JP6211752B2 - Binder resin composition for nickel metal hydride secondary battery electrode and composite ink containing the same - Google Patents
Binder resin composition for nickel metal hydride secondary battery electrode and composite ink containing the same Download PDFInfo
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- JP6211752B2 JP6211752B2 JP2012176798A JP2012176798A JP6211752B2 JP 6211752 B2 JP6211752 B2 JP 6211752B2 JP 2012176798 A JP2012176798 A JP 2012176798A JP 2012176798 A JP2012176798 A JP 2012176798A JP 6211752 B2 JP6211752 B2 JP 6211752B2
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- monomer
- weight
- nickel
- parts
- transition temperature
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 46
- -1 nickel metal hydride Chemical class 0.000 title claims description 33
- 239000011230 binding agent Substances 0.000 title claims description 31
- 239000011342 resin composition Substances 0.000 title claims description 27
- 229910052759 nickel Inorganic materials 0.000 title claims description 22
- 239000002131 composite material Substances 0.000 title claims description 21
- 229910052987 metal hydride Inorganic materials 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims description 121
- 239000002245 particle Substances 0.000 claims description 108
- 229920000642 polymer Polymers 0.000 claims description 82
- 239000000839 emulsion Substances 0.000 claims description 68
- 230000009477 glass transition Effects 0.000 claims description 47
- 239000004020 conductor Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 229920001519 homopolymer Polymers 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims 2
- 150000001993 dienes Chemical class 0.000 claims 2
- 239000004908 Emulsion polymer Substances 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 description 53
- 239000000203 mixture Substances 0.000 description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 28
- 239000003995 emulsifying agent Substances 0.000 description 28
- 125000000524 functional group Chemical group 0.000 description 26
- 239000011149 active material Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 229910000652 nickel hydride Inorganic materials 0.000 description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 230000036571 hydration Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
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- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
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- 239000003638 chemical reducing agent Substances 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
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- 239000003999 initiator Substances 0.000 description 3
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- 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
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
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- 230000001172 regenerating effect Effects 0.000 description 2
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- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
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- 230000006641 stabilisation Effects 0.000 description 2
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
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- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- BVLWNRIJQBINQL-UHFFFAOYSA-N 2,4-dimethyl-3-oxopent-4-enoic acid Chemical compound OC(=O)C(C)C(=O)C(C)=C BVLWNRIJQBINQL-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
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- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 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
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 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
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、ニッケル水素二次電池電極用バインダー樹脂組成物及びそれを含む合材インキに関する。 The present invention relates to a binder resin composition for nickel metal hydride secondary battery electrodes and a composite ink containing the same.
ニッケル水素二次電池は、単位容積あたりのエネルギー密度が大きく、充放電サイクル特性が良好であり、乾電池の代替や電化製品用途、さらには自動車等の大型用途において、すでに実用化されている。 Nickel metal hydride secondary batteries have a high energy density per unit volume and good charge / discharge cycle characteristics, and have already been put to practical use in alternatives to dry batteries, electrical appliance applications, and large-sized applications such as automobiles.
一般に、ニッケル水素二次電池の正極は、活物質である水酸化ニッケル粉末を発泡状ニッケル基材に充填することで得られる。水酸化ニッケルの表面を、導電助剤となる水酸化コバルトもしくはオキシ水酸化コバルトがコーティングされたものも市販されている。これら活物質をカルボキシルメチルセルロース（ＣＭＣ）のような増粘剤と共に水性溶媒中で混練することによって基材に充填するための合材インキが得られる。バインダーとしてポリテトラフルオロエチレン(ＰＴＦＥ)などを添加する場合もある。 In general, a positive electrode of a nickel metal hydride secondary battery is obtained by filling a foamed nickel base material with nickel hydroxide powder as an active material. A nickel hydroxide whose surface is coated with cobalt hydroxide or cobalt oxyhydroxide as a conductive additive is also commercially available. By mixing these active materials with a thickener such as carboxymethylcellulose (CMC) in an aqueous solvent, a mixed ink for filling a substrate can be obtained. In some cases, polytetrafluoroethylene (PTFE) or the like is added as a binder.
一方、負極用合材インキは、負極の電極組成物として用いられる水素吸蔵合金に、ニッケル粉末やカーボン等からなる導電性材料（Ｂ）、バインダー樹脂組成物（Ａ）を混錬することにより得られる。この負極用合材インキをパンチングメタルや金属板、発泡金属板、網状金属繊維焼結板等の金属集電体に塗布し、乾燥後にプレス処理することにより負極を作製する。 On the other hand, the composite ink for the negative electrode is obtained by kneading the hydrogen storage alloy used as the negative electrode composition with a conductive material (B) made of nickel powder, carbon, or the like, and a binder resin composition (A). It is done. This negative electrode mixture ink is applied to a metal current collector such as a punching metal, a metal plate, a foamed metal plate, or a reticulated metal fiber sintered plate, and is pressed after drying to produce a negative electrode.
ところで、変電所、自動車、電車等に用いられるニッケル水素二次電池には、従来の乾電池や携帯機器等に用いられるものに比べて、高出力、高電圧及び高容量が要求される。そのため、大型のものを使用する必要がある。車両にニッケル水素二次電池を搭載した場合、ブレーキ時に生じる回生電力を搭載されたニッケル水素二次電池に蓄えておき、車両の動力源として使用することができる。そのため、車両の運行エネルギー効率を高めることができる。ここで、回生電力をニッケル水素二次電池に充電する際には、大電流によって急速充電する必要がある。他方、ニッケル水素二次電池を利用して車両を駆動する際には、急速放電する必要がある。そのため、産業用ニッケル水素二次電池は、大型・大容量であるだけでなく、急速充放電性能も不可欠である。 Incidentally, nickel hydride secondary batteries used in substations, automobiles, trains, and the like are required to have higher output, higher voltage, and higher capacity than those used in conventional dry batteries and portable devices. Therefore, it is necessary to use a large one. When a nickel metal hydride secondary battery is mounted on a vehicle, regenerative power generated during braking can be stored in the mounted nickel metal hydride secondary battery and used as a power source for the vehicle. Therefore, the operation energy efficiency of the vehicle can be increased. Here, when the regenerative power is charged in the nickel-hydrogen secondary battery, it is necessary to rapidly charge the battery with a large current. On the other hand, when driving a vehicle using a nickel metal hydride secondary battery, it is necessary to rapidly discharge the vehicle. Therefore, industrial nickel metal hydride secondary batteries are not only large and large capacity, but also rapid charge / discharge performance is indispensable.
一般に、急速充放電特性を向上させるには、電池の内部抵抗を低減させる。その手法として、電極自体を薄膜化する。すなわち、多孔質の発泡ニッケルやニッケル焼結体に合材インキを充填する代わりに、二次元構造集電体である平滑なニッケル基板に活物質、バインダー、導電助材を含む合材インキを塗布する手法が開示されている（特許文献１）。 Generally, in order to improve rapid charge / discharge characteristics, the internal resistance of the battery is reduced. As the technique, the electrode itself is made thin. In other words, instead of filling the foamed nickel or nickel sintered body with the mixed ink, apply the mixed ink containing the active material, binder and conductive additive to the smooth nickel substrate which is a two-dimensional structure current collector. (Patent Document 1).
しかし、特許文献１のように二次元構造集電体を基材とする場合、例えば発泡状ニッケルのように、三次元的に広がったニッケルの網が水酸化ニッケルを包み、機械的密着力により固定することができない。つまり、バインダーによる化学的密着力のみが活物質と基材との接触を保持しているため活物質保持力が弱かった。これは、充放電サイクルによって、バインダーを構成するポリマーが徐々に酸化劣化し、密着力が低下することで基材と合材層が剥離するからである。その結果、電子伝導性が低下することで利用率が低下するという問題があった。 However, when a two-dimensional structure current collector is used as a base material as in Patent Document 1, for example, a nickel network that expands three-dimensionally, such as foamed nickel, wraps nickel hydroxide, and due to mechanical adhesion. It cannot be fixed. In other words, the active material holding power was weak because only the chemical adhesion by the binder kept the contact between the active material and the substrate. This is because the base material and the composite material layer are peeled off due to the oxidative deterioration of the polymer constituting the binder due to the charge / discharge cycle, and the adhesion force is reduced. As a result, there has been a problem that the utilization factor is lowered due to the decrease in electron conductivity.
本発明の目的は、アルカリ電解液によるポリマー劣化、及び充放電サイクルによる酸化劣化を抑制できることで急速充放電特性及び充放電サイクル特性に優れたニッケル水素二次電池電極用バインダー樹脂組成物及びそれを含む合材インキを提供することにある。 An object of the present invention is to provide a binder resin composition for a nickel hydride secondary battery electrode excellent in rapid charge / discharge characteristics and charge / discharge cycle characteristics by suppressing polymer deterioration due to an alkaline electrolyte and oxidation deterioration due to charge / discharge cycles, and It is to provide a composite ink containing.
本発明の一態様に係るニッケル水素二次電池電極用バインダー樹脂組成物（Ａ）は、
水和性官能基を含有する第１のモノマー（ａ−１）１〜５重量％と、
カルボキシル基を含有する第２のモノマー（ａ−２）０．１〜５重量％と、
水和性官能基及びカルボキシル基を含有しない第３のモノマー（ａ−３）９０〜９８．９重量％と、を含むモノマー群を備え、
前記モノマー群を乳化重合することにより得られるポリマーエマルションは、−２０〜２０℃のガラス転移温度を有し、
当該ポリマーエマルションのｐＨ８〜１０のときの平均粒子径が、ｐＨ１〜３のときの平均粒子径の１．２倍〜１．５倍であることを特徴とするものである。
The binder resin composition (A) for a nickel metal hydride secondary battery electrode according to one embodiment of the present invention,
1 to 5% by weight of the first monomer (a-1) containing a hydratable functional group;
0.1 to 5% by weight of the second monomer (a-2) containing a carboxyl group;
A monomer group containing 90 to 98.9% by weight of a third monomer (a-3) not containing a hydratable functional group and a carboxyl group,
The polymer emulsion obtained by emulsion polymerization of the monomer group has a glass transition temperature of -20 to 20 ° C,
The average particle diameter of the polymer emulsion at pH 8 to 10 is 1.2 to 1.5 times the average particle diameter at pH 1 to 3.
第１のモノマー（ａ−１）の水和性官能基が、ｐＨ８〜１０においてイオン化しない官能基であることが好ましい。
また、第３のモノマー（ａ−３）が、ホモポリマーのガラス転移温度が５０〜２００℃のモノマー（ａ−４）と、ホモポリマーのガラス転移温度が−１００℃以上５０℃未満のモノマー（ａ−５）と、を含むことが好ましい。
さらに、ポリマーエマルションのｐＨ１〜３のときの平均粒子径が、１５０〜２５０ｎｍであることが好ましい。
The hydratable functional group of the first monomer (a-1) is preferably a functional group that does not ionize at pH 8-10.
Further, the third monomer (a-3) is composed of a monomer (a-4) having a glass transition temperature of homopolymer of 50 to 200 ° C. and a monomer having a glass transition temperature of −100 ° C. or more and less than 50 ° C. a-5).
Furthermore, it is preferable that the average particle diameter at the time of pH 1-3 of a polymer emulsion is 150-250 nm.
