WO2021060045A1 - 非水電解質二次電池用電極及び当該電極を用いた非水電解質二次電池 - Google Patents
非水電解質二次電池用電極及び当該電極を用いた非水電解質二次電池 Download PDFInfo
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- 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 an electrode for a non-aqueous electrolyte secondary battery in which an electrode active material mixture layer containing an electrode active material and a binder is formed on a current collector, and a non-aqueous electrolyte secondary battery using the electrode. ..
- Lithium-ion secondary batteries are compact, lightweight, have high energy density, have high capacity, and can be repeatedly charged and discharged, so they are widely used as power sources for portable electronic devices such as portable personal computers, handy video cameras, and information terminals. It is used. Further, from the viewpoint of environmental problems, electric vehicles using lithium ion secondary batteries and hybrid vehicles using electric power as a part of power are being put into practical use.
- an electrode active material, a binder and a conductive auxiliary agent are dispersed in a solvent to form a slurry, and this slurry is applied to a current collector, dried, and the electrode active material is placed on the current collector.
- a coating method for preparing a mixture layer is generally used.
- the smaller the amount of the binder and the conductive auxiliary agent the larger the battery capacity per unit mass can be obtained, and a high-capacity battery can be obtained.
- the binder is a component that binds the particles to the particles and the particles to the current collector, if the binding is not sufficient due to a shortage of the binder or the like, the electrode mixture layer is cracked or peeled off. Is likely to occur, which not only reduces the capacity of the battery, but may also cause an internal short circuit of the battery. Therefore, it has been difficult to produce an electrode having an extremely low content of the binder by the coating method.
- Patent Documents 1 and 2 have been proposed. However, these have problems such as the need for a large-scale device, large energy consumption, slow film formation rate and low productivity, and easy composition fluctuation. Further, the cold spray method and the aerosol deposition method can be applied to an electrode active material having a relatively high hardness, but in the case of an organic sulfur-based electrode active material which is an electrode active material having a low hardness, a thick electrode mixture layer is used. Is difficult to manufacture.
- the organic sulfur-based electrode active material obtained by heat-treating a mixture of an organic compound and sulfur in a non-oxidizing atmosphere has a large charge / discharge capacity, and the charge / discharge capacity decreases with repeated charging / discharging. It is known as a small electrode active material (see, for example, Patent Documents 3 to 15).
- the organic sulfur-based electrode active material is mainly studied as a positive electrode active material, it can also be used as a negative electrode active material (see, for example, Patent Documents 11 to 12).
- an electrode having a binder content of 0.4% by mass or less in the electrode active material mixture layer has not been known. .. Further, the hardness of the organic sulfur-based electrode active material is insufficient to apply the cold spray method or the aerosol deposition method.
- An object of the present invention is to provide an electrode for a non-aqueous electrolyte secondary battery having an electrode active material mixture layer having a low content of a binder in order to increase the charge / discharge capacity per unit mass of the electrode. ..
- the present invention includes a current collector and an electrode active material mixture layer containing an organic sulfur-based electrode active material, a conductive auxiliary agent and a binder, and the binder is the electrode active material mixture layer.
- the electrode active material mixture layer is an electrode for a non-aqueous electrolyte secondary battery, which is contained in an amount of 0.01% by mass to 1% by mass based on the total mass of the current collector.
- an electrode for a non-aqueous electrolyte secondary battery having an electrode active material mixture layer (hereinafter, also referred to as “electrode mixture layer”) having a low content of a binder, and a unit of the electrode.
- electrode active material mixture layer hereinafter, also referred to as “electrode mixture layer”
- the charge / discharge capacity per mass can be increased.
- an organic sulfur-based electrode active material is used as the electrode active material.
- the organic sulfur-based electrode active material refers to a compound that has a sulfur-carbon bond, can occlude and release lithium ions, and can be used as an electrode active material for a secondary battery.
- the organic sulfur-based electrode active material is a compound obtained by heat-treating a mixture of an organic compound and sulfur in a non-oxidizing atmosphere.
- a sulfur-modified polyacrylonitrile, a sulfur-modified elastomer compound, and a sulfur-modified polynuclear aromatic ring compound. Sulfur-modified pitch compound, polythienoacene compound, sulfur-modified polyether compound, sulfur-modified polyamide compound, sulfur-modified aliphatic hydrocarbon oxide, polycarbon sulfide and the like.
- the sulfur-modified polyacrylonitrile is a compound obtained by heat-treating polyacrylonitrile and elemental sulfur in a non-oxidizing atmosphere.
- the polyacrylonitrile may be a homopolymer of acrylonitrile. It may also be a copolymer of acrylonitrile and another monomer. When the polyacrylonitrile is a copolymer, the battery performance is lowered when the content of acrylonitrile is low. Therefore, the content of acrylonitrile in the copolymer is preferably at least 90% by mass or more.
- Other monomers include, for example, acrylic acid, vinyl acetate, N-vinylformamide, N, N'-methylenebisacrylamide.
- the mixing ratio of polyacrylonitrile and elemental sulfur in the heat treatment is preferably 100 parts by mass to 1500 parts by mass, and more preferably 150 parts by mass to 1000 parts by mass with respect to 100 parts by mass of polyacrylonitrile.
- the temperature of the heat treatment is preferably 250 ° C. to 550 ° C., more preferably 350 ° C. to 450 ° C. Since unreacted elemental sulfur causes a decrease in the cycle characteristics of the secondary battery, it is preferable to remove it from the sulfur-modified polyacrylonitrile by, for example, heating or solvent washing after heat treatment.
- the sulfur content of the sulfur-modified polyacrylonitrile is preferably 25% by mass to 70% by mass, more preferably 30% by mass to 55% by mass, because a large charge / discharge capacity can be obtained.
- the sulfur content of the organic sulfur-based electrode active material can be calculated from the analysis result using a CHN analyzer capable of analyzing sulfur and oxygen.
- the weight average molecular weight of the polyacrylonitrile used in the present invention is not particularly limited, and a commercially available polyacrylonitrile can be used.
- the sulfur-modified elastomer compound is a compound obtained by heat-treating rubber and elemental sulfur in a non-oxidizing atmosphere.
- the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber and the like. Only one type of these rubbers may be used, or two or more types may be used in combination.
- the raw material rubber may be vulcanized rubber or unvulcanized rubber.
