WO2014142045A1 - 電気化学素子電極用複合粒子の製造方法 - Google Patents
電気化学素子電極用複合粒子の製造方法 Download PDFInfo
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- WO2014142045A1 WO2014142045A1 PCT/JP2014/056102 JP2014056102W WO2014142045A1 WO 2014142045 A1 WO2014142045 A1 WO 2014142045A1 JP 2014056102 W JP2014056102 W JP 2014056102W WO 2014142045 A1 WO2014142045 A1 WO 2014142045A1
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- particles
- composite particles
- electrode
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UCLCELYDHWWXIR-UHFFFAOYSA-N lithium dioxido(dioxo)manganese iron(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Fe+2].[Li+] UCLCELYDHWWXIR-UHFFFAOYSA-N 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 125000005641 methacryl group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method for producing composite particles for electrochemical element electrodes.
- Lithium ion secondary batteries have a relatively high energy density and are used in mobile fields such as mobile phones and notebook personal computers.
- 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.
- 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.
- Application to applications that could not meet the specifications for capacitor performance is being considered.
- 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.
- Electrodes for electrochemical elements are usually formed by laminating an electrode active material layer formed by binding an electrode active material and a conductive material used as necessary with a binder on a current collector. Is. Electrodes for electrochemical devices were manufactured by a method in which a slurry composition containing an electrode active material, a binder, a conductive material, etc. was applied onto a current collector, and the solvent was removed by heat or the like. Due to such migration, it has been difficult to produce a uniform electrochemical device. In addition, this method has a problem in that the cost is high, the working environment is deteriorated, and the manufacturing apparatus is large.
- Patent Document 1 discloses composite particles by spraying and drying an aqueous slurry composition containing an electrode active material, a particulate binder, and water as a dispersion medium. And a method of forming an electrode active material layer using the composite particles is disclosed.
- Patent Document 1 a process of obtaining an aqueous slurry composition by mixing an electrode active material, a particulate binder and a dispersion medium (water), or granulating particles by spray drying the aqueous slurry composition.
- a metal foreign matter derived from stainless steel (Fe, Cr, Ni) or the like is mixed into the obtained aqueous slurry composition or granulated particles.
- a metal foreign substance causes an internal short circuit and a cause of performance deterioration in the electrochemical element, in order to suppress performance deterioration such as an internal short circuit and self-discharge of the electrochemical element, Management of foreign metal in Japan is a very important factor.
- Patent Document 2 describes that a metal foreign matter is removed from a binder such as a particulate binder, and an electrode active material layer is formed using the binder from which the metal foreign matter has been removed.
- Patent Document 3 discloses a method in which a metal foreign matter is removed from a slurry composition containing an electrode active material, a binder, and a conductive material, and the slurry composition from which the metal foreign matter has been removed is applied onto a current collector and dried. It describes that an electrode active material layer is formed.
- Patent Documents 2 and 3 have not been able to remove metallic foreign matters from the granulated particles.
- the objective of this invention is providing the manufacturing method of the composite particle for electrochemical element electrodes which can remove a metal foreign material from granulated particle.
- the present inventor has found that the above object can be achieved by removing metallic foreign matters in a pre-process and / or a post-process for separating coarse particles from granulated particles. was completed.
- It is a manufacturing method of the composite particle for electrochemical element electrodes including the granulation process which obtains a granulated particle by this, and the separation process which isolate
- a method for producing composite particles for electrochemical element electrodes (2) The method for producing composite particles for an electrochemical element electrode according to (1), wherein the separation step separates the coarse particles from the granulated particles with a mesh, (3)
- the volume average particle diameter of the composite particles for electrochemical device electrodes is 10 to 150 ⁇ m, and the opening diameter of the mesh is 1.1 to 6 of the volume average particle size of the composite particles for electrochemical device electrodes.
- the method for producing composite particles for electrochemical element electrodes according to (2) characterized in that it is 0 times, (4) The method for producing composite particles for electrochemical element electrodes according to (2) or (3), wherein the mesh is a metal mesh, (5) The method for producing composite particles for electrochemical element electrodes according to (4), wherein the metal mesh has a function of removing metal by magnetism, (6)
- the transferring step transfers the aqueous slurry composition using a pipe containing at least one of a magnetic material or a magnetizable material.
- the slurry production step and / or the transfer step further includes a step of removing metal foreign matter from the aqueous slurry composition by magnetism.
- the manufacturing method of the composite particle for electrochemical element electrodes of the present invention includes a slurry manufacturing step (S1) for obtaining an aqueous slurry composition containing an electrode active material and a particulate binder, and the aqueous slurry.
- 1st removal process which is a manufacturing method of the composite particle for electrochemical element electrodes including a isolation
- aqueous slurry composition containing an electrode active material and a particulate binder is produced.
- the water-system slurry composition obtained in a slurry manufacturing process (S1) contains the thickener mentioned later, and may contain other components, such as a electrically conductive material and an additive as needed.
- the electrode active material used in the present invention is appropriately selected depending on the kind of electrode for electrochemical device to be produced.
- 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.
- 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.
- the positive electrode active material illustrated above may be used independently according to a use, and may be used in mixture of multiple types. Further examples include polymers such as polyacetylene, poly-p-phenylene, and polyquinone. Of these, it is preferable to use a lithium-containing metal oxide.
- dope means occlusion, support, adsorption or insertion, and is defined as a phenomenon in which lithium ions and / or soot or anions enter the positive electrode, or a phenomenon in which lithium ions enter the negative electrode.
- De-doping also means release, desorption, and desorption, and is defined as the reverse phenomenon of the dope.
- 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
- 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.
- 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 the lithium ion secondary battery is preferably 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and still more preferably 0.8 for both the positive electrode and the negative electrode. ⁇ 20 ⁇ m.
- 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 of 2 g / cm 3 or more and a negative electrode of 0.6 g / cm 3 or more are preferably used. .
- 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 and the like. Among these, activated carbon and carbon nanotube are preferable.
- 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 preferably 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and still more preferably 0.8 to 20 ⁇ m.
- the specific surface area of the 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. Up to a specific surface area of about 2,000 m 2 / g, the capacitance per unit weight of activated carbon tends to increase as the specific surface area increases, but thereafter, the capacitance does not increase so much.
- the density of the material layer is lowered, and the capacitance density tends to be lowered. 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 active material layer having desired capacity density and input / output characteristics can be obtained by appropriately selecting an electrode active material.
- 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 particulate binder used in the present invention is not particularly limited as long as it is a compound capable of binding the above-described electrode active materials to each other, but in the present invention, a dispersion type having a property of being dispersed in a solvent.
- the particulate binder is preferred.
- the dispersion type particulate binder include high molecular compounds such as silicon polymers, fluorine-containing polymers, conjugated diene polymers, acrylate polymers, polyimides, polyamides, polyurethanes, and the like. Among these, a fluorine-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 conjugated diene homopolymer 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 preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 60% by weight or more.
- 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)
- SBR carboxy-modified styrene / butadiene copolymer
- NBR acrylonitrile / butadiene copolymer
- SBR acrylonitrile / butadiene copolymer
- NBR acrylonitrile / butadiene copolymer
- 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. 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.
- Acid esters carboxylic acid-containing (meth) acrylic acid esters such as 2- (meth) acryloyloxyethylphthalic acid and 2- (meth) acryloyloxyethylphthalic acid; fluorine such as perfluorooctylethyl (meth) acrylic acid 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;
- (meth) acrylic acid esters can be used alone or in combination of two or more. Of these, (meth) acrylic acid alkyl esters are preferred, 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.
- the acrylate polymer includes, 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 ⁇ , ⁇ -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 50% from the viewpoint of improving the flexibility of the obtained electrode for electrochemical devices and increasing the resistance to cracking. It is 95% by weight, more preferably 60 to 90% by weight.
- the acrylate polymer may be a copolymer of the above-described (meth) acrylic acid ester and a monomer copolymerizable therewith.
