WO2017022845A1 - Composition de résine pour séparateur de batterie à électrolyte non aqueux, et séparateur pour batterie à électrolyte non aqueux et batterie à électrolyte non aqueux l'utilisant - Google Patents

Composition de résine pour séparateur de batterie à électrolyte non aqueux, et séparateur pour batterie à électrolyte non aqueux et batterie à électrolyte non aqueux l'utilisant Download PDF

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WO2017022845A1
WO2017022845A1 PCT/JP2016/073048 JP2016073048W WO2017022845A1 WO 2017022845 A1 WO2017022845 A1 WO 2017022845A1 JP 2016073048 W JP2016073048 W JP 2016073048W WO 2017022845 A1 WO2017022845 A1 WO 2017022845A1
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Prior art keywords
separator
electrolyte battery
resin composition
nonaqueous electrolyte
battery
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PCT/JP2016/073048
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English (en)
Japanese (ja)
Inventor
有紀 太田
俊充 田中
準治 藤岡
俊相 趙
岩崎　秀治
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株式会社クラレ
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Priority to JP2017533132A priority Critical patent/JP6869888B2/ja
Publication of WO2017022845A1 publication Critical patent/WO2017022845A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a resin composition for a non-aqueous electrolyte battery separator, and a separator for a non-aqueous electrolyte battery and a non-aqueous electrolyte battery using the same.
  • Non-aqueous electrolyte batteries are frequently used as secondary batteries used as power sources for these portable terminals. Since portable terminals are required to have more comfortable portability, miniaturization, thinning, weight reduction, and high performance have rapidly progressed, and have come to be used in various places. This trend continues today, and batteries used in mobile terminals are further required to be smaller, thinner, lighter, and higher in performance.
  • non-aqueous electrolyte batteries are spreading to large equipment such as electric cars, hybrid cars, and electric cars. Therefore, performance such as high capacity and charge / discharge characteristics at a large current is required, but because it is a non-aqueous electrolyte battery, there is a high risk of smoke, ignition, rupture, etc. compared to an aqueous battery. There is a demand for improved safety.
  • a nonaqueous electrolyte battery has a positive electrode and a negative electrode installed via a separator, and a lithium salt such as LiPF 6 , LiBF 4 LiTFSI (lithium (bistrifluoromethylsulfonylimide)), LiFSI (lithium (bisfluorosulfonylimide)). Is stored in a container together with an electrolytic solution in which an organic liquid such as ethylene carbonate is dissolved.
  • a lithium salt such as LiPF 6 , LiBF 4 LiTFSI (lithium (bistrifluoromethylsulfonylimide)), LiFSI (lithium (bisfluorosulfonylimide)
  • the risk of fuming increases due to temperature rise due to external heat, overcharge, internal short circuit, external short circuit, etc. These can be prevented to some extent by an external protection circuit.
  • the polyolefin resin porous film used as a non-aqueous electrolyte battery separator melts at around 120 ° C., and the pores are blocked to block the flow of current and ions, thereby suppressing the temperature rise of the battery. It is also possible. This is called a shutdown function.
  • the formation of the heat-resistant layer in such a separator is performed by applying a pasted metal oxide on the surface of the separator, and as a thickener or dispersant when pasting the metal oxide,
  • a pasted metal oxide on the surface of the separator, and as a thickener or dispersant when pasting the metal oxide
  • CMC carboxymethyl cellulose
  • Patent Document 3 Patent Document 3
  • CMC has good adhesion to metal oxides and separators and has thermal stability of about 150 ° C.
  • CMC has high electrical resistance and high electrical resistance during high rate and repeated charge / discharge. Short circuit easily occurs. As a result, there was a problem that heat was generated more than expected, and CMC was decomposed and it became difficult to function as a separator.
  • the present invention has been made in view of the above-mentioned problems, and has a low electrical resistance and a high heat resistance resin composition for a nonaqueous electrolyte battery separator, and a nonaqueous electrolyte battery separator and a nonaqueous solution using the same.
  • An object is to provide an electrolyte battery.
  • the present inventors have used the non-aqueous electrolyte battery separator resin composition having the following constitution (hereinafter also simply referred to as a separator resin composition) to achieve the above object.
  • the present invention has been completed by finding out to be achieved and further study based on this finding.