- the mixing ratio of rubber and elemental sulfur in the heat treatment is preferably 100 parts by mass to 1500 parts by mass, and more preferably 150 parts by mass to 1000 parts by mass with respect to 100 parts by mass of rubber.
- one or more known vulcanization accelerators can be added.
- the amount of the vulcanization accelerator added is preferably 1 part by mass to 250 parts by mass, more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the rubber.
- the heat treatment temperature is preferably 250 ° C. to 550 ° C., more preferably 300 ° C. to 450 ° C.
- the sulfur content of the sulfur-modified elastomer compound is preferably 40% by mass to 70% by mass, more preferably 45% by mass to 60% by mass, because a large charge / discharge capacity can be obtained.
- the sulfur-modified polynuclear aromatic ring compound is a compound obtained by heat-treating a polynuclear aromatic ring compound and elemental sulfur in a non-oxidizing atmosphere.
- the polynuclear aromatic ring compound include benzene-based aromatic ring compounds such as naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, picene, pyrene, benzopyrene, perylene and coronene.
- polynuclear aromatic ring compounds examples thereof include aromatic ring compounds in which a part of the benzene-based aromatic ring compound is a 5-membered ring, or a heteroatom-containing heteroatom-containing heteroaromatic ring compound in which a part of these carbon atoms is replaced with sulfur, oxygen, nitrogen or the like. ..
- these polynuclear aromatic ring compounds have a chain or branched alkyl group having 1 to 12 carbon atoms, an alkoxyl group, a hydroxyl group, a carboxyl group, an amino group, an aminocarbonyl group, an aminothio group, a mercaptothiocarbonylamino group and a carboxylalkyl group. It may have a substituent such as a carbonyl group.
- the polynuclear aromatic ring compound may be a compound having a repeating structure of an aromatic moiety and a chain hydrocarbon moiety.
- examples of the aromatic moiety of the compound having a repeating structure of the aromatic moiety and the chain hydrocarbon moiety include benzene, pyrrolidine, pyrrole, pyridine, imidazole, pyrrolidone, tetrahydrofuran, triazine, thiophene, oxazole, thiazole, and thiadiazol.
- aromatic moieties include chain or branched alkyl groups having 1 to 12 carbon atoms, alkoxyl groups, hydroxyl groups, carboxyl groups, amino groups, aminocarbonyl groups, aminothio groups, mercaptothiocarbonylamino groups, and carboxyalkylcarbonyls. It may have a substituent such as a group.
- Examples of the chain hydrocarbon moiety of the compound having a repeating structure of the aromatic moiety and the chain hydrocarbon moiety include linear or branched chain hydrocarbons such as an alkylene group, an alkenylene group, and an alkynylene group.
- the number of carbon atoms in the chain hydrocarbon moiety is preferably 2 to 20, more preferably 3 to 10, and even more preferably 4 to 8.
- alkylene group or an alkenylene group is preferable from the viewpoint of ease of handling and economy, and among them, a butane-1,4-diyl group, a hexane-1,6-diyl group, an octane-1,8-diyl group, a vinylene group, 1 , 3-butadiene-1,4-diyl group and structural isomers thereof are preferable.
- the mixing ratio of the polynuclear aromatic ring compound and the simple sulfur in the heat treatment is preferably 100 parts by mass to 1500 parts by mass, and more preferably 150 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the polynuclear aromatic ring compound.
- the temperature of the heat treatment is preferably 250 ° C. to 550 ° C., more preferably 300 ° C. to 450 ° C. Since unreacted elemental sulfur causes a decrease in the cycle characteristics of the secondary battery, it is preferable to remove it from the sulfur-modified polynuclear aromatic ring compound by, for example, heating or solvent washing.
- the sulfur content of the sulfur-modified polynuclear aromatic ring compound is preferably 40% by mass to 70% by mass, more preferably 45% by mass to 60% by mass, because a large charge / discharge capacity can be obtained.
- the sulfur-modified pitch compound is a compound obtained by heat-treating pitches and elemental sulfur in a non-oxidizing atmosphere.
- Pitches include petroleum pitch, coal pitch, mesophase pitch, asphalt, coal tar, coal tar pitch, organic synthetic pitch obtained by polycondensation of condensed polycyclic aromatic hydrocarbon compounds, and heteroatomic condensed polycyclic fragrance. Examples thereof include an organic synthetic pitch obtained by polycondensation of group hydrocarbon compounds.
- Pitches are a mixture of various compounds and contain condensed polycyclic aromatics.
- the condensed polycyclic aromatics contained in the pitches may be a single species or a plurality of species. This condensed polycyclic aromatic may contain nitrogen and sulfur in the ring in addition to carbon and hydrogen. Therefore, the main component of coal pitch is considered to be a mixture of condensed polycyclic aromatic hydrocarbons consisting only of carbon and hydrogen and a heteroaromatic compound containing nitrogen, sulfur or the like in the condensed ring.
- the mixing ratio of the pitches and the elemental sulfur in the heat treatment is preferably 100 parts by mass to 1000 parts by mass, and more preferably 150 parts by mass to 500 parts by mass with respect to 100 parts by mass of the pitches.
- the temperature of the heat treatment is preferably 300 ° C. to 500 ° C., more preferably 350 ° C. to 500 ° C. Since unreacted elemental sulfur causes a factor of lowering the cycle characteristics of the secondary battery, it is preferable to remove it from the sulfur-modified pitch compound by, for example, heating or solvent washing.
- the sulfur content of the sulfur-modified pitch compound is preferably 25% by mass to 70% by mass, more preferably 30% by mass to 60% by mass, because a large charge / discharge capacity can be obtained.
- the polythienoacene compound is a compound having a sulfur-containing polythienoacene structure represented by the following general formula (1).
- the polythienoacene compound can be obtained by heat-treating an aliphatic polymer compound having a linear structure such as polyethylene, a polymer compound having a thiophene structure such as polythiophene, and simple sulfur in a non-oxidizing atmosphere.
- the mixing ratio of the aliphatic polymer compound and the elemental sulfur is 100 parts by mass to 2000 parts by mass of the elemental sulfur with respect to 100 parts by mass of the aliphatic polymer compound. It is preferably parts by mass, more preferably 150 parts by mass to 1000 parts by mass.
- the ratio of the polymer compound having a thiophene structure to elemental sulfur is preferably 100 parts by mass to 1000 parts by mass of elemental sulfur with respect to 100 parts by mass of the polymer compound having a thiophene structure.
