WO2015166777A1 - 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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- WO2015166777A1 WO2015166777A1 PCT/JP2015/061048 JP2015061048W WO2015166777A1 WO 2015166777 A1 WO2015166777 A1 WO 2015166777A1 JP 2015061048 W JP2015061048 W JP 2015061048W WO 2015166777 A1 WO2015166777 A1 WO 2015166777A1
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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
- H01G11/84—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
-
- 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
-
- 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
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a method for producing composite particles for electrochemical element electrodes.
- Electrochemical elements such as lithium ion secondary batteries that are small and lightweight, have high energy density, and can be repeatedly charged and discharged are rapidly expanding their demands by taking advantage of their characteristics.
- Lithium ion secondary batteries are used in fields such as mobile phones, notebook personal computers, and electric vehicles because of their relatively high energy density.
- electrochemical elements are required to be further improved in accordance with expansion and development of applications, such as lowering resistance, increasing capacity, improving mechanical properties and productivity. Under such circumstances, there is a demand for a more productive manufacturing method for electrochemical element electrodes, and various improvements have been made regarding the manufacturing method capable of high-speed molding and the materials for electrochemical element electrodes suitable for the manufacturing method. Has been done.
- 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 that the cost is high, the working environment is deteriorated, and the manufacturing apparatus is large.
- Patent Document 1 discloses a step of granulating a slurry comprising an electrode active material, a conductive material, a dispersion-type binder, and a soluble resin by spray drying. Is disclosed.
- mass production of composite particles for electrochemical element electrodes has not been considered.
- the resulting composite particle moldability (dry moldability) and the characteristics of the battery using the molded electrode (cycle characteristics) declined. It was found that the cause was the broadening of the particle size distribution in the granulation process of the composite particles.
- An object of the present invention is to provide a method for producing composite particles for an electrochemical element electrode that can suppress broadening of the particle size distribution even in mass production.
- the present inventor used a slurry prepared with a predetermined concentration containing an electrode active material and a binder, and in the granulation step of the composite particles, the flow rate of dry air used during spray drying was determined.
- the inventors have found that the above object can be achieved by setting the content in a predetermined range, and have completed the present invention.
- a method for producing composite particles for electrochemical element electrodes in which a slurry is prepared by dispersing or dissolving an electrode active material and a binder in a medium to obtain a slurry, and the slurry is spray-dried to obtain granulated particles.
- a solid content concentration of the slurry obtained in the slurry preparation step is 20% by weight or more and 90% by weight or less, including a granulation step and a removal step of removing foreign substances and / or coarse particles from the granulated particles.
- a method for producing composite particles for an electrochemical element electrode wherein the flow rate of dry air during spray drying in the granulation step is 10 m / s or more and less than 40 m / s, (2) The method according to (1), further including a transfer step of transferring the granulated particles by air after the granulation step, wherein an air flow rate in the transfer step is 0.5 m / s or more and 20 m / s or less.
- FIG. 1 is a schematic view of a composite particle manufacturing apparatus used in the method for manufacturing composite particles for electrochemical element electrodes according to an embodiment of the present invention.
- the composite particle manufacturing apparatus 2 manufactures granulated particles 12 from the slurry tank 6 and the slurry 4, in which the raw material charged through the raw material charging pipe 8 is stirred by the stirring blade 10 to prepare the slurry 4.
- Granulator 14, pipe 20 for transferring granulated particles 12 produced by granulator 14, sieve 22 for removing foreign substances and / or coarse particles from granulated particles 12 transferred via pipe 20, electrochemical A storage tank 24 for storing the composite particles 26 for device electrodes is provided.
- the granulator 14 includes a drying furnace 16, and a rotary disk 18 that sprays the slurry 4 while rotating is provided inside the drying furnace 16.
- An air inflow port 17 a is provided at the upper part of the drying furnace 16, and a connection part (not shown) to the pipe 20 is provided at the lower part of the drying furnace 16.
- a connection part (not shown) to the pipe 20 is provided at the lower part of the drying furnace 16.
- two cyclones (cyclones 30 and 34) for separating the granulated particles 12 and air and letting out a part of the air are provided, and the cyclones 30 and 34 have an air outlet 30 a. , 34a are provided.
- a recovery tank 32 is provided downstream of the cyclone 30, and pressurized air is supplied to the recovery tank 32. Further, air is caused to flow into the pipe 20 on the downstream side of the recovery tank 32 from the air inlet 17b.
- slurry production process In the slurry preparation step of the present invention, an electrode active material and a binder are dispersed or dissolved in a medium to obtain a slurry.
- the slurry preparation step is performed in the slurry tank 6 of the composite particle manufacturing apparatus 2 shown in FIG. 1, and the slurry 4 is charged with the raw material containing the electrode active material, the binder and the medium into the slurry tank 6 and stirred by the stirring blade 10. Can be obtained.
- the slurry 4 can be obtained by dispersing or dissolving the electrode active material and the binder in a medium.
- the slurry 4 may contain a viscosity modifier and carbon fine particles as necessary.
- a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer and a planetary kneader may be used.
- the method or procedure for dispersing or dissolving the electrode active material, binder, and viscosity modifier or carbon fine particles used in the medium in the medium for example, the electrode active material, the binder, and the medium are used as necessary. Viscosity modifier and carbon fine particles are added and mixed; after the viscosity modifier is dissolved in the medium, the binder dispersed in the medium is added and mixed, and finally the electrode active material and carbon fine particles are added and mixed.
- the viscosity of the slurry obtained by the slurry preparation step is preferably 100 to 5000 mPa ⁇ s, more preferably 100 to 3000 mPa ⁇ s, and still more preferably 100 to 2000 mPa ⁇ s.
- the viscosity of the slurry is a value measured using a B-type viscometer at a temperature of 25 ° C. and a rotation speed of 60 rpm.
- the solid content concentration of the slurry obtained by the slurry preparation step is 20% by weight or more and 90% by weight or less, preferably 30% by weight or more and 90% by weight or less, more preferably 35% by weight or more and 90% by weight or less. is there.
- the solid content concentration of the slurry is too high, the above viscosity range cannot be obtained, and the fluidity is also deteriorated.
- the solid content concentration of the slurry is too low, the productivity of the composite particles is lowered. Further, the stability of the slurry is deteriorated.
- the electrode active material used in the present invention is appropriately selected depending on the type of electrochemical device to be produced.
- the positive electrode active material used for the positive electrode of the lithium ion secondary battery is a metal oxide capable of reversibly doping and dedoping lithium ions.
- the metal oxide include lithium cobaltate (hereinafter sometimes referred to as “LCO”), lithium nickelate, lithium manganate, lithium iron phosphate (hereinafter sometimes referred to as “LFP”), and phosphoric 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.
- lithium iron phosphate and lithium manganese phosphate are also included.
- Further examples include polymers such as polyacetylene, poly-p-phenylene, and polyquinone. Of these, LCO, NMC, and LFP are preferably used.
- dope means occlusion, support, adsorption or insertion, and is defined as a phenomenon in which lithium ions and / or anions enter the positive electrode or a phenomenon in which lithium ions enter the negative electrode.
