WO2022234827A1 - 蓄電デバイス正極用分散剤 - Google Patents
蓄電デバイス正極用分散剤 Download PDFInfo
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- WO2022234827A1 WO2022234827A1 PCT/JP2022/019385 JP2022019385W WO2022234827A1 WO 2022234827 A1 WO2022234827 A1 WO 2022234827A1 JP 2022019385 W JP2022019385 W JP 2022019385W WO 2022234827 A1 WO2022234827 A1 WO 2022234827A1
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- positive electrode
- dispersant
- conductive material
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- H01M4/622—Binders being polymers
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Definitions
- the present invention relates to a dispersant for a positive electrode of an electricity storage device.
- Patent Document 1 carbon nanotubes (CNT) are used as a conductive material, and stearyl methacrylate (SMA) and 2-hydroxyethyl methacrylate ( The addition of certain copolymers such as HEMA) is disclosed. And the examples disclose copolymers of SMA, HEMA and methacrylamide (MAAm).
- Patent Document 2 discloses that when the dispersant contained in the positive electrode paste has a high solubility in the electrolytic solution, the copolymer dissolved in the electrolytic solution clogs the separator, resulting in a decrease in resistance.
- a structural unit derived from acrylonitrile (AN) and a structural unit derived from lauryl acrylate Disclosed is a conductive adhesive composition for electrochemical device electrodes comprising a particulate binder containing structural units and a dispersion medium. It also discloses that the conductive adhesive composition for electrochemical element electrodes is used to form a conductive adhesive layer provided between an electrode active material layer and a current collector.
- the present disclosure includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3).
- the present invention relates to a dispersant for a positive electrode of an electricity storage device, which is a polymer.
- R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group
- R 4 represents a hydrocarbon group having 8 to 30 carbon atoms.
- R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- R 8 , R 9 and R 10 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- the present disclosure includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3).
- the present invention relates to a dispersant for a positive electrode of an electricity storage device, which is a polymer.
- R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and R 4 represents a hydrocarbon group having 8 to 30 carbon atoms.
- R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and the functional group X 1 has a hydrocarbon group with 1 to 4 carbon atoms. a pyridinyl group, a pyrrolidone group, or a cyano group which may be substituted.
- R 8 , R 9 and R 10 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- the present disclosure relates to a dispersant composition containing the power storage device positive electrode dispersant of the present disclosure and a solvent.
- the present disclosure relates to a conductive material slurry for a battery, containing the power storage device positive electrode dispersant of the present disclosure, a carbon material-based conductive material, and a solvent.
- the present disclosure includes a step of dispersing each component in a mixture containing the power storage device positive electrode dispersant of the present disclosure, a conductive material, and a solvent using a media stirring type dispersing machine. It relates to a slurry manufacturing method.
- the present disclosure relates to a positive electrode paste for batteries, which includes the power storage device positive electrode dispersant of the present disclosure, a carbon material-based conductive material, a positive electrode active material, a binder, and a solvent.
- the present disclosure relates to a positive electrode for a battery containing the dispersant for positive electrode of an electricity storage device of the present disclosure.
- the present disclosure has low solubility in an electrolytic solution, suppresses an increase in viscosity even when the slurry temperature is high in a dispersion process of a carbon material-based conductive material, etc., and has low viscosity and is easy to handle when preparing a slurry.
- a dispersing agent for a positive electrode of an electricity storage device which enables the preparation of a battery conductive material slurry having a good resistance.
- the present disclosure provides a dispersant composition, a battery conductive material slurry and a method for producing the same, a battery positive electrode paste, or a battery positive electrode, including the power storage device positive electrode dispersant.
- the dispersants disclosed in Patent Document 1 and Patent Document 2 are said to increase in viscosity in the process of dispersing a carbon material-based conductive material (hereinafter sometimes abbreviated as "conductive material") in a dispersion solvent.
- conductive material carbon material-based conductive material
- the temperature of the slurry rises with time in the step of dispersing the conductive material in the dispersion solvent.
- a strong shearing force is generated between the media and heat is generated.
- the temperature of the slurry becomes high, the adsorption performance of the dispersant (copolymer) to the conductive material cannot be secured sufficiently, and dispersion does not progress.
- the outlet temperature of the slurry from the dispersing machine reaches up to 50° C. for the liquid at 25° C. before the treatment.
- the present disclosure is based on new knowledge that by introducing a specific functional group into the structural unit of the dispersant, even if the slurry temperature reaches, for example, 50°C as described above, thickening is suppressed.
- a structural unit represented by the following formula (1) (hereinafter sometimes referred to as “structural unit a”) and a structural unit represented by the following formula (2) (hereinafter “structural unit and a structural unit represented by the following formula (3) (hereinafter sometimes referred to as “structural unit c”): (hereinafter sometimes abbreviated as "dispersant” or "dispersant (A)").
- structural unit a a structural unit represented by the following formula (1)
- structural unit and a structural unit represented by the following formula (3) hereinafter sometimes referred to as “structural unit c”
- R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group
- R 4 represents a hydrocarbon group having 8 to 30 carbon atoms.
- R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group. It is a functional group contained in the monomer unit of the homopolymer of formula (2) showing 0% or more.
- R 8 , R 9 and R 10 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- the structural unit a has a hydrocarbon group having 8 to 30 carbon atoms, which is a hydrophobic group, so that a carbon material-based conductive material (hereinafter abbreviated as “conductive material” There is also.
- conductive material carbon material-based conductive material
- the adsorptive power weakens as the molecular motion increases at a high temperature of, for example, 50° C. or higher, so that the dispersibility of the conductive material decreases.
- the structural unit b contains a functional group X 1 described later, it is adsorbed to the conductive material that was not completely covered by the structural unit a, and in addition, even at a high temperature of 50 ° C. or higher, for example, Since the adsorption state can be maintained, it is possible to compensate for the decrease in the adsorption force of the structural unit a and maintain the dispersibility. In addition, dissolution of the dispersant (A) in the electrolytic solution is suppressed by containing the structural unit c in the dispersant (A).
- the dispersant of the present disclosure contains the above structural units a to c, so that the dispersant has low solubility in the electrolytic solution, and suppresses the increase in viscosity even when the slurry temperature increases in the process of dispersing the carbon material-based conductive material.
- Battery conductive material slurry (hereinafter abbreviated as "conductive material slurry” or “slurry”) that provides low resistance due to its low viscosity, good handleability during slurry preparation, and good dispersion of carbon material-based conductive materials There is also.) can be provided.
- conductive material slurry battery conductive material slurry
- slurry battery conductive material slurry
- the present disclosure should not be construed as being limited to these mechanisms.
- the solubility in the electrolytic solution is low, the viscosity increase is suppressed even when the slurry temperature is high in the dispersion process of the carbon material-based conductive material, etc., and the low viscosity makes it easy to handle when preparing the slurry. It is possible to provide a dispersing agent for a positive electrode of an electric storage device, which enables preparation of a battery conductive material slurry in which a low resistance value can be obtained because the carbon material-based conductive material can be dispersed well. Further, according to one aspect, the present disclosure can provide a dispersant composition, a battery conductive material slurry and a method for producing the same, a battery positive electrode paste, or a battery positive electrode containing the power storage device positive electrode dispersant.
- the structural unit a contained in the dispersant of the present disclosure is a structural unit represented by formula (1) above.
- Structural unit a may be one type or a combination of two or more types.
- structural unit a is a component of the copolymer of the present disclosure that adsorbs to the surface of the conductive material.
- Monomers that give structural unit a include, in one or more embodiments, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) Ester compounds such as acrylate, isostearyl (meth)acrylate, and behenyl (meth)acrylate; 2-ethylhexyl (meth)acrylamide, octyl (meth)acrylamide, lauryl (meth)acrylamide, stearyl (meth)acrylamide, behenyl (meth) Amide compounds such as acrylamide are included.
- the monomer a can be lauryl (meth)acrylate, stearyl (meth)acrylate and behenyl. At least one selected from (meth)acrylates is preferable, at least one selected from stearyl (meth)acrylate and behenyl (meth)acrylate is more preferable, and at least one selected from stearyl methacrylate (SMA) and behenyl methacrylate (BeMA) Species are more preferred, and stearyl methacrylate is even more preferred.
- SMA stearyl methacrylate
- BeMA behenyl methacrylate
- the content of the structural unit a in all structural units of the dispersant of the present disclosure is preferably 10% by mass or more, more preferably 25% by mass or more, from the viewpoint of improving the adsorptivity to the surface of the conductive material and the dispersibility of the conductive material. , More preferably 35% by mass or more, more preferably 39% by mass or more, and from the same viewpoint, preferably 75% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and further Preferably, it is 45% by mass or less.
- the content of the structural unit a in all the structural units of the dispersant of the present disclosure is preferably 10 to 75% by mass, more preferably 25 to 55% by mass, still more preferably 35 to 55% by mass, Still more preferably 39 to 50% by mass, still more preferably 39 to 45% by mass.
- the structural unit a is a combination of two or more, the content of the structural unit a is their total content.
- the content of structural unit a in all structural units of the dispersant can be regarded as the ratio of the amount of monomer a used to the total amount of monomers used for polymerization.
- the structural unit b contained in the dispersant of the present disclosure is a structural unit represented by formula (2) above.
- Structural unit b may be one type or a combination of two or more types.
- the structural unit b is a component of the dispersant of the present disclosure that adsorbs to the surface of the conductive material, and in particular, even at high temperatures, the state of adsorption to the conductive material is stable, and effective dispersion performance It is a component that realizes
- the functional group X 1 is a functional group contained in a monomer unit of the homopolymer of the formula (2) exhibiting an adsorption rate to the carbon material-based conductive material of 10.0% or more. , a pyridinyl group optionally having a hydrocarbon group of 1 to 4 carbon atoms, a pyrrolidone group, or a cyano group.