本発明の他の態様に係るニッケル水素二次電池電極用合材インキは、
上記のニッケル水素二次電池電極用バインダー樹脂組成物（Ａ）と、導電性材料（Ｂ）と、を含むことを特徴とするものである。
The mixed ink for a nickel metal hydride secondary battery electrode according to another embodiment of the present invention,
The binder resin composition (A) for nickel hydride secondary battery electrodes and the conductive material (B) are included.
ニッケル水素二次電池電極用合材インキに、本発明に係るバインダー樹脂組成物（Ａ）を用いることにより、急速充放電特性及び充放電サイクル特性に優れたニッケル水素二次電池を得ることができる。 By using the binder resin composition (A) according to the present invention for the nickel-hydrogen secondary battery electrode composite ink, a nickel-hydrogen secondary battery excellent in rapid charge / discharge characteristics and charge / discharge cycle characteristics can be obtained. .
以下、本発明に適用した具体的な実施の形態について、図面を参照しながら詳細に説明する。ただし、本発明が以下の実施の形態に限定される訳ではない。 Hereinafter, specific embodiments applied to the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiment.
本実施の形態に係るニッケル水素二次電池電極用合材インキは、バインダー樹脂組成物（Ａ）及び導電性材料（Ｂ）を含む。そして、当該インキを集電体に塗布することにより電極が得られる。 The nickel-hydrogen secondary battery electrode composite ink according to the present embodiment includes a binder resin composition (A) and a conductive material (B). And an electrode is obtained by apply | coating the said ink to a collector.
電池の内部抵抗を低減するためには、結着成分であるバインダー樹脂組成物（Ａ）と導電性材料（Ｂ）の成分が、活物質の表面を必要最低限の量で覆い、活物質の電池反応を阻害しないことが求められる。 In order to reduce the internal resistance of the battery, the binder resin composition (A) and the conductive material (B), which are binding components, cover the surface of the active material with the minimum amount necessary, It is required not to inhibit the battery reaction.
発明者らは、バインダー樹脂組成物（Ａ）のアルカリ性下での分散安定性に着目した。そして、バインダー樹脂組成物（Ａ）を含むポリマーエマルションの粒子表面の水和成分を厚くすることにより、ポリマー粒子の分散安定性を高められることを見出した。強アルカリ性である合材インキ中で、バインダー樹脂組成物（Ａ）が凝集することなく均一に分散することにより、活物質及び導電性材料（Ｂ）を均一に覆うことができる。そのため、電極を形成した後も、活物質の表面をバインダー樹脂組成物（Ａ）と導電性材料（Ｂ）の成分が均一に覆われた状態を保つことができる。したがって、塗布型電極中での活物質の凝集を最小限に抑えることができる。すなわち、活物質の表面積を最大限に保持でき、これまでにない効率で、活物質の電池反応を電極の充放電に利用できる。これにより、急速充放電特性及び充放電サイクル特性が飛躍的に向上する。 The inventors paid attention to the dispersion stability of the binder resin composition (A) under alkalinity. And it discovered that the dispersion stability of a polymer particle could be improved by thickening the hydration component of the particle | grain surface of the polymer emulsion containing a binder resin composition (A). The active material and the conductive material (B) can be uniformly covered by uniformly dispersing the binder resin composition (A) without agglomeration in the strongly mixed ink. Therefore, even after the electrodes are formed, the surface of the active material can be kept in a state where the components of the binder resin composition (A) and the conductive material (B) are uniformly covered. Therefore, the aggregation of the active material in the coated electrode can be minimized. That is, the surface area of the active material can be maintained to the maximum, and the battery reaction of the active material can be used for charging / discharging of the electrode with unprecedented efficiency. Thereby, rapid charge / discharge characteristics and charge / discharge cycle characteristics are dramatically improved.
ポリマーエマルションは、粒子表面のアニオン電荷同士の反発または、水分子との水和によって立体的に安定化している。アニオン電荷同士の反発による安定化効果は、攪拌や衝撃等の機械的安定性は高いものの、化学的安定性は低い。一方、水和による立体安定化効果は、化学的安定性は高いものの、機械的安定性は低い。合材インキは強アルカリ性の分散液であるため、非常に高い化学的安定性が求められる。発明者らは、水和性官能基モノマー（ａ−１）を用いることにより、非常に高い化学的安定性が得られ、その結果、バインダー樹脂組成物（Ａ）の中和前後の粒子径が大きく変化することを発見した。すなわち、ポリマーエマルションの表面に一定の厚みの水和層があることを発見した。 The polymer emulsion is sterically stabilized by repulsion between anionic charges on the particle surface or by hydration with water molecules. The stabilization effect by repulsion between anion charges is high in mechanical stability such as stirring and impact, but is low in chemical stability. On the other hand, the steric stabilization effect by hydration is high in chemical stability but low in mechanical stability. Since the composite ink is a strongly alkaline dispersion, very high chemical stability is required. The inventors have obtained extremely high chemical stability by using the hydratable functional group monomer (a-1), and as a result, the particle size before and after neutralization of the binder resin composition (A) is increased. I found a big change. That is, it has been found that there is a hydrated layer having a certain thickness on the surface of the polymer emulsion.
水和層の厚みは、ポリマーエマルションの中和前後の粒子径によって測定することができる。すなわち、中和後の粒子径から中和前の粒子径を差し引くことによって、水和層を算出することができる。ポリマーエマルションの水和層については、バインダー樹脂組成物（Ａ）の中和後の粒子径が中和前の粒子径の１．２〜１．５倍の範囲となることが好ましく、１．２５〜１．４５倍がさらに好ましい。中和後の粒子径が中和前の粒子径の１．２倍以上になると、水分子との水和の効果により、化学的安定性が向上する。また、１．５倍以下になると、乳化重合時の安定性が高まる。即ち、エマルションの流動性が増し、エマルションが凝集しにくくなる。 The thickness of the hydration layer can be measured by the particle diameter before and after neutralization of the polymer emulsion. That is, the hydrated layer can be calculated by subtracting the particle size before neutralization from the particle size after neutralization. For the hydrated layer of the polymer emulsion, the particle size after neutralization of the binder resin composition (A) is preferably in the range of 1.2 to 1.5 times the particle size before neutralization, 1.25 ˜1.45 times is more preferable. When the particle diameter after neutralization is 1.2 times or more the particle diameter before neutralization, chemical stability is improved due to the effect of hydration with water molecules. Moreover, when it becomes 1.5 times or less, the stability at the time of emulsion polymerization will increase. That is, the fluidity of the emulsion is increased and the emulsion is less likely to aggregate.
ポリマーエマルションの粒子径は、中和前では、Ｄ５０粒子径で１５０〜２５０ｎｍの範囲が好ましく、１７０〜２３０ｎｍがさらに好ましい。ここでのＤ５０粒子径は、動的光散乱法により得られる粒径分布曲線の体積分布累積量の５０％に相当する粒子径である。具体的には、不揮発分０．０１〜０．１重量％程度に希釈し、「マイクロトラックＵＰＡ」（Ｌｅｅｄｓ＆Ｎｏｒｔｈｒｕｐ社製）を用い、Ｄ５０粒子径を求めることができる。 The particle diameter of the polymer emulsion is preferably in the range of 150 to 250 nm, more preferably 170 to 230 nm in terms of the D50 particle diameter before neutralization. The D50 particle size here is a particle size corresponding to 50% of the cumulative volume distribution of the particle size distribution curve obtained by the dynamic light scattering method. Specifically, the D50 particle diameter can be determined by diluting to a non-volatile content of about 0.01 to 0.1% by weight and using “Microtrack UPA” (Leeds & Northrup).
ポリマーエマルションのＤ５０粒子径が１５０ｎｍ以上であれば、チクソ性が大きくなり過ぎず、ニッケル水素二次電池用塗布型電極用合材インキに好適となる。また、エマルションのＤ５０粒子径が２５０ｎｍ以下であれば、活物質間に粒子が侵入することができ、活物質間の結着力が向上するため、電極形成が容易になる。ここで、ポリマーエマルションの粒子径を測定するときの中和前のｐＨは１〜３で、中和後のｐＨは８〜１０である。 If the D50 particle diameter of the polymer emulsion is 150 nm or more, the thixotropy does not become too large, and it is suitable for a coating ink for a nickel hydride secondary battery. Further, when the D50 particle diameter of the emulsion is 250 nm or less, the particles can invade between the active materials, and the binding force between the active materials is improved, so that electrode formation is facilitated. Here, the pH before neutralization when measuring the particle diameter of the polymer emulsion is 1 to 3, and the pH after neutralization is 8 to 10.
水和性官能基モノマー（ａ−１）の使用量は、１〜５重量％が好ましく、２〜４重量％がさらに好ましい。１重量％以上になると、水分子との水和の効果により、化学的安定性がより向上する。また、５重量％以下になると、乳化重合時の安定性がより高まる。即ち、エマルションの流動性が増し、エマルションが凝集しにくくなる。 The amount of the hydratable functional group monomer (a-1) used is preferably 1 to 5% by weight, and more preferably 2 to 4% by weight. If it is 1% by weight or more, chemical stability is further improved due to the effect of hydration with water molecules. Moreover, when it becomes 5 weight% or less, the stability at the time of emulsion polymerization will increase more. That is, the fluidity of the emulsion is increased and the emulsion is less likely to aggregate.
