JPWO2013118758A1 - Electrochemical device electrode composite particle manufacturing apparatus and electrochemical device electrode composite particle manufacturing method - Google Patents

Abstract

1 or 2 or more supply port for supplying the raw material which comprises the composite particle for electrochemical element electrodes which is an apparatus for manufacturing the composite particle for electrochemical element electrodes containing an electrode active material and a binder And a granulating part for granulating the raw material supplied from the supply part, and the supply part removes particulate foreign matters contained in the raw material supplied from the supply part There is provided an apparatus for producing composite particles for an electrochemical element electrode, characterized by having foreign matter removing means for the purpose.

Description

  The present invention relates to an apparatus for producing composite particles for electrochemical element electrodes and a method for producing composite particles for electrochemical element electrodes.

  The demand for electrochemical devices such as lithium-ion secondary batteries, electric double-layer capacitors, and lithium-ion capacitors is rapidly expanding by taking advantage of the small size, light weight, high energy density, and the ability to repeatedly charge and discharge. doing. Lithium ion secondary batteries have a relatively high energy density and are used in mobile fields such as mobile phones and notebook personal computers. On the other hand, since the electric double layer capacitor can be rapidly charged and discharged, the electric double layer capacitor is expected to be used as an auxiliary power source for an electric vehicle or the like in addition to being used as a memory backup small power source for a personal computer or the like. Furthermore, the lithium ion capacitor that takes advantage of the lithium ion secondary battery and the electric double layer capacitor has higher energy density and output density than the electric double layer capacitor, and therefore the electric double layer capacitor is used for the application, and the electric double layer. Application to applications that could not meet the specifications for capacitor performance is being considered. Among these, in particular, lithium ion secondary batteries have been studied for application not only to in-vehicle applications such as hybrid electric vehicles and electric vehicles, but also to power storage applications.

  While expectations for these electrochemical devices have increased, these electrochemical devices have further improvements such as lower resistance, higher capacity, and improved mechanical properties and productivity as applications expand and develop. It has been demanded. Under such circumstances, there is a demand for a more productive manufacturing method for electrochemical element electrodes, and there are various manufacturing methods capable of high-speed molding and various electrochemical element electrode materials suitable for the manufacturing method. Improvements have been made.

  Electrodes for electrochemical devices usually have an electrode active material layer (electrode mixture layer) formed by binding an electrode active material and a conductive material used as necessary with a binder on a current collector. It is formed by stacking. As a method for forming such an electrode active material layer, Patent Document 1 discloses an aqueous slurry containing electrode active material, rubber particles, and water as a dispersion medium, and spray-drying the obtained aqueous slurry. A method is disclosed in which a particulate electrode material (composite particle) is obtained, and an electrode active material layer (electrode mixture layer) is formed by a dry molding method using the obtained electrode material.

Japanese Patent No. 4219705

However, the electrode mixture layer forming method described in Patent Document 1 is smaller in production facility scale and production than the current method of applying slurry to a current collector as an electrode manufacturing method for electrochemical devices. Overall productivity, such as speed, is improved, but process failures such as the current collector or transport substrate breaking in the dry molding process occasionally occur, and even if productivity is improved, stable operation may not be ensured. I found out.
Therefore, an object of the present invention is to provide a composite particle manufacturing apparatus used for manufacturing an electrochemical element electrode by a dry molding method, which suppresses the above-mentioned process defects and has an excellent balance between productivity and stable operability. To do.

  As a result of diligent research to solve the above problems, the present inventor compresses electrochemical element electrode composite particles (hereinafter sometimes simply referred to as composite particles) using a pair of rolls in a dry molding process. In the process, it was found that the particulate foreign matter derived from the raw material or the process constituting the composite particle mixed in the composite particle damages the current collector or the conveyance base material, or causes a problem such as breakage due to the bite. It has been found that the above problem can be solved by providing means for removing particulate foreign substances derived from raw materials or processes constituting the composite particles in the supply section of the particle production apparatus, and the present invention has been completed.

  That is, according to the present invention, there is provided a manufacturing apparatus for manufacturing composite particles for electrochemical element electrodes containing an electrode active material and a binder, in order to supply a raw material constituting the composite particles for electrochemical element electrodes A supply unit that provides one or more supply ports, and a granulating unit that granulates the raw material supplied from the supply unit, the supply unit containing the raw material supplied from the supply unit There is provided an apparatus for producing composite particles for electrochemical element electrodes, characterized in that it has means for removing particulate foreign matters.

In the apparatus for producing composite particles for electrochemical element electrodes of the present invention, the granulation part can be configured to granulate the raw material by a fluidized bed drying granulation method or a spray drying granulation method.
In the apparatus for producing composite particles for electrochemical element electrodes of the present invention, the particulate foreign matter removing means may be configured to be provided in two or more with respect to one supply port.

  According to the present invention, when the raw material is supplied to the granulating means for granulating the raw material constituting the composite particle for an electrochemical element electrode, the raw material is subjected to foreign matter removal by the foreign matter removing means and then granulated means. Can prevent foreign matter from being mixed into the resulting composite particles for electrochemical element electrodes, thereby suppressing poor operation in the process of dry forming the composite particles for electrochemical element electrodes. The balance between productivity and stability in the electrochemical element electrode manufacturing process can be increased.

FIG. 1 is a schematic view showing an apparatus for producing composite particles for electrochemical element electrodes according to an embodiment of the present invention. FIG. 2 is a schematic view showing an apparatus for producing composite particles for electrochemical device electrodes according to another embodiment of the present invention.

  Hereinafter, an apparatus for producing composite particles for electrochemical element electrodes and a method for producing composite particles for electrochemical element electrodes according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing an outline of an electrochemical device electrode composite particle manufacturing apparatus 10 according to an embodiment of the present invention.

  The electrochemical device electrode composite particle manufacturing apparatus 10 shown in FIG. 1 uses an electrochemical device electrode composite particle for manufacturing electrochemical device electrode composite particles by a spray-drying granulation method. It is an apparatus for manufacturing. Although details of the composite particle slurry will be described later, it usually contains at least an electrode active material, a binder, and a solvent, which are raw materials of the composite particle for electrochemical element electrodes.

