WO2018168657A1 - 非水系二次電池機能層用スラリー組成物、非水系二次電池用機能層および非水系二次電池 - Google Patents
非水系二次電池機能層用スラリー組成物、非水系二次電池用機能層および非水系二次電池 Download PDFInfo
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- WO2018168657A1 WO2018168657A1 PCT/JP2018/009076 JP2018009076W WO2018168657A1 WO 2018168657 A1 WO2018168657 A1 WO 2018168657A1 JP 2018009076 W JP2018009076 W JP 2018009076W WO 2018168657 A1 WO2018168657 A1 WO 2018168657A1
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- functional layer
- secondary battery
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- 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
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- H—ELECTRICITY
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Definitions
- the present invention relates to a slurry composition for a non-aqueous secondary battery functional layer, a non-aqueous secondary battery functional layer, and a non-aqueous secondary battery.
- Non-aqueous secondary batteries such as lithium ion secondary batteries (hereinafter sometimes simply referred to as “secondary batteries”) have the characteristics of being small and light, having high energy density, and capable of repeated charge and discharge. Yes, it is used for a wide range of purposes.
- the non-aqueous secondary battery generally includes a battery member such as a positive electrode, a negative electrode, and a separator that separates the positive electrode and the negative electrode and prevents a short circuit between the positive electrode and the negative electrode.
- a battery member having a functional layer that imparts desired performance (for example, heat resistance and strength) to the battery member is used.
- a separator in which a functional layer is formed on a separator base material, or an electrode in which a functional layer is formed on an electrode base material in which an electrode mixture layer is provided on a current collector It is used as a battery member.
- a functional layer that can improve the heat resistance and strength of the battery member a functional layer made of a porous film layer formed by binding non-conductive particles with a binder (binder) is used.
- this functional layer has a functional layer slurry composition containing non-conductive particles, a binder, and a dispersion medium such as water on the surface of a base material (separator base material, electrode base material, etc.). It is formed by applying and drying the applied functional layer slurry composition.
- Patent Document 1 in forming a functional layer comprising a porous membrane layer, a water-soluble polymer having an average degree of polymerization of 500 to 2500, an inorganic filler, and a water-insoluble particulate polymer are used. It is proposed to contain.
- the porous membrane layer according to Patent Document 1 is excellent in film uniformity and can contribute to improvement of battery characteristics such as cycle characteristics and rate characteristics when used in the manufacture of secondary batteries.
- Patent Document 2 a heat-resistant layer formed by applying a coating liquid comprising a filler, a resin binder containing an acetal-modified water-soluble resin having an average degree of polymerization of 100 to 1000, and water on a polypropylene resin porous film.
- a laminated porous film having that is, a functional layer
- Such a laminated porous film has less dropout of filler and is excellent in heat resistance and the like.
- the functional layers described in Patent Documents 1 and 2 have room for improvement in terms of improving the heat shrinkability and improving the high-temperature cycle characteristics of the secondary battery including the functional layer.
- the porous film slurry and the coating liquid used for forming the functional layer described in Patent Documents 1 and 2 have room for improvement in terms of enhancing the dispersibility of the porous film slurry and the coating liquid.
- this invention aims at providing the slurry composition for non-aqueous secondary battery functional layers which can form the functional layer for non-aqueous secondary batteries which is excellent in a dispersibility and is excellent in heat-resistant shrinkage.
- Another object of the present invention is to provide a functional layer for a non-aqueous secondary battery that is excellent in heat shrinkage resistance and that can exhibit excellent high-temperature cycle characteristics in a non-aqueous secondary battery.
- an object of this invention is to provide the non-aqueous secondary battery which is excellent in a high temperature cycling characteristic.
- the present inventor has intensively studied for the purpose of solving the above problems. Then, the inventor has determined the average degree of polymerization of the water-soluble polymer within a predetermined range for the slurry composition for a non-aqueous secondary battery functional layer containing the water-soluble polymer, the binder, the non-conductive particles, and water. It was found that, by making it inside, the dispersibility of the slurry composition was improved, and it was possible to form a functional layer for a non-aqueous secondary battery excellent in heat shrinkage, and the present invention was completed.
- the present invention aims to advantageously solve the above-mentioned problems, and the slurry composition for a non-aqueous secondary battery functional layer of the present invention comprises non-conductive particles, a water-soluble polymer, a binder.
- the average degree of polymerization of the water-soluble polymer is within a predetermined range, the dispersibility of the slurry composition is improved and a functional layer for a non-aqueous secondary battery having excellent heat shrinkage resistance can be formed. it can.
- the “water-soluble polymer” refers to a polymer having an insoluble content of less than 1.0 mass% when 0.5 g of the polymer is dissolved in 100 g of water at a temperature of 25 ° C.
- the “average degree of polymerization of the water-soluble polymer” refers to a value calculated according to Staudinger's viscosity law using the intrinsic viscosity measured using an Ubbelohde viscometer.
- the water-soluble polymer is preferably a cellulose derivative. If the water-soluble polymer is a cellulose derivative, the high-temperature cycle characteristics of a non-aqueous secondary battery formed using the slurry composition for a non-aqueous secondary battery functional layer can be improved.
- the water-soluble polymer is preferably carboxymethyl cellulose or a carboxymethyl cellulose salt. If the water-soluble polymer is carboxymethyl cellulose or carboxymethyl cellulose salt, the high-temperature cycle characteristics of the non-aqueous secondary battery formed using the slurry composition for a non-aqueous secondary battery functional layer can be further improved.
- the water-soluble polymer preferably has a degree of etherification of 0.6 or more. If the degree of etherification of the water-soluble polymer is 0.6 or more, the water-soluble polymer can be more satisfactorily dispersed in the slurry composition for the non-aqueous secondary battery functional layer. The dispersibility of the slurry composition for battery functional layers can be further improved.
- the “degree of etherification” of a water-soluble polymer is a cellulose derivative in which at least a part of the hydroxyl group of anhydroglucose as a constituent element is substituted with a substituent.
- the “etherification degree” of the water-soluble polymer can be measured by the method described in the examples of the present specification.
- the content of the water-soluble polymer is 0.2 parts by mass or more and 4.5 parts by mass or less per 100 parts by mass of the non-conductive particles. It is preferable that If the content of the water-soluble polymer is 0.2 parts by mass or more and 4.5 parts by mass or less per 100 parts by mass of the non-conductive particles, the adhesiveness to the other members of the functional layer is improved and the heat shrink resistance Can be further improved.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention further includes a wetting agent, and the content of the wetting agent is 0.01 parts by mass or more per 100 parts by mass of the non-conductive particles. It is preferably 0.0 part by mass or less. If the slurry composition for a non-aqueous secondary battery functional layer contains a wetting agent in a content within the above specific range, the heat shrinkability of the functional layer can be further improved, and the non-aqueous system provided with such a functional layer High temperature cycle characteristics of the secondary battery can be improved.
- the mass ratio of the content of the wetting agent to the content of the water-soluble polymer is 0.05 or more and 1.0 or less. Is preferred.
- the mass ratio of the content of the wetting agent to the content of the water-soluble polymer is 0.05 or more and 1.0 or less. Is preferred.
- the functional layer for non-aqueous secondary batteries of this invention is any of the slurry composition for non-aqueous secondary battery functional layers mentioned above. It is characterized by being formed using Thus, if the slurry composition for non-aqueous secondary battery functional layers described above is used, the heat shrinkage resistance of the non-aqueous secondary battery functional layer can be improved. Therefore, the non-aqueous secondary battery provided with the functional layer for non-aqueous secondary batteries can exhibit excellent high-temperature cycle characteristics.
- the functional layer for a non-aqueous secondary battery of the present invention preferably has a thickness of 5.0 ⁇ m or less.
- a functional layer having a thickness of 5.0 ⁇ m or less formed using the slurry composition for a non-aqueous secondary battery functional layer of the present invention described above has good heat shrinkage resistance.
- the present invention aims to solve the above-mentioned problem advantageously, and the non-aqueous secondary battery of the present invention is characterized by comprising the above-described functional layer for a non-aqueous secondary battery.
- the functional layer for non-aqueous secondary batteries mentioned above is used, the high temperature cycling characteristic excellent in the non-aqueous secondary battery can be exhibited.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention is excellent in dispersibility, and according to such a slurry composition, a functional layer for a non-aqueous secondary battery excellent in heat shrinkage can be formed. Moreover, according to the functional layer for non-aqueous secondary batteries of this invention, the high temperature cycling characteristic excellent in the non-aqueous secondary battery can be exhibited. And according to this invention, the non-aqueous secondary battery excellent in a high temperature cycling characteristic is obtained.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention is used as a material for preparing a functional layer for a non-aqueous secondary battery.
- the functional layer for non-aqueous secondary batteries of this invention is formed using the slurry composition for non-aqueous secondary battery functional layers of this invention.
- the nonaqueous secondary battery of this invention is provided with the functional layer for nonaqueous secondary batteries of this invention at least.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention contains non-conductive particles, a water-soluble polymer, and a binder, and optionally further contains additives and the like. It is a slurry composition using as a medium.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention is characterized in that the average degree of polymerization of the water-soluble polymer is from 50 to 450.
- the slurry composition for non-aqueous secondary battery functional layers of this invention contains the water-soluble polymer whose average degree of polymerization is 50 or more and 450 or less, it is excellent in a dispersibility and excellent in heat-shrinkability. A functional layer can be formed satisfactorily. Therefore, when the slurry composition for a non-aqueous secondary battery functional layer of the present invention is used, a non-aqueous secondary battery having excellent high-temperature cycle characteristics can be obtained.
- the non-conductive particles are particles that do not dissolve in the dispersion medium water and the non-aqueous electrolyte solution of the secondary battery, and the shape thereof is maintained in them. And since a nonelectroconductive particle is electrochemically stable, it exists stably in a functional layer under the use environment of a secondary battery.
- nonconductive particles for example, various inorganic fine particles and organic fine particles can be used.
- non-conductive particles both inorganic fine particles and organic fine particles other than the particulate polymer described later that can be used as a binder can be used.
- material for the non-conductive particles a material that exists stably in the environment in which the non-aqueous secondary battery is used and is electrochemically stable is preferable.
- inorganic fine particles that are non-conductive particles include aluminum oxide (alumina), aluminum oxide hydrate (boehmite (AlOOH), gibbsite (Al (OH) 3 ), silicon oxide, magnesium oxide (magnesia).
- Oxide particles such as calcium oxide, titanium oxide (titania), barium titanate (BaTiO 3 ), ZrO, alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalent bonds such as silicon and diamond Crystalline particles: sparingly soluble ionic crystal particles such as barium sulfate, calcium fluoride, barium fluoride, calcium carbonate, etc., clay fine particles such as talc, montmorillonite, etc. In addition, these particles are elemental if necessary Substitution, surface treatment, solid solution, etc. may be performed.
- the organic fine particles which are non-conductive particles are organic compounds different from the particulate polymer as a binder described later. That is, the organic fine particles have no binding property.
- Preferred examples of the organic fine particles include crosslinked polymethyl methacrylate, crosslinked polystyrene, crosslinked polydivinylbenzene, crosslinked styrene-divinylbenzene copolymer, polystyrene, polyimide, polyamide, polyamideimide, melamine resin, phenol resin, benzoguanamine-
- crosslinked polymer particles such as formaldehyde condensate, and heat-resistant polymer particles such as polysulfone, polyacrylonitrile, polyaramid, polyacetal, and thermoplastic polyimide.
- these modified products and derivatives can also be used as the organic fine particles.
- the glass transition temperature of the organic fine particle as a nonelectroconductive particle exceeds 20 degreeC, and it is 350 degrees C or less normally.
- the glass transition temperature of the organic fine particles can be measured according to JIS K7121.
- non-conductive particles alumina particles, boehmite particles, and (crosslinked) polystyrene particles are preferable, and alumina particles and (crosslinked) polystyrene particles are more preferable.
- the nonelectroconductive particle mentioned above may be used individually by 1 type, and may be used in combination of 2 or more types.