- a copolymerizable monomer examples thereof include ⁇ , ⁇ -unsaturated nitrile compounds and vinyl compounds having an acid component.
- Examples of the ⁇ , ⁇ -unsaturated nitrile compound include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -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 of the ⁇ , ⁇ -unsaturated nitrile compound unit in the acrylate polymer is preferably 0.1 to 40% by weight, more preferably 0.5 to 0.5% from the viewpoint of further increasing the binding force as a binder. 30% by weight, more preferably 1 to 20% by weight.
- 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 from 1 to 10% by weight, more preferably from 1.5 to 5.5% from the viewpoint of improving the stability of the aqueous slurry composition. 0% by weight.
- the acrylate polymer may be a copolymer of other monomers copolymerizable with the above-described monomers.
- examples of such other monomers include 2 Examples include carboxylic acid esters having one or more carbon-carbon double bonds, aromatic vinyl monomers, amide monomers, olefins, diene monomers, vinyl ketones, and heterocyclic ring-containing vinyl compounds. It is done.
- the dispersion type particulate binder used in the present invention is in the form of particles, so that it has good binding properties, and can suppress deterioration of the capacity of the produced electrode and repeated charge / discharge.
- the particulate binder include those in which a particulate binder such as latex is dispersed in water, and those obtained by drying such a dispersion.
- the volume average particle size of the dispersion type particulate binder used in the present invention is excellent in strength and flexibility of the obtained electrode for an electrochemical element while making the stability when it is an aqueous slurry composition good. In view of the above, it is preferably 0.001 to 100 ⁇ m, more preferably 10 to 1000 nm, and still more preferably 50 to 500 nm.
- the content of the particulate binder is based on 100 parts by weight of the electrode active material from the viewpoint of ensuring sufficient adhesion between the electrode active material layer and the current collector and reducing the internal resistance.
- the dry weight is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, and still more preferably 1 to 15 parts by weight.
- the aqueous slurry composition preferably contains a thickener in addition to the electrode active material and the particulate binder.
- a thickener is a component which has an effect
- Specific examples of thickeners include cellulosic polymers such as carboxymethylcellulose, methylcellulose, ethylcellulose and hydroxypropylcellulose, and their ammonium or alkali metal salts, alginates such as propylene glycol alginate, and alginates such as sodium alginate.
- Salts, polyacrylic acid, and polyacrylic acid (or methacrylic acid) salts such as sodium polyacrylic acid (or methacrylic acid), polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polycarboxylic acid, oxidized starch, phosphoric acid Examples include starch, casein, various modified starches, chitin, and chitosan derivatives. 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.
- “(modified) poly” means “unmodified poly” or “modified poly”
- “(meth) acryl” means “acryl” or “methacryl”.
- the amount of these thickeners used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the electrode active material. Is 0.5 to 5 parts by weight, more preferably 0.8 to 2 parts by weight.
- 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, preferably 0.001 to 10 ⁇ m, from the viewpoint of expressing sufficient conductivity with a smaller amount of use. More preferably, the thickness is 0.05 to 5 ⁇ m, and still more preferably 0.01 to 1 ⁇ m.
- the content ratio of the conductive material is preferably 0 with respect to 100 parts by weight of the electrode active material from the viewpoint of sufficiently reducing the internal resistance while keeping the capacity of the obtained electrochemical element high. 1 to 50 parts by weight, more preferably 0.5 to 15 parts by weight, still more preferably 1 to 10 parts by weight.
- surfactant examples 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 electrode active material. .
- the aqueous slurry composition used in the present invention is a slurry using water as a solvent, and contains other components used as necessary, such as the above-mentioned electrode active material, particulate binder, thickener and conductive material. It can be obtained by mixing in water. In addition, when the particulate binder is obtained as an aqueous dispersion dispersed in water as a solvent, the particulate binder can be added in a state of being dispersed in water. There is no particular limitation on the method and order of mixing other components used as necessary, such as an electrode active material, a particulate binder, a thickener, and a conductive material, in a solvent.
- Examples of the method for producing an aqueous slurry composition include a method using a mixing apparatus such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crushed grinder, an ultrasonic disperser, a homogenizer, a homomixer, and a planetary mixer. .
- the mixing is preferably performed at room temperature to 80 ° C. for 10 minutes to several hours.
- the viscosity of the aqueous slurry composition is preferably 10 to 3,000 mPa ⁇ s, more preferably 30 to 1,500 mPa ⁇ s, more preferably 50 to 50 at room temperature from the viewpoint of increasing the productivity of the granulation step. 1,000 mPa ⁇ s.
- Transfer process (S2) In the transfer step (S2) of the present invention, the aqueous slurry composition obtained in a mixing device or the like is transferred to a sprayer such as a spray or an atomizer described later.
- the transfer step (S2) it is preferable to transfer the aqueous slurry composition to a sprayer via a pipe.
- the material of the pipe is not particularly limited, but the material having magnetism from the viewpoint that even when the material of the pipe is scraped due to wear or the like during transfer and mixed into the aqueous slurry composition, it can be removed by a magnetic filter described later.
- a material that can be magnetized by a magnetic filter is preferable, economical, and SUS304 is most preferable from the viewpoint of easy magnetization by the magnetic filter.
- piping may contain only one type of these materials, and may contain two or more types.
- granulated particles are obtained by spraying and drying the aqueous slurry composition using a sprayer such as a spray or an atomizer.
- the granulated particles of the present invention comprise at least an electrode active material and a particulate binder.
- each of the electrode active material and the particulate binder does not exist as independent particles, but two components including the electrode active material and the particulate binder as constituent components.
- one particle is formed.
- a plurality of individual particles of the two or more components are combined to form secondary particles, and a plurality (preferably several to several tens) of electrode active materials are in a particulate form. What is bound by an adhesive to form particles is preferable.
- 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 granulated particles is preferably 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m, and still more preferably 30 to 60 ⁇ m.
- the average particle size of the composite particles is a volume average particle size calculated by measuring with a laser diffraction particle size distribution analyzer (for example, SALD-3100; manufactured by Shimadzu Corporation).
- the granulated particles used in the present invention can be obtained by a spray drying granulation method. By using the spray drying granulation method, the granulated particles can be easily obtained.
- Spray drying is a method of spraying and drying an aqueous slurry composition in hot air.
- An atomizer is mentioned as a sprayer used for spraying of an aqueous slurry composition.
- the rotational speed of the disk depends on the size of the disk, but is preferably 5,000 to 30,000 rpm, more 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.
- Rotating disk type atomizers include pin type and vane type.
- a pin-type atomizer is a type of centrifugal spraying machine that uses a spraying board.
- the spraying board 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 aqueous slurry composition is introduced from the center of the spray disc, adheres to the spraying roller by centrifugal force, moves outward on the roller surface, and finally sprays away from the roller surface.
- the vane type atomizer is formed so that a slit is cut on the inner side of the spray disc and the aqueous slurry composition passes therethrough.
- the pressurization method is a method in which the aqueous slurry composition is pressurized to form a mist from a nozzle and dried, and examples thereof include a pressurization nozzle method and a pressurization two-fluid nozzle method.
- the temperature of the water-based slurry composition to be sprayed is preferably room temperature, but may be higher than room temperature by heating.
- the hot air temperature during spray drying is preferably 80 to 250 ° C., more preferably 100 to 200 ° C.
- the method of blowing hot air is not particularly limited.
- 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.
- granulated particles containing other components added as necessary such as an electrode active material, a particulate binder, a thickener, and a conductive material, are obtained by the above production method. be able to.
- First removal step (S4) In the first removal step (S4) of the present invention, metal foreign matter is removed from the granulated particles obtained as described above by magnetism. In addition, a 1st removal process (S4) is performed before performing the isolation
- magnetic foreign matter is removed by the action of the magnetic filter when the granulated particles containing the magnetic foreign metal (hereinafter sometimes referred to as “magnetic foreign matter”) pass through the magnetic filter.
