JP6287856B2 - Lithium ion secondary battery - Google Patents
Lithium ion secondary battery Download PDFInfo
- Publication number
- JP6287856B2 JP6287856B2 JP2014551139A JP2014551139A JP6287856B2 JP 6287856 B2 JP6287856 B2 JP 6287856B2 JP 2014551139 A JP2014551139 A JP 2014551139A JP 2014551139 A JP2014551139 A JP 2014551139A JP 6287856 B2 JP6287856 B2 JP 6287856B2
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- JP
- Japan
- Prior art keywords
- positive electrode
- active material
- polymer
- secondary battery
- electrode active
- Prior art date
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- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 1
- HEPLMSKRHVKCAQ-UHFFFAOYSA-N lead nickel Chemical compound [Ni].[Pb] HEPLMSKRHVKCAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 description 1
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- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 229920000151 polyglycol Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- 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
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-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
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- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229960000776 sodium tetradecyl sulfate Drugs 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- UPUIQOIQVMNQAP-UHFFFAOYSA-M sodium;tetradecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOS([O-])(=O)=O UPUIQOIQVMNQAP-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Chemistry (AREA)
Description
本発明は、リチウムイオン二次電池に関し、さらに詳しくは高容量化を可能にしうるリチウムイオン二次電池に関する。 The present invention relates to a lithium ion secondary battery, and more particularly to a lithium ion secondary battery that can enable high capacity.
近年、ノート型パソコン、携帯電話、PDA(Personal Digital Assistant)などの携帯端末の普及が著しい。これら携帯端末の電源に用いられている二次電池には、ニッケル水素二次電池、リチウムイオン二次電池などが多用されている。携帯端末は、より快適な携帯性が求められて小型化、薄型化、軽量化、高性能化が急速に進み、その結果、携帯端末は様々な場で利用されるようになっている。 In recent years, portable terminals such as notebook computers, mobile phones, and PDAs (Personal Digital Assistants) have been widely used. As a secondary battery used for the power source of these portable terminals, 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. As a result, mobile terminals are used in various places.
また、電池に対しても、携帯端末に対するのと同様に、小型化、薄型化、軽量化、高性能化が要求されている。また、電池の高容量化のために活物質層中における活物質の配合量を増加するため、活物質を集電体上に固定するための結着材や導電性を確保するための導電材などの材料を減らすことが要求されている。 In addition, the battery is required to be smaller, thinner, lighter, and higher in performance as in the case of the portable terminal. Moreover, in order to increase the amount of the active material in the active material layer in order to increase the capacity of the battery, the binder for fixing the active material on the current collector and the conductive material for ensuring conductivity It is required to reduce materials such as.
リチウムイオン二次電池の高容量化を目的とし、Si等を含有する合金系活物質を用いたリチウムイオン二次電池用負極が開発されている(例えば特許文献1)。高容量化に伴い、充放電時の電圧も高くなりつつあり、エチレンカーボネートやプロピレンカーボネートなどからなる電解液では高電圧に耐えられず、分解することがあるため、フッ素系電解液添加剤を併用することも行われている。 For the purpose of increasing the capacity of a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery using an alloy-based active material containing Si or the like has been developed (for example, Patent Document 1). Along with the increase in capacity, the voltage during charging and discharging is also increasing, and electrolytes composed of ethylene carbonate, propylene carbonate, etc. cannot withstand high voltages and may decompose, so combined with fluorine electrolyte additives It has also been done.
一方、正極では、活物質層を形成するための結着剤としては、ポリフッ化ビニリデン(PVdF)などのフッ素含有重合体が使用されてきた。フッ素含有重合体は、電解液に溶解しないため、安定した結着性が期待されるが、PVdFなどのフッ素含有重合体は硬く、曲げ難いという性質がある。このため、電池の形状や大きさによっては、電極を捲回した後、押しつぶし所定形状に成形する際に、フッ素含有重合体のみを用いた場合には、活物質層にクラックが生じることがある。 On the other hand, in the positive electrode, a fluorine-containing polymer such as polyvinylidene fluoride (PVdF) has been used as a binder for forming the active material layer. Since the fluorine-containing polymer is not dissolved in the electrolytic solution, stable binding properties are expected, but fluorine-containing polymers such as PVdF are hard and difficult to bend. For this reason, depending on the shape and size of the battery, when only the fluorine-containing polymer is used when the electrode is wound and then crushed and formed into a predetermined shape, a crack may occur in the active material layer. .
さらに、高容量化を達成するため、特に正極において導電材であるカーボンブラック等を細粒化することが検討されている。しかし、フッ素含有重合体を単独で結着剤として使用した場合には、細粒化した導電材が凝集し、分散性が不十分になり、導電性が上がらず、容量の向上が図れないことがあった。 Furthermore, in order to achieve high capacity, it has been studied to refine carbon black or the like, which is a conductive material, particularly in the positive electrode. However, when a fluorine-containing polymer is used alone as a binder, the finely divided conductive material aggregates, the dispersibility becomes insufficient, the conductivity does not increase, and the capacity cannot be improved. was there.
リチウムイオン二次電池について、高容量化を達成するため、正極において、結着剤としてフッ素含有重合体を使用すると、活物質層にクラックが生じるといった問題があった。また、正極に用いる結着剤として、フッ素含有重合体とニトリルゴムとを併用することや、フッ素含有重合体と架橋アクリレート系重合体とを併用することが検討されている。 For a lithium ion secondary battery, when a fluorine-containing polymer is used as a binder in the positive electrode in order to achieve high capacity, there is a problem that cracks occur in the active material layer. In addition, as a binder used for the positive electrode, it has been studied to use a fluorine-containing polymer and a nitrile rubber in combination, or to use a fluorine-containing polymer and a crosslinked acrylate polymer in combination.
例えば、特許文献2では、リチウムイオン二次電池の活物質層を形成するための結着剤として、フッ素含有重合体とニトリルゴムとを併用している。しかしながら、結着剤量が多くなることにより、相対的に活物質密度は低下するため、充分な電池容量が得られないことがある。また、結着剤量が多くなるため、電解液に対する活物質層の膨潤度も高くなり、特に高電位サイクル時の剥離強度が低下し、サイクル特性が低下することがある。 For example, in Patent Document 2, a fluorine-containing polymer and nitrile rubber are used in combination as a binder for forming an active material layer of a lithium ion secondary battery. However, as the amount of the binder increases, the active material density relatively decreases, so that a sufficient battery capacity may not be obtained. In addition, since the amount of the binder increases, the degree of swelling of the active material layer with respect to the electrolytic solution also increases, and the peel strength particularly at the time of a high potential cycle decreases, and the cycle characteristics may decrease.
また、特許文献3では、結着剤としてフッ素含有重合体と架橋アクリレート系重合体とを併用している。しかしながら、架橋アクリレート系重合体を使用するため、活物質層の電解液に対する膨潤は抑制されるものの、架橋アクリレート系重合体が粒子状で存在するため、分散性が不十分となり、この結果、高電位サイクル特性が低下することがある。 In Patent Document 3, a fluorine-containing polymer and a crosslinked acrylate polymer are used in combination as a binder. However, since the cross-linked acrylate polymer is used, swelling of the active material layer with respect to the electrolytic solution is suppressed. However, since the cross-linked acrylate polymer is present in the form of particles, the dispersibility becomes insufficient. Potential cycle characteristics may deteriorate.
したがって、本発明の目的は、柔軟であり、屈曲時に活物質層のクラック発生がなく高電位サイクル特性に優れた高容量のリチウムイオン二次電池を提供することにある。 Accordingly, an object of the present invention is to provide a high-capacity lithium ion secondary battery that is flexible, does not generate cracks in an active material layer when bent, and has excellent high potential cycle characteristics.
本発明者らは前記の課題を解決すべく鋭意検討した結果、正極活物質を特定の物性を有するニトリル基含有アクリル重合体で被覆することで、ニトリル基含有アクリル重合体が正極用スラリー組成物の分散媒には溶解しつつも、溶解パラメーター(SP値)の近い電解液には溶解せずに適切な範囲で膨潤させることができることを見出した。さらに、正極に導電材粉末を使用することにより、高容量化を図りつつも、正極用結着剤としてフッ素含有重合体を使用することにより、柔軟であり、屈曲時に活物質層のクラック発生がなく、しかも活物質密度の高い電極が得られること、さらに、高電位サイクル特性に優れた高容量のリチウムイオン二次電池が得られることが分かった。これらの知見に基づいて本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have coated the positive electrode active material with a nitrile group-containing acrylic polymer having specific physical properties, so that the nitrile group-containing acrylic polymer is a slurry composition for positive electrode. It was found that it can be swollen in an appropriate range without being dissolved in an electrolyte solution having a solubility parameter (SP value) close to that of the dispersion medium. Furthermore, by using a conductive material powder for the positive electrode, while increasing the capacity, using a fluorine-containing polymer as a binder for the positive electrode is flexible, and cracking of the active material layer occurs when bent. In addition, it was found that an electrode having a high active material density was obtained, and that a high-capacity lithium ion secondary battery excellent in high potential cycle characteristics was obtained. The present invention has been completed based on these findings.
本発明の要旨は以下のとおりである。
〔1〕正極、負極及び非水電解液を備えるリチウムイオン二次電池であって、
前記正極が、正極活物質、正極用結着剤および導電材を含み、
前記正極活物質が、SP値が9〜11(cal/cm3)1/2のニトリル基含有アクリル重合体で被覆されており、
前記正極用結着剤がフッ素含有重合体を含む、リチウムイオン二次電池。The gist of the present invention is as follows.
[1] A lithium ion secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte,
The positive electrode includes a positive electrode active material, a positive electrode binder and a conductive material,
The positive electrode active material is coated with a nitrile group-containing acrylic polymer having an SP value of 9 to 11 (cal / cm 3 ) 1/2 ;
A lithium ion secondary battery, wherein the positive electrode binder comprises a fluorine-containing polymer.
〔2〕前記正極活物質が、Li、Mn、Co及びNiを含むリチウム過剰層状化合物である〔1〕に記載のリチウムイオン二次電池。 [2] The lithium ion secondary battery according to [1], wherein the positive electrode active material is a lithium-excess layered compound containing Li, Mn, Co, and Ni.
〔3〕前記負極が合金系活物質を含む〔1〕または〔2〕に記載のリチウムイオン二次電池。 [3] The lithium ion secondary battery according to [1] or [2], wherein the negative electrode includes an alloy-based active material.
〔4〕前記ニトリル基含有アクリル重合体の非水電解液に対する膨潤度が3倍以下で、THF不溶解分量が30質量%以下である〔1〕〜〔3〕のいずれかに記載のリチウムイオン二次電池。 [4] The lithium ion according to any one of [1] to [3], in which the nitrile group-containing acrylic polymer has a swelling degree of 3 times or less and a THF-insoluble content is 30% by mass or less. Secondary battery.
〔5〕前記導電材の粒子径が5〜40nmである〔1〕〜〔4〕のいずれかに記載のリチウムイオン二次電池。 [5] The lithium ion secondary battery according to any one of [1] to [4], wherein the conductive material has a particle size of 5 to 40 nm.
〔6〕前記正極活物質100質量部に対し、導電材が1〜3質量部、正極用結着剤が0.4〜2質量部含まれる、〔1〕〜〔5〕のいずれかに記載のリチウムイオン二次電池。 [6] In any one of [1] to [5], 1 to 3 parts by mass of a conductive material and 0.4 to 2 parts by mass of a positive electrode binder are included with respect to 100 parts by mass of the positive electrode active material. Lithium ion secondary battery.
〔7〕前記フッ素含有重合体が、ポリフッ化ビニリデンである〔1〕〜〔6〕のいずれかに記載のリチウムイオン二次電池。 [7] The lithium ion secondary battery according to any one of [1] to [6], wherein the fluorine-containing polymer is polyvinylidene fluoride.
〔8〕前記ニトリル基含有アクリル重合体が、エチレン性不飽和酸単量体単位を含む、〔1〕〜〔7〕のいずれかに記載のリチウムイオン二次電池。 [8] The lithium ion secondary battery according to any one of [1] to [7], wherein the nitrile group-containing acrylic polymer includes an ethylenically unsaturated acid monomer unit.
〔9〕前記ニトリル基含有アクリル重合体におけるエチレン性不飽和酸単量体単位の含有割合が10〜30質量%である、〔8〕に記載のリチウムイオン二次電池。 [9] The lithium ion secondary battery according to [8], wherein a content ratio of the ethylenically unsaturated acid monomer unit in the nitrile group-containing acrylic polymer is 10 to 30% by mass.
〔10〕捲回型パウチセルである、〔1〕〜〔9〕のいずれかに記載のリチウムイオン二次電池。 [10] The lithium ion secondary battery according to any one of [1] to [9], which is a wound pouch cell.
本発明によれば、正極に導電材粉末を使用し、正極活物質を特定の物性を有するニトリル基含有アクリル重合体で被覆し、結着剤としてフッ素含有重合体を使用することにより、柔軟であり、屈曲時に活物質層のクラック発生がないことに加えて、活物質密度の高い電極が得られる。また、優れた高電位サイクル特性を有するリチウムイオン二次電池を提供することができる。 According to the present invention, a conductive material powder is used for the positive electrode, the positive electrode active material is coated with a nitrile group-containing acrylic polymer having specific physical properties, and a fluorine-containing polymer is used as a binder. In addition, there is no generation of cracks in the active material layer when bent, and an electrode having a high active material density can be obtained. In addition, a lithium ion secondary battery having excellent high potential cycle characteristics can be provided.
以下、本発明をさらに詳細に説明する。本発明に係るリチウムイオン二次電池(以下、単に「二次電池」と記載することがある)は、正極、負極及び非水電解液を備える。正極は、正極活物質、正極用結着剤および導電材を含む。正極活物質は、SP値が9〜11(cal/cm3)1/2のニトリル基含有アクリル重合体で被覆されている。正極用結着剤はフッ素含有重合体である。以下、正極、負極及び非水電解液のそれぞれをさらに具体的に説明する。Hereinafter, the present invention will be described in more detail. A lithium ion secondary battery according to the present invention (hereinafter sometimes simply referred to as “secondary battery”) includes a positive electrode, a negative electrode, and a non-aqueous electrolyte. The positive electrode includes a positive electrode active material, a positive electrode binder, and a conductive material. The positive electrode active material is coated with a nitrile group-containing acrylic polymer having an SP value of 9 to 11 (cal / cm 3 ) 1/2 . The binder for positive electrode is a fluorine-containing polymer. Hereinafter, each of the positive electrode, the negative electrode, and the nonaqueous electrolytic solution will be described more specifically.
(正極)
正極は、集電体と、前記集電体上に積層される正極活物質層とからなる。正極活物質層は、正極活物質(A)、正極用結着剤(B)および導電材(C)を含み、必要に応じその他の成分を含む。また、正極活物質(A)は、SP値が9〜11(cal/cm3)1/2のニトリル基含有アクリル重合体で被覆された正極活物質である。(Positive electrode)
The positive electrode includes a current collector and a positive electrode active material layer laminated on the current collector. The positive electrode active material layer includes a positive electrode active material (A), a positive electrode binder (B), and a conductive material (C), and includes other components as necessary. The positive electrode active material (A) is a positive electrode active material coated with a nitrile group-containing acrylic polymer having an SP value of 9 to 11 (cal / cm 3 ) 1/2 .
(A)正極活物質
正極活物質は、リチウムイオンを挿入及び脱離可能な活物質が用いられ、このような正極活物質は、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。 (A) Positive electrode active material As the positive electrode active material, an active material capable of inserting and removing lithium ions is used. Such a positive electrode active material is roughly classified into an inorganic compound and an organic compound. The
無機化合物からなる正極活物質としては、遷移金属酸化物、遷移金属硫化物、リチウムと遷移金属とのリチウム含有複合金属酸化物などが挙げられる。
上記の遷移金属としては、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Mo等が使用される。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.
遷移金属酸化物としては、MnO、MnO2、V2O5、V6O13、TiO2、Cu2V2O3、非晶質V2O−P2O5、MoO3、V2O5、V6O13等が挙げられ、中でもサイクル特性と容量からMnO、V2O5、V6O13、TiO2が好ましい。
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。Examples of 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 characteristics and capacity.
The transition metal sulfide, TiS 2, TiS 3, amorphous MoS 2, FeS, and the like.
リチウム含有複合金属酸化物としては、例えば、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。 Examples of 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.
層状構造を有するリチウム含有複合金属酸化物としては、例えば、リチウム含有コバルト酸化物(LiCoO2)、リチウム含有ニッケル酸化物(LiNiO2)、Co−Ni−Mnのリチウム複合酸化物(Li(CoMnNi)O2)、Li、Mn、Co及びNiを含むリチウム過剰層状化合物(Li[Ni0.17Li0.2Co0.07Mn0.56]O2)、Ni−Mn−Alのリチウム複合酸化物、Ni−Co−Alのリチウム複合酸化物等が挙げられる。
スピネル構造を有するリチウム含有複合金属酸化物としては、例えば、マンガン酸リチウム(LiMn2O4)やMnの一部を他の遷移金属で置換したLi[Mn3/2M1/2]O4(ここでMは、Cr、Fe、Co、Ni、Cu等)等が挙げられる。Examples of the lithium-containing composite metal oxide having a layered structure include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn lithium composite oxide (Li (CoMnNi)). O 2 ), lithium-excess layered compound containing Li, Mn, Co and Ni (Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 ), lithium composite oxidation of Ni—Mn—Al And Ni-Co-Al lithium composite oxide.
Examples of the lithium-containing composite metal oxide having a spinel structure include Li [Mn 3/2 M 1/2 ] O 4 in which lithium manganate (LiMn 2 O 4 ) or a part of Mn is substituted with another transition metal. (Where M is Cr, Fe, Co, Ni, Cu, etc.).
オリビン型構造を有するリチウム含有複合金属酸化物としては、例えば、LiXMPO4(式中、Mは、Mn,Fe,Co,Ni,Cu,Mg,Zn,V,Ca,Sr,Ba,Ti,Al,Si,B及びMoから選ばれる少なくとも1種、0≦X≦2)で表されるオリビン型燐酸リチウム化合物が挙げられる。Examples of the lithium-containing composite metal oxide having an olivine structure include Li X MPO 4 (wherein M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti). An olivine type lithium phosphate compound represented by at least one selected from Al, Si, B and Mo, 0 ≦ X ≦ 2).
これらの中でも、サイクル特性と初期容量が優れることから、リチウム含有コバルト酸化物(LiCoO2)、リチウム含有ニッケル酸化物(LiNiO2)、Co−Ni−Mnのリチウム複合酸化物(Li(CoMnNi)O2)、Li、Mn、Co及びNiを含むリチウム過剰層状化合物(Li[Ni0.17Li0.2Co0.07Mn0.56]O2)、スピネル構造を有するリチウム含有複合金属酸化物(LiNi0.5Mn1.5O4)が好ましく、リチウム含有コバルト酸化物(LiCoO2)、Li、Mn、Co及びNiを含むリチウム過剰層状化合物(Li[Ni0.17Li0.2Co0.07Mn0.56]O2)がより好ましい。Among these, since cycle characteristics and initial capacity are excellent, lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and lithium composite oxide of Co—Ni—Mn (Li (CoMnNi) O) 2 ), a lithium-excess layered compound containing Li, Mn, Co and Ni (Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 ), a lithium-containing composite metal oxide having a spinel structure (LiNi 0.5 Mn 1.5 O 4 ) is preferred, a lithium-containing layered compound containing Li-containing cobalt oxide (LiCoO 2 ), Li, Mn, Co and Ni (Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 ) is more preferred.
有機化合物からなる正極活物質としては、例えば、ポリアセチレン、ポリ−p−フェニレンなどの導電性高分子を用いることもできる。
また、電気伝導性に乏しい、鉄系酸化物は、還元焼成時に炭素源物質を存在させることで、炭素材料で覆われた電極活物質として用いてもよい。
さらに、これら化合物を、部分的に元素置換したものを用いてもよい。
リチウムイオン二次電池用の正極活物質は、上記の無機化合物と有機化合物の混合物であってもよい。As the positive electrode active material made of an organic compound, for example, a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
Further, 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.
Further, those compounds obtained by partial element substitution of these compounds may be used.
The positive electrode active material for a lithium ion secondary battery may be a mixture of the above inorganic compound and organic compound.
正極活物質の体積平均粒子径は、通常1〜50μm、好ましくは2〜30μmである。正極活物質の体積平均粒子径が上記範囲にあることにより、正極活物質層における正極用結着剤の量を少なくすることができ、電池の容量の低下を抑制できる。また、正極活物質層を形成するためには、通常、正極活物質及び正極用結着剤を含むスラリー(以下、「正極用スラリー組成物」と記載することがある。)を用意するが、この正極用スラリー組成物を、塗布するのに適正な粘度に調製することが容易になり、均一な正極活物質層を得ることができる。 The volume average particle diameter of the positive electrode active material is usually 1 to 50 μm, preferably 2 to 30 μm. When the volume average particle diameter of the positive electrode active material is in the above range, the amount of the positive electrode binder in the positive electrode active material layer can be reduced, and a decrease in battery capacity can be suppressed. In order to form the positive electrode active material layer, a slurry containing a positive electrode active material and a positive electrode binder (hereinafter sometimes referred to as “positive electrode slurry composition”) is usually prepared. This positive electrode slurry composition can be easily prepared to have a viscosity suitable for application, and a uniform positive electrode active material layer can be obtained.
正極活物質層における正極活物質の含有割合は、好ましくは90〜99.9質量%、より好ましくは95〜99質量%である。正極活物質層における正極活物質の含有量を、上記範囲とすることにより、高い容量を示しながらも柔軟性、結着性を示すことができる。 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. By setting the content of the positive electrode active material in the positive electrode active material layer within the above range, flexibility and binding properties can be exhibited while exhibiting high capacity.
本発明における正極活物質(A)は、ニトリル基含有アクリル重合体で被覆されている。ニトリル基含有アクリル重合体で被覆された正極活物質(A)を用いることで、リチウムイオン二次電池の高電位でのサイクル特性が向上する。以下、ニトリル基含有アクリル重合体について説明する。 The positive electrode active material (A) in the present invention is coated with a nitrile group-containing acrylic polymer. By using the positive electrode active material (A) coated with the nitrile group-containing acrylic polymer, the cycle characteristics at a high potential of the lithium ion secondary battery are improved. Hereinafter, the nitrile group-containing acrylic polymer will be described.
ニトリル基含有アクリル重合体
ニトリル基含有アクリル重合体は、ニトリル基含有単量体単位及び(メタ)アクリル酸エステル単量体単位を含む重合体である。ニトリル基含有単量体単位は、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い、(メタ)アクリル酸エステル単量体単位は、(メタ)アクリル酸エステル単量体を重合して形成される構造単位のことをいう。ニトリル基含有アクリル重合体は、ニトリル基含有単量体単位及び(メタ)アクリル酸エステル単量体単位を含み、さらに必要に応じ、エチレン性不飽和酸単量体単位および、架橋性単量体などのその他の単量体から導かれる単量体単位を含む。これらの単量体単位は、当該単量体を重合して形成される構造単位である。ここで、各単量体の含有割合(単量体の仕込み比)は、通常、ニトリル基含有アクリル重合体における各単量体単位の含有割合と一致する。 Nitrile group-containing acrylic polymer The nitrile group-containing acrylic polymer is a polymer containing a nitrile group-containing monomer unit and a (meth) acrylate monomer unit. A nitrile group-containing monomer unit refers to a structural unit formed by polymerizing a monomer having a nitrile group, and a (meth) acrylate monomer unit is a single (meth) acrylate ester A structural unit formed by polymerizing a body. The nitrile group-containing acrylic polymer includes a nitrile group-containing monomer unit and a (meth) acrylic acid ester monomer unit, and if necessary, an ethylenically unsaturated acid monomer unit and a crosslinkable monomer And other monomer units derived from other monomers. These monomer units are structural units formed by polymerizing the monomers. Here, the content ratio of each monomer (monomer charge ratio) usually coincides with the content ratio of each monomer unit in the nitrile group-containing acrylic polymer.