- the volume average particle diameter of the non-conductive particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, preferably 5 ⁇ m or less, more preferably 2 ⁇ m or less. If the volume average particle diameter of the non-conductive particles is 0.1 ⁇ m or more, the Gurley value of the functional layer is suppressed from increasing (that is, the ion conductivity is decreased), and the rate of the secondary battery including the functional layer is reduced. Characteristics can be improved. Moreover, if the volume average particle diameter of the non-conductive particles is 5 ⁇ m or less, the density of the functional layer can be increased and the heat shrinkage resistance of the functional layer can be increased. In the present invention, the “volume average particle diameter of non-conductive particles” means the particle diameter at which the cumulative volume calculated from the small diameter side is 50% in the particle diameter distribution (volume basis) measured by the laser diffraction method. (D50).
- the water-soluble polymer can function as a viscosity modifier that adjusts the viscosity of the slurry composition for a non-aqueous secondary battery functional layer of the present invention, and is not contained in a functional layer formed using the slurry composition for a functional layer. It can function as a component that enhances the heat shrinkability of the functional layer while binding components such as conductive particles together with the binder.
- water-soluble polymers include synthetic polymers, natural polymers, and semi-synthetic polymers. Among them, it is preferable to use a semi-synthetic polymer as the water-soluble polymer.
- a synthetic polymer is a polymer compound that is artificially made using a chemical reaction.
- Such synthetic polymers include poly (meth) acrylic acid polymer compounds, poly (meth) acrylate polymer compounds, polyvinyl polymer compounds, polyurethane polymer compounds, and polyether polymer compounds. And so on.
- Examples of the poly (meth) acrylic acid-based polymer compound include polyacrylic acid, polymethacrylic acid, and salts thereof.
- Examples of the polyvinyl polymer compound and the polyurethane polymer compound include nonionic, cationic and amphoteric compounds.
- examples of the polyether polymer compound include polyethylene glycol, polypropylene glycol, polyethylene glycol / polypropylene glycol, and the like.
- Natural polymer examples include polysaccharides and proteins derived from plants or animals. Moreover, the natural polymer by which the fermentation process by the microorganisms etc. and the process by the heat
- Examples of plant-based natural polymers include gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, cannan, quince seed (malmello), alkeocolloid (gasso extract), starch (rice, corn, potato) , Derived from wheat, etc.), glycyrrhizin and the like.
- Examples of animal-based natural polymers include collagen, casein, albumin, gelatin, chitin, and chitosan.
- examples of the microbial natural polymer include xanthan gum, dextran, succinoglucan, and bullulan.
- the semi-synthetic polymer is obtained by modifying a natural polymer using a chemical reaction.
- Such semi-synthetic polymers can be classified as cellulose derivatives, starch-based semi-synthetic polymers, alginic acid-based semi-synthetic polymers, and animal or microbial semi-synthetic polymers. Among these, it is preferable to use a cellulose derivative as the water-soluble polymer.
- Cellulose derivatives can be classified into nonionic, anionic and cationic.
- nonionic cellulose derivatives include alkylcelluloses such as methylcellulose, methylethylcellulose, ethylcellulose, and microcrystalline cellulose; hydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose stearoxy And ethers, hydroxyalkyl celluloses such as carboxymethyl hydroxyethyl cellulose, alkyl hydroxyethyl cellulose, and nonoxynyl hydroxyethyl cellulose;
- anionic cellulose derivative include substituted products obtained by substituting the above nonionic cellulose derivative with various derivative groups and salts thereof (such as sodium salt and ammonium salt).
- cationic cellulose derivative for example, low nitrogen hydroxyethyl cellulose dimethyl diallylammonium chloride (polyquaternium-4), chloride O- [2-hydroxy-3- (trimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-10), Examples include O- [2-hydroxy-3- (lauryldimethylammonio) propyl] hydroxyethylcellulose (polyquaternium-24).
- starch-based semisynthetic polymer examples include solubilized starch, carboxymethyl starch, methylhydroxypropyl starch, and modified potato starch.
- alginic acid-based semisynthetic polymer examples include sodium alginate and propylene glycol alginate.
- examples of the animal-based semi-synthetic polymer include water-soluble chitin derivatives and water-soluble chitosan derivatives
- microbial-based semi-synthetic polymers include chemicals such as xanthan gum, dehydroxanthan gum, dextran, succinoglucan, and bullulan. Examples include modified products.
- the water-soluble polymer is preferably hydroxyethyl cellulose, carboxymethyl cellulose and carboxymethyl cellulose salt, more preferably carboxymethyl cellulose or carboxymethyl cellulose salt.
- the average degree of polymerization of the water-soluble polymer needs to be 50 or more and 450 or less. Furthermore, the average degree of polymerization of the water-soluble polymer is preferably 125 or more, more preferably 150 or more, and preferably 400 or less. If the average degree of polymerization of the water-soluble polymer is not less than the above lower limit, structural strength can be imparted to the functional layer formed using the slurry composition containing the water-soluble polymer, and the heat resistance of the functional layer Shrinkage can be increased. Moreover, if the average degree of polymerization of a water-soluble polymer is below the said upper limit, the dispersibility of a slurry composition can be improved by improving the dispersibility in the slurry composition of water-soluble polymer itself.
- the cellulose derivative as the water-soluble polymer preferably has a degree of etherification of 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and 1.5 or less. Preferably, it is 1.3 or less, more preferably 1.0 or less. If the degree of etherification of the water-soluble polymer is not less than the above lower limit, the number of substituents such as carboxymethyl groups is ensured, so that the solubility in an aqueous solvent is particularly improved.
- the solubility of the water-soluble polymer in water is improved, the dispersibility of the water-soluble polymer in the slurry composition is increased, and as a result, the dispersibility of the slurry composition itself is improved.
- the improvement of the dispersibility of the slurry composition by increasing the dispersibility of the water-soluble polymer is achieved by the dispersibility (hereinafter referred to as “slurry redispersion” after the slurry composition is prepared and stored and then subjected to dispersion treatment again. (Also referred to as “sex”).
- the degree of etherification of the water-soluble polymer is not more than the above upper limit, the number of substituents such as carboxymethyl groups is not excessive, and in particular, it is possible to suppress excessive increase in solubility in aqueous solvents. it can.
- the solubility of the water-soluble polymer is excessively high, there are few water-soluble polymers that are adsorbed to the non-conductive particles in the slurry composition and act to increase the dispersibility of the non-conductive particles. Become. As a result, there is a possibility that the dispersibility of the nonconductive particles in the slurry composition cannot be sufficiently increased.
- the nonconductive particles are locally concentrated in the functional layer formed using the slurry composition containing the water-soluble polymer. Therefore, the Gurley value of the functional layer can be suppressed from being excessively increased, and the rate characteristics of the secondary battery including the functional layer can be improved.
- the content of the water-soluble polymer in the slurry composition for a non-aqueous secondary battery functional layer of the present invention is preferably 0.2 parts by mass or more per 100 parts by mass of non-conductive particles. It is more preferably 3 parts by mass or more, further preferably 0.5 parts by mass or more, more preferably 4.5 parts by mass or less, and even more preferably 4.0 parts by mass or less. More preferably, it is 5 parts by mass or less. If content of water-soluble polymer is more than the said lower limit, the adhesiveness with respect to the other member of a functional layer can be improved. Moreover, if content of water-soluble polymer is below the said upper limit, the heat-resistant shrinkage of a functional layer can be improved further.
- the binder can function as a component that binds components such as non-conductive particles in the functional layer formed using the slurry composition for a non-aqueous secondary battery functional layer of the present invention.
- the binder that can be contained in the slurry composition for a non-aqueous secondary battery functional layer of the present invention is not particularly limited, and is present in the form of particles in a known binder, for example, the slurry composition.
- a particulate polymer A particulate polymer.
- a conjugated diene polymer and an acrylic polymer are preferable, and an acrylic polymer is more preferable.
- These binders may be used alone or in combination of two or more.
- the particulate polymer may be in the form of particles or any other shape in the functional layer formed using the slurry composition for functional layers.
- the conjugated diene polymer refers to a polymer containing a conjugated diene monomer unit.
- a specific example of the conjugated diene polymer is not particularly limited, and is a copolymer containing an aromatic vinyl monomer unit such as a styrene-butadiene copolymer (SBR) and an aliphatic conjugated diene monomer unit. Examples thereof include a polymer, butadiene rubber (BR), acrylic rubber (NBR) (a copolymer containing acrylonitrile units and butadiene units), and hydrides thereof.
- “comprising a monomer unit” means “a polymer-derived structural unit is contained in a polymer obtained using the monomer”.
- an acrylic polymer the polymer containing a (meth) acrylic acid ester monomer unit is mentioned, without being specifically limited. Furthermore, it is preferable that an acrylic polymer contains more than 50 mass% of (meth) acrylic acid ester monomer units by making all the monomer units contained in a polymer into 100 mass%.
- (meth) acrylate monomer that can form a (meth) acrylate monomer unit contained in an acrylic polymer suitable as a binder
- methyl acrylate, ethyl acrylate, (Meth) acrylic acid alkyl esters such as butyl acrylate, methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl acrylate can be used.
- (meth) acryl means acryl and / or methacryl. These binders may be used alone or in combination of two or more.
- the acrylic polymer that can be preferably used as the binder preferably contains a (meth) acrylonitrile monomer unit.
- (meth) acrylonitrile means acrylonitrile and / or methacrylonitrile.
- the acrylic polymer may optionally be an acid group-containing monomer unit such as a methacrylic acid monomer unit, and a crosslinkable monomer such as an allyl glycidyl ether monomer unit or an N-methylolacrylamide monomer unit. May contain body units.
- the above-mentioned acrylic polymer is not particularly limited, and is produced, for example, by polymerizing a monomer composition containing various monomers capable of forming the above-described monomer unit in an aqueous solvent. Yes. At this time, the ratio of each monomer in the monomer composition is usually the same as the ratio of the monomer units in the acrylic polymer.
- the polymerization method 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.
- any reaction such as ionic polymerization, radical polymerization, and living radical polymerization may be used.
- the glass transition temperature of the binder is preferably 20 ° C. or less, more preferably 5 ° C. or less, and further preferably ⁇ 10 ° C. or less. If the glass transition temperature of the binder is 20 ° C. or less, it exhibits sufficiently high adhesiveness, sufficiently suppresses the components contained in the porous film from falling off the porous film, and peel strength of the porous film. Can be increased sufficiently.
- the glass transition temperature of the polymer used as the binder is usually ⁇ 60 ° C. or higher, preferably ⁇ 50 ° C. or higher.
- the glass transition temperature of the polymer can be measured according to JIS K7121.
- the volume average particle diameter (D50) of the binder is preferably 0.05 ⁇ m or more, more preferably 0.10 ⁇ m or more, preferably 0.50 ⁇ m or less, and 0.35 ⁇ m or less. It is more preferable.
- content of the binder in the slurry composition for non-aqueous secondary battery functional layers of this invention is 2 to 10 mass parts per 100 mass parts of nonelectroconductive particle.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention contains water as a dispersion medium.
- the slurry composition for a non-aqueous secondary battery functional layer may contain a small amount of a medium other than water such as an organic solvent as a dispersion medium.
- a medium other than water such as an organic solvent as a dispersion medium.
- the nonconductive particles and the binder are dispersed in water.
- the water-soluble polymer is dissolved in water.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention preferably contains a wetting agent.
- the wetting agent is not particularly limited, and a surfactant such as a nonionic surfactant or an anionic surfactant can be used.
- Nonionic surfactants are preferred from the viewpoint of uniform coating ease.
- Nonionic surfactants are not particularly limited, and specific examples thereof include polyoxyalkylene alkylaryl ether surfactants, polyoxyalkylene alkyl ether surfactants, polyoxyalkylene fatty acid ester surfactants, sorbitan fatty acid ester interfaces.
- Activators, silicone surfactants, acetylene alcohol surfactants, fluorine-containing surfactants and the like can be mentioned.
- Specific examples of the polyoxyalkylene alkyl aryl ether surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene dodecyl phenyl ether.
- Specific examples of the polyoxyalkylene alkyl ether surfactant include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
- Specific examples of the polyoxyalkylene fatty acid ester surfactant include polyoxyethylene oleate, polyoxyethylene laurate, and polyoxyethylene distearate.
- sorbitan fatty acid ester surfactant examples include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate and the like.
- silicone surfactants include dimethylpolysiloxane.
- acetylene alcohol surfactant examples include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, , 5-dimethyl-1-hexyne-3ol, and the like.
- fluorine-containing surfactant examples include a fluorine alkyl ester.
