WO2013084990A1 - 二次電池正極用バインダー組成物、二次電池正極用スラリー組成物、二次電池正極及び二次電池 - Google Patents
二次電池正極用バインダー組成物、二次電池正極用スラリー組成物、二次電池正極及び二次電池 Download PDFInfo
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- WO2013084990A1 WO2013084990A1 PCT/JP2012/081640 JP2012081640W WO2013084990A1 WO 2013084990 A1 WO2013084990 A1 WO 2013084990A1 JP 2012081640 W JP2012081640 W JP 2012081640W WO 2013084990 A1 WO2013084990 A1 WO 2013084990A1
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- Prior art keywords
- polymer
- positive electrode
- secondary battery
- mass
- active material
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- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000001846 repelling effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- This invention relates to the binder composition for secondary battery positive electrodes used in order to form the positive electrode used for secondary batteries, such as a lithium ion secondary battery.
- portable terminals such as notebook personal computers, mobile phones, and PDAs (Personal Digital Assistants) have been widely used.
- a nickel hydrogen secondary battery, a lithium ion secondary battery, and the like are frequently used.
- Mobile terminals are required to have more comfortable portability, and are rapidly becoming smaller, thinner, lighter, and higher in performance.
- mobile terminals are used in various places.
- the battery is required to be smaller, thinner, lighter, and higher in performance as in the case of the portable terminal.
- an active material containing a transition metal such as iron, manganese, cobalt, chromium and copper is used.
- transition metal ions are eluted into the electrolytic solution, resulting in a decrease in battery capacity and cycle characteristics, which is a big problem.
- transition metal ions eluted from the positive electrode are reduced and deposited on the negative electrode surface to form dendritic metal precipitates, which damage the separator, thereby reducing the safety of the battery. It is said that.
- An electrode used in a lithium ion secondary battery usually has a structure in which an electrode active material layer is laminated on a current collector.
- the electrode active material layer includes a pair of electrode active materials.
- a polymer binder (hereinafter sometimes referred to as “binder”) is used to bind the electrode active material and the current collector.
- An electrode is usually a slurry composition obtained by mixing an active material and, if necessary, a conductive agent such as conductive carbon, in a binder composition in which a polymer serving as a binder is dispersed or dissolved in a liquid medium such as water or an organic liquid. The slurry composition is applied to a current collector and dried.
- Patent Documents 1 and 2 describe secondary batteries using a binder containing a fluorine-based polymer (PVDF) such as polyvinylidene fluoride-based polymer and hydrogenated acrylonitrile-butadiene rubber (H-NBR).
- PVDF fluorine-based polymer
- H-NBR hydrogenated acrylonitrile-butadiene rubber
- Patent Documents 1 and 2 exemplify that the cycle characteristics and output characteristics of a secondary battery are improved by using a binder containing PVDF and H-NBR.
- the binder content in the electrode active material layer is 2% by mass in order to increase the binding force of the binder to such an extent that sufficient cycle characteristics can be obtained. I found that it was necessary. In particular, when an electrode active material having a large specific surface area and a small particle diameter is used, a larger amount of binder is required because the area bound to the binder increases. As a result, the amount of the binder, which is an insulating component, increases, so that the resistance of the electrode increases, and both the output characteristics and cycle characteristics of the battery may be deteriorated.
- Patent Documents 1 and 2 the dispersibility of the conductive agent and the electrode active material is insufficient, the stability of the slurry composition forming the electrode active material layer is poor, and it is difficult to obtain a smooth electrode. As a result, the cycle characteristics of the obtained battery may be further deteriorated. Furthermore, in the binders of Patent Documents 1 and 2, stress relaxation may occur in the pressing process during electrode production. Therefore, the adhesion between the electrode active material layer and the current collector is inferior, the resistance at the interface between the electrode active material layer and the current collector may increase, and as a result, the output characteristics of the secondary battery deteriorate. was there.
- an object of the present invention is to provide a binder composition having excellent binding properties even in a small amount, a slurry composition exhibiting excellent stability, a positive electrode having high smoothness, electrode winding properties, and binding properties, and an object of the present invention is to provide a secondary battery having excellent output characteristics.
- the gist of the present invention aimed at solving such problems is as follows.
- a binder composition for a secondary battery positive electrode wherein the content ratio of the polymer units having the hydrophilic group in the polymer A is 0.05 to 20% by mass.
- a secondary battery positive electrode slurry composition comprising the secondary battery positive electrode binder composition and the positive electrode active material according to any one of [1] to [5].
- a secondary battery positive electrode formed by forming a positive electrode active material layer made of the slurry composition for a secondary battery positive electrode according to [6] above on a current collector.
- a secondary battery having a positive electrode, a negative electrode, a separator, and an electrolyte solution A secondary battery, wherein the positive electrode is the secondary battery positive electrode according to [7].
- a method for producing a secondary battery positive electrode comprising a step of applying and drying the slurry composition for a secondary battery positive electrode according to [6] above on at least one surface of a current collector.
- the binder composition of the present invention includes the polymer A having a specific composition and the polymer B having a specific glass transition temperature, the binder composition has excellent binding properties and elasticity, and stress in the pressing process during electrode production. It is difficult to relax. As a result, the electrode active material bites into the current collector, and the resistance at the interface between the electrode active material layer and the current collector can be reduced. Therefore, a secondary battery having excellent output characteristics can be obtained. Moreover, the slurry composition for forming a positive electrode active material layer has the outstanding stability by using the binder composition of this invention. Furthermore, since the positive electrode active material is uniformly dispersed in the positive electrode active material layer, a positive electrode having high smoothness, electrode winding property, and binding property can be obtained.
- the secondary battery positive electrode binder composition of the present invention (sometimes referred to as “positive electrode binder composition”) contains a specific polymer A and polymer B. .
- the polymer A used in the present invention contains a polymer unit having a nitrile group, a polymer unit having a hydrophilic group, and a linear alkylene polymer unit having 4 or more carbon atoms.
- the polymer unit having a nitrile group refers to a structural unit formed by polymerizing a monomer having a nitrile group.
- the polymerized unit having a hydrophilic group refers to a structural unit formed by polymerizing a monomer having a hydrophilic group.
- the linear alkylene polymer unit having 4 or more carbon atoms refers to a structural unit formed by polymerizing monomers capable of forming a linear alkylene polymer unit having 4 or more carbon atoms.
- the ratio of each polymer unit in the polymer A usually corresponds to the ratio (preparation ratio) of the above monomers that can form each polymer unit in all monomers used for the polymerization of the polymer A.
- the number of carbon atoms is 4 or more due to the hydrogenation reaction rate described later. The proportion of the linear alkylene polymer units is controlled.
- the ratio of monomer capable of forming a linear alkylene polymer unit having 4 or more carbon atoms is a polymer unit obtained by hydrogenating a structural unit formed by polymerizing a conjugated diene monomer in polymer A. This corresponds to the ratio of the total of the polymer units not hydrogenated.
- a slurry composition for a secondary battery positive electrode for forming a positive electrode active material layer (hereinafter referred to as “positive electrode slurry composition”).
- the positive electrode active material can be stably dispersed, the slurry stability of the positive electrode slurry composition is excellent, and gelation of the positive electrode slurry composition can be prevented.
- the polymer A has a polymer unit having a hydrophilic group in an amount of 0.05 to 20% by mass, preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and particularly preferably 1 to 6%. Including mass%.
- the content ratio of the polymerization unit having the hydrophilic group is less than 0.05% by mass, the binding property between the positive electrode active materials and between the positive electrode active material layer and the current collector described later is reduced, In the manufacturing process such as winding and pressing of the positive electrode, part of the positive electrode active material layer may be detached (powder falling), which may cause damage to the separator or a short circuit between the positive electrode and the negative electrode.
- the content rate of the polymer unit having the hydrophilic group exceeds 20% by mass, the interaction between the polymer A and the positive electrode active material is too strong in the positive electrode slurry composition, and thus the slurry composition. There is a risk that the viscosity of the resin significantly increases.
- the hydrophilic group in the present invention refers to a functional group that liberates protons in an aqueous solvent, or a salt in which protons are substituted with cations, and specifically includes carboxylic acid groups, sulfonic acid groups, phosphorous groups. Examples include acid groups, hydroxyl groups and salts thereof.
- the dispersibility of the positive electrode active material in the positive electrode slurry composition is improved, and the positive electrode slurry composition can be stored in a stable state for a long period of time. it can. As a result, a uniform positive electrode active material layer can be easily manufactured. Moreover, since the lithium ion conductivity is good, the internal resistance in the battery can be reduced, and the output characteristics of the battery can be improved.
- the content ratio of the polymer unit having the nitrile group in the polymer A is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass.
- the dispersibility of the conductive agent in the positive electrode slurry composition is improved, and it is easy to produce a uniform secondary battery positive electrode.
- the linear alkylene polymer unit By uniformly dispersing the positive electrode active material and the conductive agent in the electrode, the internal resistance is reduced, and as a result, the cycle characteristics and output characteristics of a battery using this electrode are improved.
- the linear alkylene polymer unit By introducing the linear alkylene polymer unit, the degree of swelling of the positive electrode with respect to the electrolyte is optimized, and the battery characteristics are improved.
- the number of carbon atoms of the above linear alkylene polymer unit is 4 or more, preferably 4 to 16, more preferably 4 to 12.
- the content of the linear alkylene polymer unit in the polymer A is preferably 10 to 98% by mass, more preferably 10 to 80% by mass, and particularly preferably 10 to 70% by mass.
- the iodine value of the polymer A is preferably 3 to 20 mg / 100 mg, more preferably 3 to 15 mg / 100 mg, and still more preferably 3 to 10 mg / 100 mg.
- the iodine value of the polymer A exceeds 20 mg / 100 mg, the stability at the oxidation potential is low due to the unsaturated bond contained in the polymer A, and the high-temperature cycle characteristics of the battery may be inferior.
- the iodine value of the polymer A is less than 3 mg / 100 mg, the flexibility of the polymer A may decrease. As a result, powder fall etc. occur and it is inferior to safety and long-term characteristics.
- the iodine value of the polymer A is in the above range, the polymer A is chemically structurally stable with respect to a high potential, the electrode structure can be maintained even in a long-term cycle, and the cycle characteristics are excellent.
- the iodine value is determined according to JIS K6235;
- the polystyrene equivalent weight average molecular weight of the polymer A by gel permeation chromatography is preferably 10,000 to 700,000, more preferably 50,000 to 500,000, particularly preferably 100,000 to 300,000. 000.
- the positive electrode can be flexible, and it is easy to adjust the viscosity to be easily applied during the production of the positive electrode slurry composition.
- the polymer A used in the present invention contains a polymer unit having a nitrile group, a polymer unit having a hydrophilic group, and a linear alkylene polymer unit having 4 or more carbon atoms.
- a polymer A forms a monomer capable of forming a polymer unit having a nitrile group, a monomer capable of forming a polymer unit having a hydrophilic group, and a linear alkylene polymer unit having 4 or more carbon atoms. It is obtained by polymerizing the monomer to be obtained.
- a linear alkylene polymer unit having 4 or more carbon atoms is obtained by obtaining a polymer having a structural unit having an unsaturated bond (a polymer unit capable of forming a conjugated diene monomer having 4 or more carbon atoms), and then hydrogenating the polymer. It can be formed by reaction.
- Examples of the monomer capable of forming a polymer unit having a nitrile group include an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
- acrylonitrile; ⁇ -chloroacrylonitrile, ⁇ -bromoacrylonitrile, etc. ⁇ -halogenoacrylonitrile, ⁇ -alkylacrylonitrile such as methacrylonitrile, and the like Among these, acrylonitrile and methacrylonitrile are preferable. These can be used individually by 1 type or in combination of multiple types.
- hydrophilic group into the polymer A is carried out by polymerizing monomers having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a hydroxyl group, and a salt thereof.
- Examples of the monomer having a carboxylic acid group include monocarboxylic acids and derivatives thereof, dicarboxylic acids, and derivatives thereof.
- Examples of monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
- Examples of monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, ⁇ -diaminoacrylic acid, and the like.
- Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like.
- Dicarboxylic acid derivatives include methyl maleic acid, dimethyl maleic acid, phenyl maleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid and the like methyl allyl maleate, diphenyl maleate, nonyl maleate, decyl maleate, dodecyl maleate, And maleate esters such as octadecyl maleate and fluoroalkyl maleate.
- generates a carboxyl group by hydrolysis can also be used.
- the acid anhydride of dicarboxylic acid include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
- monoesters and diesters of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acids such as monobutyl itaconate and dibutyl itaconate.
- Examples of monomers having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid and 3-allyloxy-2-hydroxypropanesulfonic acid.
- Examples of the monomer having a phosphate group include 2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, ethyl phosphate- (meth) acryloyloxyethyl, and the like. .
- Examples of the monomer having a hydroxyl group include ethylenically unsaturated alcohols such as (meth) allyl alcohol, 3-buten-1-ol and 5-hexen-1-ol; 2-hydroxyethyl acrylate, acrylic acid-2 Ethylenic acid such as hydroxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl maleate, di-4-hydroxybutyl maleate, di-2-hydroxypropyl itaconate Alkanol esters of unsaturated carboxylic acids; general formula CH 2 ⁇ CR 1 —COO— (C n H 2n O) m —H (m is an integer from 2 to 9, n is an integer from 2 to 4, R 1 is hydrogen Or an ester of a polyalkylene glycol represented by (meth) acrylic acid represented by 2-hydro; Mono (meth) acrylic acid esters of dihydroxy esters of dicarboxylic acids such as cyethyl
- the hydrophilic group is preferably a carboxylic acid group or a sulfonic acid group because it is excellent in the binding property between the positive electrode active materials and the binding property between the positive electrode active material layer and the current collector described later.
- a carboxylic acid group is preferable because it efficiently captures transition metal ions that may be eluted from the positive electrode active material.
- the method for introducing the linear alkylene polymer unit into the polymer A is not particularly limited, but a method in which a polymer unit capable of forming a conjugated diene monomer is introduced and then subjected to a hydrogenation reaction is simple and preferable.
- the conjugated diene monomer is preferably a conjugated diene having 4 or more carbon atoms, and examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like. Of these, 1,3-butadiene is preferred. These can be used individually by 1 type or in combination of multiple types.
- the polymer A contains other polymerized units copolymerizable with monomers forming these polymerized units (hereinafter sometimes simply referred to as “other polymerized units”). You may contain.
- the other polymerized unit is formed by polymerizing another monomer copolymerizable with the monomer forming the polymerized unit (hereinafter, simply referred to as “other monomer”). Is a structural unit.
- the content ratio of such other polymerized units is preferably 40% by mass or less, more preferably 30% by mass or less, based on all polymerized units.
- Examples of such other monomers include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, which constitute the polymer unit of the (meth) acrylate monomer.