ニトリル基含有単量体の具体例としては、アクリロニトリルやメタクリロニトリルなどが挙げられ、中でもアクリロニトリルが、集電体との密着性を高め、電極強度を向上できる点で好ましい。 Specific examples of the nitrile group-containing monomer include acrylonitrile, methacrylonitrile, and the like. Among them, acrylonitrile is preferable because it can improve the adhesion with the current collector and improve the electrode strength.
ニトリル基含有アクリル重合体におけるニトリル基含有単量体単位の含有割合は、好ましくは5〜35質量%、さらに好ましくは10〜30質量%、特に好ましくは15〜25質量%の範囲である。ニトリル基含有単量体単位の含有割合がこの範囲であると、集電体との密着性に優れ、得られる電極の強度が向上する。 The content ratio of the nitrile group-containing monomer unit in the nitrile group-containing acrylic polymer is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass. When the content ratio of the nitrile group-containing monomer unit is within this range, the adhesiveness to the current collector is excellent, and the strength of the obtained electrode is improved.
(メタ)アクリル酸エステル単量体単位は、一般式(1):CH2=CR1−COOR2(式中、R1は水素原子またはメチル基を、R2はアルキル基またはシクロアルキル基を表す。)で表される化合物由来の単量体を重合して形成される構造単位である。The (meth) acrylic acid ester monomer unit is represented by the general formula (1): CH 2 = CR 1 -COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group or a cycloalkyl group). It is a structural unit formed by polymerizing a monomer derived from the compound represented by
一般式(1)で表される化合物の具体例としては、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸t−ブチル、アクリル酸n−アミル、アクリル酸イソアミル、アクリル酸n−ヘキシル、アクリル酸2−エチルヘキシル、アクリル酸ラウリル、アクリル酸ステアリルなどのアクリレート;メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸n−ブチル、メタクリル酸イソブチル、メタクリル酸t−ブチル、メタクリル酸n−アミル、メタクリル酸イソアミル、メタクリル酸n−ヘキシル、メタクリル酸2−エチルヘキシル、メタクリル酸ラウリル、メタクリル酸ステアリルなどのメタクリレートが挙げられる。これらの中でも、アクリレートが好ましく、アクリル酸n−ブチルおよびアクリル酸2−エチルヘキシルが、得られる電極の強度を向上できる点で、特に好ましい。 Specific examples of the compound represented by the general formula (1) include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-amyl acrylate, Acrylates such as isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl Examples thereof include methacrylates such as t-butyl acid, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate and stearyl methacrylate. Among these, acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved.
(メタ)アクリル酸エステル単量体は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせてもよい。したがって、ニトリル基含有アクリル重合体は、(メタ)アクリル酸エステル単量体を、1種類だけ含んでいてもよく、2種類以上を任意の比率で組み合わせて含んでいてもよい。 A (meth) acrylic acid ester monomer may be used individually by 1 type, and may combine two or more types by arbitrary ratios. Therefore, the nitrile group-containing acrylic polymer may contain only one type of (meth) acrylic acid ester monomer, or may contain two or more types in combination at any ratio.
ニトリル基含有アクリル重合体中の(メタ)アクリル酸エステル単量体単位の含有割合は、好ましくは35〜85質量%、より好ましくは45〜80質量%、さらに好ましくは45〜75質量%、特に好ましくは50〜70質量%である。(メタ)アクリル酸エステル単量体単位の含有割合が前記範囲であるニトリル基含有アクリル重合体を用いると、電極の柔軟性が高く、非水電解液に対する膨潤性が抑制される。また、耐熱性が高く、かつ得られる電極の内部抵抗を小さくできる。 The content ratio of the (meth) acrylic acid ester monomer unit in the nitrile group-containing acrylic polymer is preferably 35 to 85% by mass, more preferably 45 to 80% by mass, still more preferably 45 to 75% by mass, particularly Preferably it is 50-70 mass%. When the nitrile group-containing acrylic polymer in which the content ratio of the (meth) acrylic acid ester monomer unit is within the above range is used, the electrode has high flexibility and suppresses swelling with respect to the non-aqueous electrolyte. Moreover, heat resistance is high and the internal resistance of the electrode obtained can be made small.
ニトリル基含有アクリル重合体は、上記ニトリル基含有単量体単位及び(メタ)アクリル酸エステル単量体単位に加えて、エチレン性不飽和酸単量体単位を含んでいてもよい。
エチレン性不飽和酸単量体単位は、エチレン性不飽和酸単量体を重合して形成される構造単位である。エチレン性不飽和酸単量体は、カルボキシル基、スルホン酸基、ホスフィニル基等の酸基を有するエチレン性不飽和単量体であり、特定の単量体に限定されない。エチレン性不飽和酸単量体の具体例は、エチレン性不飽和カルボン酸単量体、エチレン性不飽和スルホン酸単量体、エチレン性不飽和リン酸単量体等である。The nitrile group-containing acrylic polymer may contain an ethylenically unsaturated acid monomer unit in addition to the nitrile group-containing monomer unit and the (meth) acrylic acid ester monomer unit.
The ethylenically unsaturated acid monomer unit is a structural unit formed by polymerizing an ethylenically unsaturated acid monomer. The ethylenically unsaturated acid monomer is an ethylenically unsaturated monomer having an acid group such as a carboxyl group, a sulfonic acid group, or a phosphinyl group, and is not limited to a specific monomer. Specific examples of the ethylenically unsaturated acid monomer include an ethylenically unsaturated carboxylic acid monomer, an ethylenically unsaturated sulfonic acid monomer, and an ethylenically unsaturated phosphoric acid monomer.
エチレン性不飽和カルボン酸単量体の具体例としては、エチレン性不飽和モノカルボン酸及びその誘導体、エチレン性不飽和ジカルボン酸及びその酸無水物並びにそれらの誘導体が挙げられる。 Specific examples of the ethylenically unsaturated carboxylic acid monomer include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
エチレン性不飽和モノカルボン酸の例としては、アクリル酸、メタクリル酸、及びクロトン酸が挙げられる。 Examples of ethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
エチレン性不飽和モノカルボン酸の誘導体の例としては、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、及びβ−ジアミノアクリル酸が挙げられる。 Examples of ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic acid, And β-diaminoacrylic acid.
エチレン性不飽和ジカルボン酸の例としては、マレイン酸、フマル酸、及びイタコン酸が挙げられる。 Examples of ethylenically unsaturated dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
エチレン性不飽和ジカルボン酸の酸無水物の例としては、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、及びジメチル無水マレイン酸が挙げられる。 Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
エチレン性不飽和ジカルボン酸の誘導体の例としては、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等のマレイン酸メチルアリル;並びに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が挙げられる。 Examples of derivatives of ethylenically unsaturated dicarboxylic acids include methyl maleate such as methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid; and diphenyl maleate, nonyl maleate And maleate esters such as decyl maleate, dodecyl maleate, octadecyl maleate and fluoroalkyl maleate.
エチレン性不飽和スルホン酸単量体の具体例は、ビニルスルホン酸、メチルビニルスルホン酸、スチレンスルホン酸、(メタ)アクリルスルホン酸、(メタ)アクリル酸−2−スルホン酸エチル、2−アクリルアミド−2−ヒドロキシプロパンスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸等である。 Specific examples of the ethylenically unsaturated sulfonic acid monomer include vinyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid, (meth) acryl sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamide- 2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
エチレン性不飽和リン酸単量体の具体例は、(メタ)アクリル酸−3−クロロ−2−リン酸プロピル、(メタ)アクリル酸−2−リン酸エチル、3−アリロキシ−2−ヒドロキシプロパンリン酸等である。 Specific examples of the ethylenically unsaturated phosphate monomer include (meth) acrylic acid-3-chloro-2-phosphate propyl, (meth) acrylic acid-2-ethyl phosphate, 3-allyloxy-2-hydroxypropane Such as phosphoric acid.
また、上記エチレン性不飽和酸単量体のアルカリ金属塩またはアンモニウム塩も用いることができる。 Moreover, the alkali metal salt or ammonium salt of the said ethylenically unsaturated acid monomer can also be used.
上記エチレン性不飽和酸単量体は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせてもよい。したがって、ニトリル基含有アクリル重合体は、エチレン性不飽和酸単量体を、1種類だけ含んでいてもよく、2種類以上を任意の比率で組み合わせて含んでいてもよい。 The said ethylenically unsaturated acid monomer may be used individually by 1 type, and may combine 2 or more types by arbitrary ratios. Therefore, the nitrile group-containing acrylic polymer may contain only one type of ethylenically unsaturated acid monomer, or may contain two or more types in combination at any ratio.
これらの中でも、ニトリル基含有アクリル重合体の分散性を向上するという観点から、エチレン性不飽和酸単量体としては、エチレン性不飽和カルボン酸単量体またはエチレン性不飽和スルホン酸単量体を単独で用いるか、エチレン性不飽和カルボン酸単量体とエチレン性不飽和スルホン酸単量体との併用が好ましい。 Among these, from the viewpoint of improving the dispersibility of the nitrile group-containing acrylic polymer, the ethylenically unsaturated acid monomer may be an ethylenically unsaturated carboxylic acid monomer or an ethylenically unsaturated sulfonic acid monomer. Are preferably used alone or in combination with an ethylenically unsaturated carboxylic acid monomer and an ethylenically unsaturated sulfonic acid monomer.
エチレン性不飽和カルボン酸単量体の中でも、ニトリル基含有アクリル重合体に良好な分散性を発現させるという観点から、好ましくはエチレン性不飽和モノカルボン酸であり、より好ましくはアクリル酸やメタクリル酸であり、特に好ましくはメタクリル酸である。 Among ethylenically unsaturated carboxylic acid monomers, from the viewpoint of expressing good dispersibility in the nitrile group-containing acrylic polymer, ethylenically unsaturated monocarboxylic acid is preferable, and acrylic acid or methacrylic acid is more preferable. Particularly preferred is methacrylic acid.
また、エチレン性不飽和スルホン酸単量体の中でも、ニトリル基含有アクリル重合体に良好な分散性を発現させるという観点から、好ましくは2−アクリルアミド−2−ヒドロキシプロパンスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸であり、より好ましくは2−アクリルアミド−2−メチルプロパンスルホン酸である。 Of the ethylenically unsaturated sulfonic acid monomers, 2-acrylamido-2-hydroxypropanesulfonic acid, 2-acrylamido-2 are preferable from the viewpoint of expressing good dispersibility in the nitrile group-containing acrylic polymer. -Methylpropanesulfonic acid, more preferably 2-acrylamido-2-methylpropanesulfonic acid.
ニトリル基含有アクリル重合体におけるエチレン性不飽和酸単量体単位の含有割合は、好ましくは3〜30質量%、より好ましくは10〜30質量%、さらに好ましくは12〜28質量%、特に好ましくは14〜26質量%の範囲である。エチレン性不飽和酸単量体として、エチレン性不飽和カルボン酸単量体とエチレン性不飽和スルホン酸単量体とを併用する場合、ニトリル基含有アクリル重合体におけるエチレン性不飽和カルボン酸単量体の含有割合は、好ましくは3〜30質量%、さらに好ましくは10〜30質量%、特に好ましくは12〜28質量%であり、エチレン性不飽和スルホン酸単量体の含有割合は、好ましくは0.1〜10質量%である。 The content ratio of the ethylenically unsaturated acid monomer unit in the nitrile group-containing acrylic polymer is preferably 3 to 30% by mass, more preferably 10 to 30% by mass, still more preferably 12 to 28% by mass, and particularly preferably. It is the range of 14-26 mass%. When using ethylenically unsaturated carboxylic acid monomer and ethylenically unsaturated sulfonic acid monomer together as ethylenically unsaturated acid monomer, ethylenically unsaturated carboxylic acid monomer in nitrile group-containing acrylic polymer The content of the body is preferably 3 to 30% by mass, more preferably 10 to 30% by mass, particularly preferably 12 to 28% by mass, and the content of the ethylenically unsaturated sulfonic acid monomer is preferably It is 0.1-10 mass%.
エチレン性不飽和酸単量体単位の含有割合を上記範囲とすることで、スラリー化した際のニトリル基含有アクリル重合体の分散性が向上し、正極活物質を良好に被覆でき、その結果、均一性の高い正極活物質層を形成でき、正極の抵抗を低減できる。 By making the content ratio of the ethylenically unsaturated acid monomer unit in the above range, the dispersibility of the nitrile group-containing acrylic polymer when slurried is improved, and the positive electrode active material can be satisfactorily coated. A positive electrode active material layer with high uniformity can be formed, and the resistance of the positive electrode can be reduced.
ニトリル基含有アクリル重合体は、上記各単量体単位に加え、ニトリル基含有アクリル重合体のTHF不溶解分量に影響を与えない範囲で、さらに架橋性単量体単位を含んでいてもよい。架橋性単量体単位は、架橋性単量体を加熱またはエネルギー照射により、重合中または重合後に架橋構造を形成しうる構造単位である。架橋性単量体の例としては、通常は、熱架橋性を有する単量体を挙げることができる。より具体的には、熱架橋性の架橋性基及び1分子あたり1つのオレフィン性二重結合を有する単官能性単量体、及び1分子あたり2つ以上のオレフィン性二重結合を有する多官能性単量体が挙げられる。 In addition to the above monomer units, the nitrile group-containing acrylic polymer may further contain a crosslinkable monomer unit as long as it does not affect the THF-insoluble content of the nitrile group-containing acrylic polymer. The crosslinkable monomer unit is a structural unit capable of forming a crosslinked structure during or after polymerization by heating or energy irradiation of the crosslinkable monomer. As an example of the crosslinkable monomer, a monomer having thermal crosslinkability can be usually mentioned. More specifically, a monofunctional monomer having a heat-crosslinkable crosslinkable group and one olefinic double bond per molecule, and a polyfunctional having two or more olefinic double bonds per molecule. Ionic monomers.
単官能性単量体に含まれる熱架橋性の架橋性基の例としては、エポキシ基、N−メチロールアミド基、オキセタニル基、オキサゾリン基、及びこれらの組み合わせが挙げられる。これらの中でも、エポキシ基が、架橋及び架橋密度の調節が容易な点でより好ましい。 Examples of thermally crosslinkable groups contained in the monofunctional monomer include epoxy groups, N-methylolamide groups, oxetanyl groups, oxazoline groups, and combinations thereof. Among these, an epoxy group is more preferable in terms of easy adjustment of crosslinking and crosslinking density.
熱架橋性の架橋性基としてエポキシ基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、ビニルグリシジルエーテル、アリルグリシジルエーテル、ブテニルグリシジルエーテル、o−アリルフェニルグリシジルエーテルなどの不飽和グリシジルエーテル;ブタジエンモノエポキシド、クロロプレンモノエポキシド、4,5−エポキシ−2−ペンテン、3,4−エポキシ−1−ビニルシクロヘキセン、1,2−エポキシ−5,9−シクロドデカジエンなどのジエンまたはポリエンのモノエポキシド;3,4−エポキシ−1−ブテン、1,2−エポキシ−5−ヘキセン、1,2−エポキシ−9−デセンなどのアルケニルエポキシド;並びにグリシジルアクリレート、グリシジルメタクリレート、グリシジルクロトネート、グリシジル−4−ヘプテノエート、グリシジルソルベート、グリシジルリノレート、グリシジル−4−メチル−3−ペンテノエート、3−シクロヘキセンカルボン酸のグリシジルエステル、4−メチル−3−シクロヘキセンカルボン酸のグリシジルエステルなどの不飽和カルボン酸のグリシジルエステル類が挙げられる。 Examples of the crosslinkable monomer having an epoxy group as a thermally crosslinkable group and having an olefinic double bond include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl. Unsaturated glycidyl ethers such as ether; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene Monoepoxides of dienes or polyenes such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate, Glycidyl crotonate Unsaturated carboxylic acids such as sidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of 3-cyclohexene carboxylic acid, glycidyl ester of 4-methyl-3-cyclohexene carboxylic acid Examples include glycidyl esters of acids.
熱架橋性の架橋性基としてN−メチロールアミド基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、N−メチロール(メタ)アクリルアミドなどのメチロール基を有する(メタ)アクリルアミド類が挙げられる。 Examples of the crosslinkable monomer having an N-methylolamide group as a thermally crosslinkable group and having an olefinic double bond have a methylol group such as N-methylol (meth) acrylamide (meta ) Acrylamides.
熱架橋性の架橋性基としてオキセタニル基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、3−((メタ)アクリロイルオキシメチル)オキセタン、3−((メタ)アクリロイルオキシメチル)−2−トリフロロメチルオキセタン、3−((メタ)アクリロイルオキシメチル)−2−フェニルオキセタン、2−((メタ)アクリロイルオキシメチル)オキセタン、及び2−((メタ)アクリロイルオキシメチル)−4−トリフロロメチルオキセタンが挙げられる。 Examples of the crosslinkable monomer having an oxetanyl group as a heat crosslinkable group and having an olefinic double bond include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl ) -4-trifluoromethyloxetane.
熱架橋性の架橋性基としてオキサゾリン基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、2−ビニル−2−オキサゾリン、2−ビニル−4−メチル−2−オキサゾリン、2−ビニル−5−メチル−2−オキサゾリン、2−イソプロペニル−2−オキサゾリン、2−イソプロペニル−4−メチル−2−オキサゾリン、2−イソプロペニル−5−メチル−2−オキサゾリン、及び2−イソプロペニル−5−エチル−2−オキサゾリンが挙げられる。 Examples of the crosslinkable monomer having an oxazoline group as a thermally crosslinkable group and having an olefinic double bond include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2- Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline is mentioned.
2つ以上のオレフィン性二重結合を有する多官能性単量体の例としては、アリル(メタ)アクリレート、エチレンジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、トリメチロールプロパン−トリ(メタ)アクリレート、ジプロピレングリコールジアリルエーテル、ポリグリコールジアリルエーテル、トリエチレングリコールジビニルエーテル、ヒドロキノンジアリルエーテル、テトラアリルオキシエタン、トリメチロールプロパン−ジアリルエーテル、前記以外の多官能性アルコールのアリルまたはビニルエーテル、トリアリルアミン、メチレンビスアクリルアミド、及びジビニルベンゼンが挙げられる。 Examples of multifunctional monomers having two or more olefinic double bonds include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, trimethylolpropane-tri (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylolpropane-diallyl Ethers, allyl or vinyl ethers of polyfunctional alcohols other than those mentioned above, triallylamine, methylene bisacrylamide, and divinylbenzene.
架橋性単量体としては、特に、アリル(メタ)アクリレート、エチレンジ(メタ)アクリレート、アリルグリシジルエーテル、及びグリシジルメタクリレートを好ましく用いることができる。 As the crosslinkable monomer, in particular, allyl (meth) acrylate, ethylene di (meth) acrylate, allyl glycidyl ether, and glycidyl methacrylate can be preferably used.
上記架橋性単量体は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせてもよい。したがって、ニトリル基含有アクリル重合体は、架橋性単量体を、1種類だけ含んでいてもよく、2種類以上を任意の比率で組み合わせて含んでいてもよい。 The said crosslinking | crosslinked monomer may be used individually by 1 type, and may combine 2 or more types by arbitrary ratios. Therefore, the nitrile group-containing acrylic polymer may contain only one type of crosslinkable monomer, or may contain two or more types in combination at any ratio.
ニトリル基含有アクリル重合体に架橋性単量体単位が含まれる場合、その含有割合は、好ましくは0.1質量%以上、より好ましくは0.2質量%以上、特に好ましくは0.5質量%以上であり、好ましくは5質量%以下、より好ましくは4質量%以下、特に好ましくは2質量%以下である。架橋性単量体単位の含有割合を前記範囲の下限値以上とすることにより、ニトリル基含有アクリル重合体の架橋度を高め、膨潤度が過度に上昇することを防止しうる。一方、架橋性単量体単位の比率を前記範囲の上限値以下とすることにより、ニトリル基含有アクリル重合体の分散性を良好にすることができる。したがって、架橋性単量体単位の含有割合を前記範囲内とすることにより、膨潤度及び分散性の両方を良好なものとすることができる。 When the nitrile group-containing acrylic polymer contains a crosslinkable monomer unit, the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.5% by mass. Or more, preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 2% by mass or less. By making the content rate of a crosslinkable monomer unit more than the lower limit of the said range, the crosslinking degree of a nitrile group containing acrylic polymer can be raised, and it can prevent that a swelling degree rises too much. On the other hand, the dispersibility of the nitrile group-containing acrylic polymer can be improved by setting the ratio of the crosslinkable monomer unit to the upper limit of the above range. Therefore, by setting the content ratio of the crosslinkable monomer unit within the above range, both the degree of swelling and the dispersibility can be improved.
また、ニトリル基含有アクリル重合体には、上記に加えて、芳香族ビニル単量体単位、エチレン性不飽和カルボン酸アミド単量体単位などが含まれていてもよい。 In addition to the above, the nitrile group-containing acrylic polymer may contain an aromatic vinyl monomer unit, an ethylenically unsaturated carboxylic acid amide monomer unit, and the like.
芳香族ビニル単量体の例としては、スチレン、α−メチルスチレン、ビニルトルエン、クロロスチレン、ヒドロキシメチルスチレンなどを挙げることができる。 Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and hydroxymethylstyrene.
エチレン性不飽和カルボン酸アミド単量体の例としては、(メタ)アクリルアミド、N−メトキシメチル(メタ)アクリルアミドなどが挙げられる。 Examples of the ethylenically unsaturated carboxylic acid amide monomer include (meth) acrylamide, N-methoxymethyl (meth) acrylamide and the like.
これらの単量体単位を含むことで、スラリー化した際のニトリル基含有アクリル重合体の分散性が向上し、正極活物質を良好に被覆できる。これらの単量体単位は、10質量%以下の割合で含まれていてもよい。 By including these monomer units, the dispersibility of the nitrile group-containing acrylic polymer when slurryed is improved, and the positive electrode active material can be satisfactorily coated. These monomer units may be contained in a proportion of 10% by mass or less.
ここで、各単量体の含有割合(単量体の仕込み比)は、通常、ニトリル基含有アクリル重合体における各単量体単位(例えば、(メタ)アクリル酸エステル単量体単位、エチレン性不飽和酸単量体単位、及び架橋性単量体単位)の含有割合と一致する。 Here, the content ratio of each monomer (monomer charge ratio) is usually the monomer unit in the nitrile group-containing acrylic polymer (for example, (meth) acrylate monomer unit, ethylenic). This corresponds to the content ratio of unsaturated acid monomer units and crosslinkable monomer units).
次に、ニトリル基含有アクリル重合体のSP値、非水電解液に対する膨潤度、およびニトリル基含有アクリル重合体のテトラヒドロフラン(THF)不溶解分量について説明する。 Next, the SP value of the nitrile group-containing acrylic polymer, the degree of swelling with respect to the non-aqueous electrolyte, and the tetrahydrofuran (THF) insoluble content of the nitrile group-containing acrylic polymer will be described.