- the adsorption rate of the homopolymer to the conductive material is a value obtained by the following method. For example, a mixture (1.0 mass % conductive material slurry) is subjected to ultrasonic vibration for 1 minute to disaggregate the conductive material. Using a centrifuge (KUBOTA table top high speed cooling centrifuge 3K30C, using rotor S12158), the obtained flocculation and dissociation solution is centrifuged at 25000 rpm for 3 hours to sediment the conductive material. . The supernatant liquid W 1 ( g) was separated by a decantation method and dried at 140° C. for 12 hours. It is the weight of the polymer (non-adsorbed polymer weight).
- the adsorption rate of the homopolymer of the monomer that provides the structural unit b to the carbon material-based conductive material is 10.0% or more, preferably 12.0% or more, more preferably 14.0% or more, and It is preferably 50.0% or less, more preferably 30.0% or less, still more preferably 20.0% or less.
- monomer b examples include methacrylonitrile (MeAN) (homopolymer adsorption rate: 12.1%), acrylonitrile (AN) (homopolymer (adsorption rate of homopolymer: 14.8%), 4-vinylpyridine (4-Vpy) (adsorption rate of homopolymer: 18.5%), 2-vinylpyridine (2-Vpy) (adsorption rate of homopolymer: 16.5%). 6%) and the like.
- MeAN methacrylonitrile
- AN acrylonitrile
- AN acrylonitrile
- 4-vinylpyridine 4-Vpy
- 2-vinylpyridine (2-Vpy) adsorption rate of homopolymer: 16.5%
- 6% examples of the monomer that provides the structural unit b
- the content of the structural unit b in all the structural units of the dispersant of the present disclosure is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of improving the adsorptivity to the surface of the conductive material and the dispersibility at high temperatures. , More preferably 24% by mass or more, and from the same viewpoint, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 45% by mass or less, and still more preferably 38% by mass or less .
- the content of the structural unit b in all the structural units of the dispersant of the present disclosure is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 20 to 60% by mass, Still more preferably 20 to 45 mass %, still more preferably 24 to 45 mass %, still more preferably 24 to 38 mass %.
- the structural unit b is a combination of two or more
- the content of the structural unit b is their total content.
- the content of structural unit b in all structural units of the dispersant can be regarded as the ratio of the amount of monomer b used to the total amount of monomers used for polymerization.
- the structural unit c contained in the dispersant of the present disclosure is a structural unit represented by formula (3) above. Since the dispersant of the present disclosure contains the structural unit c having an amide group in the side chain, it has low solubility in the electrolytic solution. Therefore, according to the battery positive electrode paste (hereinafter sometimes abbreviated as "positive electrode paste") containing the dispersant of the present disclosure, a positive electrode with little elution of the dispersant (copolymer) into the electrolytic solution is formed. As a result, it is possible to obtain a battery in which the rate of increase in resistance due to repeated charging and discharging is reduced. Structural unit c may be one type or a combination of two or more types.
- the monomer that provides the structural unit c (hereinafter also referred to as "monomer c") is specifically acrylamide (AAm) or methacrylamide (MAAm).
- the content of the structural unit c in all the structural units of the dispersant of the present disclosure is from the viewpoint of solubility in the solvent used for suppressing dissolution in the electrolytic solution and polymerization of the dispersant (hereinafter also referred to as “polymerization solvent”). Therefore, it is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 18% by mass or more, and still more preferably 20% by mass. From the same point of view, it is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
- the content of the structural unit c in all structural units of the dispersant of the present disclosure is preferably 3 to 45% by mass, more preferably 5 to 45% by mass, still more preferably 10 to 40% by mass, Still more preferably 15 to 40 mass %, still more preferably 18 to 35 mass %, still more preferably 20 to 35 mass %.
- the structural unit c is a combination of two or more
- the content of the structural unit c is their total content.
- the content of structural unit c in all structural units of the dispersant can be regarded as the ratio of the amount of monomer c used to the total amount of monomers used for polymerization.
- the mass ratio of the structural unit a to the structural unit b (structural unit a/structural unit b) in all the structural units of the dispersant of the present disclosure is from the viewpoint of improving the dispersion stability of the conductive material slurry and the dispersibility at high temperatures. , preferably 0.30 or more, more preferably 0.50 or more, still more preferably 0.70 or more, still more preferably 1.00 or more, and from the same viewpoint, preferably 2.30 or less, more It is preferably 2.20 or less, more preferably 2.10 or less. From the same viewpoint, the mass ratio (structural unit a/structural unit b) in all structural units of the dispersant of the present disclosure is preferably 0.30 to 2.30, more preferably 0.50 to 2.0. 20, more preferably 0.70 to 2.10, still more preferably 1.00 to 2.10.
- the mass ratio of the structural unit b to the structural unit c is preferable from the viewpoint of suppressing dissolution in the electrolytic solution and improving dispersibility at high temperatures. is 0.50 or more, more preferably 0.60 or more, still more preferably 0.70 or more, and from the same viewpoint, preferably 7.00 or less, more preferably 4.00 or less, further preferably 2 0.50 or less.
- the mass ratio (structural unit b/structural unit c) in all structural units of the dispersant of the present disclosure is preferably 0.50 to 7.00, more preferably 0.60 to 4.0. 00, more preferably 0.70 to 2.50.
- the total content of the structural unit b and the structural unit c in all the structural units of the dispersant of the present disclosure is preferably 30% by mass or more, from the viewpoint of suppressing dissolution in the electrolytic solution and improving dispersibility at high temperatures. More preferably 45% by mass or more, still more preferably 50% by mass or more, and from the same viewpoint, preferably 75% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, and still more preferably is 56% by mass or less.
- the total content of structural unit b and structural unit c in all structural units of the dispersant of the present disclosure is preferably 30 to 75% by mass, more preferably 45 to 65% by mass, and still more preferably from the same viewpoint. is 45 to 60% by weight, even more preferably 50 to 56% by weight.
- the dispersant of the present disclosure may further contain structural units other than the structural units ac, which are copolymerizable with the structural units ac.
- Examples of monomers that provide structural units other than structural units a to c include (meth)acrylic acid and styrene.
- the content of structural units other than structural units a to c in all structural units of the dispersant of the present disclosure is preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 3% by mass or less.
- Preferred combinations of structural unit a, structural unit b, and structural unit c in the dispersant of the present disclosure include the following from the viewpoint of suppressing dissolution in the electrolytic solution and improving dispersibility at high temperatures.
- the dispersant contained in the conductive material slurry or positive electrode paste of the present disclosure which will be described later, may be, for example, one or a combination of two or more of the dispersants containing the following structural units a to c.
- the arrangement of structural unit a, structural unit b, and structural unit c in the dispersant of the present disclosure may be random, block, or graft.
- the weight-average molecular weight of the dispersant of the present disclosure is preferably 5,000 or more, more preferably 7,000 or more, still more preferably 10,000 or more, from the viewpoint of improving the dispersibility of the conductive material and dissolving the dispersant in the polymerization solvent, and From the same viewpoint, it is preferably 500,000 or less, more preferably 200,000 or less, and even more preferably 100,000 or less. From the same point of view, the weight average molecular weight of the dispersant of the present disclosure is preferably 5,000 to 500,000, more preferably 7,000 to 200,000, and even more preferably 10,000 to 100,000. In the present disclosure, the weight average molecular weight is a value measured by GPC (gel permeation chromatography), and the details of the measurement conditions are as shown in Examples.
- the method for synthesizing the dispersant of the present disclosure is not particularly limited, and methods used for polymerization of ordinary (meth)acrylic acid esters and vinyl monomers are used.
- Methods for synthesizing the dispersant of the present disclosure include, for example, free radical polymerization, living radical polymerization, anionic polymerization, living anionic polymerization, and the like.
- a free radical polymerization method it can be obtained by a known method such as polymerizing monomer components including monomer a, monomer b, and monomer c by a solution polymerization method.
- polymerization solvent examples include hydrocarbons (hexane, heptane), aromatic hydrocarbons (toluene, xylene, etc.), lower alcohols (ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone), ethers (tetrahydrofuran, diethylene glycol dimethyl ether).
- hydrocarbons hexane, heptane
- aromatic hydrocarbons toluene, xylene, etc.
- lower alcohols ethanol, isopropanol, etc.
- ketones acetone, methyl ethyl ketone
- ethers tetrahydrofuran, diethylene glycol dimethyl ether
- the amount of the polymerization solvent used for polymerization of the dispersant of the present disclosure is preferably 0.5 to 10 times the mass ratio of the total amount of the monomers.
- known radical polymerization initiators can be used, such as azo polymerization initiators, hydroperoxides, dialkyl peroxides, diacyl peroxides, ketone peroxides. etc.
- the amount of polymerization initiator is preferably 0.01 to 5 mol %, more preferably 0.05 to 4 mol %, still more preferably 0.1 to 3 mol %, relative to the total amount of monomer components.
- the polymerization reaction is preferably carried out at a temperature of 40 to 180° C. under nitrogen stream, and the reaction time is preferably 0.5 to 20 hours.
- a known chain transfer agent can be used in the polymerization. Chain transfer agents include, for example, isopropyl alcohol and mercapto compounds such as mercaptoethanol.
- the present disclosure in one aspect, relates to a dispersant composition
- a dispersant composition comprising a dispersant (A) of the present disclosure above, and a solvent (C1).
- the solvent (C1) is preferably one capable of dissolving the binder during preparation of the positive electrode paste.
- the solvent (C1) is an amide-based polar organic solvent such as dimethylformamide (DMF), diethylformamide, dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP); -propanol, 2-propanol (isopropyl alcohol), 1-butanol (n-butanol), 2-methyl-1-propanol (isobutanol), 2-butanol (sec-butanol), 1-methyl-2-propanol (tert -butanol), pentanol, hexanol, heptanol, or octanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol , or
- the content of the dispersant (A) in the dispersant composition of the present disclosure is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass, from the viewpoint of the blending margin in the post-process. From the viewpoint of handling during compounding in the post-process, the content is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. From the same viewpoint, the content of the dispersant (A) in the dispersant composition of the present disclosure is preferably 10 to 80% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 50% by mass.