  As shown in FIG. 1, in the composite particle manufacturing apparatus 10 for electrochemical device electrodes according to an embodiment of the present invention, the slurry for composite particles can be stored in a hopper 11 and stored in the hopper 11. The composite particle slurry is sent to the spraying device 15 provided at the top of the drying tower 16 by the pump 12 and sprayed into the drying tower 16 from the spraying device 15. Further, when spraying the composite particle slurry into the drying tower 16, the hot air for drying is sent from the side of the spraying device 15 into the drying tower 16 through the heat exchanger 14. Thereby, the slurry for composite particles is spray-dried and granulated. The electrochemical element electrode composite particles obtained by spray-drying granulation are taken out from the drying tower 16 to the outside of the electrochemical element electrode composite particle production apparatus 10 by a suction device 17.

  Although it does not specifically limit as the spraying apparatus 15 for spraying the slurry for composite particles, For example, an atomizer is mentioned. There are two types of atomizers: a rotating disk system and a pressurizing system. In the rotating disk system, slurry is introduced almost at the center of a disk that rotates at high speed, and the slurry is removed from the disk by the centrifugal force of the disk. In this case, the slurry is atomized. In the rotating disk system, the rotational speed of the disk depends on the size of the disk, but is usually 5,000 to 30,000 rpm, preferably 15,000 to 30,000 rpm. The lower the rotational speed of the disk, the larger the spray droplets and the larger the average particle size of the resulting composite particles. Examples of the rotating disk type atomizer include a pin type and a vane type. A pin-type atomizer is a type of centrifugal spraying device that uses a spraying plate, and the spraying plate has a plurality of spraying rollers removably mounted on a concentric circle along its periphery between upper and lower mounting disks. It consists of The slurry for composite particles is introduced from the center of the spray disk, adheres to the spray roller by centrifugal force, moves outward on the roller surface, and finally sprays away from the roller surface. Further, the vane atomizer is formed so that a slit is cut on the inner side of the spray disc, and the composite particle slurry is sprayed by passing through the slit. On the other hand, the pressurization method is a method in which the composite particle slurry is pressurized and sprayed from the nozzle to be dried, and examples thereof include a pressurization nozzle method, a two-fluid nozzle method, and a four-fluid nozzle method.

  In addition, although the temperature of the slurry for composite particles sprayed from the spraying apparatus 15 is usually room temperature, it may be heated to a temperature higher than room temperature. Moreover, the temperature of the hot air for drying is 80-250 degreeC normally, Preferably it is 100-200 degreeC.

  As shown in FIG. 1, in the electrochemical device electrode composite particle manufacturing apparatus 10 according to an embodiment of the present invention, a foreign substance removing means 30 is provided in a pipe from the pump 12 to the spraying apparatus 15. Yes. Therefore, since the composite particle slurry supplied from the hopper 11 passes through the foreign material removing means 30 and is supplied to the spraying device 15, the particulate foreign material is added to the composite particle slurry stored in the hopper 11. Can be removed by the action of the foreign matter removing means 30. Thereby, the slurry for composite particles supplied to the spraying device 15 can be made substantially free of particulate foreign matter, and the spraying device 15 does not substantially contain particulate foreign matter. The drying tower 16 can be sprayed. And as a result, it can prevent appropriately that a particulate foreign material will be contained in the composite particle for electrochemical element electrodes obtained by carrying out spray-drying granulation of the slurry for composite particles.

  The state in which particulate foreign matter is contained in the composite particle slurry is a state in which particulate foreign matter is contained in the solvent constituting the composite particle slurry or an electrode active material constituting the composite particle slurry. This includes all the states that can be collected by the foreign matter removing means 30 in the present invention, such as a case where particulate foreign matter is taken into the aggregate or binder.

  In addition, although it does not specifically limit as a target of the particulate foreign material removed by the foreign material removal means 30, A metal powder, ceramic powder, etc. are mentioned typically as a thing with high mixing probability.

  Among these particulate foreign matters, foreign matter having an acute angle portion in its shape and having a Vickers hardness of 100 Hv or more easily breaks the current collector or the conveying substrate in the dry molding process. A structure that can remove these particulate foreign substances more intensively is preferable.

  Here, the “particulate” in the particulate foreign matter is the ratio of the long axis (the longest distance in the foreign matter) to the short axis (the shortest distance in the foreign matter) when the foreign matter form is observed. The form of the foreign material in which the represented aspect ratio is 5 or less is shown. The aspect ratio of the foreign matter can be obtained by collecting the foreign matter, observing it with a particle diameter / particle shape characteristic evaluation apparatus FPIA-3000 (manufactured by Sysmex Corporation), and analyzing the image.

  Further, in the case where the particulate foreign matter has an acute angle portion, the “acute angle portion” that the particulate foreign matter has is a point on the projected contour line of the particulate foreign matter as an intersection, and other than the one point on the same contour line. Two tangents circumscribing the outline can be drawn with the other two points as contact points, and the inner angle of the intersection formed by the two tangents is 90 ° or less. It is a part, and when it has such a part, it can be judged that a particulate foreign material has an acute angle part.

  Whether the particulate foreign matter has an acute angle portion can be determined by collecting the foreign matter as described above and analyzing the particulate foreign matter using an image analysis apparatus. The image analysis apparatus used for analyzing the particulate foreign matter is not particularly limited, and examples thereof include a scanning electron microscope with an image analysis function.

  Further, the Vickers hardness is a value obtained by collecting particulate foreign matter and measuring it using a micro hardness tester HMV-2T (manufactured by Shimadzu Corporation).

  As a foreign substance removal means for removing ceramic powder, removal by a filter is preferable. If the filter mesh is too large, ceramic powder as particulate foreign matter cannot be removed, which is not preferable. On the other hand, if the mesh is too fine, the pressure loss increases, resulting in problems such as poor liquid feed of the composite particle slurry. Therefore, the filter mesh is preferably in the range of 45 μm to 1000 μm, more preferably 75 μm to 300 μm, and most preferably 75 μm to 200 μm.

