active material, the binder, and the conductive material is 100% by mass, the electrode active material is 60 to 99% by mass, the binder is 0.5 to 25% by mass, and the conductive material is conductive. It is preferable that a substance is 0.1-10 mass%. More preferably, the electrode active material is 80 to 95% by mass, the binder is 2 to 15% by mass, and the conductive material is 0.5 to 5% by mass.
With the composition of the active material layer of the above electrode, sufficient binding force and conductivity improvement effect can be obtained, and the life characteristics and high rate discharge characteristics of the battery can be improved while being an electrode having a high energy density. .
Although the thickness of the active material layer of an electrode is based also on electrode capacity density, it is preferable that it is 0.5-500 micrometers, for example. By setting the thickness of the active material layer of the electrode within this range, a practical electric capacity can be obtained while the current collector supports the electrode active material.

The electrode capacity density is preferably 0.1 to 20 mAh / cm ² . For example, upon obtaining a negative electrode of the present invention with the electrode capacity density 0.1~2mAh / cm ^2, is suitable for ultra high power applications, the electrode capacity density 0.5~3mAh / cm ^2, long-life applications and high It is suitable for output applications, and an electrode capacity density of 3 to 20 mAh / cm ² is suitable for high capacity applications. The electrode capacity density can be measured, for example, by a charge / discharge cycle capacity test, or can be obtained by calculating the capacity from the active material application mass and dividing the value by the electrode area.

[Nonaqueous electrolyte secondary battery]
The positive electrode and the negative electrode thus obtained are joined via a separator and hermetically sealed in a state of being immersed in an electrolytic solution to form a secondary battery or a capacitor.

As a separator, what is used for a well-known lithium secondary battery can be used.
Examples of the shape of the separator include a microporous film, a woven fabric, a non-woven fabric, and a green compact.
The material of the separator is not particularly limited, but for example, materials such as PE, PP, PTFE, PI, polyamide, polyamideimide, aramid, and cellulose are preferable. Moreover, the separator which coat | covered the ceramic to the existing separator and improved heat resistance may be sufficient.

The electrolytic solution is not particularly limited as long as it is composed of an electrolyte and its solvent. However, when used as a lithium ion battery, since the electrolyte needs to contain lithium ions, the electrolyte salt is not particularly limited as long as it is used in a lithium secondary battery. For example, a lithium salt is preferable, and specifically, selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium trifluoromethanesulfonate imide. At least one or more can be used.
In the case of a sodium ion battery, a magnesium ion battery, or a calcium ion battery, the alkali metal site of the lithium salt may be replaced with sodium, magnesium, or calcium. In the case of a capacitor, the same element as the ions to be moved may be used at the alkali metal site.

Examples of the solvent for the electrolyte include propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), γ-butyrolactone, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl- At least one selected from the group consisting of 1,3-dioxolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, sulfolane, methyl sulfolane, nitromethane, N, N-dimethylformamide, and dimethyl sulfoxide; In particular, propylene carbonate alone, a mixture of ethylene carbonate and diethyl carbonate, or γ-butyrolactone alone is suitable. The mixing ratio of the mixture of ethylene carbonate and diethyl carbonate can be arbitrarily adjusted in the range of 10 to 90 vol% for both ethylene carbonate and diethyl carbonate.
In this case, a solid electrolyte may be used without using a solvent.

According to the non-aqueous electrolyte secondary battery having the above-described structure, it functions as a secondary battery.
The structure of the non-aqueous electrolyte secondary battery is not particularly limited, but can be applied to existing battery forms and structures such as a stacked battery and a wound battery.
Since the secondary battery including the electrode of the present invention has good output characteristics and high temperature durability, it can be used as a power source for various electric devices (including vehicles using electricity).
The nonaqueous electrolyte secondary battery according to the present invention may be a lithium ion secondary battery, a lithium polymer battery, a solid lithium battery, a sodium ion secondary battery, a polymer sodium battery, a solid sodium battery, a sodium-sulfur battery, or the like. . Among these, it is preferable that it is a lithium ion secondary battery from a viewpoint of the voltage and capacity | capacitance in a single battery.

