JP5845748B2 - Powder rolling apparatus and rolled sheet manufacturing method - Google Patents

Description

  The present invention relates to a powder rolling apparatus for rolling and forming powder between rolls, and a method for manufacturing a rolled sheet using the apparatus.

  The demand for electrochemical devices such as lithium ion secondary batteries and electric double layer capacitors that are small and light, have high energy density, and can be repeatedly charged and discharged is expected to increase in the future from the environmental viewpoint. Lithium-ion rechargeable batteries have high energy density and are used in the fields of mobile phones and laptop computers. Electric double layer capacitors are capable of rapid charge and discharge and are used as memory backup compact power sources for personal computers. Yes. In addition, lithium ion capacitors that utilize the oxidation-reduction reaction (pseudo electric double layer capacity) on the surface of metal oxides or conductive polymers are also attracting attention because of their large capacity. With the expansion and development of applications, these electrochemical devices are required to have further improved performance by reducing resistance, increasing capacity, improving mechanical properties, and the like.

  As one of powder rolling techniques, which are methods for producing electrode chemical elements, a roll heating direct powder rolling method has been conventionally known. A powder rolling apparatus for carrying out such a powder rolling method has a pair of rolling rolls arranged horizontally and in parallel, and the powder charged in a hopper provided at the upper part between the rolling rolls, In this way, a rolled sheet is produced in which the powder is continuously rolled by being drawn into the gap between the rolling rolls (see, for example, Patent Document 1).

JP 2006-303395 A

  However, when a rolled sheet is produced by rolling powder with a powder rolling device, the powder flow concentrates in the vicinity of both ends of the pair of rolls, that is, in the vicinity of the side plate 60 (see FIG. 9) in the hopper. There has been a problem in that increased portions of film thickness occur at both ends in the width direction of the rolled sheet.

  An object of the present invention is to provide a powder rolling apparatus for manufacturing a rolled sheet that suppresses an increase in film thickness at both ends in the width direction and improves film thickness accuracy, and a method for manufacturing a rolled sheet using this apparatus. is there.

  As a result of studying to achieve the above object, the present inventors have found that a rolled sheet with improved film thickness accuracy can be obtained by discharging the powder out of the hopper at both ends of a pair of rolls. . The present invention has been completed based on these findings.

According to the present invention,
(1) A pair of rolls whose rotation axes are parallel and rotate in opposite directions, a hopper provided on the pair of rolls, and the powder is discharged from the hopper toward both ends of the pair of rolls. A discharge part, and rolling the powder by the pair of rolls while discharging the powder from the discharge part , the hopper includes side plates respectively provided at both ends of the pair of rolls, The discharge portion is a cut portion along the arc shape formed in an arc shape portion corresponding to an outer periphery of the roll provided at a lower portion of the side plate, and the cut portion is the arc shape portion. A powder rolling device characterized in that it is formed in a part of
(2) The powder rolling device according to (1) , wherein the cut portion is formed in at least one of the upper, central, and lower portions of the arc shape of the side plate,
(3) A pair of rolls whose rotation axes are parallel and rotate in opposite directions, a hopper provided on the pair of rolls, and the powder is discharged from the hopper toward both ends of the pair of rolls. A discharge part, and rolling the powder by the pair of rolls while discharging the powder from the discharge part, the hopper includes side plates respectively provided at both ends of the pair of rolls, The discharge portion is a lower portion of the entire arc shape in which a radius of curvature of an arc shape portion corresponding to an outer periphery of the roll provided at a lower portion of the side plate is larger than a radius of the roll. A powder rolling device,
(4) A pair of rolls whose rotation axes are parallel and rotate in opposite directions, a hopper provided on the pair of rolls, and the powder is discharged from the hopper toward both ends of the pair of rolls. A discharge part, and rolling the powder by the pair of rolls while discharging the powder from the discharge part, the hopper includes side plates respectively provided at both ends of the pair of rolls, The powder rolling device, wherein the discharge part is a hole formed in the side plate,
(5) Using the powder rolling device according to any one of (1) to ( 4 ), the pair of powders supplied from the hoppers while discharging the powders from the discharge part of the hoppers. A rolled sheet manufacturing method characterized by manufacturing a rolled sheet by rolling with a roll of
Is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the rolling sheet which suppressed the increase in the film thickness of the width direction both ends and improved the film thickness precision can be manufactured.