- a polyoxyalkylene alkyl ether surfactant such as polyoxyethylene lauryl ether is particularly preferable.
- the content of the wetting agent in the slurry composition for a non-aqueous secondary battery functional layer of the present invention is preferably 0.01 parts by mass or more and more preferably 0.05 parts by mass or more per 100 parts by mass of the non-conductive particles.
- 0.1 part by mass or more is more preferable, 2.0 part by mass or less is preferable, 1.5 part by mass or less is more preferable, and 1.0 part by mass or less is still more preferable.
- the content of the wetting agent is not less than the above lower limit value, the wettability between the slurry composition and the base material is improved, the slurry composition can be uniformly applied, and the heat shrinkability of the resulting functional layer is improved. Can be improved.
- the content of the wetting agent is set to the upper limit value or less, the high-temperature cycle characteristics of a secondary battery including a functional layer formed using the slurry composition can be improved.
- mass ratio of wetting agent content to water-soluble polymer content Furthermore, the mass ratio of the content of the wetting agent to the content of the water-soluble polymer in the slurry composition for a non-aqueous secondary battery functional layer of the present invention (hereinafter also referred to as “wetting agent / water-soluble polymer (mass basis)”). Is preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.1 or more, preferably 1.0 or less, and 0.9 or less. More preferably, it is more preferably 0.8 or less.
- the wetting agent / water-soluble polymer (mass basis) is at least the above lower limit value, the heat shrinkage resistance of the functional layer can be improved. Moreover, if a wetting agent / water-soluble polymer (mass reference
- the slurry composition for a non-aqueous secondary battery functional layer may contain any other component in addition to the components described above.
- the other components are not particularly limited as long as they do not affect the battery reaction, and known components can be used. Moreover, these other components may be used individually by 1 type, and may be used in combination of 2 or more types. Examples of the other components include a dispersant, a leveling agent, an antioxidant, an antifoaming agent, a wetting agent, a pH adjuster (for example, hydrogen chloride; ammonia; lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.
- the dispersant is not particularly limited, and for example, a water-soluble polymer containing at least two or more acidic group-containing monomer units as disclosed in JP-A-2015-185482 is used. Can do. More specifically, a water-soluble polymer containing a sulfonic acid group-containing monomer unit and a carboxylic acid group-containing monomer unit can be used. According to such a water-soluble polymer, non-conductive particles can be well dispersed.
- the ratio of the sulfonic acid group-containing monomer unit / the carboxylic acid group-containing monomer unit in the water-soluble polymer is “the sulfonic acid group-containing monomer unit / the carboxylic acid group-containing monomer unit (mass basis). ) ", It is 1/999 or more, more preferably 0.01 or more, preferably 1 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.
- the definition of “water-soluble” in the water-soluble polymer is as described above for “water-soluble polymer”.
- the average degree of polymerization of the water-soluble polymer is preferably less than 50 or more than 450.
- the “average degree of polymerization of the water-soluble polymer” can be calculated in the same manner as the average degree of polymerization of the water-soluble polymer.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention is not particularly limited, and includes the above-described non-conductive particles, a water-soluble polymer having an average degree of polymerization of 50 to 450, and a binder. And any additive used as necessary can be obtained by mixing in the presence of water as a dispersion medium.
- the binder composition is prepared by polymerizing the monomer composition in an aqueous solvent, the binder can be mixed with other components as it is in the state of an aqueous dispersion.
- the mixing method and mixing order of the components described above are not particularly limited, but it is preferable to perform mixing using a disperser as a mixing device in order to disperse each component efficiently.
- a disperser is an apparatus which can disperse
- the disperser include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer.
- the functional layer for a non-aqueous secondary battery of the present invention is formed from the above-described slurry composition for a non-aqueous secondary battery functional layer.
- the functional layer slurry composition described above is used as a suitable base material. After forming the coating film by coating on the surface, it can be formed by drying the formed coating film. That is, the functional layer for a non-aqueous secondary battery of the present invention is composed of a dried product of the slurry composition for a non-aqueous secondary battery functional layer described above, and is usually a non-conductive particle, a water-soluble polymer, and a binder. Contains materials and optional additives.
- the binder containing the crosslinkable monomer unit is used when the slurry composition for a non-aqueous secondary battery functional layer is dried.
- it may be cross-linked during a heat treatment that is optionally performed after drying (that is, the functional layer for a non-aqueous secondary battery may include the above-described cross-linked binder).
- the functional layer for non-aqueous secondary batteries of this invention is formed using the slurry composition for non-aqueous secondary battery functional layers mentioned above, it is rich in heat-resistant shrinkage. For this reason, if the functional layer for non-aqueous secondary batteries formed using the slurry composition for non-aqueous secondary battery functional layers described above is used, the high-temperature cycle characteristics of the non-aqueous secondary battery can be improved.
- ⁇ Base material> there is no limitation on the base material on which the functional layer slurry composition is applied.
- a functional layer slurry composition coating is formed on the surface of the release base, and the coating is dried to form the functional layer. It may be formed and the release substrate is peeled off from the functional layer.
- the functional layer peeled off from the release substrate can be used as a self-supporting film for forming a battery member of a secondary battery.
- the functional layer peeled off from the release substrate may be laminated on the separator substrate to form a separator having the functional layer, or the functional layer peeled off from the release substrate may be used as the electrode substrate.
- An electrode provided with a functional layer may be formed by stacking on the substrate.
- a separator substrate or an electrode substrate as the substrate.
- the functional layer provided on the separator substrate and the electrode substrate can be suitably used as a protective layer for improving the heat resistance and strength of the separator and the electrode.
- Separator substrate Although it does not specifically limit as a separator base material, Known separator base materials, such as an organic separator base material, are mentioned.
- the organic separator substrate is a porous member made of an organic material. Examples of the organic separator substrate include a microporous membrane or a nonwoven fabric containing a polyolefin resin such as polyethylene and polypropylene, an aromatic polyamide resin, and the like. From the viewpoint of excellent strength, a polyethylene microporous film or nonwoven fabric is preferred.
- the thickness of a separator base material can be made into arbitrary thickness, Preferably they are 5 micrometers or more and 30 micrometers or less, More preferably, they are 5 micrometers or more and 20 micrometers or less, More preferably, they are 5 micrometers or more and 18 micrometers or less. If the thickness of the separator substrate is 5 ⁇ m or more, sufficient safety can be obtained. In addition, if the thickness of the separator base material is 30 ⁇ m or less, it is possible to suppress the ion conductivity from being lowered, to suppress the rate characteristics of the secondary battery from being lowered, and to heat shrink the separator base material. Heat resistance can be increased by suppressing the increase in force.
- Electrode substrate Although it does not specifically limit as an electrode base material (a positive electrode base material and a negative electrode base material), The electrode base material with which the electrode compound-material layer was formed on the electrical power collector is mentioned.
- the current collector, the electrode active material in the electrode mixture layer (positive electrode active material, negative electrode active material) and the binder for electrode mixture layer (binder for positive electrode mixture layer, binder for negative electrode mixture layer) for the method of forming the electrode mixture layer on the current collector and the current collector, known ones can be used. For example, as described in JP2013-145663A and International Publication No. 2015/129408 Things can be used.
- ⁇ Method for forming functional layer for non-aqueous secondary battery examples include the following methods. 1) The slurry composition for a non-aqueous secondary battery functional layer of the present invention is applied to the surface of a separator substrate or an electrode substrate (in the case of an electrode substrate, the surface on the electrode mixture layer side, the same applies hereinafter), and then dried.
- the method 1) includes a step of applying the functional layer slurry composition on the substrate (application step), and drying the functional layer slurry composition applied on the substrate to obtain a functional layer. Including a step of forming (functional layer forming step).
- the method for coating the functional layer slurry composition on the substrate is not particularly limited, and examples thereof include a doctor blade method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush method. Examples thereof include a coating method.
- a functional layer formation process it does not specifically limit as a method of drying the slurry composition for functional layers on a base material.
- a well-known method can be used. Examples of the drying method include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with infrared rays, electron beams, or the like.
- the drying conditions are not particularly limited, but the drying temperature is preferably 50 to 150 ° C., and the drying time is preferably 5 to 30 minutes.
- the thickness of the functional layer formed using the slurry composition for a non-aqueous secondary battery functional layer of the present invention is preferably 0.3 ⁇ m or more, more preferably 1.5 ⁇ m or more. It is preferably 0 ⁇ m or less. If the thickness of the functional layer is not less than the above lower limit value, the heat resistance and strength of the battery member provided with the functional layer can be further improved. Moreover, if the thickness of a functional layer is below the said lower limit, the rate characteristic excellent in the secondary battery can be exhibited. In addition, by using the functional layer slurry composition of the present invention, it is possible to ensure good heat shrinkage even when the thickness of the functional layer is reduced. Therefore, for example, the thickness of the functional layer can be set to 3.0 ⁇ m or less as necessary.
- the battery member (separator and electrode) provided with the functional layer of the present invention is not limited to the separator base or electrode base and the functional layer of the present invention as long as the effects of the present invention are not significantly impaired. You may provide components other than a functional layer.
- constituent elements other than the functional layer of the present invention are not particularly limited as long as they do not correspond to the functional layer of the present invention, and are provided on the functional layer of the present invention for bonding between battery members. Examples thereof include an adhesive layer used.
- the non-aqueous secondary battery of the present invention includes the above-described functional layer for a non-aqueous secondary battery of the present invention. More specifically, the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte solution, and the functional layer for the non-aqueous secondary battery described above is a battery member of the positive electrode, the negative electrode, and the separator. Included in at least one. And the non-aqueous secondary battery of this invention can exhibit the outstanding high temperature cycling characteristic.
- At least one of the positive electrode, the negative electrode, and the separator used for the secondary battery of the present invention includes the functional layer of the present invention.
- a positive electrode and a negative electrode having a functional layer an electrode in which the functional layer of the present invention is provided on an electrode substrate formed by forming an electrode mixture layer on a current collector can be used.
- a separator which has a functional layer the separator which provides the functional layer of this invention on a separator base material can be used.
- an electrode base material and a separator base material the thing similar to what was mentioned by the term of the "functional layer for non-aqueous secondary batteries" can be used.
- a positive electrode a negative electrode, and a separator which do not have a functional layer
- the electrode which consists of an electrode base material mentioned above, and the separator which consists of a separator base material mentioned above can be used.
- an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used.
- a lithium salt is used in a lithium ion secondary battery.
- 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 are preferable because they are easily dissolved in a solvent and exhibit a high degree of dissociation.
- electrolyte may be used individually by 1 type and may be used in combination of 2 or more types.
- the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
- the organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
- dimethyl carbonate (DMC) dimethyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- Carbonates such as propylene carbonate (PC), butylene carbonate (BC) and ethyl methyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfolane, Sulfur-containing compounds such as dimethyl sulfoxide; are preferably used.
- carbonates are preferable because they have a high dielectric constant and a wide stable potential region.
- the lower the viscosity of the solvent used the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted depending on the type of solvent.
- the concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate.
- a positive electrode and a negative electrode are overlapped via a separator, and this is placed in a battery container by winding or folding as necessary. It can be manufactured by pouring and sealing.
- the positive electrode, the negative electrode, and the separator at least one member is a member with a functional layer.
- an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like may be placed in the battery container to prevent an increase in pressure inside the battery or overcharge / discharge.
- the shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
- the degree of etherification and the average degree of polymerization of the water-soluble polymer, the redispersibility of the slurry composition, the peel strength and heat shrinkage resistance of the functional layer, and the high-temperature cycle characteristics of the secondary battery are as follows: Measured and evaluated.
- the degree of etherification (substitution degree) of the water-soluble polymer is a value determined by the following method. First, 0.5 to 0.7 g of a sample (carboxymethylcellulose salt of Examples 1 to 3, 5 to 10, and Comparative Examples 1 to 2: cellulose derivative having a carboxymethyl group as a substituent of anhydroglucose) was accurately weighed. It was ashed in a porcelain crucible. After cooling, 500 ml of the obtained ashed product was transferred to a beaker, and about 250 ml of water and 35 ml of N / 10 sulfuric acid were added with a pipette and boiled for 30 minutes.
- A (a ⁇ f ⁇ b ⁇ f 1 ) / sample (g) ⁇ alkalinity (or + acidity)
- Degree of substitution M ⁇ A / (10000-80A)
- M Weight average molecular weight of sample The alkalinity (or acidity) was determined by the following method and formula.