The non-aqueous electrolyte secondary battery of the present invention has a high output, a long life, and is excellent in mass productivity. Therefore, the non-aqueous electrolyte secondary battery can be used as a power source for various electric devices (including vehicles that use electricity).
Examples of electrical equipment include air conditioners, washing machines, televisions, refrigerators, freezers, air conditioners, notebook computers, computer keyboards, computer displays, desktop computers, notebook computers, CRT monitors, computer racks, printers, integrated computers , Mouse, hard disk, computer peripherals, iron, clothes dryer, window fan, walkie-talkie, blower, ventilation fan, TV, music recorder, music player, oven, range, toilet seat with washing function, hot air heater, car component, car navigation system, pocket Electric light, humidifier, portable karaoke machine, ventilation fan, dryer, dry battery, air purifier, mobile phone, vibrator, emergency light, game machine, blood pressure monitor, coffee mill, coffee maker, moss, kotatsu, copy machine, disc changer , Raj , Shaver, juicer, shredder, water purifier, lighting equipment, dehumidifier, dish dryer, rice cooker, stereo, stove, speaker, trouser press, vacuum cleaner, body fat scale, scale, health meter, movie player, electric carpet , Electric kettle, rice cooker, electric razor, table lamp, electric pot, electronic game machine, portable game machine, electronic dictionary, electronic notebook, microwave oven, electromagnetic cooker, calculator, electric cart, electric wheelchair, electric tool, electric toothbrush , Anka, haircutting equipment, telephone, clock, intercom, air circulator, electric shock insecticide, copying machine, hot plate, toaster, dryer, electric drill, water heater, panel heater, crusher, soldering iron, video camera, video Deck, facsimile, fan heater, food processor, futon drying Machine, headphones, electric kettle, hot carpet, microphone, massage machine, miniature light bulb, mixer, sewing machine, mochi machine, floor heating panel, lantern, remote control, cold storage, water cooler, refrigeration stocker, air blower, word processor, foam Appliances, electronic musical instruments, motorcycles, toys, lawn mowers, floats, bicycles, automobiles, hybrid cars, plug-in hybrid cars, electric cars, railways, ships, airplanes, artificial satellites, emergency storage batteries, etc.

[Production of paste containing carbon]
Next, the manufacturing method of the paste containing the carbon of this invention using the dispersion | distribution mixing system 100 provided with this dispersion | distribution mixing pump Y is demonstrated.
This carbon-containing paste manufacturing method is a paste material used for manufacturing a non-aqueous electrolyte secondary battery electrode as a liquid containing carbon as a solid content, specifically, powder P (solid content). A material that occludes and releases alkali metal ions (for example, LiFePO ₄ ), carbon (for example, carbon black or fibrous carbon powder, the aspect ratio of the fibrous carbon powder is 10 to 1000, and the average fiber diameter is 1. Using carbon (carbon nanotubes) of ~ 500 nm and an aqueous binder (for example, CMC (carboxylmethylcellulose)), using water as the solvent R, and applying shearing force to the liquid, dispersion and mixing of solids It is a manufacturing method of the paste containing carbon provided with the process to perform, Comprising: The said shear force is -0.01--0. It is characterized in applying a negative pressure state in the range of 10 MPa.

Here, the negative pressure state is the pressure in the first introduction chamber 13 and the second introduction chamber 14 measured by the pressure gauge 80 (in this embodiment, the pressure in the first introduction chamber 13 (here, The first introduction chamber 13 and the second introduction chamber 14 have substantially the same pressure when the shutter valve 46 is closed.
That is, in the present embodiment, the fixed amount supply device X is stopped, the shutter valve 46 disposed in the powder discharge pipe 45 is closed, and the suction of the powder P through the powder discharge pipe 45 is stopped. When the dispersive mixing pump Y is operating (when the powder P is not supplied), the pressure in the first introduction chamber 13 and the second introduction chamber 14 is −0.01 to −0.10 MPa, preferably Is the peripheral speed (rotor 5) of the rotor blade 6 of the dispersion mixing pump Y so that a negative pressure state in the range of -0.03 to -0.09 MPa, more preferably -0.04 to -0.08 MPa. Is set to 6 to 80 m / s, preferably 15 to 50 m / s.