  • the separator resin composition according to one aspect of the present invention includes a neutralized salt of an ⁇ -olefin-maleic acid copolymer obtained by copolymerizing an ⁇ -olefin and a maleic acid, and the copolymer.
  • the degree of neutralization with respect to carboxylic acid produced from maleic acids in is from 0.3 to 1.0.
  • the water solubility of the composition is improved, the viscosity is increased, and the adhesion to the current collector foil and the binding property between molecules are increased. As a result, there is an advantage that it is not necessary to use a thickener or a dispersant.
  • a separator for a non-aqueous electrolyte battery according to still another aspect of the present invention includes a coating layer made of the above-described separator resin composition.
  • a nonaqueous electrolyte battery according to still another aspect of the present invention is characterized by including the separator.
  • the present invention it is possible to obtain a separator that is heat resistant, has few short circuits, and is excellent in productivity. Further, it can be used to improve battery characteristics of a nonaqueous electrolyte battery.
  • the resin composition for a separator of this embodiment includes a neutralized salt of an ⁇ -olefin-maleic acid copolymer obtained by copolymerizing an ⁇ -olefin and maleic acid, and has a neutralization degree in the copolymer. It is 0.3 to 1.0.
  • an ⁇ -olefin-maleic acid copolymer obtained by copolymerizing an ⁇ -olefin and maleic acid is composed of a unit (A) based on ⁇ -olefin and a unit (B) based on maleic acid,
  • the unit (A) based on ⁇ -olefins is represented by the general formula —CH 2 CR 1 R 2 — (wherein R 1 and R 2 may be the same or different from each other, and hydrogen, carbon Represents an alkyl group or an alkenyl group having a number of 1 to 10.
  • the ⁇ -olefin used in this embodiment is a linear or branched olefin having a carbon-carbon unsaturated double bond at the ⁇ -position. In particular, olefins having 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms are preferred.
  • isobutylene is particularly preferable from the viewpoints of availability, polysynthesis, and product stability.
  • the isobutylene includes a mixture containing isobutylene as a main component, for example, a BB fraction (C4 fraction).
  • maleic anhydride maleic acid, maleic acid monoester (for example, methyl maleate, ethyl maleate, propyl maleate, phenyl maleate, etc.), maleic acid, as the unit (B) based on maleic acids
  • Maleic anhydride derivatives such as diesters (eg dimethyl maleate, diethyl maleate, dipropyl maleate, diphenyl maleate etc.), maleic imides or N-substituted derivatives thereof (eg maleic imide, N-methylmaleimide, N N-substituted alkylmaleimides such as ethylmaleimide, N-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-ethyl Phenyl male N-substituted alkylphenylmaleimide such as imide, or N-substi
  • maleic anhydride is preferable from the viewpoint of availability, polymerization rate, and ease of molecular weight adjustment.
  • These maleic acids may be used alone or in combination.
  • Maleic acids are neutralized with alkali salts as described above, and the resulting carboxylic acid and carboxylic acid salt form a 1,2-dicarboxylic acid or salt form. This form has a function of capturing heavy metals eluted from the positive electrode.
  • the content ratio of each structural unit in the copolymer of the present embodiment is preferably such that (A) / (B) is in the range of 1/1 to 1/3 in terms of molar ratio. This is because the advantages of hydrophilicity, water solubility, and affinity for metals and ions as a high molecular weight substance that dissolves in water can be obtained. Particularly, it is desirable that the molar ratio of (A) / (B) is 1/1 or a value close thereto, in which case the unit based on ⁇ -olefin, that is, —CH 2 CR 1 R 2 — A copolymer having a structure in which the units shown and units based on maleic acids are alternately repeated is obtained.
  • the mixing ratio of ⁇ -olefins and maleic acids to obtain the copolymer of the present embodiment varies depending on the composition of the target copolymer, but ⁇ -olefin of 1 to 3 times the number of moles of maleic acids.
  • Use of olefin is effective for increasing the reaction rate of maleic acids.
  • the method for producing the copolymer of the present embodiment is not particularly limited, and for example, the copolymer can be obtained by radical polymerization.
  • the polymerization catalyst used is an azo catalyst such as azobisisobutyronitrile, 1,1-azobiscyclohexane-1-carbonitrile, or an organic peroxide catalyst such as benzoyl peroxide or dicumyl peroxide. preferable.