- Alkalinity (acidity) (B ⁇ S) ⁇ f 1 / sample (g) f 1 : titer coefficient of N / 10 potassium hydroxide ⁇ average degree of polymerization of water-soluble polymer>
- the average degree of polymerization of the water-soluble polymer can be measured using a viscosity method.
- the intrinsic viscosity [ ⁇ ] is obtained using an Ubbelohde viscometer with 0.1N NaCl as a solvent, and the Staudinger viscosity law is used.
- the average polymerization degree P can be calculated according to the following formula (1).
- [ ⁇ ] K m ⁇ P ⁇ ⁇ (1)
- the K m and alpha is a constant determined by the type of polymer, the polymerization conditions (polymerization solvent and temperature), in this example, Km is 12.3, alpha was used 0.91.
- ⁇ Redispersibility of slurry composition> The slurry compositions for functional layers prepared in Examples and Comparative Examples were transferred to a storage container (100 L drum can), sealed and stored at 20 ° C. for 3 months. Under the present circumstances, the quantity of the slurry composition for functional layers in a storage container was adjusted, and the storage container was sealed so that the space volume formed in a storage container might be 30 volume% of the capacity
- Amount of mesh residue (mass ppm) (ab) / (W 0 ⁇ c / 100) ⁇ 1000000 (2) a: Mass of wire mesh with collected matter after drying [g] b: Mass of wire mesh [g] c: Solid content concentration [mass%] of the slurry composition for functional layers W 0 : Mass of the slurry composition for functional layer [g]
- the calculated mesh residue amount was evaluated according to the following criteria. It shows that the smaller the amount of mesh residue, the better the slurry composition for functional layer after redispersion treatment.
- the separator with functional layer produced in Examples 1 to 9 and Comparative Examples 1 and 2 and the positive electrode with functional layer produced in Example 10 were cut into rectangles each having a length of 100 mm and a width of 10 mm to obtain test pieces.
- the cellophane tape was fixed to the test stand beforehand. As the cellophane tape, one specified in “JIS Z1522” was used. The test piece was attached to a cellophane tape with the functional layer side down.
- test piece was affixed on the cellophane tape on the functional layer surface. Then, the stress when one end of the test piece was pulled in the vertical direction at a pulling speed of 10 mm / min and peeled was measured. The measurement was performed 3 times, the average value was calculated
- the separator with a functional layer produced in Examples 1 to 9 and Comparative Examples 1 and 2 and the positive electrode with a functional layer produced in Example 10 were cut into squares each having a width of 12 cm and a length of 12 cm, and the squares were cut into the squares. A square having a side of 10 cm was drawn as a test piece. Then, after placing the test piece in a thermostat at 150 ° C.
- the 800 mAh wound laminate cell prepared in Examples and Comparative Examples was charged to 4.35 V by a constant current method of 0.5 C in an atmosphere at 45 ° C., and the discharge capacity was measured by repeating 200 cycles of charging and discharging to 3 V. .
- the ratio of the electric capacity at the end of 200 cycles to the discharge capacity at the end of 3 cycles is calculated as a percentage to obtain the charge / discharge capacity retention rate, which is used as an evaluation criterion for cycle characteristics .
- Example 1 Preparation of binder> To a reactor equipped with a stirrer, 70 parts of ion-exchanged water, 0.15 part of sodium lauryl sulfate (manufactured by Kao Chemical Co., “Emar 2F”) as an emulsifier, and 0.5 part of ammonium persulfate as a polymerization initiator are supplied. The gas phase was replaced with nitrogen gas, and the temperature was raised to 60 ° C.
- Emar 2F sodium lauryl sulfate
- This monomer composition was continuously added to the reactor over 4 hours to carry out polymerization. During the addition, the reaction was carried out at 60 ° C. After completion of the addition, the mixture was further stirred at 70 ° C. for 3 hours, and then the reaction was terminated to prepare an aqueous dispersion of a binder (acrylic polymer).
- the obtained acrylic polymer was a particulate polymer present in the form of particles in the slurry composition. Further, the obtained acrylic polymer had a glass transition temperature (JIS K7121) of ⁇ 48 ° C. The particle diameter was 0.3 ⁇ m.
- 150 parts of ion-exchanged water was charged into a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 80 ° C.
- the monomer composition and 10 parts of a 30% aqueous sodium persulfate solution as a polymerization initiator were continuously added dropwise to the flask with a metering pump over 3 hours, and the polymerization reaction was performed at 80 ° C. Went.
- the system was further aged for 1 hour while maintaining the system at 80 ° C. to complete the polymerization reaction.
- 120 parts of a 32% aqueous sodium hydroxide solution was added to the flask to completely neutralize the reaction solution, and a water-soluble polymer (acrylic acid / sulfonic acid copolymer, average degree of polymerization: 12) was dispersed.
- An aqueous solution of the agent was obtained.
- the average degree of polymerization of the water-soluble polymer was measured in the same manner as for the water-soluble polymer.
- ⁇ Preparation of slurry composition for secondary battery functional layer Mixing 100 parts of alumina particles (volume average particle diameter: 0.8 ⁇ m) as non-conductive particles and 0.5 part of an aqueous solution of a water-soluble polymer as a dispersant prepared as described above in terms of solid content. Further, ion-exchanged water was added and mixed so that the solid content concentration became 55% to obtain a mixed solution.
- this mixed liquid was dispersed in one pass using a rotor / stator type medialess dispersion apparatus under the conditions of a peripheral speed of 10 m / sec and a flow rate of 200 L / h to obtain an aqueous dispersion.
- This aqueous dispersion was mixed with 37.5 parts of a 4% aqueous solution of carboxymethyl cellulose salt (degree of polymerization 310, degree of etherification 0.9) as a water-soluble polymer (1.5 parts by amount of carboxymethyl cellulose), Next, 13.3 parts (6 parts by weight of the binder) of the aqueous dispersion of the binder prepared as described above, and polyoxyalkylene alkyl ether surfactant polyoxyalkylene as a wetting agent An aqueous solution of ethylene lauryl ether (“Emulgen (registered trademark) 106”, manufactured by Kao Corporation) was mixed in an amount of 0.2 parts in terms of solid content to obtain a prepared solution.
- Emulgen registered trademark
- the magnetic substance is further removed by passing 10 passes through a magnet filter (manufactured by Tok Engineering Co., Ltd.) at room temperature and a magnetic flux density of 8000 gauss.
- a slurry composition for a functional layer was obtained.
- a separator substrate made of polyethylene polyethylene comprising 40% by mass of ultrahigh molecular weight polyethylene having a weight average molecular weight (Mw) of 2.4 ⁇ 10 6 and 60% by mass of high density polyethylene having Mw of 2.6 ⁇ 10 5
- a polyethylene organic separator substrate (sequential biaxial stretching method, thickness 7 ⁇ m) comprising a (PE) composition was prepared.
- the slurry composition subjected to the same redispersion treatment as in the evaluation of the redispersibility of the slurry composition was applied with a gravure coater so that the thickness after drying was 2 ⁇ m, Dry at 50 ° C. for 3 minutes.
- the separator formed by forming a functional layer on one side of the separator base material was obtained. Then, using the obtained separator, the peel strength and heat shrinkage resistance of the functional layer were evaluated according to the method described above. The results are shown in Table 1.
- the obtained positive electrode slurry composition was applied onto a 18 ⁇ m-thick aluminum foil as a current collector with a comma coater and dried at 120 ° C. for 3 hours to obtain a positive electrode original fabric.
- the positive electrode original fabric was rolled with a roll press to obtain a positive electrode having a thickness of 100 ⁇ m.
- the mixture was further stirred at 25 ° C. for 15 minutes to obtain a mixed solution.
- 1.0 part of an aqueous dispersion containing the binder for the negative electrode mixture layer is added in terms of solid content, and ion-exchanged water is added to adjust the final solid content concentration to 50%. Stir for minutes. This was defoamed under reduced pressure to obtain a negative electrode slurry composition having good fluidity.
- the obtained negative electrode slurry composition was applied on a copper foil having a thickness of 20 ⁇ m, which was a current collector, with a comma coater so that the film thickness after drying was about 150 ⁇ m, and dried. This drying was performed by conveying the copper foil in an oven at 60 ° C.
- the negative electrode after pressing is cut out into 50 cm ⁇ 5.2 cm, and the cut-out negative electrode is disposed on the side opposite to the positive electrode of the separator, and the surface on the negative electrode active material layer (negative electrode mixture layer) side faces the separator.
- the separator cut out into the dimension of 55 cm x 5.5 cm was arrange
- Example 3 When preparing the slurry composition, the carboxymethylcellulose sodium salt to be blended was carboxymethylcellulose sodium salt having a degree of polymerization of 130 and a degree of etherification of 0.7 (Example 2), and a degree of polymerization of 430 and a degree of etherification of 0.8, respectively.
- a slurry composition and a secondary battery were produced in the same manner as in Example 1 except that the carboxymethyl cellulose sodium salt (Example 3) was changed.
- Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 4 A slurry composition and a secondary battery were produced in the same manner as in Example 1 except that hydroxyethyl cellulose (polymerization degree 220) was blended instead of carboxymethyl cellulose sodium salt during preparation of the slurry composition. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. For hydroxyethyl cellulose, the degree of etherification could not be measured by the method described above.
- Example 5 The slurry composition and the secondary battery were prepared in the same manner as in Example 1 except that 0.2 parts of carboxymethylcellulose salt having a degree of polymerization of 310 and a degree of etherification of 0.7 was blended as carboxymethylcellulose during the preparation of the slurry composition. Manufactured. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 6 At the time of preparing the slurry composition, the blending amount of the carboxymethyl cellulose salt which is a water-soluble polymer and / or the blending amount of the wetting agent was changed as shown in Table 1, respectively.
- a slurry composition and a secondary battery were produced in the same manner as in Example 1 except that the “standard” was changed as shown in Table 1.
- Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 9 Except for blending crosslinkable polystyrene particles (volume average particle diameter: 0.5 ⁇ m; glass transition temperature: 100 ° C.) in place of alumina particles as non-conductive particles when preparing the slurry composition, the same as in Example 1. Thus, a slurry composition and a secondary battery were produced. Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1. Crosslinkable polystyrene particles were prepared by the following method.
- 0.5 parts of sodium persulfate, 5 parts of styrene, 4.5 parts of methacrylic acid, 0.5 part of 2-hydroxyethyl methacrylate, 1 part of polyvinyl alcohol and 20 parts of ion-exchanged water can be mixed as a polymerization initiator.
- the emulsion was continuously added to the reaction vessel at 80 ° C. for 3 hours to complete the polymerization and produce crosslinkable polystyrene particles.
- Example 10 A slurry composition was prepared in the same manner as in Example 1, and in forming the functional layer, a positive electrode mixture layer formed by applying the positive electrode slurry composition using the positive electrode prepared in the same manner as in Example 1 as a base material The slurry composition was applied onto the surface on the side and dried under the same conditions as in Example 1 to obtain a positive electrode having a functional layer. For the positive electrode having the obtained functional layer, peel strength and heat shrinkage resistance were evaluated in the same manner as in Example 1.
- Example 1 a lithium ion secondary battery was produced in the same manner as in Example 1, Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- the carboxymethylcellulose sodium salt to be blended was carboxymethylcellulose sodium salt having a polymerization degree of 21 and an etherification degree of 0.8 (Comparative Example 1), and a polymerization degree of 600 and an etherification degree of 0.7, respectively.
- a slurry composition and a secondary battery were produced in the same manner as in Example 1 except that the carboxymethyl cellulose sodium salt (Comparative Example 2) was changed.
- Various evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.
- PST is a cross-linkable polystyrene particle
- CMC means carboxymethylcellulose sodium salt
- HEC hydroxyethyl cellulose
- POE polyoxyethylene lauryl ether
- ACR is an acrylic polymer
- SP indicates a separator.
- the dispersibility of the slurry composition for functional layer is good.
- the obtained functional layer has high heat shrinkage resistance and can further improve the high-temperature cycle characteristics of the secondary battery.
- Comparative Example 2 using the slurry composition it can be seen that the dispersibility of the slurry composition for the functional layer is low, the heat shrinkage resistance of the functional layer obtained is low, and further, the high-temperature cycle characteristics of the secondary battery are deteriorated.