- Acrylic acid alkyl esters such as pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl Methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate Methacrylic acid alkyl esters such as acrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate
- Aromatic vinyl compounds Fluorine-containing vinyl compounds such as fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethyl styrene, vinyl pentafluorobenzoate, difluoroethylene, tetrafluoroethylene; 1,4-pentadiene, 1,4- Non-conjugated diene compounds such as hexadiene, vinyl norbornene, and dicyclopentadiene; ⁇ -olefin compounds such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene; methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, butoxy (meth) acrylate Alkoxyalkyl esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as ethyl; divinyl compounds such as divinylbenzene; di (meta) such as
- NMP N-methylpyrrolidone
- Acrylic acid alkyl ester having 2 to 12 carbon atoms in the alkyl group to be bonded is more preferable, and ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, and lauryl acrylate are particularly preferable.
- NMP is used as a solvent for the positive electrode slurry composition without eluting into the electrolyte, it exhibits solubility in NMP, and in addition, the positive electrode active material has excellent dispersibility and a uniform positive electrode can be obtained.
- aromatic vinyl compounds such as styrene and ⁇ -methylstyrene.
- the polymer A may contain polymer units that can be copolymerized therewith.
- Monomers copolymerizable with these include vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl biether; methyl vinyl ketone, ethyl vinyl ketone and butyl And vinyl ketones such as vinyl ketone, hexyl vinyl ketone and isopropenyl vinyl ketone; and heterocyclic ring-containing vinyl compounds such as N-vinyl pyrrolidone, vinyl pyridine and vinyl imidazole.
- the glass transition temperature (Tg) of the polymer A is preferably ⁇ 100 ° C. or higher and lower than 25 ° C., more preferably ⁇ 75 to 10 ° C., particularly preferably ⁇ 50 to 0 ° C.
- Tg of the polymer A is in the above range, the secondary battery positive electrode of the present invention has excellent strength and flexibility, so that powder fall-off in the positive electrode manufacturing process is suppressed, and the secondary battery using the positive electrode Cycle characteristics can be improved.
- the glass transition temperature of the polymer A can be prepared by combining various monomers.
- the production method of the polymer A is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
- the polymerization reaction any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
- the polymerization initiator used for the polymerization include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like.
- Organic peroxides, azo compounds such as ⁇ , ⁇ ′-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, and the like.
- the linear alkylene polymer unit is formed by introducing a polymer unit capable of forming a conjugated diene monomer having 4 or more carbon atoms and then hydrogenating it.
- the method for hydrogenation reaction is not particularly limited.
- unsaturated polymer polymer comprising a nitrile group-containing polymer unit, a hydrophilic group-containing polymer unit and a polymer unit capable of forming a conjugated diene monomer
- Only the carbon-carbon unsaturated bond derived from the polymerized unit capable of forming a conjugated diene monomer can be selectively hydrogenated to obtain the polymer A used in the present invention.
- the iodine value of the polymer A used for this invention can be made into the range mentioned above by hydrogenation reaction.
- the polymer A used in the present invention is preferably a hydrogenated acrylonitrile-butadiene copolymer having a hydrophilic group (hereinafter sometimes referred to as “hydrogenated NBR”).
- a selective hydrogenation method for selectively hydrogenating only carbon-carbon unsaturated bonds derived from polymerized units capable of forming a conjugated diene monomer in an unsaturated polymer a known method may be used. Either the hydration method or the aqueous layer hydrogenation method can be used, but the aqueous layer hydrogenation method is preferable because the content of impurities (for example, a coagulant or metal described later) is small in the obtained polymer A. .
- the polymer A is produced by the oil layer hydrogenation method, it is preferably carried out by the following method. That is, first, a dispersion of an unsaturated polymer prepared by emulsion polymerization is coagulated by salting out, dissolved in an organic solvent through filtration and drying. Subsequently, the unsaturated polymer dissolved in the organic solvent is subjected to a hydrogenation reaction (oil layer hydrogenation method) to obtain a hydride, and the obtained hydride solution is coagulated, filtered and dried. Polymer A to be used is obtained.
- capric acid in the polymer A finally obtained in each step of coagulation, filtration and drying by salting out the dispersion of the unsaturated polymer is used. It is preferable to prepare such that the amount of salt is 0.01 to 0.4% by mass.
- a known coagulant such as magnesium sulfate, sodium chloride, calcium chloride, or aluminum sulfate can be used in coagulation by salting out of the dispersion, but preferably an alkali such as magnesium sulfate, magnesium chloride, or magnesium nitrate.
- the amount of caprate contained in the unsaturated polymer can be reduced. Therefore, it is preferable to use an alkaline earth metal salt or a Group 13 metal salt as the coagulant, more preferably an alkaline earth metal salt, and finally by controlling the amount of use and the solidification temperature,
- the amount of caprate in the resulting polymer A can be in the above range.
- the amount of the coagulant used is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the unsaturated polymer to be hydrogenated. It is.
- the coagulation temperature is preferably 10 to 80 ° C.
- the solvent for the oil layer hydrogenation method is not particularly limited as long as it is a liquid organic compound that dissolves the unsaturated polymer, but benzene, toluene, xylene, hexane, cyclohexane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate, cyclohexanone, and acetone are preferable. used.
- any known selective hydrogenation catalyst can be used without limitation, and a palladium-based catalyst and a rhodium-based catalyst are preferable, and a palladium-based catalyst (such as palladium acetate, palladium chloride, and palladium hydroxide) is used. More preferred. Two or more of these may be used in combination, but when a rhodium catalyst and a palladium catalyst are used in combination, it is preferable to use a palladium catalyst as the main active ingredient.
- These catalysts are usually used by being supported on a carrier. Examples of the carrier include silica, silica-alumina, alumina, diatomaceous earth, activated carbon and the like.
- the amount of catalyst used is preferably 10 to 5000 ppm, more preferably 100 to 3000 ppm, in terms of the amount of metal in the hydrogenation catalyst, relative to the amount of unsaturated polymer to be hydrogenated.
- the hydrogenation reaction temperature of the oil layer hydrogenation method is preferably 0 to 200 ° C., more preferably 10 to 100 ° C., and the hydrogen pressure is preferably 0.1 to 30 MPa, more preferably 0.2 to 20 MPa.
- the reaction time is preferably 1 to 50 hours, more preferably 2 to 25 hours.
- the dispersion of the unsaturated polymer prepared by emulsion polymerization is diluted with water as necessary to carry out a hydrogenation reaction.
- aqueous layer hydrogenation method hydrogen is supplied to a reaction system in the presence of a hydrogenation catalyst to hydrogenate (I) an aqueous layer direct hydrogenation method, and in the presence of an oxidizing agent, a reducing agent and an activator.
- a hydrogenation catalyst to hydrogenate (I) an aqueous layer direct hydrogenation method, and in the presence of an oxidizing agent, a reducing agent and an activator.
- water layer indirect hydrogenation methods in which hydrogenation is carried out by reduction.
- the concentration of the unsaturated polymer in the aqueous layer is preferably 40% by mass or less in order to prevent aggregation.
- the hydrogenation catalyst used is not particularly limited as long as it is a compound that is difficult to decompose with water.
- palladium catalysts include palladium salts of carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid and phthalic acid; palladium chloride, dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) ) Palladium chloride such as palladium and ammonium hexachloropalladium (IV); Iodide such as palladium iodide; Palladium sulfate dihydrate and the like.
- carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid and phthalic acid
- palladium chloride dichloro (cyclooctadiene) palladium, dichloro (norbornadiene)
- Palladium chloride such as palladium and ammonium hexachloropalladium (IV)
- Iodide such as palladium iod
- the amount of the hydrogenation catalyst used may be determined as appropriate, but is preferably 5 to 6000 ppm, more preferably 10 to 4000 ppm, in terms of the amount of metal in the hydrogenation catalyst, relative to the amount of unsaturated polymer to be hydrogenated. is there.
- the reaction temperature in the aqueous layer direct hydrogenation method is preferably 0 to 300 ° C, more preferably 20 to 150 ° C, and particularly preferably 30 to 100 ° C. If the reaction temperature is too low, the reaction rate may decrease. Conversely, if the reaction temperature is too high, side reactions such as a hydrogenation reaction of a nitrile group may occur.
- the hydrogen pressure is preferably 0.1 to 30 MPa, more preferably 0.5 to 20 MPa.
- the reaction time is selected in consideration of the reaction temperature, hydrogen pressure, target hydrogenation reaction rate, and the like.
- the concentration of the unsaturated polymer in the aqueous layer is preferably 1 to 50% by mass, more preferably 1 to 40% by mass.
- oxidizing agent used in the water layer indirect hydrogenation method examples include oxygen, air, and hydrogen peroxide.
- the amount of these oxidizing agents used is preferably a molar ratio to the carbon-carbon double bond (oxidizing agent: carbon-carbon double bond), preferably 0.1: 1 to 100: 1, more preferably 0.8: 1. In the range of 5: 1.
- reducing agent used in the aqueous layer indirect hydrogenation method hydrazines such as hydrazine, hydrazine hydrate, hydrazine acetate, hydrazine sulfate, and hydrazine hydrochloride, or compounds that liberate hydrazine are used.
- the amount of these reducing agents used is preferably a molar ratio to the carbon-carbon double bond (reducing agent: carbon-carbon double bond), preferably 0.1: 1 to 100: 1, more preferably 0.8: It is in the range of 1-5: 1.
- activator used in the water layer indirect hydrogenation method ions of metals such as copper, iron, cobalt, lead, nickel, iron and tin are used.
- the amount of these activators to be used is a molar ratio to the carbon-carbon double bond (activator: carbon-carbon double bond), preferably 1: 1000 to 10: 1, more preferably 1:50 to 1: 2.
- the reaction in the water layer indirect hydrogenation method is carried out by heating within the range from 0 ° C. to the reflux temperature, whereby the hydrogenation reaction is carried out.
- the heating range at this time is preferably 0 to 250 ° C., more preferably 20 to 100 ° C., and particularly preferably 40 to 80 ° C.
- the direct hydrogenation method and the indirect hydrogenation method in the aqueous layer it is preferable to perform solidification by salting out, filtration and drying after the hydrogenation.
- the salting out is performed in order to control the amount of caprate in the polymer A after the hydrogenation reaction in the same manner as the salting out of the dispersion of the unsaturated polymer in the oil layer hydrogenation method.
- the filtration and drying steps subsequent to coagulation can be performed by known methods.
- the method for producing the polymer A is particularly preferably a method in which the hydrogenation reaction is carried out in two or more stages. Even when the same amount of hydrogenation catalyst is used, the hydrogenation reaction efficiency can be increased by carrying out the hydrogenation reaction in two or more stages. That is, when the polymer unit composed of the conjugated diene monomer is converted into the linear alkylene polymer unit, the iodine value of the polymer A can be further reduced.
- the hydrogenation reaction rate (hydrogenation ratio) (%) in the first stage should be 50% or more, more preferably 70% or more. Is preferred. That is, when the value obtained by the following formula is the hydrogenation reaction rate (%), this value is preferably 50% or more, and more preferably 70% or more.
- the amount of carbon-carbon double bond can be analyzed using NMR.
- the hydrogenation reaction catalyst in the dispersion is removed.
- an adsorbent such as activated carbon or ion exchange resin can be added to adsorb the hydrogenation reaction catalyst with stirring, and then the dispersion can be filtered or centrifuged. It is also possible to leave the hydrogenation reaction catalyst in the dispersion without removing it.
- the polymer A has a polymer unit having a hydrophilic group.
- a method for introducing a polymer unit having a hydrophilic group into the polymer A is not particularly limited, and a method for introducing a hydrophilic group into the polymer A in the production step of the polymer A described above (hydrophilic group is introduced). And a hydrogenation reaction by hydrogenating an unsaturated polymer comprising a polymer unit having the above nitrile group and a polymer unit capable of forming the above conjugated diene monomer.
- the obtained polymer (hereinafter sometimes referred to as “hydrogenated polymer”) is obtained, and then the hydrogenated polymer and the ethylenically unsaturated carboxylic acid or anhydride thereof are mixed (hydrogenated weight). And a method of acid-modifying the coalescence).
- a method of copolymerizing a monomer having a hydrophilic group is preferable because it is simple in the process.
- polymer A contains a hydrophilic group
- the positive electrode active material is excellent in dispersibility and a uniform positive electrode can be obtained.
- the resistance in a positive electrode is reduced, As a result, the secondary battery which shows the outstanding cycling characteristics can be obtained.
- the binding property with the current collector is improved, the positive electrode structure can be maintained even after repeated charge and discharge, and the cycle characteristics are excellent.
- the polymer after hydrogenation reaction (hydrogenated polymer) is mixed with an ethylenically unsaturated carboxylic acid or anhydride thereof to give polymer A (hereinafter referred to as “acid-modified polymer A”).
- acid-modified polymer A The method for producing the hydrogenated polymer (method for acid-modifying the hydrogenated polymer) will be described in detail.
- the ethylenically unsaturated carboxylic acid or anhydride thereof used for producing the acid-modified polymer A is not particularly limited, but the ethylenically unsaturated dicarboxylic acid or anhydride thereof having 4 to 10 carbon atoms, Maleic anhydride is particularly preferred.
- ethylenically unsaturated carboxylic acid examples include ethylenically unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid: Ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid: Ethylenically unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride: Monomethyl maleate, monoethyl maleate, monopropyl maleate, mono-n-butyl maleate, monoisobutyl maleate, mono-n-pentyl maleate, mono-n-hexyl maleate, mono-2-ethylhexyl maleate, Monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, mono-n-butyl fumarate, monoisobutyl fumarate, mono-n-pentyl fumarate, mono-
- the acid-modified polymer A can be obtained, for example, by subjecting a hydrogenated polymer and an ethylenically unsaturated carboxylic acid or an anhydride thereof to an ene type addition reaction.
- the ene type addition reaction usually occurs by kneading a hydrogenated polymer and an ethylenically unsaturated carboxylic acid or an anhydride thereof at a high temperature without using a radical generator.
- a radical generator used, in addition to the generation of a gel, an ethylenically unsaturated carboxylic acid or anhydride thereof and a hydrogenated polymer cause a radical type addition reaction, so that an ene type addition reaction cannot be performed.
- the amount of the ethylenically unsaturated carboxylic acid or anhydride thereof is not particularly limited, but is usually 0.05 to 10 parts by mass of the ethylenically unsaturated carboxylic acid or anhydride thereof with respect to 100 parts by mass of the hydrogenated polymer.
- the amount is preferably 0.2 to 6 parts by mass.
- an ene type addition reaction for example, when an open type kneader such as a roll type kneader is used, molten ethylenically unsaturated carboxylic acid such as maleic anhydride or its anhydride is scattered, It may not be possible to carry out a simple addition reaction.
- a continuous kneader such as a single-screw extruder, a same-direction twin-screw extruder, or a different-direction rotating twin-screw extruder is used, the polymer A staying at the outlet of the extruder is gelled.
- the addition reaction cannot be performed efficiently, such as clogging of the die head. Further, a large amount of unreacted ethylenically unsaturated carboxylic acid or anhydride thereof may remain in the polymer A.