  As a result, the solvent R penetrating into the aggregate (so-called lumps) of the powder P is foamed over the entire circumference of the blade chamber 8 to promote the crushing of the aggregate. Dispersion of the powder P is further promoted by the impact force when the bubbles are pressurized and disappeared in the blade chamber 8, and as a result, almost the entire paste F existing around the entire periphery of the blade chamber 8 is covered. Thus, it is possible to more reliably produce a high-quality paste F in which the powder P is well dispersed in the solvent R.

  Thus, a carbon-containing paste can be obtained, but the present invention is manufactured using the carbon-containing paste obtained by the above-described carbon-containing paste manufacturing method and the carbon-containing paste. In addition, the present invention is directed to a nonaqueous electrolyte secondary battery electrode, a nonaqueous electrolyte secondary battery including the nonaqueous electrolyte secondary battery electrode, and a device including the nonaqueous electrolyte secondary battery.

[Example 1]
(High rate discharge test)
Table 1 shows LiFePO ₄ (91 wt%), carbon (carbon black (2 wt%), fiber as materials that occlude and release alkali metal ions, which are paste materials used in the production of electrodes for nonaqueous electrolyte secondary batteries. Carbon (carbon nanotubes) (2 wt%) having an aspect ratio of 10 to 1000 and an average fiber diameter of 1 to 500 nm) and an aqueous binder (CMC (carboxyl methyl cellulose) (5 wt%)) (solid content ratio: 31 wt. %), Water is used as the solvent R, and the result of manufacturing the paste using the dispersion mixing system 100 provided with the dispersion mixing pump Y is shown.
FIG. 10 is an electron micrograph of the electrode surface and electrode cross-section coated with a carbon-containing paste ((a) is a conventional batch-type multi-axis mixer, and (b) is a carbon-containing paste of the present invention. FIG. 11 shows the discharge of a non-aqueous electrolyte secondary battery equipped with a non-aqueous electrolyte secondary battery electrode manufactured using the paste according to the carbon-containing paste manufacturing method of the present invention. The relationship between a rate and an average discharge voltage is shown.
The battery evaluation described above was carried out by applying and drying each paste obtained on an aluminum foil having a thickness of 20 μm, and then closely bonding the aluminum foil and the coating film with a roll press, followed by heat treatment (during decompression) , 150 ° C., 12 hours or longer) to obtain a test electrode (positive electrode capacity density: 1.2 mAh / cm ² ). As the counter electrode, a metal lithium foil having a capacity about 50 times the calculated capacity of the test electrode was used, a glass nonwoven fabric having a thickness of 350 μm was used as the separator, and 1 mol / L LiPF ₆ / EC: DEC (1: A coin cell (CR2032) having 1 vol%) was produced.
As the charge / discharge test conditions, the cut-off potential was set to 4.2 to 2.5 V (vs. Li ⁺ / Li), charged at 0.5 CA in a 30 ° C. environment, and then discharged at a predetermined current.

As is clear from Table 1 and FIGS. 10 and 11, according to the method for producing a carbon-containing paste of the present invention, by applying a shearing force to a liquid containing carbon as a solid content, In the method for producing a carbon-containing paste comprising the steps of dispersing and mixing, by applying the shear force in a negative pressure state in the range of -0.01 to -0.10 MPa, the dispersibility of carbon and the like Even when a substance having poor solubility is contained, a homogeneous paste can be obtained in a short time, and the state in which the solid content is dispersed and mixed can be maintained for a long time. It is possible to produce a carbon-containing paste that can reduce contamination and residue, and a non-aqueous battery produced using the paste according to the carbon-containing paste production method of the present invention. The secondary battery electrode has a small gap and a dense coating formation layer is formed. Furthermore, the nonaqueous electrolyte secondary battery equipped with the nonaqueous electrolyte secondary battery electrode has a discharge rate and an average discharge. It was confirmed that good battery characteristics were exhibited in relation to voltage.
Therefore, it was proved that a nonaqueous electrolyte secondary battery excellent in output characteristics can be obtained by applying the shearing force in a negative pressure state within the above range.