水和性官能基モノマー（ａ−１）は、ｐＨ８〜１０においてイオン化しない官能基である。ここで、イオン化しない官能基とは、水中でイオン解離せず、水分子と水和する官能基を有する親水性のモノマーである。例えば、アクリル酸ヒドロキシエチル（ホモポリマーのガラス転移温度Ｔｇ＝−１５℃、以下同様）、アクリル酸ヒドロキシプロピル（Ｔｇ＝−７℃）、アクリル酸ヒドロキシブチル（Ｔｇ＝−８０℃）、メタクリル酸ヒドロキシエチル（Ｔｇ＝５５℃）、メタクリル酸ヒドロキシプロピル（Ｔｇ＝２６℃）、メタクリル酸ヒドロキシブチル等（Ｔｇ＝−４０℃）のヒドロキシ基含有モノマー、アクリルアミド（Ｔｇ＝１５３℃）、メタクリルアミド（Ｔｇ＝７７℃）、ダイアセトンアクリルアミド（Ｔｇ＝７７℃）、Ｎ‐イソプロピルアクリルアミド（Ｔｇ＝１３４℃）、Ｎ‐メチルアクリルアミド（Ｔｇ＝１３０℃）、Ｎ‐メチルメタクリルアミド（Ｔｇ＝６５℃）、Ｎ，Ｎ‐ジメチルアクリルアミド（Ｔｇ＝１１９℃）、Ｎ‐エチルアクリルアミド（Ｔｇ＝１００℃）、Ｎ，Ｎ‐ジエチルアクリルアミド（Ｔｇ＝８１℃）、Ｎ‐ブチルアクリルアミド（Ｔｇ＝４６℃）、ヒドロキシエチルアクリルアミド（Ｔｇ＝９８℃）、アクリロイルモルホリン（Ｔｇ＝１４５℃）等のアミド基含有モノマー、メタクリル酸グリシジル（Ｔｇ＝４１℃）、アクリル酸グリシジル（Ｔｇ＝１０℃）等のグリシジル基含有モノマー、等が挙げられる。これらの中で、アミド基含有モノマーが特に好ましい。これはアミド基の水素結合力が水酸基やグリシジル基よりも強いために、水分子との水和による水和層を厚く形成しやすいためである。
The hydratable functional group monomer (a-1) is a functional group that does not ionize at pH 8-10. Here, the functional group that is not ionized is a hydrophilic monomer that has a functional group that does not ionize in water and hydrates with water molecules. For example, hydroxyethyl acrylate (homopolymer glass transition temperature Tg = −15 ° C., hereinafter the same), hydroxypropyl acrylate (Tg = −7 ° C.), hydroxybutyl acrylate (Tg = −80 ° C.), hydroxy methacrylate Hydroxy group-containing monomers such as ethyl (Tg = 55 ° C.), hydroxypropyl methacrylate (Tg = 26 ° C.), hydroxybutyl methacrylate (Tg = −40 ° C.), acrylamide (Tg = 153 ° C.), methacrylamide (Tg = 77 ° C), diacetone acrylamide (Tg = 77 ° C), N-isopropylacrylamide (Tg = 134 ° C), N-methylacrylamide (Tg = 130 ° C), N-methylmethacrylamide (Tg = 65 ° C), N, N-dimethylacrylamide (Tg = 119 ° C.), N-ethyl alcohol Rilamide (Tg = 100 ° C.), N, N-diethylacrylamide (Tg = 81 ° C.), N-butylacrylamide (Tg = 46 ° C.), hydroxyethylacrylamide (Tg = 98 ° C.), acryloylmorpholine (Tg = 145 ° C.) Amide group-containing monomers such as glycidyl methacrylate (Tg = 41 ° C.), glycidyl group-containing monomers such as glycidyl acrylate (Tg = 10 ° C.), and the like. Of these, amide group-containing monomers are particularly preferred. This is because the hydrogen bond strength of the amide group is stronger than that of the hydroxyl group or glycidyl group, so that it is easy to form a thick hydrated layer by hydration with water molecules.
カルボキシル基含有モノマー（ａ−２）について説明する。カルボキシル基含有モノマー（ａ−２）を用いることにより、乳化重合時の重合安定性を向上させることができる。カルボキシル基含有モノマー（ａ−２）は、例えば、アクリル酸（ホモポリマーのガラス転移温度Ｔｇ＝１０６℃、以下同様）、メタクリル酸（Ｔｇ＝１３０℃）、イタコン酸（Ｔｇ＝１００℃）、マレイン酸（Ｔｇ＝１３０℃）、２−メタクリロイルプロピオン酸等を挙げることができる。 The carboxyl group-containing monomer (a-2) will be described. By using the carboxyl group-containing monomer (a-2), the polymerization stability during emulsion polymerization can be improved. The carboxyl group-containing monomer (a-2) includes, for example, acrylic acid (homopolymer glass transition temperature Tg = 106 ° C., hereinafter the same), methacrylic acid (Tg = 130 ° C.), itaconic acid (Tg = 100 ° C.), maleic An acid (Tg = 130 degreeC), 2-methacryloyl propionic acid, etc. can be mentioned.
カルボキシル基含有モノマー（ａ−２）の使用量は、全モノマー中０．１〜５重量％が好ましく、０．５〜４重量％がより好ましく、０．８〜３重量％がさらに好ましい。０．１重量％以上になると、乳化重合時の安定性がより向上し、重合時に凝集しにくくなる。また、５重量％以下であれば、重合時にカルボキシル基同士の絡み合いによる凝集が生じにくくなる。 The amount of the carboxyl group-containing monomer (a-2) used is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 4% by weight, even more preferably from 0.8 to 3% by weight, based on the total monomers. When it is 0.1% by weight or more, stability during emulsion polymerization is further improved, and aggregation during polymerization becomes difficult. Moreover, if it is 5 weight% or less, it will become difficult to produce aggregation by the entanglement of carboxyl groups at the time of superposition | polymerization.
その他のモノマー（ａ−３）について説明する。
本実施の形態におけるその他のモノマー（ａ−３）とは、上記水和性官能基モノマー（ａ−１）及びカルボキシル基含有モノマー（ａ−２）以外のラジカル重合性のモノマーである。その他のモノマー（ａ−３）は、ホモポリマーのガラス転移温度Ｔｇが５０〜２００℃のモノマー（ａ−４）及び、ホモポリマーのガラス転移温度Ｔｇが−１００℃以上５０℃未満のモノマー（ａ−５）を含むことが好ましい。
The other monomer (a-3) will be described.
The other monomer (a-3) in the present embodiment is a radical polymerizable monomer other than the hydratable functional group monomer (a-1) and the carboxyl group-containing monomer (a-2). Other monomers (a-3) are a monomer (a-4) having a glass transition temperature Tg of 50 to 200 ° C. of the homopolymer and a monomer (a) having a glass transition temperature Tg of the homopolymer of −100 ° C. or more and less than 50 ° C. −5) is preferably included.
モノマー（ａ−４）について説明する。モノマー（ａ−４）を使用することで、バインダー樹脂組成物（Ａ）の耐アルカリ性をより向上できる。
例えば、メタクリル酸メチル（Ｔｇ＝１００℃）、メタクリル酸エチル（Ｔｇ＝６５℃）、メタクリル酸ブチル（Ｔｇ＝２０℃）、メタクリル酸イソブチル（Ｔｇ＝６７℃）、メタクリル酸ターシャリーブチル（Ｔｇ＝１０７℃）、メタクリル酸２−エチルヘキシル（Ｔｇ＝−１０℃）、メタクリル酸シクロヘキシル（Ｔｇ＝６６℃）等のメタクリル酸エステル類；
スチレン（ホモポリマーのガラス転移温度Ｔｇ＝１００℃、以下同様）、α−メチルスチレン（Ｔｇ＝１６８℃）及びベンジルメタクリレート（Ｔｇ＝５４℃）等の芳香環含有モノマー類；
等を挙げることができる。これらの中でも、耐アルカリ性の観点から、芳香環含有モノマーを用いることが好ましい。芳香環含有モノマーを用いることにより、アルカリ溶液中で加水分解され易い例えばアクリル酸アルキルエステルの使用量を削減できるため、耐アルカリ性をより向上できる。さらに、ポリマーのガラス転移点を適切な範囲にコントロールすることにより、集電材への密着性をより向上できる。
A monomer (a-4) is demonstrated. By using the monomer (a-4), the alkali resistance of the binder resin composition (A) can be further improved.
For example, methyl methacrylate (Tg = 100 ° C.), ethyl methacrylate (Tg = 65 ° C.), butyl methacrylate (Tg = 20 ° C.), isobutyl methacrylate (Tg = 67 ° C.), tertiary butyl methacrylate (Tg = 107 ° C.), methacrylic acid esters such as 2-ethylhexyl methacrylate (Tg = −10 ° C.), cyclohexyl methacrylate (Tg = 66 ° C.);
Aromatic ring-containing monomers such as styrene (glass transition temperature of homopolymer Tg = 100 ° C., the same applies hereinafter), α-methylstyrene (Tg = 168 ° C.) and benzyl methacrylate (Tg = 54 ° C.);
Etc. Among these, it is preferable to use an aromatic ring-containing monomer from the viewpoint of alkali resistance. By using an aromatic ring-containing monomer, it is possible to reduce the amount of, for example, an acrylic acid alkyl ester that is easily hydrolyzed in an alkaline solution, so that the alkali resistance can be further improved. Furthermore, the adhesion to the current collector can be further improved by controlling the glass transition point of the polymer within an appropriate range.
モノマー（ａ−４）の量としては、２０〜６０重量％が好ましく、２５〜５５重量％がより好ましい。２０重量％以上になると、ポリマーの耐アルカリ性がより向上する。また、６０重量％以下であれば、集電材への密着性がより向上する。
The amount of the monomer (a-4) is preferably 20 to 60% by weight, and more preferably 25 to 55% by weight. When it is 20% by weight or more, the alkali resistance of the polymer is further improved. Moreover, if it is 60 weight% or less, the adhesiveness to a current collection material will improve more.
モノマー（ａ−５）について説明する。モノマー（ａ−５）を使用することで、集電材への密着性をより向上できる。モノマー（ａ−５）はホモポリマーのガラス転移温度Ｔｇが−１００℃以上５０℃未満である。例えば、アクリル酸メチル（ホモポリマーのガラス転移温度Ｔｇ＝−８℃、以下同様）、アクリル酸エチル（Ｔｇ＝−２０℃）、アクリル酸ブチル（Ｔｇ＝−４５℃）、アクリル酸−２−エチルヘキシル等（Ｔｇ＝−５５℃）のアクリル酸エステル類；
酢酸ビニル（Ｔｇ＝３０℃）、等を挙げることができる。
A monomer (a-5) is demonstrated. By using the monomer (a-5), adhesion to the current collector can be further improved. The monomer (a-5) has a glass transition temperature Tg of the homopolymer of −100 ° C. or higher and lower than 50 ° C. For example, methyl acrylate (homopolymer glass transition temperature Tg = −8 ° C., hereinafter the same), ethyl acrylate (Tg = −20 ° C.), butyl acrylate (Tg = −45 ° C.), acrylate-2-ethylhexyl acrylate Etc. (Tg = −55 ° C.) acrylic acid esters;
And vinyl acetate (Tg = 30 ° C.).
その他のモノマー（ａ−３）は、ポリマーの理論ガラス転移温度Ｔｇが、−２０〜２０℃となるように、ホモポリマーのガラス転移温度Ｔｇが５０〜２００℃のモノマー（ａ−４）とガラス転移温度Ｔｇが−１００℃以上５０℃未満のモノマー（ａ−５）とを適宜選択することが好ましい。また、ポリマーの理論ガラス転移温度Ｔｇの範囲は−１５〜１５℃がさらに好ましい。ガラス転移温度Ｔｇを−２０〜２０℃にすることにより、密着性及び耐アルカリ性を両立させ易くなる。 The other monomer (a-3) is composed of the monomer (a-4) and glass having a homopolymer glass transition temperature Tg of 50 to 200 ° C. so that the theoretical glass transition temperature Tg of the polymer is -20 to 20 ° C. It is preferable to appropriately select a monomer (a-5) having a transition temperature Tg of −100 ° C. or more and less than 50 ° C. The range of the theoretical glass transition temperature Tg of the polymer is more preferably −15 to 15 ° C. By setting the glass transition temperature Tg to -20 to 20 ° C, it becomes easy to achieve both adhesion and alkali resistance.
本実施の形態におけるポリマーの理論ガラス転移温度Ｔｇは下記の式[I]により導かれる。
１／Ｔｇ
＝［（Ｗ１／Ｔｇ１）＋（Ｗ２／Ｔｇ２）＋・・・＋（Ｗｎ／Ｔｇｎ）］／１００
・・・［I］
ただし、
Ｗ１：単量体１の重量％、
Ｔｇ１：モノマー１のみから形成され得るホモポリマーのガラス転移温度（Ｋ）、
Ｗ２：モノマー２の重量％、
Ｔｇ２：モノマー２のみから形成され得るホモポリマーのガラス転移温度（Ｋ）、
Ｗｎ：モノマーｎの重量％、
Ｔｇｎ：モノマーｎのみから形成され得るホモポリマーのガラス転移温度（Ｋ）、
（ここで、Ｗ１＋Ｗ２＋・・・・＋Ｗｎ＝１００）
The theoretical glass transition temperature Tg of the polymer in the present embodiment is derived from the following formula [I].