- the slurry composition for a non-aqueous secondary battery functional layer of the present invention is excellent in dispersibility, and according to such a slurry composition, a functional layer for a non-aqueous secondary battery excellent in heat shrinkage can be formed. Moreover, according to the functional layer for non-aqueous secondary batteries of this invention, the high temperature cycling characteristic excellent in the non-aqueous secondary battery can be exhibited. And according to this invention, the non-aqueous secondary battery excellent in a high temperature cycling characteristic is obtained.
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Abstract
Description
具体的には、特許文献1では、多孔膜層よりなる機能層の形成にあたり、平均重合度が500~2500である水溶性高分子と、無機フィラーと、非水溶性の粒子状高分子とを含有させることが提案されている。特許文献1に従う多孔膜層は、膜均一性に優れ、二次電池の製造に用いられた場合に、サイクル特性やレート特性等の電池特性の改善に寄与し得る。
また、本発明は、耐熱収縮性に優れ、非水系二次電池に優れた高温サイクル特性を発揮させることができる非水系二次電池用機能層を提供することを目的とする。
そして、本発明は、高温サイクル特性に優れる非水系二次電池を提供することを目的とする。
なお、本発明において、「水溶性高分子」とは、温度25℃において高分子0.5gを100gの水に溶解した際に、不溶分が1.0質量%未満となる高分子を指す。
また、本発明において、「水溶性高分子の平均重合度」は、ウベローデ粘度計を用いて測定した極限粘度を用いて、Staudingerの粘度則に従って算出した値を指す。
ここで、本発明において、水溶性高分子の「エーテル化度」は、水溶性高分子が、構成要素である無水グルコースの有する水酸基の少なくとも一部が置換基により置換されてなるセルロース誘導体である場合に、無水グルコース1単位当たり、カルボキシルメチル基などの置換基により置換された水酸基の数の平均値をいい、0超3未満の値を取り得る。エーテル化度が大きくなればなるほどセルロース誘導体である水溶性高分子1分子中の水酸基の割合が減少し(即ち、置換基の割合が増加し)、エーテル化度が小さいほどセルロース誘導体である水溶性高分子1分子中の水酸基の割合が増加する(即ち、置換基の割合が減少する)ということを示している。
なお、本発明において、水溶性高分子の「エーテル化度」は、本明細書の実施例に記載の方法で測定することができる。
また、本発明の非水系二次電池用機能層によれば、非水系二次電池に優れた高温サイクル特性を発揮させることができる。
そして、本発明によれば、高温サイクル特性に優れる非水系二次電池が得られる。
ここで、本発明の非水系二次電池機能層用スラリー組成物は、非水系二次電池用機能層を調製する際の材料として用いられる。そして、本発明の非水系二次電池用機能層は、本発明の非水系二次電池機能層用スラリー組成物を用いて形成される。また、本発明の非水系二次電池は、少なくとも本発明の非水系二次電池用機能層を備えるものである。
本発明の非水系二次電池機能層用スラリー組成物は、非導電性粒子と、水溶性高分子と、結着材とを含有し、任意に、添加剤などを更に含有する、水を分散媒としたスラリー組成物である。また、本発明の非水系二次電池機能層用スラリー組成物は、水溶性高分子の平均重合度が、50以上450以下であることを特徴とする。
ここで、非導電性粒子は、分散媒である水および二次電池の非水系電解液に溶解せず、それらの中においても、その形状が維持される粒子である。そして、非導電性粒子は、電気化学的にも安定であるため、二次電池の使用環境下で機能層中に安定に存在する。
具体的には、非導電性粒子としては、無機微粒子と、結着材として使用され得る後述の粒子状重合体以外の有機微粒子との双方を用いることができる。非導電性粒子の材料としては、非水系二次電池の使用環境下で安定に存在し、電気化学的に安定である材料が好ましい。
なお、非導電性粒子としての有機微粒子のガラス転移温度は20℃超であることが好ましく、通常、350℃以下である。有機微粒子のガラス転移温度は、JIS K7121に従って測定することができる。
なお、上述した非導電性粒子は、1種類を単独で使用してもよいし、2種類以上を組み合わせて用いてもよい。
なお、本発明において、「非導電性粒子の体積平均粒子径」とは、レーザー回折法にて測定した粒子径分布(体積基準)において、小径側から計算した累積体積が50%となる粒子径(D50)を指す。
水溶性高分子は、本発明の非水系二次電池機能層用スラリー組成物の粘度を調整する粘度調整剤として機能し得ると共に、機能層用スラリー組成物を用いて形成した機能層中において非導電性粒子等の成分を結着材と共に結着しつつ機能層の耐熱収縮性を高める成分として機能し得る。そして、水溶性高分子としては、合成高分子、天然高分子および半合成高分子が挙げられる。中でも、水溶性高分子としては、半合成高分子を用いることが好ましい。
合成高分子とは、化学反応を用いて人工的に作られた高分子化合物である。このような合成高分子としては、ポリ(メタ)アクリル酸系高分子化合物、ポリ(メタ)アクリル酸エステル系高分子化合物、ポリビニル系高分子化合物、ポリウレタン系高分子化合物、ポリエーテル系高分子化合物等として分類することができる。
ここで、天然高分子としては、例えば、植物もしくは動物由来の多糖類およびたんぱく質等が挙げられる。また、場合により微生物等による発酵処理や、熱による処理がされた天然高分子を例示できる。これらの天然高分子は、植物系天然高分子、動物系天然高分子および微生物系天然高分子等として分類することができる。
また、動物系天然高分子としては、例えば、コラーゲン、カゼイン、アルブミン、ゼラチン、キチン、キトサン等が挙げられる。
更に、微生物系天然高分子としては、例えば、キサンタンガム、デキストラン、サクシノグルカン、ブルラン等が挙げられる。
また、半合成高分子とは、天然高分子を、化学反応を用いて変性させたものである。このような半合成高分子は、セルロース誘導体、澱粉系半合成高分子、アルギン酸系半合成高分子、並びに、動物または微生物系半合成高分子等として分類することができる。中でも、水溶性高分子として、セルロース誘導体を用いることが好ましい。
そして、ノニオン性セルロース誘導体としては、例えば、メチルセルロース、メチルエチルセルロース、エチルセルロース、マイクロクリスタリンセルロース等のアルキルセルロース;ヒドロキシエチルセルロース、ヒドロキシブチルメチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロースステアロキシエーテル、カルボキシメチルヒドロキシエチルセルロース、アルキルヒドロキシエチルセルロース、ノノキシニルヒドロキシエチルセルロース等のヒドロキシアルキルセルロース;等が挙げられる。
また、アニオン性セルロース誘導体としては、上記のノニオン性セルロース誘導体を各種誘導基により置換した置換体並びにその塩(ナトリウム塩およびアンモニウム塩など)が挙げられる。具体例を挙げると、セルロース硫酸ナトリウム、カルボキシメチルセルロース(CMC)およびその塩が挙げられる。
更に、カチオン性セルロース誘導体としては、例えば、低窒素ヒドロキシエチルセルロースジメチルジアリルアンモニウムクロリド(ポリクオタニウム-4)、塩化O-[2-ヒドロキシ-3-(トリメチルアンモニオ)プロピル]ヒドロキシエチルセルロース(ポリクオタニウム-10)、塩化O-[2-ヒドロキシ-3-(ラウリルジメチルアンモニオ)プロピル]ヒドロキシエチルセルロース(ポリクオタニウム-24)等が挙げられる。
水溶性高分子の平均重合度は、50以上450以下である必要がある。さらに、水溶性高分子の平均重合度は、125以上であることが好ましく、150以上であることがより好ましく、400以下であることが好ましい。
水溶性高分子の平均重合度が上記下限値以上であれば、かかる水溶性高分子を含むスラリー組成物を用いて形成した機能層に構造的な強度を付与することができ、機能層の耐熱収縮性を高めることができる。また、水溶性高分子の平均重合度が上記上限値以下であれば、水溶性高分子自体のスラリー組成物中における分散性を高めることにより、スラリー組成物の分散性を向上させることができる。
水溶性高分子としてのセルロース誘導体は、エーテル化度が0.6以上であることが好ましく、0.7以上であることがより好ましく、0.8以上であることが更に好ましく、1.5以下であることが好ましく、1.3以下であることがより好ましく、1.0以下であることが更に好ましい。
水溶性高分子のエーテル化度が上記下限値以上であれば、カルボキシメチル基等の置換基の数が確保されるため、特に水系溶媒への溶解度が向上する。これにより、水溶性高分子の水に対する溶解性が向上し、スラリー組成物中における水溶性高分子の分散性が高まり、結果的にスラリー組成物自体の分散性が向上する。特に、水溶性高分子の分散性を高めることによるスラリー組成物の分散性の向上は、スラリー組成物を調製後保管した後に、再度分散処理を施した後の分散性(以下、「スラリー再分散性」とも称する)に良好な影響を与える。また、水溶性高分子のエーテル化度が上記上限値以下であれば、カルボキシメチル基等の置換基の数が過剰とならず、特に水系溶媒への溶解度が過度に高まることを抑制することができる。水溶性高分子の溶解度が過度に高い場合、スラリー組成物中にて非導電性粒子に対して吸着して存在し、非導電性粒子の分散性を高めるように作用する水溶性高分子が少なくなる。この結果、スラリー組成物中における非導電性粒子の分散性を十分に高めることができなくなる虞がある。よって、水溶性高分子のエーテル化度を上記上限値以下とすることにより、かかる水溶性高分子を含むスラリー組成物を用いて形成した機能層中にて非導電性粒子が局所的に密集して機能層のガーレー値が過度に高まることを抑制して、機能層を備える二次電池のレート特性を向上させることができる。
そして、本発明の非水系二次電池機能層用スラリー組成物中における水溶性高分子の含有量は、非導電性粒子100質量部当たり、0.2質量部以上であることが好ましく、0.3質量部以上であることがより好ましく、0.5質量部以上であることが更に好ましく、4.5質量部以下であることが好ましく、4.0質量部以下であることがより好ましく、3.5質量部以下であることが更に好ましい。水溶性高分子の含有量が上記下限値以上であれば、機能層の他部材に対する接着性を向上することができる。また、水溶性高分子の含有量が上記上限値以下であれば、機能層の耐熱収縮性を一層向上させることができる。
結着材は、本発明の非水系二次電池機能層用スラリー組成物を用いて形成した機能層中において非導電性粒子等の成分を結着する成分として機能し得る。そして、本発明の非水系二次電池機能層用スラリー組成物に含有され得る結着材としては、特に限定されることなく、既知の結着材、例えば、スラリー組成物中において粒子形状で存在する粒子状重合体が挙げられる。そして、粒子状重合体としては、共役ジエン系重合体およびアクリル系重合体が好ましく、アクリル系重合体がより好ましい。これらの結着材は、1種類を単独で使用してもよいし、2種類以上を組み合わせて用いてもよい。なお、粒子状重合体は、機能層用スラリー組成物を用いて形成された機能層中では、粒子形状であってもよいし、その他の任意の形状であってもよい。
これらの結着材は、1種類を単独で使用してもよいし、2種類以上を組み合わせて用いてもよい。
そして、重合方法としては、特に限定されず、例えば溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法を用いてもよい。また、重合反応としては、例えばイオン重合、ラジカル重合、リビングラジカル重合などいずれの反応を用いてもよい。
また、結着材のガラス転移温度は、好ましくは20℃以下であり、より好ましくは5℃以下であり、更に好ましくは-10℃以下である。結着材のガラス転移温度が20℃以下であれば、十分に高い接着性を発揮し、多孔膜に含まれる成分が、多孔膜から脱落するのを十分に抑制すると共に、多孔膜のピール強度を十分に高めることができる。なお、結着材として用いられる重合体のガラス転移温度は、通常、-60℃以上であり、好ましくは-50℃以上である。そして、重合体のガラス転移温度は、JIS K7121に従って測定することができる。
結着材の体積平均粒子径(D50)は、0.05μm以上であることが好ましく、0.10μm以上であることがより好ましく、0.50μm以下であることが好ましく、0.35μm以下であることがより好ましい。