- the state in which the magnetic foreign matter is contained in the granulated particles means that the magnetic foreign matter is contained in the aggregate (powder) of the granulated particles, and the electrode active in the granulated particles.
- the electrode active material or particulate binder that forms granulated particles.
- the magnetic filter only needs to form a magnetic field having a magnetic flux density capable of collecting magnetic foreign substances that may be mixed into the granulated particles, but as the magnetic flux density, when the magnetic foreign substances are contained in the granulated particles, From the viewpoint of adequately adsorbing and removing the magnetic foreign matter, it is preferably 200 gauss or more, more preferably 400 gauss or more, and even more preferably 1000 gauss or more.
- the upper limit of the magnetic flux density is not particularly limited, but it is preferably not more than 100 gauss lower than the magnetic flux density at which a non-foreign material such as an electrode active material is collected.
- Magnetic foreign matter removed by the magnetic filter is not particularly limited, but iron powder, stainless steel powder and the like are representatively exemplified.
- the magnetic foreign substances described above exhibit various forms of granular forms depending on how the foreign substances are generated, such as wear, and there are also particles having sharp angles.
- the magnetic foreign matter is not removed, not only the foreign particles are mixed into the electrode for the electrochemical element by mixing the above-mentioned magnetic foreign particles having sharp angles into the granulated particles, but also containing composite particles as described later.
- a portion having a sharp angle (acute angle portion) of the magnetic foreign material particle may damage and break the current collector.
- the breakage of the current collector results in a defective process in the electrode forming process, which is not preferable for production of an electrode for an electrochemical element. Therefore, the removal of the magnetic foreign matters by installing the magnetic filter is effective not only from the viewpoint of suppressing the contamination of the electrochemical element electrodes but also from the viewpoint of improving the productivity in the electrode forming process.
- Separatation step (S5) In the separation step (S5) of the present invention, coarse particles are separated from the granulated particles.
- a method for separating coarse particles from granulated particles is not particularly limited, but a method of separating coarse particles with a mesh is preferable.
- the coarse particles are preferably 5 times or more, more preferably 4 times or more, and further preferably 3 times or more with respect to the volume average particle diameter of the obtained composite particles. That is, by separating coarse particles from granulated particles in the separation step, composite particles for electrochemical device electrodes (hereinafter, simply referred to as “composite particles”) can be obtained.
- the opening diameter of the mesh used when separating coarse particles with a mesh is preferably 1.1 to 6.0 times, more preferably 1.1 to 5.0 times the volume average particle size of the resulting composite particles. More preferably, it is 1.1 to 4.0 times.
- the material of the mesh used when separating coarse particles by the mesh is not particularly limited, but is usually selected from resin, metal, and magnetic material, and preferably metal.
- the resin mesh examples include a polyolefin resin mesh, an engineering plastic resin mesh, a fluorine resin mesh, and the like.
- a stainless steel mesh is usually used, and a tantalum mesh or a molybdenum mesh may be used.
- a magnetic filter which will be described later, even if they are mixed in composite particles by being scraped or damaged due to wear due to contact with granulated particles.
- a material that can be magnetized by a filter is preferable, economical, and SUS304 is most preferable from the viewpoint of easy magnetization by a magnetic filter.
- the magnetic material mesh is not particularly limited as long as it is a magnetic mesh, but as the magnetic material used for the magnetic material mesh, SUS430, SUS440C, SUS420J2, SUS410S, magnetic stainless steel dermalloy, Magnesten, etc. Is mentioned.
- a mesh made of a magnetic material from the viewpoint of further removing foreign metal particles in the separation step (S5).
- movement forms such as vibration, in-plane movement, and ultrasonic can be used.
- vibration type those that vibrate only in the horizontal direction are preferable.
- metal foreign matter may be removed from the aqueous slurry composition by magnetism.
- a metal foreign material can be removed using a magnetic filter. That is, when the aqueous slurry composition containing the magnetic foreign matter passes through the magnetic filter, the magnetic foreign matter is removed by the action of the magnetic filter.
- a magnetic filter similar to the magnetic filter that can be used in the first removal step (S4) can be used.
- the portion that can be contacted by the aqueous slurry and granulated particles and made of a metal material is the material of the piping in the transfer step (S2) or the mesh in the separation step (S5).
- the above materials even if they are mixed in an aqueous slurry composition or composite particles due to wear or destruction, they are magnetized by magnetic materials or magnetic filters from the viewpoint that they can be removed by a magnetic filter described later.
- the material to be obtained is preferred, economical, and SUS304 is most preferred from the viewpoint of easy magnetization by a magnetic filter.
- Examples of the apparatus including the above-described part preferably made of a material having magnetism or a material that can be magnetized by a magnetic filter include, for example, each of the mixing apparatuses exemplified as the aqueous slurry mixing apparatus in the slurry manufacturing step (S1).
- Each sprayer exemplified as a sprayer used for spraying the aqueous slurry in the granule step (S3), a separation apparatus incorporating a mesh or the like in the separation step (S5), and a magnetic filter in the removal step (S4, S6) are incorporated.
- Examples include a removal device. Among these devices and the like, it is particularly preferable that the inner wall portion in contact with the aqueous slurry, granulated particles, etc. is made of a magnetic material or a material that can be magnetized by a magnetic filter.
- the composite particles according to the present invention are obtained by performing at least the granulation step (S3), the separation step (S5), the first removal step (S4) and / or the second removal step (S5).
- the steps S1 to S7 shown in FIG. 1 are performed, but either the first removal step (S4) or the second removal step (S6) may be omitted. .
- the volume average particle diameter of the composite particles obtained by the method for producing composite particles for electrochemical element electrodes of the present invention is preferably 10 to 150 ⁇ m, more preferably 10 to 130 ⁇ m, and still more preferably 10 to 120 ⁇ m.
- the average particle diameter of the composite particles is a volume average particle diameter calculated by measuring with a laser diffraction particle size distribution measuring apparatus (for example, Microtrack: manufactured by Nikkiso).
- Electrochemical element electrode An electrochemical element electrode using composite particles of the present invention (hereinafter sometimes simply referred to as “electrode”) is formed by laminating an electrode active material layer containing composite particles on a current collector.
- the current collector material used for the electrode include metal, carbon, conductive polymer, and the like, and a suitable material is metal.
- the current collector metal usually include aluminum, platinum, nickel, tantalum, titanium, stainless steel, and other alloys. Among these, aluminum or an aluminum alloy is preferable in terms of conductivity and voltage resistance. Further, when high voltage resistance is required, high-purity aluminum as disclosed in JP-A-2001-176757 can be suitably used.
- the current collector is in the form of a film or a sheet, and the thickness is appropriately selected according to the purpose of use, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m.
- the electrode active material layer may be formed by forming an electrode material containing composite particles into a sheet shape, and then stacking on the current collector. However, the electrode material containing composite particles may be directly formed on the current collector and the active material layer Is preferably formed.
- a method for forming an electrode active material layer made of an electrode material there are a dry molding method such as a pressure molding method and a wet molding method such as a coating method, but a drying process is not required and an electrode is manufactured with high productivity. It is possible to use a dry molding method that can easily form a thick active material layer uniformly. Examples of the dry molding method include a pressure molding method and an extrusion molding method (also referred to as paste extrusion).
- the pressure forming method is a method of forming an electrode active material layer by applying pressure to the electrode material to perform densification by rearrangement and deformation of the electrode material.
- the extrusion molding method is a method in which an electrode material is formed into an extruded film, a sheet, or the like with an extruder, and the electrode active material layer can be continuously formed as a long product. Among these, it is preferable to use pressure molding because it can be performed with simple equipment.
- an electrode material containing composite particles is supplied to a roll-type pressure molding device with a feeder such as a screw feeder, and a roll pressure molding method for molding an electrode active material layer, or an electrode material Is applied to the current collector, the thickness of the electrode material is adjusted with a blade or the like, the thickness is adjusted, and the molding is then performed with a pressurizing device, and the mold is filled with the electrode material, and the mold is pressurized and molded.