As a metal powder as an example of the particulate foreign matter having a high mixing probability, stainless steel powder and iron powder mixed due to wear of stainless steel and the like are typically exemplified. The size of these particulate foreign substances varies, but generally there are many that are 100 μm or less. Therefore, if such fine powder is to be removed with a filter in the same manner as ceramic powder, it is necessary to make the mesh finer, and as described above, liquid composite slurry is likely to be poorly fed due to an increase in pressure loss. Therefore, it is not preferable.
Therefore, it is preferable to employ a removing means utilizing the magnetic properties of the foreign matter as the foreign matter removing means for removing the metal powder, particularly stainless steel powder and iron powder. Examples of means for removing foreign matter using magnetism include a magnet strainer and an electromagnet. The magnetic flux density for adsorbing and removing foreign substances is preferably set to a magnetic flux density that removes only the particulate foreign metal foreign substances without adsorbing the necessary components of the composite particle slurry.

  When the particulate foreign matter removing means is not performed, when the particulate foreign particles having the aforementioned acute angle and having a Vickers hardness of 100 Hv or more are mixed in the composite particle slurry, a dry molding which is a subsequent process is performed. There is a risk that the spraying device 15 and the drying tower 16 may be damaged and damaged, as well as causing a process failure such as breaking the current collector or the conveyance substrate in the process. In this case, the spraying device 15 and the drying tower 16 need to be repaired, which is not preferable for production. Further, when the atomizer of the spraying device is a pressure nozzle type, the mixed particulate foreign matter may cause the nozzle tip to be clogged (nozzle clogging), resulting in an operational failure such as poor liquid feeding. On the other hand, in the present invention, by using the foreign matter removing means 30, when the foreign particles are contained in the composite particle slurry, the particulate foreign matter can be removed. It becomes possible to remove the particulate foreign matters which are particularly problematic in the manufacturing process of the electrochemical element electrode by the conventional dry molding method.

  And, due to such effects, various process failures such as breakage of the current collector or transport substrate most frequently generated in the electrochemical element electrode manufacturing process by the dry molding method using composite particles, liquid feeding failure in the composite particle manufacturing process, etc. Generation | occurrence | production can be suppressed and it becomes possible to highly balance productivity and stable operativity in an electrochemical element electrode manufacturing process.

  In the example of the composite element manufacturing apparatus 10 for electrochemical element electrodes shown in FIG. 1, the mode in which the foreign matter removing means 30 is provided in the pipe from the pump 12 to the spraying apparatus 15 is exemplified. There is no particular limitation as long as it is configured to pass through the foreign matter removing means 30 before being supplied to the spraying device 15. For example, the foreign matter removing means 30 may be provided in a pipe from the hopper 11 to the pump 12, or inside the hopper 11 (for example, a storage port for storing the composite particle slurry in the hopper 11, the hopper 11 The foreign matter removing means 30 may be provided at the outlet of the Further, from the viewpoint of improving the removal efficiency of particulate foreign matters, two or more foreign matter removing means 30 may be installed between the hopper 11 and the spraying device 15, and in this case, a plurality of two or more installed foreign matter removing means 30 may be installed. The specifications such as the capability and mechanism of the foreign matter removing means 30 may be the same or different. Further, in the present invention, in order to remove particulate foreign matter mixed from the hot air for drying supplied from the pump 13 via the heat exchanger 14, the foreign matter is also applied to the piping from the heat exchanger 14 to the drying tower 16. The removing means 30 may be additionally provided.

  As described above, when the foreign material removing means 30 is applied to the electrochemical device electrode composite particle manufacturing apparatus 10, particulate foreign materials are contained in the electrochemical device electrode composite particles as an effect of the present invention. In addition, it is possible to suppress poor operation in the electrochemical element electrode manufacturing process by the dry molding method. In order to feel the effect more, it is preferable to remove the particulate foreign matter so as to be 100 ppm by weight or less with respect to the composite particles for electrochemical element electrodes. More preferred is 50 ppm by weight or less, and most preferred is 20 ppm by weight or less. In particular, the mixing ratio of particulate foreign substances having an acute angle portion can be preferably 50 ppm by weight or less, more preferably 20 ppm by weight or less, and still more preferably 10 ppm by weight or less.

(Slurry for composite particles)
Next, the composite particle slurry used to produce the electrochemical device electrode composite particles using the electrochemical device electrode composite particle production apparatus 10 shown in FIG. 1 will be described.
The slurry for composite particles used in the present invention contains an electrode active material, a binder and a solvent, and may contain other dispersants, conductive materials and additives as necessary.

The electrode active material used in the present invention is appropriately selected depending on the kind of electrode for electrochemical device to be produced. For example, when the electrochemical device electrode to be produced is a positive electrode for a lithium ion secondary battery, examples of the positive electrode active material include metal oxides capable of reversibly doping and dedoping lithium ions. Examples of the metal oxide include lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, lithium iron vanadate, nickel-manganese-lithium cobaltate, nickel-cobalt acid. Lithium, nickel-lithium manganate, iron-lithium manganate, iron-manganese-lithium cobaltate, lithium iron silicate, iron silicate-manganese lithium, vanadium oxide, copper vanadate, niobium oxide, titanium sulfide, molybdenum oxide, molybdenum sulfide , Etc. In addition, the positive electrode active material illustrated above may be used alone according to the application, or a plurality of types may be mixed and used. Furthermore, polymers such as polyacetylene, poly-p-phenylene, and polyquinone are also included. Of these, it is preferable to use a lithium-containing metal oxide.
Here, in the present invention, dope means occlusion, support, adsorption or insertion, and is defined as a phenomenon in which lithium ions and / or anions enter the positive electrode, or a phenomenon in which lithium ions and / or cations enter the negative electrode. De-doping also means release, desorption, and desorption, and is defined as the reverse phenomenon of the dope.

  In addition, when the manufactured electrode for an electrochemical device is a negative electrode as a counter electrode of the positive electrode for the lithium ion secondary battery described above, as the negative electrode active material, graphitizable carbon, non-graphitizable Low crystalline carbon (amorphous carbon) such as carbon, activated carbon, pyrolytic carbon, graphite (natural graphite, artificial graphite), carbon nanowall, carbon nanotube, or composite carbon material of carbon with different physical properties, Examples thereof include alloy materials such as tin and silicon, oxides such as silicon oxide, tin oxide, vanadium oxide and lithium titanate, and polyacene. In addition, the electrode active material illustrated above may be used independently according to a use, and may be used in mixture of multiple types.