- the heat-sealed kneader can be arbitrarily selected from batch-type heat-sealed kneaders such as a pressure kneader, Banbury mixer, Brabender, etc. Among them, a pressure kneader is preferable.
- a specific process is performed at a temperature at which the ene-type addition reaction does not substantially occur. Specifically, an ethylenically unsaturated carboxylic acid or anhydride thereof and a hydrogenated polymer are pre-kneaded at 60 to 170 ° C., preferably 100 to 150 ° C., and the ethylenically unsaturated carboxylic acid or anhydride thereof is washed with water. Disperse uniformly in the addition polymer.
- the hydrogenated polymer may slip in the kneader and the ethylenically unsaturated carboxylic acid or its anhydride and the hydrogenated polymer may not be sufficiently mixed.
- the pre-kneading temperature is excessively high, the ethylenically unsaturated carboxylic acid or anhydride thereof thrown into the kneader may be scattered in a large amount, and the ene type addition reaction rate may be lowered.
- the temperature of the mixture of the hydrogenated polymer and the ethylenically unsaturated carboxylic acid or its anhydride during kneading is usually kept at 200 to 280 ° C., preferably 220 to 260 ° C.
- the method for maintaining the temperature is not particularly limited, but is usually achieved by flowing warm water or steam through the jacket of the kneader, or using shear heat generation.
- the jacket temperature is usually maintained at 70 to 250 ° C., preferably 130 to 200 ° C.
- shearing heat generation it is preferable to continue kneading with a kneader at a shear rate of 30 to 1000 S ⁇ 1 , preferably 300 to 700 S ⁇ 1 .
- shearing heat generation it is preferable because the temperature of the mixture can be easily controlled.
- the kneading time in the heat-sealed kneader is not particularly limited, but is usually 120 seconds to 120 minutes, preferably 180 seconds to 60 minutes.
- the ene type addition reaction may not sufficiently proceed. Moreover, when too high, generation
- the shear rate is excessively high, it is difficult to control the temperature of the mixture by shearing heat generation, the temperature of the mixture becomes too high, and generation of gels and burned products occurs, which is not preferable as an industrial production method. . On the other hand, if the shear rate is excessively low, the temperature of the mixture becomes too low, so that a sufficient ene-type addition reaction cannot be expected.
- gelling of the polymer A can be prevented by adding an anti-aging agent during kneading.
- an anti-aging agent is not particularly limited, amine type, amine ketone type, phenol type, benzimidazole type and other anti-aging agents for binders can be used.
- amine-based antioxidants include phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamide) diphenylamine, N, N-di-2-naphthyl-p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-N-isopropyl-p-phenylenediamine, N-phenyl-N- (1,3- And dimethylbutyl) -p-phenylenediamine and N-phenyl-N- (3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine.
- Examples of the amine ketone type antioxidant include 2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline and the like.
- phenolic antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2-methylenebis (4-ethyl- 6-tert-butylphenol), 2,2-methylenebis (4-methyl-6-tert-butylphenol), 4,4-butylidenebis (3-methyl-6-tert-butylphenol), 4,4-thiobis (3-methyl) -6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, and the like.
- benzimidazole antioxidant examples include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, metal salt of 2-mercaptomethylbenzimidazole, and the like.
- anti-aging agents are usually used in an amount of 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polymer A.
- the polymer A used in the present invention by adding 80% or more of the charged amount of the ethylenically unsaturated carboxylic acid or anhydride used for the ene type addition reaction to the hydrogenated polymer.
- the unreacted ethylenically unsaturated carboxylic acid or anhydride thereof remaining in the polymer A can be reduced to 5% or less of the charged amount. Therefore, this method is extremely useful for industrially stable production.
- the polymer A containing 0.05 to 20% by mass of a polymer unit having a hydrophilic group can be obtained by the production method described above.
- the polymer B is a polymer different from the polymer A, and has a glass transition temperature (Tg) of 25 ° C. or higher, preferably 35 ° C. or higher, more preferably 50 ° C. or higher.
- the upper limit of the Tg of the polymer B is not particularly limited, but is preferably 500 ° C. or less, more preferably 300 ° C. or less, and particularly preferably 200 ° C. or less.
- Tg of the polymer B is less than 25 ° C., the stress relaxation by the polymer B occurs in the pressing step when manufacturing the secondary battery positive electrode described later, and the positive electrode active material does not bite into the current collector surface.
- the interface resistance between the current collector and the positive electrode active material layer increases, and the output characteristics of the secondary battery deteriorate.
- the Tg of the polymer B in the above range, the binding property between the positive electrode active material layer and the current collector is improved and the interface resistance is lowered, and a secondary battery having excellent output characteristics can be obtained.
- the glass transition temperature of the polymer B can be adjusted by combining the kind of monomer which comprises the polymer B, or adjusting the quantity of the monomer which comprises.
- polymer B examples include polyvinyl chloride, styrene polymer, acrylonitrile polymer, polymethyl methacrylate, polycarbonate, polyphenylene oxide, polysulfone, polyethersulfone, polyarylate, polyetherimide, polyimide, polyaminobis.
- Maleimide polyethylene, polypropylene, nylon 6, nylon 66, polyoxymethylene, polyethylene terephthalate, polymethylpentene, polyphenylene sulfide, polyether ether ketone, polyvinylidene fluoride, polytetrafluoroethylene, polyfluorinated ethylene, hexafluoropropylene copolymer
- the polymer include aromatic polyesters and copolymers thereof. Among these, a styrene polymer, an acrylonitrile polymer, and polyvinylidene fluoride are preferable, and a styrene polymer and an acrylonitrile polymer are more preferable.
- the styrene polymer is a polymer having a styrene polymer unit, and specifically, a styrene homopolymer (polystyrene) or a copolymer of styrene and a monomer copolymerizable therewith.
- a styrene homopolymer polystyrene
- a copolymer of styrene and a monomer copolymerizable therewith the proportion of the styrene polymer unit is usually 10% by mass or more, preferably 15 to 98% by mass.
- Examples of monomers copolymerizable with styrene include aromatic monovinyl compounds other than styrene such as ⁇ -methylstyrene, fluorostyrene, and vinylpyridine; Acrylic ester monomers such as methyl acrylate, butyl acrylate, 2-ethylhexyl ethyl acrylate; Methacrylic acid ester monomers such as methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate; Conjugated diene monomers such as butadiene and isoprene; Vinyl ester compounds such as vinyl acetate; ⁇ -olefin compounds such as 4-methyl-1-pentene; Ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid; Ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid; Ethylen
- the acrylonitrile-based polymer is a polymer having an acrylonitrile polymer unit or a methacrylonitrile polymer unit, and specifically, polyacrylonitrile, polymethacrylonitrile, a copolymer of acrylonitrile and a monomer copolymerizable therewith.
- the ratio of acrylonitrile polymer units or methacrylonitrile polymer units in a copolymer of acrylonitrile or methacrylonitrile and a monomer copolymerizable therewith is usually 10% by mass or more, preferably 15 to 98% by mass. is there.
- Examples of the monomer copolymerizable with acrylonitrile and methacrylonitrile include the same monomers as those exemplified for the monomer copolymerizable with styrene.
- the polystyrene equivalent weight average molecular weight of the polymer B by gel permeation chromatography is preferably 10,000 to 10,000,000, more preferably 50,000 to 5,000,000, particularly preferably 100,000. 000 to 2,000,000.
- the production method of the polymer B is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be used.
- the polymerization reaction any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used.
- the polymerization initiator used for the polymerization include lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 3,3,5-trimethylhexanoyl peroxide, and the like.
- Organic peroxides, azo compounds such as ⁇ , ⁇ ′-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, and the like.
- the polymer A or the polymer B is a dispersion or a solution in which the polymer A or the polymer B is dispersed in a dispersion medium (water or an organic solvent) (hereinafter referred to as “polymer dispersion A” or It may be described as “polymer dispersion B”).
- the dispersion medium is not particularly limited as long as the polymer A or the polymer B can be uniformly dispersed or dissolved.
- water can be used as a dispersion medium from the viewpoint of being excellent in environmental viewpoint and having a high drying speed, but an organic solvent is preferably used from the viewpoint of dispersibility of the polymer A or the polymer B.
- organic solvents examples include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexane, and ethylcyclohexane.
- cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane
- aromatic hydrocarbons such as toluene, xylene, and ethylbenzene
- ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexane, and ethylcyclohexane.
- Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride; esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, ⁇ -caprolactone; acylonitriles such as acetonitrile and propionitrile; tetrahydrofuran, ethylene Ethers such as glycol diethyl ether: Alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; N-methyl Amides such as pyrrolidone and N, N-dimethylformamide may be mentioned.
- These dispersion media may be used alone, or two or more of these dispersion media may be mixed and used as a mixed solvent.
- the average particle diameter (dispersed particle diameter) of the polymer A dispersed in the particulate form is preferably 50 to 500 nm, more preferably 70 to 400 nm. Particularly preferred is 100 to 250 nm. When the average particle diameter of the polymer A is within this range, the strength and flexibility of the resulting positive electrode are good.
- the average particle size (dispersed particle size) of the polymer B is preferably 50 to 1,000 nm, more preferably 70 to 700 nm, and particularly preferably 100 to 500 nm. When the average particle diameter of the polymer B is within this range, the strength and flexibility of the positive electrode obtained are good.
- the average particle size of the polymer can be measured using a laser diffraction particle size measuring device (SALAD-2000A, manufactured by Shimadzu Corporation).
- the solid content concentration of the polymer dispersion A or the polymer dispersion B is usually 15 to 70% by mass, and 20 to 65%. % By mass is preferable, and 30 to 60% by mass is more preferable.
- the solid content concentration is within this range, workability in producing the positive electrode slurry composition described later is good.
- the polymer A or the polymer B may be obtained through a particulate metal removal step of removing particulate metal contained in the polymer dispersion A or the polymer dispersion B in the production process.
- the content of the particulate metal component contained in the polymer dispersion A or the polymer dispersion B is 10 ppm or less, thereby preventing metal ion crosslinking over time between the polymers in the positive electrode slurry composition described later. , Can prevent an increase in viscosity. Furthermore, there is little concern about self-discharge increase due to internal short circuit of the secondary battery or dissolution / precipitation during charging, and the cycle characteristics and safety of the battery are improved.
- the method for removing the particulate metal component from the polymer dispersion in the particulate metal removal step is not particularly limited.
- the particulate metal component is removed by filtration using a filtration filter, the removal method using a vibration sieve, or the centrifugation.
- the method, the method of removing by magnetic force, etc. are mentioned.
- the removal object is a metal component
- the method of removing by magnetic force is preferable.
- the method for removing by magnetic force is not particularly limited as long as it can remove the metal component, but in consideration of productivity and removal efficiency, a magnetic filter is preferably arranged in the production line of polymer A or polymer B. It is done by doing.
- the dispersant used in the above polymerization method may be one used in ordinary synthesis.
- Specific examples include sodium dodecylbenzenesulfonate, dodecylphenylethersulfonic acid.
- Benzene sulfonates such as sodium; alkyl sulfates such as sodium lauryl sulfate and sodium tetradodecyl sulfate; sulfosuccinates such as sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate; fatty acid salts such as sodium laurate; polyoxyethylene lauryl ether Ethoxy sulfate salts such as sulfate sodium salt, polyoxyethylene nonylphenyl ether sulfate sodium salt; alkane sulfonate salt; alkyl ether phosphate sodium salt; Nonionic emulsifiers such as xylethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyoxyethylene-polyoxypropylene block copolymer; gelatin, maleic anhydride-styrene copolymer, polyvinylpyrrolidon
- benzenesulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate
- alkyl sulfates such as sodium lauryl sulfate and sodium tetradodecylsulfate
- oxidation resistance is more preferable.
- it is a benzenesulfonate such as sodium dodecylbenzenesulfonate and sodium dodecylphenylethersulfonate.
- the addition amount of the dispersant can be arbitrarily set, and is usually about 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of monomers.
- the pH when the polymer A or the polymer B is dispersed in the dispersion medium is preferably 5 to 13, more preferably 5 to 12, and most preferably 10 to 12.
- the pH of the polymer A or the polymer B is in the above range, the storage stability of the polymer A or the polymer B is improved, and further, the mechanical stability is improved.
- the pH adjusting agent for adjusting the pH of the polymer A or the polymer B is an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide, or an alkali such as calcium hydroxide, magnesium hydroxide or barium hydroxide.
- Hydroxides such as metal hydroxides belonging to Group IIIA in the long periodic table such as earth metal oxides and aluminum hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earths such as magnesium carbonate
- organic amines include alkylamines such as ethylamine, diethylamine, and propylamine; alcohol amines such as monomethanolamine, monoethanolamine, and monopropanolamine; aqueous ammonia and the like Of ammonia; and the like.
- alkali metal hydroxides are preferable from the viewpoints of binding properties and operability, and sodium hydroxide, potassium hydroxide, and lithium hydroxide are particularly preferable.
- the content ratio of the polymer A and the polymer B in the binder composition for a positive electrode of the secondary battery of the present invention is preferably 1: 9 to 9: 1, more preferably 8: 2 by weight ratio (A: B). To 2: 8, particularly preferably 7: 3 to 3: 7.
- the secondary battery positive electrode binder composition of the present invention by setting the weight ratio of the content ratio of the polymer A and the polymer B within the above range, in the secondary battery positive electrode, the current collector, the positive electrode active material layer, Interfacial resistance is reduced, and a secondary battery positive electrode excellent in flexibility can be obtained. Moreover, since peeling (powder off) of the positive electrode active material layer in the secondary battery positive electrode can be suppressed, a secondary battery excellent in output characteristics can be obtained.
- the binder composition for a secondary battery positive electrode of the present invention may further contain other binder components.
- binder components various resin components can be used in combination.
- polyacrylate can be used.
- Specific examples of the polyacrylate include polybutyl acrylate and polyethyl acrylate.
- the content ratio of the other binder component is 100% by mass when the total amount of the binder (the total of the amount of the polymer A and the polymer B and the amount of the other binder) is 100% by mass. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. When the content ratio of the other binder component is within the above range, the resistance inside the battery is not increased, and excellent cycle characteristics can be exhibited.
- the binder composition for a secondary battery positive electrode of the present invention contains the polymer A and the polymer B, and is added to improve the coating properties of the slurry composition and the charge / discharge characteristics of the secondary battery, which will be described later.
- An agent can be added.
- additives include cellulose polymers such as carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, polyacrylates such as sodium polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, acrylic acid-vinyl alcohol copolymer, Examples include methacrylic acid-vinyl alcohol copolymer, maleic acid-vinyl alcohol copolymer, modified polyvinyl alcohol, polyethylene glycol, ethylene-vinyl alcohol copolymer, and partially saponified polyvinyl acetate.
- cellulose polymers such as carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose
- polyacrylates such as sodium polyacrylate
- polyvinyl alcohol polyethylene oxide
- polyvinyl pyrrolidone acrylic acid-vinyl alcohol copolymer
- methacrylic acid-vinyl alcohol copolymer maleic acid-vinyl alcohol copolymer
- modified polyvinyl alcohol polyethylene glycol
- the use ratio of these additives is preferably less than 300% by mass, more preferably 30% by mass or more and 250% by mass or less, and particularly preferably 40% by mass or more and 200% by mass with respect to the total solid content of the binder composition. It is as follows. If it is this range, the secondary battery positive electrode excellent in smoothness can be obtained.