- the electrode active material layer may be directly laminated on the current collector by feeding the current collector to the roll simultaneously with the supply of the electrode material.
- the molding temperature is preferably 0 to 200 ° C. from the viewpoint of ensuring sufficient adhesion between the electrode active material layer and the current collector, and the glass transition temperature of the particulate binder contained in the composite particles. More preferably, the temperature is 20 ° C. or higher.
- Roll press molding is performed at a molding speed of preferably 0.1 to 40 m / min, more preferably 1 to 40 m / min from the viewpoint of improving the uniformity of the thickness of the electrode active material layer.
- the pressing linear pressure between the rolls is preferably 0.2 to 30 kN / cm, more preferably 0.5 to 10 kN / cm.
- post-pressurization may be further performed as necessary.
- the post-pressing method is generally a press process using a roll.
- the roll press process two cylindrical rolls are arranged in parallel at a narrow interval in the vertical direction, and each is rotated in the opposite direction.
- An electrochemical element can be obtained using the electrode for an electrochemical element.
- the electrochemical element include lead storage batteries, alkaline batteries, lithium ion secondary batteries, electric storage devices such as electric double layer capacitors and lithium ion capacitors, lithium ion secondary batteries having excellent energy density and output density, electric double layers Capacitors and lithium ion capacitors are preferred.
- components other than the electrode for an electrochemical element include a separator and an electrolytic solution.
- a separator will not be specifically limited if it can insulate between the electrodes for electrochemical elements, and can pass a cation and an anion.
- polyolefins such as polyethylene and polypropylene, aromatic polyamides, microporous membranes or nonwoven fabrics made of rayon or glass fiber; porous membranes generally made of pulp called electrolytic capacitor paper; porous containing inorganic ceramic powder A quality resin coat or the like can be used.
- a separator is arrange
- the thickness of the separator is appropriately selected depending on the purpose of use, but is preferably 1 to 100 ⁇ m, more preferably 10 to 80 ⁇ m, and still more preferably 20 to 60 ⁇ m.
- an electrolyte is dissolved in an electrolytic solution solvent.
- an aprotic polar solvent can be used as the electrolyte solution solvent.
- Such aprotic polar solvent forms an aprotic organic electrolyte solution.
- aprotic polar solvent examples include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ⁇ -butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, dimethyl sulfate, sulfolane and the like. . Furthermore, you may use the liquid mixture which mixed 2 or more types of these aprotic polar solvents. When graphite is used as the active material for the negative electrode, it is preferable to include ethylene carbonate.
- the electrolyte dissolved in the electrolytic solution includes an electrolyte capable of generating lithium ions.
- electrolyte capable of generating lithium ions examples thereof include LiClO 4 , LiAsF 6 , LiBF 4 , LiPF 6 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiBC 4 O 8 , LiCF 3 SO 3 and the like.
- the electrolytes may be used alone or in combination. If the electrolyte contains an electrolyte capable of generating lithium ions as exemplified above, the cation is quaternary ammonium cation or spiro- (1,1 ′)-bipyrrole to such an extent that the properties are not adversely affected. An electrolyte which becomes a dinium cation may be included in the electrolytic solution.
- additives such as vinylene carbonate, fluoroethylene carbonate, ethylene sulfite, methyl acetate, and vinyl acetate may be added to the electrolyte as an additive for improving characteristics.
- an additive for flame retardancy such as Phoslite (manufactured by Nippon Chemical Industry Co., Ltd.) may be added.
- Electrochemical element is obtained by impregnating the above electrode and separator with electrolyte.
- the electrode and separator can be produced by winding, laminating or folding the electrode and separator into a container as necessary, and pouring the electrolyte into the container and sealing it.
- what impregnated electrolyte solution previously to the said electrode and separator may be accommodated in a container. Any known container such as a coin shape, a cylindrical shape, or a square shape can be used as the container.
- composite particles obtained by removing metal foreign substances from the granulated particles can be obtained.
- separated the coarse particle from the granulated particle can be obtained.
- Example 1 Preparation of aqueous carboxymethyl cellulose solution
- CMC carboxymethylcellulose having a solution viscosity of 8000 mPa ⁇ s (“Serogen BSH-12” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as carboxymethylcellulose (hereinafter, sometimes referred to as “CMC”)
- CMC carboxymethylcellulose
- aqueous slurry composition for negative electrode 100 parts of natural graphite was added as a negative electrode active material, and 1.0 part of the above CMC 1% aqueous solution was added to the solid content, and the solid content concentration was adjusted to 35% with ion-exchanged water, and then dispersed at 25 ° C. for 60 minutes. . Next, 2 parts of a solid binder (BM-400B) was added in solid content, and further mixed for 10 minutes to obtain an aqueous slurry composition for negative electrode. The produced negative electrode aqueous slurry composition was passed through a high magnetic mag filter (1.7 T) manufactured by Aisin.
- BM-400B a solid binder
- the negative electrode aqueous slurry composition passed through the mag filter is supplied to a spray dryer (made by Okawara Chemical Co., Ltd.), and using a rotating disk type atomizer (65 mm in diameter), the rotational speed is 25,000 rpm, Spray drying granulation was performed under the conditions of a hot air temperature of 150 ° C. and a particle recovery outlet temperature of 90 ° C. to obtain granulated particles for negative electrode.
- the obtained granulated particles for negative electrode were passed through a lattice mag filter manufactured by Aisin Co., and then coarse particles were removed with a magnetic mesh (opening diameter: 125 ⁇ m). Further, the composite particles for negative electrode having a volume average particle diameter of 75 ⁇ m were obtained through a lattice mag filter made by Aisin. When the iron content of the obtained composite particles for negative electrode was measured by ICP, the result was A.
- the composite particles for negative electrode obtained above are placed on a roll (roll temperature rough roll, manufactured by Hirano Giken Kogyo Co., Ltd.) roll (roll temperature 100 ° C., press linear pressure 4.0 kN / cm), current collector
- the positive electrode slurry composition obtained above was supplied to a spray dryer (“OC-16” manufactured by Okawara Chemical Industries Co., Ltd.), and a rotating disk type atomizer (diameter 65 mm) was used to rotate at 25,000 rpm and hot air temperature at 150 ° C. Then, spray drying granulation was performed under the condition of a particle recovery outlet temperature of 90 ° C. to obtain positive electrode granulated particles.
- the composite particles for positive electrode obtained above are pressed using a quantitative feeder (“Nikka Spray K-V” manufactured by Nikka Co., Ltd.) in a roll press machine (“Rough Surface Heat Roll” manufactured by Hiran Giken Co., Ltd.) (Roll temperature 100 ° C., press linear pressure 500 kN / m).
- An aluminum foil having a thickness of 20 ⁇ m is inserted between press rolls, and the positive electrode composite particles supplied from a quantitative feeder are adhered onto the aluminum foil (current collector) and pressed at a molding speed of 1.5 m / min. Molding was performed to obtain a positive electrode having a positive electrode active material layer.
- An aluminum packaging exterior was prepared as the battery exterior.
- the positive electrode obtained above was cut into a square of 4.6 ⁇ 4.6 cm 2 to obtain a square positive electrode.
- This square positive electrode was placed so that the current collector-side surface was in contact with the aluminum packaging exterior.
- a separator made of a square polypropylene porous film was disposed on the surface of the square positive electrode on the positive electrode active material layer side.
- the negative electrode after pressing obtained above was cut into a 5 ⁇ 5 cm 2 square to obtain a square negative electrode.
- the square negative electrode was placed on the square separator so that the surface on the negative electrode active material layer side faces the separator.
- Example 2 In the production of composite particles for negative electrode, the granulated particles for negative electrode obtained by spray-drying granulation were passed through a lattice mag filter manufactured by Aisin Co., and then coarse particles were removed with a magnetic mesh. Thereafter, the composite particles for negative electrode and the negative electrode were produced in the same manner as in Example 1 except that the composite particles for negative electrode having a volume average particle diameter of 73 ⁇ m were obtained without passing through a lattice mag filter made by Aisin.