It is the perspective view which looked at the powder rolling device concerning an embodiment from the upper part. It is the schematic diagram which looked at the powder rolling device concerning an embodiment from the side. It is a figure which shows the shape of the side board of the hopper which concerns on embodiment. It is a figure which shows the shape of the side board of the hopper which concerns on embodiment. It is a figure which shows the shape of the side board of the hopper which concerns on embodiment. It is a figure which shows the shape of the side board of the hopper which concerns on embodiment. It is a figure which shows the shape of the side board of the hopper which concerns on embodiment. It is a graph which shows the dispersion | variation in the film thickness of the width direction of the rolling sheet manufactured using the powder rolling apparatus provided with the side plate which concerns on embodiment. It is a figure which shows the shape of the side board which comprises the conventional hopper.

  Hereinafter, a powder rolling apparatus and a rolled sheet manufacturing method according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a perspective view of a powder rolling apparatus according to the embodiment as viewed from above, and FIG. 2 is a schematic view of the powder rolling apparatus according to the embodiment as viewed from the side.

  The powder rolling apparatus 2 includes a compression roll 4 including a pair of rolls 4A and 4B whose rotation axes are arranged horizontally and in parallel and rotate downward in the proximity portion. Powder 8 is stored in a hopper 6 formed on the upper part of the pair of rolls 4A and 4B.

  As shown in FIG. 2, the lower part of the side plate 10a (10b) disposed at both ends of the pair of rolls 4A and 4B constituting the hopper 6 has an arc shape corresponding to the outer periphery of each of the pair of rolls 4A and 4B. A cut-out portion 11 is formed at a substantially central portion of the arc-shaped portion along the arc shape of the arc-shaped portion. Here, the cutting part 11 functions as a discharge port for the powder 8. Further, the cut portion 11 is provided in the vicinity of the upper portion of the roll nip point P (the point where the distance between the rolls 4A and 4B is the shortest) between the pair of rolls 4A and 4B.

  The rolls 4A and 4B of the compression roll 4 respectively rotate in the direction of the arrow shown in FIG. 1 to bite the powder 8 and roll the powder 8 with the rolls 4A and 4B to produce a rolled sheet. Here, the rolls 4A and 4B of the compression roll 4 rotate by being driven by a motor or the like, but the rotation speeds of the rolls 4A and 4B can be freely changed. The compression roll 4 is provided with a temperature adjustment mechanism capable of adjusting the temperature such as cooling and heating according to the kind and properties of the powder. Examples of the temperature adjusting mechanism include a method of using a heat medium disposed inside the rolls 4A and 4B, a method of heating with a direct heat transfer wire, and the like.

  When the powder 8 is bitten by the pair of rolls 4A and 4B, portions where the flow of the powder 8 is concentrated in the vicinity of both ends of the pair of rolls 4A and 4B, that is, in the vicinity of the side plates 10a and 10b of the hopper 6. However, the powder 8 is rolled by the rolls 4A and 4B while the powder 8 in this portion is discharged from the cut portion 11 to the outside of the hopper 6 to produce a rolled sheet. Therefore, an increase in film thickness at both ends in the width direction of the rolled sheet can be prevented, and the film thickness in the width direction of the rolled sheet can be made uniform.

  Examples of the powder 8 stored in the hopper 6 include composite particles containing an electrode active material. When composite particles containing an electrode active material are used as the powder 8, the obtained rolled sheet can be used as an electrode layer made of an electrode material.

  The composite particles used in the present invention include an electrode active material and a binder, and may include other dispersants, conductive materials, and additives as necessary.

