JP5141011B2 - 電池電極用バインダー組成物、電池電極用ペースト、及び電池電極 - Google Patents
電池電極用バインダー組成物、電池電極用ペースト、及び電池電極 Download PDFInfo
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- JP5141011B2 JP5141011B2 JP2006352675A JP2006352675A JP5141011B2 JP 5141011 B2 JP5141011 B2 JP 5141011B2 JP 2006352675 A JP2006352675 A JP 2006352675A JP 2006352675 A JP2006352675 A JP 2006352675A JP 5141011 B2 JP5141011 B2 JP 5141011B2
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- FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 244000215747 Pachyrhizus erosus Species 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- CQLZEWXXRJJDKG-UHFFFAOYSA-N azanium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-nonadecafluorodecanoate Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CQLZEWXXRJJDKG-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SKECXRFZFFAANN-UHFFFAOYSA-N n,n-dimethylmethanethioamide Chemical compound CN(C)C=S SKECXRFZFFAANN-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000652 nickel hydride Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 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
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明の電池電極用バインダー組成物(以下、単に「バインダー組成物」ともいう)の一実施形態は、(A)多価金属イオンと結合可能な官能基を有する非架橋ポリマー(以下、「(A)成分」ともいう)と、(B)多価金属、及び分子量が30以上である配位子を含む多価金属化合物(以下、「(B)成分」ともいう)と、(C)N−メチルピロリドンとを含有するものである。以下、その詳細について説明する。
(A)成分は、多価金属イオンと結合可能な官能基を有する非架橋ポリマーである。「多価金属イオンと結合可能な官能基」の好適例としては、カルボキシル基、スルホン酸基カルボニル基、ヒドロキシル基、アミノ基等を挙げることができる。なかでも、カルボキシル基、スルホン酸基、及びアミノ基が更に好ましい。(A)成分は、これらの官能基の二種以上を有するものであってもよい。
(B)成分は、多価金属、及び分子量が30以上である配位子を含む多価金属化合物である。この(B)成分に含有される多価金属は、イオン化された場合に、(A)成分の官能基と結合して(A)成分を架橋させることのできる金属であれば特に限定されない。具体的な多価金属としては、アルミニウム(Al)、チタン(Ti)、ジルコニウム(Zr)、ニッケル(Ni)、コバルト(Co)等を挙げることができる。なかでも、Al、Ti、Niが好ましい。
本発明のバインダー組成物には、その分子構造中にフッ素を含有するフッ素系重合体(以下、単に「(D)成分」ともいう)が更に含まれていることが好ましい。この(D)成分は、その分子構造中にフッ素を含有するものであれば特に限定されないが、具体的には、(d−1)フッ化ビニリデンに由来する構成単位(以下、「(d−1)構成単位」ともいう)と、(d−2)六フッ化プロピレンに由来する構成単位(以下、「(d−2)構成単位」ともいう)とを有する共重合体を好適例として挙げることができる。なお、本発明のバインダー組成物に(D)成分が含有される場合において、この(D)成分は(A)成分とともに、いわゆる複合化重合体を形成していることが好ましい。
本発明のバインダー組成物は、例えば以下に示す方法に従って製造することができる。先ず、(A)成分、及び要すれば(D)成分を含有する水分散体と、(C)成分とを混合して混合組成物原料を得る。次いで、得られた混合組成物原料から水分を除去し、(B)成分を添加すれば、本発明のバインダー組成物を製造することができる。なお、水分を除去する方法については、特に限定されないが、具体的には、蒸留法、限外濾過法、分別濾過法、分散媒相転換法等を挙げることができる。
本発明の電池電極用ペーストの一実施形態は、前述の電池電極用バインダー組成物と、電極活物質とを含有するものである。本発明の電池電極用ペーストは、バインダー組成物と電極活物質とを、必要に応じて添加される各種添加剤とともに混合することにより、調製することができる。