1 / Tg
= [(W1 / Tg1) + (W2 / Tg2) + ... + (Wn / Tgn)] / 100
... [I]
However,
W1:% by weight of monomer 1,
Tg1: glass transition temperature (K) of a homopolymer that can be formed only from monomer 1;
W2:% by weight of monomer 2,
Tg2: glass transition temperature (K) of a homopolymer that can be formed from monomer 2 only,
Wn:% by weight of monomer n,
Tgn: glass transition temperature (K) of a homopolymer that can be formed only from monomer n,
(W1 + W2 + ... + Wn = 100)
なお、ラジカル重合性不飽和モノマーを水性媒体中で重合する際に乳化剤として、ラジカル重合性不飽和基を有するものを使用する場合には、ラジカル重合性不飽和モノマーの構成の特定及び共重合体のＴｇの計算に際して、ラジカル重合性不飽和基を有する乳化剤はモノマーには含めないものとする。 In addition, when using what has a radically polymerizable unsaturated group as an emulsifier when superposing | polymerizing a radically polymerizable unsaturated monomer in an aqueous medium, identification of the structure of a radically polymerizable unsaturated monomer and a copolymer In the calculation of Tg, an emulsifier having a radically polymerizable unsaturated group is not included in the monomer.
本実施の形態でバインダー樹脂組成物（Ａ）は、乳化重合で共重合することが重要である。共重合の際、重合安定性の観点から乳化剤を用いることが好ましい。
乳化剤は、用いるモノマーの合計１００重量部に対して、０．１重量部以上５重量部以下が好ましく、１重量部以上３重量部以下がより好ましい。乳化剤量が０．１重量部以上になると、重合安定性がより向上する。また、乳化剤量が５重量部以下になると、二次電池電極の耐アルカリ性がより向上する。
In the present embodiment, it is important that the binder resin composition (A) is copolymerized by emulsion polymerization. During copolymerization, it is preferable to use an emulsifier from the viewpoint of polymerization stability.
The emulsifier is preferably 0.1 parts by weight or more and 5 parts by weight or less, and more preferably 1 part by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the total amount of monomers used. When the amount of the emulsifier is 0.1 parts by weight or more, the polymerization stability is further improved. Moreover, when the amount of the emulsifier is 5 parts by weight or less, the alkali resistance of the secondary battery electrode is further improved.
本実施の形態では、乳化剤として、アニオン性乳化剤やノニオン性乳化剤を単独若しくは併用できる。また、乳化剤は、ラジカル重合性の官能基を有する反応性乳化剤であってもよいし、ラジカル重合性の官能基を有さない非反応性乳化剤であってもよい。あるいは、両者を併用することもできる。 In the present embodiment, an anionic emulsifier or a nonionic emulsifier can be used alone or in combination as an emulsifier. The emulsifier may be a reactive emulsifier having a radical polymerizable functional group or a non-reactive emulsifier having no radical polymerizable functional group. Or both can be used together.
本実施の形態において用いられる乳化剤のうち、反応性乳化剤は、分子内にラジカル重合可能な不飽和２重結合を１個以上有するアニオン性またはノニオン性の乳化剤である。例えば、スルホコハク酸エステル系（市販品としては、例えば、花王（株）製ラテムルＳ−１２０Ｐ、Ｓ−１８０Ａ、三洋化成（株）製エレミノールＪＳ−２等）、アルキルフェノールエーテル系（市販品としては、第一工業製薬（株）製アクアロンＫＨ−１０、ＲＮ−２０等）が挙げられる。 Among the emulsifiers used in the present embodiment, the reactive emulsifier is an anionic or nonionic emulsifier having at least one unsaturated double bond capable of radical polymerization in the molecule. For example, sulfosuccinic acid ester type (for example, Latemul S-120P, S-180A, Sanyo Kasei Co., Ltd. Eleminol JS-2, etc. manufactured by Kao Corporation), alkylphenol ether type (commercially available products, Dai-Ichi Kogyo Seiyaku Co., Ltd. Aqualon KH-10, RN-20, etc.).
本実施の形態において用いられる乳化剤のうち、非反応性乳化剤としては、
ポリオキシエチレンアルキルフェニルエーテル硫酸塩、ポリオキシエチレン多環フェニルエーテル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩等のアニオン系非反応性乳化剤と、
ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンジスチレン化フェニルエーテル等のポリオキシ多環フェニルエーテル類；ポリオキシエチレンソルビタン脂肪酸エステル等のノニオン系非反応性乳化剤と、が挙げられる。
Among the emulsifiers used in the present embodiment, as a non-reactive emulsifier,
Anionic non-reactive emulsifiers such as polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxyethylene alkyl ether sulfate,
Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; And polyoxypolycyclic phenyl ethers such as oxyethylene distyrenated phenyl ether; and nonionic non-reactive emulsifiers such as polyoxyethylene sorbitan fatty acid ester.
具体的には、アニオン系非反応性乳化剤としては、ハイテノールＮＦ−０８〔エチレンオキサイド単位の繰り返し数（以下、「ＥＯユニット数」という）：８〕、ＮＦ−１７（ＥＯユニット数：１７）〔以上、第一工業製薬（株）製〕、エレミノールＣＬＳ−２０（ＥＯユニット数：１０）、エレミノールＥＳ−１２（ＥＯユニット数：６）、ＥＳ−３０（ＥＯユニット数：１５）、ＥＳ−７０（ＥＯユニット数：３５）〔以上、三洋化成工業（株）製〕等が挙げられる。 Specifically, as anionic non-reactive emulsifiers, hightenol NF-08 [repetition number of ethylene oxide units (hereinafter referred to as “number of EO units”): 8], NF-17 (number of EO units: 17) [Above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], Eleminol CLS-20 (EO unit number: 10), Eleminol ES-12 (EO unit number: 6), ES-30 (EO unit number: 15), ES- 70 (number of EO units: 35) [Sanyo Chemical Industries, Ltd.] and the like.
ノニオン系非反応性乳化剤としては、エマルゲン１１０８（ＥＯユニット数：８）、１１１８Ｓ−７０（ＥＯユニット数：１８）、１１３５Ｓ−７０（ＥＯユニット数：３５）、１１５０Ｓ−７０（ＥＯユニット数：５０）〔以上、花王（株）製〕等が挙げられる。
上記の非反応性乳化剤は単独で用いてもよく、複数種併用することも可能である。
なお、乳化剤のうち、反応性乳化剤としては、従来公知のものを使用できる。
Nonionic non-reactive emulsifiers include Emulgen 1108 (EO unit number: 8), 1118S-70 (EO unit number: 18), 1135S-70 (EO unit number: 35), 1150S-70 (EO unit number: 50). ) [Above, manufactured by Kao Corporation].
Said non-reactive emulsifier may be used independently and can also be used together multiple types.
In addition, a conventionally well-known thing can be used as a reactive emulsifier among emulsifiers.
本実施の形態において用いることができるラジカル重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩類が挙げられる。 Examples of the radical polymerization initiator that can be used in the present embodiment include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate.
重合開始剤の使用量は、乳化重合に使用するモノマーの合計１００重量部に対し０．１〜１重量部であることが好ましく、０．２〜０．８重量部であることがより好ましい。０．１重量部以上になると、重合安定性がより向上する。また、１重量部以下になると、耐水性がより向上する。 The amount of the polymerization initiator used is preferably 0.1 to 1 part by weight and more preferably 0.2 to 0.8 part by weight based on 100 parts by weight of the total amount of monomers used for emulsion polymerization. When the amount is 0.1 parts by weight or more, the polymerization stability is further improved. Moreover, when it becomes 1 weight part or less, water resistance will improve more.
また、過酸化物系開始剤と還元剤の組み合わせたレドックス開始剤を用いることも好ましい。レドックス開始剤としては、過酸化物系開始剤と還元剤の組み合わせが好ましい。過酸化物系開始剤としては、パーブチルＨ（ターシャリーブチルハイドロパーオキサイド）、パーブチルＯ（ターシャリーブチルペルオキシ−２−エチルヘキサノエート）、キュ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が挙げられる。還元剤としては、エルビットＮ（イソアスコルビン酸ナトリウム）、Ｌ−アスコルビン酸（ビタミンＣ）、亜硫酸ナトリウム、亜硫酸水素ナトリウム、ピロ亜硫酸ナトリウム（ＳＭＢＳ）、次亜硫酸ナトリウム（ハイドロサルファイト）が挙げられる。 It is also preferable to use a redox initiator in which a peroxide-based initiator and a reducing agent are combined. As the redox initiator, a combination of a peroxide-based initiator and a reducing agent is preferable. Examples of the peroxide initiator include perbutyl H (tertiary butyl hydroperoxide), perbutyl O (tertiary butyl peroxy-2-ethylhexanoate), cumene hydroperoxide, and p-menthane hydroperoxide. . Examples of the reducing agent include Erbit N (sodium ascorbate), L-ascorbic acid (vitamin C), sodium sulfite, sodium hydrogen sulfite, sodium pyrosulfite (SMBS), and sodium hyposulfite (hydrosulfite).
本実施の形態のニッケル水素二次電池電極用合材インキは、ニッケル水素二次電池電極用バインダー樹脂組成物（Ａ）と、導電性材料（Ｂ）と、活物質とを含むことが好ましい。 It is preferable that the composite ink for nickel-hydrogen secondary battery electrodes of this Embodiment contains the binder resin composition (A) for nickel-hydrogen secondary battery electrodes, an electroconductive material (B), and an active material.
ニッケル水素二次電池電極用合材インキは、活物質１００重量部に対してバインダー樹脂組成物（Ａ）を０.０５〜２０重量部用いることが好ましく、０．１〜１０重量部がより好ましい。０.０５重量部以上になると、活物質を集電材に結着させる力がより向上し、その結果、電池の容量がより向上する。また、２０重量部以下になると、電池特性がより向上する。 The nickel-hydrogen secondary battery electrode composite ink is preferably used in an amount of 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the active material. . When the amount is 0.05 parts by weight or more, the force for binding the active material to the current collector is further improved, and as a result, the capacity of the battery is further improved. Moreover, when it becomes 20 parts weight or less, a battery characteristic will improve more.