  When the composite particles are used as an electrode material 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 such metal oxides 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-lithium manganese oxide, 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 independently according to a use, and may be used in mixture of multiple types.

  Furthermore, polymers such as polyacetylene, poly-p-phenylene and polyquinone can be mentioned. Of these, it is preferable to use a lithium-containing metal oxide.

  In addition, as an active material of the negative electrode as a counter electrode of the positive electrode for the lithium ion secondary battery, low crystalline carbon (amorphous carbon) such as graphitizable carbon, non-graphitizable carbon, activated carbon, pyrolytic carbon, Graphite (natural graphite, artificial graphite), carbon nanowalls, carbon nanotubes, or composite carbon materials of carbon having different physical properties, alloy materials such as tin and silicon, silicon oxide, tin oxide, vanadium oxide And oxides such as lithium titanate, polyacene, and the like. 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 diameter of the electrode active material for a lithium ion secondary battery electrode is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.8 to 20 μm for both the positive electrode and the negative electrode.

The tap density of the electrode active material for a lithium ion secondary battery is not particularly limited, but a material having a positive electrode of 2 g / cm ³ or more and a negative electrode of 0.6 g / cm ³ or more is preferably used.

  When composite particles are used as electrode materials for lithium ion capacitors, active materials for positive electrodes include activated carbon, polyacene organic semiconductor (PAS), carbon nanotubes, carbon whiskers that can be reversibly doped and dedoped with anions and / or cations. And graphite. Preferred electrode active materials are activated carbon and carbon nanotubes.

  In addition, as the negative electrode active material as the counter electrode of the positive electrode for a lithium ion capacitor, any of the materials exemplified as the negative electrode active material for a lithium ion secondary battery can be used. The volume average particle diameter of the electrode active material used for the electrode 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.

When using activated carbon as the lithium ion capacitor electrode active material, the specific surface area of activated carbon, ^{30 m} 2 / g or more, preferably 500~3,000m ² / g, more preferably 1,500~2,600m 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.

  When the composite particles are used as an electrode material for an electric double layer capacitor, any of the materials exemplified as the positive electrode active material for a lithium ion capacitor can be used as the positive electrode active material and the negative electrode active material.

  The binder used for the composite particles is not particularly limited as long as it is a compound capable of binding the electrode active materials to each other. A suitable binder is a dispersion type binder having a property of being dispersed in a solvent. Examples of the dispersion-type binder include high molecular compounds such as silicon polymers, fluorine-containing polymers, conjugated diene polymers, acrylate polymers, polyimides, polyamides, polyurethanes, and preferably fluorine-containing polymers. Polymers, conjugated diene polymers and acrylate polymers, more preferably conjugated diene polymers and acrylate polymers.

  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 proportion 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 the 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 A polymer containing a monomer unit derived from a compound represented by the formula (1), which may have an ether group, a hydroxyl group, a phosphate group, or an amino group. A homopolymer of the compound 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 Recall, (meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid phenoxyethyl, (meth) acrylic acid tetrahydrofurfuryl ether group-containing (meth) acrylic acid ester; (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; Phosphoric acid group-containing (meth) acrylic acid esters such as ethyl phosphate; Epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate; Amino group content such as dimethylaminoethyl (meth) acrylate ( (Meth) acrylic acid ester; and the like.

  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 swelling property 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 in the above range, the flexibility in forming the electrode can be improved, and the resistance to cracking can be increased.

  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 monomer unit having an acid component in the acrylate polymer is preferably 1.0 to 10% by weight, more preferably 1.5 to 5.0% by weight. By making the content rate of the vinyl monomer unit which has an acid component into the said range, stability at the time of setting it as a slurry can be improved.

  The shape of the dispersion-type binder 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 the particles of the binder 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 is preferably 0.001 to 100 μm, more preferably 10 to 1000 nm, and still more preferably 50 to 500 nm. By setting the average particle diameter of the dispersion-type binder particles in the above range, the strength and flexibility as the obtained electrode are improved while the stability in the slurry is improved.