- the method for producing the dispersant composition of the present disclosure includes a step of dissolving the dispersant (A) and optionally added optional components in the solvent (C1).
- the dispersant (A) may be added to the solvent (C1) in a dry state obtained by volatilizing the polymerization solvent used in the above [Method for producing a dispersant], but the polymerization solvent and the solvent (C1 ) are the same, for example, the dispersant (A) may be mixed with other components in the form of a polymer solution dissolved in a polymerization solvent.
- the present disclosure relates to a conductive material slurry containing the dispersant (A) of the present disclosure, the carbon material-based conductive material (D), and the solvent (C2).
- the conductive material slurry of the present disclosure may optionally contain an organic basic compound (B) (hereinafter sometimes abbreviated as “compound (B)”).
- the conductive material (D) includes carbon nanotubes (hereinafter sometimes referred to as "CNT"), carbon black, graphite, graphene, etc.
- CNT carbon nanotubes
- high conductivity From the viewpoint of realizing the above, at least one selected from carbon black, CNT, and graphene is preferable, and from the same viewpoint, CNT or graphene is more preferable.
- the carbon material-based conductive material (D) may be of one type or a combination of two or more types.
- the average diameter of the CNTs that can be used as the conductive material (D) is not particularly limited, and is preferably 2 nm or more and 100 nm or less, more preferably 3 nm or more and 70 nm or less, still more preferably from the viewpoint of improving the dispersibility and conductivity of the CNTs. It is 5 nm or more and 50 nm or less.
- the average diameter of CNTs can be measured by Scanning Electron Microscopy (SEM) or Atomic Force Microscopy (AFM).
- CNT means an aggregate containing multiple carbon nanotubes.
- the form of the CNTs used in the production of the conductive material slurry is not particularly limited. Mixtures of forms are also good.
- the CNTs may be a mixture of two or more CNTs having different numbers of layers or different diameters in order to achieve both conductivity and dispersibility.
- CNTs may contain impurities (eg, catalysts and amorphous carbon) from the process in which the CNTs are manufactured.
- CNTs that can be used as the conductive material (D) include Nanocyl's NC-7000 (hereafter the numerical value is the average diameter, 9.5 nm), NX7100 (10 nm), and Cnano's FT6100 (9 nm) and FT-6110 (9 nm).
- Examples of combinations when using two types of CNT include a combination of CNTs40 (40 nm) and HCNTs4 (4.5 nm) or HCNTs5 (7.5 nm) from Cabot Performance Material (Shenzhen), CNTs40 (40 nm) and GCNTs5 ( 7.5 nm), CNTs40 (40 nm) and Cnano FT-7010 (9 nm), CNTs40 (40 nm) and FT-9100 (12.5 nm), CNTs40 (40 nm) and LG Chem BT A combination with -1003M (12.5 nm) is included.
- Carbon black Various carbon blacks such as furnace black, channel black, thermal black, acetylene black, and ketjen black can be used as the carbon black that can be used as the conductive material (D).
- carbon black subjected to oxidation treatment, hollow carbon, and the like, which are commonly used, can also be used.
- Carbon black is oxidized by high temperature treatment in the air, or secondary treatment with nitric acid, nitrogen dioxide, ozone, etc., to remove, for example, phenol groups, quinone groups, carboxyl groups, and carbonyl groups. This is a treatment that directly introduces (covalently bonds) oxygen-containing polar functional groups to the carbon surface. These treatments are commonly used to improve the dispersibility of carbon black.
- the conductivity of carbon black generally decreases as the amount of functional groups introduced increases, it is preferable to use carbon black that has not been oxidized.
- the specific surface area of carbon black that can be used as the conductive material (D) the more points of contact between carbon black particles, which is advantageous for lowering the internal resistance of the electrode.
- the specific surface area (BET) determined from the nitrogen adsorption amount is preferably 20 m 2 /g or more and 1500 m 2 /g or less, more preferably 50 m 2 /g or more and 1000 m 2 /g or less, and still more preferably 100 m 2 /g or more. 2 /g or more and 800 m 2 /g or less.
- the primary particle size (diameter) of carbon black that can be used as the conductive material (D) is preferably 5 to 1000 nm, more preferably 10 to 200 nm, from the viewpoint of conductivity.
- the primary particle size of carbon black is the average of particle sizes measured with an electron microscope or the like.
- graphene that can be used as a conductive material (D) generally refers to a two-dimensional sheet (single-layer graphene) in which sp 2 hybridized carbon atoms form a hexagonal honeycomb lattice and have a thickness of one atom.
- graphene also includes a substance having a flaky form in which single-layer graphene is laminated.
- the thickness of graphene that can be used as the conductive material (D) is not particularly limited, but is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less.
- the size in the direction parallel to the graphene layer is not particularly limited, but from the viewpoint of ensuring good conductivity in the positive electrode, it is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and still more preferably 1 ⁇ m or more. be.
- the size in the direction parallel to the graphene layer means the average of the maximum diameter and the minimum diameter when observed from the direction perpendicular to the plane direction of the graphene.
- the content of the conductive material (D) in the conductive material slurry of the present disclosure is preferably 1% by mass or more, more preferably 2% by mass or more, and 3% by mass or more from the viewpoint of improving the convenience of adjusting the concentration of the positive electrode paste. is more preferable, and from the viewpoint of making the conductive material slurry easy to handle, it is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 6% by mass or less. From the same viewpoint, the content of the conductive material (D) in the conductive material slurry of the present disclosure is preferably 1 to 10% by mass, more preferably 2 to 7% by mass, and even more preferably 3 to 6% by mass.
- the content of the dispersant (A) in the conductive material slurry of the present disclosure is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the conductive material (D) from the viewpoint of improving the dispersibility of the conductive material (D). , More preferably 1 part by mass or more, more preferably 5 parts by mass or more, and from the viewpoint of high conductivity, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less is.
- the content of the dispersant (A) in the conductive material slurry of the present disclosure is preferably 0.1 to 200 parts by mass, more preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the conductive material. 5 to 50 parts by mass is more preferable.
- the organic basic compound (B) includes alkylamines, amino group-containing alcohols, imidazoles, and piperazines.
- the alkylamines are preferably branched or linear alkyl groups or primary to tertiary amines having an alicyclic group, and more preferably have alkyl groups so that the total number of carbon atoms in the molecule is 15 or less. Specific examples include hexylamine, octylamine, diethylamine, dibutylamine, trimethylamine, triethylamine, tributylamine, N-propylethylamine, N-butylethylamine and N,N-dimethylcyclohexylamine.
- the alkyl group may also be substituted with an amino group, in which case it will contain two or more primary to tertiary amino groups, and examples thereof include di- or triamines such as ethylenediamine and diethylenediaminetriamine. Primary or secondary amines are more preferred. Diethylamine, dibutylamine, hexylamine, octylamine are preferred.
- the amino group-containing alcohols are preferably alkylamines in which the hydrogen of the alkyl group is substituted with OH, such as monoethanolamine, diethanolamine, triethanolamine, N-butyldiethanolamine, N,N-dimethylaminoethanol, N -n-butylethanolamine, 2-(methylamino)ethanol, N-methylethanolamine, N-ethylethanolamine, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 1-amino -2-propanol, 2-amino-1,3-propanediol, diethanolamine, and the like.
- alkylamines in which the hydrogen of the alkyl group is substituted with OH, such as monoethanolamine, diethanolamine, triethanolamine, N-butyldiethanolamine, N,N-dimethylaminoethanol, N -n-butylethanolamine, 2-(methylamino)ethanol, N-methylethanolamine, N-eth
- the imidazoles include 1,2-dimethylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-methyl-4-ethylimidazole and the like.
- Piperazines include piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-dipropylpiperazine, 2-methylpiperazine, 2 -ethylpiperazine, 3-propylpiperazine, 2,6-dimethylpiperazine, 2,6-diethylpiperazine, 2,6-dipropylpiperazine, 2,5-dimethylpiperazine, 2,5-diethylpiperazine, 2,5-di Propylpiperazine and the like can be mentioned.
- the compound (B) may be contained in the conductive material slurry, or may be added during preparation of the positive electrode paste, which will be described later.
- the content of the compound (B) in the conductive material slurry of the present disclosure is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the conductive material (D) from the viewpoint of improving the dispersibility of the conductive material (D). , More preferably 1.0 parts by mass or more, more preferably 5 parts by mass or more, and from the viewpoint of high conductivity, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less . From the same point of view, the content of the compound (B) is preferably 0.5 to 200 parts by mass, more preferably 1.0 to 100 parts by mass, with respect to 100 parts by mass of the conductive material (D). Parts by mass are more preferred.
- the viscosity of the conductive material slurry of the present disclosure at 25°C is preferably as low as possible. From the viewpoint of suppressing sedimentation of the conductive material (D), when the content of the conductive material (D) is 5% by mass, for example, it is preferably 0.01 Pa s or more, more preferably 0.05 Pa s or more, and 0 0.1 Pa ⁇ s or more is more preferable.
- the viscosity of the conductive material slurry at 25 ° C. is preferably 10 Pa s or less, and 5 Pa s or less when the content of the conductive material (D) is 5% by mass, from the viewpoint of improving handling properties when preparing the positive electrode paste. It is more preferable, and 2 Pa ⁇ s or less is even more preferable.
- the conductive material slurry of the present disclosure contains a dispersant (A), a conductive material (D), a solvent (C2), and, if necessary, a compound (B), using a mixing and dispersing machine. It can be prepared by mixing using and dispersing each component.
- the solvent (C2) preferably includes the same solvents as the solvent (C1) that can be used in the preparation of the dispersant composition of the present disclosure described above.
- Examples of the mixing and dispersing machine include at least one selected from ultrasonic homogenizers, vibration mills, jet mills, ball mills, bead mills, sand mills, roll mills, homogenizers, high-pressure homogenizers, ultrasonic devices, attritors, desolvers, and paint shakers.