The shape of the electrode active material for a lithium ion secondary battery electrode is preferably a granulated particle. When the shape of the particles is spherical, a higher density electrode can be formed during electrode molding. The volume average particle size of the positive electrode active material and the negative electrode active material for a lithium ion secondary battery is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0 for both the positive electrode active material and the negative electrode active material. .8 to 20 μm. Furthermore, the tap density of the positive electrode active material and the negative electrode active material for the lithium ion secondary battery is not particularly limited, but those having a positive electrode density of 2 g / cm ³ or more and a negative electrode of 0.6 g / cm ³ or more are preferably used. .

  Or when the electrode for electrochemical devices to be manufactured is a positive electrode of a lithium ion capacitor, the active material for the positive electrode is activated carbon, polyacene organic semiconductor capable of reversibly doping and dedoping anions and / or cations. (PAS), carbon nanotube, carbon whisker, graphite, graphene and the like. Among these, activated carbon, carbon nanotube, and graphene are preferable.

  Moreover, when the electrode for electrochemical devices to be manufactured is a negative electrode as a counter electrode of the positive electrode of the lithium ion capacitor described above, the negative electrode active material is exemplified as a negative electrode active material for a lithium ion secondary battery. Any material can be used.

The volume average particle diameter of the positive electrode active material and the negative electrode active material for a lithium ion capacitor is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, and more preferably 0.8 to 20 μm. Moreover, when using activated carbon as a positive electrode active material for lithium ion capacitors, the specific surface area of activated carbon is 30 m ² / g or more, preferably 500 to 3,000 m ² / g, more preferably 1,500 to 2,600 m ^2. / G. The capacitance per unit weight of activated carbon tends to increase as the specific surface area increases up to about 2,000 m ² / g, but thereafter the capacitance does not increase so much. The density of the material layer tends to decrease, and the capacitance density tends to decrease. Moreover, it is preferable in terms of rapid charge / discharge characteristics, which is a feature of a lithium ion capacitor, that the pore size of the activated carbon is compatible with the size of the electrolyte ion. Therefore, an electrode mixture layer having desired capacity density and input / output characteristics can be obtained by appropriately selecting an electrode active material.

  Moreover, when the electrode for electrochemical elements to be produced is a positive electrode or a negative electrode for an electric double layer capacitor, the positive electrode active material and the negative electrode active material are exemplified as the above-described positive electrode active material for a lithium ion capacitor. Any of the materials made can be used.

  The binder used in the present invention is not particularly limited as long as it is a compound capable of binding the above-mentioned electrode active materials to each other, but in the present invention, a dispersion type binder having a property of being dispersed in a solvent is preferable. . Examples of the dispersion type binder include high molecular compounds such as silicon polymers, fluorine-containing polymers, conjugated diene polymers, acrylate polymers, polyimides, polyamides, and polyurethanes. A containing polymer, a conjugated diene polymer, and an acrylate polymer are preferable, and a conjugated diene polymer and an acrylate polymer are more preferable.

  The conjugated diene polymer is a homopolymer of a conjugated diene or a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene, or a hydrogenated product thereof. The ratio of the conjugated diene in the monomer mixture is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more. Specific examples of conjugated diene polymers include conjugated diene homopolymers such as polybutadiene and polyisoprene; aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR) A vinyl cyanide / conjugated diene copolymer such as acrylonitrile / butadiene copolymer (NBR); hydrogenated SBR, hydrogenated NBR, and the like.

The acrylate polymer has a general formula (1): CH ₂ = CR ¹ -COOR ² (wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group or a cycloalkyl group, and R ² further represents An ether group, a hydroxyl group, a carboxylic acid group, a fluorine group, a phosphoric acid group, an epoxy group, and an amino group.), A polymer containing a monomer unit derived from a compound represented by , A homopolymer of the compound represented by the general formula (1), or a copolymer obtained by polymerizing a monomer mixture containing the compound represented by the general formula (1). Specific examples of the compound represented by the general formula (1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylate n. -Butyl, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isopentyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as isodecyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and tridecyl (meth) acrylate; butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate , (Meth) acrylic acid methoxydipropylene group Ether, methacrylic acid (meth) acrylic acid ester, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid phenoxyethyl, ether group-containing (meth) acrylic acid ester such as tetrahydrofurfuryl (meth) acrylate; (meth) acrylic acid-2-hydroxyethyl, Hydroxyl-containing (meth) acrylic such as (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxy-3-phenoxypropyl, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid Acid ester; 2- (meth) acryloyloxyethylphthalic acid, carboxylic acid-containing (meth) acrylic acid ester such as 2- (meth) acryloyloxyethylphthalic acid; Fluorine such as perfluorooctylethyl (meth) acrylate Group-containing (meth) acrylic acid ester; (meth) acrylic Phosphoric acid group-containing (meth) acrylic acid ester such as ethyl acid phosphate; Epoxy group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate; Amino group containing such as dimethylaminoethyl (meth) acrylate (meta ) Acrylic acid ester;

These (meth) acrylic acid esters can be used alone or in combination of two or more. Among these, (meth) acrylic acid alkyl ester is preferable, and methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and alkyl groups have 6 to 12 carbon atoms. (Meth) acrylic acid alkyl ester is more preferred. By selecting these, it becomes possible to reduce the swellability with respect to the electrolytic solution, and to improve the cycle characteristics.
Furthermore, acrylate polymers include, for example, carboxylic acid esters having two or more carbon-carbon double bonds, aromatic vinyl monomers, amide monomers, olefins, diene monomers, Copolymerizable monomers such as vinyl ketones and heterocyclic ring-containing vinyl compounds can also be copolymerized. Further, an α, β-unsaturated nitrile compound or a vinyl compound having an acid component can be copolymerized.

  The content ratio of the (meth) acrylic acid ester unit in the acrylate polymer is preferably 50 to 95% by weight, more preferably 60 to 90% by weight. By setting the content ratio of the (meth) acrylic acid ester unit within the above range, the flexibility of the electrode for an electrochemical element of the present invention can be improved, and the resistance to cracking can be increased.

  The acrylate polymer may be a copolymer of the above-described (meth) acrylic acid ester and a monomer copolymerizable therewith. As such a copolymerizable monomer, Examples thereof include an α, β-unsaturated nitrile compound and a vinyl compound having an acid component.