- an isothiazoline compound or a chelate compound can be added. In addition to the method of adding these additives to the binder composition, these additives can also be added to the slurry composition for a secondary battery positive electrode of the present invention described later.
- the manufacturing method of the binder composition for secondary battery positive electrode of this invention is not specifically limited, The above-mentioned polymer dispersion A, polymer dispersion B, and an additive are added and mixed as needed. It is manufactured by.
- the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
- a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.
- Secondary battery positive electrode slurry composition The secondary battery positive electrode slurry composition of the present invention (sometimes referred to as "positive electrode slurry composition") is a secondary battery positive electrode binder composition and a positive electrode active material. Containing. Below, the aspect which uses the slurry composition for secondary battery positive electrodes of this invention as a slurry composition for lithium ion secondary battery positive electrodes is demonstrated.
- the positive electrode active material an active material capable of occluding and releasing lithium ions is used.
- the electrode active material for the positive electrode of the lithium ion secondary battery (positive electrode active material) is largely divided into an inorganic compound and an organic compound. Separated.
- Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
- Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
- Transition metal oxides include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O. 5 , V 6 O 13 and the like. Among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle stability and capacity of the obtained secondary battery.
- the lithium-containing composite metal oxide include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
- lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, and Ni—Mn—Al.
- Li 2 MbO 3 (0 ⁇ x ⁇ 1, Ma is an average
- Mb is one or more transition metals having an oxidation state of 4+).
- Li a [Mn 2 ⁇ x Md x ] O 4 (wherein a part of Mn of lithium manganate (LiMn 2 O 4 ) is substituted with another transition metal)
- Li a was replaced Mn with Fe Fe x Mn 2-x O 4-z (0 ⁇ a ⁇ 1,0 ⁇ x ⁇ 1,0 ⁇ z ⁇ 0.1) , since the cost is inexpensive
- LiNi 0.5 Mn 1.5 O 4 or the like in which Mn is replaced with Ni can replace all of Mn 3+ which is considered to be a structural deterioration factor, and the electrochemical reaction from Ni 2+ to Ni 4+ Therefore, a high operating voltage and a high capacity can be obtained, which is preferable.
- Mc is one or more transition metals having an average oxidation state of 3+
- Mc Mn, Co, etc., 0 ⁇ y ⁇ 2
- An olivine type lithium phosphate compound represented by Mn or Co may be partially substituted with other metals, and examples of metals that can be substituted include Fe, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, Si, B, and Mo. Can be mentioned.
- a positive electrode active material having a polyanion structure such as Li 2 MeSiO 4 (where Me is Fe, Mn), LiFeF 3 having a perovskite structure, Li 2 Cu 2 O 4 having an orthorhombic structure, and the like.
- a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
- An iron-based oxide having poor electrical conductivity may be used as an electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
- the positive electrode active material may be a mixture of the above inorganic compound and organic compound.
- the particle diameter of the positive electrode active material used in the present invention is appropriately selected in consideration of other constituent elements of the battery.
- the 50% volume cumulative diameter is Usually, the thickness is 0.1 to 50 ⁇ m, preferably 0.4 to 30 ⁇ m, and more preferably 1 to 20 ⁇ m. When the 50% volume cumulative diameter is within this range, a secondary battery having excellent output characteristics and a large charge / discharge capacity can be obtained, and a positive electrode slurry composition and a positive electrode for forming a positive electrode active material layer can be obtained. Easy to handle when manufacturing.
- the 50% volume cumulative diameter can be determined by measuring the particle size distribution by laser diffraction.
- the BET specific surface area of the positive electrode active material is preferably 0.1 to 10 m 2 / g, more preferably 0.2 to 1.0 m 2 / g.
- the “BET specific surface area” means a BET specific surface area determined by a nitrogen adsorption method, and is a value measured according to ASTM D3037-81.
- the positive electrode active material used in the present invention has a charging average voltage of less than 3.9 V with respect to lithium metal from the viewpoint of the high structural stability of the positive electrode active material itself during a long-term cycle and the oxidation stability of the electrolytic solution. It is preferable.
- the charging average voltage refers to a potential (plateau) at which the secondary battery is charged to the upper limit voltage by the constant current method and lithium is desorbed at that time.
- the upper limit voltage is a voltage that exceeds the voltage and may cause expansion and heat generation of the battery, which is the limit of ensuring safety.
- the total content (solid content equivalent amount) of the binder composition and the positive electrode active material is 100 parts by mass (solid content equivalent amount) of the positive electrode slurry composition.
- the amount is preferably 10 to 90 parts by mass, and more preferably 30 to 80 parts by mass.
- the content of the binder composition relative to the total amount of the positive electrode active material (solid content equivalent amount) is preferably 0.1 to 5 parts by mass, and more preferably 0. 5 to 2 parts by mass.
- the dispersion medium in the positive electrode slurry composition is not particularly limited as long as it can uniformly dissolve or disperse the binder composition, and either water or an organic solvent can be used.
- organic solvents include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexane, and ethylcyclohexane.
- Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone and ⁇ -caprolactone; Acylonitriles such as acetonitrile and propionitrile; Tetrahydrofuran, Ethers such as ethylene glycol diethyl ether; alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; N-methyl Amides such as lupyrrolidone and N, N-dimethylformamide may be mentioned.
- These dispersion media may be used alone or in combination of two or more as a mixed solvent.
- a positive electrode active material and a conductive agent described later are excellent in dispersibility, and a solvent having a low boiling point and high volatility is preferable because it can be removed in a short time and at a low temperature.
- Acetone, toluene, cyclohexanone, cyclopentane, tetrahydrofuran, cyclohexane, xylene, water, N-methylpyrrolidone, or a mixed solvent thereof is preferable.
- the solid content concentration of the positive electrode slurry composition is not particularly limited as long as it can be applied and immersed and has a fluid viscosity, but is generally about 10 to 80% by mass.
- the slurry composition for positive electrodes it is preferable to contain a electrically conductive agent.
- a electrically conductive agent conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used.
- the content of the conductive agent in the positive electrode slurry composition is preferably 1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material.
- the positive electrode slurry composition preferably contains a thickener.
- thickeners include cellulose polymers such as carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, and ammonium salts and alkali metal salts thereof; (modified) poly (meth) acrylic acid and ammonium salts and alkali metal salts thereof; ) Polyvinyl alcohols such as polyvinyl alcohol, copolymers of acrylic acid or acrylate and vinyl alcohol, maleic anhydride or copolymers of maleic acid or fumaric acid and vinyl alcohol; polyethylene glycol, polyethylene oxide, polyvinyl pyrrolidone, modified Examples include polyacrylic acid, oxidized starch, phosphate starch, casein, and various modified starches.
- the blending amount of the thickener is preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the positive electrode active material.
- the coating property and the adhesion with the current collector are good.
- “(modified) poly” means “unmodified poly” or “modified poly”
- “(meth) acryl” means “acryl” or “methacryl”.
- the positive electrode slurry composition may further contain other components such as a reinforcing material, a leveling agent, and an electrolytic solution additive having a function of suppressing electrolytic solution decomposition. It may be contained in the secondary battery positive electrode. These are not particularly limited as long as they do not affect the battery reaction.
- the reinforcing material various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used.
- a reinforcing material By using a reinforcing material, a tough and flexible positive electrode can be obtained, and excellent long-term cycle characteristics can be exhibited.
- the content of the reinforcing material in the slurry composition is usually 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material. By being included in the said range, a high capacity
- the leveling agent examples include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants.
- the content of the leveling agent in the positive electrode slurry composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material.
- the productivity, smoothness, and battery characteristics during the production of the positive electrode are excellent.
- the surfactant By containing the surfactant, the dispersibility of the positive electrode active material and the like in the positive electrode slurry composition can be improved, and the smoothness of the positive electrode obtained thereby can be improved.
- the electrolytic solution additive vinylene carbonate used in the positive electrode slurry composition and the electrolytic solution can be used.
- the content of the electrolytic solution additive in the positive electrode slurry composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material.
- the room temperature cycle characteristics and the high temperature characteristics are excellent.
- Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nano fine particles, the thixotropy of the positive electrode slurry composition can be controlled, and the leveling property of the positive electrode obtained thereby can be improved.
- the content of the nanoparticles in the positive electrode slurry composition is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material.
- the nanoparticles are in the above range, the slurry stability and productivity are excellent, and high battery characteristics are exhibited.
- the slurry composition for a secondary battery positive electrode is obtained by mixing the binder composition, the positive electrode active material, a conductive agent used as necessary, and the like.
- the amount of the dispersion medium used when preparing the positive electrode slurry composition is such that the solid content concentration of the positive electrode slurry composition is usually in the range of 1 to 80% by mass, preferably 5 to 50% by mass. .
- the binder composition is preferably dispersed uniformly.
- the mixing method is not particularly limited, and examples thereof include a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type.
- a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, a planetary mixer, and a planetary kneader can be used.
- the viscosity of the positive electrode slurry composition is usually 10 to 50,000 mPa ⁇ s, preferably 100 to 10,000 mPa ⁇ s, at room temperature when the positive electrode production method described later is carried out by the wet forming method (II). More preferably, it is in the range of 300 to 2,000 mPa ⁇ s.
- the positive electrode production method described later is carried out by the dry molding method (III)
- it is usually 10 to 3,000 mPa ⁇ s, preferably 30 to 1. , 500 mPa ⁇ s, more preferably in the range of 50 to 1,000 mPa ⁇ s.
- the viscosity of the positive electrode slurry composition is within this range, a uniform electrode can be obtained in the wet molding method, and the cycle characteristics of the resulting battery are also improved. In the dry molding method, the productivity of composite particles described later can be increased. Further, the higher the viscosity of the positive electrode slurry composition, the larger the spray droplets, and the larger the weight average particle diameter of the resulting composite particles.
- the viscosity is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
- the secondary battery positive electrode (sometimes referred to as “positive electrode”) of the present invention is formed by forming a positive electrode active material layer comprising the slurry composition for a secondary battery positive electrode of the present invention on a current collector. Become.
- the manufacturing method of the secondary battery positive electrode of the present invention is not particularly limited. Specifically, (I) a method of forming the positive electrode slurry composition into a sheet, laminating the obtained sheet on a current collector, and forming a positive electrode active material layer (sheet forming method), (II) A method of forming a positive electrode active material layer by applying the slurry composition for positive electrode on at least one side, preferably both sides of the current collector, and drying the mixture (wet molding method), and (III) composite particles from the positive electrode slurry composition Examples thereof include a method (dry molding method) that is prepared, supplied onto a current collector and sheet-molded to form a positive electrode active material layer.
- (II) wet molding method or (III) dry molding method is preferable.
- the wet molding method is excellent in the production efficiency of the secondary battery positive electrode, and
- the dry molding method is excellent in that the capacity of the obtained secondary battery positive electrode can be increased and the internal resistance can be reduced.
- the method for applying the positive electrode slurry composition onto the current collector is not particularly limited.
- the method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method.
- drying method examples include drying with warm air, hot air, low-humidity air, vacuum drying, and drying by irradiation with (far) infrared rays or electron beams.
- the drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
- the composite particles in the dry molding method refer to particles in which the binder composition, the positive electrode active material, and the like contained in the positive electrode slurry composition are integrated.
- the composite particles suitably used in the present invention are produced by granulating the binder composition of the present invention, the positive electrode active material, and a conductive agent used as necessary.
- the granulation method of the composite particles is not particularly limited, and is spray drying granulation method, rolling bed granulation method, compression granulation method, stirring granulation method, extrusion granulation method, crushing granulation method, fluidized bed It can be produced by a known granulation method such as a granulation method, a fluidized bed multifunctional granulation method, a pulse combustion type drying method, or a melt granulation method.
- the spray-drying granulation method is preferable because composite particles in which the binder composition and the conductive agent are unevenly distributed near the surface can be easily obtained.
- the secondary battery positive electrode of the present invention can be obtained with high productivity. Moreover, the internal resistance of the secondary battery positive electrode can be further reduced.
- the slurry composition for secondary battery positive electrode of the present invention is spray dried and granulated to obtain composite particles.
- Spray drying is performed by spraying and drying the positive electrode slurry composition in hot air.
- An atomizer is mentioned as an apparatus used for spraying the slurry composition for positive electrodes.
- the rotating disk method the positive electrode slurry composition is introduced almost at the center of the high-speed rotating disk, and the positive electrode slurry composition is released out of the disk by the centrifugal force of the disk. It is a method to form.
- the rotational speed of the disk depends on the size of the disk, but is usually 5,000 to 40,000 rpm, preferably 15,000 to 40,000 rpm. The lower the rotational speed of the disk, the larger the spray droplets and the larger the weight average particle diameter of the resulting composite particles.
- the rotating disk type atomizer include a pin type and a vane type, and a pin type atomizer is preferable.
- a pin-type atomizer is a type of centrifugal spraying device that uses a spraying plate, and the spraying plate has a plurality of spraying rollers removably mounted on a concentric circle along its periphery between upper and lower mounting disks.
- the slurry composition for the positive electrode is introduced from the center of the spray plate, adheres to the spray roller by centrifugal force, moves outward on the roller surface, and finally sprays away from the roller surface.
- the pressurization method is a method in which the positive electrode slurry composition is pressurized and sprayed from a nozzle to be dried.
- the temperature of the positive electrode slurry composition to be sprayed is usually room temperature, but it may be heated to room temperature or higher.
- the hot air temperature at the time of spray drying is usually 80 to 250 ° C., preferably 100 to 200 ° C.
- the method of blowing hot air is not particularly limited, for example, a method in which the hot air and the spray direction flow in the horizontal direction, a method in which the hot air is sprayed at the top of the drying tower and descends with the hot air, and the sprayed droplets and hot air are in countercurrent contact. And a system in which sprayed droplets first flow in parallel with hot air and then drop by gravity to make countercurrent contact.
- the minor axis diameter L s and the major axis diameter L l are values measured from a transmission electron micrograph image.
- the volume average particle diameter of the composite particles is usually in the range of 10 to 100 ⁇ m, preferably 20 to 80 ⁇ m, more preferably 30 to 60 ⁇ m.
- the volume average particle diameter can be measured using a laser diffraction particle size distribution analyzer.
- the feeder used in the step of supplying the composite particles onto the current collector is not particularly limited, but is preferably a quantitative feeder capable of supplying the composite particles quantitatively.
- the quantitative feeder preferably used in the present invention has a CV value of preferably 2 or less.
- Specific examples of the quantitative feeder include a gravity feeder such as a table feeder and a rotary feeder, and a mechanical force feeder such as a screw feeder and a belt feeder. Of these, the rotary feeder is preferred.
- the current collector and the supplied composite particles are pressurized with a pair of rolls to form a positive electrode active material layer on the current collector.