[Example 2]
(High rate discharge test)
Table 2 shows LiFePO ₄ (89 wt%), carbon (carbon black (1.5 wt%) as materials that occlude and release alkali metal ions, which are paste materials used in the manufacture of nonaqueous electrolyte secondary battery electrodes. Carbon (carbon nanofiber) (1.5 wt%), activated carbon (3 wt%) having an aspect ratio of 10 to 500 and an average fiber diameter of 150 nm, and an aqueous binder (acrylic ester (5 wt%)) ) (Solid content ratio: 37 wt%), water is used as the solvent R, and the result of manufacturing the paste using the dispersion mixing system 100 equipped with the dispersion mixing pump Y is shown.
The test electrode (positive electrode) was obtained by applying and drying each obtained paste on an aluminum foil having a thickness of 20 μm, and then closely bonding the aluminum foil and the coating film with a roll press machine, followed by heat treatment (during decompression, 150 ° C. for 12 hours or more) to obtain an electrode having a positive electrode capacity density of 2.1 mAh / cm ² . As the counter electrode, a metal lithium foil having a capacity about 50 times the calculated capacity of the test electrode was used, a glass nonwoven fabric having a thickness of 350 μm was used as the separator, and 1 mol / L LiPF ₆ / EC: DEC (1: A coin cell (CR2032) having 1 vol%) was produced.
As the charge / discharge test conditions, the cut-off potential was set to 4.2 to 2.0 V (vs. Li ⁺ / Li), charged at 0.2 CA in a 30 ° C. environment, and then discharged at a predetermined current.
FIG. 12 shows the discharge capacity of the active material of a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte secondary battery electrode manufactured using the paste according to the method for manufacturing a carbon-containing paste of the present invention, and shearing into the paste. The relationship with the pressure when applying force is shown.
As apparent from FIG. 12, in the low rate discharge (0.2 to 1 CA), the difference in discharge capacity is hardly seen in the pressure to apply the shear force, but in the high rate discharge (3 to 10 CA), the shear force. It can be seen that the pressure to apply is preferably a negative pressure. In particular, the pressure was high in the range of -0.04 to 0.08 MPa, and -0.07 MPa showed the highest capacity. As an example, FIG. 13 shows a high rate discharge curve of a battery obtained in a negative pressure state of −0.07 MPa, which has the best performance.

(Battery enlargement)
A non-aqueous electrolyte secondary battery having a nominal capacity of 1100 Ah was fabricated using a paste obtained by applying the shearing force having the best performance in a negative pressure state of −0.07 MPa.
The test electrode (positive electrode) was prepared by applying and drying the paste on an aluminum foil having a thickness of 20 μm, and then closely bonding the aluminum foil and the coating film with a roll press, followed by heat treatment (under reduced pressure, 150 ° C., 12 hours or more) to obtain a test electrode (positive electrode capacity density: 1 mAh / cm ² ).
As the counter electrode (negative electrode), as the material that occludes and releases alkali metal ions, SiO (79 wt%), carbon (carbon black (1.5 wt%), fibrous carbon powder has an aspect ratio of 10 to 500, average fiber diameter (Carbon nanofiber) (1.5 wt%)) and water-based binder (polyimide (18 wt%)) (solid content ratio: 25 wt%), water as the solvent R, and the above-mentioned dispersion mixing pump Y A paste is produced using a dispersion mixing system 100 equipped with a coating material, and this is applied and dried on a stainless steel foil having a thickness of 10 μm. (Under reduced pressure at 250 ° C. for 2 hours or more), and a metal lithium foil for an irreversible capacity was laminated to the negative electrode (negative electrode capacity density: 2.7 m) h / cm ²⁾ was obtained. The mixing condition of the paste for the counter electrode is obtained by applying in a negative pressure state of -0.05 MPa.
As the battery, an aramid microporous film having a thickness of 20 μm was used as a separator, and a laminate cell having 1 mol / L LiPF ₆ / EC: DEC: EMC (1: 0.7: 0.3 vol%) as an electrolyte was produced. .
As the charge / discharge test conditions, the cut-off potential was set to 4.0-2.0 V, and 19 cycles were charged / discharged at 0.2 CA in a 30 ° C. environment, and aging was performed after 20 cycles. .
FIG. 14 shows a charge / discharge curve of a nonaqueous electrolyte secondary battery having a nominal capacity of 1100 Ah, and FIG. 15 shows cycle life characteristics.
Even when the battery size was increased, stable capacity was maintained and it was confirmed that it was operating normally.