- the temperature of the heat treatment is preferably 300 ° C. to 600 ° C., more preferably 350 ° C. to 500 ° C. Since unreacted elemental sulfur causes a factor of lowering the cycle characteristics of the secondary battery, it is preferable to remove it from the polythienoacene compound by, for example, heating or solvent washing.
- the sulfur content of the polythienoacene compound is preferably 30% by mass to 80% by mass, more preferably 40% by mass to 70% by mass, because a large charge / discharge capacity can be obtained.
- the sulfur-modified polyether compound is a compound obtained by heat-treating a polyether compound and elemental sulfur in a non-oxidizing atmosphere.
- the polyether compound include polyethylene glycol, polypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene glycol and the like.
- the polyether compound may be an alkyl ether group, an alkylphenyl ether group, an acyl group at the end, or may be an ethylene oxide adduct of a polyol such as glycerin or sorbitol.
- the mixing ratio of the polyether compound and the simple substance sulfur in the heat treatment is preferably 100 parts by mass to 1000 parts by mass, and more preferably 200 parts by mass to 500 parts by mass with respect to 100 parts by mass of the polyether compound.
- the temperature of the heat treatment is preferably 250 ° C. to 500 ° C., more preferably 300 ° C. to 450 ° C. Since unreacted elemental sulfur causes a factor of lowering the cycle characteristics of the secondary battery, it is preferable to remove it from the sulfur-modified polyether compound by, for example, heating or solvent washing.
- the sulfur content of the sulfur-modified polyether compound is preferably 30% by mass to 75% by mass, more preferably 40% by mass to 70% by mass, because a large charge / discharge capacity can be obtained.
- the sulfur-modified polyamide compound is an organic sulfur compound having a carbon skeleton derived from a polymer having an amide bond. Specifically, an aminocarboxylic acid compound and elemental sulfur, or a polyamine compound, a polycarboxylic acid compound and elemental sulfur are used. , A compound obtained by heat treatment in a non-oxidizing atmosphere.
- the aminocarboxylic acid compound means a compound having one amino group and at least one carboxyl group in the molecule.
- the aminocarboxylic acid compound include aminobenzoic acids such as 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, p-aminobenzoic acid and m-aminobenzoic acid, 4-aminophenylacetic acid and 3-aminophenyl.
- Acids cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, theanine, trichoromic acid, chinic acid, doumoy acid, ibotenic acid, achrominic acid. Amino acids such as are also included.
- the polyamine compound means a compound having at least two amino groups in the molecule.
- the polyamine compound include urea, ethylenediamine, diethylenetriamine, putresin, cadaverine, hexamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4-aminobenzenemethaneamine, 4-aminobenzeneethaneamine, and the like.
- examples thereof include melamine, 1,2,4-triaminobenzene, 1,3,5-triaminobenzene and benzoguanamine.
- the polycarboxylic acid compound means a compound having at least two carboxyl groups in the molecule.
- the polycarboxylic acid compound include terephthalic acid, fumaric acid, tartaric acid, maleic acid, benzene-1,3-dicarboxylic acid, phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid.
- phthalic anhydride, maleic anhydride and the like can be mentioned, and an acid anhydride may be used.
- the ratio of the polyamine compound to the polycarboxylic acid compound is preferably 0.9 to 1.1 in terms of molar ratio.
- the ratio of the aminocarboxylic acid compound to the elemental sulfur in the heat treatment is preferably 100 parts by mass to 500 parts by mass of the elemental sulfur with respect to 100 parts by mass of the aminocarboxylic acid compound, and more preferably 150 parts by mass to 400 parts by mass.
- the mixing ratio of the polyamine compound, the polycarboxylic acid compound, and the simple substance sulfur is preferably 100 parts by mass to 500 parts by mass, and 150 parts by mass to 400 parts by mass, based on 100 parts by mass of the total mass of the polyamine compound and the polycarboxylic acid compound.
- the portion is more preferable.
- the temperature of the heat treatment is preferably 250 ° C. to 600 ° C., more preferably 350 ° C. to 500 ° C.
- the sulfur content of the sulfur-modified polyamide compound is preferably 40% by mass to 70% by mass, more preferably 45% by mass to 60% by mass, because a large charge / discharge capacity can be obtained.
- the sulfur-modified aliphatic hydrocarbon oxide is a compound obtained by heat-treating an aliphatic hydrocarbon oxide and elemental sulfur in a non-oxidizing atmosphere.
- the aliphatic hydrocarbon oxide refers to a compound having an aliphatic hydrocarbon skeleton and having at least one group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group or an epoxy group, and carbonized.
- the hydrocarbon skeleton may have unsaturated bonds.
- the aliphatic hydrocarbon skeleton of the aliphatic hydrocarbon oxide may be a straight chain or a branched chain, but is preferably a straight chain because a large charge / discharge capacity can be obtained.
- the number of carbon atoms of the aliphatic hydrocarbon oxide is preferably 4 to 12, more preferably 6 to 10, because a large charge / discharge capacity can be obtained. Since oxygen atoms in the aliphatic hydrocarbon oxide are separated by heat treatment with elemental sulfur, the ratio of the number of carbon atoms to the number of oxygen atoms in the aliphatic hydrocarbon oxide is preferably 3 or more, and 4 The above is more preferable.
- Preferred aliphatic hydrocarbon oxides include 1-butanol, 2-butanol, 1-pentanol, 3-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-.
- Alcohol compounds such as butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, 1-nonanol, 1-decanol; butanal, pentanal, hexanal, heptanal, octanal, nonanal, decanal, etc.
- Alaldehyde compounds such as methyl ethyl ketone, diethyl ketone, methyl hexyl ketone; carboxylic acid compounds of octanoic acid, nonanoic acid, decanoic acid; 1,2-butane oxide, 1,2-hexane oxide, 1,2-octane oxide, Examples thereof include epoxy compounds such as 1,2-decaneoxide.
- the mixing ratio of the aliphatic hydrocarbon oxide and the elemental sulfur in the heat treatment is preferably 100 parts by mass to 1000 parts by mass of the elemental sulfur with respect to 100 parts by mass of the aliphatic hydrocarbon oxide, and further is 200 parts by mass to 500 parts by mass. preferable.
- the temperature of the heat treatment is preferably 300 ° C. to 500 ° C., more preferably 350 ° C. to 450 ° C. When the temperature of the heat treatment is higher than the boiling point of the aliphatic hydrocarbon oxide, it is preferable to carry out the production while refluxing the aliphatic hydrocarbon oxide.