  • the amount of the polymerization catalyst used is required to be in the range of 0.1 to 5 mol%, preferably 0.5 to 3 mol% with respect to maleic acids.
  • As a method for adding the polymerization catalyst and the monomer they may be added all at the beginning of the polymerization, but it is desirable to add them sequentially as the polymerization proceeds.
  • the molecular weight can be appropriately adjusted mainly depending on the monomer concentration, the amount of catalyst used, and the polymerization temperature.
  • the polymerization temperature is preferably 40 ° C.
  • the polymerization time is usually preferably about 1 to 24 hours, more preferably 2 to 10 hours.
  • the amount of the polymerization solvent used is preferably adjusted so that the concentration of the obtained copolymer is 5 to 40% by weight, more preferably 10 to 30% by weight.
  • the weight average molecular weight of the copolymer of the present embodiment can be measured by, for example, a light scattering method or a viscosity method.
  • the copolymer of this embodiment preferably has an intrinsic viscosity in the range of 0.05 to 1.5.
  • the copolymer of this embodiment is usually obtained in the form of a powder having a grain size of about 16 to 60 mesh.
  • the neutralized salt of the copolymer means that the active hydrogen of carbonyl acid generated from maleic acid reacts with a basic substance to form a salt to become a neutralized salt.
  • a basic substance containing a monovalent metal and / or ammonia is used as the basic substance from the viewpoint of coating properties. It is preferable.
  • the amount of the basic substance containing monovalent metal and / or ammonia is not particularly limited and is appropriately selected depending on the purpose of use and the like, but usually in the maleic acid copolymer.
  • the amount is preferably 0.6 to 2.0 mol per mol of maleic acid unit. If it is such usage-amount, it will be possible to adjust the neutralization degree of the binder composition of this embodiment to a predetermined range.
  • the amount of the basic substance containing a monovalent metal is preferably 0.8 to 1.8 moles per mole of maleic acid units in the maleic acid copolymer, so that there is little residual alkali and water solubility.
  • the copolymer salt can be obtained.
  • Examples of basic substances containing monovalent metals that can be used in the present embodiment include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metals such as sodium carbonate and potassium carbonate. Carbonates of alkali metals such as sodium acetate and potassium acetate; phosphates of alkali metals such as trisodium phosphate, and the like.
  • ammonia, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable.
  • ammonia or lithium hydroxide as a binder for a lithium ion secondary battery.
  • the basic substance containing monovalent metal and / or ammonia may be used alone or in combination of two or more.
  • a neutralized salt of an ⁇ -olefin-maleic acid copolymer is used in combination with a basic substance containing an alkali metal hydroxide such as sodium hydroxide as long as the battery performance is not adversely affected. May be prepared.
  • the degree of neutralization can be determined by a method such as titration with a base, an infrared spectrum, or an NMR spectrum.
  • titration with a base can be performed.
  • the specific titration method is not particularly limited, but it can be dissolved in water with little impurities such as ion-exchanged water, and a basic substance such as lithium hydroxide, sodium hydroxide, potassium hydroxide, It can be carried out by neutralization.
  • the indicator for the neutralization point is not particularly limited, but an indicator such as phenolphthalein indicating pH with a base, and a PH meter can be used.
  • the basic substance containing monovalent metal and / or ammonia is preferably used in an amount of preferably 0.6 to 2.0 mol per mol of maleic acid unit in the maleic acid copolymer. Can be adjusted to the above range. More preferably, the basic substance containing a monovalent metal and / or ammonia is added more reliably by adding 0.6 to 1.8 moles per mole of maleic acid units in the maleic acid copolymer. It is possible to adjust to the above range.
  • the ring-opening rate of the copolymer represents the hydrolysis rate of the site of maleic anhydride that is polymerized with ⁇ -olefins when maleic anhydride is used as the maleic acid.
  • a preferable ring opening rate is 60 to 100%, more preferably 70% to 100%, and still more preferably 80 to 100%.
  • the structural freedom of the copolymer becomes small and the stretchability becomes poor, so that the force for adhering adjacent electrode material particles may be reduced, which is not preferable. Furthermore, there is a possibility that problems such as low affinity for water and poor solubility may occur.