活物質は、ニッケル水素二次電池に通常使用されるものであれば、制限なく使用できる。例えば、正極活物質としては、水酸化ニッケル、オキシ水酸化ニッケルのニッケル化合物が挙げられる。水酸化ニッケルの種類としては、水酸化ニッケルを水酸化コバルトやオキシ水酸化コバルトで被覆したコバルトコート品がより好ましい。水酸化ニッケルの表面をコバルトコートすることで、水酸化ニッケルの導電性をより高めることができる。
負極の電極組成物として用いられる水素吸蔵合金は、例えば、ＬａＮｉ５やＭｍＮｉｘ(Ｍｍ：ミッシュメタル；希土類金属の混合物、ｘ＝４．７〜５．２)などのＡＢ５型がある。前者では、Ｎｉの一部をＣｕ、Ａｌ、Ｃｏ、Ｓｉなどで置換した材料や、Ｌａの一部をＮｄやＺｒで置換した材料が開発されている。また、現在一般的に使用されている材料は後者であり、希土類に比較的安価なＭｍを用い、Ｎｉの一部をＣｏ、Ｍｎ、Ａｌなどで置換している。このほか、ＴｉＮｉ、Ｔｉ２Ｎｉ等のＡＢ／Ａ２Ｂ型（チタン系）、ＺｒＮｉ２系やＺｒＶ２系等のＡＢ２型がある。
If an active material is normally used for a nickel hydride secondary battery, it can be used without a restriction | limiting. For example, examples of the positive electrode active material include nickel hydroxide and nickel oxyhydroxide nickel compounds. As the kind of nickel hydroxide, a cobalt coated product obtained by coating nickel hydroxide with cobalt hydroxide or cobalt oxyhydroxide is more preferable. By coating the surface of nickel hydroxide with cobalt, the conductivity of nickel hydroxide can be further increased.
Hydrogen storage alloy used as the electrode composition of the negative electrode, for example, LaNi 5 or MmNi x (Mm: misch metal; a mixture of rare earth metals, x = from 4.7 to 5.2) is AB 5 type, such as. In the former, a material in which a part of Ni is replaced with Cu, Al, Co, Si or the like, or a material in which a part of La is replaced with Nd or Zr has been developed. Moreover, the material currently generally used is the latter, using relatively inexpensive Mm as a rare earth, and replacing a part of Ni with Co, Mn, Al or the like. In addition, TiNi, Ti 2 AB / A 2 B types such as Ni (titanium-based), there are two systems or ZrV AB 2 type, such as 2-based ZrNi.
活物質に併用される導電性材料（Ｂ）としては、例えば、ニッケル粉末、酸化コバルト、カーボン等を挙げることができる。カーボンとしては、アセチレンブラック、ケッチェンブラック、ファーネスブラック、炭素繊維、フラーレン類を挙げることができる。好ましくは、アセチレンブラック、ファーネスブラックである。導電性材料（Ｂ）の粒子径は大きいため、あらかじめ、水、分散樹脂を用いて０．１〜５０μｍに分散して使用するのが好ましい。分散樹脂としては、アクリル系水溶性樹脂、スチレン／アクリル系水溶性樹脂、水溶性ポリエステル樹脂、水性ウレタン樹脂等が好ましい。 Examples of the conductive material (B) used in combination with the active material include nickel powder, cobalt oxide, and carbon. Examples of carbon include acetylene black, ketjen black, furnace black, carbon fiber, and fullerenes. Acetylene black and furnace black are preferred. Since the particle diameter of the conductive material (B) is large, it is preferable to use the conductive material (B) by dispersing it in advance to 0.1 to 50 μm using water or a dispersion resin. As the dispersion resin, an acrylic water-soluble resin, a styrene / acrylic water-soluble resin, a water-soluble polyester resin, an aqueous urethane resin, and the like are preferable.
導電性材料（Ｂ）の使用量は、活物質１００重量部に対して０.２〜１０.０重量部が好ましい。０.２重量部以上になると、導電性が向上し、ニッケル水素二次電池の高いレートで充放電した場合の容量がより向上する。また、１０．０重量部以下になると、合材層の集電体への密着性がより向上し、その結果、電池の容量がより向上する。 The amount of the conductive material (B) used is preferably 0.2 to 10.0 parts by weight with respect to 100 parts by weight of the active material. When the amount is 0.2 parts by weight or more, the conductivity is improved, and the capacity when charging / discharging at a high rate of the nickel hydride secondary battery is further improved. Moreover, when it becomes 10.0 weight part or less, the adhesiveness to the electrical power collector of a compound material layer will improve more, and, as a result, the capacity | capacitance of a battery will improve more.
本実施の形態のニッケル水素二次電池電極用合材インキの配合は、正極用と負極用で異なる。正極合材インキの場合、活物質である水酸化ニッケル、バインダー樹脂組成物（Ａ）、導電性材料（Ｂ）、溶媒である水を配合する。塗工適性を向上させるため、必要に応じ、増粘剤、レベリング剤、消泡剤等の添加剤を用いることができる。負極合材インキの場合、負極の電極組成物として用いられる水素吸蔵合金、バインダー樹脂組成物（Ａ）、導電性材料（Ｂ）、溶媒である水を配合する。正極合材インキと同様、塗工適性を向上させるため、必要に応じ、増粘剤、レベリング剤、消泡剤等の添加剤を用いることができる。 The composition of the ink mixture for nickel hydride secondary battery electrode of the present embodiment is different for the positive electrode and the negative electrode. In the case of the positive electrode mixture ink, nickel hydroxide as an active material, binder resin composition (A), conductive material (B), and water as a solvent are blended. In order to improve the coating suitability, additives such as thickeners, leveling agents, and antifoaming agents can be used as necessary. In the case of the negative electrode mixture ink, a hydrogen storage alloy used as a negative electrode composition, a binder resin composition (A), a conductive material (B), and water as a solvent are blended. As with the positive electrode mixture ink, additives such as a thickener, a leveling agent, and an antifoaming agent can be used as necessary in order to improve the coating suitability.
電極は、集電体にニッケル水素二次電池電極用合材インキを塗布することで製造できる。集電体の材質は、金、銀、銅、鉄、ニッケル及びアルミニウム等の公知の導電性金属を使用できる。これらの中でも、鉄材質の表面を電解液による腐食防止のためにニッケルメッキしたものが好ましい。集電体の形状としては、箔状金属板、発泡金属板、網状金属繊維焼結板等が挙げられる。この中でも、集電体の厚みを薄くでき、電池の内部抵抗を低減可能なことから、箔状金属板が好ましい。ニッケルメッキ部分を含めた箔状集電体の総厚は、１０〜７０μｍが好ましく、１５〜６０μｍがさらに好ましい。箔状集電体の総厚が１０μｍ以上になると、集電体自身の強度がより向上し、塗工及びプレス加工時に電極の破損が生じにくくなる。また、箔状集電体の総厚が７０μｍ以下であれば、集電体自身の強度を適切にしやすく、塗工時の集電体の巻き取りがより容易になる。 An electrode can be manufactured by apply | coating the mixture ink for nickel hydride secondary battery electrodes to a collector. As a material of the current collector, a known conductive metal such as gold, silver, copper, iron, nickel, and aluminum can be used. Among these, the surface of the iron material is preferably nickel-plated to prevent corrosion by the electrolytic solution. Examples of the shape of the current collector include a foil-like metal plate, a foam metal plate, and a mesh metal fiber sintered plate. Among these, a foil-shaped metal plate is preferable because the thickness of the current collector can be reduced and the internal resistance of the battery can be reduced. The total thickness of the foil-like current collector including the nickel-plated portion is preferably 10 to 70 μm, and more preferably 15 to 60 μm. When the total thickness of the foil-shaped current collector is 10 μm or more, the strength of the current collector itself is further improved, and the electrode is less likely to be damaged during coating and pressing. In addition, when the total thickness of the foil-like current collector is 70 μm or less, it is easy to make the current collector itself appropriate in strength, and it becomes easier to wind the current collector during coating.
ニッケルメッキの厚みは、０．１〜５μｍであることが好ましく、０．５〜４μｍがさらに好ましい。ニッケルメッキの厚みが、０．１μｍ以上になると、電解液による腐食が生じにくくなる。また、ニッケルメッキの厚みが５μｍ以下になると、コスト的に有利になる。 The thickness of the nickel plating is preferably 0.1 to 5 μm, and more preferably 0.5 to 4 μm. When the thickness of the nickel plating is 0.1 μm or more, corrosion due to the electrolytic solution hardly occurs. Further, when the thickness of the nickel plating is 5 μm or less, it is advantageous in terms of cost.
合材インキを金属箔集電体の表面に塗工する方法としては、グラビアコート、グラビアリバースコート、ロールコート、マイヤーバーコート、ブレードコート、ナイフコート、エアーナイフコート、スロットダイコート、スライドダイコート、デイップコート、ダイコード、コンマコート、コンマリバースコート等が挙げられる。 The method of coating the composite ink on the surface of the metal foil current collector includes gravure coating, gravure reverse coating, roll coating, Meyer bar coating, blade coating, knife coating, air knife coating, slot die coating, slide die coating, and dip. A coat, a die code, a comma coat, a comma reverse coat, etc. are mentioned.
乾燥工程における熱源としては、熱風、赤外線、マイクロ波、高周波等及びそれらの組み合わせが挙げられる。乾燥後の合材層の厚さは２０〜２００μｍ、好ましくは５０〜１５０μｍの範囲であり、このような厚さになるように前記塗工時の塗工量を設定する。活物質層の厚みが２０μｍ以上であれば、より短い電極板の長さで所定の容量の電極を製造しやすくなる。また、厚みが２００μｍ以下であれば、電極板を巻き取ったとき集電体に亀裂等が生じにくくなる。 Examples of the heat source in the drying process include hot air, infrared rays, microwaves, high frequencies, and combinations thereof. The thickness of the mixed material layer after drying is in the range of 20 to 200 μm, preferably 50 to 150 μm, and the coating amount at the time of coating is set so as to have such a thickness. If the thickness of the active material layer is 20 μm or more, it becomes easy to manufacture an electrode having a predetermined capacity with a shorter electrode plate length. Moreover, if thickness is 200 micrometers or less, when an electrode plate is wound up, it will become difficult to produce a crack etc. in a collector.
正極合材層または負極合材層の均質性及び密度をより向上させるために、金属ロール、加熱ロール、シートプレス機等を用いて、合材層にプレス処理を施すことが好ましい。プレス条件としては、合材層の圧縮率が５〜７０％になるようにプレス処理を施すことが好ましく、１０〜６０％がより好ましい。圧縮率が５％以上になると、合材層が均一化しやすくなる。また、圧縮率が７０％以下になると、集電体を含めて電極が破損しにくくなる。 In order to further improve the homogeneity and density of the positive electrode composite material layer or the negative electrode composite material layer, it is preferable to press the composite material layer using a metal roll, a heating roll, a sheet press machine or the like. As press conditions, it is preferable to perform a press treatment so that the compression ratio of the composite material layer is 5 to 70%, and more preferably 10 to 60%. When the compression rate is 5% or more, the composite layer is easily made uniform. Further, when the compression ratio is 70% or less, the electrodes including the current collector are not easily damaged.
ニッケル水素二次電池では、正極の合材層（Ｃ）と負極の合材層（Ｄ）とがセパレータを介して交互に対向配置され、アルカリ電解液と共に容器内に収納されている。セパレータとしては、一般のアルカリ二次電池に使用されるものが用いられる。例えば、ポリエチレン不織布、ポリプロピレン不織布、ポリアミド不織布及びそれらに親水性処理を施したものが挙げられる。電解液としては、水酸化カリウム水溶液や、水酸化カリウム水溶液に水酸化ナトリウム及び／または水酸化リチウムを添加したもの等が挙げられる。 In a nickel-metal hydride secondary battery, a positive electrode mixture layer (C) and a negative electrode mixture layer (D) are alternately arranged opposite to each other via a separator, and are stored in a container together with an alkaline electrolyte. As a separator, what is used for a general alkaline secondary battery is used. For example, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to hydrophilic treatment can be mentioned. Examples of the electrolytic solution include an aqueous potassium hydroxide solution and an aqueous potassium hydroxide solution obtained by adding sodium hydroxide and / or lithium hydroxide.