  The amount 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. is there. When the amount of the binder is within this range, sufficient adhesion between the obtained electrode mixture layer and the current collector can be secured, and the internal resistance can be lowered.

  As described above, a dispersant may be used for the composite particles as necessary. 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.

  As described above, a conductive material may be used for the composite particles as necessary. Specific examples of the conductive material include conductive carbon black such as furnace black, acetylene black, and ketjen black (registered trademark of Akzo Nobel Chemicals Bethloten Fennaut Shap). Among these, acetylene black and ketjen black are preferable.

  The volume average particle diameter of the conductive material is preferably smaller than the volume average particle diameter of the electrode active material, and the range is usually 0.001 to 10 μm, preferably 0.05 to 5 μm, more preferably 0.01 to 1 μm. It is. When the volume average particle diameter of the conductive material is within this range, high conductivity can be obtained with a smaller amount of use. These conductive materials can be used alone or in combination of two or more.

  The amount of these conductive materials used is not particularly limited as long as the effects of the present invention are not impaired, but is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the electrode active material. 0.5 to 15 parts by weight, more preferably 1 to 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 electric capacity of the obtained electrochemical element high.

  The composite particles are obtained by granulating using an electrode active material, a binder, and other components such as the conductive material added as necessary, and include at least an electrode active material and a binder, Each of the above does not exist as an independent particle, but forms one particle by two or more components including an electrode active material and a binder as constituent components. Specifically, a plurality of (more preferably several to several tens) electrode active materials are formed by combining a plurality of the individual particles of the two or more components to form secondary particles. It is preferable that the particles are bound to form particles.

The shape of the composite particles is preferably substantially spherical 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.

  The volume average particle diameter of the composite particles is usually in the range of 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 size of the composite particles is a volume average particle size calculated by measuring with a laser diffraction particle size distribution measuring device (for example, SALD-3100; manufactured by Shimadzu Corporation).

  The structure of the composite particle 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.

  The method for producing the composite particles is not particularly limited, but the composite particles can be easily obtained by the following two production methods.

  The first method for producing composite particles is a fluidized bed granulation method. The fluidized bed granulation method is a step of obtaining a binder, and optionally a slurry containing a conductive material, a dispersing agent and other additives, and flowing the electrode active material in a heated air stream, The slurry is sprayed to bind the electrode active materials to each other and dry the slurry. Hereinafter, the fluidized bed granulation method will be described.

(Fluidized bed granulation method)
First, a slurry containing a binder and, if necessary, a conductive material, a dispersant and other additives is obtained. Water is most preferably used as the solvent used to obtain the slurry, 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 2-pyrrolidone (hereinafter sometimes referred to as NMP) and amides such as dimethylimidazolidinone, and alkyl alcohols are preferred. When an organic solvent having a lower boiling point than water is used in combination, the drying rate can be increased during fluid granulation. In addition, when an organic solvent having a boiling point lower than that of water is used in combination, the dispersibility of the binder or the solubility of the soluble resin changes, and the viscosity and fluidity of the slurry can be adjusted depending on the amount or type of the solvent. Can be improved.

  The amount of the solvent used when preparing the slurry is such that the solid content concentration of the slurry is usually in the range of 1 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 30% by weight. Amount. When the amount of the solvent is within this range, the binder is preferably dispersed uniformly.

  The method or procedure for dispersing or dissolving the binder, if necessary, the conductive material, the dispersant and other additives in the solvent is not particularly limited. For example, the binder, the conductive material, the dispersant and the other in the solvent. Method of adding and mixing the additive, after dissolving the dispersant in the solvent, adding and mixing the binder (for example, latex) dispersed in the solvent, and finally adding the conductive material and other additives And a method in which a conductive material is added to a dispersant dissolved in a solvent and mixed, and a binder dispersed in a solvent is added thereto and mixed. Examples of the mixing means 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.