ニトリル基含有アクリル重合体のSP値は、9〜11(cal/cm3)1/2であり、好ましくは9〜10.5(cal/cm3)1/2であり、より好ましくは9.5〜10(cal/cm3)1/2である。ニトリル基含有アクリル重合体のSP値を、上記範囲にすることにより、後述する正極用スラリー組成物を製造する際に用いる分散媒(以下、「スラリー分散媒」と記載することがある。)への溶解性を維持しながら、非水電解液への適度な膨潤性をもたせることができる。それにより、得られる電極の均一性がより向上し、それを用いた二次電池のサイクル特性を向上させることができる。The SP value of the nitrile group-containing acrylic polymer is 9 to 11 (cal / cm 3 ) 1/2 , preferably 9 to 10.5 (cal / cm 3 ) 1/2 , more preferably 9. 5 to 10 (cal / cm 3 ) 1/2 . By setting the SP value of the nitrile group-containing acrylic polymer within the above range, to the dispersion medium (hereinafter, sometimes referred to as “slurry dispersion medium”) used in producing the positive electrode slurry composition described below. Thus, it is possible to impart appropriate swelling property to the non-aqueous electrolyte solution while maintaining the solubility. Thereby, the uniformity of the obtained electrode is further improved, and the cycle characteristics of the secondary battery using the same can be improved.
SP値とは、溶解度パラメーターのことを意味する。このSP値は、J.BrandrupおよびE.H.Immergut編‘‘Polymer Handbook’’ VII Solubility Paramet Values,pp519−559(John Wiley & Sons社、第3版1989年発行)に記載される方法に従って求めることができる。 The SP value means the solubility parameter. This SP value is calculated according to J.J. Brandrup and E.I. H. It can be determined in accordance with the method described in “Immediat Edition” “Polymer Handbook” VII Solidity Paramet Values, pp 519-559 (John Wiley & Sons, 3rd edition, 1989).
また、上記の文献‘‘Polymer Handbook’’に記載のないポリマーのSP値は、Smallが提案した「分子引力定数法」に従って求めることができる。この方法は、化合物分子を構成する官能基(原子団)の特性値、すなわち、分子引力定数(G)の統計と分子量とから次式に従ってSP値(δ)を求める方法である。
δ=ΣG/V=dΣG/M
前記の式において、δはSP値を表し、ΣGは分子引力定数Gの総計を表し、Vは比容を表し、Mは分子量を表し、dは比重を表す。In addition, the SP value of a polymer not described in the above-mentioned document “Polymer Handbook” can be determined according to the “molecular attraction constant method” proposed by Small. This method is a method for obtaining the SP value (δ) according to the following equation from the characteristic value of the functional group (atomic group) constituting the compound molecule, that is, the statistics of the molecular attractive constant (G) and the molecular weight.
δ = ΣG / V = dΣG / M
In the above formula, δ represents the SP value, ΣG represents the total molecular attractive constant G, V represents the specific volume, M represents the molecular weight, and d represents the specific gravity.
さらに、2種類以上のニトリル基含有アクリル重合体を組み合わせて正極活物質の表面を被覆する場合には、ニトリル基含有アクリル重合体全体のSP値は、個々のニトリル基含有アクリル重合体のSP値と混合モル比とから計算で求めることができる。具体的には、個々のニトリル基含有アクリル重合体のSP値についてモル比によって重み付けした加重平均として、ニトリル基含有アクリル重合体全体のSP値を算出する。 Further, when the surface of the positive electrode active material is coated by combining two or more types of nitrile group-containing acrylic polymers, the SP value of the entire nitrile group-containing acrylic polymer is the SP value of each nitrile group-containing acrylic polymer. And the mixing molar ratio. Specifically, the SP value of the entire nitrile group-containing acrylic polymer is calculated as a weighted average weighted by the molar ratio with respect to the SP value of each nitrile group-containing acrylic polymer.
ニトリル基含有アクリル重合体が上記のようなSP値を有することは、ニトリル基含有アクリル重合体がスラリー分散媒には溶解するが、非水電解液には膨潤することを意味する。したがって、リチウムイオン二次電池において、正極活物質のニトリル基含有アクリル重合体に被覆された部分は、非水電解液に接触しないので、正極活物質の劣化が抑制され、充放電サイクルを繰り返してもサイクル特性の低下を防止できる。 The fact that the nitrile group-containing acrylic polymer has the SP value as described above means that the nitrile group-containing acrylic polymer is dissolved in the slurry dispersion medium but swells in the non-aqueous electrolyte. Therefore, in the lithium ion secondary battery, the portion of the positive electrode active material covered with the nitrile group-containing acrylic polymer does not come into contact with the non-aqueous electrolyte, so that the deterioration of the positive electrode active material is suppressed and the charge / discharge cycle is repeated. Can also prevent deterioration of cycle characteristics.
また、ニトリル基含有アクリル重合体が上記のようなSP値を有することは、ニトリル基含有アクリル重合体がリチウムイオン二次電池の非水電解液に膨潤しうることを意味する。したがって、本発明のリチウムイオン二次電池においてニトリル基含有アクリル重合体はイオンの移動を妨げないので、リチウムイオン二次電池の正極における内部抵抗を小さく抑えることができる。また、通常は、リチウムイオン二次電池には水は含まれないか、含まれるとしても少量であるので、ニトリル基含有アクリル重合体が膨潤しても正極活物質の溶出による集電体の腐食は進行し難くなっている。 In addition, the nitrile group-containing acrylic polymer having the SP value as described above means that the nitrile group-containing acrylic polymer can swell in the non-aqueous electrolyte of the lithium ion secondary battery. Therefore, since the nitrile group-containing acrylic polymer does not hinder the movement of ions in the lithium ion secondary battery of the present invention, the internal resistance in the positive electrode of the lithium ion secondary battery can be kept small. In addition, since the lithium ion secondary battery usually does not contain water or a small amount if it is contained, even if the nitrile group-containing acrylic polymer swells, corrosion of the current collector due to elution of the positive electrode active material Is difficult to progress.
ニトリル基含有アクリル重合体の非水電解液に対する膨潤度は、かかる重合体の体積が非水電解液中で著しく変化することを避けるため、好ましくは1.0倍以上3倍以下であり、より好ましくは1.0倍以上2.8倍以下、さらに好ましくは1.0倍以上2.6倍以下である。ここで、非水電解液は、本発明のリチウムイオン二次電池を構成する電解液である。非水電解液に対するニトリル基含有アクリル重合体の膨潤度を上記範囲とすることで、充放電サイクルを繰り返しても、正極活物質層の集電体に対する密着性が維持され、サイクル特性が向上する。非水電解液に対する膨潤度は、例えば、前述した各単量体単位の含有割合により制御することができる。具体的には、ニトリル基含有単量体単位の含有割合を増やすと増大する。また、エチレン性不飽和酸単量体単位の含有割合を増やすと減少する。 The degree of swelling of the nitrile group-containing acrylic polymer with respect to the non-aqueous electrolyte is preferably 1.0 to 3 times, in order to avoid a significant change in the volume of the polymer in the non-aqueous electrolyte. Preferably they are 1.0 times or more and 2.8 times or less, More preferably, they are 1.0 times or more and 2.6 times or less. Here, the nonaqueous electrolytic solution is an electrolytic solution constituting the lithium ion secondary battery of the present invention. By adjusting the degree of swelling of the nitrile group-containing acrylic polymer to the non-aqueous electrolyte within the above range, even when the charge / discharge cycle is repeated, the adhesion of the positive electrode active material layer to the current collector is maintained, and the cycle characteristics are improved. . The degree of swelling with respect to the nonaqueous electrolytic solution can be controlled by, for example, the content ratio of each monomer unit described above. Specifically, it increases when the content ratio of the nitrile group-containing monomer unit is increased. Moreover, it decreases when the content ratio of the ethylenically unsaturated acid monomer unit is increased.
また、ニトリル基含有アクリル重合体のテトラヒドロフラン(THF)不溶解分量は、かかる重合体をスラリー分散媒に適度に溶解させるため、好ましくは30質量%以下であり、より好ましくは25質量%以下であり、さらに好ましくは20質量%以下の範囲にある。THF不溶解分は、ゲル量の指標であり、THF不溶解分量が多いと、N−メチルピロリドン(以下、NMPと記載することがある)などの有機溶剤を用いたスラリー中において粒子状で存在する可能性が高くなり、スラリー中での分散性が損なわれることがある。THF不溶解分量は、後述するように、重合反応温度、単量体の添加時間、重合開始剤量等により制御することができる。具体的には、重合反応温度を上げる、重合開始剤、連鎖移動剤を多くするなどの方法でTHF不溶解分量が減少する。なお、THF不溶解分量の下限は特に限定されないが、好ましくは0質量%以上であり、より好ましくは0質量%より大きく、特に好ましくは5質量%以上である。 Further, the tetrahydrofuran (THF) insoluble content of the nitrile group-containing acrylic polymer is preferably 30% by mass or less, more preferably 25% by mass or less in order to appropriately dissolve the polymer in the slurry dispersion medium. More preferably, it is in the range of 20% by mass or less. The THF-insoluble matter is an index of the amount of gel, and if the amount of THF-insoluble matter is large, it exists in the form of particles in a slurry using an organic solvent such as N-methylpyrrolidone (hereinafter sometimes referred to as NMP). The dispersibility in a slurry may be impaired. As described later, the THF-insoluble content can be controlled by the polymerization reaction temperature, the monomer addition time, the polymerization initiator amount, and the like. Specifically, the amount of THF-insoluble matter is reduced by increasing the polymerization reaction temperature, increasing the polymerization initiator, and the chain transfer agent. The lower limit of the THF insoluble content is not particularly limited, but is preferably 0% by mass or more, more preferably greater than 0% by mass, and particularly preferably 5% by mass or more.
非水電解液とスラリー分散媒である有機溶剤とは、溶解パラメーター(SP値)が近いため、重合体の非水電解液に対する膨潤度を適切な範囲内とすると、スラリー分散媒である有機溶剤にはかかる重合体が溶解しない(THF不溶解分量が過多となる)場合があり、反対に、かかる重合体が有機溶剤に溶解しやすくすると、該重合体の非水電解液に対する膨潤度が適切な範囲外となってしまう場合があるが、本発明では、これらの膨潤度およびTHF不溶解分量が、共に、適切な範囲内にある。 Since the nonaqueous electrolytic solution and the organic solvent that is the slurry dispersion medium have close solubility parameters (SP values), if the swelling degree of the polymer with respect to the nonaqueous electrolytic solution is within an appropriate range, the organic solvent that is the slurry dispersion medium In some cases, such a polymer does not dissolve (excess amount of THF insoluble). On the other hand, when such a polymer is easily dissolved in an organic solvent, the degree of swelling of the polymer with respect to the non-aqueous electrolyte is appropriate. However, in the present invention, both the degree of swelling and the amount insoluble in THF are within the appropriate ranges.
ニトリル基含有アクリル重合体の製法は特に限定はされないが、上述したように、ニトリル基含有アクリル重合体を構成する単量体を含む単量体混合物を、乳化重合して得ることができる。乳化重合の方法としては、特に限定されず、従来公知の乳化重合法を採用すればよい。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。 Although the manufacturing method of a nitrile group containing acrylic polymer is not specifically limited, As mentioned above, the monomer mixture containing the monomer which comprises a nitrile group containing acrylic polymer can be obtained by emulsion polymerization. The method for emulsion polymerization is not particularly limited, and a conventionally known emulsion polymerization method may be employed. 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. In addition, 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.
乳化重合に使用する重合開始剤としては、たとえば、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、過リン酸カリウム、過酸化水素等の無機過酸化物;t−ブチルパーオキサイド、クメンハイドロパーオキサイド、p−メンタンハイドロパーオキサイド、ジ−t−ブチルパーオキサイド、t−ブチルクミルパーオキサイド、アセチルパーオキサイド、イソブチリルパーオキサイド、オクタノイルパーオキサイド、ベンゾイルパーオキサイド、3,5,5−トリメチルヘキサノイルパーオキサイド、t−ブチルパーオキシイソブチレート等の有機過酸化物;アゾビスイソブチロニトリル、アゾビス−2,4−ジメチルバレロニトリル、アゾビスシクロヘキサンカルボニトリル、アゾビスイソ酪酸メチル等のアゾ化合物等が挙げられる。 Examples of the polymerization initiator used for emulsion polymerization include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide Organic peroxides such as oxide and t-butylperoxyisobutyrate; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc. Is .
これらのなかでも、無機過酸化物が好ましく使用できる。これらの重合開始剤は、それぞれ単独でまたは2種類以上を組み合わせて使用することができる。また、過酸化物開始剤は、重亜硫酸ナトリウム等の還元剤と組み合わせて、レドックス系重合開始剤として使用することもできる。 Among these, inorganic peroxides can be preferably used. These polymerization initiators can be used alone or in combination of two or more. The peroxide initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.
重合開始剤の使用量は、重合に使用する単量体混合物の全量100質量部に対して、好ましくは0.05〜5質量部、より好ましくは0.1〜2質量部である。上記範囲で、重合開始剤を使用することで、得られるニトリル基含有アクリル重合体のTHF不溶分量を適切に調節し得る。 The amount of the polymerization initiator used is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of the monomer mixture used for the polymerization. By using a polymerization initiator within the above range, the amount of THF-insoluble matter in the resulting nitrile group-containing acrylic polymer can be adjusted appropriately.
得られるニトリル基含有アクリル重合体のTHF不溶分量を調節するために、乳化重合時に連鎖移動剤を使用してもよい。連鎖移動剤としては、たとえば、n−ヘキシルメルカプタン、n−オクチルメルカプタン、t−オクチルメルカプタン、n−ドデシルメルカプタン、t−ドデシルメルカプタン、n−ステアリルメルカプタン等のアルキルメルカプタン;ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物;ターピノレンや、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物;2,6−ジ−t−ブチル−4−メチルフェノール、スチレン化フェノール等のフェノール系化合物;アリルアルコール等のアリル化合物;ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物;チオグリコール酸、チオリンゴ酸、2−エチルヘキシルチオグリコレート、ジフェニルエチレン、α−メチルスチレンダイマーなどが挙げられる。 In order to adjust the amount of THF-insoluble matter in the resulting nitrile group-containing acrylic polymer, a chain transfer agent may be used during emulsion polymerization. Examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfides; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenols such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol Compounds; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide; thioglycolic acid, Oringo acid, 2-ethylhexyl thioglycolate, diphenylethylene, etc. α- methylstyrene dimer.
これらのなかでも、アルキルメルカプタンが好ましく、t−ドデシルメルカプタンがより好ましく使用できる。これらの連鎖移動剤は、単独または2種以上組み合わせて使用することができる。 Among these, alkyl mercaptans are preferable, and t-dodecyl mercaptan can be more preferably used. These chain transfer agents can be used alone or in combination of two or more.
連鎖移動剤の使用量は、単量体混合物100質量部に対して、好ましくは0.05〜2質量部、より好ましくは0.1〜1質量部である。 The amount of the chain transfer agent used is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the monomer mixture.
乳化重合時に、界面活性剤を使用してもよい。界面活性剤は、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤のいずれであってもよい。アニオン性界面活性剤の具体例としては、ナトリウムラウリルサルフェート、アンモニウムラウリルサルフェート、ナトリウムドデシルサルフェート、アンモニウムドデシルサルフェート、ナトリウムオクチルサルフェート、ナトリウムデシルサルフェート、ナトリウムテトラデシルサルフェート、ナトリウムヘキサデシルサルフェート、ナトリウムオクタデシルサルフェートなどの高級アルコールの硫酸エステル塩;ドデシルベンゼンスルホン酸ナトリウム、ラウリルベンゼンスルホン酸ナトリウム、ヘキサデシルベンゼンスルホン酸ナトリウムなどのアルキルベンゼンスルホン酸塩;ラウリルスルホン酸ナトリウム、ドデシルスルホン酸ナトリウム、テトラデシルスルホン酸ナトリウムなどの脂肪族スルホン酸塩;などが挙げられる。 A surfactant may be used during the emulsion polymerization. The surfactant may be any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Specific examples of the anionic surfactant include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, ammonium dodecyl sulfate, sodium octyl sulfate, sodium decyl sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and the like. Sulfuric acid ester salts of higher alcohols; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, sodium lauryl benzene sulfonate, sodium hexadecyl benzene sulfonate; fats such as sodium lauryl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfonate Group sulfonates; and the like.
界面活性剤の使用量は、単量体混合物100質量部に対して、好ましくは0.5〜10質量部、より好ましくは1〜5質量部である。 The amount of the surfactant used is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the monomer mixture.
さらに乳化重合の際に、水酸化ナトリウム、アンモニアなどのpH調整剤;分散剤、キレート剤、酸素捕捉剤、ビルダー、粒子径調節のためのシードラテックスなどの各種添加剤を適宜使用することができる。シードラテックスとは、乳化重合の際に反応の核となる微小粒子の分散液をいう。微小粒子は粒径が100nm以下であることが多い。微小粒子は特に限定はされず、ジエン系重合体やアクリル系重合体などの汎用の重合体が用いられる。シードラテックスを用いた乳化重合法によれば、比較的粒径の揃った重合体粒子が得られる。 Further, in the emulsion polymerization, various additives such as a pH adjusting agent such as sodium hydroxide and ammonia; a dispersing agent, a chelating agent, an oxygen scavenger, a builder, and a seed latex for adjusting the particle size can be appropriately used. . Seed latex refers to a dispersion of fine particles that becomes the nucleus of the reaction during emulsion polymerization. The fine particles often have a particle size of 100 nm or less. The fine particles are not particularly limited, and general-purpose polymers such as diene polymers and acrylic polymers are used. According to the emulsion polymerization method using seed latex, polymer particles having a relatively uniform particle size can be obtained.
重合反応を行う際の重合温度は、特に限定されないが、通常、0〜100℃、好ましくは40〜80℃とする。このような温度範囲で乳化重合し、所定の重合転化率で、重合停止剤を添加したり、重合系を冷却したりして、重合反応を停止する。重合反応を停止する重合転化率は、好ましくは93質量%以上、より好ましくは95質量%以上である。また、重合温度を上記範囲とすることにより、得られるニトリル基含有アクリル重合体のTHF不溶分量を適切に調節し得る。 Although the polymerization temperature at the time of performing a polymerization reaction is not specifically limited, Usually, 0-100 degreeC, Preferably you may be 40-80 degreeC. Emulsion polymerization is performed in such a temperature range, and the polymerization reaction is stopped at a predetermined polymerization conversion rate by adding a polymerization terminator or cooling the polymerization system. The polymerization conversion rate for stopping the polymerization reaction is preferably 93% by mass or more, more preferably 95% by mass or more. Moreover, the amount of THF insolubles in the resulting nitrile group-containing acrylic polymer can be appropriately adjusted by setting the polymerization temperature within the above range.
重合反応を停止した後、所望により、未反応単量体を除去し、pHや固形分濃度を調整して、重合体が分散媒に分散された形態(ラテックス)でニトリル基含有アクリル重合体が得られる。その後、必要に応じ、分散媒を置換してもよく、また分散媒を蒸発し、粒子状のニトリル基含有アクリル重合体を粉末形状で得てもよい。 After stopping the polymerization reaction, if desired, the unreacted monomer is removed, the pH and solid content concentration are adjusted, and the nitrile group-containing acrylic polymer is in a form (latex) in which the polymer is dispersed in the dispersion medium. can get. Thereafter, if necessary, the dispersion medium may be replaced, or the dispersion medium may be evaporated to obtain a particulate nitrile group-containing acrylic polymer in powder form.
ニトリル基含有アクリル重合体の分散液には、公知の分散剤、増粘剤、老化防止剤、消泡剤、防腐剤、抗菌剤、ブリスター防止剤、pH調整剤などを必要に応じて添加することもできる。 Addition of known dispersants, thickeners, anti-aging agents, antifoaming agents, antiseptics, antibacterial agents, anti-blistering agents, pH adjusting agents, etc., to the nitrile group-containing acrylic polymer dispersion You can also
上記のニトリル基含有アクリル重合体を用いて正極活物質を被覆する方法は特に限定されず、例えば、正極用スラリー組成物を調整する際に、正極活物質とニトリル基含有アクリル重合体とを混合し攪拌することで得ることができる。混合・攪拌する方法は特に限定されない。また、ニトリル基含有アクリル重合体の量は、正極活物質100質量部に対して、好ましくは0.05〜1.95質量部、より好ましくは0.1〜1.0質量部、特に好ましくは0.2〜0.6質量部である。ニトリル基含有アクリル重合体の量が上記範囲にあると、正極活物質を良好に被覆することができる。なお、本発明において、ニトリル基含有アクリル重合体は、正極活物質を被覆する機能だけでなく、結着剤としての機能も有することができる。 The method for coating the positive electrode active material with the nitrile group-containing acrylic polymer is not particularly limited. For example, when preparing a positive electrode slurry composition, the positive electrode active material and the nitrile group-containing acrylic polymer are mixed. It can be obtained by stirring. The method for mixing and stirring is not particularly limited. The amount of the nitrile group-containing acrylic polymer is preferably 0.05 to 1.95 parts by mass, more preferably 0.1 to 1.0 parts by mass, particularly preferably 100 parts by mass of the positive electrode active material. 0.2 to 0.6 parts by mass. When the amount of the nitrile group-containing acrylic polymer is in the above range, the positive electrode active material can be satisfactorily coated. In the present invention, the nitrile group-containing acrylic polymer can have not only a function of coating the positive electrode active material but also a function as a binder.
(B)正極用結着剤
正極用結着剤(B)は、フッ素含有重合体を含む。 (B) Positive electrode binder The positive electrode binder (B) contains a fluorine-containing polymer.
フッ素含有重合体
正極用結着剤には、フッ素含有重合体を用いる。正極用結着剤が、フッ素含有重合体を含むことで、スラリーの安定性が向上し、また非水電解液に対する結着剤の膨潤を抑制し、サイクル特性が向上する。 A fluorine-containing polymer is used as the binder for the fluorine-containing polymer positive electrode. When the positive electrode binder contains a fluorine-containing polymer, the stability of the slurry is improved, the swelling of the binder with respect to the non-aqueous electrolyte is suppressed, and the cycle characteristics are improved.
フッ素含有重合体は、フッ素含有単量体単位を含む重合体である。フッ素含有単量体単位は、フッ素含有単量体を重合して形成される構造単位である。フッ素含有重合体は、具体的には、フッ素含有単量体の単独重合体、フッ素含有単量体とこれと共重合可能な他のフッ素含有単量体との共重合体、フッ素含有単量体とこれと共重合可能な単量体との共重合体、フッ素含有単量体とこれと共重合可能な他のフッ素含有単量体とこれらと共重合可能な単量体との共重合体が挙げられる。 A fluorine-containing polymer is a polymer containing a fluorine-containing monomer unit. The fluorine-containing monomer unit is a structural unit formed by polymerizing a fluorine-containing monomer. Specifically, the fluorine-containing polymer is a homopolymer of a fluorine-containing monomer, a copolymer of a fluorine-containing monomer and another fluorine-containing monomer copolymerizable therewith, a fluorine-containing monomer Copolymer of copolymer and monomer copolymerizable therewith, copolymerization of fluorine-containing monomer and other fluorine-containing monomer copolymerizable therewith and monomer copolymerizable therewith Coalescence is mentioned.