- the composite particles heated as necessary are formed into a sheet-like positive electrode active material layer by a pair of rolls.
- the temperature of the supplied composite particles is preferably 40 to 160 ° C., more preferably 70 to 140 ° C. When composite particles in this temperature range are used, there is no slip of the composite particles on the surface of the press roll, and the composite particles are continuously and uniformly supplied to the press roll. A positive electrode active material layer with little variation can be obtained.
- the temperature at the time of molding is usually 0 to 200 ° C., preferably higher than the melting point or glass transition temperature of the binder used in the present invention, and more preferably 20 ° C. or more higher than the melting point or glass transition temperature.
- the forming speed is usually larger than 0.1 m / min, preferably 35 to 70 m / min.
- the press linear pressure between the press rolls is usually 0.2 to 30 kN / cm, preferably 0.5 to 10 kN / cm.
- the arrangement of the pair of rolls is not particularly limited, but is preferably arranged substantially horizontally or substantially vertically.
- the current collector is continuously supplied between a pair of rolls, and the composite particles are supplied to at least one of the rolls so that the composite particles are supplied to the gap between the current collector and the rolls.
- the positive electrode active material layer can be formed by pressurization.
- the current collector is transported in the horizontal direction, the composite particles are supplied onto the current collector, and the supplied composite particles are leveled with a blade or the like as necessary.
- the positive electrode active material layer can be formed by supplying between a pair of rolls and applying pressure.
- the positive electrode active material is subjected to pressure treatment using a die press or a roll press. It is preferable to have a step of reducing the porosity of the layer.
- a preferable range of the porosity is 5 to 30%, more preferably 7 to 20%. If the porosity is too high, charging efficiency and discharging efficiency are deteriorated. When the porosity is too low, it is difficult to obtain a high volume capacity, and there arises a problem that the positive electrode active material layer easily peels off from the current collector. Further, when a curable polymer is used for the positive electrode binder composition, it is preferably cured.
- the thickness of the positive electrode active material layer in the secondary battery positive electrode of the present invention is usually 5 to 300 ⁇ m, preferably 10 to 250 ⁇ m. When the thickness of the positive electrode active material layer is in the above range, both load characteristics and cycle characteristics are high.
- the content ratio of the positive electrode active material in the positive electrode active material layer is preferably 90 to 99.9% by mass, more preferably 95 to 99% by mass.
- the current collector used in the present invention is not particularly limited as long as it is an electrically conductive and electrochemically durable material.
- a metal material is preferable because it has heat resistance.
- aluminum is particularly preferable as the current collector used for the secondary battery positive electrode.
- the shape of the current collector is not particularly limited, but a sheet shape having a thickness of about 0.001 to 0.5 mm is preferable.
- the current collector is preferably used after roughening in advance. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
- an abrasive cloth paper with a fixed abrasive particle, a grindstone, an emery buff, a wire brush provided with a steel wire or the like is used.
- an intermediate layer may be formed on the surface of the current collector, and among them, it is preferable to form a conductive adhesive layer.
- the secondary battery of the present invention is a secondary battery comprising a positive electrode, a negative electrode, a separator, and an electrolytic solution, and the positive electrode is the secondary battery positive electrode.
- the negative electrode is formed by laminating a negative electrode active material layer containing a negative electrode active material and a secondary battery negative electrode binder composition on a current collector.
- the negative electrode active material used in the present invention is a material that transfers electrons within the secondary battery negative electrode.
- Specific examples of negative electrode active materials for lithium ion secondary batteries include carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microbeads (MCMB), and pitch-based carbon fibers; high conductivity such as polyacene Examples include molecules. Crystalline carbonaceous materials such as graphite, natural graphite, and mesocarbon microbeads (MCMB) are preferable.
- a negative electrode active material metals, such as silicon, tin, zinc, manganese, iron, nickel, these alloys, the oxide or sulfate of the said metal or alloy can be used.
- lithium alloys such as lithium metal, Li—Al, Li—Bi—Cd, and Li—Sn—Cd, lithium transition metal nitride, silicone, and the like can be used.
- the said negative electrode active material can be used individually or in combination of 2 or more types.
- the shape of the negative electrode active material is preferably a granulated particle.
- a higher density electrode can be formed during electrode molding.
- the volume average particle diameter of the negative electrode active material is appropriately selected in consideration of other constituent elements of the battery, but is usually 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 5 to 20 ⁇ m. Further, the 50% volume cumulative diameter of the negative electrode active material is usually 1 to 50 ⁇ m, preferably 15 to 30 ⁇ m, from the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics.
- the tap density of the negative electrode active material is not particularly limited, but 0.6 g / cm 3 or more is preferably used.
- the content ratio of the negative electrode active material in the negative electrode active material layer is preferably 85 to 99% by mass, more preferably 88 to 97% by mass.
- the density of the negative electrode active material layer of secondary battery negative electrode is preferably 1.6 ⁇ 1.9g / cm 3, more preferably 1.65 ⁇ 1.85g / cm 3.
- the density of the negative electrode active material layer is in the above range, a high-capacity battery can be obtained.
- the binder composition for secondary battery negative electrode is not particularly limited, and a known one can be used.
- resins such as polyethylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyacrylic acid derivatives, polyacrylonitrile derivatives, acrylic soft heavy
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- polyacrylic acid derivatives polyacrylonitrile derivatives
- acrylic soft heavy A soft polymer such as a polymer, a diene soft polymer, an olefin soft polymer, or a vinyl soft polymer can be used. These may be used alone or in combination of two or more.
- the negative electrode further contains other components such as the above-described conductive agent, thickener, reinforcing material, leveling agent, and electrolyte additive having functions such as electrolyte solution decomposition suppression. Also good. These are not particularly limited as long as they do not affect the battery reaction.
- the current collector used for the above-described positive electrode of the secondary battery can be used, and is not particularly limited as long as it is a material having electrical conductivity and electrochemical durability. Copper is particularly preferred for the battery negative electrode.
- the thickness of the negative electrode active material layer is usually 5 to 300 ⁇ m, preferably 10 to 250 ⁇ m. When the thickness of the negative electrode active material layer is in the above range, both load characteristics and energy density are high.
- the negative electrode can be produced in the same manner as the above-described secondary battery positive electrode.
- the separator is a porous substrate having pores
- usable separators include (a) a porous separator having pores, and (b) a porous separator in which a polymer coat layer is formed on one or both sides. Or (c) a porous separator in which a porous resin coat layer containing an inorganic ceramic powder is formed.
- Non-limiting examples of these include solids such as polypropylene, polyethylene, polyolefin, or aramid porous separators, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoropropylene copolymers.
- the electrolytic solution used in the present invention is not particularly limited.
- a solution obtained by dissolving a lithium salt as a supporting electrolyte in a non-aqueous solvent can be used.
- the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and other lithium salts.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferably used. These can be used alone or in admixture of two or more.
- the amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered and the battery charging and discharging characteristics are lowered.
- the solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte.
- Alkyl carbonates such as carbonate (BC) and methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; tetrahydrofuran; sulfolane and dimethyl sulfoxide Sulfur-containing compounds are used.
- dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These can be used alone or in admixture of two or more. Moreover, it is also possible to use an electrolyte containing an additive. As the additive, carbonate compounds such as vinylene carbonate (VC) are preferable.
- VC vinylene carbonate
- Examples of the electrolytic solution other than the above include a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide and polyacrylonitrile with an electrolytic solution, and an inorganic solid electrolyte such as lithium sulfide, LiI, and Li 3 N.
- the manufacturing method of the secondary battery of the present invention is not particularly limited.
- the above-described negative electrode and positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery and placed in the battery container, and the electrolytic solution is injected into the battery container and sealed.
- an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate and the like can be inserted to prevent an increase in pressure inside the battery and overcharge / discharge.
- the shape of the battery may be any of a laminated cell type, a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
- Tg glass transition temperatures of polymer A and polymer B
- the glass transition temperatures (Tg) of the polymer A and the polymer B were measured based on JIS K 7121; 1987 using a differential scanning calorimeter (DSC6220SII manufactured by Nanotechnology Co., Ltd.).
- Viscosity change rate (%) (BA) / A ⁇ 100 A: Less than 10% B: 10% or more and less than 50% C: 50% or more and less than 100% D: 100% or more and less than 200% E: 200% or more and less than 500% F: 500% or more
- the positive electrode on which the positive electrode active material layer is formed is cut into a rectangle having a width of 1.0 cm and a length of 10 cm to form a test piece, and fixed with the positive electrode active material layer surface facing up.
- the stress when the cellophane tape was peeled off from one end of the test piece at a rate of 50 mm / min in the 180 ° direction was measured.
- the measurement was performed 10 times, the average value was obtained, and this was taken as the peel strength (N / m) and evaluated according to the following criteria. The higher the peel strength, the better the binding property of the positive electrode active material layer.
- C 10 N / m or more and less than 40 N / m
- D Less than 10 N / m
- the positive electrode was washed with acetone and the positive electrode active material layer was peeled off, and then cut into 10 mm ⁇ 50 mm strips to prepare five sample pieces.
- the arithmetic average roughness Ra was measured from the obtained contour curve according to JIS B0601; 2001 (ISO 4287; 1997). Measurement was performed on five sample pieces, and an average value was calculated.
- a 10-cell lithium ion secondary battery is charged to 4.3 V by a constant current method of 0.2 C, and then discharged to 3.0 V at 0.2 C to obtain a 0.2 C discharge capacity. Thereafter, the battery is charged to 4.3 V at 0.2 C, and then discharged to 3.0 V at 2 C to obtain the 2 C discharge capacity.
- the average value of 10 cells is a measured value (0.2C discharge capacity a, 2C discharge capacity b), and is expressed as a ratio of electric capacity between 2C discharge capacity b and 0.2C discharge capacity a (b / a (%)). Capacity retention ratio is obtained, and this is used as an evaluation criterion for output characteristics, and is evaluated according to the following criteria. Higher values indicate better output characteristics, that is, lower internal resistance.
- Example 1 [Production of polymer (A1)] In an autoclave equipped with a stirrer, 240 parts of ion exchange water, 2.5 parts of sodium alkylbenzenesulfonate, 20 parts of acrylonitrile, 30 parts of butyl acrylate and 4.5 parts of methacrylic acid were put in this order, and the inside of the bottle was replaced with nitrogen. Thereafter, 45.5 parts of 1,3-butadiene was injected, 0.25 part of ammonium persulfate was added, and a polymerization reaction was carried out at a reaction temperature of 40 ° C. to polymerize a polymer unit having a nitrile group, a polymer unit having a hydrophilic group, and a conjugate. A polymer comprising polymerized units capable of forming a diene monomer was obtained. The polymerization conversion was 85%, and the iodine value was 280 mg / 100 mg.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A1). Further, 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A1). After 100 g of the NMP solution was solidified with 1 liter of methanol, it was vacuum dried overnight at 60 ° C. to obtain a dried product and analyzed by NMR. As a result, the polymer (A1) was a nitrile group based on the total amount of the polymer.
- polymerized units 20% by mass of polymerized units (polymerized units derived from acrylonitrile), 45.5% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized from methacrylic acid) Unit) and other polymerized units (polymerized units derived from butyl acrylate) of 30% by mass.
- the polymerized units derived from 1,3-butadiene include 39.3% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.1% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer units 4 .1% by mass.
- the glass transition temperature of the polymer (A1) was ⁇ 30 ° C.
- the iodine value of the polymer (A1) was 10 mg / 100 mg.
- a combined aqueous dispersion was obtained. Subsequently, the polymer aqueous dispersion was cooled to 25 ° C., and ammonia water was added thereto to adjust the pH to 7. After that, steam was introduced to remove unreacted monomers, and the average particle size was 250 ⁇ m. An aqueous dispersion of the polymer (B1) was obtained. The polymerization conversion rate determined from the solid content concentration was approximately 99%. Further, 320 parts of N-methylpyrrolidone was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (B1). The glass transition temperature of the polymer (B1) was 66 ° C.
- An aluminum foil having a thickness of 20 ⁇ m was prepared as a current collector.
- the positive electrode slurry composition is applied on an aluminum foil with a comma coater so that the film thickness after drying is about 65 ⁇ m, dried at 60 ° C. for 20 minutes, 120 ° C. for 20 minutes, and then heated at 150 ° C. for 2 hours.
- a positive electrode raw material was obtained.
- This positive electrode original fabric was rolled by a roll press to produce a positive electrode comprising a positive electrode active material layer having a density of 2.5 g / cm 3 and an aluminum foil.
- the positive electrode had a thickness of 70 ⁇ m.
- peel strength measurement, electrode winding property evaluation, and current collector surface roughness evaluation were performed. The results are shown in Table 1.
- the positive electrode is cut into a disk shape with a diameter of 16 mm, and a separator made of a disk-shaped porous polypropylene film having a diameter of 18 mm and a thickness of 25 ⁇ m, a metallic lithium used as the negative electrode, and an expanded metal are sequentially laminated on the surface of the positive electrode active material layer.
- This was stored in a stainless steel coin-type outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.25 mm) provided with polypropylene packing.
- the electrolyte is poured into the container so that no air remains, and the outer container is fixed with a 0.2 mm thick stainless steel cap through a polypropylene packing, and the battery can is sealed, and the diameter is A lithium ion coin battery (half cell) having a thickness of 20 mm and a thickness of about 2 mm was produced.
- Example 2 Except that the following polymer (A2) was used as the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode, and a battery was produced. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- polymerized units derived from acrylonitrile 45% by mass of polymerized units (polymerized units derived from acrylonitrile), 19% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized units derived from methacrylic acid) 6% by mass and 30% by mass of other polymerized units (polymerized units derived from butyl acrylate).
- the polymerized units derived from 1,3-butadiene include 15.6% by mass of linear alkylene polymer units having 4 or more carbon atoms, 1.7% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer unit 1 .7% by mass.
- the glass transition temperature of the polymer (A2) was ⁇ 8 ° C.
- the iodine value of the polymer (A2) was 8 mg / 100 mg.
- Example 3 Except that the following polymer (A3) was used as the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode, thereby producing a battery. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A3).
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A3).
- 100 g of the NMP solution was coagulated with 1 liter of methanol, and then vacuum dried at 60 ° C. overnight to obtain a dried product, which was analyzed by NMR.
- the polymer (A3) was a nitrile group based on the total amount of the polymer.
- polymerized units polymerized units derived from acrylonitrile
- polymerized units derived from 1,3-butadiene polymerized units having a hydrophilic group (carboxylic acid group)
- polymerized units derived from methacrylic acid 6% by mass and 30% by mass of other polymerized units (polymerized units derived from butyl acrylate).
- the polymerized units derived from 1,3-butadiene are 48.4% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.6% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer unit 5 It was formed with 0.0 mass%.
- the glass transition temperature of the polymer (A3) was ⁇ 45 ° C.
- the iodine value of the polymer (A3) was 12 mg / 100 mg.