- the sulfur content of the sulfur-modified aliphatic hydrocarbon oxide is preferably 45% by mass to 75% by mass, more preferably 50% by mass to 70% by mass, because a large charge / discharge capacity can be obtained.
- Polycarbon sulfide is a compound represented by the general formula (CS x ) n (x is 0.5 to 2 and n is a number of 4 or more), and is, for example, an alkali metal sulfide such as sodium sulfide. It can be obtained by heat-treating a precursor obtained by reacting a composite of elemental sulfur with a halogenated unsaturated hydrocarbon such as hexachlorobutadiene. The temperature of the heat treatment is preferably 320 ° C. to 400 ° C., and the sulfur content of the polycarbon sulfide compound is preferably 65% by mass to 75% by mass because a large charge / discharge capacity can be obtained.
- the non-oxidizing atmosphere means that the oxygen concentration in the gas phase is 5% by volume or less, preferably 2% by volume or less, and more preferably oxygen is substantially contained. It can be an atmosphere that does not contain oxygen, for example, an inert gas atmosphere such as nitrogen, helium, or argon, or a sulfur gas atmosphere.
- the organic compound and sulfur which are the raw materials for the organic sulfur-based electrode active material, are refined as necessary, mixed, and heat-treated. Since an organic sulfur-based electrode active material with little variation in quality can be obtained, it is preferable that the organic compound and sulfur are mixed even during the heat treatment.
- the mixing method include a container rotary type mixing in which the heating container itself is rotated and mixed, and stirring and mixing by a stirring blade inserted in the heating container.
- the container rotary mixing heat treatment device include a rotary kiln and the like
- examples of the stirring and mixing heat treatment device include a heat treatment device having screw blades, helical ribbon blades and the like.
- the heat treatment device for stirring and mixing may be a vertical device having a bottom or a horizontal device having a tunnel structure or the like.
- a container rotary type mixing heat treatment device is preferable because an active material having excellent battery characteristics can be obtained. It is unclear why an active material with excellent battery characteristics can be obtained when a container rotary mixing device is used, but in a stirring mixing device, an intermediate of an organic sulfur-based electrode active material is generated during heat treatment. , It is presumed that the stirring blades apply a load such as compression.
- the particle size of the organic sulfur-based electrode active material is preferably 0.1 ⁇ m to 50 ⁇ m in average particle size.
- the particle diameter is a volume-based diameter, and the diameter of secondary particles is measured by the laser diffracted light scattering method.
- the average particle size refers to the 50% particle size (D 50 ) measured by the laser diffracted light scattering method. It takes a lot of labor to make the average particle size of the organic sulfur-based electrode active material smaller than 0.1 ⁇ m, but further improvement in battery performance cannot be expected. If it is larger than 50 ⁇ m, the electrode mixture layer is peeled off. Etc. may occur easily.
- the average particle size of the organic sulfur-based electrode active material is more preferably 0.5 ⁇ m to 30 ⁇ m, further preferably 1 ⁇ m to 20 ⁇ m.
- the specific surface area of the organic sulfur-based electrode active material is preferably 0.5 m 2 / g to 30 m 2 / g.
- the specific surface area means the specific surface area measured by the BET (Brunauer-Emmett-Teller) method.
- BET Brunauer-Emmett-Teller
- the specific surface area of the organic sulfur-based electrode active material is more preferably 1 m 2 / g to 20 m 2 / g, further preferably 3 m 2 / g to 15 m 2 / g.
- a known conductive auxiliary agent for the electrode of the non-aqueous electrolyte secondary battery can be used, and specifically, natural Graphite, artificial graphite, carbon black, Ketjen black, acetylene black, channel black, furnace black, lamp black, thermal black, carbon nanotube, vapor grown carbon fiber (VGCF), flaky graphite, expansion Carbon materials such as graphite, graphene, fullerene, needle coke; metal powders such as aluminum powder, nickel powder and titanium powder; conductive metal oxides such as zinc oxide and titanium oxide; La 2 S 3 , Sm 2 S 3 , Ce 2 S 3, TiS sulfides such as 2.
- the average particle size of the conductive auxiliary agent is preferably 0.0001 ⁇ m to 50 ⁇ m, more preferably 0.01 ⁇ m to 40 ⁇ m. If the content of the conductive auxiliary agent is too small, the conductivity of the electrode mixture layer becomes insufficient and a sufficient capacity may not be obtained. If the content of the conductive auxiliary agent is too large, the organic sulfur-based electrode activity Since the content of the substance decreases and the volume decreases, the content of the conductive additive is preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the organic sulfur-based electrode active material, and 2 parts by mass to 20 parts by mass. Parts by mass are even more preferred.
- the electrode mixture layer of the electrode for a non-aqueous electrolyte secondary battery of the present invention contains a binder in an amount of 0.4% by mass or less.
- the binder that can be used for the electrode of the present invention include polydiene-based binders such as ethylene-propylene-diene rubber, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, and styrene-isoprene rubber; polyacrylic acid and polymethylmethacrylate.
- Polycarboxylic acid binders such as polyacrylates, ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers; polyolefin binders such as polyethylene, polypropylene and propylene / ⁇ -olefin copolymers; Fluorinated polymer-based binders such as vinylidene conjugation and polyethylene tetrafluoride; polydiene-based binders such as butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, styrene-isoprene rubber, and ethylene-propylene-diene rubber; Polyether-based binders such as ethylene oxide and modified polyphenylene oxide; Amidimide-based binders such as polyamide resins, polyimide resins and polyamideimide resins; carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, cellulose nanofibers, cellulose nano
- Cellulosic binders such as polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyvinyl acetate; Polyacrylonitrile binders such as polyacrylonitrile; Polypropylene binders such as polyester polyols; Polyurethane Examples thereof include a binder, and in the case of a binder having an acidic group such as a carboxyl group, the binder may be neutralized with an alkali metal such as lithium, sodium or potassium.
- an alkali metal such as lithium, sodium or potassium.
- binder Only one type of binder may be used, or two or more types may be used in combination.
- a polyolefin-based binder, a polydiene-based binder, a polycarboxylic acid-based binder, a polyether-based binder, and a polyvinyl alcohol-based binder can be obtained.
- Agents, polyacrylonitrile-based binders, cellulose-based binders, polyester-based binders, and polyurethane-based binders are preferable.