- media stirring type dispersers such as ball mills, bead mills, and sand mills are preferred for uniform dispersion.
- a media agitation type disperser gives the beads rotational motion in the grinding chamber and makes the object finer by the collision and shear force between the beads, which is accompanied by heat generation.
- Glass, alumina, and zirconia are mainly used as the bead material, but zirconia is preferable from the viewpoint of hardness of the beads and avoidance of contamination of the slurry with impurities.
- the particle size of the beads a large particle size is preferable for a large object, and a small particle size is preferable for a fine target particle size. Beads with a particle size of 0.1 mm to 20 mm are preferred for dispersing the conductive material.
- the amount of beads put into the grinding chamber is preferably 50% to 90% of the volume of the grinding chamber, and preferably 60% to 80% from the viewpoint of dispersion efficiency and heat generation.
- the rotational motion to be applied to the beads is preferably 5 m/s or more, preferably 7 m/s or more from the viewpoint of dispersion efficiency, and preferably 16 m/s or less and 14 m/s or less from the viewpoint of heat generation.
- the conductive material slurry is sent from the tank to the disperser via a pump, dispersed by beads stirred at high speed, and returned to the tank. By repeating this, the slurry is circulated and the conductive material can be dispersed.
- a dispersant (A), a conductive material (D), a solvent (C2), and optionally a compound (B) A step of dispersing each component using a media stirring type dispersing machine to form a slurry, in which the mixture (coarse dispersion) in the process of dispersion is sent from the media stirring type dispersing machine to a container (tank), The crude dispersion is sent from the tank to the media agitating type dispersing machine via a pump and subjected to dispersion treatment. This process is repeated several times to obtain a battery conductive material slurry.
- a part of the components of the conductive material slurry may be mixed and then mixed with the rest, or the entire amount of each component may be added at once. Alternatively, each may be added in multiple batches.
- the conductive material (D) may be mixed in a dry state with other components, or may be mixed with the solvent (C2) and then mixed with other components.
- the solvent (C2) is preferably the same as the solvent (C1) described above.
- the present disclosure relates to a positive electrode paste for an electricity storage device, including the dispersant (A), the solvent (C3), the conductive material (D), the positive electrode active material, and the binder of the present disclosure.
- the positive electrode paste of the present disclosure further contains the organic basic compound (B) as necessary.
- Solvent (C3) is preferably the same as the polymerization solvent or solvent (C1) described above.
- the positive electrode paste of the present disclosure contains the dispersant composition of the present disclosure or the conductive material slurry of the present disclosure.
- the positive electrode paste of the present disclosure has low solubility in the electrolytic solution, and can suppress an increase in the viscosity of the slurry even when the temperature of the slurry increases during preparation of the conductive material slurry, and suppresses the dispersion of the conductive material by suppressing the viscosity increase. Since it is prepared using the conductive material slurry of the present disclosure containing the dispersant (A), which is considered to be good, the positive electrode for a battery formed using the positive electrode paste of the present disclosure has a low volume resistance value and a high discharge capacity. It can be compatible with the maintenance rate. Preferred forms of the dispersant (A), solvent (C3), conductive material (D), dispersant composition, and conductive material slurry are as described above.
- the positive electrode paste of the present disclosure may further contain a conductive material other than the carbon material-based conductive material (D).
- a conductive material other than the carbon material-based conductive material (D) include conductive polymers such as polyaniline.
- the positive electrode active material is not particularly limited as long as it is an inorganic compound, and for example, a compound having an olivine structure or a lithium transition metal composite oxide can be used.
- compounds having an olivine structure include compounds represented by the general formula Li x M1 s PO 4 (where M1 is a 3d transition metal, 0 ⁇ x ⁇ 2, 0.8 ⁇ s ⁇ 1.2).
- a compound having an olivine structure may be coated with amorphous carbon or the like.
- Lithium - transition metal composite oxides include lithium-manganese oxides having a spinel structure; ⁇ ⁇ ⁇ 0.5), and the like.
- the lithium-transition metal composite oxide may further contain one or more elements selected from Al, Mn, Fe, Ni, Co, Cr, Ti, Zn, P, and B.
- the transition metal M may contain Co, Ni or Mn.
- the content of the positive electrode active material in the positive electrode paste of the present disclosure is not particularly limited as long as it can be adjusted according to the viscosity suitable for applying the positive electrode paste to the current collector, but from the viewpoint of energy density and From the viewpoint of the stability of the positive electrode paste, it is preferably 40% by mass to 90% by mass, more preferably 50% by mass to 85% by mass, and still more preferably 70% by mass to 80% by mass.
- the content of the positive electrode active material in the total solid content of the positive electrode paste of the present disclosure may be the same as that in the total solid content of the conventionally known positive electrode paste. 0% by mass or more is preferable, and 99.9% by mass or less is preferable in order to ensure the conductivity and coating properties of the positive electrode mixture layer. From the same point of view, 90.0 to 99.9% by mass is preferable.
- Binder resin polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, styrene-butadiene rubber, polyacrylonitrile, etc. can be used alone or in combination.
- PVDF polyvinylidene fluoride
- vinylidene fluoride-hexafluoropropylene copolymer vinylidene fluoride-hexafluoropropylene copolymer
- styrene-butadiene rubber polyacrylonitrile, etc.
- the content of the binder in the positive electrode paste of the present disclosure is preferably 0.05% by mass or more from the viewpoint of the coating properties of the positive electrode mixture layer and the binding property with the current collector, and the energy density of the battery is increased. 10% by mass or less is preferable from the viewpoint of maintaining the high degree.
- the content of the dispersant (A) in the positive electrode paste of the present disclosure is preferably 0.01 to 2.0% by mass, more preferably 0.03 to 1.0% by mass, from the viewpoint of reducing the resistance of the positive electrode mixture layer. is more preferred, and 0.05 to 0.5% by mass is even more preferred.
- the content of the compound (B) in the positive electrode paste of the present disclosure is preferably 0.012% by mass or more, more preferably 0.02% by mass, from the viewpoint of increasing the solid content concentration of the positive electrode paste and reducing the viscosity. % or more, and from the viewpoint of the solubility of the compound (B) in the solvent (C3) and the stability of the positive electrode paste, it is preferably 0.2% by mass or less, more preferably 0.1% by mass or less. .
- the compound (B) may be contained in the conductive material slurry, or may be added during production of the positive electrode paste, which will be described later.
- the content of the conductive material (D) in the positive electrode paste of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably, from the viewpoint of the conductivity of the positive electrode mixture layer. It is 0.1% by mass or more, and from the viewpoint of maintaining a high energy density of the battery, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.
- the positive electrode paste of the present disclosure includes a positive electrode active material, a conductive material slurry of the present disclosure, a binder (binder resin), and a solvent (additional solvent) for adjusting the solid content, etc. It can be produced by mixing and stirring. Other dispersants, functional materials, and the like may be added.
- a solvent additional solvent
- non-aqueous solvents such as N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) and dimethylsulfoxide (DMSO), water, and the like can be used.
- the solvent (additional solvent) it is preferable to use a non-aqueous solvent as the solvent (additional solvent), and among them, it is more preferable to use NMP.
- the solvent (additional solvent) and the solvent (C2) contained in the conductive material slurry become the solvent (C3) constituting the positive electrode paste of the present disclosure.
- a planetary mixer, a bead mill, a jet mill, or the like can be used for mixing and stirring, and these can also be used in combination.
- the positive electrode paste of the present disclosure can also be obtained by premixing a part of all the components used for manufacturing the positive electrode paste and then mixing it with the remainder. Also, each component may be added in multiple batches instead of adding the entire amount at once. As a result, the mechanical load on the stirrer can be reduced.
- the solid content concentration of the positive electrode paste of the present disclosure, the amount of the positive electrode active material, the amount of the binder, the amount of the conductive material slurry, the amount of the additive component added, and the amount of the solvent (C3) are determined by using the positive electrode paste as a current collector. It can be adjusted according to the viscosity suitable for application to. From the viewpoint of dryness, it is preferable that the amount of the solvent (C3) is small, but from the viewpoint of the uniformity of the positive electrode mixture layer and the smoothness of the surface, it is preferable that the viscosity of the positive electrode paste is not too high. On the other hand, it is preferable that the viscosity of the positive electrode paste is not too low from the viewpoint of suppressing drying and obtaining a sufficient thickness of the positive electrode mixture layer.
- the positive electrode paste of the present disclosure preferably has a high concentration from the viewpoint of manufacturing efficiency, but a significant increase in viscosity is not preferable from the viewpoint of workability. By adding additives, it is possible to maintain a preferable viscosity range while maintaining a high concentration.
- a method for producing a positive electrode paste of the present disclosure includes, for example, mixing a conductive material, a positive electrode active material, a solvent (additional solvent), a binder, and a dispersant composition of the present disclosure. Each component may be mixed in any order.
- the method for producing the positive electrode paste of the present disclosure preferably includes a step of mixing the conductive material slurry of the present disclosure, a binder, a solvent (additional solvent), and a positive electrode active material. Each component may be mixed in any order.
- the conductive material slurry of the present disclosure, an additional solvent, and a binder are mixed and dispersed until they are homogeneous, and then the positive electrode active material is mixed and these are homogeneous.
- the order of addition of these components is not limited to this.
- the dispersant composition, the conductive material slurry, and the positive electrode paste of the present disclosure may each further contain other components as long as the effects of the present disclosure are not hindered.
- Other components include, for example, antioxidants, neutralizers, antifoaming agents, preservatives, dehydrating agents, rust preventives, plasticizers, binders, and the like.
- the present disclosure relates to a positive electrode for a battery formed using the positive electrode paste of the present disclosure.
- preferred forms of the positive electrode paste of the present disclosure are as described above.
- the positive electrode is produced by coating the above positive electrode paste on a current collector such as aluminum foil and drying it.