  Examples of the α, β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-bromoacrylonitrile and the like. These may be used alone or in combination of two or more. Among these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable.

  The content ratio of the α, β-unsaturated nitrile compound unit in the acrylate polymer is usually 0.1 to 40% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20 parts by weight. is there. By setting the content ratio of the α, β-unsaturated nitrile compound unit in the above range, the binding force as the binder can be further increased.

  Examples of the vinyl compound having an acid component include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid. These may be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid and itaconic acid are preferable, methacrylic acid and itaconic acid are more preferable, and it is particularly preferable to use methacrylic acid and itaconic acid in combination.

  The content ratio of the vinyl compound unit having an acid component in the acrylate polymer is preferably 1 to 10% by weight, more preferably 1.5 to 5.0% by weight. By making the content rate of the vinyl compound unit which has an acid component into the said range, stability at the time of setting it as a slurry can be improved.

  Further, the acrylate polymer may be a copolymer of other monomers copolymerizable with the above-described monomers. Examples of such other monomers include 2 Carboxylic acid esters having two or more carbon-carbon double bonds, aromatic vinyl monomers, amide monomers, olefins, diene monomers, vinyl ketones, heterocyclic ring-containing vinyl compounds, etc. It is done.

  The shape of the dispersion type binder used in the present invention is not particularly limited, but is preferably particulate. By being particulate, the binding property is good, and it is possible to suppress deterioration of the capacity of the manufactured electrode and deterioration due to repeated charge and discharge. Examples of the particulate binder include those in which binder particles such as latex are dispersed in water, and particulates obtained by drying such a dispersion.

  The volume average particle diameter of the dispersion type binder used in the present invention is preferably 0.001 to 100 μm, more preferably 10 to 1000 nm, and still more preferably 50 to 500 nm. By making the average particle diameter of the dispersed binder particles used in the present invention within the above range, the strength and flexibility as the electrode for an electrochemical device of the present invention can be improved while making the slurry stable. It becomes good.

  The content of the binder is usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight based on 100 parts by weight of the electrode active material. . When the binder content is within this range, sufficient adhesion between the electrode mixture layer and the current collector can be secured, and the internal resistance can be lowered.

  The composite particle slurry used in the present invention is produced by dispersing the above-described electrode active material and binder in a solvent. In this case, when the binder is dispersed in water as a dispersion medium, it can be added in a state dispersed in water. As the solvent, water is most preferably used, but an organic solvent can also be used. Examples of the organic solvent include alkyl alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; alkyl ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; diethylformamide, dimethylacetamide and N-methyl- Examples include amides such as 2-pyrrolidone and dimethylimidazolidinone, but alkyl alcohols are preferred. When an organic solvent having a boiling point lower than that of water is used in combination, the drying rate can be increased during granulation. In addition, when an organic solvent having a lower boiling point than water is used in combination, the dispersibility of the binder or the solubility of the soluble resin is changed, and the viscosity and fluidity of the slurry can be adjusted depending on the amount or type of the solvent, thereby improving the production efficiency. Can be made.

  Moreover, in addition to an electrode active material, a binder, and a solvent, you may make a slurry for composite particles contain a electrically conductive material and a dispersing agent as needed.

  The conductive material may be any particulate material having electrical conductivity, and specific examples of the conductive material include furnace black, acetylene black, and ketjen black (registered trademark of Akzo Nobel Chemicals Bethloten Fennaut Shap). And conductive carbon black. Among these, acetylene black and ketjen black are preferable. The average particle diameter of the conductive material is not particularly limited, but is preferably smaller than the average particle diameter of the electrode active material, usually 0.001 to 10 μm, more preferably 0.05 to 5 μm, and still more preferably 0.01. It is in the range of ˜1 μm. When the average particle diameter of the conductive material is within the above range, sufficient conductivity can be expressed with a smaller amount of use. When the conductive material is added, the content ratio of the conductive material is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 15 parts by weight, and still more preferably 1 to 100 parts by weight of the electrode active material. -10 parts by weight. By setting the content ratio of the conductive material in the above range, the internal resistance can be sufficiently reduced while keeping the capacity of the obtained electrochemical element high.

  Further, the dispersant is a component having an action of uniformly dispersing each component in a solvent when obtaining a composite particle slurry. Specific examples of the dispersant include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose and hydroxypropylcellulose, and ammonium salts or alkali metal salts thereof, alginates such as propylene glycol alginate, and alginates such as sodium alginate. , Polyacrylic acid, and polyacrylic acid (or methacrylic acid) salts such as sodium polyacrylic acid (or methacrylic acid), polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polycarboxylic acid, oxidized starch, phosphoric acid starch , Casein, various modified starches, chitin, chitosan derivatives and the like. These dispersants can be used alone or in combination of two or more. Among these, a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable. The amount of these dispersants used is not particularly limited as long as the effect of the present invention is not impaired, but is usually 0.1 to 10 parts by weight, preferably 0, with respect to 100 parts by weight of the electrode active material. .5 to 5 parts by weight, more preferably 0.8 to 2 parts by weight.

  In addition, the method or procedure for dispersing or dissolving the electrode active material and the binder (and optional components such as a conductive material and a dispersant added as necessary) in a solvent is not particularly limited. , And a binder (and optional components such as a conductive material and a dispersant added if necessary), a method of mixing, a binder (for example, latex) dispersed in a solvent after the dispersant is dissolved in the solvent Add and mix, and finally add electrode active material (and optional components such as conductive materials and dispersants added if necessary) and mix, electrode active material (and add if necessary) Examples thereof include a method in which an optional component such as a conductive material and a dispersing agent is added and mixed, and a binder dispersed in a solvent is added thereto and mixed. Examples of the mixing apparatus include mixing equipment such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer. Mixing is usually performed in the range of room temperature to 80 ° C. for 10 minutes to several hours.

  The viscosity of the composite particle slurry is preferably in the range of 10 to 3,000 mPa · s, more preferably 30 to 1,500 mPa · s, and still more preferably 50 to 1,000 mPa · s at room temperature. When the viscosity of the slurry for composite particles is within this range, the productivity of composite particles for electrochemical device electrodes by spray drying granulation can be increased.