  Next, the electrode active material is fluidized, and the slurry is sprayed thereon for fluid granulation. Examples of fluidized granulation include a fluidized bed, a deformed fluidized bed, and a spouted bed. In the fluidized bed method, the electrode active material is fluidized with hot air, and the slurry is sprayed from the spray or the like to perform agglomeration and granulation. The modified fluidized bed is the same as the fluidized bed, but is a method of giving a circulating flow to the powder in the bed and discharging the granulated material that has grown relatively large by using the classification effect. In addition, the method using the spouted bed is a method in which slurry from a spray or the like is attached to coarse particles using the characteristics of the spouted bed and granulated while being dried at the same time. As the method for producing composite particles in the present invention, a fluidized bed or a deformed fluidized bed is preferred among these three methods.

  The temperature of the slurry to be sprayed is usually room temperature, but may be heated to room temperature or higher. The temperature of the hot air used for fluidization is usually 70 to 300 ° C, preferably 80 to 200 ° C.

  By the above production method, composite particles containing an electrode active material, a binder, and, if necessary, a conductive material, a dispersant, and other additives can be obtained.

  The second production method of the composite particles is a spray drying granulation method. The spray drying granulation method described below is preferable because the composite particles of the present invention can be obtained relatively easily. Hereinafter, the spray drying granulation method will be described.

(Spray drying granulation method)
First, a slurry for composite particles containing an electrode active material and a binder is prepared. The slurry for composite particles can be prepared by dispersing or dissolving an electrode active material, a binder, and a conductive material added as necessary 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 used for obtaining the composite particle slurry, water is usually used, but a mixed solvent of water and an organic solvent may be used. Examples of the organic solvent that can be used in this case 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, Examples thereof include amides such as dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylimidazolidinone. Among these, alcohols are preferable. By using water and an organic solvent having a lower boiling point than water, the drying rate can be increased during spray drying. Thereby, the viscosity and fluidity of the slurry for composite particles can be adjusted, and the production efficiency can be improved.

  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 the spray drying granulation step can be increased.

  Moreover, in this invention, when preparing the slurry for composite particles, you may add a dispersing agent and surfactant as needed.

  Examples of the surfactant include amphoteric surfactants such as anionic, cationic, nonionic, and nonionic anions, and anionic or nonionic surfactants that are easily thermally decomposed are preferable. The compounding amount of the surfactant is preferably 50 parts by weight or less, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the positive electrode active material. .

  The method or order of dispersing or dissolving the electrode active material, the binder, and the conductive material added as necessary in the solvent is not particularly limited. Moreover, as a mixing apparatus, a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a homomixer, a planetary mixer, etc. can be used, for example. Mixing is usually performed in the range of room temperature to 80 ° C. for 10 minutes to several hours.

  Subsequently, the obtained slurry for composite particles is granulated by spray drying. Spray drying is a method of spraying and drying a slurry in hot air. An atomizer is used as an apparatus used for spraying slurry. 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, and a pin type atomizer is preferable. 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. On the other hand, the pressurization method is a method in which the slurry for composite particles is pressurized and sprayed from a nozzle to be dried.

  The temperature of the slurry for composite particles to be sprayed is usually room temperature, but may be higher than room temperature by heating. Moreover, the hot air temperature at the time of spray-drying is 80-250 degreeC normally, Preferably it is 100-200 degreeC. In the spray drying method, the method of blowing hot air is not particularly limited. For example, the method in which the hot air and the spraying direction flow in parallel to each other, the method in which the hot air is sprayed at the top of the drying tower and descends with the hot air, Examples include a contact method, and a method in which sprayed droplets first flow in parallel with hot air, then drop by gravity and contact countercurrent.

  In addition to the method of spraying the composite particle slurry having the electrode active material and the binder in a lump as the spraying method, the slurry containing the binder and other additives as required is fluidized. A method of spraying on the electrode active material can also be used. From the standpoint of ease of particle size control, productivity, and reduction in particle size distribution, an optimal method may be appropriately selected according to the components of the composite particles.

