TWI770263B - Positive electrode active material coating, positive electrode, and secondary battery - Google Patents
Positive electrode active material coating, positive electrode, and secondary battery Download PDFInfo
- Publication number
- TWI770263B TWI770263B TW107130801A TW107130801A TWI770263B TW I770263 B TWI770263 B TW I770263B TW 107130801 A TW107130801 A TW 107130801A TW 107130801 A TW107130801 A TW 107130801A TW I770263 B TWI770263 B TW I770263B
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- Taiwan
- Prior art keywords
- positive electrode
- active material
- mass
- electrode active
- polyvinyl alcohol
- Prior art date
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002612 dispersion medium Substances 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- -1 conductive auxiliary Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims 1
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000003973 paint Substances 0.000 description 7
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical group FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018087 Al-Cd Inorganic materials 0.000 description 1
- 229910018188 Al—Cd Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000011179 visual inspection Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本發明之課題在於提供一種可提供電池特性優異之二次電池之正極活性物質塗料、正極、及二次電池。 本發明之正極活性物質塗料之特徵在於：其係含有正極活性物質、導電助劑、分散介質、分散劑者，分散介質為N-甲基吡咯啶酮，分散劑含有聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物，相對於上述聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物100質量%，聚乙烯醇之含量為10質量%以上且90質量%以下。An object of the present invention is to provide a positive electrode active material coating material, a positive electrode, and a secondary battery capable of providing a secondary battery having excellent battery characteristics. The positive electrode active material coating of the present invention is characterized in that it contains a positive electrode active material, a conductive assistant, a dispersion medium and a dispersant, the dispersion medium is N-methylpyrrolidone, and the dispersant contains polyvinyl alcohol-polyvinylpyrrole The pyridone graft copolymer has a content of polyvinyl alcohol of 10% by mass or more and 90% by mass or less with respect to 100% by mass of the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer.
Description
本發明係關於一種正極活性物質塗料、正極、及二次電池。The present invention relates to a positive electrode active material coating, a positive electrode, and a secondary battery.
近年來，作為二次電池，能夠達成高能量密度、高輸出密度之鋰離子二次電池引人注目。於二次電池之電極之製造所使用之溶劑配方中，以N-甲基吡咯啶酮作為溶劑，聚偏二氟乙烯(以下，亦有時稱為PVDF)發揮作為集電體與活性物質之黏結劑之功能。然而，PVDF與集電體之黏結性較弱，與水系正極或負極之黏合劑之使用量相比，必須相對於活性物質大量地使用，因此，為了推進電池之高電容化，必須減少PVDF之添加量。又，於正極中，為了隨著活性物質之體積變化確保導電通路，需要體積上與活性物質相同量程度之導電助劑，因此亦必須充分使其分散。 於專利文獻1中，提出一種黏合劑，其使用聚丙烯腈系樹脂作為黏合劑，進而賦予有於該系中難以達成之觸變性。於專利文獻2中提出將聚乙烯吡咯啶酮(以下，亦有時稱為PVP)用於導電助劑之分散。 [先前技術文獻] [專利文獻]In recent years, lithium ion secondary batteries capable of achieving high energy density and high output density have attracted attention as secondary batteries. In the solvent formulation used in the manufacture of electrodes for secondary batteries, N-methylpyrrolidone is used as a solvent, and polyvinylidene fluoride (hereinafter, also sometimes referred to as PVDF) plays a role as a collector and an active material. The function of adhesive. However, the adhesion between PVDF and the current collector is weak. Compared with the amount of the binder used in the water-based positive electrode or negative electrode, it must be used in a large amount relative to the active material. Therefore, in order to promote the high capacitance of the battery, it is necessary to reduce the amount of PVDF. Add amount. In addition, in the positive electrode, in order to secure a conductive path according to the volume change of the active material, a conductive auxiliary agent is required in an amount equivalent to the volume of the active material, and therefore it is necessary to sufficiently disperse it. In Patent Document 1, an adhesive is proposed which uses a polyacrylonitrile-based resin as the adhesive and further imparts thixotropy, which is difficult to achieve in this system. In Patent Document 2, it is proposed to use polyvinylpyrrolidone (hereinafter, also referred to as PVP in some cases) for dispersion of the conductive aid. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2013-122913號公報 [專利文獻2]日本專利特開2004-281096號公報[Patent Document 1] Japanese Patent Laid-Open No. 2013-122913 [Patent Document 2] Japanese Patent Laid-Open No. 2004-281096
[發明所欲解決之問題][Problems to be Solved by Invention]
然而，於將聚丙烯腈系樹脂用作黏合劑之情形時，對於疏水性較強之導電助劑之分散無法發揮充分之分散性能(專利文獻1)。又，PVP溶解於電解液，導致內部電阻之上升，因此不合適(專利文獻2)。 因此，本發明之目的在於提供一種可提供電池特性優異之二次電池之正極活性物質塗料、正極、及非水系二次電池。 [解決問題之技術手段]However, when a polyacrylonitrile-based resin is used as a binder, sufficient dispersing performance cannot be exhibited for dispersing a conductive auxiliary agent having a strong hydrophobicity (Patent Document 1). In addition, PVP dissolves in the electrolytic solution and causes an increase in internal resistance, which is not suitable (Patent Document 2). Therefore, an object of the present invention is to provide a positive electrode active material coating material, a positive electrode, and a non-aqueous secondary battery which can provide a secondary battery having excellent battery characteristics. [Technical means to solve problems]
作為本發明之第一實施形態，係一種正極活性物質塗料，其特徵在於：其係含有正極活性物質、導電助劑、分散介質、分散劑者，分散介質為N-甲基吡咯啶酮，分散劑含有聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物，相對於上述聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物100質量%，聚乙烯醇之含量為10質量%以上且90質量%以下。As a first embodiment of the present invention, a positive electrode active material coating is characterized in that: it contains a positive electrode active material, a conductive aid, a dispersion medium, and a dispersant, the dispersion medium is N-methylpyrrolidone, and the dispersion medium is N-methylpyrrolidone. The agent contains a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer, and the content of polyvinyl alcohol is 10% by mass or more and 90% by mass relative to 100% by mass of the above-mentioned polyvinyl alcohol-polyvinylpyrrolidone graft copolymer the following.