- the electrode mixture layer of the present invention contains 0.01% by mass or more based on the total mass thereof. ..
- the amount of the binder in the electrode mixture layer is 0.4% by mass or less based on the total mass of the electrode mixture layer.
- the content of the binder in the electrode mixture layer is preferably 0.05% by mass to 0.4% by mass, more preferably 0.1% by mass to 0.4% by mass.
- a slurry prepared by adding an organic sulfur-based electrode active material and a conductive auxiliary agent to a solvent and further adding a binder is applied to a current collector and dried to form an electrode mixture layer.
- the solvent include dimethyl carbonate, acetonitrile, tetrahydrofuran, N-methylpyrrolidone, N, N-dimethylformamide, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, ethanol, water and the like, and among them, N-methylpyrrolidone. , Ethanol, water is preferred.
- a method for preparing the slurry for example, a ball mill, a rotation / revolution mixer, a planetary mixer, a dispenser, or the like can be used.
- the thickness of the electrode mixture layer per one side is preferably 10 ⁇ m to 500 ⁇ m, more preferably 40 ⁇ m to 300 ⁇ m, because it is easy to carry out.
- the current collector conductive materials such as titanium, titanium alloy, aluminum, aluminum alloy, copper, nickel, stainless steel, nickel-plated steel, and carbon are used.
- the thickness of the current collector is usually about 5 ⁇ m to 50 ⁇ m, for example, in the case of aluminum or an aluminum alloy, it is about 7 ⁇ m to 30 ⁇ m, and in the case of copper or a copper alloy, it is about 5 ⁇ m to 15 ⁇ m.
- the electrode having the electrode mixture layer containing the organic sulfur-based electrode active material may be pressed after drying, if necessary.
- Examples of the press processing method include a die pressing method and a roll pressing method.
- An electrode having an electrode mixture layer containing an organic sulfur-based electrode active material may be used as a positive electrode or a negative electrode of the non-aqueous solvent secondary battery of the present invention.
- an electrode having an electrode mixture layer containing an organic sulfur-based electrode active material is used as a positive electrode of a lithium ion secondary battery
- an electrode having a negative electrode active material known as a negative electrode may be used and used as a negative electrode.
- an electrode having a known positive electrode active material may be used as the positive electrode.
- a negative electrode when an electrode using an organic sulfur-based electrode active material as an electrode active material is used as a positive electrode, and a positive electrode when used as a negative electrode are referred to as counter electrodes.
- a known negative electrode active material used when an electrode using an organic sulfur-based electrode active material as an electrode active material is used as a positive electrode and the counter electrode is a negative electrode is a lithium ion secondary battery, for example, natural.
- a negative electrode active material containing no lithium atom and a negative electrode active material in which the lithium atom is replaced with a sodium atom can be used. Good.
- the negative electrode active material is lithium or a lithium alloy, or sodium or a sodium alloy, the electrode itself may be used as an electrode without using a current collector.
- a known positive electrode active material used when an electrode using an organic sulfur-based electrode active material as an electrode active material is used as a negative electrode and the counter electrode is a positive electrode is a lithium ion secondary battery, for example, lithium.
- Examples thereof include a transition metal composite oxide, a lithium-containing transition metal phosphoric acid compound, and a lithium-containing silicate compound.
- the transition metal of the lithium transition metal composite oxide vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper and the like are preferable.
- the lithium transition metal composite oxide examples include a lithium cobalt composite oxide such as LiCoO 2 , a lithium nickel composite oxide such as LiNiO 2 , and a lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4 , and Li 2 MnO 3.
- a lithium cobalt composite oxide such as LiCoO 2
- a lithium nickel composite oxide such as LiNiO 2
- a lithium manganese composite oxide such as LiMnO 2 , LiMn 2 O 4
- Li 2 MnO 3 Li 2 MnO 3.
- Some of the transition metal atoms that are the main constituents of these lithium transition metal composite oxides are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, etc. Examples thereof include those substituted with other metals.
- substituted ones include, for example, Li 1.1 Mn 1.8 Mg 0.1 O 4 , Li 1.1 Mn 1.85 Al 0.05 O 4 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.5 Mn.
- the transition metal of the lithium-containing transition metal phosphoric acid compound is preferably vanadium, titanium, manganese, iron, cobalt, nickel or the like, and specific examples thereof include phosphorus such as LiFePO 4 and LiMn X Fe 1-X PO 4.
- Iron acid compounds, cobalt phosphate compounds such as LiCoPO 4 , and some of the transition metal atoms that are the main constituents of these lithium transition metal phosphate compounds are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, Examples thereof include those substituted with other metals such as nickel, copper, zinc, magnesium, gallium, zirconium and niobium, and vanadium phosphate compounds such as Li 3 V 2 (PO 4 ) 3.
- the lithium-containing silicate compound include Li 2 FeSiO 4 and the like. Only one kind of these may be used, or two or more kinds may be used in combination.
- the positive electrode active material in which the lithium atom of the positive electrode active material in the case of the lithium ion secondary battery described above is replaced with a sodium atom may be used.
- the counter electrode can be manufactured by replacing the above-mentioned organic sulfur-based electrode active material with the known negative electrode active material or the known positive electrode active material.
- an electrode using an organic sulfur-based electrode active material as an electrode active material is used as a positive electrode and the counter electrode is a negative electrode in which a compound containing no lithium is a negative electrode active material, both the positive electrode and the negative electrode are lithium. Does not include. Therefore, a lithium pre-doping treatment is required in which lithium is inserted into either or both of the negative electrode and the positive electrode in advance.
- the lithium predoping method a known method may be followed.
- the negative electrode when the negative electrode is doped with lithium, a semi-battery is assembled using metallic lithium as the counter electrode, and lithium is inserted by the electrolytic doping method in which lithium is electrochemically doped, or a metallic lithium foil is attached to the electrode.
- An example is a method in which lithium is inserted by a pasting pre-doping method in which the electrode is left in an electrolytic solution and then doped by utilizing the diffusion of lithium into the electrode.
- the above-mentioned electrolytic doping method or pasting pre-doping method can be used.
- non-aqueous electrolyte of the non-aqueous electrolyte secondary battery of the present invention examples include a liquid electrolyte obtained by dissolving the supporting electrolyte in an organic solvent, and a polymer gel electrolyte obtained by dissolving the supporting electrolyte in an organic solvent and gelling with a polymer.