- De-doping also means release, desorption, and desorption, and is defined as the reverse phenomenon of the dope.
- a negative electrode active material used for the negative electrode of a lithium ion secondary battery as a counter electrode of the positive electrode of the lithium ion secondary battery mentioned above graphitizable carbon, non-graphitizable carbon, activated carbon, pyrolytic carbon, etc.
- the electrode active material illustrated above may be used independently according to a use, and may be used in mixture of multiple types.
- the binder used in the present invention is not particularly limited as long as it is a compound capable of binding the above-mentioned electrode active materials to each other, but in the present invention, a dispersion type binder having a property of being dispersed in a medium is preferable.
- the dispersion type binder include high molecular compounds such as silicon polymers, fluorine-containing polymers, conjugated diene polymers, acrylate polymers, polyimides, polyamides, and polyurethanes. A diene polymer and an acrylate polymer are preferred.
- 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 10% by weight or more, more preferably 20% by weight or more, and further preferably 30% 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
- hydrogenated SBR hydrogenated NBR
- SBR acrylonitrile / butadiene copolymer
- NBR acrylonitrile / butadiene copolymer
- SBR acrylonitrile / butadiene copolymer
- NBR acrylonitrile / butadiene copolymer
- SBR, NBR, and hydrogenated NBR are preferable.
- the acrylate polymer is a polymer containing a (meth) acrylic acid ester monomer unit.
- a polymer containing a (meth) acrylic acid ester monomer unit and further containing at least one of an ⁇ , ⁇ -unsaturated nitrile monomer unit and an acidic functional group-containing monomer unit is preferred, and ⁇ , ⁇ -More preferred are polymers comprising both unsaturated nitrile monomer units and acidic functional group-containing monomer units.
- the binding force of the binder can be further improved.
- “including a monomer unit” means “a monomer-derived structural unit is contained in a polymer obtained using the monomer”.
- Examples of (meth) acrylic acid ester monomers that can be used in the production of the acrylate polymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, Acrylic acid alkyl esters such as hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl Methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate , Hex
- An alkyl group bonded to a non-carbonyl oxygen atom preferably has 4 to 13 carbon atoms, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable. These may be used alone or in combination of two or more.
- the content ratio of the (meth) acrylic acid ester monomer unit in the acrylate polymer is preferably 50% by weight or more, more preferably 60% by weight or more, preferably 95% by weight or less, more preferably 90% by weight. % Or less.
- ⁇ ⁇ -unsaturated nitrile monomer
- acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable in order to improve mechanical strength and binding properties.
- these may be used individually by 1 type and may be used in combination of 2 or more types.
- the content ratio of the ⁇ , ⁇ -unsaturated nitrile monomer unit in the acrylate polymer is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 40% by weight or less, more preferably 30%. % By weight or less.
- Examples of the acidic functional group-containing monomer that can be used in the production of the acrylate polymer include a monomer having a carboxylic acid group, a monomer having a sulfonic acid group, and a monomer having a phosphoric acid group. Can be mentioned.
- Examples of the monomer having a carboxylic acid group include monocarboxylic acid and derivatives thereof, dicarboxylic acid, acid anhydrides and derivatives thereof, and the like.
- Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
- Examples of monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, ⁇ -diaminoacrylic acid, etc. Is mentioned.
- Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
- Examples of the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
- Dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid and other methyl allyl maleate, diphenyl maleate, nonyl maleate, decyl maleate, maleic acid Mention may be made of maleic esters such as dodecyl, octadecyl maleate and fluoroalkyl maleate.
- Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid. In the present specification, “(meth) allyl” means allyl and / or methallyl.
- Examples of the monomer having a phosphoric acid group include 2-((meth) acryloyloxy) ethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, and ethyl phosphate- (meth) acryloyloxyethyl phosphate. It is done.
- acidic functional group-containing monomers include acrylic acid, methacrylic acid, methyl methacrylate, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and 2-((meth) acryloyl phosphate. Oxy) ethyl is preferred.
- acrylic acid, methacrylic acid, and itaconic acid are preferable, and itaconic acid is particularly preferable from the viewpoint that the storage stability of the acrylate polymer can be increased.
- these may be used individually by 1 type and may be used in combination of 2 or more types.
- the content ratio of the acidic functional group-containing monomer unit in the acrylate polymer is preferably 0.5% by weight or more, more preferably 1% by weight or more, and particularly preferably 1.5% by weight or more. Is 5% by weight or less, more preferably 4% by weight or less.
- the acrylate polymer may contain a crosslinkable monomer unit in addition to the monomer unit described above.
- the crosslinkable monomer include a monomer containing an epoxy group, a monomer containing a carbon-carbon double bond and an epoxy group, a monomer containing a halogen atom and an epoxy group, and N-methylol.
- examples thereof include a monomer containing an amide group, a monomer containing an oxetanyl group, a monomer containing an oxazoline group, and a polyfunctional monomer having two or more olefinic double bonds.
- the content ratio of the crosslinkable monomer unit in the acrylate polymer used as the binder indicates that the acrylate polymer exhibits an appropriate swelling property with respect to the electrolyte solution, and in particular, the rate characteristics and cycle characteristics of the lithium ion secondary battery. From the viewpoint of further improving the amount, it is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, preferably 0.5% by weight or less, more preferably 0.3% by weight or less. is there.
- the acrylate polymer may contain monomer units derived from monomers other than those described above.
- monomer units include polymerized units derived from vinyl monomers and hydroxyl group-containing monomer units.
- vinyl monomers include carboxylic acid esters having two or more carbon-carbon double bonds such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate; monomers containing halogen atoms such as vinyl chloride and vinylidene chloride; vinyl acetate , Vinyl esters such as vinyl propionate and vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone and isopropenyl vinyl ketone A heterocyclic compound containing a heterocyclic ring such as N-vinylpyrrolidone, vinylpyridine, and vinylimidazole.
- hydroxyl group-containing monomer examples include ethylenically unsaturated alcohols such as (meth) allyl alcohol, 3-buten-1-ol and 5-hexen-1-ol, 2-hydroxyethyl acrylate, and acrylic acid-2- Ethylenic acids such as hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl maleate, di-4-hydroxybutyl maleate and di-2-hydroxypropyl itaconate
- Alkanol esters of saturated carboxylic acids general formula CH 2 ⁇ CR 1 —COO— (C n H 2n-1 O) m —H (m is an integer from 2 to 9, n is an integer from 2 to 4,
- R 1 is 2-hydroxyethyl-2 ′-(meth) ester of polyalkylene glycol represented by (representing hydrogen or methyl group) and (meth) acrylic acid )
- Vinyl ethers (meth) allyl-2-hydroxyethyl ether, (meth) allyl-2-hydroxypropyl ether, (meth) allyl-3-hydroxypropyl ether, (meth) allyl-2-hydroxybutyl ether, (meth) allyl Mono (meth) allyl ethers of alkylene glycols such as -3-hydroxybutyl ether, (meth) allyl-4-hydroxybutyl ether, (meth) allyl-6-hydroxyhexyl ether, diethylene glycol Polyoxyalkylene glycol (meth) monoallyl ethers such as coal mono (meth) allyl ether and dipropylene glycol mono (meth) allyl ether, glycerin mono (meth) allyl ether, (meth) allyl-2-chloro-3- Of polyhydric phenols such as mono (meth) allyl ethers of eugenol, isoeugen
- the method for producing the binder such as the acrylate polymer described above is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used. . Among these, an emulsion polymerization method using an emulsifier is preferable. In addition, when manufacturing a binder using an emulsion polymerization method, it is preferable to use at least a polyoxyethylene-type surfactant for the surfactant to add as an emulsifier used for superposition
- addition polymerization such as ionic polymerization, radical polymerization, living radical polymerization and the like can be used.