(High temperature durability test of large battery)
A large battery having a nominal capacity of 1100 Ah was manufactured using paste obtained by applying a shearing force in each negative pressure state of -0.003 MPa, -0.053 MPa, and -0.070 MPa. This large battery was charged and discharged at 1 CA in an environment of 60 ° C. to confirm the high temperature durability of the battery. Other conditions not described are the same as those for the large battery.
FIG. 16 shows cycle life characteristics (high temperature durability) at 60 ° C. and 1 CA of a nonaqueous electrolyte secondary battery having a nominal capacity of 1100 Ah.
As is clear from FIG. 16, in a high temperature environment of 60 ° C., the battery in which the paste was mixed in the negative pressure state of −0.070 MPa showed excellent high temperature durability.

Example 3
Table 3 shows LiMn _0.33 Ni _0.33 Co _0.33 O ₂ (91 wt%) as a material that occludes and releases alkali metal ions, which is a paste material used in the manufacture of non-aqueous electrolyte secondary battery electrodes. ), Carbon (carbon black (2 wt%), carbon carbon (carbon nanofiber) (2 wt%) having an aspect ratio of 10 to 500, and an average fiber diameter of 150 nm) and an aqueous binder (acrylic ester (5 wt) %)) (Solid content ratio: 32 wt%), water is used as the solvent R, and the result of manufacturing the paste using the dispersion mixing system 100 equipped with the dispersion mixing pump Y is shown.

The test electrode (positive electrode) was obtained by applying and drying each obtained paste on an aluminum foil having a thickness of 20 μm, and then closely bonding the aluminum foil and the coating film with a roll press machine, followed by heat treatment (during decompression, 150 ° C. for 12 hours or more) to obtain an electrode having a positive electrode capacity density of 1.5 mAh / cm ² . As a counter electrode, a metal lithium foil having a capacity about 50 times the test electrode calculated capacity is used, a polyethylene microporous film having a thickness of 25 μm is used as a separator, and 1 mol / L LiPF ₆ / EC: DEC ( A coin cell (CR2032) having 1: 1 vol% was produced.
As the charge / discharge test conditions, the cut-off potential was set to 4.2-2.0 V (vs. Li ⁺ / Li), charged at 0.5 CA in a 30 ° C. environment, and then discharged at a predetermined current.

FIG. 17 shows the relationship between the discharge rate and the discharge capacity of a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte secondary battery electrode manufactured using the paste according to the method for manufacturing a carbon-containing paste of the present invention. FIG. 18 shows the relationship between the discharge rate and the average discharge voltage.
As is clear from FIG. 17 and FIG. 18, in low rate discharge (0.5 to 1 CA), it is difficult to see the difference in discharge capacity with the pressure to apply shear force, but when high rate discharge (3 to 5 CA) is achieved. The difference increases. It can be seen that the pressure for applying the shearing force is preferably in the range of -0.06 to 0.89 MPa even if it is a negative pressure. It can also be seen that the average discharge voltage is preferably in the range of -0.06 to 0.89 MPa. In particular, the battery having a pressure of -0.089 MPa exhibited the highest capacity and the highest average discharge voltage. As an example, FIG. 19 shows a high-rate discharge curve of a battery obtained in a negative pressure state of −0.089 MPa, which has the best performance.

  As mentioned above, although the manufacturing method of the paste containing the carbon of this invention was demonstrated based on the embodiment, this invention is not limited to description of the said embodiment, In the range which does not deviate from the meaning The configuration can be changed as appropriate.