- Example 4 Except having used the following polymer (A4) as a polymer (A1), operation similar to Example 1 was performed, the positive electrode slurry composition and the positive electrode were obtained, and the battery was produced. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- polymerized units 20% by mass of polymerized units (polymerized units derived from acrylonitrile), 49.9% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized from methacrylic acid) Unit) and 0.1% by mass of other polymerized units (polymerized units derived from butyl acrylate).
- the polymerized units derived from 1,3-butadiene are 43.3% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.1% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer units 4 And 5% by mass.
- the glass transition temperature of the polymer (A4) was ⁇ 32 ° C.
- the iodine value of the polymer (A4) was 10 mg / 100 mg.
- Example 5 Except that the following polymer (A5) was used as the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode, thereby producing a battery. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A5).
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A5).
- 100 g of the NMP solution was solidified with 1 liter of methanol, it was vacuum dried overnight at 60 ° C. to obtain a dried product and analyzed by NMR.
- the polymer (A5) was a nitrile group based on the total amount of the polymer.
- polymerized units 20% by mass of polymerized units (polymerized units derived from acrylonitrile), 42% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized units derived from methacrylic acid) 8% by mass and 30% by mass of other polymerized units (polymerized units derived from butyl acrylate).
- the polymerized units derived from 1,3-butadiene are 36.1% by weight of linear alkylene polymer units having 4 or more carbon atoms, 2.1% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer units 3 Further, the glass transition temperature of the polymer (A5) comprising -8% by mass was ⁇ 23 ° C. The iodine value of the polymer (A5) was 10 mg / 100 mg.
- Example 6 Except having used the following polymer (A6) as a polymer (A1), operation similar to Example 1 was performed, the positive electrode slurry composition and the positive electrode were obtained, and the battery was produced. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- polymerized units 20% by mass of polymerized units (polymerized units derived from acrylonitrile), 35% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized units derived from methacrylic acid) 15% by mass and 30% by mass of other polymerized units (polymerized units derived from butyl acrylate).
- the polymerized units derived from 1,3-butadiene are 29.9% by mass of linear alkylene polymer units having 4 or more carbon atoms, 1.9% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer units 3 .2% by mass.
- the glass transition temperature of the polymer (A6) was ⁇ 5 ° C.
- the iodine value of the polymer (A6) was 9 mg / 100 mg.
- Example 7 Except having used the following polymer (A7) as a polymer (A1), operation similar to Example 1 was performed, the positive electrode slurry composition and the positive electrode were obtained, and the battery was produced. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A7).
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A7).
- 100 g of the NMP solution was coagulated with 1 liter of methanol, it was vacuum dried overnight at 60 ° C. to obtain a dried product and analyzed by NMR.
- the polymer (A7) was a nitrile group based on the total amount of the polymer.
- the polymerized units derived from 1,3-butadiene include 39.3% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.1% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer units 4 .1% by mass.
- the glass transition temperature of the polymer (A7) was ⁇ 28 ° C.
- the iodine value of the polymer (A7) was 10 mg / 100 mg.
- Example 8 Except that the following polymer (A8) was used as the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode, thereby producing a battery. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A8).
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A8).
- 100 g of the NMP solution was coagulated with 1 liter of methanol, and then vacuum dried at 60 ° C. overnight to obtain a dried product, which was analyzed by NMR.
- the polymer (A8) was a nitrile group based on the total amount of the polymer.
- polymerized units 20% by mass of polymerized units (polymerized units derived from acrylonitrile), 14% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized units derived from methacrylic acid) And 61.5 mass% of other polymerized units (20 mass% of polymerized units derived from butyl acrylate and 41.5 mass% of polymerized units derived from methyl methacrylate).
- the polymerized unit derived from 1,3-butadiene is 11.2% by mass of linear alkylene polymer unit having 4 or more carbon atoms, 1.5% by mass of unhydrogenated butadiene polymer unit, and 1,2-addition polymer unit 1 And 3% by mass.
- the glass transition temperature of the polymer (A8) was 12 ° C.
- the iodine value of the polymer (A8) was 7 mg / 100 mg.
- Example 9 In the production of the positive electrode binder composition, the NMP solution of the polymer (A1) and the NMP solution of the polymer (B1) are mixed so that the solid content weight ratio is 2: 8, and the positive electrode binder composition is prepared. Except having been obtained, the same operation as in Example 1 was performed to obtain a slurry composition for positive electrode and a positive electrode, and a battery was produced. The results of each evaluation are shown in Table 1.
- Example 10 In the production of the positive electrode binder composition, the NMP solution of the polymer (A1) and the NMP solution of the polymer (B1) are mixed so that the solid content weight ratio is 1: 9, and the positive electrode binder composition is prepared. Except having been obtained, the same operation as in Example 1 was performed to obtain a slurry composition for positive electrode and a positive electrode, and a battery was produced. The results of each evaluation are shown in Table 1.
- Example 11 In the production of the positive electrode binder composition, the NMP solution of the polymer (A1) and the NMP solution of the polymer (B1) are mixed so that the solid content weight ratio is 8: 2, and the positive electrode binder composition is prepared. Except having been obtained, the same operation as in Example 1 was performed to obtain a slurry composition for positive electrode and a positive electrode, and a battery was produced. The results of each evaluation are shown in Table 1.
- Example 12 In the production of the positive electrode binder composition, the NMP solution of the polymer (A1) and the NMP solution of the polymer (B1) are mixed so that the solid content weight ratio is 9: 1. Except having obtained, operation similar to Example 1 was performed, the positive electrode slurry composition and the positive electrode were obtained, and the battery was produced. The results of each evaluation are shown in Table 1. (Example 13) Except having used the following polymer (B2) as a polymer (B1), operation similar to Example 1 was performed, the positive electrode slurry composition and the positive electrode were obtained, and the battery was produced. The results of each evaluation are shown in Table 1.
- a combined aqueous dispersion was obtained.
- the polymer aqueous dispersion was cooled to 25 ° C., and ammonia water was added thereto to adjust the pH to 7. Then, steam was introduced to remove unreacted monomers, and the average particle size was 280 ⁇ m.
- An aqueous dispersion of the polymer (B2) was obtained.
- the polymerization conversion rate determined from the solid content concentration was approximately 99%.
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (B2).
- the glass transition temperature of the polymer (B2) was 36 ° C.
- Example 1 Comparative Example 1 Except that the following polymer (A9) was used as the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode, thereby producing a battery. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A9).
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A9).
- 100 g of the NMP solution was coagulated with 1 liter of methanol, and then vacuum dried at 60 ° C. overnight to obtain a dried product, which was analyzed by NMR.
- the polymer (A9) was a nitrile group based on the total amount of the polymer.
- the polymerized units derived from 1,3-butadiene include 38.8% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.1% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer units 4 .1% by mass.
- the glass transition temperature of the polymer (A9) was ⁇ 26 ° C.
- the iodine value of the polymer (A9) was 10 mg / 100 mg.
- Example 2 Comparative Example 2 Except that the following polymer (A10) was used as the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode, thereby producing a battery. The results of each evaluation are shown in Table 1.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the contents were returned to room temperature, the inside of the system was made into a nitrogen atmosphere, and then concentrated using an evaporator until the solid content concentration became 40% to obtain an aqueous dispersion of polymer (A10).
- 320 parts of NMP was added to 100 parts of this aqueous dispersion, and water was evaporated under reduced pressure to obtain an NMP solution of the polymer (A10).
- 100 g of the NMP solution was coagulated with 1 liter of methanol, and then vacuum dried at 60 ° C. overnight to obtain a dried product, which was analyzed by NMR.
- the polymer (A10) was a nitrile group based on the total amount of the polymer.
- polymerized units 36.2% by mass of polymerized units (polymerized units derived from acrylonitrile) and 63.8% by mass of polymerized units derived from 1,3-butadiene.