- the polymerization initiator known polymerization initiators such as those described in JP 2012-184201 A can be used.
- the dispersion type binder used in the present invention preferably has a particulate shape. By being in the form of particles, the binding property is good, and it is possible to suppress deterioration of the capacity of the produced electrode and deterioration due to repeated charge and discharge.
- the binder include those in which the binder is dispersed in water, such as latex, and those obtained by drying such a dispersion.
- the volume average particle diameter of the dispersion-type binder used in the present invention is preferably 0.001 to 100 ⁇ m, more preferably 10 to 1000 nm, more preferably 10 to 1000 nm, from the viewpoint of improving the strength and flexibility of the obtained electrode for electrochemical devices. Preferably, it is 50 to 500 nm.
- the amount of the binder used is preferably 0.5 to 0.5 in terms of solid content with respect to 100 parts by weight of the electrode active material, from the viewpoint of good electrode moldability and good performance of the resulting electrochemical device.
- the amount is 10 parts by weight, more preferably 0.5 to 8 parts by weight, still more preferably 0.5 to 5 parts by weight.
- the slurry obtained in the slurry preparation step of the present invention may contain a viscosity modifier as necessary.
- the viscosity modifier include cellulose derivatives such as carboxymethylcellulose (hereinafter sometimes referred to as “CMC”); poly (meth) acrylates such as sodium poly (meth) acrylate; polyvinyl alcohol, modified polyvinyl alcohol, poly Examples include ethylene oxide; polyvinyl pyrrolidone, polycarboxylic acid, oxidized starch, phosphate starch, casein, various modified starches, chitin, chitosan derivatives, and the like. Among these, CMC is preferable.
- the viscosity modifier is preferably used in an amount of 0.5 to 2 parts by weight, more preferably 0.7 to 1.5 parts by weight with respect to 100 parts by weight of the electrode active material.
- the slurry obtained in the slurry preparation step of the present invention may contain carbon fine particles as necessary.
- the carbon fine particles conductive carbon such as furnace black, acetylene black, and ketjen black (registered trademark of Akzo Nobel, Chemicals, Bethloten, and Fennot Shap), carbon nanotube, carbon nanohorn, and graphene are preferably used. Among these, acetylene black is more preferable.
- the average particle size of the carbon fine particles is not particularly limited, but from the viewpoint of developing sufficient conductivity with a smaller amount of use, those smaller than the average particle size of the electrode active material are preferable, preferably 0.001 to 10 ⁇ m, More preferably, the thickness is 0.005 to 5 ⁇ m, and still more preferably 0.01 to 1 ⁇ m.
- the amount of carbon fine particles used is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the electrode active material.
- the amount of carbon fine particles used is too large, it becomes difficult to produce a slurry.
- fine-particles there exists a possibility that the resistance of the electrochemical element obtained may rise.
- the medium used for the slurry of the present invention is preferably water.
- a medium in which a hydrophilic solvent is mixed with water may be used as long as the dispersion stability of the slurry is not impaired.
- the hydrophilic solvent include methanol, ethanol, N-methylpyrrolidone and the like, and it is preferably 5% by weight or less based on water.
- granulated particles are obtained by spray drying the slurry obtained in the slurry preparation step.
- a granulation process can be implemented using the granulation apparatus 14 of the composite particle manufacturing apparatus 2 shown in FIG. 1, for example. That is, the granulated particles 12 can be obtained by spraying the slurry 4 obtained in the slurry preparation step while rotating the rotary disk 18 provided in the drying furnace 16.
- each of the electrode active material and the binder does not exist as independent particles, but one particle is formed by two or more components including the electrode active material and the binder as constituent components. Is. Specifically, 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 bound by a binder. Those that are deposited to form particles are preferred.
- 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 200 ⁇ m, more preferably 20 to 180 ⁇ m, and still more preferably 30 to 170 ⁇ m.
- the average particle diameter of the granulated particles is a volume average particle diameter calculated by measuring with a laser diffraction particle size distribution measuring device (for example, Microtrack; manufactured by Nikkiso Co., Ltd.).
- Spray drying is a method of spraying and drying slurry in dry air.
- An atomizer is used as an apparatus used for spraying slurry.
- the slurry is introduced almost at the center of the disk rotating at high speed, and the slurry is released out of the disk by the centrifugal force of the disk, and the slurry is made into a mist at that time.
- 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.
- the temperature of the slurry to be sprayed is preferably room temperature, but may be heated to a temperature higher than room temperature.
- the temperature of the drying air at the time of spray drying is preferably 25 to 250 ° C, more preferably 50 to 200 ° C, and further preferably 80 to 200 ° C.
- the flow rate of the dry air is 10 m / s or more and less than 40 m / s, preferably 10 m / s or more and 35 m / s or less, more preferably 10 m / s or more and 30 m / s or less, and further preferably 10 m / s or more and 25 m / s. s or less. If the flow rate of dry air is too high, the granulated particles are destroyed. Moreover, when the flow rate of dry air is too slow, the productivity of the granulated particles decreases.
- the flow rate of the dry air is determined by the cyclone differential pressure (the air flow of the cyclone 30 located on the drying furnace 16 side of the two cyclones provided in the middle of the air inlet 17a of the drying furnace 16 and the pipe 20).
- the pressure is controlled by the differential pressure with respect to the outlet 30a.
- the composite particle for an electrochemical element electrode of the present invention may include a transfer step.
- the transfer step the granulated particles produced in the granulation step are transferred through the pipe 20 by air.
- the granulated particles separated from the air are collected by the cyclone 30 located on the drying furnace 16 side. It collect
- the flow velocity of the flowing air at the time of transfer is the amount of air flowing in from the air inlet 17b in the pipe 20 shown in FIG. 1 and the air flow in the cyclone 34 located farther from the drying furnace 16 in the two cyclones.
- it can be controlled by the amount of air flowing out from the outlet 34a, it is preferably 0.5 m / s or more and 20 m / s or less, more preferably 1 m / s or more and 20 m / s or less, further preferably 1 m / s or more and 15 m / s or less, particularly Preferably they are 1 m / s or more and 8 m / s or less. If the flow velocity of the flowing air during transfer is too high, the granulated particles may be destroyed. Moreover, when the flow velocity of the flowing air at the time of transfer is too slow, the productivity of the granulated particles is deteriorated.
- the density in the transfer process can be defined by the solid-gas ratio at the time of transfer.
- the solid / gas ratio at the time of transfer is preferably 5 to 150, more preferably 10 to 150.