- compaction can also be performed using a pressing machine.
- a die head, a comma reverse roll, a direct roll, a gravure roll, or the like can be used for coating the positive electrode paste. Drying after coating can be carried out by heating, air flow, infrared irradiation, etc. alone or in combination.
- the positive electrode can be pressed using a roll press machine or the like.
- the present application further discloses the following power storage device positive electrode dispersant, use of the power storage device positive electrode dispersant, and method for producing battery conductive material slurry.
- Dispersant for positive electrode of power storage device R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and R 4 represents a hydrocarbon group having 8 to 30 carbon atoms.
- R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and the functional group X 1 has a hydrocarbon group with 1 to 4 carbon atoms.
- R 8 , R 9 and R 10 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- the content of the structural unit represented by the formula (3) in all structural units of the power storage device positive electrode dispersant is 20% by mass or more and 35% by mass or less, according to the above ⁇ 1>.
- a dispersant for the positive electrode of an electrical storage device is 20% by mass or more and 35% by mass or less, according to the above ⁇ 1>.
- ⁇ 3> The power storage device positive electrode dispersant according to ⁇ 1> or ⁇ 2>, wherein the weight average molecular weight of the power storage device positive electrode dispersant is 5000 or more and 500,000 or less.
- a dispersant composition comprising the dispersant for a positive electrode of an electricity storage device according to any one of ⁇ 1> to ⁇ 3>, an organic basic compound, and a solvent.
- ⁇ 6> Each component in a mixture containing the power storage device positive electrode dispersant according to any one of ⁇ 1> to ⁇ 3>, a carbon material-based conductive material, a solvent, and, if necessary, an organic basic compound is dispersed using a media stirring type dispersing machine to form a slurry, and in the process, the mixture (coarse dispersion) in the middle of dispersion is sent from the media stirring type dispersing machine to a container (tank), and the coarse A method for producing a conductive material slurry for a battery, wherein the dispersion liquid is sent from a tank to the media stirring type dispersing machine via a pump to be dispersed, and this process is repeated a plurality of times to obtain a conductive material slurry for a battery.
- ⁇ 7> The method for producing a conductive material slurry for a battery according to ⁇ 6> above, wherein the temperature (outlet temperature) of the mixture coming out through the media stirring type dispersing machine is 50° C. or higher.
- ⁇ 8> Use of the power storage device positive electrode dispersant according to any one of ⁇ 1> to ⁇ 3> for producing battery conductive material slurry.
- ⁇ 9> Use of the power storage device positive electrode dispersant according to any one of ⁇ 1> to ⁇ 3> for producing battery positive electrode paste.
- the mass of the copolymer dissolved in the mixed solvent was measured by drying the filtered solution at 140° C. under reduced pressure under a nitrogen stream. From the following formula, the dissolution rate in the mixed solvent was determined as the electrolyte solubility. Table 6 shows the dissolution rates obtained.
- the positive electrode paste was dripped onto a polyester film and applied uniformly with a 100 ⁇ m applicator.
- the coated polyester film was dried at 100° C. for 1 hour to obtain a 40 ⁇ m-thick positive electrode mixture layer.
- the volume resistance value was measured at a limiting voltage of 10 V using a Loresta-GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) equipped with a PSP probe. The results are shown in Table 6.
- a negative electrode was manufactured. Specifically, 94.8 parts by weight of commercially available graphite for the negative electrode active material, 1.7 parts by weight of acetylene black, 2 parts by weight of SBR (styrene-butadiene rubber) and 1.5 parts by weight of CMC (carboxymethyl cellulose) were mixed. Subsequently, a slurry was prepared by adding distilled water as a solvent to this mixture. The slurry was coated on the surface of the electrodeposited copper foil to a thickness of about 100 ⁇ m using a doctor blade, dried at 120° C., and then subjected to a roll press process to manufacture a negative electrode.
- Positive electrode active material manufactured by Nippon Kagaku Kogyo Co., Ltd., NCM523
- PVDF polyvinylidene fluoride
- CNT manufactured by Cabot Performance material (Shenzhen)
- GCNTs5 each copolymer shown in Table 2, and compound B
- a slurry was prepared by mixing with NMP as an organic solvent at a weight ratio of 97:2:1:0.225:0.025. The slurry was coated on both sides of an aluminum foil having a thickness of 20 ⁇ m and then dried to prepare a positive electrode.
- an electrolytic solution was prepared by dissolving 1M LiPF 6 as a solute in a non-aqueous organic solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a weight ratio of 1:1.
- EC ethylene carbonate
- DEC diethyl carbonate
- Copolymer O was prepared in the same manner as in Synthesis Example of Copolymer D, except that a mixed solution consisting of 30 g of PEG(2)MA and 60 g of NMP (solvent) was used instead of dropping monomer solution 3. A 30% by weight solution of was obtained.
- the conductive material slurry (2-1) was prepared by mixing 200 g of the conductive material, 133 g of the copolymer A solution, and 3667 g of NMP (additional solvent) at room temperature to prepare 4000 g of a coarse dispersion.
- the resulting coarse dispersion was passed through a media stirring type dispersing machine (Dyno Mill KDL-PILOT Model 1.4 manufactured by Shinmaru Enterprises) at a flow rate of 300 g/min.
- the conditions of the dispersing device were zirconia beads with an average diameter of 0.5 mm at a packing rate of 70% and a peripheral speed of 10 m/s.
- NCM523 lithium nickel manganese cobalt oxide, manufactured by Nippon Kagaku Kogyo Co., Ltd.
- NCM523 lithium nickel manganese cobalt oxide, manufactured by Nippon Kagaku Kogyo Co., Ltd.
- the mass ratio of the positive electrode active material, the binder (PVDF), the conductive agent (carbon nanotubes) and the dispersant was 98.85:0.5:0.5:0.1 (in terms of solid content), and the positive electrode paste
- the solid content (% by mass) of was set to 77% by mass.
- the solid content of the positive electrode paste is mass % of the solid content of the material including the copolymer, the positive electrode active material, the conductive agent, and the binder contained in the positive electrode paste.
- the viscosity difference ⁇ is not large, but the solubility in the electrolytic solution is as high as 3.5%, so when charging and discharging are repeated In addition, an increase in the volume resistance value and a decrease in the discharge capacity retention rate were observed in the battery performance.
- the viscosity and the viscosity difference ⁇ of the conductive material slurry 2-10 of Example 9 are smaller than the viscosity and the viscosity difference ⁇ of the conductive material slurry 2-1 of Example 1, respectively.
- the dispersibility of the conductive material is improved.
- Examples in which the content of component c in all structural units of the dispersant is 20 to 35% by mass include structural units a to c, and the content of component c in all structural units of the dispersant is 20% by mass. It can be seen that the volume resistance value is lower than those of Examples and Comparative Examples in which the content is less than % by mass.
- the dispersant of the present disclosure can satisfactorily disperse the carbon material-based conductive material, and as a result, it is possible to reduce the viscosity of the conductive material slurry and the positive electrode paste. Then, if the dispersant of the present disclosure is used for preparation of the conductive material paste and the positive electrode paste, the viscosity of the conductive material slurry and the positive electrode paste is also low, which can contribute to the reduction of the resistance of the positive electrode coating film.