  • the ring-opening rate can be determined, for example, by measuring the hydrogen at the ⁇ -position of the maleic acid opened by 1H-NMR with reference to the hydrogen at the ⁇ -position of maleic anhydride.
  • the ratio of the carbonyl group derived from the carbonyl group and the ring-opened maleic anhydride can also be determined by IR measurement.
  • the mass reduction rate of the ⁇ -olefin-maleic acid copolymer at 150 ° C. is preferably less than 4%, and the mass reduction rate is more preferably less than 2%. If the mass reduction rate is 4% or more, there is a possibility that the capacity is reduced by heat generated when charging and discharging are repeated.
  • the mass reduction rate is not particularly limited, but can be measured by, for example, a method described in Examples described later.
  • the separator resin composition of the present embodiment may contain the ⁇ -olefin-maleic acid copolymer alone, and if necessary, a dispersing agent such as inorganic particles and surfactant. , Thickeners, wetting agents, antifoaming agents, and the like.
  • Nitride ceramics such as boron, silicon carbide, calcium carbonate, aluminum sulfate, aluminum hydroxide, magnesium hydroxide, potassium titanate, talc, synthetic kaolinite, kaolin clay, kaolinite, flybontite, stevensite, dickite, nacrite , Halloysite, pyrophyllite, audnite, montmorillonite, beidellite, nontronite, bolcon score, saponite, hectorite, fluorine hectorite, soconite, swin Rudite, vermiculite, fluorine vermiculite, burcerin, sericite, amesite, keriaite, fraponite, brindriaite, bentonite, zeolite, biotite, phlogopite, fluorophlogopite, iron mica, yeastite, teniolite, siderophyllite Tetraferri iron mica, scale mica, fluorosilica mica,
  • dispersant such as a surfactant
  • anionic surfactants such as sulfate ester type, phosphate ester type, carboxylic acid type and sulfonic acid type
  • cation type activities such as quaternary ammonium salt type and amidoamine type.
  • amphoteric surfactants such as alkyl betaine type, amide betaine type and amine oxide type, nonionic surfactants such as ether type, fatty acid ester type and alkyl glucooxide, polyacrylic acid, polyacrylic acid salt, polysulfonic acid
  • Various surfactants such as salts, polynaphthalene sulfonates, polyalkylene polyamine alkylene oxides, polyalkylene polyimine alkylene oxides, polyvinyl pyrrolidone, and cellulose type polymer surfactants can be used.
  • these may be used alone or in combination of two or more.
  • the dispersant is not limited to these as long as the same effects as those described above can be obtained.
  • the amount of the dispersant in the separator resin composition is usually 0.01 to 10 with respect to 100 parts by weight of the ⁇ -olefin-maleic acid copolymer.
  • the amount is preferably parts by weight, more preferably 0.1 to 5 parts by weight.
  • the thickener examples include synthetic polymers such as polyethylene glycol, urethane-modified polyether, polyacrylic acid, polyvinyl alcohol, vinyl methyl ether-maleic anhydride copolymer, carbomethoxy cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc. Natural polysaccharides such as cellulose derivatives, xanthan gum, dieutan gum, welan gum, gellan gum, guar gum, carrageenan gum, and starches such as dextrin and pregelatinized starch. These may be used alone or in combination of two or more.
  • the thickener is not limited to those as long as the same effects as those described above can be obtained.
  • the amount of the thickener in the separator resin composition is usually 0.01 with respect to 100 parts by weight of the ⁇ -olefin-maleic acid copolymer. It is preferably ⁇ 10 parts by weight, more preferably 0.1 to 5 parts by weight.
  • an aliphatic polyether type nonionic surfactant for example, an aliphatic polyether type nonionic surfactant, a polyoxyalkylene type nonionic surfactant, a modified silicone, a modified polyether, or a dimethylsiloxane polyoxyalkylene copolymer can be used. These are used singly or in combination of two or more.
  • the wetting agent is not limited to these as long as the same effects as those described above can be obtained.
  • the amount of the wetting agent in the separator resin composition is usually 0.01 to 10 with respect to 100 parts by weight of the ⁇ -olefin-maleic acid copolymer.
  • the amount is preferably parts by weight, more preferably 0.1 to 5 parts by weight.
  • antifoaming agent for example, various defoaming agents of mineral oil type, silicone type, acrylic type and polyether type can be used. These are used singly or in combination of two or more.