作為較佳之實施形態，相對於正極活性物質、導電助劑、及分散劑之合計量100質量%，分散劑之含量為0.1質量%以上且20質量%以下。As a preferable embodiment, the content of the dispersant is 0.1% by mass or more and 20% by mass or less with respect to 100% by mass of the total amount of the positive electrode active material, the conductive aid, and the dispersant.
作為本發明之其他實施形態，係一種正極，其特徵在於：其係具備集電體及形成於上述集電體上之正極活性物質合劑層者，上述正極活性物質合劑層係使上述正極活性物質塗料乾燥而成者。As another embodiment of the present invention, there is a positive electrode comprising a current collector and a positive electrode active material mixture layer formed on the current collector, wherein the positive electrode active material mixture layer is composed of the positive electrode active material Paint dries.
作為本發明之其他實施形態，係一種二次電池，其係具備負極與正極、配置於負極與正極之間之間隔件、及電解液者，正極為上述正極。 [發明之效果]As another embodiment of the present invention, there is provided a secondary battery comprising a negative electrode and a positive electrode, a separator disposed between the negative electrode and the positive electrode, and an electrolyte, and the positive electrode is the positive electrode described above. [Effect of invention]
本發明能夠提供一種可提供電池特性優異之二次電池之正極活性物質塗料、正極、及非水系二次電池。The present invention can provide a positive electrode active material coating material, a positive electrode, and a non-aqueous secondary battery capable of providing a secondary battery having excellent battery characteristics.
繼而，對本發明之實施形態詳細地進行說明。Next, embodiments of the present invention will be described in detail.
本實施形態之正極活性物質塗料(以下，有時簡稱為塗料)係含有正極活性物質、導電助劑、分散介質、及分散劑者，分散介質為N-甲基吡咯啶酮，分散劑含有聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物(以下，有時簡稱為接枝共聚物)，相對於上述聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物100質量%，聚乙烯醇之含量為10質量%以上且90質量%以下。The positive electrode active material coating of the present embodiment (hereinafter, sometimes simply referred to as a coating) contains a positive electrode active material, a conductive aid, a dispersion medium, and a dispersant, the dispersion medium is N-methylpyrrolidone, and the dispersant contains a polymer Vinyl alcohol-polyvinylpyrrolidone graft copolymer (hereinafter, sometimes abbreviated as graft copolymer), the content of polyvinyl alcohol relative to 100% by mass of the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer It is 10 mass % or more and 90 mass % or less.
作為上述正極活性物質，只要能夠使鋰離子插入、脫離，則並無特別限制。例如，作為正極活性物質，可列舉CuO、Cu2 O、MnO2 、MoO3 、V2 O5 、CrO3 、MoO3 、Fe2 O3 、Ni2 O3 、CoO3 等金屬氧化物，Lix CoO2 、Lix NiO2 、Lix Mn2 O4 等鋰與過渡金屬之複合氧化物，或TiS2 、MoS2 、NbSe3 等金屬硫屬化物，多并苯、聚對伸苯、聚吡咯、聚苯胺等導電性高分子化合物等。The positive electrode active material is not particularly limited as long as it can intercalate and deintercalate lithium ions. For example, as the positive electrode active material, metal oxides such as CuO , Cu2O , MnO2 , MoO3 , V2O5 , CrO3 , MoO3 , Fe2O3 , Ni2O3 , CoO3 , etc. , Li Composite oxides of lithium and transition metals such as x CoO 2 , Li x NiO 2 , Li x Mn 2 O 4 , or metal chalcogenides such as TiS 2 , MoS 2 , NbSe 3 , polyacene, polyparaphenylene, polyphenylene Conductive polymer compounds such as pyrrole and polyaniline, etc.