- the granulated particles for positive electrode obtained by spray-drying granulation were passed through a lattice mag filter manufactured by Aisin Co., and then coarse particles were removed with a magnetic mesh. Thereafter, the composite particles for positive electrode and the positive electrode were manufactured in the same manner as in Example 1 except that the composite particles for positive electrode having a volume average particle diameter of 65 ⁇ m were obtained without passing through a lattice mag filter made by Aisin.
- a lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- Example 3 In the production of composite particles for negative electrode, coarse particles were removed by a magnetic mesh without passing the granulated particles for negative electrode obtained by spray-drying granulation through a lattice mag filter made by Aisin. Thereafter, the composite particles for negative electrode and the negative electrode were manufactured in the same manner as in Example 1 except that the composite particles for negative electrode having a volume average particle diameter of 77 ⁇ m were obtained through a lattice mag filter manufactured by Aisin.
- composite particles for positive electrode coarse particles were removed by a magnetic mesh without passing the granulated particles for positive electrode obtained by spray-drying granulation through a lattice mag filter made by Aisin. Thereafter, the composite particles for positive electrode and the positive electrode were manufactured in the same manner as in Example 1 except that the composite particles for positive electrode having a volume average particle diameter of 66 ⁇ m were obtained through a lattice mag filter manufactured by Aisin.
- a lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- Example 4 In the production of composite particles for negative electrode, the granulated particles for negative electrode obtained by spray-drying granulation were passed through a lattice magnet filter made by Aisin Co., and then coarse particles were removed with a non-magnetic mesh (opening diameter: 125 ⁇ m). . Thereafter, the composite particles for negative electrode and the negative electrode were manufactured in the same manner as in Example 1 except that the composite particles for negative electrode having a volume average particle diameter of 75 ⁇ m were obtained through a lattice mag filter manufactured by Aisin.
- composite particles for positive electrode after passing the granulated particles for positive electrode obtained by spray-drying granulation through a lattice mag filter made by Aisin, coarse particles are formed by a non-magnetic mesh (opening diameter 125 ⁇ m). Removed. Thereafter, the composite particles for positive electrode and the positive electrode were manufactured in the same manner as in Example 1 except that the composite particles for positive electrode having a volume average particle diameter of 67 ⁇ m were obtained through a lattice mag filter manufactured by Aisin. A lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- Example 5 In the production of composite particles for negative electrode, the granulated particles for negative electrode obtained by spray-drying granulation were passed through a lattice magnet filter made by Aisin Co., and then coarse particles were removed with a non-magnetic mesh (opening diameter: 125 ⁇ m). . Thereafter, the composite particles for negative electrode and the negative electrode were produced in the same manner as in Example 1 except that the composite particles for negative electrode having a volume average particle diameter of 73 ⁇ m were obtained without passing through a lattice mag filter made by Aisin.
- composite particles for positive electrode after passing the granulated particles for positive electrode obtained by spray-drying granulation through a lattice mag filter made by Aisin, coarse particles are formed by a non-magnetic mesh (opening diameter 125 ⁇ m). Removed. Thereafter, the composite particles for positive electrode and the positive electrode were manufactured in the same manner as in Example 1 except that the composite particles for positive electrode having a volume average particle diameter of 65 ⁇ m were obtained without passing through a lattice mag filter made by Aisin. A lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- Example 6 In the production of composite particles for negative electrode, coarse particles were removed with a non-magnetic mesh (opening diameter 125 ⁇ m) without passing the granulated particles for negative electrode obtained by spray-drying granulation through a lattice mag filter made by Aisin. . Thereafter, the composite particles for negative electrode and the negative electrode were manufactured in the same manner as in Example 1 except that the composite particles for negative electrode having a volume average particle diameter of 77 ⁇ m were obtained through a lattice mag filter manufactured by Aisin.
- the granulated particles for positive electrode obtained by spray-drying granulation are not passed through a lattice magnet filter made by Aisin Co., and coarse particles are formed with a non-magnetic mesh (opening diameter 125 ⁇ m). Removed. Thereafter, the composite particles for positive electrode and the positive electrode were manufactured in the same manner as in Example 1 except that the composite particles for positive electrode having a volume average particle diameter of 66 ⁇ m were obtained through a lattice mag filter manufactured by Aisin.
- a lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- aqueous slurry composition for negative electrode was produced in the same manner as in Example 1 except that the aqueous slurry composition for negative electrode prepared in the production of the aqueous slurry composition for negative electrode was not passed through a high magnetic mag filter made by Aisin. .
- negative electrode granulated particles were obtained by spray drying granulation of the aqueous slurry composition for negative electrode obtained as described above. This granulated particle for negative electrode was not passed through a lattice magnet filter made by Aisin Co., and the composite particles for negative electrode having a volume average particle diameter of 73 ⁇ m were obtained by removing coarse particles with a non-magnetic mesh. In the same manner as in No. 1, composite particles for negative electrode and negative electrode were manufactured.
- a positive electrode aqueous slurry composition was produced in the same manner as in Example 1 except that the positive electrode aqueous slurry composition produced in the production of the positive electrode aqueous slurry composition was not passed through a high magnetic mag filter made by Aisin. .
- positive electrode granulated particles were obtained by spray-drying and granulating the aqueous slurry composition for positive electrode obtained as described above.
- This granulated particle for positive electrode was not passed through a lattice mag filter made by Aisin Co., and the composite particles for positive electrode having a volume average particle diameter of 65 ⁇ m were obtained by removing coarse particles with a non-magnetic mesh.
- the composite particles for positive electrode and the positive electrode were manufactured.
- a lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- Comparative Example 2 In the production of composite particles for negative electrode, the granulated particles for negative electrode obtained by spray-drying granulation were passed through a lattice mug filter manufactured by Aisin. Thereafter, composite particles for negative electrode were produced in the same manner as in Example 1 except that composite particles for negative electrode having a volume average particle diameter of 73 ⁇ m were obtained without removing coarse particles using a magnetic mesh. Further, when the negative electrode was produced in the same manner as in Example 1, the negative electrode could not be produced.
- the granulated particles for positive electrode obtained by spray-drying granulation were passed through a lattice mug filter manufactured by Aisin. Thereafter, positive electrode composite particles were produced in the same manner as in Example 1 except that the composite particles for positive electrode having a volume average particle diameter of 66 ⁇ m were obtained without removing coarse particles using a magnetic mesh. Moreover, when the positive electrode was manufactured in the same manner as in Example 1, the positive electrode could not be manufactured.
- the granulated particles for positive electrode obtained by spray-drying granulation are not passed through a lattice mag filter made by Aisin Co., and further, the coarse particles are removed by a mesh having no magnetism.
- the composite particles for positive electrode and the positive electrode were manufactured in the same manner as in Example 1 except that the composite particles for positive electrode having an average particle diameter of 67 ⁇ m were obtained.
- a lithium ion secondary battery was produced in the same manner as in Example 1 using the negative electrode and the positive electrode obtained as described above.
- a slurry production process for obtaining an aqueous slurry composition containing an electrode active material and a particulate binder, a transfer process for transferring the aqueous slurry composition to a sprayer, and the sprayer are used.
- a method for producing composite particles for an electrochemical device electrode comprising a granulation step of obtaining granulated particles by spraying and drying, and a separation step of separating coarse particles from the granulated particles, wherein A first removal step of removing metal foreign matter magnetically from the obtained granulated particles and / or a second removal step of removing metal foreign matter magnetically from the granulated particles from which the coarse particles have been removed from the separation step.
- the composite particles obtained by the method for producing the composite particles contained had a small amount of residual metal foreign matter and good self-discharge characteristics.