- the polymerized units derived from 1,3-butadiene include 55.5% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.6% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer unit 5 .7% by mass.
- the glass transition temperature of the polymer (A10) was ⁇ 28 ° C.
- the iodine value of the polymer (A10) was 12 mg / 100 mg.
- the autoclave was returned to atmospheric pressure, and 25 mg of palladium acetate as a hydrogenation reaction catalyst was dissolved in 60 ml of water added with 4-fold mol of nitric acid with respect to Pd and added. After the inside of the system was replaced twice with hydrogen gas, the contents of the autoclave were heated to 50 ° C. while being pressurized with hydrogen gas up to 3 MPa, and the hydrogenation reaction (referred to as “second stage hydrogenation reaction”) was performed for 6 hours. )
- the polymer (A11) When analyzed by NMR, the polymer (A11) was found to have 20% by mass of polymerized units (polymerized units derived from acrylonitrile), 55% by mass of polymerized units derived from 1,3-butadiene, and polymerized units having a hydrophilic group (carboxylic acid group) (polymerized units derived from methacrylic acid) In an amount of 25% by mass.
- the polymerized units derived from 1,3-butadiene are 47.7% by mass of linear alkylene polymer units having 4 or more carbon atoms, 2.3% by mass of unhydrogenated butadiene polymer units, and 1,2-addition polymer unit 5 0.0 mass%.
- the glass transition temperature of the polymer (A11) was 8 ° C.
- the iodine value of the polymer (A11) was 11 mg / 100 mg.
- Example 4 Except that the NMP solution of the polymer (A1) was used as the positive electrode binder composition without using the polymer (B1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode. A battery was produced. The results of each evaluation are shown in Table 1.
- Example 5 Comparative Example 5 Except that the NMP solution of the polymer (B1) was used as the positive electrode binder composition without using the polymer (A1), the same operation as in Example 1 was performed to obtain a positive electrode slurry composition and a positive electrode. A battery was produced. The results of each evaluation are shown in Table 1.
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Abstract
Description
〔1〕ニトリル基を有する重合単位、親水性基を有する重合単位、及び炭素数4以上の直鎖アルキレン重合単位を含有する重合体A、及び
前記重合体Aとは異なる重合体であって、ガラス転移温度が25℃以上である重合体Bを含有し、
前記重合体Aの前記親水性基を有する重合単位の含有割合が0.05~20質量%であることを特徴とする二次電池正極用バインダー組成物。
前記正極が、〔7〕に記載の二次電池正極である二次電池。
本発明の二次電池正極用バインダー組成物(「正極用バインダー組成物」と記載することがある。)は、特定の重合体Aと重合体Bとを含有する。
本発明に用いる重合体Aは、ニトリル基を有する重合単位、親水性基を有する重合単位、及び炭素数4以上の直鎖アルキレン重合単位を含有する。ニトリル基を有する重合単位とは、ニトリル基を有する単量体を重合して形成される構造単位のことをいう。親水性基を有する重合単位とは、親水性基を有する単量体を重合して形成される構造単位のことをいう。炭素数4以上の直鎖アルキレン重合単位とは、炭素数4以上の直鎖アルキレン重合単位を形成しうる単量体を重合して形成される構造単位のことをいい、具体的には、炭素数4以上の共役ジエンモノマーを重合することにより形成される構造単位の、炭素-炭素二重結合の少なくとも一部を、水素添加することにより直鎖アルキレン構造とした構造単位をいう。ここで、重合体Aにおける各重合単位の割合は、通常、重合体Aの重合に用いる全単量体における、各重合単位を形成しうる上記単量体の比率(仕込み比)に一致する。なお、炭素数4以上の直鎖アルキレン重合単位を、上記の共役ジエンモノマーを重合して形成される構造単位の水素添加により形成する場合には、後述する水素添加反応率により、炭素数4以上の直鎖アルキレン重合単位の割合は制御される。したがって、炭素数4以上の直鎖アルキレン重合単位を形成しうる単量体の比率(仕込み比)は、重合体Aにおける共役ジエンモノマーを重合して形成される構造単位を水素添加した重合単位と、水素添加していない重合単位を合計したものの比率に一致する。
重合体A中の親水性基を有する重合単位の含有割合を上記範囲とすることで、正極活物質間及び正極活物質層と後述する集電体との間の結着性が向上し、正極の製造工程における正極活物質の一部の脱離(粉落ち)を低減できる。
ニトリル基を有する重合単位を形成し得る単量体としては、α,β-エチレン性不飽和ニトリル単量体が挙げられる。α,β-エチレン性不飽和ニトリル単量体としては、ニトリル基を有するα,β-エチレン性不飽和化合物であれば特に限定されないが、例えば、アクリロニトリル;α-クロロアクリロニトリル、α-ブロモアクリロニトリルなどのα-ハロゲノアクリロニトリル;メタクリロニトリルなどのα-アルキルアクリロニトリル;などが挙げられる。これらのなかでも、アクリロニトリルおよびメタクリロニトリルが好ましい。これらは一種単独でまたは複数種併せて用いることができる。
モノカルボン酸としては、アクリル酸、メタクリル酸、クロトン酸などが挙げられる。
モノカルボン酸誘導体としては、2-エチルアクリル酸、イソクロトン酸、α―アセトキシアクリル酸、β-trans-アリールオキシアクリル酸、α-クロロ-β-E-メトキシアクリル酸、β-ジアミノアクリル酸などが挙げられる。
ジカルボン酸としては、マレイン酸、フマル酸、イタコン酸などが挙げられる。
ジカルボン酸誘導体としては、メチルマレイン酸、ジメチルマレイン酸、フェニルマレイン酸、クロロマレイン酸、ジクロロマレイン酸、フルオロマレイン酸などマレイン酸メチルアリル、マレイン酸ジフェニル、マレイン酸ノニル、マレイン酸デシル、マレイン酸ドデシル、マレイン酸オクタデシル、マレイン酸フルオロアルキルなどのマレイン酸エステル;が挙げられる。
また、加水分解によりカルボキシル基を生成する酸無水物も使用できる。
ジカルボン酸の酸無水物としては、無水マレイン酸、アクリル酸無水物、メチル無水マレイン酸、ジメチル無水マレイン酸などが挙げられる。
その他、マレイン酸モノエチル、マレイン酸ジエチル、マレイン酸モノブチル、マレイン酸ジブチル、フマル酸モノエチル、フマル酸ジエチル、フマル酸モノブチル、フマル酸ジブチル、フマル酸モノシクロヘキシル、フマル酸ジシクロヘキシル、イタコン酸モノエチル、イタコン酸ジエチル、イタコン酸モノブチル、イタコン酸ジブチルなどのα,β-エチレン性不飽和多価カルボン酸のモノエステルおよびジエステルも挙げられる。
ここで、水層水素化法には、水素化触媒存在下の反応系に水素を供給して水素化する(I)水層直接水素化法と、酸化剤、還元剤および活性剤の存在下で還元して水素化する(II)水層間接水素化法とがある。
また、用いる水素化触媒としては、水で分解しにくい化合物であれば特に限定されない。水素化触媒の具体例として、パラジウム触媒では、ギ酸、プロピオン酸、ラウリン酸、コハク酸、オレイン酸、フタル酸などのカルボン酸のパラジウム塩;塩化パラジウム、ジクロロ(シクロオクタジエン)パラジウム、ジクロロ(ノルボルナジエン)パラジウム、ヘキサクロロパラジウム(IV)酸アンモニウムなどのパラジウム塩素化物;ヨウ化パラジウムなどのヨウ素化物;硫酸パラジウム・二水和物などが挙げられる。これらの中でもカルボン酸のパラジウム塩、ジクロロ(ノルボルナジエン)パラジウムおよびヘキサクロロパラジウム(IV)酸アンモニウムが特に好ましい。水素化触媒の使用量は、適宜定めればよいが、水素化する不飽和重合体の量に対して、水素化触媒の金属量換算で、好ましくは5~6000ppm、より好ましくは10~4000ppmである。
=100×(水素添加反応前の炭素-炭素二重結合量-水素添加反応後の炭素-炭素二重結合量)/(水素添加反応前の炭素-炭素二重結合量)
なお、炭素-炭素二重結合量は、NMRを用いて分析することができる。
マレイン酸、フマル酸、イタコン酸、シトラコン酸等のエチレン性不飽和ジカルボン酸:
無水マレイン酸、無水イタコン酸、無水シトラコン酸等のエチレン性不飽和ジカルボン酸無水物:
マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノプロピル、マレイン酸モノ-n-ブチル、マレイン酸モノイソブチル、マレイン酸モノ-n-ペンチル、マレイン酸モノ-n-ヘキシル、マレイン酸モノ-2-エチルヘキシル、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノプロピル、フマル酸モノ-n-ブチル、フマル酸モノイソブチル、フマル酸モノ-n-ペンチル、フマル酸モノ-n-ヘキシル、フマル酸モノ-2-エチルヘキシル、イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノプロピル、イタコン酸モノ-n-ブチル、イタコン酸モノイソブチル、イタコン酸モノ-n-ペンチル、イタコン酸モノ-n-ヘキシル、イタコン酸モノ-2-エチルヘキシル、シトラコン酸モノメチル、シトラコン酸モノエチル、シトラコン酸モノプロピル、シトラコン酸モノ-n-ブチル、シトラコン酸モノイソブチル、シトラコン酸モノ-n-ペンチル、シトラコン酸モノ-n-ヘキシル、シトラコン酸モノ-2-エチルヘキシル、メサコン酸モノメチル、メサコン酸モノエチル、メサコン酸モノプロピル、メサコン酸モノ-n-ブチル、メサコン酸モノイソブチル、メサコン酸モノ-n-ペンチル、メサコン酸モノ-n-ヘキシル、メサコン酸モノ-2-エチルヘキシル、グルタコン酸モノメチル、グルタコン酸モノエチル、グルタコン酸モノプロピル、グルタコン酸モノ-n-ブチル、グルタコン酸モノイソブチル、グルタコン酸モノイソブチル、グルタコン酸モノ-n-ペンチル、グルタコン酸モノ-n-ヘキシル、グルタコン酸モノ-2-エチルヘキシル、アリルマロン酸モノメチル、アリルマロン酸モノエチル、アリルマロン酸モノプロピル、アリルマロン酸モノ-n-ブチル、アリルマロン酸モノイソブチル、アリルマロン酸モノ-n-ペンチル、アリルマロン酸モノ-n-ヘキシル、アリルマロン酸モノ-2-エチルヘキシル、テラコン酸モノメチル、テラコン酸モノエチル、テラコン酸モノプロピル、テラコン酸モノ-n-ブチル、テラコン酸モノイソブチル、テラコン酸モノ-n-ペンチル、テラコン酸モノ-n-ヘキシル、テラコン酸モノ-2-エチルヘキシル等の不飽和ジカルボン酸モノアルキルエステル等が挙げられる。
重合体Bは、上記重合体Aとは異なる重合体であって、ガラス転移温度(Tg)が25℃以上、好ましくは35℃以上、より好ましくは50℃以上の重合体である。重合体BのTgの上限は特に限定されないが、好ましくは500℃以下、より好ましくは300℃以下、特に好ましくは200℃以下である。重合体BのTgが25℃未満であると、後述する二次電池正極を製造する際のプレス工程において、重合体Bによる応力緩和がおこり、正極活物質の集電体表面への食い込みが不十分となる結果、集電体と正極活物質層との間の界面抵抗が増大し、二次電池の出力特性が悪化する。重合体BのTgを上記範囲にすることにより、正極活物質層と集電体との結着性が向上すると共に界面抵抗が低下し、優れた出力特性を有する二次電池を得ることができる。なお、重合体Bのガラス転移温度は、重合体Bを構成する単量体の種類を組み合わせたり、構成する単量体の量を調整したりすることによって調整可能である。
その中でも、スチレン系重合体、アクリロニトリル系重合体、ポリフッ化ビニリデンが好ましく、スチレン系重合体、アクリロニトリル系重合体がより好ましい。
メチルアクリレート、ブチルアクリレート、2-エチルヘキシルエチルアクリレートなどのアクリル酸エステルモノマー;
メチルメタクリレート、ブチルメタクリレート、2-エチルヘキシルメタクリレートなどのメタクリル酸エステルモノマー;
ブタジエン、イソプレンなどの共役ジエンモノマー;
酢酸ビニルなどのビニルエステル化合物;
4-メチル-1-ペンテンなどのα-オレフィン化合物;
アクリル酸、メタクリル酸、クロトン酸などのエチレン性不飽和モノカルボン酸;
マレイン酸、フマル酸、イタコン酸などのエチレン性不飽和ジカルボン酸;
2-エチルアクリル酸、イソクロトン酸、α-アセトキシアクリル酸、β-trans-アリールオキシアクリル酸、α-クロロ-β-E-メトキシアクリル酸、β-ジアミノアクリル酸などのエチレン性不飽和モノカルボン酸の誘導体;
無水マレイン酸、アクリル酸無水物、メチル無水マレイン酸、ジメチル無水マレイン酸などのエチレン性不飽和ジカルボン酸の酸無水物;
メチルマレイン酸、ジメチルマレイン酸、フェニルマレイン酸、クロロマレイン酸、ジクロロマレイン酸、フルオロマレイン酸等のマレイン酸メチルアリルや、マレイン酸ジフェニル、マレイン酸ノニル、マレイン酸デシル、マレイン酸ドデシル、マレイン酸オクタデシル、マレイン酸フルオロアルキル等のマレイン酸エステルなどのエチレン性不飽和ジカルボン酸の誘導体;が挙げられる。
本発明においては、環境の観点に優れ、乾燥速度が速いという観点から分散媒として水を用いることもできるが、重合体Aまたは重合体Bの分散性の観点から有機溶媒を用いることが好ましい。
有機溶媒としては、シクロペンタン、シクロヘキサンなどの環状脂肪族炭化水素類;トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素類;アセトン、エチルメチルケトン、ジイソプロピルケトン、シクロヘキサノン、メチルシクロヘキサン、エチルシクロヘキサンなどのケトン類;メチレンクロライド、クロロホルム、四塩化炭素など塩素脂肪族炭化水素;芳酢酸エチル、酢酸ブチル、γ-ブチロラクトン、ε-カプロラクトンなどのエステル類;アセトニトリル、プロピオニトリルなどのアシロニトリル類;テトラヒドロフラン、エチレングリコールジエチルエーテルなどのエーテル類:メタノール、エタノール、イソプロパノール、エチレングリコール、エチレングリコールモノメチルエーテルなどのアルコール類;N-メチルピロリドン、N,N-ジメチルホルムアミドなどのアミド類が挙げられる。
これらの分散媒は、単独で使用しても、これらを2種以上混合して混合溶媒として使用してもよい。これらの中でも特に、後述の正極用スラリー組成物作製時に工業上使用されていること、製造上揮発しにくいこと、その結果、スラリー組成物の揮発を抑えられ、得られる正極の平滑性が向上することから、水、若しくはN-メチルピロリドンが好ましく、N-メチルピロリドンがより好ましい。
その他の結着剤成分としては、様々な樹脂成分を併用することができ、例えばポリアクリレートを用いることができる。ポリアクリレートの具体例としては、ポリブチルアクリレートやポリエチルアクリレートが挙げられる。
本発明の二次電池正極用バインダー組成物は、上記重合体Aおよび重合体Bを含有し、その他に、後述するスラリー組成物の塗布性や二次電池の充放電特性を向上させるために添加剤を加えることができる。これらの添加剤としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースなどのセルロース系ポリマー、ポリアクリル酸ナトリウムなどのポリアクリル酸塩、ポリビニルアルコール、ポリエチレンオキシド、ポリビニルピロリドン、アクリル酸-ビニルアルコール共重合体、メタクリル酸-ビニルアルコール共重合体、マレイン酸-ビニルアルコール共重合体、変性ポリビニルアルコール、ポリエチレングリコール、エチレン-ビニルアルコール共重合体、ポリ酢酸ビニル部分ケン化物などが挙げられる。これらの添加剤の使用割合は、バインダー組成物の固形分合計質量に対して、好ましくは300質量%未満、より好ましくは30質量%以上250質量%以下、特に好ましくは40質量%以上200質量%以下である。この範囲であれば、平滑性が優れた二次電池正極を得ることができる。また、添加剤として、イソチアゾリン系化合物やキレート化合物を加えることもできる。これらの添加剤は、バインダー組成物に添加する方法以外に、後述する本発明の二次電池正極用スラリー組成物に添加することもできる。
本発明の二次電池正極用バインダー組成物の製造方法は、特に限定されず、上述の重合体分散液Aと、重合体分散液Bと、必要に応じて添加剤とを添加し、混合することで製造される。混合方法は特に限定されず、例えば、撹拌式、振とう式、および回転式などの混合装置を使用した方法が挙げられる。また、ホモジナイザー、ボールミル、サンドミル、ロールミル、プラネタリーミキサーおよび遊星式混練機などの分散混練装置を使用した方法が挙げられる。
本発明の二次電池正極用スラリー組成物(「正極用スラリー組成物」と記載することがある。)は、上記二次電池正極用バインダー組成物及び正極活物質を含有する。以下においては、本発明の二次電池正極用スラリー組成物を、リチウムイオン二次電池正極用スラリー組成物として用いる態様について説明する。
正極活物質としては、リチウムイオンの吸蔵放出可能な活物質が用いられ、リチウムイオン二次電池正極用電極活物質(正極活物質)は、無機化合物からなるものと有機化合物からなるものとに大別される。
遷移金属硫化物としては、TiS2、TiS3、非晶質MoS2、FeS等が挙げられる。
リチウム含有複合金属酸化物としては、層状構造を有するリチウム含有複合金属酸化物、スピネル構造を有するリチウム含有複合金属酸化物、オリビン型構造を有するリチウム含有複合金属酸化物などが挙げられる。
正極用スラリー組成物においては、導電剤を含有することが好ましい。導電剤としては、アセチレンブラック、ケッチェンブラック、カーボンブラック、グラファイト、気相成長カーボン繊維、およびカーボンナノチューブ等の導電性カーボンを使用することができる。導電剤を含有することにより、正極活物質同士の電気的接触を向上させることができ、二次電池に用いる場合に放電レート特性を改善することができる。正極用スラリー組成物における導電剤の含有量は、正極活物質の総量100質量部に対して、好ましくは1~20質量部、より好ましくは1~10質量部である。
正極用スラリー組成物においては、増粘剤を含有することが好ましい。増粘剤としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースなどのセルロース系ポリマーおよびこれらのアンモニウム塩並びにアルカリ金属塩;(変性)ポリ(メタ)アクリル酸およびこれらのアンモニウム塩並びにアルカリ金属塩;(変性)ポリビニルアルコール、アクリル酸又はアクリル酸塩とビニルアルコールの共重合体、無水マレイン酸又はマレイン酸もしくはフマル酸とビニルアルコールの共重合体などのポリビニルアルコール類;ポリエチレングリコール、ポリエチレンオキシド、ポリビニルピロリドン、変性ポリアクリル酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプンなどが挙げられる。
正極用スラリー組成物には、上記成分のほかに、さらに補強材、レベリング剤、電解液分解抑制等の機能を有する電解液添加剤等の他の成分が含まれていてもよく、後述の二次電池正極中に含まれていてもよい。これらは電池反応に影響を及ぼさないものであれば特に限られない。
二次電池正極用スラリー組成物は、上記バインダー組成物、正極活物質および必要に応じ用いられる導電剤等を混合して得られる。正極用スラリー組成物を調製するときに使用する分散媒の量は、正極用スラリー組成物の固形分濃度が、通常1~80質量%、好ましくは5~50質量%の範囲となる量である。固形分濃度がこの範囲にあるときに、上記バインダー組成物が均一に分散するため好適である。