フッ素含有単量体としては、フッ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、三フッ化塩化ビニル、フッ化ビニル、パーフルオロアルキルビニルエーテルなどが挙げられるが、フッ化ビニリデンが好ましい。 Examples of the fluorine-containing monomer include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, vinyl trifluoride chloride, vinyl fluoride, and perfluoroalkyl vinyl ether, and vinylidene fluoride is preferable.
フッ素含有重合体における、フッ素含有単量体単位の割合は、通常70質量%以上、好ましくは80質量%以上である。なお、フッ素含有重合体における、フッ素含有単量体単位の割合の上限は100質量%である。 The ratio of the fluorine-containing monomer unit in the fluorine-containing polymer is usually 70% by mass or more, preferably 80% by mass or more. In addition, the upper limit of the ratio of the fluorine-containing monomer unit in the fluorine-containing polymer is 100% by mass.
フッ素含有単量体と共重合可能な単量体としては、エチレン、プロピレン、1−ブテンなどの1−オレフィン;スチレン、α−メチルスチレン、p−t−ブチルスチレン、ビニルトルエン、クロロスチレンなどの芳香族ビニル化合物;(メタ)アクリロニトリル(アクリロニトリルおよびメタクリロニトリルの略記。以後同様。)などの不飽和ニトリル化合物;(メタ)アクリル酸メチル、(メタ)アクリル酸ブチル、(メタ)アクリル酸2−エチルヘキシルなどの(メタ)アクリル酸エステル化合物;(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミド、N−ブトキシメチル(メタ)アクリルアミドなどの(メタ)アクリルアミド化合物;(メタ)アクリル酸、イタコン酸、フマル酸、クロトン酸、マレイン酸などのカルボキシル基含有ビニル化合物; アリルグリシジルエーテル、(メタ)アクリル酸グリシジルなどのエポキシ基含有不飽和化合物;(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸ジエチルアミノエチルなどのアミノ基含有不飽和化合物;スチレンスルホン酸、ビニルスルホン酸、(メタ)アリルスルホン酸などのスルホン酸基含有不飽和化合物;3−アリロキシ−2−ヒドロキシプロパン硫酸などの硫酸基含有不飽和化合物;(メタ)アクリル酸−3−クロロ−2−燐酸プロピル、3−アリロキシ−2−ヒドロキシプロパン燐酸などの燐酸基含有不飽和化合物などが挙げられる。 Monomers that can be copolymerized with fluorine-containing monomers include 1-olefins such as ethylene, propylene, and 1-butene; styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene, chlorostyrene, and the like. Aromatic vinyl compounds; unsaturated nitrile compounds such as (meth) acrylonitrile (abbreviations for acrylonitrile and methacrylonitrile; hereinafter the same); methyl (meth) acrylate, butyl (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid ester compounds such as ethylhexyl; (meth) acrylamide compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide; (meth) acrylic acid, itaconic acid, fumar Carbohydrates such as acid, crotonic acid and maleic acid Sil group-containing vinyl compounds; epoxy group-containing unsaturated compounds such as allyl glycidyl ether and glycidyl (meth) acrylate; amino group-containing unsaturated compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Sulphonic acid group-containing unsaturated compounds such as styrene sulfonic acid, vinyl sulfonic acid and (meth) allyl sulfonic acid; Sulfuric acid group-containing unsaturated compounds such as 3-allyloxy-2-hydroxypropanesulfuric acid; (meth) acrylic acid-3- And phosphoric acid group-containing unsaturated compounds such as propyl-2-chlorophosphate and 3-allyloxy-2-hydroxypropanephosphoric acid.
フッ素含有重合体における、フッ素含有単量体と共重合可能な単量体単位の割合は、通常30質量%以下、好ましくは20質量%以下である。 The ratio of the monomer unit copolymerizable with the fluorine-containing monomer in the fluorine-containing polymer is usually 30% by mass or less, preferably 20% by mass or less.
フッ素含有重合体の中でも、フッ素含有単量体としてフッ化ビニリデンを含む重合体、具体的には、フッ化ビニリデンの単独重合体、フッ化ビニリデンとこれと共重合可能な他のフッ素含有単量体との共重合体、フッ化ビニリデンとこれと共重合可能な他のフッ素含有単量体とこれらと共重合可能な単量体との共重合体、フッ化ビニリデンとこれと共重合な単量体との共重合体が好ましい。 Among fluorine-containing polymers, polymers containing vinylidene fluoride as a fluorine-containing monomer, specifically, vinylidene fluoride homopolymer, vinylidene fluoride and other fluorine-containing monomers copolymerizable therewith Copolymer, vinylidene fluoride and other fluorine-containing monomers copolymerizable therewith, and monomers copolymerizable therewith, vinylidene fluoride and copolymerizable monomers A copolymer with a monomer is preferred.
上記のようなフッ素含有重合体の中でも、フッ化ビニリデンの単独重合体(ポリフッ化ビニリデン)、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、ポリフッ化ビニルが好ましく、ポリフッ化ビニリデンがより好ましい。 Among the fluorine-containing polymers as described above, a homopolymer of vinylidene fluoride (polyvinylidene fluoride), a vinylidene fluoride-hexafluoropropylene copolymer, and polyvinyl fluoride are preferable, and polyvinylidene fluoride is more preferable.
フッ素含有重合体は、一種単独であってもよく、また2種以上を併用してもよい。2種以上を併用する場合は、低分子量体と高分子量体とを併用することが好ましい。具体的には、ASTM D3835 /232℃100sec−1で測定されるフッ素含有重合体の溶融粘度が35kpoise未満であるものを低分子量、35kpoise以上であるものを高分子量とし、両者を併用することが好ましい。
例えば、高分子量のポリフッ化ビニリデンとして、アルケマ社製KYNAR HSV900、ソルベイ社製Solef6020、Solef6010、Solef1015、Solef5130 クレハ社製KF7208が挙げられる。また、低分子量のポリフッ化ビニリデンとして、例えば、アルケマ社製KYNAR710 720 740 760 760A、ソルベイ社製Solef6008、クレハ社製KF1120が挙げられる。The fluorine-containing polymer may be one kind alone, or two or more kinds may be used in combination. When using 2 or more types together, it is preferable to use a low molecular weight body and a high molecular weight body together. Specifically, a fluorine-containing polymer having a melt viscosity of less than 35 kpoise measured at ASTM D3835 / 232 ° C. 100 sec −1 has a low molecular weight, and a polymer having a melt viscosity of 35 kpoise or higher has a high molecular weight. preferable.
Examples of the high molecular weight polyvinylidene fluoride include KYNAR HSV900 manufactured by Arkema, Solef 6020, Solef 6010, Solef 1015, Solef 5130 manufactured by Kureha, and KF7208 manufactured by Kureha. Examples of the low molecular weight polyvinylidene fluoride include KYNAR 710 720 740 760 760A manufactured by Arkema, Solef 6008 manufactured by Solvay, and KF 1120 manufactured by Kureha.
フッ素含有重合体として、高分子量体と低分子量体とを組み合わせて用いる場合、フッ素含有重合体の低分子量体と高分子量体との重量比(低分子量体/高分子量体)は、好ましくは、30/70〜70/30である。
低分子量体と高分子量体とをかかる範囲の比率で併用することにより、正極活物質同士の結着性や集電体と正極活物質との結着性、スラリーの均一性をより有効に保つことができる。When a high molecular weight substance and a low molecular weight substance are used in combination as the fluorine-containing polymer, the weight ratio (low molecular weight substance / high molecular weight substance) of the low molecular weight substance and the high molecular weight substance of the fluorine-containing polymer is preferably 30/70 to 70/30.
By combining the low molecular weight body and the high molecular weight body in such a ratio, the binding property between the positive electrode active materials, the binding property between the current collector and the positive electrode active material, and the uniformity of the slurry are more effectively maintained. be able to.
フッ素含有重合体のゲル・パーミエーション・クロマトグラフィによるポリスチレン換算値の重量平均分子量は、好ましくは100,000〜2,000,000、より好ましくは200,000〜1,500,000、特に好ましくは400,000〜1,000,000である。 The weight average molecular weight in terms of polystyrene by gel permeation chromatography of the fluorine-containing polymer is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000, particularly preferably 400. , 1,000 to 1,000,000.
フッ素含有重合体の重量平均分子量を上記範囲とすることで、正極活物質層における正極活物質(A)、導電材(C)などの脱離(粉落ち)が抑制され、また正極用スラリー組成物の粘度調整が容易になる。 By setting the weight-average molecular weight of the fluorine-containing polymer within the above range, detachment (powder off) of the positive electrode active material (A), the conductive material (C), etc. in the positive electrode active material layer is suppressed, and the positive electrode slurry composition The viscosity of the product can be easily adjusted.
フッ素含有重合体のガラス転移温度(Tg)は、好ましくは0℃以下、より好ましくは−20℃以下、特に好ましくは−30℃以下である。フッ素含有重合体のTgの下限は特に限定されないが、好ましくは−50℃以上、より好ましくは−40℃以上である。フッ素含有重合体のTgが上記範囲にあることにより、正極活物質層における正極活物質(A)、導電材(C)などの脱離(粉落ち)が抑制できる。また、フッ素含有重合体のTgは、様々な単量体を組み合わせることによって調整可能である。なお、Tgは示差走査熱量分析計を用いて、JIS K 7121;1987に基づいて測定できる。 The glass transition temperature (Tg) of the fluorine-containing polymer is preferably 0 ° C. or lower, more preferably −20 ° C. or lower, particularly preferably −30 ° C. or lower. Although the minimum of Tg of a fluorine-containing polymer is not specifically limited, Preferably it is -50 degreeC or more, More preferably, it is -40 degreeC or more. When the Tg of the fluorine-containing polymer is in the above range, detachment (powder off) of the positive electrode active material (A), the conductive material (C), etc. in the positive electrode active material layer can be suppressed. The Tg of the fluorine-containing polymer can be adjusted by combining various monomers. Tg can be measured based on JIS K 7121; 1987 using a differential scanning calorimeter.
フッ素含有重合体の融点(Tm)は、好ましくは190℃以下、より好ましくは150〜180℃、さらに好ましくは160〜170℃である。フッ素含有重合体のTmが上記範囲にあることにより、柔軟性と密着強度に優れる正極を得ることができる。また、フッ素含有重合体のTmは、様々な単量体を組み合わせること、もしくは重合温度を制御することなどによって調整可能である。なお、Tmは示差走査熱量分析計を用いて、JIS K 7121;1987に基づいて測定できる。 The melting point (Tm) of the fluorine-containing polymer is preferably 190 ° C. or less, more preferably 150 to 180 ° C., and further preferably 160 to 170 ° C. When the Tm of the fluorine-containing polymer is in the above range, a positive electrode excellent in flexibility and adhesion strength can be obtained. The Tm of the fluorine-containing polymer can be adjusted by combining various monomers or controlling the polymerization temperature. Tm can be measured based on JIS K 7121; 1987 using a differential scanning calorimeter.
フッ素含有重合体の製造方法は特に限定はされず、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法も用いることができる。これらの中でも、懸濁重合法や乳化重合法が好ましい。乳化重合法によりフッ素含有重合体を製造することで、フッ素含有重合体の生産性を向上できると共に、所望の平均粒径を有するフッ素含有重合体を得ることができる。重合反応としては、イオン重合、ラジカル重合、リビングラジカル重合などいずれの反応も用いることができる。重合に用いる重合開始剤としては、たとえば過酸化ラウロイル、ジイソプロピルパーオキシジカーボネート、ジ−2−エチルヘキシルパーオキシジカーボネート、t−ブチルパーオキシピバレート、3,3,5−トリメチルヘキサノイルパーオキサイドなどの有機過酸化物、α,α’−アゾビスイソブチロニトリルなどのアゾ化合物、または過硫酸アンモニウム、過硫酸カリウムなどが挙げられる。 The method for producing the fluorine-containing polymer 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. Among these, the suspension polymerization method and the emulsion polymerization method are preferable. By producing a fluorine-containing polymer by an emulsion polymerization method, productivity of the fluorine-containing polymer can be improved and a fluorine-containing polymer having a desired average particle diameter can be obtained. As the polymerization reaction, any reaction such as ionic polymerization, radical polymerization, and living radical polymerization can be used. Examples of the polymerization initiator used for 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 α, α′-azobisisobutyronitrile, ammonium persulfate, potassium persulfate, and the like.
フッ素含有重合体は、分散媒に分散された分散液または溶解された溶液の状態で使用される。分散媒としては、フッ素含有重合体を均一に分散または溶解し得るものであれば、特に制限されず、水や有機溶媒を用いることができる。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ノン、エチルシクロヘキノ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;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ルキルニトリル類;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。 The fluorine-containing polymer is used in the state of a dispersion liquid or a dissolved solution dispersed in a dispersion medium. The dispersion medium is not particularly limited as long as it can uniformly disperse or dissolve the fluorine-containing polymer, and water or an organic solvent can be used. Examples of organic solvents include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; acetone, ethyl methyl ketone, diisopropyl ketone, cyclohexanone, methylcyclohexanone, and ethylcyclohexanosan. Ketones; methylene chloride, chloroform, carbon tetrachloride and other chlor aliphatic hydrocarbons; ethyl acetate, butyl acetate, γ-butyrolactone, ε-caprolactone and other esters; acetonitrile, propionitrile and other alkyl nitriles; tetrahydrofuran, Ethers such as ethylene glycol diethyl ether: alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; Amides such as tilpyrrolidone and N, N-dimethylformamide may be mentioned.
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、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、正極用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、シクロヘキサノンやトルエン等が好ましい。 These dispersion media may be used alone, or two or more of these dispersion media may be mixed and used as a mixed solvent. Among these, it is industrially used at the time of preparing the positive electrode slurry composition, is difficult to volatilize in production, and as a result, volatilization of the positive electrode slurry composition can be suppressed, and the smoothness of the resulting positive electrode is improved. Therefore, water, N-methylpyrrolidone, cyclohexanone, toluene and the like are preferable.
フッ素含有重合体が分散媒に粒子状で分散している場合において、フッ素含有重合体を含む分散液の固形分濃度は、取扱い性の観点から、通常1〜25質量%であり、3〜20質量%が好ましく、5〜15質量%がさらに好ましい。 In the case where the fluorine-containing polymer is dispersed in the dispersion medium in the form of particles, the solid content concentration of the dispersion containing the fluorine-containing polymer is usually 1 to 25% by mass from the viewpoint of handleability, and 3 to 20 % By mass is preferable, and 5 to 15% by mass is more preferable.
また、フッ素含有重合体を8%溶液となるようにN−メチルピロリドン(以下、「NMP」と記すことがある。)に溶解させた時の粘度は、好ましくは10〜5000mPa・s、より好ましくは100〜2000mPa・sである。フッ素含有重合体の8%NMP溶液粘度を上記範囲とすることで、正極用スラリー組成物の製造時に正極用スラリー組成物を塗工しやすい粘度に調整することが容易である。フッ素含有重合体の8%NMP溶液粘度は、フッ素含有重合体を8%溶液となるようにNMPに溶解させ、これに対し25℃、60rpmで、B型粘度計(東機産業製 RB−80L)を用いて、JIS K 7117−1;1999に基づいて測定できる。 The viscosity when the fluorine-containing polymer is dissolved in N-methylpyrrolidone (hereinafter sometimes referred to as “NMP”) so as to be an 8% solution is preferably 10 to 5000 mPa · s, more preferably. Is 100 to 2000 mPa · s. By setting the viscosity of the 8% NMP solution of the fluorine-containing polymer in the above range, it is easy to adjust the viscosity of the positive electrode slurry composition so that it can be easily applied during the production of the positive electrode slurry composition. The viscosity of the 8% NMP solution of the fluorine-containing polymer is obtained by dissolving the fluorine-containing polymer in NMP so that it becomes an 8% solution, and against this, a B-type viscometer (RB-80L manufactured by Toki Sangyo Co., Ltd.) ) And can be measured based on JIS K 7117-1; 1999.
正極用結着剤は、上記したフッ素含有重合体を含む。正極活物質が特定のニトリル基含有アクリル重合体により被覆されていることに加え、正極用結着剤がフッ素含有重合体を含むことで、捲回体の折り曲げ性の優れた正極電極や、初期容量、出力特性、高電位サイクル特性の優れたリチウムイオン二次電池が得られる。 The binder for positive electrodes contains the above-mentioned fluorine-containing polymer. In addition to the positive electrode active material being coated with a specific nitrile group-containing acrylic polymer, the positive electrode binder contains a fluorine-containing polymer. A lithium ion secondary battery having excellent capacity, output characteristics, and high potential cycle characteristics can be obtained.
正極用結着剤の全量100質量%に対して、フッ素含有重合体の割合は、好ましくは50〜100質量%、より好ましくは60〜90質量%、さらに好ましくは70〜85質量%である。 The ratio of the fluorine-containing polymer is preferably 50 to 100% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 85% by mass with respect to 100% by mass of the total amount of the binder for positive electrode.
正極用結着剤は、上記したフッ素含有重合体に加え、必要に応じ、結着剤として使用可能なその他の重合体を含んでいてもよい。併用してもよいその他の重合体としては、たとえば、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、アクリレート軟質重合体、ジエン軟質重合体、オレフィン軟質重合体、ビニル軟質重合体等の軟質重合体が挙げられる。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。前記その他の重合体は、正極用結着剤の全量100質量%に対して、30質量%以下、さらには0.1〜20質量%、特に0.2〜10質量%の割合で含まれていてもよい。なお、ここでいう、正極用結着剤の量には、SP値が9〜11(cal/cm3)1/2のニトリル基含有アクリル重合体の量は含まない。In addition to the above-mentioned fluorine-containing polymer, the positive electrode binder may contain other polymers that can be used as a binder, if necessary. Examples of other polymers that may be used in combination include resins such as polyacrylic acid derivatives and polyacrylonitrile derivatives, and soft heavy polymers such as acrylate soft polymers, diene soft polymers, olefin soft polymers, and vinyl soft polymers. Coalescence is mentioned. These may be used alone or in combination of two or more. The other polymer is contained in an amount of 30% by mass or less, further 0.1 to 20% by mass, particularly 0.2 to 10% by mass with respect to 100% by mass of the total amount of the binder for the positive electrode. May be. Here, the amount of the positive electrode binder does not include the amount of the nitrile group-containing acrylic polymer having an SP value of 9 to 11 (cal / cm 3 ) 1/2 .
正極用結着剤の量は、正極活物質100質量部に対して、好ましくは0.4〜2質量部、より好ましくは1〜2質量部、特に好ましくは1.5〜2質量部の範囲である。正極用結着剤の量がかかる範囲にあると、得られる正極活物質層と集電体との密着性が充分に確保でき、リチウムイオン二次電池の容量を高く且つ内部抵抗を低くすることができる。 The amount of the positive electrode binder is preferably 0.4 to 2 parts by mass, more preferably 1 to 2 parts by mass, and particularly preferably 1.5 to 2 parts by mass with respect to 100 parts by mass of the positive electrode active material. It is. When the amount of the binder for the positive electrode is within such a range, sufficient adhesion between the obtained positive electrode active material layer and the current collector can be secured, the capacity of the lithium ion secondary battery is increased, and the internal resistance is decreased. Can do.
(C)導電材
正極は、導電材を含有する。正極に含まれる導電材の粒子径は、個数平均粒子径で、好ましくは5〜40nm、より好ましくは10〜38nm、さらに好ましくは15〜36nmである。正極における導電材の粒子径が小さすぎると、凝集しやすくなり、均一分散が困難になる結果、電極の内部抵抗が増大し、容量の向上が困難になる傾向にある。しかし、上述した正極用結着剤を使用することで、微粒化された導電材を均一に分散することが可能になり、容量向上が図られる。また、導電材の粒子径が大きすぎると、正極活物質間に存在することが困難になり、正極活物質層の内部抵抗が増大し、容量の向上が困難になる。導電材の個数平均粒子径は、導電材を水中に0.01質量%で超音波分散させた後、動的光散乱式粒子径・粒度分布測定装置(例えば、日機装株式会社製、粒度分布測定装置 Nanotrac Wave−EX150)を使用して測定することにより求めることができる。 (C) The conductive material positive electrode contains a conductive material. The particle diameter of the conductive material contained in the positive electrode is a number average particle diameter, preferably 5 to 40 nm, more preferably 10 to 38 nm, and still more preferably 15 to 36 nm. If the particle diameter of the conductive material in the positive electrode is too small, aggregation tends to occur and uniform dispersion becomes difficult. As a result, the internal resistance of the electrode increases and the capacity tends to be difficult to improve. However, by using the positive electrode binder described above, the atomized conductive material can be uniformly dispersed, and the capacity can be improved. On the other hand, if the particle size of the conductive material is too large, it becomes difficult to exist between the positive electrode active materials, the internal resistance of the positive electrode active material layer increases, and it is difficult to improve the capacity. The number average particle size of the conductive material is obtained by ultrasonically dispersing the conductive material in water at 0.01% by mass, and then measuring a dynamic light scattering particle size / particle size distribution measuring device (for example, Nikkiso Co., Ltd., particle size distribution measurement). It can obtain | require by measuring using apparatus Nanotrac Wave-EX150).
また、正極における導電材の比表面積(BET式)は、好ましくは1500m2/g以下、より好ましくは1000m2/g以下、特に好ましくは400m2/g以下である。導電材の比表面積が大きすぎると、凝集しやすくなり、均一分散が困難になる結果、正極活物質層の内部抵抗が増大し、容量の向上が困難になる。なお、導電材としては、上述した比表面積を有する1種類の導電材を単独で用いてもよいし、互いに異なる比表面積を有する2種類以上の導電材を、混合後の導電材のBET比表面積が上述した範囲内の大きさになるように組み合わせて用いてもよい。The specific surface area (BET type) of the conductive material in the positive electrode is preferably 1500 m 2 / g or less, more preferably 1000 m 2 / g or less, and particularly preferably 400 m 2 / g or less. If the specific surface area of the conductive material is too large, aggregation tends to occur and uniform dispersion becomes difficult. As a result, the internal resistance of the positive electrode active material layer increases and it is difficult to improve the capacity. In addition, as a conductive material, one type of conductive material having the above-described specific surface area may be used alone, or two or more types of conductive materials having different specific surface areas may be used together with the BET specific surface area of the conductive material after mixing. May be used in combination so as to have a size within the above-described range.
導電材としては、負極と同様に、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。導電材を含有することにより、正極用スラリー組成物製造時の安定性が向上し、また正極活物質層における正極活物質同士の電気的接触を向上させることができ、高容量化が図られる。導電材の含有量は、正極活物質の総量100質量部に対して、好ましくは1〜3質量部、より好ましくは1.2〜2.8質量部、特に好ましくは1.5〜2.5質量部である。導電材の含有量が少なすぎると、正極活物質層における内部抵抗が増大し、高容量化が困難になる場合がある。また導電材の含有量が多すぎると、正極の高密度化が困難になり、初期容量が低下する場合がある。 As the conductive material, conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used as in the negative electrode. By containing a conductive material, the stability at the time of manufacturing the positive electrode slurry composition can be improved, and the electrical contact between the positive electrode active materials in the positive electrode active material layer can be improved, thereby increasing the capacity. The content of the conductive material is preferably 1 to 3 parts by mass, more preferably 1.2 to 2.8 parts by mass, and particularly preferably 1.5 to 2.5 parts by mass with respect to 100 parts by mass of the total amount of the positive electrode active material. Part by mass. If the content of the conductive material is too small, the internal resistance in the positive electrode active material layer increases, and it may be difficult to increase the capacity. Moreover, when there is too much content of a electrically conductive material, it will become difficult to increase the density of a positive electrode, and initial capacity may fall.