- the solid-gas ratio means the mass flow rate (kg / h) of the granulated particles per unit time as the mass flow rate (kg / h) of the air consumed for transferring the granulated particles per unit time. It is calculated by dividing. The larger the value of the solid-gas ratio, the more granulated particles can be transferred with a small amount of air, and the efficiency is good. If the solid-gas ratio is too small, the granulated particles may be destroyed during transfer.
- removing step of the present invention foreign substances and / or coarse particles are removed from the granulated particles obtained in the granulating step or the granulated particles transferred in the transferring step.
- a method for removing foreign substances and / or coarse particles from the granulated particles is not particularly limited, but it is preferable to remove foreign substances and / or coarse particles with a sieve 22 (see FIG. 1). By removing foreign substances and / or coarse particles from the granulated particles, it is possible to obtain composite particles 26 for electrochemical element electrodes.
- the foreign matter refers to impurities originally mixed in the electrode active material or the binder that is the raw material of the granulated particles, or a part of the pipe (the inner wall of the pipe or the like during the transfer of the granulated particles). This refers to those that are mixed into granulated particles due to wear or the like.
- the coarse particles preferably have a volume average particle diameter of 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.
- the opening diameter of the sieve 22 used when the foreign substances and / or coarse particles are separated by the sieve 22 is preferably 1.1 to 6.0 times the volume average particle diameter of the obtained composite particles, more preferably 1. 1 to 5.0 times, more preferably 1.1 to 4.0 times.
- the material of the sieve 22 when the foreign substance and / or coarse particles are separated by the sieve 22 there is no particular limitation on the material of the sieve 22 when the foreign substance and / or coarse particles are separated by the sieve 22. Usually selected from resin, metal and magnetic materials.
- the movement form of the fluid 22 there is no particular limitation on the movement form of the fluid 22, but a movement form such as a vibration type, an in-plane movement type, and an ultrasonic type can be used.
- a vibration type those that vibrate only in the horizontal direction are preferable.
- the granulated particles transferred by air are packed after removing foreign substances and / or coarse particles.
- the composite particles according to the present invention are obtained by a production method including at least a slurry preparation step, a granulation step, and a removal step.
- the transfer process is provided, but the transfer process may be omitted.
- 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, copper, and other alloys.
- 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 to form an 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 a pressure molding method because it can be performed with simple equipment.
- Examples of the pressure molding method include a roll pressure molding method in which an electrode material containing composite particles is supplied to a roll-type pressure molding device with a supply device such as a screw feeder, and an electrode active material layer is molded. Disperse the material on the current collector, adjust the thickness by leveling the electrode material with a blade, etc., then mold with a pressure device, fill the mold with the electrode material, and press the mold to mold The method etc. are mentioned.
- the roll pressure forming method is preferred.
- 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 sufficient adhesion between the electrode active material layer and the current collector, and is 20 ° C. higher than the glass transition temperature of the binder contained in the composite particles. A higher temperature is more preferable.
- the molding speed is 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.
- the electrochemical element uses the electrochemical element electrode obtained as described above as at least one of a positive electrode and a negative electrode, and further includes a separator and an electrolytic solution.
- Examples of the electrochemical element include a lithium ion secondary battery and a lithium ion capacitor.
- the electrochemical element is a lithium ion secondary battery will be described.
- separator for example, a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing an aromatic polyamide resin; a porous resin coat containing an inorganic ceramic powder;
- the thickness of the separator is preferably 0.5 to 40 ⁇ m from the viewpoint of workability when manufacturing a lithium ion battery.
- Electrode As an electrolytic solution for a lithium ion secondary battery, for example, a nonaqueous electrolytic solution in which a supporting electrolyte is dissolved in a nonaqueous solvent is used.
- a lithium salt is preferably used.
- the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable.
- One of these may be used alone, or two or more of these may be used in combination at any ratio. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
- the concentration of the supporting electrolyte in the electrolytic solution is preferably used at a concentration of 0.5 to 2.5 mol / L depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity may decrease.
- the non-aqueous solvent is not particularly limited as long as it can dissolve the supporting electrolyte.
- non-aqueous solvents include carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC);
- DMC dimethyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- PC propylene carbonate
- BC butylene carbonate
- MEC methyl ethyl carbonate
- esters such as ⁇ -butyrolactone and methyl formate
- ethers such as 1,2-dimethoxyethane and tetrahydrofuran
- sulfur-containing compounds such as sulfolane and dimethyl sulfoxide
- ionic liquids used also as supporting electrolytes used also as supporting electrolytes.
- a non-aqueous solvent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. In general, the lower the viscosity of the non-aqueous solvent, the higher the lithium ion conductivity, and the higher the dielectric constant, the higher the solubility of the supporting electrolyte, but since both are in a trade-off relationship, the lithium ion conductivity depends on the type of solvent and the mixing ratio. It is recommended to adjust the conductivity.
- the nonaqueous solvent may be used in combination or in whole or in a form in which all or part of hydrogen is replaced with fluorine.
- an additive may be included in the electrolytic solution.
- the additive include carbonates such as vinylene carbonate (VC); sulfur-containing compounds such as ethylene sulfite (ES); and fluorine-containing compounds such as fluoroethylene carbonate (FEC).
- An additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- a polymer electrolyte such as polyethylene oxide or polyacrylonitrile
- a gel polymer electrolyte obtained by impregnating the polymer electrolyte with an electrolyte solution
- an inorganic solid electrolyte such as LiI or Li 3 N; May be used.
- Electrochemical elements are obtained by impregnating the above electrodes and separators with an electrolytic solution.
- the electrode and separator can be produced by winding, laminating or folding the electrode and separator into the 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 in which broadening of the particle size distribution is suppressed can be obtained even in mass production.
- the particle size distribution, the long dry formability and the cycle characteristics of the composite particles were evaluated as follows.
- D The particle size distribution is very broad (the ratio of the half width to the peak base length is 0.50 or more) or the particle size distribution of primary particles.
- Example 1 Preparation of carboxycellulose solution as viscosity modifier
- CMC carboxymethyl cellulose
- a slurry tank 6 (see FIG. 1) (for example, a planetary mixer with a disper), 100 parts of artificial graphite having an average particle diameter of 24.5 ⁇ m is placed as an electrode active material for a negative electrode through a raw material input tube 8. After adding 100 parts of a 1% aqueous solution of CMC and adjusting the solid content concentration to 53.5% by weight with ion-exchanged water, the mixture was stirred at 25 ° C. for 60 minutes by stirring with the stirring blade 10. Next, after adjusting the solid content concentration to 40% by weight with ion exchange water, the mixture was further mixed at 25 ° C. for 15 minutes.
- the slurry obtained above is used with a granulator 14 (see FIG. 1) (specifically, a spray dryer (manufactured by Okawara Chemical Co., Ltd.)), a rotary disk 18 having a diameter of 85 mm, and a rotational speed of 25.
- Spray drying granulation was performed under the conditions of 1,000 rpm, dry air temperature of 180 ° C., and particle recovery outlet temperature of 90 ° C., and granulated particles for negative electrode were obtained by cyclone recovery.