  The method for producing a carbon-containing paste of the present invention can obtain a homogeneous paste in a short time even when containing a substance having poor dispersibility and solubility such as carbon, and the solid content is dispersed. The mixed state can be maintained for a long time, and moreover, since it is possible to reduce the mixing and remaining of bubbles in the paste, it is suitable for use in the production of pastes used in the production of electrodes for non-aqueous electrolyte secondary batteries. Can do.

DESCRIPTION OF SYMBOLS 1 Casing 5 Rotor 6 Rotary blade 6a Back part 7 Stator 7a Restriction flow path (through-hole)
7b Restricted flow path (through hole)
8 Wing chamber (exit area)
9 Scraping blade 10 Annular groove 11 First supply part 12 Discharge part (exit area)
13 1st introduction chamber 14 2nd introduction chamber 14a Restriction part 15 Partition plate 16 Circulation flow path 16P Circulation pump 17 Second supply part 22 Discharge path 50 Solvent supply part 51 Storage mixing tank 52 Supply pipe 52P Delivery pump 60 Mixing Mechanism (Supply mechanism)
70 Recirculation mechanism part 71 Cylindrical container (separation part)
80 Pressure gauge 100 Dispersion mixing system Y Dispersion mixing pump F Paste Fp Preliminary mixture Fr Undispersed paste P Powder (solid content)
R solvent (liquid phase dispersion medium)
G Air (gas)

Claims (5)

A method for producing a paste containing carbon comprising a step of dispersing and mixing a solid content by applying a shearing force to a liquid containing a solvent and a carbon powder as a solid content,
In a negative pressure state in the range of -0.04 to -0.08 MPa, the peripheral speed of the rotating blade that is a stirring member is stirred at 6 to 80 m / s, and the scraped blade that rotates integrally with the rotating blade is When the tip and the solvent introduced into the annular groove are scraped by the tip of the scraping blade, the tip and the solvent are arranged so as to be able to circulate while entering the annular groove provided in the casing. A method for producing a paste containing carbon, wherein the shear force is applied and the powder and the solvent are mixed in a negative pressure state. A method for producing a carbon-containing paste comprising a step of dispersing and mixing a solid content by applying a shear force to a liquid containing a solvent and a carbon powder as a solid content, wherein the shear force is , Applied in a negative pressure state in the range of -0.04 to -0.08 MPa,
The stirring member is a rotor blade, and a rotor provided with the rotor blade is disposed concentrically inside a cylindrical casing, and the rotor provided with the rotor blade is driven to rotate, whereby the solid content and the The solvent is sucked into the first introduction chamber formed inside the cylindrical casing through the first supply unit, stirred by the rotary blade, discharged from the discharge unit through the discharge chamber, and discharged. The liquid discharged from the part is circulated to the second supply part via the circulation channel, and is formed by partitioning the first introduction chamber and the partition plate from the second supply part into the inside of the cylindrical casing. The air was sucked into the second introduction chamber, passed through the throttle channel formed in the stator, stirred by the rotary blade, discharged from the discharge portion through the discharge chamber, and further discharged from the discharge portion. Circulate the liquid through the circulation channel to the second supply section Using a dispersion mixing pump which is adapted,
The scraping blade that rotates integrally with the rotary blade is arranged to be able to circulate in a state in which the tip portion enters the annular groove provided in the casing, and the powder and the solvent introduced into the annular groove are: A method for producing a carbon-containing paste , wherein the shearing force is applied when scraped by the tip of the scraping blade .   The method for producing a carbon-containing paste according to claim 1, wherein the liquid contains a material that occludes and releases alkali metal ions in the solid content.   The said liquid uses water as a solvent, The manufacturing method of the paste containing the carbon of any one of Claims 1-3 characterized by the above-mentioned. The said carbon contains fibrous carbon powder, The aspect-ratio of this fibrous carbon powder is 10-1000, and an average fiber diameter is 1-500 nm, The any one of Claims 1-4 characterized by the above-mentioned. A method for producing a paste containing carbon.

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