(Composite particles for electrochemical device electrodes)
The composite particle for an electrochemical element electrode of the present invention can be manufactured by using the above-described composite particle slurry by the electrochemical element electrode composite particle manufacturing apparatus 10 according to an embodiment of the present invention shown in FIG. it can. That is, the composite particle slurry described above is supplied to the hopper 11, and the composite particle slurry is sprayed onto the drying tower 16 by the spray device 15, whereby the composite particle slurry is spray dried and granulated. be able to. In this case, the electrochemical device electrode composite particle manufacturing apparatus 10 according to an embodiment of the present invention shown in FIG. 1 is provided with a foreign substance removing means 30 in a pipe from the pump 12 to the spraying device 15. Therefore, when particulate foreign matter is contained in the composite particle slurry, such particulate foreign matter can be removed by the foreign matter removing means 30, thereby causing an operation failure in the manufacturing process of the electrochemical element electrode. Can be effectively suppressed.

  In addition, the electrochemical device electrode composite particles of the present invention are produced by using the composite particle slurry described above, and the electrochemical device electrode composite particle manufacturing apparatus 10 according to one embodiment of the present invention shown in FIG. Therefore, it can have the following structure.

  That is, the composite particle for an electrochemical element electrode of the present invention is obtained by granulation using an electrode active material as a raw material, a binder, and a conductive material and a dispersant added as necessary, and at least an electrode An active material and a binder are included, but each of these does not exist individually as independent particles, but one particle is formed by two or more components including an electrode active material and a binder as constituent components. . Specifically, a plurality of these two or more individual particles are combined to form secondary particles, and a plurality (preferably several to several tens) of electrode active materials are bound by a binder. Those that are deposited to form particles are preferred.

Moreover, it is preferable that the composite particle for electrochemical element electrodes of the present invention has a substantially spherical shape from the viewpoint of fluidity. That is, the short axis diameter of the composite particles is L _s , the long axis diameter is L _l , L _a = (L _s + L _l ) / 2, and a value of (1− (L ₁ −L _s ) / L _a ) × 100 Is a sphericity (%), the sphericity is preferably 80% or more, more preferably 90% or more. Here, the minor axis diameter L _s and the major axis diameter L _l are values measured from a scanning electron micrograph image.

  Furthermore, the composite particle for an electrochemical element electrode of the present invention has a volume average particle diameter of usually 0.1 to 1000 μm, preferably 1 to 200 μm, more preferably 30 to 150 μm. By making the volume average particle diameter of the composite particles in this range, an electrode mixture layer having a desired thickness can be easily obtained, which is preferable. The average particle diameter of the composite particles is a volume average particle diameter calculated by measuring with a laser diffraction particle size distribution analyzer (for example, SALD-3100; manufactured by Shimadzu Corporation).

  The structure of the composite particle for an electrochemical element electrode is not particularly limited, but a structure in which the binder is uniformly dispersed in the composite particle without being unevenly distributed on the surface of the composite particle is preferable.

  Such composite particles for electrochemical element electrodes of the present invention are used, for example, for producing electrochemical element electrode materials and electrochemical element electrodes.

  That is, the electrochemical element electrode material obtained using the electrochemical element electrode composite particles of the present invention comprises the above-described electrochemical element electrode composite particles of the present invention. The composite particle for an electrochemical element electrode of the present invention is used as an electrochemical element electrode material by including other binders or other additives alone or as necessary. The content of the composite particle for an electrochemical element electrode contained in the electrochemical element electrode material is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more.

  As another binder used as needed, the binder contained in the composite particle for electrochemical element electrodes of this invention mentioned above can be used, for example. Since the composite particle for an electrochemical element electrode of the present invention already contains a binder as a binder, it is not necessary to add another binder separately when preparing the electrochemical element electrode material. In order to further increase the binding force between the composite particles for electrochemical element electrodes, other binders may be added. In addition, when the other binder is added, the amount of the other binder added is preferably the sum of the binder in the composite particle for electrochemical element electrodes and 100 parts by weight of the electrode active material. 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Other additives include molding aids such as water and alcohol, and these can be added by appropriately selecting an amount that does not impair the effects of the present invention.

  Moreover, the electrochemical element electrode obtained by the dry molding method using the composite particle manufacturing apparatus for electrochemical element electrode of the present invention has an electrode mixture layer made of the above-described electrochemical element electrode material of the present invention on the current collector. It is formed by laminating. As the current collector material, for example, metal, carbon, conductive polymer and the like can be used, and metal is preferably used. As the metal, copper, aluminum, platinum, nickel, tantalum, titanium, stainless steel, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance. In addition, when high voltage resistance is required, high-purity aluminum disclosed in JP 2001-176757 A can be suitably used. The current collector is in the form of a film or a sheet, and the thickness thereof is appropriately selected according to the purpose of use, but is usually 1 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm.

  When laminating the electrode mixture layer on the current collector, the electrode composite layer is formed into a sheet shape on a transport substrate such as a PET film, and the electrochemical element electrode composite particles as the electrode mixture layer, Next, the electrode mixture layer may be transferred onto the current collector for lamination, but a method in which the electrochemical element electrode composite particles are directly dry-molded on the current collector is preferred. As dry molding, for example, using a roll-type pressure molding device equipped with a pair of rolls, the composite element for electrochemical element electrodes is roll-pressed with a supply device such as a screw feeder while feeding the current collector with the roll. By supplying to the forming device, a forming method for forming an electrode mixture layer on the current collector, or the composite particles for electrochemical element electrodes are dispersed on the current collector, and the composite particles for electrochemical element electrodes are blades, etc. For example, a method of forming an electrode mixture layer on the current collector by adjusting the thickness and then performing pressure molding with a roll pressure molding device or a belt pressure molding device can be used. Since the composite particles for electrochemical device electrodes obtained by the device for manufacturing composite particles for electrochemical devices of the present invention have high fluidity, dry molding is possible even at high line speeds due to their high fluidity. With this, an electrochemical element electrode can be manufactured with high productivity.