そして、本発明の非水系二次電池機能層用スラリー組成物中における結着材の含有量は、非導電性粒子100質量部当たり、2質量部以上10質量部以下であることが好ましい。結着材の含有量を上記範囲内とすることにより、機能層のピール強度を向上させるとともに、機能層の内部抵抗が増加することを抑制して、非水系二次電池のレート特性を向上させることができる。
本発明の非水系二次電池機能層用スラリー組成物は、分散媒として水を含む。なお、非水系二次電池機能層用スラリー組成物は、有機溶媒などの水以外の媒体を分散媒として少量含有していてもよい。
ここで、通常、機能層用スラリー組成物では、非導電性粒子および結着材は水に分散している。一方、水溶性高分子は、水に溶解している。
本発明の非水系二次電池機能層用スラリー組成物は、濡れ剤を含むことが好ましい。濡れ剤としては、特に限定されることなく、ノニオン性界面活性剤やアニオン性界面活性剤等の界面活性剤を使用することができる。均一塗工容易性の観点からノニオン性界面活性剤が好ましい。ノニオン界面活性剤は、特に限定されることなく、その具体例として、ポリオキシアルキレンアルキルアリールエーテル界面活性剤、ポリオキシアルキレンアルキルエーテル界面活性剤、ポリオキシアルキレン脂肪酸エステル界面活性剤、ソルビタン脂肪酸エステル界面活性剤、シリコーン系界面活性剤、アセチレンアルコール系界面活性剤、含フッ素系界面活性剤等が挙げられる。
ポリオキシアルキレンアルキルアリールエーテル界面活性剤の具体例としては、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテルを挙げることができる。
ポリオキシアルキレンアルキルエーテル界面活性剤の具体例としては、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテルを挙げることができる。
ポリオキシアルキレン脂肪酸エステル界面活性剤の具体例としては、ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンラウリン酸エステル、ポリオキシエチレンジステアリン酸エステルを挙げることができる。
ソルビタン脂肪酸エステル界面活性剤の具体例としては、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等を挙げることができる。
シリコーン系界面活性剤の具体例としては、ジメチルポリシロキサン等を挙げることができる。
アセチレンアルコール系界面活性剤の具体例としては、2,4,7,9-テトラメチル-5-デシン-4,7-ジオール、3,6-ジメチル-4-オクチン-3,6-ジオール、3,5-ジメチル-1-ヘキシン-3オール等を挙げることができる。
含フッ素系界面活性剤の具体例としては、フッ素アルキルエステル等を挙げることができる。
中でも、濡れ剤としては、ポリオキシエチレンラウリルエーテルなどのポリオキシアルキレンアルキルエーテル界面活性剤が特に好ましい。
そして、本発明の非水系二次電池機能層用スラリー組成物における濡れ剤の含有量は、非導電性粒子100質量部当たり、0.01質量部以上が好ましく、0.05質量部以上がより好ましく、0.1質量部以上が更に好ましく、2.0質量部以下が好ましく、1.5質量部以下がより好ましく、1.0質量部以下が更に好ましい。濡れ剤の含有量を上記下限値以上とすれば、スラリー組成物と基材との間における濡れ性が向上して、スラリー組成物の均一塗布が可能となり、得られる機能層の耐熱収縮性を向上させることができる。濡れ剤の含有量を上記上限値以下とすれば、スラリー組成物を用いて形成した機能層を備える二次電池の高温サイクル特性を向上させることができる。
さらに、本発明の非水系二次電池機能層用スラリー組成物における水溶性高分子の含有量に対する濡れ剤の含有量の質量比(以下「濡れ剤/水溶性高分子(質量基準)」とも表記する)は、0.05以上であることが好ましく0.08以上であることがより好ましく、0.1以上であることが更に好ましく、1.0以下であることが好ましく、0.9以下であることがより好ましく、0.8以下であることが更に好ましい。濡れ剤/水溶性高分子(質量基準)が上記下限値以上であれば、機能層の耐熱収縮性を向上し得る。また、濡れ剤/水溶性高分子(質量基準)が上記上限値以下であれば、機能層の他部材に対する接着性を向上させることができる。
非水系二次電池機能層用スラリー組成物は、上述した成分以外にも、任意のその他の成分を含んでいてもよい。前記その他の成分は、電池反応に影響を及ぼさないものであれば特に限られず、公知のものを使用することができる。また、これらのその他の成分は、1種類を単独で使用してもよいし、2種類以上を組み合わせて用いてもよい。
前記その他の成分としては、例えば、分散剤、レベリング剤、酸化防止剤、消泡剤、湿潤剤、pH調整剤(例えば、塩化水素;アンモニア;水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物;水酸化カルシウム、水酸化マグネシウムなどのアルカリ土類金属の水酸化物等)、並びに、電解液分解抑制の機能を有する電解液添加剤などの既知の添加剤が挙げられる。例えば、分散剤としては、特に限定されることなく、例えば、特開2015-185482号に開示されたような、少なくとも2種以上の酸性基含有単量体単位を含む水溶性重合体を用いることができる。より具体的には、スルホン酸基含有単量体単位とカルボン酸基含有単量体単位とを含む水溶性重合体を用いることができる。かかる水溶性重合体によれば、非導電性粒子を良好に分散し得る。そして、水溶性重合体中におけるスルホン酸基含有単量体単位/カルボン酸基含有単量体単位の比率は、「スルホン酸基含有単量体単位/カルボン酸基含有単量体単位(質量基準)」で、1/999以上、より好ましくは0.01以上であり、好ましくは1以下、より好ましくは0.5以下、特に好ましくは0.3以下でありうる。なお、水溶性重合体の「水溶性」の定義は、「水溶性高分子」について上述した通りである。また、水溶性重合体の平均重合度は、50未満または450超であることが好ましい。ここで、「水溶性重合体の平均重合度」は、水溶性高分子の平均重合度と同様にして算出することができる。
本発明の非水系二次電池機能層用スラリー組成物は、特に限定されることなく、上述した非導電性粒子と、平均重合度が50以上450以下である水溶性高分子と、結着材と、必要に応じて用いられる任意の添加剤とを、分散媒としての水の存在下で混合して得ることができる。なお、水系溶媒中で単量体組成物を重合して結着材を調製した場合には、結着材は、水分散体の状態でそのまま他の成分と混合することができる。また、結着材を水分散体の状態で混合する場合には、水分散体中の水を分散媒として使用してもよい。
本発明の非水系二次電池用機能層は、上述した非水系二次電池機能層用スラリー組成物から形成されたものであり、例えば、上述した機能層用スラリー組成物を適切な基材の表面に塗布して塗膜を形成した後、形成した塗膜を乾燥することにより、形成することができる。即ち、本発明の非水系二次電池用機能層は、上述した非水系二次電池機能層用スラリー組成物の乾燥物よりなり、通常、非導電性粒子と、水溶性高分子と、結着材と、任意の添加剤とを含有する。なお、上述した結着材が架橋性単量体単位を含有する場合には、当該架橋性単量体単位を含有する結着材は、非水系二次電池機能層用スラリー組成物の乾燥時、或いは、乾燥後に任意に実施される熱処理時などに架橋されていてもよい(即ち、非水系二次電池用機能層は、上述した結着材の架橋物を含んでいてもよい)。
ここで、機能層用スラリー組成物を塗布する基材に制限は無く、例えば離型基材の表面に機能層用スラリー組成物の塗膜を形成し、その塗膜を乾燥して機能層を形成し、機能層から離型基材を剥がすようにしてもよい。このように、離型基材から剥がされた機能層を自立膜として二次電池の電池部材の形成に用いることもできる。具体的には、離型基材から剥がした機能層をセパレータ基材の上に積層して機能層を備えるセパレータを形成してもよいし、離型基材から剥がした機能層を電極基材の上に積層して機能層を備える電極を形成してもよい。
しかし、機能層を剥がす工程を省略して電池部材の製造効率を高める観点からは、基材としてセパレータ基材または電極基材を用いることが好ましい。セパレータ基材および電極基材上に設けられた機能層は、セパレータおよび電極の耐熱性や強度などを向上させる保護層として好適に使用することができる。
セパレータ基材としては、特に限定されないが、有機セパレータ基材などの既知のセパレータ基材が挙げられる。有機セパレータ基材は、有機材料からなる多孔性部材であり、有機セパレータ基材の例を挙げると、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、芳香族ポリアミド樹脂などを含む微多孔膜または不織布などが挙げられ、強度に優れることからポリエチレン製の微多孔膜や不織布が好ましい。なお、セパレータ基材の厚さは、任意の厚さとすることができ、好ましくは5μm以上30μm以下であり、より好ましくは5μm以上20μm以下であり、更に好ましくは5μm以上18μm以下である。セパレータ基材の厚さが5μm以上であれば、十分な安全性が得られる。また、セパレータ基材の厚さが30μm以下であれば、イオン伝導性が低下するのを抑制し、二次電池のレート特性が低下するのを抑制することができると共に、セパレータ基材の熱収縮力が大きくなるのを抑制して耐熱性を高めることができる。
電極基材(正極基材および負極基材)としては、特に限定されないが、集電体上に電極合材層が形成された電極基材が挙げられる。
ここで、集電体、電極合材層中の電極活物質(正極活物質、負極活物質)および電極合材層用結着材(正極合材層用結着材、負極合材層用結着材)、並びに、集電体上への電極合材層の形成方法には、既知のものを用いることができ、例えば特開2013-145763号公報および国際公開第2015/129408号に記載のものを用いることができる。
上述したセパレータ基材、電極基材などの基材上に機能層を形成する方法としては、以下の方法が挙げられる。
1)本発明の非水系二次電池機能層用スラリー組成物をセパレータ基材または電極基材の表面(電極基材の場合は電極合材層側の表面、以下同じ)に塗布し、次いで乾燥する方法;
2)本発明の非水系二次電池機能層用スラリー組成物にセパレータ基材または電極基材を浸漬後、これを乾燥する方法;
3)本発明の非水系二次電池機能層用スラリー組成物を離型基材上に塗布し、乾燥して機能層を製造し、得られた機能層をセパレータ基材または電極基材の表面に転写する方法;
これらの中でも、前記1)の方法が、機能層の層厚制御をしやすいことから特に好ましい。前記1)の方法は、詳細には、機能層用スラリー組成物を基材上に塗布する工程(塗布工程)と、基材上に塗布された機能層用スラリー組成物を乾燥させて機能層を形成する工程(機能層形成工程)を含む。
そして、塗布工程において、機能層用スラリー組成物を基材上に塗布する方法としては、特に制限は無く、例えば、ドクターブレード法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗り法などの方法が挙げられる。
また、機能層形成工程において、基材上の機能層用スラリー組成物を乾燥する方法としては、特に限定されず公知の方法を用いることができる。乾燥法としては、例えば、温風、熱風、低湿風による乾燥、真空乾燥、赤外線や電子線などの照射による乾燥が挙げられる。乾燥条件は特に限定されないが、乾燥温度は好ましくは50~150℃で、乾燥時間は好ましくは5~30分である。
そして、本発明の非水系二次電池機能層用スラリー組成物を用いて形成される機能層の厚みは0.3μm以上であることが好ましく、1.5μm以上であることがより好ましく、5.0μm以下であることが好ましい。機能層の厚みが上記下限値以上であれば、機能層を設けた電池部材の耐熱性や強度を更に向上させることができる。また、機能層の厚みが上記下限値以下であれば、二次電池に優れたレート特性を発揮させることができる。加えて、本発明の機能層用スラリー組成物を用いることで、機能層の厚みを薄層化した場合であっても、良好な耐熱収縮性を確保することが可能になる。従って、例えば、必要に応じて機能層の厚みを、3.0μm以下等とすることも可能である。
本発明の機能層を備える電池部材(セパレータおよび電極)は、本発明の効果を著しく損なわない限り、セパレータ基材または電極基材と、本発明の機能層との他に、上述した本発明の機能層以外の構成要素を備えていてもよい。
本発明の非水系二次電池は、上述した本発明の非水系二次電池用機能層を備えるものである。より具体的には、本発明の非水系二次電池は、正極、負極、セパレータ、および電解液を備え、上述した非水系二次電池用機能層が、電池部材である正極、負極およびセパレータの少なくとも一つに含まれる。そして、本発明の非水系二次電池は、優れた高温サイクル特性を発揮し得る。
本発明の二次電池に用いる正極、負極およびセパレータは、少なくとも一つが本発明の機能層を含む。具体的には、機能層を有する正極および負極としては、集電体上に電極合材層を形成してなる電極基材の上に本発明の機能層を設けてなる電極を用いることができる。また、機能層を有するセパレータとしては、セパレータ基材の上に本発明の機能層を設けてなるセパレータを用いることができる。なお、電極基材およびセパレータ基材としては、「非水系二次電池用機能層」の項で挙げたものと同様のものを用いることができる。