- the obtained granulated particles 12 had a volume average particle diameter of 70 ⁇ m.
- the flow rate of the dry air was controlled to 20 m / s by setting the cyclone differential pressure in the drying furnace 16 of the granulator 14 to 1 kpa.
- the obtained granulated particles for negative electrode are transferred to a vibrating sieve facility by air, and a sieve 22 having an opening of 130 ⁇ m is installed in a lateral vibration type vibrating sieve, and the coarse particles are removed by applying the granulated particles for negative electrode to a sieve.
- Composite particles for a negative electrode were obtained.
- the particles were transferred by flowing air through the pipe 20.
- the flow rate of flowing air is controlled to 5 m / s, and the solid-gas ratio is controlled to 30 (granulated particles (kg / h) / air (kg / h)). did.
- LiCoO 2 LiCoO 2
- PVDF polyvinylidene fluoride
- KF-1100 Kureha Chemical Co., Ltd.
- N-methyl-2-pyrrolidone 6 parts of acetylene black (“HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) and 20 parts of N-methyl-2-pyrrolidone were added and mixed with a planetary mixer to prepare a slurry for the positive electrode.
- This positive electrode slurry was applied to an aluminum foil having a thickness of 18 ⁇ m, dried at 120 ° C. for 30 minutes, and then roll-pressed to obtain a positive electrode for a lithium ion secondary battery having a thickness of 60 ⁇ m.
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut into a square of 5 ⁇ 5 cm 2 .
- the positive electrode for a lithium ion secondary battery obtained above was cut into a 4 ⁇ 4 cm 2 square and placed so that the current collector-side surface was in contact with the aluminum packaging exterior.
- the square separator obtained above was disposed on the surface of the positive electrode active material layer of the positive electrode for a lithium ion secondary battery.
- the negative electrode for a lithium ion secondary battery obtained above was cut into a square of 4.2 ⁇ 4.2 cm 2 and arranged on the separator so that the surface on the negative electrode active material layer side faced the separator. Further, containing the vinylene carbonate 2.0%, was charged with LiPF 6 solution having a concentration of 1.0 M.
- Example 2 Preparation of carboxycellulose solution as viscosity modifier
- slurry for positive electrode 100 parts of LCO as a positive electrode active material and 4.0 parts of acetylene black (“HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) as carbon fine particles are put into a slurry tank 6 (see FIG. 1) (for example, a planetary mixer with a disper). And dry blended for 10 minutes. Next, 1.0 part of the 1% aqueous solution of carboxymethylcellulose prepared above was added in terms of solid content. Next, ion-exchanged water was added until the solid content became 85% by weight, and the mixture was stirred with a stirring blade 10 and kneaded at 30 ° C. for 30 minutes.
- HS-100 manufactured by Denki Kagaku Kogyo Co., Ltd.
- a conjugated diene latex having a solid content of 40% (BM-600B (manufactured by Nippon Zeon Co., Ltd.) was added as a binder to a mixture of the positive electrode active material and carbon fine particles in terms of solid content. After the binder was added, the mixture was stirred with a stirring blade 10 for uniform dispersion, and kneaded for 3 minutes to obtain a positive electrode slurry (final solid content concentration 85% by weight).
- the slurry obtained above is used with a granulator 14 (see FIG. 1) (specifically, a spray dryer (manufactured by Okawara Chemical Co., Ltd.)), a rotary disk 18 having a diameter of 85 mm, and a rotational speed of 25.
- Spray drying granulation was performed under the conditions of 1,000 rpm, dry air temperature of 180 ° C., and particle recovery outlet temperature of 90 ° C., and granulated particles for the positive electrode were obtained by cyclone recovery.
- the obtained granulated particles 12 had a volume average particle size of 40 ⁇ m.
- the flow rate of the dry air was controlled to 20 m / s by setting the cyclone differential pressure in the drying furnace 16 of the granulator 14 to 1 kpa.
- the obtained granulated particles for positive electrode are transferred to a vibrating sieve facility by air, and a sieve 22 having an opening of 130 ⁇ m is installed in a lateral vibration type vibrating sieve, and the coarse particles are removed by applying the granulated particles for positive electrode to a sieve.
- Composite particles for positive electrode were obtained.
- the particles were transferred by flowing air through the pipe 20.
- the flow rate of flowing air is controlled to 5 m / s, and the solid-gas ratio is controlled to 30 (granulated particles (kg / h) / air (kg / h)). did.
- 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.
- BM-400B butadiene copolymer latex
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut into a square of 5 ⁇ 5 cm 2 .
- the positive electrode for a lithium ion secondary battery obtained above was cut into a 4 ⁇ 4 cm 2 square and placed so that the current collector-side surface was in contact with the aluminum packaging exterior.
- the square separator obtained above was disposed on the surface of the positive electrode active material layer of the positive electrode for a lithium ion secondary battery.
- the negative electrode for a lithium ion secondary battery obtained above was cut into a square of 4.2 ⁇ 4.2 cm 2 and arranged on the separator so that the surface on the negative electrode active material layer side faced the separator. Further, containing the vinylene carbonate 2.0%, was charged with LiPF 6 solution having a concentration of 1.0 M.
- Example 3 Except for the final solid content concentration of 30% by weight, the production of the slurry for the negative electrode, the granulation of the granulated particles for the negative electrode, the transfer and the removal of the coarse particles, the production of the negative electrode for the lithium ion secondary battery, as in Example 1. And the lithium ion secondary battery was manufactured.
- Example 4 A negative electrode slurry was prepared in the same manner as in Example 1. Using the obtained negative electrode slurry, the granulated particles for negative electrode were granulated by controlling the flow rate of dry air to 15 m / s by setting the cyclone differential pressure of the spray dryer to 0.8 kpa. In the same manner as in Example 1, the granulated particles for the negative electrode were transferred and the coarse particles were removed, the negative electrode for the lithium ion secondary battery was manufactured, and the lithium ion secondary battery was manufactured.
- Example 5 A negative electrode slurry was prepared in the same manner as in Example 1. Using the obtained negative electrode slurry, the granulated particles for negative electrode were granulated by controlling the flow rate of dry air to 30 m / s by setting the cyclone differential pressure of the spray dryer to 1.3 kpa. In the same manner as in Example 1, the granulated particles for the negative electrode were transferred and the coarse particles were removed, the negative electrode for the lithium ion secondary battery was manufactured, and the lithium ion secondary battery was manufactured.
- Example 6 In the same manner as in Example 1, preparation of the slurry for the negative electrode and granulation of the granulated particles for the negative electrode were performed.
- the flow rate of flowing air is 10 m / s and the solid-gas ratio is 13 (granulated particles (kg / h) / air by setting the amount of flowing air to 1.0 Nm 3 / min. (Kg / h)), except for controlling each, the transfer of the granulated particles for negative electrode and the removal of coarse particles, the production of the negative electrode for lithium ion secondary battery and the production of lithium ion secondary battery, as in Example 1. Went.