  The electrode mixture layer produced by the dry molding method includes the composite particles described above. The composite particles can obtain an electrode mixture layer having desired physical properties by containing other binders and other additives alone or as necessary. The content of the composite particles contained in the electrode mixture layer 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 necessary, for example, the binder contained in the composite particles described above can be used. Since the composite particles already contain a binder, it is not necessary to add another binder separately when manufacturing the electrode composite layer, but in order to further increase the binding force between the composite particles. Other binders may be added. In addition, when the other binder is added, the amount of the other binder added is preferably 0.01 with respect to 100 parts by weight of the electrode active material in total with the binder in the composite particles. -10 parts by weight, more preferably 0.1-5 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.

  In the powder rolling apparatus according to this embodiment, it is possible to manufacture a rolled sheet that suppresses an increase in film thickness at both ends in the width direction of the pair of rolls 4A and 4B and improves film thickness accuracy. Moreover, since the powder discharged | emitted from the cutting part 11 can be reused as it is, it can aim at the fall of manufacturing cost.

  When rolling the rolled sheet from the powder 8, the rolled sheet may be rolled on one or both sides of the backup base material. Here, the backup substrate may be a thin film substrate, and usually has a thickness of 1 μm to 1000 μm, preferably 5 μm to 800 μm. Examples of the backup substrate include metal foils such as aluminum, copper, stainless steel, and iron, paper, natural fibers, polymer fibers, fabrics, polymer resin films, and the like, and can be appropriately selected according to the purpose. Examples of the polymer resin film include polyester resin films such as polyethylene terephthalate and polyethylene naphthalate, plastic films and sheets including polyimide, polypropylene, polyphenylene sulfide, polyvinyl chloride, aramid film, PEN, PEEK, and the like. It is done. Further, the surface of the backup base material may be subjected to treatment such as coating treatment, drilling, buffing, sand blasting and / or etching. A substrate obtained by applying an adhesive or the like to the backup substrate surface is particularly preferable because it can hold the sheet-like powder firmly.

  Further, in the above-described embodiment, the cut portion 11 along the arc shape is formed at the substantially central portion of the arc shape portion of the side plate 10a (10b) constituting the hopper 6, but FIG. As shown in FIG. 3, a cutout portion 11a may be formed over the substantially central portion and the lower portion of the arc-shaped portion of the side plate 10a (10b) to form a discharge portion, or as shown in FIG. A cutout portion 11b may be formed over the substantially central portion and the upper portion of the arc-shaped portion 10b) to form a discharge portion. In addition, the shape shown with a dashed-two dotted line in a figure is the circular arc shape of the lower part of the conventional side plate 60 shown in FIG.

  Further, as shown in FIG. 4 (a), a cutout portion 11c may be formed on the upper portion of the arc-shaped portion of the side plate 10a (10b) to form a discharge portion, or the side plate 10a as shown in FIG. 4 (b). A cutout part 11d may be formed at the lower part of the arcuate part of (10b) to form a discharge part. In addition, the shape shown with a dashed-two dotted line in a figure is the circular arc shape of the lower part of the conventional side plate 60 shown in FIG.

  Further, as shown in FIG. 5A, the radius of curvature of the arc-shaped portion of the side plate 10a (10b) is made larger than that of the conventional side plate shown in FIG. 8, and the arc-shaped portion of the side plate 10a (10b) is obtained. The whole lower portion 11e may be used as the discharge portion. Moreover, as shown in FIG.5 (b), the lower end part of the conventional side board 60 shown in FIG. 9 is cut | disconnected, and it is good also considering the lower part 11f of the circular-arc-shaped part of the side board 10a (10b) as a discharge part. In addition, the shape shown with a dashed-two dotted line in a figure is the circular arc shape of the lower part of the conventional side plate 60 shown in FIG.