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Abstract
Description
電気化学素子用電極は、電極活物質、結着剤、導電材等を含むスラリー組成物を集電体上に塗布し、溶剤を熱などにより除去する方法で製造されていたが、結着剤などのマイグレーションにより、均一な電気化学素子の製造が困難であった。また、この方法はコスト高で作業環境が悪くなり、製造装置が大きくなる課題があった。
本発明の目的は、造粒粒子から金属異物を除去することができる電気化学素子電極用複合粒子の製造方法を提供することである。
(1) 電極活物質及び粒子状結着剤を含む水系スラリー組成物を得るスラリー製造工程と、前記水系スラリー組成物を噴霧機に移送する移送工程と、前記噴霧機を用いて噴霧、乾燥することにより造粒粒子を得る造粒工程と、前記造粒粒子から粗大粒子を分離する分離工程とを含む電気化学素子電極用複合粒子の製造方法であって、前記造粒工程により得られた前記造粒粒子から磁気により金属異物を除去する第1除去工程および/または前記分離工程より前記粗大粒子が除去された前記造粒粒子から磁気により金属異物を除去する第2除去工程を含むことを特徴とする電気化学素子電極用複合粒子の製造方法、
(2) 前記分離工程は、メッシュにより前記造粒粒子から前記粗大粒子を分離することを特徴とする(1)記載の電気化学素子電極用複合粒子の製造方法、
(3) 前記電気化学素子電極用複合粒子の体積平均粒子径は10~150μmであって、前記メッシュの開口径は前記電気化学素子電極用複合粒子の体積平均粒子径の1.1~6.0倍であることを特徴とする(2)記載の電気化学素子電極用複合粒子の製造方法、
(4) 前記メッシュは、金属製メッシュであることを特徴とする(2)または(3)記載の電気化学素子電極用複合粒子の製造方法、
(5) 前記金属製メッシュは、磁気による金属除去機能を有することを特徴とする(4)記載の電気化学素子電極用複合粒子の製造方法、
(6) 前記移送工程は、磁性を有する材料または磁化され得る材料の少なくとも一方を含む配管を用いて前記水系スラリー組成物を移送することを特徴とする(1)~(5)の何れかに記載の電気化学素子電極用複合粒子の製造方法、
(7) 前記スラリー製造工程および/または前記移送工程は、さらに前記水系スラリー組成物から磁気により金属異物を除去する工程を含むことを特徴とする(1)~(6)の何れかに記載の電気化学素子電極用複合粒子の製造方法、
が提供される。
本発明のスラリー製造工程(S1)においては、電極活物質及び粒子状結着剤を含む水系スラリー組成物が製造される。また、スラリー製造工程(S1)において得られる水系スラリー組成物は、後述する増粘剤を含有するのが好ましく、必要に応じて導電材および添加剤等のその他の成分を含んでもよい。
本発明で用いる電極活物質は、製造される電気化学素子用電極の種類によって適宜選択される。たとえば、製造される電気化学用素子用電極が、リチウムイオン二次電池用の正極である場合、正極活物質としては、リチウムイオンを可逆的にドープ・脱ドープ可能な金属酸化物が挙げられる。かかる金属酸化物としては、例えば、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、燐酸鉄リチウム、燐酸マンガンリチウム、燐酸バナジウムリチウム、バナジン酸鉄リチウム、ニッケル-マンガン-コバルト酸リチウム、ニッケル-コバルト酸リチウム、ニッケル- マンガン酸リチウム、鉄-マンガン酸リチウム、鉄-マンガン-コバルト酸リチウム、珪酸鉄リチウム、珪酸鉄- マンガンリチウム、酸化バナジウム、バナジン酸銅、酸化ニオブ、硫化チタン、酸化モリブデン、硫化モリブデン、等を挙げることができる。なお、上記にて例示した正極活物質は適宜用途に応じて単独で使用してもよく、複数種混合して使用してもよい。さらに、ポリアセチレン、ポリ-p-フェニレン、ポリキノンなどのポリマーが挙げられる。これらのうち、リチウム含有金属酸化物を用いることが好ましい。
本発明で用いる粒子状結着剤としては、上述した電極活物質を相互に結着させることができる化合物であれば特に制限はないが、本発明においては、溶媒に分散する性質を有する分散型の粒子状結着剤が好ましい。分散型の粒子状結着剤としては、たとえば、シリコン系重合体、フッ素含有重合体、共役ジエン系重合体、アクリレート系重合体、ポリイミド、ポリアミド、ポリウレタン等の高分子化合物が挙げられ、これらのなかでもフッ素系含有重合体、共役ジエン系重合体及びアクリレート系重合体が好ましく、共役ジエン系重合体及びアクリレート系重合体がより好ましい。
水系スラリー組成物には、電極活物質及び粒子状結着剤に加えて、増粘剤を含有するのが好ましい。増粘剤は、電極用複合粒子を構成する各成分を、溶媒に分散又は溶解させて水系スラリー組成物とする際に、各成分を溶媒中に均一に分散させる作用を有する成分である。増粘剤の具体例としては、カルボキシメチルセルロース、メチルセルロース、エチルセルロース及びヒドロキシプロピルセルロースなどのセルロース系ポリマー、ならびにこれらのアンモニウム塩又はアルカリ金属塩、アルギン酸プロピレングリコールエステルなどのアルギン酸エステル、ならびにアルギン酸ナトリウムなどのアルギン酸塩、ポリアクリル酸、及びポリアクリル酸(又はメタクリル酸)ナトリウムなどのポリアクリル酸(又はメタクリル酸)塩、ポリビニルアルコール、変性ポリビニルアルコール、ポリエチレンオキシド、ポリビニルピロリドン、ポリカルボン酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプン、キチン、キトサン誘導体などが挙げられる。これらの分散剤は、それぞれ単独で又は2種以上を組み合わせて使用できる。中でも、セルロース系ポリマーが好ましく、カルボキシメチルセルロース又はそのアンモニウム塩もしくはアルカリ金属塩が特に好ましい。本発明において、「(変性)ポリ」は「未変性ポリ」又は「変性ポリ」を意味し、「(メタ)アクリル」は、「アクリル」又は「メタアクリル」を意味する。
また、水系スラリー組成物には、電極活物質、粒子状結着剤及び増粘剤に加えて、必要に応じて、導電材、界面活性剤等を含有させてもよい。
導電材としては、導電性を有する粒子状の材料であればよく、導電材の具体例としては、ファーネスブラック、アセチレンブラック、及びケッチェンブラック(アクゾノーベル ケミカルズ ベスローテン フェンノートシャップ社の登録商標)などの導電性カーボンブラックが挙げられる。これらの中でも、アセチレンブラックおよびケッチェンブラックが好ましい。導電材の平均粒子径は、特に限定されないが、より少ない使用量で十分な導電性を発現させる観点から、電極活物質の平均粒子径よりも小さいものが好ましく、好ましくは0.001~10μm、より好ましくは0.05~5μm、さらに好ましくは0.01~1μmである。
界面活性剤としては、アニオン性、カチオン性、ノニオン性、ノニオニックアニオン等の両性の界面活性剤が挙げられるが、アニオン性又はノニオン性界面活性剤で熱分解しやすいものが好ましい。界面活性剤の配合量は、電極活物質100重量部に対して、好ましくは50重量部以下であり、より好ましくは0.1~10重量部、さらに好ましくは0.5~5重量部である。
本発明に用いる水系スラリー組成物は、水を溶媒として用いたスラリーであり、上述の電極活物質、粒子状結着剤、増粘剤及び導電材等の必要に応じて用いられるその他の成分を水中で混合することにより得ることができる。なお、粒子状結着剤が溶媒としての水に分散された水分散体として得られる場合には、粒子状結着剤を水に分散させた状態で添加することができる。
電極活物質、粒子状結着剤、増粘剤及び導電材等の必要に応じて用いられるその他の成分を溶媒中に混合する方法、順序は、特に限定されない。
本発明の移送工程(S2)では、混合装置等において得られた上記水系スラリー組成物を後述するスプレーやアトマイザー等の噴霧機に移送する。
本発明の造粒工程(S3)では、スプレー、アトマイザー等の噴霧機を用いて上記水系
スラリー組成物を噴霧、乾燥することにより造粒粒子を得る。
本発明の第1除去工程(S4)においては、上述のように得られた造粒粒子から磁気により金属異物を除去する。なお、第1除去工程(S4)は、造粒粒子から粗大粒子を分離する分離工程(S5)を行う前に行われる。