以下、実施例、比較例を挙げて本実施の形態を詳細に説明する。しかしながら、本実施の形態は、以下の実施例のみに限定されるものではない。 Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples.
＜バインダー樹脂組成物合成＞
［実施例１］
水和性官能基含有モノマー（ａ−１）としてアクリル酸２ヒドロキシエチル３．０重量部、カルボキシル基含有モノマー（ａ−２）としてアクリル酸１．５重量部、モノマー（ａ−４）としてスチレン５０重量部、モノマー（ａ−５）としてアクリル酸２−エチルへキシル４５．５重量部、乳化剤としてエレミノールＣＬＳ−２０（三洋化成工業（株）製の反応性乳化剤）１．４重量部、イオン交換水５３．１重量部の混合物を板羽根で乳化し、モノマープレエマルションを作成し、滴下槽に入れた。
<Binder resin composition synthesis>
[Example 1]
3.0 parts by weight of 2-hydroxyethyl acrylate as the hydratable functional group-containing monomer (a-1), 1.5 parts by weight of acrylic acid as the carboxyl group-containing monomer (a-2), and styrene as the monomer (a-4) 50 parts by weight, 45.5 parts by weight of 2-ethylhexyl acrylate as monomer (a-5), 1.4 parts by weight of Eleminol CLS-20 (reactive emulsifier manufactured by Sanyo Chemical Industries, Ltd.) as an emulsifier, ion A mixture of 53.1 parts by weight of exchange water was emulsified with a plate blade to prepare a monomer pre-emulsion and put into a dropping tank.
還流冷却器、攪拌機、温度計、窒素導入管、原料投入口を具備する容積２Ｌの４つ口フラスコを反応容器とし、該反応容器にイオン交換水８９．４重量部を入れ、窒素を導入しつつ攪拌しながら、液温を６０℃に温めた。次いで、反応容器中に、乳化剤としてＣＬＳ−２０を０．１重量部添加し、滴下槽から上記モノマープレエマルションを５時間かけて連続的に滴下し、過硫酸アンモニウムを０．６重量部用いて、７０℃で５時間かけて乳化重合した。 A reaction vessel is a 2 L four-necked flask equipped with a reflux condenser, a stirrer, a thermometer, a nitrogen inlet tube, and a raw material inlet, and 89.4 parts by weight of ion-exchanged water is introduced into the reaction vessel and nitrogen is introduced. While stirring, the liquid temperature was raised to 60 ° C. Next, 0.1 part by weight of CLS-20 as an emulsifier is added to the reaction vessel, the monomer pre-emulsion is continuously dropped from a dropping tank over 5 hours, and 0.6 part by weight of ammonium persulfate is used. Emulsion polymerization was performed at 70 ° C. over 5 hours.
滴下終了後、３時間、７０℃に保ち、熟成を行った。その後冷却を開始し、５０℃まで冷却し、１８０メッシュのポリエステル製の濾布で濾過し、バインダー樹脂組成物（Ａ）を含むポリマーエマルションを得た。濾布に残った凝集物はなく、重合安定性は良好であった。
濾過後のエマルションの一重量部を測り取り、１５０℃で２０分間乾燥し、不揮発分濃度を求めたところ４０．０重量％であった。また、前記エマルションは、ｐＨ２．０、粘度１０ｍＰａ・ｓであった。
マイクロトラックＵＰＡ（Ｌｅｅｄｓ＆Ｎｏｒｔｈｒｕｐ社製）を用い、動的光散乱法によりｐＨ２．０におけるＤ５０粒子径を測定したところ、１９０ｎｍであった。また、アンモニア水を添加し、中和した後にｐＨ９．０におけるＤ５０粒子径を測定したところ、２３０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２１倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
After completion of dropping, the mixture was kept at 70 ° C. for 3 hours for aging. Thereafter, cooling was started, the temperature was reduced to 50 ° C., and the mixture was filtered through a 180 mesh polyester filter cloth to obtain a polymer emulsion containing the binder resin composition (A). There was no aggregate remaining on the filter cloth, and the polymerization stability was good.
One part by weight of the emulsion after filtration was weighed and dried at 150 ° C. for 20 minutes, and the nonvolatile content concentration was determined to be 40.0% by weight. The emulsion had a pH of 2.0 and a viscosity of 10 mPa · s.
Using a Microtrac UPA (Leeds & Northrup), the D50 particle size at pH 2.0 was measured by a dynamic light scattering method, which was 190 nm. Further, after neutralization by adding ammonia water, the D50 particle size at pH 9.0 was measured and found to be 230 nm. That is, the post-neutralization D50 particle size is 1.21 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例２］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてメタクリル酸グリシジル３．０重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１８０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２２０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２２倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 2]
As shown in Table 1, a polymer emulsion was obtained in the same manner as in Example 1 except that 3.0 parts by weight of glycidyl methacrylate was used as the hydratable functional group-containing monomer (a-1). About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 180 nm. Moreover, it was 220 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.22 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例３］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてダイアセトンアクリルアミド３．０重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２７０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３５倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 3]
As shown in Table 1, a polymer emulsion was obtained in the same manner as in Example 1 except that 3.0 parts by weight of diacetone acrylamide was used as the hydratable functional group-containing monomer (a-1). About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 200 nm. Moreover, it was 270 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.35 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例４］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてアクリルアミド３．０重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２７０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３５倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 4]
As shown in Table 1, a polymer emulsion was obtained in the same manner as in Example 1 except that 3.0 parts by weight of acrylamide was used as the hydratable functional group-containing monomer (a-1). About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 200 nm. Moreover, it was 270 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.35 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例５］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてＮ，Ｎ‐ジエチルアクリルアミド３．０重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２０５ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２７０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３２倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 5]
As shown in Table 1, a polymer emulsion was obtained in the same manner as in Example 1 except that 3.0 parts by weight of N, N-diethylacrylamide was used as the hydratable functional group-containing monomer (a-1). With respect to this polymer emulsion, the D50 particle size at pH 2.0 was measured in the same manner as in Example 1. As a result, it was 205 nm. Moreover, it was 270 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.32 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例６］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてメタクリルアミド３．０重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２０５ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２７０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３２倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 6]
As shown in Table 1, a polymer emulsion was obtained in the same manner as in Example 1 except that 3.0 parts by weight of methacrylamide was used as the hydratable functional group-containing monomer (a-1). With respect to this polymer emulsion, the D50 particle size at pH 2.0 was measured in the same manner as in Example 1. As a result, it was 205 nm. Moreover, it was 270 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.32 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例７］
表１に示すように、モノマー（ａ−４）としてメタクリル酸メチル５０重量部を用いた以外は、実施例３と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２５０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２５倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 7]
As shown in Table 1, a polymer emulsion was obtained in the same manner as in Example 3 except that 50 parts by weight of methyl methacrylate was used as the monomer (a-4). About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 200 nm. Moreover, it was 250 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.25 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例８］
表１に示すように、モノマー（ａ−４）としてスチレン４４．５重量部、モノマー（ａ−５）としてアクリル酸ブチル５１．０重量部を用いた以外は、実施例４と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１７０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２１０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２４倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 8]
As shown in Table 1, a polymer was prepared in the same manner as in Example 4 except that 44.5 parts by weight of styrene was used as the monomer (a-4) and 51.0 parts by weight of butyl acrylate was used as the monomer (a-5). An emulsion was obtained. About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 170 nm. Moreover, it was 210 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.24 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例９］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてメタクリルアミド４．５重量部を用い、（ａ−４）としてスチレン４８．５重量部を用いた以外は、実施例６と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２１０ｎｍであった。また、アンモニア水を添加後のＤ５０粒子径を測定したところ、３００ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．４３倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 9]
As shown in Table 1, Examples were used except that 4.5 parts by weight of methacrylamide was used as the hydratable functional group-containing monomer (a-1) and 48.5 parts by weight of styrene was used as (a-4). In the same manner as in 6, a polymer emulsion was obtained. With respect to this polymer emulsion, the D50 particle size at pH 2.0 was measured in the same manner as in Example 1. As a result, it was 210 nm. Moreover, it was 300 nm when the D50 particle diameter after adding ammonia water was measured. That is, the post-neutralization D50 particle size is 1.43 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例１０］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてＮ，Ｎ‐ジエチルアクリルアミド１．５重量部を用い、（ａ−４）としてスチレン５１．５重量部を用いた以外は、実施例５と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１９０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２３５ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２４倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 10]
As shown in Table 1, 1.5 parts by weight of N, N-diethylacrylamide was used as the hydratable functional group-containing monomer (a-1), and 51.5 parts by weight of styrene was used as (a-4). Obtained a polymer emulsion in the same manner as in Example 5. About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 190 nm. Moreover, it was 235 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.24 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例１１］
表１に示すように、モノマー（ａ−４）としてスチレン３０重量部を用い、モノマー（ａ−５）としてアクリル酸２−エチルへキシル６５．５重量部を用いた以外は、実施例４と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２６０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３０倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは−１９℃である。
[Example 11]
As shown in Table 1, Example 4 was used except that 30 parts by weight of styrene was used as the monomer (a-4) and 65.5 parts by weight of 2-ethylhexyl acrylate was used as the monomer (a-5). Similarly, a polymer emulsion was obtained. About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 200 nm. Moreover, it was 260 nm when the D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.30 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is −19 ° C.
［実施例１２］
表１に示すように、モノマー（ａ−４）としてスチレン５９重量部を用い、モノマー（ａ−５）としてアクリル酸２−エチルへキシル３６．５重量部を用いた以外は、実施例５と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２１０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２７０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２９倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは１５℃である。
[Example 12]
As shown in Table 1, Example 5 was used except that 59 parts by weight of styrene was used as the monomer (a-4) and 36.5 parts by weight of 2-ethylhexyl acrylate was used as the monomer (a-5). Similarly, a polymer emulsion was obtained. With respect to this polymer emulsion, the D50 particle size at pH 2.0 was measured in the same manner as in Example 1. As a result, it was 210 nm. Moreover, it was 270 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.29 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 15 ° C.