  Further, as shown in FIG. 6 (a), a triangular opening 11g may be provided in the vicinity of the lower roll nip point of the side plate 10a (10b) as a discharge portion, or the side plate as shown in FIG. 6 (b). An opening portion 11h having an inverted triangle may be provided in the vicinity of the lower roll nip point of 10a (10b) to serve as a discharge portion.

  Further, as shown in FIG. 7A, a circular opening 11i may be provided in the vicinity of the lower roll nip point of the side plate 10a (10b) to serve as a discharge portion, or as shown in FIG. A diamond-shaped opening 11j may be provided in the vicinity of the lower roll nip point of 10a (10b) to serve as a discharge portion.

  Even when the discharge part shown in FIGS. 3 to 7 is formed on the side plate 10a (10b), the powder 8 is rolled by the rolls 4A and 4B while the powder 8 is discharged out of the hopper 6 from the discharge part. In order to manufacture a sheet | seat, the increase in the film thickness in the width direction both ends of a rolled sheet can be prevented, and the film thickness in the width direction of a rolled sheet can be made uniform.

  In addition, as mentioned above, when manufacturing the electrode layer which consists of electrode material as a rolling sheet using the composite particle containing an electrode active material as the powder 8, as thickness of the electrode layer obtained, Preferably it is 10-1000 micrometers. More preferably, it is 20-500 micrometers.

(Experimental result)
2 is provided on the side plate 10a (10b) constituting the hopper 6 of the powder rolling apparatus 2 (I), the discharge unit shown in FIG. 3B is provided on the side plate 10a (10b). In the case (II), the powder 8 was rolled to produce a rolled sheet, and the thickness of the rolled sheet was measured at each part in the width direction. The film thickness was measured at 2 cm intervals. The measurement results are shown in the graph of FIG.

  As shown in the graph of FIG. 8, in the case of (I), the film thickness does not increase at both ends in the width direction of the rolled sheet, and the variation in film thickness is 2.0%. The accuracy is improved as compared with a 7% variation in the film thickness in the width direction of the rolled sheet produced by the powder rolling apparatus including the plate 60.

  In the case of (II), there is no increase in the film thickness at both ends in the width direction of the rolled sheet, the film thickness variation is 2.5%, and the powder rolling apparatus provided with the conventional side plate 60 shown in FIG. The accuracy is improved as compared with 7% variation in the film thickness in the width direction of the rolled sheet produced by the above, but it does not reach the accuracy in the case of (I).

  From these results, it was found that providing a discharge port near the upper portion of the roll nip point P is effective in preventing an increase in film thickness at both ends in the width direction of the rolled sheet.

2 ... powder rolling device, 4 ... compression roll, 4A, 4B ... roll, 6 ... hopper, 8 ... powder, 10a, 10b ... side plate, 11 ... cut-out part

Claims (3)

A pair of rolls whose rotation axes are parallel and rotate in opposite directions; a hopper provided on the pair of rolls; and a discharge unit for discharging the powder from the hopper toward both ends of the pair of rolls. Rolling the powder with the pair of rolls while discharging the powder from the discharge unit,
The hopper includes side plates provided at both ends of the pair of rolls,
The discharge portion is a lower portion of the entire arc shape in which a radius of curvature of an arc shape portion corresponding to an outer periphery of the roll provided at a lower portion of the side plate is larger than a radius of the roll. A powder rolling machine. A pair of rolls whose rotation axes are parallel and rotate in opposite directions; a hopper provided on the pair of rolls; and a discharge unit for discharging the powder from the hopper toward both ends of the pair of rolls. Rolling the powder with the pair of rolls while discharging the powder from the discharge unit,
The hopper includes side plates provided at both ends of the pair of rolls,
The powder rolling device, wherein the discharge part is a hole formed in the side plate. Using the powder rolling apparatus according to claim 1 or 2 , the powder supplied from the hopper is rolled by the pair of rolls while discharging the powder from the discharge portion of the hopper, and a rolled sheet is obtained. A method for producing a rolled sheet, characterized by comprising:

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