該等之中，一般稱為高電壓系之選自鈷、鎳、錳等過渡金屬之1種以上與鋰之複合氧化物就鋰離子之釋放性、可獲得高電壓之方面而言較佳。作為鈷、鎳、錳與鋰之複合氧化物之具體例，可列舉：LiCoO2 、LiMnO2 、LiMn2 O4 、LiNiO2 、LiNix Co(1 -x) O2 、LiMna Nib Coc (a＋b＋c＝1)等。Among these, complex oxides of one or more kinds of transition metals such as cobalt, nickel, and manganese, which are generally referred to as high-voltage systems, and lithium are preferred in terms of release properties of lithium ions and high voltage. Specific examples of the composite oxide of cobalt, nickel, manganese and lithium include LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , LiNiO 2 , LiNi x Co (1 - x) O 2 , LiMn a Ni b Co c (a+b+c=1) and so on.
作為上述導電助劑，只要為不對電池性能造成不良影響之電子傳導性材料，則可無特別限定地使用。通常，使用乙炔黑或科琴黑等碳黑，但亦可為天然石墨(鱗狀石墨、鱗片狀石墨、土狀石墨等)、人造石墨、碳晶鬚、碳纖維或金屬(銅、鎳、鋁、銀、金等)粉末、金屬纖維、導電性陶瓷材料等導電性材料。該等導電劑之中，可列舉石墨、乙炔黑、碳黑、科琴黑、奈米碳管或其衍生物、碳纖維。該等亦可作為2種以上之混合物使用。其添加量相對於正極活性物質量100質量%，較佳為0.1質量%以上且30質量%以下，尤佳為0.2質量%以上且20質量%以下。As the above-mentioned conductive aid, it can be used without any particular limitation as long as it is an electron conductive material that does not adversely affect battery performance. Usually, carbon black such as acetylene black or ketjen black is used, but it can also be natural graphite (flake graphite, flake graphite, earthy graphite, etc.), artificial graphite, carbon whisker, carbon fiber or metal (copper, nickel, aluminum, etc.) , silver, gold, etc.) powder, metal fibers, conductive ceramic materials and other conductive materials. Among these conductive agents, graphite, acetylene black, carbon black, Ketjen black, carbon nanotubes or derivatives thereof, and carbon fibers are exemplified. These can also be used as a mixture of 2 or more types. The addition amount is preferably 0.1 mass % or more and 30 mass % or less, and particularly preferably 0.2 mass % or more and 20 mass % or less with respect to 100 mass % of the positive electrode active material mass.
上述分散介質為N-甲基吡咯啶酮，但只要不妨礙本發明之效果，則可併用其他分散介質。作為其他分散介質，並無特別限定，具體而言，可列舉N-乙基吡咯啶酮、N,N-二甲基甲醯胺、四氫呋喃、二甲基乙醯胺、二甲基亞碸、六甲基磺醯胺、四甲基脲、丙酮、甲基乙基酮等。The above-mentioned dispersion medium is N-methylpyrrolidone, but other dispersion medium may be used in combination as long as the effect of the present invention is not inhibited. The other dispersion medium is not particularly limited, and specifically, N-ethylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethylsulfoxide, Hexamethylsulfonamide, tetramethylurea, acetone, methyl ethyl ketone, etc.
上述分散劑含有聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物，且相對於聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物100質量%，聚乙烯醇之含量為10質量%以上且90質量%以下。The above-mentioned dispersant contains a polyvinyl alcohol-polyvinylpyrrolidone graft copolymer, and the content of polyvinyl alcohol is 10% by mass or more and 90% by mass relative to 100% by mass of the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer. mass % or less.
上述聚乙烯醇之聚合度之下限較佳為200以上，更佳為500以上，進而較佳為1000以上。上限較佳為4000以下，更佳為3000以下，進而較佳為2000以下。於聚乙烯醇之聚合度為上述範圍內之情形時，可利用少量之分散劑分散正極活性物質及分散助劑，可獲得電池特性優異之正極活性物質塗料。The lower limit of the degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, and still more preferably 1000 or more. The upper limit is preferably 4,000 or less, more preferably 3,000 or less, and still more preferably 2,000 or less. When the polymerization degree of polyvinyl alcohol is within the above range, a small amount of dispersant can be used to disperse the positive electrode active material and dispersing aid, and a positive electrode active material coating with excellent battery characteristics can be obtained.
上述聚乙烯醇之皂化度之下限較佳為70莫耳%以上，更佳為80%以上，另一方面，上限較佳為100莫耳%以下，更佳為90莫耳%以下。於上述皂化度為上述範圍內之情形時，導電助劑之分散性變優異。The lower limit of the saponification degree of the polyvinyl alcohol is preferably 70 mol % or more, more preferably 80 mol % or more, and on the other hand, the upper limit is preferably 100 mol % or less, more preferably 90 mol % or less. When the said degree of saponification is in the said range, the dispersibility of a conductive auxiliary agent becomes excellent.