- examples thereof include a genuine polymer electrolyte in which a supporting electrolyte is dispersed in a polymer, a hydride-based solid electrolyte, and an inorganic solid electrolyte, which do not contain an organic solvent.
- a conventionally known lithium salt is used as the supporting electrolyte used for the liquid electrolyte and the polymer gel electrolyte, and for example, LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiCF.
- LiN (CF 3 SO 2 ) 2 LiN (C 2 F 5 SO 2 ) 2 , LiN (SO 2 F) 2 , LiC (CF 3 SO 2 ) 3 , LiB (CF 3 SO 3 ) 4 , LiB (C 2 O 4) 2 , LiBF 2 (C 2 O 4), LiSbF 6, LiSiF 5, LiSCN, LiClO 4, LiCl, LiF, LiBr, LiI, LiAlF 4, LiAlCl 4, LiPO 2 F 2 and their Derivatives and the like are mentioned, and among these, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 or a derivative thereof, LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , It is preferable to use one or more selected from the group consisting of LiN (SO 2 F) 2 and LiC (CF 3 SO 2 ) 3 or a derivative thereof.
- LiN (CF 3 SO 2 ) 2 LiN (C 2 F 5 SO 2 ) 2 , LiN (SO 2 F) 2 , LiC Examples thereof include (CF 3 SO 2 ) 3 , LiB (CF 3 SO 3 ) 4 , and LiB (C 2 O 4 ) 2 .
- Examples of the hydride-based solid electrolyte include LiBH 4 , LiBH 4- LiI, LiBH 4- P 2 S 5 , LiAlH 4 , Li 3 AlH 6, and the like.
- the inorganic solid electrolyte may be coated with a polymer gel electrolyte.
- a layer of a polymer gel electrolyte may be provided between the layer of the inorganic solid electrolyte and the electrode.
- a supporting electrolyte in which the lithium atom in the case of the lithium ion secondary battery described above is replaced with a sodium atom may be used.
- the organic solvent used for preparing the liquid non-aqueous electrolyte used in the present invention only one type usually used for the liquid non-aqueous electrolyte may be used, or two or more types may be used in combination. May be good. Specific examples thereof include saturated cyclic carbonate compounds, saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds, amide compounds, saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds, saturated chain ester compounds and the like. ..
- the saturated cyclic carbonate compound, the saturated cyclic ester compound, the sulfoxide compound, the sulfone compound and the amide compound play a role of increasing the dielectric constant of the non-aqueous electrolyte because of their high relative permittivity, and particularly the saturated cyclic carbonate compound.
- saturated cyclic carbonate compounds include ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,1-dimethylethylene carbonate and the like. Can be mentioned.
- Examples of the saturated cyclic ester compound include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -hexanolactone, and ⁇ -octanolactone.
- Examples of the sulfoxide compound include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene and the like.
- sulfone compound examples include dimethyl sulfone, diethyl sulfone, dipropyl sulfone, diphenyl sulfone, sulfolane (also referred to as tetramethylene sulfone), 3-methyl sulfolane, 3,4-dimethyl sulfolane, and 3,4-diphenylmethyl sulfolane.
- Sulfolene, 3-methylsulfolene, 3-ethylsulfolene, 3-bromomethylsulfone and the like, and sulfolane and tetramethylsulfone are preferable.
- the amide compound examples include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like.
- the saturated chain carbonate compound, the chain ether compound, the cyclic ether compound and the saturated chain ester compound can lower the viscosity of the non-aqueous electrolyte and increase the mobility of the electrolyte ions. It is possible to improve the battery characteristics such as output density. Further, a saturated chain carbonate compound is particularly preferable because it has a low viscosity and can improve the performance of the non-aqueous electrolyte at a low temperature.
- saturated chain carbonate compound examples include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, t-butyl propyl carbonate and the like.
- chain ether compound or cyclic ether compound examples include dimethoxyethane, ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolane, dioxane, 1,2-bis (methoxycarbonyloxy) ethane, and 1,2-bis (.
- saturated chain ester compound a monoester compound and a diester compound having a total number of carbon atoms in the molecule of 2 to 8 are preferable.
- Specific compounds thereof include, for example, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, and the like.
- Ethyl, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, and ethyl propionate are preferred.
- organic solvent used for the preparation of the non-aqueous electrolyte for example, acetonitrile, propionitrile, nitromethane, derivatives thereof, and various ionic liquids can also be used.
- Examples of the polymer used for the polymer gel electrolyte include polyethylene oxide, polypropylene oxide, polyvinyl chloride, polyacrylonitrile, polymethylmethacrylate, polyethylene, polyvinylidene fluoride, and polyhexafluoropropylene.
- Examples of the polymer used for the genuine polymer electrolyte include polyethylene oxide, polypropylene oxide, and polystyrene sulfonic acid.
- the blending ratio in the gel electrolyte and the compounding method are not particularly limited, and a blending ratio known in the present art and a known compounding method may be adopted.
- the non-aqueous electrolyte may further contain known additives such as an electrode film forming agent, an antioxidant, a flame retardant, and an overcharge inhibitor in order to improve battery life and safety.
- additives such as an electrode film forming agent, an antioxidant, a flame retardant, and an overcharge inhibitor in order to improve battery life and safety.
- the additive it is usually 0.01 part by mass to 10 parts by mass, preferably 0.1 part by mass to 5 parts by mass, based on the whole non-aqueous electrolyte.
- the non-aqueous electrolyte secondary battery to which the present invention can be applied may have a separator between the positive electrode and the negative electrode.
- a polymer microporous film usually used for a non-aqueous electrolyte secondary battery can be used without particular limitation.
- the film include polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, and polyethers such as polyethylene oxide and polypropylene oxide.
- celluloses such as carboxymethyl cellulose and hydroxypropyl cellulose, polymer compounds and derivatives mainly composed of poly (meth) acrylic acid and various esters thereof, films composed of copolymers and mixtures thereof, etc. These films may be coated with a ceramic material such as alumina or silica, magnesium oxide, an aramid resin, or polyvinylidene chloride.
- These films may be used alone or may be laminated and used as a multi-layer film. Further, various additives may be used in these films, and the type and content thereof are not particularly limited.
- a film made of polyethylene, polypropylene, polyvinylidene fluoride, polysulfone or a mixture thereof is preferably used in the method for producing a secondary battery.
- the non-aqueous solvent electrolyte is a pure polymer electrolyte or an inorganic solid electrolyte
- the separator may not be included.
- the exterior member a laminated film or a metal container can be used.