［実施例１３］
表１に示すように、カルボキシル基含有モノマー（ａ−２）としてアクリル酸０．３重量部を用い、モノマー（ａ−４）としてスチレン５１．２重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２１０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２５５ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２１倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 13]
As shown in Table 1, Example 1 was used except that 0.3 part by weight of acrylic acid was used as the carboxyl group-containing monomer (a-2) and 51.2 parts by weight of styrene was used as the monomer (a-4). Similarly, a polymer emulsion was obtained. With respect to this polymer emulsion, the D50 particle size at pH 2.0 was measured in the same manner as in Example 1. As a result, it was 210 nm. Moreover, it was 255 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.21 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例１４］
表１に示すように、カルボキシル基含有モノマー（ａ−２）としてアクリル酸４．２重量部を用い、モノマー（ａ−４）としてスチレン４７．３重量部を用いた以外は、実施例２と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１８０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２２０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２２倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 14]
As shown in Table 1, Example 2 was used except that 4.2 parts by weight of acrylic acid was used as the carboxyl group-containing monomer (a-2) and 47.3 parts by weight of styrene was used as the monomer (a-4). Similarly, a polymer emulsion was obtained. About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 180 nm. Moreover, it was 220 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.22 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例１５］
表１に示すように、実施例１４の組成物は、実施例２と同一組成であるが、異なる合成方法によりポリマーエマルションを得た。具体的には、乳化剤としてＣＬＳ−２０を１．０重量部、イオン交換水５３．１重量部の混合物を板羽根で乳化し、モノマープレエマルションを作成し、滴下槽に入れた。反応容器中に、乳化剤としてＣＬＳ−２０を０．５重量部添加し、滴下槽から上記モノマープレエマルションを５時間かけて連続的に滴下し、過硫酸アンモニウムを０．６重量部用いて、７０℃で５時間かけて乳化重合した。
このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、１３０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３０倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 15]
As shown in Table 1, the composition of Example 14 had the same composition as Example 2, but a polymer emulsion was obtained by a different synthesis method. Specifically, a mixture of 1.0 part by weight of CLS-20 and 53.1 parts by weight of ion-exchanged water as an emulsifier was emulsified with a plate blade to prepare a monomer pre-emulsion, which was placed in a dropping tank. In the reaction vessel, 0.5 part by weight of CLS-20 as an emulsifier was added, the monomer pre-emulsion was continuously dropped from a dropping tank over 5 hours, and 0.6 part by weight of ammonium persulfate was used at 70 ° C. For 5 hours.
About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 100 nm. Moreover, it was 130 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.30 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［実施例１６］
表１に示すように、実施例１５の組成物は、実施例５と同一組成であるが、異なる合成方法によりポリマーエマルションを得た。具体的には、乳化剤としてＣＬＳ−２０を１．４９重量部、イオン交換水５３．１重量部の混合物を板羽根で乳化し、モノマープレエマルションを作製し、滴下槽に入れた。反応容器中に、乳化剤としてＣＬＳ−２０を０．０１重量部添加し、滴下槽から上記モノマープレエマルションを５時間かけて連続的に滴下し、過硫酸アンモニウムを０．６重量部用いて、７０℃で５時間かけて乳化重合した。
このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、３００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、３８０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２７倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは７℃である。
[Example 16]
As shown in Table 1, the composition of Example 15 had the same composition as Example 5, but a polymer emulsion was obtained by a different synthesis method. Specifically, a mixture of 1.49 parts by weight of CLS-20 and 53.1 parts by weight of ion-exchanged water as an emulsifier was emulsified with a plate blade to prepare a monomer pre-emulsion and put in a dropping tank. In the reaction vessel, 0.01 part by weight of CLS-20 as an emulsifier was added, the monomer pre-emulsion was continuously dropped from a dropping tank over 5 hours, and 0.6 part by weight of ammonium persulfate was used at 70 ° C. For 5 hours.
About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 300 nm. Moreover, it was 380 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.27 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 7 ° C.
［比較例１］
表１に示すように、モノマー（ａ−４）としてスチレン１１重量部を用い、モノマー（ａ−５）としてアクリル酸２−エチルへキシル８４．５重量部を用いた以外は、実施例２と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１３０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、１６０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．２３倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは−４０℃である。
[Comparative Example 1]
As shown in Table 1, Example 2 was used except that 11 parts by weight of styrene was used as the monomer (a-4) and 84.5 parts by weight of 2-ethylhexyl acrylate was used as the monomer (a-5). Similarly, a polymer emulsion was obtained. About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 130 nm. Moreover, it was 160 nm when D50 particle diameter in pH 9.0 was measured. That is, the D50 particle diameter after neutralization is 1.23 times the D50 particle diameter before neutralization.
The theoretical glass transition temperature Tg of the polymer obtained from the monomer is −40 ° C.
［比較例２］
表１に示すように、モノマー（ａ−４）としてスチレン７１重量部を用い、モノマー（ａ−５）としてアクリル酸２−エチルへキシル２４．５重量部を用いた以外は、実施例５と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、１４０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、１９０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．３６倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは４０℃である。
[Comparative Example 2]
As shown in Table 1, Example 5 was used except that 71 parts by weight of styrene was used as the monomer (a-4) and 24.5 parts by weight of 2-ethylhexyl acrylate was used as the monomer (a-5). Similarly, a polymer emulsion was obtained. About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 140 nm. Moreover, it was 190 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.36 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer obtained from the monomer is 40 ° C.
［比較例３］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてメタクリルアミド０．２重量部を用い、モノマー（ａ−４）としてスチレン５０．８重量部を用い、モノマー（ａ−５）としてアクリル酸２−エチルへキシル４７．５重量部を用いた以外は、実施例６と同様にしてポリマーエマルションを得た。このポリマーエマルションについて、実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２００ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、２０３ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．０２倍になっている。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは５℃である。
[Comparative Example 3]
As shown in Table 1, 0.2 parts by weight of methacrylamide was used as the hydratable functional group-containing monomer (a-1), and 50.8 parts by weight of styrene was used as the monomer (a-4). A polymer emulsion was obtained in the same manner as in Example 6 except that 47.5 parts by weight of 2-ethylhexyl acrylate was used as 5). About this polymer emulsion, when the D50 particle diameter in pH 2.0 was measured similarly to Example 1, it was 200 nm. Moreover, it was 203 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.02 times the pre-neutralization D50 particle size.
The theoretical glass transition temperature Tg of the polymer determined from the monomer is 5 ° C.
［比較例４］
表１に示すように、水和性官能基含有モノマー（ａ−１）としてアクリル酸２ヒドロキシエチル１０．０重量部を用い、モノマー（ａ−４）としてスチレン４１重量部を用い、モノマー（ａ−５）としてアクリル酸２−エチルへキシル４７．５重量部を用いた以外は、実施例１と同様にしてポリマーエマルションを得た。実施例１と同様にｐＨ２．０におけるＤ５０粒子径を測定したところ、２２０ｎｍであった。また、ｐＨ９．０におけるＤ５０粒子径を測定したところ、３５０ｎｍであった。つまり、中和後Ｄ５０粒子径は中和前Ｄ５０粒子径の１．５９倍になっている。中和後のポリマーエマルションの安定性は低い状態であり、ポリマーエマルションの一部に凝集が起こり、流動性の低下が観察された。
モノマーから求められるポリマーの理論ガラス転移温度Ｔｇは９℃である。
[Comparative Example 4]
As shown in Table 1, 10.0 parts by weight of 2-hydroxyethyl acrylate was used as the hydratable functional group-containing monomer (a-1), and 41 parts by weight of styrene was used as the monomer (a-4). A polymer emulsion was obtained in the same manner as in Example 1 except that 47.5 parts by weight of 2-ethylhexyl acrylate was used as -5). It was 220 nm when the D50 particle diameter in pH2.0 was measured similarly to Example 1. Moreover, it was 350 nm when D50 particle diameter in pH 9.0 was measured. That is, the post-neutralization D50 particle size is 1.59 times the pre-neutralization D50 particle size. The stability of the polymer emulsion after neutralization was in a low state, agglomeration occurred in a part of the polymer emulsion, and a decrease in fluidity was observed.
The theoretical glass transition temperature Tg of the polymer obtained from the monomer is 9 ° C.
以下の項目は、全ての実施例及び比較例に共通である。
＜導電性材料＞
アセチレンブラックであるＨＳ１００（電気化学工業（株）製）１００重量部に対し、分散樹脂であるアクリル樹脂１．５重量部及びイオン交換水４０８重量部を混合し、直径０．８ｍｍガラスビーズ２００重量部を入れた後、ペイントコンディショナーで２時間分散処理した。更にビーズを取り除いて、不揮発分２０重量％の導電性材料分散体を得た。
The following items are common to all examples and comparative examples.
<Conductive material>
To 100 parts by weight of HS100 (manufactured by Denki Kagaku Kogyo Co., Ltd.), which is acetylene black, 1.5 parts by weight of acrylic resin, which is a dispersion resin, and 408 parts by weight of ion-exchanged water are mixed, and glass beads having a diameter of 0.8 mm are 200 weights After adding a portion, the mixture was dispersed for 2 hours with a paint conditioner. Further, the beads were removed to obtain a conductive material dispersion having a nonvolatile content of 20% by weight.
＜電極用合材インキ＞
正極活物質として、水酸化コバルトを表面コーティングした水酸化ニッケルＣＺ（田中化学研究所（株）製）１００重量部、導電性材料分散体２５重量部、バインダー樹脂組成物（Ａ）として実施例１で得られたバインダー樹脂組成物（Ａ）５．０重量部をディスパーで混錬し、正極用合材インキを得た。その際の粘度は４０００ｍＰａ・ｓであった。負極の電極組成物として用いられる水素吸蔵合金１００重量部、導電性材料分散体２５重量部、実施例１で得られたバインダー樹脂組成物（Ａ）５．０重量部をディスパーで混錬し、負極用合材インキを得た。その際の粘度は６０００ｍＰａ・ｓであった。
<Electrode compound ink>
As a positive electrode active material, nickel hydroxide CZ (manufactured by Tanaka Chemical Research Co., Ltd.) 100 parts by weight of cobalt hydroxide surface coated, 25 parts by weight of conductive material dispersion, binder resin composition (A), Example 1 5.0 parts by weight of the binder resin composition (A) obtained in the above was kneaded with a disper to obtain a mixture ink for positive electrode. The viscosity at that time was 4000 mPa · s. 100 parts by weight of a hydrogen storage alloy used as the negative electrode composition, 25 parts by weight of the conductive material dispersion, 5.0 parts by weight of the binder resin composition (A) obtained in Example 1 were kneaded with a disper, A negative electrode mixture ink was obtained. The viscosity at that time was 6000 mPa · s.
次いで、得られた合材インキを用いて作製された電極について密着性試験を下記のように行なった。合材インキを、厚み３μｍのニッケルメッキを施した総厚３０μｍの箔状集電体に塗工、１００℃で乾燥、ロールプレスで厚さを調整した後、所定の大きさに切断して電極を作製した。この時合材層に割れ欠けは見られなかった。 Next, an adhesion test was performed as follows for the electrodes produced using the obtained composite ink. The composite ink was applied to a foil-like current collector with a total thickness of 30 μm plated with nickel of 3 μm thickness, dried at 100 ° C., adjusted in thickness with a roll press, and then cut into a predetermined size to form an electrode Was made. At this time, no cracks were found in the composite material layer.
（密着性試験）
得られた電極のうち１枚について密着性試験を行なった。電極表面にナイフを用いて、塗膜面から集電体に達する深さまでの切り込みを１ｍｍ間隔で縦横それぞれ１１本入れて碁盤目の切れ目を入れた。この切り込みにセロハンテープを貼り付けて直ちに引き剥がし、活物質の脱落の程度をセロハンテープの目視により判定した。評価基準を下記に、評価結果を表１に示す。
(Adhesion test)
An adhesion test was performed on one of the obtained electrodes. Using a knife on the surface of the electrode, 11 cuts from the coating surface to the depth reaching the current collector were made at 1 mm intervals both vertically and horizontally to make a grid cut. A cellophane tape was affixed to the cut and immediately peeled off, and the degree of the active material falling off was determined by visual inspection of the cellophane tape. The evaluation criteria are shown below, and the evaluation results are shown in Table 1.