また、機能層を有さない正極、負極およびセパレータとしては、特に限定されることなく、上述した電極基材よりなる電極および上述したセパレータ基材よりなるセパレータを用いることができる。
電解液としては、通常、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、例えば、リチウムイオン二次電池においてはリチウム塩が用いられる。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。なかでも、溶媒に溶けやすく高い解離度を示すので、LiPF6、LiClO4、CF3SO3Liが好ましい。なお、電解質は1種類を単独で用いてもよく、2種類以上を組み合わせて用いてもよい。通常は、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傾向があるので、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。
なお、電解液中の電解質の濃度は適宜調整することができる。また、電解液には、既知の添加剤を添加してもよい。
上述した本発明の非水系二次電池は、例えば、正極と負極とをセパレータを介して重ね合わせ、これを必要に応じて、巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口することで製造することができる。なお、正極、負極、セパレータのうち、少なくとも一つの部材を機能層付きの部材とする。また、電池容器には、必要に応じてエキスパンドメタルや、ヒューズ、PTC素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をしてもよい。電池の形状は、例えば、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、何れであってもよい。
また、複数種類の単量体を共重合して製造される重合体において、ある単量体を重合して形成される単量体単位の前記重合体における割合は、別に断らない限り、通常は、その重合体の重合に用いる全単量体に占める当該ある単量体の比率(仕込み比)と一致する。
実施例および比較例において、水溶性高分子のエーテル化度および平均重合度、スラリー組成物の再分散性、機能層のピール強度および耐熱収縮性、二次電池の高温サイクル特性は、下記の方法で測定および評価した。
水溶性高分子のエーテル化度(置換度)は、以下の方法により求めた値である。
まず、試料(実施例1~3、5~10、および比較例1~2のカルボキシメチルセルロース塩:無水グルコースの置換基としてカルボキシメチル基を有するセルロース誘導体)0.5~0.7gを精密に量り、磁製ルツボ内で灰化した。冷却後、得られた灰化物500mlをビーカーに移し、水約250ml、さらにピペットでN/10硫酸35mlを加えて30分間煮沸した。これを冷却し、フェノールフタレイン指示薬を加えて、過剰の酸をN/10水酸化カリウムで逆滴定して、次式から置換度を算出した。
A=(a×f-b×f1)/試料(g)-アルカリ度(または+酸度)
置換度=M×A/(10000-80A)
A:試料1g中の結合アルカリ金属イオンに消費されたN/10硫酸の量(ml)
a:N/10硫酸の使用量(ml)
f:N/10硫酸の力価係数
b:N/10水酸化カリウムの滴定量(ml)
f1:N/10水酸化カリウムの力価係数
M:試料の重量平均分子量
なお、アルカリ度(または酸度)は、以下の方法および式により求めた。
試料約1gを200mlの水に溶解させ、これにN/10硫酸5mlを加え、10分間煮沸した後、冷却して、フェノールフタレイン指示薬を加え、N/10水酸化カリウムで滴定した。このときの滴定量をSmlとする。同時に空試験を行い、そのときの滴定量をBmlとし、次式からアルカリ度(または酸度)を求めた。(B-S)×f1値がプラス値の場合はアルカリ度が得られ、マイナスの場合は酸度が得られた。
アルカリ度(酸度)=(B-S)×f1/試料(g)
f1:N/10水酸化カリウムの力価係数
<水溶性高分子の平均重合度>
水溶性高分子の平均重合度は、粘度法を用いて測定することができ、例えば、0.1NのNaClを溶媒としてウベローデ粘度計を用いて極限粘度[η]を求め、Staudingerの粘度則に基づく下式(1)に従って、平均重合度Pを算出可能である。
[η]=Km×P×α・・・(1)
〔式(1)中、Kmおよびαは高分子の種類、重合条件(重合溶媒および温度)により定まる定数であり、本例では、Kmは12.3、αは0.91を用いた。〕
<スラリー組成物の再分散性>
実施例、比較例で調製した機能層用スラリー組成物を保管容器(100Lドラム缶)に移送後密封し、20℃で3月間保管した。この際、保管容器内に形成される空間体積が、保管容器の容量の30体積%となるように、保管容器内の機能層用スラリー組成物の量を調節し、保管容器を密封した。3月間保管後、回転軸の傾斜角度が70°である傾斜撹拌装置にセットして、保管容器の上下面の中心を貫通する軸線を回転軸に合わせて、時計回りに15回転させた後に反時計まわりに15回転させる操作を1パスとして、かかる操作を32パス繰り返して再分散処理を行った。回転速度は60rpmとした。再分散処理した機能層用スラリー組成物W0[g]を635メッシュSUS金網でろ過した。次いで、金網上の捕集物をイオン交換水で洗浄した後に、105℃で1時間乾燥し、乾燥後の捕集物が付着した金網を秤量して、以下の式(2)に従ってメッシュ残渣量を算出した。
メッシュ残渣量(質量ppm)=(a-b)/(W0×c/100)×1000000・・・(2)
a:乾燥後の捕集物が付着した金網の質量[g]
b:金網の質量[g]
c:機能層用スラリー組成物の固形分濃度[質量%]
W0:機能層用スラリー組成物の質量[g]
算出したメッシュ残渣量を下記の基準に従って評価した。メッシュ残渣量が少ないほど、再分散処理後の機能層用スラリー組成物が分散性に優れることを示す。
A:メッシュ残渣量が50質量ppm未満
B:メッシュ残渣量が50質量ppm以上150質量ppm未満
C:メッシュ残渣量が150質量ppm以上
<機能層のピール強度>
実施例1~9および比較例1~2で作製した機能層付きセパレータ、並びに実施例10で作製した機能層付き正極を、それぞれ長さ100mm、幅10mmの長方形に切り出して試験片とした。また、予め試験台にセロハンテープを固定した。このセロハンテープとしては、「JIS Z1522」に規定されるものを用いた。前記の試験片を、機能層面を下にしてセロハンテープに貼り付けた。これにより、試験片は機能層表面でセロハンテープに貼り付けた。その後、試験片の一端を垂直方向に引張り速度10mm/分で引っ張って剥がしたときの応力を測定した。測定を3回行い、その平均値を求めて、下記の基準により評価した。ピール強度が大きいほど、機能層とセパレータ基材/電極との結着力が大きい、すなわち密着強度が大きいことを示す。
A:ピール強度が、130N/m以上
B:ピール強度が、120N/m以上130N/m未満
C:ピール強度が、120N/m未満
<機能層の耐熱収縮性>
実施例1~9および比較例1~2で作製した機能層付きセパレータ、並びに実施例10で作製した機能層付き正極を、それぞれ、幅12cm×長さ12cmの正方形に切り出し、かかる正方形の内部に1辺が10cmの正方形を描いて試験片とした。そして、試験片を150℃の恒温槽に入れて1時間放置した後、内部に描いた正方形の面積変化(={(放置前の正方形の面積-放置後の正方形の面積)/放置前の正方形の面積}×100%)を熱収縮率として求め、以下の基準で評価した。この熱収縮率が小さいほど、機能層を有するセパレータ/電極の耐熱収縮性が優れていることを示す。
A:熱収縮率が5%未満
B:熱収縮率が5%以上10%未満
C:熱収縮率が10%以上
<二次電池の高温サイクル特性>
実施例、比較例で作製した800mAh捲回型ラミネートセルを45℃雰囲気下、0.5Cの定電流法によって4.35Vに充電し、3Vまで放電する充放電を200サイクル繰り返し放電容量を測定した。5セルの平均値を測定値とし、3サイクル終了時の放電容量に対する200サイクル終了時の電気容量の割合を百分率で算出して充放電容量保持率を求め、これをサイクル特性の評価基準とする。この値が高いほど二次電池が高温サイクル特性に優れることを示す。
A:充放電容量保持率が80%以上である。
B:充放電容量保持率が70%以上80%未満である。
C:充放電容量保持率が60%以上70%未満である。
D:充放電容量保持率が60%未満である。
<結着材の調製>
攪拌機を備えた反応器に、イオン交換水70部、乳化剤としてラウリル硫酸ナトリウム(花王ケミカル社製、「エマール2F」)0.15部、および重合開始剤として過硫酸アンモニウム0.5部を供給し、気相部を窒素ガスで置換し、60℃に昇温した。一方、別の容器にイオン交換水50部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム0.8部、そして(メタ)アクリロニトリル単量体としてアクリロニトリル5部、(メタ)アクリル酸エステル単量体としてブチルアクリレート90.8部、酸性基含有単量体としてメタクリル酸2部、架橋性単量体としてアリルグリシジルエーテル1部およびN-メチロールアクリルアミド1.2部、並びにキレート剤としてのエチレンジアミン4酢酸ナトリウム4水和物、(キレスト社製、「キレスト400G」)0.15部を混合して、単量体組成物を得た。この単量体組成物を4時間かけて前記反応器に連続的に添加して、重合を行った。添加中は、60℃で反応を行った。添加の終了後、さらに70℃で3時間攪拌してから反応を終了し、結着材(アクリル系重合体)の水分散液を調製した。得られたアクリル系重合体は、スラリー組成物中において粒子形状で存在する粒子状重合体であった。また、得られたアクリル系重合体は、ガラス転移温度(JIS K7121)が-48℃であった。また、粒子径は0.3μmであった。
<分散剤の調製>
イオン交換水50部、カルボン酸基を有する単量体としてのアクリル酸80部、並びにスルホン酸基を有する単量体としての2-アクリルアミド-2-メチルプロパンスルホン酸19.92部および2-(N-アクリロイル)アミノ-2-メチル-1,3-プロパン-ジスルホン酸0.08部を混合して、単量体組成物を得た。次いで、温度計、攪拌機および還流冷却器を備えた四つ口フラスコにイオン交換水150部を仕込み、80℃まで昇温した。攪拌下に、前記の単量体組成物と、重合開始剤としての30%過硫酸ナトリウム水溶液10部とを、それぞれ3時間にわたって定量ポンプでフラスコに連続的に滴下供給し、80℃で重合反応を行った。滴下終了後、更に系を80℃に保ったまま1時間熟成し、重合反応を完了した。その後、32%水酸化ナトリウム水溶液120部をフラスコ中に加えて反応液を完全に中和させて、水溶性重合体(アクリル酸/スルホン酸系共重合体、平均重合度:12)である分散剤の水溶液を得た。なお、水溶性重合体の平均重合度は、水溶性高分子と同様にして測定した。
<二次電池機能層用スラリー組成物の調製>
非導電性粒子としてアルミナ粒子(体積平均粒子径:0.8μm)100部と、上述のようにして調製した分散剤としての水溶性重合体の水溶液を固形分換算で0.5部とを混合し、さらに固形分濃度を55%になるようにイオン交換水を添加して混合し、混合液を得た。次いでこの混合液をローター/ステーター型のメディアレス分散装置を用いて、周速10m/sec、流量200L/hの条件で1パス分散させ、水分散体を得た。
この水分散体と、水溶性高分子としてのカルボキシメチルセルロース塩(重合度310、エーテル化度0.9)の4%水溶液37.5部(カルボキシメチルセルロースの量で1.5部)を混合し、次いで、上述のようにして調製した結着材の水分散液を13.3部(結着材の量で6部)、および、濡れ剤としてのポリオキシアルキレンアルキルエーテル界面活性剤であるポリオキシエチレンラウリルエーテル(「エマルゲン(登録商標) 106」、花王社製)の水溶液を固形分換算で0.2部混合し、調製溶液を得た。得られた調製溶液をフィルター(平均孔径10μm)でろ過した後、さらに室温、磁束密度8000ガウスの条件で、マグネットフィルター(トックエンジニアリング株式会社製)を10パス通過させることにより磁性物質を除去し、機能層用スラリー組成物を得た。
<機能層およびセパレータの製造>
ポリエチレン製のセパレータ基材として、重量平均分子量(Mw)が2.4×106の超高分子量ポリエチレン40質量%と、Mwが2.6×105の高密度ポリエチレン60質量%とからなるポリエチレン(PE)組成物を含んでなるポリエチレン製の有機セパレータ基材(逐次二軸延伸法、厚さ7μm)を用意した。用意したセパレータ基材の片面上に、スラリー組成物の再分散性の評価時と同じ再分散処理を行ったスラリー組成物を、乾燥後の厚さが2μmとなるようにグラビアコーターで塗布し、50℃で3分間乾燥させた。このようにして、セパレータ基材の片面上に機能層を形成してなるセパレータを得た。そして、得られたセパレータを用いて、上述の方法に従って機能層のピール強度および耐熱収縮性を評価した。結果を表1に示す。
<正極の製造>
正極活物質としてのLiCoO2を95部、導電材としてのアセチレンブラック(電気化学工業社製、「HS-100」)を2部、正極合材層用結着材としてのポリフッ化ビニリデン(クレハ社製、「KF-1100」)を固形分相当で3部、およびN-メチルピロリドンを20部混合し、正極用スラリー組成物を調製した。