その他の正極成分
また、正極にはさらに、任意の成分として、後述する負極と同様に、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が含まれていてもよく、さらに、正極製造時に調製するスラリーに含まれる増粘剤等が残留していてもよい。 Other positive electrode components The positive electrode may further contain, as an optional component, a reinforcing material, a leveling agent, an electrolytic solution additive having a function of inhibiting decomposition of the electrolytic solution, etc., as described later. Furthermore, the thickener etc. which are contained in the slurry prepared at the time of positive electrode manufacture may remain | survive.
補強材としては、各種の無機および有機の球状、板状、棒状または繊維状のフィラーが使用できる。補強材を用いることにより強靭で柔軟な正極を得ることができ、優れた長期サイクル特性を示すことができる。補強材の含有量は、正極活物質の総量100質量部に対して通常0.01〜20質量部、好ましくは1〜10質量部である。補強材が上記範囲含まれることにより、高い容量と高い負荷特性を示すことができる。 As the reinforcing material, various inorganic and organic spherical, plate-like, rod-like or fibrous fillers can be used. By using a reinforcing material, a tough and flexible positive electrode can be obtained, and excellent long-term cycle characteristics can be exhibited. Content of a reinforcing material is 0.01-20 mass parts normally with respect to 100 mass parts of total amounts of a positive electrode active material, Preferably it is 1-10 mass parts. By including the reinforcing material in the above range, high capacity and high load characteristics can be exhibited.
レベリング剤としては、アルキル系界面活性剤、シリコーン系界面活性剤、フッ素系界面活性剤、金属系界面活性剤などの界面活性剤が挙げられる。レベリング剤を混合することにより、塗工時に発生するはじきを防止したり、正極の平滑性を向上させることができる。レベリング剤の含有量は、正極活物質の総量100質量部に対して、好ましくは0.01〜10質量部である。レベリング剤が上記範囲含まれることにより、正極作製時の生産性、平滑性及び電池特性に優れる。 Examples of the leveling agent include surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, and metal surfactants. By mixing the leveling agent, repelling that occurs during coating can be prevented and the smoothness of the positive electrode can be improved. The content of the leveling agent 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. When the leveling agent is included in the above range, the productivity, smoothness, and battery characteristics during the production of the positive electrode are excellent.
電解液添加剤としては、電解液に使用されるビニレンカーボネートなどを用いることができる。電解液添加剤の含有量は、正極活物質の総量100質量部に対して、好ましくは0.01〜10質量部である。電解液添加剤の含有量が、上記範囲であることにより、得られるリチウムイオン二次電池のサイクル特性及び高温特性に優れる。その他には、フュームドシリカやフュームドアルミナなどのナノ微粒子が挙げられる。ナノ微粒子を混合することにより正極を製造する際に調整するスラリー組成物のチキソ性をコントロールすることができ、さらにそれにより得られる正極のレベリング性を向上させることができる。ナノ微粒子の含有量は、正極活物質の総量100質量部に対して、好ましくは0.01〜10質量部である。正極用スラリー組成物にナノ微粒子を上記比率となるように用いると、スラリー安定性、生産性に優れ、高い電池特性を示す。 As the electrolytic solution additive, vinylene carbonate used in the electrolytic solution can be used. The content of the electrolytic solution additive 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. When the content of the electrolytic solution additive is in the above range, the obtained lithium ion secondary battery is excellent in cycle characteristics and high temperature characteristics. Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the slurry composition adjusted when producing the positive electrode can be controlled, and the leveling property of the positive electrode obtained thereby can be improved. The content of the nanoparticles 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. When nanoparticles are used in the positive electrode slurry composition so as to have the above ratio, the slurry composition is excellent in slurry stability and productivity and exhibits high battery characteristics.
リチウムイオン二次電池正極用スラリー組成物の製造方法
リチウムイオン二次電池正極用スラリー組成物は、上述した正極活物質、ニトリル基含有アクリル重合体、正極用結着剤(B)、導電材(C)及びその他の添加剤を分散媒中で混合して得られる。正極活物質とニトリル基含有アクリル重合体とを分散媒中で混合することにより、ニトリル基含有アクリル重合体に含まれるシアノ基や、エチレン性不飽和酸単量体単位を含む場合にニトリル基含有アクリル重合体に含まれる酸基等が、正極活物質の表面における水酸基等の官能基と相互作用し、ニトリル基含有アクリル重合体が正極活物質に優先的に吸着する。そして、得られたリチウムイオン二次電池正極用スラリー組成物を、後述する集電体に塗布し乾燥することにより、ニトリル基含有アクリル重合体で被覆された正極活物質、つまり、本発明に用いる正極活物質(A)を形成できる。
また、上記のようにして得られたスラリー組成物では、上記シアノ基や酸基等が、後述する集電体の表面における水酸基等の官能基と相互作用して吸着するため、正極活物質層と集電体との密着性を向上させることができる。 Method for Producing Slurry Composition for Lithium Ion Secondary Battery Positive Electrode The slurry composition for a lithium ion secondary battery positive electrode includes the above-described positive electrode active material, nitrile group-containing acrylic polymer, positive electrode binder (B), conductive material ( It is obtained by mixing C) and other additives in a dispersion medium. Mixing a positive electrode active material and a nitrile group-containing acrylic polymer in a dispersion medium to contain a cyano group contained in the nitrile group-containing acrylic polymer or a nitrile group containing an ethylenically unsaturated acid monomer unit Acid groups and the like contained in the acrylic polymer interact with functional groups such as hydroxyl groups on the surface of the positive electrode active material, and the nitrile group-containing acrylic polymer is preferentially adsorbed on the positive electrode active material. And the positive electrode active material coat | covered with the nitrile group containing acrylic polymer by apply | coating to the collector mentioned later and drying the obtained slurry composition for lithium ion secondary battery positive electrodes, ie, used for this invention. A positive electrode active material (A) can be formed.
Further, in the slurry composition obtained as described above, the cyano group, acid group, etc. interact with and adsorb functional groups such as hydroxyl groups on the surface of the current collector described later, so that the positive electrode active material layer And the current collector can be improved.
分散媒としては、有機溶媒が使用できる。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系脂肪族炭化水素;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ルキルニトリル類;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。 An organic solvent can be used as the dispersion medium. Examples of organic solvents include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; ketones such as acetone, ethylmethylketone, diisopropylketone, cyclohexanone, methylcyclohexane, and ethylcyclohexane. Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, γ-butyrolactone and ε-caprolactone; Alkyl nitriles such as acetonitrile and propionitrile; Tetrahydrofuran and Ethylene Ethers such as 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.
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、正極活物質の分散性にすぐれ、沸点が低く揮発性の高い分散媒が、短時間でかつ低温で除去できるので好ましい。具体的には、アセトン、トルエン、シクロヘキサノン、シクロペンタン、テトラヒドロフラン、シクロヘキサン、キシレン、若しくはN−メチルピロリドン、またはこれらの混合溶媒が好ましい。 These dispersion media may be used alone, or two or more of these dispersion media may be mixed and used as a mixed solvent. Among these, a dispersion medium having excellent dispersibility of the positive electrode active material and having a low boiling point and high volatility is preferable because it can be removed at a low temperature in a short time. Specifically, acetone, toluene, cyclohexanone, cyclopentane, tetrahydrofuran, cyclohexane, xylene, or N-methylpyrrolidone, or a mixed solvent thereof is preferable.
混合法は特に限定はされないが、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、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。 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. Further, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader can be used.
リチウムイオン二次電池正極
リチウムイオン二次電池正極は、上述したリチウムイオン二次電池正極用スラリー組成物を集電体に塗布、乾燥してなる。 Lithium ion secondary battery positive electrode A lithium ion secondary battery positive electrode is obtained by applying the slurry composition for a lithium ion secondary battery positive electrode described above to a current collector and drying it.
リチウムイオン二次電池正極の製造方法は、上記正極用スラリー組成物を、集電体の片面または両面に、塗布、乾燥して、正極活物質層を形成する工程を含む。 The manufacturing method of a lithium ion secondary battery positive electrode includes the process of apply | coating and drying the said slurry composition for positive electrodes on the one or both surfaces of a collector, and forming a positive electrode active material layer.
上記正極用スラリー組成物を集電体上に塗布する方法は特に限定されない。例えば、ドクターブレード法、ディップ法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、およびハケ塗り法などの方法が挙げられる。 The method for applying the positive electrode slurry composition onto the current collector is not particularly limited. Examples of 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.
乾燥方法としては、例えば、温風、熱風、低湿風による乾燥、真空乾燥、(遠)赤外線や電子線などの照射による乾燥法が挙げられる。乾燥時間は通常5〜30分であり、乾燥温度は通常40〜180℃である。 Examples of the drying method include drying by 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.
リチウムイオン二次電池正極を製造するに際して、集電体上に上記正極用スラリー組成物を塗布、乾燥後、金型プレスやロールプレスなどを用い、加圧処理により正極活物質層の空隙率を低くする工程を有することが好ましい。正極活物質層の空隙率は、好ましくは5〜30%、より好ましくは7〜20%である。正極活物質層の空隙率が高すぎると充電効率や放電効率が悪化する場合がある。一方、正極活物質層の空隙率が低すぎると、高い体積容量が得難く、正極活物質層が集電体から剥がれ易く不良を発生し易くなる場合がある。さらに、正極用結着剤(B)として硬化性の重合体を用いる場合は、硬化させることが好ましい。 When producing a positive electrode for a lithium ion secondary battery, the positive electrode slurry composition is applied onto a current collector, dried, and then subjected to pressure treatment using a die press or a roll press to increase the porosity of the positive electrode active material layer. It is preferable to have a lowering step. The porosity of the positive electrode active material layer is preferably 5 to 30%, more preferably 7 to 20%. If the porosity of the positive electrode active material layer is too high, charging efficiency and discharging efficiency may be deteriorated. On the other hand, if the porosity of the positive electrode active material layer is too low, it is difficult to obtain a high volume capacity, and the positive electrode active material layer is likely to be peeled off from the current collector, and a defect may be easily generated. Further, when a curable polymer is used as the positive electrode binder (B), it is preferably cured.
リチウムイオン二次電池正極における正極活物質層の厚みは、通常5〜300μmであり、好ましくは30〜250μmである。正極活物質層の厚みが上記範囲にあることにより、負荷特性及びサイクル特性が共に高い二次電池を得ることができる。 The thickness of the positive electrode active material layer in the lithium ion secondary battery positive electrode is usually 5 to 300 μm, preferably 30 to 250 μm. When the thickness of the positive electrode active material layer is in the above range, a secondary battery having high load characteristics and cycle characteristics can be obtained.
正極活物質層における正極活物質の含有割合は、好ましくは85〜99質量%、より好ましくは88〜97質量%である。正極活物質層における正極活物質の含有割合が上記範囲であることにより、高い容量を示しながらも柔軟性、結着性を示す二次電池を得ることができる。 The content ratio of the positive electrode active material in the positive electrode active material layer is preferably 85 to 99% by mass, more preferably 88 to 97% by mass. When the content ratio of the positive electrode active material in the positive electrode active material layer is within the above range, it is possible to obtain a secondary battery that exhibits flexibility and binding properties while exhibiting high capacity.
正極活物質層の密度は、好ましくは3.0〜4.0g/cm3であり、より好ましくは3.4〜4.0g/cm3である。正極活物質層の密度が上記範囲であることにより、高容量の二次電池を得ることができる。The density of the positive electrode active material layer is preferably 3.0 to 4.0 g / cm 3 , and more preferably 3.4 to 4.0 g / cm 3 . When the density of the positive electrode active material layer is in the above range, a high-capacity secondary battery can be obtained.
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、リチウムイオン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してもよい。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、正極活物質層の接着強度や導電性を高めるために、集電体表面にプライマー層などを形成してもよい。 The current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material, but is preferably a metal material because of its heat resistance, for example, iron, copper, aluminum, nickel, stainless steel. Examples include steel, titanium, tantalum, gold, and platinum. Among these, aluminum is particularly preferable as a current collector used for a lithium ion 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. In order to increase the adhesive strength with the positive electrode active material layer, the current collector may be used after being roughened. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical 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. In addition, a primer layer or the like may be formed on the current collector surface in order to increase the adhesive strength or conductivity of the positive electrode active material layer.
(負極)
負極は、集電体と、前記集電体上に積層される負極活物質層とからなる。負極活物質層は、負極活物質(a)として、好ましくは合金系活物質(a1)を含有し、必要に応じその他の炭素系活物質(a2)を含有し、また通常は負極用結着剤(b)、導電材(c)等を含有する。(Negative electrode)
The negative electrode includes a current collector and a negative electrode active material layer laminated on the current collector. The negative electrode active material layer preferably contains an alloy-based active material (a1) as the negative electrode active material (a), and optionally contains another carbon-based active material (a2). Contains agent (b), conductive material (c) and the like.
(a)負極活物質
負極活物質は、負極内で電子(リチウムイオン)の受け渡しをする物質である。負極活物質としては、合金系活物質(a1)が用いられ、また必要に応じ炭素系活物質(a2)を用いることができる。負極活物質は、合金系活物質と炭素系活物質とを含むことが好ましく、合金系活物質と炭素系活物質とを併用することで、合金系活物質のみを用いて得られる負極よりも容量の大きい二次電池を得ることができ、かつ負極の密着強度の低下、サイクル特性の低下といった問題も解決することができる。 (A) Negative electrode active material The negative electrode active material is a substance that delivers electrons (lithium ions) in the negative electrode. As the negative electrode active material, an alloy-based active material (a1) is used, and a carbon-based active material (a2) can be used as necessary. The negative electrode active material preferably includes an alloy-based active material and a carbon-based active material. By using the alloy-based active material and the carbon-based active material in combination, the negative-electrode active material is more than a negative electrode obtained using only the alloy-based active material. A secondary battery having a large capacity can be obtained, and problems such as a decrease in adhesion strength of the negative electrode and a decrease in cycle characteristics can be solved.
(a1)合金系活物質
合金系活物質とは、リチウムの挿入可能な元素を構造に含み、リチウムが挿入された場合の重量あたりの理論電気容量が500mAh/g以上(当該理論電気容量の上限は、特に限定されないが、例えば5000mAh/g以下とすることができる。)である活物質をいい、具体的には、リチウム合金を形成する単体金属およびその合金、及びそれらの酸化物、硫化物、窒化物、珪化物、炭化物、燐化物等が用いられる。 (A1) Alloy-based active material An alloy-based active material includes an element into which lithium can be inserted, and has a theoretical electric capacity of 500 mAh / g or more when lithium is inserted (the upper limit of the theoretical electric capacity) Is not particularly limited, but can be, for example, 5000 mAh / g or less.), Specifically, a single metal forming a lithium alloy and an alloy thereof, and oxides and sulfides thereof Nitride, silicide, carbide, phosphide and the like are used.
リチウム合金を形成する単体金属及び合金としては、Ag、Al、Ba、Bi、Cu、Ga、Ge、In、Ni、P、Pb、Sb、Si、Sn、Sr、Zn等の金属や該金属を含有する化合物が挙げられる。それらの中でもケイ素(Si)、スズ(Sn)または鉛(Pb)の単体金属若しくはこれら原子を含む合金、または、それらの金属の化合物が好ましい。さらに、これらの中でも、低電位でリチウムの挿入脱離が可能なSiの単体金属がより好ましい。 Examples of simple metals and alloys that form lithium alloys include Ag, Al, Ba, Bi, Cu, Ga, Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, and Zn. The compound to contain is mentioned. Among them, silicon (Si), tin (Sn) or lead (Pb) simple metals, alloys containing these atoms, or compounds of these metals are preferable. Further, among these, a Si simple metal capable of inserting and extracting lithium at a low potential is more preferable.
合金系活物質は、さらに、一つ以上の非金属元素を含有していてもよい。具体的には、例えばSiC、SiOxCy(以下、「SiOC」と呼ぶ)(0<x≦3、0<y≦5)、Si3N4、Si2N2O、SiOx(x=0.01以上2未満)、SnOx(0<x≦2)、LiSiO、LiSnO等が挙げられ、中でも低電位でリチウムの挿入脱離が可能なSiOC、SiOx、及びSiCが好ましく、SiOC、SiOxがより好ましい。
例えば、SiOCは、ケイ素を含む高分子材料を焼成して得ることができる。SiOCの中でも、容量とサイクル特性の兼ね合いから、0.8≦x≦3、2≦y≦4の範囲が好ましく用いられる。The alloy-based active material may further contain one or more nonmetallic elements. Specifically, for example, SiC, SiO x C y (hereinafter referred to as “SiOC”) (0 <x ≦ 3, 0 <y ≦ 5), Si 3 N 4 , Si 2 N 2 O, SiO x (x = 0.01 or more and less than 2), SnO x (0 <x ≦ 2), LiSiO, LiSnO, and the like. Among them, SiOC, SiO x , and SiC that can insert and desorb lithium at a low potential are preferable, and SiOC SiO x is more preferred.
For example, SiOC can be obtained by firing a polymer material containing silicon. Among SiOC, the range of 0.8 ≦ x ≦ 3 and 2 ≦ y ≦ 4 is preferably used in view of the balance between capacity and cycle characteristics.
リチウム合金を形成する単体金属およびその合金の酸化物、硫化物、窒化物、珪化物、炭化物、燐化物としては、リチウムの挿入可能な元素の酸化物、硫化物、窒化物、珪化物、炭化物、燐化物等が挙げられ、中でも酸化物が特に好ましい。具体的には酸化スズ、酸化マンガン、酸化チタン、酸化ニオブ、酸化バナジウム等の酸化物、Si、Sn、PbおよびTi原子よりなる群から選ばれる金属元素を含むリチウム含有金属複合酸化物が好ましい。 Lithium alloy-forming elemental metal and its oxides, sulfides, nitrides, silicides, carbides and phosphides include lithium-insertable element oxides, sulfides, nitrides, silicides and carbides And phosphides, and oxides are particularly preferable. Specifically, an oxide such as tin oxide, manganese oxide, titanium oxide, niobium oxide, vanadium oxide, or a lithium-containing metal composite oxide containing a metal element selected from the group consisting of Si, Sn, Pb, and Ti atoms is preferable.
リチウム含有金属複合酸化物としては、更にLixTiyMzO4で示されるリチウムチタン複合酸化物(0.7≦x≦1.5、1.5≦y≦2.3、0≦z≦1.6、Mは、Na、K、Co、Al、Fe、Ti、Mg、Cr、Ga、Cu、ZnおよびNb)が挙げられ、中でもLi4/3Ti5/3O4、Li1Ti2O4、Li4/5Ti11/5O4が好ましい。As the lithium-containing metal composite oxide, a lithium titanium composite oxide represented by Li x Ti y M z O 4 (0.7 ≦ x ≦ 1.5, 1.5 ≦ y ≦ 2.3, 0 ≦ z ≦ 1.6, M includes Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb), among which Li 4/3 Ti 5/3 O 4 , Li 1 Ti 2 O 4 and Li 4/5 Ti 11/5 O 4 are preferred.
これらの合金系活物質の中でもケイ素を含む活物質が好ましい。ケイ素を含む活物質を用いることにより、二次電池の電気容量を大きくすることが可能となる。さらに、ケイ素を含む活物質の中でも、SiOxCy、SiOx、及びSiCがさらに好ましい。ケイ素および炭素を組み合わせて含む活物質においては、高電位でSi(ケイ素)、低電位ではC(炭素)へのLiの挿入脱離が起こると推測され、他の合金系活物質よりも膨張・収縮が抑制されるため、本発明の効果がより得られ易い。Among these alloy-based active materials, active materials containing silicon are preferable. By using an active material containing silicon, the electric capacity of the secondary battery can be increased. Furthermore, among the active materials containing silicon, SiO x C y , SiO x , and SiC are more preferable. In an active material containing a combination of silicon and carbon, it is assumed that Si (silicon) is inserted at a high potential, and Li is inserted into and desorbed from C (carbon) at a low potential. Since the shrinkage is suppressed, the effect of the present invention is more easily obtained.
合金系活物質は、粒子状に整粒されたものが好ましい。粒子の形状が球形であると、電極成形時に、より高密度な電極が形成できる。合金系活物質が粒子である場合、その体積平均粒子径は、好ましくは0.1〜50μm、より好ましくは0.5〜20μm、特に好ましくは1〜10μmである。合金系活物質の体積平均粒子径がこの範囲内であれば、負極を製造するために用いるスラリー組成物の作製が容易となる。なお、本発明における体積平均粒子径は、レーザー回折で粒径分布を測定することにより求めることができる。 The alloy-based active material is preferably sized in the form of particles. When the shape of the particles is spherical, a higher density electrode can be formed during electrode molding. When the alloy-based active material is particles, the volume average particle diameter is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm, and particularly preferably 1 to 10 μm. When the volume average particle diameter of the alloy-based active material is within this range, the slurry composition used for producing the negative electrode can be easily produced. In addition, the volume average particle diameter in this invention can be calculated | required by measuring a particle size distribution by laser diffraction.
合金系活物質のタップ密度は、特に制限されないが、0.6g/cm3以上のものが好適に用いられる。The tap density of the alloy-based active material is not particularly limited, but is preferably 0.6 g / cm 3 or more.
合金系活物質の比表面積(BET式)は、好ましくは3.0〜20.0m2/g、より好ましくは3.5〜15.0m2/g、特に好ましくは4.0〜10.0m2/gである。合金系活物質の比表面積が上記範囲にあることで、合金系活物質表面の活性点が増えるため、リチウムイオン二次電池の出力特性に優れる。なお、本発明において、「BET比表面積」とは、窒素吸着法によるBET比表面積のことをいい、ASTM D3037−81に準じて、測定される値である。The specific surface area (BET type) of the alloy-based active material is preferably 3.0 to 20.0 m 2 / g, more preferably 3.5 to 15.0 m 2 / g, and particularly preferably 4.0 to 10.0 m. 2 / g. When the specific surface area of the alloy-based active material is in the above range, the active points on the surface of the alloy-based active material are increased, so that the output characteristics of the lithium ion secondary battery are excellent. In the present invention, the “BET specific surface area” refers to a BET specific surface area determined by a nitrogen adsorption method, and is a value measured according to ASTM D3037-81.
(a2)炭素系活物質
炭素系活物質とは、リチウムが挿入可能な炭素を主骨格とする活物質をいい、具体的には、炭素質材料と黒鉛質材料が挙げられる。炭素質材料とは、一般的に炭素前駆体を2000℃以下で熱処理して炭素化させた黒鉛化度の低い(すなわち、結晶性の低い)炭素材料である。前記熱処理の温度の下限は、特に限定されないが、例えば500℃以上とすることができる。黒鉛質材料とは、易黒鉛性炭素を2000℃以上で熱処理することによって得られた黒鉛に近い高い結晶性を有する黒鉛質材料である。前記処理温度の上限は、特に限定されないが、例えば5000℃以下とすることができる。 (A2) Carbon-based active material The carbon-based active material refers to an active material having carbon as a main skeleton into which lithium can be inserted, and specifically includes a carbonaceous material and a graphite material. The carbonaceous material is generally a carbon material having a low graphitization degree (that is, low crystallinity) obtained by carbonizing a carbon precursor by heat treatment at 2000 ° C. or less. Although the minimum of the temperature of the said heat processing is not specifically limited, For example, it can be 500 degreeC or more. The graphite material is a graphite material having high crystallinity close to that of graphite obtained by heat-treating graphitizable carbon at 2000 ° C. or higher. Although the upper limit of the said processing temperature is not specifically limited, For example, it can be 5000 degrees C or less.