上述聚乙烯醇-聚乙烯吡咯啶酮接枝共聚物100質量%中之聚乙烯醇之含量之下限為10質量%以上，較佳為20質量%以上，更佳為40質量%以上。另一方面，上限為90質量%以下，較佳為80質量%以下，更佳為60質量%以下。於含量為上述範圍內之情形時，可利用少量之分散劑分散正極活性物質及分散助劑，可獲得剝離強度優異之正極及電池特性優異之正極活性物質塗料。The lower limit of the content of polyvinyl alcohol in 100% by mass of the polyvinyl alcohol-polyvinylpyrrolidone graft copolymer is 10% by mass or more, preferably 20% by mass or more, and more preferably 40% by mass or more. On the other hand, the upper limit is 90 mass % or less, preferably 80 mass % or less, and more preferably 60 mass % or less. When the content is within the above range, a small amount of dispersing agent can be used to disperse the positive electrode active material and dispersing aid, and a positive electrode with excellent peel strength and a positive electrode active material coating with excellent battery characteristics can be obtained.
作為上述接枝共聚物之一實施形態，可利用下述實施例所記載之方法製造。As one embodiment of the above-mentioned graft copolymer, it can be produced by the method described in the following examples.
上述分散劑可於不妨礙本發明之效果之範圍內含有其他分散劑。作為其他分散劑，並無特別限定，具體而言，可列舉苯乙烯-丁二烯橡膠、聚乙烯吡咯啶酮、聚(甲基)丙烯腈、乙烯-乙烯醇共聚物、聚乙烯吡咯啶酮-聚丙烯腈接枝共聚物、乙酸乙烯酯聚合物等聚合物；聚偏二氟乙烯、四氟乙烯、五氟丙烯等氟系聚合物。該等可使用1種或將2種以上併用而使用。The above-mentioned dispersing agent may contain other dispersing agents within a range that does not hinder the effects of the present invention. It does not specifically limit as another dispersing agent, Specifically, styrene-butadiene rubber, polyvinylpyrrolidone, poly(meth)acrylonitrile, ethylene-vinyl alcohol copolymer, polyvinylpyrrolidone can be mentioned - Polymers such as polyacrylonitrile graft copolymers and vinyl acetate polymers; fluorine-based polymers such as polyvinylidene fluoride, tetrafluoroethylene, and pentafluoropropylene. These can be used alone or in combination of two or more.
於上述正極活性物質塗料中，關於上述分散劑之含量，相對於正極活性物質、導電助劑、及分散劑之合計量100質量%，分散劑之含量為0.1質量%以上且20質量%以下。含量之下限較佳為1質量%以上。又，含量之下限較佳為10質量%以下。於含量為上述範圍內之情形時，可利用少量之分散劑分散正極活性物質及分散助劑，可獲得電池特性優異之正極活性物質塗料。In the positive electrode active material coating material, the content of the dispersing agent is 0.1 mass % or more and 20 mass % or less with respect to 100 mass % of the total amount of the positive electrode active material, the conductive aid, and the dispersing agent. The lower limit of the content is preferably 1 mass % or more. In addition, the lower limit of the content is preferably 10% by mass or less. When the content is within the above-mentioned range, a small amount of dispersant can be used to disperse the positive electrode active material and the dispersing aid, and a positive electrode active material coating with excellent battery characteristics can be obtained.
上述正極活性物質塗料可藉由添加正極活性物質、導電助劑、分散劑及其他添加劑並加以混合，進而利用分散介質稀釋而製備。上述混合、分散並無特別限制，可利用行星式混合機或分散機等藉由通常之製法進行。上述正極活性物質塗料之黏度可適當設定，具體而言，下限為1,000 mPa·s(25℃)以上，較佳為2,000 mPa·s(25℃)以上。另一方面，上限較佳為10,000 mPa·s(25℃)以下，更佳為7,000 mPa·s(25℃)以下。於上述黏度為上述範圍內之情形時，成為塗敷性優異之塗料，因此較佳。The above-mentioned positive electrode active material coating can be prepared by adding and mixing the positive electrode active material, conductive assistant, dispersant and other additives, and then diluting with a dispersion medium. The above-mentioned mixing and dispersion are not particularly limited, and can be performed by a usual production method using a planetary mixer, a disperser, or the like. The viscosity of the positive electrode active material coating material can be appropriately set, and specifically, the lower limit is 1,000 mPa·s (25°C) or more, preferably 2,000 mPa·s (25°C) or more. On the other hand, the upper limit is preferably 10,000 mPa·s (25° C.) or less, and more preferably 7,000 mPa·s (25° C.) or less. When the said viscosity is in the said range, since it becomes a coating material excellent in coatability, it is preferable.
上述正極係藉由將上述正極活性物質塗料塗敷於集電體，並使分散介質揮發而形成正極活性物質層。In the positive electrode, the positive electrode active material layer is formed by applying the positive electrode active material coating material to the current collector and volatilizing the dispersion medium.