  The temperature at the time of pressure molding in the powder molding step is preferably 0 to 200 ° C, and more preferably 20 ° C or higher than the glass transition temperature of the binder. By setting the pressure molding temperature within the above range, the adhesion between the electrode mixture layer and the current collector can be made sufficient. Moreover, the press linear pressure between rolls when performing pressure molding with a roll-type pressurizer is preferably 0.2 to 30 kN / cm, more preferably 1.5 to 15 kN / cm. By setting the linear pressure within the above range, the uniformity of the thickness of the electrode mixture layer can be improved. Moreover, the shaping | molding speed at the time of performing a dry-type shaping | molding process with a roll-type pressure-forming apparatus becomes like this. Preferably it is 0.1-100 m / min, More preferably, it is 4-100 m / min.

  The electrode mixture layer once formed by roll compression or the like in the dry molding step is preferably finished into an electrochemical element mixture layer having desired electrode physical properties, that is, an electrochemical element electrode, by further applying a pressing operation. In the additional pressurizing step, pressurization is performed by using a roll press or the like. In this case, the temperature of the roll may be adjusted as necessary, such as heating or cooling.

  As described above, the dry molding method is a manufacturing method in which the electrode mixture layer is molded into a sheet at a high speed by applying a pressing operation to the composite particles and the resultant mixture layer a plurality of times. In the process until the desired electrode mixture layer thickness is achieved, the electrode mixture layer for an electrochemical element electrode obtained by the dry molding method has the thickness of the electrode mixture layer when it is first subjected to a pressing operation. Compressed to 50-30%.

  On the other hand, in the conventional electrode manufacturing method in which an electrode mixture layer is formed by applying an electrode mixture slurry to a current collector, the desired electrode physical properties (electrode mixture layer density, electrode mixture layer thickness) are finished. There is a step of compressing the electrode mixture layer using a roll press or the like. However, in general, in an electrode manufacturing method using a coating method, the compression ratio of the electrode mixture layer in the roll press step is 90 to 70% of the thickness of the electrode mixture layer before pressing.

  As described above, compared with the method for producing an electrochemical element electrode by a coating method, the method for producing an electrochemical element electrode by a dry molding method is such that the constituent components of the electrode mixture layer are immobilized on a current collector or the like. This is a manufacturing method with a very large amount of displacement from the end to the final mixture layer. Therefore, in the method for producing an electrochemical element electrode using the dry molding method, when the particulate particles contain particulate foreign matter, the particulate foreign matter also moves greatly from the existing location at the time of fixation like the constituent components of the electrode mixture layer. Then, when the particulate foreign matter moves in the process of being finished into an electrode mixture layer having desired electrode properties, the current collector or transport base is damaged or bite into the current collector or transport base. It is conceivable that the material is broken and causes a process failure in the dry molding process.

  Therefore, the process failure such as the breakage of the current collector due to the mixing of particulate foreign matter into the electrode constituent material is a problem peculiar to the dry molding method, which is difficult to occur in the conventional method of manufacturing an electrochemical element electrode by the coating method. Such a problem can be solved for the first time by the present invention.

  According to the present invention, as shown in FIG. 1, when supplying the composite particle slurry to the spraying device 15 via the hopper 11 and the pump 12, the foreign matter removing means 30 is provided in front of the spraying device 15. Then, the composite particle slurry is passed through the foreign matter removing means 30 and then supplied to the spraying device 15 and sprayed by the spraying device 15, whereby the composite particle slurry is spray-dried and granulated. And according to such this invention, when the particulate foreign material is contained in the slurry for composite particles by allowing the composite particle slurry to pass through the foreign matter removing means 30, such particulate foreign matter is contained. Can be removed by the action of the foreign matter removing means 30, thereby appropriately preventing the particulate foreign matter from being contained in the obtained composite particles for electrochemical element electrodes. As a result, the resulting composite particles for electrochemical device electrodes are used to effectively suppress process failures such as breakage of the current collector or transport substrate that occur in the process of producing electrochemical device electrodes by dry molding. It is possible to improve the productivity of the electrochemical element electrode. In particular, in the present invention, in order to remove the particulate foreign matter in the state of the composite particle slurry, when removing the particulate foreign matter in the post-granulation step (for example, the particulate state in the state of the composite particle for electrochemical device electrode) Compared with the case of removing foreign matters, etc., the material loss of the composite particle constituents can be reduced.

  In addition, according to the present invention, the particulate foreign matter is removed by the action of the foreign matter removing means 30, so that the spraying device 15 and the drying tower 16 are damaged and damaged, or the pressure nozzle is used to electrically Operation failure such as nozzle clogging when producing composite particles for chemical element electrodes can be effectively suppressed.

  In the embodiment shown in FIG. 1, the hopper 11, the pump 12, the pipe connecting these, and the pipe connecting the pump 12 and the spraying device 15 correspond to the supply unit of the present invention, and the spraying device 15 and the drying device are connected. The tower 16 corresponds to the granulating part of the present invention.

  Moreover, in the above, although the electrode shaping | molding apparatus and electrode shaping | molding method of this invention were demonstrated based on one Embodiment shown in FIG. 1, the electrode shaping | molding apparatus and electrode shaping | molding method of this invention are one implementation shown in FIG. The present invention is not limited to the embodiments, and various modifications can be made without departing from the scope of the present invention.

  For example, as a production apparatus for producing composite particles for electrochemical element electrodes, production of composite particles for electrochemical element electrodes shown in FIG. 2 is used instead of the production apparatus 10 for composite particles for electrochemical element electrodes shown in FIG. The device 20 may be used.

  Here, FIG. 2 is a view showing the electrochemical device electrode composite particle manufacturing apparatus 20 according to another embodiment of the present invention, and the electrochemical device electrode composite particle manufacturing apparatus 20 shown in FIG. This is an apparatus for producing composite particles for electrochemical element electrodes by fluidized bed granulation. In the fluidized bed granulation method, a binder slurry containing a binder and optional components such as a conductive material and a dispersant added as necessary is sprayed onto an electrode active material that is flowed in a heated air stream. This is a method for producing composite particles for electrochemical element electrodes by binding electrode active materials to each other and drying them.