本発明の電池電極の一実施形態は、集電材と、前述の電池電極用ペーストが集電材の表面上に塗布及び乾燥されて形成された電極層とを備えたものである。本発明の電池電極は、前述の電池電極用ペーストが集電材の表面上に塗布及び乾燥されて形成された電極層を備えたものである。従って、本発明の電池電極は、電極層と集電体との密着性に優れたものであり、高速放電での容量低下が少なくサイクル特性に優れた電池を製造し得るものである。
容量維持率(%)={(所定サイクル経過後の放電容量)/(5サイクル目の放電容量)}×100 (1)
○:流動性がある(ゲル化しなかった)。
×:流動性がない(ゲル化した)。
○:沈降物が確認されない。
△:軟らかい沈降物(容易に再撹拌が可能な程度のもの)が僅かに確認される。
×:固い沈降物(再撹拌が容易にはできない程度のもの)が確認される、又は多量の沈降物が確認される。
電磁式撹拌機を備えた内容積約6リットルのオートクレーブの内部を十分に窒素置換した後、脱酸素した純水2.5リットル、及び乳化剤としてパーフルオロデカン酸アンモニウム25gを仕込み、350rpmで撹拌しながら60℃まで昇温した。次いで、フッ化ビニリデン(VDF)44.2%、及び六フッ化プロピレン(HFP)55.8%からなる混合ガスを、内圧が20kg/cm2Gに達するまで仕込んだ。その後、重合開始剤としてジイソプロピルパーオキシジカーボネートを20%含有するフロン113溶液25gを、窒素ガスを使用して圧入し、重合を開始させた。重合中はVDF60.2%、及びHFP39.8%からなる混合ガスを逐次圧入して、圧力を20kg/cm2Gに維持した。また、重合の進行とともに重合速度が低下するため、3時間経過後に、先と同量の重合開始剤を、窒素ガスを使用して圧入して、更に3時間反応を継続させた。反応液を冷却するとともに撹拌を停止し、未反応単量体を放出して反応を停止させ、フッ素系重合体ラテックスを得た。
表1に示す配合処方としたこと以外は、前述の実施例1の場合と同様の操作により、バインダー組成物(実施例2〜4、比較例1、2)を得た。得られたバインダー組成物の金属箔への密着性、及び粘度安定性の評価結果を表1に示す。また、得られたバインダー組成物を用いて調製した正極用ペーストのペースト安定性の評価結果を表1に示す。更に、得られたバインダー組成物を用いて作製した二次電池の容量維持率の測定結果を表1に示す。なお、実施例4で用いたチタンラクテートは、松本製薬工業製の商品名「オルガチックスTC−310」である。また、表1の配合処方における単量体成分の略称は、以下に示す通りである。
MMA:メチルメタクリレート
ST:スチレン
AA:アクリル酸
MAA:メタクリル酸
EDMA:エチレングリコールジメタクリレート
ATBS:2−アクリルアミド−2−メチルプロパンスルホン酸
NASS:スチレンスルホン酸ナトリウム
酸化亜鉛14部、炭酸アンモニウム12部、25体積%アンモニア水40部、及び水30部を混合することにより、Zn/アンモニア錯体を調製した。アルミニウムトリスアセチルアセトナートに代えて、調製したZn/アンモニア錯体を用いたこと、及び表1に示す配合処方としたこと以外は、前述の実施例1の場合と同様の操作により、バインダー組成物(比較例3)を得た。得られたバインダー組成物の金属箔への密着性、及び粘度安定性の評価結果を表1に示す。また、得られたバインダー組成物を用いて調製した正極用ペーストのペースト安定性の評価結果を表1に示す。更に、得られたバインダー組成物を用いて作製した二次電池の容量維持率の測定結果を表1に示す。
Claims (8)
- (A)多価金属イオンと結合可能な官能基を有する非架橋ポリマーと、
(B)多価金属、及び分子量が30以上である配位子を含む多価金属化合物と、
(C)N−メチルピロリドンと、を含有し、
前記(A)非架橋ポリマーが、
(a−1)(メタ)アクリル酸アルキルエステルに由来する構成単位40〜80質量%、
(a−2)官能基含有不飽和単量体に由来する構成単位0.01〜20質量%、及び
(a−3)その他の不飽和単量体0〜40質量%(但し、(a−1)+(a−2)+(a−3)=100質量%)、からなるものである電池電極用バインダー組成物。 - 前記官能基が、カルボキシル基、スルホン酸基、カルボニル基、ヒドロキシル基、及びアミノ基からなる群より選択される少なくとも一種である請求項1に記載の電池電極用バインダー組成物。
- 前記配位子が、アセチルアセトン、アセト酢酸エチル、及び乳酸からなる群より選択される少なくとも一種である請求項1又は2に記載の電池電極用バインダー組成物。
- 前記(B)多価金属化合物が、アルミニウムアセチルアセトナート錯体、アルミニウムエチルアセトアセテート錯体、チタンラクテート錯体、及びチタンアセチルアセトナート錯体からなる群より選択される少なくとも一種である請求項1〜3のいずれか一項に記載の電池電極用バインダー組成物。
- (d−1)フッ化ビニリデンに由来する構成単位50〜80質量%、
(d−2)六フッ化プロピレンに由来する構成単位20〜50質量%、及び
(d−3)その他の不飽和単量体に由来する構成単位0〜30質量%(但し、(d−1)+(d−2)+(d−3)=100質量%)、
からなる(D)フッ素系重合体を更に含有する請求項1〜4のいずれか一項に記載の電池電極用バインダー組成物。 - 請求項1〜5のいずれか一項に記載の電池電極用バインダー組成物と、
電極活物質と、
を含有する電池電極用ペースト。 - 集電材と、
前記集電材の表面上に請求項6に記載の電池電極用ペーストが塗布及び乾燥されて形成された電極層と、
を備えた電池電極。 - 集電材の表面上に、請求項6に記載の電池電極用ペーストを塗布した後、80℃以上の温度で乾燥して、
前記集電材と、前記集電材の表面上に形成された電極層とを備えた電池電極を得る電池電極の製造方法。
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