  • the antifoaming agent is not limited to these as long as the same effects as those described above can be obtained.
  • the amount of the antifoaming agent in the separator resin composition is usually 0.01 with respect to 100 parts by weight of the ⁇ -olefin-maleic acid copolymer. It is preferably ⁇ 10 parts by weight, more preferably 0.1 to 5 parts by weight.
  • Examples of the solvent in the separator resin composition of the present embodiment include water, alcohols such as methanol, ethanol, propanol, and 2-propanol, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, N, N-dimethyl, and the like.
  • Examples include amides such as formamide and N, N-dimethylacetamide, cyclic amides such as N-methylpyrrolidone and N-ethylpyrrolidone, and sulfoxides such as dimethylsulfoxide.
  • use of water is preferable from a viewpoint of safety
  • Esters such as ⁇ -butyrolactone and methyl lactate; amides such as N-methylpyrrolidone, N, N-dimethylacetamide and dimethylformamide; and organic dispersion media such as sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane.
  • the amount of the solvent in the separator resin composition is usually preferably 40 to 150 parts by weight, more preferably 70 to 130 parts by weight with respect to 10 parts by weight of the ⁇ -olefin-maleic acid copolymer. is there. If the amount of the ⁇ -olefin-maleic acid copolymer is excessively small, the viscosity becomes low, the coating property is lowered, the separator substrate surface cannot be sufficiently covered, and a short circuit occurs. It may not develop. On the contrary, if the amount of ⁇ -olefin-maleic acid copolymer is excessively large, the viscosity becomes high and the coating property may be lowered, and the separator substrate surface may not be sufficiently coated, and the electrical resistance also increases. Therefore, the discharge capacity may be reduced.
  • the present invention includes a separator for a non-aqueous electrolyte battery provided with a coating layer made of the separator resin composition.
  • the amount of adhered layers coated with separator resin composition preferably 1.0 ⁇ 30g / m 2, further 4.0 ⁇ 20g / m 2 is more preferable.
  • the adhesion amount of the coating layer is less than 1.0 g / m 2 , the separator base material surface cannot be sufficiently coated, the pore diameter becomes large, short circuit occurs, and good battery characteristics do not appear. There is.
  • the adhesion amount of the coated layer exceeds 30 g / m 2 , it may be difficult to reduce the thickness of the separator.
  • the resin composition for a separator of the present embodiment can be used as an optional member as a separator base material that can prevent short-circuiting of electrodes in a nonaqueous electrolyte battery without hindering charging / discharging of the battery.
  • separator substrate for example, a porous film or a nonwoven fabric made of an organic material having fine pores can be used.
  • the thickness of the separator substrate is usually 0.5 ⁇ m or more, preferably 1 ⁇ m or more, and usually 40 ⁇ m or less, preferably 30 ⁇ m or less. Within this range, the resistance due to the separator substrate in the battery is reduced, and the workability during battery production is excellent.
  • the method of drying after applying a solvent such as water contained in the resin composition for a separator to the separator base material is not particularly limited.
  • aeration drying with hot air, hot air, or low-humidity air for example, aeration drying with hot air, hot air, or low-humidity air; ; Irradiation drying of infrared rays, far infrared rays, electron beams, and the like.
  • the drying conditions are as fast as possible while the layer covered with the separator resin composition cracks due to stress concentration or the layer covered with the separator resin composition does not peel from the separator. It is good to adjust as possible.
  • the basis weight of the separator is preferably from 10.0 ⁇ 50.0g / m 2, more preferably 15.0 ⁇ 40.0g / m 2.
  • the thickness of the separator is preferably 10.0 to 50.0 ⁇ m, and more preferably 15.0 to 40.0 ⁇ m.
  • the separator coating layer may be smoothed by calendaring for the purpose of controlling the flattening and thickness of the coating layer surface.
  • the current collector used for the negative electrode and the positive electrode of the nonaqueous electrolyte battery of the present embodiment is not particularly limited as long as it is made of a conductive material.
  • a conductive material For example, iron, copper, aluminum, nickel, stainless steel, titanium, Metal materials such as tantalum, gold, and platinum can be used. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microbeads (MCMB), pitch-based carbon fibers; conductive polymers such as polyacene; composite metal oxidation represented by SiOx, SnOx, LiTiOx And metal compounds such as TiS 2 , LiTiS 2, and the like.