本発明の二次電池正極(「正極」と記載することがある。)は、本発明の二次電池正極用スラリー組成物からなる正極活物質層を集電体上に形成してなる。
本発明の二次電池正極の製造方法は、特に限定されない。具体的には、(I)上記正極用スラリー組成物をシート成形し、得られたシートを集電体上に積層し、正極活物質層を形成する方法(シート成形法)、(II)上記正極用スラリー組成物を集電体の少なくとも片面、好ましくは両面に塗布、乾燥し、正極活物質層を形成する方法(湿式成形法)、及び(III)上記正極用スラリー組成物から複合粒子を調製し、これを集電体上に供給してシート成形し、正極活物質層を形成する方法(乾式成形法)等が挙げられる。これらの中でも、(II)湿式成形法、又は(III)乾式成形法が好ましい。(II)湿式成形法は二次電池正極の生産効率に優れており、(III)乾式成形法は得られる二次電池正極の容量を高くでき、且つ内部抵抗を低減できる点で優れている。
本発明で用いる集電体は、電気導電性を有しかつ電気化学的に耐久性のある材料であれば特に制限されないが、耐熱性を有するため金属材料が好ましく、例えば、鉄、銅、アルミニウム、ニッケル、ステンレス鋼、チタン、タンタル、金、白金などが挙げられる。中でも、二次電池正極に用いる集電体としてはアルミニウムが特に好ましい。集電体の形状は特に制限されないが、厚さ0.001~0.5mm程度のシート状のものが好ましい。集電体は、正極活物質層との接着強度を高めるため、予め粗面化処理して使用するのが好ましい。粗面化方法としては、機械的研磨法、電解研磨法、化学研磨法などが挙げられる。機械的研磨法においては、研磨剤粒子を固着した研磨布紙、砥石、エメリバフ、鋼線などを備えたワイヤーブラシ等が使用される。また、正極活物質層と集電体との接着強度や導電性を高めるために、集電体表面に中間層を形成してもよく、中でも、導電性接着剤層を形成するのが好ましい。
本発明の二次電池は、正極、負極、セパレーター及び電解液を備えてなる二次電池であって、正極が、上記二次電池正極である。
負極は、負極活物質及び二次電池負極用バインダー組成物を含む負極活物質層が、集電体上に積層されてなる。
本発明に用いる負極活物質は、二次電池負極内で電子の受け渡しをする物質である。
リチウムイオン二次電池用負極活物質としては、具体的には、アモルファスカーボン、グラファイト、天然黒鉛、メソカーボンマイクロビーズ(MCMB)、及びピッチ系炭素繊維などの炭素質材料;ポリアセン等の導電性高分子などが挙げられる。好ましくは、グラファイト、天然黒鉛、メソカーボンマイクロビーズ(MCMB)などの結晶性炭素質材料である。また、負極活物質としては、ケイ素、錫、亜鉛、マンガン、鉄、ニッケル等の金属やこれらの合金、前記金属又は合金の酸化物や硫酸塩を使用できる。加えて、金属リチウム、Li-Al、Li-Bi-Cd、Li-Sn-Cd等のリチウム合金、リチウム遷移金属窒化物、シリコーン等も使用できる。上記負極活物質は、単独または2種類以上を組み合わせて使用することができる。
二次電池負極用バインダー組成物としては、特に制限されず公知のものを用いることができる。例えば、ポリエチレン、ポリテトラフルオロエチレン(PTFE)、ポリフッ化ビニリデン(PVDF)、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体(FEP)、ポリアクリル酸誘導体、ポリアクリロニトリル誘導体などの樹脂や、アクリル系軟質重合体、ジエン系軟質重合体、オレフィン系軟質重合体、ビニル系軟質重合体等の軟質重合体を用いることができる。これらは単独で使用しても、これらを2種以上併用してもよい。
セパレーターは気孔部を有する多孔性基材であって、使用可能なセパレーターとしては、(a)気孔部を有する多孔性セパレーター、(b)片面または両面に高分子コート層が形成された多孔性セパレーター、または(c)無機セラミック粉末を含む多孔質の樹脂コート層が形成された多孔性セパレーターが挙げられる。これらの非制限的な例としては、ポリプロピレン系、ポリエチレン系、ポリオレフィン系、またはアラミド系多孔性セパレーター、ポリビニリデンフルオリド、ポリエチレンオキシド、ポリアクリロニトリルまたはポリビニリデンフルオリドヘキサフルオロプロピレン共重合体などの固体高分子電解質用またはゲル状高分子電解質用の高分子フィルム、ゲル化高分子コート層がコートされたセパレーター、または無機フィラー、無機フィラー用分散剤からなる多孔膜層がコートされたセパレーターなどがある。
本発明に用いられる電解液は、特に限定されないが、例えば、非水系の溶媒に支持電解質としてリチウム塩を溶解したものが使用できる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどのリチウム塩が挙げられる。特に溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liは好適に用いられる。これらは、単独、または2種以上を混合して用いることができる。支持電解質の量は、電解液に対して、通常1質量%以上、好ましくは5質量%以上、また通常は30質量%以下、好ましくは20質量%以下である。支持電解質の量が少なすぎても多すぎてもイオン導電度は低下し電池の充電特性、放電特性が低下する。
本発明の二次電池の製造方法は、特に限定されない。例えば、上述した負極と正極とをセパレーターを介して重ね合わせ、これを電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口する。さらに必要に応じてエキスパンドメタルや、ヒューズ、PTC素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をすることもできる。電池の形状は、ラミネートセル型、コイン型、ボタン型、シート型、円筒型、角形、扁平型などいずれであってもよい。
重合体A及び重合体Bのガラス転移温度(Tg)は、示差走査熱量分析計(ナノテクノロジー社製 DSC6220SII)を用いて、JIS K 7121;1987に基づいて測定した。
重合体AのNMP溶液100グラムをメタノール1リットルで凝固した後、60℃で一晩真空乾燥した。乾燥した重合体Aのヨウ素価をJIS K6235;2006に従って測定した。
JIS Z8803:1991に準じて単一円筒形回転粘度計(25℃、回転数=60rpm、スピンドル形状:4)により正極用スラリー組成物の粘度を測定し、測定開始後1分の値を求め、これをスラリー粘度Aとした。また、正極用スラリー組成物作製1日後のスラリー粘度Bを測定した。正極用スラリー組成物の粘性変化率を下記の式より算出し、以下の基準で評価する。粘性変化率が低いほどスラリー安定性に優れることを示す。
粘性変化率(%)=(B-A)/A×100
A:10%未満
B:10%以上50%未満
C:50%以上100%未満
D:100%以上200%未満
E:200%以上500%未満
F:500%以上
正極活物質層を形成した正極を、幅1.0cm×長さ10cmの矩形に切って試験片とし、正極活物質層面を上にして固定する。試験片の正極活物質層表面にセロハンテープを貼り付けた後、試験片の一端からセロハンテープを50mm/分の速度で180°方向に引き剥がしたときの応力を測定した。測定を10回行い、その平均値を求めて、これをピール強度(N/m)とし、以下の基準で評価した。ピール強度が大きいほど正極活物質層の結着性に優れることを示す。
A:80N/m以上
B:40N/m以上80N/m未満
C:10N/m以上40N/m未満
D:10N/m未満
正極の正極活物質層側に径の異なる棒を載置し、正極を棒に巻き付けて正極活物質層が割れるかどうかを評価した。棒の直径が小さいほど、正極の捲回性に優れることを示す。捲回性に優れると、正極活物質層の剥がれを抑制することができるため、二次電池の出力特性に優れる。
A:2mmφで割れない
B:3mmφで割れない
C:4mmφで割れない
D:5mmφで割れない
集電体の表面粗さRaは次の方法で評価した。正極をアセトンで洗浄して正極活物質層を剥がした後、10mm×50mmの短冊に裁断し、試料片を5枚作製した。試料片(集電体)の表面粗さの測定はJIS B0651;2001(ISO3274;1996)に準拠した触針式表面粗さ測定機(触針先端の半径=0.5μm)で行った。JIS B0601;2001(ISO4287;1997)に準じ、得られた輪郭曲線より、算術平均粗さRaを測定した。5枚の試料片で測定を行い、平均値を算出した。表面粗さRaが大きいほど、正極活物質の集電体表面への食い込みが大きく、界面抵抗が小さいことを示す。
A:0.5μm以上
B:0.4μm以上0.5μm未満
C:0.3μm以上0.4μm未満
D:0.2μm以上0.3μm未満
E:0.2μm未満
10セルのリチウムイオン二次電池を0.2Cの定電流法によって4.3Vまで充電し、その後0.2Cにて3.0Vまで放電し、0.2C放電容量を求める。その後0.2Cにて4.3Vまで充電し、その後2Cにて3.0Vまで放電し、2C放電容量を求める。10セルの平均値を測定値(0.2C放電容量a、2C放電容量b)とし、2C放電容量bと0.2C放電容量aの電気容量の比(b/a(%))で表される容量保持率を求め、これを出力特性の評価基準とし、以下の基準で評価する。この値が高いほど出力特性に優れている、すなわち内部抵抗が小さいことを意味する。
A:60%以上
B:50%以上60%未満
C:40%以上50%未満
D:30%以上40%未満
E:20%以上30%未満
F:20%未満
〔重合体(A1)の製造〕
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート30部、メタクリル酸4.5部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン45.5部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
撹拌機付きのオートクレーブに、イオン交換水300部、アクリルニトリル25部、メチルメタクリレート40部、エチルアクリレート30部、メタクリル酸5部および分子量調整剤としてt一ドデシルメルカプタン0.05部、重合開始剤として過硫酸カリウム0.3部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム1.0部を入れ、十分に撹拝した後、70℃に加温して重合を行い、未反応の単量体を含有する重合体水分散液を得た。次いで、該重合体水分散液を25℃に冷却し、これにアンモニア水を添加してpHを7に調整後、スチームを導入して未反応の単量体を除去し、平均粒子径250μmの重合体(B1)の水分散液を得た。なお、固形分濃度から求めた重合転化率はほぼ99%であった。また、この水分散液100部にN-メチルピロリドン320部を加え、減圧下に水を蒸発させて、重合体(B1)のNMP溶液を得た。また、重合体(B1)のガラス転移温度は66℃であった。
上記の工程で得られた重合体(A1)のNMP溶液と重合体(B1)のNMP溶液とを、固形分重量比が6:4となるように混合し、正極用バインダー組成物を得た。
正極活物質として層状構造を有するコバルト酸リチウム(LiCoO2)(粒子径:12μm)100部と、アセチレンブラック(HS-100:電気化学工業)2.0部と、前記バインダー組成物を固形分相当量で1.0部と、適量のNMPとをプラネタリーミキサーにて攪拌し、正極用スラリー組成物を調製した。作製した正極用スラリー組成物を用いてスラリー安定性の評価を行った。結果を表1に示す。
前記正極を直径16mmの円盤状に切り抜き、この正極の正極活物質層面側に直径18mm、厚さ25μmの円盤状のポリプロピレン製多孔膜からなるセパレーター、負極として用いる金属リチウム、エキスパンドメタルを順に積層し、これをポリプロピレン製パッキンを設置したステンレス鋼製のコイン型外装容器(直径20mm、高さ1.8mm、ステンレス鋼厚さ0.25mm)中に収納した。この容器中に電解液を空気が残らないように注入し、ポリプロピレン製パッキンを介して外装容器に厚さ0.2mmのステンレス鋼のキャップをかぶせて固定し、電池缶を封止して、直径20mm、厚さ約2mmのリチウムイオンコイン電池(ハーフセル)を作製した。 なお、電解液としては、エチレンカーボネート(EC)とエチルメチルカーボネート(EMC)とをEC:EMC=3:7(20℃での容積比)で混合してなる混合溶媒にLiPF6を1モル/リットルの濃度で溶解させた溶液を用いた。この電池を用いて出力特性を評価した。結果を表1に示す。
重合体(A1)として、下記の重合体(A2)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル45部、ブチルアクリレート30部、メタクリル酸6部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン19部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は250mg/100mgであった。
重合体(A1)として、下記の重合体(A3)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル8部、ブチルアクリレート30部、メタクリル酸6部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン56部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は300mg/100mgであった。
重合体(A1)として、下記の重合体(A4)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート30部、メタクリル酸0.1部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン49.9部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
重合体(A1)として、下記の重合体(A5)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート30部、メタクリル酸8部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン42部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
重合体(A1)として、下記の重合体(A6)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート30部、メタクリル酸15部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン35部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
重合体(A1)として、下記の重合体(A7)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート30部、アクリルアミド-2-メチルプロパンスルホン酸4.5部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン45.5部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
重合体(A1)として、下記の重合体(A8)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート20部、メチルメタクリレート41.5部、メタクリル酸4.5部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン14部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は250mg/100mgであった。
正極用バインダー組成物の製造において、重合体(A1)のNMP溶液と重合体(B1)のNMP溶液とを、固形分重量比が2:8となるように混合し、正極用バインダー組成物を得たこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
正極用バインダー組成物の製造において、重合体(A1)のNMP溶液と重合体(B1)のNMP溶液とを、固形分重量比が1:9となるように混合し、正極用バインダー組成物を得たこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
正極用バインダー組成物の製造において、重合体(A1)のNMP溶液と重合体(B1)のNMP溶液とを、固形分重量比が8:2となるように混合し、正極用バインダー組成物を得たこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
正極用バインダー組成物の製造において、重合体(A1)のNMP溶液と重合体(B1)のNMP溶液とを、固形分重量比が9:1となるように混合し、正極用バインダー組成物を得たこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
(実施例13)
重合体(B1)として、下記の重合体(B2)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水300部、アクリルニトリル20部、メチルメタクリレート25部、エチルアクリレート50部、メタクリル酸5部および分子量調整剤としてt一ドデシルメルカプタン0.05部、重合開始剤として過硫酸カリウム0.3部、乳化剤としてドデシルベンゼンスルホン酸ナトリウム1.0部を入れ、十分に撹拝した後、70℃に加温して重合を行い、未反応の単量体を含有する重合体水分散液を得た。次いで、該重合体水分散液を25℃に冷却し、これにアンモニア水を添加してpHを7に調整後、スチームを導入して未反応の単量体を除去し、平均粒子径280μmの重合体(B2)の水分散液を得た。なお、固形分濃度から求めた重合転化率はほぼ99%であった。また、この水分散液100部にNMP320部を加え、減圧下に水を蒸発させて、重合体(B2)のNMP溶液を得た。また、重合体(B2)のガラス転移温度は36℃であった。
重合体(A1)として、下記の重合体(A9)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、ブチルアクリレート35部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン45部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
重合体(A1)として、下記の重合体(A10)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル36.2部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン63.8部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は300mg/100mgであった。
重合体(A1)として、下記の重合体(A11)を用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
撹拌機付きのオートクレーブに、イオン交換水240部、アルキルベンゼンスルホン酸ナトリウム2.5部、アクリロニトリル20部、メタクリル酸25部をこの順で入れ、ボトル内を窒素で置換した後、1,3-ブタジエン55部を圧入し、過硫酸アンモニウム0.25部を添加して反応温度40℃で重合反応させ、ニトリル基を有する重合単位、親水性基を有する重合単位及び共役ジエンモノマーを形成し得る重合単位を含んでなる重合体を得た。重合転化率は85%、ヨウ素価は280mg/100mgであった。
重合体(B1)を用いず、重合体(A1)のNMP溶液を正極用バインダー組成物として用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
重合体(A1)を用いず、重合体(B1)のNMP溶液を正極用バインダー組成物として用いたこと以外は、実施例1と同様の操作を行い、正極用スラリー組成物および正極を得、電池を作製した。各評価の結果を表1に示す。
Claims (9)
- ニトリル基を有する重合単位、親水性基を有する重合単位、及び炭素数4以上の直鎖アルキレン重合単位を含有する重合体A、及び
前記重合体Aとは異なる重合体であって、ガラス転移温度が25℃以上である重合体Bを含有し、
前記重合体Aの前記親水性基を有する重合単位の含有割合が0.05~20質量%であることを特徴とする二次電池正極用バインダー組成物。 - 前記重合体Aのヨウ素価が、3~20mg/100mgである請求項1に記載の二次電池正極用バインダー組成物。
- 前記重合体Aの前記ニトリル基を有する重合単位の含有割合が、2~50質量%である請求項1または2に記載の二次電池正極用バインダー組成物。
- 前記重合体Aのガラス転移温度が-100℃以上25℃未満である請求項1~3のいずれかに記載の二次電池正極用バインダー組成物。
- 前記重合体Aと前記重合体Bとの含有割合が、重量比でA:B=1:9~9:1である請求項1~4のいずれかに記載の二次電池正極用バインダー組成物。
- 請求項1~5のいずれかに記載の二次電池正極用バインダー組成物及び正極活物質を含有してなる二次電池正極用スラリー組成物。
- 請求項6に記載の二次電池正極用スラリー組成物からなる正極活物質層を集電体上に形成してなる二次電池正極。
- 正極、負極、セパレーター及び電解液を有する二次電池であって、
前記正極が、請求項7に記載の二次電池正極である二次電池。 - 請求項6に記載の二次電池正極用スラリー組成物を集電体の少なくとも片面に塗布、乾燥する工程を有する二次電池正極の製造方法。
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JPWO2013084990A1 (ja) | 2015-04-27 |
KR101941428B1 (ko) | 2019-01-23 |
KR20140106546A (ko) | 2014-09-03 |
US20150030922A1 (en) | 2015-01-29 |
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