◎：「無色（透明、わずかに点転着）」
○：「かすかに灰色（透明、わずかに転着）」
△：「灰色（半透明、部分転着）」
×：「黒色（不透明、全転着）」
A: “Colorless (transparent, slightly point transfer)”
○: “Slightly gray (transparent, slightly transferred)”
Δ: “Gray (translucent, partial transfer)”
×: “Black (opaque, all transferred)”
表１に示すように、実施例については、実施例１１、１４が△であった以外は、いずれも○または◎の評価結果であった。比較例については、比較例１は○、比較例３は△であったものの、比較例２は×の評価結果であった。比較例２の評価結果が悪い理由は、理論ガラス転移温度Ｔｇ＝４０℃と高いためであると考えられる。 As shown in Table 1, with respect to the examples, all were the evaluation results of ◯ or い ず れ except that Examples 11 and 14 were Δ. As for the comparative example, Comparative Example 1 was evaluated as ◯, while Comparative Example 3 was evaluated as △, while Comparative Example 2 was evaluated as x. The reason why the evaluation result of Comparative Example 2 is bad is considered to be that the theoretical glass transition temperature Tg is as high as 40 ° C.
（電池組み立て）
先に作製した正極を直径１５．９ｍｍに、負極を直径１６．１ｍｍに打ち抜き、セパレータとして親水化処理ポリプロピレンを２３ｍｍに打ち抜き、セパレータを介して互いに合材層を対向させ、電解液（水酸化カリウム４．８規定＋水酸化ナトリウム１．２規定） を満たして二極密閉式金属セルを組み立てた。セル組み立て後、所定の電池特性評価を行った。
(Battery assembly)
The positive electrode prepared earlier was punched to a diameter of 15.9 mm, the negative electrode was punched to a diameter of 16.1 mm, a hydrophilized polypropylene as a separator was punched to 23 mm, the mixture layers were opposed to each other through the separator, and an electrolyte solution (potassium hydroxide) 4.8 normal + 1.2 sodium hydroxide) was satisfied, and a two-pole sealed metal cell was assembled. After the cell assembly, a predetermined battery characteristic evaluation was performed.
（充放電サイクル特性試験）
上記のように作製した試験電池について、充放電サイクル試験を行ない、サイクル経過による充放電特性の推移を測定した。この充放電サイクル試験では、最初に活性化充放電を５サイクル行った後に１Ｃ−１Ｃ充放電サイクルを行なった。活性化充放電及び１Ｃ−１Ｃ充放電における試験条件はそれぞれ以下のとおりである。
(Charge / discharge cycle characteristics test)
About the test battery produced as mentioned above, the charging / discharging cycle test was done and the transition of the charging / discharging characteristic by cycling progress was measured. In this charging / discharging cycle test, 1C-1C charging / discharging cycle was performed after 5 cycles of activation charging / discharging first. The test conditions in activation charge / discharge and 1C-1C charge / discharge are as follows.
（活性化充放電）
充電：定電流０．２Ｃ（定格充電容量の１００％まで充電）
放電：定電流０．２Ｃ（放電終止電圧０．８Ｖ）
（充放電）
充電：定電流１．０Ｃ（定格充電容量の１００％まで充電）
放電：定電流１．０Ｃ（放電終止電圧０．８Ｖ）
(Activated charge / discharge)
Charging: Constant current 0.2C (charging up to 100% of rated charging capacity)
Discharge: Constant current 0.2C (discharge end voltage 0.8V)
(Charge / discharge)
Charging: Constant current 1.0C (charging up to 100% of rated charging capacity)
Discharge: Constant current 1.0C (end-of-discharge voltage 0.8V)
充放電サイクル特性試験は、１０００サイクル充放電した後の利用率で評価を行なった。利用率は、以下の式で表される。
利用率（％）＝放電容量（ｍＡｈ）／正極理論電池容量（ｍＡｈ）×１００
The charge / discharge cycle characteristic test was evaluated based on the utilization rate after 1000 cycles of charge / discharge. The utilization rate is expressed by the following formula.
Utilization rate (%) = discharge capacity (mAh) / positive electrode theoretical battery capacity (mAh) × 100
充放電サイクル特性試験は、以下のように評価した。結果を表１に示す。
９０〜１００％：極めて良好（◎）
８０〜９０％ ：良好（○）
６０〜８０％ ：比較的良好（△）
〜６０％ ：不良（×）
The charge / discharge cycle characteristic test was evaluated as follows. The results are shown in Table 1.
90 to 100%: very good (◎)
80-90%: Good (○)
60 to 80%: relatively good (△)
-60%: Defect (x)
表１に示すように、すべての実施例について、△以上の評価結果であった。一方、すべての比較例について、×の評価結果であった。比較例１の評価結果が悪い理由は、理論ガラス転移温度Ｔｇ＝−４０℃と低過ぎるためであると考えられる。比較例２の評価結果が悪い理由は、理論ガラス転移温度Ｔｇ＝４０℃と高過ぎるためであると考えられる。比較例３の評価結果が悪い理由は、水和性官能基含有モノマー（ａ−１）の組成が０．３重量部と低過ぎるためであると考えられる。 As shown in Table 1, the evaluation results were Δ or more for all the examples. On the other hand, it was the evaluation result of x about all the comparative examples. The reason why the evaluation result of Comparative Example 1 is poor is considered to be that the theoretical glass transition temperature Tg = −40 ° C. is too low. The reason why the evaluation result of Comparative Example 2 is bad is considered to be that the theoretical glass transition temperature Tg = 40 ° C. is too high. The reason for the poor evaluation results of Comparative Example 3 is considered to be because the composition of the hydratable functional group-containing monomer (a-1) is too low at 0.3 parts by weight.
（急速充放電特性試験）
急速充放電特性試験は、１Ｃ−１Ｃで５０サイクル経過した後に評価を行なった。レート条件は、２Ｃ−２Ｃ、５Ｃ−５Ｃ、１０Ｃ−１０Ｃで行なった。急速充放電特性の評価は、１０Ｃ−１０Ｃ時の利用率で評価を行なった。
(Rapid charge / discharge characteristics test)
The rapid charge / discharge characteristic test was evaluated after 50 cycles at 1C-1C. Rate conditions were 2C-2C, 5C-5C, and 10C-10C. The rapid charge / discharge characteristics were evaluated based on the utilization rate at 10C-10C.
急速充放電特性試験は、以下のように評価した。結果を表１に示す。
９０〜１００％：極めて良好（◎）
８０〜９０％ ：良好（○）
６０〜８０％ ：比較的良好（△）
〜６０％ ：不良（×）
The rapid charge / discharge characteristic test was evaluated as follows. The results are shown in Table 1.
90 to 100%: very good (◎)
80-90%: Good (○)
60 to 80%: relatively good (△)
-60%: Defect (x)
表１に示すように、すべての実施例について、△以上の評価結果であった。一方、すべての比較例について、×の評価結果であった。比較例１の評価結果が悪い理由は、理論ガラス転移温度Ｔｇ＝−４０℃と低過ぎるためであると考えられる。比較例２の評価結果が悪い理由は、理論ガラス転移温度Ｔｇ＝４０℃と高過ぎるためであると考えられる。比較例３の評価結果が悪い理由は、水和性官能基含有モノマー（ａ−１）の組成が０．３重量部と低過ぎるためであると考えられる。比較例４の評価結果が悪い理由は、水和性官能基含有モノマー（ａ−１）の組成が１０．０重量部と多過ぎるため、エマルションの安定性が低下し、その結果、得られた合材インキの安定性が低下したためであると考えられる。 As shown in Table 1, the evaluation results were Δ or more for all the examples. On the other hand, it was the evaluation result of x about all the comparative examples. The reason why the evaluation result of Comparative Example 1 is poor is considered to be that the theoretical glass transition temperature Tg = −40 ° C. is too low. The reason why the evaluation result of Comparative Example 2 is bad is considered to be that the theoretical glass transition temperature Tg = 40 ° C. is too high. The reason for the poor evaluation results of Comparative Example 3 is considered to be because the composition of the hydratable functional group-containing monomer (a-1) is too low at 0.3 parts by weight. The reason why the evaluation result of Comparative Example 4 was bad was that the composition of the hydratable functional group-containing monomer (a-1) was too large as 10.0 parts by weight, so that the stability of the emulsion was lowered, and as a result, obtained. This is thought to be because the stability of the composite ink decreased.
Claims (2)
カルボキシル基を含有する第２のモノマー（ａ−２）としてアクリル酸を０．１〜５重量％と、
水酸基、グリシジル基、アミド基及びカルボキシル基を含有しない第３のモノマー（ａ−３）（ただし、共役ジエンモノマーを除く）を９０〜９８．９重量％と、を含むモノマー群の乳化重合物（ただし、Ｎ−メチロールアクリルアミド、ダイアセトンアクリルアミドもしくは共役ジエンモノマーの少なくともいずれか１つを含む乳化重合物を除く）であるポリマーエマルションを有し、
前記第３のモノマー（ａ−３）が、
ホモポリマーのガラス転移温度が５０〜２００℃であって、かつ、メタクリル酸エステル類および芳香環含有モノマー類のいずれかであるモノマー（ａ−４）と、
ホモポリマーのガラス転移温度が−１００℃以上５０℃未満であって、かつ、アクリル酸エステル類および酢酸ビニルのいずれかであるモノマー（ａ−５）と、を含み、
前記ポリマーエマルションは、−２０〜２０℃のガラス転移温度を有し、
当該ポリマーエマルションのｐＨ２のときのＤ５０粒子径が１５０〜２５０ｎｍであって、かつ、ｐＨ９のときのＤ５０粒子径が、ｐＨ２のときのＤ５０粒子径の１．２倍〜１．５倍であることを特徴とするニッケル水素二次電池電極用バインダー樹脂組成物（Ａ）。 A first monomer (a-1) containing an amide group (excluding N-methylolacrylamide and diacetoneacrylamide) in an amount of 1.5 to 5% by weight (excluding 5% by weight) ;
0.1 to 5% by weight of acrylic acid as the second monomer (a-2) containing a carboxyl group;
90-98.9% by weight of a third monomer (a-3) containing no hydroxyl group, glycidyl group, amide group and carboxyl group (excluding the conjugated diene monomer) However, it has a polymer emulsion which is an emulsion polymer containing at least one of N-methylolacrylamide, diacetoneacrylamide or conjugated diene monomer),
The third monomer (a-3) is
A homopolymer having a glass transition temperature of 50 to 200 ° C. and a monomer (a-4) that is one of methacrylic acid esters and aromatic ring-containing monomers,
A homopolymer having a glass transition temperature of −100 ° C. or higher and lower than 50 ° C., and a monomer (a-5) that is either an acrylate ester or vinyl acetate,
The polymer emulsion has a glass transition temperature of -20 to 20 ° C,
The D50 particle size at pH 2 of the polymer emulsion is 150 to 250 nm, and the D50 particle size at pH 9 is 1.2 to 1.5 times the D50 particle size at pH 2. A binder resin composition (A) for nickel metal hydride secondary battery electrodes.
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