炭素質材料としては、例えば、熱処理温度によって炭素の構造を容易に変える易黒鉛性炭素や、ガラス状炭素に代表される非晶質構造に近い構造を持つ難黒鉛性炭素などが挙げられる。 Examples of the carbonaceous material include graphitizable carbon that easily changes the carbon structure depending on the heat treatment temperature, and non-graphitic carbon having a structure close to an amorphous structure typified by glassy carbon.
易黒鉛性炭素としては、例えば、石油や石炭から得られるタールピッチを原料とした炭素材料が挙げられる。具体例を挙げると、コークス、メソカーボンマイクロビーズ(MCMB)、メソフェーズピッチ系炭素繊維、熱分解気相成長炭素繊維などが挙げられる。MCMBとはピッチ類を400℃前後で加熱する過程で生成したメソフェーズ小球体を分離抽出した炭素微粒子である。メソフェーズピッチ系炭素繊維とは、前記メソフェーズ小球体が成長、合体して得られるメソフェーズピッチを原料とする炭素繊維である。熱分解気相成長炭素繊維とは、(1)アクリル高分子繊維などを熱分解する方法、(2)ピッチを紡糸して熱分解する方法、(3)鉄などのナノ粒子を触媒として用いて炭化水素を気相熱分解する触媒気相成長(触媒CVD)法により得られた炭素繊維である。 Examples of graphitizable carbon include carbon materials made from tar pitch obtained from petroleum or coal. Specific examples include coke, mesocarbon microbeads (MCMB), mesophase pitch carbon fibers, pyrolytic vapor grown carbon fibers, and the like. MCMB is carbon fine particles obtained by separating and extracting mesophase spherules produced in the process of heating pitches at around 400 ° C. The mesophase pitch-based carbon fiber is a carbon fiber using as a raw material mesophase pitch obtained by growing and coalescing the mesophase microspheres. Pyrolytic vapor-grown carbon fibers are (1) a method for pyrolyzing acrylic polymer fibers, (2) a method for spinning by spinning a pitch, and (3) using nanoparticles such as iron as a catalyst. It is a carbon fiber obtained by a catalytic vapor deposition (catalytic CVD) method in which hydrocarbon is vapor-phase pyrolyzed.
難黒鉛性炭素としては、フェノール樹脂焼成体、ポリアクリロニトリル系炭素繊維、擬等方性炭素、フルフリルアルコール樹脂焼成体(PFA)、ハードカーボンなどが挙げられる。 Examples of the non-graphitizable carbon include phenol resin fired bodies, polyacrylonitrile-based carbon fibers, pseudo-isotropic carbon, furfuryl alcohol resin fired bodies (PFA), and hard carbon.
黒鉛質材料としては、例えば、天然黒鉛、人造黒鉛が挙げられる。人造黒鉛としては、主に2800℃以上で熱処理した人造黒鉛、MCMBを2000℃以上で熱処理した黒鉛化MCMB、メソフェーズピッチ系炭素繊維を2000℃以上で熱処理した黒鉛化メソフェーズピッチ系炭素繊維などが挙げられる。 Examples of the graphite material include natural graphite and artificial graphite. Examples of artificial graphite include artificial graphite heat-treated at 2800 ° C or higher, graphitized MCMB heat-treated at 2000 ° C or higher, graphitized mesophase pitch carbon fiber heat-treated at 2000 ° C or higher. It is done.
前記の炭素系活物質の中でも、黒鉛質材料が好ましい。黒鉛質材料を用いることで、負極活物質層の密度を上げやすくなり、負極活物質層の密度が1.6g/cm3以上(当該密度の上限は、特に限定されないが、2.2g/cm3以下とすることができる。)である負極の作製が容易となる。負極活物質層の密度が前記範囲である負極活物質層を有する負極であれば、本発明の効果が顕著に現れる。Among the carbon-based active materials, a graphite material is preferable. By using the graphite material, it becomes easy to increase the density of the negative electrode active material layer, and the density of the negative electrode active material layer is 1.6 g / cm 3 or more (the upper limit of the density is not particularly limited, but 2.2 g / cm 3) or less.) Can be easily produced. If the negative electrode has a negative electrode active material layer in which the density of the negative electrode active material layer is in the above range, the effect of the present invention is remarkably exhibited.
炭素系活物質は、粒子状に整粒されたものが好ましい。粒子の形状が球形であると、電極成形時に、より高密度な電極が形成できる。炭素系活物質が粒子である場合、炭素系活物質の体積平均粒子径は、好ましくは0.1〜100μm、より好ましくは0.5〜50μm、特に好ましくは1〜30μmである。炭素系活物質の体積平均粒子径がこの範囲内であれば、負極を製造するために用いるスラリー組成物の作製が容易となる。 The carbon-based active material preferably has a particle size. When the shape of the particles is spherical, a higher density electrode can be formed during electrode molding. When the carbon-based active material is a particle, the volume-average particle diameter of the carbon-based active material is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and particularly preferably 1 to 30 μm. When the volume average particle diameter of the carbon-based active material is within this range, it becomes easy to prepare a slurry composition used for manufacturing the negative electrode.
炭素系活物質のタップ密度は、特に制限されないが、0.6g/cm3以上のものが好適に用いられる。The tap density of the carbon-based active material is not particularly limited, but is preferably 0.6 g / cm 3 or more.
炭素系活物質の比表面積は、好ましくは3.0〜20.0m2/g、より好ましくは3.5〜15.0m2/g、特に好ましくは4.0〜10.0m2/gである。炭素系活物質の比表面積が上記範囲にあることで、炭素系活物質表面の活性点が増えるため、リチウムイオン二次電池の出力特性に優れる。比表面積は例えばBET法により測定できる。The specific surface area of the carbon-based active material is preferably 3.0 to 20.0 m 2 / g, more preferably 3.5 to 15.0 m 2 / g, and particularly preferably 4.0 to 10.0 m 2 / g. is there. When the specific surface area of the carbon-based active material is in the above range, the active points on the surface of the carbon-based active material are increased, so that the output characteristics of the lithium ion secondary battery are excellent. The specific surface area can be measured by, for example, the BET method.
負極活物質は、合金系活物質1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。また、負極活物質の好ましい態様として、合金系活物質及び炭素系活物質を組み合わせた活物質を挙げることができる。負極活物質(a)として合金系活物質(a1)と炭素系活物質(a2)とを併用する場合、その混合方法としては、特に限定されず、従来公知の乾式混合や湿式混合が挙げられる。 As the negative electrode active material, one type of alloy-based active material may be used alone, or two or more types may be used in combination at any ratio. Moreover, the active material which combined the alloy type active material and the carbon type active material can be mentioned as a preferable aspect of a negative electrode active material. When the alloy-based active material (a1) and the carbon-based active material (a2) are used in combination as the negative electrode active material (a), the mixing method is not particularly limited, and conventionally known dry mixing and wet mixing may be mentioned. .
負極活物質(a)において、合金系活物質(a1)と炭素系活物質(a2)とを併用する場合、炭素系活物質(a2)100質量部に対して、合金系活物質(a1)を1〜50質量部含むことが好ましい。合金系活物質と炭素系活物質とを上記範囲で混合することにより、従来の炭素系活物質のみを用いて得られる負極よりも容量の大きい電池を得ることができ、かつ負極の密着強度の低下やサイクル特性の低下を防ぐことができる。合金系活物質(a1)と炭素系活物質(a2)とを前記範囲で併用する負極活物質層を有する負極であれば、本発明の効果が顕著に現れる。 In the negative electrode active material (a), when the alloy-based active material (a1) and the carbon-based active material (a2) are used in combination, the alloy-based active material (a1) with respect to 100 parts by mass of the carbon-based active material (a2). It is preferable that 1-50 mass parts is included. By mixing the alloy-based active material and the carbon-based active material in the above range, a battery having a larger capacity than the negative electrode obtained using only the conventional carbon-based active material can be obtained, and the adhesion strength of the negative electrode can be increased. It is possible to prevent deterioration and cycle characteristics. If it is a negative electrode which has a negative electrode active material layer which uses an alloy type active material (a1) and a carbon type active material (a2) together in the said range, the effect of this invention will show up notably.
(b)負極用結着剤
負極用結着剤は、負極において負極活物質を集電体の表面に結着させる成分であり、負極活物質を保持する性能に優れ、集電体に対する密着性が高いものを用いることが好ましい。通常、結着剤の材料としては重合体を用いる。結着剤の材料としての重合体は単独重合体でもよく、共重合体でもよい。負極用結着剤の重合体としては、特に限定はされないが、例えば、フッ素重合体、ジエン重合体、アクリレート重合体、ポリイミド、ポリアミド、ポリウレタン等の高分子化合物が挙げられ、中でも、フッ素重合体、ジエン重合体またはアクリレート重合体が好ましく、耐電圧を高くでき、かつ二次電池のエネルギー密度を高くすることができる点でジエン重合体またはアクリレート重合体がより好ましく、電極の強度を向上させる点でジエン重合体が特に好ましい。 (B) Negative electrode binder The negative electrode binder is a component that binds the negative electrode active material to the surface of the current collector in the negative electrode, has excellent performance of holding the negative electrode active material, and adheres to the current collector. It is preferable to use one having a high value. Usually, a polymer is used as the binder material. The polymer as the binder material may be a homopolymer or a copolymer. The polymer for the binder for the negative electrode is not particularly limited, and examples thereof include polymer compounds such as fluoropolymers, diene polymers, acrylate polymers, polyimides, polyamides, polyurethanes, among others, fluoropolymers. A diene polymer or an acrylate polymer is preferable, and a diene polymer or an acrylate polymer is more preferable in that the withstand voltage can be increased and the energy density of the secondary battery can be increased, and the strength of the electrode is improved. Diene polymers are particularly preferred.
ジエン重合体は、共役ジエン単量体を重合して形成される構造単位(以下、「共役ジエン単量体単位」と記すことがある。)を含む重合体であり、具体的には、共役ジエンの単独重合体;異なる種類の共役ジエン同士の共重合体;共役ジエンを含む単量体混合物を重合して得られる共重合体、またはそれらの水素添加物などが挙げられる。前記共役ジエンとしては、例えば、1,3−ブタジエン、2−メチル−1,3−ブタジエン、2,3−ジメチル−1,3−ブタジエン、2−エチル−1,3−ブタジエン、2−クロル−1,3−ブタジエン、1,3−ペンタジエン、1,3−ヘキサジエン、および2,4−ヘキサジエンなどが挙げられる。これらの中でも、1,3−ブタジエン、2−メチル−1,3−ブタジエンが好ましい。なお、共役ジエンは、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。ジエン重合体における共役ジエン単量体単位の割合は、好ましくは20質量%以上60質量%以下、好ましくは30質量%以上55質量%以下である。 The diene polymer is a polymer including a structural unit formed by polymerizing a conjugated diene monomer (hereinafter sometimes referred to as “conjugated diene monomer unit”). Examples include diene homopolymers; copolymers of different types of conjugated dienes; copolymers obtained by polymerizing monomer mixtures containing conjugated dienes, or hydrogenated products thereof. Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, and 2-chloro- Examples include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and 2,4-hexadiene. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable. In addition, a conjugated diene may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. The ratio of the conjugated diene monomer unit in the diene polymer is preferably 20% by mass to 60% by mass, and preferably 30% by mass to 55% by mass.
前記ジエン重合体は、共役ジエン単量体単位の他に、ニトリル基含有単量体単位を含んでいてもよい。ニトリル基含有単量体単位を構成するニトリル基含有単量体の具体例としては、アクリロニトリル、メタクリロニトリル、α−クロロアクリロニトリル、α−エチルアクリロニトリル等のα,β−不飽和ニトリル化合物などが挙げられ、中でもアクリロニトリルが好ましい。ジエン重合体におけるニトリル基含有単量体単位の割合は、好ましくは5〜40質量%、より好ましくは5〜30質量%の範囲である。ニトリル基含有単量体単位の割合を上記範囲とすることで、得られる電極強度がより向上する。なお、ニトリル基含有単量体は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。 The diene polymer may contain a nitrile group-containing monomer unit in addition to the conjugated diene monomer unit. Specific examples of the nitrile group-containing monomer constituting the nitrile group-containing monomer unit include α, β-unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, and the like. Of these, acrylonitrile is preferred. The ratio of the nitrile group-containing monomer unit in the diene polymer is preferably 5 to 40% by mass, more preferably 5 to 30% by mass. By setting the ratio of the nitrile group-containing monomer unit within the above range, the obtained electrode strength is further improved. In addition, a nitrile group containing monomer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
また、前記ジエン重合体には、上記単量体単位の他に、他の単量体を重合して形成される構造単位を含んでいてもよい。他の単量体単位を構成する他の単量体としては、アクリル酸、メタクリル酸、イタコン酸、フマル酸などの不飽和カルボン酸類;スチレン、クロロスチレン、ビニルトルエン、t−ブチルスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルナフタレン、クロロメチルスチレン、ヒドロキシメチルスチレン、α−メチルスチレン、ジビニルベンゼン等のスチレン系単量体;エチレン、プロピレン等のオレフィン類;酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類;アクリルアミド、N−メチロールアクリルアミド、アクリルアミド−2−メチルプロパンスルホン酸などのアミド系単量体;メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類;メチルビニルケトン、エチルビニルケトン、ブチルビニルケトン、ヘキシルビニルケトン、イソプロペニルビニルケトン等のビニルケトン類;N−ビニルピロリドン、ビニルピリジン、ビニルイミダゾール等の複素環含有ビニル化合物が挙げられる。なお、前記他の単量体は、それぞれ、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。 Further, the diene polymer may contain a structural unit formed by polymerizing another monomer in addition to the monomer unit. Other monomers constituting other monomer units include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid; styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoate Styrene monomers such as acid, methyl vinyl benzoate, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, α-methyl styrene, divinylbenzene; olefins such as ethylene, propylene; vinyl acetate, vinyl propionate, vinyl butyrate Vinyl esters such as vinyl benzoate; amide monomers such as acrylamide, N-methylol acrylamide, and acrylamide-2-methylpropane sulfonic acid; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; Ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, such as isopropenyl vinyl ketone; N- vinylpyrrolidone, vinylpyridine, and a heterocyclic containing vinyl compounds such as vinyl imidazole. In addition, the said other monomer may be used individually by 1 type, respectively, and may be used combining two or more types by arbitrary ratios.
アクリレート重合体は、一般式(1):CH2=CR1−COOR2(式中、R1は水素原子またはメチル基を、R2はアルキル基またはシクロアルキル基を表す。)で表される化合物由来の単量体を重合して形成される単量体単位((メタ)アクリル酸エステル単量体単位)を含む重合体である。(メタ)アクリル酸エステル単量体単位を構成する単量体の具体例としては、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸t-ブチル、アクリル酸n−アミル、アクリル酸イソアミル、アクリル酸n−ヘキシル、アクリル酸2−エチルヘキシル、アクリル酸ラウリル、アクリル酸ステアリルなどのアクリル酸エステル;メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸n−ブチル、メタクリル酸イソブチル、メタクリル酸t-ブチル、メタクリル酸n−アミル、メタクリル酸イソアミル、メタクリル酸n−ヘキシル、メタクリル酸2−エチルヘキシル、メタクリル酸ラウリル、メタクリル酸ステアリルなどのメタクリル酸エステル等が挙げられる。これらの中でも、アクリル酸エステルが好ましく、アクリル酸n−ブチルおよびアクリル酸2−エチルヘキシルが、得られる電極の強度を向上できる点で、特に好ましい。アクリレート重合体中の(メタ)アクリル酸エステル単量体単位の割合は、通常50質量%以上、好ましくは70質量%以上である。前記(メタ)アクリル酸エステル単量体単位の割合が前記範囲であるアクリレート重合体を用いると、耐熱性が高く、かつ得られる電極の内部抵抗を小さくできる。The acrylate polymer is represented by the general formula (1): CH 2 = CR 1 —COOR 2 (wherein R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group or a cycloalkyl group). It is a polymer containing a monomer unit ((meth) acrylate monomer unit) formed by polymerizing a monomer derived from a compound. Specific examples of the monomer constituting the (meth) acrylate monomer unit include ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, Acrylic acid esters such as n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate; ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n methacrylate -Methyl methacrylate such as butyl, isobutyl methacrylate, t-butyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate Ester, and the like. Among these, acrylic acid esters are preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable in that the strength of the obtained electrode can be improved. The ratio of the (meth) acrylic acid ester monomer unit in the acrylate polymer is usually 50% by mass or more, preferably 70% by mass or more. When an acrylate polymer in which the proportion of the (meth) acrylic acid ester monomer unit is in the above range is used, the heat resistance is high and the internal resistance of the obtained electrode can be reduced.
前記アクリレート重合体は、(メタ)アクリル酸エステル単量体単位の他に、ニトリル基含有単量体単位を含んでいることが好ましい。ニトリル基含有単量体としては、アクリロニトリルやメタクリロニトリルなどが挙げられ、中でもアクリロニトリルが、集電体と負極活物質層との結着性が高まり、電極強度が向上できる点で好ましい。アクリレート重合体におけるニトリル基含有単量体単位の割合は、好ましくは5〜35質量%、より好ましくは10〜30質量%の範囲である。ニトリル基含有単量体単位の量を上記範囲とすることで、得られる電極強度がより向上する。 The acrylate polymer preferably includes a nitrile group-containing monomer unit in addition to the (meth) acrylic acid ester monomer unit. Examples of the nitrile group-containing monomer include acrylonitrile, methacrylonitrile, and the like. Among them, acrylonitrile is preferable in that the binding strength between the current collector and the negative electrode active material layer is increased and the electrode strength can be improved. The ratio of the nitrile group-containing monomer unit in the acrylate polymer is preferably in the range of 5 to 35% by mass, more preferably 10 to 30% by mass. By setting the amount of the nitrile group-containing monomer unit within the above range, the obtained electrode strength is further improved.
前記アクリレート重合体には、上記単量体単位の他に、共重合可能なカルボン酸基含有単量体を重合して形成される構造単位(以下、「カルボン酸基含有単量体単位」と記すことがある。)を用いることができる。カルボン酸基含有単量体の具体例としては、アクリル酸、メタクリル酸などの一塩基酸含有単量体;マレイン酸、フマル酸、イタコン酸などの二塩基酸含有単量体が挙げられる。なかでも、二塩基酸含有単量体が好ましく、集電体との結着性を高め、電極強度を向上できる点で、イタコン酸が特に好ましい。これらの一塩基酸含有単量体、二塩基酸含有単量体は、それぞれ単独でまたは2種以上を組み合わせて使用できる。アクリレート重合体中のカルボン酸基含有単量体単位の割合は、好ましくは1〜50質量%、より好ましくは1〜20質量%、特に好ましくは1〜10質量%の範囲である。カルボン酸基含有単量体単位の量を上記範囲とすることで、得られる電極の強度がより向上する。 In addition to the above monomer units, the acrylate polymer includes a structural unit formed by polymerizing a copolymerizable carboxylic acid group-containing monomer (hereinafter referred to as “carboxylic acid group-containing monomer unit”). May be used). Specific examples of the carboxylic acid group-containing monomer include monobasic acid-containing monomers such as acrylic acid and methacrylic acid; dibasic acid-containing monomers such as maleic acid, fumaric acid, and itaconic acid. Among these, a dibasic acid-containing monomer is preferable, and itaconic acid is particularly preferable in terms of enhancing the binding property with the current collector and improving the electrode strength. These monobasic acid-containing monomers and dibasic acid-containing monomers can be used alone or in combination of two or more. The ratio of the carboxylic acid group-containing monomer unit in the acrylate polymer is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass. By setting the amount of the carboxylic acid group-containing monomer unit in the above range, the strength of the obtained electrode is further improved.
さらに、前記アクリレート重合体には、上記単量体単位の他に、共重合可能な単量体を重合して得られる構造単位を含んでいてもよい、前記他の単量体の具体例としては、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレートなどの2つ以上の炭素−炭素二重結合を有するカルボン酸エステル類;パーフルオロオクチルエチルアクリレートやパーフルオロオクチルエチルメタクリレートなどの側鎖にフッ素を含有する不飽和エステル類;スチレン、クロロスチレン、ビニルトルエン、t−ブチルスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルナフタレン、クロロメチルスチレン、ヒドロキシメチルスチレン、α−メチルスチレン、ジビニルベンゼン等のスチレン単量体;アクリルアミド、N−メチロールアクリアミド、アクリルアミド−2−メチルプロパンスルホン酸などのアミド単量体;エチレン、プロピレン等のオレフィン類;ブタジエン、イソプレン等のジエン単量体;塩化ビニル、塩化ビニリデン等のハロゲン原子含有単量体;酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類;メチルビニルエーテル、エチルビニルエーテル、ブチルビエルエーテル等のビニルエーテル類;メチルビニルケトン、エチルビニルケトン、ブチルビニルケトン、ヘキシルビニルケトン、イソプロペニルビニルケトン等のビニルケトン類;N−ビニルピロリドン、ビニルピリジン、ビニルイミダゾール等の複素環含有ビニル化合物;アリルグリシジルエーテルなどのグリシジルエーテル類;グリシジルアクリレート、グリシジルメタクリレートなどのグリシジルエステル類などが挙げられる。アクリレート重合体におけるこれらの共重合可能な他の単量体単位の割合は、利用目的によって適宜調整されればよい。 Further, the acrylate polymer may contain a structural unit obtained by polymerizing a copolymerizable monomer, in addition to the monomer unit, as a specific example of the other monomer. Is a carboxylic acid ester having two or more carbon-carbon double bonds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane triacrylate; side chain such as perfluorooctylethyl acrylate and perfluorooctylethyl methacrylate Unsaturated ester containing fluorine in styrene, chlorostyrene, vinyltoluene, t-butylstyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylnaphthalene, chloromethylstyrene, hydroxymethylstyrene, α-methylstyrene, divinylbenzene Stills such as Monomers; Amide monomers such as acrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid; Olefins such as ethylene and propylene; Diene monomers such as butadiene and isoprene; Vinyl chloride and vinylidene chloride Halogen atom-containing monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; methyl vinyl ketone, ethyl vinyl ketone, Vinyl ketones such as butyl vinyl ketone, hexyl vinyl ketone and isopropenyl vinyl ketone; heterocycle-containing vinyl compounds such as N-vinyl pyrrolidone, vinyl pyridine and vinyl imidazole; glycidyl such as allyl glycidyl ether Ether like; glycidyl acrylate, and glycidyl esters such as glycidyl methacrylate. The proportion of these other copolymerizable monomer units in the acrylate polymer may be appropriately adjusted depending on the purpose of use.