  • the amount of thickener used is preferably about 0.1 to 4 parts by weight, more preferably 0.3 to 3 parts by weight, and still more preferably 0.5 to 2 parts by weight with respect to 100 parts of the negative electrode active material. It is. If the thickener is excessively small, the viscosity of the slurry composition containing the negative electrode active material and the solvent (hereinafter, also simply referred to as the negative electrode slurry composition) may be too low and the thickness of the mixed layer may be reduced. If there is too much thickener, the discharge capacity may decrease.
  • examples of the conductive auxiliary compounded in the negative electrode slurry composition as needed include metal powder, conductive polymer, acetylene black, and the like.
  • the amount of the conductive aid used is usually preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight with respect to 100 parts by weight of the negative electrode active material.
  • the negative electrode is prepared by mixing the negative electrode active material as described above with a conductive assistant and a binder such as SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylidene fluoride in a solvent.
  • a conductive assistant such as SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylidene fluoride
  • the negative electrode slurry thus prepared can be applied to a current collector as described above, for example, a negative electrode current collector such as copper, and the solvent can be dried to obtain a negative electrode.
  • the positive electrode a positive electrode usually used for a nonaqueous electrolyte battery is used without any particular limitation.
  • the positive electrode active material TiS 2 , TiS 3 , amorphous MoS 3 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O 5, V 6 O 13 Transition metal oxides such as LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 and other lithium-containing composite metal oxides are used.
  • the positive electrode active material is mixed with the same conductive assistant and thickener as the negative electrode, a binder such as SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylidene fluoride, and the boiling point at normal pressure described above.
  • a binder such as SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylidene fluoride, and the boiling point at normal pressure described above.
  • a positive electrode current collector such as aluminum, and the solvent is dried to form a positive electrode.
  • the method for drying a solvent such as water contained in the slurry composition is not particularly limited, and examples thereof include aeration drying with hot air, hot air, and low-humidity air; vacuum drying; drying with infrared rays, far infrared rays, electron beams, and the like. .
  • the drying conditions are preferably adjusted so that the solvent can be removed as soon as possible while the active material layer is cracked by stress concentration or the active material layer does not peel from the current collector.
  • the pressing method include a die press and a roll press.
  • an electrolytic solution in which an electrolyte is dissolved in a solvent can be used.
  • the electrolyte solution may be liquid or gel as long as it is used for a normal non-aqueous electrolyte battery, and if it appropriately selects a battery that functions as a battery depending on the type of the negative electrode active material and the positive electrode active material. Good.
  • the solvent for dissolving such an electrolyte is not particularly limited. Specific examples include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, and diethyl carbonate; lactones such as ⁇ -butyllactone; trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, and 2-ethoxyethane.
  • Ethers such as tetrahydrofuran, 2-methyltetrahydrofuran; sulfoxides such as dimethyl sulfoxide; oxolanes such as 1,3-dioxolane, 4-methyl-1,3-dioxolane; nitrogen-containing compounds such as acetonitrile and nitromethane; formic acid Organic acid esters such as methyl, methyl acetate, ethyl acetate, butyl acetate, methyl propionate and ethyl propionate; inorganic acid esters such as triethyl phosphate, dimethyl carbonate and diethyl carbonate Terigres; diglymes; triglymes; sulfolanes; oxazolidinones such as 3-methyl-2-oxazolidinone; sultones such as 1,3-propane sultone, 1,4-butane sultone, naphtha sultone, etc.
  • a gel electrolyte a nitrile polymer, an acrylic polymer, a fluorine polymer, an alkylene oxide polymer, or the like can be added as a gelling agent.
  • the method for producing the non-aqueous electrolyte battery of the present embodiment is not particularly limited, and for example, the following production method is exemplified. That is, the negative electrode and the positive electrode are overlapped via the separator of the present embodiment described above, wound or folded according to the shape of the battery, put into a battery container, injected with an electrolyte, and sealed.
  • the shape of the battery may be any known coin type, button type, sheet type, cylindrical type, square type, flat type, and the like.