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Abstract
Description
特開2018-170218号公報(特許文献2)には、正極ペーストに含まれる分散剤の電解液に対する溶解性が高いと、電解液に溶出した共重合体によってセパレーターに目詰まりが生じ、抵抗が増大するため、メタクリル酸ステアリル(SMA)とメトキシポリエチレングリコールメタクリレート(PEG(2)MA)とメタクリルアミド(MAAm)の共重合体等の特定の共重合体を、分散剤として添加することが開示されている。
また、特開2014-137916(特許文献3)には、高電位向けの活物質を用いた場合でもサイクル特性を良好なものとするために、アクリロニトリル(AN)由来の構成単位とラウリルアクリレート由来の構成単位を含む粒子状結着剤と分散媒とを含む電気化学素子電極用導電性接着剤組成物が開示されている。そして、電気化学素子電極用導電性接着剤組成物は、電極活物質層と集電体との間に設ける導電性接着剤層を形成するために用いることが開示されている。
本開示は、一態様において、下記式(1)で表される構成単位(以下「構成単位a」と称する場合がある。)と、下記式(2)で表される構成単位(以下「構成単位b」と称する場合がある。)と、下記式(3)で表される構成単位(以下「構成単位c」と称する場合がある。)と、を含む共重合体である、蓄電デバイス正極用分散剤(以下、「分散剤」または「分散剤(A)」と略称する場合もある。)に関する。
本開示の分散剤(A)のうちの、構成単位aは、疎水基である炭素数8~30の炭化水素基を有することにより、炭素材料系導電材(以下「導電材」と略称する場合もある。)に吸着し、分散性を発現すると考えられる。しかし、その吸着力は例えば50℃以上の高温下で分子運動が大きくなるにつれて弱まるため、導電材の分散性が低下する。これに対し、構成単位bは、後述する官能基X1を含んでいるので、構成単位aでは被覆しきれなかった前記導電材に吸着し、加えて、例えば、50℃以上という高温下でもその吸着状態を保持できることから、構成単位aの吸着力低下を補って分散性の維持を可能とする。また、分散剤(A)に、構成単位cが含まれていることにより、電解液への分散剤(A)の溶解が抑制される。したがって、本開示の分散剤は、上記構成単位a~cを含むことにより、電解液に対する溶解性が低く、炭素材料系導電材の分散工程でスラリー温度が高くなっても粘度上昇を抑制し、低粘度でスラリー調製時のハンドリング性が良好で炭素材料系導電材の分散が良好であるため低い抵抗値が得られる電池用導電材スラリー(以下「導電材スラリー」または「スラリー」と略称する場合もある。)の提供を可能とする。ただし、本開示はこれらのメカニズムに限定して解釈されない。
本開示の分散剤に含まれる構成単位aは、上記式(1)で表される構成単位である。構成単位aは、1種でもよいし、2種以上の組合せでもよい。本開示において、構成単位aは、本開示の共重合体のうちの、導電材の表面に吸着する成分である。
本開示において、分散剤の全構成単位中における構成単位aの含有量は、重合に用いるモノマー全量に対するモノマーaの使用量の割合とみなすことができる。
本開示の分散剤に含まれる構成単位bは、上記式(2)で表される構成単位である。構成単位bは、1種でもよいし、2種以上の組合せでもよい。本開示において、構成単位bは、本開示の分散剤のうちの、導電材表面に吸着する成分であり、特に、高温時でも、導電材への吸着状態が安定しており、有効な分散性能を実現する成分である。
例えば、ホモポリマー0.3gを溶媒(NMP)29.4gと混合して得られる1.0質量%ポリマー溶液と炭素材料系導電材(Nanocyl製CNT NC7000)0.3gの混合物(1.0質量%導電材スラリー)に、超音波振動を1分間与えて、導電材の凝集解離を行う。得られた凝集解離液に対して、遠心分離機(KUBOTA テーブルトップ高速冷却遠心機3K30C、ローターS12158を使用)を用いて、回転数25000rpmで3時間の遠心分離処理を行い、導電材を沈降させる。上澄み液W1(g)をデカンテーション法で分離し、それを140℃にて12時間かけて乾燥し、得られる乾燥物の重量測定値W2(g)を、導電材に吸着しなかったポリマーの重量(非吸着ポリマー重量)とする。初期のポリマー重量(0.3g)との差分を吸着ポリマーとして、下記式にて吸着率を算出する。
本開示において、分散剤の全構成単位中における構成単位bの含有量は、重合に用いるモノマー全量に対するモノマーbの使用量の割合とみなすことができる。
本開示の分散剤に含まれる構成単位cは、上記式(3)で表される構成単位である。本開示の分散剤は、側鎖にアミド基を有する上記構成単位cを含むため、電解液への溶解性が低い。従って、本開示の分散剤を含む電池用正極ペースト(以下「正極ペースト」と略称する場合もある。」)によれば、電解液への分散剤(共重合体)の溶出が少ない正極を形成でき、その結果、充放電の繰り返しに伴う抵抗増加率が低減された電池を得ることができる。構成単位cは、1種でもよいし、2種以上の組合せでもよい。
本開示において、分散剤の全構成単位中における構成単位cの含有量は、重合に用いるモノマー全量に対するモノマーcの使用量の割合とみなすことができる。
・SMA/AN/MAAm
・SMA/AN/AAm
・SMA/MeAN/MAAm
・SMA/MeAN/AAm
・SMA/4-Vpy/MAAm
・SMA/4-Vpy/AAm
・SMA/2-Vpy/MAAm
・SMA/2-Vpy/AAm
本開示の分散剤の合成方法は特に限定されず、通常の(メタ)アクリル酸エステル類、及びビニルモノマーの重合に使用される方法が用いられる。本開示の分散剤の合成方法としては、例えば、フリーラジカル重合法、リビングラジカル重合法、アニオン重合法、リビングアニオン重合法等が挙げられる。例えば、フリーラジカル重合法を用いる場合は、モノマーa、モノマーb、及びモノマーcを含むモノマー成分を溶液重合法で重合させる等の公知の方法で得ることができる。
本開示は、一態様において、上記本開示の分散剤(A)、及び溶媒(C1)を含む、分散剤組成物に関する。
溶媒(C1)は、正極ペーストの調製時に結着剤を溶解できるものであることが好ましい。具体的には、前記溶媒(C1)は、ジメチルホルムアミド(DMF)、ジエチルホルムアミド、ジメチルアセトアミド(DMAc)、N-メチル-2-ピロリドン(NMP)などのアミド系極性有機溶媒;メタノール、エタノール、1-プロパノール、2-プロパノール(イソプロピルアルコール)、1-ブタノール(n-ブタノール)、2-メチル-1-プロパノール(イソブタノール)、2-ブタノール(sec-ブタノール)、1-メチル-2-プロパノール(tert-ブタノール)、ペンタノール、ヘキサノール、ヘプタノール、またはオクタノールなどのアルコール類;エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,3-ブタンジオール、1,5-ペンタンジオール、またはヘキシレングリコールなどのグリコール類;グリセリン、トリメチロールプロパン、ペンタエリスリトール、またはソルビトールなどの多価アルコール類;エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、テトラエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、テトラエチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、またはテトラエチレングリコールモノブチルエーテルなどのグリコールエーテル類;アセトン、メチルエチルケトン、メチルプロピルケトン、またはシクロペンタノンなどのケトン類;酢酸エチル、γ-ブチルラクトン、およびε-プロピオラクトンなどのエステル類などが挙げられ、これらのいずれか1種または2種以上の混合物が使用できる。
正極ペースト中の結着剤がPVDF(ポリフッ化ビニリデン樹脂)である場合、前記溶媒(C1)は、結着剤に対して高い溶解性を示す観点から、N-メチル-2-ピロリドン(NMP)が好ましい。
本開示の分散剤組成物中の分散剤(A)の含有量は、後工程での配合マージンの観点から、好ましくは10質量%以上、より好ましくは15質量%以上、更に好ましくは20質量%以上であり、そして、後工程での配合時のハンドリングの観点から、好ましくは80質量%以下、より好ましくは60質量%以下、更に好ましくは50質量%以下である。本開示の分散剤組成物中の分散剤(A)の含有量は、同様の観点から、10~80質量%が好ましく、15~60質量%がより好ましく、20~50質量%が更に好ましい。
本開示の分散剤組成物の製造方法は、分散剤(A)と必要に応じて添加される任意成分を溶媒(C1)に溶解させる工程を含む。分散剤(A)は、前記[分散剤の製造方法]で用いられる重合溶媒を揮発させて得られた乾燥状態で溶媒(C1)に添加してもよいが、前記重合溶媒と上記溶媒(C1)とが、例えば同じであれば、前記分散剤(A)が重合溶媒に溶解されたポリマー溶液の状態で他の成分と混合されてもよい。
本開示は、一態様において、上記本開示の分散剤(A)、炭素材料系導電材(D)、及び溶媒(C2)を含有する、導電材スラリーに関する。本開示の導電材スラリーには、必要に応じて有機塩基性化合物(B)(以下「化合物(B)」と略称する場合もある。)が含まれていてもよい。
導電材(D)としては、一又は複数の実施形態において、カーボンナノチューブ(以下、「CNT」と表記することもある)、カーボンブラック、グラファイト、グラフェン等が挙げられ、これらの中でも、高い導電性を実現する観点から、カーボンブラック、CNT、及びグラフェンから選ばれる少なくとも1種が好ましく、同様の観点から、CNT又はグラフェンがより好ましい。炭素材料系導電材(D)は、1種でもよいし、2種以上の組合せでもよい。
導電材(D)として使用できるCNTの平均直径は、特に限定されず、CNTの分散性向上及び導電性向上の観点から、好ましくは2nm以上100nm以下、より好ましくは3nm以上70nm以下、更に好ましくは5nm以上50nm以下である。本開示において、CNTの平均直径は、走査型電子顕微鏡(SEM)や原子間力顕微鏡(AFM)により測定できる。
2種類のCNTを使用する場合の組み合わせとしては、例えば、Cabot Performance material(Shenzhen)社のCNTs40(40nm)とHCNTs4(4.5nm)又はHCNTs5(7.5nm)との組合せ、CNTs40(40nm)とGCNTs5(7.5nm)との組合せ、CNTs40(40nm)とCnano社のFT-7010(9nm)との組合せ、CNTs40(40nm)とFT-9100(12.5nm)との組合せ、CNTs40(40nm)とLG Chem社BT-1003M(12.5nm)との組合せ等が挙げられる。