また上記の他にも負極用結着剤としては、ポリエチレン、ポリプロピレン、ポリイソブチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルイソブチルエーテル、ポリアクリロニトリル、ポリメタクリロニトリル、ポリメタクリル酸メチル、ポリアクリル酸メチル、ポリメタクリル酸エチル、ポリ酢酸アリル、ポリスチレンなどのビニル重合体;ポリオキシメチレン、ポリオキシエチレン、ポリ環状チオエーテル、ポリジメチルシロキサンなど主鎖にヘテロ原子を含むエーテル重合体;ポリラクトン、ポリ環状無水物、ポリエチレンテレフタレート、ポリカーボネートなどの縮合エステル重合体;ナイロン6、ナイロン66、ポリ−m−フェニレンイソフタラミド、ポリ−p−フェニレンテレフタラミド、ポリピロメリットイミドなどの縮合アミド系重合体、後述する増粘剤などが挙げられる。 In addition to the above, binders for negative electrodes include polyethylene, polypropylene, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl acetate, polyvinyl alcohol, polyvinyl isobutyl ether, poly Vinyl polymers such as acrylonitrile, polymethacrylonitrile, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyallyl acetate, and polystyrene; polyoxymethylene, polyoxyethylene, polycyclic thioether, polydimethylsiloxane, etc. Ether polymers containing hetero atoms in the chain; condensed ester polymers such as polylactone, polycyclic anhydride, polyethylene terephthalate, polycarbonate; nylon 6, nylon 66, poly-m- E d isophthalamide, poly -p- phenylene terephthalamide, condensation amide polymers such as poly pyromellitic imide, and the like thickeners which will be described later.
負極用結着剤の形状は、特に制限はないが、集電体との密着性が良く、また、作成した電極の容量の低下や充放電の繰り返しによる劣化を抑えることができるため、粒子状であることが好ましい。粒子状結着剤は、分散媒に分散させた状態において粒子形状を保持・存在するものであればよいが、負極活物質層においても粒子形状を保持した状態で存在できるものが好ましい。本発明において、「粒子状態を保持した状態」とは、完全に粒子形状を保持した状態である必要はなく、その粒子形状をある程度保持した状態であればよい。粒子状結着剤としては、例えば、ラテックスのごとき結着剤の粒子が水に分散した状態のものや、このような分散液を乾燥して得られる粉末状のものが挙げられる。 The shape of the binder for the negative electrode is not particularly limited, but it has good adhesion to the current collector, and since it can suppress deterioration of the capacity of the created electrode and repeated charge / discharge, it is particulate. It is preferable that The particulate binder is not particularly limited as long as it retains and exists in the state of being dispersed in a dispersion medium. However, it is preferable that the particulate binder can be present in a state of retaining the particle shape even in the negative electrode active material layer. In the present invention, the “state in which the particle state is maintained” does not have to be a state in which the particle shape is completely maintained, and may be in a state in which the particle shape is maintained to some extent. Examples of the particulate binder include those in which the binder particles such as latex are dispersed in water, and powders obtained by drying such a dispersion.
負極用結着剤のガラス転移温度(Tg)は、好ましくは50℃以下、さらに好ましくは−40〜0℃である。結着剤のガラス転移温度(Tg)がこの範囲にあると、少量の使用量で密着性に優れ、電極強度が強く、柔軟性に富み、電極形成時のプレス工程により電極密度を容易に高めることができる。 The glass transition temperature (Tg) of the negative electrode binder is preferably 50 ° C. or lower, more preferably −40 to 0 ° C. When the glass transition temperature (Tg) of the binder is within this range, the adhesiveness is excellent with a small amount of use, the electrode strength is strong, the flexibility is high, and the electrode density is easily increased by the pressing process at the time of electrode formation. be able to.
負極用結着剤が粒子状結着剤である場合、その個数平均粒子径は、格別な限定はないが、通常は0.01〜1μm、好ましくは0.03〜0.8μm、より好ましくは0.05〜0.5μmである。結着剤の個数平均粒子径がこの範囲であるときは、少量の使用でも優れた密着力を負極活物質層に与えることができる。ここで、個数平均粒子径は、透過型電子顕微鏡写真で無作為に選んだ結着剤粒子100個の径を測定し、その算術平均値として算出される個数平均粒子径である。粒子の形状は球形、異形、どちらでもかまわない。
これらの結着剤は単独でまたは二種類以上を組み合わせて用いることができる。When the negative electrode binder is a particulate binder, the number average particle diameter is not particularly limited, but is usually 0.01 to 1 μm, preferably 0.03 to 0.8 μm, more preferably. 0.05 to 0.5 μm. When the number average particle diameter of the binder is within this range, excellent adhesion can be imparted to the negative electrode active material layer even with a small amount of use. Here, the number average particle diameter is a number average particle diameter calculated as an arithmetic average value obtained by measuring the diameter of 100 binder particles randomly selected in a transmission electron micrograph. The shape of the particles can be either spherical or irregular.
These binders can be used alone or in combination of two or more.
負極用結着剤の量は、負極活物質100質量部に対して、通常は0.1〜50質量部、好ましくは0.5〜20質量部、より好ましくは1〜10質量部の範囲である。結着剤の量がこの範囲にあると、得られる負極活物質層と集電体との密着性が充分に確保でき、二次電池の容量を高く、且つ内部抵抗を低くすることができる。 The amount of the binder for negative electrode is usually 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material. is there. When the amount of the binder is within this range, sufficient adhesion between the obtained negative electrode active material layer and the current collector can be ensured, the capacity of the secondary battery can be increased, and the internal resistance can be decreased.
(c)導電材
負極活物質層は、導電材を含有してもよい。負極に含まれる導電材の粒子径は、個数平均粒子径で、5〜40nm、好ましくは10〜38nm、より好ましくは15〜36nmである。導電材としては、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。導電材を含有することにより、負極活物質同士の電気的接触を向上させることができ、リチウムイオン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。導電材の含有量は、負極活物質の総量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。 (C) The conductive material negative electrode active material layer may contain a conductive material. The particle diameter of the conductive material contained in the negative electrode is a number average particle diameter of 5 to 40 nm, preferably 10 to 38 nm, and more preferably 15 to 36 nm. As the conductive material, conductive carbon such as acetylene black, ketjen black, carbon black, graphite, vapor-grown carbon fiber, and carbon nanotube can be used. By containing a conductive material, electrical contact between the negative electrode active materials can be improved, and when used in a lithium ion secondary battery, the discharge rate characteristics can be improved. The content of the conductive material 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 negative electrode active material.
その他の負極成分
また、負極にはさらに、任意の成分としては、上記した正極と同様に、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が含まれていてもよく、さらに、負極製造時に調整するスラリーに含まれる増粘剤等が残留していてもよい。 Other negative electrode components In addition, the negative electrode may further contain, as an optional component, a reinforcing material, a leveling agent, an electrolytic solution additive having a function of inhibiting electrolytic solution decomposition, etc. Furthermore, the thickener etc. which are contained in the slurry adjusted at the time of negative electrode manufacture may remain | survive.
リチウムイオン二次電池負極用スラリー組成物の製造方法
リチウムイオン二次電池負極用スラリー組成物は、上述した負極活物質(a)、負極用結着剤(b)、導電材(c)、その他の添加剤を分散媒中で混合して得られる。分散媒としては、水および有機溶媒のいずれも使用できる。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ノン、エチルシクロヘキサノンなどのケトン類;メチレンクロライド、クロロホルム、四塩化炭素など塩素系脂肪族炭化水素;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。 Method for Producing Slurry Composition for Lithium Ion Secondary Battery Negative Electrode The slurry composition for a lithium ion secondary battery negative electrode includes the negative electrode active material (a), the binder for negative electrode (b), the conductive material (c), and the like. Obtained by mixing these additives in a dispersion medium. As the dispersion medium, either water or an organic solvent can be used. Examples of 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, methylcyclohexanone and ethylcyclohexanone. Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, γ-butyrolactone and ε-caprolactone; Acylonitriles such as acetonitrile and propionitrile; Tetrahydrofuran and Ethylene Ethers such as glycol diethyl ether: alcohols such as methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether; Amides such as tilpyrrolidone and N, N-dimethylformamide may be mentioned.
これらの分散媒は、単独で使用しても、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、各成分の分散性に優れ、沸点が低く揮発性の高い分散媒が、短時間でかつ低温で除去できるので好ましい。具体的には、アセトン、トルエン、シクロヘキサノン、シクロペンタン、テトラヒドロフラン、シクロヘキサン、キシレン、水、若しくはN−メチルピロリドン、またはこれらの混合溶媒が好ましい。 These dispersion media may be used alone or in combination of two or more as a mixed solvent. Among these, a dispersion medium having excellent dispersibility of each component and having a low boiling point and high volatility is preferable because it can be removed in a short time and at a low temperature. Specifically, acetone, toluene, cyclohexanone, cyclopentane, tetrahydrofuran, cyclohexane, xylene, water, N-methylpyrrolidone, or a mixed solvent thereof is preferable.
混合方法は特に限定はされないが、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、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。 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. Further, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader can be used.
リチウムイオン二次電池負極
リチウムイオン二次電池負極は、上述したリチウムイオン二次電池負極用スラリー組成物を集電体に塗布、乾燥してなる。 Lithium ion secondary battery negative electrode A lithium ion secondary battery negative electrode is obtained by applying and drying the above-described slurry composition for a lithium ion secondary battery negative electrode on a current collector.
リチウムイオン二次電池負極の製造方法は、上記負極用スラリー組成物を、集電体の片面または両面に、塗布、乾燥して、負極活物質層を形成する工程を含む。 The manufacturing method of a lithium ion secondary battery negative electrode includes the process of apply | coating and drying the said slurry composition for negative electrodes on the single side | surface or both surfaces of a collector, and forming a negative electrode active material layer.
負極用スラリー組成物を集電体上に塗布する方法は特に限定されない。例えば、ドクターブレード法、ディップ法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、およびハケ塗り法などの方法が挙げられる。 The method for applying the slurry composition for negative electrode on the current collector is not particularly limited. Examples of 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.
乾燥方法としては、例えば、温風、熱風、低湿風による乾燥、真空乾燥、(遠)赤外線や電子線などの照射による乾燥法が挙げられる。乾燥時間は通常5〜30分であり、乾燥温度は通常40〜180℃である。 Examples of the drying method include drying by 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.
リチウムイオン二次電池負極を製造するに際して、集電体上に上記負極用スラリー組成物を塗布、乾燥後、金型プレスやロールプレスなどを用い、加圧処理により負極活物質層の空隙率を低くする工程を有することが好ましい。負極活物質層の空隙率は、好ましくは5〜30%、より好ましくは7〜20%である。負極活物質層の空隙率が高すぎると充電効率や放電効率が悪化する場合がある。空隙率が低すぎると、高い体積容量が得難く、負極活物質層が集電体から剥がれ易く不良を発生し易くなる場合がある。さらに、負極用結着剤として硬化性の重合体を用いる場合は、硬化させることが好ましい。 When producing a negative electrode for a lithium ion secondary battery, after applying the above slurry composition for the negative electrode on the current collector and drying, the porosity of the negative electrode active material layer is increased by pressure treatment using a die press or a roll press. It is preferable to have a lowering step. The porosity of the negative electrode active material layer is preferably 5 to 30%, more preferably 7 to 20%. If the porosity of the negative electrode active material layer is too high, charging efficiency and discharging efficiency may be deteriorated. If the porosity is too low, it is difficult to obtain a high volume capacity, and the negative electrode active material layer is likely to be peeled off from the current collector, which may cause defects. Further, when a curable polymer is used as the binder for the negative electrode, it is preferably cured.
リチウムイオン二次電池負極における負極活物質層の厚みは、通常5〜300μmであり、好ましくは30〜250μmである。負極活物質層の厚みが上記範囲にあることにより、負荷特性及びサイクル特性共に高い特性を示す二次電池を得ることができる。 The thickness of the negative electrode active material layer in the lithium ion secondary battery negative electrode is usually 5 to 300 μm, preferably 30 to 250 μm. When the thickness of the negative electrode active material layer is in the above range, it is possible to obtain a secondary battery that exhibits high load characteristics and cycle characteristics.
負極活物質層における負極活物質の含有割合は、好ましくは85〜99質量%、より好ましくは88〜97質量%である。負極活物質層における負極活物質の含有割合が上記範囲であることにより、高い容量を示しながらも柔軟性、結着性を示す二次電池を得ることができる。 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. When the content ratio of the negative electrode active material in the negative electrode active material layer is in the above range, it is possible to obtain a secondary battery that exhibits flexibility and binding properties while exhibiting high capacity.
負極活物質層の密度は、好ましくは1.6〜1.9g/cm3であり、より好ましくは1.65〜1.85g/cm3である。負極活物質層の密度が上記範囲であることにより、高容量の二次電池を得ることができる。The density of the negative electrode active material layer is preferably 1.6 to 1.9 g / cm 3 , and more preferably 1.65 to 1.85 g / cm 3 . When the density of the negative electrode active material layer is within the above range, a high-capacity secondary battery can be obtained.
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、リチウムイオン二次電池負極に用いる集電体としては銅が特に好ましい。 The current collector is not particularly limited as long as it is an electrically conductive and electrochemically durable material, but is preferably a metal material because of its heat resistance, for example, iron, copper, aluminum, nickel, stainless steel. Examples include steel, titanium, tantalum, gold, and platinum. Among these, copper is particularly preferable as the current collector used for the negative electrode of the lithium ion secondary battery.
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、負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してもよい。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、負極活物質層の接着強度や導電性を高めるために、集電体表面にプライマー層などを形成してもよい。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 may be used after roughening in advance in order to increase the adhesive strength with the negative electrode active material layer. Examples of the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method. In the mechanical 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. Further, a primer layer or the like may be formed on the current collector surface in order to increase the adhesive strength or conductivity of the negative electrode active material layer.
(リチウムイオン二次電池)
本発明に係るリチウムイオン二次電池は、上記した正極および負極を備え、非水電解液を有し、通常はセパレータを含む。(Lithium ion secondary battery)
The lithium ion secondary battery according to the present invention includes the above-described positive electrode and negative electrode, has a non-aqueous electrolyte, and usually includes a separator.
非水電解液
非水電解液は、特に限定されず、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、非水電解液に対して、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。 Nonaqueous Electrolytic Solution The nonaqueous electrolytic solution is not particularly limited, and a nonaqueous electrolytic solution obtained by dissolving a lithium salt as a supporting electrolyte in a nonaqueous solvent can be used. Examples of 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. In particular, 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 nonaqueous electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity is lowered, and the charging characteristics and discharging characteristics of the battery are degraded.
非水電解液に使用する溶媒としては、支持電解質を溶解させるものであれば特に限定されないが、通常、ジメチルカーボネート(DMC)、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)、プロピレンカーボネート(PC)、ブチレンカーボネート(BC)、およびメチルエチルカーボネート(MEC)などのアルキルカーボネート類;γ−ブチロラクトン、ギ酸メチルなどのエステル類、1,2−ジメトキシエタン、およびテトラヒドロフランなどのエーテル類;スルホラン、およびジメチルスルホキシドなどの含硫黄化合物類;が用いられる。特に高いイオン伝導性が得易く、使用温度範囲が広いため、ジメチルカーボネート、エチレンカーボネート、プロピレンカーボネート、ジエチルカーボネート、メチルエチルカーボネートが好ましい。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。 The solvent used for the non-aqueous electrolyte is not particularly limited as long as it can dissolve the supporting electrolyte, but is usually dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC). , Alkyl carbonates such as butylene carbonate (BC), and methyl ethyl carbonate (MEC); esters such as γ-butyrolactone, methyl formate, ethers such as 1,2-dimethoxyethane, and tetrahydrofuran; sulfolane, and dimethyl sulfoxide Sulfur-containing compounds such as In particular, 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.
上記以外の非水電解液としては、ポリエチレンオキシド、ポリアクリロニトリルなどのポリマー電解質に非水電解液を含浸したゲル状ポリマー電解質や、硫化リチウム、LiI、Li3Nなどの無機固体電解質を挙げることができる。Examples of non-aqueous electrolytes other than the above include gel polymer electrolytes in which a polymer electrolyte such as polyethylene oxide and polyacrylonitrile is impregnated with a non-aqueous electrolyte, and inorganic solid electrolytes such as lithium sulfide, LiI, and Li 3 N. it can.
また、非水電解液には添加剤を含有させて用いることも可能である。添加剤としてはビニレンカーボネート(VC)などのカーボネート系の化合物の他に、フルオロエチレンカーボネート等の含フッ素カーボネート、エチルメチルスルフォンが好ましい。これらの中でも、含フッ素カーボネートのようなフッ素系電解液添加材は、耐電圧が高い。高容量化に伴い、充放電時の電圧も高くなりつつあり、エチレンカーボネートやプロピレンカーボネートなどからなる電解液では高電圧に耐えられず、分解することがあるため、上記のフッ素系電解液添加材を非水電解液に配合することが好ましい。 Moreover, it is also possible to use the non-aqueous electrolyte with an additive. As the additive, in addition to carbonate compounds such as vinylene carbonate (VC), fluorine-containing carbonates such as fluoroethylene carbonate and ethyl methyl sulfone are preferable. Among these, a fluorinated electrolyte additive such as fluorinated carbonate has a high withstand voltage. As the capacity increases, the voltage during charging and discharging is also increasing, and electrolytes made of ethylene carbonate, propylene carbonate, etc. cannot withstand high voltages and may decompose, so the above-mentioned fluorine-based electrolyte additive Is preferably blended into the non-aqueous electrolyte.
セパレータ
セパレータ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としては、(a)気孔部を有する多孔性セパレータ、(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、または(c)無機セラミック粉末などの非導電性粒子及び結着剤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、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、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などがある。 The separator separator is a porous substrate having pores, and usable separators include (a) a porous separator having pores, and (b) a porous material having a polymer coating layer formed on one or both sides. Examples of the separator include (c) a porous separator on which a porous resin coat layer containing non-conductive particles such as inorganic ceramic powder and a binder 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. There are polymer films for polymer electrolytes or gel polymer electrolytes, separators coated with a gelled polymer coating layer, or separators coated with a porous membrane layer made of a dispersant for inorganic fillers or inorganic fillers. .
リチウムイオン二次電池の製造方法
本発明のリチウムイオン二次電池の製造方法は、特に限定されない。例えば、上述した正極と負極とをセパレータ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、捲回型パウチセルなどいずれであってもよい。特に、本発明によれば、活物質層が柔軟であり、屈曲時に活物質層のクラック発生がないため、捲回型パウチセルの製造に好ましく適用できる。 Manufacturing method of lithium ion secondary battery The manufacturing method of the lithium ion secondary battery of this invention is not specifically limited. For example, the above-described positive electrode and negative 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. Further, if necessary, 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 shape, a flat type, a wound type pouch cell, and the like. In particular, according to the present invention, the active material layer is flexible, and the active material layer does not crack when bent, and therefore can be preferably applied to the production of a wound pouch cell.
以下に、実施例を挙げて本発明を説明するが、本発明はこれに限定されるものではない。なお、本実施例における部および%は、特記しない限り質量基準である。実施例および比較例において、各種物性は以下のように評価した。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, unless otherwise indicated, the part and% in a present Example are a mass reference | standard. In the examples and comparative examples, various physical properties were evaluated as follows.
(SP値)
SP値とは、溶解度パラメーターのことを意味する。このSP値はSmallが提案した「分子引力定数法」によって求めた。この方法は、化合物分子を構成する官能基(原子団)の特性値である分子引力定数(G)の統計と分子量から、次式にしたがって求める方法である。
δ=ΣG/V=dΣG/M
前記の式において、δはSP値を表し、ΣGは分子引力定数Gの総計を表し、Vは比容を表し、Mは分子量を表し、dは比重を表す。
さらに、2種類以上のポリマーを組み合わせた場合は、ポリマー全体のSP値として個々のポリマーのSP値と混合モル比とから計算、前述の計算式を用いて求めた。(SP value)
The SP value means the solubility parameter. The SP value was determined by the “molecular attractive constant method” proposed by Small. This method is a method for obtaining from the statistics of the molecular attraction constant (G), which is the characteristic value of the functional group (atomic group) constituting the compound molecule, and the molecular weight according to the following formula.
δ = ΣG / V = dΣG / M
In the above formula, δ represents the SP value, ΣG represents the total molecular attractive constant G, V represents the specific volume, M represents the molecular weight, and d represents the specific gravity.
Furthermore, when two or more types of polymers were combined, the SP value of the whole polymer was calculated from the SP value of each polymer and the mixing molar ratio, and was determined using the above-described calculation formula.
(正極活物質の被覆確認)
正極活物質と正極用結着剤とニトリル基含有アクリル重合体の混合比を100:1.6:0.4としてスラリーを作製し、集電体(アルミ箔)上に塗布乾燥し電極とした。
電極表面を走査型電子顕微鏡(日立製作所製S−3400N)にて観察を行った。観察条件は、倍率を2000倍、加速電圧を15kVにて、100μm×100μm方形の画像観察を行った。さらに、同走査型電子顕微鏡に付属のエネルギー分散型X線分析装置(Bruker製 Quantax)で、ニッケル原子と窒素原子および炭素原子の元素マッピングを行いそれぞれのマッピング画像を作製した。この操作を電極上の5か所をランダムに選び5回行った。
その画像上で、長辺と短辺が10μm以上であり、正極活物質粒子の表面が他の粒子と重ならず90%以上観察できる、正極活物質粒子をランダムに10個選択した。
前記の選択した元素マッピング正極活物質粒子画像において、窒素元素の存在が確認された部分の面積を、ニトリル基含有アクリル重合体により被覆された活物質表面であると判断した。さらに、被覆割合が60%以上である場合を、ニトリル基含有アクリル重合体が正極活物質粒子表面を被覆しているとし、「可」と評価した。(Confirmation of positive electrode active material coating)
A slurry was prepared with a mixing ratio of the positive electrode active material, the positive electrode binder, and the nitrile group-containing acrylic polymer of 100: 1.6: 0.4, and applied to a current collector (aluminum foil) and dried to obtain an electrode. .
The electrode surface was observed with a scanning electron microscope (S-3400N manufactured by Hitachi, Ltd.). The observation condition was that a 100 μm × 100 μm square image was observed at a magnification of 2000 times and an acceleration voltage of 15 kV. Furthermore, the elemental mapping of nickel atoms, nitrogen atoms, and carbon atoms was performed using an energy dispersive X-ray analyzer (manufactured by Bruker, Quantax) attached to the scanning electron microscope, and respective mapping images were prepared. This operation was performed 5 times randomly selecting five locations on the electrode.
On the image, 10 positive electrode active material particles whose long side and short side are 10 μm or more and whose surface of the positive electrode active material particles can be observed 90% or more without overlapping with other particles were randomly selected.
In the selected element mapping positive electrode active material particle image, the area of the portion where the presence of the nitrogen element was confirmed was determined to be the active material surface covered with the nitrile group-containing acrylic polymer. Furthermore, when the coating ratio was 60% or more, the nitrile group-containing acrylic polymer was evaluated as “possible”, assuming that the surface of the positive electrode active material particles was coated.