- Example 3 A negative electrode slurry was prepared in the same manner as in Example 1. Using the obtained negative electrode slurry, the granulated particles for negative electrode were granulated by controlling the flow rate of dry air to 40 m / s by setting the cyclone differential pressure of the spray dryer to 1.5 kpa. In the same manner as in Example 1, the granulated particles for the negative electrode were transferred and the coarse particles were removed, the negative electrode for the lithium ion secondary battery was manufactured, and the lithium ion secondary battery was manufactured.
- a negative electrode slurry was prepared in the same manner as in Example 1. Using the obtained negative electrode slurry, the granulated particles for negative electrode were granulated by controlling the flow rate of dry air to 5 m / s by setting the cyclone differential pressure of the spray dryer to 0.5 kpa. In the same manner as in Example 1, the granulated particles for the negative electrode were transferred and the coarse particles were removed, the negative electrode for the lithium ion secondary battery was manufactured, and the lithium ion secondary battery was manufactured.
- a method for producing composite particles for an electrochemical element electrode is a slurry preparation step in which an electrode active material and a binder are dispersed or dissolved in a medium to obtain a slurry; And a removal step of removing foreign substances and / or coarse particles from the granulated particles, and the solid content concentration of the slurry obtained in the slurry preparation step is 20 wt% or more, 90 wt% %, And the flow rate of dry air during spray drying in the granulation step is 10 m / s or more and less than 40 m / s, the particle size distribution of the obtained composite particles, the dry moldability is good, Moreover, the cycle characteristic of the lithium ion secondary battery manufactured using the obtained composite particle was favorable.
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Abstract
Description
(1) 電気化学素子電極用複合粒子の製造方法であって、電極活物質及びバインダーを媒体に分散または溶解させてスラリーを得るスラリー作製工程と、前記スラリーを噴霧乾燥して造粒粒子を得る造粒工程と、前記造粒粒子から異物及び/又は粗大粒子を除去する除去工程と、を含み、前記スラリー作製工程で得られるスラリーの固形分濃度が20重量%以上、90重量%以下であって、前記造粒工程における噴霧乾燥時の乾燥空気の流速が10m/s以上、40m/s未満である電気化学素子電極用複合粒子の製造方法、
(2) 前記造粒工程後において、前記造粒粒子を空気により移送する移送工程を有し、前記移送工程における空気流速が0.5m/s以上、20m/s以下である(1)に記載の電気化学素子電極用複合粒子の製造方法、
(3) 前記移送工程において、単位時間あたりの造粒粒子の質量流量(kg/h)を前記単位時間あたりの造粒粒子の移送のために消費された空気の質量流量(kg/h)で除することにより算出される固気比が、5以上、150以下である(2)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。
ここで、造粒装置14は乾燥炉16を備え、乾燥炉16の内部には、回転しながらスラリー4を噴霧するロータリーディスク18が設けられている。また、乾燥炉16の上部には、空気流入口17aが設けられ、乾燥炉16の下部には、配管20との接続部(図示せず)が設けられている。配管20の途中には、造粒粒子12と空気とを分離し、空気の一部を流出させるサイクロンが2箇所(サイクロン30,34)設けられており、サイクロン30,34には空気流出口30a,34aがそれぞれ設けられている。また、サイクロン30の下流側には、回収タンク32が設けられ、回収タンク32には加圧空気が供給される。また、回収タンク32の下流側の配管20には、空気流入口17bより空気を流入させる。
本発明のスラリー作製工程においては、電極活物質及びバインダーを媒体に分散または溶解させてスラリーを得る。
スラリー作製工程は、図1に示す複合粒子製造装置2のスラリータンク6において実施され、スラリー4は、スラリータンク6に電極活物質、バインダー及び媒体を含む原料を投入し、撹拌翼10により撹拌することにより得ることができる。
ここで、スラリー4は、電極活物質及びバインダーを媒体に分散または溶解させて得ることができる。また、スラリー4は必要に応じて粘度調整剤、炭素微粒子を含んでいてもよい。
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素子が、リチウムイオン二次電池である場合、リチウムイオン二次電池の正極に用いる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(以下、「LCO」ということがある。)、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(以下、「LFP」ということがある。)、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(以下、「NMC」ということがある。)、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。また、リン酸鉄リチウムやリン酸マンガンリチウムもあげられる。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。これらのなかでも、LCO、NMC、LFPを用いることが好ましい。
本発明で用いるバインダーとしては、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、媒体に分散する性質を有する分散型のバインダーが好ましい。分散型のバインダーとしては、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、共役ジエン系重合体、アクリレート系重合体が好ましい。
本発明のスラリー作製工程で得られるスラリーは、必要に応じて粘度調整剤を含んでいても良い。粘度調整剤としては、カルボキシメチルセルロース(以下、「CMC」ということがある。)などのセルロース誘導体;ポリ(メタ)アクリル酸ナトリウムなどのポリ(メタ)アクリル酸塩;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。これらの中でもCMCが好ましい。 粘度調整剤は、上記電極活物質100重量部に対して、0.5~2重量部用いることが好ましく、0.7~1.5重量部用いることがより好ましい。