上述集電體只要為於所構成之電池中不產生不良影響之電子傳導體，則可使用任意者。例如除了銅、不鏽鋼、鎳、鋁、鈦、焙燒碳、導電性高分子、導電性玻璃、Al-Cd合金等以外，基於提高接著性、導電性、耐氧化性之目的，可使用對銅等之表面利用碳、鎳、鈦或銀等進行處理而成者。該等集電體材料亦可對表面進行氧化處理。又，關於其形狀，除箔狀以外，亦可使用膜狀、片狀、網狀、經沖切或膨脹者、板條體、多孔質體、發泡體等成形體。厚度並無特別限定，通常使用1〜100 μm者。As the current collector, any one can be used as long as it is an electron conductor that does not adversely affect the constituted battery. For example, in addition to copper, stainless steel, nickel, aluminum, titanium, calcined carbon, conductive polymers, conductive glass, Al-Cd alloys, etc., for the purpose of improving adhesion, conductivity, and oxidation resistance, copper or the like can be used. The surface is treated with carbon, nickel, titanium or silver. These current collector materials can also be oxidized to the surface. Moreover, as for the shape, in addition to the foil shape, a film shape, a sheet shape, a mesh shape, a die-cut or expanded one, a lath body, a porous body, a foam body, or the like can also be used. The thickness is not particularly limited, but usually 1 to 100 μm is used.
上述正極活性物質層之每單位面積之單位面積重量係適當設定，通常為3〜20 mg/cm2 以上。The weight per unit area of the positive electrode active material layer is appropriately set, and is usually 3 to 20 mg/cm 2 or more.
本發明之二次電池具備上述正極作為正極。一實施形態之二次電池之構造並無特別限定，例如可包含正極、負極、間隔件、及電解質，負極係使用上述本實施形態之電極。作為一實施形態，電池可具備隔著間隔件將正極與負極交替地積層所得之積層體、收容該積層體之容器、及注入至容器內之電解液等電解質而成。 [實施例]The secondary battery of the present invention includes the above positive electrode as a positive electrode. The structure of the secondary battery of one embodiment is not particularly limited, and may include, for example, a positive electrode, a negative electrode, a separator, and an electrolyte, and the negative electrode uses the electrode of the present embodiment described above. In one embodiment, the battery may include a laminate obtained by alternately laminating positive electrodes and negative electrodes with separators interposed therebetween, a container for accommodating the laminate, and an electrolyte such as an electrolytic solution injected into the container. [Example]
繼而，對實施例與比較例一起進行說明。但本發明並不限定於該等實施例。再者，例中，「%」只要無特別限定則意指質量基準。Next, an Example is demonstrated together with a comparative example. However, the present invention is not limited to these examples. In addition, in an example, unless it is specifically limited, "%" means a quality standard.
[接枝共聚物之合成] (接枝共聚物1) 於純水800質量份中溶解聚乙烯醇(聚合度1700、完全皂化、製品名：PVA-117、庫拉雷股份有限公司製造)100質量份，繼而添加N-乙烯基吡咯啶酮100質量份並加以混合，藉由驅放氮氣而進行脫氧。繼而，將反應系統之溫度調節至70℃。於其中添加1重量%硫酸銅0.01質量份、28重量%氨水1質量份及30質量%過氧化氫水1.5質量份(相對於系統之濃度為450 ppm)，開始聚合。聚合中將溫度維持為70〜80℃，藉由氨將pH值維持為5.5〜6.5，每隔15分鐘添加30重量%過氧化氫水1.5質量份計10次，藉此聚合率成為90%以上。其間，過氧化氫濃度為600 ppm以下。繼而，作為殘存N-乙烯基吡咯啶酮處理步驟，添加30質量%過氧化氫水4質量份，一面藉由氨水將pH值保持為5以上一面進行合計210分鐘之反應，獲得接枝共聚物1之水溶液。將所獲得之水溶液進行噴霧乾燥，獲得接枝共聚物1(聚乙烯醇含量50質量%)。[Synthesis of Graft Copolymer] (Graft Copolymer 1) Polyvinyl alcohol (polymerization degree 1700, complete saponification, product name: PVA-117, manufactured by Kuraray Co., Ltd.) 100 was dissolved in 800 parts by mass of pure water parts by mass, and then 100 parts by mass of N-vinylpyrrolidone was added and mixed, and deoxidation was performed by expelling nitrogen gas. Then, the temperature of the reaction system was adjusted to 70°C. To this, 0.01 mass part of 1 wt % copper sulfate, 1 mass part of 28 wt % ammonia water, and 1.5 mass parts of 30 mass % hydrogen peroxide water (450 ppm with respect to the concentration of the system) were added, and polymerization was started. During the polymerization, the temperature was maintained at 70 to 80°C, the pH was maintained at 5.5 to 6.5 with ammonia, and 1.5 parts by mass of 30% by weight hydrogen peroxide solution was added 10 times every 15 minutes, whereby the polymerization rate became 90% or more. . Meanwhile, the hydrogen peroxide concentration was 600 ppm or less. Next, as a residual N-vinylpyrrolidone treatment step, 4 parts by mass of 30 mass % hydrogen peroxide water was added, and the reaction was carried out for a total of 210 minutes while keeping the pH value at 5 or more with ammonia water to obtain a graft copolymer. 1 in aqueous solution. The obtained aqueous solution was spray-dried, and the graft copolymer 1 (polyvinyl alcohol content 50 mass %) was obtained.