- the thickness of the exterior member is usually 0.5 mm or less, preferably 0.3 mm or less.
- Examples of the shape of the exterior member include a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type.
- the laminate film a multilayer film having a metal layer between resin films can also be used.
- the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
- the resin film for example, a polymer material such as polypropylene, polyethylene, nylon, or polyethylene terephthalate can be used.
- the laminated film can be sealed in the shape of an exterior member by heat fusion.
- the metal container can be formed from, for example, stainless steel, aluminum, an aluminum alloy, or the like.
- the aluminum alloy an alloy containing elements such as magnesium, zinc, and silicon is preferable.
- Raw material PAN mixture 10 parts by mass of polyacrylonitrile powder (manufactured by Sigma Aldrich, average particle size 200 ⁇ m, weight average molecular weight: about 150,000) and 30 parts by mass of sulfur powder (manufactured by Sigma Aldrich, average particle size 200 ⁇ m) using a dairy pot. They were mixed and used as a raw material for the sulfur-modified polyacrylonitrile in Production Examples 1 to 3.
- the obtained sulfur-modified product was pulverized using a ball mill, and coarse particles were removed using a sieve having a mesh size of 40 ⁇ m to obtain a sulfur-modified polyacrylonitrile SPAN1 having an average particle size of 10 ⁇ m.
- a glass thin tube made of heat-resistant glass having an outer diameter of 7 mm, an inner diameter of 5 mm, and a length of 100 mm was attached to the hole for use as a reactor.
- the reactor was attached to a tubular electric furnace having a heating portion of 300 mm, and the electric furnace was tilted so that the reactor was tilted at 5 °.
- the temperature of the electric reactor was set to 420 ° C., and the mixture was heated at 0.5 rpm.
- Table 1 shows the sulfur content and specific surface area of SPAN1 to 3 and SPE.
- the sulfur content was calculated from the analysis results using a CHN analyzer (Model: varioMICROcube manufactured by Elementar Analysensystemme GmbH) capable of analyzing sulfur and oxygen.
- the specific surface area was measured in accordance with JISZ8830 (a method for measuring the specific surface area of powder (solid) by gas adsorption).
- Comparative electrode active material NCM LiNi 1/3 Co 1/3 Mn 1/3 O 2 (manufactured by Nihon Kagaku Sangyo Co., Ltd.)
- Conductive aid AB Acetylene Black (manufactured by Denka, trade name: Denka Black Li-100)
- Binder ACB Polyacrylic acid (polycarboxylic acid-based binder)
- a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1.0 mol / L in a mixed solvent consisting of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate.
- the batteries of Examples 1 to 9 using the organic sulfur-based electrode active material have a higher discharge capacity B, which is the discharge capacity per mass of the electrode active material mixture layer, as compared with the batteries of Comparative Examples 1 to 4. It is shown that a good electrode active material mixture layer is formed even if the amount of the binder is reduced, and the charge / discharge capacity per unit mass of the electrode can be increased.
- the sulfur-modified polyacrylonitrile has a larger discharge capacity B than the polythienoacene compound.
- sulfur-modified produced by heat-treating polyacrylonitrile and sulfur using a rotary heating container. In the case of polyacrylonitrile (SPAN3), the discharge capacity B becomes large.
- Example 10 A positive electrode of Example 10, Example 11, Comparative Example 10 and Comparative Example 11, a disk-shaped negative electrode obtained by cutting a lithium metal having a thickness of 500 ⁇ m to a predetermined size, and a glass filter as a separator were sandwiched and held in the case. Then, the previously prepared non-aqueous electrolyte was injected into the case, and the case was sealed and sealed to prepare a non-aqueous electrolyte secondary battery ( ⁇ 20 mm, thickness 3.2 mm, coin type).