  As shown in FIG. 2, in the electrochemical device electrode composite particle manufacturing apparatus 20 according to another embodiment of the present invention, the binder slurry can be stored in the hopper 21 and stored in the hopper 21. The binder slurry is sent to the spraying device 25 by the pump 22 and sprayed into the fluidized tank 26 from the spraying device 25. And in the state which put the electrode active material in the fluid tank 26, the hot air for a flow and drying is sent to the fluid tank 26 from the pump 23 through the heat exchanger 24, The electrode active material in the fluid tank 26 (Indicated by symbol P in FIG. 2) While circulating and flowing as indicated by the arrows, the binder slurry is sprayed onto the flowing electrode active material from the spraying device 25, thereby bringing the electrode active materials into contact with each other. The composite particles for electrochemical device electrodes can be produced by binding and drying. In addition, in the example shown in FIG. 2, although the circulation flow was given to the powder in the fluid tank 26, the method of obtaining the granulated material which grew comparatively large using the classification effect by this was illustrated. The method is not particularly limited.

The temperature of the binder slurry sprayed from the spray device 25 is usually room temperature, but may be heated to room temperature or higher. The temperature of the hot air for fluidization and drying is usually 70 to 300 ° C, preferably 80 to 200 ° C.
Examples of the spray device 25 for spraying the binder slurry include a rotating disk method, a pressure nozzle method, an ultrasonic method, a two-fluid nozzle method, a three-fluid nozzle method, and a four-fluid nozzle method. It is preferable to adopt a two-fluid nozzle method, a three-fluid nozzle method, or a four-fluid nozzle method in order to refine the droplets. Moreover, it is preferable that these nozzles have a mechanism in which binder slurry and compressed air are mixed outside the nozzles in order to suppress clogging of the nozzles during operation.

  Further, as shown in FIG. 2, the electrochemical device electrode composite particle manufacturing apparatus 20 according to another embodiment of the present invention is similar to the electrochemical device electrode composite particle manufacturing apparatus 10 shown in FIG. A foreign matter removing means 30a is provided in the pipe from the pump 22 to the spraying device 25. Therefore, since the binder slurry supplied from the hopper 21 passes through the foreign matter removing means 30a and is supplied to the spraying device 25, the particulate foreign matter is contained in the composite particle slurry stored in the hopper 21. In such a case, the particulate foreign matter can be removed by the action of the foreign matter removing means 30a. In addition, in the electrochemical element electrode composite particle manufacturing apparatus 20 according to another embodiment of the present invention, particulate foreign matter mixed in from the flowing and drying hot air supplied from the pump 23 via the heat exchanger 24. In order to remove the foreign matter, foreign matter removing means 30b is also provided in the pipe from the heat exchanger 24 to the fluidized tank 26. As the foreign matter removing means 30a and 30b, the same foreign matter removing means 30 as shown in FIG. 1 described above can be used. Further, in the example shown in FIG. 2, a configuration including both the foreign matter removing means 30a and 30b is preferable, but at least the foreign matter removing means 30a may be provided. Further, as in the example shown in FIG. 1, two or more foreign matter removing means 30a and 30b may be provided.

  Furthermore, in the electrochemical device electrode composite particle manufacturing apparatus 20 according to another embodiment of the present invention, in order to remove particulate foreign matters contained in the electrode active material to be flowed in the fluid tank 26, the electrode As the active material, it is desirable to use a material that has been passed through a foreign matter removing means in advance from the viewpoint that the content of the particulate foreign matter in the obtained composite particle for an electrochemical element electrode can be further reduced.

  In addition, as the binder slurry used when producing the composite particles for electrochemical element electrodes by the fluidized bed granulation method using the electrochemical element electrode composite particle production apparatus 20 shown in FIG. 2, an electrode active material is blended. Except not, it can prepare similarly to the slurry for composite particles used in the example shown in FIG.

  Moreover, the electrochemical element electrode composite particles obtained by the fluidized bed granulation method using the electrochemical element electrode composite particle manufacturing apparatus 20 shown in FIG. Electrochemical element electrode composite particles similar to those obtained when the particle manufacturing apparatus 10 is used can be obtained, and the same effects can be obtained.

DESCRIPTION OF SYMBOLS 10,20 ... Electrochemical element electrode composite particle production apparatus 11, 21 ... Hopper 12, 13, 22, 23 ... Pump 14, 24 ... Heat exchanger 15, 25 ... Spraying device 16 ... Drying tower 26 ... Fluidized tank

Claims (8)

A production apparatus for producing composite particles for an electrochemical element electrode containing an electrode active material and a binder,
A supply unit provided with one or more supply ports for supplying a raw material constituting the composite particle for an electrochemical element electrode;
A granulation unit for granulating the raw material supplied from the supply unit,
The said supply part has the foreign material removal means for removing the particulate foreign material contained in the raw material supplied from the said supply part, The manufacturing apparatus of the composite particle for electrochemical element electrodes characterized by the above-mentioned.   The said granulation part granulates the said raw material by the fluidized-bed dry granulation method or the spray-drying granulation method, The manufacturing apparatus of the composite particle for electrochemical element electrodes of Claim 1 characterized by the above-mentioned.   The apparatus for producing composite particles for electrochemical element electrodes according to claim 1 or 2, wherein two or more foreign substance removing means are provided for one supply port.   The said foreign substance removal means is a filter, The manufacturing apparatus of the composite particle for electrochemical element electrodes in any one of Claims 1-3.   The said foreign material removal means is a means which removes a particulate foreign material using magnetism, The manufacturing apparatus of the composite particle for electrochemical element electrodes in any one of Claims 1-3. A hot air introduction part for sending hot air to the granulation part,
The electrochemical element electrode composite according to any one of claims 1 to 5, wherein the hot air introduction part includes a foreign matter removing means for removing particulate foreign matters contained in the hot air introduced from the hot air introduction part. Particle production equipment. A method for producing composite particles for an electrochemical element electrode containing an electrode active material and a binder,
Supplying a raw material constituting the composite particle for electrochemical element electrodes to a granulating means;
A granulating step of granulating the raw material by the granulating means, and supplying the raw material to the granulating means after passing the raw material through the particulate foreign matter removing means in the supplying step; The manufacturing method of the composite particle for electrochemical element electrodes characterized by removing the particulate foreign material contained. Electrochemical element electrode composite particles produced by the production method according to claim 7,
The composite particle for an electrochemical element electrode, wherein a content ratio of the particulate foreign matter contained in the composite particle for an electrochemical element electrode is 100 ppm by weight or less.

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