(接枝共聚物2) 將聚乙烯醇變更為部分皂化聚乙烯醇(聚合度1700、皂化度88%、製品名：PVA-217、庫拉雷股份有限公司製造)160質量份，將N-乙烯基吡咯啶酮變更為40質量份，除此以外與接枝共聚物1同樣地進行製造，獲得接枝共聚物2(聚乙烯醇含量80質量%)。(Graft Copolymer 2) The polyvinyl alcohol was changed to 160 parts by mass of partially saponified polyvinyl alcohol (polymerization degree 1700, saponification degree 88%, product name: PVA-217, manufactured by Kuraray Co., Ltd.), and N- Except having changed vinylpyrrolidone to 40 mass parts, it carried out similarly to the graft copolymer 1, and obtained the graft copolymer 2 (polyvinyl alcohol content 80 mass %).
(接枝共聚物3) 將聚乙烯醇變更為部分皂化聚乙烯醇(聚合度1700、皂化度88%、製品名：PVA-217、庫拉雷股份有限公司製造)，除此以外，與接枝共聚物1同樣地進行製造，獲得接枝共聚物3(聚乙烯醇含量50質量%)。(Graft Copolymer 3) Polyvinyl alcohol was changed to partially saponified polyvinyl alcohol (degree of polymerization 1700, degree of saponification 88%, product name: PVA-217, manufactured by Kuraray Co., Ltd.), and the grafted The branch copolymer 1 was produced similarly, and the graft copolymer 3 (polyvinyl alcohol content 50 mass %) was obtained.
(接枝共聚物4) 將聚乙烯醇變更為部分皂化聚乙烯醇(聚合度1700、皂化度88%、製品名：PVA-217、庫拉雷股份有限公司製造)40質量份，將N-乙烯基吡咯啶酮變更為160質量份，除此以外，與接枝共聚物1同樣地進行製造，獲得接枝共聚物4(聚乙烯醇含量20質量%)。(Graft Copolymer 4) The polyvinyl alcohol was changed to 40 parts by mass of partially saponified polyvinyl alcohol (polymerization degree 1700, saponification degree 88%, product name: PVA-217, manufactured by Kuraray Co., Ltd.), and N- Except having changed vinylpyrrolidone to 160 mass parts, it carried out similarly to the graft copolymer 1, and obtained the graft copolymer 4 (polyvinyl alcohol content 20 mass %).
[正極活性物質塗料之製備] (塗料1) 於高型燒杯中添加分散劑(接枝共聚物1)4質量份與分散介質(N-甲基吡咯啶酮)66.7質量份並加以混合，一面藉由分散機於1000 rpm下進行攪拌，一面緩緩添加預先經粉-粉混合之正極活性物質(LiMna Nib Coc (a＋b＋c＝1))92質量份與導電助劑(導電性碳黑、製品名：SuperP、Imerys G.C. Japan股份有限公司製造)4質量份，於2000 rpm下攪拌90分鐘，進而靜置一晚而獲得塗料1。[Preparation of positive electrode active material coating material] (Coating 1) 4 parts by mass of a dispersant (graft copolymer 1) and 66.7 parts by mass of a dispersion medium (N-methylpyrrolidone) were added to a tall beaker and mixed. Stir at 1000 rpm by a disperser, and slowly add 92 parts by mass of the positive electrode active material (LiMn a Ni b Co c (a+b+c=1)) and a conductive auxiliary (conductive carbon black mixed in advance by powder-powder) , product name: SuperP, manufactured by Imerys GC Japan Co., Ltd.) 4 parts by mass, stirred at 2000 rpm for 90 minutes, and then left to stand overnight to obtain paint 1.
(塗料2至6) 除如下述表1所示變更分散劑以外，與塗料1同樣地進行製備而獲得塗料2至6。(Coating materials 2 to 6) Except having changed the dispersing agent as shown in the following Table 1, it carried out similarly to the coating material 1, and obtained the coating materials 2-6.
[塗料之評價] 對塗料1至6按以下之評價基準進行評價。將其結果示於下述表1。[Evaluation of Paint] Paints 1 to 6 were evaluated according to the following evaluation criteria. The results are shown in Table 1 below.
(黏度) 依據JIS Z8803使用BM型黏度計(單圓筒型旋轉黏度計)測定25℃下之正極活性物質塗料之黏度。此時，(a)將轉子轉數設為60 rpm進行測定，(b)於上述(a)中之測定值為8000 mPa·s以上之情形時，將轉子轉數變更為30 rpm進行測定，(c)於上述(b)中之測定值為16000 mPa·s以上之情形時，將轉子轉數變更為12 rpm進行測定。(Viscosity) The viscosity of the positive electrode active material coating at 25°C was measured using a BM type viscometer (single-cylinder rotational viscometer) in accordance with JIS Z8803. At this time, (a) the rotor revolution was set to 60 rpm for measurement, and (b) when the measured value in the above (a) was 8000 mPa·s or more, the rotor revolution was changed to 30 rpm for measurement, (c) When the measured value in the above (b) is 16000 mPa·s or more, the rotor rotation speed is changed to 12 rpm and the measurement is performed.