得られた正極用スラリー組成物を、コンマコーターで、集電体である厚さ18μmのアルミ箔の上に塗布し、120℃で3時間乾燥させ、正極原反を得た。正極原反をロールプレスで圧延して、厚さが100μmの正極を得た。
<負極の製造>
攪拌機付き5MPa耐圧容器に、1,3-ブタジエン33部、イタコン酸3.5部、スチレン63.5部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム4部、イオン交換水200部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、50℃に加温して重合を開始した。12時間経過後、スチームを導入して未反応の単量体を除去した。これにより、所望の負極合材層用結着材を含む水分散液を得た。ディスパー付きのプラネタリーミキサーに、負極活物質としての人造黒鉛(比表面積:4m2/g、体積平均粒子径:24.5μm)70部、およびSiOx(体積平均粒子径5μm)30部、並びに、増粘剤としてカルボキシメチルセルロース塩(第一工業製薬社製、「BSH-12」)の1%水溶液を固形分相当で1部を加え、イオン交換水で固形分濃度55%に調整し、25℃で60分混合した。次に、イオン交換水で固形分濃度52%に調整した。その後、さらに25℃で15分攪拌し、混合液を得た。この混合液に、負極合材層用結着材を含む水分散液を固形分換算で1.0部入れ、イオン交換水を入れて最終固形分濃度50%となるように調整し、さらに10分間攪拌した。これを減圧下で脱泡処理して、流動性の良い負極用スラリー組成物を得た。得られた負極用スラリー組成物を、コンマコーターで、集電体である厚さ20μmの銅箔の上に、乾燥後の膜厚が150μm程度になるように塗布し、乾燥させた。この乾燥は、銅箔を0.5m/分の速度で60℃のオーブン内を2分間かけて搬送することにより行った。その後、120℃にて2分間加熱処理して負極原反を得た。この負極原反をロールプレスで圧延して、厚さが100μmの負極を得た。
<リチウムイオン二次電池の製造>
プレス後の正極を49cm×5cmに切り出した。切り出された正極の正極活物質層(正極合材層)上に、55cm×5.5cmに切り出したセパレータの機能層が対向するように配置した。さらに、プレス後の負極を50cm×5.2cmに切り出し、この切り出された負極を前記セパレータの正極とは反対側に、負極活物質層(負極合材層)側の表面がセパレータに向かい合うよう配置した。更に、寸法55cm×5.5cmに切り出したセパレータを負極の集電体側の表面上に配置した。これを捲回機によって捲回し、捲回体を得た。この捲回体を60℃0.5MPaでプレスし、扁平体とした。この扁平体を、電池の外装としてのアルミニウム包材外装で包み、電解液(溶媒:EC/EMC/VC=68.5/30/1.5体積比、電解質:濃度1MのLiPF6)を空気が残らないように注入した。さらに、アルミニウム包材の開口を密封するために、150℃のヒートシールをしてアルミニウム外装を閉口した。これにより、800mAhの捲回型リチウムイオン二次電池を製造した。
そして、得られたリチウムイオン二次電池について、上述した方法で、高温サイクル特性を評価した。
スラリー組成物の調製時に、配合するカルボキシメチルセルロースナトリウム塩を、それぞれ、重合度130、エーテル化度0.7のカルボキシメチルセルロースナトリウム塩(実施例2)、および、重合度430、エーテル化度0.8のカルボキシメチルセルロースナトリウム塩(実施例3)に変更した以外は実施例1と同様にして、スラリー組成物および二次電池を製造した。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
スラリー組成物の調製時に、カルボキシメチルセルロースナトリウム塩に代えて、ヒドロキシエチルセルロース(重合度220)を配合した以外は実施例1と同様にして、スラリー組成物および二次電池を製造した。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。なお、ヒドロキシエチルセルロースについては、上述した方法によっては、エーテル化度は測定不能であった。
スラリー組成物の調製時に、カルボキシメチルセルロースとして、重合度310、エーテル化度0.7のカルボキシメチルセルロース塩を0.2部配合した以外は実施例1と同様にして、スラリー組成物および二次電池を製造した。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
スラリー組成物の調製時に、水溶性高分子であるカルボキシメチルセルロース塩の配合量、および/または、濡れ剤の配合量を表1に示す通りにそれぞれ変更し、「濡れ剤/水溶性高分子(質量基準)」を表1に示す通りにそれぞれ変更した以外は、実施例1と同様にして、スラリー組成物および二次電池を製造した。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
スラリー組成物の調製時に、非導電性粒子として、アルミナ粒子に代えて架橋性ポリスチレン粒子(体積平均粒子径:0.5μm;ガラス転移温度:100℃)を配合した以外は、実施例1と同様にして、スラリー組成物および二次電池を製造した。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
架橋性ポロスチレン粒子は以下の方法により準備した。まず、撹拌機を備えた反応容器に、重量平均分子量が17,000の平均粒子径が0.2μmポリスチレン粒子を9部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム4部、架橋性単量体としてのジビニルベンゼン70部、スチレン10部、重合開始剤として過硫酸ナトリウム1部、イオン交換水800部を仕込み、窒素ガスを吹き込みながら撹拌下80℃で1時間重合した。次いで、重合開始剤として過硫酸ナトリウム0.5部、スチレン5部、メタクリル酸4.5部、2-ヒドロキシエチルメタクリレート0.5部、ポリビニルアルコール1部、イオン交換水20部を混合してできるエマルションを80℃で3時間にわたり連続的に反応容器に添加して、重合を完結させ架橋性ポリスチレン粒子を製造した。
実施例1と同様にしてスラリー組成物を調製し、機能層の形成にあたり、実施例1と同様にして作製した正極を基材として、正極用スラリー組成物の塗布により形成された正極合材層側の表面上にスラリー組成物を塗布し、実施例1と同じ条件で乾燥させて機能層を有する正極を得た。得られた機能層を有する正極について、実施例1と同様にしてピール強度および耐熱収縮性を評価した。
そして、かかる正極、実施例1と同様にして得た負極、および、ポリエチレン製の多孔基材であるセパレータ基材を用いて、実施例1と同様にしてリチウムイオン二次電池を製造して、実施例1と同様にして各種評価を行った。結果を表1に示す。
スラリー組成物の調製時に、配合するカルボキシメチルセルロースナトリウム塩を、それぞれ、重合度21、エーテル化度0.8のカルボキシメチルセルロースナトリウム塩(比較例1)、および、重合度600、エーテル化度0.7のカルボキシメチルセルロースナトリウム塩(比較例2)に変更した以外は実施例1と同様にして、スラリー組成物および二次電池を製造した。そして、実施例1と同様にして各種評価を行った。結果を表1に示す。
「PST」は、架橋性ポリスチレン粒子を、
「CMC」は、カルボキシメチルセルロースナトリウム塩を、
「HEC」は、ヒドロキシエチルセルロースを、
「POE」は、ポリオキシエチレンラウリルエーテルを、
「ACR」は、アクリル系重合体を、
「SP」は、セパレータを、それぞれ示す。
また、表1より、水溶性高分子の平均重合度が50未満である機能層用スラリー組成物を用いた比較例1、および、水溶性高分子の平均重合度が450超である機能層用スラリー組成物を用いた比較例2では、機能層用スラリー組成物の分散性が低く、得られる機能層の耐熱収縮性も低く、さらに、二次電池の高温サイクル特性が低下することが分かる。
また、本発明の非水系二次電池用機能層によれば、非水系二次電池に優れた高温サイクル特性を発揮させることができる。
そして、本発明によれば、高温サイクル特性に優れる非水系二次電池が得られる。
Claims (10)
- 非導電性粒子、水溶性高分子、結着材および水を含む非水系二次電池機能層用スラリー組成物であって、
前記水溶性高分子の平均重合度が、50以上450以下である
非水系二次電池機能層用スラリー組成物。 - 前記水溶性高分子が、セルロース誘導体である請求項1に記載の非水系二次電池機能層用スラリー組成物。
- 前記水溶性高分子が、カルボキシメチルセルロースまたはカルボキシメチルセルロース塩である請求項1または2に記載の非水系二次電池用機能層スラリー組成物。
- 前記水溶性高分子のエーテル化度が、0.6以上である請求項2または3に記載の非水系二次電池用機能層スラリー組成物。
- 前記水溶性高分子の含有量が、前記非導電性粒子100質量部当たり、0.2質量部以上4.5質量部以下である、請求項1~4のいずれかに記載の非水系二次電池機能層用スラリー組成物。
- 濡れ剤を更に含み、
前記濡れ剤の含有量が、前記非導電性粒子100質量部当たり、0.01質量部以上2.0質量部以下である、請求項1~5のいずれかに記載の非水系二次電池機能層用スラリー組成物。 - 前記水溶性高分子の含有量に対する前記濡れ剤の含有量の質量比が、0.05以上1.0以下である、請求項6に記載の非水系二次電池機能層用スラリー組成物。
- 請求項1~7のいずれかに記載の非水系二次電池機能層用スラリー組成物を用いて形成した、非水系二次電池用機能層。
- 厚みが5.0μm以下である、請求項8に記載の非水系二次電池用機能層。
- 請求項8または9に記載の非水系二次電池用機能層を備える、非水系二次電池。
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CN201880013672.2A CN110326137B (zh) | 2017-03-13 | 2018-03-08 | 非水系二次电池功能层用浆料组合物、非水系二次电池用功能层以及非水系二次电池 |
KR1020197025885A KR102563083B1 (ko) | 2017-03-13 | 2018-03-08 | 비수계 이차 전지 기능층용 슬러리 조성물, 비수계 이차 전지용 기능층 및 비수계 이차 전지 |
US16/487,565 US11394029B2 (en) | 2017-03-13 | 2018-03-08 | Slurry composition for non-aqueous secondary battery functional layers, non-aqueous secondary battery functional layer, and non-aqueous secondary battery |
JP2019505949A JP7031657B2 (ja) | 2017-03-13 | 2018-03-08 | 非水系二次電池機能層用スラリー組成物、非水系二次電池用機能層および非水系二次電池 |
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EP4024504A4 (en) * | 2019-08-30 | 2024-07-03 | Zeon Corp | BINDER COMPOSITION FOR NON-AQUEOUS SECONDARY BATTERY HEAT-RESISTANT LAYER, SLURRY COMPOSITION FOR NON-AQUEOUS SECONDARY BATTERY HEAT-RESISTANT LAYER, NON-AQUEOUS SECONDARY BATTERY HEAT-RESISTANT LAYER, AND NON-AQUEOUS SECONDARY BATTERY |
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KR20200060369A (ko) * | 2017-09-28 | 2020-05-29 | 니폰 제온 가부시키가이샤 | 비수계 이차 전지 기능층용 조성물, 비수계 이차 전지용 기능층, 비수계 이차 전지 부재, 및 비수계 이차 전지 |
CN112563492B (zh) * | 2020-12-11 | 2021-09-24 | 广东凯金新能源科技股份有限公司 | 一种表面微氧化多孔碳基负极材料及其制备方法 |
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CN110326137B (zh) | 2022-06-17 |
US20190379048A1 (en) | 2019-12-12 |
EP3598543A4 (en) | 2021-01-06 |
JP7031657B2 (ja) | 2022-03-08 |
EP3598543A1 (en) | 2020-01-22 |
KR102563083B1 (ko) | 2023-08-02 |
US11394029B2 (en) | 2022-07-19 |
JPWO2018168657A1 (ja) | 2020-01-09 |
KR20190123274A (ko) | 2019-10-31 |
CN110326137A (zh) | 2019-10-11 |
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