導電材(D)として使用できるカーボンブラックとしては、ファーネスブラック、チャンネルブラック、サーマルブラック、アセチレンブラック、ケッチェンブラックなど各種のものを用いることができる。また、通常行われている酸化処理されたカーボンブラックや、中空カーボン等も使用できる。カーボンブラックの酸化処理は、カーボンブラックを空気中で高温処理し、または硝酸や二酸化窒素、オゾン等で二次的に処理することより、例えばフェノール基、キノン基、カルボキシル基、カルボニル基の様な酸素含有極性官能基をカーボン表面に直接導入(共有結合)する処理である。これらの処理は、カーボンブラックの分散性を向上させるために一般的に行われている。しかしながら、官能基の導入量が多くなる程カーボンブラックの導電性が低下することが一般的であるため、酸化処理をしていないカーボンブラックの使用が好ましい。
導電材(D)として使用できるグラフェンとは、一般には、sp2混成炭素原子が六角形のハニカム格子を形成し、原子1個分の厚みをもつ二次元シート(単層グラフェン)を指すが、本開示においては、単層グラフェンが積層した薄片上の形態を持つ物質も含めてグラフェンと呼ぶことにする。
本開示の導電材スラリー中の導電材(D)の含有量は、正極ペーストの濃度調整の利便性向上の観点から、1質量%以上が好ましく、2質量%以上がより好ましく、3質量%以上が更に好ましく、そして、導電材スラリーを取り扱いやすい粘度とする観点から、10質量%以下が好ましく、7質量%以下がより好ましく、6質量%以下が更に好ましい。本開示の導電材スラリー中の導電材(D)の含有量は、同様の観点から、1~10質量%が好ましく、2~7質量%がより好ましく、3~6質量%が更に好ましい。
本開示の導電材スラリー中の分散剤(A)の含有量は、導電材(D)の分散性向上の観点から、導電材(D)100質量部に対し、好ましくは0.1質量部以上、より好ましくは1質量部以上、更に好ましくは5質量部以上であり、そして、高導電性の観点から、好ましくは200質量部以下、より好ましくは100質量部以下、更に好ましくは50質量部以下である。本開示の導電材スラリー中の分散剤(A)の含有量は、同様の観点から、導電材100質量部に対し、0.1~200質量部が好ましく、1~100質量部がより好ましく、5~50質量部が更に好ましい。
有機塩基性化合物(B)としては、一又は複数の実施形態において、アルキルアミン類、アミノ基含有アルコール類、イミダゾール類、ピペラジン類が挙げられる。
本開示の導電材スラリー中の化合物(B)の含有量は、導電材(D)の分散性向上の観点から、導電材(D)100質量部に対して、0.5質量部以上が好ましく、1.0質量部以上がより好ましく、5質量部以上が更に好ましく、そして、高導電性の観点から、200質量部以下が好ましく、100質量部以下がより好ましく、50質量部以下が更に好ましい。同様の観点から、化合物(B)の含有量は、導電材(D)100質量部に対して、0.5~200質量部が好ましく、1.0~100質量部がより好ましく、5~50質量部が更に好ましい。
本開示の導電材スラリーは、一又は複数の実施形態において、分散剤(A)と、導電材(D)と、溶媒(C2)と、必要に応じて化合物(B)を、混合分散機を用いて混合し、各成分を分散することにより調製できる。前記溶媒(C2)としては、好ましくは、上述した本開示の分散剤組成物の調製に用いることができる溶媒(C1)と同様のものが挙げられる。
本開示は、一態様において、上記本開示の分散剤(A)、溶媒(C3)、導電材(D)、正極活物質、及び結着剤、を含む蓄電デバイス用正極ペーストに関する。本開示の正極ペーストは、必要に応じて、前記有機塩基性化合物(B)をさらに含有する。溶媒(C3)は、好ましくは、上述した重合溶媒または溶媒(C1)と同じものが挙げられる。本開示の正極ペーストは、一又は複数の実施形態において、本開示の分散剤組成物または本開示の導電材スラリーを含有する。本開示の正極ペーストは、電解液に対する溶解性が低く、導電材スラリーの調製最中にスラリー温度が高くなっても当該スラリーの粘度上昇を抑制可能とし、粘度上昇の抑制により導電材の分散を良好とする、分散剤(A)を含む本開示の導電材スラリーを用いて調製されるので、本開示の正極ペーストを用いて形成される電池用正極において、低い体積抵抗値と、高い放電容量維持率との両立が行える。
分散剤(A)、溶媒(C3)、導電材(D)、分散剤組成物、導電材スラリーの好ましい形態は上述のとおりである。本開示の正極ペーストには、一又は複数の実施形態において、炭素材料系導電材(D)以外の導電材が更に含まれていてもよい。炭素材料系導電材(D)以外の導電材としては、ポリアニリン等の導電性ポリマー等が挙げられる。
正極活物質としては、無機化合物であれば特に制限はなく、例えば、オリビン構造を有する化合物やリチウム遷移金属複合酸化物を用いることができる。オリビン構造を有する化合物としては、一般式LixM1sPO4(但し、M1は3d遷移金属、0≦x≦2、0.8≦s≦1.2)で表される化合物を例示できる。オリビン構造を有する化合物は、非晶質炭素等を被覆して用いてもよい。リチウム遷移金属複合酸化物としては、スピネル構造を有するリチウムマンガン酸化物、層状構造を有し一般式LixMO2-δ(但し、Mは遷移金属、0.4≦x≦1.2、0≦δ≦0.5)で表されるリチウム遷移金属複合酸化物等が挙げられる。前記リチウム遷移金属複合酸化物は、さらに、Al、Mn、Fe、Ni、Co、Cr、Ti、Zn、P、およびBから選ばれる一種又は二種以上の元素を含有していてもよい。前記遷移金属Mとしては、Co、Ni又はMnを含むものとすることができる。
本開示の正極ペースト中の正極活物質の含有量は、正極ペーストが集電体に塗布するのに適した粘度に応じて調整することができる限り、特に制限はないが、エネルギー密度の観点と正極ペーストの安定性の観点から、好ましくは40質量%~90質量%、より好ましくは50質量%~85質量%、さらに好ましくは70~80質量%である。
結着剤(バインダー樹脂)としては、ポリフッ化ビニリデン(PVDF)、フッ化ビニリデン-ヘキサフルオロプロピレン共重合体、スチレン-ブタジエンゴム、ポリアクリロニトリル等を単独で、あるいは混合して用いることができる。
本開示の正極ペースト中の結着剤の含有量は、正極合材層の塗膜性や集電体との結着性の観点から、0.05質量%以上が好ましく、電池のエネルギー密度を高度に保つ観点からは10質量%以下が好ましい。
本開示の正極ペースト中の分散剤(A)の含有量は、正極合材層の低抵抗化の観点から、0.01~2.0質量%が好ましく、0.03~1.0質量%がより好ましく、0.05~0.5質量%がさらに好ましい。
本開示の正極ペースト中の化合物(B)の含有量は、正極ペーストの固形分濃度を高くする観点、及び粘度低下の観点から、好ましくは0.012質量%以上、より好ましくは0.02質量%以上であり、そして、化合物(B)の溶媒(C3)への溶解性と正極ペーストの安定性の観点から、好ましくは0.2質量%以下、より好ましくは0.1質量%以下である。化合物(B)は、導電材スラリーに含まれていてもよいが、後述する正極ペーストの製造時に添加してもよい。
本開示の正極ペースト中の導電材(D)の含有量は、正極合材層の導電性の観点から、好ましくは0.01質量%以上、より好ましくは0.05質量%以上、更に好ましくは0.1質量%以上であり、そして、電池のエネルギー密度を高度に保つ観点から、好ましくは5質量%以下、より好ましくは3質量%以下、更に好ましくは2質量%以下である。
本開示の正極ペーストの製造方法は、例えば、導電材、正極活物質、溶媒(追加溶媒)、結着剤及び本開示の分散剤組成物を混合する工程を含む。各成分は任意の順で混合しても良い。本開示の正極ペーストの製造方法は、一又は複数の実施形態において、好ましくは本開示の導電材スラリーと結着剤と溶媒(追加溶媒)と正極活物質とを混合する工程を含む。各成分は任意の順に混合してもよい。また、一又は複数の実施形態において、本開示の導電材スラリーと追加溶媒と結着剤とを混合し、これらが均質になるまで分散したのち、正極活物質を混合し、これらが均質になるまで攪拌することにより正極ペーストを得る方法が挙げられるが、これら成分の添加順序はこの限りではない。
本開示は、一態様において、本開示の正極ペーストを用いて形成された電池用正極に関する。本態様において、本開示の正極ペーストの好ましい形態は上述のとおりである。
<2>前記蓄電デバイス正極用分散剤の全構成単位中における、前記式(3)で表される構成単位の含有量が、20質量%以上35質量%以下である、前記<1>に記載の蓄電デバイス正極用分散剤。
<3>前記蓄電デバイス正極用分散剤の重量平均分子量は、5000以上50万以下である、前記<1>又は<2>に記載の蓄電デバイス正極用分散剤。
<4>前記<1>から<3>のいずれかに記載の蓄電デバイス正極用分散剤、有機塩基性化合物、及び溶媒を含む、分散剤組成物。
<5>前記<1>から<3>のいずれかに記載の蓄電デバイス正極用分散剤、炭素材料系導電材、有機塩基性化合物、及び溶媒を含む電池用導電材スラリー。
<6> 前記<1>から<3>のいずれかに記載の蓄電デバイス正極用分散剤と、炭素材料系導電材と、溶媒と、必要に応じて有機塩基性化合物を含む混合物中の各成分を、メディア撹拌型分散機を用いて分散させてスラリーとする工程を含み、前記工程において、分散途中の混合物(粗分散液)を、メディア撹拌型分散機から容器(タンク)へ送り、当該粗分散液をタンクからポンプを介して前記メディア撹拌型分散機へ送って分散処理し、これを複数回繰り返して、電池用導電材スラリーを得る、電池用導電材スラリーの製造方法。
<7>前記メディア撹拌型分散機を通過して出てくる前記混合物の温度(出口温度)が50℃以上である、前記<6>に記載の電池用導電材スラリーの製造方法。
<8>電池用導電材スラリー製造のための<1>~<3>のいずれか1つに記載の蓄電デバイス正極用分散剤の使用。
<9>電池用正極ペースト製造のための<1>~<3>のいずれか1つに記載の蓄電デバイス正極用分散剤の使用。
[ポリマーの重量平均分子量の測定]
ポリマーの重量平均分子量は、GPC法により測定した。詳細な条件は以下の通りである。
測定装置:HLC-8320GPC(東ソー社製)
カラム:α-M + α-M(東ソー社製)
カラム温度:40℃
検出器:示差屈折率
溶離液:60mmol/LのH3PO4及び50mmol/LのLiBrのN,N-ジメチルホルムアミド(DMF)溶液
流速:1mL/min
検量線に用いる標準試料 :ポリスチレン
試料溶液:共重合体の固形分を0.5wt%含有するDMF溶液