(分散狀態) 對正極活性物質塗料之正極活性物質及導電助劑之分散狀態按以下之評價基準進行評價。 ◎：藉由目視未觀察到存在因分散不良所導致之較小之正極活性物質或導電助劑之固化物。 ○：藉由目視觀察到存在些許因分散不良所導致之較小之正極活性物質或導電助劑之固化物。 △：藉由目視觀察到存在明顯可知為分散不良之較大之正極活性物質或導電助劑之固化物。(Dispersion state) The dispersion state of the positive electrode active material and the conductive aid in the positive electrode active material coating was evaluated according to the following evaluation criteria. ⊚: The presence of a small positive electrode active material or a cured product of a conductive aid due to poor dispersion was not observed by visual inspection. ○: The presence of a small amount of the cured product of the positive electrode active material or the conductive aid due to poor dispersion was observed visually. (triangle|delta): The presence of the hardened|cured material of a large positive electrode active material or a conductive auxiliary agent which was clearly recognized as being poor in dispersion was observed by visual observation.
[表1]
根據表1，使用接枝共聚物1至4之塗料1至4獲得了分散狀態良好之塗料。另一方面，使用聚偏二氟乙烯代替接枝共聚物1至4之塗料5之分散狀態不良，且將聚乙烯醇與聚乙烯吡咯啶酮併用之塗料6凝膠化。According to Table 1, paints 1 to 4 using graft copolymers 1 to 4 obtained paints in good dispersion state. On the other hand, the dispersion state of the coating material 5 using polyvinylidene fluoride instead of the graft copolymers 1 to 4 was poor, and the coating material 6 using polyvinyl alcohol and polyvinylpyrrolidone in combination was gelled.
[正極之製作] (正極1) 將塗料1以厚度成為100 μm之方式調整並塗敷敷料器於鋁箔(厚度10 μm)，以100℃進行預乾燥後，以130℃進行8小時真空乾燥。將乾燥而獲得之電極藉由輥壓機進行加壓成形，藉此獲得具有銅箔之單面之電極密度為2.1 g/cm3
之正極合劑層之電極片。其後，將上述電極片利用
(正極2至5) 如表2所示變更塗料以外，與正極1同樣地進行製作，獲得正極2至5。再者，由於塗料6靜置一晚後凝膠化，故而未進行正極之製作。(Positive Electrodes 2 to 5) Except having changed the coating materials as shown in Table 2, the same procedure as that of the positive electrode 1 was carried out, and the positive electrodes 2 to 5 were obtained. In addition, since the coating material 6 gelled after being left to stand overnight, the production of the positive electrode was not performed.
[正極之評價] 對正極1至5按下述之評價基準進行評價。將評價結果示於表2。[Evaluation of Positive Electrode] The positive electrodes 1 to 5 were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
(剝離強度之測定) 將上述電極片切割成18 cm×2 cm之短條狀，於集電體側利用雙面膠接著厚度1 mm之鋼板，將塗敷面貼附於雙面膠帶，將賽珞玢黏著帶貼附於集電體，藉由拉伸試驗機(島津製作所，自動立體測圖儀AGS-X)測定以50 mm/min之速度向180°方向剝離時之應力。(Measurement of peel strength) The above electrode sheet was cut into short strips of 18 cm × 2 cm, and a steel plate with a thickness of 1 mm was attached to the collector side with double-sided tape. The coated surface was attached to the double-sided tape. The cellophane adhesive tape was attached to the current collector, and the stress when peeled off in the direction of 180° at a speed of 50 mm/min was measured by a tensile tester (Shimadzu Corporation, AGS-X).