(非水電解液膨潤度の測定)
ニトリル基含有アクリル重合体の8%のN−メチルピロリドン(NMP)溶液を乾燥後の厚みが100μmになるようにテフロン(登録商標)シャーレに流しこみ、重合体フィルムを作成した。得られたフィルムを16mmφに打ち抜き重量を測定した(重量を「A」とする)。エチレンカーボネートとエチルメチルカーボネートとの3対7重量比の混合物に5%のフルオロエチレンカーボネートを混合し、1mol/リットルの濃度になるように六フッ化リン酸リチウム(LiPF6)を溶解させたものを非水電解液として用意した。非水電解液20gに16mmφに打ち抜いたフィルムを浸漬させ、60℃で72時間、浸漬した。その後、浸漬させたフィルムを取り出し、表面の非水電解液を軽くふき取り重量を測定した(重量を「B」とする)。これらの値より非水電解液膨潤度(=B/A)を求めた。非水電解液膨潤度が大きい程、非水電解液中での変形が大きくなることを示す。(Measurement of swelling degree of non-aqueous electrolyte)
An 8% N-methylpyrrolidone (NMP) solution of a nitrile group-containing acrylic polymer was poured into a Teflon (registered trademark) petri dish so that the thickness after drying was 100 μm, to prepare a polymer film. The obtained film was punched to 16 mmφ, and the weight was measured (weight is assumed to be “A”). 5% fluoroethylene carbonate mixed in a 3 to 7 weight ratio mixture of ethylene carbonate and ethyl methyl carbonate, and lithium hexafluorophosphate (LiPF 6 ) dissolved to a concentration of 1 mol / liter Was prepared as a non-aqueous electrolyte. A film punched to 16 mmφ was dipped in 20 g of a non-aqueous electrolyte, and dipped at 60 ° C. for 72 hours. Thereafter, the immersed film was taken out, and the nonaqueous electrolyte solution on the surface was lightly wiped, and the weight was measured (weight is set to “B”). The nonaqueous electrolyte swelling degree (= B / A) was determined from these values. It shows that the deformation | transformation in a non-aqueous electrolyte becomes so large that a non-aqueous electrolyte swelling degree is large.
(THF不溶解分量の測定)
ニトリル基含有アクリル重合体の8%のNMP溶液を乾燥後の厚みが100μmになるようにテフロン(登録商標)シャーレに流しこみ、重合体フィルムを作成した。得られたフィルムを16mmφに打ち抜き重量を測定した(重量を「C」とする)。テトラヒドロフラン20gに16mmφに打ち抜いたフィルムを浸漬させ、25℃で24時間かけ、可溶分を完全に溶解させた。その後、不溶分である残留固形物を取り出し、赤外線乾燥機でテトラヒドロフランを完全に揮発させた後、重量を測定した(重量を「D」とする)。これらの値よりTHF不溶解分量(=D/C×100)を求めた。THF不溶解分量が小さい程、重合体分子間の架橋が少ないことを示す。(Measurement of insoluble THF content)
A polymer film was prepared by pouring an 8% NMP solution of a nitrile group-containing acrylic polymer into a Teflon (registered trademark) petri dish so that the thickness after drying was 100 μm. The obtained film was punched to 16 mmφ, and the weight was measured (weight is assumed to be “C”). A film punched to 16 mmφ was immersed in 20 g of tetrahydrofuran, and the soluble component was completely dissolved at 25 ° C. for 24 hours. Then, the residual solid which is an insoluble matter was taken out, tetrahydrofuran was completely volatilized with an infrared dryer, and the weight was measured (weight is assumed to be “D”). From these values, the THF-insoluble content (= D / C × 100) was determined. It shows that there are few bridge | crosslinking between polymer molecules, so that THF insoluble content is small.
(捲回体の折り曲げ特性)
シート状正極およびシート状負極を、セパレータを介在させて直径20mmの芯を用いて捲回し、捲回体を得た。セパレータとしては、厚さ20μmのポリプロピレン製微多孔膜を用いた。捲回体は、10mm/秒のスピードで厚さ4.5mmになるまで一方向から圧縮した。圧縮後に捲回体を解体し、正極電極を観察し、下記評価基準に従って評価を行った。
A…割れなし
B…微小割れ
C…電極からの剥がれ(Bending characteristics of wound body)
The sheet-like positive electrode and the sheet-like negative electrode were wound using a core having a diameter of 20 mm with a separator interposed therebetween to obtain a wound body. As the separator, a polypropylene microporous film having a thickness of 20 μm was used. The wound body was compressed from one direction at a speed of 10 mm / second until a thickness of 4.5 mm was reached. The wound body was disassembled after compression, the positive electrode was observed, and evaluation was performed according to the following evaluation criteria.
A ... No crack B ... Small crack C ... Peel from electrode
(高電位サイクル特性)
非水電解質電池について、25℃環境下で、600mAで電池電圧が4.8Vになるまで充電し、600mAで電池電圧が3Vになるまで放電する操作を100回繰り返した。
そして、一回目の放電容量に対する100回目の放電容量の比を算出した。(High potential cycle characteristics)
For a nonaqueous electrolyte battery, an operation of charging at 600 mA until the battery voltage reached 4.8 V and discharging at 600 mA until the battery voltage reached 3 V was repeated 100 times in a 25 ° C. environment.
Then, the ratio of the 100th discharge capacity to the first discharge capacity was calculated.
(ニトリル基含有アクリル重合体)
ニトリル基含有アクリル重合体(1)〜(6)を以下のように調整した。(Nitrile group-containing acrylic polymer)
The nitrile group-containing acrylic polymers (1) to (6) were prepared as follows.
[調整例1]
ニトリル基含有アクリル重合体(1)の製造
撹拌機付きのオートクレーブに、イオン交換水164部、2−エチルヘキシルアクリレート(2EHA)67.5部、メタクリル酸(MAA)17部、アクリロニトリル(AN)15部、2−アクリルアミド−2−メチルプロパンスルホン酸(AMPS)0.5部、重合開始剤として過硫酸カリウム0.3部、及び界面活性剤としてラウリル硫酸ナトリウム1.6部を入れ、十分に撹拝した後、70℃で3時間、さらに80℃で2時間加温して重合を行い、ニトリル基含有アクリル重合体(1)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96%であった。また、この水分散液100部にN−メチルピロリドン500部を加え、減圧下に水及び残留モノマーを蒸発させたのち、N−メチルピロリドンを81部蒸発させて、ニトリル基含有アクリル重合体(1)の8質量%のNMP溶液を得た。この時の非水電解液膨潤度は2倍、THF不溶解分量は10%以下であった。また、ニトリル基含有アクリル重合体のSP値は、9.9(cal/cm3)1/2であった。[Adjustment Example 1]
Production of nitrile group-containing acrylic polymer (1) In an autoclave equipped with a stirrer, 164 parts of ion exchange water, 67.5 parts of 2-ethylhexyl acrylate (2EHA), 17 parts of methacrylic acid (MAA), 15 parts of acrylonitrile (AN) 2 parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 0.3 part of potassium persulfate as a polymerization initiator, and 1.6 parts of sodium lauryl sulfate as a surfactant are thoroughly stirred. Then, polymerization was performed by heating at 70 ° C. for 3 hours and further at 80 ° C. for 2 hours to obtain an aqueous dispersion of the nitrile group-containing acrylic polymer (1). The polymerization conversion rate determined from the solid content concentration was 96%. Further, 500 parts of N-methylpyrrolidone was added to 100 parts of this aqueous dispersion, water and residual monomers were evaporated under reduced pressure, 81 parts of N-methylpyrrolidone was evaporated, and a nitrile group-containing acrylic polymer (1 8 mass% NMP solution was obtained. At this time, the swelling degree of the nonaqueous electrolyte solution was doubled, and the THF-insoluble content was 10% or less. The SP value of the nitrile group-containing acrylic polymer was 9.9 (cal / cm 3 ) 1/2 .
[調整例2〜6]
ニトリル基含有アクリル重合体(2)〜(6)の製造
単量体の仕込み量、種類を表1のように変更した他は、調整例1と同様とした。なお、表1において、ANはアクリロニトリル、2EHAは2−エチルヘキシルアクリレート、EAはエチルアクリレート、BAはブチルアクリレート、MAAはメタクリル酸、AMPSは2−アクリルアミド−2−メチルプロパンスルホン酸、GMAはグリシジルメタクリレートを指す。非水電解液膨潤度、THF不溶解分量およびSP値を表1に示す。[Adjustment Examples 2 to 6]
Preparation of the nitrile group-containing acrylic polymers (2) to (6) The procedure was the same as in Preparation Example 1 except that the amounts and types of monomers were changed as shown in Table 1. In Table 1, AN is acrylonitrile, 2EHA is 2-ethylhexyl acrylate, EA is ethyl acrylate, BA is butyl acrylate, MAA is methacrylic acid, AMPS is 2-acrylamido-2-methylpropanesulfonic acid, GMA is glycidyl methacrylate. Point to. Table 1 shows the degree of swelling of the nonaqueous electrolyte, the amount of insoluble THF, and the SP value.
(実施例1)
〔正極用スラリー組成物および正極の製造〕
正極活物質としてLi過剰層状化合物(Li[Ni0.17Li0.2Co0.07Mn0.56]O2)100部と、正極導電材としてアセチレンブラック(AB35,電気化学工業社製デンカブラック粉状品:個数粒子径35nm、比表面積68m2/g)2.0部と、正極用結着剤のフッ素含有重合体として混合ポリフッ化ビニリデン(アルケマ社製KYNAR HSV900とKYNAR720との1:1混合物)1.6部およびニトリル基含有アクリル重合体として上記のニトリル基含有アクリル重合体(1)を固形分相当量で0.4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。なお、KYNAR HSV900のASTM D3835 /232℃100sec−1で測定される溶融粘度は50kpoiseであり、KYNAR720の溶融粘度は9kpoiseである。Example 1
[Production of slurry composition for positive electrode and positive electrode]
100 parts of Li-excess layered compound (Li [Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ] O 2 ) as the positive electrode active material, and acetylene black (AB35, Denka Black powder manufactured by Denki Kagaku Kogyo Co., Ltd.): number particle diameter 2.0 parts of 35 nm, specific surface area 68 m 2 / g), 1.6 parts of a mixed polyvinylidene fluoride (1: 1 mixture of KYNAR HSV900 and KYNAR720 manufactured by Arkema) as a fluorine-containing polymer for a positive electrode binder, and As a nitrile group-containing acrylic polymer, 0.4 part of the above-mentioned nitrile group-containing acrylic polymer (1) in a solid equivalent amount and an appropriate amount of NMP are stirred with a planetary mixer to prepare a positive electrode slurry composition. did. The melt viscosity of KYNAR HSV900 measured by ASTM D3835 / 232 ° C. 100 sec −1 is 50 kpoise, and the melt viscosity of KYNAR720 is 9 kpoise.
集電体として、厚さ15μmのアルミ箔を準備した。上記正極用スラリー組成物をアルミ箔の両面に乾燥後の塗布量が25mg/cm2になるように塗布し、60℃で20分、120℃で20分間乾燥後、150℃、2時間加熱処理して正極原反を得た。これら操作によりニトリル基含有アクリル重合体(1)によって、正極活物質及び正極活物質で被覆されていない集電体表面が被覆された。この正極原反をロールプレスで圧延し、密度が3.9g/cm3の正極活物質層とアルミ箔とからなるシート状正極を作製した。これを幅4.8mm、長さ50cmに切断し、アルミニウムリードを接続した。また、得られた正極について捲回体の折り曲げ特性を評価した。結果を表2に示す。An aluminum foil having a thickness of 15 μm was prepared as a current collector. The positive electrode slurry composition was applied to both sides of an aluminum foil so that the coating amount after drying was 25 mg / cm 2 , dried at 60 ° C. for 20 minutes, 120 ° C. for 20 minutes, and then heated at 150 ° C. for 2 hours. Thus, a positive electrode raw material was obtained. By these operations, the nitrile group-containing acrylic polymer (1) covered the positive electrode active material and the current collector surface not covered with the positive electrode active material. This positive electrode original fabric was rolled by a roll press to produce a sheet-like positive electrode comprising a positive electrode active material layer having a density of 3.9 g / cm 3 and an aluminum foil. This was cut into a width of 4.8 mm and a length of 50 cm, and an aluminum lead was connected. Moreover, the bending characteristic of the wound body was evaluated about the obtained positive electrode. The results are shown in Table 2.
〔負極用スラリー組成物および負極の製造〕
負極活物質として球状人造黒鉛(粒子径:12μm)90部とSiOx(粒子径:10μm)10部、結着剤としてスチレンブタジエンゴム(粒子径:180nm、ガラス転移温度:−40℃)1部、増粘剤としてカルボキシメチルセルロース1部及び適量の水をプラネタリーミキサーにて攪拌し、負極用スラリー組成物を調製した。[Production of slurry composition for negative electrode and negative electrode]
90 parts of spherical artificial graphite (particle diameter: 12 μm) and 10 parts of SiOx (particle diameter: 10 μm) as a negative electrode active material, 1 part of styrene butadiene rubber (particle diameter: 180 nm, glass transition temperature: −40 ° C.) as a binder, As a thickener, 1 part of carboxymethylcellulose and an appropriate amount of water were stirred with a planetary mixer to prepare a slurry composition for a negative electrode.
集電体として、厚さ15μmの銅箔を準備した。上記負極用スラリー組成物を銅箔の両面に乾燥後の塗布量が10mg/cm2になるように塗布し、60℃で20分、120℃で20分間乾燥後、150℃、2時間加熱処理して負極原反を得た。この負極原反をロールプレスで圧延し、密度が1.8g/cm3の負極活物質層と銅箔とからなるシート状負極を作製した。これを幅5.0mm、長さ52cmに切断し、ニッケルリードを接続した。A copper foil having a thickness of 15 μm was prepared as a current collector. The negative electrode slurry composition was applied to both sides of the copper foil so that the coating amount after drying was 10 mg / cm 2 , dried at 60 ° C. for 20 minutes, 120 ° C. for 20 minutes, and then heat-treated at 150 ° C. for 2 hours. Thus, a negative electrode raw material was obtained. This negative electrode original fabric was rolled with a roll press to prepare a sheet-like negative electrode comprising a negative electrode active material layer having a density of 1.8 g / cm 3 and a copper foil. This width 5.0 mm, was cut to a length 5 2 cm, was connected to a nickel lead.
〔リチウムイオン二次電池の製造〕
得られたシート状正極およびシート状負極を、セパレータを介在させて直径20mmの芯を用いて捲回し、捲回体を得た。セパレータとしては、厚さ20μmのポリプロピレン製微多孔膜を用いた。捲回体は、10mm/秒のスピードで厚さ4.5mmになるまで一方向から圧縮した。前記略楕円の短径に対する長径の比は7.7である。[Manufacture of lithium ion secondary batteries]
The obtained sheet-like positive electrode and sheet-like negative electrode were wound using a core having a diameter of 20 mm with a separator interposed therebetween to obtain a wound body. As the separator, a polypropylene microporous film having a thickness of 20 μm was used. The wound body was compressed from one direction at a speed of 10 mm / second until a thickness of 4.5 mm was reached. The ratio of the major axis to the minor axis of the substantially ellipse is 7.7.
また、エチレンカーボネートとエチルメチルカーボネートとの3対7重量の混合物に5質量%のフルオロエチレンカーボネートを混合し、1mol/リットルの濃度になるように六フッ化リン酸リチウムを溶解し、ビニレンカーボネート2vol%を添加し、非水電解液を用意した。 Further, 5% by mass of fluoroethylene carbonate was mixed with a 3 to 7 weight mixture of ethylene carbonate and ethyl methyl carbonate, and lithium hexafluorophosphate was dissolved to a concentration of 1 mol / liter, and vinylene carbonate 2 vol. % Was added to prepare a non-aqueous electrolyte.
前記捲回体は、所定のアルミラミネート製ケース内に3.2gの非水電解液とともに収容した。そして、負極リードおよび正極リードを所定の箇所に接続したのち、ケースの開口部を熱で封口し、捲回型パウチセルであるリチウムイオン二次電池を完成した。この電池は、幅35mm、高さ48mm、厚さ5mmのパウチ形であり、電池の公称容量は700mAhである。得られた二次電池の高電位サイクル特性を表2に示す。 The wound body was accommodated together with 3.2 g of a non-aqueous electrolyte in a predetermined aluminum laminate case. And after connecting a negative electrode lead and a positive electrode lead to a predetermined location, the opening part of the case was sealed with heat, and the lithium ion secondary battery which is a wound type pouch cell was completed. This battery is a pouch having a width of 35 mm, a height of 48 mm, and a thickness of 5 mm, and the nominal capacity of the battery is 700 mAh. Table 2 shows the high potential cycle characteristics of the obtained secondary battery.
(実施例2)
ニトリル基含有アクリル重合体(1)に代えて、上記の重合体(2)を用いたこと以外は、実施例1と同様とした。結果を表2に示す。(Example 2)
It replaced with the nitrile group containing acrylic polymer (1), and it was the same as that of Example 1 except having used said polymer (2). The results are shown in Table 2.
(実施例3)
ニトリル基含有アクリル重合体(1)に代えて、上記の重合体(3)を用いたこと以外は、実施例1と同様とした。結果を表2に示す。(Example 3)
It replaced with the nitrile group containing acrylic polymer (1), and it was the same as that of Example 1 except having used said polymer (3). The results are shown in Table 2.
(実施例4)
ニトリル基含有アクリル重合体(1)に代えて、上記の重合体(4)を用いたこと以外は、実施例1と同様とした。結果を表2に示す。Example 4
It replaced with the nitrile group containing acrylic polymer (1), and it was the same as that of Example 1 except having used said polymer (4). The results are shown in Table 2.
(実施例5)
ニトリル基含有アクリル重合体(1)に代えて、上記の重合体(5)を用いたこと以外は、実施例1と同様とした。結果を表2に示す。(Example 5)
It replaced with the nitrile group containing acrylic polymer (1), and it was the same as that of Example 1 except having used said polymer (5). The results are shown in Table 2.
(比較例1)
ニトリル基含有アクリル重合体(1)を用いなかったこと以外は、実施例1同様とした。結果を表2に示す。(Comparative Example 1)
Example 1 was repeated except that the nitrile group-containing acrylic polymer (1) was not used. The results are shown in Table 2.
(比較例2)
ニトリル基含有アクリル重合体(1)に代えて、ポリプロピレン(和光純薬製 Polypropylene)を用いたこと以外は、実施例1と同様とした。結果を表2に示す。なお、ポリプロピレンのSP値は、8.35(cal/cm3)1/2であり、ポリプロピレンでは正極活物質を被覆することができなかった。また、ポリプロピレンの非水電解液膨潤度は1.1倍、THF不溶解分量は0質量%であった。(Comparative Example 2)
It replaced with the nitrile group containing acrylic polymer (1), and it was the same as that of Example 1 except having used the polypropylene (Polypropylene made from Wako Purechemical). The results are shown in Table 2. The SP value of polypropylene was 8.35 (cal / cm 3 ) 1/2 , and the positive electrode active material could not be coated with polypropylene. Moreover, the nonaqueous electrolyte swelling degree of polypropylene was 1.1 times, and the THF insoluble content was 0% by mass.
(比較例3)
ニトリル基含有アクリル重合体(1)に代えて、上記の重合体(6)を用いたこと以外は、実施例1同様とした。結果を表2に示す。(Comparative Example 3)
Example 1 was repeated except that the polymer (6) was used instead of the nitrile group-containing acrylic polymer (1). The results are shown in Table 2.
表1および2から、本発明の要件を充足する実施例については、全ての評価項目についてバランス良く良好な結果が得られた。これに対し、ニトリル基含有アクリル重合体を用いていない比較例1,2や、SP値が特定範囲外のニトリル基含有アクリル重合体を用いた比較例3では、全ての評価項目について劣る結果となった。 From Tables 1 and 2, for the examples satisfying the requirements of the present invention, good results were obtained with good balance for all the evaluation items. On the other hand, in Comparative Examples 1 and 2 in which the nitrile group-containing acrylic polymer is not used, and in Comparative Example 3 in which the nitrile group-containing acrylic polymer having an SP value outside the specific range is used, all the evaluation items are inferior. became.
Claims (9)
前記正極が、正極活物質、正極用結着剤および導電材を含み、
前記正極活物質が、SP値が9〜11(cal/cm3)1/2のニトリル基含有アクリル重合体で被覆されており、
前記ニトリル基含有アクリル重合体の非水電解液に対する膨潤度が3倍以下で、THF不溶解分量が30質量%以下であり、
前記正極用結着剤がフッ素含有重合体を含む、リチウムイオン二次電池。 A lithium ion secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte,
The positive electrode includes a positive electrode active material, a positive electrode binder and a conductive material,
The positive electrode active material is coated with a nitrile group-containing acrylic polymer having an SP value of 9 to 11 (cal / cm 3 ) 1/2 ,
The degree of swelling of the nitrile group-containing acrylic polymer with respect to the non-aqueous electrolyte is 3 times or less, and the THF-insoluble content is 30% by mass or less.
A lithium ion secondary battery, wherein the positive electrode binder comprises a fluorine-containing polymer.
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US20180102542A1 (en) * | 2015-04-22 | 2018-04-12 | Toagosei Co., Ltd. | Binder for nonaqueous electrolyte secondary battery electrode, and use thereof |
CN105449186B (en) * | 2015-11-18 | 2018-11-27 | 深圳先进技术研究院 | A kind of secondary cell and preparation method thereof |
WO2017099247A1 (en) * | 2015-12-11 | 2017-06-15 | 富士フイルム株式会社 | Solid-state electrolyte composition, sheet for all-solid-state secondary battery, electrode sheet for all-solid-state second battery and manufacturing method therefor, and all-solid-state secondary battery and manufacturing method therefor |
JP6728716B2 (en) * | 2016-01-28 | 2020-07-22 | 住友金属鉱山株式会社 | Method for producing coated nickel-based lithium-nickel composite oxide particles |
JP2017160294A (en) * | 2016-03-07 | 2017-09-14 | 三洋化成工業株式会社 | Resin composition for coating nonaqueous secondary battery active material and coated active material for nonaqueous secondary battery |
CN107325225B (en) * | 2016-04-29 | 2019-12-03 | 四川茵地乐科技有限公司 | Negative electrode of lithium ion battery aqueous binder and preparation method thereof |
WO2018043484A1 (en) * | 2016-08-31 | 2018-03-08 | 東亞合成株式会社 | Binder for nonaqueous electrolyte secondary battery electrodes and use of same |
JP7095683B2 (en) * | 2017-03-28 | 2022-07-05 | 日本ゼオン株式会社 | Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, non-aqueous secondary battery electrode and non-aqueous secondary battery, and method for manufacturing non-aqueous secondary battery electrode. |
JP7156859B2 (en) | 2017-08-31 | 2022-10-19 | 三洋化成工業株式会社 | Dispersant for carbon material, dispersion containing dispersant for carbon material, electrode slurry for all-solid lithium ion secondary battery, method for producing electrode for all-solid lithium ion secondary battery, electrode for all-solid lithium ion secondary battery and all-solid lithium-ion secondary battery |
WO2019131805A1 (en) * | 2017-12-27 | 2019-07-04 | Agc株式会社 | Dispersion, metal laminate plate, and production method for printed board |
JP7415915B2 (en) * | 2018-03-23 | 2024-01-17 | 日本ゼオン株式会社 | Binder composition for secondary batteries, conductive material paste for secondary battery electrodes, slurry composition for secondary battery electrodes, method for producing slurry composition for secondary battery electrodes, electrode for secondary batteries, and secondary battery |
KR102285981B1 (en) | 2018-04-06 | 2021-08-05 | 주식회사 엘지에너지솔루션 | Electrode, secondary battery comprising the same, and method for preparing the electrode |
CN110148709B (en) * | 2019-05-25 | 2020-10-23 | 珠海冠宇电池股份有限公司 | Preparation method of positive pole piece comprising conductive lithium-conducting composite material coated with positive pole material and lithium ion battery |
JP7281091B2 (en) * | 2020-02-10 | 2023-05-25 | トヨタ自動車株式会社 | Positive electrode materials for secondary batteries, and secondary batteries |
WO2022024940A1 (en) * | 2020-07-31 | 2022-02-03 | 日本ゼオン株式会社 | Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, non-aqueous secondary battery electrode, and non-aqueous secondary battery |
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