  • the nonaqueous electrolyte battery of the present embodiment is a battery that is less prone to internal short circuit and resistance rise, and is useful for various applications. For example, it is useful as a battery used in portable terminals that are required to be reduced in size, thickness, weight, and performance, and as a battery used in large equipment such as an electric vehicle that requires high safety. Very useful.
  • the separator resin composition according to one aspect of the present invention includes a neutralized salt of an ⁇ -olefin-maleic acid copolymer obtained by copolymerizing an ⁇ -olefin and a maleic acid, and the copolymer.
  • the degree of neutralization with respect to carboxylic acid produced from maleic acids in is from 0.3 to 1.0.
  • the coating property is very good. There is an advantage that it is excellent.
  • the water solubility of the composition is improved, the viscosity is increased, and the adhesion to the current collector foil and the binding property between molecules are increased. As a result, there is an advantage that it is not necessary to use a thickener or a dispersant.
  • a separator for a non-aqueous electrolyte battery according to still another aspect of the present invention includes a coating layer made of the above-described separator resin composition.
  • Example 1 ⁇ Resin composition for separator> 25 g (0.16 mol) of a water-soluble lithium-modified isobutene-maleic anhydride copolymer resin (average molecular weight 325,000, neutralization degree 1.0, ring opening rate 100%) is used as the resin composition for the separator, % Aqueous solution was prepared and used in the following tests. The degree of neutralization was adjusted by adding 2.0 equivalents (0.320 mol) of lithium hydroxide to the maleic acid unit in the maleic acid copolymer.
  • the 10% by weight separator resin composition was diluted to 5% by weight as a separator substrate surface coating solution, and a separator (27 cm ⁇ 25 cm, non-woven fabric) was immersed in the diluted solution.
  • a manual mangle for experiment manufactured by Kumagai Riki Kogyo Co., Ltd.
  • the separator coated with the diluent for the separator substrate surface coating solution was squeezed and then dried at room temperature for 12 hours.
  • the dried sheet was pressed with a hot press (manufactured by Furukawa Seisakusho) and adjusted to a thickness of 20 ⁇ m (roll temperature room temperature, speed 1 m / min, linear pressure 100 hg / cm).
  • the adhesion amount was 2.1 g / m 2 .
  • the slurry for the electrode was prepared by using a solid dispersion of a 48.3 wt% aqueous dispersion of styrene-butadiene rubber (SBR, TRD2001, manufactured by JSR) as a binder with respect to 94 parts by weight of natural graphite (DMGS, manufactured by BYD) as an active material.
  • SBR styrene-butadiene rubber
  • DGS natural graphite
  • the slurry for the electrode is made of 92 parts by weight of nickel / cobalt / manganese (NCM) as an active material, 5 parts by weight of polyvinylidene fluoride (PVDF) as a solid as a binder, and Denka as a conductive additive (conductivity imparting agent). 3 parts by weight of black (powder, manufactured by Denki Kagaku Kogyo Co., Ltd.) as a solid was put into a special container and kneaded using a planetary stirrer (ARE-250, manufactured by Shinky Corporation).
  • NCM nickel / cobalt / manganese
  • PVDF polyvinylidene fluoride
  • Denka a conductive additive
  • ⁇ Preparation of positive electrode for battery> The obtained slurry was coated on a current collector aluminum foil (IN30-H, manufactured by Fujishi Paper) using a film applicator (manufactured by Tester Sangyo), and hot air dryer (manufactured by Yamato Scientific) for 30 minutes at 80 ° C. After the primary drying, rolling was performed using a roll press (made by Hosen). Then, after punching out as a battery electrode ( ⁇ 14 mm), a coin battery electrode was produced by secondary drying under reduced pressure conditions at 120 ° C. for 3 hours.
  • Example 3 As a resin composition for a separator, a coated separator was formed as in Example 1 above using 50% Na salt of a 51.2 w% aqueous solution of polyacrylic acid (average molecular weight 187,000, degree of neutralization 0.5, manufactured by Aldrich) as a solid content. It produced by the same method. The adhesion amount was 2.1 g / m 2 . Further, a negative electrode for a battery was prepared by the same method as in Example 1 to obtain a coin battery, and a charge / discharge characteristic test was performed. The results are shown in Table 1 below.