(電極狀態) 對正極活性物質塗料之正極活性物質及導電材之電極狀態按以下之評價基準進行評價。 ◎：於5 cm×5 cm之電極切片內，藉由目視觀察到完全不存在判斷為分散不良之自電極表面上向上成為凸狀之較小之正極活性物質或導電助劑之固化物 ○：於5 cm×5 cm之電極切片內，藉由目視觀察到存在1個以下之判斷為分散不良之自電極表面上向上成為凸狀之較小之正極活性物質或導電助劑之固化物 △：於5 cm×5 cm之電極切片內，藉由目視觀察到存在2個以上之判斷為分散不良之自電極表面上向上成為凸狀之較小之正極活性物質或導電助劑之固化物 ×：於5 cm×5 cm之電極切片內，藉由目視觀察到存在10個以上之判斷為分散不良之自電極表面上向上成為凸狀之較小之正極活性物質或導電助劑之固化物(Electrode State) The electrode states of the positive electrode active material and the conductive material of the positive electrode active material coating were evaluated according to the following evaluation criteria. ◎: In the electrode slice of 5 cm × 5 cm, there is no solidified product of the positive electrode active material or the conductive auxiliary agent which is judged to be poorly dispersed and becomes convex upward from the surface of the electrode, which is judged to be poorly dispersed by visual observation ○: In the electrode slice of 5 cm×5 cm, there is one or less solidified product of positive electrode active material or conductive assistant that is judged to be poorly dispersed and becomes convex upward from the electrode surface by visual observation △: In the electrode slice of 5 cm × 5 cm, there are two or more small positive electrode active materials or cured products of conductive additives that are judged to be poorly dispersed and that are convex upward from the electrode surface by visual observation ×: In the electrode slice of 5 cm × 5 cm, there are more than 10 solidified products of positive electrode active material or conductive assistant that are judged to be poorly dispersed and are convex upward from the electrode surface by visual observation.
[表2]
根據表2，藉由使用接枝共聚物1至4之塗料1至4而製成的正極1至4獲得不產生乾燥破裂之良好之正極。另一方面，藉由使用聚偏二氟乙烯代替接枝共聚物1至4之塗料5而製成的正極5成為剝離強度顯著較低之結果。According to Table 2, the positive electrodes 1 to 4 prepared by using the coatings 1 to 4 of the graft copolymers 1 to 4 obtained good positive electrodes without drying cracking. On the other hand, the positive electrode 5 made by using polyvinylidene fluoride instead of the coating 5 of the graft copolymers 1 to 4 resulted in a significantly lower peel strength.
[鋰離子二次電池之製作] (實施例1) 將上述獲得之正極1、間隔件(THANK-METAL公司製造之Celgard 2325)、作為工作電極之鋰金屬(
(實施例2〜4) 除將正極1分別變更為正極2至4以外，與實施例1同樣地進行製作而獲得二次電池。再者，塗料5由於分散狀態不理想，而且沖切電極時合劑層破裂、掉粉，故而未進行二次電池之製作。(Examples 2 to 4) A secondary battery was obtained in the same manner as in Example 1, except that the positive electrode 1 was changed to the positive electrode 2 to 4, respectively. Furthermore, since the dispersion state of the paint 5 was not ideal, and the mixture layer was cracked and powdered when the electrode was punched, the secondary battery was not produced.
[電池特性之評價] 對實施例1至4所獲得之二次電池按以下之評價方法及評價基準進行評價。將其結果示於表3。[Evaluation of Battery Characteristics] The secondary batteries obtained in Examples 1 to 4 were evaluated according to the following evaluation methods and evaluation criteria. The results are shown in Table 3.
(初次充放電特性) 於20℃之氛圍下，利用基於上述正極之實效電容而獲得之0.1 C之電流值，在定電流定電壓條件下進行充電直至電壓值成為0.01 V，於電流值降低至0.05 C之時間點停止充電。繼而，於電流值0.1 C之條件下進行放電直至對金屬Li之電壓成為1.0 V，測定初次放電電容。(Initial charge-discharge characteristics) In an atmosphere of 20°C, using the current value of 0.1 C obtained from the effective capacitance of the positive electrode, charge under constant current and constant voltage conditions until the voltage value becomes 0.01 V, and when the current value decreases to 0.01 V The charging was stopped at the time point of 0.05 C. Then, discharge was performed under the condition of a current value of 0.1 C until the voltage to metal Li became 1.0 V, and the initial discharge capacitance was measured.
(放電速率特性) 於20℃之氛圍下，利用基於第2次之放電電容而獲得之0.2 C之電流值，於定電流定電壓條件下進行充電直至電壓值成為0.01 V，於電流值降低至0.05 C之時間點停止充電。繼而，於電流值1 C之條件下進行放電直至對金屬Li之電壓成為1.0 V，測定1 C之放電電容。進而，同樣地進行充電，於電流值3 C之條件下進行放電，測定3 C之放電電容。將以1 C之放電電容作為100%時之3 C之放電電容設為3 C電容維持率。(Discharge rate characteristics) In an atmosphere of 20°C, using the current value of 0.2 C obtained from the second discharge capacitor, charge under constant current and constant voltage conditions until the voltage value becomes 0.01 V, and when the current value decreases to The charging was stopped at the time point of 0.05 C. Then, discharge was performed under the condition of a current value of 1 C until the voltage to metal Li became 1.0 V, and the discharge capacitance of 1 C was measured. Furthermore, charging was performed in the same manner, and discharge was performed under the condition of a current value of 3 C, and the discharge capacity of 3 C was measured. Set the discharge capacitance of 3 C when the discharge capacitance of 1 C is taken as 100% as the 3 C capacitance maintenance rate.
[表3]
本發明之正極活性物質塗料及使用其之正極以及二次電池可廣泛地用於攜帶式機器等。The positive electrode active material coating material of the present invention and the positive electrode and secondary battery using the same can be widely used in portable devices and the like.
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