試料溶液の注入量:100μL
分散剤(共重合体)の電解液への溶解性を確認する目的で、電解液に使用される溶媒への溶解率を測定した。得られた共重合体溶液をシャーレに入れ、140℃、窒素気流下にて12時間以上減圧乾燥した。得られた共重合体1gにエチレンカーボネートとジエチレンカーボネートとの混合溶媒(体積比50/50)9gを添加し、10%懸濁液を調製した。得られた懸濁液を40℃、1時間静置した。その後、0.5μmのPTFEフィルターでろ過し、溶解していない共重合体を除去した。ろ過した溶液を140℃、減圧、窒素気流下で乾燥することで、混合溶媒に溶解した共重合体の質量を測定した。以下の式より、電解液溶解性として、混合溶媒への溶解率を求めた。得られた溶解率を表6に示す。
導電材スラリーの25℃の時の粘度、及び50℃の時の粘度は、それぞれ、Anton Paar社のMCR302レオメーターに、コンプレートCP50を装着し、せん断速度10s-1で粘度測定を開始し、5分後の粘度を記録し、それを表6に示した。
正極ペーストを、ポリエステルフィルムに垂らし、100μmのアプリケータで均一に塗工した。この塗工したポリエステルフィルムを100℃で1時間乾燥し厚み40μmの正極合材層を得た。
PSPプローブを装着したLoresta-GP(株式会社三菱ケミカルアナリテック製)にて限界電圧10vにて体積抵抗値を測定した。その結果は表6に示した。
まず、負極を製造した。具体的には、負極活物質用に市販されるグラファイト94.8質量部と、アセチレンブラック1.7質量部と、SBR(スチレンブタジエンゴム)2重量部およびCMC(カルボキシメチルセルロース)1.5質量部を混合した。引き続き、この混合物に溶剤である蒸溜水を添加することによってスラリーを製造した。ドクターブレードを利用して前記スラリーを約100μm厚さで電解銅箔表面上に塗布し、120℃で乾燥させた後ロールプレス工程を遂行することによって負極を製造した。
(充電条件)
0.2C CC-CV4.2V(0.02C Cut off)
(放電条件)
0.2,0.5,1,3,4,5,10C CC(3V Cut off)
5Cの放電容量維持率(%)=(5Cの放電容量/0.2Cの放電容量)×100
[使用原料]
共重合体の合成に使用した原料の詳細は、下記及び表1、表2に記載の通りである。
(モノマーa)
SMA:ステアリルメタクリレート(新中村化学工業株式会社製、品番:NK-エステルS)
BeMA:ベヘニルメタクリレート(日油株式会社製、品番:ブレンマーVMA)
(モノマーb)
AN:アクリロニトリル(富士フイルム和光純薬株式会社製)
4-VPy:4-ビニルピリジン(東京化成工業株式会社製)
(モノマーc)
MAAm:メタクリルアミド(東京化成工業株式会社製)
(モノマーd)
MEMA:メトキシエチルメタクリレート(東京化成工業株式会社製、ホモポリマーの吸着率1.5%)
PEG(2)MA:メトキシジエチレングリコールメタクリレート(新中村化学工業株式会社製、品番:NK-エステルM-20G、エチレンオキサイドの平均付加モル数=2)
(有機塩基性化合物)
オクチルアミン(ファーミン08D 花王株式会社製)
(重合開始剤)
V-65B:2,2'-アゾビス(2,4-ジメチルバレロニトリル)(富士フイルム和光純薬株式会社製)
(溶媒)
NMP:N-メチル-2-ピロリドン(富士フイルム和光純薬株式会社製)
下記の滴下用モノマー溶液1~3と滴下用開始剤溶液を作製した。モノマーの滴下溶液はモノマー量に対し2倍量のNMPで希釈して調製した。
滴下用モノマー溶液1:44gのSMA(モノマーa1)と88gのNMP(溶媒)からなる混合溶液
滴下用モノマー溶液2:36gのAN(モノマーb1)と72gのNMP(溶媒)からなる混合溶液
滴下用モノマー溶液3:20gのMAAm(モノマーc1)と40gのNMP(溶媒)からなる混合溶液
滴下用開始剤溶液:1.6gのV-65B(重合開始剤)及び16gのNMP(溶媒)からなる混合溶液
滴下用モノマー溶液の調製において、共重合体C,D,F,G,H,Q,Pの合成に使用される各モノマーの質量比を、各々、表2に記載の値とし、重合終了後、[共重合体Aの合成例]と同様にしてNMPで希釈することで、共重合体C,D,F,G,H,Q,Pの30質量%溶液を得た。
滴下用モノマー溶液1として、44gのBeMA(モノマーa2)と88gのNMP(溶媒)からなる混合溶液を用いたこと以外は、[共重合体Aの合成例]と同様にして、共重合体Bの30質量%溶液を得た。
滴下用モノマー溶液2として、36gの4-VPy(モノマーb2)と72gのNMP(溶媒)からなる混合溶液を用いたこと以外は、[共重合体Aの合成例]と同様にして、共重合体Eの30質量%溶液を得た。
滴下用モノマー溶液2に代えて、36gのMEMAと72gのNMP(溶媒)からなる混合溶液を用いたこと以外は、[共重合体Aの合成例]と同様にして、共重合体Nの30質量%溶液を得た。
滴下用モノマー溶液3に代えて、30gのPEG(2)MAと60gのNMP(溶媒)からなる混合溶液を用いたこと以外は、共重合体Dの合成例と同様にして、共重合体Oの30質量%溶液を得た。
滴下用モノマー溶液2に代えて、26gのPEG(2)MAと52gのNMP(溶媒)からなる混合溶液を用いたこと以外は、共重合体Dの合成例と同様にして、共重合体Rの30質量%溶液を得た。
表2に示す共重合体と、下記表3に示す導電材と、有機溶媒(NMP)と、必要に応じて有機塩基性化合物(B)とを、表4に示す組成となるように、均一に混合し、導電材スラリーを得た。
各温度での粘度差が大きいほど、分散機中での分散性が低下している。同様にして2-2以降の導電材スラリーを調製した。
表4に示す導電性スラリーと、正極活物質と、バインダー溶液と、NMP(追加溶媒)とを、表5に示す組成となるように、均一に混合し、正極ペーストを得た。
具体的には、導電材スラリー(2-1)と、NMP(追加溶媒)と、PVDFのNMP溶液(固形分8% KFポリマーL#7208、株式会社クレハ製、バインダー溶液)を、50mlのサンプルビンに秤取り、スパーテルで均一にかき混ぜた。その後、正極活物質としてNCM523(ニッケルマンガンコバルト酸リチウム、日本化学工業株式会社製)を添加し、再度スパーテルで均一になるまでかき混ぜた。さらに自転公転ミキサー(AR-100 株式会社シンキー製)にて、10分間撹拌し、正極ペーストを得た。なお、正極活物質、結着剤(PVDF)、導電剤(カーボンナノチューブ)及び分散剤の質量比率は98.85:0.5:0.5:0.1(固形分換算)とし、正極ペーストの固形分量(質量%)は、77質量%とした。ここで、正極ペーストの固形分量とは、正極ペーストが含有する、共重合体、正極活物質、導電剤及び結着剤からなる材料の固形分の質量%である。
Claims (16)
- 下記式(1)で表される構成単位と、下記式(2)で表される構成単位と、下記式(3)で表される構成単位と、を含む共重合体である、蓄電デバイス正極用分散剤。
- 前記式(2)において、官能基X1は、炭素材料系導電材への吸着率が12.0%以上を示す式(2)のホモポリマーのモノマー単位に含まれる官能基である、請求項1に記載の蓄電デバイス正極用分散剤。
- 前記式(2)において、官能基X1は、炭素数1以上4以下の炭化水素基を有していてもよいピリジニル基、ピロリドン基、又はシアノ基である、請求項1又は2に記載の蓄電デバイス正極用分散剤。
- 蓄電デバイス正極用分散剤の全構成単位中における、前記式(3)で表される構成単位の含有量が、3質量%以上45質量%以下である、請求項1から4のいずれかの項に記載の蓄電デバイス正極用分散剤。
- 蓄電デバイス正極用分散剤の全構成単位中における、前記式(2)で表される構成単位の含有量が、10質量%以上70質量%以下である、請求項1から5のいずれかの項に記載の蓄電デバイス正極用分散剤。
- 前記式(2)で表される構成単位に対する前記式(1)で表される構成単位との質量比が、0.30以上2.30以下である、請求項1から6のいずれかの項に記載の蓄電デバイス正極用分散剤。
- 前記式(3)で表される構成単位に対する式(2)で表される構成単位の質量比が、0.50以上7.00以下である、請求項1から7のいずれかの項に記載の蓄電デバイス正極用分散剤。
- 蓄電デバイス正極用分散剤の全構成単位中における、前記式(2)で表される構成単位と前記式(3)で表される構成単位の含有量の合計が、30質量%以上75質量%以下である、請求項1から8のいずれかの項に記載の蓄電デバイス正極用分散剤。
- 請求項1から9のいずれかの項に記載の蓄電デバイス正極用分散剤、及び溶媒を含む、分散剤組成物。
- 請求項1から9のいずれかの項に記載の蓄電デバイス正極用分散剤、炭素材料系導電材、及び溶媒を含む電池用導電材スラリー。
- 前記炭素材料系導電材が、カーボンブラック、カーボンナノチューブ及びグラフェンから選ばれる1種以上である、請求項11に記載の電池用導電材スラリー。
- 請求項1から9のいずれかの項に記載の蓄電デバイス正極用分散剤、炭素材料系導電材、及び溶媒を含む混合物中の各成分を、メディア撹拌型分散機を用いて分散させる工程を含む、電池用導電材スラリーの製造方法。
- 分散機を通過して出てくる前記混合物の温度が50℃以上である、請求項13に記載の電池用導電材スラリーの製造方法。
- 請求項1から9のいずれかの項に記載の蓄電デバイス正極用分散剤、炭素材料系導電材、正極活物質、結着剤、及び溶媒を含む、電池用正極ペースト。
- 請求項1から9のいずれかの項に記載の蓄電デバイス正極用分散剤を含む電池用正極。
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JP2014203555A (ja) * | 2013-04-02 | 2014-10-27 | 東洋インキScホールディングス株式会社 | 二次電池電極形成用組成物、その製造方法、二次電池電極、及び二次電池 |
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JP2014203555A (ja) * | 2013-04-02 | 2014-10-27 | 東洋インキScホールディングス株式会社 | 二次電池電極形成用組成物、その製造方法、二次電池電極、及び二次電池 |
JP2018170218A (ja) | 2017-03-30 | 2018-11-01 | 株式会社Gsユアサ | 電池用正極ペースト |
WO2020208880A1 (ja) | 2019-04-12 | 2020-10-15 | 花王株式会社 | カーボンナノチューブ用分散剤組成物 |
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