- the discharge capacity D which is the discharge capacity per mass of the electrode active material mixture layer, is higher than that of the batteries of Comparative Examples 10 and 11, and the binder It is shown that a good electrode active material mixture layer is formed even if the amount is reduced, and the charge / discharge capacity per unit mass of the electrode can be increased.
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Abstract
Description
本発明で用いるポリアクリロニトリルの重量平均分子量は特に限定されず、また、市販のポリアクリロニトリルを使用することができる。
特開2013-054957号公報の製造例に準じた方法で硫黄変性ポリアクリロニトリルを製造した。即ち、原料PAN混合物20gを外径45mm、長さ120mmの有底円筒状ガラス管に収容したのち、ガラス管の開口部にガス導入管及びガス排出管を有するシリコーン栓を取り付けた。ガラス管内部の空気を窒素で置換した後、ガラス管の下部をルツボ型電気炉に入れ、ガス導入管から窒素を導入して発生する硫化水素を除去しながら400℃で1時間加熱した。なお、硫黄蒸気はガラス管の上部又は蓋部で凝結して還流する。冷却後、生成物をガラスチューブオーブンに入れ、真空吸引しつつ250℃で2時間加熱することにより単体硫黄を除去した。得られた硫黄変性生成物を、ボールミルを用いて粉砕後、目開き40μmのふるいを用いて粗粒を除去し、平均粒子径が10μmの硫黄変性ポリアクリロニトリルSPAN1を得た。
特開2014-022123号公報の実施例に準じた方法で硫黄変性ポリアクリロニトリルを製造した。即ち、外径50mm、内径45mm、長さ500mmの耐熱ガラス製のガラス管に、軸が直径5mm、長さ600mmで、スクリュー径42mm、スクリュー長450mm、スクリューピッチ30mmのリボン型スクリューを入れ、中央部にスクリュー用の穴、及び中央部から離れた位置にガスの導入用又は排出用の2つの穴を有するシリコーンゴム栓をガラス管の両端に取り付け、更にシリコーンゴム栓のガスの導入用又は排出用の穴に、外径7mm、内径5mm、長さ100mmの耐熱ガラス製のガラス細管を取り付け、反応器とした。加熱部分が300mmの管状電気炉に反応器を取り付け、反応器が5°の傾斜になるように電気炉を傾けた。傾斜した反応器の上部から原料PAN混合物30gを仕込み、反応器内を窒素ガスで置換した後、電気炉の温度を420℃とし、毎分0.5回転させながら加熱した。なお、加熱中は、反応器の下端のガラス細管から100ml/分の流速で窒素ガスを送り、上端のガラス細管から、生成する硫化水素ガスを排出した。また、昇華して上端のガラス細管に付着した硫黄は、適宜加熱して溶解し還流させた。
反応器の加熱部分を通過した生成物は、冷却後、製造例1と同様の操作を行い、平均粒子径が10μmの硫黄変性ポリアクリロニトリル粉末SPAN2を得た。
外径10mm、内径6mmの耐熱ガラス製のガラス管の中央部分を加熱しながら膨張させ、中央部に外径30mm、長さ50mmの膨張部分を有し、両端に外径10mm、長さ150mmの細管を有するホールピペット型のガラス製炉心管を作製した。
原料PAN混合物5gを前記炉心管の膨張部分に入れ、炉心管が5°の傾斜になるように設置し、炉心管内を窒素ガスで置換した後、毎分1回転させながら400℃で1時間加熱した。なお、加熱中は、炉心管の下部端から100ml/分の流速で窒素ガスを送り、炉心管の上部端から生成する硫化水素ガスを排出できるようにした。また、炉心管の加熱箇所は、膨張部分全体としたが、昇華して細管部分に付着した硫黄は、適宜加熱して溶解し膨張部分に還流させた。
生成物は、冷却後、製造例1と同様の操作を行い、平均粒子径が10μmの硫黄変性ポリアクリロニトリル粉末SPAN3を得た。
原料PAN混合物の代わりに、27μm~32μmのポリエチレン(コアフロント社製) 10質量部及び硫黄粉末(シグマアルドリッチ製、平均粒径200μm)30質量部を、乳鉢を用いて混合したものを使用した以外は製造例1と同様の操作を行い、平均粒子径が10μmのポリチエノアセン化合物粉末SPEを得た。
厚さ500μmのリチウム金属を所定の大きさにカットし、円盤状の負極1を作製した。
表2に示す組成になるように、電極活物質、導電助剤、結着剤及び溶剤として水を混合し、自転・公転ミキサーを用いて混合したスラリーを、ドクターブレード法により集電体に塗布し、90℃で3時間乾燥した。その後、この電極を所定の大きさにカットし、120℃で2時間真空乾燥を行い、円盤状電極を作製した。なお、集電体は、有機硫黄系電極活物質にはカーボンコートアルミニウム箔、NCMにはアルミニウム箔を用いた。
NCM:LiNi1/3Co1/3Mn1/3O2(日本化学産業製)
導電助剤
AB:アセチレンブラック(デンカ製、商品名:デンカブラックLi-100)
結着剤
ACB:ポリアクリル酸(ポリカルボン酸系結着剤)
エチレンカーボネート50体積%、ジエチルカーボネート50体積%からなる混合溶媒に、LiPF6を1.0mol/Lの濃度で溶解し非水電解質を調製した。
実施例1~9及び比較例1~9の正極、厚さ500μmのリチウム金属を所定の大きさにカットした円盤状の負極、セパレータとしてガラスフィルターを挟んでケース内に保持した。その後、先に調製した非水電解質をケース内に注入し、ケースを密閉、封止して、非水電解質二次電池(φ20mm、厚さ3.2mmのコイン型)を製作した。なお、比較例8~9の正極は、電極活物質合剤層の結着性が不十分で、電池を作製できなかったため、充放電試験は行わなかった。
非水電解質二次電池を30℃の恒温槽に入れ、有機硫黄系電極活物質を電極活物質とする実施例1~9及び比較例1~5では充電終止電圧を3.0V、放電終止電圧を1.0V、NCMを電極活物質とする比較例6~9では充電終止電圧を4.2V、放電終止電圧を3.0Vとし、充電レート0.1C、放電レート0.1Cの充放電を5サイクル行った。5サイクル目の電極活物質の質量あたりの放電容量である放電容量Aと、電極活物質合剤層の質量あたりの放電容量である放電容量Bを、表2に示す。
実施例10、実施例11、比較例10及び比較例11の正極、厚さ500μmのリチウム金属を所定の大きさにカットした円盤状の負極、セパレータとしてガラスフィルターを挟んでケース内に保持した。その後、先に調製した非水電解質をケース内に注入し、ケースを密閉、封止して、非水電解質二次電池(φ20mm、厚さ3.2mmのコイン型)を作成した。
非水電解質二次電池を0℃の恒温槽に入れ、充電終止電圧を3.0V、放電終止電圧を1.0Vとし、充電レート0.1C、放電レート0.1Cの充放電を3サイクル行った。3サイクル目の電極活物質の質量あたりの放電容量である放電容量Cと、電極活物質合剤層の質量あたりの放電容量である放電容量Dを、表3に示す。
Claims (8)
- 集電体、並びに
有機硫黄系電極活物質、導電助剤及び結着剤を含有する電極活物質合剤層を含み、
前記結着剤は、前記電極活物質合剤層の総質量に対し0.01質量%~0.4質量%で含有され、かつ、前記電極活物質合剤層は前記集電体上に形成されている、非水電解質二次電池用電極。 - 有機硫黄系電極活物質の平均粒子径が0.1μm~50μm、かつBET法による比表面積が0.5m2/g~30m2/gである、請求項1に記載の非水電解質二次電池用電極。
- 有機硫黄系電極活物質が硫黄変性ポリアクリロニトリルである、請求項1又は2に記載の非水電解質二次電池用電極。
- 結着剤が、ポリオレフィン系結着剤、ポリジエン系結着剤、ポリカルボン酸系結着剤、ポリエーテル系結着剤、ポリビニルアルコール系結着剤、ポリアクリロニトリル系結着剤、セルロース系結着剤、ポリエステル系結着剤、ポリウレタン系結着剤からなる群から選択される少なくとも1種である請求項1~3のいずれか1項に記載の非水電解質二次電池用電極。
- 請求項1~4のいずれか1項に記載の非水電解質二次電池用電極を正極とする、非水電解質二次電池。
- 請求項1~4のいずれか1項に記載の非水電解質二次電池用電極を負極とする、非水電解質二次電池。
- 有機硫黄系電極活物質、導電助剤及び結着剤を溶剤に添加してスラリーを調製する工程、及び
当該スラリーを集電体に塗布して電極活物質合剤層を形成する工程を含む、非水電解質二次電池用電極の製造方法であって、
前記結着剤は、前記電極活物質合剤層の総質量に対し0.01質量%~0.4質量%で含有されている、製造方法。 - 有機硫黄系電極活物質が硫黄変性ポリアクリロニトリルである、請求項7に記載の非水電解質二次電池用電極の製造方法。
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