本発明の分離工程(S5)においては、造粒粒子から粗大粒子を分離する。造粒粒子から粗大粒子を分離する方法としては、特に限定されないが、メッシュにより粗大粒子を分離する方法が好ましい。
金属製メッシュとしては、通常ステンレス製メッシュが用いられ、タンタル製メッシュ、モリブデン製メッシュを用いてもよい。また、ステンレス製メッシュの中でも、造粒粒子との接触による摩耗により削られたり、破損したりすることにより、複合粒子中に混入した場合でも後述する磁気フィルタにより除去が可能である観点から、磁気フィルタによって磁化され得る材料が好ましく、経済的であり、磁気フィルタによる磁化のされやすさの観点から、SUS304が最も好ましい。
磁性材料製メッシュとしては、磁性を帯びているメッシュであれば特に制限はないが、磁性材料製メッシュに用いられる磁性材料としては、SUS430、SUS440C、SUS420J2、SUS410S、磁性ステンレス鋼ダーマロイ、マグネステン等が挙げられる。
本発明の第2除去工程(S6)においては、上述のように分離工程(S5)により粗大粒子が分離された造粒粒子から磁気により金属異物を除去する。造粒粒子から磁気により金属異物を除去する方法としては、特に制限はないが、上記第1除去工程(S4)に用いることができる方法と同様の方法を用いることができる。
本発明の上記スラリー製造工程(S1)および/または上記移送工程(S2)において、水系スラリー組成物から磁気により金属異物を除去してもよい。水系スラリー組成物から金属異物を除去する方法としては、特に制限はないが、たとえば磁気フィルタを用いて金属異物を除去することができる。即ち、磁性異物が含有されている水系スラリー組成物が磁気フィルタを通過する際に、磁気フィルタの作用により磁性異物が除去される。
磁気フィルタとしては、上記第1除去工程(S4)に用いることができる磁気フィルタと同様の磁気フィルタを用いることができる。
磁性を有する材料あるいは磁気フィルタによって磁化され得る材料で構成するのが好ましい前記部分を含む装置等としては、例えば、スラリー製造工程(S1)における水系スラリーの混合装置として例示した前記各混合装置、造粒工程(S3)における水系スラリーの噴霧に用いる噴霧機として例示した前記各噴霧機、分離工程(S5)におけるメッシュ等を組み込んだ分離装置及び除去工程(S4、S6)における、磁気フィルタを組み込んだ除去装置などが挙げられる。これらの装置等の中でも特に、水系スラリーや造粒粒子等が接触する内壁部分が磁性を有する材料あるいは磁気フィルタによって磁化され得る材料で構成されているのが好ましい。
本発明に係る複合粒子は、少なくとも上記造粒工程(S3)、上記分離工程(S5)及び上記第1除去工程(S4)および/または上記第2除去工程(S5)を行うことにより得られる。
本発明の複合粒子を用いた電気化学素子電極(以下、単に「電極」ということがある。)は、複合粒子を含む電極活物質層を集電体上に積層してなる。電極に使用される集電体用材料としては、例えば、金属、炭素、導電性高分子などが挙げられ、好適な材料としては金属が挙げられる。集電体用金属としては、通常、アルミニウム、白金、ニッケル、タンタル、チタン、ステンレス鋼、その他の合金等が挙げられる。これらの中で導電性、耐電圧性の面からアルミニウムまたはアルミニウム合金が好ましい。また、高い耐電圧性が要求される場合には特開2001-176757号公報等で開示されるような高純度のアルミニウムを好適に用いることができる。集電体は、フィルムまたはシート状であり、その厚みは、使用目的に応じて適宜選択されるが、好ましくは1~200μm、より好ましくは5~100μm、さらに好ましくは10~50μmである。
上記電気化学素子用電極を用いて電気化学素子を得ることができる。電気化学素子としては、鉛蓄電池、アルカリ電池、リチウムイオン二次電池、電気二重層キャパシタやリチウムイオンキャパシタ等の蓄電デバイスが挙げられ、エネルギー密度と出力密度に優れるリチウムイオン二次電池、電気二重層キャパシタやリチウムイオンキャパシタが好ましい。
電気化学素子用電極以外の他の構成要素としては、セパレータおよび電解液が挙げられる。
セパレータは、電気化学素子用電極の間を絶縁でき、陽イオンおよび陰イオンを通過させることができるものであれば特に限定されない。具体的には、ポリエチレンやポリプロピレンなどのポリオレフィンや芳香族ポリアミド、レーヨンもしくはガラス繊維製の微孔膜または不織布;一般に電解コンデンサ紙と呼ばれるパルプを主原料とする多孔質膜;無機セラミック粉末を含む多孔質の樹脂コートなどを用いることができる。セパレータは、上記一対の電極活物質層が対向するように、電気化学素子用電極の間に配置され、素子が得られる。セパレータの厚みは、使用目的に応じて適宜選択されるが、好ましくは1~100μm、より好ましくは10~80μm、さらに好ましくは20~60μmである。
電解液には、電解液溶媒に電解質が溶解されている。リチウムイオン二次電池、およびリチウムイオンキャパシタの場合には、電解液溶媒には、例えば、非プロトン性極性溶媒を使用することができる。かかる非プロトン性極性溶媒は、非プロトン性有機電解質溶液を形成する。非プロトン性極性溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、γ -ブチロラクトン、アセトニトリル、ジメトキシエタン、テトラヒドロフラン、ジオキソラン、塩化メチレン、ジメチルサルフェート、スルホラン等が挙げられる。さらに、これら非プロトン性極性溶媒の二種以上を混合した混合液を用いても構わない。負極の活物質に黒鉛を用いる場合にはエチレンカーボネートを含むことが好ましい。
実施例および比較例で調製した正極用複合粒子及び負極用複合粒子について酸で煮沸することで溶解し、ICP(Inductively Coupled Plasma)高周波プラズマ発光分析により金属異物含有量として、鉄含有量を測定し、下記の基準により評価した。結果を表1に示した。
A:鉄含有量が30ppm未満
B:鉄含有量が30ppm以上35ppm未満
C:鉄含有量が35ppm以上45ppm未満
D:鉄含有量が45ppm以上55ppm未満
E:鉄含有量が55ppm以上
ラミネート型のリチウムイオン二次電池について25℃で0.1Cの定電流法によって、満充電し、24時間25℃で放置し、電圧低下の割合を測定し、結果を表1に示した。値が小さいほど自己放電特性に優れることを示す。
(カルボキシメチルセルロース水溶液の作製)
カルボキシメチルセルロース(以下、「CMC」ということがある。)として、溶液粘度が8000mPa・sであるCMC(第一工業製薬株式会社製「セロゲンBSH-12」)を用い、CMCの1%水溶液を調整した。
負極活物質として天然黒鉛100部を入れ、これに上記CMC1%水溶液を固形分相当で1.0部加え、イオン交換水で固形分濃度35%に調整した後、25℃で60分ディスパー混合した。次に、粒子状結着剤(BM-400B)を固形分で2部入れ、さらに10分混合して負極用水系スラリー組成物を得た。作製した負極用水系スラリー組成物をエイシン社製高磁力マグ・フィルター(1.7T)に通した。
次に、マグ・フィルターを通した負極用水系スラリー組成物を、スプレー乾燥機(大川原化工機社製)に供給し、回転円盤方式のアトマイザ(直径65mm)を用いて、回転数25,000rpm、熱風温度150℃、粒子回収出口の温度90℃の条件にて、噴霧乾燥造粒を行い、負極用造粒粒子を得た。得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通した後、磁性メッシュ(開口径125μm)により粗大粒子を除去した。さらにエイシン社製格子マグ・フィルターに通し体積平均粒子径が75μmの負極用複合粒子を得た。ICPにより、得られた負極用複合粒子の鉄の含有量を測定したところ、A判定であった。
上記にて得られた負極用複合粒子を、ロールプレス機(押し切り粗面熱ロール、ヒラノ技研工業社製)のロール(ロール温度100℃、プレス線圧4.0kN/cm)に、集電体としての電解銅箔(厚さ:20μm)とともに供給し、成形速度20m/分で、集電体としての電解銅箔上に、シート状に成形し、厚さ80μmの負極活物質層を有する負極を得た。