本発明のスラリー作製工程で得られるスラリーは、必要に応じて炭素微粒子を含んでいてもよい。
本発明のスラリーに用いる媒体は、水を用いることが好ましい。なお、本発明においては、スラリーの分散安定性を損なわない範囲であれば、媒体として水に親水性の溶媒を混ぜたものを使用してもよい。親水性の溶媒としては、メタノール、エタノール、N-メチルピロリドンなどがあげられ、水に対して5重量%以下であることが好ましい。
本発明の造粒工程においては、スラリー作製工程で得られたスラリーを噴霧乾燥することにより造粒粒子を得る。造粒工程は、例えば、図1に示す複合粒子製造装置2の造粒装置14を用いて実施することができる。即ち、スラリー作製工程で得られたスラリー4を乾燥炉16内に設けられたロータリーディスク18を回転させながら噴霧することにより造粒粒子12を得ることができる。ここで、造粒粒子12においては、電極活物質及びバインダーのそれぞれが個別に独立した粒子として存在するのではなく、構成成分である電極活物質、バインダーを含む2成分以上によって一粒子を形成するものである。具体的には、前記2成分以上の個々の粒子の複数個が結合して二次粒子を形成しており、複数個(好ましくは数個~数十個)の電極活物質が、バインダーによって結着されて粒子を形成しているものが好ましい。
本発明の電気化学素子電極用複合粒子は、移送工程を含んでいても良い。移送工程においては、造粒工程で製造された造粒粒子を、配管20内を空気により移送する。ここで、移送工程においては、配管20を介した流動空気による移送を行うことが好ましい。また、移送工程においては、低速かつ高密度で移送することが好ましい。配管20を介した流動空気により低速かつ高密度で造粒粒子を移送するためには、具体的には、前記の乾燥炉16側に位置するサイクロン30で空気と分離された造粒粒子を回収タンク32に一旦回収し、高密度状態のまま加圧することにより移送する。
本発明の除去工程においては、造粒工程において得られた造粒粒子または移送工程において移送された造粒粒子から異物及び/又は粗大粒子を除去する。造粒粒子から異物及び/又は粗大粒子を除去する方法としては、特に限定されないが、フルイ22(図1参照)により異物及び/又は粗大粒子を除去することが好ましい。造粒粒子から異物及び/又は粗大粒子を除去することにより、電気化学素子電極用複合粒子26を得ることができる。
本発明に係る複合粒子は、上述の通り、少なくともスラリー作製工程、造粒工程及び除去工程を含む製造方法により得られる。
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、銅、その他の合金等が挙げられる。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。
電気化学素子は、上述のようにして得られる電気化学素子電極を正極および負極の少なくとも一方に用い、さらにセパレーターおよび電解液を備える。電気化学素子としては、例えば、リチウムイオン二次電池、リチウムイオンキャパシタ等が挙げられる。以下、電気化学素子がリチウムイオン二次電池である場合について説明する。
セパレーターとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂や、芳香族ポリアミド樹脂を含んでなる微孔膜または不織布;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。セパレーターの厚さは、リチウムイオン電池を製造する際の作業性の観点から、好ましくは0.5~40μmである。
リチウムイオン二次電池用の電解液としては、例えば、非水溶媒に支持電解質を溶解した非水電解液が用いられる。支持電解質としては、リチウム塩が好ましく用いられる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどが挙げられる。中でも、溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liが好ましい。これらは1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。解離度の高い支持電解質を用いるほど、リチウムイオン伝導度が高くなるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。
マイクロトラック(日機装製)を用い、乾式法にて測定を行った。結果を表1に示した。
A:粒度分布が非常にシャープ(半値幅とピーク底辺の長さの比が0.25未満)
B:粒度分布がややシャープ(半値幅とピーク底辺の長さの比が0.25以上0.35未満)
C:粒度分布がややブロード(半値幅とピーク底辺の長さの比が0.35以上0.50未満)
D:粒度分布が非常にブロード(半値幅とピーク底辺の長さの比が0.50以上)または一次粒子の粒度分布になっている。
実施例、比較例で得られた複合粒子をエッジド箔にロール成形し、長尺成形性を確認した。結果を表1に示した。
A:10m以上欠陥なく成形可能
B:10m成形可能だが、欠陥がみられる
C:流動性が悪く5m成形することができない
D:流動性が悪く1m成形することができない
作製したリチウムイオン二次電池を24時間静置させた後に、0.1Cの充放電レートにて、4.2Vまで充電し、その後、3.0Vまで放電する充放電の操作を行い、初期容量C0を測定した。さらに、温度25℃の環境下で充放電を繰り返し、100サイクル後の容量C2を測定した。そして、ΔC=(C2/C0)×100(%)で示される容量維持率ΔCを求めた。この容量維持率ΔCの値が高いほど、サイクル特性に優れることを示す。結果を表1に示した。
A:容量維持率90%以上
B:容量維持率80%以上90%未満
C:容量維持率80%未満
D:測定不能
(粘度調整剤としてのカルボキシセルロース溶液の調製)
溶液粘度が8000mPa・sであるカルボキシメチルセルロース(以下、「CMC」ということがある。)(第一工業製薬株式会社製「セロゲンBSH-12」)の1%水溶液を調整した。
スラリータンク6(図1参照)(例えば、ディスパー付きのプラネタリーミキサー)に、原料投入管8を介して負極用の電極活物質として平均粒子径24.5μmの人造黒鉛100部を入れ、これにCMCの1%水溶液を100部加え、イオン交換水で固形分濃度53.5重量%に調整した後、撹拌翼10により撹拌することにより25℃で60分間混合した。次に、イオン交換水で固形分濃度40重量%に調整した後、さらに25℃で15分間混合した。次に、バインダーとして、SBRラテックス(BM-400B(日本ゼオン社製))を固形分濃度40重量%に調整し、室温にて90日保存後のものを2.9部加えて撹拌翼10により撹拌することによりさらに10分間混合した。これを減圧下で脱泡処理して艶のある流動性の良い負極用スラリー(最終固形分濃度40重量%)を得た。
上記で得られたスラリーを、造粒装置14(図1参照)(具体的には、スプレー乾燥機(大川原化工機社製))を使用し、直径85mmのロータリーディスク18を用い、回転数25,000rpm、乾燥空気温度180℃、粒子回収出口の温度90℃の条件にて、噴霧乾燥造粒を行い、サイクロン回収により負極用造粒粒子を得た。得られた造粒粒子12の体積平均粒子径は70μmであった。尚、乾燥空気の流速は、造粒装置14の乾燥炉16におけるサイクロン差圧を1kpaとすることにより、20m/sに制御した。
得られた負極用造粒粒子を、空気により振動フルイ設備へ移送し、横振動型振動フルイ機に目開き130μmのフルイ22を設置し、負極用造粒粒子をフルイにかけ粗大粒子を除去し、負極用複合粒子を得た。造粒粒子の振動フルイ設備への移送工程においては、配管20を介して流動空気により移送した。流動空気量を0.5Nm3/分にすることにより、流動空気の流速を5m/s、固気比を30(造粒粒子(kg/h)/空気(kg/h))に、それぞれ制御した。
得られた負極用複合粒子をロータリーバルブにより切り出し、ポリエチレン製の袋に梱包した。
次に、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リチウムイオン二次電池用負極を得た。
正極活物質としてのLiCoO2(以下、「LCO」と略記することがある。)92部に、正極用バインダーとしてポリフッ化ビニリデン(PVDF;クレハ化学社製「KF-1100」)を固形分量が2部となるように加え、さらに、アセチレンブラック(電気化学工業社製「HS-100」)を6部、N-メチル-2-ピロリドン20部を加えて、プラネタリーミキサーで混合して正極用スラリーを得た。この正極用スラリーを厚さ18μmのアルミニウム箔に塗布し、120℃で30分乾燥した後、ロールプレスして厚さ60μmのリチウムイオン二次電池用正極を得た。
単層のポリプロピレン製セパレーター(幅65mm、長さ500mm、厚さ25μm、乾式法により製造、気孔率55%)を、5×5cm2の正方形に切り抜いた。