  • the separator coated with the separator substrate surface coating solution was equivalent to the case where a separator not coated with electrical resistance was used, but when SBR / CMC-Na used for general purpose was used (Comparative Example) 1) It has been shown that resistance increases and battery performance also decreases. It is considered that the neutralized salt of the ⁇ -olefin-maleic acid copolymer constituting the separator substrate surface coating solution improves ion transmission in the battery. Furthermore, in Comparative Example 3 using polyacrylic acid, which is also an ordinary product, it can be seen that the DC resistance is high despite having a carboxylic acid moiety as in the present invention.
  • the present invention has wide industrial applicability in the technical field of non-aqueous electrolyte batteries.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne : une composition de résine pour un séparateur de batterie à électrolyte non aqueux, la composition étant caractérisée en ce qu'elle comprend un sel neutre d'un copolymère d'acide maléique et de α-oléfine obtenu par copolymérisation de α-oléfines et d'acides maléiques, et en ce que le degré de neutralisation de l'acide carboxylique généré à partir des acides maléiques dans le copolymère est de 0,3 à 1,0 ; un séparateur pour une batterie à électrolyte non aqueux ; et une batterie à électrolyte non aqueux.
PCT/JP2016/073048 2015-08-06 2016-08-05 Composition de résine pour séparateur de batterie à électrolyte non aqueux, et séparateur pour batterie à électrolyte non aqueux et batterie à électrolyte non aqueux l'utilisant WO2017022845A1 (fr)

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WO2019049510A1 (fr) * 2017-09-11 2019-03-14 株式会社クラレ Liquide de revêtement pour séparateur de batterie à électrolyte non aqueux, séparateur de batterie à électrolyte non aqueux l'utilisant et batterie à électrolyte non aqueux
CN111052445A (zh) * 2017-07-24 2020-04-21 株式会社可乐丽 非水电解质电池用分隔膜、及使用其的非水电解质电池

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JP2001176483A (ja) * 1999-12-21 2001-06-29 Mitsubishi Paper Mills Ltd 電池用セパレータおよび電池
JP2003031199A (ja) * 2001-07-12 2003-01-31 Showa Denko Kk 亜鉛二次電池用セパレータ及びそれを用いた亜鉛二次電池
JP2013251205A (ja) * 2012-06-01 2013-12-12 Mitsubishi Paper Mills Ltd リチウムイオン電池セパレータ用塗工液およびリチウムイオン電池セパレータ

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JP2010146960A (ja) * 2008-12-22 2010-07-01 Mitsubishi Chemicals Corp 非水系電解液二次電池並びに非水系電解液二次電池用正極及び負極
JP2010146961A (ja) * 2008-12-22 2010-07-01 Mitsubishi Chemicals Corp 非水系電解液二次電池及び非水系電解液二次電池用セパレータ
JP5998622B2 (ja) * 2012-05-11 2016-09-28 住友化学株式会社 樹脂組成物、非水電解液二次電池用セパレーター及びその製造方法、並びに、非水電解液二次電池
WO2014050708A1 (fr) * 2012-09-28 2014-04-03 日本ゼオン株式会社 Séparateur à membrane poreuse pour batteries secondaires, son procédé de fabrication, et batterie secondaire

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JP2001176483A (ja) * 1999-12-21 2001-06-29 Mitsubishi Paper Mills Ltd 電池用セパレータおよび電池
JP2003031199A (ja) * 2001-07-12 2003-01-31 Showa Denko Kk 亜鉛二次電池用セパレータ及びそれを用いた亜鉛二次電池
JP2013251205A (ja) * 2012-06-01 2013-12-12 Mitsubishi Paper Mills Ltd リチウムイオン電池セパレータ用塗工液およびリチウムイオン電池セパレータ

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111052445A (zh) * 2017-07-24 2020-04-21 株式会社可乐丽 非水电解质电池用分隔膜、及使用其的非水电解质电池
WO2019049510A1 (fr) * 2017-09-11 2019-03-14 株式会社クラレ Liquide de revêtement pour séparateur de batterie à électrolyte non aqueux, séparateur de batterie à électrolyte non aqueux l'utilisant et batterie à électrolyte non aqueux
JPWO2019049510A1 (ja) * 2017-09-11 2020-10-15 株式会社クラレ 非水電解質電池セパレータ用塗工液、並びに、それを用いた非水電解質電池用セパレータ及び非水電解質電池

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