ディスパー付プラネタリーミキサーに、LCO(「LiCoO2」の略称)系正極活物質を100部、アセチレンブラック(電気化学工業社製「HS-100」)を4.0部、CMCの1%水溶液(第一工業製薬社製「BSH-12」)を固形分相当で1.0部加え、イオン交換水で全固形分濃度が85%(水分率15%)となるように調製して混合物を得た。得られた混合物を、プラネタリーミキサーを用いて、25℃で60分間混練した。そこに、アクリル系粒子状結着樹脂の40%水分散液を固形分相当で2.0部加え、イオン交換水で全固形分濃度が75%(水分率25%)となるように調製して混合し、正極用スラリー組成物を得た。得られた正極用スラリー組成物の粘度を測定したところ、830mPa・sであった。
上記で得た正極用スラリー組成物を、スプレー乾燥機(大川原化工機社製「OC-16」)に供給し、回転円盤方式のアトマイザー(直径65mm)を用いて回転数25000rpm、熱風温度150℃、粒子回収出口温度90℃の条件にて、噴霧乾燥造粒を行い、正極用造粒粒子を得た。得られた正極用造粒粒子をエイシン社製格子マグ・フィルターに通した後、磁性メッシュ(開口径125μm)により粗大粒子を除去し、さらにエイシン社製格子マグ・フィルターに通し体積平均粒子径は67μmであった。ICPにより、得られた正極用複合粒子の鉄の含有量を測定したところA判定であった。
上記で得られた正極用複合粒子を、定量フィーダ(ニッカ社製「ニッカスプレーK-V」)を用いてロールプレス機(ヒラノ技研工業社製「押し切り粗面熱ロール」)のプレス用ロール(ロール温度100℃、プレス線圧500kN/m)に供給した。プレス用ロール間に、厚さ20μmのアルミニウム箔を挿入し、定量フィーダから供給された上記正極用複合粒子をアルミニウム箔(集電体)上に付着させ、成形速度1.5m/分で加圧成形し、正極活物質層を有する正極を得た。
電池の外装として、アルミ包材外装を用意した。上記で得られた正極を、4.6×4.6cm2の正方形に切り出し、正方形の正極を得た。この正方形の正極を、その集電体側の表面がアルミ包材外装に接するように配置した。正方形の正極の正極活物質層側の面上に、正方形のポリプロピレン製多孔膜からなるセパレータを配置した。
上記で得られたプレス後の負極を、5×5cm2の正方形に切り出し、正方形の負極を得た。この正方形の負極を、上記の正方形のセパレータ上に、負極活物質層側の表面がセパレータに向かい合うよう配置した。電解液(溶媒:EC/DEC/VC=68.5/30/1.5体積比(25℃)、電解質:濃度1MのLiPF6)を空気が残らないように注入し、さらに、150℃のヒートシールをしてアルミ外装を閉口し、アルミ包材の開口を密封した。これにより、リチウムイオン二次電池を製造した。得られたリチウムイオン二次電池について、得られたリチウムイオン二次電池の自己放電特性を測定したところ0.10%であった。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通した後、磁性メッシュにより粗大粒子を除去した。その後エイシン社製格子マグ・フィルターに通さずに体積平均粒子径73μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造及び負極の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通さずに、磁性メッシュにより粗大粒子を除去した。その後エイシン社製格子マグ・フィルターに通して体積平均粒子径77μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造及び負極の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通した後、磁性を有しないメッシュ(開口径125μm)により粗大粒子を除去した。その後エイシン社製格子マグ・フィルターに通して体積平均粒子径75μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造及び負極の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通した後、磁性を有しないメッシュ(開口径125μm)により粗大粒子を除去した。その後エイシン社製格子マグ・フィルターに通さずに体積平均粒子径73μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造及び負極の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通さずに、磁性を有しないメッシュ(開口径125μm)により粗大粒子を除去した。その後エイシン社製格子マグ・フィルターに通して体積平均粒子径77μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造及び負極の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
負極用水系スラリー組成物の製造において作製した負極用水系スラリー組成物をエイシン社製高磁力マグ・フィルターに通さなかった以外は、実施例1と同様に負極用水系スラリー組成物の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通した。その後磁性メッシュを用いた粗大粒子の除去を行わずに体積平均粒子径73μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造を行った。また、実施例1と同様に負極の製造を行ったところ、負極を製造することができなかった。
負極用複合粒子の製造において、噴霧乾燥造粒により得られた負極用造粒粒子をエイシン社製格子マグ・フィルターに通さず、さらに、磁性を有しないメッシュにより粗大粒子を除去して体積平均粒子径73μmの負極用複合粒子を得た以外は、実施例1と同様に負極用複合粒子の製造及び負極の製造を行った。
上述のようにして得られた負極および正極を用いて実施例1と同様にリチウムイオン二次電池の製造を行った。
Claims (7)
- 電極活物質及び粒子状結着剤を含む水系スラリー組成物を得るスラリー製造工程と、
前記水系スラリー組成物を噴霧機に移送する移送工程と、
前記噴霧機を用いて噴霧、乾燥することにより造粒粒子を得る造粒工程と、
前記造粒粒子から粗大粒子を分離する分離工程と
を含む電気化学素子電極用複合粒子の製造方法であって、
前記造粒工程により得られた前記造粒粒子から磁気により金属異物を除去する第1除去工程および/または前記分離工程より前記粗大粒子が除去された前記造粒粒子から磁気により金属異物を除去する第2除去工程を含むことを特徴とする電気化学素子電極用複合粒子の製造方法。 - 前記分離工程は、メッシュにより前記造粒粒子から前記粗大粒子を分離することを特徴とする請求項1記載の電気化学素子電極用複合粒子の製造方法。
- 前記電気化学素子電極用複合粒子の体積平均粒子径は10~150μmであって、前記メッシュの開口径は前記電気化学素子電極用複合粒子の体積平均粒子径の1.1~6.0倍であることを特徴とする請求項2記載の電気化学素子電極用複合粒子の製造方法。
- 前記メッシュは、金属製メッシュであることを特徴とする請求項2または3記載の電気化学素子電極用複合粒子の製造方法。
- 前記金属製メッシュは、磁気による金属除去機能を有することを特徴とする請求項4記載の電気化学素子電極用複合粒子の製造方法。
- 前記移送工程は、磁性を有する材料または磁化され得る材料の少なくとも一方を含む配管を用いて前記水系スラリー組成物を移送することを特徴とする請求項1~5の何れか一項に記載の電気化学素子電極用複合粒子の製造方法。
- 前記スラリー製造工程および/または前記移送工程は、さらに前記水系スラリー組成物から磁気により金属異物を除去する工程を含むことを特徴とする請求項1~6の何れか一項に記載の電気化学素子電極用複合粒子の製造方法。
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JP6304236B2 (ja) | 2018-04-04 |
CN104995768A (zh) | 2015-10-21 |
KR20150132082A (ko) | 2015-11-25 |
CN104995768B (zh) | 2017-08-18 |
JPWO2014142045A1 (ja) | 2017-02-16 |
KR102230705B1 (ko) | 2021-03-19 |
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