電池の外装として、アルミ包材外装を用意した。上記で得られたリチウムイオン二次電池用正極を、4×4cm2の正方形に切り出し、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。リチウムイオン二次電池用正極の正極活物質層の面上に、上記で得られた正方形のセパレーターを配置した。さらに、上記で得られたリチウムイオン二次電池用負極を、4.2×4.2cm2の正方形に切り出し、負極活物質層側の表面がセパレーターに向かい合うように、セパレーター上に配置した。更に、ビニレンカーボネートを2.0%含有する、濃度1.0MのLiPF6溶液を充填した。このLiPF6溶液の溶媒はエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)との混合溶媒(EC/EMC=3/7(体積比))である。さらに、アルミニウム包材の開口を密封するために、150℃でヒートシールをしてアルミニウム外装を閉口し、ラミネート型のリチウムイオン二次電池(ラミネート型セル)を製造した。
(粘度調整剤としてのカルボキシセルロース溶液の調製)
溶液粘度が8000mPa・sであるカルボキシメチルセルロース(第一工業製薬株式会社製「セロゲンBSH-12」)の1%水溶液を調整した。
正極活物質としてLCOを100部、炭素微粒子としてアセチレンブラック(電気化学工業社製「HS-100」)4.0部をスラリータンク6(図1参照)(例えば、ディスパー付きプラネタリーミキサー)に投入し、10分間ドライブレンドを行った。次いで、前記で調製したカルボキシメチルセルロースの1%水溶液を固形分換算量で1.0部添加した。次いで、イオン交換水を固形分85重量%になるまで投入し、撹拌翼10により撹拌することにより30℃で30分間混練した。バインダーとして固形分40%の共役ジエン系ラテックス(BM-600B(日本ゼオン社製))を固形分換算で1部を正極活物質と炭素微粒子の混合物に投入した。バインダーの投入後、均一分散のため撹拌翼10により撹拌することにより3分間混練し正極用スラリー(最終固形分濃度85重量%)を得た。
上記で得られたスラリーを、造粒装置14(図1参照)(具体的には、スプレー乾燥機(大川原化工機社製))を使用し、直径85mmのロータリーディスク18を用い、回転数25,000rpm、乾燥空気温度180℃、粒子回収出口の温度90℃の条件にて、噴霧乾燥造粒を行い、サイクロン回収により正極用造粒粒子を得た。得られた造粒粒子12の体積平均粒子径は40μmであった。尚、乾燥空気の流速は、造粒装置14の乾燥炉16におけるサイクロン差圧を1kpaとすることにより、20m/sに制御した。
得られた正極用造粒粒子を、空気により振動フルイ設備へ移送し、横振動型振動フルイ機に目開き130μmのフルイ22を設置し、正極用造粒粒子をフルイにかけ粗大粒子を除去し、正極用複合粒子を得た。造粒粒子の振動フルイ設備への移送工程においては、配管20を介して流動空気により移送した。流動空気量を0.5Nm3/分にすることにより、流動空気の流速を5m/s、固気比を30(造粒粒子(kg/h)/空気(kg/h))に、それぞれ制御した。
得られた正極用複合粒子をロータリーバルブにより切り出し、ポリエチレン製の袋に梱包した。
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。
負極活物質として人造黒鉛(平均粒子径:24.5μm、黒鉛層間距離(X線回折法による(002)面の面間隔(d値):0.354nm)96部、カルボキシメチルセルロースの1.5%水溶液(DN-800H:ダイセル化学工業社製)を固形分換算量で1.0部混合し、さらにイオン交換水を固形分濃度が55%となるように加え、混合分散した。次いで、スチレン-ブタジエン共重合ラテックス(BM-400B)を固形分換算量で3.0部混合して最終固形分濃度が50%の負極用スラリーを得た。この負極用スラリーを厚さ18μmの銅箔に塗布し、120℃で30分間乾燥した後、ロールプレスして厚さ50μmの負極を得た。
単層のポリプロピレン製セパレーター(幅65mm、長さ500mm、厚さ25μm、乾式法により製造、気孔率55%)を、5×5cm2の正方形に切り抜いた。
電池の外装として、アルミ包材外装を用意した。上記で得られたリチウムイオン二次電池用正極を、4×4cm2の正方形に切り出し、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。リチウムイオン二次電池用正極の正極活物質層の面上に、上記で得られた正方形のセパレーターを配置した。さらに、上記で得られたリチウムイオン二次電池用負極を、4.2×4.2cm2の正方形に切り出し、負極活物質層側の表面がセパレーターに向かい合うように、セパレーター上に配置した。更に、ビニレンカーボネートを2.0%含有する、濃度1.0MのLiPF6溶液を充填した。このLiPF6溶液の溶媒はエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)との混合溶媒(EC/EMC=3/7(体積比))である。さらに、アルミニウム包材の開口を密封するために、150℃でヒートシールをしてアルミニウム外装を閉口し、ラミネート型のリチウムイオン二次電池(ラミネート型セル)を製造した。
最終固形分濃度を30重量%とした以外は、実施例1と同様に負極用スラリーの作製、負極用造粒粒子の造粒、移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
実施例1と同様に負極用スラリーを作製した。得られた負極用スラリーを用い、乾燥空気の流速を、スプレー乾燥機のサイクロン差圧を0.8kpaとすることにより、15m/sに制御して負極用造粒粒子の造粒を行った以外は、実施例1と同様に、負極用造粒粒子の移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
実施例1と同様に負極用スラリーを作製した。得られた負極用スラリーを用い、乾燥空気の流速を、スプレー乾燥機のサイクロン差圧を1.3kpaとすることにより、30m/sに制御して負極用造粒粒子の造粒を行った以外は、実施例1と同様に、負極用造粒粒子の移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
実施例1と同様に負極用スラリーの作製及び負極用造粒粒子の造粒を行った。負極用造粒粒子の移送工程において、流動空気量を1.0Nm3/分にすることにより、流動空気の流速を10m/s、固気比を13(造粒粒子(kg/h)/空気(kg/h))に、それぞれ制御した以外は、実施例1と同様に負極用造粒粒子の移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
最終固形分濃度を15重量%とした以外は、実施例1と同様に負極用スラリーの作製、負極用造粒粒子の造粒、移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
最終固形分濃度を93重量%とした以外は、実施例2と同様に正極用スラリーの作製、正極用造粒粒子の造粒、移送及び粗大粒子の除去、リチウムイオン二次電池用正極の製造及びリチウムイオン二次電池の製造を行った。
実施例1と同様に負極用スラリーを作製した。得られた負極用スラリーを用い、乾燥空気の流速を、スプレー乾燥機のサイクロン差圧を1.5kpaとすることにより、40m/sに制御して負極用造粒粒子の造粒を行った以外は、実施例1と同様に、負極用造粒粒子の移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
実施例1と同様に負極用スラリーを作製した。得られた負極用スラリーを用い、乾燥空気の流速を、スプレー乾燥機のサイクロン差圧を0.5kpaとすることにより、5m/sに制御して負極用造粒粒子の造粒を行った以外は、実施例1と同様に、負極用造粒粒子の移送及び粗大粒子の除去、リチウムイオン二次電池用負極の製造及びリチウムイオン二次電池の製造を行った。
Claims (3)
- 電気化学素子電極用複合粒子の製造方法であって、
電極活物質及びバインダーを媒体に分散または溶解させてスラリーを得るスラリー作製工程と、
前記スラリーを噴霧乾燥して造粒粒子を得る造粒工程と、
前記造粒粒子から異物及び/又は粗大粒子を除去する除去工程と、を含み、
前記スラリー作製工程で得られるスラリーの固形分濃度が20重量%以上、90重量%以下であって、
前記造粒工程における噴霧乾燥時の乾燥空気の流速が10m/s以上、40m/s未満である電気化学素子電極用複合粒子の製造方法。 - 前記造粒工程後において、前記造粒粒子を空気により移送する移送工程を有し、
前記移送工程における空気流速が0.5m/s以上、20m/s以下である請求項1に記載の電気化学素子電極用複合粒子の製造方法。 - 前記移送工程において、
単位時間あたりの造粒粒子の質量流量(kg/h)を前記単位時間あたりの造粒粒子の移送のために消費された空気の質量流量(kg/h)で除することにより算出される固気比が、5以上、150以下である請求項2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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